[0001]The present invention provides an apparatus for electrolytic etching to extract and separate the metal compound particles in the metal material, provided with a member made of a specific metal on at least a portion of the cathode is related to the electrolytic etching apparatus.
BACKGROUND
[0002] Metallic material, in particular, steel materials, the trace additive elements and various heat treatment, the type of inclusions and precipitated phases present in the material matrix, the shape such as an aspect ratio, by controlling the size, etc., required for the steel material it has been widely practiced to control the strength and characteristics.
　Accordingly, observation and the inclusions and / or precipitation phase, measuring the components, the amount is in conducting analysis of the quality control and manufacturing processes of the steel material, it has important implications.
[0003]
　In order to perform the observation of inclusions and precipitated phases by SEM or the like, it is necessary to expose the viewing surface of the inclusions and precipitated phases in the state of buried in the matrix, by a conventional electrolysis in various electrolyte solution the inclusions and precipitation phase is exposed to the sample surface, and an observable state.
[0004]
　Recently, advances in manufacturing techniques for steel materials, with the type of inclusions and precipitated phases are diverse, and they have also finely dispersed, upon observation, as well as selectively dissolving only the matrix (Fe), interposed For the goods and precipitated phase, they even fine particles, held in securely viewing surface, an electrolyte that does not dissolve is determined.
[0005]
　Further, in the case of identification and quantitative analysis of these inclusions and precipitated phases, similarly to dissolve the matrix steel sample in an electrolytic solution, to recover the inclusions and precipitated phases as the electrolytic residue, identification and this it has been performed to quantitatively analyze.
[0006]
　In the case of the quantitative analysis, electrolysis with only efficiently electrolyzing the matrix portion of the steel material holds dissolved in reliably electrolyte solution in Fe content, a portion corresponding to the other inclusions and precipitated phases it is required that can reliably collected as a residue.
[0007]
　Patent Document 1, an electrolyte composition for the steel samples, inclusions and using the same analysis method of precipitates is described.
　The electrolyte composition is that the conventional electrolytic solution were often acidic, by alkaline triethanolamine is added, even fine inclusions and precipitated phases, dissolved It becomes hard, particles of these inclusions and precipitates easily remains on the steel sample surface, after drying removed the steel sample from the electrolyte, thereby enabling the observation and analysis by SEM, etc. as it is.
[0008]
　Further, Patent Document 2, an extraction for a non-aqueous solvent electrolyte of inclusions and precipitates in the steel sample, the invention relates to electrowinning method for steel samples using the same are disclosed.
　The electrolyte, and maleic acid, and tetramethylammonium chloride, are those containing methanol at a predetermined ratio, and an electrolytic solution having excellent ability to electrolysis a large number of steel samples at a time are included in the liquid maleic anhydride, having the characteristics to generate an iron complex, to prevent the complex precipitation such as Fe hydroxides.
[0009]
　Inclusions and precipitation phase in the steel sample to be observed in situ in SEM or the like, a sample is electrolyzed, it holds the Fe component constituting the matrix, the electrolytic solution in Fe ion chelator, inclusions Ya precipitated phase is electrolytically to remain on the sample surface.
　On the other hand, if the quantitative analysis of inclusions and precipitated phases, the Fe content of the matrix holds the electrolytic solution by the chelating agent, using an electrolytic solution which does not dissolve the inclusions and precipitation phase separated from the sample by electrolysis , to recover them as electrolytic residue and identification and quantitative analysis of residue.
　Therefore, for the purpose of residue collected for identification and quantitative analysis of the inclusions and precipitation phase, and focus is placed on being able to maintain the dissolved state of Fe content as chelate complex in the electrolyte, in electrolytic operation for such the contamination for the inclusions and precipitation phase, special consideration has not been made.
CITATION
Patent Document
[0010]
Patent Document 1: JP 2002-303620 Patent Publication
Patent Document 2: JP 2000-137015 JP
Summary of the Invention
Problems that the Invention is to Solve
[0011]
　During metal compound analysis in steel by electrolytic etching or the like in the conventional non-aqueous solvent electrolyte solution, fine particles of inclusions and precipitated phases, in particular, various metal compounds, among them the surface layer of MnS, other than electrolysis operation was sometimes than content measured by means unexplained phenomenon high concentration of CuS is observed is observed. Therefore, there is possible to detect the MnS particles though as CuS (Artifact CuS).
[0012]
　The present inventors have, for the cause, a study result, electrolysis operation in detail, solubility product K in the electrolyte sp small metal ions of (Cu 2+ when) is generated at the surface of the metal sulfide (MnS), solubility product K sp large metal ions (Mn 2+ ) is, the solubility product K sp less metal ions of (Cu 2+ was found to be substituted (exchange) in). The substitution of metal ions in such sulfide surface, at room temperature and atmospheric pressure, moreover have found that to proceed easily in aqueous solutions and non-aqueous solvent.
[0013]
　As a result, in the steel samples, the presence to have inclusions and precipitated phases originally as MnS, as long as observation of the surface, will be observed as CuS, also on the surface of MnS, Cu ions in the electrolyte the originating CuS is exchanged several tens of nm in thickness (1 ~ 100nm) MnS
that, even if mass spectrometry from the residue, in the case of fine particles is occupied by the CuS a substantial portion of the volume since the, had become an accurate quantification is impossible.
[0014]
　Above has been described in the case of attack on the MnS surface by Cu (substitution phenomenon of Mn atoms and Cu atoms of MnS surface), it can be estimated that express a similar phenomenon in the metal other than Cu. That is, the substitution of metal ions on the surface metal compound, the solubility product K sp magnitude difference corresponding to (10 digits (10 10 when there are) (Below, in the present specification, this phenomenon is called "Artifact"). More particularly, the solubility product K sp pK of two compounds having different sp when the difference (sometimes hereinafter referred to as delta) is about 10 or more, pK sp large (solubility product K sp small) compound and pK sp substitution with a small compound (solubility greater product) can be estimated easily be advanced.
The above conditions can be expressed by the following equation.
