1402

J. E l e c t r o c h e m . Soc.: E L E C T R O C H E M I C A L

SCIENCE AND TECHNOLOGY

J u n e 1987

Acknowledgment
F i n a n c i a l s u p p o r t p r o v i d e d by the National S c i e n c e F o u n d a t i o n u n d e r grant No. CBT-8518479 is gratefully appreciated. M a n u s c r i p t s u b m i t t e d April 3, 1986; r e v i s e d man u script received Dec. 10, 1986. REFERENCES 1. A. R. Despic, and K. I. Popov, in " M o d e r n Aspects of Electrochemistry," No. 7, Chap. 4, B. E. Conway and J. O'M Bockris, Editors, P l e n u m Press, N e w York (1972). 2. G. Wranglen, Electrochim. Acta, 2, 130 (1960). 3. J. L. Barton, and J. O'M Bockris, Proc. R. Soc. London, Ser. A, 268, 485 (1962). 4. J. W. Diggle, A. R. Despic, and J. O'M Bockris, This Journal, 116, 1503 (1969). 5. A. R. Despic and M. M. Purenovic, Solid Solution, 121, 3, 329 (1974). 6. J. H. Shyu, M. S. Thesis, Case Western Reserve University (1980).

7. J. H. Shyu, Ph.D. Thesis, Case Western Reserve University (1982). 8. U. Landau, and J. H. Shyu, Report EM-2937, Electric Power Research Institute, Palo Alto, CA (1983). 9. R. Aogaki, K. Kitazawa, Y. Kose, and K. Fueki, Electrochim. Acta, 25, 965 (1980). 10. R. Aogaki, and T. Makino, ibid, 26, 1509 (1981). 11. Y. Oren, and U. Landau, ibid., 27, 739 (1982). 12. K. E. Yee, and J. Jorne, ED A Monthly Report, Task No. 12240 (1982). 13. S. Tajima and M. Ogata, Comite International de T h e r m o d y n a m i q u e et de Cinetique Electrochimiques Meeting, Extended Abstracts, p. 170 (1968). 14. S. Tajima, and M. Ogata, Electrochim. Acta, 13, 1845 (1968). 15. Y-J. Lii and J. Jorne, In preparation (1987). 16. Y-J. Lii, M. S. Thesis, University of Rochester, (1985). 17. K. E. Yee, Ph.D. Dissertation, Wayne State University, Detroit, MI (1986). 18. J. T. Kim, and J. Jorne, This Journal, 127, 8 (1980). 19. D. Rajhenbah, J. Faltemier, and C. W. Tobias, LBL15338, Lawrence Berkeley Laboratory, University of California (1983). 20. J. Jo r n e and E. Roayaie, This Journal, 133, 696 (1986).

A Mathematical Model for the Electrolytic Codeposition of Particles with a Metallic Matrix
J. P. Celis, J. R. Roos,* and C. Buelens
Department of Metallurgy and Materials Engineering, Katholieke Universiteit Leuven, de Croylaan 2, 3030 Heverlee, Belgium
ABSTRACT Over the last decade the general knowledge of the electrolytic codeposition of inert particles with metals has increased markedly, and a few models have been proposed. In this paper a new model that overcomes several of the shortcomings of the previously proposed models is developed starting from a statistical approach of the incorporation of particles. The validity of the new model is shown for two experimental codeposition systems, namely, Cu-A1203 from acidic sulfate baths and Au-Al~O3 from additive-free potassium cyanide baths. s o r p t i o n and c o d e p o s i t i o n b e h a v i o r i m p r o v e d drastically. As more and more practical data c o n c e r n i n g the effect of e l e c t r o l y s i s p a r a m e t e r s on the c o d e p o s i t i o n of inert particles with metals were gathered, a few attempts were m a d e to cast the e x p e r i m e n t a l data into models. Saifullin et al. (11) p r e s e n t e d a f o r m u l a to c a l c u l a t e t h e c o m p o s i tion of c o m p o s i t e coatings, m a k i n g a b s t r a c t i o n of any m e c h a n i s m in 1968. Bazzard et al. (12) proposed a mathem a t i c a l e x p r e s s i o n of the e l e c t r o l y t i c c o d e p o s i t i o n of solid c o n d u c t i n g particles with metals. T h e y o b t a i n e d for the case of the incorporation of one particle during a deposition time, t, the following equation 4 ~ - ~r3pn X, = 4 ~ - ~r:~pp + 4 ~r2item [2]

In t h e early days of c o m p o s i t e p la ti n g m o s t a t t e n t i o n was directed toward practical problems; few efforts were m a d e to elucidate the m e c h a n i s m of codeposition. Three possible m e c h a n i s m s were put forward, namely: electrop h o r e s i s p r o p o s e d by Whithers in 1962 (1), m e c h a n i c a l e n t r a p m e n t suggested by Martin in 1964 (2), and adsorption of particles on the c a t h o d e m e n t i o n e d by B r a n d e s (3) in 1967. Various investigators (4, 5) m e a s u r e d the zetap o t e n t i a l in dilute solutions. S i n c e in e l e c t r o l y t i c cod e p o s i t i o n s o l u t i o n s of high ionic s t r e n g t h usually are used, e x t r a p o l a t i o n from dilute solutions gives no reliable e v i d e n c e of p o s s i b l e e l e c t r o p h o r e t i c effects. Based on a mass t r a n s p o r t analysis t o w a r d r o t a t i n g disk electrodes, it was c a l c u l a t e d by Van C a m p (6) that particles will not reach the surface of a rotating electrode by inertial forces alone as long as 0.88ppo~d2v i < 3/4 [1]

w h e r e p, = specific w e i g h t of particles, d = d i a m e t e r of particles, ~o = rotation speed of the electrode, and v = kine m a t i c viscosity. C o n c e r n i n g a p o s s i b l e a d s o r p t i o n effect of particles onto the c a t h o d e by Van der Waals attractive forces, To m a s z e w s k i (7) was the first to point out the effect of m o n o v a l e n t cations on the codeposition process, e.g., t h a l l i u m ions drastically p r o m o t e the a m o u n t of c o d e p o s i t e d particles from c o p p e r sulfate p lat i n g baths, as was c o n f i r m e d later by d i f f e r e n t r e s e a r c h e r s (8-10). In this respect Foster et al. (10) reported a very low degree of adsorption of copper ions on alumina particles, w h i c h was s u p p o s e d to be a s s o c i a t e d with th e r a t h e r poor degree of codeposition. H o w e v e r by the addition of te tra e t h y l e n e p e n t a m i n e and e s p e c i a l l y Tl+-ions, ad*Electrochemical Society Active Member.

w h e r e Xp = w e i g h t p e r c e n t e m b e d d e d s e c o n d p ha s e particles, em = e l e c t r o c h e m i c a l e q u i v a l e n t of the metal, Pm= density of the metal, p, = density of the particle, and r = radius of the particle. This f o r m u l a has n e v e r b e e n c o n s i d e r e d as a tool to calculate and predict the composition of the co m p o si t e coatings since it does not take into a c c o u n t the i m p o r t a n t effects of pH, t e m p e r a t u r e , and bath constituents. An i m p o r t a n t step forwards was the m a t h e m a t i c a l m o d e l d e r i v e d by G u g l i e l m i in 1972 (13). B a s e d on a striking similarity of the curves relating the v o l u m e percent of co d ep o si t ed particles (v/o) to the v o l u m e p er c e nt of p ar t i cl es s u s p e n d e d in t h e p l at i n g bath (Cv) with the w e l l - k n o w n adsorption isotherm (Fig. 1), he postulated a m e c h a n i s m based on two successive adsorption steps. A

