Electroplating
Electroplating
Electroplating
Prepared for the Committee for the Promotion of Electroplating by Joseph Edwards The Committee for the Promotion of Electroplating is sponsored by the Institute of Metal Finishing, the British Metal Finishing Suppliers Association and the Metal Finishing Association, and comprises representatives of these bodies, and of Inco Europe Limited and the Zinc Development Association. For further information please refer to: The Committee for the Promotion of Electroplating c/o The Institute of Metal Finishing, Exeter House, 48 Holloway Head, Birmingham B11NQ Telephone 021-622 7387
Foreword
The UK plating industry - in common with that of most other countries - is highly fragmented, and therefore lacks the concerted marketing and industry development so effectively practiced by the paint and galvanizing industries. This Guide is a further step by the Committee for the Promotion of Electroplating in bridging the information gap between the plating industry and the engineering and production management of the manufacturing industry. Today, electrodeposition technology offers the engineer the capability of providing specific surface properties, such as wear resistance, lubricity, hardness, solderability, electrical conductivity, corrosion resistance onto constructional metals or plastics which in turn satisfy the need for particular mechanical design needs. In these applications, the deposition of surface films is almost always cost effective and highly efficient; technology well suited to society's thrust for energy and material conservation. CPE hopes that this Guide will enable the discerning engineer to think in broader design concepts than perhaps hitherto, and that through electrodeposition technology, industry can more effectively accept the challenge of the eighties.
Committee Members
March 1983
J.D.C. Hemsley, Chairman J.E. Thomason, Treasurer E.P. Arnull M.J. Ashton J. M.Bennett A.R. Poeton R. H. Pinner F. C. Porter P.G.L. Vivian British Metal Finishing Suppliers Association British Metal Finishing Suppliers Association Inca Europe Limited Metal Finishing Association Metal Finishing Association. Metal Finishing Association Institute of Metal Finishing Zinc Development Association Institute of Metal Finishing
Contents
1. The uses of electroplating Decoration Corrosion protection Engineering applications Electrical applications Electroforming 1 1 9 15 23 25
2. The nature of the electroplating process Electrode reactions Current and coating thickness distribution General considerations
27 27 29 33
3. Design for electroplating Cost factors Good and bad design Types of plant Plating processes Preparation for plating
35 35 37 43 49 53
4. Specifying and purchasing electroplating Requirements of customer and supplier Pricing Conditions of quotation and sale
59 59 61 63
65 65 67 69
Introduction
Surfaces are not always given their proper due. In the design of manufactured goods and engineering components, they may come low in the order of priority. To allow this to happen could be a serious miscalculation. The surface of any article is the interface with its surroundings. It determines its response to chemical and physical circumstances, its resistance to corrosion and tarnishing, its tolerance of impact and abrasion, its frictional and contact behaviour. It is what the consumer sees and touches, and so it contributes positively, or otherwise, to his satisfaction, both when the article is new and when it is well into its expected lifespan. Unless the immediate environment is controlled, there are surprisingly few applications in which homogenous materials give an adequate account of themselves. The obvious resort is to coatings, which enable the bulk properties of one material to be combined with the surface properties of another. Many types of coating are employed. Organic finishes account for the greatest coverage. Conversion coating procedures are widely used: one, phosphating, is mainly a preparative treatment for painting, while another, anodising, is a finishing process in its own right. Metal coatings are applied by hot dipping, spraying, cladding, chemical and physical deposition methods. There is currently a great deal of interest in advanced physical techniques, such as ion plating and ion implantation, and these are likely to make great headway in specialized applications. But the group of processes offering the greatest diversity of properties and applications is that with which this guide is concerned: electroplating. Electroplating is well established but not very well known. Unlike painting (some kinds, anyway), it is hardly a domestic art. Its apparent difficulty and complexity may obstruct its wider utilization. The object of this guide is to penetrate the aura of mystery surrounding electroplating, as a step towards procuring its full industrial potential. It is directed principally at those concerned in the design and specification of manufactured metal products. The sequence followed is to summarise existing applications as an illustration of the usefulness of electroplated coatings; to outline the fundamentals of electroplating; to review the factors to be borne in mind in designing articles to be electroplated and the relevant characteristics of individual basis materials and plating processes; and to give some guidance on commercial matters. A list is included of useful sources of further information.
Grateful acknowledgement is made to all the many people who assisted in the preparation and production of this guide.
Historical note
Shortly after Volta had invented the first battery, the so-called voltaic pile, one of his colleagues, Brugnatelli, used it as a source of current to electrodeposit gold on two silver medals, thus becoming the world's first electroplater. The year was 1803. Not unusually, the innovation was slow to develop. Only a few plated articles survive from the early years of the nineteenth century, but there is a famous one in the Royal Collection at Windsor Castle: a gilt silver cup, made by Storr in 1814 and known as the Galvanic Goblet.
A further quarter-century passed before the Elkington cousins established the electroplating of silver and gold on an industrial scale in 1839. Meanwhile, Faraday had defined the first and second laws of electrolysis in 1833-4 and Daniell, in 1836, had developed the cell named after him, a much more reliable source of current than had existed before. The Elkingtons installed Daniell cells in their first plating shop; however, when Woolrich's Electro-magnetic Machine (based on Faraday's discovery of electro-magnetic induction) became available in 1845, they were quick to take it up.
Nickel plating was first performed by Bird in 1837, but it was not until 1868 that Adams, having made many improvements, was able to put the process into commercial operation. Zinc and copper electrodeposition were developed over the same period. There was a long gap, however, before chromium plating emerged, by a tortuous process in which many people were involved (Sargent, Fink, Schwartz, Udy and Liebreich), during the decade of the 1920' s.
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1.
* 25 m = 1 thousands of an inch.
Page 2 penetration to the base can occur within a short time. The solution to this problem was found about 20 years ago. Simple but paradoxical, it is to create a high density of very small discontinuities in the chromium. In aggressive environments attack occurs at all these sites, but the wide spread of the total corrosion current brings about a drastic reduction in the rate of penetration. Very long life can thus be assured, with only gradual loss of lustre resulting from the widely dispersed superficial corrosion. The very tiny discontinuities deliberately produced in the chromium may be either cracks or pores. Depending on the particular processes employed the top coats of microcracked and microporous chromium have minimum thicknesses in the range 0.3 - 0.8 m. Benefit is also gained by using nickel deposits that are more resistant to penetration than single-layer bright-deposited coatings, for example: dull or semi-bright deposits requiring polishing to give full brightness, or double-layer coatings comprising a semi-bright lower and a bright upper layer. In BS 1224 these three types are designated: b, p and d, respectively. The types of chromium are distinguished as follows: r for regular (or conventional), mc for microcracked and mp for microporous. The British Standard recommends 20 m of any of these nickel deposits plus any of the chromium deposits for steel articles intended for moderately severe indoor conditions, e.g. in kitchens and bathrooms. For service outdoors in exceptionally severe conditions, however, it recommends one of the combinations shown in Table 1 (the standard gives equivalent guidance also for coatings on zinc alloy, copper or copper alloys and aluminium or aluminium alloys). Table 1. Nickel plus chromium coatings on steel suitable for severely corrosive outdoor conditions. Ni 40 mp 30 mp 30 mp 40 md 30 md 30 md Cr r mc mp r mc mp
Note that for these service conditions single layer bright nickel is excluded and regular chromium requires a thicker undercoat. Choosing the correct combination guarantees the maintenance of a bright appearance for a very long time, even in severe environments. Chrome plate can be applied to plastics as well as to metallic materials. (Figure 3.) The polymer most commonly used is ABS (acrylonitrile-butadiene-styrene), but others can be successfully plated, for example, polypropylene, polyphenylene oxide and polyarylethers. There is a British Standard specification (BS 4601) for electroplated coatings of nickel plus chromium on plastics material. The pretreatment of plastics for
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Figure 3
Page 4 plating is rather complicated, but good results are consistently obtained by the platers who specialize in this kind of work. It has been shown that the decorative appeal of chrome plating can be enhanced by texture patterning. The parts of the surface that are to retain full brightness are shielded by a stencil, which need be nothing more substantial than plastic tape, while the article is bombarded by a water slurry of tiny glass beads. When the stencil is removed, the pattern is revealed. (Figure 4.) The treatment has no adverse effect on the durability of the finish. Figure 4
Page 5 A tin-cobalt alloy electrodeposit containing about 20% cobalt can be used as an alternative to chromium on top of nickel. It looks rather different from chromium, but behaves equally well, and possesses process advantages that enable it to be used where chromium plating is not practicable (e.g. bulk plating of small items is feasible in conventional barrels). Another tin alloy, tin-nickel, containing 35% nickel, is highly resistant to tarnish and corrosion, and is used by itself as a decorative and durable finish on a variety of goods. It has a bright, metallic appearance with a pink tinge. The coating is so noble that rapid attack on the basis metal occurs in corrosive conditions, if any pores are present; consequently, it is not much used in outdoor applications.
