ACADEMY OF SCIENCES OF THE U. S. s , R.

K. M. Gorbunova and A. A. Nikiforova

Physicochemical Principles of Nickel Plating

TRANSLATED FROM RUSSIAN

Published for the National Science Foundation. Washington D. C. and the Department of Commerce

by the Israel Program for Scientific Translations

PI ATINr.

JL .4. .\.3

i.'

!zdatel'stvo Akadernii Nauk SSSR Moskva 1960

Translated from Russian

Published for the National Science Foundat ion, Washington Do C. , by the Israel Pr-ogr-am for Scientific Translations,

Jerusalem. 1963

OTS 63-11003

Published Pursuant to an Agreement with THE DEPARTMENT OF COMMERCE, U. S. A, and

THE NATIONAL SCIENCE FOUNDATION, WASHINGTON, D. C. by the

ISRAEL PROGRAM FOR SCIENTIFIC TRANSLATIONS

Copyright © 1963

Israel Program for Scientific Translations, Ltd

Translated by Abraham J. Aladjem, B. Sc.

Printed in Jerusalem by Sivan Press

IPST Cat. No. 803

Price: $ 1.50

Available from the Office of Technical Services,

U. S. Department of Commerce, Washington 25, D. C.

T ABLE OF CONTENTS

Introduction .•••••••••••••••••••••••••

C h a pt er 1. A SHORT HISTORY OF THE RESEARCH ON THE REDUCING ACTION OF HYPOPHOSPHITE ON THE SALTS OF

HEAVY METALS • • • • • • • • • • • • • • . • • • • • • • • • 4

C h apt e r II, THE CONDITIONS UNDER WHICH NICKEL COATINGS

ARE FORMED IN AN ACID MEDIUM .•••••••••••• 11

1. The influence of the nature of the metal to be coated • • 13

2. The influence of various factors on the rate of reduc-

tion of nickel

3. The coefficient of utilization of hypophosphite 23

4. The influence of some impurities in the solution on the

rate of reduction of nickel . • • • • • • • • e • • • • • • • 28

Chapter III. METHODS FOR IMPROVING THE PROCESS.......... 33

1. Da ta from the literature . • • • • • • • • • • • • • • • • • • • • • 33

2. The rate of the process as a function of the ratio of hypo-

phosphite concentration to buffer additive concentration 34

3. The influence of complex-forming agents on the nickel

reduction process ••••••••••••••••••••••••••

4. A study of the nickel reduction process at increased hypophosphite concentrations •••••••••••••••••••

5. The methods of regeneration of the nickel solution •••••

Chapter IV. THE COURSE OF THE PROCESS IN ALKALINE SOLUTIONS C hap t e r V. PROPER TIES OF THE COATINGS • 1. Physical and chemical properties

• • • 0·0 • " " " •••••• (I

2. Magnetic prope.rties •••••••••••••••••••••••••

3. Hardness .. ,. e I> e " .. e ell' " It e • II •• " eo ••••• " •• e

4. The hydrogen content of chemically reduced nickel .•••

5. Adhesion .•••••••••••••••••••••••••••••••

6. Brittleness .••••••••••••••••••••••••••••••

7 eo Wear resistance ..•. ". 01 • CI • " e 0 • 0 • " • • .

8. The mechanical properties of steel chemically plated

with nickel ••••••••••••••••••••••••••••• 77

9. The porosity of the coatings •••••••••••••••••• 82

10. The protective properties of the coatings .••••••••• 84

11. The uniformity of the coatings. • • • • • • • • • • • • • • • • • 92

C h a p t e r VI. THE STRUCTURE OF THE DEPOSITS

15

40

45 49

53

61 61 64 65 69 70 72 72

94

C h a p t e r VII, THE MECHANISM OF THE PROCESS OF REDUCTION OF

NICKEL BY HYPOPHOSPHITE • 0 •••••••••••••••• 0 102

L Special features of the chemical nickel plating process. o. 102

2. Development of the concepts of the mechanism of the

reduction process by hypophosphite 0 ••••••••••• ,.. 103

3. The mechanism of the process, including the stage of

reduction by atomic hydrogen . 0 0 • • • • • • • • • • • • • e •• 106

4. The study of the mechanism of hypophosph it e decomposi-

tion ••••• 0 •• 0 • 0 0 • • • • • • • • • ••••••• 0 0 • 0 • • •• 109

5, The mechanism of the phosphorus reduction reaction with

the formation of phosphides .•••• 0 •••• 0 0 e 0 •• 0 , • •• 112

C h apt e r VIII. SOME DATA ON THE INDUSTRIAL APPLICATIONS OF

CHEMICAL NICKEL PLATING. • • • • • • • • • • • • • c • • •• 115

1. Description of the chemical nickel plating methods .•••• i 15

2. Equipment for the chemical nickel plating process • • • • •• 125

3. The range of application of chemical nickel plating. • • •• 128

4. Technical and costing data of the process .•••••••• , •• 131

Chapter IX.
1.
2.
3.
4.
Chapter X.
Chapter XI.
t ,
2.
3. Bibliography

METHODS FOR THE QUANTITATIVE DETERMINATION

OF HYPO PHOSPHITE AND PHOSPHITE IN THE SOLUTIONS 133 Determination of phosphite •• , • • • • • • • • • • • • • •• 134 The simultaneous oxidation of hypophosphite and phosphite

by means of potassium bromate (variant I) ••••••••••• 135 The simultaneous oxidat'ion of hypophosphite and phosphite

by means of iodine (variant II) • 0 •••••••• , e • , ••• , 136 Determination of hypophosphite by other methods •••••• 137

SOME DATA ON THE DEPOSITION OF NICKEL ON NON-

METALLIC SURFACES. , •••••••••• , , • • • • • • • • •• 138

THE CONDITIONS UNDER WHICH COBALT AND NICKELCOBALT COATINGS ARE FORMED .••••••• ,...... 147

The reduction of cobalt salts • • • • • • • • • • • • • • • • • • •• 147 The simultaneous reduction of nickel and cobalt salts. 0 •• 151 Some data on the magnetic properties of cobalt and nickel-

cobalt deposits ••••••••••• , , • • • • • • • • • • • • • • •• 152

153

TRANSLATOR'S NOTE

All photographs in this book have been reduced by approximately 25 %.

INTRODUCTION

Nickel coatings are widely used in practice as they improve the appearance of products while protecting them from rapid corrosive destruction /1/.

Until recently the deposition of nickel was carried out by an electroplating method only. This method can be varied so as to control the rate of deposition and the properties of the coatings, in particular their hardness and brightness. The throwing power of the nickel electrolytes is, however, low, in spite of all the study devoted to methods for the improvement of the uniformity of the coating on irregular objects, and so the deposition of nickel by the chemical reduction of its salts using hypophosphite is most interesting.

The chemical nickel plating process was developed in 1946 by the American investigators Brenner and Riddell /2/ and can be used for the deposition of coatings of uniform thickness and quality on any areas of an irregular surface to which the solution has access. The rate of deposition of the nickel is approximately equal to that obtained in electroplating processes

at moderate current densities, and may reach 20-25 microns/hr.

The resulting coatings do not consist of pure nickel but have a complex composition, and contain up to 15 % phosphorus in addition to the nickel. The presence of the phosphorus substantially affects the properties of the coating both physical, e. g., specific gravity, melting point, magnetic characteristics, etc., and chemical; chemically reduced nickel is more resistant to the action of various corrosive agents than electroplated nickel.

The most characteristic property of chemically reduced nickel is its great hardness which can be increased considerably by heat treatment. The nature of the variation in hardness with temperature, as well as other properties which distinguish these coatings from the electroplated ones,

are due to the special properties of the chemically reduced nickel. Structural studies have shown that the deposit has initially a liquid-like structure which changes on heating with the formation of two phases: nicke 1 phosphide, and a solid solution of phosphorus in the nickel lattice. The transformations which take place on annealing are responsible for the variations of hardness mentioned above as well as for other properties which permit chemically reduced nickel to be used more and more widely in practice.

Chemical nickel plating is carried out by immersing the objects with the surface prepared by the same methods as those used in electroplating, in a solution heated to 90°-95°. The main components of the solution are nickel salts, hypophosphite, and organic compounds which prevent an increase in the concentration of hydrogen ions formed during the reaction and increase the r-ate of the process.

Other substances which act as solution stabilizers are also added to the solution in addition to these components. The stabilizing of the solution

is necessary as, on the one hand, the reaction between hypophosphite and nickel ions causes a rapid change in the composition of the solution with the formation of phosphorous acid, which is a product of the oxidation of the hypophosphite. An insoluble compound which has a detrimental effect on the rate of the reaction is formed by the reaction between nicke 1 i.ons and phosphorous acid ions. On the other hand, the stability of the solution is disturbed under certain conditions by the separation of nickel powder

in the bath. As the nicke 1 powder also acts as a catalyst, a side reaction occurs simultaneously with the coating process, which results in a loss of the main components of the solution.

It is known from the literature that in the USA, where a continuous chemical nickel plating process has been developed, special substances

are used to increase the stability of the solution. The results of research in this direction, however, have not been sufficiently clarified in the published papers. The introduction of chemical nickel plating in the USSR has also necessitated the organization of special investigations, with particular emphasis on the problems of the stability of the solution, and of methods

of increasing the productivity of the process.

The reduction of the metal from its salts by hypophosphite is a complex process which takes place only on surfaces which catalyze the reaction. Thus, the study of the mechanism of chemical ni cke 1 plating is important not only from the point of view of its practical application. An additional aspect of this subject, of theoretical interest, is that under the conditions of the reaction amorphous deposits are formed with a structure unusual for compact metals.

Such deposits are characteristic of certain electrodeposited metals, e. g. , rhenium, manganese, as well as of nickel and copper which have been deposited in the presence of special brighteners. The nature of the processes which give rise to such metallic deposits (termed by us "deposits with a concealed crystalline structure II) has not yet been clarified; it can be assumed that the study of the structure and the properties of chemically reduced metals will help us to understand the mechanism by which these deposits are formed.

In a discussion on the possible application of chemical nickel plating to our industry we must take into account its relatively high cost as compared with that of the electroplating process. The main cause of the high cost of nicke 1 reduction is the present high price of hypophosphite.

It can be assumed that the increase in the production of hypophosphite, which is planned for the near future to help the industrial application of chemical nickel plating, will reduce the cost of this reagent, especially as no chemically pure reagents are needed for the process and the quality requirements could be lowered.

The aim of this monograph is to summarize the data of various investigations dealing with the conditions under which the process takes place, the mechanism of the reaction, and the properties of the resulting coatings; the results of research carried out by the scientists of the Physical Chemistry Institute of the Academy of Sciences of the USSR, as we 11 as those

of other investigators, have been used. Due to the scarcity of papers !3! d.ealing with the industrial applications of the process, the authors considered it necessary to pay some attention to the technical side of thf' nro(,p"'Q +AA

The publication of this monograph has been hastened because of the great interest shown by industry in chemical nickel plating. For this reason, as well as the fact that the present review is the first attempt to Summarize the existing ma.terial, it is possible that the literature has not been completely covered.

A number of papers by both Soviet and foreign authors. which appeared after the work on this book had been completed, have not been used as fully as possible. The monograph does not include the interesting data published in the paper of Gutzeit 190 I. in which an attempt was made to establish a theoretical foundation for the experimentally observed rules governing the autocatalytic reduction of nickel by hypophosphite. The author discusses

a scheme of the process from the kinetic point of view, and includes a

stage of the reaction between the nickel ions and certain intermediate agents which follows the rules of first-order reactions. The calculations of the activation energy and of the activation entropy of the process, which appear for the first time in the above paper, are also of interest.

There has been a considerable increase in the number of works dealing with different aspects of the process over the last years; this is due to a wider range of application and to an increase in the production of chemical nickel coatings; it is therefore necessary to prepare in the very near future reviews dealing with a number of more specialized problems.

The present monograph, which deals with all aspects of the problem, cannot give a complete summary.

All critical remarks and additions will be accepted with gratitude. The authors are grateful to P. P. Belyaev and M. 1. Zil'berfarb for a number of helpful suggestions, as well as to K. V. Chmutov and A. T. Vagramyan, who reviewed this work.

The authors express their sincere thanks to A. A. Sutyagina for her valuable suggestions on the style of presentation.

CHAPTER 1

A SHORT HISTORY OF THE RESEARCH ON THE REDUCING ACTION OF HYPOPHOSPHITE ON THE SALTS

OF HEAVY METALS

The ability of hypophosphorous acid and its salts to reduce metals has been known since the middle of the last century. Wurtz was the first to investigate this reaction /4/. He prepared copper hydride by the action of hypophosphorous acid on a solution of cupric sulfate. The same author reported that an aqueous solution of nickel hypophosphite decomposes at 1000 with the separation of nickel powder.

A detailed study on the reducing action of hypophosphorous and phosphorous acids and their salts on the salts of gold, silver, copper, platinum, palladium, nickel, cobalt, and iron was carried out by Sieverts /5/ and Sieverts and Loessner /6/. Contrary to the reports by Wurtz, Sieverts

did not observe any reducing action by hypophosphorous acid in its reaction on nickel and cobalt salts. At the same time Sieverts noted that nickel

or cobalt powders, prepared by reduction of their oxides with hydrogen, catalyze the decomposition of hypophosphite in solution. The reaction is accompanied by the evolution of hydrogen and the oxidation of the hypophosphite to phosphite, according to the equation:

The failure of hypophosphorous acid to reduce the nickel and cobalt salts can be attributed to the unfavorable conditions under which the experiments of Sieverts were carried out, as shown by later research. Hypophosphorous acid created a strongly acid medium, which had an unfavorable effect on the reaction. A higher concentration of the reducingagent than that used by Sieverts is needed for the formation of a powdered reduction product in the solution.

A series of experiments on the reduction of nickel salts by hypophosphite was later carried out by Breteau /7/, in order to obtain catalysts for the hydrogenation of organic compounds. In his work Wurtz showed that aqueous solutions of nickel salts are reduced by sodium hypophosphite to metallic nickel which separates either as a metallic mirror or as a powder, depending on the experimental conditions.

For these experiments a solution containing 100 g of hypophosphite in 300 ml of water was added to 150 ml of a solution containing 20 g of nickel sulfate. The author notes that when the solution is heated over a water bath, metallic nickel first appears only after several hours, but a vigorous process takes place afterwards, with the evolution of hydrogen. Under these conditions the nickel is reduced to brilliant mp.tal1ir-rni ..... ".,. fl",lr""

In another experiment 70 g of dry sodium hypophosphate were added with stirring to a hot solution of 20 g of nicke 1 sulfate in 100 ml of water. The process was complete within one hour, with the formation of a black powder.

Thus, the effect of the concentration of hypophosphite on the structure of the deposit formed was already observed by Breteau. Breteau assumed erroneously that the product is pure nickel. Actually, the powders formed in the process always contain some phosphorus, as was revealed later. Another observation made by Breteau was that the product formed in the process has a catalytic effect on the hypophosphite , causing it to decompose with the evolution of H2.

In a later work, Paal and Friederici i8/ attempted to separate palladium from a mixed catalyst containing nickel and a small amount of palladium by means of hypophosphite. This attempt was based on the data of Sieverts, according to which the nickel is not reduced by hypophosphite in

a solution, while the palladium is. The catalyst sample was dissolved in hydrochloric acid containing a small amount of nitric aeid, ammonia was added until the solution was alkaline, and then the hypophosphite. Contrary to expectation, heating the solution caused an almost quantitative reduction of the nickel accompanied by the evolu.tion of hydrogen. The authors then studied the conditions under which nickel and cobalt salts are reduced by hypophosphite, with the aim of preparing these metals as powders.

The authors repeated the experiments described by Breteau and noted that the powder formed by the reduction of nickel salts by hypophosphite does not consist of pure nickel but of nickel containing about 13-140/0 of phosphorus. The reduction product was partly a black or gray powder and partly flakes or granular grains. The density of the powder obtained in the different experiments varied within the range 7.637-7.596 g/cm3, and the composition of these powders was nonuniform. According to Paal and Friederici, the reduction product resisted the action of acetic and of hydrochloric acids, but dissolved readily in nitric acid and in aqua regia with the oxidation of the phosphorus to phosphoric acid.

According to these authors, the reduction of the nickel was considerably faster in an ammoniacal sn.utton, and a smaller amount of hypophosphite was required for the separation of the metal. The product formed under these conditions contained 2.7-3.3 % phosphorus, i. e., much less than the nickel prepared by the method of Breteau.

The reduction in an ammoniacal solution was even faster when palladium chloride was added to the solution. In the presence of 0.0005 g palladium per 1 g nickel the phosphorus content of the precipitate changed from 2.3 to 3.7 0/0.

According to Paal and Friederiei, the reduction of nickel in a solution containing nickel sulfate mixed with an alkaline solution of sodium potassium tartrate only takes place if palladium is present. The reduction product always contained oxygen in addition to nickel and phosphorus. The reduction proceeded more smoothly (without the formation of large amounts of oxygen-containing by-products) if sodium acetate was present in the solution. The phosphorus content in this case was lower than that in the product obtained by the method of Breteau but higher than that in the reduction product in ammoniacal solution. Paal and Friederici thought that the phosphorus content of the precipitate depends on the rate of reduction, and increases with increase in the concentration of the nickel salt and of the hypophosphite.

Paal and Friederici observed that cobalt chloride, in contrast to nickel salts, is not reduced by hypophos phi.te in a neutral medium (or in the presence of sodium acetate), even if a small amount of palladium is added to the solution. In ammoniacal solutions, however, the reduction of cobalt salts takes place readily without a catalyst.

The authors note that the reaction product consists of a mixture of co-

balt and cobalt phosphide. The addition of palladium to the solution accelerated the reaction. The phosphorus content of the product decreased with increase in the concentration of the catalyst. The reduction product obtained

in the presence of ins ignificant amounts of catalyst (one part palladium to 500-550 parts cobalt) contained approximately the same amount of phosphorus as the product obtained in the absence of palladium. Phosphorus -free precipitates were obtained in the presence of relatively large amounts of palladium (one part of palladium to 25-50 parts cobalt), but these precipitates contained palladium.

The authors note that the reduction of cobalt salts in an ammoniacal solution is slower than the reduction of nickel salts under the same conditions, and the phosphorus content in the cobalt is higher (about 3.6 %) than that in the nickel (2.7%). In solutions containing sodium potassium tartrate the reduction of cobalt, unlike that of nickel. takes place even without palladium.

Scholder and Heckel /9/ and Scholder and Hakeri /101 carried out extensive research on the reduction of nicke 1 and cobalt salts by hypophosphite. The attention of the authors was directed mainly to a study of the reduction products obtained in the form of powders.

The authors noted the unusual course of the reaction, which differs from simple reduction reactions because a large excess of the reducing agent,

in this case an alkali-metal hypophosphite, must be used. When such a solution with a large amount of hypophosphite is heated. the formation of the powder-like precipitate starts suddenly and is accompanied by a vigorous evolution of hydrogen.

As large amounts of froth were formed in the process. big reactors with a volume 20 times that of the solution had to be used. No reaction took place in the solution, even after prolonged heating. if an insufficiently large excess of hypophosphite was taken. The authors recommended the use of the readily soluble potassium hypophosphite in the reaction. No reaction occurred when the ammonium salt was used even at very high hypophosphite concentrations and on prolonged heating of the solution.

In agreement with the results of Sieverts, no reaction took place when hypophosphorous acid was used instead of its salts. The authors correctly attributed the absence of reduction of the nickel salts in these experiments to the high acidity of the solution. and assumed that the process takes place only in neutral or alkaline media. Contrary to the data of Paal and Friederici, Scholder and Heckel established that nickel powder can be formed in an acetate solution even in the absence of palladium.

For the preparation of large amounts of nickel powder the authors recommend that the reaction be carried out at 900, using a solution of 1 kg of potassium hypophosphite in 2 liters of a nickel acetate solution saturated at room temperature. The solution becomes strongly acidic during the process, and the reduction of the nickel is not complete. From 80 g of nickel taken for

the reaction 80 g of a product containing 68 g of nickel is obtained. The

authors correctly attribute the incomplete reduction of the nickel to the increase in the acidity of the solution.

Scholder and He eke 1 report that cobalt salts are reduced by hypopho s - phite only if an alkali is added to the solution. In the presence of certain alkalies the reaction takes place even at room temperature if a small amount of the r-e act i.on product is first added to the solution. In order to obtain a powder free from occ luded cobalt hydroxide, the authors recommended the addition of a tartrate to the solution until it was clear. The rate of the reaction increases considerably with increase in temperature. Experiments in an autoclave showed that lower hypophosphite concentrations can be used at higher temperatures of the order of 165°-170°.

To obtain a fairly high yield of cobalt powder the authors recommend that a solution of 63 g of cobalt acetate in 300 ml of water be added to a solution containing 155g potassium tartrate, 50ml of water, and 250ml

of a 50 % potassium hydroxde solution. Potassium hypophosphite is added to the above mixture as a solution (400 gin 200 ml of water) Strong frothing starts when the solution is heated to 80°-900, and a black powder is precipitated.

TABLE 1

Phosphorus content in the precipitates as a function of the conditions under which the reaction was carried out

Composition of the solution

Ni

P

Average Ni: P ratio

Author

Composition of the reaction product, %

Nickel salt + H3P02 .

medium

No reaction takes place Sieverts
Schol der
84.8-86.8 13.1-14.2 1:0.299 Paal
84.3-85.8 10.8-12.2 1:0.258 Scholder
96.89 2.70(3.29) 1: 0.053 Paal
94.5-96 2.3-3.8 1: 0.056 Paa l
81.6 8.3 1: 0.19 Scholder
89.7 6.1 1:0.128 Paal
The reduction takes place only to Scholder
K2[Ni(CN13J. no separation of
nickel occurs NiS04 + NaH2P02 .

Ni(CH3COO}z + KH2P02 .

NiS04 + NaH2P02 in all ammoniacal

NiS04 + NaH2P02 in an ammoniacal medium in the presence of a palladium

salt ...........•......•..

Ni(CH3COO)2 + KH2P02 + sodium

potass ium tartrate + KOH .

NiS04 + CH3COONa + NaH2P02 in the presence of palladium salt

NiCIZ + an alkaline cyanide solution +

+ KHZP02 .

The authors note that no reduction takes place in the reaction between hypophosphite and a cobalt cyanide complex, while the nickel salt is reduced only to monovalent nickel.

Independently of Paal and Friederici, Scholder and Heckel showed that the product of the reduction of nicke 1 and cobalt salts by hypophosphite always contains phosphorus, in amounts from 2.5 to 14%. The authors noted

that the phosphorus is present in the precipitate as phos phide s , The ph os - phorus content in the precipitate increased with increase in the acidity ofthe solu-tion during the reduction process. To confirm this relationship, Scholder and Haken present the data on the composition ofthe products of the reduction of nickel salts. obtained by different investigators under various conditions (Table I},

The formation of products with a high phosphorus content was attributed by the authors to the action of the acid formed in the reaction which dissolves the metal more rapidly than the phosphides and thus causes the reaction product to be enriched with phosphorus. In addition, a phosphide with

a low phosphorus content can be converted during the process into a ph os - phide with a high phosphorus content. Scholder and Hecke 1 made a detail-

ed study of the product formed in the reduction, and paid particular attention to the nature of the phosphorus containing compound and to its behavior towards acids. They showed that the product of the reduction of the nicke 1 salts in acid solutions has a nonuniform composition and is bas ical ly a mixture of various phosphides. The nicke 1 and cobalt which were precipitated from alkaline solutions contain elementary nickel or cobalt, respectively, besides the phosphides. The nickel powder prepared from acid solutions is therefore nonmagnetic, while the precipitates formed in alkaline solutions contain both phosphides and metallic nickel and show magnetic prope rties.

According to the observations of these authors, the product is dissolved by dilute mineral acids and acetic acid with the evolution of hydrogen, but the process is slow even on heating. The process is somewhat more rapid in dilute nitric acid and the rate increases with increase in the concentration of the acid. Phosphorus hydride is either not formed when the product is dissolved in acids, or formed only in trace amounts. As the nickel dissolves in acids more rapidly than the phosphides, the undissolved precipitate becomes enriched in phosphorus.

Scholder and Heckel succeeded in separating a number of phosphides

with well defined compositions. The residues after the action of dilute acetic acid or hydrochloric acid are Ni5P2 and Ni2P, respectively. If the Ni5P2 is subsequently treated with Hel it is also converted to Ni2P. The action of hydrochloric or acetic acid on the reduction product is presented schematically as follows:

Reduction product Ni4P

Hydrochloric acid ~ Acetic acid

I '-- .Ni2P_--1

Acetic acid Hydrochloric acid

The authors showed that the solution of the phosphides in hydrochloric acid is accompanied by the formation of phosphorous acid and the evolution of hydrogen. On the basis of the amounts of the various products formed in the solution of the phosphides, Scholder and Heckel showed that the process can be represented by the following equations:'

Ni2P + 4HCl -{- 3H20 '" 2NiC12 + H3P03 + 31/2H2;

(1)

(2)

The authors believe that the formation of phosphorous acid during the dissolving of the phosphides passes through an intermediate stage of PCls which then reacts with water. The authors represented the intermediate reaction as follows:

NiZP + 7HCl '" 2NiCl2 + PCl3 + 3 J/2H2, PC13 + 3H20 '" H3P03 + 3HCl.

From these reactions the authors concluded that the phosphides present in the reduction product are not true phosphides (i . e .. derivatives of phosphorus hydride) but compounds of an intermetallic type.

The experimental results enabled Scholder and Hecke 1 to put forward a theory on the course of reduction of nickel salts by hypophosphite, which will be discussed in the chapter dealing with the mechanism of the chemical reduction process.

The above research considerably widened our concepts of the mechanism of the reduction of metallic salts by hypophosphite, and of the nature of the resulting products. Although all these works describe the conditions under which a powder is formed in the solution, the rules established are of great importance for the chemical nickel plating process, which is the subject of this monograph.

The utilization of the reducing action of hypophosphite on nickel salts for the preparation of compact and strongly adherent metal coatings was described for the first time in the patent of Roux in 1916 /11/. This patent gave a method for the deposition of nickel coatings by immersion of metallic products in a hot solution containing nickel citrate, ammonia, and the hypophosphite of an alkali metal. The author showed that it was possible

to deposit nickel on certain metals but the work found no further development.