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Vol. 134, No. 6

MATHEMATICAL 1 r f r

MODEL

1403 [5]

8
0

h = h*(qhE + Li 2 - ab)

6
/.
~ ~ o o ~ o ~

E 2
o >

f//
//

/~/o ~ u

~ 2 A/dm 2 u 5 A/din 2 o 10 A/dm2

0./4 05 0.8 1:0

Becau se of the c o m p l e x interrelationship b e t w e e n some of t h e s e factors, only a l i m i t e d a m o u n t of q u a n t i t a t i v e work was done to prove the validity of e x p r e s s i o n [4]. Alt h o u g h t h e c a l c u l a t i o n or e s t i m a t i o n of sev er al p ar a me ters incorporated in formulas [3] and [5] is quite impossible, i m p o r t a n t benefits of G u g l i e l m i ' s and F o s t e r ' s m o d e l s lie in t h ei r c o n t r i b u t i o n to a b e t t e r u n d e r s t a n d ing of the m e c h a n i s m of codeposition. The m a t h e m a t i c a l m o d e l p r o p o s e d in this p a p e r (21) c o n t a i n s m e a s u r a b l e parameters so that prediction of the a m o u n t of codeposited particles for a given system now b e c o m e s feasible. D e s c r i p t i o n of the M o d e l The p r o p o s e d m e c h a n i s m of electrolytic c o d e p o s i t i o n of inert particles with metals is based on two f u n d ame ntal postulates: 1. An adsorbed layer of ionic species is created around the i n er t particles at the t i m e the particles are a d d e d to the plating s o l u t i o n or d u r i n g the p r e t r e a t m e n t of t h e s e particles in ionic solutions. 2. T h e r e d u c t i o n of s o m e of t h e s e a d s o r b e d ionic species is r e q u i r e d for t h e i n c o r p o r a t i o n of particles in t he metallic matrix. On its way from the bulk of the solution to the site of i n c o r p o r a t i o n at t h e active c a t h o d e surface t h e ine r t particle has to proceed t h r o u g h five stages (see Fig. 2): (i) adsorption of ionic species u p o n the particle surface; (ii) m o v e m e n t of the particle by forced c o n v e c t i n n t o w a r d s t h e h y d r o d y n a m i c b o u n d a r y layer (8,,) at t h e c a t h o d e ; (iii) d i f f u si o n of the particle t h r o u g h the d i f f u si o n double layer (8); (iv) a d s o r p t i o n of the particle, still with its a d s o r b e d ionic cloud, at the c a t h o d e surface; (v) reduction of some adsorbed ionic species by w h i ch the particle b e c o m e s i r r e v e r s i b l y i n c o r p o r a t e d in the m e t a l matrix. F o r t h e c o n s t r u c t i o n of t h e m o d e l it is a s s u m e d t h a t steady-state c o n d i t i o n s exist, so that n e i t h e r concentration, pressure, temperature, nor overpotential variations occur during the process, that the cathode surface is uniformly accessible for the plating solution and for the inert particles, and finally that a h o m o g e n e o u s suspension of particles in the plating solution is maintained. We can then focus our attention on what is h a p p e n i n g in the diffusion layer. At the diffusion layer the ions are m o v i n g towards the cathode by diffusion and simultaneously take along inert p ar t i cl es onto w h i c h a n u m b e r of ions are ad so r be d. Once at t h e e l e c t r o d e surface, ions are r e d u c e d to m e e t t h e d e m a n d s of t h e r e d u c t i o n p r o c e s s at the a p p l i e d c a t h o d i c o v e r p o t e n t i a l . What is t h e n h a p p e n i n g to t he

0.2

Vat% TiO 2 in s u s p e n s i o n
Fig. 1. Volume percent of codeposited particles vs. amount of particles suspended in the plating bath for a Ni-Ti02 system (13). l oos e a d s o r p t i o n (a), w h i c h has an e s s e n t i a l l y p h y s i c a l character, r es u l t s in a rather high d e g r e e of c o v e r a g e of t he c a t h o d e by particles. A s u b s e q u e n t strong adsorption (O) wh i ch is t h o u g h t to be field assisted and therefore e l e c t r o c h e m i c a l in nature, p e r m i t s the e n t r a p m e n t of particles in the growing metal layer. The formula so ded u c e d is

Cv v/~

__.Mi"B/A i._B/A) ( = nFpmv,, ~

)
+ C,. [3]

w he re F = Faraday constant; n = v a l e n c e of the electrod e p o s i t e d metal; k* = L a n g m u i r i s o t h e r m c o n s t an t , largely d e t e r m i n e d by the i n t e n s i t y of i n t e r a c t i o n bet w e e n p art i cl es and c a t h o d e ; M = a t o m i c w e i g h t of the e l e c t r o d e p o s i t e d metal; i,, = e x c h a n g e c u r r e n t density; pm= d e n s i t y of e l e c t r o d e p o s i t e d metal; and v,,, A, B = c o n s t a n t s . T h e v a l i d i t y of this m o d e l has b e e n verified for different codeposition systems like SiC and TiO2 with nickel from sulfamate baths (13), a- and T-A120:~with coppe r f r o m acidic c o p p e r sulfate baths with and w i t h o u t the addition of thallium ions (14), A1~O3 with nickel from Watts-type e l e c t r o l y t e (15), and TiO,., with c o p p e r from acidic c o p p e r sulfate baths (16). This s u b s t a n t i a t i o n of G u g l i e l m i ' s m o d e l c o m i n g from s e v e r a l i n v e s t i g a t o r s proves the s o u n d n es s and the significance of this mathematical t r e a t m e n t of electrolytic codeposition. However, s o m e o b j e c t i o n s ar r iv e d at by critically e x a m i n i n g t h e d e r i v a t i o n and f r o m i n e x p l i c a b l e e x p e r i m e n t a l results from literature question the generality of the model. By c o n s i d e r i n g the two parameters i and C as solely process c o n t r o l l i n g , o t h er i m p o r t a n t p r o c e s s p a r a m e t e r s are o v e r l o o k e d as h y d r o d y n a m i c s (17), effect of size type and p r e t r e a t m e n t of particles (8, 14), effect of bath c o n st i t u ents (18), and electrolysis conditions as pH (19) and bath t e m p e r a t u r e . G u g l i e l m i ' s m o d e l does not allow prediction of w h i c h way t h o s e p a r a m e t e r s will affect the electrolytic codeposition. F o s t e r and K a r i a p p e r (20), in 1974, p r o p o s e d a m a t h e m a t i c a l e x p r e s s i o n that c o u l d d e s c r i b e the effect of hyd r o d y n a m i c s . T h e y a s s o c i a t e d the rate of c o d e p o s i t i o n arbitrarily with the following e x p r e s s i o n

E L ECTRODE

~.#~,//~/////~//~,////.//J//~///'//.#~

:: epo :i::::iiiill ili:i:.:iii::i

: :. ,. . :::::::::::::::::::::::::::::

!
14

i:::ii!:i
:.:: :::::

:
:1 :::::::

::::
::::{ , ;:~:; :

: ::::: ::: ::::::::::::::::::::::::::::::

adsorption+

5 diffusion layer

.~@~.. ls
diffusion

reduction

dVp dt

N*hC,. 1 + hC,.