Delta = pK sp [compound (K sp less ones of)] - pK sp [compound (K sp larger of)]
= (- log 10 K sp [compound (K sp less ones of)]) - (- log 10 K sp [compound (K sp large ones)])
≧ 10
, where the solubility product K of certain compounds sp is K sp represents the [compound], pK sp [compound] = - log 10 K sp [compound] and represent.
[0015]
　Indeed, the present inventors have conducted simulations to act Ag in MnS, Ag is to attack the MnS, together expel the ionized in the electrolytic solution Mn, itself, Ag in MnS surface 2 S it remains as it was confirmed. Here, Ag 2 S and MnS solubility product (or pK sp Comparing), Ag 2 solubility product K of S sp small (pK sp is large), the solubility product K of MnS sp is large (pK sp is smaller ). Ag 2 solubility product K S and MnS sp difference is 37 digits, pK sp is the difference Δ of a 36.6. Expressed in equation or less.
= PK delta sp [Ag 2 S] -pK sp [MnS]
　= 50.1-13.5
　= 36.6 ≧ 10
[0016]
　Further, the electrolytic operation, some of the ions may be deposited on the cathode, the deposited metal and do not have high affinity for the cathode constituent material, the deposited metal is easily peeled off, the metal in the re electrolyte or precipitates as, and may become a metal ion source, that result can be a contamination source of inclusions and precipitated phases and electrolytic residue, the present inventor has found.
[0017]
　Therefore, an object of the present invention to provide or less.
- the fine metal particles (inclusions, precipitates) of a metal material by electrolytic etching method or the like in solvent electrolyte in the extraction and analysis, without changing the conventional extraction and analysis methods large, fine metal particles of Cu ions suppressing resurfacing of an object to prevent the formation of such Artifact (fictitious) CuS.
Especially metal sulfide (MnS, FeS, etc.) focused on, and an object thereof is to prevent the formation of such Artifact (fictitious) CuS.
And metals such as Cu deposited on the cathode is easily peeled off and precipitation, so as not to contamination source of inclusions and precipitated phases and electrolytic residue, it is an object to be positively deposited on the cathode.
Means for Solving the Problems
[0018]
　The present inventors, the technique for solving the above problems, intensive studies.
　As a result, in a solvent system electrolytic solution, if the presence of a metal (attack metals) forming the Artifact (fictitious) metal sulfide, substitution phenomenon from finding that not expressed, to supplement such attack metal It led feelings. In other words, at least a portion of the cathode of the electrolysis apparatus, by installing a member made of a metal element to be supplemented, and facilitate electroless deposition of the metal on the cathode, holding the precipitated attack metal on the cathode, the electrolyte free attack metal is reduced in, and conceived that Artifact (fictitious) metal sulfide is not produced.
[0019]
　By electrolysis, the matrix (Fe) ions are dissolved out from the steel sample and the like, Fe ions are retained in the electrolytic solution by the chelating agent. On the other hand, by electrolysis, it may Matrix (Fe) other than the metal ions, for example of Cu ions from dissolving, such ions (eg Cu ions) is deposited by moving to the cathode, since no capture site after precipitation easily peeled off from the cathode, or precipitated as a metal Cu in the electrolyte can be a metal ion (Cu ion) source. That can be a contamination source of inclusions and precipitated phases and electrolyte residue. By such actively established a capture site for attaching (precipitation sites) metal ions (Cu ion) as the deposited metal, peeling and precipitation after electrolytic deposition of these metals ions (Cu ions) is at the cathode without, it has been found that it is possible to reduce the metal ions into the electrolyte solution (Cu ion) source. Therefore, for example, it does not attack the MnS surface observation for steel sample surface Cu ion, or, even in the electrolytic operation for identification and quantitative analysis of the inclusions and precipitation phase, similarly, created from inclusions and precipitated phases to have been quantitatively analyzed for residue, by such metal Cu and CuS are not mixed, it is possible to allow observation of the inclusions and precipitated phase of the steel sample for surface observation remains original form, Further, the electrolytic residue is analyzed, free of metal Cu and CuS, etc. from Cu ions eluted from the matrix or the like of the sample, originally due to inclusions and precipitation phase which contained the steel sample the element only, it has been found that properly can be identified and quantified.
[0020]
　The present invention has been made based on the above findings, its gist the following.
(1) comprising an anode and a cathode, the metal material was electrolytically etched by energizing between the anode and the cathode, an apparatus for electrolytic etching to separate extract metal compound particles in the metal material,
a metal compound M ' x ' a y' of the solubility product K sp [M ' x' a y ' and,
extraction target metal compound M included in the metal material in x a y the solubility product K sp [M x a y When' ,
metal M Δ is defined by the following equation becomes 10 or more 'of the member that includes, provided on at least a portion of the cathode,
the metal M' electrolyte containing a drug and a non-aqueous solvent to form a complex comprising characterized in that it comprises an electrolytic tank for accommodating a device for electrolytic etching.

= PK delta sp [M ' x' A y ' ] -pK sp [M x A
y ] = (- log 10 K sp [M' x ' A y' ]) - (- log 10 K sp [M x A y ])
here, M and M 'are different metal elements, a is M or M' is a single atom or group to form a compound, x, x ', y, y' is M, M ' represents the composition ratio of the compound depends on the valence of a, said solubility product K sp is the value at 25 ° C. in an aqueous solution
[0021]
(2) the extraction target metal compound M x A y is characterized in that it is a one or two MnS or FeS, electrolytic etching apparatus according to (1).
[0022]
(3) the metal compound M ' x' A 'y metal M' is, for Hg, Ag, Cu, Pb, Cd, Co, characterized in that at least one of Zn, and Ni, the (1 ) or (2) electrolytic etching apparatus according to.
[0023]
(4) member provided in the cathode, above, characterized in that are provided so as to cover the surface of the cathode (1) to (3) apparatus for electrolytic etching according to any one of.
[0024]
(5) the cathode, apparatus for electrolytic etching according to any of it, characterized in that is made of the metal M '(1) ~ (3).
[0025]
(6) member provided in the cathode, the (1), characterized in that it consists of 99.9% of Cu and unavoidable impurities in terms of mass% apparatus for electrolytic etching according to any one of (5) .
