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Juan Hajdu
Electroless nickel is plated over a large number of metallic and nonmetallic substrates of very different compositions and properties. For these reasons, it is impossible to select a single general approach to surface preparation. Specific procedures are required for each type of substrate. In broad terms, we can classify the substrates as metallic and nonmetallic. Most electroless nickel plating is done on metal parts, and in this chapter we will discuss mainly the preparation of metal surfaces. An important characteristic of plating metals is the strength of the bond that can develop between the base metal and the coating. Metal-to-metal bonds with high adhesion values require thorough surface preparation-removing from the base metal surface foreign contaminants (soil, dirt, corrosion products, oxides, tarnish, and others), and eliminating mechanically distorted surface layers-to present a clean, healthy surface structure. The removal of foreign contaminants is generally accomplished by using commercial alkaline cleaners. The selection is based on the nature of the contaminants and the type of substrate. The suppliers of cleaners will assist in the selection of the right material; there are also numerous literature sources that discuss metal surface cleaning (1-5). The removal of surface oxidation and unwanted metal is accomplished by chemical attack. Acid pickling solutions and alkaline deoxidizing materials, similar to those used in electroplating, are also effective for electroless nickel plating. In some cases, mechanical surface treatments, such as shot peening or sandblasting, are used in surface finishing prior to chemical treatment, especially with large, expensive parts that allow the use of manual processing. Electroless plating differs from other metal coating techniques (electroplating, vacuum metallizing, hot dip galvanizing) in that the substrate initiates the autocatalytic chemical reduction process. Some of the metals, such as nickel, are catalytic when immersed in an electroless plating solution, while steel and aluminum become catalytic by the formation of an immersion nickel deposit in the electroless nickel bath. Other metals, such as copper, are passive and require activating steps in order to initiate the electroless nickel plating process. It should be noted that even naturally active surfaces can become passive when contaminated by foreign residues or oxide layers. For this reason, surface preparation for electroless nickel plating requires the highest degree of care and control of all metal finishing procedures.
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Another reason for the need of a very careful selection of the preparation process is that it can significantly affect the porosity of the metal deposit. This is particularly true for electroless nickel. Residues from cleaners and deoxidizers can increase the porosity of electroless nickel, creating passive spots that will not initiate electroless plating (6). Thin (less than 5 pm) electroless nickel deposits are more porous than electrodeposited nickel of comparable thickness. During electroless nickel plating, the deposition process initiates at discrete sites and the substrate will become fully covered through the lateral growth of these sites. Short plating times will not allow full coverage of the base material, causing porous electroless deposits.
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embrittlement than acid solutions. Alkaline deoxidizers are used electrolytically, either in the anodic mode (the parts become the anode), or using periodically reversed (PR) currents where the parts are sequentially the anode or the cathode in the process. The use of PR with alkaline deoxidizers is especially useful in combination with acid pickling of steels, where carbon and other alloying constituents can form loosely adherent layers on the substrate. These Surface products must be removed effectively prior to plating, in order to obtain good bonding of the nickel to the substrate. The procedures required to obtain initiation and adhesion of the coating to the substrate (substrate activation) will depend mainly on the composition of the substrate. In the case of mild steels and carbon steels, good cleaning and deoxidation is in most cases sufficient for good bonding. In the case of cast iron parts and high alloy steels, special techniques are needed for obtaining good coverage and adhesion. Cast iron parts are normally