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Precious metals
Silver was the first electrodeposited metal to be used for decorative purposes. It is still to be seen on personal and domestic articles and musical instruments. Stainless steel has made inroads into its use as the dominant finish for cutlery and tableware, but the application survives. BS 4290 advocates minimum thicknesses of 10 to 50 m on cutlery and flat ware and 5 to 25 /-m on hollow ware. Nickel silver, an alloy of copper, nickel and zinc, is the preferred basis metal. On high quality cutlery, special techniques are employed to ensure that the greatest deposit thicknesses are applied to areas subject to most wear. Even articles made of solid silver are sometimes silver plated to improve their appearance. Polished silver is a superb finish but it is rapidly tarnished by sulphur compounds. The only fully effective preventative is a coating of rhodium about 0.3 m thick; this is highly resistant to both abrasion and tarnish, but it is slightly darker than silver and expensive. Lacquer coatings are therefore more often used, or sometimes thin films of tin or silica. Gold plating is seen on jewellery, watches, some hollow ware and musical instruments, and quite frequently on bathroom fittings. An undercoat of bright nickel is often used. The minimum coating thicknesses specified in BS 4292 range from 0.5 to 2 /-m or, for special applications, from 4 to 16 m. Gold alloy coatings, generally harder than pure gold, are usually employed; these can be produced in various colours, so-called 'green' (with silver), 'red' (with copper) and 'rose' (with both silver and copper). (Figure 6.)
Others
Modern bright zinc finishes are attractive in appearance and so are used in some applications as much for decoration as protection. Lacquered, they compete with chrome plate on supermarket trolleys and baskets. (Figure 7.) Tin is another metal that can be deposited in a bright form. On the whole, however, it seems best to give full consideration to both zinc and tin under the heading of corrosion resistance. The point is made, however, that most, perhaps all, electroplated coatings tend to have a good appearance, certainly as produced. The visual impression is not a negligible factor, even when the coating is applied primarily for another purpose. In manufacturing operations it has often been noted that a superior finish on components induces greater care and cleanliness on the part of assembly workers. The consumer also likes a trim, professional appearance even on items that are not normally on display, but which he will see from time to time, such as those under the bonnet of his car.
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Page 10 Figure 8
Page 11 The service life of a zinc coating is very much a function of its thickness, as it is eventually corroded away. BS 1706 recommends a minimum 5 m for dry interiors and 25 m for marine atmospheres and tropical conditions of high humidity. The ability of zinc to provide sacrificial protection to a substrate such as iron or steel comes into play if the coating is incomplete or is damaged during assembly or service. Such protection is vital in some circumstances. Under moist conditions, however, unless the gap is plugged with corrosion product, exposure of the basis metal will locally accelerate dissolution of the zinc. An increasing area of basis metal will be exposed. Inevitably, at some point in time, the protective action of the zinc will cease to extend as far as the middle of this bare area, and the substrate itself will be subject to corrosion. It is good practice therefore to exploit sacrificial protection as a secondary, rather than a primary, line of defence. There is considerable interest at present in the possibility of increasing the corrosion resistance of zinc coatings by making alloying additions. About 10% of nickel incorporated in the zinc plate lowers the corrosion rate considerably, and a few manufacturers are marketing steel strip coated with such an alloy as a competitor to the well established electrogalvanized, i.e. zinc plated, material. Sacrificial protection ceases if the nicke1 content is raised much above this level. Other alloying constituents have been found to increase the corrosion resistance of zinc, e.g. cobalt.
Cadmium
Cadmium has a great deal in common with zinc, but it is much more expensive, and the metal and its compounds are highly toxic if inhaled or ingested. It is whiter and somewhat more attractive in appearance than zinc. (Figure 9.) It withstands a marine environment notably better, because of the greater insolubility of its basic chloride, but it is inferior in industrial atmospheres. Although its corrosion potential is not as negative as that of zinc, it can cathodically protect steel. It is less prone to form bulky corrosion products, which could for example interfere with the operation of mechanisms, It is preferred in the electronics industry because it has lower contact resistance and is easier to solder. Where the application warrants the extra cost, cadmium is favoured on threaded components, as it has less tendency to stick and tightening to a prescribed tension is thus easier. Passivation treatments can be applied to cadmium in the same way as to zinc, and give similar benefits. In spite of the hazards and the cost, cadmium plating is often specified, especially by the defence and aviation industries, and is still carried out on a reasonably large scale. BS 1706 advocates a range of coating thicknesses between 5 and 10 m for varying conditions of service. The upper end of this range is much lower than is specified for zinc. The standard warns, however, that the protection afforded by cadmium and zinc coatings of the same class is not equal. Table 2 shows the time to the first appearance of rust in various environments on steel plated with 25 m of zinc or cadmium, as-plated or after passivation
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Figure 9
Table 2. Rusting of steel plated with 25 m Zn or Cd Conditions of exposure Years to appearance of rust Zinc Cadmium as - plated passivated as - plated passivated 2.1 3.0 4.0 2.1 2.6 3.8 4.8 2.1 0.9 2.1 7.5 1.9 1.5 3.0 15.0 4.0
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Silver
Silver has a high resistance to many chemicals and foodstuffs, and so is used to coat equipment, vessels, pipes, etc. used in the chemicals and food processing industries. Coatings of 100 m or more in thickness are met with in this application, in spite of the high cost of silver.
Prince of Wales Coronet, produced by electroforming technology. (Courtesy of The Worshipful Company of Goldsmiths)
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Figure11
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An application that well illustrates the benefits of hard chromium is on car engine exhaust valves. These are subjected to heavy loads and operate, very many times per second, at temperatures up to about 750C. To survive these conditions they are made of special steel and their stems are coated with 5 -8 / m chromium. (Figure 12.) Figure12
Other well established applications are on gauges, cutting tools, shafts, gears, rams, moulds and dies. On components such as cylinder liners, piston rings, etc., chromium coatings may be deliberately made porous by chemical or electrochemical etching to make them able to retain lubricants. Much use is made also of nickel coatings on engineering components. Conventionally described as heavy nickel deposits, they can be extremely thick: up to 500ILm on new pacts and even up to 5 or 6 mm on salvaged components. These coatings can be finished either by grinding or machining. Their hardness is much less than that of chromium, about 200 HV being usual; the considerably harder deposits (up to 600 HV) produced from solutions containing organic addition agents are generally unsuitable for engineering use, although it is possible to modify the bath composition without adding organic substances and increase the hardness to about 350 HV. Furthermore, in contrast to chromium, nickel tends to gall when rubbed against steel or another like surface. Consequently, it is mainly used on parts requiring enhanced corrosion resistance, or as an undercoat for hard chromium.
Page 17 Hardness as high as 500 HV can be achieved in nickel-cobalt alloy electrodeposits at cobalt contents around 35%. Over the last two or three decades there has been a steady increase, recently at a rate of about 15% per annum, in the use made of electroless nickel, mainly in engineering applications. No supply of electric current is needed to produce electroless nickel coatings; instead, nickel ions in solution are reduced to metal by the action of a chemical reducing agent. The nickel surface itself acts as a catalyst for this reaction, so a more fully descriptive name for the process is 'autocatalytic chemical reduction'; 'electroless' is the .name by which it was first known, however, and it has stuck. The reducing agent most commonly used is sodium hypophosphite, and a variable amount of phosphorus (around 10%) is co-deposited with the nickel. Boron compounds, such as sodium borohydride, are sometimes used instead, in which case the coatings produced contain about 4% boron, and still lower boron contents are attainable using one of the latest processes. All these reducing agents are costly, and the baths have a relatively short life before they must be renewed; hence the process is dearer than electroplating. It has one major advantage, however: an ability to coat the entire surface of the most complex shaped articles with a nickel-alloy layer of almost uniform thickness. (Figure 13.) Almost as important is the improvement in mechanical properties compared with nickel electrodeposits. The nickel-phosphorus alloy, for example, has a hardness of 500 HV as deposited and this can be increased to about 1000 HV by heat treatment at 400C. Abrasion resistance is higher, and even the galling resistance is improved, especially in contact with aluminium, titanium or stainless steel. The corrosion resistance appears to be better in some environments than that of electrodeposited nickel but worse in others. Figure13
Autocatalytic nickel plating of the sectionalised component on the left shows a uniform deposit, even in the bore. On the right, conventional electrolytic nickel plating has caused an uneven deposit, with build-up particularly on the shoulders and minimal deposit in the bore.