(7) said non-aqueous solvent, electrolytic etching apparatus according to any one of characterized in that it comprises at least one of methanol or ethanol (1) to (6).

(8) agents which form a complex containing the metal M 'is either polyethylene amines, ethylenediaminetetraacetic acid, characterized in that it comprises at least one cyclohexane diamine tetraacetic acid (1) to (7) electrolytic etching apparatus crab according.

(9) the medicament is characterized in that it comprises triethylenetetramine, electrolytic etching apparatus according to (8).

(10) electrolytic etching apparatus according to any one of further comprising a stirring means of the electrolytic solution (1) to (9).

(11) a bubble generator that irradiates gas bubbles on the anode surface, electrolytic etching apparatus according to further comprising (10).
[0026]
(12) comprising an anode and a cathode, the metal material was electrolytically etched by energizing between the anode and the cathode, a method of extracting the metal compound particles in the metal material,
a metal compound M ' x' A y ' solubility the product K sp [M ' x' a y ' and,
extraction target metal compound M included in the metal material in x a y the solubility product K sp [M x a y When,
as defined by the following formula that Δ metal M to be 10 or more 'of the member that includes, provided on at least part of the surface of the cathode,
the metal M' the use of an electrolyte containing a drug and a non-aqueous solvent to form a complex comprising wherein, the method for extracting the metal compound particles.

= PK delta sp [M ' x' A y ' ] -pK sp [M x A
y ] = (- log 10 K sp [M' x ' A y' ]) - (- log 10 K sp [M x A y ])
where M and M 'are different metal elements, a is M or M' is a single atom or group to form a compound, x, x ', y, y' is M, M ', represents a composition ratio of the compound depends on the valence of a, said solubility product K sp is the value at 25 ° C. in an aqueous solution

(13) when performing the electrolytic etch, stirring electrolytic etching an electrolytic solution method of extracting the metal compound particles according to (12) to.

(14) method for extracting metal compound particles according to, characterized in that stirring the electrolyte solution with a magnetic stirrer (13).

(15) method for extracting metal compound particles according to said bubbling gas bubbles in the electrolyte (13).
Effect of the invention
[0027]
According-to the present invention, the surface analysis of the extracted metal particles, reality disappears be misidentified as CuS particulate is MnS and FeS, true form (size, components) of the metal sulfide can know news can also be accurately determined amount of metal sulfide in the steel material.
According-to the present invention, except that it is possible to observe in nature present are the components and form steel sample inclusions or precipitates equality exposed on the steel sheet sample surface by electrolytic operation, the analysis of electrolyte residue when quantitative analysis of inclusions and precipitation phase component, without being affected such as Cu contamination from the electrolyte, it is possible to correctly quantitative analysis, structure observation and the steel samples, inclusions in the steel sample or in which it contributes to greatly improve the accuracy of the identification and quantitative analysis of the precipitate phase.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028]
It illustrates an example of a sketch of FIG. 1 for electrolytic etching according to the present invention apparatus.
FIG. 2 is a graph showing the analysis results of the electrolytic residue steel samples.
3 is a graph showing the SEM photograph and the element concentration of inclusions near the specular polished steel sample.
DESCRIPTION OF THE INVENTION
[0029]
　The present invention includes an anode and a cathode, the metal material was electrolytically etched by energizing between the anode and the cathode, an apparatus for electrolytic etching to separate extract metal compound particles in the metal material,
a metal compound M ' x ' a y' of the solubility product K sp [M ' x' a y ' and,
the metallic material extraction target metal compound contained in the M x a y solubility product of K sp [M x a y ] and Then,
metal M Δ is defined by the following equation becomes 10 or more 'of the member that includes, provided on at least a portion of the cathode,
electrolyte containing the metal M' agents and non-aqueous solvent to form a complex comprising characterized in that it comprises an electrolytic tank for accommodating the liquid, there is provided an apparatus for electrolytic etching.

= PK delta sp [M ' x' A y ' ] -pK sp [M x A
y ] = (- log 10 K sp [M' x ' A y' ]) - (- log 10 K sp [M x A y ])
here, M and M 'are different metal elements, a is M or M' is a single atom or group to form a compound, x, x ', y, y' is M, M ' represents the composition ratio of the compound depends on the valence of a, said solubility product K sp is the value at 25 ° C. in an aqueous solution
[0030]
　In the electrolytic etching apparatus of the present invention, to extract the metal compound particles in the metal material. That is, by etching the metal material in an electrolytic solution, to selectively dissolve the matrix (Fe, etc.), to expose the metal compound particles of inclusions and precipitation phase etc. contained in the metal material on the sample surface. This allows the metal compound particles in the observable state.
　As an extraction method of the fine particles of the metal in the sample, for example, acid decomposition method to dissolve the iron matrix of the steel sample in an acid solution, halogen dissolution to dissolve iron matrix steel samples with iodine methanol mixed solution or a bromine-methanol mixed solution Law, non-aqueous solvent constant current electrolysis, or, non-aqueous solvent controlled potential electrolysis (SPEED: Selective potentiostatic Etching by electrolytic Dissolution method) method, or the like. Of these, SPEED method using a non-aqueous solvent, when the fine particles are dispersed in a solvent, unlikely to occur change in the composition and size, is suitable because it can extract also stable in unstable particles. With the present embodiment, with reference to FIG. 1, as an example of the evaluation method of the particulates in the steel materials according to the general electrowinning method in which non-aqueous solvent controlled potential electrolysis method (SPEED method), but a description the method of extraction in the present invention is not limited to the SPEED method.
[0031]
　Initially, the metal sample 4, for example, processed to dimensions of 20 mm × 40 mm × 2 mm, an oxide film such as a surface layer such as scale is removed by chemical polishing or mechanical polishing, etc., it should issue the metal layer . Conversely, when analyzing particles contained in the oxide film layer, leaving intact form.
