ISSN 0033-1732, Protection of Metals, 2006, Vol. 42, No. 6, pp. 560569. Pleiades Publishing, Inc., 2006.

. Original Russian Text F.I. Danilov, V.S. Protsenko, T.E. Butyrina, E.A. Vasileva, A.S. Baskevich, 2006, published in Zashchita Metallov, 2006, Vol. 42, No. 6, pp. 603612.

Electroplating of Chromium Coatings from Cr(III)-Based Electrolytes Containing Water Soluble Polymer
F. I. Danilov, V. S. Protsenko, T. E. Butyrina, E. A. Vasileva, and A. S. Baskevich
Ukrainian State Chemical and Technological University, pr. Gagarina 8, Dnepropetrovsk, 49005 Ukraine
Received August 3, 2005

AbstractThe effect of certain water-soluble synthetic polymers on the current efciency, the kinetics of partial cathodic reactions, and certain properties of coatings at the chrome plating from sulfateformate baths based on Cr(III) salts is studied. A polymeric additive of the nonionogenic type N1 (3 106 g/mol) is proposed, which favors the deposition of chromium coatings that have good adhesion to the surface, do not crack, and have a thickness of several tens micrometers. It is found that the polymers have an accelerating effect on the aggregation of the particles of the chromium-hydroxide sol formed in the near-electrode layer, which, apparently, improves the deposit quality and enhances the current efciency. It is shown that the resulting amorphouscrystalline chromium deposits are sufciently hard and exhibit good protectiven ability at the anodic dissolution in aggressive media. PACS numbers: 81.15.Fg, 82.45.Gj DOI: 10.1134/S0033173206060075

INTRODUCTION A steady interest in the development of chromeplating baths based on trivalent chromium salts is caused by their certain advantages over the conventional chromate baths (substantially lower toxicity and corrosivity, reduced costs of materials and energy, enhanced technological characteristics of the process, etc.). However, up to recently [17], the attempts to overcome their certain disadvantages failed. The most signicant of disadvantages is a sharp decrease in the coating quality with at an increase in their thickness (to above several micrometers). As a consequence, the application sphere of such technologies was restricted to decorative chrome plating. They were useless in applying hard and wear-resistant deposits. Only recently, the reports on the compositions that allow sufciently thick coatings to be deposited from aqueous Cr(III) solutions have appeared. Thus, in [8, 9], a bath based on chromium(III) sulfate and simultaneously containing sodium formate and carbamide was proposed. It makes possible obtaining good deposits with a thickness of several tens micrometers at a current efciency of 30 35%. However, the deposition of chromium from this bath starts at a cathodic current density of 10 A/dm2, i.e., its covering power is low. In a cycle of studies [1013], a sulfateoxalate electrolyte based on Cr(III) was proposed, which allows thick bright coating to be deposited at a current efciency of 40%. At the same time, to work with this bath, it is necessary to either separate the electrode compartments with an ion-exchange membrane or use anodes

of platinized titanium, which makes this technology more complicated and costly. In [67], the use of a sulfateformate chrome-plating bath based on Cr(III) salts is described. The proposed technology uses titanmanganese dioxide anodes (TMDAs) with nonseparated anolyte and catholyte. The electrolyte is characterized by a high covering power and makes it possible to obtain bright deposits ~12-m thick. As shown in [67], the exterior of the coating deteriorates with the deposition time because the coagulating particles of the Cr(III) hydroxide sol formed in a near-electrode layer cover the electrode surface and are incorporated into the coating structure, which reduces the current efciency and causes cracking and darkening of deposits. It was shown [14] that certain surfactants selectively adsorbed on chromium hydroxide, optimize the grain size of the sol and allows one to increase the maximum thickness of quite adequate deposits up to 510 m. Obviously, the possibility of solving the problem of applying thick chromium layers by selecting particular surfactants is not yet clear to the full extent. Water-soluble synthetic polymers (WSPs) widely used in the sb zinc-, cadmium-, copper-plating baths, etc. [15] might form a promising class of such additives. However, the literature contains virtually no information on the use of WSP in the chrome plating. This study is aimed at the elucidation of the effect of WSP on the kinetics of cathodic reactions, current efciency of the chromium deposition, certain properties of the chromium deposits formed, and the possibility of obtaining thick Cr coatings of adequate quality in the presence of polymer additives.