The possibility of depositing compact nickel and cobalt coatings on various metals by reduction of their salts by hypophosphite was established again by Brenner and Riddell in 1946-1947 /2/. The reducing action of hypophosphite which gives the above results was observed entirely by chance under the following circumstances. The authors were engaged in an investigation for the preparation of a nicke l-tungsten alloy by e lectrodeposition from an ammoniacal citrate electrolyte. The resulting deposits were

rather stressed, [sic], which the authors attribu.ted to the effect of the oxidation products of the citrate formed in the solution. A number of reducing agents, one of them hypophosphite, were added to the bath to prevent the oxidation of the cttr-ate s , A stee 1 tube was used as the cathode, and the anode was placed inside; thus, deposition of the alloy took place only on the internal surface of the cathode. The electrolysis was carried out at an e levated temperature.

It was observed that when hypophosphite was added to the solution, the external surface of the tube was also coated with nickel; in addition, in spite of the considerable amount of gas formed on the cathode, the current

efficiency was above 100 o/a. The authors explained this phenomenon by the deposition of nickel, simultaneously with the cathodic reduction process, because of the reduction of the nickel salt by the hypophosphite.

The fact that the reaction is confined to the surface, and the absence of a reaction in the bulk of the solution, in contradiction to the results obtained by earlier investigators, were attributed by the authors to the lower hypophosphite concentration. The deposition of ni cke 1 on the surface of the sample is caused by the catalytic nature of the process.

The unusual results obtained in the work with the hypophosphite - containing electrolytes initiated the development of further research and the establishment of a new method for the deposition of metallic coatings, called by the authors "e lectroless", i. e., a process for the plating of ni.cke 1 without the use of electricity.

CHAPTER 2

THE CONDITIONS UNDER WHICH NICKEL COATINGS ARE FORMED IN AN ACID MEDIUM

A series of experiments were carried out by Brenner and Riddell /2/

to establish the conditions under which nickel (and cobalt) coatings are formed. In accordance with the data of earlier investigators on the conditions under which a powder is formed by reduction, Brenner and Riddell found that the process is a catalytic one, i , e.. the nicke 1 is not reduced on every surface, but only on the surface of metals which catalyze the reaction.

As nickel itself is one of these metals, the growth of the deposit could be prolonged indefinitely under appropriate conditions, and layers of any thickness obtained. The process starts spontaneously on nicke 1. cobalt. palladium, iron, and aluminum surfaces.

In their first experiments Brenner and Riddell used alkaline ammonia-

cal solutions. These solutions were, however, unstable because of the evaporation of the ammonia at the elevated temperatures required for the reaction, and so these authors turned to a study of the process in acid media.

As a result of a large number of experiments it was found that acid solutions have a number of advantages over alkaline ones, i.e., the acid solutions are more stable at elevated temperatures, the process is more rapid, and the resulting coatings are of a better quality. As a consequence, the interest of scientists in later experiments was directed mainly to acid solutions. It must be noted, however, that from certain points of view the alkaline ammoniacal solutions are of considerable interest.

The results of the studies on acid and alkaline solutions will be presented separately, due to the specific features of the course of the process in each of these media.

In their search for the optimum conditions of the process in acid solutions, Brenner and Riddell studied the effects of the temperature, the acidity, and the composition of the solution. These studies showed that the rate of the process depends to a considerable extent on the temperature

of the solution. Practical rates of reduction of the nickel are obtained at about 90°

As the acid formed in the reaction reduces the rate of formation of the coating, the authors recommended that the solution be neutralized systematically, while to maintain an optimum pH value they proposed the addition of buffer compounds to the solution. A number of salts of organic acids, namely of glycolic, citric, acetic, tartaric, formic and other acids were tried as buffers, and the best results were obtained with sodium glycolate. On the basis of their experimental results Brenner and Riddell recommended the use of certain solutions; the compositions are presented in Table 2.

TABLE 2

Cornpos it io ns of the ada nickel solurtons recomrcended by Hrenner and Ridden

r~\--T-~T~~v---

---}----+-----;~-rl 30

Nickel chloride NiCI2- 6H20 30 _

Nicke! sulfate NiS04-7HZO Sodium hypophosphite NaH2P02- H20 Sodium glycolate CH20HCOONa Sodium acetate CH3COONa' 3HZO Sodium c itrat e Na3C6H50T 51/2 H20 pH 4-6, temperature 90°_92° Rate of formation of the coating,

microns/hr . _ .. , . • . . • . . . . . . . 15

Outer appearance of the coating ... Sem ibrtght

I

30

10

10 10 10
10
10
10
13 5 25
Semtbright Semihright Coarse.
uneven 50

Besides the search for optimum process conditions, the authors also paid much attention to the study of the mechanism of nicke 1 reduction and of the properties of the resulting deposits. Some of the results of these studies will be presented in the respective chapters.

The complete course of the reaction taking place in hypophosphite solutions containing nickel salts can be represented by the following equations:

NiCl2 + NaH2P02 + H20 _., Ni + NaH2P03 + 2HC1; (1)

NaH2P02 + H20 -> NaH2P03 + H2. (2)

Reaction (1) causes reduction of the nickel and acidification of the solution. Earlier investigators assumed that reaction (2) was a side one.

The data of Brenner and Riddell were the basis for further research on the chemical nickel plating process, to study the effect of various factors on the rate of deposition and on the qual ity of the deposit so that the process could be applied to the commercial plating of irregular objects with uniform layers. The mechanism of the process was also studied, as a knowledge of this is a prerequisite for efficient control of the process.

The necessity for such research arose from the special characteristics of the process which had been observed since the earliest studies. The main characteristic is the change in the composition of the solution which occurs during the process. The most important change is a decrease in the concentration of the nickel salt and of the hypophosphite. The amount of phosphite, a product of the oxidation of the hypophosphite, increases simultaneously, and the acidity rises. As a result of the above changes, the rate of reduction of the nickel decreases continuously if the components are

not replaced. The nature of these changes, however, depends on a number

of factors. .

As the reduction of the nickel takes place only on the surface of the metal immersed in the solution, the rate at which the changes in the composition occur, and consequently the decrease in the rate of the reaction depend to a great extent on the area being coated in a given volume of the solution. Consequently, when the effect of different individual factors is being studied,

the experiments must be carried out under conditions which ensure a constant composition of the solution during the process, i. e., Iar-ge volumes of the

solution must be used and. the area to be coated must be small. Otherwise, a comparison of the effect of the individual parameters on the rate of the process will be possible only if a constant ratio of the coated surface to

the volume of the solution is maintained, and if the duration of the process is the same in each case.

In the investigations /12,13/ carried out by the authors of the present monograph the ratio of coated sur-face (in dm2) to volume of the solution (in liters) was 0.8: 1, while in

the majority of the experiments it was 1: 1, and the experimental time was one hr. In order to keep the rate of the process approximately equal to the rate in the initial compo-

sition of the solution, the experimental time was shortened in some cases to 30 min.

As can be seen from the above, the results of a 30 minute experiment recalculated for a one hour one do not give the same results as those obtained in actual one hour experiments. The recalculation naturally gives too high a resuit for the rate per hour.

The curve in Figure 1 shows the change in the rate of reduction of the nickel during several hours of immersion in the bath, when the components are not replaced. The experiments were carried out in a solution containing 30 g nickel chloride, 10 g sodium hypophosphite, and 10 g sodium glycolate per liter (the latter acting as a buffer). The volume of the solution was 300 m 1 and the surface area of the sample was 25 cm 2. It is evident from

the figure that the rate of deposition decreases rapidly under these conditions.

To obtain a constant rate of deposition it is necessary to replace the components which are used up during the nickel plating process; however, as

it will be seen later on in the text, the maintenance of a constant composition is very difficult due to the increase in the concentration of the hypophosphite oxidation products.

The character of the changes in the composition of the solution described above greatly complicates the application of the process in practice. The present day process is based on data which show the effect of various factors on the course of the reaction and on the properties of the deposits.

FIGURE 1. Decrease in the rate of

deposition during chemical nickel plating when the components in the

solution are not replaced

1. The Influence of the Nature of the Metal to be Coated

We have already mentioned that the reduction of nickel salts by hypophosphite starts spontaneously only on the surfaces of certain metals, such as nickel. cobalt, palladium, iron, and aluminum. Other metals on which the deposition of nickel is not spontaneous, such as copper, brass, and platinum, can also be plated with nickel by immersing the metal in the solution and bringing its surface into contact w ith nickel or another metal Glore

electronegative than nickel, e. g., iron or aluminum. A galvanic cell is created as a result of this contact, a nickel layer is deposited on the surface of the metal, and the reduction process continues on this layer. Similarly, in the case of aluminum or iron on which the process starts spontaneously when they are immersed in the solution, a nickel film is apparently formed during the first moments by displacement from the solution.

If we take this point of view we cannot consider, as did Brenner and Riddell, that iron and aluminum belong to the group of metals which catalyze the reaction.

In another method proposed by Brenner and Riddell for the coating of catalytically inactive metals such as copper and brass, catalytically active metals such as palladium or rhodium are deposited on their surface. The palladium is deposited by immersing the objects in a solution containing

0.02 g of palladium and 20 m l of hydrochloric acid per liter. The authors note that the formation of the palladium film on the prepared metallic surface is carried out immediately before the immersion of the objects in the hot nicke 1 solution. At the same time the objects must be washed after their treatment in the palladium solution to prevent the entry of palladium salts into the nickel bath. The time of immersion in the palladium bath depends on the temperature of the latter and on the state of the metallic surface. Thus, in the case of a copper surface which has been subjected to bright etching (in a mixture of H2S04 and HN03, or H3P04 and HN03) the authors recommended immersion in the palladium solution for several seconds

at 25°.

In certain cases immersion in the palladium solution for several minutes is necessary depending on the method of preparation of the surface. A solution heated to 60° is used for deposition of palladium on brass, regardless

of the method used for the preparation of the surface; the immersion time is about 1 min.

TABLE 3

Effect of the advance treatment on catalytically inactive metals + the surface can be coated with. nickel

- the surface cannot be coated with nickel

Contact process Immersion in a palladiwn solution
Metal surface an alkaline an acid an alkaline an alkaline an acid an alkaline
nickel nickel cobalt nickel nickel cobalt
solution solution solution solution solution solution
Copper + + + + + +
Brass + + + + + +
Platinum + + + - - -
Gold + + + + + +
Silver + + + - - -
Lead - - - - - - The thickness of the palladium, equal to one molecular layer (2' 10- B em) is enough to start the nickel reduction process. The authors of this method be lieve that in spite of the high price of the palladium the cost of this treatment is not high, as the amounts of palladium used are insignificant. One

liter of a solution containing 0.01 g of palladium can be used for coating

200 dm2 of a metallic surface. Table 3 shows the results of the experiments of Brenner and Riddell on the activation of catalytically inactive surfaces before the nickel plating. These results were obtained with alkaline and acid nickel solutions and with alkaline cobalt solutions.

It must be noted that the deposition of nickel on certain metals such as lead, cadmium, zinc, tin, bismuth, and antimony is impossible even when these methods are used.

2. The Influence of Various Factors on the Rate of Reduction of Nickel

Effect of the temperature. One of the main factors determining the rate of the process is the temperature. It has been established in a large number of works by various authors on the effect of temperature on the rate of deposition that the process hardly occurs at low temperatures.

Data on the effect of temperature on the rate of the process are shown

in Figure 2. The experiments were carried out with a solution containing

30 g nickel chloride, 10 g sodium hypophosphite, and 8 g sodium acetate

per liter, at pH 5. In contrast to the other experiments, the process time

in this case was 30 min. The volume of the solution was 100 m l and the surface area of the samples was 10cm2. A similar influence of the temperature on the rate of deposition was also observed by other authors in solutions of various composition. These data show that the reduction of the nickel becomes noticeable at 40°-50°. The rate of the process increases with increase in temperature, and in solutions heated to 900 it reaches values comparable to those observed in the electroplating process at moderate current densities. The rate of the process is further increased when the temperature is raised to 980-990, and at 980 this rate is 300/0-400/0 higher than at 900•

- o

s

oj

P:: 50 60 70 80 90 tOO

Temperature, =c

FIGURE 2. The influence of the temperature on the rate of deposition

The influence of the acidity of the sol uti 0 n. The acidity of the solution has a considerable influence on the reduction process. It is essential to take this effect into account since, as already mentioned, a spontaneous increase in the acidity of the solution occurs during the reduction process.

The data of various investigators show that the best results as regards the rate of reduction of the nickel and the quality of the coatings are obtained in solutions with pH 5.0-5.5.

The influence of the pH on the rate of deposition in a solution containing 30 g nickel chloride, 10 g sodium hypophosphite, and 10 g sodium glycolate per liter at 90° is shown in Figure 3. The data in this figure show that the rate of the process decreases noticeably with increase in the acidity of the solution, and the reduction

of the nickel practically ceases at pH 3. The rate

of r-e duct ion 01 ni cke 1 from freshly prepared solutions increases when the acidity is reduced to pH 6.0--6.5, but it is difficult to maintain the pH at this value, because of the formation of sparingly soluble nickel compounds during the process.

The results of a study on the influence of the acidity of the solution on the rate of reduction of the nickel, carried out by Minjer and Brenner /14/, are presented in Figure 4.

The experiments were performed in solutions containing various organic compounds at a constant concentration of the main components, 30g nickel chloride and 109 sodium hypophosphite per liter. A s arnp ie with a small surface was taken for coating and a relatively large volume of the solution was used in order to prevent sharp changes in the pH caused by the acids formed during the reaction (the volume of the solution was one liter, the surface area of the sample was 12 cm+). The experimental time was one hour.

Figure 4 shows the above mentioned decrease in the rate of reduction of the nickel with decrease in the pH of the solution. As is evident from the figure, the variation in the rate

of deposition of the nickel as a function of pH, as well as the intensity of the variation of the acidity of the solution during the experiment (shown in the figure by the length of the horizontal sections) depend both on the nature and on the concentration of the organic compound used.

Bosdorf and Muller /15/ who studied the influence of the acidity of the solution on the rate of the process, present data on the variations in pH during the plating of nickel in solutions containing different amounts of sodium glycolate. The stability of the pH increased with increase in the concentration of the sodium glycolate (up to 60 g /1), but the rate of the process decreased at the same time. The maximum rate of the process in these experiments was observed at a sodium glycolate concentration of

30 gil, in spite of the fact that the acidity of the solution under these conditions varied more than in the solutions with a higher glycolate content. This lack of agreement between the rate of the process and the acidity of the solution is attributed to the specific action of the organic substances which have more effect on the process than that due only to their buffering properties.

Deviations from the established relationship between the rate of the process and the acidity have also been observed in a number of other cases. For example, in solutions containing sodium succinate (15 gil) no reduction of the nickel was observed at a hypophosphite concentration of 10 gil and at pH 6, while a fairly rapid process started when the acidity was increased to pH 5.

Such deviations from the general rules have also been observed in solutions containing relatively large amounts of sodium acetate, i. e., 20 g!l,

wi th a hypophosphite concentration of 10 gil. The rate of de pos it ion of tt.e

nickel in the above solution was higher at pH 4.5 than at pH 5.

pH of the inittal solution

FIGURE 3. Influence of the act-

dity of the solution on the rate of deposition

It must be noted that to establish the opt irnum conditions for the pi_'OCeSS with respect to the acidity of the solution, the discussion must not be con" fined to the influence of the pH on the rate of reduction of the nickel. The influence of the pH on the stability of the solution, as shown by the ability of the latter to retain in solution the phosphite formed during the reaction, is also of great interest.

The effect of the acidity on the solubility of the phosphite, the precipitation of which has a detrimental effect on the nickel plating process, will

be discussed in the fourth section of this chapter.

Influence of the concentration of hypophosphi.te.

Brenner and Riddell noted in their first study on the chemical nickel plating process that the rate of deposition is not noticeably affected when the hypophosphite concentration is varied within a wide range of concentrations, i , e. , from 10 to 100 gIl. The authors therefore concluded that the rate of the process in an acid solution does not depend on the hypophosphite concentration.

In our experiments with a solution containing 30 g nickel chloride and

109 sodium glycolate per liter, we also did not notice any appreciable influence of the hypophosphite concentration, which is in agreement with the data of Brenner and Riddell. Although a small increase in the rate of reduction of the nickel was observed when the concentration of hypophosphite was increased from 5 to 10 gIL, the rate of deposition decreased when this concentration was further increased to 30 gl s, The experimental results are presented in Figure 5.

pH of the solution

FIGURE 4. Relationship between the rate of deposition and the actdity of the solutions containing different buffer addttrves, the length of the section represents the variations in the pH of the solution dur-ing the experiments; experimental time - one hr.

- sodium glycolate (as the acid) 39g/1;

- - - sodium glycolate (ditto) 25 gil;

------ sodium citrate 15 gIl + sodium acetate

5g/l; _. _._. sodium citrate 15g/1 (from reference 114/).

P.P. Be lyae v, M.L Zi l.tber-far-b, and lVI.P. Garetovskaya /16/, who studied the dependence of the rate of the process on the concentration of lo"~~hhn"nhitp in " ",ollltion containing 100 g nickel sulfate and 10 g sodium

fO

-0

o

5 10 IS 20 25 -10

Concentration of sodium hypophosphite, g/ I

0102030405050 70 800100 Concentration of nickel chloride, gil

FIGURE 5. Influence of the concentration of sodium hypophosphite on the rate of deposition

FIGURE 6. Influence of the concentration of nickel chloride on the rate of deposition

acetate per liter (as a buffer), state that the rate of deposition increases slightly when the concentration of the hypophosphite is increased from 10 to 30 gil (the th ic kne s s of the deposit after 30 min was 10 and 12 microns respectively), but this rate remains practically constant with further increase in concentration.

It must be noted, however, as shown by our later experiments, that the rate of reduction of the nickel is independent of the hypophosphite concentration only under certain conditions, i. e., in solutions in which only the hypophosphite concentration is varied while that of the other components, i. e., the nickel salt and the buffer additives, is kept constant during the experiment. We shall show below that when the ratio of the amounts of the other components of the solutions to that of the hypophosphite is varied,

the concentration of the latter considerably affects the rate of reduction

of the nicke 1.

I n flu e n ceo f the con c e n t rat ion 0 f the n i c k e 1 sal t. It was found during the study of nickel plating solutions with a low hypophos - phite content (about 109 10 that variations in the concentration of the nicke 1 salt over a wide range have little influence on the rate of the process. Brenner and Riddell indicate in their work that variations in the nickel salt concentration within the range from 3 to 50 gil cause no substantial changes in the rate of reduction of the metal, but the rate of reduction decreases slightly at a nickel chloride concentration of 100 gil.

In our experiments 112/, carried out with solutions containing 10 g hypophosphite and 10 g sodium glycolate per liter, we also did not observe any sharp changes in the rate of the process as a function of the nickel chloride content. The results of these experiments are presented in Figure 6. The data show that the highest rate of the process in these solutions was obtained at a nickel salt concentration of 30 gil. The rate of reduction of the nickel decreases slightly when the concentration of the nickel chloride is increased to 50 gil, and then remains constant. In solutions containing 10 g hypophosphite and 8 g sodium acetate per liter (as a buffer). the rate of the process was also little affected by variations in the concentration of the nickel salt. The results of these experiments are presented in Table 4.

TABLE 4

Relationship between the rate of the process and the concentration of the nickel sa lt in a solution containing 10 g sodium hypophosph lte and 10 g sodium acetate pel' liter

pHr--'S. T'e m pera tur e e-> 95°.

----
Nickel chloride
concentration, s/! 10 15 20 25 30 40 50 60 70 80 90 100
Rate of deposition,
microns/hour 12.3 13.3 13.6 14.5 14.5 14.6 14.5 14.7 14.8 14.5 13.8 13.9 The results of P. P. Belyaev, M.1. Zil'berfarb, and M. P. Garetovskaya, who carried out experiments with a solution containing 20 g hypophosphite and 10 g sodium acetate per liter, were somewhat different from the above. They used the sulfate as the nickel salt. According to the authors, the maximum rate of the process was obtained at a nickel sulfate concentration of 100 g /1. The influence of the concentration of the nickel salt was, however, negligible under these conditions too; when the nickel sulfate concentration was increased from 30 to 120 gil, the thickness of the nickel layer obtained in 30 min increased only from 9 to 11 microns.

It should be noted that the weak relationship between the rate of the nickel plating process and the concentration of the nickel salt is characteristic of solutions with a low hypophosphite concentration. The behavior observed in solutions with a higher hypophosphite content will be given later.

The influence of the nature and of the concentration oft h e buff era d d i t i v e. The salts of organic acids considerably affect the reduction process. These salts are used to maintain the pH at the optimum value. A large number of works have shown, however, that their effect is not only confined to the buffering action; these salts have a specific influence, dependent on their nature, on the process and on the rate of reduction of the nicke 1.

In their work Brenner and Riddell used the salts of glycolic, acetic, and citric acids as buffer additives, with a preference for sodium glycolate.

The use of the salts of saturated dibasic organic acids as the buffer additive, in particular those of succinic, malonic, and glutaric acids, was proposed by Gutzeit and Ramirez 117/.

It has been shown in a number of papers that the rate of reduction of

the nickel and the quality of the deposit is related to a great extent to the concentration of the buffer additive, and that the optimum concentration

of the additive for the highest rate of deposition and a good quality deposit depends on the nature of the buffer additive. As shown by our experiments, the optimum concentration of the buffer additive depends also on the hypophosphite concentration in the solution.

Brenner and Riddell noted the considerable influence of the concentration of the buffer additive on the process, and present the data obtained in experiments carried out with solutions of nickel sulfate or chloride containing 10 g of sodium hypophosphite per liter in the presence of sodium acetate. The results of these experiments are presented in Table 5.

As is evident from the above data, the rate of reduction of the nickel in the different solutions reaches a maximum value at different concentrations

TABLE 5

Relationship between the rate c£ the. process and the concentration of sodium acetate

Composition of the base Concentration of Rate of deposition,

solution, gil sodiu.rn acetate, g/l microns/hr

4.5 20
Nickel sulfate 35 10 25
Sodium hypophosphite 10 15 10
Nickel chloride 30 2.2 5
5.5 15
Sodium hypophosphite 10 15 2.6
45 1.6 of the bu.ffer additives, and the rate of the process decreases when the concentration is higher or lower than these.

In the above mentioned paper of P. P. Belayev, M.1. Zil'berfarb, and

M. P. Garetovskaya /16/, which deals with the influence of sodium acetate on the process taking place in a solution containing 100 g nickel sulfate and 20 g sodium hypophosphite per liter, it is stated that the highest rate of the process is obtained at a sodium acetate concentration of 10-20 g /1. The authors also note that the concentration of the sodium acetate considerably affects the quality of the coating; thus, a bright, uniform coating is obtained at a concentration of 109 /1, while at 20 g /1 the coating is stratified and spotted. Dark deposits are obtained when the sodium acetate concentration is increased to 30 gil.

We observed in our experiments /18/ that the concentr-at ion of sodium acetate at which the highest rate of reduction of the nicke 1 is obtained and

a good-quality deposit, depends on the hypophosphite concentration. In a solution containing 20 g nickel chloride and 10 g hypophosphite per liter, the best results were obtained at a sodium acetate concentration of 8-10 gil. According to the data of the above mentioned investigators, an increase in the concentration of sodium acetate above the optimum value causes a deterioration in the quality of the coating, More detailed data on the results of the study of solutions containing sodium acetate as an additive are presented below (chapter 3).

Brenner and Riddell noticed not only the favorable influence of sodium acetate in the presence of which fairly high rates of reduction of the nickel are obtained in comparison with those obtained with other substances, but also the disadvantages of this buffer additive. They note in particular that solutions containing sodium acetate become turbid during the process, and the coatings obtained in these solutions become dark and rough. From this point of view better results were obtained with solutions containing sodium glycolate as the additive. Experimental results showing the influence of the concentration of this additive on the rate of reduction of the nickel are presented in Table 6.

In a study of the chemical nickel plating process with a solution containing 30 gnickel chloride and 10 g sodium hypophosphite per liter, in the presence of sodium glycolate, we observed that the maximum rate of the process is obtained at a sodium glycolate concentration of 20 gil (Figure 7).

The rate of the process decreased when the concentration was increased above this value, and the quality of the deposit deteriorated at the same time. It should be noted that we did not succeed in obtaining bright coatings at the high sodium glycolate concentrations (50 gIl) recommended by a number of authors.

Bosdorf and Muller 115 I also observed a maximum in the curve' showing the relationship between the rate of deposition and the concentration of the buffer additive during their study of chemical nickel plating in solutions containing sodium glycolate. A solution containing 30 g nickel chloride,

10 g sodium hypophosphite, and 2.5 g cobalt acetate per liter, was used in this experiment. The cobalt acetate was added to increase the brightness of the coating. The experiments were carried out at 97°-98°, at pH 4.5, and a ratio of surface to be coated (in drn ~ to volume of solution (1), equal

to 0.5: 1. Five g of sodium hypophosphite per liter were added to the solution each 30 min. The maximum rate of the process was obtained at a sodium glycolate concentration of 30 gIl, the thickness of the nickel layer deposited during 2 hrs was 34.5 microns; the rate of deposition was 29 microns/2hrs at a concentration of buffer additive of 60 g II, and only 11.3 microns I 2 hrs in the absence of such an additive.

TABLE 6

Relationship between the rate of the process and the concentration of sodium glycolate

Composition of the base solution, gil

Concentrationofso-. Rate of deposition,

diumglycolate, gil microns/hr

Nickel sulfate 35 10 3
50 10
Sodium hypophosphite 10 100 8
200 7
Nickel chloride 30 10 10
50 15
Sodium hypophosphite 10 100 18 The position of the maximum was somewhat different from that obtained in our experiments, apparently because of the different conditions under which the experiments were carried out.

According to the data of Brenner and Riddell, and also to the data of our experiments, the addition of sodium citrate (within the concentration range 10-50g/1) has a certain favorable influence on the process, but the rate of reduction of the nickel in the presence of this additive is very low. The

low rate of deposition of the nickel, as compared with that from solutions containing other additives (e. g., sodium acetate) is attributed to the formation of a complex compound between the nickel and the sodium citrate, which renders the reduction of the nickel more difficult. Brenner and Riddell studied the effect of such buffer additives as the salts of tartaric, maleic, and formic acids, and concluded that they have little influence on the rate of the process.