[4]

60 h ydrodynomic boundary layer

12 convection

w h e r e N* = n u m b e r of collisions of particles suitable for c o d e p o s i t i o n per s e c o n d and Vp -~ v o l u m e f r a c t i o n of particles in the deposit. The p a r a m e t e r h is further associated with the adsorbed charge density (q) on a particle, the p o t e n t i a l field at th e c a t h o d e (hE), the rate (i) at w hi ch the metal is deposited, the bond strength (L) of the metal/particle interface per surface area, the shape, size, and density of the particles (a), and finally the rate of agitation (b), according to Eq. [5], in which h* is a constant

7 bulk of the solution 9

formation of ionic cloud

Fig. 2. The five stages in the codeposition of a particle

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1404

J. Electrochem. Soc.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY

June 1987

p a r t i c l e s w h i c h are p o p u l a t i n g t h e c a t h o d e s u r f a c e b u t
a r e still s c r e e n e d o f f b y t h e i r i o n i c c l o u d ? H e r e t h e pri-

m a r y h y p o t h e s i s o f t h e m o d e l is i n v o l v e d : " A p a r t i c l e will o n l y b e i n c o r p o r a t e d w h e n a c e r t a i n a m o u n t k o u t o f K - a d s o r b e d ionic species, d e p e n d i n g on the c o m b i n a t i o n of plating solution characteristics and particle characteri s t i c s , is r e d u c e d . " A s a c o n s e q u e n c e o f t h i s h y p o t h e s i s still a n o t h e r h y p o t h e s i s s h o u l d b e a d d e d : " N o d i s t i n c t i o n is m a d e b e t w e e n f r e e a n d a d s o r b e d i o n i c s p e c i e s a n d b o t h are c o n s i d e r e d e q u a l w i t h r e s p e c t to t r a n s p o r t and reduction processes." The quantitative d e s c r i p t i o n of the i n c o r p o r a t i o n of an inert particle into a growing metallic matrix can thus be d e r i v e d f r o m a s t a t i s t i c a l a p p r o a c h in w h i c h t h e coeffic i e n t P r e p r e s e n t s t h e p r o b a b i l i t y for a p a r t i c l e to bec o m e i n c o r p o r a t e d a n d N,, t h e n u m b e r o f p a r t i c l e s c r o s s i n g t h e d i f f u s i o n l a y e r at t h e w o r k i n g e l e c t r o d e p e r u n i t o f t i m e a n d s u r f a c e area. T h e p r i m a r y h y p o t h e s i s f o r m u l a t e d a b o v e can n o w b e t r a n s l a t e d i n t o a n e x p r e s s i o n for AWp = w e i g h t i n c r e a s e p e r u n i t o f t i m e a n d s u r f a c e a r e a d u e to p a r t i c l e i n c o r p o r a t i o n AW,=W,.Np.P
where

w i t h C~,,n = b u l k c o n c e n t r a t i o n o f m e t a l i o n s , C,, = c o n c e n t r a t i o n o f m e t a l i o n s at t h e w o r k i n g e l e c t r o d e s u r f a c e , a n d 8 = t h e d i f f u s i o n layer t h i c k n e s s . The first t e r m of t h e d e n o m i n a t o r is a n a p p r o x i m a t i o n o f t h e m e a n c o n c e n t r a t i o n in t h e d o u b l e layer, a n d t h e s e c o n d t e r m repr e s e n t s t h e m o l e s e n t e r i n g t h e d i f f u s i o n l a y e r d u e to i. A c c o r d i n g to t h e t h e o r y o f L e v i e h t h e d i f f u s i o n l a y e r t h i c k n e s s 8 is g i v e n b y 5 = 1.61 Di,m1/3. 1.'l/'i" 03-1/2 [12]

w i t h D~on = d i f f u s i o n c o e f f i c i e n t of t h e ion, v = t h e v i s c o s ity o f t h e s o l u t i o n , a n d oa = r o t a t i o n s p e e d o f a r o t a t i n g working electrode. From the equality between diffusion flux a n d r e d u c t i o n flux, it c a n b e d e r i v e d t h a t

-D,,,,,(C,,,,, - C,,)
8 so t h a t E q . [11] c a n b e r e w r i t t e n

as

i nF

[131

Pi =

[6]

i8 2 nFC~,,. + - - +

[14]
i

Wp = w e i g h t o f o n e p a r t i c l e , N , h a v i n g t h e d i m e n s i o n o f m -2 9 s -1. A s s u m i n g t h e p a r t i c l e s are all s p h e r i c a l , t h e w e i g h t o f o n e p a r t i c l e is g i v e n b y 4~rr a W,, = - 9 p,, 3 [7]

2D~on

w i t h p, = d e n s i t y o f t h e p a r t i c l e a n d r = r a d i u s o f t h e particle. The weight increase per unit of time and surface a r e a d u e to p u r e m e t a l d e p o s i t i o n (hWm) c a n b e d e r i v e d f r o m F a r a d a y ' s law a s s u m i n g a 100% c u r r e n t e f f i c i e n c y 5Wm Mi

nF

[8]

By inserting Eq. [14] in Eq. [10] it is now possible to calculate the probability for the incorporation of one particle P~wK.,), vs. current density, for different values of k and K with given values ofS, D,,,n, and C. Figure 3 shows this probability for K = i000 and Fig. 4 for K = 315. Some general features of this P~k/K.i~function are: (i) a higher K demands a higher current density for an equal probability, (ii) the higher K, the smaller the probability for the incorporation of one particle at a given current density. In order to take into account hydrodynamic effects, the probability for the incorporation of one particle can hence be written as
P = H . P,wK.~

[15]

with M = molecular w e i g h t of the e l e m e n t deposited, n = n u m b e r o f e l e c t r o n s p a r t i c i p a t i n g in t h e r e d u c t i o n react i o n M n+ + h e - --~ M, F = F a r a d a y c o n s t a n t , a n d i .= curr e n t d e n s i t y . T h e w e i g h t p e r c e n t (w/o) e m b e d d e d p a r t i c l e s in a c o m p o s i t e c o a t i n g c a n g e n e r a l l y b e e x p r e s s e d as AW,, w/o particles e m b e d d e d 100
A W m 4- AWp Wp " N p " P - -

w h e r e H = 1 u n d e r l a m i n a r flow ( w h e r e 8 is d e f i n e d b y L e v i c h ' s law). H = 0 u n d e r h i g h t u r b u l e n t flow w h e r e t h e particles collide frequently and can hardly enter the very t h i n d i f f u s i o n layer. E x p e r i m e n t a l e v i d e n c e s u p p o r t i n g this h y p o t h e s i s has already b e e n s h o w n b a s e d on rotati n g d i s k e x p e r i m e n t s (22). 0 < H < 1 in t h e t r a n s i t i o n a n d early t u r b u l e n t regimes.
C a l c u l a t i o n o f c o e f f i c i e n t N , , . - - T h e n e x t p a r a m e t e r in f o r m u l a [7] to b e d e t e r m i n e d is N,,, t h e n u m b e r o f p a r t i c l e s c r o s s i n g t h e d i f f u s i o n l a y e r at t h e w o r k i n g elect r o d e p e r u n i t o f t i m e a n d s u r f a c e area. I n a n a l o g y w i t h t h e c a l c u l a t i o n w h e r e t h e p r o b a b i l i t y to i n c o r p o r a t e o n e p a r t i c l e (P) w a s r e l a t e d to t h e p r o b a b i l i t y to r e d u c e o n e i o n (P0 (cf. f o r m u l a [10]), Np is h e r e a s s o c i a t e d w i t h t h e n u m b e r o f i o n s b e i n g r e d u c e d (N,,,,,)

