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Influence of carbon on the properties of sulfamate nickel electrodeposits
Surface Technology, 4 (1976) 217 - 222
217
© Elsevier Sequoia S.A., Lausanne -- Printed in the Netherlands
I N F L U E N C E OF CARBON ON THE P R O P E R T I E S OF SU L FA MA T E NICKEL E L E C T R O D E P O S I T S
J. W. DINI and H. R. JOHNSON Metallurgy and Electroplating Division 8312, Sandia Laboratories, Livermore, Calif. 94550 (U.S.A.)
(Received November 19, 1975)
S u m mar y Poisson's ratio and a n u m b e r of mechanical properties were obtained for sulfamate nickel deposits plated in three solutions. The data showed the deposits from any given solution were isotropic. However, a wide variation was n o t e d when the properties f r om the various solutions were compared. It appeared that perhaps carbon c o n t e n t in the deposit was the influencing factor. Additional experiments confirmed this hypothesis.
Introduction At Sandia Laboratories, Livermore, electroplating is used to join metals t h a t can n o t be joined by conventional techniques. The process and applications are described in detail elsewhere [1, 2] . As part of a procedure for determining the suitability o f nickel electrodeposits for use as structural members o f a plated joint, Poisson's ratio was needed. This i nform at i on could n o t be f o u n d in the literature, therefore data were obtained in our laboratory. Concurrently, a n u m b e r of ot her properties including modulus o f elasticity, yield strength, tensile strength and shear modulus were measured. Three nickel sulfamate plating solutions were used. T h e y were of the same general composition, e x c e p t for the fact that one contained an inorganic p r o p r ietar y additive. Chemical formulation and operating conditions are included in Table 1. Tubes were e l e c t r o f o r m e d by plating on aluminum rods 12.1 mm (0.475 inches) in diameter, machining to size and then dissolving the aluminum in caustic solution. The length o f the finished elect r o f o r m s was 102 m m (4 in); the wall thickness was 1 m m (40 mils) on the ends, e x c e p t for a 38 m m (11~ in) reduced section in the middle which was 0.5 m m (20 mils) thick. Testing was accomplished by threading adaptors into the ends of the e l e c t r o f o r m e d tubes and applying axial force or internal oil pressure to obtain either axial or h o o p loading, respectively, at 21 °C. The outside surface
218 TABLE 1 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 for nickel s u l f a m a t e s o l u t i o n s Code Nickel Nickel s u l f a m a t e Nickel chloride Boric acid Sulfamex anode activator 3 Surface t e n s i o n pH Anodes C u r r e n t density Temperature
A 1 and B 2 81 g/] 4 5 0 g/1 1.0 g/l 40 g/l
C2 81 g/l 4 5 0 g/I
38 d y n / c m 3.8 - 4.0 Sulfur d e p o l a r i z e d 268 A / m 2 49 °C
40 g/l 75 ml/1 38 d y n / c m 3.8 - 4.0 Sulfur depolarized 268 A / m 2 49 C
1 S o l u t i o n v o l u m e was 40 1. Electrolysis t i m e was 6 A h/1. 2 S o l u t i o n v o l u m e was 120 I. Electrolysis t i m e was greater t h a n 250 A h/l. 3The Sel Rex Co., N u t l e y , New Jersey (U.S.A.).
strains at the center of each specimen were measured by using four biaxial strain gages spaced 90 ° apart around the circumference. Shear modulus values were obtained for some tubes from static t orque torsion tests. The angle of twist was measured by using a laser and a mirror. The data for the nickel deposits are presented in Table 2. The properties varied noticeably from lot to lot. For example, Poisson's ratio e x t e n d e d over the range 0.24 - 0.34. Ultimate strengths varied from a minimum of 496 MN/m 2 (72 060 psi) to a m a x i m u m of 910 MN/m 2 (132 000 psi).Yield strength and modulus o f elasticity showed similar trends. However, within each lot, the h o o p and axial properties were quite close in value, indicating t h a t deposits f r o m any given solution were isotropic. In an a t t e m p t to try and understand the reason for the variation in strength from lot to lot some samples were analysed spectrographically. In addition, hydrogen, oxygen, nitroTABLE 3 C h e m i c a l analysis o f nickel d e p o s i t s Deposit code
M e t h o d of analysis
B
C
N (ppm) O (ppm) H (ppm) S (ppm) C (ppm) Co (%) Cu ( p p m )
1 1 1 2 3 4 5
15 40 8 <10 28 0.52 20
10 34 8 12 48 0.75 20
A 15 46 10 <10 69 1.1 20
1, gas fusion; 2, w e t c h e m i s t r y t e c h n i q u e of Luke [ 3 ] ; 3, c o m b u s t i o n in o x y g e n , t h e n use o f a residual gas a n a l y s e r using t h e t e c h n i q u e o f R. S t u m p (private c o m m u n i c a t i o n , May 29, 1 9 7 4 ) ; 4, w e t c h e m i s t r y m e t h o d described in ref. [4] ; 5, a t o m i c a b s o r p t i o n analysis.