[0032]
　Next, the metal sample, the description will be continued with reference to an example of electrolysis using the SPEED method. Specifically, it meets the electrolytic solution 9 to the electrolytic cell 10, by immersing the metal sample 4 therein, the reference electrode 7 is brought into contact with the metal sample 4. Connecting the platinum electrode 6 and the metal sample 4 in the electrolytic device 8. By energizing between the metal sample 4 and the platinum electrode 6 can be platinum electrode 6 is operated as a cathode. Generally use of the above electrolysis method, compared to the electrolysis potential of the metal portion serving as the matrix of the metal sample 4, the electrolytic potential of the steel in the fine particles such as precipitates with high electrolysis potential. Therefore, by using the electrolytic apparatus 8 was dissolved matrix metal sample 4, and between the electrolyte potential does not dissolve the fine particles of the precipitate or the like, by setting the voltage, it is possible to selectively dissolve only matrix to become. The Fe electrolytic eluted sample surface of the surface matrix portions, inclusions or precipitation phase 5 is raised in a state suitable for observation by SEM or the like. Moreover, continued electrolysis, the inclusions and precipitation phase is disengaged from the surface of the sample, recovered as electrolytic residue 11, and filtered off from the electrolyte, it may be subjected to identification and quantitative analysis.
[0033]
　Electrolytic solution for a metal material according to the present invention, i.e., or electrolysis Fe matrix of the surface in order to observe the inclusions and precipitation phase, in order to quantitatively analyze the inclusions and precipitated phases, electrolyze Fe matrix, electrolyte for use in electrolytic for recovering residues, preferably,
　(1) complexing agent for Fe ions,
　(2) electrolyte order to ensure conductivity to the electrolyte,
　of Fe or the like which is (3) formed solvent, for holding the complex in the liquid
containing.
[0034]
　The complexing agent for Fe ions, acetylacetonate, maleic anhydride, maleic acid, triethanolamine, salicylic acid, may select one or more from among the methyl salicylate.
[0035]
　The electrolyte, tetramethylammonium chloride (TMAC), sodium chloride (NaCl), it is possible to select one or more from among lithium chloride (LiCl).
[0036]
　Solvents, and various complexing agents, must be one that can hold a complex thereof with Fe in solution, or may be a non-aqueous solvent. To a relatively low electrolytic voltage in aqueous electrolyte solution (e.g., -300mV or less) even various precipitates to degrade, non-aqueous solvent electrolyte is wide stable electrolysis region, superalloys, high alloy, stainless it can be applied to almost any steel material to the carbon steel from. When using a non-aqueous solvent electrolyte, primarily, the dissolution of the matrix, dissolved in the Fe ions and the chelating agent is only (complexation) reaction occurs, inclusions or precipitation phase 5 without dissolving, it is possible to perform a three-dimensional observation and analysis in the "in situ" state on the base material. As the non-aqueous solvent, proceeds smoothly electrolysis, moreover, a compound that dissolves and a complexing organic compound capable supporting electrolyte is suitable, for example, lower alcohols, for example, be methanol, ethanol, or isopropyl alcohol can. Methanol or ethanol, or may be selected mixtures thereof.
[0037]
　The conventional constant-potential electrolytic method, an electrolytic solution, for example, 10 mass% acetylacetone (hereinafter referred to as "AA") -1 mass% tetramethylammonium chloride (hereinafter referred to as "TMAC") - methanol, or 10 wt% maleic anhydride -2 wt% TMAC- methanol solution is used. In these electrolyte solutions, electrolyte eluted Fe generates a complex, resulting Fe complex because preferable from the viewpoint that dissolves in the electrolyte, are widely used.
[0038]
　Metals other than the matrix (Fe) in the electrolytic solution, although relatively if Hisure matrix (Fe) is slight, it may be eluted. Its solubility product K elution metal sp is small (in other words, pK sp (= -log 10 K sp ) is large), inclusions or precipitated phases 5 and electrolyte residue 11 is the solubility product K sp large (pK sp is smaller ) if it contains metal of the metal compound, the surface of the metal compound, the solubility product K sp large (pK sp is small) metal ions (e.g. Mn 2+ ) is, the solubility product K sp small (pK sp is large) metal ions (e.g. Cu 2+ to be replaced) (exchange), the present inventor has discovered. This substitution solubility product K sp difference of 10 digits (10 10 when there is a magnitude difference) than about, more specifically, the solubility product K sp pK of two compounds having different sp difference Δ of about 10 or more when it is considered that proceeds easily. Solubility product K sp difference of 20 digits (10 20 when there is a magnitude difference) than about, and more particularly, pK sp when the difference Δ is about 20 or more, substitution is considered to more readily proceeds.
[0039]
　Table 1, the solubility product K sulfide at 25 ° C. in an aqueous solution sp and, pK between sulfide sp (= -log 10 K sp indicates a difference Δ in). In the table, the frame of the double line (or dark gray frame) is pK sp is the combination of sulfide difference Δ is 22 or more, expected exchange reaction readily or proceed in seconds in those combinations It is. Expressed in simplified manner symbol, the expectation of the exchange reaction (prediction) is expressed as ◎. Thick lines (or light gray box) are pK sp is a combination of the difference Δ sulfide is less than 10 or more 22, it is possible to it takes from a few minutes to several hours units are expected to exchange reaction proceeds that. Expressed in simplified manner symbol, the expectation of the exchange reaction (prediction) is expressed as ○ ~ △. Thin line frame (or white frame) is pK sp is the combination of sulfide difference Δ is less than 10, the exchange reaction is a combination thereof are expected to hardly proceed. Expressed in simplified manner symbol, the expectation of the exchange reaction (prediction) is expressed as △ ~ ×.
　Regarding the solubility product of sulfide, a sulfide of the same element by crystal form such also, there is shown a different solubility product. In Table 1, pK sp is listed sulfide having a crystal form such difference Δ is small. This, pK sp be in a form difference Δ increases, pK of the sulfide to be sp difference Δ becomes 10 or more, it is considered that exchange reaction proceeds.
[0040]
[Table 1]

[0041]
　The above solubility product K sp but is a value in aqueous solution, it is estimated that there is the same tendency even nonaqueous solvent such as methanol in the same polar solvent.
