572

D. R. MASO

uniform, complete and the smallest of lines on the original wax coronet had been reproduced to perfection on the gold surface. A small quantity of silver from the metallising process was removed electrolytically in a sodium cyanide/sodium hydroxide electrolyte before final trimming.

Chapter 41

Moon Models

Another recent application with which the writer was also closely concerned, was tbe electroforming of moon models in gold to commemorate the first moon landing of the Apollo astronauts. In this instance, PVC moulds were made from the original steel model and the electroform was produced in two halves, which were ubsequently joined by cold welding and soldering. The final electroform weighed 2-3 ounces.

DECORATIVE PLATING

B. M. DICK.INSON

REFERENCES

1 "Gold-Recovery, Properties & Use", E. M. Wise (Ed.), Chapter 9, Van Nostrand,

New York (1964).

2 WonlwilJ E., Z. Elektrochem., 4, 379, 401 (1898).

3 "Finishing Handbook & Directory", Sawell Publications, London (1973). 4 Beutel E. B., Z. angew Chem. 25, 995 (19J 2).

5 Mornheim A. F., Plating; 47, 819 (.1961).

6 Paweck R., Weiner R., Z. Elektrochem., 36, 972 (1930). 7 Kutnetsova A. N., Med Prom. SSR J2 46-8 (1958).

8 Yampolsky A. M., Electroplg Metal Finish., 16, 3, 76 (1963).

9 "Finishing Handbook & Directory", Sawell Publications, London (1973i.

10 Korbelak A, "Metal Finishing Guidebook & Directory", Metals & Plastics

Publications, Inc. Westwood, ew Jersey (1969).

11 Seegmiller R., Gore J. K. Proc. Am. Electropl. Soc., 47, 74 (1960). 12 Bauer C. L., Plating, 39, 1335 (1952).

13 . Seidell A., "Solubilityof Inorganic and Organic Compounds", Van Nostrand, New York

(1940).

14 Yamamura K., Nagano-Ken, Hayashi, S., U.S. Pat., 3,475,290 (1969). 15 Brit. PaL, 9,431 (1842).

] 6 Woolrich J. S., Dinglers poly tee" J .• 88, 48 (1845). 17 Smith P. T., U.S. Pat., 3.057,789 (1962).

I8 Shoushanian R., U.S. Pat., 3,475,292 (1969).

19 Wiesner H. J., Frey W. P., Plating, 56, 527 (J969). 20 Wiesner H. J., Distler W. B., Plating, 56, 799 (1969).

21 Bandaver V. V., Krupnikova E. t., Rodionova L. 1., TR Gos. Nauch-Issled Inst.

Splavov Obrab Tvset Metal, 31,93 (1970). 22 Heilmann G., U.S. Pat., 3,586,611 (1971).

23 Bertorelle D. E., Galuanotechnic, 4, 6, 141 (1953).

24 Winkler J., German Pat., 576,585 (1933); German Pat" 723,497 (1942). 25 Avila A. J., Brown M. 1., Plating, 57, 1105 (1970).

26 Litton Systems Inc .. U.S. Pat., 3,427,231 (1969).

27 Vrobel L., Trails .. //1Sf. Metal Finish., 44,4, 161 (1966). 28 Electroplg Metal Finish., 17, 6, 217 (1964).

29 Electroplg Metal Finish., 14,2, 69 (1961).

30 GeT. Pat., 880,678 (1935).

31 Tuckfield W. I, Aust . J. DeI/I., (1938).

32 Mason D. R., Electroplg Metal Finish .. 22, 8, (1969). 33 Cheh H. Y., J. electrochem Soc., 118, 551 (1971).

The description "decorative" embraces all applications of gold plating of a non-technical nature and thus covers a very wide field ranging from purely ornamental uses where the thickness of gold applied may be less than 0.5 microns (usually with a clear coating of lacquer to improve corrosion and wear resistance) to those, as exemplified by high quality watchcase plating, where functional requirements dictate the use of coatings of 8-20 microns and sometimes even thicker. In the latter case the importance of adequate specifications of thickness and quality of coatings has long been recognised, but it is only comparatively recently that a general move has been made towards extending specifications to a wider range of decorative gold plating.