Mi
nF

,100

[9]

+ Wp. N,,. P

Calculation of the coefficient P . - - L e t us c o n s i d e r the c a s e w h e r e a c o a t i n g is d e p o s i t e d at a c u r r e n t d e n s i t y i. I f o n e c o n s i d e r s t h a t t h e p r o b a b i l i t y f o r o n e i o n to b e red u c e d (P0 at c u r r e n t d e n s i t y i is available, t h e n t h e p r o b a b i l i t y for t h e i n c o r p o r a t i o n o f o n e p a r t i c l e b a s e d o n t h e r e d u c t i o n o f k - i o n s o u t o f K - i o n s [P(wK.~] at c u r r e n t d e n sity i c a n b e c a l c u l a t e d f r o m a b i n o m i a l d i s t r i b u t i o n

P,~Ka, =

4;

2.~
z=k

C~K[1- pi]K-~pi~

[10]

T h e c a l c u l a t i o n o f t h e p r o b a b i l i t y for o n e i o n to b e red u c e d (P0 is s i m p l i f i e d b y t h e c o n s i d e r a t i o n t h a t n o dist i n c t i o n h a s to b e m a d e b e t w e e n f r e e a n d a d s o r b e d i o n s so t h a t b o t h c a n b e t r e a t e d e q u a l w i t h r e s p e c t to t r a n s port and reduction processes. The number of moles w h i c h are r e d u c e d p e r u n i t o f s u r f a c e area a n d p e r u n i t o f t i m e is g i v e n b y i / n F . T h e p r o b a b i l i t y t h a t a n ion p r e s e n t in t h e d i f f u s i o n l a y e r will b e r e d u c e d , is t h e r a t i o o f t h e p r e v i o u s e x p r e s s i o n to t h e n u m b e r o f m o l e s p r e s e n t i n the diffusion layer i nF

0.5-

0 " 0 5 Current density

k=500 10 {Afdm 2)
vs.

p, =

Ci{,n

@ CI,

8+--

[11]

nF

Fig. 3. Probability for the incorporation of one particle density for K = 1000.

current

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Vol. 134, N o . 6
N,, = Nmn"
C*lJ

MATHEMATICAL [16]

MODEL

1405

w i t h N,, = n u m b e r o f p a r t i c l e s c r o s s i n g t h e d i f f u s i o n l a y e r p e r s e c o n d a n d p e r u n i t of s u r f a c e area, N,,n = n u m ber of ions crossing the diffusion layer per second and p e r u n i t o f s u r f a c e area, C% = n u m b e r of p a r t i c l e s in t h e b u l k o f t h e s o l u t i o n , C*,,n = n u m b e r o f i o n s in t h e b u l k of t h e s o l u t i o n . C a l c u l a t i o n of C*p a n d C*~,,,~ c a n b e d o n e b y c o n v e r t i n g , r e s p e c t i v e l y , m a s s c o n c e n t r a t i o n s of p a r t i c l e s a n d i o n s i n t o n u m b e r of p a r t i c l e s a n d i o n s a c c o r d i n g to t h e f o l l o w i n g e q u a t i o n s
COp -

- osl

/ k=31o

Cp W,, Ci.nNA

o
r~

~
Current 5 density 10 (A/dm 2)
vs.

C*io n -

M i . NA nF

N,, n -

Fig. 4. Probability for the incorporation of one particle density for K = 315.

current

w i t h Cp = c o n c e n t r a t i o n o f p a r t i c l e s i n p l a t i n g b a t h a n d NA = A v o g a d r o ' s n u m b e r . E q u a t i o n [16] is v a l i d as l o n g as p a r t i c l e s a n d i o n s m o v e at t h e s a m e rate. T h i s is o n l y t h e c a s e w h e n t h e rea c t i o n is u n d e r c h a r g e - t r a n s f e r o v e r v o l t a g e c o n t r o l , i.e., w h e n t h e r e d u c t i o n o f i o n s , e i t h e r free or a d s o r b e d , is t h e r a t e c o n t r o l l i n g s t e p w h i l e d i f f u s i o n is f a s t e n o u g h to p r o v i d e t h e i o n s for r e d u c t i o n . I n t h e c o n c e n t r a t i o n overvoltage region the transport step, which takes place by diffusion in the diffusion layer, dominates the reaction rate. Since the particles with their ionic cloud diffuse much slower than the free ions, and since this effect is more pronounced at higher current densities, the relative diffusion of the particles can be written as

where it,.= transition current density from charge transfer to concentration overvoltage control and c~ = measure of interaction between free and adsorbed ions due to current density effects, a is equal to zero for a reduction process under charge transfer overvoltage control. For a reduction process which is under mass transfer eontro] c~ is not equal to zero. By combination of formula [9], with [7], [15], and [17] one can now derive the final expression for the weight percent embedded spherical particles as a function of current density w/o emb. spherical part. = 4~rr:'p, 9 N~,,n " C * ' ~ ' ( ~ ) ~ ' H ' P , k / K , }

C*hm

100

[18]

- -

nF

+ 4~r:~p,,N~,,,.

C%,n

H . P~k/~ ,,

"

O n e o f t h e m a i n p a r a m e t e r s o f t h e m o d e l is itT, i.e., t h e c u r r e n t d e n s i t y at w h i c h t h e r e d u c t i o n r e a c t i o n c h a n g e s f r o m c h a r g e - t r a n s f e r to m a s s t r a n s p o r t c o n t r o l . I t d e t e r m i n e s t h e p o s i t i o n of t h e m a x i m u m i n t h e c u r v e of N,, vs. i and indirectly the value of the maximum codeposition level. H e n c e a n e x t r e m e l y a c c u r a t e m e a s u r e m e n t or calc u l a t i o n o f t h e v a l u e of itr is n e c e s s a r y for t h e p r e d i c t i o n of any codeposition curve. Any shift of the polarization c u r v e d u e to t h e a d d i t i o n o f p a r t i c l e s i n t h e s o l u t i o n m u s t t h u s b e d e t e r m i n e d s i n c e it will i n f l u e n c e itr. W i t h i n c r e a s i n g b a t h l o a d of p a r t i c l e s , itr will c h a n g e a n d c o n sequently the location of the maximum of the curve N, vs. i will c h a n g e . The formulation of the present model shows that the process depends on many variables of which the most i m p o r t a n t are: (i) t h e c u r r e n t d e n s i t y or o v e r p o t e n t i a l w h i c h i n f l u e n c e s all t h e t e r m s i n f o r m u l a [18] e x c e p t t h o s e r e l a t e d to t h e p a r t i c l e : (ii) t h e a d s o r b e d l a y e r o n