porous and may require a number of special alkaline and acid steps to clean the pores and to avoid bleeding-out of rust through the nickel coating. Cast iron parts should be immersed in weak acid pickling solutions only briefly, to avoid exposing and loosening the graphite present in the casting, as well as to minimize acid entrapment. High alloy steels, such as the 300 and 400 series of stainless steel, require special treatments to activate the surface for fast initiation and good bonding. In general, hydrochloric acid at relatively high concentrations is used for activating stainless steel. Alkaline deoxidizers used with periodic reverse current are also employed for surface preparation. When this type of deoxidation is used on high alloy steels, the last cycle should be run with the parts on the cathodic side to avoid formation of passive oxide layers under anodic conditions. One approach that has been used very successfully for obtaining active surfaces is to strike the parts electrolytically in a chloride nickel-hydrochloric acid bath (Woods strike). Sulfamate nickel- and nickel glycolate-based strikes are used sometimes for activation (5). These electrolytic nickel strikes act by chemical deoxidation, and by depositing a thin layer of active nickel to overcome passivity and to provide a catalytic surface for the preparation of the electroless nickel process. Typical cycles for ferrous surfaces are:
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Alkaline soak clean or electroclean Water rinse Deoxidize in 40 percent HCI (and/or alkaline electrolytic deoxidize) Water rinse Electroless nickel plate
Stainless Steel or Nickel Alloys Alkaline clean Water rinse Alkaline deoxidizer with periodic reverse current Water rinse Activate with 40 percent HCI Woods strike-cathodic 2 A/dm' Electroless nickel plate Cast Iron Alkaline clean Water rinse Alkaline deoxidizer with periodic reverse current Water rinse Electroless nickel plate
Wood8 Strlke (4) Nickel chloride 240 g/L Hydrochloric acid (32percent) 320 mL/L Current density: 1 A/dm2, 30 to 60 sec. anodic 2 A/dm2, 2 to 6 min. cathodic
Sulfamate Strlke (4) Nickel sulfamate Boric acid Hydrochloric acid Sulfamic acid Current density Glycolate Strlke (4) Nickel acetate Boric acid Glycolic acid (70percent) Sodium saccharin Sodium acetate PH Current density
320 g/i 30 g/i 12 g/i 20 g/L 1 to 10 A/dm2 65 g/L 45 g/L 60 mL/L 1.5g/L
50 g/L
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of a zincate bath consists of zinc oxide (50 to 100 g/L) and sodium hydroxide (250 to 500 g/L). Proprietary zincate solutions contain other ingredients, such as copper and iron salts and organic chelating agents, to produce more uniform coatings and to permit the use of lower concentrations of zinc ("dilute zincates"). Many formulations for this type of material can be found in the patent literature (13,14). Typical formulationsfordilutezincatesolutionscontain5 to l o g ofzinc oxide and 50 to 120 g/L of sodium hydroxide. Acid zinc immersion systems have also been reported (16) using zinc sulfate (720 g/L) and hydrofluoric acid (17.5 mL/L) . The mechanism of zincating and the reaction of the zinc immersion deposits in the electroless plating bath have been reported in several papers (8,12,15). The basic mechanism of zincating is the displacement of zinc from an alkaline zincate solution by aluminum:
3ZnOf + 2AI" + 2H20= 3Zn" + 40H- + 2AIOi
The rate of this reaction is determined by the composition of the zincate solution and the type of aluminum alloy. There is a strong relation between the structure, uniformity, and thickness of the zinc film and the adhesion and protective value of the electroless nickel coating. In general, fine-grained, thin, and tight zinc films produce the best results. Thus, the zincating bath's composition, temperature, and immersion times must be controlled and adjusted to the nature of the aluminum alloy to be treated. A zincating process that performs well for one type of aluminum alloy may not be effective if the substratealloy ischanged (17,19,20). Figures7.1 and 7.2illustrate the influence of temperature and alloy composition on the thickness of the zinc immersion deposit. One important aspect of the zincating process to be considered is the mechanism of the initiation of the electroless deposition on zincated aluminum surfaces. The bulk of the zinc immersion deposit is dissolved in acid electroless nickel plating solutions, exposing the aluminum, which is covered by nickel by immersion, initiating the autocatalytic