One difficulty in this connection stems from the problem of physically controlling the very thin coatings that may be applied to decorative articles under the description of "gilding"." The most recent British Standard Specification on gold plating, BS 429~: 1968 defines the term "gilding" a applying to coatings of less than 0.5 microns; the description "gold plating" is applicable to coatings of not less than 0.5 microns, with a gold content of at least 90 %, OJ to coatings of not less than 2 microns with a minimum gold content of 62.5 % (approx. 15 carat). Most specifications of other countries make a similar distinction between gilding and gold plating, though not necessarily at the same levels of thickness and purity. In discussions of international specifications] it has been proposed that the term "gilding" should be dropped and replaced by the generic description "gold electroplated", which would apply to coatings of a minimum thickness of 0.5 microns and a minimum gold content of 50 %, so that thinner coatings would be automatically excluded if this proposal is ultimately adopted.

A further difficulty which is encountered in attempting to formulate international specifications for decorative gold plating ari es from tbe existence in many countries of national legislation governing the quality, description and marking of gold plated wares, and it would seem that this will only be resolved in the long term. There is. however, a good measure of agreement on technical aspects.

573

* Gilding is also referred to as "Gold Washing" and "Gold Flashing".

t For a more detailed treatment of international specifications, the reader is advised. to study the APPENDIX by Mills.

574

B. M. DICKl SON

A distinctive feature of decorative gold plating is the importance of the colour of coatings and the need for accurate colour matching when, as frequently happens, parts which may be used in conjunction with each other, e.g., watchcases and bracelets, are plated by different establishments. To achieve colour uniformity together with the necessary hardness and wear resistance of the deposit, decorative plating is based almost entirely on the use of alloy rather than pure gold deposits.

The present chapter is concerned' primarily with the types of basis metal, pretreatment, plating procedures and electrolyte generally used in trade finishing, with particular reference to UK practice. Gold plating in the watch industry is dealt with in more detail in Chapter 42.

DECORATIVE PLAT! G

575

ZI C-BASE ALLOYS (MAZAK, etc.)

Very widely used for the casting of intricate shapes, e.g., brooches, necklaces, cuff-link faces, watch bezels and so forth.

PLATING PROCESSES

The suggested pretreatment and plating sequences for these basis metals are summarised in Table 41.1. The same pretreatmen is used for copper,

Table 41.1

Pretreatment and Plating Sequences for Various Basis Metals

BASIS METALS

Metal

Sequence

The basis metals most frequently encountered in the finishing of fancy goods are as follows:

Brass }

Copper

Nickel Silver Silver

Gold (low carat)

Mild steel

BRASS

Extensively used in the manufacture of watch bezels, watch straps, buckles, pen nibs, pen tops, cuff-links, etc.

COPPER

Zin c- based alloys Nickel plate Stainless steel

N - W - G(s) - W - G - D(I':) H-W-D-W-S<

G(s) - W - G - D(R) H - W - D - W - S - W - G - D(~)

H - W - D - W - S - W - G - D(R)

, C. - C(b) then plate as copper

H - W - D - W - H(A) - W - W <

C. - Polish 01' burnish

then plate as copper M - vv -D - W - A- W - C.- Cb then plate as copper

H- v.; -Nea) - W-H(B)- W -0(.)- W -G- D(R)

H - W - D - W - S(.) - W - W' - G, - W - G - D(R)

Code

A ~ 2.5% IfF or 0.5% H,S04 C = Heavy copper plate

C,b) - Bright copper plate (acid or pyrophosphate) Cs = Cyanide copper strike

Less widely employed than brass, mainly on account of its higher cost.

Beryllium-copper and phosphor-bronze are sometimes used as springs in cuff-links and ear clips.

SILVER

Used in the manufacture of better class costume jewellery. Frequently, a decorative effect is obtained by plating with 2-3 microns of gold followed by diamond cutting to expose a silver design against a gold background.

