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Laboratory Scale Electrodeposition Practice and Applications
Thomas J. Bnnn, Thermophysics Divlslon, Center For Chemical Engineering, National Bureau of Standards, Boulder, CO 80303
In this paper, some of the ~ractical asoeds of electrodeoo- . . . sition or electroplating are-discussed. Special emphasis is given to the techniques required to make electrodeposition work reliahlv in the lahoratorv. We will then discuss some of the prohlek-solving applications that have been of value in the author's laboratory.
The Deposltlon Solutions Solutions from which electrodeposition is conducted are
usuallv com~lex mixtures containine comoonents that serve - - multiple purposes (1, 2). The principal component of the deposition solution is the source of primary ion(s) (the ion or ions which are to be deposited). Simple salts are used most often as the source of the platable ion, even in the case of the complex anion systems. I t is desirable to have a high concen- tration of platable ions in the solution: thus, onlv the most . . soluble sd t s should be used. For example, as a source of copper ions, both the sulfate and the fluohorate salts have been used, but the fluoborate is the more soluble of the two. Perchlorate salts are also quite soluble but involve an in- creased degree of hazard. Nitrates are usually not accept- able, since the NO; ion tends to he reduced easily. This renders some metals unolatable from nitrate solutions. since at higher potentials the kvo~ution of ammonia at the cathode presents difficulty. The effect of the anion (of the primary ion source) must also be considered in the formulation of a solution. Adsorption of the anion on the cathode will effect the deposit and will also influence the activity of the metal ion. Metal chlorides are sometimes used as a source of metal ions, but their primary purpose is to furnish chloride anions, which aid in anode corrosion (or dissolution). This will be discussed in more detail later. There has been limited use of organic anion salts as the source of primary metal ion. These include sulfonic acid and aryl acid salts. These solutions tend to he weakly ionized and expensive and are never used commerciallv.
In the complex anionic solutions, a source of liganda must be vrovided rto form the corn~lexl in addition to the metal . . ions. The most popular complexing ligand is the cyanide ion, which is used for the deposition of copper, gold, silver, zinc, cadmium, and indium (3.8). These solutions are usually maintained in a strongly alkaline condition since the com- plex is decomposed b&id (with the evolution of poisonous HCN). The only exception to this rule is the gold complex (cyanoaurate), which is stable a t a pH as low as 3. The most common sources of the CN- ion are either sodium or potassi- um cyanide. The potassium salt is preferred due to its higher solubility, although it is more costly. The cyanide ion is maintained in laree excess in the com~lex solutions. The quantity of cyan& which is not neededin the formation of the complex is termed free cyanide. Free cyanide has a profound effect on the depoait because of its tendency to adsorb on the cathode surface. I t increases throwing power
This work was done at the National Bureau of Standards, not subject to copyright.
and total polarization, hut a t a sacrifice in current efficiency and olatine rate. Some lone-term reactions of the cyanide ion ihould-be borne in mind. I t can slowly hydroiize to produce ammonia and formate,
CN- + 2H,O - NH, + OOCH- I t can also be oxidized to cyanate, especially a t an anode which is evolving oxyEen. Carbonate ion is usually present in the cyanide sol&io&, due to the reaction with atmospheric carbon dioxide. This is not detrimental a t low concentra- tions; carbonate isoften added tocyanide solutions when the possibility of iron contamination exists (3). This is done when large scale steel tanks are used for plating and storage, since the carbonate addition will precipitate the iron impuri- ties.
Other, less-common anionic complexes are formed using hydroxy and pyrophosphate ligands. The most notable ex- ample of a noncyanide anionic complex is Sn(OH)i used in the electrodeposition of tin.
An electrodeposition solution must have a high electrical conductivity to allow optimum current densities to be used without excessively high voltages. Pny ionic solu;.;un will be electrically conducting, hut often the conductivity will be low because of low ionic mobilities. For this reason, most plating solutions require the use of conduction additives. The hvdronium and the hvdroxv ions are the best conduc- tors available. Thus, in s i iple sil t solutions, sulfuric acid is added. while in the alkaline (com~lexed) solutions, the most . . common conduction additive is either sodium or potassium hydroxide. In the latter case, the presence of excess OH- ions in a cyanide complex solution will help prevent the decomposition of CN- and the evolution of HCN. Simple sodium and potassium salts are also used to increase conduc- tivity, with the potassium salts being generally more soluble. In the case of cyanide solutions, the presence of KCN or NaCN will aid in the dissolution of the metal ion salt. For example, AgCN is poorly soluble in water, hutwilldissolve in an aqueous KCN solution. In addition to providing in- creased conductivitv. added acid or base will serve to stahi- ~ ~
lize a solution against hydrolysis. Hydrolysis is always unde- sirable since it will often cause the precipitation of the pri- mary metal ion as an insoluble hydroxide.