the particle which determines the probability for codeposition through the ratio k/K, the position of the maximum on the current-axis, and the factor Np in the concentration overvoltage zone; (iii) the particle itself with its proper weight and its amount in suspension; (iv) the metal ions to be reduced which determine where the codeposition goes through a maximum and the factor N,,; (v) hydrodynamic conditions which influence toa great extent Np and the probability for codeposition. At this stage of the discussion, one has to give some attention to the applicability of the present model. Considering the electrolytic codeposition of particles, one has to differentiate between the codeposition of electrical nonconducting particles and conducting particles. Conducting particles are generally codeposited to a much larger weight percent than nonconducting particles, and they also tend to cause dendritic outgrowth of the metallic matrix. Looking back to the present model, one could object that the specific electrical conductivity of the particles is not included as a parameter. Nevertheless the effect of this electrical conductivity is indirectly reflected by the k value selected for the calculation of the c o e f f i c i e n t P,k/K.,- I n d e e d , i n t h e c a s e o f c o n d u c t i n g p a r t i c l e s , t h e n u m b e r o f a d s o r b e d i o n s to b e r e d u c e d o u t o f K a d s o r b e d i o n s n e c e s s a r y to o b t a i n a c o d e p o s i t i o n , will be smaller than in the case of nonconducting part i c l e s b e c a u s e of t h e p o l a r i z a t i o n of c o n d u c t i n g p a r t i c l e s . T h i s m e a n s t h a t for all o t h e r p a r a m e t e r s b e i n g c o n s t a n t , a h i g h e r p r o b a b i l i t y o f c o d e p o s i t i o n is e x p e c t e d for c o n ducting particles. The outgrowth of the metallic matrix is s t r i c t l y r e l a t e d to t h e p o l a r i z a t i o n of t h e s e c o n d u c t i n g p a r t i c l e s w h i c h a l l o w s t h e f o r m a t i o n of m e t a l l i c n u c l e i over the outward surface of the particles once these are in direct contact with the cathode. F i n a l l y , o n e c a n w o n d e r w h y a c r i t i c a l w a i t i n g t i m e of p a r t i c l e s a t t h e c a t h o d e is n o t c o n s i d e r e d e x p l i c i t l y in t h e p r e s e n t m o d e l . I n d e e d s o m e r e s e a r c h e r s (10) h a v e tried, but without success, to include a critical time in their model. In the present model a possible critical time is i n c o r p o r a t e d i n t h e c a l c u l a t i o n o f t h e p r o b a b i l i t y coeff i c i e n t P(k/K.~,. C o n s i d e r i n g t h e c o l l i s i o n o f i n c o m i n g particles with partly embedded particles, one can say that in the case of nonconducting particles a codeposit i o n a t t h e t o p of a p a r t l y e m b e d d e d p a r t i c l e will n o t occ u r s i n c e t h e r e d u c t i o n of k a d s o r b e d i o n s c a n n o t o c c u r . I n t h e c a s e of c o n d u c t i n g p a r t i c l e s t h e p o l a r i z a t i o n o f t h e p a r t i c l e s c a n i n d e e d a l l o w t h e c o d e p o s i t i o n of a n i n c o m ing particle at the top of a partly embedded particle. In analogy with the preceding discussion this will further i n c r e a s e t h e p r o b a b i l i t y o f c o d e p o s i t i o n t h r o u g h t h e lowe r i n g o f t h e v a l u e k i n P~k/K.i,

Application of the Present Model to Real Codeposition Data

The codeposition of A120~-particles with copper from a c i d i c s u l f a t e p l a t i n g b a t h s h a s b e e n e x t e n s i v e l y re-

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1406

J. Electrochem.

Soc.: ELECTROCHEMICAL

SCIENCE

AND TECHNOLOGY

June

1987

Table I. Experimental conditions and relevant dato for Cu-AI20.~ codeposition using rotating disk electrodes Solution CuSO4 - 5H20 pH 0.3 C(.~2+ 30 g/liter = Mcu = 63.5 g/mol dc~2+ = 2.2A
n=2

O n c e k is k n o w n , t h e v a l u e o f a i n t h e c o n c e n t r a t i o n overvoltage region can be deduced from the experimental codeposition results. The model in the region of concentration overvoltage then becomes w/o e m b e d d e d A120.~ = 66.8 x (2/i) '~ x Pc~,.i~ [24]

Particles

~-Al2Oa

Adsorbed ions on particles

Reduction

Cu ++, H +
Cu~ --~ Cu +

v = 2 cSt D = 0.147 x 10-:' em'-'/s T = 20~ p,, = 3.7 g/cm :~ d,, = 0.05 ixm Ca,2,,:, = 20 g/liter Specific surface area 80 m~/g 0.2 mg Cu ++ on lg AI.,O:,
i,,. - 2 Aldm ~

reaction Flow regime

Laminar

i,,,,, - 10 AJdm z Rotation speed: 400 rpm 8 = 50 t~m

T h e o r e t i c a l a n d e x p e r i m e n t a l r e s u l t s a r e p l o t t e d in Fig. 6 a n d a r e f o u n d to fit well. B a s e d o n t h e s e v a l u e s o f ~ a n d k obtained on a rotating disk electrode under controlled m a s s t r a n s p o r t c o n d i t i o n s , d a t a p u b l i s h e d e a r l i e r for t h e c o d e p o s i t i o n of a l u m i n a w i t h c o p p e r o n a v e r t i c a l c a t h ode with vibrating perforated bottom plate providing the n e c e s s a r y a g i t a t i o n (14) c a n b e c h e c k e d . S i n c e a n i d e n t i c a l c o d e p o s i t i o n s y s t e m is c o n s i d e r e d , w h e r e o n l y t h e agitation rate varies, the model parameters do not need t o b e m o d i f i e d , e x c e p t H t h a t will d i f f e r f r o m u n i t y w h i l e itr d e r i v e d f r o m a p o l a r i z a t i o n m e a s u r e m e n t is t a k e n e q u a l to 1.65 A / d i n 2. W i t h H = 0.25 t h e m o d e l is t h e n expressed by w/oembeddedAl~O, = 0 . 1 6 7 ( ~ 1'~ 5 )~ x P ~ . . , [25]

p o r t e d i n l i t e r a t u r e (7, 8, 14, 23, 24). E x p e r i m e n t a l c o n d i t i o n s u s e d i n t h e p r e s e n t s t u d y a n d d a t a n e c e s s a r y for t h e c a l c u l a t i o n a r e s u m m a r i z e d i n T a b l e I. B a s e d o n these data the different parameters of the model can be calculated separately W, Mi
AWm -

4~rr =' 3

p, = 2.4 x 10 -~' k g

[19]

nF

- 0.33 x 10 -6 x i k g - m -~ . s -~

[20]

N,

= Nion '

C$ion

9.187

i i

10" m -2. s - ' i 45.3 + 6.4 i

[21]