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EXPERIMENTAL For the deposition of chromium the following basic bath was used [6, 7] (mol/l): 0.5 KCr(SO4)2 12H2O, 0.75 HCOOH, 2 (NH4)2SO4, 0.5 H3BO3; pH 3. The following substances were chosen as the additives: anionic polyelectrolyte of the polycarboxylic acid class (designated as A1), two cationic polyelectrolytes, one of which belongs to the class of polyhexaalkylene guanidines (1000 g/mol), and the macromolecule of the other includes ternary nitrogen atoms (designated as K1 and K2, respectively), and a nonionogenic polymer which includes a heterocycle with a nitrogen atom in an amide group (3 106 and 8 103 g/mol) (designated as N1).1 When determining the current efciency, the electrolysis was carried out under galvanostatic conditions in temperature-controlled cells with both separated (a glass diaphragm) and nonseparated electrode compartments. A titaniummanganese dioxide electrode served as the anode [16]. The working electrode of copper foil (S = 0.018 dm2) was xed in a Teon holder. The current efciency was calculated by comparing the weight gain of the cathodes placed in the chromeplating bath with that of a copper coulometer connected in series. The calculations were carried out for the overall three-electron reaction of chromium deposition. Partial polarization curves of the cathodic processes were measured during a 20-min electrolysis under potentiostatic conditions (potentiostat PI-50-1.1). According to the current balance for the staged discharge of Cr(III) ions, which we described earlier [17], the partial current density of chromium deposition i2 in the two-electron reaction Cr(II) Cr(0) was determined from the cathodic increase in weight upon the chrome plating. The partial current density of hydrogen evolution i H2 was calculated based on volumetric measurements (from the evolved gas volume brought to the normal conditions and corrected for the saturated water vapor pressure). The overall current density i was found with a copper coulometer. The current density i1 for the reaction Cr(III) Cr(II) was calculated according to the formula i 1 = i i 2 i H2 . (1) The effect of WSP on the aggregative stability of the Cr(OH)3 sol was studied by the turbidimetric method [18]. The Cr(OH)3 sol was obtained by adding certain portions of NaOH solution to the 250-times diluted basic electrolyte up to pH 8.5. The sol was stabilized for 30 min and then a polymer solution was added and the optical density was measured by means of a photoelectric colorimeter KFK-2-UkhL-4.2 (the cell thickness
1 All

CECr, % 12 2 3 4 5 1 4

10

20

30

40 , min

Fig. 1. Current efciency in chromium as a function of the electrolysis time in the presence of various polymeric additives (mg/l): (1) basic bath, (2) 11.8 N1; (3) 5 K1, (4) 12.3 A1, (5) 1.39 K2; i = 15 A/dm2; T = 298 K; pH 3.

was 3 mm, the wavelength was 540 nm, the reference liquid was water). The coating structure was studied using an x-ray diffractometer DRON-3 in the monochromatized Mo-K radiation. The curves of anodic dissolution of coatings on copper and steel (3) substrates were measured in deaerated solutions under potentiodynamic conditions (20 mV/s) at T = 298 K. The microhardness of chromium coatings was assessed using a PTM-3 set-up at a load of 100 g and the coating thickness of no less than 20 m. On line with microhardness measurements, the microscope of the PTM-3 set-up allowed studying the surface morphology (magnication 487) The adhesion of chromium deposits to the substrate was assessed by the bend tests. In doing so, the samples were bent to and fro manually at an angle of 90 up to their break. The covering power of the electrolyte was determined using a Hull cell (250 ml, I = 5 A, = 3 min). RESULTS ANF DISCUSSION Kinetic Peculiarities of Chromium Electrodeposition As was shown earlier [17, 19], the reaction of chromium electrodeposition proceeds in steps and produces intermediates, viz., complex ions of Cr(II) a part of which diffuse to the solution volume Cr(III) + e

the polymers studied are manufactured at the plants of the Russian Federation. For polymers A1 and K2, the average molecular weights were not specied by the manufacturer. PROTECTION OF METALS Vol. 42 No. 6 2006

Cr(II), Cr(0).