deposition process. Still, this dissolution process is not complete, and in general, residual zinc is found under the nickel layer. The influence of this zinc-rich layer has been investigated by Mallory (18), and its presence can be considered beneficial to the performance of the electroless nickel plating. An approach that has been widely used for cast and wrought aluminum alloys is the double zincating procedure. In this process, the initial zinc layer is removed by a dip in 50 percent nitric acid, and a second zinc layer is deposited by ashort immersion in thezincatesolution. The benefitsof this treatment come from the use of a less critical first zincating step to deoxidize the substrate and remove alloying inclusions, while the second zincate treatment can be adjusted to produce a thin, tight zinc deposit on the uniformly conditioned surface (11,12,17). An important factor to consider here is change in composition of electroless nickel solutions as they age, by accumulation of byproducts of the chemical
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.-
g
m
. I
a c
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is
reduction of nickel (21). Older solutions become more aggressive and give less adherent nickel coatings, and for this reason, surface preparation procedures that produce good results with relatively fresh electroless nickel plating baths may yield nonadherent or blistered deposits as the bath ages. This is the main reason why electroless nickel baths have a shorter life when used for plating aluminum than when used on steel. The use of a non-aggressive electroless nickel strike has been proposed to remedy this problem (22) and extend the useful life of the electroless plating bath. While the plating of aluminum may appear too complex for consistent processing, industry has been very successful in resolving the requirements of depositing electroless nickel on a broad variety of alloys and satisfying many end use requirements. Experience is the key to success in the plating of aluminum and it cannot be substituted by standard pre-established procedures. The following cycles are presented to illustrate industry practice:
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ELECTROLESS PLATING
F -..
c
CD
s
0
0 0
..S
CI
CD
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Immersion time, min
Fig. 7.2-Weight of rlnc film obtained from the alkaline rlnc lmmerslon process wlth several aluminum alloys.
Wrought Aluminum Alloys Solvent preclean (if necessary) Water rinse Alkaline soak clean Water rinse Etch in 15 percent by vol. sulfuric acid (80"C) or 50 g/L sodium hydroxide (50" C) for 1 to 3 min. Water rinse Nitric acid (50 percent) 30 to 60 sec Water rinse Second zincate treatment 10 to 20 sec Water rinse Electroless nickel plate
NOTE: For aluminum alloys containing 99 percent AI (1000series), etching and the second zincate treatment may be omitted.
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Alkaline soak clean Water rinse Acid etch 30 sec in nitric acid (50 percent), sulfuric acid (25 percent), and ammonium bifluoride (120 g/L) Water rinse Zincate treatment 20 to 30 sec Water rinse Electroless nickel plate
There is a great interest in using magnesium alloys for weight reduction, and electroless nickel offers good protection for magnesium-based parts. While used for commercial applications, plating magnesium alloys is not an easy task. Magnesium is a highly reactive metal and conventional cleaning and deoxidizing
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solutions are not adequate for preparing magnesium. A general discussion of Preparation of magnesium can be found in the literature of electroplating (1.25). The two recommended approaches are based on zincating or fluoride predips after alkaline cleaning and pickling with chromic acid solutions. The most widely used processes are based on fluoride predips and use special electroless nickel plating solutions that contain fluorides to improve adhesion (26). A typical cycle is: Alkaline rack clean Rinse Activate in mineral acids containing fluorides Rinse Cyanide copper plate Rinse Proceed as with copper parts
BERYLLIUM
Beryllium surfaces require protective, corrosion-resistant coatings for nuclear energy and aerospace applications. Since beryllium exposed to air is covered by an oxide layer, zincate treatment is used to remove the oxide and protect the base metal (1,27). A typical surface preparation uses double zincating after alkaline cleaning and acid deoxidation (28).