Page 18 Electroless nickel coatings are applied to many kinds of components used in the nuclear power and chemical industries, as well as to moulds, tools, mechanisms, etc. it is unusual for the coating thickness to exceed 100 m. A recent development is the use of a barrel, bulk plating method to apply electroless nickel coatings of only a few micrometres thickness to the steel cans of primary alkaline manganese batteries. Thick coatings of copper have various applications. They are deposited on steel wire to give high strength electric cables, on stainless steel cooking vessels to improve heat distribution and on electroformed nickel shells to confer higher strength and thermal conductivity. Worn and over machined parts are sometimes built up with copper, which is especially useful in conferring protection against fretting corrosion. Table 3 summarises the properties and major uses of copper, nickel and chromium coatings on engineering components.
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Miscellaneous
As noted in Table 3, copper coatings (usually 10 - 40 m thick) are employed as a stop-off in the selective nitriding or carburizing of steel. An important application of brass plating is to obtain adhesion of rubber to metal. In contrast, chromium is plated onto moulds in which rubber articles are made to prevent the rubber sticking. Silver coatings applied to the mating surfaces of stainless steel aero-engine casings stop spontaneous welding in service. An intriguing application is the use of a gold coating on an aluminium seal to ensure that, after a certain period of immersion in sea water, the controlled corrosion induced by the bimetallic couple will cause the seal to break. Gold is also used, because of its high reflectivity in the infra-red, to coat the reflectors used in drying equipment. Over many years there has been a slow growth in what is facetiously termed 'dirty plating', the deliberate addition of solid particles to an agitated plating solution in order to incorporate them in the deposit. The first application to become established was the incorporation of diamond particles in nickel to produce far better cutting surfaces on burrs, bits, routers, saws, etc. Using smaller particles of diamond or other hard materials, smooth wear-resistant coatings can be obtained. Nickel/silicon carbide is used to coat the cylinder walls of aluminum i.c. engines. Cobalt/chromium carbide has a special ability to resist high temperature fretting in aero-engine compressors. One way of producing chrome finishes with a satin appearance, whether purely for decoration or specifically for anti-glare or other properties, is by incorporating particles of insoluble materials such as barium sulphate or silica in the nickel undercoat; this is often a less expensive procedure than mopping the deposit with an abrasive composition. If very fine particles are used, the brightness of the coating is not affected, but discontinuities occur in a chromium top coat where the particles are present in the nickel surface; this is how microporous chromium coatings are produced. All the electrodeposition processes referred to so far are carried out on work pieces that are fully immersed in the plating solution. Equipment is available, however, for local application of electrodeposited coatings by a method generically known as 'brush plating'. A tool of graphite is used, wrapped in absorbent cotton or polyester material soaked in plating solution. This is connected to the positive lead of a D.C. power supply, the article to be plated being connected to the negative lead. Plating begins as soon as the covered anode and work piece are brought into contact, and as it continues it is important that they are kept in motion relative to each other; in some cases the tool will simply be moved to and fro by hand, in others the work, or occasionally the tool, will be continuously rotated.
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The conditions under which brush plating is performed are very different from those of ordinary plating, and so special solutions have been developed for the purpose. Most are proprietary and so their compositions are not disclosed; in general, they contain high concentrations of organically complexed metal ions. It is claimed that over 100 metals and alloys can be deposited by this method, considerably more than it is practical to apply by orthodox means. The coatings are not identical in properties with conventional deposits; chromium, for example, is significantly softer. Brush plating is applied in many different industries, mainly but not solely for repair purposes. It is of outstanding value for applying coatings to areas of components that are too large to immerse in a plating bath or form part of structures that would be very expensive to dismantle completely (e.g. in ships, aircraft, etc). The technique could conceivably be applied under mass production conditions - at least one computer controlled brush-plating lathe has been made, which is capable of automatically depositing controlled thicknesses of coating on a succession of components.
Fig 14
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Electrical applications
Coating properties important in electrical applications include resistivity, contact resistance, wear resistance, porosity and corrosion resistance, solderability, strength and ductility. Contact resistance is especially important in electronics equipment where operating voltages may be very small. If a low contact resistance is to be maintained over a long lifetime the contact material must be tarnish and wear resistant; if it is a coating, it must not only resist corrosion itself, but also be free from pores and penetrating cracks, so that there is no likelihood of substrate corrosion products ~spreading over the surface. Electrodeposited golds, available in some variety, meet most requirements, with the much harder rhodium preferred on heavy duty rotary switches. (Figures 14 and 15.) Because of the high cost of these metals, however, there is constant pressure to economise by reducing the area coated and the thickness applied to the absolute minima, or by using alternatives. BS 4292 specifies gold coatings between 0.5 and 20 m thick for functional purposes, and for a long time the specification thickness for contact applications was 5 m. This has now been lowered to 2.5 m, subject to satisfying a porosity test. The fact is that by careful attention to substrate preparation, solution purity and process conditions, pore-free deposits can be produced at much lower thicknesses than used to be thought possible. Very thin coatings, sometimes diffused by heat treatment, are applied to components intended for use in controlled environments. When gold plated articles are soft soldered, tin and gold are apt to form a brittle alloy, which may fail in use. The danger is avoided if the gold coating is not more than about 1 m thick, as the alloy then formed has too low a gold content to be brittle. It is feasible to use such a coating on a nickel undercoat, but it is essential to ensure that the contact design minimizes wear. Nickel itself of course offers corrosion resistance, freedom from porosity, good mechanical properties and fair solderability; without a top coat of gold, however, it has too high a contact resistance for most applications. At one time all-over plating with gold as an etch resist was common, but this is now a rare requirement. If gold is needed only on contact surfaces, various shielding techniques ('selective' and 'spot' plating) are used to limit the area plated to the minimum. Palladium is the most promising alternative to gold and it has been widely used in telephone applications. There is reluctance to employ it on printed circuit boards, partly because of its reported tendency to catalyse the polymerization of organic vapours to produce partially insulating films; this danger has probably been exaggerated. A more conspicuous shortcoming is that, of existing palladium plating solutions, one group gives highly wear resistant but cracked, and therefore non-protective, deposits, while another produces deposits that are quite free from discontinuities but highly prone to galling. Fortunately, it appears that this difficulty can be overcome by applying the former coating on top of the latter. Bright palladium-
Page 24 nickel alloy deposits, with quite high nickel contents, are also making headway in this area of application. Laminates clad with high purity electrolytic copper are used in the manufacture of printed circuit boards. To make contacts through the thickness of a board, through-hole plating is practiced, employing electroless copper followed by a special copper electrodeposit. To facilitate soldering, which may be selective or carried out by a flow technique, a tin-lead alloy coating (40% lead) is usually plated on to the copper. Specifications such as those of the European Space Agency require these coatings to be fused on to the copper, preferably by immersion in hot oil. This eliminates overhangs, prevents copper oxidation, improves solderability and assists inspection. Fusing and soldering impose strains arising from the difference in coefficient of linear expansion between copper and epoxy/glass laminate. It is important that the copper should be able to accommodate these strains without cracking. Because of its low resistivity copper is also used in much microwave equipment (wave guides, transponders etc.). At high frequencies all the current is carried in the outer layers of a conductor: the higher the frequency, the thinner the skin involved. In some cases, therefore, the still higher conductivity of silver makes it the preferred material, so a microwave conductor may be constructed of aluminium and electroplated with silver. On a component that is complex in shape, some recesses may have little or no coating, but this will generally be unimportant, as the total conductivity at high frequency will be hardly affected. If the part is to operate in a difficult environment, e.g. in a submarine, corrosion of the aluminium, accelerated by contact with the silver, may lead to early failure. In such circumstances, an undercoat of electroless nickel provides the answer. Where tarnish of the silver is unacceptable, a thin top coat of gold may be required. The electrical resistance of electrodeposits may be markedly affected by the presence of alloying constituents. Electroplated silver has perhaps a 10% higher resistivity than metallurgically produced material. Alloying with antimony, bismuth or arsenic however, to increase hardness or brightness, may raise the resistivity by a factor of three or four. Reliability is vital in electrical equipment required for defence, space and telecommunications purposes. In this area specialist advice should be sought during the design stage and appropriate specifications invoked to ensure the requisite quality is achieved and maintained.
