Studies on Alloys and Composites that Undergo Anomalous Codeposition

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1 Studies on Alloys and Composites that Undergo Anomalous Codeposition Electrochemical of of South Columbia, SC908 09, 1998 Electrochemical

2 Systems Studied FeNi alloys and FeNiSiO composites Electrodeposition Corrosion Mathematical Model Electrodeposition ZnNi alloys and ZnNiSiO composites Electrodeposition (D.C., Pulse) Corrosion and Hydrogen Permeation Mathematical Model Hydrogen Permeation Electrochemical

3 Anomalous Alloys Applications Electrochemical

4 Anomalous Alloys Applications Zn Zn e Iron H e H ZnNi Electrochemical

5 Anomalous Codeposition When certain metals are codeposited from certain solutions under certain conditions, the less noble metal deposits preferentially over the more noble one Electrochemical

6 0.7 V Cathodic (less noble) 0.44 V Fe e Fe 0.5 V Ni e Ni 0.00 V H e H Electrochemical

7 Anomalous Codeposition Metals such as: Fe, Co, Ni (Iron group; VIII B) B) Zn, Cd, Pb Not due to to the faster kinetics of of the less noble metal Temperature, current density, and bath composition are critical factors Electrochemical

8 Objectives: FeNi System To study the deposition and to to characterize the corrosion resistance of of FeNi alloys and FeNiSiO composites To develop a mathematical model that will explain FeNi deposition and SiO inclusion Electrochemical

9 Why SiO? SiO films on certain metals ms a barrier layer to to reduce metal dissolution rate ** Electrodeposited ZnSiO composites show good corrosion resistance ** ** SiO composites with permalloy also provide excellent soft magnetic properties * * Kato. Kato. K, K, J. J. Mat. Mat. Sci., Sci., 8, 8, (1993). (1993). * * Hashimoto. Hashimoto. S S and and Abe. Abe. M, M, Corr. Corr. Sci., Sci., 36, 36, (1994). (1994). Electrochemical

10 Effect Effect of of Electrode Electrode Rotation Rotation Speed Speed on on Fe Fe Weight Weight Fraction Fraction M NiSO NiSO M FeSO FeSO M Na Na SO SO 4, 4, ph=3.0 ph=3.0 Fe Fe Weight Weight Fraction Fraction rpm rpm E E(V(V vs. vs. SCE) SCE) Electrochemical

11 Effect Effect of of SiO SiO colloid colloid on on Fe Fe Weight Weight Fraction Fraction M NiSO NiSO M FeSO FeSO M Na Na SO SO 4 ; 4 ; ph=3.0 ph= Weight Weight Percent Percent Fe Fe g/l g/l SiO SiO E E(V(V vs. vs. SCE) SCE) Electrochemical

12 Cyclic Cyclic Voltammogram's obtained obtained various various SiO SiO Concentrations Scan Scan Rate Rate mv/s mv/s M NiSO NiSO M FeSO FeSO M Na Na SO SO 4 ; 4 ; ph=3.0 ph= Current Current (A) (A) H g/l g/l SiO SiO E (mv (mv vs vs SCE) SCE) Electrochemical

13 Vol. Vol. fraction fraction SiO SiO in in deposit deposit Relation Relation between between Volume Volume Fraction Fraction of of SiO SiO in in Deposit Deposit and and in in Solution Solution V V V Vol Vol % SiO SiO in in Solution Solution Electrochemical

14 Schematic of of a twostep inclusion Process Solution Substrate θ ϕ N. Guglielmi, J. Electrochem. Soc., 119, 1009 (197). Electrochemical

15 SiO Inclusion Volume of SiO included: dv SiO dt = θ SiO v 0 exp(be) Electrochemical

16 Ni Deposition * Model Reactions Ni Fe Deposition Fe H Evolution ( ) OH e Ni OH ( ) OH e Fe OH H e H * M., S. N. Popova, B. N. Popov, R. E. White, and K. M. Yin, J. Electrochem. Soc., 143, 164 (1996). Electrochemical

17 Mathematical Model Predicts the effect of various plating parameters on the alloy composition and current efficiency Mass transfer is governed by convection, diffusion and migration Rotating disk electrode; steady state The system of coupled nonlinear equations is solved by finite difference technique, using BAND routine. Electrochemical

18 Experimental and and Theoretical i Fe i Fe various various SiO SiO concentrations i i Fe (ma/cm Fe (ma/cm ) ) g/l g/l SiO SiO E E(V(V vs vs SCE) SCE) Electrochemical