TITANI UM
Titanium surfacesarealwayscovered bya tight oxide film that interferes with the good bonding of plated metal coatings. The oxide layer must be removed, preferably by mechanical and chemical attack. The pickling solutions are, in general, based on nitric and hydrofluoric acids (1,29). After removing the oxide, the surface is protected by a conversion coating using fluorides (30), chromates (31), or zinc immersion deposits (1). The most widely used processes are based on fluoride-containing acid solutions, applied either by immersion or anodically prior toelectroless nickel plating. It should be noted that both electroless and electrolytic plating of titanium are plagued by adhesion problems. A possible cycle could be: Mechanically treat surface Activate in 50 percent HCI solution Woods nickel strike Electroless nickel plate
ZINC
At the present time, a number of commercial zinc die casting operations involve direct plating of electroless nickel for enhanced appearanceand protection. The
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largest single use of electroless nickel-plated zinc die castings is for carburetors used with alcohol fuel, especially in Brazil. In many operations, the partsare striked first with electrolytic cyanide copper prior to electroless nickel plating. The copper strike baths typically contain 20 to 45 g/L cuprous cyanide, 10 to 20 g/L free sodium cyanide, and 15 t o 75 g/L sodium carbonate. Copper strike baths have the ability to cover complex shapes and recessed areas when used under the right operating conditions. Most textbooks on electroplating extensively describe the operation of copper strike baths and the cleaning of parts prior to copper plating (1,32). While this approach gives excellent results, there is a continuous interest in finding a less costly process that requires no electroplating and avoids the use of cyanide compounds. Several methods have been proposed, and proprietary materials are available commercially that allow direct electroless plating of zinc die castings.
NONMETALLIC SUBSTRATES
The main difference between metallic and nonmetallic surfaces resides i n the nature of the bond between substrate and coating. While adhesion to metal is of an atomic nature, the adhesion to organic and inorganic substrates is only mechanical. The basis for obtaining adhesion to these materials is to develop the right topography on the surface by means of chemical or mechanical treatment.
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ELECTROLESS PLATING
Nonmetallic surfaces lack catalytic properties and therefore require activating treatments that will render them catalytic. In general, this activation is done by seeding the surface with a catalytically active metal. Parts are plated with the electroless nickel for several reasons. One of the major uses for electroless nickel is to form a conductive base for electroplating on plastic or ceramic substrates. Ceramic and glass parts are electroless nickel plated for bonding or soldering applications. Diamond and other abrasive particles are encapsulated in electroless nickel for manufacturing plasticbonded cutting tools. The use of electroless nickel for metallizing plastics is discussed in Chapter 14, Plating on Plastics. There are only limited uses of electroless nickel on plastics for mechanical or decorative applications. A novel application of electroless nickel is to protect electroless copper deposits used in electronic devices, such as shields for electromagnetic interference. This application is also discussed in a separate chapter. Electroless nickel has been applied extensively to ceramic, glass, and silicon parts used mainly in the electronics industry. Typical uses are to metallize conductors, capacitors, transducers, silicon devices, hybrid circuits, and other electronic components. The processing steps generally include roughening by chemical attack (if the surface requires it), activating with a catalytic metal, and then electroless nickel plating. The composition of the chemical etch will depend on the nature of the substrate. Some typical etch applications are as follows:
Alumina Ceramics Soak clean with alkaline cleaner Rinse Etch in 25 vol. percent hydrofluoric acid (50 percent) for 5 min at room temperature Barium and Zirconium Titanates Soak clean with alkaline cleaner Rinse Etch in 10 vol. percent fluoboric acid (48 percent) for 10 min at room temperature
Glass and Ceramlcs Soak clean with detergent Rinse Etch with hydrofluoric acid (40 percent) Ammonium fluoride
40 m u g 18 g/L
Silicon Devices
Hydrofluoric acid solutions with an addition of ammonium fluoride of Varying concentration, depending on the type of etch desired, are used in the metallization of silicon wafers.
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The roughened parts are rinsed and then rendered catalytic either by the two-step sensitizing and activating process or by using commercial activators. Sensitizing is accomplished by immersing the parts in an acid stannous chloride solution (10 to 100 g/L of SnCIz, 2Hz0), then rinsing and activating with a solution of palladium chloride (0.1 to 0.5 g/L PdCl in 1 to 3 mL/L HCI). Commercial activators containing mixed palladium-tin compounds are also used at 1 to 5 percent dilution. After activation, the parts should be ready for electroless plating either with hydrophosphite- or amino borane-reduced electroless nickel solutions. It must be remembered that the final adherence of the electroless nickel deposit will depend not only on the pretreatment, but also on the characteristics of the plating process. Aggressive plating baths or deposits with high internal stresses should be avoided, and thick deposits are very difficult to produce on this type of substrate.