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Electroforming
Coatings can be electrodeposited on some substrates and subsequently removed to form independent objects. The process is known as electroforming. The article on which the metal is deposited is usually termed a mandrel. Separation of the electroform from the mandrel is most often accomplished mechanically, the mandrel surface being chosen or treated so that too strong an adhesive bond is not developed. It is also feasible to employ mandrels that are dissolved, melted or collapsed to make separation possible. The most important attribute of electroforming is its ability to replicate patterns and textures accurately in a rigid and durable material. Thus the oldest application is in the production of electrotypes for printing, and perhaps the most characteristic is in the production of gramophone record masters, mothers and stampers. Moulds and dies are made for moulding plastics, confectionery, glass and some metals, and for pressing sheet metal. Both copper and nickel are used in these applications, copper being favoured where high electrical or thermal conductivity are desirable and nickel where greater hardness, toughness and corrosion resistance are required. At present the largest use of nickel is in the manufacture of rotary screen-printing cylinders. (Figure 16.) Other mesh products include tobacco tapes, razor meshes and filters. Continuous electroforming, especially of copper foil, on rotating cylindrical mandrels is practised on a large scale. Figure 16
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1.
Electrode reactions
Every electroplating bath contains electrically equivalent amounts of positively charged particles (cations) and negatively charged particles (anions) dissolved in a solvent, usually water. There are several different kinds of cation and anion in any single bath, together with unionized molecules of solvent and other possible substances, such as addition agents. Electroplating is performed by passing a direct electric current through the solution between one or more anodes, connected to the positive terminal of the dc source, and one or more cathodes (the work to be plated), connected to the negative terminal. In the external circuit, negatively charged electrons flow from anode to cathode via the power source. Within the solution, all the cations migrate under the influence of the electric field towards the cathodes and all the anions towards the anodes. Different types of ion move at different rates, depending mainly on their size and the magnitude of their charge. The sum of their movements in both directions produces a total flow of charge (i.e. current) equal to the external current. Most anodes are soluble; that is, when the current is flowing the metal ions in their surface lose electrons and pass into the solution as ions. Once in solution the ions invariably become co-ordinated, either with water molecules to form aquo-ions (still generally known as simple ions, however) or with anions to form complex ions. Other reactions may occur at the anode, depending on the voltage difference between it and the solution, i.e. the anode potential. For example, water molecules or hydroxyl ions may be oxidized to gaseous oxygen. Where insoluble anodes are employed, as in chromium plating, this is the predominant anode reaction. Other substances present in the solution may also be oxidized at the anode. The most important reaction at the cathode is the reduction of certain ions by electrons to give metal in the form of a coating. The ions reduced may be aquo-cations or complex anions. If the latter, they can move towards the cathode only under the influence of diffusion resulting from the concentration gradient developed as they are consumed, since the direction of the electric field is such as to tend to drive them away. Even when they are cations, their rate of discharge is always higher than their rate of arrival as part of the current flow, simply because some of the current is due to the movement of other ions. So in this case too diffusion has an essential part to play in bringing depositable ions to the cathode surface. The higher the rate of deposition, the steeper the concentration gradient with respect to depositing ions in the adjacent layer of solution and the lower their concentration at the cathode surface. As the surface concentration of depositing ions gets lower, the voltage difference at the interface gets larger, i.e. the cathode potential becomes more negative, the effect being known as concentration polarization. The deposition process is subject also to activation polarization. This is the difference in potential required to drive the deposition reaction itself, even in the presence of an ample supply of depositing ions. Like concentration polarization, activation polarization increases with the deposition rate.
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This interpretation is over-simplified, but perhaps complicated enough. It is worth taking a little trouble over it, as the consequences are so important. Consider the question of competing cathodic processes: in the general case, metal deposition and hydrogen deposition. The considerations regarding polarization apply to both. If in particular circumstances, a single process accounts for virtually all the flow of current, raising the current density will increase the likelihood of the other process intervening. Indeed there is a maximum rate of deposition possible for any species, determined by its maximum rate of transport to the cathode. Beyond that, any increase in current must be accommodated by another reaction. Common electroplating processes cover the whole gamut of possibilities. A rather noble metal like copper can be deposited at high rate from a simple salt solution (e.g. sulphate) with no simultaneous generation of hydrogen. The rather less noble nickel is also readily deposited from simple salt solution but some hydrogen is always liberated as well. The fact is that the activation polarization accompanying nickel deposition is high, while that accompanying hydrogen deposition, on a nickel surface, is low. Just as the hydrogen overpotential, as it is called, is low on nickel, so it is high on zinc. It is solely because of this that such a base metal as zinc can be deposited from acid solutions with high efficiency and even from complex cyanide solutions with moderately high efficiency. Although not quite as base as zinc, chromium does not fare nearly as well. It is usually plated from complex chromic acid solution and the competition with hydrogen evolution is so intense that at low current density only hydrogen is produced, and even at best, chromium deposition efficiency remains below 20%. Co-deposition of hydrogen has many consequences. Low efficiencies are uneconomic in power terms. Bubble formation may cause pitting. Spray may be a serious problem. Discharge of hydrogen, by lowering the acidity of the solution next to the cathode, may cause basic compounds to be precipitated and incorporated in the deposit, to the detriment of its properties. Important consequences follow from the trend in metal deposition efficiency with increasing current density. If this is downwards, as is often the case when metal is deposited from complex ions, coating thickness distribution on a shaped article will be improved. On the other hand, if the efficiency increases with current density, the nonuniformity of coating thickness is aggravated. This question is considered more fully below.
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The current density is high on all the prominences, E, F, G, H and I. It is highest at G because of the high convex curvature here and the deep recesses on either side. It is almost as high as I, because the radius of curvature is fairly small, the bottom of the cathode does not compete strongly, and there is the boost in this region resulting from the projection of the anodes beyond the cathode and the wide current path below the electrodes. Similar influences operate at E, rather less strongly; giving a current density slightly higher than at H, where again it will be a little higher than at F, because of the transmitted effect of the more favourable current flow below, than above, the cathode.
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Figure 18
The drawing in (Figure 17) is too crude to show all these minor differences, but the principles underlying them are important. The reality, however, always differs from this representation. Because of concentration and activation polarization, the potential difference between the cathode and the adjacent solution is always higher where the current density is higher. The cathode, being a metallic conductor, maintains an approximately uniform potential, so it is the potential of the solution adjacent to its surface which varies, being less negative where the local current density is high than where it is low. The potential difference in the solution phase between cathode and anode is therefore significantly less for points E, F, G, H and I in Figure 17 than for points A, B, C and D. Hence the extent to which the flow of current favours the former set of points is moderated, and the current density variation is diminished. The 'secondary current distribution', as it is called, is thus less extreme than the primary current distribution. The extent of the difference depends on the particular plating process. It can be large, lowering the ratio of maximum to minimum current density by a factor of perhaps four or five, but complete uniformity is out of the question, as differences in current density are necessary to maintain the potential variations that produce departure from primary current distribution. (Figure 18.)
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Many plating processes have a cathode efficiency approaching 100% over a wide range of current density. For these processes, the secondary current distribution determines the variation in coating thickness over a plated article. Where cathode efficiency is substantially less than 100%, it often falls with increasing current density, so yielding a further improvement in thickness distribution. In the rare cases in which efficiency increases with rise in current density, e.g. in chromium plating, the thickness distribution will be less uniform than the secondary current distribution. The extent to which coating thickness distribution is more uniform than primary current distribution is known as the 'throwing power'. This is a real and important characteristic of plating processes, but it can be measured quantitatively only for arbitrarily defined electrode arrangements and dimensions.