(2) (3)

Cr(II) + 2e

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Simultaneously with reactions (2) and (3), hydrogen is evolved on the cathode 2H + 2e
+

H2 .

(4)

The dependence of the current efciency of chromium deposition (CECr) on the electrolysis time in the basic electrolyte (Fig. 1, curve 1) represents a curve with a maximum which corresponds to a deposition time 5 min (deposit thickness 1 m). The increase in CE in the rst 5 min upon switching the current could be associated with the accumulation in the near-electrode layer of intermediates, namely, Cr(II) ions [20]. On the other hand, during this period, the cathode nature changes (the copper substrate is covered with the chromium deposit), which causes a redistribution of the current between the partial electrode processes. At a longer electrolysis ( > 510 min), the current efciency decreases, and the coatings change the appearance: their brightness disappears, deposits crack, nonmetal phase inclusions can be visually observed on the surface). According to [8], the decrease in the current efciency of chromium deposition in the course of electrolysis is caused by the incorporation into the deposit of the nonmetal phase, cracking, and the increase in the real surface area of the deposit, which under galvanostatic conditions shifts the potential in the positive direction up to the values at which the metal deposition rate falls virtually to zero. However, the experiments on chromium deposition at a constant electrode potential have shown that, in this case too, the deposit appearance sharply deteriorates with time
CECr, % 12 10 2 8 6 4 2 0 10 20 30 40 50 60 , min 1 4 3

Fig. 2. Current efciency in chromium as a function of the electrolysis time in (1) basic bath and that with additions of N1 polymer (11.8 mg/l) of different molecular weight (g/mol): (2, 4) 3 106, (3) 8 103. i = 15 A/dm2; T = 298 ; pH: (13) 3, (4) 2.4.

