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Journal of Chinese Society for Corrosion and protection  2018, Vol. 38 Issue (2): 210-218    DOI: 10.11902/1005.4537.2017.017
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Passivation of T2 Cu and QCr0.5 Cu-alloy with Chromate-free Solutions of Molybdate Compound
Jiulong SONG, Wenge CHEN(), Nannan LEI
School of Materials Science and Engineering, Xi'an University of Technology, Xi'an 710048, China
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Abstract  

T2 Cu and QCr0.5 Cu-alloy were passivated in chromate-free solutions with single molybdate and complex molybdate respectively. The formed passivation films were then characterized by electrochemical method, nitric acid drop test, neutral salt spray test, SEM and XRD etc., taking the passivation film prepared with conventional chromate containing solution as comparison. Results show that the addition of polyaspartic acid (PASP) and H2O2 could improve the passivation effect of molybdate, especially the addition of the both simultaneously, which promoted the formation of passive film, the decrease of dissolution of Cu-alloy, and thereby the formation of a passivation film of copper oxide-based, significantly improved the corrosion resistance of T2 Cu and QCr0.5 Cu-alloy. After salt spray test, the surface of passivation treated samples presents metallic lustrousness to certain extent, while with less corrosion pits. In particular, the free-corrosion current density for T2 Cu passivated in molybdate solution with PASP+H2O2 is only 3.10×10-6 A/cm2, which is close to that for the chromate passivation film i.e. 9.06×10-7 A/cm2.
Key words:  T2 Cu      QCr0.5 Cu-alloy      passivation      molybdate      polyaspartic acid     
Received:  04 February 2017     
Fund: Supported by Xi'an Science and Technology Project (2017080CG/RC043)
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Jiulong SONG
Wenge CHEN
Nannan LEI

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Jiulong SONG, Wenge CHEN, Nannan LEI. Passivation of T2 Cu and QCr0.5 Cu-alloy with Chromate-free Solutions of Molybdate Compound. Journal of Chinese Society for Corrosion and protection, 2018, 38(2): 210-218.

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https://www.jcscp.org/EN/10.11902/1005.4537.2017.017     OR     https://www.jcscp.org/EN/Y2018/V38/I2/210

Material Cu Zn Pb Ni Fe Sb Cr
T2 Cu 99.9 0.005 0.005 0.005 0.005 0.002 ---
QCr0.5 Bal. --- --- 0.050 0.100 --- 0.4~1.1
Table 1  Chemical compositions of T2 Cu and QCr0.5 Cu-alloy
(mass fraction / %)
Number Component Process condition
a Unchromation ---
b 25 g/L Na2MoO4 20 ℃, 3 min
c 25 g/L Na2MoO4+40 mL/L 30%H2O2 20 ℃, 3 min
d 25 g/L Na2MoO4+50 mg/L PASP 20 ℃, 3 min
e 25 g/L Na2MoO4+40 mL/L 30%H2O2+50 mg/L PASP 20 ℃, 3 min
f 80 g/L CrO3+30 g/L H2SO4+1 g/L NaCl 20 ℃, 3 min
Table 2  Passivating solution components and process conditions of T2 Cu and QCr0.5 Cu-alloy
Number Components of passivation solution Initial bubbling time / s
T2 QCr0.5
a Unchromation 6 5
b Na2MoO4 9 9
c Na2MoO4+H2O2 11 14
d Na2MoO4+PASP 13 12
e Na2MoO4+H2O2+PASP 21 19
f CrO3+H2SO4+NaCl 20 24
Table 3  Nitric acid-testing results of T2 Cu and QCr0.5 with different passivation treatments
Fig.1  Morphologies of T2 Cu and QCr0.5 Cu-alloy samples without (a1~a6) and with passivation treatments in Na2MoO4 (b1~b6), Na2MoO4+H2O2 (c1~c6), Na2MoO4+PASP (d1~d6), Na2MoO4+H2O2+PASP (e1~e6) and CrO3+H2SO4+NaCl (f1~f6) solutions after salt spray test for different time
Fig.2  Weight gain curves of T2 Cu (a) and QCr0.5 Cu-alloy (b) samples without and with passivation treatments in different solutions during salt spray tests for 100 h
Fig.3  XRD spectra of T2 Cu (a) and QCr0.5 Cu-alloy (b) samples before and after passivation treatments
Fig.4  SEM images of T2 Cu (a1~f1) and QCr0.5 Cu-alloy (a2~f2) samples without (a1, a2) and with passivation treatments in Na2MoO4 (b1, b2), Na2MoO4+H2O2 (c1, c2), Na2MoO4+PASP (d1, d2), Na2MoO4+H2O2+PASP (e1, e2) and CrO3+ H2SO4+ NaCl (f1, f2) soulutions after exposure in atmosphere for 7 d
Fig.5  SEM images of T2 Cu (a1~f1) and QCr0.5 Cu-alloy (a2~f2) samples without (a1, a2) and with passivation treatments in Na2MoO4 (b1, b2), Na2MoO4+H2O2 (c1, c2), Na2MoO4+PASP (d1, d2), Na2MoO4+H2O2+PASP (e1, e2) and CrO3+ H2SO4+NaCl (f1, f2) solutions after salt spray test and then exposure in atmosphere for 7 d
Fig.6  Electrochemical polarization curves of T2 Cu (a) and QCr0.5 Cu-alloy (b) samples with passivation treatments after immersion in 3.5%NaCl solution for 1.5 h
Passivation solution Icorr / Acm-2 Ecorr / V η / %
T2 QCr0.5 T2 QCr0.5 T2 QCr0.5
Unchromation 3.18×10-5 2.16×10-5 -0.366 -0.271 --- ---
Na2MoO4 7.83×10-6 4.61×10-6 -0.236 -0.240 75.3 78.7
Na2MoO4+H2O2 6.70×10-6 3.51×10-6 -0.235 -0.242 78.0 83.8
Na2MoO4+PASP 6.66×10-6 3.63×10-6 -0.256 -0.255 79.0 83.2
PASP+H2O2+Na2MoO4 3.10×10-6 3.23×10-6 -0.204 -0.199 90.3 85.1
CrO3+H2SO4+NaCl 9.06×10-7 1.44×10-6 -0.212 -0.207 97.1 93.3
Table 4  Fitting results of electrochemical polarization curves of T2 Cu and QCr0.5 Cu-alloy samples with various passivation treatments
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