D = Cathodic degrease

D(R) - Drag-out G = Gold plate

GOLD

G{.) ~ Acid gold strike

H = Hot soak clean

H{A) ~ 50% HCI

M - Mild alkali clean N - Nickol plate

(no) = ickel activator· S = 5-10% H2S04 dip

Sa ~ Stainless steel cathodic activator (10% H1SO. +5% HAc)

W ,.;;; Water rinse

* ~roprietary, or cathodic treatment in Cold Cleaner Solution with 4 oz/gallon of sodium cyanide,

Notes

. 1 Difficulty ma~ be e perienced in removing polishing compounds from deep recesses to the article, ]"0 this end It may be found advantageous to incorporate an ultrasonic tank at. the hot cleaner stage, as this ,~i11 greatl~ increase the possibility of removing the soil, without having to resort to brushing the article,

2 Mild Steel and Zinc-Based Alloys-As a general rule it will be found quite satisfactory to plate 5 tim copper and 5 tim nickel as the base for the precious metal deposit but more complete recommendations are given in BS 4292.

3 Stainless Steel-Aiter activation it is essential to plate in the acid gold strike without any undue delay, as this can result in passivation of the steel.

Articles fabricated from low carat gold, e.g., 9 carat are often flashed over with a higher carat gold to conceal any differences in colour between the metal used in fabrication and the brazing alloy used. The thin coating of gold also gives a more appealing colour and enhances the tarnish resistance.

MILD STEEL

Employed in the manufacture of cheap watch buckles, handbag frames, and similar goods.

576

B. M. DICKfNSON

DECORATIVE PLATING

brass and nickel-silver, which are relatively easy metals to plate and require no special precautions. Although they may be plated directly with gold, bright nickel is often used as an intermediate coating.

Mild steel is not normally plated directly with gold because adhesion of gold to the basis metal i extremely suspect, and even when tbis is satisfactory, corrosion through pores in the deposit will readily occur due to the large difference in potential of the plate and substrate. A substantial copper or copper/nickel undercoat is therefore applied prior to gold plating.

Care is necessary with zinc-base alloys to prevent the deposit peeling. The plating cycle indicated will give a sound and adherent deposit. Occasionally both zinc alloys and mild steel are plated directly with nickel prior to gold plating, but this is not advisable as the nickel deposit has a tendency to peel from the basis metal.

577

Approximately 0.2 microns of gold is deposited in 4 minutes at the higher temperature. The colour is affected by the metal dissolved during the replacement reaction and for this reason the solution should not be replenished. with gold salt. Some 80-85 % of the metal may be deposited before the colour of the deposit becomes unacceptable.

At a pH of 6.9-7.1 and a temperature of lOO°C this solution will deposit on nickel approximately 0.25 microns in 3 minutes. At lower temperatures, deposits on nickel tend to be non-adherent. Copper and copper alloys plate more slowly, but good adherent deposits may be obtained at temperatures as low as 80°C over the whole of the stated pH range.

A minute addition of 54 % potassium silver cyanide to either of these solutions will give rise to a green gold deposit, but the consistency of colour is very poor.

Gold (as 68 % KAu (CNh) Dipotassium hydrogen phosphate EDTA, di-potassium salt

pH

Temperature

GILDING

Immersion Gilding*

This, as its description implies, involves tbe deposition of a thin gold coaling by chemical ratber than by electrolytic means, Use of this process is confined mainly to the finishing of relatively cheap mass produced articles such as hoe and watch strap buckles, although it is employed to orne extent on slightly more expensive items like watch straps brooch settings and cufflinks. Copper, brass and nickel plated articles are the most suitable for immersion gilding. Other metals and alloys must first be plated with copper ornickel.

The parts to be gilded must be thoroughly cleaned prior to immersion in the gilding olution to produce an active surface completely free from any traces of oxide or tarnish films. A suggested treatment cycle is as follow :

(i) hot soak clean (ii) water rinse (iii) cathodic degrease (iv) water rinse (v) dip in 1:1 hydrochloric acid solution containing a surfactant (vi) water rinse (vii) water rinse (viii) immersion gild Ox) drag-out (2) (x) water rinse (xi) dry (trichloroethylene or similar).