MASKING
Many parts may require only partial coverage with electroless nickel, and portions of the substrate must be prctected by masking. Many stop-off materials (tapes and coatings) used for electroplating can be applied for masking partsfor electroless plating. Since most electroless nickel solutions operate at high temperatures, and the parts may stay in the bath for a long time, the masking materials should be tested thoroughly before using them on expensive parts. Masking materials may also release organic or metallic contaminants that may harm the nickel deposits. A problem commonly encountered when plating small areas in large parts is how to adjust the plating process to very low surface-to-volume ratios. All electroless plating solutions will perform best above minimum loading levels, which may be difficult to reach with masked parts.
REFERENCES
1. F.A. Lowenheim, Modern Electroplating, third edition, John Wiley and Sons, New York, 1974 2. F.A. Lowenheim, Electroplating, McGraw-Hill Book Co., New York, 1978. 3. L.J. Durney, Electroplating Engineering Handbook, fourth edition, Van Nostrand Reinholt, New York, 1984. 4. ASTM 6656-86, Standard Guide for Autocatalytic Nickel-Phosphorus Deposits on Metals for Engineering Use. 5. ASTM 6322-68, Standard Practice for Cleaning Metals Prior to Electroplating. 6. E.B. Saubestre and J. Haydu, Oberflaeche-Surface, 9(3), 53 (1968). 7. G.S. Petit et al., Plating, 59, 567 (1972).
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8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19.
20.
21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33.
D.S. Lashmore, Plat. and Surf. Fin., 65(4), 74 (1978). D.S. Lashmore, ibid., 68(4), 48 (1981). E.W. Hewiston, U.S. patent 1,627,900 (1927). J. Korpinn, US. patent 2,142,564 (1939). D.S. Lashmore, Plat. and Surf. Fin., 67(1), 37 (1980). W.G. Zelley, US. patent 2,650,886 (1953). E.B. Saubestre and L.J. Durney, US. patent 3,329,522 (1967). E.B. Saubestre and J.L. Morrico, Plating, 53,899 (1966). J. Heiman, J . Electrochem. SOC., 95, 205 (1949). I. Keller and W.G. Zelley, ibid.. 97, 145 (1950). G. Mallory, Proc. 70th A ES Annual Technical Conference, 1983. D.S. Lashmore, J. Electrochem, SOC.,127,543 (1980). .A.W. Blackwood, E.F. Yarkosky and J. Boupo, Proc. 68th AES Annual Technical Conference, 1981. E.F. Yarkosky, M. Alexsinas and A. Marzak, Proc. 66th AES Annual Technical Conference, 1979. J. Haydu, E.F. Yarkosky and P. Schultz, Proc. 3rd AES Electroless Plating Symp., 1986. T. Brezins, U.S. patent 3,096,182 (1963). N. Feldstein, U.S. patent 3,993,380 (1976); U.S. patent 4,305,997 (1981). D.G. McBride, Plating, 59(9), 858 (1972). ASTM 8480-68, Recommended Practices for Preparation of Magnesium and Magnesium Alloys for Electroplating. H.K. DeLong, US. patent 3,152,209 (1967). K. Parker and H.Shah, J. Electrochem. SOC.,117, 1091 (1970). W.H. Roberts, Coating Beryllium with Electroless Nickel, U.S. Atomic Energy Commission Contract AT(29-1) 1106, Ber RFP-478. ASTM 8418-69, Recommended Practices for Preparation of Titanium and Titanium Alloys. D.S. Harshorn, U.S. patent 3,725,217 (1973). M. Thoma, Plat. and Surf. Fin., 59(6), 76 (1983). ASTM 8252, Practice for Plating Zinc Alloy Die Castings for Electroplating and Conversion Coatings.