19 Model Model Predictions Predictions and and Experimental Experimental Data Data Mass Mass Fraction Fraction of of SiO SiO Wt Wt Fraction Fraction SiO SiO g/l g/l SiO SiO E E(V(V vs vs SCE) SCE) Electrochemical

20 Tafel Tafel Plots Plots FeNiSiO deposits deposits various various SiO SiO concentrations E (V (V vs. vs. SCE) SCE) g/l g/l SiO SiO log log [i] [i](i(i in in A/cm A/cm )) Electrochemical

21 Corrosion Corrosion Rate Rate of of Various Various FeNiSiO Composites Fe Fe Ni Ni SiO SiO Composites Composites Fe Fe Ni Ni SiO SiO Fe Fe Ni Ni SiO SiO Fe Fe Ni Ni SiO SiO Fe Fe Ni Ni Corrosion Corrosion rate rate (mpy) (mpy) Electrochemical

22 Objectives: ZnNi System To develop a methodology the deposition of of corrosion and hydrogen permeation resistant Zn NiSiO composites* Develop a mathematical model characterizing the hydrogen permeation under corroding conditions, and determine the effect of of ZnNi as as hydrogen permeation inhibitor** ** B. B. N. N. Popov, Popov, M. M.,, S. S. N. N. Popova, Popova, R. R. E. E. White, White, and and K.M. K.M. Yin, Yin, J. J. Chem. Chem. Soc. Soc. Faraday Faraday Trans., Trans., 9, 9, (1996) (1996) ** ** M. M.,, B. B. N. N. Popov, Popov, and and R. R. E. E. White, White, J. J. Electrochem. Electrochem. Soc., Soc., 145, 145, (1998) (1998) Electrochemical

23 96 Weight Percent of Zinc in Electrodeposited ZnNi Alloy 0.5 M NiSO M ZnSO M Na SO 4, ph = Wt % Zn i (ma/cm ) Electrochemical

24 Tafel Plots Various ZnNiSiO Composites E (V vs. SCE) g/l SiO log(i) (i in A/cm ) Electrochemical

25 Hydrogen Permeation Hydrogen in steel can cause damage via: Hydrogen Embrittlement Hydrogen Blistering Hydrogen Induced Cracking Hydrogen Permeation can be inhibited by: Inhibiting the adsorption reaction rate Increasing the recombination reaction rate Decreasing the amount of absorbed hydrogen Forming a diffusion barrier Electrochemical

26 Hydrogen Permeation Zn Zn e M H e MH ads Iron MH ads H e H M ZnNi Electrochemical

27 Hydrogen Permeation Setup Electrochemical

28 40 40 E c and c and j j Electrodeposited ZnNi ZnNi in in ph=5. ph=5. Solution Solution j j (µa) (µa) E c c (V (V vs. vs. SCE) SCE) Time Time (s) (s) Electrochemical

29 Permeation current densities a ZnNi alloy at various solution ph in the Cathodic compartment 60 Permeation Current (µa) ph= Time (s) Electrochemical

30 Steady State i c and j iron and ZnNi Alloy i c, ZnNi i (A/cm ) i c, Fe j inf, Fe j inf, ZnNi ph Electrochemical

31 Summary Studied the characteristics of electrodeposited corrosion resistant FeNiSiO composites Developed a mathematical model the electrodeposition of anomalous alloys under potentiostatic conditions Extended the above model was to include inert particle inclusion by a two step adsorption mechanism Electrochemical

32 Summary Characterized the electrodeposition of ZnNi alloys and ZnNiSiO composites Studied the hydrogen permeation characteristics of ZnNi alloys and ZnNiSiO composites under applied polarization and corroding conditions Developed a model hydrogen permeation through substrates under corroding conditions Studied the effectiveness of ZnNi alloys as hydrogen permeation inhibitors using the above model Electrochemical

33 Other Projects Worked On Electroless deposition of copper on PdCatalyzed Polyimide Substrates: Experimental Study and Mathematical Model Solution equilibrium characteristics of electroless copper on thermally activated palladiumcatalyzed polyimide substrates, M., B. N. Popov, R. E. White, and K. S. Chen, J. Appl. Electrochem., 8, A mathematical model electroless copper deposition on planar electrodes, M., B. N. Popov, R. E. White, and K. S. Chen, J. Electrochem. Soc., submitted (January, 1998). Passivation of iron in alkaline environments Inhibiting action of calcium nitrite on steel rebars, M., B. N. Popov, and R. E. White, in Materials the New Millenium, Ken. P. Chong Ed., Published by the American Society of Civil Engineers, New York,, 1007 (1996).

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