Pi =

i82 C~,,,SnF + - - + 2D .... K

=

[22]

w i t h a = 0 for i < 1.65 A / d i n 2 a n d a = 6 for i > 1.65 A / d m 2. The comparison between experimental and theoretical d a t a is s h o w n i n Fig. 7. T h e d e v i a t i o n b e t w e e n t h e o r y a n d e x p e r i m e n t is p r o b a b l y d u e to t h e e x p e r i m e n t a l s e t u p , in w h i c h n o c o n s t a n t d o u b l e l a y e r t h i c k n e s s is obt a i n e d , a n d t h e f l u x o f i o n s a n d p a r t i c l e s is n o t u n i f o r m over the electrode surface. Notice the lower predicted a n d e x p e r i m e n t a l l y v e r i f i e d c o d e p o s i t i o n w h e n o n e goes f r o m a r o t a t i n g e l e c t r o d e s e t u p to a n o n r o t a t i n g v e r t i c a l electrode setup. A second codeposition system which was studied u s i n g r o t a t i n g e l e c t r o d e is t h e c o d e p o s i t i o n of a l u m i n a with gold from a potassium gold cyanide solution. Exp e r i m e n t a l c o n d i t i o n s a n d d a t a n e c e s s a r y for c a l c u l a t i o n a r e s u m m a r i z e d in T a b l e II. T w o d i f f e r e n t i,,. v a l u e s h a v e to b e u s e d s i n c e t w o t r a n s i t i o n s f r o m c h a r g e t r a n s f e r o v e r v o l t a g e c o n t r o l to c o n c e n t r a t i o n o v e r v o l t a g e c o n t r o l appear from potentiokin~tic polarization measurements (25). D e r i v e d d a t a a r e Wp = 2.4 x 10-'" k g [26] [27] [28]

740 i o n s / p a r t i c l e ,

H = 1

AWm = 2.04 x 10 -s x i k g . m -2- s -~ H = 1

P = H 9 P~k/K.i) = 1 " P(WK.i, p l o t t e d in Fig. 5, for d i f f e r e n t ratios of k/K. For the application of the model two parame-

t e r s h a v e still to b e d e t e r m i n e d , n a m e l y k a n d ~. A c c o r d i n g to t h e m o d e l it is a s s u m e d t h a t i n t h e c h a r g e - t r a n s f e r c o n t r o l r e g i o n a = 0. F r o m t h e c o m p a r i s o n b e t w e e n e x perimental and theoretical results k may be evaluated. T h e final f o r m u l a t i o n of t h e m o d e l in t h e c h a r g e - t r a n s f e r o v e r v o l t a g e r e g i o n is t h e n w/o e m b e d d e d A120:~ = 66.8 x P~r,,s,, [23]
"--, r J

E 1.5 [

/ A t ~

1 ex perimen~G[ jccl[

Q---t::I t h e o r e t

1.0

o.s/-

/ / /

/ /

0.5

'
0 , ,

~
0 5

I/X_. ,. ,
10
"~" 0 2 L 6

Current density (A/dm 2}

Fig. 5. Probability for the incorporation of one particle density for K = 740.
vs.

Current

density

{A/dm 2}

current

Fig. 6. Experimental and predicted results for Cu-AI20:~ codeposition on a rotating disk electrode.

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Vol. 134, No. 6

MATHEMATICAL

MODEL
' I 1 I I

1407

o
9

experiment
<[

2~

03

theory 20g/I y- AI203 0.2

I

ae ~, ~I \

e--* experiment ~--~ model ......sum(model)

_~22
1:9

20

-A1203 I

.s

I". I //
, I

/ Au_A[203
,

(3)

"~ 0,1
.E)

6
density

8
(A/dm 2)

10

E (D
.4-o

Current

Fig. 8. Experimental and theoretical codeposition curve for the AuAI203 codeposition system.
For the reduction of the second species
~ [32]

~ 2 Current

~ 4

' 5

w/o e m b e d d e d A12Oa = 1.94 x P,~7,.,) x

d e n s i t y (A/dm 2)

Fig. 7. Experimental and predicted results for Cu-AI~O:{ codeposition on o vertical cathode.

w i t h a = 0 f o r i < 4.25 A / d m ~ a n d c~ = 0.5 f o r i > 4.25 A / d m ~. E x p e r i m e n t a l a n d t h e o r e t i c a l e o d e p o s i t i o n c u r v e s for t h e Au-A120~ o n R D E are c o m p a r e d in Fig. 8.

Conclusions
N,= 1.65 x 101'3 x i x @ m - 2 . s -~ [29] A n e w m o d e l (21), b a s e d o n a s t a t i s t i c a l a p p r o a c h , h a s b e e n d e v e l o p e d for t h e e l e c t r o l y t i c c o d e p o s i t i o n o f i n e r t p a r t i c l e s w i t h m e t a l s . T h e b a s i c h y p o t h e s i s for t h e d e v e l o p m e n t o f t h e m o d e l is e x p r e s s e d as f o l l o w s : a p a r t i c l e w i l l o n l y b e i n c o r p o r a t e d w h e n a c e r t a i n a m o u n t o f ads o r b e d i o n s , d e p e n d i n g o n t h e c o d e p o s i t i o n s y s t e m itself, is r e d u c e d . T h i s is t r a n s l a t e d i n t o t h e e x p r e s s i o n w/o p a r t i c l e s e m b e d d e d = W~ 9N , . P AWm+Wp. Np.P 100

I n t h e a b s e n c e o f d a t a , t h e a m o u n t o f c o m p o n e n t s inv o l v e d i n t h e r e a c t i o n is a s s u m e d to b e p r o p o r t i o n a l to t h e c o n c e n t r a t i o n o f g o l d in s o l u t i o n Pi i 1.88 i + 2.12 [30]

P = Pck/K.~) p l o t t e d in Fig. 3 for K = 1000 a n d d i f f e r e n t values of k/K. F o r t h e p a r a m e t e r s o f t h e m o d e l , t h r e e p a r a m e t e r s still h a v e t o b e d e t e r m i n e d for t h e r e d u c t i o n o f t h e t w o s p e c i e s , n a m e l y , k, K, a n d a, w i t h a = 0 in c h a r g e - t r a n s f e r o v e r v o l t a g e r e g i o n . T h e b e s t fit o f t h e e x p e r i m e n t a l res u l t s is f o u n d b y i n s e r t i n g t h e f o l l o w i n g v a l u e s for t h e first s p e c i e s : k / K = 0.15 a n d K = 200. F o r t h e s e c o n d s p e cies, t h e b e s t fit is o b t a i n e d w i t h k / K = 0.15 a n d K = 500. T h e m o d e l is e x p r e s s e d as: F o r t h e r e d u c t i o n o f t h e first s p e c i e s

w/o e m b e d d e d AI~O.~ = 1.55 x P , ~ . ,

[31]

w i t h c~ = 0 f o r i < 0.35 A / d m ~ a n d c~ = 0.6 f o r i > 0.35 A / d m ~.