21

S. M. Panchenko and M. A. Krokhina /19/ made a more detailed study of the influence of sodium formate on the deposition of nickel from a solution containing 30g nickel chloride and 109 sodium hypophosphite per liter. The authors confirmed the validity of the general rule for substances of this type, according to which the rate of the process passes through a maximum when the concentration of the substance is varied; when sodium formate is used

in the above solution, the maximum rate is obtained when the concentration of this salt is 6-8 g /1.

o 5 W ~ M U ~ ~ M Concentration of sodium glycolate, gil

FIGURE 7. Effect of the concentration of sodium glycolate on the rate of deposition

The low rate of reduction of the nickel, and the formation of dark deposits from solutions with a low hypophosphite content, are the drawbacks to the use of this buffer additive,

N. A. Solov'ev /20/ used ammonium fluoride as the buffer additive. This author studied the relationship between the rate of deposition and the concentration of ammonium fluoride in solutions containing 25 g nickel sulfate and 30 g sodium hypophosphite per liter; the ratio of the surface to be coated to the volume of the solution was 3dm2/1. The experiments showed that

in this case also the rate of reduction of the nickel passed through a maximum (11 microns/20 min) when the ammonium fluoride concentration was 15 g/1. A further increase in the concentration of the ammonium fluoride causes both a decrease in the rate of the process and a deterioration in the quality of the deposit.

It should be noted, however, that two parameters were simultaneously varied in these experiments, i. e. , the concentration of the ammonium fluoride and the pH of the solution; consequently, it is difficult to give an unambiguous decision on the influence of the additive.

We obtained good results with respect to the stability of the solution and the quality of the deposit by using glycine as the buffer additive /13/, but the rate of deposition was lower than that from solutions containing sodium acetate.

Our study of the nickel reduction process in solutions containing sodium succinate or malonate showed that the rate of deposition increases in the presence of these substances as it does with sodium acetate. The advantage of these additives, however, is that the nickel deposits remain bright even if the concentration of the additives is varied over a wide range.

The re lationship between the rate of reduction of the nicke 1 and the concentration of the salts of organic acids was also studied by Minjer and

22

Brenner /14/. The study was carried out in solutions containing 30 g nickel chloride and 109 sodium hypophosphite per liter at pH 4.2-4.3, at the boiling point. In each experiment the volume of the solution was one

z

- o

~

" ~

o IOZOJOt,{JS06070BO

Concentration, gIl

FIGURE 8. Relationship between tbe rate of deposition and the concentration of the buffer additives added to the solution as the acids: 1-glycolic acid; 2-tartaric acid; 3-succinic acid; 4- lactic acid; 5- glycine; 6- phthalic acid, 7- salicylic acid. (From reference /141).

liter, and the surface of the sample for coating was 12 cm2• The experimental results are presented in Figure 8.

It is evident from the figure that the rate of reduction of the nicke 1 at first increases with increase in the concentration of the organic acid, then reaches a maximum, and finally decreases. The highest rate of reduction was observed in the solutions containing lactic acid; in the presence of glycolic acid this rate was somewhat lower. Under these conditions succinic acid had a smaller effect on the rate of deposition than glycolic and lactic acids, and the slope of the curve in the region of the maximum was steeper, i. e., the rate of the process is high for a narrow range of change in concentration.

The increase in the rate of the process with increase in the concentration of the organic acid might be attributed to the buffer action of these additives, but the fact that the curves pass through a maximum, followed by a decrease in the rate of reduction of the nickel does not agree with such a concept, since the buffer action remains the same for this range also.

The attribution of the effect of the organic substances to their buffer action alone disagrees also with the fact that the buffer activity of the substances studied is not proportional to their effect on the rate of the process.

3. The Coefficient of Utilization of the Hypophosphite

The action of hypophosphite in the chemical reduction of metals can be compared to the action of the electric current in electroplating processes. The utilization of the electric energy is called the "current efficiency"; any

23

deviation from 100 '10 is caused by side reactions. In the process under discussion the coefficient of utilization represents the amount of hypophosphite used for the reduction of the nickel expressed in per cent of the total amount of hypophosphite consumed in the reaction. A "by-pr-oduct" of the process is hydrogen, which is always evolved during the reduction of the nickel. The simultaneous course of these reactions in various solutions

is presented in Figure 9. This relationship between the reactions is observed under all conditions of the process.

According to the equation for the main reaction:

1.8 g of hypophosphite is needed for the reduction of 1 g of nickel, but the actual consumption of hypophosphite is about 5 g per 1 g nickel. This increase in the consumption of hypophosphite is attributed, as already mentioned, tothe side reaction accompanying the reduction of the nickel, which causes evolution of hydrogen according to the reaction:

( 2)

In addition, some hypophosphite is used up in the reduction of phosphorus to the elemental state.

Ni H2 g ml az~ 720

al6 al2 Q08 QII*-

o

Time, hrs

FIGURE 9. The simultaneous reduction of nickel and hydrogen evolution during chemical nickel plating. Composition of the solution: nickel chloride-30g/l; sodium hypophosphite-10g/l. I-without a buffer additive; II - 50 g sodium citrate per liter; Ill- 10 g sodium glycolate per liter

As we shall show later, such an individual description of the processes of reduction of these substances (Ni, H2 and P) is not completely correct; at the same time the general course of the process corresponds to the course of the reactions described by the above equations.

The last conclusion is based on the results of hypophosphite consumption, from the data of our experiments, which we assumed took place according to equations (1) and (;2). The consumption of hypophosphite during the chemical nickel plating process was determined by chemical analysis of the

24

TABLE 7

The consumption of hypophosphite according to data from the analysis of the solution and calculations based on equations (1) and (2)

Hypophos- R eductien products Amount of hypophosphite, g Deviation from the intttal
Experimental phite. content remained in consum ed in the total hypophosphite content Utilization of
time, hrs before the the solution reduction of amount the hypo-
experiment, nickel, g hydrogen, g % deposit ion, %
g cm3 nickel hydrogen
1 1.2462 0.0556 45.3 0.8725 0.1005 0.2145 1.1875 -0.0587 -4.7 31.9
2 1.2462 0.0151 13.4 0.7137 0.1356 0.>470 1.196" -0.0499 -4.0 28.1
3 1.2462 0.0970 109.9 0.5475 0.1751 0.5200 1.2437 -0.0025 -0.2 25.3
- ----- Note. The volume of the solution-125 ml, the surface area of the sample - 25 ern 2.

TABLE 8

Influence of the nature of the buffer substance on the coefficient of utilization of the hypophosph ite

pH of the Amount of the Consumption of hypophosphit e, g Coeffc ot
solution reduced Ni
Buffer substance Volume of liz2t.:iOl
(concentration 10 gil) l'. thickness of the H2 for the reduction of the hy
:t resulting coat- (atNTPlcm3 total. phosph
.g ~ ~ amount
'" x ~ g tng , microns Ni HZ %
.<> '" " "
No buffer 5.3 3.1 0.0732 3.3 65 0.132 0.308 0.440 30.
Sodium glycolate 5.03 3.5 0.1930 8.9 112.5 0.348 0.532 0.880 39 ..
Glycine 4.9 4.1 0.1846 8.4 114 0.333 0.539 0.872 38.
Sodium formate 4.9 4.2 0.1746 8.0 110.5 0.315 0.521 0.836 37.
Sodium citrate 5.0 3.5 0.1032 4.7 80 0.186 0.378 0.564 33.\
Sodium acetate 5.0 3.9 0.3830 17.5 212 0.691 1.004 1.695 40.
.. _..!....._...-- ;;T=~::

.t OJ )1 (i1' hVi;Ophos-

1'0- "

ire plrlte, g per

, g Ni

~-~~--

I 1.56

2 4.72

: I!::;

•• ~ __ t,._".__~'~"'~'~""_" ~~...,... •.

o

solution before and after the reaction. The theoretical amount of hypophosphite needed was calculated from equations (1) and (2) on the basis of

the experimentally measured amounts of nickel reduced and of hydrogen evolved in the process. The results of these measurements and calculations are presented in Table 7.

To prevent complications due to the possible oxidation of the buffer compounds during the analysis, the se compounds were not added to the nickel plating solution. The solution contained 30 gil nickel chloride and 10g/l sodium hypophosphite. The last column in the table shows that under these conditions only about 320/0 of the hypophosphite is used in the nickel reduction process, while the remaining hypophosphite is lost during hydrogen formation.

The divergences found in the consumption of hypophosphite, which, however, do not exceed 5,,/0, could apparently be attributed to the fact that the hypophosphite consumed in the reduction of the phosphorus was not taken into account.

The data in Table 7 confirm that the course of the process can be quantitatively described by equations (1) and (2) (within the above mentioned range of accuracy). The distribution of the hypophosphite between the main and the side reactions is important for the technology and economy of the process. The efficiency of a solution with a given composition can be evaluated from the fraction of hypophosphite (in "/0 of the total) consumed in the reduction of the nickel, i. e" in reaction (1). This value will be called "the coefficient

of utilization of hypophosphite".

The amounts of nickel reduced and of hydrogen evolved must be measured in order to determine this coefficient. Data on the coefficient of utilization of the hypophosphite in solutions containing 30 g nickel chloride and 109 hypophosphite per liter, with different buffer additives, are presented in Table 8.

It is clear from the table that the coefficient of utilization of the hypophosphite in the solutions studied does not exceed 400/0, and that its values vary somewhat with the nature of the buffer additive; the highest degree of utilization of the hypophosphite was observed in the solution containing sodium acetate, the lowest is that with sodium citrate (with the exception of the solution without additive).

Data on the variation in the coefficient of utilization of the hypophosphite during prolonged processes (5 hr-s}, without any replacement of the solution, are presented in Table 9. The experiments were carried out with a solution of sodium glycolate, and a solution with no additive was used for comparison.

The data in Table 9 show that the coefficient of utilization of the hypophosphite decreases during the process when the solution is not replaced, and that this decrease takes place in the solution containing no additive as well as in that containing sodium glycolate. It is interesting to note that in the experiments in which solutions containing sodium glycolate were used the value of the coefficient of utilization of the hypophosphite was lower during the first hour of work than during the following hour. This phenomenon cannot be explained as there is no sufficient data.

The variation in the coefficient of utilization of the hypophosphite as a function of the experimental conditions can apparently be attributed to

TABLE 9

Change in the coefficient of utilization of the hypophosphite during nickel plating when the solution is not replaced

Consumption of hypophosphite, g Co eff ic.i
Amount of reduced of utfl iza
Composition of the Concentra-. Time of for the reduction of total of the hy.
hydrogen,
solution tion, gil operation, hrs nickel, g cm3 amount phosphit
nickel hydrogen
Nickel chloride 30 1 0.2233 149 0.403 0.704 1.107 36.3
2 0.1268 77 0.229 0.364 0.593 38.6
Sodium hypophosphite 10 3 0.0682 57.S 0.123 0.272 0.395 I 31.1
Sodium glycolate 15 4 0.0402 41 0.073 0.193 0.266 27.4
5 0.0262 37 0.047 0.175 0.222 21.2
The same, but without I
the addition of sodium i
glycolate 1 0.0433 41 0.078 0.194 0.272 I 2.G.G
2 0.0302 38 0.055 0.180 0.235 I 23.4
3 0.0212 - 0.038 - _. --
4 0.0192 37 0.034 0.175 0.209 I 16.5
5 0.0177 35.5 0.032 0.168 0.200 ie»
L_. ___ e nt tion

poe,%

var-iat ions in the ratio of the rates of the separate reactions. This problem is discussed in more de tai l in the section dealing with the me c hanis rn of the process.

Brenner and Riddell noted in their work that the coefficient of utilization of the hypophosphite is very dependent on the surface area immersed in a given volume of the solution. Thus. the va lue of this coefficient is about 37% when a sample with a surface area of 0.5 dm2 is immersed in 100 ml of the solution. while its value is 200/0 when the same sample is immersed in one liter of the solution, i , e., according to these authors it is advantageous to carry out the nickel plating on relatively large surfaces of the metallic samples.

It must be noted, however, that the above results of Brenner and Riddell cannot be explained. as there is insufficient data on the experimental conditions ( duration, correction of acidity, etc). A possible cause for the decrease in the coefficient of utilization of the hypophosphite when relatively large volumes of the solution are used is an increase in the probability that nickel powder is formed in the solution, causing a waste of the hypophosphite.

It is evident from the above data that the value of the coefficient of utilization of the hypophosphite was about 40 % both in our experiments and in those of other investigators. There is reason to assume that certain lim itations

to the yield of the nickel reduction reaction are caused by the mechanism of the process itself. Unfortunately, our present knowledge in this field is not sufficient to allow us to control the ratio of the rates of formation of nickel and hydrogen. To increase the value of the coefficient of utilization of the hypophosphite it is necessary to carry out additional research over a wider range of experimental conditions.

4. The Influence of some Impurities in the Solution on the Rate of Reduction of Nickel

The influence of various impurities on the reduction of metals by hypophosphite must be studied as the process is catalytic and it is possible that, as in other catalytic reactions, small amounts of an impurity can have considerable influence on the course of the reaction.

Foreign substances may find their way into the solution as impurities

in the main reagents and if the solution is replaced during the operation, the concentration of these impurities might increase until the process is affected adversely. In addition, substances formed in the oxidation-reduction reactions (L e., phosphite and acid) might also affect the course of the process. The amounts of Cl" or SO~- ions added with the nickel salts when the solution is replaced may also be of special significance. As the acid formed in the process is usually neutralized with sodium hydroxide. the concentration of Na+ ions in the solution also increases.

Brenner and Riddell carried out a series of experiments to determine the influence of certain substances on the chemical reduction of metals. The results of these experiments are presented in Table 10.

The data in the table show that minute amounts of thiocyanate and lead ions completely stop the process in both acid and alkaline nickel solutions as well as in alkaline cobalt solutions.

Cadmium salts and cyanides have a detrimental influence on the process; this is exhibited more strongly in alkaline nickel and cobalt solutions

TABLE 10

Influence of certain substances on the chemical reduction of metals

Alkaline nickel solution Acid nickel solution Alkaline cobalt solution
Substance concen- COncen- concen-
tration, effect tratlon, effect trat lcn, effect
gfl gil gil
CuS04 0.01 Deposition of 0.1 Reduction of the 0.1 Normal coating
copper rate
ZnCl2 1.0 Reduction of the 0.1 Normal coating 1.0 Reduction of
rate the rate
CdCl2 0.1 No coating 0.1 Reduction of the 0.1 Sharp reduction
rate of the rate
MgCl2 1.0 Normal coating 0.1 Normal coating 1 Reduction of
the rate
AlCl3 1.0 " " 0.1 " " 1 Normal coating
FeCl2 1.0 " " 0.1 " " 1 Reduction of
the rate
KCNS 0.01 No coating 0.1 No coating 0.01 No coating
PbCl2 0.1 " " 0.1 " " - -
KCN 0.01 " " 0.01 Normal coating 0.01 No coating
NaH2P02 10 Reduction of the - - 10 R eduction of
rate the rate than in acid solutions. As can be seen from the table, the chlorides of zinc, magnesium, aluminum, or iron in amounts of 0.1 g per liter, have no appreciable influence on the process in acid solution.

The authors state in their paper 121 that this interference with the course of the process can be attributed to a poisoning of the catalytic surface. The plating of nickel on a gold surface treated in a cyanide solution is a relevant example. The palladium film which is deposited on certain metals to form catalytically active surface does not always have the desired effect; usually freshly prepared films are the active ones. Contamination of the solution with palladium salts does not interfere with the reduction of the nickel; this impurity, however, has an adverse influence on the process as some hypophosphite decomposes on the surface of the palladium powder

and thus causes a waste of the reducing agent.

According to Brenner and Riddell, cadmium ions, which have a detrimental effect on the process, can be separated by passing hydrogen sulfide through the solution at pH 3.5-4. The cadmium is precipitated under these conditions while the nickel remains in the solution.

We studied the influence of certain impurities on the nickel reduction process in acid solutions containing 30 g nickel chloride, 10 g sodium hypophosphite, and 10 g sodium acetate per liter.

In agreement with the data of Brenner and Riddell, we observed that impurities of lead chloride (0.1 gIl) and potassium thiocyanate (0.1 gil) completely stop the process.

29

We also observed the negative influence of cadmium chloride (0.1 gil), zinc chloride (0.1-1 gil), and aluminum chloride (1-3 gil); the process was stopped when these substances were adrJed to the solution.

The addition of 1 g of ferrous chloride per liter had no appreciable influence on the rate of reduction of the nickel but the solution turned turbid, due, apparently, to the precipitation of insoluble iron compounds as phosphite or hydroxide. The rate of the process decreased considerably when the concentration of ferrous chloride was increased to 3 gil.

P. P. Belyaev, M.1. Zil'berfarb, and M. P. Garetovskaya /16i, studied the effect of adding iron to the solution as Mohr's salt in an amount of 5 gil, and noted a certain decrease in the rate of reduction of the nickel aCCOmpanied by precipitation of nickel powder in the bulk of the solution.

As shown by our experiments, magnesium chloride (1-3 gil) or cupric sulfate (0,03-0.1 gil) have no appreciable influence on the nickel reduction process.

Minjer and Brenner /14/ showed that the rate of reduction of the nickel is somewhat lowered (from 21 to 16 microns/hr) when the iron salt (0.5 g ferrous chloride per liter) is added to a solution containing glycolic acid (39 gIl), but this addition does not affect the stability of the solution,

The above authors note that the impurity CUS04· 5H20 has a detrimental effect on the quality of the coating, and causes dark, coarse deposits due

to the simultaneous separation of copper. Later on in the experiments, the coating assumes a normal appearance when the copper has been separated from the solution.

Some data on the influence of cobalt acetate, zinc sulfate, cadmium sulfate, and uranium acetate on the plating of nickel on aluminum in alkaline solutions is presented in the paper of Machu and El-Gendi /21/, who studied the influence of the above substances on the brightness and on the rate of deposition of the coating.

The authors note that when the concentration of zinc sulfate is increased, the rate of reduction of the nickel passes through a maximum; this maximum is observed at a zinc sulfate concentration of about 1 g 11. Cadmium sulfate has a similar effect on the process at low concentrations, but completely stops the process at high concentrations. The rate of the process was also reduced when uranium acetate was added as a brightener.

The authors explain the influence of the salts of heavy metals on the rate of the process and on the brightness of the deposit as a result of the inhibiting action of the hydroxides of these metals appearing at the surface; no clear relationship was established for the effects noticed.

The above is far from being an exhaustive list of all the substances which have a negative influence on the nickel reduction process. Research on

this subject must be continued in order to determine more exactly the specifications for the reagents used in chemical nickel plating.

Among the substances which are invariably formed in the solution during the reduction with hypophosphite are sodium chloride (or sulfate) and phosphite.

We studied the influence of various amounts of sodium chloride up to

100 gIl. A concentration of sodium chloride such as this is obtained in the solution when, for example, a surface of 57dm2 is coated with a nickel layer 10 microns thick, These experiments showed that the concentrations of s odium chloride studied had no appreciable influence on the nickel plating process.

Another product formed during the r-e act ion

is phosphorous acid ions, which have a very detrimental influence on the course of the process due to the ability of the phosphite ion to form an insoluble compound, nickel phosphite, under these conditions. This precipitate has a harmful effect on the rate of the process and on the quality of the coating, and interferes with the replacement of the solution. The amount of this precipitate in

the bulk of the solution increases constantly during the process, and thus interferes to an even greater extent with the normal operation of the bath.

To keep the nickel phosphite in solution, Minjer and Brenner /14/ suggested carrying out the nickel plating process at a lower pH value of the solution.

In order to determine the optimum pH value for solutions of different composition the authors carried out a series of experiments with solutions containing 30 g nickel chloride and 10 g sodium hypophosphite per liter as the main components,

at different acidities and at different phosphite concentrations. Solutions containing no buffer

additives, as well as solutions containing either sodium citrate or sodium glycolate were studied.

Phosphite (as phosphorous acid neutralized by an alkali) was added to these solutions at a given pH in increasing amounts, up to the limit of its solubility at the boiling point». The temperature at which the solubility of the nickel phosphite was determined as a function of the pH of the solution was selected in accordance with the conditions under which the nickel plating took place (above 90°). The saturation point of the solution with phosphite was established by the appearance of a precipitate after boiling the solution for

30 minutes. The experimental results are presented in Figure 10.

The shape of the curves indicates that the solubility of nickel phosphite decreases sharply within a definite range of pH for each solution; the solubility of the phosphite in solutions containing no buffer additives is considerably lower than that in solutions containing the salts of organic acids, at all pH values. The figure shows that the curves have a sharp inflexion. The authors accepted arbitrarily that the acidity at the inflexion point is the limiting pH value, and that above this it is not worthwhile carrying the nickel plating process any further.

On the basis of their experiments Minjer and Brenner recommended carrying out the nickel plating at the following pH values; in solutions containing no organic acids, 3.5; with sodium citrate, 4.2; in solutions containing 39 and 78g (as the acid) of sodium glycolate per liter, 5 and 5.7, respectively.

200

20 OL-~~~~~~~~ 789

pH of the solution

FIGURE 10. Relationship be-

tween the solubility of the phos-

phite, added as phosphorous acid,

and the pH, in solutions of dif-

ferent composition. 1- without a buffer additive; 2- sodium citrate 15 gfl (as the acid); 3- sodium glycolate 39g/1 (ditto);

4- sodium glycolate 78 gIl (ditto). (From reference /14/)

* On the influence of the temperature On the solubility of the phosphite,see also Chapter III, Section 3.

31

The above are optimal pH values for each solution from the point of view of both the rate of the process and the replacement of the solution. In fact, the rate of reduction of the nickel decreases when the pH is lowered, while at higher pH values the process is complicated by the formation of precipitates.

The formation of nickel phosphite precipitates can also be prevented by adding to the solution substances which form complexes with the nickel without any harmful effect on the course of the reduction reaction. This important topic will be discussed in more detail in the next chapter.

CHAPTER III

METHODS FOR IMPROVING THE PROCESS

Chemical nickel plating, in the form proposed by Brenner and Riddell /2/, attracted considerable interest, but a number of significant dis ad - vantages were revealed during its application. Among these are the insufficiently high rate of deposition, the instability of the bath, the difficulty of replacing the solution, the deterioration in the quality of the coating after prolonged operation, and the high cost of the process.

These disadvantages found in the practical application have determined the direction of the research towards improving the method.

1. Data from the Literature

A number of patents /17,22-25/ deal with the results of research carried out to remove the drawbacks of the chemical nickel plating process. Thus, Gutzeit and Krieg /23/, studied methods for increasing the rate of the process, discussed the factors known to have a considerable influence on this rate (such as temperature and acidity), and also the effect of the ratio of the concentrations of the components in the solution. According

to the data of these authors the highest rate of deposition of nickel and the best quality coating are obtained when the molar ratio of nickel to hypophosphite in the solution is within the range 0.25-0.60; the optimum ratio

is 0.4. The rate of reduction of the nickel can be increased by increasing the hypophosphite concentration; the recommended range of variation of

the hypophosphite concentration is 0.15-0.35 M (16-37 g NaH2P02• HP per liter). These authors suggested that the concentration of the buffer additive, in particular that of sodium acetate, be such as to give two carboxyl groups per ion of reducible nickel. It is recommended that the process be carried out at 98°-99°, at pH 4.5-5.5. The ratio of the volume of the solution (in m l) to the surface area to be coated (in cm~ must not be lower

than 10.

In addition to the above conditions, Gutzeit and Ramirez /17/ recommended that the salts of aliphatic dicarboxylic acids containing 3-6 carbon atoms in their molecule and with an ionization constant above 5, be used as buffer additives.

The authors considered the salts of malonic, succinic, glutaric and adipic acids to be suitable. As in the previous case, it was recommended that the additives be added so as to give two carboxyl groups for each ion of reducible nickel. The use of these substances as buffer additives improved the rate of the process and the stability of the solution.

33

The results of furthe r research on the improvement of the chemical nicke I plating process are found in the Gutzeit patent /24/ in which the author indicates that in the reduction of nickel by hypophosphite it is an advantage to add fluorides (e .g .• NaF) and salts of saturated aliphatic dicarboxylic acids (e. g., sodium citrate) to the solution. It is recommended in this case that the pH be maintained within the range 4.5-6.5; the molar ratio of the amount of nickel to that of hypo phosphite can be varied within a wider range than that previously recommended, i. e., 0.25- 1.6; the F- content should be 0.01-0.12 M (or 0.4 g NaF per liter), and the amount of hypophosphite 0.15-1.2M (16-127 g NaH2P02 per liter); the buffer is added according to the above -rnent ione d patents.

The data of the Metheny and Talmey patent /25/ on improving the quality of the coating must also be noted. This improvement is carried out

by bubbling through the bath a light gas (inert with respect tothe solution)" with a molecular weight below 28", during the reduction process. Hydrogen, helium, methane, or neon are recommended. The authors note that the brightness and the adherence of the coating are increased under these conditions, and blemishes, such as pitting and roughness are eliminated. The patent recommends buffer solutions containing malic, lactic and succinic acid, or malic together with aminoacetic acid, or malic with succinic acid.

2. The Rate of the Process as a Function of the Ratio of Hypophosphite Concentration to Buffer Additive Concentration

As is evident from the material in the preceding section, the ratio of the amounts of the components in the solution was also found to influence the reduction process.

For the optimum ratio of nickel to hypophosphite ions (0.25-0.60) at a hypophosphite content of 0.15 to 0.35 M (16-37 gNaH2P02' HP per liter), Gutzeit /261 recommended the addition of 0.12 moles of sodium acetate per liter without taking into account the above-mentioned range of variation in the concentration of the remaining components.

Our study of solutions with different ratios of nickel to hypophosphite ion at various hypophosphite concentrations (10-30 gil) and at a constant concentration of the buffer additive (10 g of sodium acetate per liter) failed to show any noticeable change in the rate of reduction of the nickel.

Our further research to increase the rate of the process revealed a new rule for the rate as a function of the hypophosphite concentration, when the concentration of the buffer compounds is varied simultaneously. This relationship was established in experiments with sodium acetate as the buffer. The influence of the ratio of the above-mentioned components was also investigated with other buffers.