and the deposition rate also decreases (as well as the current efciency). Apparently, the main reason for the observed negative phenomena is the blocking of the electrode surface by chromium(III) hydroxide colloid particles, which are formed in the near-electrode layer (due to the hydrogen evolution and the corresponding increase in the pHS) [6, 7, 21] and get incorporated into the deposit. The formation of the dispersedphase particles in the surface layer and their incorporation into the growing deposits occurs within a certain period (510 min), after which we observed the deterioration of the deposit appearance and the decrease in CECr. During the rst ten minutes of the electrolysis, the addition of all WSP types studied into the electrolyte results in the reduction of CECr (as compared with a solution containing no additives) (see Fig. 1, curves 25). For a longer electrolysis ( > 1020 min), the current efciency in the presence of WSP stabilizes at a higher level compared with the basic electrolyte. The appearance of coatings improves: they become lighter and lose partially or completely (depending on polymer type and concentration) their tendency to cracking and exfoliating during the electrolysis. It should be noted that the benecial effect of additives manifests itself only in a certain range of their concentration. Once the threshold (its height depends on the polymer nature) is exceeded, the current efciency sharply decreases, becoming even lower than that of the basic solution, while the coatings darken. The best results (coating of adequate quality with a thickness of several m) were obtained with the nonionogenic polymer N1, which was chosen for the further experiments. A decrease in the average molecular mass of N1 polymer from 3 106 to 8 103 g/mol results in the decrease in CECr (the current efciency becomes lower compared with the basic electrolyte, Fig. 2, curves 1 and 3) and in the deteriorated outward appearance of the electroplates. Note that the results shown in Fig. 1 were obtained in the experiments with separated electrode compartments, while all the subsequent results correspond to nonseparated anolyte and catholyte. These experimental peculiarities cause slight deviations in the position of curves 1 and 2 in Figs. 1 and 2, respectively. The use of TMDA allows one to organize the chrome plating without any membrane or diaphragm and ensures the durable steady operation of the bath, which is the important advantage of the technology proposed. With a decrease in the pH from 3.0 to 2.4 in the N1containing electrolyte, CECr decreases (Fig. 2, curve 4), and dark, easily exfoliable deposits are formed. An increase above pH 3 is also undesirable, because this
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accelerates the decomposition of the N1 additive (this information is given by the manufacturer of the polymer). Thus, the N1 additive should be used in electrolytes with pH close to 3. In both the basic electrolyte and that containing N1 additive, the dependence of CECr on the cathodic current density has a maximum at i = 15 A/dm2 (Table 1). This value should be considered optimal for the operation of the bath. The additive insignicantly increases the current efciency for i = 15 A/dm2 but decreases it for both lower and higher current densities. Note that in contrast to the basic electrolyte, in which the coating quality decreases with an increase in the current density (the coating loses its brightness, forms cracks, and exfoliates from the substrate), in a solution containing N1 the appearance of coatings of equal thickness only weakly depends on the current density. The decrease in CE with an increase in the current density also enhances the throwing power of the electrolyte with respect to the metal (TPMe). This makes the proposed bath particularly advantageous compared with the conventional chromate electrolytes for which the current efciency continues to decrease with an increase in the current density and TP even becomes negative in some cases. An increase in the temperature (for the electrolysis time over 1020 min) results in the decrease in the current efciency (Table 2). In the electrolyte containing N1 polymer, once T= 343 K is reached, the deposits darken and lose their adhesion with the substrate due to accelerating Cr(OH)3 hydroxide formation and weakening the polymer effect in the near-electrode layer. The temperature close to ambient (298 K) is considered as optimal. It is known [15] that polymers can decompose in the electroplating baths. To study the stability of N1 polymer in the chrome-plating bath, a series of experiment was fullled in which the deposition was started after certain time intervals upon the additive introduction. The electrolyte was not subjected to electrolysis before the addition of N1 and switching on of the current. As seen from Table 3, the current efciency of chromium deposition remained virtually unchanged for several days. The visual appearance of coatings also remained unchanged. Hence, N1 polymer is sufciently stable in the chrome-plating bath used. Thus, to improve technological characteristics of chrome plating from sulfateformate electrolytes it is advisable to use the polymeric additive of a molecular kind N1 (3 106 g/mol) in a concentration range from 1 to 100 mg/l (optimally, ~10 mg/l). For i 15 A/dm2, T = 298 K, and pH ~3, the proposed bath allows one to deposit chromium coatings of adequate quality with a thickness of 30 m and more. Under these conditions, the average deposition rate is approximately 8 m/h. With the introduction of N1 additive, the covering
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Table 1. Dependence of CECr on the cathodic current density (T = 298 K) Current density, A/dm2 5 10 15 20 25 30 CECr , % Basic bath 3.6 7.5 8.6 8.4 7.4 6.0 Bath with N1 (11.8 mg/l) 1.5 4.8 9.2 6.2 4.6 3.0

Table 2. Dependence of CECr on the electrolysis time for different solution temperatures (i = 15 A/dm2) CECr , % Electrolysis time, min Basic bath Bath with N1 (11.8 mg/l)

T = 298 K T = 343 K T = 298 K T = 343 K 20 30 40 50 60 8.6 8.4 8.0 7.6 7.4 8.3 7.0 7.8 6.8 6.4 9.1 9.2 9.2 9.0 9.2 8.8 7.7 6.9 6.3 6.0

Table 3. Dependence of CECr and the chromium coating thickness on the time passed from the introduction of the additive (11.8 mg/l) up to the beginning of the electrolysis (T = 298 K, i = 15 A/dm2, = 1 h) Time after the introduction of the additive, h CECr , % 0 1 2 5 16 24 72

9.8 10.0 9.8 10.0 9.8 9.8 9.8

power of the chrome-plating bath decreases from 70 to 60 mm (in the Hull cell), which is quite sufcient for the deposition of thick chromium coatings onto the workpieces of not too irregular shape. In this process, dimensionally steady TMDA are used in cells with unied electrode compartments. The chromium deposition proceeds at potentials E 1 V (Fig. 3) and is accompanied by the hydrogen evolution reaction, the kinetics of which is described by an i vs. E dependence of the exponential form. The partial voltammetrical curve of chromium deposition is shaped as a wave with a current plateau. The i vs.