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gen, sulfur, carbon, copper and cobalt contents were also obtained. The spectrographic analysis data revealed no quantitative difference bet w een samples, nor any impurities of significance. The other analysis data, presented in Table 3, show t hat the only noticeable variables from lot to lot were carbon and cobalt concentration. Previous work by the present authors [5] and others [6, 7] does not lead to the conclusion that strengths as high as those reported in Table 2 would be ex p ected with cobalt concentrations as low as 1.0 wt.%. However, there is perhaps some relationship between carbon c o n t e n t and mechanical propertie~. A p lo t of yield strength, tensile strength and Poisson's ratio v e r s u s carbon clearly shows this. Figures 1 and 2 show such plots for the latter two properties as a function of carbon concentration. Based on this observation, additional data were obtained and analysed in an a t t e m p t to confirm or d e n y this apparent influence of carbon on properties. Data were accumulated for ot he r deposits, produced w i t h o u t additives o th er than a wetting agent, either in this laboratory or by others. Once .
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Fig. 1. I n f l u e n c e o f c a r b o n on tensile strength. Fig. 2. Influence o f c a r b o n on P o i s s o n ' s ratio.
again, some mechanical properties were measured and deposits were analysed spectrographically; equivalent measurements were also obtained for hydrogen, oxygen, nitrogen, carbon and cobalt. The data obtained from this additional study are presented in Table 4 and Fig. 3. Agreement with the earlier work r e p o r t e d above [5 - 7] is quite good. For example, tensile strengths ranged from 629 to 1000 MN/m 2, while carbon contents varied f r om 37 to 70 ppm. Once again, o t h e r impurities showed no significant trends. A least squares plot of these data, including the data f r o m our earlier study [ 5 ] , is shown in Fig, 3. Also included in Fig. 3 is t h e plot from our earlier study. The agreement between the two plots is quite evident.
Conclusion This r ep o r t includes data on Poisson's ratio and tensile properties for sulfamate nickel deposits. Data are included which show that deposits from
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-----
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Fig. 3. I n f l u e n c e of c a r b o n o n tensile s t r e n g t h : full curve, all data; b r o k e n curve, r e p i o t o f Fig. 1.
any given solution were isotropic. However, a wide variation was noted when the properties from the various solutions were compared. Early work in this program suggested that perhaps carbon content in the deposits was the influencing factor. This was confirmed by an additional study which showed good agreement with the original results.
Acknowledgements The authors would like to acknowledge the help of R. A. Thompson in obtaining the property data, J. R. Helms for plating support and F. J. Cupps for computer programming.
References 1 J. W. Dini a n d H. R. J o h n s o n , Metals Eng. Quart., 14 ( 1 9 7 4 ) 6. 2 J. W. Dini a n d H. R. J o h n s o n , J o i n i n g B e r y l l i u m by Plating, Sandia L a b o r a t o r i e s , L i v e r m o r e (U.S.A.) S L L - 74 - 5011, J u l y 1974. 3 C. L. Luke, Anal. Chem., 29 ( 1 9 5 7 ) 1227. 4 K. E. L a n g f o r d , Analysis o f E l e c t r o p l a t i n g a n d R e l a t e d S o l u t i o n s , 3rd edn., R o b e r t D r a p e r Ltd., T e d d i n g t o n (Gt. Britain), 1 9 6 2 . 5 J. W. Dini a n d H. R. J o h n s o n , Proc. S y m p . o n E l e c t r o d e p o s i t e d Metals for Selected A p p l i c a t i o n s , 1 9 7 3 , Battelle C o l u m b u s L a b o r a t o r i e s , Metals a n d Ceramics I n f o r m a tion C e n t e r Rep. No. MCIC 74 - 17, or A D 7 7 9 1 5 2 / 8 G A . 6 A. W. T h o m p s o n a n d H. J. S a x t o n , Met. Trans., 4 ( 1 9 7 3 ) 1599. 7 A. J. Dill, Plating, 61 ( 1 9 7 4 ) 1001. 8 C. H. S a m p l e a n d B. B. K n a p p , S y m p . o n E l e c t r o f o r m i n g , ASTM Spec. Tech. Publ. No. 318, 1 9 6 2 , p. 32. 9 J. W. Dini a n d H. R. J o h n s o n , Metal Finishing, 68 ( 1 9 7 0 ) 52. 10 J. W. Dini, H. R. J o h n s o n a n d M. I. Baskes, Metals T e c h n o l . , 1 ( 1 9 7 4 ) 391.