The experimental conditions and the results are presented be low /18 r. The solution with sodium acetate. The influence of the ratio of hypophosphite to sodium acetate concentrations on the rate of the process was studied with solutions containing 25 g nickel chloride per liter and different amounts of sodium hypophosphite (0-50 gIl).

* The laboratory technician L. S. Barybma took part in the experiments described L., this and in some other chapters.

Three separate sodium acetate concentrations, 10, 15, and 20 gIl were used for each concentration of the hypophosphite. The volume of the solution was 100 ml and the surface of the sample for coating 10 cm '. The process was carried out at 90".

TABLE 11

Influence of the concentration of sodium acetate on the rate of the process and on the qual ity of the coating in solutions containing various amounts of hypophosphite (nickel chloride concentration, 25 gill

Sodium Sodium pH of the solution Rate offor-
No.of hypophos - before the ; mation of the Quality of the coating
acetate after the
expt, phite, gil expt. expt, coating,
gil microns/hr
1 10 10 5.09 4.16 16.7 Uniform, bright
2 10 15 5.1 4.5 13.5 Matt, striated
3 10 20 5.05 4.61 8.8 .. ..
4 20 10 5.1 4.42 16.6 Uniform, bright
5 20 15 5.08 4.54 22.3 " "
6 20 20 5.04 4.33 20.6 " "
7 30 10 5.07 4.21 13.9 Untform , bright
8 30 15 5.08 4.32 18.3 " "
9 30 20 5.1 4.38 24.5 " "
10 30 25 5.09 4.56 23.8 Slightly matt, striated The experimental results are presented in Table 1l.

As is evident from the table, the rate of the process increases with increase in the hypophosphite concentration. The rate increases, however, only when the sodium acetate concentration is simultaneously increased, up to the optimum value. In a solution containing 10 g of hypophosphite per liter the maximum rate of reduction of the nickel was obtained at a sodium acetate concentration of 10 gIl. An increase in the concentration of the latter causes a reduction in the rate of the process and a deterioration in the quality of the coating: the deposits become matt and striated, and even dark at a sodium acetate concentration of 20 gIl.

The data in Table 11 show that both the rate of deposition and the quality of the coating obtained in a solution containing 20 g of sodium acetate per liter vary considerably with increase in the hypophosphite concentration (experiments 3,6, and 9). The optimum concentration of hypophosphite under these conditions is about 30 gIl, the rate of the process is almost

25 microns fhr, and a bright coating is deposited.

Figure 11 gives a better picture of the relationship between the rate of the process and the hypophosphite concentration. The curve was drawn from the data of experiments with solutions containing the optimum sodium acetate concentration (Tables 11 and 17).

Thus, our experiments did not confirm the assumption of earlier papers, that the rate of reduction of nickel in acid solutions is independent of the hypophosphite concentration. Increase in the hypophosphite concentration affects the process except when the concentration of thp hl1ffpY' "r'lr'liH"" io

kept constant and when the ratio of the buffer concentration to the hypophosphite concentration is beyond the range of optimum values. Tab le 12 illustrates this rule. A comparison is given between the results of experiments with solutions containing 10 or 20 g of sodium acetate per liter and different amounts of sodium hypophosphite. The nickel chloride concentration was the same in each case, 25 gIl; the acidity of the initial solutions corresponded to pH ~ 5; the temperature was 90°.

As can be seen from Table 12, increase in

the hypophosphite concentration from 10 to 40

gIl has practically no influence on the rate of reduction of the nicke 1 in a solution containing

10 g of sodium acetate per liter. In a solution containing 20 g of sodium acetate per liter, however, increase in the hypophos phite concentration from 10 to 20 gil causes a sharp increase of more than two fold in the rate of the process. When the hypophosphite content in this solution

is increased still further, the rate of reduction of the nickel increases slightly at first, and

then remains constant.

Experiments with other buffer additives were also carried out to find out whether this rule is general and valid for any of the buffer additives used, or whether it can be applied only to the solutions containing sodium acetate. The experimental results are presented below.

-:

-:

~ 20 o§

0-

~ 10

10

20

Hypophosphit e concentration, g/l

FIGURE 11. Influence of the

sodium hypophosphite conceri-

tration on the rate of deposi-

tion in solutions with the opti-

mum sodium acetate content

.50

TABLE 12

Influence of the concentration of hypophosphite on the rate of the process and on the quality of the coatings obtained in solutions containing 10 or 20g of sodium acetate per liter (nickel chloride concentration, 25 gIll

10 g of sodium acetate per liter 20 g of sodium acetate per liter
Sodium
hypo phosphite , Rate of Rate of
gIl deposition, Quality of the coating deposition, Quality of the coating
microns/hr microns/hr
10 16.7 Uniform, bright 8.8 Matt, striated
20 16.6 " " 20.7 Uniform, bright
30 14.3 " " 24.5 " u
40 15.5 u " - " u
SO - - 23.4 Uniform J bright The sol uti 0 n wit h sod i u m malo nat e. The experiments with sodium malonate were carried out in solutions containing 10 or 30 g sodium hypophosphite per liter. The nickel chloride concentration was constant and equal to 25 gil. The process was carried out at 90°, at pH 5. The experimental results are presented in Table 13.

TABLE 13

Influence of the concentration of sodium malonate on the rate of the process and On the quality of coating obtained in solutions containing various amounts of hypophosphite

(nickel chloride concentration, 25 g/1)

Sodium rna- 109 of sodium hypo phosphite per liter 30 g of sodium hypophosph ite per liter
lonat e (as Rate of Rate of
the acid) deposition, Quality of the coating deposition, Quality of the coating
gil microns/hr m icrcnsyhr
5 8.2 Uniform, bright 5 Uniform, bright
10 10.3 " " 13.5 " "
15 13 Semimatt 16.4 " "
20 - - 23.9 " "
25 12.5 Matt 24.8 " "
30 - - 20 Matt, striated
50 - - 20 Poor adherence The data in Table 13 show that the rate of the process increases with increase in the hypophosphite concentration only when the concentration

of the buffer additive is simultaneously increased to the optimum value under these conditions. Thus, at a hypophosphite concentration of 10 gIl and at a buffer additive concentration corresponding to 10 g of malonic

acid per liter (which is 'the optimum value), the rate of reduction of the nickel was 10.3 microns/hr; in a solution containing 30g of sodium hypophosphite per liter and an amount of sodium malonate corresponding to 20-25 g of the acid per liter (which is the optimum under these conditions), the rate of the deposition was about 24 microns/hour.

The sol uti 0 n wit h sod i urns u c c ina t e. As in the preceding experiments, the influence of the concentration of sodium succinate was studied with solutions containing 10 or 30 g of hypophosphite per liter. The nickel chloride concentration was maintained at 25 gil, and the temperature of the solution was kept within the range 90°-92°.

The experimental results are presented in Table 14.

It is evident from the data in Table 14 that the rate of the process increases with increase in the hypophosphite concentration. But in the abovementioned solutions, the concentration of the additive must also be increased to obtain the maximum rate. It should be noted, however, that the variations in the concentration of the sodium succinate have a smaller influence on the rate of reduction of the nickel than those of sodium malonate, or, especially, than those of sodium acetate. The changes in the quality of the coating

as a function of the additive concentration were also observed in solutions containing sodium succinate; thus, in a solution containing 10 g of hypophosphite per liter, bright coatings were only obtained when the sodium succinate concentration was 5 and 7 gil (as the acid); the coating became semimatt when this concentration was increased to 10 gIl (as the acid). Thus, the rule governing the variations in the quality of the deposits is valid in this case too, but these variations are more pronounced in the solutions containing sodium acetate at a low hypophosphite concentration.

TABLE 14

Influence of the concentration of sodium succinate on the rate of the process and on the quality of the coating in solutions containing various amounts of hypophosph ite (nickel chloride concentration, 25 g/I)

109 of sodium hypo phosphite 30 g of sodium hypophosphite
Sodium succinate per liter per liter
(as the acid), rate of rate of
g/l deposition, quality of the deposition, quality of the
microns/hr coating rn icrons/hr coating
5 15.5 Uniform, bright 12 Uniform, bright
7.5 16.2 " " -
10 14.8 Sem ima tt 15.7 Uniform, bright
15 - - 18.8 " "
20 - - 20.2 " "
25 - - 17.7 " " The solution with sodium formate. The experiments with solutions containing sodium formate as the buffer additive were carried out under the same conditions as those with sodium malonate and succinate.

The experimental results are presented in Table 15.

TABLE 15

Influence of the concentration of sodium formate on the rate of the process and on the quality of the coatings obtained in solutions containing various amounts of hypophosphite (nickel chloride concentration, 25 g/ I)

109 of sodium hypophosphite 30 g of sodium hypophosphite
Sodium formate, per liter per liter
gIl rate of rate of
deposition, quality of the deposition, quality of the
microns/hr coating mic:rons/hr coating
5 9.3 Matt, striated 9.0 Uniform, bright
7.5 8.2 " " 11.2 " "
10 6.6 " " 12.8 " u
15 4.7 u " 15.7 Matt
20 - - 15.9 " The results indicate that the rate of deposition increases with increase

in the hypophosphite concentration. But as in the solutions with the other buffer additives, the concentration of the additive must be increased in order to attain the maximum rate of the process. It is evident from Table 15 that the quality of the coating depends to a great extent on the hypophosphite: buffer ratio.

To compare the results obtained with solutions containing different buffer additives, Table 16 lists the buffer: hypophosphite ratios for the optimum results with respect to both the rate of the process and the quality of the coating. The experiments were carried out with solutions containing 30 g of hypophosphite per liter at pH ~ 5.

It is evident from Table 16 that the hypophosphite: buffer ratios at which the optimum results are obtained depend to some extent on the nature of the additive. In the solutions containing 30 g of hypophosphite per liter

---0.5 g-mole sodium acetate or 0.5 g-mole sodium formate per g-mole

hypophosphite are needed for the maximum rate of the process, while

~ 0.85 g-mole of the additive per g-mole hypophosphite are necessary in the solutions containing sodium malonate, and for. sodium succinate, 0.6 gmole per g-mole hypophosphite.

TABLE 16

Optimum ratios of the amount of buffer compound to that of hypophosphite; hypo phosphite concentration 30 gil (0.283 M)

Molar ratio Rate of reduc-
Molecular Optimwn concentration of buffer tion of the
Buffer additive Formula of the addtttve
weight additive to nickel at 9001
gfl M hypophosphite microns/hr
Na acetate CH3COONa' 3H20 136.08 20 0.147 0.5 : 1 24.5
Na malonate* CH2(COONa)2 148.01 35 0.240 0.85: 1 24.8
Na succtnatef (CH2COONa)2 161.02 27.3 0.17 0.6 : 1 20.2
Na formate HCOONa 68.01 10 0.148 0.5: 1 12.8 * Sodium malonate and sodium succinate were added to the solution as the respective acids which were then neutralized with sodium hydroxide. The optimum concentrations of these acids are 25 and 20 g/ I respectively.

The above optimum (molar) ratios were obtained, as already mentioned, in solutions containing 30 g of hypophosphite per liter, i. e., 0.283 M. It was interesting to observe whether these ratios hold true in solutions with a different (higher or lower) hypophosphite content. The process was therefore studied in a solution containing 50 g of sodium hypophosphite per liter (i , e .• 0.471 M) in the presence of sodium acetate. If the same ratio (0.5: 1) were true, the maximum rate of deposition should be expected at a sodium

acetate concentration of 0.47;.136 = 32 gil.

The experimental results are presented in Table 17.

It is evident from Table 17 that the maximum rate of reduction of the nickel was obtained at a sodium acetate concentration of about 50 gil, i. e. , at a molar ratio of ,._, 0.8: 1. The deviation in the hypophosphite: sodium acetate ratio observed in these experiments from that obtained in solutions containing 30 g of hypophosphite per liter (0.5: 1) was also observed in the solutions containing 10 g of hypophosphite per liter. These deviations can be explained by the fact that all these experiments were carried out at a constant concentration of the nickel salt (25 gil), while in such a complex process all the components affect one another. It should be noted that the

calculated hypophosphite: buffer ratio might be different in the different solutions because the activity coefficient of the buffer additive varied with its concentration.

TABLE 17

Influence of the concentration of sodium acetate On the rate of the process in a solution containing 50 g sodium hypophosphite and 25 g nickel chloride per liter. Te mperature e-. 95°

Sodium acetate pH of the solution Rate of
concentration, deposition, Quality of the
gil before expt after expt rnicrons/hr coat ing
10 5.11 4.34 14.9 Uniform, bright
20 5.02 4.24 16.2 " "
30 5.07 4.39 27.9 " "
40 5.07 4.56 31.5 " "
SO 4.95 4.48 36.9 " "
60 5.02 - 32.3 Sem im att The rule presented in this section is undoubtedly related to the rne chani.sm of action of the additive in the nickel reduction process, which has not yet been clarified.

3. The Influence of Complex-Forming Agents on the Nickel Reduction Process

As mentioned above, one of the disadvantages of the chemical nickel plating process is the difficulty of maintaining the solution at constant composition, so there is a continuous decrease in the rate of reduction of the nickel.

The difficulty of replacing the solution is associated primarily with the formation of phosphite during the reaction, which causes the precipitation of the sparingly soluble nickel phosphite. The accumulation of this precipitate in the bath disturbs the whole process; the quality of the coating deteriorates, it becomes rough and dark; the nickel concentration in the solution decreases, and reduction in the bulk of the solution is apparently more probable. The precipitation of nickel phosphite is promoted by the same conditions which favor high rates of the process, namely high temperature and low acidity of the solution.

The increase in the amount of precipitate with increase in temperature is attributed to the decomposition of the soluble Naz[NilHP03>.t' nHzO complex (formed in the process) on heating, with precipitation of insoluble nicke 1 phosphite /27/.

In attempts to develop a continuous process, a number of investigators searched for special additives which would form complexes with the nickel and so prevent the precipitation. According to data from the literature /26,28-32/, a number of enterprises in the U. S. A. succeeded in solving

this problem (the Kanigen pr-oces s) ", but the published data on the composition of the solutions and on the process conditions are insufficient. Additives which have a considerable influence on the process are mentioned in these papers under the general names "accelerators of the process", "substances which control the precipitation of phosphite" or "stabilizers of

the solution", etc.

Although the ability to form nickel complexes has been attributed to some of the proposed additives (e. g., the salts of glycolic, succinic, or malonic acids), our experiments showed that they fail to prevent the precipitation of nickel phosphite, and so stronger complex-forming agents had to be found.

Not all substances which form nickel complexes have the desired effect.

Thus, compounds such as triethanolamine, propylenediamine, the disodium salt of ethylenediaminetetraacetic acid (Trilon B) did not prevent the precipitation of nickel phosphite.

Data of experiments with substances which interfere to some extent with the precipitation of nickel phosphite are presented below. The experiments were carried out at 95° with solutions containing 25 g of nickel chloride, 30 g of sodium hypophosphite, and 20 g of sodium acetate per liter, at pH --' 5.

Sod i u m cit rat e. Sodium citrate concentrations within the range 10- 50 gil were used to study the effect of this reagent on the chemical nickel plating process in the above-mentioned solution.

These experiments showed that the rate

of the process is reduced noticeably in the presence of 10 g of sodium citrate per liter, and decreases continuously with increase in the concentration of the complex-forming agent.

Data showing the relationship between the rate of reduction of the nickel and the concentration of sodium citrate are presented in Figure 12.

Solutions containing 10 and 30 g of sodium citrate per liter were used in the experiments in which the solution was replaced by the addition of sodium hypophosphite and a nickel salt, and the optimum pH value was maintained by the addition of sodium hydroxide. The above components were added after each experiment, the duration of the experiment was one hour.

When the solution was replaced at a low temperature, and contained 10 g of sodium citrate per liter, the precipitation of nickel phosphite was observed immediately upon heating, so that sodium citrate at the above concentration does not prevent the precipitation of phosphite.

When the sodium citrate concentration was 30 gil, the process could be carried out for 3 hrs by replacing the solution without any precipitate, but a rapid precipitation of nicke I powder started at the end of this time, and

o

40

50

20

30

10

Sodium citrate concentration, gil

FIGURE 12. Influence of the sodi-

urn citrate concentration on the rate of deposition. Composition of the solution: nickel chloride, 25 gIl;

sodium hypophosphite, 30 gIl; sodi-

urn acetate, 20 gIl; pH~5, tem-

peratur e-r-> 95°.

* The name Kanigen denotes the continuous nickel plating process developed by the General American Transportation Corporation in the U. S. A. The same name is applied to the coating obtained by this process

(see Chapter VIII).

41

the rate of the pr-ocess was cons ide rab iy red'c'.csd_ It can be assumed that the formation of an unusually large amount of nickel powder in the bulk of the solution is caused by the reduction of nickel ions on the particles of precipitated nickel phosphite, the latter being dissolved afterwards because of the increased acidity.

The experimental results obtained with these solutions are presented in Table 18.

G 1 Y c in e CH2NH2COOH. Glycine was added to the solution as the complex-forming agent together with the buffer which increased the rate of reduction of the n ic ke l . The effect of this substance wa,s studied mainly in a solution containing 25 g of nickel chloride, 30 g of sodium hypophosphtte , and 20 g of sodium acetate per liter at pH ~ 5.

TABLE 18

Variations in the rate of the process with replaced solutions containing JOg of sodium citrate per liter

working time, Rate of
deposition, Note
hours microns/hr
1 16.9 The coating is uniform and bright;
2 17.8 the solution is clear.
3 16.3
4 11.6 Vigorous formation of nickel
5 9.5 powder is observed. As has already been noted, the rate of the process in the above solution is fairly high, a nicke 1 layer 25 microns thick is formed in one hour at 90°- 92". The precipitation of nickel phosphite in this solution, however, starts during the first hour. Preliminary experiments showed that the addition

of glycine to the solution eliminates this disadvantage, and permits replacement of the solution over a more or less prolonged period. The effect of glycine on the chemical nickel plating process was also studied in the absence of sodium acetate. The results of these experiments are presented in Table 19.

Table 19 shows that the addition of glycine to the solution prevents the precipitation of phosphite. But the low rate of deposition of the nickel under these conditions, makes it necessary to combine this additive with other substances, such as sodium acetate, which have a strong influence on the rate of reduction.

The solution containing sodium acetate was tested for a prolonged time while replacing the components which had been used up; the pH was maintained at the optimum value of~ 5. The solution was analyzed periodically for the content of hypophosphite and phosphite. The rate of reduction of the nickel remained constant when the composition of the solution was maintained constant. The process was carried out using either small (l00-200 m l) or large (0.5-1 1) volumes of the solution. The r-at io of surface to be coated to volume of the solution was 1 dm 2/1.

TABLE 19

Relationship between the rate of the process and the concentration of glycine in a solution containing 2S g of nickel chloride and 30 g of sodium hypophosphite per liter at pH""" 5; temperature 90°_92°

Glycine concen- Sodium acetate Rate of deposition J
tration, gIl concentration, micronsjhr Quality of the
gil coating
0 0 2.5 Bright, uniform
10 0 7.4 " "
20 0 10.1 " "
30 0 11.3 " "
30 20 21.1 " " Note: 'The solution remained clear in all experiments.

This solution can be used continuously for about 8 hours. A considerable amount of phosphite accumulates in the solution during this time. The results of analysis show that the content of phosphite in the completely clear solution is 87 gil (as Na2HPOs· 5H20), while in the absence of glycine the solution becomes turbid when the phosphite concentration is as low as 10 gil. When the time of operation is longer, the glycine-containing solution also becomes turbid and must be replaced with a fresh solution.

Some attempts at regenerating the above solution will be discussed in section 5.

JQ

30

o

to zq 3D 40 5IJ

o

10 20 30

Nickel chloride concentration, gIl FIGURE 13. Influence of the nickel chloride concentration on the rate of deposition. Composition of the solution: sodium hypophosphite, 30 gIl; sodium acetate, 20g/l; pH --5, temperature ,-'950

Glycine concentration, g/ I

FIGURE 14. Influence of the glycine concentration on the rate of deposition, Compostion of the solution: nickel chloride, 20 g/l; sodium hypophosphite, 30 gIl; sodium acetate, 20g/l; pH~5, temperatuxe >-: 95°

In order to determine the optimum composition of a solution containing sodium acetate and glycine, it is first necessary to know the optimum concentration of nickel in a solution containing no glycine, and then, to select the most favorable concentration of the complex-forming agent.

43

The experimental results are presented in Tables 20 and 21 and in Figures 13 and 14.

TABLE 20

Relationship between the rate of the process and the nickel chloride concentration in a solution containing 30 g of sodium hypophosphite and 20 g of sodium acetate per liter. Temperature 95°

Nickel chloride, Rate of deposition,
gIl microns/hr
10 20.0
15 24.6
17.5 24.8
20 25.3
22.5 24.9
25 25.0
30 23.6
3S 21.4
40 20.7
4S 18.1
50 9.2 Matt, striated Uniform, bright

Quality of the coating

Weak matt strips on a bright surface

Matt, striated

It is evident from Table 20 that the highest rate is obtained at a nickel salt concentration of 15-25 gil. At higher or lower concentrations the rate

of reduction of the nickel decreases and the quality of the coating deteriorates.

TABLE 21

Relationship between the rate of the process and the glycine COncentration in a solution containing 20 g of nickel chloride, 30 g of sodium hypophosphite, and 20g of sodium acetate per liter.

Temperature 95°

pH of the solution
Glycine conceri- Ra te of deposition,
tration, gil before the after the microns/hr
experiment experfment
0 5.01 4.20 25.3
10 5.02 - 23.4
20 5.05 4.84 21.8
30 5.05 4.93 20.6
40 5.01 4.90 18.0
SO 5.01 4.89 16.1 The experimental results of Table 21 show that the rate of the process decreases with increase in the glycine concentration. This decrease is

4. A Study of the Nickel Reduction Process at Increased Hypophosphite Concentrations

evidently caused by the smaller concentration of free nicke I ions due to complex formation.

Thus, the effect of glycine as a complex-forming agent is exhibited in

two directions. On the one hand, it decreases the rate of reduction of the nickel, and on the other hand it permits the solution to be replaced and so prolongs the times of operation. The second effect gives reproducible results with regard to both the rate of the process and the quality of the coating.

When the concentration of the complex-forming agent in the bath, in particular that of glycine, is determined, the many-sided influence of the substance on the process must be taken into consideration. As mentioned above, the solution with 30 g of glycine per liter was quite stable on prolonged operation, and the rate of deposition of the rricke I was maintained at a fairly high level.

It is quite probable, however, that as a result of further research it will be possible to reduce the concentration of the complex-forming agent and thus increase the rate of the process even more without causing any noticeable decrease in the time-stability of the solution.

The results of our experiments on the influence of complex-forming agents on the process revealed the complex nature of the reaction between the components of a chemical nickel plating solution. Thus, a number of very effective complex-forming agents such as triethanolamine, diethanolamine, and trilon had no beneficial influence while glycine or sodium citrate favored the process. Their role is evidently not confined to their complexforming action alone, and their ability to affect the rate of the process and the quality of the deposit is determined by specific properties related to structure and other parameters. This is indicated, for example, by the specific action of glycine which accelerates the course of the process in solutions containing no other buffer additives (Table 19), while with solutions containing sodium acetate it lowers the rate of reduction of the nickel (Table 21), A similar effect is observed with sodium citrate and other complex-forming agents.

The above results indicate that it is possible to overcome +he difficulties associated with the replacement of the solution, and thus show the way towards a continuous process. At the same time, it is necessary to devise new experiments to study the mechanism of the action of these additives, and to widen the search for more effective complex-forming agents so as

to increase the time of operation of the solution.

We showed in section 2 that the rate of the process can be increased by increasing the hypophosphite concentration if the solution contains a sufficient amount of the buffer additive. At the same time it is known from previous experiments that at the high temperatures generally used for high rates a spontaneous decomposition of the hypophosphite occurs, at a rate which increases with increase in hypophosphite concentration. As the decomposition of the hypophosphite causes waste, the simultaneous application of the two factors to increase the rate of the process is not worthwhile.

As it is advisable to carry out the process at lower temperatures, we considered the possibility of maintaining a high process rate by applying the second factor, namely, by increasing the hypophosphite concentration.

We therefore carried out nickel plating experiments in solutions containing 30 and 50 g of hypophosphite per liter. The concentrations of sodium acetate were chosen from the data of the experiments described in section

2 (Tables 11 and 17 for the solutions containing 30 and 50 g of hypophosphite per liter respectively) so as to obtain the maximum rate of reduction of the nickel. Nickel chloride (25 gil) and glycine (30 gil) were added to both solutions.

Temperature, °c

Nickel chloride concentration, g/l

(J

Iii ZO JQ

o 5IJ

FIGURE 15. Influence of temperature on the rate of deposition in solutions I and II (for the composition of these solutions see Table 22)

FIGURE 16. Influence of the nickel chloride concentration on the rate of deposttion, Composition of the solution: sodium hypophosphite, SO/I; sodium acetate, 50/1; sodium succinate. 50/1; pH,._,5, tempeeature r-- 95°.

Data on the rate of deposition of nickel in these solutions at different temperatures is presented in Table 22 and Figure 15.

It is clear from Table 22 that a rate of 24 microns/hour is attained at 98° in solution II and at 90° in solution I.

Even at 85° the rate of the process remains fairly high (19 microns /hr) in the solution containing 50 g of hypophosphite per liter. However, the rate of reduction of the nickel in this solution also decreases considerably with further decrease in the temperature.

FIGURE 22

Relationship between the rate of the process and the temperature

Composition of the solution, gIl Rate of deposition (microns/hr)
Solution at temperatures (0C)
nickel sodium hypo- sodium 95
.glycine pH 80 85 90 98
chloride phosph ite acetate
I 25 50 50 30 5 9,2 In 2-t.5 27.7 31.1
-'"
II 25 30 20 30 5 S.4 13 16.6 21.5 24.1 The above results indicate that in solutions with a high hypophosphite content it i& possible to carry out the process at a fairly high rate at lower temperatures, and so we studied some properties of the solutions with higher hypophos phite contents.

Data on the influence of the concentration of the nicke I salt on the rate of reduction of the nickel are presented below (Table 23, Figure 16).

TABLE 23

Relationship between the rate of the process and the nickel chloride concep.tration in solutions containing 50 g of sodium hypophosphite and 50 g of sodium acetate per liter.