564 i1, A/dm2 7 6 5 4 3 2 1 0 1.0 1.2 1.4 1.6 1' 1

DANILOV et al. CE, % 100 3' 3

80

60

40 1.8

20 2'

i2, A/dm2 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0 iH2 20 3' 15 10 5 0 3 1.0 , A/dm2 1.2 1.4 1.6 1.8 2' 2 0 1.0 1.2

1'

1.4

1.6

1.8 E, V

Fig. 4. Dependence of the current efciency of reactions Cr(II), (2, 2') Cr(II) + 2e (1, 1') Cr(III) + e H2 on the electrode potenCr(0), and (3, 3') 2H+ + 2e tial: (13) basic bath, (1'3') that with addition of N1 (11.8 mg/l).

uble forms of Cr(III) ions decrease in the near-electrode layer. As a result, the current of reaction (2) decreases. Similar concepts were developed in [17] when analyzing the reasons for the formation of a plateau of the apparent limiting current in the polarization curves of chromium deposition (see Fig. 3, curves 2 and 2'). Actually, this plateau appears as a result of the approximate compensation of the electric-eld effect and the electrode blockading with Cr(OH)3 hydroxide (the latter increases with cathodic polarization).
1.8

1.0

1.2

1.4 E, V

1.6

Upon the introduction of N1 into the bath, the discharge rates of Cr(III) and Cr(II) ions decrease, whereas the hydrogen evolution rate increases (Fig. 3, curves 1'3').2 The dependences of the current efciencies of reactions (2)(4) on the electrode potential have no simple analytical equivalent (Fig. 4). The general trend is that the current efciencies of the discharge reactions of Cr(III) and Cr(II) ions decrease starting from a potential E < (1.41.5) V. It is also essential that the current efciency of chromium deposition in the electrolyte containing N1 additive exceeds that in the basic bath only in a rather narrow potential range from 1.4 to
2 The

Fig. 3. Partial voltamograms of reactions (1, 1') Cr(III) + Cr(II), (2, 2') Cr(II) + 2e Cr(0), and (3, 3') e + + 2e H2: (13) basic bath, (1'3') with addition 2H of N1 (11.8 mg/l).

E curve of the reaction Cr(III) Cr(II) has a current maximum at potentials from 1.4 to 1.5 V. The maximum in the curve (1) is apparently associated with the fact that the pHs near the cathode reaches the threshold of hydrate formation (Cr(OH)3). The particles of poorly soluble hydroxide blockade the electrode. Moreover, the concentration of electroactive sol-

acceleration of hydrogen evolution in the presence of N1 polymer could be caused by different reasons, which are not discussed in this work. PROTECTION OF METALS Vol. 42 No. 6 2006

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1.6 V. Both above and below these limits, the additive reduces the current efciency of reaction (3). The optimum total current density i= 15 A/dm2 in the bath containing no additives is reached at E 1.65 V and a current efciency ~4%, whereas in the N1-containing electrolyte it is reached at E 1.45 V and a current efciency of ~6% (both current efciencies were estimated for the two-electron reaction (3); hence, to be correctly compared with the data in Figs. 1 and 2 and Tables 13, they should be recalculated to the overall three-electron reaction by their multiplication by a coefcient 3/2). The changes in the characteristics of chromium deposition caused by the additives to the bath could be the result of both the adsorption of polymer macromolecules on the cathode and their effect on the aggregative stability of the Cr(OH)3 sol formed in the near-electrode layer. To check these assumptions, we performed a turbidimetric study of the Cr(OH)3 sol in the presence of different polymers. The time dependence of the optical density of the sol in a solution without polymeric additives represents a curve with a weakly pronounced maximum (Fig. 5, curve 1). According to the well-known eq. [22] D = kV ,
2

D 0.28 1 0.24 2 0.20 0.16 3 4 5 0.12 0 10 20 30 40 50 , min

Fig. 5. Time dependence of the optical density of Cr(OH)3 sol: (1) without WSP additions and with WSP additions (mg/l): (2) 11.8 N1, (3) 50 K1, (4) 12.3 A1, (5) 13.9 K2.