[0042]
　For example, if there is MnS in the steel sample surface or electrolyte residue, sulfides Cu ions eluted in the electrolyte solution, pK of the MnS sp for the difference is 22.6, attack the MnS and, together with the expel the electrolyte to ionize the Mn, itself, remains as CuS the MnS surface. That is, in a Cu-containing steel sample, originally inclusions were present as MnS and precipitation phase, as long as observing the surface, will be observed as CuS. Further, the surface of MnS, CuS due to Cu ions in the electrolyte, by replacing the thickness of several tens of nm (1 ~ 100nm) MnS, be subjected to mass spectrometry from the residue, if fine particles the, since the occupying a substantial portion of the volume of CuS, accurate quantification becomes possible. The phenomenon of metal such surface vicinity is replaced, in this specification, sometimes referred to as Artifact (fictitious).
[0043]
　Further, sulfides Ag ions, pK of the MnS sp for the difference Δ is 36.6, and attack the MnS, together with ionized Mn expelled into the electrolytic solution, itself, Ag on MnS surface 2 remains as S. This is confirmed in Figure 3 obtained by the following procedure.
· MnS was prepared confirmed steel sample that contains as inclusions, in order to remove surface impurities, subjected to a pre-polished.
- include sulfides are conventionally known inclusions can recovered as a residue 4 wt% methyl salicylate + 1% by mass salicylic acid + 1% by mass tetramethylammonium chloride (TMAC), the electrolyte solvent is methanol (4% MS ) is prepared.
- the steel sample performing electrolysis in the electrolytic solution.
- After the end of electrolysis, mixed dropwise Ag ion solution in the electrolyte.
· Ag ion solution before and after the dropwise addition, the steel samples electrolytic surface, to observe and measure the surface element density by EDS scanning electron microscope (SEM).
- Figure 3 is of post-Ag ions dropping, the top left image is an SEM observation image, the upper right image SEM observation image, which shows superimposed charts Ag concentration measured by the EDS, the bottom left image There is limited to showing overlapping charts Mn concentration, in which the lower right image showed overlapping charts S concentration.
- In addition, as a matter of course, in front of Ag ions dropping, the presence of Ag was observed.
[0044]
　From the chart of the element concentration in FIG. 3, only the surface portion of the MnS particles Ag 2 it is confirmed substituted with S. The height of each element in the chart (concentration) is relative, the following can be read. Specifically, in a portion of the inclusion particles, the value of the graph of Mn and S has increased to a mountain type, it is inclusion particles, containing Mn and S, that is, specifically, a main component of MnS it is particles is confirmed. Ag is increased concentration at the end of the inclusion particles, it is confirmed that Ag is concentrated at the surface of the inclusion particles. Further, in the central portion of the inclusion particles, the concentration of Ag is not Takamara, since higher concentrations of Mn and S, it is confirmed that only the surface of the MnS is replaced with Ag.
[0045]
　The present inventors have provided an anode and a cathode, the metal material was electrolytically etched by energizing between the anode and the cathode, the apparatus for electrolytic etching to separate extract metal compound particles in the metal material,
　' ' specific member, by providing at least a portion of the cathode, the free attack metal (M ') is reduced in the electrolyte was newly found that it is possible to prevent the Artifact (fictitious). Certain members, the metal compound M ' x' A 'y comprises a metal (attack metal) M', wherein the metal compound M ' x' A 'y the solubility product K sp [M' x ' a y ' and,
extraction target metal compound M contained in the metallic material x a y the solubility product K sp [M x a y When,
delta = pK sp [M' x ' a y' ] -pK sp [M x a y
] = (- log 10 K sp [M ' x' a y ' ]) - (- log 10 K sp [M x a y ])
≧ 10
is.
　Furthermore, by using an electrolytic solution comprising an agent that forms a complex including attack metal M ', free attack metals in the electrolyte is reduced, the new found that it is possible to prevent the Artifact (fictitious).
　Here, M and M 'are different metal elements, A is M or M' is a single atom or group to form a compound, x, x ', y, y' is M, M ', A represents a composition ratio of the compound depends on the valence, the solubility product K sp is the value at 25 ° C. in an aqueous solution.
[0046]
　By electrolysis, the matrix (Fe) ions are dissolved out from the steel sample and the like, Fe ions are retained in the electrolytic solution by the chelating agent. On the other hand, by electrolysis, may Matrix (Fe) other than the metal ions, for example ions of attack metal M 'such as Cu leach, such ions (eg Cu ions) is deposited by moving to the cathode , easily peeled off from the cathode since no capture site after deposition, or precipitated as metal Cu in the electrolyte can be an attack metal M 'sources (Cu, etc.). That can be a contamination source of inclusions and precipitated phases and electrolyte residue.
　Electrolytic etching apparatus of the present invention comprises a member containing the attack metal M 'on at least a portion of the cathode. 'In that it contains a, attack the metal M' the member provided in a portion of the cathode attack metal M serves as a (Cu, etc.) captured sites to actively adhere the ions (precipitation sites). Incidentally, 'As the content of high, attack the metal M' attack metal M in the member considered (Cu, etc.) the effect of action to actively adhere the ions increases. Therefore, the content of the attack metal M 'in the member may be 90 mass% or more, preferably 95 mass% or more, and more preferably be 99 mass% or more. Precipitated attack metal M and 'a, attack the metal M contained in the member provided in a portion of the cathode', are the same material, because of its high affinity, attack the metal M which is electrolytically deposited on the cathode '( Cu, etc.) is separated after precipitation, it is possible to suppress the precipitation as a metal Cu. Further, it is possible to reduce the attack metal M '(Cu, etc.) supply to the electrolytic solution.
　Therefore, pK sp difference Δ is large metal compound M of x A y be present, attack the metal M 'is a metal compound M x A y replaced with a metal M on the surface (i.e., Artifact (onomatopoeic)) It can not be carried out freely. In other words, M ' x' A y ' generation of is suppressed.