Temperature 95°

Nickel chlo- pH of the solution Rate of
ride concen- deposition, Quality of the Note
tration, g/l before expt after expt microns/hr coating
15 5.03 4.66 26.6 Matt, striated A small amount of
20 5.0 4.49 34.2 Uniform, .bright nickel powder was
25 5.02 4.42 35.4 " " formed in the bulk
of the solution
30 5.0 4.59 28.2 Bright with local- Large amounts of
ized matt stripes nickel powder were
35 5.02 4.89 16.7 formed in the bulk
Matt, striated of the solution
45 5.04 4.72 10.6 A salt-like preci-
p itate is formed
on the sample As can be seen from Table 23, the highest rate of deposition was obtained at a nickel chloride concentration of 20-25 gil. Considerable amounts of nickel powder are formed in the bulk of the solution when the nickel chloride concentration is increased, while the rate of the process drops and the quality of the coating deteriorates.

Accordingto the recommendations of Gutzeit /24/, the best results are obtained when the molar ratio of the concentration of the nickel salt to that of the hypophosphite is 0.4. The best results with the solution containing 50 g of sodium hypophosphite per liter (0.47 M) might have been expected at a nickel chloride concentration of 45 gil. Table 23 shows, however, that the rate of the process was low under these conditions and poor quality coatings were obtained.

The above discrepancy can evidently be attributed to the incomplete data regarding the components of the solution described in the Gutzeit patent.

At the same time it should be noted that the experimental results presented in this section, as well as those presented in section 3, Table 20, show that the nickel salt concentration does influence the rate of the process, which is in agreement with the data of Gutzeit. This phenomenon was not observed in solutions with low hypophosphite content.

The curves in Figure 17, corresponding to solutions with different hypophosphite contents, show that the higher the hypophosphite concentration, the more pronounced is the influence of the nicke 1 salt concentration on the rate of the process.

47

It is undoubtedly necessary to have a more detailed knowledge of the processes which occur at high concentrations of hypophosphite in order to

be able to use these solutions. The following problems must be investigated in particular: increased probability of a spontaneous reaction in the bulk of the solution; the ratio of the rates of the reactions which result in the reduction of nickel and the evolution of hydrogen; and the course of the reaction by which phosphorus is formed under these conditions.

Thus, the rule that in acid solutions the rate of the process does not depend on the concentrations of the hypophosphite and of the nickel salt must not be regarded as a general one for the nickel plating process in any acid solution.

The influence of the concentration of hypophosphite on the rate of deposition becomes clearly evident when the data are examined on the variations in rate caused by the increase in sodium acetate concentration in solutions containing various amounts of hypophosphite (Figure 18). The nickel salt concentration in those solutions was equal to the optimum value at the given hypophosphite content (see Tables 20 and 23).

t,{J

120

B

o, ~

"

'010

3

ee

0:;

Q

20

(jfJ

80

100

Nickel chloride concentration, gil

FIGURE 17. Influence of the nickel chloride concentration On the rate of deposition in solutions containing various amounts of hypophosphite with the optimum sodium acetate content 1 - 10 g of sodium hypophosphite, 10 g of

sodium acetate per Iiter:

2 - 30 g of sodium h ypophosphite, 20 g of sodium acetate per liter;

3 - 50 g of sodium hypophosphite, 50 g of sodium acetate per liter.

The rules presented in this chapter for the relationship between the rate of the process and the concentration of the various components in the solution must be taken into account in the further development of our theories on the mechanism of the chemical nickel plating process.

o 10152025 30J5 t,Q45S< Sodium acetate concentration, gIl

FIGURE lB. Influence of the sodium acetate concentration on the rate of deposition in solutions containing various amounts of hypophosphite

1 -lOg(l; 2 -30g(l; 3 -SOg!l (the time unit is 30 min).

5. The Methods of Regeneration of the Nickel Solution

As we have mentioned above, the addition of a complex-forming agent

to the solution prevents the precipitation of nickel phosphite, but when the phosphite concentration reaches a certain value the precipitation occurs even in the presence of the complex-forming agent. Evidently the amount of phosphite which can be kept in solution depends on the nature and on the concentration of the complex-forming agent. For a stable operation a suitable complex-forming agent must first be chosen. It is then necessary not only to maintain the main components at their optimum concentration but also to separate the phosphite and other accumulated impurities, either continuously or periodically.

Although a continuous chemical nickel plating process has been developed in a number of plants in the U. S. A. (the Kanigen process), there are almost no data in the literature on methods for regenerating the solution. There are only short reports /33,34/ that ion-exchange resins can be used to purify the solution from phosphites.

It should be noted that our experiments with different forms of the anionexchange resins MN, MMG-l and NO have so far failed to give very encouraging results. Although the phosphite was adsorbed on certain resins

(MN and NO), no complete separation was achieved under the conditions of our experiments. Moreover, a certain (although lower) adsorption of hypophosphite accompanied the adsorption of the phosphite in the majority of the expe rim ents.

Besides organic anionic resins, we also tested other adsorbents, such as activated carbon, glauconite, sand, and cationic resins in the barium form without, however, the desired effect, so the above adsorbents did not solve the problem of the regeneration of the solutions.

As such a wide variety of adsorbents are known in modern technology,

the search for new and more effective adsorbents for phosphite must be continued, and methods for their use improved.

Vie studied another possible method for the removal of accumulated phosphite from the solution, namely the reaction between the phosphite and ferric chloride. It is known from the literature /27/ that sodium phosphite reacts with ferric chloride to form a complex compound, NadFe (OH){HPO~)21' ·20Hp. This substance is light yellow and insoluble in cold water; it decomposes in hot water to form the colorless iron phosphite.

We examined the possible application of this method for the separation of the phosphites, with a nickel solution which had been in use for several hours. The initial composition of this nickel solution was: 25 g of nickel chloride, 30 g of sodium hypophosphite, 20 g of sodium acetate, and 30 g of glycine per liter; the initial pH was 5. The components were replaced during the operation.

The amount of phosphite formed in the solution by oxidation of the hypophosphite was determined by chemical analysis. The amount of ferric chloride needed to separate the phosphite from the solution was calculated from the equation for the reaction (one mole Fee13 for each two moles Na2HP03), but the amount actually added was less than this to prevent contamination of the solution with this reagent. The ferric chloride was dissolved in a small amount of water before it was added to the bath.

In order to prevent, or at least to reduce, the losses of nickel and other components during the filtration of the solution, the Na2[Fe{OH)(HP03)2]' ·20H20 precipitate, formed in large amounts as a result of the reaction, was washed with water until the washings were colorless. The volume of the filtrate was adjusted to its initial value by addition of the washings. If

a more thorough washing of the precipitate was necessary, the washings were partially evaporated.

The analysis showed that the addition of ferric chloride to the solution caused a considerable reduction in the phosphite content, but a certain (although small) decrease in the hypophosphite content was also observed, caused possibly by losses during the filtration. Moreover, the acidity of the solution increased (to pH ~ 3.0-3.5), and it was necessary to neutralize the nickel plating solution of pH ~ 5 before use, and to adjust the concentrations of the various components to their initial values. The extent to which the acidity increases depends on the amount of phosphite to be separated, and can reach a considerable value.

The high acidity of the solution can cause losses of acetic acid by evaporation, and these losses increase when the solutionis heated. A decrease in the acetic acid concentration upsets the optimum composition of the solution and reduces the rate of the process. It is recommended that the solution be neutralized Simultaneously with the addition of the ferric chloride

to prevent loss of the buffer additive.

Table 24 shows the results of the experiments on the separation of phosphite, by the addition of ferric chloride, from a solution containing nickel chloride, hypophosphite, 20g of sodium acetate, and 30g of glycine per liter.

The possibility of separating the phosphite from the solution by ferric chloride was also studied with a solution containing 109 of sodium glycolate as the buffer additive. Glycine was added to the solution as a complexforming agent, to prevent the precipitation of nickel chloride during the replacement of the solution and the nickel plating process. As in the previous case, the phosphite was not separated completely from the used solution, to prevent contamination of the solution with ferric ions

TABLE 24

Experimental data on nickel plating in solutions conta inmg sodium acetate, before and after the separation of the phosphite. pH ,..._,S. Temperature 9SQ

Solution without replace- Hypophosphite
added to the solution
Data of chemical analysis ment of the to bring the concentration
Solution hypophosphite to 30g/i
-
rate of quality of rate of
phosphite, hypophosph it e , quality of
gil gil deposition, the coating deposition, the coating
In icrons/ hr microns/hr
Before the Bright with
separation matt
of the stripes
phosphite 71.9 18.1 17.4 20.6 Bright
After the
separation
of the
phosphite 29.6 15.6 16.6 Matt 21.9 Bright The results of the experiments with the above solution are presented in Table 25.

TABLE 25

Experimental data On nickel plating in solutions containing sodium glycolate, before and after the separation of the phosphate. Temperature 950

Data of chemical analysis Rate of
Solution pH Quality of the
phosphite, hypophosphite, deposition, coating
gil gIl In icrons/ hr
Before the separation
of the phosphite 51 9.1 4.91 10.4 Coating bright and
uniform; solution
clear
After separation of
the phosphite 28 9.7 4.92 10.8 Ditto The data in Tables 24 and 25 show that ferric chloride can be used to separate the phosphite from the two solutions studied. Moreover, the reaction between the phosphite and the ferric chloride caused no noticeable change in the rate of the process or in the quality of the coating. As the precipitate has an unfavorable effect on the process, if we had used solutions with limiting amounts of phosphite above which precipitation occurs, there should evidently have been an increase in the rate of the process, and an improvement in the quality of the coating.

The data in Table ~4 again ShOW me inttuerice 01 the r-at io 01 the amount of hypophosphite to that of the buffer additive on the nickel plating process. Thus, a reduction of the hypophosphite concentration to 15-18 gil (at a sodium acetate concentration of 20 gil) causes a decrease in the rate of reduction of the nickel to 16-17 microns/hr, accompanied by the formation of matt coatings (Table 24). The replacement of the hypophosphite in the solution to 30 gil causes an increase in the rate of the process and improvement in the quality of the coating.

Of the methods for the regeneration of the used solutions, the most promising results were obtained with that in which the phosphite is separated by ferric chloride. The data of our experiments showed that the addition of iron salt in amounts which will be bound in the insoluble precipitate does not interfere with the course of the process. It is, however, necessary

to examine the possibility of repeating this operation more than once, and to make a more prolonged study of the performance of the solution afterwards. At the same time other ways of regenerating the solution must be sought.

CHAPTER IV

THE COURSE OF THE PROCESS IN ALKALINE SOLUTIONS

While much has been published on chemical nickel plating in acid media. and the commercial application of the process has been based mainly on the use of acid solutions, chemical nickel plating from alkaline solutions has until recently received much less attention. However, with the data of later research alkaline solutions have found successful practical application.

The main disadvantages of the alkaline baths are the instability due to the evaporation of ammonia at high temperatures (~900) required by the process, and the low rate of reduction of the nickel compared with that in add solutions. However, the presence of complex-forming agents (cttr'ate s and ammonia salts) in the alkaline solutions facilitates replacement and thus permits prolonged operating times.

In their first studies of the chemical nickel plating process Brenner and Ridde 11 /2/ used alkaline solutions. These authors studied the conditions under which the process takes place in the solutions with compositions given in Table 26.

The best results were obtained with solution I. The rate of the process in solution II, which contained no sodium citrate, was somewhat higher

than in solution I but the resulting deposits were dark and rough and the solution became turbid after prolonged use. The disadvantage of solution III, which contained no ammonium salts, was that the reduction of the nickel was soon finished.

The reduction of nickel in alkaline solutions follows the same course as in acid solutions, and is accompanied by the evolution of hydrogen and the oxidation of the hypophosphite to phosphite. The solution becomes more acid as a result of the reactions (see the equations for the reaction in Chapter 11). The authors recommended the addition of ammonia to neutralize the acids formed in the reaction. Their attempts to replace the ammonia by organic amines failed to give satisfactory results.

According to Brenner and Riddell the role of the sodium citrate and of the ammonium chloride is to retain the nickel salts in a dissolved state at . pH 8-9. The salts of other organic hydroxyacids, such as tartaric acid, can be used instead of sodium citrate.

These authors showed that variations in the nickel salt concentration within wide limits have no noticeable influence on the rate of reduction of the nickel, while variations in the hypophosphite concentration affect the I>!'ocess considerably. The data are presented in Table 27.

TABLE 26

Alkaline ammoniacal nickel solutions studied by Brenner and Riddell

Concentration, g/l
Components of the solution
I Il III
Nickel chloride NiCI2' 6H20 .....•.. 30 30 30
Sodium bypcphosphtte NaH21'02' H20 .. 10 10 10
Ammonium chloride NH4Cl .......• SO 100 -
Sodium citrate Na3C6HSOT 5tH20 ... 100 - 100
pH8~, temperature 900
Rate of deposition, m icronsjthr ...... 6 12 5
Appearance of the coatings ......... Mediwn bright Dark Bright Although increase in the hypophosphite concentrations improves the rate of reduction of the nickel, the authors do not recommend large amounts of the reducing agent as these may cause the process to take place in the bulk of the solution, with the formation of nickel powder.

High concentrations of the nickel salts cause deterioration in the quality of the coatings, with formation of rough coatings in particular.

TABLE 27

Influence of the concentration of the main components on the rate of the process

Nickel chloride, Sodium hypophosphite, Rate of deposition,
gIl g/l microns/hr
30 2 0.8
30 4 1.5
30 10 6.1
30 SO 16.5
15 10 5.5
30 10 6.6
60 10 7.6 As in acid solutions, the temperature has a considerable influence on

the rate of the process·, as shown by the data of Brenner and Riddell presented in Table 28.

To maintain the process at a constant rate, the authors recommend that the hypophosphite and nickel salt be added periodically or better still continuously, as they are used up. Moreover, ammonia must be added regularly to the bath to neutralize the acid formed in the reduction process,

and to compensate for the losses of ammonia through evaporation.

The nickel deposits from alkaline ammoniacal solution usually contain 5-70/0 of phosphorus which is less than in the deposits from acid solutions.

TABLE 28

Influence of temperature on the rate of the process

54 68 78 87 92

0.39 0.% 1.63 2.4 2.8

Temperature , 0 C

Rate of deposition, m icrons/Bn min

West /35/ notes that these baths can be used with more success than the acid solutions for the deposition of nickel on stainless steel, aluminum, titanium, and certain other metals.

The following solution is used in the process described by West (the composition is given in g /1):

Nickel chloride. . . . . . . . •• 30 Sodium hypophosphite. • . . .• 7.5 Sodium citrate ......•••. 70 Ammonium chloride ..... " 50

pH .•...••.•..•.•.••• 10

Temperature ...•...•..• 82°-87°

As is evident from the above data, both the composition of the solution and the experimental conditions differ somewhat from those recommended by Brenner and Riddell, but the author gives no reason for these changes.

The author recommends the continuous addition of ammonia to maintain the process at a constant rate. It was determined experimentally that 500 ml of ammonia solution (200/0 NH3) were consumed in the coating of one batch of articles with a surface area of 2.7 m2• West notes that this alkaline solution can be used for a long time if the components are continuously replaced.

The author recommends the addition of a small amount (0.06g/l) of aluminum sulfate to the solution which is to be used for the coating of aluminum; this additive is unnecessary when nickel is coated on copper or brass. West indicates that in the reduction of nickel on titanium, the nickel deposit contains some occluded titanium besides phosphorus.

As in the case of the acid baths, the solution recommended by West can be used either by suspending the article in it or by using revolving barrels.

The paper of MacLean and Karten /36/ describes the operating conditions for the coating of smaH articles in an alkaline ammoniacal solution containing sodium citrate. They considered that an alkaline solution had two advantages; the resulting coat was good and it was easy to replace the solution.

As a result of laboratory investigations before the industrial-scale application of the process, the authors selected the composition of the solutions and the procedure for replacing the components of the baths. MacLean and Karten used four solutions in their work. The compositions of these solutions are presented be Low.

I. Initial solution (gill

Nickel chloride NiCI2' 6H20 . . . . . . . . . . . . .. 38 Ammonium chloride NH4Cl ....•..•...... 42

Sodium citrate Na3C6HSOT SH20 84

II. Solution for replacing the components of the nickel bath (gil)

Nickel chloride NiCI2' 6HZO ..•....•...••. 12S

Ammonium chloride NH4CI 12

Sodium citrate Na3C6HS07' 5H20 38

III. Sodium hypophosphite solution (g/l)

............•.. 375

IV. Ammonia solution

Consists of one part concentrated ammonia and two parts water.

According to the data of these authors the work was carried out as follows. Solution I was poured into the bath and heated to 900, then 18.7ml of the hypopho phite solution III were added fo:..' each liter of solution 1. The ammonia solution IV was added to the bath until the nickel solution acquired a stable blue color, which corresponds to a pH of 8.5-9.

The solution was replaced as the bath was used by the addition of the above solutions. As there are no rapid methods of analysis, the amount of the reagents needed to replace the components of the solution was determined empirically.

The nickel salt was replaced by the addition of 2.5 m l of solution II per liter of bath each hour. The fact that the further addition of solution II to the bath causes a white precipitate may be used as an indication of the presence of a sufficient amount of nickel.

The consumption of hypophosphite was compensated for by the addition

of B m l of solution III per liter of the nickel bath every 30 min. The amount of hypophosphite in the bath can be estimated from the evolution of gases during the process. Weak evolution of hydrogen indicates an insufficient concentration of the hypophosphite, and vigorous evolution indicates an excess. Large amounts of hypophosphite are undesirable, as nickel powder may be formed in the bulk of the solution.

The required pH of the solution is obtained by the addition of the ammonia solution IV, and is determined by r the color of the solution as described above.

The chemical nickel plating is carried out in stainless steel baskets immersed in enameled baths with a volume of 10-12 liters. The authors note

that such relatively small baths are easy to clean. with periodic shaking of the articles once a minute. with a ventilating device.

The plating time is 8 min, Each bath is equipped

* The usual formula for sodium hypophosphite is NaH2P02' H20.

There is an essential difference between this method for the replacement of the components of the solution and that proposed by Brenner and RiddelL In the method of MacLean and Karten the solution is replaced by the addition of both the main components, hypophosphite and the nicke 1 salt,

and of the complex-forming agents; this may be the reason for the increased stability of the solution.

In the procedure described for the alkaline bath, attention must be drawn to the high concentration of hypophosphite in the solution used to replace

the nickel bath. Local decomposition of the hypophosphite may occur at

this concentration, accompanied by the formation of nickel powder, and waste of the components.

A number of papers /37 -40 / with data on the influence of various factors on chemical nickel plating in alkaline solutions, and on the possibility of using these baths for a long time have been published in the USSR during the last years.

As a result of their study of the chemical nickel plating process in solutions containing 45 g of nicke 1 chloride, 20 g of sodium hypophosphite, 45 g of sodium citrate, and 50 g of ammonium chloride per liter, at pH 8-9,

D.l. Efros, Z.V. Sharygina, and M.A. Muzychuk /37/ obtained data showing that the rate of deposition is directly proportional to the concentration of hypophosphite. When the temperature was 88°-900, and the ratio of the area to be coated (in dm2) to the volume of the solution (in liters) was 0.3: 1, increasing the hypophosphite concentration from 5 to 20 gil caused the rate to increase from 5 to 20 microns /hour.

A similar, almost linear, relationship between the rate of deposition of nickel on aluminum and the hypophosphite concentration was observed in the work of Machu and El-Gendi /21/. Thus, these authors note that in a solution containing 30 g of nickel chloride, 50 g of ammonium chloride,

100 g of sodium citrate per liter (pH 9.15, temperature 82Q) and 10, 15,

or 20 g of sodium hypophosphite per liter, the rate of deposition of the nicke 1 was 5.3, 7.8, or 9.4 microns/hour respectively.

E. Ya. Kel'man /38/, who studied the process in a solution containing

21 g of nickel chloride, 11 g of sodium hypophosphite, 13-15 g of citric acid, and 30-35 g of ammonium chloride per liter, and enough ammonia to maintain the pH within the range 8-9, noted that when the hypophosphite concentration was changed from 5 to 30 g It, the rate of deposition at 85°-880 increased from 5 to 20 microns /hour.

A study of the process as a function of the temperature showed that the rate of deposition in this solution was 7-8 microns/hour at 75°-77°, and 12-13 microns/hour at 88°-89°. In a solution with an analogous composition, except for a hypophosphite concentration of 23 gil, a similar change in the temperature caused the rate of deposition to increase f.com 9 to 17-18 m ic rons /hour.

In spite of the increase in the rate of deposition with increase in temperature, the authors of the papers /37-38/ do not recommend heating the solution to temperatures above 900• They point out that in accordance with the reports of other investigators the probability that the process will take

place in the bulk of the solution, with the formation of nickel powder, increases at higher temperatures.

The concentration of sodium citrate in the compositions of the alkaline nickel solution proposed by different authors varies quite markedly.

E. Ya. Kellman /38/ carried out experiments to find the influence of this component on the rate of the process. He used citric ac id instead of sodium citrate, and then neutralized the acid with ammonia. The influence of the citric acid was examined with concentrations of 10. 15. 25, 35 and 60 gil, in a solution of the above composition. The author notes that the highest rate

of deposition, 16 microns /hour, was obtained at a citric acid concentration of 10 gil, but the coating was matt, with dark striations. By inc rcas ing

the citric acid concentration to 15 gil, the rate of the process was reduced to 13-14 microns/hour, but the quality of the coating was improved and light, bright coatings were obtained.

Unfortunately, the paper of E. Ya. Ke l iman gives no data on the rate of the process and on the quality of the coatings obtained from solutions with the higher citric acid concentrations.

The possibility of using the alkaline baths for prolonged times with replacement of the components was studied by D. 1. Efros, Z. V. Sharygina and M. A. Muzychuk /37/. Their results are in agreement with those of other investigators, and show that these solutions are fairly stable. Thus, no interference with the process was encountered from the phosphite accumulating in the solution at concentrations up to 340 gil. This phosphite concentration was reached after the deposition of 44 g of nickel from one liter of the bath, with replacement and periodic filtration of the solution.

A further increase in the concentration caused turbidity in the solution, due to the formation of a precipitate. The concentration of phosphite can be reduced by cooling the solution to 5°_8° and filtering off the precipitate formed.

According to M. 1. Zil'berfarb and M. P. Garetovskaya /39/, the phosphite concentration reached 2.33 M after a prolonged time of operation. These authors used a solution containing 22 g of nickel chloride, 30 g of sodium hypophosphite, 50-100 g of sodium citrate, and 50 g of ammonium chloride per liter. The process was carried out at pH 8-9 and at 93°-95°.

D.1. Efros, Z. V. Sharygina, and M. A. Muzychuk replaced the components in their solution by the method proposed by MacLean and Karten /36/, and made certain changes in the composition of the solutions added to the nickel plating bath. A solution containing 150 g of nickel chloride, 50 g of ammonium chloride, and 45 g of sodium citrate per liter, was used to replace the nickel salt; the hypophosphite concentration was replaced with a solution containing 400-500 gIl of this salt. This concentrated solution

of hypophosphite was usually added to the bath before the immersion of the articles. The optimum pH value (8-9) was maintained by the addition of ammonium hydroxide until the solution assumed a stable blue color.

The majority of authors do not use specially prepared solutions. Prior

to its addition to the bath the nickel salt is usually dissolved in water, without the other components, while the hypophosphite is added as a more dilute solution to prevent local decomposition.

The amounts 6f the nickel salt and of the hypophosphite to be added to the bath to replace its components are calculated on the basis of the amount of nickel already deposited; the consumption of hypophosphite is assumed to be approximately 5 st« of nickel.

The advantage of adding further amounts of sodium citrate together with the nickel salts is not confirmed by the investigators using this method. It is possible that the addition of this salt increases the stability of the nickel

Nickel chloride . . . . . . . . .. 21

plating solution. The necessity of adding further amounts of ammonium chloride is doubtful . as the concentration of this salt increases constantly during prolonged times of operation, due to the neutr-a.ltz at ion of the <:Lei,.! formed by ammonia ..

The conditions under which alkaline s o lut iorie can be used for the

of nickel on atum inum alloys were studied by .'3. A. Vish.""kov /40/. 'Il!2 author recommends the use of a solution of the following compos it ior, (1.n !?;!l):

Sodium hypophosphtte .... " 24

Sodium citrate 45

Amrnontum chloride. . . . . .. 30

pH " 8.5-9

Instead of sodium citrate citric acid (l0-12g!O can be used, and neutralized with ammonia. The pH is maintained within the range 8.5-9 by the addition of ammonia. In addition to the above components the author recommends that 0.3 g of aluminum sulfate per liter be added to the solution.

As in the other methods for plating on aluminum, the success depends ·on the adherence, and is determined by the method of preparation of the aluminum surface. The latter must be free of oxide film at the moment immediately before the deposition of the first layers of nickel.

In the development of a technique for the chemical plating of nickel on aluminum alloys, S. A. Vishenkov used the results of V. 1. Lainer and Yu.

A. Velichko /41/, who studied the problem of preparing the surface of these metals prior to their plating.

The author recommends that the surface be prepared by the following procedure: 1) de greasing with an organic solvent (gasoline B-70); 2) drying with compressed air; 3) rubbing with vienna paste; 4) washing with cold running water; 5) etching to eliminate the oxide film.

The composition of the etching solution was changed in accordance with the type of alloy. Alloys Dl and D16 were etched in 25 % sulfuric acid at 80°-82° for 40-60 sec. After they had been washed the particles were treated with a 1 : 1 solution of nitric acid to brighten the surface.

Alloys AK-2, AK-4, AK-6, AMu [not clear in the Russian text], and AMg were etched in a 3-5% sodium hydroxide solution at 70°-75° for 45-60 sec. After they had been washed with hot water the articles were treated as in the previous case, with a nitric acid solution (1 : 1) until the sludge was completely removed from the surface.

Alloys AL-3, AL-3A, and AL4, which contain considerable amounts

of silicon, were etched in a 3-5"/0 sodium hydroxide solution at 70°-75° for 45-60 sec., and then washed thoroughly with hot water and "brightened'"

in a mixture of nitric and hydrofluoric acids (650: 350 by volume) until the sludge was completely removed from the surface. The time of the "brighterring" operation was 7-10 sec.