ment of the coating appearance at a long-term electrolysis. Structure and Properties of Deposits The deposits obtained from baths with N1 additive have an amorphous-crystalline structure (Fig. 6). The formation of amorphous deposits in formate-containing chrome-plating electrolytes was observed earlier [2326]. The amorphous halo in the diffraction pattern is overlapped by small diffraction peaks of crystalline phases Cr7C3 and Cr3C2. It is known that amorphous structures are metastable and once heated pass into the crystalline state. Upon a 30-min isothermal annealing in the argon atmosphere at T = 1073 K, the diffraction pattern reveals diffraction peaks of Cr, Cr7C3, and Cr3C 2 crystalline phases. A voltamogram of a Cr coating deposited from N1containing electrolytes measured in 0.5 M H2SO4 (Fig. 7) is similar to those described earlier [23, 24, 2729], namely, compared with ordinary chromium (deposited from a standard chromate bath), the potential ranges of the hydrogen cathodic evolution and the transpassive dissolution of chromium are shifted to more positive potentials, while the active dissolution range is altogether absent. Such an anomalous shape of i vs. E curves was associated [2729] with the formation of a special protective lm enriched in carbon and its compounds on the top of the amorphous deposit. The current peak in the voltamogram in a potential range from 0.4 to 0.8 V is caused by the anodic dissolution of the copper substrate through the pores in the chromium coating [28]. With an increase in the deposit

(5)

(where k is a certain constant, is the partial concentration of the dispersed system, and V is the particle volume) the bell-shape of the D vs. curve is associated with the processes of coagulation and sedimentation of the dispersed phase which occur in time. Upon the introduction of the WSP into the solution containing a Cr(OH)3 sol, the solution optical density sharply decreases (Fig. 5, curves 25). This is typical of all the studied polymers in a wide range of their concentrations (from 0.01 to 100 mg/l), being caused by the acceleration of occulation and coagulation followed by the sedimentation of particles to form a deposit on the cell bottom. Hence, the used WSP are effective occulants. As a result of the occulation effect of N1 additive, a coarsely dispersed system Cr(OH)3electrolyte is formed, which should have oppose the considerable effect of the hydrosol on the kinetics of the cathodic reactions. However, N1 macromolecules adsorb at the electrode, thus inhibiting the chromium electrodeposition, as follows from Fig. 3. Apparently, the macromolecular adsorption layer impedes the incorporation of the Cr(OH)3 nonmetal phase into the deposit, which is the reason for the CTCr stabilization and the improvePROTECTION OF METALS Vol. 42 No. 6 2006

566 Iimp/s 1000 900 800 700 600 500 400 300 200 100 0 10 20

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30

40

50

60

70 2

Fig. 6. X-ray pattern of chromium deposit from N1-containing electrolyte (11.8 mg/l, 3 106 g/mol).

i, A/dm2 60 2 40 3

20 5 0 1 24 20 4 5

40 0.8 0.4 0 0.4 E, V 0.8 1.2

Fig. 7. Voltamograms of (1) copper substrate and (25) chromium coatings on a copper substrate measured in 0.5 M H2SO4. Coating thickness (m): (2) 5.7, (3) 12.0, (4) 23.5, (5) 20. (24) Chrome-plating electrolyte containing N1; (5) chromate electrolyte (250 g/l CrO3, 25 g/l H2SO4; T = 323 K; i = 30 A/dm2). PROTECTION OF METALS Vol. 42 No. 6 2006

ELECTROPLATING OF CHROMIUM COATINGS i, A/dm2 6 1 4 2 2 4 0 5 3

567

2 0.8 0.4 0 E, V
Fig. 8. Voltamograms of (1) steel substrate and (25) chromium coating on steel substrate in 0.8 M NaH2PO4 (pH 3.5). Coating thickness (m): (2) 5.0, (3) 7.4, (4) 9.0, (5) 18.0. (2) Basic bath, (35) that with N1 additive.