Some deposition solutions have pH values fairly close to 7, and require careful pH control to insure proper operation. In these solutions, a buffer system is often added. Commonly used buffers are boric acid (enough in excess to exist as ~olvmers) and citric acidlsodium citrate. Formates have also found limited use as huffers in deposition solutions.
As was mentioned earlier, a source of chloride ion is often added to a solution to aid in the corrosion (dissolution) of a soluble anode. We will reserve detailed discussion of the different types of anodes until later but will briefly mention the problem of passivation now. Passivity is a condition in which a metal or allov will corrode at a much lower rate than would be expected &om purely electrochemical consider- ations. This is due to the formation of a thin oxide layer on the surface of the metal and is responsible for the excellent corrosion resistance of aluminum and stainless steels. To prevent passivation and to aid in soluble anode corrosion
Volume 63 Number 10 October 1986 883
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the primary metal ion. Ideally, for each equivalent of metal deposited from the solution, one equivalent will dissolve from the anode and he incorporated into the solution. I t is desirable that these types of anodes should undergo uniform dissolution. under the influence of current onlv. and nroduce metal ions in the proper oxidation state ( u s u k y thk lowest possible). Thev should have a hieh surface-area-to-mass ra- tio and should-he made from higg-purity rolled metal. Cast- ings are unsuitable due to their microscopic ~orositv. A problem with soluble anodes is that they can ofien produce too high a concentration of metal in the anode film, with the resultbeing the formation of a metal sludge.
The second type of anode used is the insoluble anode, the sole purpose of which is to remove the electrons which are introduced a t the cathode. Thus, the metal ions are supplied only by the solution, which will require periodic replenish- ment or replacement. Insoluble anodes are nsed when soln- hle anodes are unavailable or too costly. For example, chro- mium is too hard amaterial to fabricate in acrack-free rolled form, and gold is simdv too expensive to use as an anode. The most common n~aterials fokuse as insoluble anodes are graphite, titanium, lead, and sometin~es stainless steels. Ti- tanium and stninless steels are usable because of their natu- ral thin oxide films, while a red oxide film must be produced on lead before use. Insoluble anodes areoften used incornbi- nation with soluble anodes. This allows the use of high cur- rent densities without an excess of metal ions (and sludge) being introduced into the bath. In this case, the potential a ~ n l i e d to the insoluble anode must be hieher than that applied to the soluble anode. If equal p o t e n t k are used, no current will flow from the insoluble anode. This usuallv requires the uJe of two separate power supplies.
The placement of anodes and cathodes isa critical ronsid- eratioi in setting up a plating bath. Current will always concentrate on the corners and edges of a cathode. Thus, these areas will receive a heavier deposit than the rest of the piece unless the current distribution is changed. Since cnr- rent does not readily flow around a nonconductor in a bath, snch high intensity areas may be shadowed by sheets of insulator such as PTFE. Also, one conductor will rob anoth- er of current. Thus, two cathodic pieces can he arranged
Graphite Copper rod
t Nylon holder
(C)
Graphite Copper block rod
Figure I. Sketcnes of (a) cup ancaeo made from copper, nickel, graphm and titanium. Ib) cdpanode used lor si ver: (clpencll anode (the mnon ball. w h m 5 tviSled arouna the grsphlle rod. s not shown): (d) trough slechode.
close to one another to distribute current more evenly. An- other consideration is the inability of current to penetrate into deep recesses, such as the inside of a tube. I t may therefore be necessary to position an anode inside a work- piece to achieve a useful coating.