Although the above procedure for the preparation of the surface of aluminum alloys removes the oxide film, it does not protect the metal from further oxidation. To prevent the reappearance of the oxide film further treatment namely with zincate, is carried out. The articles are immersed

in a zincate solution, as a result of which a thin, dense gray film is formed by displacement of the zinc from the solution.

Good results are obtained by using a solution containing 100 g of zinc oxide and 500 g of sodium hydroxide per liter or a solution prepared by dissolving 100 g of zinc sulfate and 500 g of sodium hydroxide in water, and adjusting the volume to one liter. The articles are treated in the zincate solution for 25-30 sec at 20"-25°.

The zincate solution does not always give satisfactory results with certain types of aluminum alloys u», D2); the film for-med is loose, spotted, and dark, instead of being dense and uniform. In such a case the film is removed by immersing the articles for several seconds in 1 : 1 nitric acid. The treatment in the zincate solution is then repeated for 10-12 sec.

After the zincate treatment the articles are washed and transferred to the chemical nickel plating bath.

Machu and El-Gendi /21/ describe a method for the preparation of aluminum surfaces before nickel plating in alkaline baths without zincate treatment. The authors state that good results were obtained by using the following procedure: 1) degreasing in a solution containing 30 g of sodium carbonate and 30 g of trisodium phosphate per liter, for 2 min; 2) washing; 3) etching in 10% hydrofluoric acid, 30 sec; 4) washing; 5) etching in 1: 1 nitric acid, 30 sec; 6) washing.

CHAPTER V

PROPERTIES OF THE COATINGS

1. Physical and Chemical Properties

The nickel deposits prepared by chemical reduction from acid solutions have a smooth and fairly bright surface; the coatings obtained from alkaline solutions have a less bright surface.

The deposits of chemically reduced metal always contain 3 to 15 % of phosphorus, depending on the conditions of the process.

The deposits obtained in acid solutions under optimum conditions contain from 6 to 100/0 of phosphorus. The phosphorus content of the nickel deposits obtained in an alkaline solution is somewhat lower, ranging from 5 to 7 %.

The results of analysis of nickel deposits which 'we obtained from different solutions are presented in Table 29.

The data in Table 29 show that the phosphorus content of the coatings depends to a considerable extent on the acidity of the solution. Thus, the amount of phosphorus in deposits obtained from solutions containing sodium glycolate as the buffe r varie d from 9.9 to 15.6 %, depending on the ac id ity of the solution. The smallest amount of phosphorus was found in the deposits obtained from alkaline solution.

The continuous plating of nickel by the chemical process, with replacement of the components of the solution, is usually associated with an increase in the phosphite concentration. To determine the influence of this factor on the phosphorus content of the coating, we carried out experiments /42/ with a solution containing sodium malate and glycine, besides the nicke 1 salt and the hypophosphite. This solution (the composition of which

is presented in Table 29) enabled us to maintain a constant concentration

of the main components and a constant acidity for a long period of time; the rate of deposition was 20-22 microns/hour at 95°. The experimental results are presented in Table 29a.

The data in Table 29a show that when the phosphite concentration is increased to 200 gil it has no significant influence on the amount of phosphorus in the coating.

According to the data of Scholder and Heckel /9/ (chapter 1), the phosphorus in the coating is not present as a phosphide (i , e., a hydrogen phosphide derivative) but as an intermetallic compound. In spite of the fact that these compounds are not really phosphides, we shall use the term "phosphide" to designate them below. There is reason to assume that the deposit is not composed of one phase only, but that it contains free nickel in addition to

the phosphide phase, or rather a solid solution of phosphorus in nickel. This structure considerably affects the properties of the coating, in particular

61

its chemical properties, The nature of the cnange s in the physical properties, observed when the deposit is heated, becomes clear when the above structure is considered.

TABLE 29

Phosphorus content of the coating as a function of the conditions of the process

Composition of the solution

Concentration pH of the solution Phosphorus

1-----.------; content of the deposit, %

gf!

before the

after the

experiment experiment

Nickel chloride ....... 30
Sodium hvpophosph ite . ' . [0 8.7 8.44* 5.5
Ammonium chloride .... 50
Sodium citrate 100
Nickel chloride ....... 30 5.68 4.6 9.95
Sodium hypophosphite ... 10 4.25 3.33 12.2
Sodium glycolate ...... 10 3.92 13.9
Nickel chloride ....... 30 2.95 2.86 15.65
Sodium hypophosph ite ... 10
Sodium formate ....... 10 5.25 3.7 9.15
Nickel sulfate ........ 30
Sodium hypophosph ite ... [0 5.4 6.87
Sodium acetate ....... 10
Nickel chloride ....... 25 5.6 5.8** 8.3
Sodium hypophosphite ... 30 5.02 4.87 9.8
Sodium malate ....... 45 4.57 4.49 10.5
Glycine ............ 30 4.00 3.98 12.1
Note: Ammonia was used to maintain a constant pH in the solution marked with
(*), and sodium hydroxide in that marked with (**); the pH was not corrected
in the remaining solutions. Data of the spectral analysis of the nickel deposits, presented by Gutzeit and Mapp /29/, tndicate .the presence of traces (less than 0.1"/0) of the following elements: aluminum, calcium, iron, lead, magnesium, and silicon. In addition, the presence of the following has been established: carbon 0.040/0, oxygen 0.00230/0, nitrogen 0.0005,,/0, and hydrogen 0.0016%.

Because of the presence of phosphorus the melting point of chemically reduced nicke 1 is lower than that of pure nicke 1, and varies with the phosphorus content.

According to Gutzeit /26/, the melting point of the nickel deposit fluctuates between 11 00" and 1200". Data of a later work / 29/ give a some-

what different melting point (890°) for a deposit obtained by the Kanigen process,

TABLE 29a

Phosphorus content in coatings obtained from solutions with different phosphite concentrations

Sodium phosphite, pH of th~ solution !
before the after the Phosphorus content,
g/l %
experiment e xper imerit
5 -10 5.02 4.87 9.8
150 5.09 4.95 9.4
200 5.09 4.85 9.3 The differences in the melting point, as well as in other properties of chemically reduced nicke 1, are associated with differences in the ph os - phorus content. Data on certain physical properties of chemically reduced nickel are presented below:

Specific gravity: 7.B5 ± 0.03 g/cm3 according to /29/, and 7.95-B.05 g/cm3 according to our experiments, which were carried out in acid solutions.

Coefficient of linear (thermal) expansion: 13.10-6 per °C /29/.

Thermal conductivity, calculated from data on the electrical conductivity: 0.0105-0.0135 ca l y cm- sec' "C /29/ .

Specific electrical resistance: 60 microohms/cm /29/.

Data on the electrical resistivity of deposits prepared by Kell and Pforzheim /43/ are presented in Table 30.

TABLE 30

Electrical resistivity of chemically reduced nickel

Solu- Composition of the Thickness of
Concentration Ohm·cm·l0S
the deposit, Note
tion solution gIl
microns
I Nickel chloride ..... 30 1.5 5.5 - 6.5
Sodium hypophosph ite . 10
Sodium glycolate .... SO 2.5 5.2-6.8
pH 4 - 6 .........•
II Nickel chloride ..... 30 The deposits were prepared
Sodium hypophosphite . 10 9 3.0 - 4.0 by successive plating, first
Sodium citrate ..... 100 11 4.5 - 5.5 in solution I, then in solu-
Ammonium chloride .. tion II
pH B - 10 ........ SO As can be seen from Table 30, the electrical resistivity of the deposits varies as a function of the conditions under which the deposition was carried out.

According to Aitken /31/, coatings formed by the Kanigen method have an internal compressive stress of about 3.5 kg /mm 2.

According to Gutzeit and Mapp /29/, chemically reduced nickel can undergo an elongation of 3 to 6%. As a consequence, the authors recommend that these coatings be applied to articles which are subjected to a limited degree of bending.

2. Magnetic Properties

The presence of phosphorus in the nickel coating also affects its magnetic properties. Brenner and Riddell compared the behavior of electrolytic and chemically reduced nickel towards a permanent magnet. The authors noted that the chemically reduced nickel is i.nferior to electrolytic nickel deposited from a Watts bath. The authors state, however, that the force between samples plated with chemically reduced nickel and a permanent magnet increases if the samples are first heated for 30 min at 400°.

Wesley /44/ notes more specifically that chemically reduced nickel containing 3% of phosphorus is "less magnetic" than electrolytic, while coatings containing 11.4 % of phosphorus are completely "non-magnetic".

Data on the magnetic properties of various nickel deposits, obtained in our laboratory by Yu. M. Polukarov, are presented in Table 31.

TABLE 31

Magnetic properties of various nickel deposits

Chemically reduced nickel
from acid solutions from alkaline solutions Electro -depo-
in the initial after heat treat- in the initial after heat treat- sited nickel
state ment( 400°, 1 hr) state ment( 400°, 1 hr)
Hc Nonferromag , 140 4.1 140 40 - 120
s, netic 850 45 3000 - 3300 200 - 4500
Bm 1500-1700 140 3400 - 3700 ~7000 He - coercive force (in oersteds); Br -residual induction (in gauss); Bm -maximum induction ( in gauss).

The magnetic properties of electrodeposited nickel vary with the conditions under which the electrolysis is carried out /45/.

V. B. Evdokimov carried out magnetic susceptibility measurements at the laboratories of the Moscow State University, and showed that the "satur ation" susceptibility of electrolytic nickel (0), calculated for one gram,

is 14.9.10-3 (the thickness of the coating is 60 microns), while that of chemically reduced nickel is 1.6.10-3 (the thickness of the coating is 42 microns). The relative magnetic susceptibility of electrolytic nickel (taking cast nickel as a standard) was 37.30/0, while that of chemically deposited nickel was only 4.00/0.

3. Hardness

The hardness of chemically reduced nickel i s higher than that of deposits prepared by electroplating from the usual electrolytes, and is approximately equal to the hardness of deposits prepared from the special electrolytes used for hard nickel plating. In contrast to that of the el e ctr odeposited coatings, the hardness of the chemically reduced nickel increases after heat-treatment.

According to Brenner and Riddell, the maximum hardness of these coatings can be obtained by heat-treatment at 400°. 'The hardness of the coat~ngs decreases with further increase in the temperature. Heating to 800° causes a reduction in the hardness to that of the coating immediately upon its deposition, and in some cases the hardness was even less. Gostin /4.6/ notes that the maximum hardness is obtained by heating within the temperature range 370°-500°.

The results of the measurements of hardness carried out by various authors are presented in Table 32.

Gutzeit and Mapp /29/ present data of a detailed study of the hardness

of the coatings as a function of the temperature to which they were heated; these data indicate that the maximum hardness is obtained at 400°, and that the hardness decreases with further increase in the temperature (see Figure 19).

1100

100 200 JOO Temperature, 0 C

FIGURE 19. Relationship between the hardness of the coating and the conditions of the neat treatment. {From /29/)

Goldenstein, Rostoker, Schossberger, and Gutzeit (47/ investigated the hardness of nickel deposits as a function of the time of heat treatment at 200°, 300°, and 400°. The specimens were prepared by cutting a steel ribbon coated with a nickel layer. 250 microns thick. The measurement of the microhardness of the heat-treated specimens was carried out 011 the polished surface of a cross section of the deposit. The results of these experiments are presented 'in Figure 20.

These results show that the maximum hardness at 400° is obtained within about 10 minutes and that increase in the time of soaking has no noticeable effe ct on the hardness of the coating. When the specimen is annealed at 300°, the maximum hardness is obtained within 1.5-2 hrs. Heat treatment at 200° caused no change in the hardness of the nickel coating, even after

21 hours.

TABLE 32

Hardness of the chemically reduced nickel

Hardness of the coating before Hardness of chemically reduced nickel
the heat treatment, kg/mm2 after heat treatment, kg/mrn2
Authors
electrolytic chemically Annealing time of
nickel reduced temperature, annealing, hardness
nickel °C hours
120--450 500 400 1/2 800 Brenner and Riddell /2/
800 1/2 470
270 5&0 400 1 900 K. M. Gorbunova and
A. A. Nikiforova /12/
- 480-530 20O--Z60 2 550-590 P. P. Belyaev, M.1. Zil'-
berfarb, M. P. Garetov-
400 '2(3 530-570 skaya /16/
- 350-500 300--350 1 700--800 S. M. Panchenko, M.A.
Krokhina /19/
600,00 - - - N. A. Solov'ev /20/
- 500 450--500 1 900 Gutzeit /26/
600 1112 700
800 1 500
270,00 570/20* 350--400 2 67O--S20* D.!. Efros, Z. V. Shary-
gina,N.A. Muzychuk/37/
200 21 650 Van Royen /49/
300 1/6 650
300 2 1000
- - 400 1/6 1200
500 1 850
600 1 650
750 1 600
- 320 280 1 380 D. N. Garkunov, S.A Vi-
350 1 650 sheukov /54/
500 1 720
650 1 720
750 1 650
900 1 530
- 450--600 350--400 1/3 95Q--1000 N. N. Maslov /56/
600 1/3 650,00
- 620-680 250"""300 2 730/60 V. A. Antskaitis /59/
200--450 500--600 - - - E. F. Lyakhovich /63/ * The hardness data are those of coatings deposited from an alkaline solution.

The relationship between the hardness of chemically plated nickel and the conditions of heat tr-eatment was also studied by G. G. Zusrnanovich /48/. The data of this study are presented in Figure 21.

In agreement with the data. of Gutzeit and Mapp, it was found that the hardness of the coatings after heat treatment at 200° differs little from that of the initial specimen, and does not vary even after a prolonged time of heating. At 300°, an increase in hardness is observed after one hour, the maximum hardness is obtained after 2 hours; further soaking at this temperature does not affect the hardness.

The maximum hardness is observed in the samples which have been heat-treated at 400°, the maximum value is obtained within 15-20 min. Further soaking of the specimens at 400° had no effect on the hardness.

Time of heat treatment) min

FIGURE 20. Relationship between the hardness of the coating and the time of heat treatment at 200°, 300°, and 400°. (From /471)

Heat treatment at higher temperatures, 600°, 750°, causes a reduction in hardness. The extent of this reduction in the hardness of the coating depends on both the temperature and the time of heat treatment, as is evident from the curves in Figure 22.

fIlIJO- 90fJ -

N~ 8OIJ,

..._

Jf "lQ(I-

1600r- -;-----750.