Table II. Experimental conditions and derived data for Au-AI203 codeposition using rotating disk electrodes
Solution KAu(CN)2 pH 4 CA~+= 10.3 g/liter MA, = 197 g/mol n=l dA,+ = 2.5A u = 0.867 cSt D = 0.98 x 10-~ cm2/s T = 40~ pp = 3.7 g/cma d, = 0.05 ~xm CA~2o3= 20 g/liter Au(CN)c, Au(CN) it~ = 0.35 A/dm 2 itr = 4.25 A/dm 2 Rotation speed: 600 rpm 8 = 43 I~m

w h e r e W, = w e i g h t o f o n e p a r t i c l e (kg), N,, = a m o u n t o f p a r t i c l e s c r o s s i n g t h e d i f f u s i o n l a y e r at t h e w o r k i n g elect r o d e p e r u n i t o f t i m e a n d s u r f a c e a r e a at c u r r e n t d e n s i t y i (s -1 m-2), P = p r o b a b i l i t y f o r t h e i n c o r p o r a t i o n o f o n e p a r t i c l e at a c u r r e n t d e n s i t y i, AWm = m a s s o f m e t a l mat r i x d e p o s i t e d p e r u n i t o f t i m e a n d s u r f a c e a r e a at c u r r e n t d e n s i t y i (kg m -2 s-~). The m o d e l was f o u n d to be valid for the electrolytic c o d e p o s i t i o n o f Cu-A12Oa f r o m a c i d i c s u l f a t e b a t h s a n d Au-A120:3, f r o m c y a n i d e b a t h s a n d t h e r e f o r e w e e x p e c t it to b e v a l i d for all o t h e r c o m p o s i t e p l a t i n g s y s t e m s . I f t h e n e c e s s a r y d a t a for t h e c a l c u l a t i o n o f t h e p r o b a b i l i t y coeff i c i e n t P are n o t available, t h e m o d e ] p a r a m e t e r s c a n b e d e t e r m i n e d b y c o m p a r i n g t h e o r y a n d e x p e r i m e n t . We b e l i e v e t h i s m o d e l will c o n t r i b u t e to a d e e p e r a n d m o r e complete insight into the mechanism of the electrolytic codeposition processes. M a n u s c r i p t s u b m i t t e d J u n e 27, 1986; r e v i s e d m a n u s c r i p t r e c e i v e d Dec. 17, 1986.

LIST
C~,,, C,,

OF SYMBOLS

Particles

y-A1203

Adsorbed ions o n particles

Reduction reaction Flow regime

Au complexes, H First species Second species Laminar

b u l k c o n c e n t r a t i o n o f m e t a l i o n s (mol m 3) c o n c e n t r a t i o n o f m e t a l i o n s at t h e w o r k i n g e l e c t r o d e s u r f a c e (mol m -3) Cp c o n c e n t r a t i o n o f p a r t i c l e s in p l a t i n g b a t h (kg m -:~) C*p n u m b e r o f p a r t i c l e s in t h e b u l k o f t h e s o l u t i o n (m 3) C*~o, n u m b e r o f i o n s in t h e b u l k o f t h e s o l u t i o n (m -~) Cv v o l u m e p e r c e n t o f p a r t i c l e s in t h e p l a t i n g b a t h (%) d d i a m e t e r o f p a r t i c l e s (m) D~,,, d i f f u s i o n c o e f f i c i e n t o f t h e i o n (m 2 - S - 1 ) em m e t a l e q u i v a l e n t (kg A ' s - ' ) E p o t e n t i a l g r a d i e n t (V) F F a r a d a y c o n s t a n t (96,500 A, s m o l 1) H coefficient of hydrodynamic effects (-) i c u r r e n t d e n s i t y (A 9 m -2)

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1408

J. E l e c t r o c h e m . Soc.: E L E C T R O C H E M I C A L

SCIENCE

AND TECHNOLOGY

J u n e 1987

e x c h a n g e c u r r e n t d e n s i t y ( A . m -2) t r a n s i t i o n c u r r e n t d e n s i t y f r o m c h a n g e - t r a n s f e r to c o n c e n t r a t i o n o v e r v o l t a g e c o n t r o l (A 9 m -2) k* Langmuir constant (-) K a m o u n t of ions a d s o r b e d on a p a r t i c l e ( - ) M a t o m i c or m o l a r m a s s (kg mo1-1) n v a l e n c e of e l e c t r o d e p o s i t e d m e t a l ( - ) Ni,,, n u m b e r of i o n s c r o s s i n g t h e d i f f u s i o n l a y e r p e r u n i t of t i m e a n d s u r f a c e area (s -1 - m 2) N, n u m b e r of particles c r o s s i n g t h e d i f f u s i o n layer at t h e w o r k i n g e l e c t r o d e per u n i t of t i m e a n d s u r f a c e area (s -1 m -2) N* n u m b e r o f c o l l i s i o n s o f p a r t i c l e s s u i t a b l e for cod e p o s i t i o n p e r u n i t of t i m e a n d s u r f a c e a r e a (s -1 m-2) N, A v o g a d r o ' s n u m b e r (6.022 9 102" kg 1) P1 p r o b a b i l i t y for t h e ion to be r e d u c e d ( - ) P p r o b a b i l i t y for a p a r t i c l e to b e c o m e i n c o r p o r a t e d (-) r r a d i u s of a p a r t i c l e (m) X, w e i g h t p e r c e n t of e m b e d d e d particles (%) W~, w e i g h t of one p a r t i c l e (kg) Wm w e i g h t i n c r e a s e of d e p o s i t e d m e t a l per u n i t of t i m e and s u r f a c e area m e a s u r e of i n t e r a c t i o n b e t w e e n free and a d s o r b e d " ions d u e to c u r r e n t d e n s i t y effects ( - ) 8 d i f f u s i o n layer t h i c k n e s s (m) ~,, h y d r o d y n a m i c b o u n d a r y layer t h i c k n e s s (ro) 0 strong adsorption coverage ( ) v k i n e m a t i c v i s c o s i t y (kg m -1 s - 9 Pm d e n s i t y of e l e c t r o d e p o s i t e d m e t a l (kg 9 m -:1) p, d e n s i t y of particles (kg m -:~) loose adsorption coverage (-) ~o r o t a t i o n s p e e d of t h e e l e c t r o d e (s -1) itr REFERENCES 1. J. C. Whithers, Prod. Fin., 8 (1962). 2. P . W . Martin and R. V. Williams, Proc. I n t e r f i n i s h '64, pp. 182-188, B r i t i s h I r o n and S t e e l R e s e a r c h Ass., L o n d o n (1964).

