Surface Technology, 16 (1982) 227 - 234

227

ELECTRODEPOSITED Cr-AI203 COMPOSITE COATINGS

RAJ NARAYAN and S. CHATTOPADHYAY*

Department of Metallurgical Engineering, Indian Institute of Technology, Kanpur 208016 (India)

(Received January 4, 1982)

Summary Electrodeposited Cr-A1203 composite coatings could be produced only when the A1203 particles were either coated with nickel or dry ground before mixing in the conventional hexavalent chromium plating bath. The nickel-coated AI20 3 particles were, however, unstable in the plating bath. Using dry ground A1203 powder it was shown that increasing the bath load of A1203 increased its content in the coating at all current densities. At all bath loads, maximum codeposition t o o k place at 35 A dm -2. When the bath temperature was increased above 40 C the A1203 content of the coating decreased. At 40 C the coating was very uneven and cracked. The microhardness of the composite coating increased with increasing A1203 content and it was always larger than that of the pure chromium coating. The twostep adsorption mechanism proposed by Guglielmi does not hold in this system. It is proposed that the mechanism of codeposition consists of three processes, i.e. adsorption, transportation by hydrodynamic and electrophoretic forces and entrapment in the chromium matrix.

1. Introduction Particles of materials such as borides, e.g. TiB2 [1] and ZrB 2 [2, 3], carbides, e.g. B4C [1, 4], BeC [1, 4 ] , CraC 2 [5] and TiC [1], sulphides, e.g. MoS2 [ 1 ] , oxides, e.g. SiO2 [5, 6] and ZrO2 [6], and graphite [7] have been codeposited with chromium. Very little work has been reported on the codeposition of A120 3 particles with chromium. Early attempts to codeposit A120 3 with chromium from conventional hexavalent and trivalent baths were unsuccessful [ 1, 8, 9]. Skominas et al. [6] reported that codeposition of A120 3 with chromium was possible. However, Addison and Kedward [5] reported that codeposition of A1203 was possible only from trivalent chromium baths. There was a severe limitation on the thickness and *Present address: Department of Metallurgical Engineering, University of British Columbia, Vancouver, Canada. 0376-4583/82/0000-0000/$02.75 Elsevier Sequoia/Printed in The Netherlands

228 uniformity of coatings produced from these baths. Young [1] showed that by the addition of T1NO3 to the hexavalent chromium bath, codeposition of A1203 was possible. However, Cr-A1203 composite coatings produced in this manner had poor wear resistance compared with ordinary hard chromium. The present investigation was undertaken to explore the possibility of electrodepositing Cr-A1203 composite coatings from conventional hexavalent chromium plating baths without any addition agents. 2. Experimental details A1203 powder particles were added to a chromium plating bath of the following composition: 250 (g chromic acid) 1-1; 2.5 (g sulphuric acid) 1-1 . The conditions were as follows: temperature, 50 C; current density, 50 A d m - 2 ; plating time, 10 h unless otherwise stated. The solution containing the A120 ~ powder was blended for a b o u t 3 4 h to ensure good wetting and uniform distribution of the powder particles in the bath. Water was added to make up for evaporation loss during plating. The A1203 content of the coating was determined gravimetrically by dissolving it in concentrated sulphuric acid (which was diluted to approximately 4:1 to prevent it from attacking the filter paper) containing a few drops of formaldehyde, filtering it through Whatman filter paper no. 40 and drying and reweighing it. The microhardness of the coating was measured on a Tukon microhardness tester by using a diamond pyramid indenter with an open angle of 136 at a load of 1 kgf. 3. Results Initially, attempts were made to codeposit as-received A1203 with chromium from a conventional hexavalent bath. However, variation in the particle size between 0.3 and 37/~m, in the A1203 content in the bath and in the current density did not produce any composite coatings. Foster and Kariapper [10] showed that the concentration of nickel ions in the bath affects the codeposition o f Ni-AlzOs composite coatings. Changing the CrOa concentration from 150 to 400 g 1-1 , however, did not produce any Cr-A120 a composite coatings. It has been claimed [ 3 ] t h a t codeposition of bath-insoluble particles occurs only after the plating bath has been preworked using d u m m y electrodes. Preworking the bath for 8, 16 and 24 h, however, did not produce any Cr-AlzO3 composite coatings. From the above experiments it became evident that codeposition of asreceived A12Oa with chromium from the conventional hexavalent chromium bath was n o t possible. The surface properties of A1203 had to be altered before it could be codeposited with chromium.