~ Saar 15~0 and 20~0 M x~ --

~~~------4$~-+'w~h~-M~·~--~~~~!~fW~~M.~~~~GM

_~- __ 4!J0" ~--:::----- ----350· e=:

.,' .... __ ._. __ , ._, .. _··-301J"

:::;.-_._. -,_./

....... "'::;.."J---600"

Time, min

FIGURE 21. Relationship between the hardness of the coating and the. time and temperature of heat treatment. (From /481)

The hardness data presented by G. G. Zusmanovich are those of coatings obtained from an acid solution containing 30 g of nickel chloride, 10 g of sodium hypophosphite, and 109 of sodium acetate per liter at pH 4-5.

Data of the measurements of the hardness of coatings deposited from solutions containing glycine as the complex-forming agent. after prolonged times of operation and with replacement of the components (see chapter III), are presented in Table 33. The solution used for this deposition had the following composition: 25 g of nickel chloride, 30 g of sodium hypophosphite,

TOOO,

190Ur .E_ 8QO

bIJ

~. 70°1

~ 600

-c

~ SOUl ~o ~~~~~~~~b-~

o 100 ZOO 300 «J(j SOO liDO 100 8QC

Temperature, (I C

FIGURE 22. Relationship between the hardness of the coating and the temperature of the heat treatment for different ttmes- 1 ~lSmini 2-30 minj 3- 60 min. (From j48f)

Van Royen /49/ presents data on the influence of the temperature of heat treatment on the hardness as well as on other properties of the coating, under various heat treatment conditions. The author separates the heat treatment procedures into three types, according to the use to which the nicke 1 plated article is to be put.

a) armealing at 4000 for one hour in an inert atmosphere, to obtain a maximum hardness equal to the hardness of chromium;

b) annealing at 6000 for 1.5 hours in an inert atmosphere. This treatment improves the elasticity of the coatings while retaining a considerable degree of hardness. Coatings with a maximum wear resistance are obtained under these conditions;

c) annealing at 7500 for 5 hours in an inert atmosphere, followed by slow cooling. This treatment is applied when a high resistance to corrosion is required. The use of this treatment is, however, limited by the mechanical properties of the base metal.

The above results, which were obtained by different investigators, show that there is a general rule governing the relationship between the hardness of chemically plated nickel and the heat treatment, but an inspection of the data shows that there are considerable differences between the absolute hardness values; these are related to the conditions under which the chemical nickel plating was carried out r-ather- than to differences in the accuracy of measurement.

TABLE 34

TABLE 33

Hardness of chemically reduced and electrolytic nickel measured at elevated temperatures <in kgjmm2)

300 400 600 800

Temperature of annealing

Hardness, kg/mm2

Temperature, a C

Chemically Teduced Electrclyttcnlckel nickel

520 750 940 660 500

25 780 325
400 205
600 17 45
BOO 3 30
25 355 85 4. The Hydrogen Content of Chemically Reduced Nickel

This re lationship between the hardness of chern ica lly plated nicke land the temperature and time of heat treatment is undoubtedly associated with structural and phase transformations, which will be discussed in more detail later (see chapter VI).

The considerable degree of hardness of heat-treated chemically plated nickel measured after cooling the specimens to room temperature is substantially different from the hardness of the coating at the heat treatment temperature. The coatings have a very low hardness at elevated temperatures.

Data of the measurement of the hardness at elevated temperatures are presented in Table 34; these data were obtained by Brenner /30/, who used a high-temperature microhardness tester. It is of interest to note that at 6000 and 8000 the microhardness of chemically reduced nickel is lower

than that of e lectrodeposited nicke 1.

Data on the amount of hydrogen which can be absorbed by the deposit, and on the permeability of the deposit to hydrogen, indicate the extent of possible hydrogen embrittlement of the nicke 1 plated articles and are of considerable interest.

Data on the amount of hydrogen in chemically reduced nickel. and for comparison in electrodeposited nickel/50, 51(" are given below.

The amount of hydrogen occluded in the coating was determined by degassing the deposits by heating to about 5500 in vacuum (l0-3mm Hg). The vacuum apparatus is shown schematically in Figure 23.

8

l

To the vacuum pump

12

Trap

To the vacuum pump

FIGURE 23. Diagram of the vacuum apparatus. 1- thermocouple with galvanometen 2- ground-glass joint for introducing the specimen; 3- heating chamber; 4- electric furnace; 5,6,7,8,9,10:- stopcocksj 11,12- liquid air traps; 13- Macleod manometer; 14- measuring flask for calibrating the system; 15- autotransformer. (From /51/).

The nickel was deposited on copper or iron plates; preliminary experiments showed that the base metal does not absorb hydrogen during the nickel plating.

The results of the measurements of the amount of hydrogen occluded in the nickel coating are presented in Table 35 .

.. The amount of hydrogen in the coatings was measured by O. S. Popova.

A.s Cc_D be seen f'r-orn these data, the chern ical ly reduced nic ke 1 dissolves

cor.s i de r-ably less hydrogen. than the electrodeposited nickel, e spe c ie.lty if

these deposits are obtained from electrolytes containing brighteners.

Aecording to Aitken /31/, coatings deposited by the Kanigen process contain about 20 ClT;3 of hydrogen per iOO g metal.

TABLE 35

Data on the amount of hydrogen in nickel coatings

--I Conditions under which the nickel was deposited Amount of
occluded
Com position of the Current deri- ~emperature hydrogen,
Method Concentration sity
solution gil amp. (dm2 °C cm3/100g
Electrochem- Nickel sulfate 140
ical Boric acid 30 1 Room 60-80
Sodium chloride 3
Sodium fluoride 5
Same Same + the sodium salt
of 2.6-2.7 dlsulfonaph-
thal entc acid 4 1 Room 140-160
Chemical Nickel chloride 25
Sodium hypo phosphite 30 - 95 30
Sodium acetate 20
Glycine 30 It should be noted that there is a complete lack of direct data on the permeability of chemically reduced nickel to hydrogen, although this is of considerable importance for the nickel plating of steel subject to hydrogen embrittlement. Certain indirect indications as to this permeability can be obtained from data on the changes in fatigue strength, which are apparently associated with the penetration of hydrogen into the base metal.

5. Adhesion

The nickel coating adheres very strongly to iron, low carbon steel, copper and its alloys, nickel and cobalt. The nickel layer, 10-12 microns thick, on sheet specimens did not show signs of peeling even after bending the sheet through 1800 and back, although the base metal was completely fractured. Cracking and partial breaking off of the nickel were observed

at the fracture site when specimens plated with a thicker layer of nickel (20-30 microns) were subjected to bending.

Gutzeit /26/ measured the adhesion on low carbon stee 1 samples coated with a nickel layer 50 microns thick. The test was carried out by bending the specimens around a rod 50mm in diameter. No peeling of the nickel was observed after this test, but the metal w8,S broken on bending back.

Adhesion tests with a rod of larger diameter (76 mrn) did not show obvious

eking of the coating, but microscopic cracks, parallel to the bending cr~~ ~ere observed on the outer and inner sides of the specimen (subject~~-~~ elongation and compression respectively). A careful examination ;evealed that the cra.cking only occurred within the coating, and that there was no lifting of the coating from the base metal.

It is noted in the same paper that tensile tests performed with nickeldated low carbon stee 1 specimens revealed that the coating is not damaged before the moment of fracture of the base metal. The author notes that

the coating is lifted only within a range of 1.6 mm from the fracture site.

S. A. Vishenkov, V. S. Borisov, and D. N. Garkunov /52, 53! observed lifting of the deposit in tensile tests with nickel-plated steel specimens which had not been subjected to heat treatment. The nickel layer remained intact only at some distance from the fracture site. No lifting was observed when heat-treated nickel-plated specimens were tested under the same conditions.

Thus, these authors recommend heat treatment for one hour at 4000 to increase the adhesion of the coating to the base metal, especially for articles which will be subjected to the action of mechanical forces. Heat treatment for one hour at 2300 is recommended for increasing the adhesion of these coatings to aluminum.

A comparison between the results of the above authors and those of Gutzeit is difficult, as the latter does not describe the test conditions or the heat treatment.

In a study of the fatigue strength, we carried out experiments with specimens of steel 45, plated with a nickel layer 30 microns thick, and no lifting of the deposit was observed after fatigue tests in which the specimens were subjected to large mechanical stresses; the samples used in these tests were not subjected to heat treatment.

According to Dickinson /33/, the adhesion of nickel coatings to low carbon steel and brass exceeds 35 kg/mm2•

According to Wesley /44/, the adhesion of coatings deposited from acid and alkaline solutions is 41.5 and 21.9 kg/mm2 respectively.

P. P. Belyaev, M. I. Zil'berfarb, and M. P. Garetovskaya /16/, as well as Gutzeit /26/, note that interruptions during the chemical nickel plating process have no effect on the adhesion of the nickel coating.

The adhesion of the coating to high carbon steels, stainless steels, and aluminum is much lower than with iron, copper, and copper alloys. The adhesion to the above metals depends to a great extent on the preparation of the surface before the plating. The strength of adhesion of the nickel coatings to aluminum can be increased by heat treatment. Gutzeit recommends heat treatment at 1900 C for one hour.

Even a superficial comparison of the plating conditions during electrolysis and during reduction of the metal by hypophosphite leads to the conclusion that better adhesion is obtained in the second case, as the deposit can be formed (when the wetting is good) in microcavities, which results

In a high mechanical adherence of the coating to the base metal. Very few of these microbonds are formed during electrolysis under low throwing power conditions. Dickinson /33/ attributed the greate r strength of adhesion of chemically plated nickel to the base metal to this phenomenon. Unfortunate ly, the data available are as yet insufficient for a comparison between the adhesion of electrolytic deposits and that of the chemically reduced metal.

6. Brittleness

The disadvantage of chern ically plated nicke 1 is its brittleness, which causes fracture of the metal under the action of mechanical forces (bending or impact). The breaking off of the metal is exhibited when the thickness of the layer reaches about 10 microns.

According to Gutzeit /26/, the brittleness of the coatings can be noticeably reduced by heat treatment for 2 hours at 600e. Although the har-dne s s is lower after heat treatment at this temperature than after treatment at 400°, the simultaneous decrease in brittleness, and the fairly high hardness retained yield good results to wear resistance.

The author notes that the maximum elasticity of the coating is obtained by heat treatment for 5 hours at 7500 or more, in an inert atmosphere. After the above treatment, slow cooling is recommended, at least to 200°. When this heat treatment procedure is followed, the coatings acquire both higher elasticity and higher corrosion resistance, but the hardness falls in this case to the initial value.

7. Wear Resistance

We have noted above that because of its great hardness (especially after heat treatment) chemically reduced nickel can be used as a coating for articles which will have to withstand wear, and to replace chromium coatings in certain cases.

The data. on the hardness and on the elasticity of the coatings give

some indication of their wear resistance,but more reliable results are obtained by direct tests on the wear resistance of the surface.

Data on the mechanical properties of chemically plated nickel coatings are given by S. A. Vishenkov, D. N. Garkunov, V. S. Borisov, and M. F. Ofitserov /52-55/.

The wear resistance of the nickel coatings was studied by D. N. Garkunov and S. A. Vishenkov /54/, who used a 77MT-l friction apparatus with a reciprocal motion, and an AE-5 friction apparatus with a rotary movement. In these tests, the nickel was subjected to friction with 30 KhGSA (HRc-32) steel as the mating surface; for comparison, the wear resistance of the steel subjected to friction with chromium coatings or, in certain cases,

with specimens of the same stee 1, was tested under the same conditions.

The specimens were nickel plated in a solution containing 30 g of nickel sulfate, 10 g of sodium hypophosphite, and 10 g of sodium acetate per liter at pH 5.

Preliminary tests carried out on the 77 MT-1 friction apparatus with a load of 50 kg/cm2, in the presence of a lubricant (600/0 glycerol and 400/0 alcohol), showed that nickel coatings which have not been subjected to heat treatment, or those heat treated at 150°, cannot be used as wear resistant material. Separation of the coating from the base metal took place Udder these conditions.

Much better results were obtained with specimens heat-treated at 400°.

In this case, the wear of the steel specimen in contact with the nickel was approximately equal to that in friction with chromium.

The following tests of these authors were always carried out with nickel plated specimens which had been heat-treated at 400° for one hour.

TABLE 36

Results of tests on the wear resistanr:e of chemically plated nickel. in comparison with the wear resistance of chromium. on steel 30KhGSA (HRc-32) in the 77 MT-l and AE-5 friction de vi.ce s , are presented in Tables 36 and 37 respectively.

Results of wear resistance tests with the 77 MT-l friction apparatus

Loss in
Specimens in the pz ir weight of Total loss in
Test conditions
subjected to friction each speed- weight, mg
men, mg
Load: SO kg/cm2; alcohol- 1. Steel 2.3 5.9
glycerine lubr-Icant; time: 2. Nickel plated steel 3.6
20 hours
Same 1. Steel 0.5 2.5
2. Chromium plated
steel 2.0
Load: 100 kg/cru2; lubri- 1. Steel 0.8 7.8
cant: AMG-10 oil; t irne t 2. Nickel plated steel 7.0
20 hours
Same 1. Steel 1.8 44.3
2. Steel 42.5
Load: 10 kg/cm2; no lu- 1. Steel 20 36
br icantj time:l0 hours 2. Nickel plated steel 16
Same 1. Steel 39 47
2. Chromium plated
steel 8 The data obtained in these tests show that chemically plated nickel coatings which have been subjected to heat treatment for one hour at 4000 have a lower wear resistance than electrodeposited chromium. but the wear of steel surfaces when in friction with nickel is lower than when in friction with chromium.

D. N. Garkunov and S. A. Vishenkov also tested the wear resistance of nickel coatings plated on an aluminum alloy. The friction was applied to the nickel-plated specimens by contact with dur-a'lum inum: the wear resistance of the aluminum alloy on friction with a specimen of the same alloy was also examined for comparison.

The chemical nickel plating on duraluminum samples was carried out in an alkaline solution; the nickel-plated specimens were heat-treated for one hour at 200°-250°, to increase the adhesion of the coating to the base metal.

The results of tests carried out with the 77 MT -1 friction apparatus are presented in Table 38.

The data in Table 38 show that the deposition of nicke 1 on dur a lum inum reduces the wear of surfaces subjected to friction. Under the specified

TABLE 37

Results of weal' resistance tests with the AE-5 Irict ion apparatus

Specimens in the pair I Loss in weight Total loss in
Test conditions subjected to friction of each spe- weight,
c im e n, mg
mg
Load: 50 kg/cm2; sl iding 1. Steel 1.0
32.6
velocity: 4.5 ml sec, Iu - 2. Nickel-plated steel 31.6
bricant: MS-20 oil; time:
Hi hours
Same 1. Steel 7.7
2. chromium-plated 25.2
steel 17.5
Load: 100 kg/cm2; sliding 1. Steel 84
velocity: 0.6 m/sec; lu- 2. Nickef -plated steel 83
bricant: MS-20 oil; time:
100 hours
Same 1. Steel 21
2. Chromium-plated
steel 18 test conditions, the wear of the specimen was reduced by a factor of 6 when MS-20 oil was used as the lubricant, while the total loss of weight was reduced by a factor of more than 20 when AMG-IO oil was used.

In addition to the above tests, D. N. Garkunov and S. V. Vishenkov studied the wear resistance of chemically plated nickel on friction with BrAZhMts bronze. The tests were carried out with the 77 MT-l friction apparatus

for 8 hours under loads of 120 and 30 kg/ ern 2, with an alcohol-glycerol lubricant.

TABLE 38

Results of tests On the wear resistance of nickel coatings plated on duraluminum

Specimens in the pair Loss in weight Total loss in
Test conditions of each spe -
subjected to friction c lmen, we.ight, mg
mg
Load: 10 kg/cm2; lubricant: 1. Duralwninum 0.8
14.2
MS-20 oil; time: 50 hours 2. ~ickel-plated dura-.
luminum 13.4
Same 1. Duraluminurn 40.5 92.5
2. Duralwninum 52.0
Load: 10 kg/cru2; lubricant: 1. Duralwninum 23.0 64.5
AMG io-eu, time: 50 hours 2. Nickel-plated dur-
aluminum 41.5
Same 1. Duraluminum 569 1439
2. Dura lum inurn 870 The se tests showed that the we ar of the rric kel cG9.ting is s orne what greater than that of the c hr-orn ium c oat iug, howeve r , the total loss of wsight in both specimens of the bronze -nicke 1 pair arte r- friction contact 'Nas lowe r than that after friction of bronze with chr-orn iurn .

N. N. Mas lov /56/ studied the wear resistance of nickel coatings 2.S a function of the heat treatment procedure, The specimens subjected to Ir-iction were steel rollers 40 mm in diameter, coated with a nickel layer- 100 microns thick which had been heat-treated at various temperatures. A block of gray cast iron with a hardness of 260 kg/mm 2 was used as the

m at ing surface. The 'Near resistance test v.;as carried out at a sliding ve-

loc ity of 0.4'7 m/sec,under a specific pressure of 25 kg/cmz with "avtol AK-IO!ll" as the lubricant. The specimens were 'weighed after the completion

of a predetermined number of test cycles, corresponding to a path of 500 m. The wear resistance was evaluated from the change in we ight of the specimens.

A curve showing the wear resistance of coatings which had been heattreated at various temperatures is pr-es ente d in Figure 24. These results show that the specimen which had been heat-treated at 350-400° exhibited the smallest wear of the coating on friction with cast iron. In order to obtain data for the comparative evaluation of the wear resistance of chemically plated nickel, N. N. Maslov carried out analogous wear resistance tests on steel 45 (hardened by a high-frequency current treatment) and on chromium.

Blocks of gray cast iron, bronze, and Babbitt alloy were used as the mating surface.

These tests showed that the wear of nickel coatings, which had been heat-treated at 350°-400°, on contact with bronze or Babbitt alloy is similar to the wear of the steel or chromium. The wear of the nickel was greater than that of the steel or chromium, when gray cast iron was used as the mating surface. Nickel which has not been subjected to heat treatment has

a wear resistance 1j2 or 1/3 of that of steel or chromium.

In addition to the fairly high wear resistance of chemically plated nickel after heat treatment at 350°-400°, which is similar to the wear resistance of hardened stee land chromium, the author notes the good wearing-in of the nicke 1 against the contacting surface. The wearing-in of the coating

on friction with cast iron is complete within 15 - 20 minutes. This process can be accelerated by increasing the load to 50 kg/ mm", or more.

The better wearing-in properties of chemically plated nickel are attributed by N. N. Maslov to its higher fluidity, caused by the presence of phosphorus. This property can be utilized to improve the wearing-in of contacting surfaces subjected to friction.

The limiting load to which the coating can be subjected when in friction with another surface is of great importance in the evaluation of the possible use of these coatings as wear-resistant materials.

E

100 200 JOO 400 500 fi{)(}

.. " <IJ

~

o

Temperature of heat treatment, °C

FIGURE 24. Changes in the wear (as in-

dicated by changes in the weight) of the

coatings as a function of the temperature of heat treatment (from {56/)

* [t'Avrol" is a petroleum-derived lubricating oil for cars and tt-a ctors . ]

D. N. Garkunov and S. A. Vishenkov /54/ carried out tests to determine the limiting loads for chemically plated nickel coatings annealed at various temperatures (2800, 3500, 5000, 6500, 7500, and 9000). The tests were carried out with the 77MT-l friction apparatus at room temperature, with AMG-IO oil as the lubricant. A specimen made of 30KhGSA (HRc-32) steel was used as the mating surface.

These tests showed that for a coating which has not been heat-treated the limiting load which can be applied without causing seizing is 45 kg/cm2, while for a coating which has been heat-treated for one hour at 280° it is 80kg/cm2, and it exceeds 420kg/cm2 for a coating which has been heattreated at 350° or above. This value of 420 kg/cm2 was the maximum load for the friction apparatus.

For nickel coatings which had been deposited from alkaline solutions and heat-treated for 2 hours at 4000, the limiting load was also found to exceed 420 kg / em 2.

The non-seizing properties of the nickel coatings when rubbed against steel were checked by comparison with 30KhGSA steel and chromium coatings.

The tests, which were carried out at different temperatures under conditions of both dry and lubricated friction, showed that the seizing behavior

of nickel coatings which have been heat-treated at 4000 is similar to that of chromium coatings.

In a study of the coefficient of friction of nicke I coatings which had been subjected to heat treatment for one hour at 400°, the above authors also found that the coefficient of friction of the nickel coating is close to that of chromium coatings. The coefficient of friction was determined with a rotarymovement friction apparatus, using MS oil and AMG-I0 oil as the lubricants, at a sliding velocity of 0.6m/sec, under specific loads of 15 to 120 kg/cm2; 30KhGSA steel was used as the mating surface.

According to the estimates of N. N. Maslov, the coefficient of friction of chemically plated nickel is 0.025-0.08 with respect to cast iron, 0.02- 0.06 with respect to bronze, and 0.024-0.09 with z-e spe ct to Babbit alloy.

Campbell /57/ reports the results of comparative tests of the wear resistance of heat-treated nickel coatings; according to these a coating 25 microns thick is completely worn off within 9 hours, the average rate of wear being 2.8 microns/hour. In a similar test, the average rate of wear of low-carbon steel was found to be 25 microns/hour, i. e., 9 times higher than that of the nickel coating. The rate of wear of a nickel-carbon steel under the same conditions was 3.8 microns/hour, i. e., greater than that of chemically plated nickel.

Gostin /46/ presents data on the wear resistance of nicke I coatings obtained in a test under dry friction conditions; he used a 0.95 inch rod with a hardness of 60 Rc rotated at a speed of 400 rpm under a load of 45 kg.

This test showed that the wear resistance of the nickel coating is approximately equal to that of tempered steel and 10 times higher than that of non-tempered steel.

It can be assumed on the basis of the above data that the higher wear resistance of chemically reduced nickel can be attributed both to its greater hardness and to the fact that the phosphides present in the coating lower

the coefficient of friction.

8. The Mechanical Properties of Steel Chemically Plated with Nickel

On account of the possible influence of the conditions under which chernical nickel plating takes place (e. g., the evolution of hydrogen which invariably accompanies the process) and of the stresses in the coating on the properties of the base metal. it is interesting to review the data on the mechanical properties of the metals subjected to nickel plating, and in particular on changes in the fatigue strength.

"'llllIlllllIllIlIlIlIlIlIlIllIlIliIlIl1•

~:~-----~----~~

FIGURE 25. Diagram of the apparatus for measuring fatigue strength: 1- specimen; 2- axle-box; 3- loading device; 4- Cardan shaft; 5- coupling; 6- electric motor; 7- revolutions counter; 8- diagram of the forces and moments

L. N. Gazez'yan and E. N. Romanova /58/ studied the properties of 30KhGSA and El415 steels before and after the deposition of a nickel layer 20 microns thick. and found that the mechanical properties. such as the limiting tensile strength. the l irn it of fluidity. the relative elongation. and the transverse compression are not noticeably changed. The data of V. S. Borisov and S. A. Vishenkov /53/ are in agreement with the above results; these authors also found that the nickel coating does not affect the impact strength of the stee Is.

D.1. Efros, Z. V. Sharygina,

and N. A. Muzychuk /37/. who determined the mechanical properties of steel before and after chemical nickel plating in alkaline solutions, also found that the coating had no noticeable effect on the tensile strength.

The variations in the fatigue strength of the base metal as a result of the deposition of the nickel coating were studied by various authors. These studies showed that the fatigue strength varies as a function of factors such as the conditions under which the coating is deposited, the use of heat-treatment, the nature of the base metal, the nature of the specimens, (whether notched or not). etc.

According to Gutzeit /26/. the nickel coating has no harmful effect on the fatigue strength of low carbon steel,

,- .. " -~ '"'~'''' ~~o n"ivpn on the test conditions. We studied the effect of the

Number of cycles of loading

FIGURE 26. Variations in the fatigue

strength as a result of the deposition of

a nickel coating: 1- polished specimen; 2- nickel-plated specimen

r.ickel coating on the f8.i:j_gE8 strength w tth smooth specimens of 8-45 steel coate d w i th ;::;_ nickel layer 30··33 rn icr-ons th ick. 'The deposition of the coat - ing was carried out in 8. so lut ion containing 25 g of nickel ch lor-ide , 30 g of hypophosphite, 20 g of sodium acetate, and 30 g of glycine per li.ter, at pH ,~5. The coat ing was not subjected to heat treatment. The mechanical tests were car-rie d out by A. T. Sanzharovskii at the Moscow Institute for the Electrification and Mechanization of Agriculture, using the apparatus diagramatically shown in Figure 25. The results of the tests are presented in Figure 26, and show that the decrease in the fatigue strength under these conditions does not exceed 15 0/0.

L. N. Gazez'yan and E. N. Romanova /58/ present data of a study of the variations in the fatigue strength of 30 KhGSA and EI-415 steels caused by the chemical deposition of nickel (20 microns) from acid solutions.

The tests were carried out on notched and plain samples subjected to cantilever beam bending (10 million cycles). The length of the specimen was 114 mm; the diameter of the working part was 5 mm. The results of these tests are presented in Table 39.

TABLE 39

Results of tests of the fatigue strength of the steel

Fatigue strength limit,
kg/mm2
Steel Surface of the
specimens specimen specimen
without with notch
notch
30 KhGSA ...... Not coated 52 26
30 KhGSA ...... Nickel plated 50 16
EI-415 . ~ ...... Not coated 60 35
EI-415 ........ Nickel plated 50 24 As can be seen from the table, the decrease in fatigue strength in the 30KhGSA steel samples caused by the deposition of the nickel was only 3.8"/0 in the specimens without a notch, and 40% in those with a notch. The decrease in fatigue strength in the EI-415 steel specimens was about 17% in those without a notch and about 30 % in those with a notch. Analogous tests carried out on specimens of the same steel electrolytically plated with a nickel layer of the same thickness (20 microns) showed that the fatigue strength of the specimens with a notch decreased sharply, namely,

to 21 kg/mm2 for 30KhGSA steel and to 18 kg/mm2 for EI-415 steel.

V. A. Antskaitis /59 /investigated the influence of various coatings on

the fatigue strength of 30 KhGSA steel. The chemical nickel plating on the specimens was carried out in an acid solution. A ten-million-cycle fatigue test under repeated reversed bending was carried out with the Moore tester. The length of the specimen was 114 mm , the diameter of the working part

5 mm, and the radius of the notch 0.75 mm. The data are presented in Table 40.

V. S. Borisov and S. A. Vishenkov /53/ studied the fat.igue strength of various stee ls nickel-plated under different conditions. Ten -million -cycle tests were carried out with a cantilever-type tester; the stress frequency was 3000 cycles /min. The di ame te r of the specimens was 12 mm.

TABLE 40

The influence of various coatings on the fatigue strength of 30 KhGSA steel

Nature of the samples

Fatigue strength limit,

Thickness kg/mm2.

of the layer,f----,-...:::..-.---:-::--

microns

without a with a
notch notch
50 26
52 22
44 20
24 16
42 18
52 26 Steel .

Chemically nickel-plated steel .

Same .

Electrolytically nickel-plated steel ..

Chromium-plated steel .

Zinc-plated steel .

8-10

18-20 8-10 8-10 7-10

Data on the variations in the fatigue strength of 40KhNMA steel, nickelplated with a layer 30 microns thick in an acid bath, in relation to the influence of heat treatment (for one hour at 400°) are presented in Table 41.

TABLE 41

Results of fatigue strength tests on nickel-plated 40KhNMA steel

Nature of the samples

kg/mm2

compared with steel, %

Fatigue strength limit

100 100 98.5 54

Steel without heat treatment. . . . . . • . . 61

Steel after heat treatment 61

Nickel-plated steel without heat treatment 60

Nickel-plated steel after heat treatment. . 33

According to the data in Table 41, the fatigue strength of the steel is not affected by the deposition of nickel without heat treatment, but it is reduced considerably when the deposition of nickel is fo l lowe d by heat treatment.

In spite of these results, all further research on the fatigue strength was carried out with heat-treated samples, as only this treated nickel coating can be used as a wear-resistant material.

Results of fatigue strength tests on 30KhGSA and 30KhGSNA steels before and after the deposition of a layer 20 microns thick from an acid solution are presented in Table 42. Both the initial steel samples and the coated samples were subjected before the test to heat treatment for one hour at 400°

As can be seen from the table, the deposition of nickel on the above steels reduces the fatigue strength by 41-420/0, as in the previous case.

TABLE 42

Results of fatigue strength tests on nickel-plated 30 KhGSA and 30 KhGSNA steel

Natur e of the samples

COIn pared with steel, %

Fatigue strength limit

30 KhGSA steel . ............. . 64 100
Same, nickel-plated ....... .... . 38 59
30 KhGSNA steel . .......... . .. . 76 100
Same, nickel plated 44 58 Simultaneously wi.th the study of the influence of nickel plating from acid solutions on the fatigue strength of steel, similar tests were carried out on specimens nicke I-plated in alkaline solutions. In these tests the fatigue strength was measured as a function of the thickness of the nickel layer. The nickel-plated specimens were heat-treated for one hour at 400·, while the steel specimens used for comparison were not subjected to additional heat treatment. The results of these tests are presented in Table 43.

TABLE 43

Results of fatigue strength tests on 30 KhGSA steel after nickel plating in an alkaline solution

Thickness of F atigue strength lim it
Nature of the samples the nickel
layer, microns kg/mm2 compared
with steel, %
Steel .........•..•• - 61 100
Nickel-plated steel ..••. 10 58 95
" " " ..... 20 54 -55 88.5-90
" " " ..... 35 51 83.5 A comparison between the data of Tables 42 and 43 shows that the coatings deposited from an alkaline solution have a smaller effect on the fat igue strength of the steel. than those deposited from an acid solution. The data of the tables also show that the fatigue strength decreases linearly with increase in the thickness of the ni cke 1 layer.

Tests on chromium-plated specimens, carried out under identica! conditions for comparison, showed that the fatigue strength is reduced by 20- 25 0/0.

The authors note that nickel plating on aluminum alloys followed by heat treatment for one hour at 2300 has no effect on the fatigue strength, or on other mechanical properties such as tensile strength, creep limit, relative elongation, etc.

Steel , .

32.4

D.1. Efros, Z. V. Sharygina, and N. A. lVIuzychuk /3'1! studied the influence of coating on the fatigue strength of 40 KT-50 s te e l . Five millioncycle tests were carried out with the MU test apparatus. The nickel plating of the specimens was carried out in an alkaline solution.

The results of the tests are presented in Table 44.

TABLE 44

Results of fatigue strength tests On 40 KT -50 steel) after nickel plating in an alkaline solution

Nature of the specimens

without notch with notch

Fatigue. stxength, kg/mm2

22.2

Nicke l-plated steel without heat treatment ..

30.6

15.8

Nickel-plated steel after heat treatment ....

31.4

18.2

These data show that chemical nickel plating reduces the fatigue strength of specimens without a notch by 5.5%, while the decrease in fatigue strength of similar specimens which have been subjected to heat treatment is slightly lower, namely 3.10/0. In specimens with a notch the decrease in fatigue strength is 29 and 18"(0, respectively.

It should be noted that no clear relationship was revealed between the fatigue strength of stee 1 and the conditions under which the heat treatment of the nickel coatings was carried out. Thus, according to the data in

Table 41, the decrease in fatigue strength of steel is greater when the nickel coating is heat treated than when it is not. The data. in Table 44 indicate that the opposite is true.

These controversial data can evidently be attributed to the different conditions under which the tests were carried out. According to the data of various investigators, the deposition of nickel on steel causes a decrease in the fatigue strength. The extent of the change in fatigue strength, however, varies within wide limits as a function of the type of steel used and of the conditions under which the chemical nickel plating is carried out.

In view of the above results of mechanical tests, it must be taken into account that the deposition of nickel might change the fatigue strength of the steel, especially if the coated articles have holes or notches or if they operate under variable loading conditions.