In the case of copper or brass articles, it is preferable to bright dip or chemical polish before the pretreatment cycle.

2-4 gIl 20 gil

30 gIL 6.0-8.0 90-100QC

Colour Gilding

or many years there were no generally accepted standards for the colours of gold deposi ts ; vague terms such as " 18 carat colour", 'pink" and "green" golds were used as the only definition. These terms are still widely used in gilding, but a more precise system is employed in colour matching of components plated by different establishments. This is the Swiss Standard colour table, based on a number of plates of gold alloys of standard compositions, each of which is assigned a numerical coding (see Chapter 42, 'fable 42.1). The most commonly used colour standards are IN-J4, 2N-18, 3N, 4N and 5 the first corresponding to a green gold and the 4N and 5N to pink golds in the old nomenclature.

To produce this range of colours requires the use of one or more alloying additions to a pure gold deposit to give the desired shade. The following indicates the effect of various metals on the colour of deposits.

Solutions for Immersion Gilding

Two suggested formulations are as follows:

Gold (as 68 % KAU(CN)2) Sodium cyanide

Sodium carbonate Temperature

Metal Silver Zinc

Tin Nickel Cobalt Copper Cadmium

Green Green Green Hamilton Yellow Pink Green

2-4 gIl 30 g/l

30 gIl 65-85°C

* The reader is referred to Chapter 10 for a fully comprehensive treatment of Immersion Plating.

Colour

-> White

-> White

-> White

-> Pale Yellow

-> Red

578

DECORATIVE PLATING

B. M. DICKINSON

Most gilding solutions operate at a pH above 7.0 and for this reason the adhesion of coatings, particularly on nickel, is sometimes suspect. In practice, it has been found that an acid gold strike is beneficial to the overall quality of the deposit, since this not only provides a good basis for the main gold coating, but assists in producing an even colour.

The metal concentration in gilding solution is u ually very low, with the twofold purpose of reducing metal investment cost and minimising dragout losses which could be considerable in view of the relatively short plating times and high throughputs usually involved. The solutions listed in Table 41.2 have been found to cover most of the requirements of the fancy goods trade. Due to the complexity of shapes to be plated it is customary to apply a constant voltage to the bath. rather than to calculate the work area and apply a specific current density. Colour variations may be obtained by varying the applied voltage, anode area, degree of agitation, etc., and also by the use of interrupted current. To maintain the nominal colour, however, the metal content should not be allowed to fall by more than 10 % before replenishing.

579

Testing

Gilding deposits are of unspecified thickness, but do not exceed 0.5 microns.

Tests made to assess porosity, tarnish and wear resistance, can only be empi rical, and based on comparison with agreed standards.

Porosity is checked by immersion in 30 % (v{v) nitric acid solution at room temperature and observing the time taken for bubbles to form on tbe surface.

Tarnish resistance is assessed by suspending the article under test about 1 inch above the surface of a freshly prepared 2 % solution of ammonium polysulphide (50 ml) in a closed bottle or jar of 250 ml capacity, at room temperature. The time for the surface to discolour is recorded and again compared with an accepted standard.

The wearing quality of the coating is tested by holding the piece under test together with a known standard against a scratch brush (nickel silver or brass) or a leather mop and noting the time taken for the basis metal to be exposed, as a relative indication of wearability,

Table 41.2

Bath Composition (gIl) & Operating Conditions of Typical Colour Gilding Solutions

GOLD PLA TING Vat

Balli I ssa«: Bath 3 Bath 4
(24 ct (18 ct (18 ct (deep pink
orange-yellow) green) pale pink) -red)
u(as 68 % KAl1(CN)z) 1.0-2.0 1.0-2.0 2,0 2.0
Cll(as EDTA complex) 2.0 2.5-5.0
Ag(as 54% KAg(CNh) 0.125 .4 0.05
KZHP04 20 10 10 10
K2EDTA 10 20 5.0 5.0
pH 6-8 6-8 6-8 6-8
Temperature, °C 35-65 35-50 35-60 35-60
Voltage 3-5 2-6 4-6 3-6
Anodes stainless steel stainless steel stainless steel stainless steel
(EN58J or
similar)
Time, sec 5-30 5-25 10-30 10-30 As stated earlier, this definition is reserved for the thicker coatings. The most common practice in the fancy goods trade is to employ one or two solutions as "work 11 orses " , i.e., to deposit the greater part of the coating, and to achieve the required exact colour match by gilding to about 0, 5 microns with a gilding solution of the appropriate composition.

