TY - JOUR
T1 - Liquid phase formation of alkyl- and perfluoro-phosphonic acid derived monolayers on magnesium alloy AZ31 and their chemical properties
AU - Ishizaki, Takahiro
AU - Teshima, Katsuya
AU - Masuda, Yoshitake
AU - Sakamoto, Michiru
N1 - Funding Information:
This research was supported by the Adaptable and Seamless Technology Transfer Program through Target-driven R&D (A-STEP) from Japan Science and Technology Agency and was carried out by the joint research program of the EcoTopia Science Institute, Nagoya University.
PY - 2011/8/1
Y1 - 2011/8/1
N2 - Alkyl- and perfluoro-phosphonic acid derived SAMs were successfully formed on Mg alloy by liquid phase method for the first time. The chemical and anticorrosive properties of the prepared SAMs on magnesium alloys were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and electrochemical measurements. Water contact angle measurements revealed that the maximum advancing/receding water contact angles of n-octyl (OP: CH3(CH2)7PO(OH)2), n-dodecyl (DP: CH3(CH2)11PO(OH)2), n-octadecyl (ODP: CH3(CH2)17PO(OH)2) phosphonic acid, and 2-(perfluorohexyl)ethyl (PFEP: CF3(CF2)5CH2CH2PO(OH)2) phosphonic acid were 105.1/64.7°, 108.3/69.6°, 111.9/75.2°, and 115.2/67.4° respectively. In the case of alkylphosphonic acid SAMs (OP, DP, and ODP), the advancing and receding water contact angles increased with an increase in the preparation time. The angle-resolved XPS (AR-XPS) data revealed that the film thicknesses of the OP, DP, ODP, PFEP on Mg alloy were estimated to be 0.8, 1.2, 1.7, and 1.1nm, respectively. The XPS O 1s data support that the phosphonic acid derived SAM is covalently bound to the oxide or hydroxide surface of the Mg alloy in a monodenate or bidenate manner. Chemical stability of the alkyl- and perfluoro-phosphonic acid modified Mg alloy surfaces was investigated using aqueous solutions at pH=4.0, 7.0, and 10.0. The contact angles of OP, DP, and PFEP modified Mg surface decreased rapidly within the first 5min after immersion in all the aqueous solutions and were less than 20°. On the other hand, the contact angles of the ODP modified Mg alloy after immersion in aqueous solutions at pH 4, 7 and 10 for 5min were 45.1°, 89.3,° and 85.5°, respectively. The ODP modified Mg alloy had highest chemical stability in four types of the phosphonic acid derived SAMs used in this study, indicating that the molecular density of ODP on Mg alloy would be higher than those of OP, DP, PFEP on Mg alloy. The corrosion resistance of ODP modified Mg alloy was investigated by potentiodynamic polarization curve measurements. The ODP modified Mg alloy exhibits protective properties in a solution containing Cl- ions compared to unmodified Mg alloy.
AB - Alkyl- and perfluoro-phosphonic acid derived SAMs were successfully formed on Mg alloy by liquid phase method for the first time. The chemical and anticorrosive properties of the prepared SAMs on magnesium alloys were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and electrochemical measurements. Water contact angle measurements revealed that the maximum advancing/receding water contact angles of n-octyl (OP: CH3(CH2)7PO(OH)2), n-dodecyl (DP: CH3(CH2)11PO(OH)2), n-octadecyl (ODP: CH3(CH2)17PO(OH)2) phosphonic acid, and 2-(perfluorohexyl)ethyl (PFEP: CF3(CF2)5CH2CH2PO(OH)2) phosphonic acid were 105.1/64.7°, 108.3/69.6°, 111.9/75.2°, and 115.2/67.4° respectively. In the case of alkylphosphonic acid SAMs (OP, DP, and ODP), the advancing and receding water contact angles increased with an increase in the preparation time. The angle-resolved XPS (AR-XPS) data revealed that the film thicknesses of the OP, DP, ODP, PFEP on Mg alloy were estimated to be 0.8, 1.2, 1.7, and 1.1nm, respectively. The XPS O 1s data support that the phosphonic acid derived SAM is covalently bound to the oxide or hydroxide surface of the Mg alloy in a monodenate or bidenate manner. Chemical stability of the alkyl- and perfluoro-phosphonic acid modified Mg alloy surfaces was investigated using aqueous solutions at pH=4.0, 7.0, and 10.0. The contact angles of OP, DP, and PFEP modified Mg surface decreased rapidly within the first 5min after immersion in all the aqueous solutions and were less than 20°. On the other hand, the contact angles of the ODP modified Mg alloy after immersion in aqueous solutions at pH 4, 7 and 10 for 5min were 45.1°, 89.3,° and 85.5°, respectively. The ODP modified Mg alloy had highest chemical stability in four types of the phosphonic acid derived SAMs used in this study, indicating that the molecular density of ODP on Mg alloy would be higher than those of OP, DP, PFEP on Mg alloy. The corrosion resistance of ODP modified Mg alloy was investigated by potentiodynamic polarization curve measurements. The ODP modified Mg alloy exhibits protective properties in a solution containing Cl- ions compared to unmodified Mg alloy.
KW - Corrosion resistance
KW - Mg alloy
KW - Self-assembled monolayer
KW - Wetting property
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U2 - 10.1016/j.jcis.2011.04.039
DO - 10.1016/j.jcis.2011.04.039
M3 - Article
C2 - 21565354
AN - SCOPUS:79957839986
SN - 0021-9797
VL - 360
SP - 280
EP - 288
JO - Journal of Colloid and Interface Science
JF - Journal of Colloid and Interface Science
IS - 1
ER -