The change in the fatigue strength of steel as a result of the deposition of nickel is apparently associated with the permeability of the coating to hydrogen. However, the absence of data with a direct bearing on this property of the chemically plated nickel does not permit a detailed examination of the problem. It should be noted that coatings of chemically reduced nicke 1 are not exceptional from this point of view. Due to the difficulty encountered in the setting-up of tests, such data are also very limited in the case of other coatings.

9. The Porosity of the Coatings

In all cases when the metal used for the coating is nobler than the base metal, the porosity of the coating is of considerable importance as it determines the number of local cells the action of which causes corrosive destruction of the base metal. From this point of view, the great attention paid by the investigators to the porosity of nickel coatings on iron or steel can be well understood.

According to various investiga.tors, the porosity of nickel coatings formed by chemical deposition is lower than that of electrode posited coatings of simila.r thickness.

We determined /12/ the porosity of nickel coatings of various thickness by means of potassium ferricyanide, and found that the porosity of a chemically plated coating 8-10 microns thick is similar to that of an electrodeposited coating 20 microns thick.

Data on the porosity of chemically plated nickel coatings are also presented in the paper of P. P. Be lyaev, M. 1. Zil'berfarb and M. P. Garetovskaya. The porosity of nickel coatings of various thickness was determined by the GOST 3247-46 method. The surface of the initial specimens Vias subjected by the authors to sand blasting, the corresponding data for the electroplated coatings were obtained with specimens with a surface prepared by an identical method. The nickel plating solution contained 30 g of nickel sulfate, 109 of sodium hypophosphite, and 5-10g of sodium acetate per liter. Thick layers of n icke 1 were deposited in several stages.

As a result of these studies the authors conclude that the porosity of chemically plated nickel coatings with a thickness of 9 to 122 microns is almost equal to that of the e lectrodeposi.ted coatings. The authors note that the porosity is reduced sharply when the nickel coating is deposited in several sta.ges {the surface was rubbed before each consecutive plating with

a magnesium oxide - water paste, and was etched for 2 min in 1: 1 Hen.

A. I. Lip in, S. A. Vishenkov, and M. M. Livshits /60/ also note that the porosity of a coating which has been deposited in two stages is lower than that of a coating with a similar thickness which has peen deposited in one stage. Thus, a nickel coating 10 microns thick deposited from an acid bath contains 19-25 pores/10 cm2 when deposited in a two-stage process, and 40-50 pores / 1 0 ern 2 when deposited in one stage. When the nickel layer was 25 microns thick the porosity was 12-15 and 15-18 poz-e s Z l Ocmj, respectively.

The authors note that the porosity is reduced by heat treatment at 4000 for one hour. The number of pores in nickel layers 10 and 25 microns thick deposited by the two-stage process was reduced by heat treatment to 16- 18 and 4-5 respectively.

According to this study, the porosity of nickel coatings which have been deposited from an alkaline solution is 1.5-2 times higher than that of the coatings deposited from an acid solution, and is similar to the porosity of e lectrodeposited nicke 1 coatings of equal thickness.

D. I. Efros, Z. V. Sharygina, and N. A. Muzychuk /37/ studied chemical nickel plating in alkaline solutions, and showed that the porosity of the coatings depends on the previous mechanical preparation of the articles. Thus the number of pores on steel samples with a surface which had been machined to a class of 4-6 and coated wi.th a nickel layer 8-11 microns thick was

6-7 pores/crn2, while on samples which had been m a.ch ine d to 8. class of 7-9 and coated with a nickel la.yer- of similar thickness there were only 1-2 pores/crr2.

The authors al s o present data on the relationship between the poros ity and the conditions of nickel plating and heat treatment. In agreement w ith the results of other investigators, the porosity was reduced by heat treatment. Thus, specimens plated with a nickel layer 11. microns thick contained 7-8 pOl'esicm2 and this was reduced to 5 pores/cm2 by heat treatment for one hour at 4000•

In the above research, the application of a two-stage nickel plating process, with intermediate rubbing of the surface with magnesium oxide and etching in hydrochloric acid, had no considerable effect on the porosity of the coating.

According to Gutzeit /26/, coatings obtained by chemical nicke 1 plating in a continuous process were completely free of pores even at a layer thickness of 5 microns. The absence of pores was established by various tests on the surface: a) specimens plated with a nickel layer 5 microns thick were kept in hot water for 30-60 min. while a current of air was passed through the water; b) the effect of a potassium ferricyanide solution was observed on specimens plated with nickel layers 2.5 microns thick or more; c) specimens coated with a nickel layer 6 microns thick were tested by

the gaseous diffusion method; d) the activity of nickel-plated specimens (thickness of the nickel layer 5 microns or more) was measured after the deposition of a radioactive iron layer between the base metal and the ni cke 1 layer.

The low porosity of chemically deposited nickel is apparently related to the amorphous nature of these deposits (see chapter VI).

Wolf, Henderson, and Eisler /61/ used a radioactive tracer method in

a comparative study of the porosity of nickel coatings obtained by various methods, and found that these deposits can be arranged in order of increasing porosity as follows:

a) Coatings formed by chemical nickel plating in a continuous process (the Kanigen method).

b) Coatings formed by chemical nickel plating by the Brenner and Riddell method.

c) Electrodeposited bright ni cke 1 coatings.

d) Electrodeposited rricke I-phosphorus coatings obtained by the method of Brenner, COUCh. and Williams /62/, at a low pH.

e) Coatings obtained by electrodeposition from a Watts solution.

In spite of some controversial data presented by different investigators on the quantitative evaluation of chemically plated nickel coatings, it can be assumed with a fair degree of certainty that the porosity of these coatings does not exceed, and in many cases is lower than that of the electrodeposited coatings. The variations in the data on porosity of different investigators are apparently associated with the sharp changes in the composition of the solutions used for the plating of nickel by reduction with hypophosphite without replacement of the components of the solution; these cause substantial changes in the properties of the deposits.

10. The Protective Pr-ope r-t ie s of the Coatings

As is generally known, the protective properties of a coating are determined by the inherent chemical resistance of the deposited metal, as well as by structural par-arrie te r-s , such as the presence of cracks, pores, and other defects which damage the compactness of the coating.

As the coatings formed by the reduction of nickel salts by hypophosphite do not consist of pure nickel but contain some phosphorus, it is natural to expect that the chemical properties are different from those of pure nickel; this has been established by a large amount of research.

As we have already noted, the phosphorus exists in these coatings as nickel phosphide, which occurs in the deposit together with pure nickel or

as a solid solution of phosphorus in nickel. The presence of several phases in chemically deposited nickel is due to the nonuniform distribution in the deposit; this distribution is determined both by the conditions under which the de+-position took place and by the course of the subsequent heat treatment. As will be shown in the section dealing with the structure of the coatings,

the phosphide phase can be present in the deposit at a greater or lesser degree of dispersion. Thus, it is natural to expect substantial differences in the chem ical properties of these coatings.

The properties of chemically deposited nickel coatings are described in the following table, taken from the paper of Gutzeit and Mapp /29/, which presents results of a study on the corrosion resistance of these coatings in various media (Table 45). The nickel deposits used in the corrosion tests were prepared by the continuous process (by the Kanigen method).

The data in Table 45 are interesting a" they can be used to estimate the possibility of using chemically deposited nickel in various media, and as they show the much higher resistance of the coatings which have been heattreated at 7500 (in an inert atmosphere).

Gutzeit notes that chemically deposited nickel coatings are always more resistant than electrodeposited coatings of comparable thickness. The author particularly notes their resistance to alkaline media; thus, in a 72% sodium hydroxide solution at 1150 the chemically deposited nickel is 5 to

10 times as resistant as pure nickel. The author notes, however, that chemically deposited nickel is rapidly destroyed by highly active media which readily dissolve pure nickel; among these are nitric, monochloroacetic, concentrated chromic, sulfuric and hydrochloric acids, as well as solutions of sodium hypochlorite, and of some other salts.

The protective properties of the chemically deposited coatings have been studied by a number of authors; the corrosion tests showed that the protective action of these coatings is not inferior, and in most cases is superior

to that of the electrodeposited deposits.

We carried out salt-spray corrosion tests, using a 3 % sodium chloride solution; these tests showed that the corrosion resistance of chemically deposited coatings 10-12 microns thick is comparable to that of electrodeposited coatings 20 microns thick.

In his standard tests of the corrosion resistance of the nickel coatings

(in the salt spray chamber with a sodium chloride solution) Gutzeit observed an interesting peculiarity in the behavior of the coating: the rust spots which appeared in the surface did not spread over the surface even after prolonged times of exposure of the specimens to the corrosive medium.

TABLE 45

Results of tests on the corrosion behavior of coatings prepared by the Kan ig en process

u ec
,,- .~ ~ Rate of destruc-
!1 S ~
Corrosive medium C; .... ~ ,,- tionofthe coatmg,
0 D 0
~ 'r ~ ·E
t -0 ... .g microns/ year
c. c 0 Q) j
Ii 11 E 8 ~. t: ~
Q) Q) .5 '" Q) ~
f-' ::E B « f-< ::
Amyl acetace · . Room Total No 24 0.05
Amyl alcohol. 24 No action
Ammoniacal solution of ammonium nitrate. 16 7.9
Same (as vapor). . . ... . ~ .. .... . . .. 16 6.5
Aniline hydrochloride, saturated solution i6 11.9
Concentrated orange juice. 4 0.33
Acetylene bromide · . No action
Acetylene bromide - 1 % water " . 3 Slight increase
in weight
Acetone ... 16 0.075
Benzyl acetate .. . . 24 No action
Benzyl alcohol · . · . 28 0.1
Gasoline · . 4 0.56
Benzene. 24 No action
Boric acid · . · . . . . .. · . 8 13.4
Borax, saturated solution. ... 32 3.0
Deionized water ... Yes 12 0.51
.. . . · . 49 No 12 0.30
.. . '" . . . · .. ~ · . 82 12 Slight increase
in weight
Distilled water .. . . · . Room 4 0.74
Ammoniwn hydroxide (30% NH3) . .. .. . 4 58.4
Sodium hydrosulfide (40 % solution) · . Yes 20 Slight increase
in weight
Glucose. · . · . .. .. . · . · . No 16 No action
Dibutyl phthalate · . .. . ..... 8 0.15
Molten diphenyl · . ..... ... . 71 8 0.23
Tanning solution . · . .... · . · . Room 1.22
Sodium hydroxide, 10% solution. ....... 4 No action
Sodium hydroxide, 72 % solution .• •• , e ••• 115 16 1.75
Isoamyloctyl orthophosphate, 7S % solution .• Room No action
Insecticide oil ... ~ . · . . . .......... . 0.20
Rosin oil:
concentrated . .. . ... •• le ••••••• 90 0.20
50% ....... .. . . .. ........ . 90 1.47
Kerosene. .. . . . . . . .. . . ........ Room 3 No action
The cobalt salt of linoleic acid ..... · . " 16
Cresol, technical ..... • 0 •• 16 0.05
Citric acid:
5% solution . . .... .. . .. . . . · . 16 0.84
same . . . · . · . . . .. . . . '.' . · . " Yes 8 1.9
Lemon juice:
canned. .. . ...... No 4 5.84
" + 0.1 % sodium benzoate .. , .. · . Yes 23 days 23.1
Methyl alcohol " . . .. · . No ! 24 No action T ABtE 45 (continued)

----------------- .. -------------------,----,-----,------r---r------

.~ ~ I

,f,.I (";j Rate of deetruc-

:a.... - -

.:..0 t!,

- '" " o c, .g

-g C> 5 .s -;;; g

'" ~ g

::E B .~

u

o

tionofthe coating, mic!'on6/ year

45% ....

------------------------j-----il-----+---t---.j-------

La ctic acid:

52-me .••

80% .•..

same .. 0 Urea:

25 % solution ..

saturated solution

Wetting solution, 5% D • 0 •

Soda lye ..•.....•...•.•..

Purified petroleum (odorless) .•.•

Crude oil Oleic acid

Beer .... . .... 0 • D ••••••

Photographic solutions:

developer .

hyposulfite. . • . . .......•.•••...

Ammonium thiocyanate. . . .

Sulfuric acid, 1 % .••••••.•.••••••.•

Sulfuric acid, 5 % ...•.....•..•..•..

Ammonium sulfite, saturated solution .

Aluminum sulfate, saturated solution .

Ammonium sulfate, saturated solution .

5 % solution .

Carbon disulfide .......•.•

Carbon disulfide + water .••.••••..... Purified salt solution .••••.••••

Hydrochloric acid: pH 1.5

pH1.5 .

pH 2.0

pH 2.0 pH 2.5 pH 3.0 pH _3.5 pH 3.5 pH 4.0 pH 4.0

Stearic acid Tan oil: purified

rav{ .

Sodium carbonate, 10% solution Acetic acid,S %

Same .

Formaldehyde .•..•....• Ammonium phosphate, 5% solution

Room

70

Total

No Yes No Yes

No

Yes No

Yes

No Yes No

Yes No Yes No

Yes No

16 4 32 8

16 16 4 12 3 2 10

4

4 4 20 4 1 20

4 20

8 21 21 23

4 4 4

12 4 4 4 4 4

10 4

32 12 4 4 4

16 4

2.44 39,7 1.32 17.88

1,14 1.16 0,94 0.25

No action 0.025 0,30 5.5

No action

4.3 28.4 30.2 0.4i 6.5 1.27

30.2

No action

31.75 135.1 23.6 63.5 8.4 3.5 1.9

10.4 1.37 3.27 0.50

0.43 0.79 No action 20

151

3.8 18.0

Room

TABLE 45 [co nt inue d]

Corrosive medium

eo
'9. ·3 Rate of destruc-
~ tion of the coating,
~ [< .~ oJ
o "" microns/year
-o ~ ~ B
0 0 " ·3
-B " S ~ ~ ~
v ~ "
::E B ,s <II V <II
< f-< ~
Total No 12 days 39.6
4 0.45
4 0.30
24
24 0.33
16 5.8
16 36.6
32 0.2
Yes 32 1.0
No 3 0.81
8 0.2
4 13.2
32 0.13
24 0.16 u

F lUl"'-rcphosphoric acid . Chlorine wa'!:er:

5 g C12/106 g H20. lag C12/106 g H20 Allyl chloride ....•.

Amyl chloride .

Ammonium chloride, saturated in 30% am-

monium hydroxide .. ~ .

Benzyl chloride ...•.••.......•..•• Calciwn chloride:

48.5 % solution

same .

Thionyl chloride .•••..•.

Cetyl alcohol, molten ......•....

Sodium cyanide, 5% solution .

Carbon tetrachloride .

Ethyl alcohol ...•.•...•........•..

Room

71 Room

Corrosion behavior of the coating after heat treatment at 7SQc

Ammonium nitrate, 63 % solution .

Same .

Ammonium nitrate, solution saturated with

ammonia .

Same, as vapor ~ ~ .

Wine, sherry ..•...•..•....

Ammonium hydroxide (30% NH3)

Same .

Sodium hydrosulfide, 40 % solution

Sodium hydroxide, 72% solution .... Lactic acid:

45% ...••.

same .

80% .••••....•.•. ,

same .•.......

Urea:

25 % solution .•••..•.••••..•.•.

saturated solution .

Beer ••.•••.•••••..•.....•..•.

Sulfuric acid:

1 % ••••••••••••••••• 5% .•.•••..••.•••... 5% •••..••..•.••••••

Ammonium sulfate, saturated solution ....

5 % solution .•••.•••..•..•.••••

Room

Chilled Room

115

Room

Total

No

28 0.34
24 0.26
12 0.79
16 7.1
32 0.10
29 1.57
24 4.0
24 Slight increase
in weight
24 9.2
32 0.23
16 20.9
32 0.15
16 3.68
16 0.23
16 0.20
4 0.20
8 39.4
16 11.2
4 43.4
20 0.41
20 2.29 Partial Total

Yes

No

Y2S No Yes

No

Yes No Yes

TABLE 45 (continued)

Ccrros ive medium

pH 2 .. 5 pI-! 3.0 pH 3.5 pH 4.0

Acetic acid:

5% ...••..•.••....•......•. 10% ..••••.•••••.••.•••••••• 10% ..••••...•........•.....

50% 50%

Glacial acetic acid .... 0 •••••••••••

Same ... o ••• " •• 0 •• , ••••••••••

Fonnaldehyde, 37% ..•.•..•....•..•

Same .

Phosphoric acid, 85 % .•...•.........

Calcium chloride, 48.5 % solution .

Same , .

Ethylene glycol .•.•............•..

Partial Total

No Yes No Yes No Yes No

1---

- I Rat e o ".-~

S )tion of the coatin.g,

:c ~ . microns/year

t; '" I

.. ..

!-4 ~

Yes

Yes Standard corrosion tests

77.5
8 16.0
12 16.2
12 4.27
32 2.34
32 0.38
20 21.5
16 4.6
8 28.7
20 4.2
8 S1.0
20 0.5
25.1
28 0.18
2.4 0.30
28 0.20
32 0.025
20 0.28
0.63 Thus, specimens on which rust spots appeared after a test time of 200 hours could be exposed to the corrosive medium for a further 700 hours (in some cases for a further 2000 hours) without any additional damage to the surface. Rust spots which appeared on the surface of electrodeposited coatings usually spread rapidly.

This peculiar behavior of chemically deposited nickel causes difficulties when the standard test method is used to compare the protective values of chemically deposited and electrodeposited coatings.

According to Gutzeit /26/ the corrosion resistance of articles protected by chemical nickel plating can be increased considerably by the deposition of a thin sublayer of copper. The results of corrosion tests on specimens coated by this method, carried out in the salt-spray chamber with a sodium chloride solution, are presented in Table 46.

According to the data of Dicki.nson /33/, no noticeable rusting was found! in specimens coated with a chemically deposited nickel layer 25 microns thick after 8-day tests in a salt-spray chamber with a sodium chloride solution, after 180-day tests in the atmosphere, or after 42 days of immersion in water heated to 82° (through which air was blown).

Minjer and Brenner /14/ compared the protective properties of chemically deposited and electrodeposited nickel coatings, as well as those of eiectrodeposited nickel-phosphorus alloy coatings containing 3 and 9%

TABLE 46

Influence of the copper sublayer on the protective value of the nickel coating

Thickness of the Thickness of the Test time until the appearance of rust
copper sublayer, nickel layer, spots, hrs
microns microns
average minimum maximum
- 25 96-120 72 2000
7.5 2.5 - 24 48
7.5 5 - 92 112 phosphorus. In addition to the salt-spray tests, these authors also studied the behavior of the specimens under atmospheric conditions, namely, in

a marine environment and in the atmosphere of an industrial area. Steel plates of an area of 10 X 15 cm, coated with a nickel layer 12.5 or 25 microns thick were used as the test specimens. The phosphorus content was 9--10,,/0 in the coatings deposited from acid solutions and 7-8% in those deposited from alkaline solutions.

TABLE 47

Composition of the solutions used for the chemical nickel plating of the specimens tested for corrosionj temperature 95° - 1000

Components of the solution

Concentration, gIl

II

III IV
30 30
10 10
100 100
50 50
0.1
8,5 -9 Nickel chloride ..••.•••••.•.•. Sodium hypophosphite .•.••...•••

Glycolic acid

Succinic acid .

Sodium citrate .

Ammonium chloride .••••.••.•.•

Wetting agent* ..••••.•••••.••

pH .••.•.•.••••••••..•..••

30 10 39

22 30

15

* A substance known as "N accanol EP ", with a composition not disclosed by the authors, was used as the wetting agent; it was added to the solution to prevent pitting.

4.2 - 4.3

The authors evaluated the corrosion resistance of the specimens by a system arbitrarily based on ten points. Ten points were assigned to sample s on which no rust was observed; zero points to those on which rust covered more than 50 % of the surface area. The duration of the corrosion tests was 14-15 months, the samples were periodically examined during this period. The compositions of the solutions used in the deposition of the chemical and of the electrolytic coatings are presented in Tables 47 and 48 respectively.

The results of the corrosion tests on the specimens prepared by the chemical and by the electrochemical methods are presented in Table 49.

On the basis of these data, the authors reached the conclusion that the coatings prepared by chemical deposition from acid solutions have a higher protective value than electrodeposited nickel (compare the behavior of specimens I, 2, and 3 with that of 10 and 11 in Table 49).

89

TABLE 48

Composition of the solutions used in the e Iectrodepos l tion of nickel on the specimens tested for corrosion

II III
NiCI2· 6H20 .......• 240 40 40
NiS04'7H20 •• •••• 0 160 160
NiC03 ........... 20 40
H3B03 • 0 ••••••••• 30
H3P04 •• 0 •••••••• 50 50
H3P03 ...... .... . 5.4 44
Wetting substance
(Naccanol EP) ...... 0.1 0.1
pH • 0 ••••••• ..... 2-2.5 2 0.5-1.0
Temperature, "C ..... 43 85-90 85-90
Current density, ampydm S 4.5 5 5 Concentration, g/l

Components of the solution

Note: The coatings deposited from solutions II and III contain 3 % and 9% phosphorus, respectively.

The coatings deposited by chemical reduction from acid solutions have a higher protective value than the coatings deposited from alkaline solutions; the protective value of the latter is comparable to that of electrodeposited nickel.

The protective value of the nickel-phosphorus alloy containing about 9 % phosphorus, prepared by electrodeposition, was similar to that of the deposit formed in the solution containing glycolic acid.

Electrolytic deposits with a lower phosphorus content (3% P) gave less protection from corrosion than the deposits with a higher phosphorus content, but their protective value was still higher than that of electrodeposited nickel.

All the coatings lost their brightness and became covered with spots on exposure to air. This phenomenon caused some difficulty in the evaluation of the degree of rusting of the specimens. The loss of brightness was less pronounced in the coatings of types 2, 3, and 9; these specimens could be brought back to their initial appearance by slight .rubbing with an abrasive.

The results of the s alt+spr-ay tests were in agreement with those of the tests under atmospheric conditions. However, the difference in the behavior of the specimens was exhibited more sharply in the latter case.

A.1. Lip in, S. A. Vishenkov, and M. M. Livshits /60/ carried out a study of the corrosion resistance of chemically deposited nickel coatings, and compared this with the behavior of electrodeposited nickel or chromium coatings under similar conditions.

Specimens of 30KhGSA and 30 KhNVA steels were subjected to chemical nickel plating in a solution containing 30 g of nickel sulfate, 10 g of sodium hypophosphite, and 10 g of sodium acetate per liter, at pH 5-6 and at 90°- 92°. The deposition was carried out in most cases as a two-stage process, between the stages the specimens were rubbed with Vienna lime and etched in dilute hydrochloric acid. Some of the nickel-coated specimens were heattreated for one hour at 400~.

TABLE 49

Deposits formed by the chemical method
With glycolic acid (Table 47, solution 1) . 12.5 8,5 4.5
2 Same . . .. · . 25 9+ 9
With succinic acid (Table 47, solutionll) 25 9
4 Ammoniacal, without wetting agent
(Table 47, solution !II) 12.5 2
Same . . .. 25 3
6 Ammoniacal + wetting agent (Table 47,
solution IV) . . · . 12.5 0
7 Same . . . . · . . . .. 25 2 2 Deposits formed by the electrochemical method

8 Solution containing phosphorus com-
ponnds (Table 48, solution II, 3% P) .. 25 9+ 5
9 Same (Table 48, solution III, 9% P) ... 25 9+ 9
10 Nickel-plating solution (without ad-
ditives)(Table 48, solution I) ....... 12.5 0.5 0
11 Same ...................... 25 8 9
9 9
9 10
2
2 6
I.S 3.5
8.5 7.5 9 4

9 9

3 3.5

The corrosion tests were carried out in a chamber, with a 3 % sodium chloride solution to create a mist, at room temperature.

The results of these tests are presented in Table 50.

The data in Table 50 give additional evidence that the corrosion resistance of chemically deposited nickel coatings is higher than that of electrodeposited nickel coatings of similar thickness; the corrosion resistance of the specimens was increased by heat treatment after the deposition of the coating. The corrosion resistance was also increased by using a two-stage process for the chemical deposition of the nickel.

The above authors carried out a comparative study of the behavior of chemically deposited nickel, steel, and bronze in TS-1 kerosene. The specimens were immersed periodically in the kerosene by means of a special apparatus, at the rate of one immersion per second. These tests showed that the weight of specimens coated with a nickel layer 10-12 microns thick did not change during c. prolonged period of time, while that of the non-coated specimens changed, although only very slightly, during the first three months.

E. F. Lyakhovich /63/ examined the corrosion resistance of chemically deposited nickel coatings in order to estimate the possibility of using them for protection against corrosion under tropical conditions. The chemical nickel plating was carried out with a solution containing 20 g of nickel chloride,

17 g of potassium hypophosphite , and 15 g of sodium succinate per liter at pH 5-6 and at 92°-98°C. -,

The corrosion tests were conducted in a moisture chamber, the temperature was changed every 12 hours and maintained at either 20° or 356• Both matt and bright nickel coatings, electrodeposited from an electrolvte containing naphthalenedisulfonic acid as an additive, were tested under "the same conditions.

Specimens coated with layers 10, 14, 16 and 19 microns thick were subjected to these tests; in the case of chemically deposited coatings, specimens coated with a nickel layer 24 microns thick were also tested, in addition

to those mentioned above. The total test time was 84 days, and the specimens were examined at seven- day intervals.

On specimens coated with chemically depo-

s ite d nickel, when the layer was 10 and 15 microns thick, the first signs of corrosion appeared after 28 and 63 days, respectively, but when the layer was 20 microns thick, no corrosion was seen during the entire test period.

The behavior of the coatings electrodeposited from the usual baths is characterized by the following data: the first signs of corrosion were observed after 7 and 28 days on the specimens coated with nickel layers 10 and 15-20 microns thick, respectively, the number of corrosion centers increased rapidly on further exposure of the specimens to the atmosphere of the chamber.

Signs of corrosion were observed after 14 days on specimens coated with bright nickel layers 10 microns thick; the corrosion increased on further exposure.

Thus, the above tests gave additional evidence of the higher value of chemicaliy deposited

nickel coatings for protection against corrosion as compared with electrodeposited nickel.

The greater protective value of the chemically deposited nickel coatings revealed in a number

cross sections of nickel plated

screws, showing the uniform thick- of investigations is apparently associated with the

ness of the deposit: a- on the thread; presence of phosphorus (in the form of phosphides) b- on the groove; c= shows the exact in the nicke 1 deposits, as these phosphides are

reproduction of the outline of the more resistant to the chemical action of various

coated surface. (From paper 13ll) reagents than pure nickel. Moreover, as we noted

above, such coatings are less porous than the e le ctrodeposited ones, which might also be a reason for thir higher protective value.

FIGURE 27. Microphotographs of

11. The Uniformity of the Coatings

The most characteristic feature of the chemical nickel plating process is the possibi.lity it affords of obtaining uniform coatings on articles of complex shape. The reduction of the nickel proceeds at the same r-ate o n

TABLE 50

Results of corrosion tests in the mist of a 3 % sodium chloride solution

Test time until the appearance of the first signs of corrosion, hrs
Thickness of
the coating, Chemically deposited niokel coatings Electrcdepostted coatings
microns without heat treatment with heat
treatment) nickel chromium
single layer double layer double layer
10 72 96 120 72 72
15 120 144 144 24 144
20 168 192 192 72 192
25 280 240 240 96 240
30 234 288 600* 72 600*
45 288 336 600* 72 600*
50 354 384 600* 72 600* * No signs of corrosion were found after a test-time of 600 hours.

any part of the surface which is in contact with a solution of the same composition and which has been properly prepared.

According to Gutzeit /26/, the deviations from uniform distribution of the coating formed by the Kanigen process (see chapter 'VIII) do not exceed 10% for a layer 25 microns thick.

Aitken /31/ presents microphotographs of the cross s cc t'ion of nickelplated screws showing the uniformity of the coatings formed by the Kanigen process. These photographs (Figure 27) show the uniform thickness of the nickel layer on both the threads (Figure 27a) and the grooves (Figure 27b) of the screw. Figure 27c shows that the coating accurately follows the outline of the coated surface.

This feature of the chemical nickel plating process is of special value for coating the inner surfaces of long, narrow tubes.

CHAPTER VI

THE STR UCTURE OF THE DEPOSITS

As we have already noted, the coatings formed by chemical reduction do not consist of pure nickel but always contain phosphorus, the amount of which is a function of the process conditions (see chapter V).

The phase diagram of the system Ni-P (Figure 28), which was studied by

N. Konstantinov as early as 1908 /64/, shows that in addition to the solid phase of phosphorus in nickel there are three intermetaUic compounds Ni3P, NisP2, and Ni2P.The first of these, Ni3P, is an incongruently melting compound which forms a eutectic mixture with the solid solution melting at 880°. N. Konstantinov did not succeed in determining the limit of solubility of the phosphorus in the nickel. From data on atomic sizes and on relative values of electronegativity, Goldenstein, Rostoke r, Sohossber-ge r and Gutzeit /47/ estimated the maximum solubility of the phosphorus to be about 5"/0.

Scholder and Hecke 1 /9/ made a detailed study of nicke 1 powder prepared by chemical reduction in the presence of large amounts of hypophosphite. The authors used chemical methods for the separation of the phases and reached the conclusion that there are at least two phases in the powder, and that one of them is NisP2 (see Chapter 1).

The X-ray method for the study of the nickel-phosphorus deposit, described by Brenner, Couch,and Williams /62/, and used also in our laboratory by N. A. Shishakov and later by Goldenstein, Rostoker, Schossberger, and Gutzeit, failed to yield data which could establish the nature of the compounds. Photographs indicating an "amorphous" phase, with one diffusion ring situated in the proximity of the central ray, were obtained in all cases when the coatings were examined immediately after their deposition (I. e .• without subsequent heat treatment).

Considerable light was thrown on the structure of these special coatings by the detailed study of the deposits, containing 7-10"/0 of phosphorus, obtained by the Kanigen process. This investigation is described in the work of Goldenstein, Rostoke r , Schossberger, and Gutzeit mentioned above.

Evidence confirming the fact that the chemically reduced nickel has an a.morphous structure and not the structure of a highly dispersed substance is found by the above authors in a number of phenomena. First, it is well known that the site of the first diffusion ring ("halo") on the X-ray diagrams of liquid and liquid-like (amorphous) substances corresponds to the site of the first intense line of the crystalline modification of the same substance. The more detailed X-ray studies of glass-like silica, amorphous selenium, and amorphous antimony showed that the diffusion ring is slightly shifted with respect to this line. The same phenomenon is observed in the

amination of chemically reduced nickel. The site of the diffusion ring ~~es not fully correspond to that of the intense line (111) found in the X -ray

diagram of metallic nickel {and on the diagram of chemically reduced nickel which has been subjected to heat-treatment}. The diffusion ring is shifted with respect to this line in the direction away from the central beam. The considerable width and diffuseness of the "halo" make the determination of the extent of this shift quite difficult. If the diffusion pattern is caused by exceptionally small crystals, the widening of the line is symmetrical in both directions. Moreover, a tentative calculation (from data on the widening of the line) based on the

Scherrer equation gave unreal sizes for the crystals, of the order of several atomic distances.

The authors found evidence for the amorphous nature of the coatings in their investigation by the electron diffraction method of 15 deposits obtained under different conditions.

Goldenstein, Rostoker, Schossberger, and Gutzeit assumed that chemically reduced nickel is the first known example of a compact metallic body with amorphous structure. They did not, apparently, have the data on similar electrolytic deposits obtained under specific conditions (in particular, in the presence of brighteners) in our laboratory /51, 65, 66/. Such deposits, which were named "cryptocrystalline deposits" (and which include chemically reduced nickel), appear to have an amorphous structure even when examined under a high -resolution electron microscope.

The surface structure of such deposits is shown on an electron-microscope photograph of the surface of chemically reduced rricke 1. obtained in our laboratory by Yu. M. Polukarov (Figure 29).

The inner structure of the deposit, as studied by X-ray methods, varies according to the sharpness of the pattern from amorphous to crystalline, and depends on the nature of the metal, on the conditions under which it was formed, and on the period of time from the moment of its formation to that of

its X-ray or electronographic examination. The transition of these structures to the crystalline

state apparently proceeds at different rates: in some cases it is instantaneous while in other it requires

a considerable time. Our investigations showed

that heating accelerated the transition to the crystalline state, which could be observed by the appearance of the normal diffraction pattern of the metal. A similar transition from the amorphous deposit to the crystalline state is also observed in the case of chemically deposited nicke 1.

Phosphorus, %

FIGURE 28. Phase diagram of the system Ni-P, based on the data of N. Konstantinov(seereference /641)

FIGURE 29. Electron micro-

scope photograph of the StIX-

face of a coating deposited frem a solution containing 30 g of nickel chloride, 109 of sodium hypophosphite and 10 g

of sodium glycolate per literj pH""""S, ternperature e-e Sf)", Magnification X 4000