0.4

0.8

1.2

thickness, their porosity and, hence, the substrate dissolution current decrease. To assess the protective ability of chromium coatings deposited on steel substrates, the voltamograms of their anodic dissolution were measured in 0.8 M NaH2PO4 solutions [30]. The current peak in the E range from 0.3 to 0.4 V (Fig. 8) correspond to the anodic dissolution of steel. The protection degree of coatings was calculated by the equation [31] Ii Z = --------- 100%, I (6)

where I and i are the maximum dissolution currents of the coated and noncoated substrate, respectively. With an increase in the coating thickness, its protective ability increases; at a thickness of 20 m, the steel dissolution current virtually disappears from the voltamogram (Table 4). Thus, chromium deposits from solutions containing N1 additive exhibit adequate protective ability. The adhesion of coatings to the substrate was assessed in the bend tests. Deposits 20-m thick which were obtained in chrome-plating baths with N1 additive did not exfoliate from the substrate after 14-fold bending (the copper substrate was broken). The studied chromium deposits had a smooth even surface with spheroid inclusions. Such a deposit growth is typical of the electrocrystallization under the condiPROTECTION OF METALS Vol. 42 No. 6 2006

tions of strong inhibition (particularly, in the presence of phase and colloidal lms on the surface) [32]. The average diameter of the spheroid base was within 10 20 m and exhibited a trend towards growth with an increase in both the current density and the deposit thickness (Table 5). The surface fraction occupied by spheroids increased with an increase in the current density. Using the PMT-3 set-up, it was shown that the microhardness of spheroids substantially exceeded that of smooth surface areas. With an increase in the current density, the microhardness decreased both for spheroids and smooth surface areas. However, we failed to reveal its unambiguous dependence on the deposit thickness.
Table 4. Protective ability of chromium coatings Protective ability Z, % Coating thickness, m 1.0 5.0 7.4 9.0 18.0 20.0 Basic bath 8.0 59.3 Bath with N1 (11.8 mg/l) 12.0 60.0 63.0 88.9 92.6 >99

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Table 5. The effect of the current density and the coating thickness on the morphology and microhardness of chromium deposits Surface parameters Cathodic current density, A/dm2 10 15 20 15 15 Coating thickness, m 23 24 27 33 50 Spheroid base diameter, m 13 12 19 12 19 Apparent surface area occupied by spheroids, % 10 80 90 80 60 Microhardness of spheroid surface, kg/mm2 713 687 654 687 638 Microhardness of the smooth area, kg/mm2 357 334 298 298 317

The assumption that the spheroid fragments in the coatings are the crystalline carbide inclusions to the amorphous matrix require special studies. CONCLUSIONS The effect of certain water-soluble synthetic polymers on the electrodeposition of chromium from a sulfateformate bath based on Cr(III) compounds was studied. It was shown that in the presence of certain polymers the coatings improve their appearance and the current efciency increases. Thus, the introduction of a molecular-type additive N1 into the bath allowed goodquality coating well adhered with the substrate and with the thickness of above 30 m to be deposited. Their corrosion and electrochemical properties were studied, the protective ability was assessed, and the microhardness of thick crystallographically amorphous coatings obtained from chrome-plating baths with N1 additives was determined. The occulating effect of polymers on the chromium(III) hydroxide sol formed in the near-electrode layer was observed. It was assumed that a macromolecular adsorption layer of N1 formed on the electrode surface affects the kinetics of chromium electrodeposition and prevents the incorporation of coarsely dispersed nonmetallic particles into the coatings. REFERENCES
1. Kudryavtsev, N.T., Potapov, I.I., and Sorokina, N.G., Zashch. Met., 1965, vol. 1, no. 3, p. 304. 2. Datta, J., Galvanotechnik, 1982, vol. 73, no. 2, p. 106. 3. Smart, D., Such, T.E., and Wake, S.J., Trans. Inst. Metal. Finish., 1983, vol. 61, no. 3, p. 105. 4. Roubal, I., Galvanotechnik, 1978, vol. 69, no. 4, p. 301. 5. Kolotyrkin, Ya.M., Larchenko, E.A., and Florianovich, G.M., Elektrokhimiya, 1996, vol. 32, no. 3, p. 431. 6. Demin, A.A., Gusarova, I.A., Motyagina, G.G., and Danilov, F.I., Vopr. Khim. Khim. Tekhnol., 1983, no. 71, p. 18.

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