217
© Elsevier Sequoia S.A., Lausanne -- Printed in the Netherlands
I N F L U E N C E OF CARBON ON THE P R O P E R T I E S OF SU L FA MA T E NICKEL E L E C T R O D E P O S I T S
J. W. DINI and H. R. JOHNSON Metallurgy and Electroplating Division 8312, Sandia Laboratories, Livermore, Calif. 94550 (U.S.A.)
(Received November 19, 1975)
S u m mar y Poisson's ratio and a n u m b e r of mechanical properties were obtained for sulfamate nickel deposits plated in three solutions. The data showed the deposits from any given solution were isotropic. However, a wide variation was n o t e d when the properties f r om the various solutions were compared. It appeared that perhaps carbon c o n t e n t in the deposit was the influencing factor. Additional experiments confirmed this hypothesis.
Introduction At Sandia Laboratories, Livermore, electroplating is used to join metals t h a t can n o t be joined by conventional techniques. The process and applications are described in detail elsewhere [1, 2] . As part of a procedure for determining the suitability o f nickel electrodeposits for use as structural members o f a plated joint, Poisson's ratio was needed. This i nform at i on could n o t be f o u n d in the literature, therefore data were obtained in our laboratory. Concurrently, a n u m b e r of ot her properties including modulus o f elasticity, yield strength, tensile strength and shear modulus were measured. Three nickel sulfamate plating solutions were used. T h e y were of the same general composition, e x c e p t for the fact that one contained an inorganic p r o p r ietar y additive. Chemical formulation and operating conditions are included in Table 1. Tubes were e l e c t r o f o r m e d by plating on aluminum rods 12.1 mm (0.475 inches) in diameter, machining to size and then dissolving the aluminum in caustic solution. The length o f the finished elect r o f o r m s was 102 m m (4 in); the wall thickness was 1 m m (40 mils) on the ends, e x c e p t for a 38 m m (11~ in) reduced section in the middle which was 0.5 m m (20 mils) thick. Testing was accomplished by threading adaptors into the ends of the e l e c t r o f o r m e d tubes and applying axial force or internal oil pressure to obtain either axial or h o o p loading, respectively, at 21 °C. The outside surface
218 TABLE 1 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 for nickel s u l f a m a t e s o l u t i o n s Code Nickel Nickel s u l f a m a t e Nickel chloride Boric acid Sulfamex anode activator 3 Surface t e n s i o n pH Anodes C u r r e n t density Temperature
A 1 and B 2 81 g/] 4 5 0 g/1 1.0 g/l 40 g/l
C2 81 g/l 4 5 0 g/I
38 d y n / c m 3.8 - 4.0 Sulfur d e p o l a r i z e d 268 A / m 2 49 °C
40 g/l 75 ml/1 38 d y n / c m 3.8 - 4.0 Sulfur depolarized 268 A / m 2 49 C
1 S o l u t i o n v o l u m e was 40 1. Electrolysis t i m e was 6 A h/1. 2 S o l u t i o n v o l u m e was 120 I. Electrolysis t i m e was greater t h a n 250 A h/l. 3The Sel Rex Co., N u t l e y , New Jersey (U.S.A.).
strains at the center of each specimen were measured by using four biaxial strain gages spaced 90 ° apart around the circumference. Shear modulus values were obtained for some tubes from static t orque torsion tests. The angle of twist was measured by using a laser and a mirror. The data for the nickel deposits are presented in Table 2. The properties varied noticeably from lot to lot. For example, Poisson's ratio e x t e n d e d over the range 0.24 - 0.34. Ultimate strengths varied from a minimum of 496 MN/m 2 (72 060 psi) to a m a x i m u m of 910 MN/m 2 (132 000 psi).Yield strength and modulus o f elasticity showed similar trends. However, within each lot, the h o o p and axial properties were quite close in value, indicating t h a t deposits f r o m any given solution were isotropic. In an a t t e m p t to try and understand the reason for the variation in strength from lot to lot some samples were analysed spectrographically. In addition, hydrogen, oxygen, nitroTABLE 3 C h e m i c a l analysis o f nickel d e p o s i t s Deposit code
M e t h o d of analysis
B
C
N (ppm) O (ppm) H (ppm) S (ppm) C (ppm) Co (%) Cu ( p p m )
1 1 1 2 3 4 5
15 40 8 <10 28 0.52 20
10 34 8 12 48 0.75 20
A 15 46 10 <10 69 1.1 20
1, gas fusion; 2, w e t c h e m i s t r y t e c h n i q u e of Luke [ 3 ] ; 3, c o m b u s t i o n in o x y g e n , t h e n use o f a residual gas a n a l y s e r using t h e t e c h n i q u e o f R. S t u m p (private c o m m u n i c a t i o n , May 29, 1 9 7 4 ) ; 4, w e t c h e m i s t r y m e t h o d described in ref. [4] ; 5, a t o m i c a b s o r p t i o n analysis.