229

Young [1] showed that codeposition of diamond particles with chromium became possible when they were covered with a nickel coating. A120 a particles were, therefore, coated with nickel using an electroless nickel plating bath. It was observed that it was possible to codeposit nickelcoated Al203 with chromium. The a m o u n t of A1203 in the composite coating increased with increasing AI2O3 content in the bath (Fig. 1). The hardness of the composite coating increased with increasing A12O3 content (Fig. 2). The experiments were, however, discontinued because it was observed that nickel-coated AI203 particles were not stable in the chromium plating bath and it was not possible to codeposit these particles if they were left in the bath over long periods. This, therefore, could not be a viable commercial method. Electrophoretic studies on AI203 particles in different electrolytes in our laboratory showed that on dry grinding, A1203 powder particles attain a charge and tend to move towards the cathode when a potential is applied. A1203 powder that had been dry ground in a ball mill for 12 h was used in further experiments. The average particle size as determined by the Fisher subsieve sizer m e t h o d was found to be 1.7 pm. X-ray diffraction analysis showed that it was ~-A1203. This dry ground A1203, hereinafter referred to as A1203 powder, could be codeposited with chromium. Variation in the A1203 content in the plating bath showed that at 20 A dm -2 codeposition t o o k place only when the A1203 content in the bath was more than 60 g 1-1 ; b e y o n d this value its a m o u n t in the composite coating increased with increasing bath load of AI203. Similar behaviour was observed at higher current densities except that codeposition started at much lower bath loads (Fig. 3).

16

850
830

E ; lZ i
g

810 79o
77o

u 8
.E
<

i 750 40 80 120 160 200 Ni cooted AI203 in the both (g/I}

I = I = I r I , i

730

I I 4 AI203 in the

I 8
coating

J 12 (wt %)

16

Fig. 1. Variation in AI203 content in the coating with increase in nickel-coated AI203 content in the chromium plating bath. Fig. 2. Effect of Al203 content in the chromium coating on its hardness.

230 Variation in the current density between 20 and 50 A dm-2 showed that at all bath loads m a x i m u m codeposition took place at 35 A dm -2 (Fig. 4).
1.0

C.D., A/dm
o.8
20 ,,30

3s

/~ j/~ 7 / / //,,

0.8
2 =" o.6

AI203bat~
10/62n 0g 00 1 i e120

0./.

0./'

0.2
,q

Bothad lo of
/'0

80 alurnino, g/I

120

J 10 20 30 40 50 Current density, A/drn 2

Fig. 3. Effect of bath load of A1203 on its content in the coating at 50 C. Fig. 4. Effect of current density on the A1203 content in Cr-AI203 composite coatings at different bath loads. Aging for up to 18 days of the plating bath containing A1203 particles had almost no effect on the a m o u n t of A1203 codeposited at different current densities and bath loads except at 30 A dm -2 and a bath load of 20 g 1-1 where m a x i m u m codeposition t o o k place only after aging for 10 days (Fig. 5). Variation in the bath temperature at 30 A dm-2 and different bath loads showed that heavily cracked deposits were formed at temperatures below 40 C. At higher temperatures an increase in bath temperature decreased the a m o u n t of A1203 codeposited at bath loads lower than 60 g 1-1. At higher bath loads, increasing the temperature b e y o n d 50 C had almost no effect (Fig. 6). At 40 C, although the A1203 content in the coating was at a maximum, metallographic examination showed that the coating deposited at this temperature was very rough and cracked and from these considerations the o p t i m u m bath temperature was about 50 C. The thickness variation of the composite coating was of the same order as that of the chromium coating (Fig. 7). The microhardness of the Cr-A120 a composite coatings was always higher than that of a pure chromium coating deposited under the same plating conditions (Fig. 8). At a given current density the microhardness of the composite coating increased with increase in A1203 c o n t e n t either in the bath or in the coating {Fig. 8). At a given bath load, the microhardness of composite coating increased with decreasing bath temperature and increasing current density (Fig. 9). At 20 A d m - 2 chromium plating was n o t possible when there was no A1203 in the bath. The addition of 20 - 60 (g A1203) 1-1 resulted in a constant cathode efficiency. Further addition of A1203 increased the cathode current efficiency which again became constant after approximately

