Method for extracting metal compound particles, method for analyzing the metal compound particles, and electrolytic solution used therefor
The object of the present invention is such that a surface exchange of metal fine particles by Cu ions, or the like is inhibited in order to prevent formation of Artificial CuS or the like, in extraction and analysis of the metal fine particles (inclusions and precipitates) in a metal material by electrolytic corrosion in a solvent-based electrolytic solution, without significantly changing conventional extraction and analysis methods. A method for extracting metal compound particles in a metal material by etching the metal material in an electrolytic solution, characterized by using the following electrolytic solution, wherein it comprises a chemical agent that forms a complex containing metal M′ wherein Δ defined by the following formula is 10 or more, Δ = pKsp [ M ′ x ′ Ay ′ ] - pKsp [ MxAy ] = ( - log 10 Ksp [ M ′ x ′ Ay ′ ] ) - ( - log 10 Ksp [ MxAy ] ) wherein a solubility product of metal compound M′x′Ay′ is defined as Ksp[M′x′Ay′], and a solubility product of metal compound to be extracted MxAy, which is contained in the metal material, is defined as Ksp└MxAy┘, as well as the electrolytic solution therefor.
1. An electrolytic solution for extracting metal compound particles in a metal material by etching the metal material,
wherein the electrolytic solution comprises a nonaqueous solvent, a metal compound M′x′Ay′, a metal compound to be extracted MxAy, and a chemical agent that forms a complex containing metal M′,
wherein the chemical agent comprises at least one of a crown ether, a polyethylene amine, ethylenediamine tetraacetic acid and cyclohexanediamine tetraacetic acid, and the nonaqueous solvent comprises at least one of methanol, ethanol and isopropyl alcohol,
wherein a value Δ defined by the following formula is 10 or more
Δ= pKsp [ M′x′Ay ′]− pKsp [ MxAy ]=(−log 10 Ksp [ M′x′Ay ′])−(−log 10 Ksp [ MxAy ])
wherein Ksp[M′x′Ay′] represents a solubility product of metal compound M′x′Ay′ and Ksp[MxAy] represents a solubility product of the metal compound to be extracted MxAy, which is contained in the metal material,
wherein M and M′ are different metal elements, A consists of one or more of C, N, H, S, Se, Te, O, P and F for forming a compound with M or M′, and x, x′, y and y′ represent a composition ratio of compound determined according to the valence of M, M′ and A, and the solubility product Ksp is a value in an aqueous solution at 25° C., and
wherein the metal compound to be extracted MxAy is one or more of MnS, FeS, MnSe or FeSe.
2. The electrolytic solution according to claim 1 , wherein the metal compound to be extracted MxAy is one or two of MnS or FeS.
3. The electrolytic solution according to claim 1 , wherein the metal M′ of the metal compound M′x′Ay′ whose solubility product Ksp is smaller, is at least one of Hg, Ag, Cu, Pb, Cd, Co, Zn and Ni.
4. The electrolytic solution according to claim 1 , wherein the chemical agent comprises a crown ether.
5. The electrolytic solution according to claim 1 , wherein the chemical agent comprises any one kind or two or more kinds of polyethylene amines, ethylenediamine tetraacetic acid, cyclohexanediamine tetraacetic acid.
6. The electrolytic solution according to claim 5 , wherein the chemical agent comprises triethylenetetramine.
7. The electrolytic solution according to claim 1 , wherein the metal material is a steel material.
8. The electrolytic solution according to claim 1 , wherein the metal compound to be extracted MxAy is one or two of MnS or FeS;
the metal M′ of the metal compound M′x′Ay′ whose solubility product Ksp is smaller, is at least one of Hg, Ag, Cu, Pb, Cd, Co, Zn and Ni;
the chemical agent comprises any one kind or two or more kinds of polyethylene amines, ethylenediamine tetraacetic acid, cyclohexanediamine tetraacetic acid; and
the nonaqueous solvent contains at least one of methanol and ethanol.
9. An electrolytic solution for extracting metal compound particles in a metal material by etching the metal material,
wherein the electrolytic solution consists essentially of a nonaqueous solvent, a metal compound M′x′Ay′, a metal compound to be extracted MxAy, and a chemical agent that forms a complex containing metal M′,
wherein the chemical agent is selected from the group consisting of at least one of a crown ether, a polyethylene amine, ethylenediamine tetraacetic acid and cyclohexanediamine tetraacetic acid, and the nonaqueous solvent consists of at least one of methanol, ethanol and isopropyl alcohol,
wherein a value Δ defined by the following formula is 10 or more
Δ= pKsp [ M′x′Ay ′]− pKsp [ MxAy ]=(−log 10 Ksp [ M′x′Ay ′])−(−log 10 Ksp [ MxAy ])
wherein Ksp[M′x′Ay′] represents a solubility product of metal compound M′x′Ay′ and Ksp[MxAy] represents a solubility product of the metal compound to be extracted MxAy, which is contained in the metal material,
wherein M and M′ are different metal elements, A consists of one or more of C, N, H, S, Se, Te, O, P and F for forming a compound with M or M′, and x, x′, y and y′ represent a composition ratio of compound determined according to the valence of M, M′ and A, and the solubility product Ksp is a value in an aqueous solution at 25° C., and
wherein the metal compound to be extracted MxAy is one or more of MnS, FeS, MnSe or FeSe.