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General considerations
Several of the topics mentioned here will be treated in more detail later. Much attention has already been given to plating as an electrical process. It should be added that articles suspended in a plating bath need to be securely gripped to achieve both mechanical support and electrical contact. No plating, of course, will occur in the contact area. Large articles, especially if they are thin and made of a poorly conducting alloy such as steel, will need multiple contacts which must be carefully positioned. The plating process takes place in solution. To ensure full coverage, entrapment of air or evolved gas must be avoided. If solid particles are allowed to enter the bath they are likely to settle on upward-facing surfaces and cause roughness. Good drainage is highly desirable to minimize drag-out. Plating solutions are rather concentrated and may be acid or alkaline. Some are very poisonous and many aggressive to a variety of materials. Extraction and scrubbing of fume or spray may be a requirement; coping with effluent treatment and disposal. problems almost invariably is. In spite of the difficulties of operation, cleanliness is essential. Solution composition must be monitored and controlled and contamination avoided. Organic substances in very low concentrations can affect the properties and appearance of electrodeposits. Carefully selected and in controlled amounts, they are used as addition agents to obtain brightness or other desired properties, but the effects of accidental contamination can be serious. Foreign inorganic ions can likewise have deleterious effects. Methods exist for removing many impurities from plating solutions, but it is especially important that they are not continuously introduced into the solution, for example, via the work itself. In some cases it is virtually impossible to prevent this occurring. In the plating of tubular steel furniture some iron is almost certain to dissolve from the inside of the tubes, and it is therefore desirable to choose processes able to tolerate this. Good quality, adherent coatings can be obtained only if the basis metal is chemically clean: free from grease, oxide films, etc. Preparative treatments generally comprise several stages, with intermediate rinses, and may differ substantially according to the nature of the substrate. Suitability for plating is something that ought to be considered at an early stage in design. Apart from the particular problems that individual materials present, it should be noted that assemblages of different materials may pose exceptional difficulties. Means may be found to overcome these, but generally speaking, where possible, it is preferable to plate components separately and assemble them afterwards.
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Cost factors
The design of an article rarely makes the plating of it impossible, but it may make it unnecessarily difficult; generally speaking, the more difficult, the more expensive. If cost effectiveness is the target, if one wants to obtain the desired properties and appearance for the lowest overall cost, it is helpful to have some understanding of the problems that the metal finisher has to deal with. Overall cost is emphasised, however. Finishing is only one part of the manufacturing process and should not be considered in isolation. Increased finishing costs may be justified if they allow greater savings to be made elsewhere. On the other hand, it may be worth spending more in other directions to economize in finishing; to take a particular example, buying pre-finished instead of cold-rolled steel to make the pressed sides of electric toasters may reduce the overall cost of manufacture by enabling mechanical polishing to be omitted or much reduced.
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Page 38
The plater has at his disposal various ways of improving distribution. They could be classified as ordinary and extraordinary means. It might be thought that the most ordinary of ordinary means would be to choose a plating solution with good throwing power, but this is an option that is only occasionally available. It can be done if characteristically different processes exist for depositing the same metal; it is not much use, however, offering a cyanide copper deposit where a hard chromium coating is required. The principal ordinary means are: choice of appropriate anode size and position, with use of conforming anodes where possible; and judicious arrangement of components in relation to each other to achieve a degree of mutual shielding or compensation. These procedures can be quite effective. The extraordinary means are the use of shields, burners and auxiliary anodes. Shields are non-conductors, such as sheets of plastic, shaped and positioned so as to obstruct the flow of current to prominences. Burners, sometimes known as thieves or robbers, are auxiliary cathodes, often simple wire frames, placed where they can draw excess current away from edges and corners; they are, of course, inherently wasteful of the depositing metal. Auxiliary anodes are not as widely used as might be expected. Connected to the positive terminal of the power supply, or sometimes an auxiliary supply, they can be located near or within recesses or holes so ensuring an adequate flow of current. They present problems, however. Their positioning must be very accurate. If they are soluble, they change shape rapidly and so need frequent replacement, and any solid residue they produce may be a cause of roughness. Insoluble anodes are perfectly satisfactory in some baths, but in others it is hard to identify a suitable, and reasonably economical, material of construction. The consequence of these difficulties is that all these methods are more likely to be used in connection with electroforming or the deposition of thick coatings for engineering purposes than in the application of decorative and protective coatings. It is in the manufacturer's own interest to do what he can to help the plater achieve a reasonably uniform thickness, by observing a small number of simple design principles. There is a British Standard (BS 4479) that gives appropriate recommendations. Figure 20 is taken from the section dealing with electroplated coatings. The diagrams are not, of course, rigid guidelines but merely illustrative examples.
Page 39 Figure 20
Page 40
Page 41 good finish. A lubricating and protective film should also be used to avoid scratches and other surface defects, so minimizing the cost of polishing operations. The cost of plating die castings, both in terms of the processes that have to be used and the percentage of rejects incurred, is highly sensitive to surface quality. Care taken in designing the die to obtain smooth metal flow, in finishing the mould surfaces, and in establishing optimum process conditions is well repaid. The effect of design shape on coating thickness uniformity and the trapping of gas or fluid is independent of the way the component is produced, but there are additional considerations if the process involves solidification, e.g. casting of metals or moulding of plastics. A plated finish draws attention to any imperfections. Thus, it is best to avoid large, flat areas, and to prefer either convex or textured surfaces. Where ribs are required, they should be thinner than the main wall, to avoid visible sink marks on the outer surfaces. They should be tapered and radiused, both where they meet the wall and at their outer edge. Bosses also should be tapered and radiused, and made as short as possible; they should preferably be cored to give minimum wall thickness. If they are to take inserts of other materials, it is better for them to be put in after plating. If it is essential, however, to mould them into the component, the compatibility of the material used with all the processing solutions should be verified. In plating plastics, it should be remembered that many polymers lose strength at the processing temperatures. Wall thicknesses must be sufficient to prevent distortion and racking points (where significant pressure may be applied), strong enough to withstand distortion or situated in non-critical areas. Joined plastics, whether welded or cemented, can rarely be successfully plated. Welded metals do not present such great difficulty, although, as already mentioned, welds can create trouble if they trap processing solutions. A heavy scale may be associated with gas and arc welding. Removing it, whether mechanically or chemically, is an extra process stage and may give rise to roughness requiring further treatment. If greasy surfaces are welded, an adherent carbonaceous film may be produced, which is more difficult to remove than ordinary welding scale; it is preferable in such cases to degrease before welding. Soldered joints rarely present any particular difficulty. The plater will have to make sure, however, that flux residues are removed and that the processing solutions have no adverse reaction with the components of the solder. . Any post-fabrication operations should be scrutinized for possible effects. Heat treatment, for example, could give rise to heavy scaling; it is important to select treatments and conditions that avoid this.
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Barrel plating
The characteristic feature of barrel plating is that no permanent contact is established with any individual article. The items being plated comprise a sliding and tumbling bed within a rotating vessel, i.e. barrel, of insulating material. Fully immersed barrels are the most common. These are usually prismatic (often hexagonal) or cylindrical in shape, with perforated walls, and rotate about their horizontal axis. The anodes are outside the barrel, and cathode contact is made by various means, most often via the ends of insulated cable dipping into the bed (danglers). Many automatic plants are in operation employing this type of barrel. (Figure 22.) Open ended barrels are much less used than formerly, but can be very economical and are suitable for very small items. These have no perforations, and the plating solution is retained inside them. They are usually narrower at the mouth than at the base, may have flat or curved walls, and rotate during plating with their axis inclined at about 45 to the vertical. The anode is a disc of metal supported from above, while the cathode contacts are mushroom headed bolts penetrating the base.
Page 44 The main advantage of barrel plating is that it eliminates the need for racking, with its expensive labour content. It also avoids contact marks, and carries very little risk of roughness, pitting or high current density burning. Coating thickness distribution is more predictable and often better than is obtained with rack plating, because the current is better distributed and partly because the tumbling action may abrade the softer coatings on projecting areas. Figure 22
Page 45 Barrel plating cannot be applied, however, to large or easily damaged components, or to any requiring a mirror smooth surface. Parts that tend to become entangled with each other or stick together can sometimes be plated in small loads in special barrels. Shielding or stopping off is not feasible in barrel plating. Thickness variation from one article to another in the same load is governed by a typical bell-shaped frequency distribution curve; it may be necessary to establish a high average in order to ensure a given minimum thickness. (Figure 23.) Most electroplated finishes can be applied by barrel methods, but a special type of equipment is required for chromium plating, which imposes tighter limits on the sort of components that can be processed.