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gen, sulfur, carbon, copper and cobalt contents were also obtained. The spectrographic analysis data revealed no quantitative difference bet w een samples, nor any impurities of significance. The other analysis data, presented in Table 3, show t hat the only noticeable variables from lot to lot were carbon and cobalt concentration. Previous work by the present authors [5] and others [6, 7] does not lead to the conclusion that strengths as high as those reported in Table 2 would be ex p ected with cobalt concentrations as low as 1.0 wt.%. However, there is perhaps some relationship between carbon c o n t e n t and mechanical propertie~. A p lo t of yield strength, tensile strength and Poisson's ratio v e r s u s carbon clearly shows this. Figures 1 and 2 show such plots for the latter two properties as a function of carbon concentration. Based on this observation, additional data were obtained and analysed in an a t t e m p t to confirm or d e n y this apparent influence of carbon on properties. Data were accumulated for ot he r deposits, produced w i t h o u t additives o th er than a wetting agent, either in this laboratory or by others. Once .
.
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.
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.
.
.
.
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.
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52 cppm)
56
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64
6B
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40
44
48
52
56
60
64
68
CARBON ( p p m )
Fig. 1. I n f l u e n c e o f c a r b o n on tensile strength. Fig. 2. Influence o f c a r b o n on P o i s s o n ' s ratio.
again, some mechanical properties were measured and deposits were analysed spectrographically; equivalent measurements were also obtained for hydrogen, oxygen, nitrogen, carbon and cobalt. The data obtained from this additional study are presented in Table 4 and Fig. 3. Agreement with the earlier work r e p o r t e d above [5 - 7] is quite good. For example, tensile strengths ranged from 629 to 1000 MN/m 2, while carbon contents varied f r om 37 to 70 ppm. Once again, o t h e r impurities showed no significant trends. A least squares plot of these data, including the data f r o m our earlier study [ 5 ] , is shown in Fig, 3. Also included in Fig. 3 is t h e plot from our earlier study. The agreement between the two plots is quite evident.
Conclusion This r ep o r t includes data on Poisson's ratio and tensile properties for sulfamate nickel deposits. Data are included which show that deposits from
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72
76
80
CARBON(ppm) - -
CURVE FOR ALL DATA
-----
REPLOT OF FIGURE
I
Fig. 3. I n f l u e n c e of c a r b o n o n tensile s t r e n g t h : full curve, all data; b r o k e n curve, r e p i o t o f Fig. 1.
any given solution were isotropic. However, a wide variation was noted when the properties from the various solutions were compared. Early work in this program suggested that perhaps carbon content in the deposits was the influencing factor. This was confirmed by an additional study which showed good agreement with the original results.
Acknowledgements The authors would like to acknowledge the help of R. A. Thompson in obtaining the property data, J. R. Helms for plating support and F. J. Cupps for computer programming.
References 1 J. W. Dini a n d H. R. J o h n s o n , Metals Eng. Quart., 14 ( 1 9 7 4 ) 6. 2 J. W. Dini a n d H. R. J o h n s o n , J o i n i n g B e r y l l i u m by Plating, Sandia L a b o r a t o r i e s , L i v e r m o r e (U.S.A.) S L L - 74 - 5011, J u l y 1974. 3 C. L. Luke, Anal. Chem., 29 ( 1 9 5 7 ) 1227. 4 K. E. L a n g f o r d , Analysis o f E l e c t r o p l a t i n g a n d R e l a t e d S o l u t i o n s , 3rd edn., R o b e r t D r a p e r Ltd., T e d d i n g t o n (Gt. Britain), 1 9 6 2 . 5 J. W. Dini a n d H. R. J o h n s o n , Proc. S y m p . o n E l e c t r o d e p o s i t e d Metals for Selected A p p l i c a t i o n s , 1 9 7 3 , Battelle C o l u m b u s L a b o r a t o r i e s , Metals a n d Ceramics I n f o r m a tion C e n t e r Rep. No. MCIC 74 - 17, or A D 7 7 9 1 5 2 / 8 G A . 6 A. W. T h o m p s o n a n d H. J. S a x t o n , Met. Trans., 4 ( 1 9 7 3 ) 1599. 7 A. J. Dill, Plating, 61 ( 1 9 7 4 ) 1001. 8 C. H. S a m p l e a n d B. B. K n a p p , S y m p . o n E l e c t r o f o r m i n g , ASTM Spec. Tech. Publ. No. 318, 1 9 6 2 , p. 32. 9 J. W. Dini a n d H. R. J o h n s o n , Metal Finishing, 68 ( 1 9 7 0 ) 52. 10 J. W. Dini, H. R. J o h n s o n a n d M. I. Baskes, Metals T e c h n o l . , 1 ( 1 9 7 4 ) 391.