i,

3. E. A. B r a n d e s and D. G o l t h o r p e , Metallurgica, 195 (1967). 4. J. E. H o f f m a n and C. L. Mantell, Trans. Met. Soc. AIME, 236, 1015 (1966). 5. D. W. S n a i t h and P. D. Groves, Trans. Inst. Met. Finish., 51, 27 (1973). 6. M. Van Camp, E n g i n e e r i n g Thesis, KU. L e u v e n (1979). 7. T. W. Tomaszewski, L. L. Tomaszewski, and H. Brown, Plating, 56, 1234 (1969). 8. E. S. Chen, G. R. L a k s h m i n a r a y a n a n , and F. K. Sautter, Met. Trans., 2, (4), 937 (1971). 9. J. R. Roos, J. P. Cells, and J. A. Helsen, Trans. Inst. Met. Finish., 55, 113 (1977). 10. J. F o s t e r and A. M. J. Kariapper, ibid., 50, 207 (1972). 11. R. S. S a i f u l l i n and R. G. K h a l i l o v a , J. Appl. Chem. USSR, 43 (1970). 12. R. B a z z a r d and P. J. B o d e n , Trans. Inst. Met. Finish., 50, 63 (1972). 13. N. Guglielmi, This Journal, 119, 1009 (1972). 14. J. P. Cells and J. R. Roos, ibid., 124, 1508 (1977). 15. N. M a s u k o and K. M u s h i a k e , J. Met. Finish. Soc. Japan, 28, 534 (1977). 16. M. K. T o t l a n i and S. N. A t h a v a l e , J. Electrochem. Soc. India, 31, 119 (1982). 17. J. Z a h a v i and J. Hazan, Plating Surf. Finish., 70, 57 (1983). 18. T. Hayashi, in Proc. Interfinish '76, A m s t e r d a m (1976). 19. F. K. Sautter, This Journal, l l 0 , 557 (1963). 20. A. M. J. K a r i a p p e r and J. Foster, Trans. Inst. Me~. Finish., 52, 87 (1974). 21. C. Buelens, Ph.D. Thesis, KU. L e u v e n (1984). 22. J. P. Cells, J. R. Roos, W. Van Vooren, and J. V a n h u m beeck, P a p e r K, pp. 1-10, Proc. 3rd A E S F P u l s e Plating S y m p o s i u m , Washington, DC (1986). 23. C. White and J. Foster, in Proc. A n n u a l T e c h n i c a l Conference IMF, T o r q u a y (1978). 24. J. E. H o f f m a n n and R. C. Ernst, I N C R A - P r o j e c t No. 31 (1964). 25. C. B u e l e n s , J. P. Cells, and J. R. Roos, J. Appl. Electrochem., 13, 541 (1983).

The Composition of Electrodeposited Zinc-Nickel Alloy Coatings

Mark F. Mathias** and Thomas W. Chapman*
Department of Chemical Engineering, University o f Wisconsin, Madison, Wisconsin 53706
ABSTRACT T h e c o m p o s i t i o n of z i n c - n i c k e l alloy films d e p o s i t e d on a r o t a t i n g d i s k e l e c t r o d e is a n a l y z e d in t e r m s o f a oned i m e n s i o n a l t r a n s p o r t - r e a c t i o n m o d e l . T h e m a s s - t r a n s f e r m o d e l i n c l u d e s t h e effects of m i g r a t i o n and e o m p l e x a t i o n of zinc by chloride. It is found that m i g r a t i o n in this system can e n h a n c e the interfacial c o n c e n t r a t i o n of nickel d e p o s i t i o n to levels e x c e e d i n g that in the bulk solution. A simple electrode kinetics m o d e l is postulated to d e s c r i b e the partial c u r r e n t d e n s i t y of each m e t a l c e d u c t i o n reaction in t e r m s of e l e c t r o d e potential, interfacial concentrations, and t e m p e r a t u r e . Kinetics p a r a m e t e r s a p p e a r i n g in the m o d e l are e s t i m a t e d f r o m e x p e r i m e n t a l d e p o s i t c o m p o s i t i o n data. The resulting m o d e l can predict alloy c o m p o s i t i o n o v e r a range of plating conditions, but electrode polarization is not p r e d i c t e d accurately. A m o r e c o m p l e t e kinetics model, d e s c r i b i n g zinc-nickel interactions, is needed. ties, of t h e i n d i v i d u a l m e t a l r e d u c t i o n r e a c t i o n s and t h a t t h e k i n e t i c s of t h e s e r e a c t i o n s are d e t e r m i n e d by t h e local i n t e r f a e i a l c o n d i t i o n s of s o l u t e c o n c e n t r a t i o n s , pot e n t i a l , t e m p e r a t u r e ; and s u r f a c e p r o p e r t i e s . W h i l e t h e e l e c t r o d e k i n e t i c s m a y be e x p r e s s e d in t e r m s of t h e s e interracial c o n d i t i o n s , the l a t t e r m u s t be r e l a t e d to b u l k sol u t i o n c o n d i t i o n s by m e a n s of a m a s s t r a n s f e r m o d e l . L a r g e - s c a l e a l l o y e l e c t r o d e p o s i t i o n is u s u a l l y d o n e at h i g h c u r r e n t d e n s i t i e s f r o m b a t h s in w h i c h t h e r e a c t i n g s p e c i e s are also m a j o r c o n s t i t u e n t s o f t h e s o l u t i o n . F o r e x a m p l e , a z i n c - n i c k e l alloy can be e l e c t r o d e p o s i t e d suec e s s f u l l y at 400 m A / c m ~ f r o m a b a t h c o n t a i n i n g m a i n l y n i c k e l and zinc salts (3). U n d e r t h e s e c o n d i t i o n s ionic mig r a t i o n is clearly an i m p o r t a n t m e c h a n i s m of m a s s transp o r t t h a t m u s t be i n c l u d e d in a c o m p l e t e analysis of t h e deposition process. Because migration effects depend s t r o n g l y on t h e c o n c e n t r a t i o n s a n d c h a r g e s of t h e spec i e s in t h e s o l u t i o n , t h e s p e c i a t i o n of t h e s o l u t e m e t a l ions m u s t also be c o n s i d e r e d . T h i s p a p e r c o n s i d e r s zincn i c k e l alloy d e p o s i t i o n on an R D E a n d relates a v e r a g e al-

A l l o y c o a t i n g s on b a s e m e t a l s u b s t r a t e s can p r o v i d e d e s i r a b l e s u r f a c e p r o p e r t i e s w i t h r e s p e c t to c o r r o s i o n protection, wear resistance, and electromagnetic phen o m e n a . F o r e x a m p l e , z i n c - n i c k e l c o a t i n g s on steel g i v e b e t t e r c o r r o s i o n p r o t e c t i o n t h a n do p u r e zinc films (1). I n m a n y cases, i n c l u d i n g z i n c - n i c k e L t h e a l l o y c o a t i n g can be f o r m e d by e l e c t r o d e p o s i t i o n (2). T h i s p a p e r c o n s i d e r s t h e q u e s t i o n of h o w b a t h c o m p o s i t i o n a n d o p e r a t i n g c o n d i t i o n s d e t e r m i n e e l e c t r o d e p o s i t e d alloy c o m p o s i tion. In p a r t i c u l a r , a m a s s t r a n s f e r m o d e l is d e v e l o p e d for z i n c - n i c k e l e h l o r i d e b a t h s t h a t p e r m i t s c o r r e l a t i o n of t h e c o m p o s i t i o n of t h e d e p o s i t on a r o t a t i n g d i s k elect r o d e (RDE) w i t h p l a t i n g c o n d i t i o n s in t e r m s of e l e c t r o d e k i n e t i c s p a r a m e t e r s . S u c h a c o r r e l a t i o n , b a s e d on interfacial c o n d i t i o n s , s h o u l d a p p l y to o t h e r e l e c t r o d e configurations. T h e p r e m i s e of this w o r k is t h a t a l l o y c o m p o s i t i o n is d e t e r m i n e d by t h e r e l a t i v e rates, or partial c u r r e n t densi* Electrochemical Society Active Member. ** Electrochemical Society Student Member.

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