Figure 23
Page 46 Many types of article are successfully barrel plated, most of them small, but including certain things, such as spanners, up to quite large sizes. Among the components processed in the largest quantities are threaded fasteners, bolts, screws, nuts etc. Thicknesses of coatings adequate for most purposes are specified in BS 3382: Parts 1-6. Thicker coatings may be required in some applications, but a risk arises that they will interfere with the free engagement of the male and female threads. Even a uniform coating of thickness, t, applied to an external screw thread, increases its effective diameter by about 4t, given a typical angle between the flanks of the thread. (Figure 24.) The effect is accentuated by the tendency for thickness to increase towards the crest of the thread and the end of the component, and by the variability between one fastener and another. On internal threads, the deposit is concentrated on the first one or two threads at each end.
Figure 24
Page 47 These problems are well understood, and a further section of the British Standard mentioned above (BS 3382: Part 7) describes the following practices that may be adopted to accommodate them. a) Accept some risk of interference, necessitating a degree of selective assembly. The risk can be estimated from the scatter of plating thickness and dimension tolerances, and is usually quite small, so that this practice is often acceptable, except where automatic assembly methods are used. b) Make a special allowance on thread dimensions. External threads may be produced undersize or internal threads oversize to leave room for the specified coating. c) Adjust the thread dimensions by chemical or electrochemical treatment before plating. This is appropriate where quantities are too small to justify special manufacture of threads with sufficient allowance. d) Selectively plate parts of fasteners. This cannot be done if the fasteners are barrel plated, but it is standard procedure for bumper bar bolts, which are rack plated in such a way that the head receives a much greater thickness of deposit than the thread. e) Use special deposits. Certain alloy or multiple deposits, though more expensive, offer better protection than conventional coatings, and so can be employed at lower thicknesses. In barrel plating, it is standard practice to specify the average thickness of a production batch rather than the minimum thickness. The specification often includes both a minimum batch average thickness to ensure adequate protection and a maximum batch average thickness to reduce the danger of interference between mated threads. Sampling and inspection procedures are laid down which enable sufficiently accurate estimates of thickness to be made for statistically homogeneous batches. Measurement of coating thickness at selected points is difficult on threaded and other barrel plated items, but to meet average thickness specifications, it is sufficient to determine the total weight of the deposit and divide by the density and total surface area.
Selective plating
In ordinary electroplating and electroforming practice, it is usual to 'stop-off' areas which are not to be plated. Stopping-off is the application of an electrically insulating covering, which must adhere well, resist all the processing solutions at the temperature of operation and be easy to remove completely when processing is complete. Special lacquers and waxes are available for this purpose. Appropriately formulated adhesive plastic tapes can also be used. The thickness of an electroplated deposit tends to increase towards the edge defined by a stop-off coating, and where this is undesirable, conducting tapes are sometimes used. The most common type is made of lead, bonded with adhesive, but aluminium and copper foils may also be used. Tapes of this type are in electrical contact with the cathode; they therefore receive a deposit themselves and so act as thieves. Occasionally, when the work comprises a succession of identical, accurately machined parts, it is worthwhile machining a metal mask to cover the area that is to receive no plate; this also acts as a thief, but can be stripped and re-used.
Page 48 A method of selective plating that is being increasingly applied in the area, especially, of gold plating for contact applications is based on the flow cell principle. The limited areas that are to be plated are left exposed when masks, often of silicone rubber, are pressed against them. Plating solution is circulated rapidly through the cell and a current is passed. Under these hydrodynamic conditions, current density can be high and plating times correspondingly short. Brush plating, already described in section 1.3.3, offers another means of controlling the distribution of an electroplated coating. It is difficult with this method, however, to define accurately the boundary between plated and unplated areas, and so if this aspect is important it is necessary to employ normal stop-off methods to shield the areas that are not to be coated.
Continuous plating
Steel and other metals or alloys, in the form of sheet or strip, are continuously electroplated in highly specialized plant, often at very high rates. A coating of uniform thickness may be applied to both sides or to one side only of the strip. Articles can be made from the precoated metal by normal fabrication procedures and frequently require no further electroplating operations. The best known example is the production of tinplate and its use mainly in the manufacture of containers. Continuous electroplating with other metals, such as zinc and nickel, is also well established. The continuous plating of wire is another important industrial process. Particular applications are tin coated copper wire for electrical use, zinc plated steel wire for ropes and hawsers, and brass coated steel wire for use in tyres. For the economical manufacture of components required by the electronics industry, reelto-reel plating is coming into increasing use, the principal coatings applied being gold and tin-lead. A simple coated strip may be produced, then blanked and formed to yield the finished components. Often, however, the basis material is pre-blanked but held together at one or both edges, so that it can still be plated continuously, and possibly undergo other manufacturing stages, before being separated into individual components. Selective plating using permanent masks, as described above, is increasingly common in reel-to-reel as well as batch plating
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Plating processes
This section is intended for reference only. lt provides basic information about the principal processes available for deposition of the more important plated metals and alloys. lt does not pretend to be comprehensive, but there are many texts available to which reference could be made for a fuller and more detailed view. Metals are listed in alphabetical order, and the information concerning each process is tabulated in standard form to aid consultation. Table 4. Characteristics of selected plating processes.
Principal constituents
sodium cyanide cadmium oxide (brighteners)*
Acidity or alkalinity
alkaline
Temperature
Plating rate
Throwing power
good
Major uses
cool
medium
functional
Chromium hexavalent
acid
warm
low
poor
decorative functional
trivalent
slightly acid
cool to warm
low
good
decorative
Copper acid
acid
cool
medium
poor/fair
cyanide
alkaline
hot
medium
good
general undercoats
pyrophosphate
slightly alkaline
warm
medium fair
functional undercoats
electroless
alkaline
cool to warm
low
excellent
functional
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Principal constituents
sodium cyanide copper cyanide zinc cyanide (brighteners)
Acidity or alkalinity
alkaline
Temperature
Plating rate
Throwing power
good
Major uses
cool
low
Gold cyanide
slightly alkaline
hot
low
good
decorative
acid potassium gold cyanide potassium citrate citric acid (phosphates alloying additions) Lead fluoborate slightly acid warm low good electrical decorative
acid
warm
high
good
Lead-tin fluoborate
acid
cool
medium
good
Nickel Watts
nickel sulphate nickel chloride boric acid (brighteners levellers, antipit agents)
slightly acid
warm
medium
fair
decorative functional
Sulphamate nickel sulphamate boric acid nickel chloride (anti-pit agents) electroless nickel sulphate (or chloride) sodium salt of a carboxylic acid plus sodium hypophosphite* slightly acid hot low excellent functional slightly acid warm / hot high fair functional
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Principal constituents
Acidity or alkalinity
Temperature
Plating rate
Throwing power
Major uses
alkaline
cool
medium
good
decorative functional
Tin stannate
sodium stannate sodium hydroxide (or potassium salts for higher plating rate)
alkaline
hot
medium
good
protective electrical
Acid Phenol sulphonic acid (and/or sulphuric acid) stannous sulphate graindefining additions (or brighteners) fluoborate fluoboric acid tin fluoborate boric acid Zinc cyanide acid cool/warm high good wire bearings acid cool high/ medium fair continuous or barrel: functional bright; decorative
alkaline
cool/warm
medium
good
protective decorative
zincate sodium hydroxide zinc oxide (brighteners) acid zinc sulphate (or zinc chloride) other salts (brighteners) slightly acid cool/warm medium fair wire cast and wrought iron alkaline cool low good general (but cyanide free)
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Page 54
substances being cathodically deposited on the surface, it is often followed by a brief anodic treatment (occasionally, the current is reversed several times). Cathodic cleaning is used alone, however, on metals that are rapidly etched under anodic conditions. Cleaning is usually followed by a rinse in water, then a dip in a dilute mineral acid solution, followed by a further rinse, before entering the plating bath. The function of the acid dip is to neutralize the alkali remaining on the part, dissolve any oxide film that might have formed and etch the surface slightly. Sometimes the acid dip is replaced by an electrolytic acid etch.
