Effect of Chloride on the Anodic Dissolution of Titanium in Methanolic Solutions

Parry, E. P.; Hern, D. H.

doi:10.1149/1.2404429

Cited by 16 publications

(6 citation statements)

References 13 publications

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“…The esr data definitely indicate two different species at low temperature. In anhydrous methanol, absorption 1 (see Figure 4) has been attributed to [TiCl(MeOD)g]2+ and absorption h to [TiCl2(MeOD)4]+.2 This was based on the following: (1) Chmelnick and Fiat found that in con- exhibit a very broad line and would be difficult to observe above liquid nitrogen temperatures in dilute solutions. It was further observed that at room temperature, absorptions 1 and h begin to broaden which suggests that there is an exchange between ligands of each complex in solution.…”

Section: Discussionmentioning

confidence: 99%

Effect of water on the titanium complexes in methanolic solutions containing hydrogen chloride

Parry¹,

Goldberg²,

Hern³

et al. 1973

J. Phys. Chem.

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Publication costs assisted by the North American Rockwell Corp.The electrochemical behavior of the Ti(III) |Ti(IV) couple was investigated in methanol solutions containing 0.02-0.22 M chloride ion and 0.02-7.0 M water. The presence of two electrochemically distinct Ti(III) complexes was observed and the mechanism of the electrode processes was shown to consist of the reactions e-+ Ti(IV) ^Ti(IH)(a) (E1/2 ~-0.4 V); Ti(III)(a) + H20 ^Ti(III)(b) + C1"(K); Ti(III)(b)T i(IV) + e~( E1/2 ~0.1 V). The equilibrium constant K was evaluated from pulse polarographic and cyclic voltammetric data to be 0.029 ± 0.006. The reaction rates have been calculated from the kinetic contribution to the kinetic polarographic current, and the parameters ks and a of the first electron transfer reaction were estimated from pulse polarographic data. Combining these results with electron spin resonance measurements, the species Ti(III)(a) comprised [TiCl2(CH3OH)4]+ and [TiCl(CH3OH)5]2+. These two species equilibrate rapidly on an electrochemical time scale. Ti(III)(b) was assigned the structure [TiCl(CH3OH)4H20]2+. In addition, the Ti(IV) in methanol containing more than 0.3 M H20 contains at least one more water ligand than the Ti(III), based on the negative shift of the half-wave potential with the concentration of water.

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Section: Discussionmentioning

confidence: 99%

Effect of water on the titanium complexes in methanolic solutions containing hydrogen chloride

Parry¹,

Goldberg²,

Hern³

et al. 1973

J. Phys. Chem.

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“…[12][13][14][15] In contrast to the oxidized titanium, the heattreated Ti-Ni underwent local activation in HCl solutions up to 2 M. This was attributed to the presence of defects in the oxide film on Ti-Ni. Such a phenomenon has been shown to exist in the case of aluminum-nickel oxidation.…”

Section: Corrosion Science Sectionmentioning

confidence: 99%

Corrosion Behavior of Heat-Treated Intermetallic Titanium-Nickel in Hydrochloric Acid Solutions

Starosvetsky¹,

Khaselev²,

Yahalom³

1998

CORROSION

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Samples of 45% Ti-55% Ni alloy (Ti-Ni) were and their anodic behavior in 0.3 M, 1 M, 2 M, and 4 M hydrochloric acid (HCl) solutions was studied. In 0.3 M HCl, heat-treated Ti-Ni was passive, and very low anodic currents were observed. In 1 M and 2 M HCl, heattreated Ti-Ni was dissolved actively, while heat-treated and surface-ground Ti-Ni became passive. The effect was explained by selective oxidation of Ti-Ni and formation of a layered structure on its surface with discontinuous titanium oxide and a nickel-enriched zone underneath. The latter was dissolved in the HCl solutions, thus accelerating failure of the Ti-Ni samples. In 4 M HCl, heat-treated and heat-treated/ ground samples were dissolved readily.

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“…[6,7]. Due to the expansion of existing applications and the development of new ones, the knowledge of the properties of titanium in various organic solvents has been systematically expanded [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

“…The reason for this interest is found in the search for efficient anodes for the oxidation of alcohols [25,26], new ways of producing TiO 2 nanoparticles [27] and the explanation of titanium stress corrosion in anhydrous alcohol electrolytes [11,12,15]. Most of the studies are devoted to the corrosion behaviour of Ti in neutral and acidic methanol solutions of chlorides [8,13,[17][18][19][20]23,28,29]. The literature reports that passive titanium oxide is found to be very sensitive to the presence of aggressive ions in methyl alcohol and undergoes cracking along the intergranular paths due to applied stress [18][19][20][21][22].…”

Section: Introductionmentioning

confidence: 99%

“…Most of the studies are devoted to the corrosion behaviour of Ti in neutral and acidic methanol solutions of chlorides [8,13,[17][18][19][20]23,28,29]. The literature reports that passive titanium oxide is found to be very sensitive to the presence of aggressive ions in methyl alcohol and undergoes cracking along the intergranular paths due to applied stress [18][19][20][21][22]. The stability of the oxide layer on the Ti surface in methanolic solutions strongly depends on the water concentration [8].…”

Section: Introductionmentioning

confidence: 99%

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The Effect of the Methanol–Water Interaction on the Surface Layer on Titanium in CH3OH-H2O-LiClO4 Solutions

2020

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The purpose of this study was to explain the mechanism of formation and to examine the composition of the anodic film formed on the surface of titanium in an anhydrous neutral methanol solution of electrolytes. In an environment deprived of water molecules, the growth of a 3D-phase titanium oxide layer is not possible. Electrochemical investigations demonstrated that the Ti surface in CH3OH-LiClO4 solutions experienced a pseudo-passivation with the formation of a methoxy layer, which resulted from the reaction of the metal surface with alcohol molecules. The presence of this methoxy surface film was confirmed through XPS and in situ FTIR measurements. The layer blocked the Ti anodic dissolution at the potential range corresponding to the stability of methanol and methoxy ions (i.e., <0.55 V). At potentials over 0.55 V, the methoxy layer was oxidised, which caused the “depassivation” of the metal surface and the etching of titanium. The addition of water changed the properties of Ti in CH3OH-LiClO4 solutions, but only with a water content above 0.2 mole fraction. Below this concentration of water, titanium behaved like it would in an anhydrous solution of methanol. In the range of water concentration of 0.2 to 0.7 mole fraction, the structure of the solution is strengthened because both components of the solvent formed separate percolating networks. The strengthening of the solution structure resulted in a strengthening of the surface layer of Ti(OH)m(OCH3)n. Such a layer had strong barrier properties similar to the properties of an organic polymer film. The formation and growth of a stable layer of TiO2 were possible only in a solvent when the water concentration was higher than ≈0.7 mole fraction.

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Effect of Chloride on the Anodic Dissolution of Titanium in Methanolic Solutions

Cited by 16 publications

References 13 publications

Effect of water on the titanium complexes in methanolic solutions containing hydrogen chloride

Effect of water on the titanium complexes in methanolic solutions containing hydrogen chloride

Corrosion Behavior of Heat-Treated Intermetallic Titanium-Nickel in Hydrochloric Acid Solutions

The Effect of the Methanol–Water Interaction on the Surface Layer on Titanium in CH3OH-H2O-LiClO4 Solutions

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