　Thus, for example, it does not attack the MnS surface observation for steel sample surface Cu ion, or, even in the electrolytic operation for identification and quantitative analysis of the inclusions and precipitation phase, similarly, created from inclusions and precipitated phases to have been quantitatively analyzed for residue, by such metal Cu and CuS are not mixed, it is possible to allow observation of the inclusions and precipitated phase of the steel sample for surface observation remains original form, Further, the electrolytic residue is analyzed, free of metal Cu and CuS, etc. from Cu ions eluted from the matrix or the like of the sample, originally due to inclusions and precipitation phase which contained the steel sample only, it can be correctly identified and quantified elements.
[0047]
　Artifact (constructive) as prone attack metal M 'of, the content and the solubility product K sp of low, in other words pK sp Cu from a height of is remarkable. Cu is, pK against Cu compounds sp easily attacked the difference Δ is MnS and FeS surface is approximately 20, may result in Artifact (fictitious). However, attack by Artifact (onomatopoeic) or attack metal M 'is pK sp as the difference Δ is large, considered likely to occur, subject of the present invention is not limited to the combination of Cu and MnS and FeS. Specifically, large pK sp metal compound having an M ' x' A 'y metal M' is well Hg, Ag, Cu, Pb, Cd, Co, be at least one of Zn, and Ni , these can be a attack metal M '. Attack metal M 'is mainly, metal M contained in the steel material in the sample' considered or compounds thereof are those eluted in the electrolyte solution. However, the electrolytic solution or the electrolytic device may be reused, 'may or compounds are present, which attack the metal M' metal M in the reused electrolyte or electrolytic device sometimes becomes . Further, in case of electrowinning operations, metal M 'or a compound is mixed in the electrolytic solution as contaminants, attack the metal M' may be a.
M 'is, Hg, Ag, Cu, Pb , Cd, Co, Zn, and may be at least one of Ni, a metal element different from M. A is a single atom or group forming a M or M 'and the compound, C, N, H, S, O, one or more atoms independently selected from the group consisting of atoms of P and F it may also include a. Hg, Ag, Cu, Pb, Cd, Co, and sulfides of Zn, and Ni, pK of the MnS sp difference Δ of 10 or more. In particular, Hg, Ag, and sulfides of Cu, pK of the MnS sp difference Δ of 20 or more. PK
　of extraction target metal compound MxAy and attack metal compound M'x'Ay ' sp when the difference Δ of about 10, Artifact (fictitious) can occur in a few hours. Actual electrowinning analysis is often carried out on the order of a few hours. Therefore, pK sp combinations difference Δ of about 10 is likely to affect the analysis. In the present invention, pK sp difference Δ has defined as 10 or more, it is possible to suppress the Artifact (fictitious) which may occur when the. PK
　of extraction target metal compound MxAy and attack metal compound M'x'Ay ' sp as the difference Δ is large, Artifact (fictitious) can occur easily or quickly. In the present invention, pK sp can select a combination of MxAy difference Δ is large and M'x'Ay ', whereby it is possible to suppress may occur easily or quickly Artifact (fictitious), preferred. In this regard, M'x'Ay 'pK a sp [M'x'Ay'] is, pK of extraction target metal compound MxAy sp compared to [MxAy], it may be preferable 11 or more large, large 12 or more more preferably, more preferably 13 or more large, more preferably 14 or more larger, more preferably greater than 15, more preferably 16 or more larger, more preferably 17 or more large, 18 or more greater and even more preferably, more preferably 19 or more large, more preferably 20 or more large, it is preferably 21 or more large, it is more preferably 22 or more large, more preferably 23 or more larger, more preferably greater than 24, 25 more preferably greater than, more preferably it is 26 or more large Ku, is more preferably 27 or more large, more preferably 28 or more large, more preferably 29 or more large, more preferably greater than 30, it is preferably 31 or more large, that more than 32 large More preferably, more preferably 33 or more large, more preferably 34 or more larger, more preferably greater than 35, more preferably 36 or more large, more preferably 37 or more large, more preferably 38 or more large, 39 or more more preferably greater, more preferably greater than 40.
　Incidentally, solubility product K sp but is a value in aqueous solution, as shown in Table 2, a non-aqueous solvent K even when a (lower alcohol) sp obtained from the pK sp (-log 10 K sp difference) delta There more than 10, the reaction that is observed is confirmed. Specifically, it was subjected to the following confirmation test.
And extracting the object as a sample containing, two steel containing MnS (as the particle size of MnS is not less than 1 [mu] m, and those having a particle size of 100 ~ 150 nm) was prepared, was mirror polished on their surface .
- 'As + ions, Ag, Cu, Pb, Co , Zn, a metal ion concentration of Ni, 6 kinds of atomic absorption spectrometry standard solution for each 1000 [mu] g / ml (M' attack metal M was prepared + solution). The M 'solution 0.1ml was mixed with methanol 0.3ml a non-aqueous solvent.
- The mixture is coated on the steel surface was confirmed changes in the steel surface.
Those coated with a mixture containing Ag and Cu, the surface of the steel material is changed to black within 5 minutes of application. Those coated with a mixture containing Pb, the surface of the steel material is changed to black in about 10 minutes from the application. Co, Zn, obtained by coating a mixed solution containing Ni, the surface of the steel material is changed to black in about 20 minutes from the application.
- In addition, it was subjected to SEM and EDS observed for was discolored steel, substitution of Mn and the attack metal M 'on the surface of any MnS particles (i.e., Artifact (onomatopoeic)) it was confirmed that occurs It was.
Therefore, the scope of the present invention, the solubility product K sp but is an indication of an aqueous solution, it is possible to apply the non-aqueous solution, wherein solubility product K in sp it shows the same tendency as in an aqueous solution There are estimated.
Further, pK sp as the difference Δ is large, substituted (Artifact (onomatopoeic)) reaction was also confirmed fast that. On the other hand, pK sp even small differences Δ of, although relatively reaction rate becomes slow, steady substituted (Artifact (onomatopoeic)) reaction was also confirmed to proceed. Electrolytic extraction analysis of steel are often performed in the order of a few hours. For example, there is a time soak the sample in the electrolytic solution, even if planned in about 2 hours, also be further extended about 1 hour. pK sp If the difference Δ is using Ni-containing solution and MnS to be 10, was observed color change in about 20 minutes. That, pK sp difference Δ is the 10 or more, substituted (Artifact (onomatopoeic)) reaction, that can be problematic is confirmed.