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Copper-base materials
The following sequence is commonly used to prepare brass for plating: solvent degrease, cathodic clean, brief anodic clean, rinse, hydrochloric acid dip, rinse. A somewhat more elaborate sequence may be followed when plating for engineering applications. For example, the work may be scrubbed with pumice after cathodic cleaning, and the hydrochloric acid dip replaced either by a nitric acid dip or by a brief anodic treatment in acid ammonium citrate solution. Some prefer to carry out an anodic etch in a cool solution of sodium hydroxide containing a little cyanide, and then to dip in dilute sulphuric acid to remove any stains. Reference should be made to specialist texts for pretreatment sequences for alloys such as beryllium copper.
Zinc-base materials
The alloy used in zinc-based die castings contains about 4 % aluminium. The castings are often plated with decorative coatings of nickel plus chromium, but an undercoat of copper is almost always present. In preparing zinc die castings for plating, it must be borne in mind that the alloy is readily attacked by both acid and alkaline solutions. As much as possible of surface contamination is removed by solvent cleaning, then the castings are immersed in an alkaline soak cleaner and subsequently anodically cleaned for a brief period, and rinsed. Only mild cleaners should be used, specially formulated to avoid attack on the basis metal. A very mild acid dip follows, followed by thorough rinsing. A copper coating about 10 m thick is then applied before nickel and chromium plating. The copper may be deposited in one layer from a cyanide solution, but sometimes only 3-5 m is applied from this solution (the minimum necessary to protect the basis metal) and then the coating is built up to the total thickness required in a pyrophosphate or levelling acid sulphate solution.
Page 56 pattern described above for plating zinc alloys, i.e. usually copper plate before finishing with nickel plus chromium or other top coat. Various modifications to the zincate process have been described, some adapted to the plating of particular alloys. One proprietary process based on a dilute zincate solution containing additions of other metals, such as copper and nickel, in complex form, gives a coating that can be plated direct with nickel and various other metals; it can be used without modification on a wide variety of alloys. Another well established proprietary process employs a replacement deposit of tin instead of zinc and is preferably followed by a bronze undercoat. A complete preplating sequence comprises the following steps (plus rinses): 1) degrease (if alkaline soak cleaner is employed, make sure it is free from caustic alkali and silicate); 2) cathodic clean (again in solution appropriate for aluminium); 3) dip in strong nitric acid solution or, for some alloys, a nitric-hydrofluoric acid mixture; 4) immerse in the zincate or similar solution (it may be advisable to strip the first coating in nitric acid solution and apply a second in a shorter immersion time); 5) proceed to first electroplating stage. Non-metallic materials, including plastics It is possible to electroplate almost any kind of non-conducting solid article, after first applying a conductive coating. If the material is porous or likely to be attacked by the processing solutions, it will be necessary to protect it with an impermeable film. Sometimes a conductive paint performs both functions or, alternatively, an article may be encapsulated in a lacquer film and subsequently metallized by a chemical spray or immersion method. When plating begins on such a thin conductive film it is essential to maintain a low current density, but the current can be increased progressively as the deposit gets thicker and thicker. Coatings applied in this way have limited adhesion to the substrate, and so must form a complete envelope if the integrity of the coated article is to be preserved. In the case of certain materials, e.g. plastics, the adhesion can be improved by roughening the surface before plating, using abrasive blasting or tumbling. A break-through occurred about 20 years ago when it was found that truly adherent deposits could be applied to a particular grade of ASS (acrylonitrile-butadiene-styrene). The necessary pretreatment involves an etch in chromic-sulphuric acid solution. This dissolves polybutadiene globules at the surface of the plastic leaving tiny holes that provide secure anchoring points for subsequently applied metal coatings; possibly it also, by oxidising carbon-to-carbon double bonds in the polymer, lays a basis for chemical links to be established. A similar degree of adhesion can nowadays be attained on other types of plastic as well, including polypropylene. While some plastics may require solvent treatment, alkaline clean and acid dip, these can usually be omitted on ABS or polypropylene. These go straight into the etch or conditioning solution and then, after a rinse or acid dip, into the activator. The activator, which may comprise only one or more stages, is designed to achieve a uniform distribution of tiny palladium or copper nuclei, which will act as catalyst in the
Page 57
subsequent electroless copper or nickel plating stage - these electroless solutions are slightly alkaline and generally operated at room temperature. Subsequent processing depends on the application; a possible sequence would be: bright, levelling acid or pyrophosphate copper (starting at low current density, as explained above), bright nickel, chromium.
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4.
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Pricing
It is impossible to give firm guidelines on prices, but an indication of the basis on which prices are calculated can be obtained from the following breakdown of a typical electroplating company's costs: Wages, salaries and on-costs Energy Depreciation, rates, insurance, post, etc Plating materials Transport 40 - 50% 15 - 20% 15 - 20% 10 - 20% 5 -10%
Clearly, excepting the case of precious metal plating, materials costs are low compared with most manufacturing industries; employment and energy costs, in particular, are relatively high. To recover his costs a plating contractor will often base the price on the total processing time, a combination of handling and machine time. Factors to bear in mind are: 1) 2) 3) 4) Machine time usually depends on the duration of the plating operation, which is proportional to the thickness of the deposit. Jigging requires individual handling, in contrast to bulk processing in barrels. The area and shape of a component determine the space it occupies in the plant. The degree of special skill or ancillary work required is often significant.
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Page 65
1.
Books General
Automation in the Metal Finishing Industry, Ed. RR Read, Institute of Metal Finishing & Portcullis Press Ltd., Redhill, 146pp, 1976. Canning Handbook of Surface Finishing Technology, (formerly Handbook on Electroplating), 23rd ed., W. Canning plc/ E. & F.N. Spon Ltd., Birmingham, 1094pp, 1982. Electroplating - Fundamentals of Surface Finishing, FA Lowenheim, McGraw-Hill Book Co., London, 594pp, 1978. Electroplating Engineering Handbook, Ed. AK. Graham, Van Nostrand Reinhold Co. Ltd., USA 845pp, 1971. Modern Electroplating, Ed. FA Lowenheim, John Wiley & Sons Ltd., 801pp, 1974. Principles of Metal Surface Treatment and Protection, D.H. Gabe, 2nd ed., Pergamon Press, Oxford, 211pp, 1978. Protective and Decorative Coating for Metals, H Silman, G. Isserlis and AF. Averill, Finishing Publications Ltd., Teddington, 620pp 1978. Surface Technology and Electroplating in the Electronics Industry, AF. Bogenschutz, Portcullis Press Ltd., Redhill, 394pp, 1974.
Testing
Corrosion Testing for Metal Finishing, V.E. Carter, Butterworths, London, 128pp, 1982. Handbook of Metal Treatment and Testing, RB. Ross, E. & F.N. Spon Ltd., London, 480pp, 1977. Methods of Testing Metallic Coatings, T. Biestek and S. Sekowski, Finishing Publications Ltd., Teddington, 420pp, 1980. Testing of Metallic Coatings, S. Baier, Institute of Metal Finishing and Portcullis Press Ltd., Redhill, Vol. 1, 78pp, 1979; Vol. 2, 82pp, 1981.
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Hard Chrome Plating, J.D. Greenwood, 3rd ed., Portcullis Press Ltd., Redhill, 216pp, 1981. Nickel and Chromium Plating, J.K. Dennis and T.E. Such, Newnes-Butterworth, London, 1972.
Plating on plastics
Electroplating of Plastics, Ed. R Weiner, Finishing Publications Ltd., Teddington, 360pp. 1977.