The solutions listed in the following paragraphs cover most general requirements and any standard colour can be obtained by using one of these in conjunction with the gilding solutions listed in Table 41.2.

It is normal to employ an acid gold strike prior to entering the gold solution

18 carat green

6-10 gil

0.5-2.0 gil

20 gil

75-100 gil 20-30°C

0.4-0.8 A/dm 2 Stainless steel (EN58J or similar)

This type of solution will deposit J micron of gold in approximately 5 minutes. Additions of wetting agents, reducing agents and grain refiners such as nickel and cobalt are added to impart the desired characteristics to the deposit for specific applications.

Gold (as 68 % KAu(CN)2) Silver (as 54 % NaAu(CN)z) Potassium carbonate Potassium cyanide Temperature

Current density

Anode

Notes

Bath No.2 When replenishing, add 0.2 g silver for each 1 g of gold.

Bath No.3 Copper-EDTA complex is prepared by mixing cupric carbonate with

seqnestric acid solution. When effervescence ceases, potassium hydroxide is added until the solution is a clear blue.

Gold and copper are replenished according to analysis. Silver content requires very little maintenance. If additions are necessary, these should be made in very small quantities only since silver concentration has a marked effect on deposit colour, particularly in low current density areas.

Care should be taken in jigging or wiring work to be gilded, particularly chain as there is a tendency for deposition of a green gold in extremely low current density areas.

580

B. M. DICKINSON

DECOM TIVE PLATING

581

This patented solution is based on a weak polybasic organic acid and its sodium salt, citric acid and citrates being most commonly employed. A typical formulation is:

Organic acid Sodium salt

Gold (as KAu(CN)2) Brightener .;.

pH

Temperature

Current density Anodes

80 gil

30 gIl

3-10 gil

0.5-10 gil

3.5-4.5

30-35°C

0.5-2.0 A/dm:! Platinised titanium, carbon or stainless steel. t

Barrel PJating*

Many cheap articles such as buckles are gilded by barrel plating, the applied voltage and other conditions being exactly the same as for rack plating, but the time being increased to 11-2 minutes, Solutions containing silver are generally not satisfactory since the silver tends to deposit by immersion in low current density areas. Silver may be replaced by cadmium in green gold solutions intended for barrel plating, a suitable concentration of cadmium being 0.5 gil.

9 carat colour (23.5-23.9 carat)

* Brighteners are various complexes of zinc, nickel, cobalt, indium etc.

t Stainless steel is not recommended if large quantitie of inorganic ions, e.g., sulphate, are present (sometimes found in brightener).

18 carat pink

Gold (as KAu(CN)z) 4 gil

Copper as EDTA complex 2 gil

Zinc as EDT A complex 2 gil

Trisodium citrate 60 gIl

EDTA 20 gJl

pH approximately neutral

Temperature 3 SoC

Current density 0.7-1.0 Ajdm2

The colour produced is in the order of 4N-5N on the standard colour table.

Jigging

Jigs should be fully insulated with contact points maintained at a minimum to avoid wastage of gold. Where an article is composed of many individual sections, such as chain, spring loaded jigs should be used to maintain tension and good contact between the joints, otherwise variations in colour may occur along the length, particularly iu solutions containing silver as an alloying metal. Jig connections must be kept clean as poor contact can also lead to variation in colour.

Articles to be plated should be well spaced out. As a rule, allowance should be made for one component space between each component. Crowding of articles leads to poor deposit distribution and colour variation.

* The reader is referred to Chapter 14 for a full discussion on barrel plating.