231
C.D. A/din 2 Bath load g/I

30 S0 60

20
60

1.2 AI203 content, g/I 20 60 x 80 100 120

z~

20
6O

20 : 0.8

~' o.s

"- 0.~ -: u

-:/o
0

.,.
~

g o.4
A u

I 0 8
Ageing time. day 16 40

50 60 Bath temperature, =C

Fig. 5. Effect of aging time of the plating bath on the amount of A1203 codeposited with chromium at different current densities and different loads of A1203 in the bath at 50 C.
Fig. 6. E f f e c t o f plating bath t e m p e r a t u r e o n t h e A1203 c o n t e n t in the coating at 30 d m - 2 and different c o n t e n t s o f A 1 2 0 3 in the bath.
A

170; D

At the

middle

50A/dm2]

r m Atthe edge

I t

,o.,o.
35A/din2 30A/din2

""o'I 1

II/

110
~ 9O

~ 7o
50 Pure Cr 120 g/I A[203 in the plating bath

Fig. 7. Variation in thickness of pure chromium and C r - A ] 2 0 3 composite coatings deposited at different current densities.

100 (g A1203) 1-1 had been added to the bath (Fig. 10). At 30 and 35 A dm - 2 the cathode current efficiency remained constant up to 20 (g A1203} 1-1 in that bath; b e y o n d this concentration the cathode current efficiency increased and became constant at bath loads greater than 100 g 1-1 . At 50 A dm - 2 the cathode current efficiency increased with increasing a m o u n t o f A]203 in the bath and became constant at bath loads higher than 6 0 g 1-1 (Fig. 10). Aging the plating bath decreased the cathode efficiency at all bath loads o f Al203 and at all bath temperatures {Fig. 11). In both unaged and aged

232 %

E
I000

tooo

600

(a)

40 80 AI;~O 3in the both, g / I

120

: oop
40 50 60 Both temperature, "C E 1000

(a)
%

E
I000

600 .u
2E

.D., A / d m 2 2O 3O 35 50 I 1.2

J m
E
600 u 2
I [ I 120 J

(b)

I K I i 0.4 0.8 AIz03 in the coating, wt %

(b)

20

30
Current

40
density.

50 A/dm 2

Fig. 8. Variation in the microhardness of the coating with A120 3 content in (a) the bath and (b) the coating at 50 C. Fig. 9. Variation in microhardness with (a) bath temperature and (b) current density.
2O
>, >,
s

20

._e u

Both Iood,g/I oe 20 ,xA 60 o 100

12
._v
a 2

~
8 ~

"
[ 40 k

20'

30 3s
50

3
--

Unoged

'-- Aged
[ I

I L 80 Am203 content in the bath, g / I

[ 120

40

50 60 Both temperature, 'C

Fig. 10. Variation in cathode efficiency at different bath loads and current densities. Fig. 11. Effect of bath temperature on the cathode current efficiency at 30 A dm -2 and different bath loads of Al203 in aged and unaged conditions. c o n d i t i o n s t h e c a t h o d e current e f f i c i e n c y increased w i t h increasing bath l o a d o f A120 a and decreasing bath t e m p e r a t u r e (Fig. 11).

4. D i s c u s s i o n It has b e e n s h o w n b y several investigators [7, 11, 12] that Guglielmi's t w o - s t a g e a d s o r p t i o n m e c h a n i s m [ 11] is applicable in c o m p o s i t e plating sys-