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Journals
Anti-Corrosion Methods & Materials, Sawell Publications Ltd., 127 Stanstead Road, London SE23 1JE. British Corrosion Journal, The Metals Society, 1 Carlton House Terrace, London SW14 SOB. Corrosion Protection and Control, Scientific Surveys Ltd., 4 Burke's Parade, Beaconsfield, Bucks. Finishing, Wheatland Journals Ltd., Penn House, Penn Place, Rickmansworth, Herts W03 1SN. Metal Finishing, One University Plaza, Hackensack, N.J. 07601, USA Metal Finishing Abstracts, Finishing Publications Ltd., 28 High Street, Teddington TWl18EW. Metal Finishing Plant & Processes, Finishing Publications Ltd., 28 High Street, Teddington TW11 8EW Plating and Surface Finishing, American Electroplaters' Society Inc., 1201 Louisiana Ave., Winter Park. EL 32789, USA Product Finishing, Sawell Publications Ltd., 127 Stanstead Road, London SE23 1JE. Products Finishing, Gardener Pubs, Inc., 600 Main Street, Cincinatti 2, Ohio, USA Surface Technology, Elsevier Sequoia S.A, P.O. Box 851, 1001 Lausanne 1, Switzerland. Transactions of the Institute of Metal Finishing, Exeter House, 48 Holloway Head, Birmingham B11NQ.
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Standards
The following are published by the British Standards Institution, British Standards House, 2 Park 51, London WI Y 4AA. Where there is a corresponding document issued by the International Organization for Standardization (ISO), its number is given in brackets after the title.
Precious metals
BS 2816 Electroplated coatings of silver for engineering purposes. BS 4290 Electroplated coatings of silver for decorative purposes. BS 4292 Electroplated coatings of gold and gold alloy.
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Threaded components
BS 3382 Part 1 Part 2 Part 3 Part 4 Electroplated coatings on threaded components. Cadmium on steel components. Zinc on steel components. Nickel or nickel plus chromium on steel components. Nickel or nickel plus chromium on copper and copper alloy (including brass) components. Tin on copper and copper alloy (including brass) components. Silver on copper and copper alloy (including brass) components. Thicker platings for threaded components.
Test methods
BS 5411 Part 1 Methods of test for metallic and related coatings. Definitions and conventions concerning the measurement of thickness (ISO 2064). Review of methods for the measurement of thickness (ISO 3882). Eddy-current method for measurement of coating thickness of nonconductive coatings on non-magnetic basis metals (ISO 2360). Coulometric method for the measurement of coating thickness (ISO 2177). Measurement of the local thickness of metal and oxide coatings by the microscopical examination of cross sections (ISO 1463). Vickers and Knoop microhardness tests (ISO 5416) Profilometric method for measurement of coating thickness (ISO 4518) Measurement of coating thickness of metallic coatings: X-ray spectrometric methods (ISO 3497) Measurement of coating thickness of electro-deposited nickel coatings on magnetic and non-magnetic substrates: magnetic method (ISO 2361).
Part 2 Part 3
Part 4 Part 5
Part 9
Part 10 Review of methods available for testing adhesion of electrodeposited and chemically deposited metallic coatings on metallic substrates (ISO 2819/1).
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Part 11
Measurement of coating thickness of non-magnetic metallic and vitreous or porcelain enamel coatings on magnetic basis metals: magnetic method (ISO 2178). Beta back scatter method for measurement of thickness (ISO 3543) Chromate conversion coatings on zinc and cadmium (ISO 3613) Gravimetric method for the determination of coating mass per unit area of conversion coatings on metallic materials (ISO 3892)
BS 5466 Methods for corrosion testing of metallic coatings. Part 1 Part 2 Part 3 Part 4 Part 5 Part 6 Neutral salt spray test (NSS test) (ISO 3768). Acetic acid salt spray test (ASS test) (ISO 3769). Copper-accelerated acetic acid salt spray test (CASS test) (ISO 3770). Thioacetamide test (TAA test) (ISO 4538). Corrodkote test (CORR test) (ISO 4541). Rating of results of corrosion tests on electroplated coatings cathodic to the substrate (ISO 4540) Guidance on stationary outdoor exposure corrosion tests (ISO 4542) The evaluation of results of accelerated corrosion tests on metallic coatings (ISO 1462).
Part 7 BS 3745
Miscellaneous
CP 3012 Cleaning and preparation of metal surfaces. BS 4479 Recommendations for the design of metal articles that are to be coated. BS 6001 Sampling procedures and table for inspection by attributes. BS 6041 Method of sampling of electrodeposited metallic coatings and related finishes.
Index
ABS (acrylonitrile-butadiene-styrene) plating on pre-treatment Activation polarization Aluminium plating on pre-treatment Auxiliary anodes Barrel plating Bearings, plated deposits Black Chrome Nickel Book list Brass plating decorative rubber adhesion solutions Brass, pre-treatment Bright chrome plating nickel plating tin plating zinc plating Bronze plating Brush plating Burners Cadmium plating Solutions Chrome plate Chromium plating alternatives to decorative engineering applications (Table) hard microcracked microporous moulds plastics solutions Composite electrodeposits Concentration polarization Continuous plating Copper foil, electroformed Copper plating Electroforming engineering applications (Table) selective carburizing/nitriding solutions Corrosion protection 2 56 27, 32 55-56 38 43-47 20 1 4 65-66 5 20 50 55 1 1-2 6 6 5 20-21, 48 38 11 49 1-4 4-5 1-4 19 15-16 2 2, 20 20 2 49 20 27, 32 48 25 25 19 20 49 9-14
Cost factors in design Costing of electroplating Current distribution Decorative electroplating Design for electroplating coating thickness distribution cost factors diagrams, preferred shapes diecastings fabrication requirements rinsing requirements Diamond tools Diecastings, design requirements pre-treatment Effluent treatment Electrical applications Electroless nickel plating engineering applications (Table) Electrode reactions Electroforming Electroplating major applications (Table) Electroplating plant barrel continuous rack selective Electrotypes Engineering plating Fasteners, plating Fume extraction Gold plating Decorative electrical applications infra-red reflectors solutions History of electroplating Iron, pre-treatment Lead plating solutions Lead-indium plating on bearings Lead-tin plating on bearings Solutions
35 61 29-32 1-6 35-41 37-38 35 39 41 40 40 20 41 55 33 23-34 17-18 19 27-28 25 Intro 43-47 48 43 47-48 25 15-21 46-47 33
6 23 20 50 Intro 54
50 20 20 50
Lead-tin-copper plating on bearings Microcracked chrome Microporous chrome Nickel plating Bearings Black Bright Decorative Electroforming engineering applications (Table) heavy deposits solutions undercoat for brass undercoat for gold Nickel-cobalt alloy plating Nickel-iron alloy plating Non-metallic materials pre-treatment Palladium plating Passivation of cadmium zinc Plastics design requirements plating on pre-treatment Polypropylene, plating on pre-treatment Plating processes Polarization Polyarylether, plating on Polyphenylene oxide, plating on Precious metals plating Preparation for plating Pre-treatment of aluminium and its alloys brass copper and its alloys iron non-metallic materials plastics steel Pre-treatment sequences Pricing of electroplating Printed circuit boards Properties of plated coatings Purchase requirements
20 2 2, 20
Quotation conditions Reel to reel plating Rinsing, interstage Rhodium plating decorative electrical applications Rubber bonding Sale conditions Satin finishes chrome nickel Selective plating brush gold Shields Silver plating conductivity decorative protective solid silver solutions stainless steel wave guides Soldered joints design requirements Soldered plated connectors Specification of electroplating Specifications classified list BS 1224 BS 1706 BS 1872 BS 3382 BS 4290 BS 4292 BS 4601 BS 5466 ISO/4520 Spot plating of gold Steel, pre-treatment Stopping off techniques Strip plating Tables
63 48 40 6 23 20 63 1, 20 1 20 47-48 20-21 23 38 24 6 14 6 51 20 24 41 23 59
69-71 2 11 13 46-47 6 6 2 9 9 23 54 47 48
properties of plated coatings Intro Wear and corrosion resistant finishes 19 Plating processes 49-51 Books 65-66
Technical journals Specifications Texture patterning Theory of electroplating Thickness distribution Diagrams Tin plate Tin and tin alloy plating solutions Tin-cobalt alloy plating Tin-lead alloy plating printed circuit boards solutions Tin-nickel alloy plating Tin-zinc alloy plating Uses of electroplating Wave guides Zinc base alloy diecastings design requirements pre-treatment Zinc plating solutions Zinc nickel alloy plating
41 55 6, 9-11 51 11
Originally published by Committee for Promotion of Electroplating Originally Printed by K & N Press Limited, Hampton, Middlesex
Scanned and assembled for editing at request of The Institute of Metal Fishing By Ladbrook Mfg Ltd. Participant Partners in N-Coat 70 Project. 2005 - 2008