To overcome most of the difficulties of bath arrangement for laboratory-scale operations, we have designed and fabri- cated cup anodes, which have proven to be extremely useful (see Fig. la). These anodes are easily machined from short lengths (20 cm) of appropriate high-purity barstock. The cvlindrical walls and hemispherical bottoms movide an ideal current distribution for sm& laboratory components. These anodes are connected to the power supply (to be discussed later) using standard banana plugs. Soluble anodes have been fabricated from copper (C11000, tough pitch electro- lytic barstock) and nickel (high-purity alloy 270). These materials are readily available, and short lengths can usually he obtained as free sam~lesfrom most snn~liers. The CUD for silver deposition (Fig. ib ) was made from'a length of P?FE rod, with the soluble anode being a slice of pure silver given to the author by a commercial electrode manufacturer. Cup anodes of the insoluble type have been machined from sec- tions of graphite (obtained as blocks from a bearing manu- facturer) and titanium. These anodes are not affected bv the passivation problems mentioned earlier and have given-bet- ter performance than our soluble cup anodes for most appli- cations.
In addition to the cup anodes, we have made an insoluble nencil anode. shown in Finnre lc. In this aonlication. the - . . plating solution saturates a ball of cotton which is securely w r a ~ ~ e d around a small eraohite rod. Platine is then simnlv brushed on the preparei metal surface (8) i f ter curreni applied. To aid in snch "brush datine" a~nlications. we .. L G e fuund the trough electrode tobeof value (Fig.'ld). This issimply ngraphire block with J 3-mm t r o u ~ ' milled in the top surface. A copper rod inserted through the cencer of the block supplies uniform current distribution. A work- piece such &;flat electronic contact is placed in the trough and brush plated using the anode pencil.
These simple, homemade electrodes perform better than commercial small scale plating tools, and are ideally suited to laboratory use. In addition, they can be easily constructed for a fraction of the cost of commercial devices and kits. Most of the materials nsed for the anodes were, in fact, obtained just for the asking.
The Dower sundv for laboratom scale electrodenosition is most convenienifi a direct current source capable 6f deliver- ing a current of up to 1 A at a maximum of 6 V. On the industrial scale, the power supplies are much more sophisti- cated. Commercial power supplies provide for the selection of complex waveforms, as wellas pulse operation and period- ic current reversal. The purpose of these different profiles is to disrupt and reform the cathode film and to electropolish the deposit in sitn. The relative benefits of these techniques are of& not clear, and i t would seem that the industry is influenced by fads. Bothan ammeter (0 to 1 A) anda voltme- ter (0 to 6 V) are needed for the laboratory unit, as well as
I A . 1 2 5 V
Solid state
P~CI Lamp Power C0"tlDl
Source Voltage Control
Figure 2. An easily constructed but serviceable power supply for laboratory scale electrodeposition. The resistance and power ratings required for the variable resl~tors are dependent upon the particular solid state power supply chosan.
Volume 83 Number 10 October 1986 885
provisions to adjust hoth the current and voltage. A work- able power supply can he easily built using a commercial solid state power regulator (obtained as a packaged "black box" unit) and appropriate circuit components that are readily available ih-recail outlets. The unit built for use in the author's laboratow is shown schematically in Figure 2, and the total materials cost was under $120.
.
In practice, the appropriate solution is warmed in a water bath to the optimum temperature. Whena cup anode is to he used, it is warmed as well. Just prior to use, the anode is removed and dried and connected to the positive terminal of the power supply. The solution is introduced into the cup usine a pinet. The workpiece. connected to the neeative terminal; then dipped into the solution, and the <roper current density is applied. To determine the current density (amperes per unit area), the area to he plated should be estimated to within 10%. The voltage is usually maintained - at between 2 and 5 V.
Safely Conslderatlom It cannot he stressed too strongly that most plating solu-
tions are extremely toxic. The strictest rules of lahoratory safety must be observed at all times. We have already dis- cussed some of the aspects of chemical incompatibility, such as acidification of cyanide solutions. The acidic deposition solutions are not only toxic but also highly corrosive. The organic additives also require great respect. For example, the CS9 + KCN solution (see table) is hoth toxic and corro- sive; a eoncentrated solution will &ck and dissolve many metals.
It is illegal to dispose of cyanide solutions in municipal sewer systems (POTW-publically owned treatment works). The cyanide ion must he destroyed prior to disposal. This is easily done using an aqueous solution of chlorine,
CN- + C1, - CNCl + C1-
CNCl + 20H- - CNO- + C1- + H,O 2CNO- + 40H- + 3CI2 - 2C0, + 2H,O + N, + 6C1-
The first step will occur at all pH levels; the second requires high pH; the third requires a pH near 7. Thus, careful acidi- fication using HC1 will complete the reaction, producing harmless nitrogen and carbon dioxide. Actually, it may be permissible (by local ordinance) to dispose of CNO- after sten 2, since wanate is far less toxic than cvanide.