　In this connection, in addition to the confirmation test of the attack metal M '+ solution and triethylenetetramine as further complexing agent in a mixture of methanol (TETA) plus 0.1 ml (complexing agent additive liquid ) was prepared, it was carried out it is also the case that was applied to the mirror-finished steel observation. If you make a complexing agent additive solution, several hours later discoloration of the steel surface is not observed, a good mirror-polished state is held. Even in SEM and EDS observation, Artifact (fictitious) was not confirmed.
[0048]
[Table 2]

[0049]
　Members comprising attack metal M 'provided in the cathode may be provided so as to cover the surface of the cathode. Surface of the cathode, because the attack metal M the effect of suppressing the peeling-precipitation after deposition of 'act as a capture site for ions, precipitated attack metal M' (Cu, etc.) is increased.
　Alternatively, it said cathode, said small solubility product K sp (large pK sp may be made of metal) That is, the entire cathode, 'made, attack the metal M' attack metal M affinity is enhanced more with the ion, attack the metal M 'act more effectively as a capture site for ions, precipitated attack metal M' (Cu the effect of suppressing the peeling-precipitation after precipitation etc.) This is because even higher.
[0050]
　Member made of attack metal M 'provided in the cathode may be made of 99.9% of Cu and unavoidable impurities in mass%. As described above, as Artifact (fictitious) prone attack metal M 'a, Cu is remarkable. Attack metal M 'a member made of, by those consisting of 99.9% of Cu and unavoidable impurities in terms of mass%, attack the metal M' ensure high effect of suppressing the peeling-precipitation of Cu as can do.
[0051]
　As an agent for forming a complex comprising an attack metal M ', it is available crown ethers. Crown (Crown) ether is a cyclic polyether (which ether units led some), it is possible to change the size of the hole of the annular. Therefore, the attack metal species M 'depending on, ready crown ethers having suitable holes, whereby the attack metal species M' can selectively capture only.
[0052]
　Agent to form a complex including attack metal M 'is selected from the group consisting of polyethylene amines, ethylenediaminetetraacetic acid, one kind or may contain two or more of cyclohexane diamine tetraacetic acid. These act as a chelating agent to trap the attack metal M '. As polyethylene amines, triethylenetetramine (TETA), penicillamine, pentaethylenehexamine and the like. In particular, chelating agents such as triethylene tetramine has a high selectivity for Cu ions and Ni ions, attack the metal M 'is in the case of Cu and Ni and the like, are exhibited particularly high trapping effect.
　Table 3 attack Cu or Ni as the metal M 'when captured by various chelating agents, complexes of the stability constant (Log 10 K d shows a). More stability constant is high, the captured the attack metal, considered less likely to again liberated, preferred. Compound M ' x' A y , especially inhibiting the formation of CuS, as an agent for forming a complex comprising an attack metal M ', those stability constant of 10 or more, preferably one of the 12 or more, more preferably 14 more than that, more preferably of 16 or more, more preferably 18 or more of, and more preferably of 20 or more, may be selected. In general, compounds M 'should suppress generation x' A y the solubility product K sp [M ' x' A 'y When, pK] sp [M' x ' A y' ] (= - Log 10 K sp [M ' x' a y ' ]) and Log K d the difference between, pK sp [M' x ' a y' ] -log K d is, of less than 26, preferably of less than 24, more preferably less than 22 ones, more preferably of less than 20, more preferably of less than 18, more preferably of less than 16, may be selected.
[0053]
[table 3]

[0054]
　Attack metal M 'is captured, attack the metal M' complex is formed. Complex attack metal M 'is maintained in a dissolved state in the above-mentioned solvent. Therefore, pK sp difference Δ is large metal compound M of x A y be present, attack the metal M 'is a metal compound M x A y replaced with a metal M on the surface (i.e., Artifact (onomatopoeic)) It can not be carried out freely. In other words, M ' x' A y ' generation of is suppressed.
[0055]
　Agent to form a complex or electrolyte containing this, may be stirred in the electrolytic bath. Thus, unreacted drug 'likely to contact with, attack the metal M' attack metal M becomes is easily captured. It means the stirring is not particularly limited, bubbling with bubble generator may be used vortex due magnetic stirrer. Or it may be formed by dropping droplets of medicament unreacted in the vicinity of the attack metal M '. As unreacted drug is easily contacted to attack the metal M ', if bubbling 100 cc / min, preferably 200 cc / min, 100 rpm if stirrer, preferably at 200 rpm, may be lower. When bubbling amount and stirrer speed is too high, resulting in problems such as peeling of the electrolyte surface of the object. Therefore, if the bubbling 600cc / min, preferably 500 cc / min, if stirrer 600 rpm, preferably may be up to 500 rpm.
　In the case where in a general electrolytic operation performs agitation of the electrolyte solution, as electrolyte flow is not in contact with the electrolyte object caused by stirring, stirring operation is performed. This is based on the idea that the electrolyte flow generated by the stirring so as not to affect the electrolytic object. In the present invention, from the viewpoint of the drug to form a complex is likely to contact the attack metal M 'or a source thereof, such electrolyte flow is in contact with the electrolyte object caused by stirring or the like, stirring or supplying the drug it may be.
　Further, nitrogen gas or helium, an inert gas such as argon may be mentioned as a gas for bubbling. Active gas such as oxygen and hydrogen, may affect the concentration of dissolved oxygen in the electrolyte, since it may affect the electrolytic object, which is not preferable.
[0056]
　The present invention, using the same action as the above-described electrolytic etching apparatus, a method of extracting the metal compound particles in the metal material is also provided. The method includes an anode and a cathode, the metal material was electrolytically etched by energizing between the anode and the cathode, to a method of extracting the metal compound particles in the metal material. In this way, the extracted metal particles, reality disappears be misidentified as CuS particulate is MnS and FeS, true form (size, components) of the metal sulfide can know, more steel material the content of the metal sulfides can also be accurately determined. Further, according to this method, it extracts other it becomes possible to observe (e.g. inclusion or precipitated phase etc. were exposed on the steel sheet sample surface by electrolysis operation) in component and form that was originally present in the steel sample , extracts (e.g., electrolyte residue) inclusions and precipitation phase component from the analysis in the case of quantitative analysis of, without being affected such as Cu contamination from the electrolyte, it is possible to correctly quantitative analysis of steel samples structure observation and, thereby contributing greatly to the accuracy of the identification and quantitative analysis of inclusions or precipitation phase in the steel sample.