233 terns. According to this model a plot of C/a versus C (where C and ~ are the amounts (vol.%) of particles in the bath and in the coating respectively) gives a sheaf of straight lines converging at a point. However, this was not observed in the present Cr-A1203 system. Obviously other mechanisms based on purely electrophoretic deposition and mechanical entrapment of solid particles in the coating are also unable to explain all the present results. It is proposed that in the present case transportation of A1203 particles towards the cathode and their subsequent codeposition within the chromium matrix would depend on the following. (i) The A1203 particles have a surface charge which may be modified because of the adsorption of certain species from the plating bath. (ii) The particles are transported towards the cathode because of hydrodynamic and electrophoretic effects. (iii) The particles are entrapped in the growing chromium matrix. AI~O~ particles which are initially negatively charged move because of the h y d r o d y n a m i c and electrophoretic charge towards the anode where H ions produced during chromium plating are strongly adsorbed on their surface. The adsorption of H ions would either neutralize the charge on A1203 particles or reverse its polarity. A1203 particles having a positive charge move towards the cathode because of hydrodynamic and electrophoretic forces, become codeposited with the growing chromium matrix and cause adsorbed hydrogen to be evolved as hydrogen gas. At a given current density, increasing the bath load of A1208 particles should increase the a m o u n t of A1203 particles codeposited with chromium whereas increasing the current density will have the following mutually opposing effects. (i) The amount of H ions produced at the anode will increase; this would increase the probability of their adsorption on AI203 particles. This would result in higher amounts of codeposited alumina. (ii) The evolution of H2 gas bubbles at the cathode will increase, thereb y making codeposition of A1203 particles difficult. This would tend to decrease the a m o u n t of codeposited A1203. The above explains why at a low current density (20 A dm -2 } codeposition starts b e y o n d 60 (g A12Oa) 1-1 in the bath whereas at higher current densities codeposition occurs at lower bath loads. This would also explain why the initial rate of increase in A1203 content in the coating with its content in the bath is less at higher current densities compared with low current densities (see Fig. 3). The above mechanism would also explain w h y o p t i m u m codeposition at a load up to 100 g 1-1 occurs at a b o u t 35 A dm -2 whereas at a higher bath load o f 120 g 1-1 no such o p t i m u m is observed (see Fig. 4). The effect of bath temperature on the a m o u n t of A1203 codeposited with chromium (Fig. 6) can also be explained in terms of its effect on the a m o u n t of H ion adsorption on A120 a particles because increasing the temperature would decrease this adsorption in accordance with Langmuir adsorption.

234 5. C o n c l u s i o n s (1) A1203 could be codeposited with c h r o m i u m only if it was either coated with nickel or was dry ground before mixing in the plating bath. Nickel-coated A12Oa was not, however, very stable in the plating bath. (2) At a given cur r ent density, the A1203 c o n t e n t in t he coating increased with increase in A1203 (dry ground) c o n t e n t in t he bath. (3) At all bath loads, m a x i m u m codeposition occurred at 35 A dm -~. (4) Increasing the bath t e m p e r a t u r e above 40 C decreased the A1203 c o n t e n t in th e coating. Although m a x i m u m codeposition t o o k place at 40 C, the deposit was very rough and cracked. (5) The microhardness of the composite coating was always higher than that o f pure c h r o m i u m coatings and it increased with increasing A120 3 c o n t e n t in the coating. (6) The mechanism o f codeposition is t h o u g h t to consist o f three processes, i.e. adsorption, transportation by h y d r o d y n a m i c and electrophoretic forces and particle e n t r a p m e n t in t he c h r o m i u m matrix.

Acknowledgments The authors are grateful t o the Head, D e p a r t m e n t of Metallurgical Engineering, and the Director, Indian Institute of Technology, Kanpur, for extending research facilities. T h e y also t hank the Ministry of Defence, G o v e r n m e n t o f India, for providing the financial support for t he above work.

References

1 J. P. Young, NBSIR Rep. 74-615, November 1974 (Research Directorate, Weapons

Laboratory, Rock Island Arsenal, IL).

2 E. C. Kedward, K. W. Wright and A. A. B. Tennett, TriboL Int., 7 (5) (1974) 221 227. 3 E. C. Kedward, B. Kieman and R. A. Duffin, Br. Patent 1,220,331, 1971. 4 J. P. Young, Plat. Surf. Finish., 62 (4) (1975) 348 - 350. 5 C. A. Addison and E. C. Kedward, Trans. Inst. Met. Finish, 55 (Part 2) (1977) 41 46. 6 V. Skominas, E. Maniliene and J. Matulis, Liet. TSR Mokslu Akad. Darb., Ser. B, i (1971) 101 - 106; Chem. Abstracts, number 75-14103W. 7 R. Narayan and B. H. Narayana, J. Electrochem. Soc., 128 (8) (1981) 1704 - 1708. 8 E. A. Brandes and D. Goldthorpe, MetaUurgia, 75 (457) (1967) 195 - 198. 9 E. C. Kedward, C. A. Addison and A. B. B. Tennett, Trans. Inst. Met. Finish., 54 (1976) 8 - 16. 10 J. Foster and A. M. J. Kariapper, Trans. Inst. Met. Finish., 51 (1973) 27 - 31. 11 N. Guglielmi, J. Electrochem. Soc., 119 (8) (1972) 1009 - 1112. 12 J. P. Celis and J. R. Ross, J. Electrochem. Soc., 124 (10) (1977) 1508 - 1511.