Some mino; explosion hazards also musihe kept in mind. The diammine dinitrite solutions of the platinum metals become shock sensitive if the ammoniacal~mixtures are al- lowed to evaporate to dryness.
Appllcatlons The techniques described above and in Part I have been in
use in the author's lahoratory for over a year. Some illustra- tive examples will now he presented as typical applications.
Commercial stainless steel compression-type tuhe fittings are an indispensihle component of instrument "plumbing". When used under severe conditions (near their maximum allowable working temperature and pressure), leaks are a common and persistent problem (9,lO). The application of a
deposit of silver to the contact surfaces will solve most seal- ing problems, since the soft layer will cover microscopic scratches and prevent galling. Galling is a combination of severe wear and seizing, which occurs when two identical materials are in contact under high loading. Deposition to stainless steel is not straightforward due to the presence of the passive oxide film. TI& must he removed hyimmersiou in a hot mixture of concentrated H2S04 and HC1. Since the oxide will reform auicklv. it is not nossihle to plate silver directly on stainles; steec A cladding'(or strike) i f copper or' nickel must be aoolied first. Co~oer is more advantaeeous in this case and wasapplied using'the rochelle soluti& in the soluble comer CUD anode. Silver was then aoolied over the . . . . trike using the argentocyanide complex. Ferrules and fit- tings treated in this wav have a negligible failure rate.
Electrical contacts which must &&ate at high tempera- tures and in corrosive atmospheres are particularly suscepti- ble to corrosion and oxidation. The terminal bar contacts for a gas chromatographic sampler oven were therefore given a thin deposit of gold toprevent oxidation (11). The cyanoaur- ate complex solution was used; it was applied using the anode pencil and trough electrode (to support and contain the contacts during plating). After several months of opera- tion, the treated contacts are oxide free, whereas untreated surfaces would probably have failed.
In the construction of a fugacity measurement device, a brazed joint between sections of stainless steel and palladi- um tubing was required (12). The brazing process is much easier if a deposit of palladium is first applied to thestainless steel tuhe. This was done using diammine dinitrite solution in the graphite cup anode, after the application of a nickel strike. Other applications which have been of value include nickel coatings which have been applied to several fluid mixing devices, and an emergency ignition wire for a flame ionization detector.
Note: Certain commercial equipment, instruments, or ma- terials are identified in this paper in order to specify the experimental procedure adequately. Such identification does not i m ~ l v recommendatiou or endorsement bv the Na- tional ~ure&of standards, n& does it imply that the mate- rials or equipment identified are necessarily the best avail- able for the purpose.
Acknowledgment The assistance of T. G. Waldorf with aspects of anode
fabrication is gratefully acknowledged, as is the financial support of the Gas Research Institute and the United States Department of Energy.
Lkerature Clted (1) Lowenheim, F. A. "Electroplating": MeGraw-Hill: New York, 1978. (21 Lowcnheim, F. A. "Modem Eleetmplsting", 3rd ed.; Wilcy: New York. 1914. (3) ~odgera, T. ~ . " ~ a n d h m k of Prenical ~lectmplating": ~acmillan: ~m ~ o r k , 1959. (4) Bmgger. a. "Nickel Plating"; Draper: Teddington. 1970. (5) Guidebook and Directory: MFtal Flniahing, 1981. (6) Reid. F. H.; Galdie, W. "Gold Plating Technology"; Electrochemical Publieationa:
Glaagow. 1974. (7) Ficher J.; Weimer, D. E. "PmciousMetal Plating": haper:Teddington. 1964. (8) Straachlll, M. "Modem Practice in the Piclrliog of Met& and Related Pmeear";
Draper: Teddingfon. 1963. (9) Bruno. T. J.; Hum.. G. L.: Ely,J. F. I"t. J. Therrnophy*., inpmaa.
(10) B,"no.T. J.: nume, 0. L. 1nt. J. Thennophys., inprsss. (111 Brun0.T. J. J. Chmrnotagr. Sci. 1985.23.325. (12) Bruno,T. J.J.Res.Nat.Bur. Stds. (US.) 198S.W(2).127.
886 Journal of Chemical Education