[0057]
　Incidentally, in the steel, Mn precipitates MnS is easily replaced by Se, and it is reported that may precipitate as MnSe, as the reason, the same NaCl type structure MnS and MnSe, the lattice constant is very it is said to be due to close. From the Periodic, S, for also Sb and Te and the adjacent group is Se and cognate be easily replaced with S of MnS, are also expected to precipitate as MnTe and MnSb. Then, MnS is, MnSe, MnTe and, or if being easily replaced MnSb, correct quantitative analysis of MnS is, MnSe, believed to also help improve the accuracy of quantitative analysis of MnTe and MnSb.
[0058]
　Further, MnSe further may result in substitution (Artifact (onomatopoeic) reactions with other selenide in. Table 4, pK between selenide at 25 ° C. in an aqueous solution resulting from the substitution or the like of MnS sp (= -log 10 K sp ) difference delta. in table showing of a double line border (or dark gray frame) is pK sp is the combination of selenide is difference delta is 22 or more, the exchange reaction is a combination thereof expressed easily or is expected to proceed in seconds. simply by the symbol, the expectation of the exchange reaction (prediction) is expressed as ◎. thick lines (or light gray box) are pK sp difference Δ is a combination of selenide is less than 10 to 22, it is possible to it takes from a few minutes to several hours units, if indicated by the. simplified manner symbols that are expected to exchange reaction proceeds, the expected exchange reaction (Prediction) is expressed as ○ ~ △. Thin line frame (or white frame) is pK sp is the combination of selenide difference Δ is less than 10, the exchange reaction is a combination thereof and hardly proceeds if indicated by the expected. simplified manner symbol, the expectation of the exchange reaction (prediction) is expressed as △ ~ ×.
[0059]
[Table 4]

[0060]
　According to the present invention, also selenides, it is possible to prevent Artifact (fictitious).
Example
[0061]
　Hereinafter, through examples illustrate the present invention. However, the present invention should not be construed as being limited to the following Examples.
[0062]
　By electrolysis using an electrolytic etching apparatus according to the present invention, it was subjected to quantitative analysis of inclusions or precipitation phase in the steel samples. As a control example was prepared comparative example electrolysis using the conventional electrolytic solution.
[0063]
　In the present embodiment, as the steel samples, steel containing 0.4 wt% Cu, after solution heat treatment of 1350 ° C. × 30min, with samples quenched in water.
　The electrolytic solution was prepared to provide the following two types.
(1) 4% MS: are those containing 4 wt% methyl salicylate + 1% by mass salicylic acid + 1% by mass tetramethylammonium chloride can be recovered sulfide inclusions which have been conventionally known as a residue (TMAC), SPEED it is one of the electrolyte used in law.
(2) 4% MS + 5 % TETA: (1) a 4% MS, and is obtained by adding triethylene tetramine (TETA) 5 vol% to form a Cu ions and complexes.
Incidentally, the solvent was methanol either (1) to (2).
[0064]
　Using an electrolytic solution of each, and if the electrode on the cathode side was set to Pt plate made, for the case of fixing the Cu-made plate to the Pt plates made, samples were approximately 1g corresponding electrolyte, contained in the obtained electrolytic residue the content of Mn and Cu and quantified by wet chemical analysis which was calculated content in the 1g steel sample. A method for fixing a Cu-made plate to the Pt plate made were as follows. The Cu plate for fixing to the one that satisfies the substantially same size as the Pt plate, superimposing the plates, a hole in the end of the plates, through Pt wire into the hole, fixing the two plates with Pt wire (unity) was.
[0065]
　The results are shown in Figure 2.
　In the figure, 4 bands graph of this are those indicated in% overlapping the detected Mn and Cu from the respective electrolyte residue, from the left, (1) General electrolyte (4% MS) in, when the electrolysis of Pt electrode as the cathode, (2) a general electrolyte (4% MS), when the electrolysis secure the Cu plate to the cathode, and (3) common electrolyte, TETA5 volume % when the electrolyte (4% MS + 5% TETA) and Pt electrodes and electrolysis using the cathode side with the addition of (4) to the common electrolyte, electrolyte obtained by adding TETA5 vol% (4% MS + 5% TETA ) with the case of electrolysis by fixing the Cu plates to the cathode, showing a.
[0066]
　Incidentally, the steel samples employed in Example by mirror polishing analyzed the distribution of component elements by EDS or the like, Cu contained in the sample have been mostly dissolves in the matrix portion of the sample, CuS Ya Cu 2 that does not exist in the sulfide form such as S is confirmed.
[0067]
　Nevertheless, in the electrolysis of the electrolytic solution was the cathode side of a conventional Pt electrode shown in (1) in FIG. 2 (4% MS) is an electrolytic residue sulfides in steel sample are observed mainly from, Cu concentration in concentrations above Mn concentration of 0.018 wt% (0.04% = 400ppm) was measured. The reason for this is considered below. Attack metal melted from steel sample (Cu) is deposited by Pt cathode, and those which precipitated residue as peeling easily metal Cu after precipitation, and precipitated in an electrolytic solution supply source of the attack metal (Cu) Become. The attack metal supplied from the supply source (Cu), substitution of the metal (Cu) on the surface (MnS) of the metal compound (i.e., Artifact (fictitious)) resulted in CuS that was.
[0068]
　The graph shown in (2), the Cu plate was fixed to the Pt steel cathode, a case where the electrolysis of the electrolytic solution (4% MS), Cu component of the electrolytic residue is to 0.0103 wt% (103 ppm) It has been reduced to. This suppression Cu plate fixed to the Pt cathode acts as a capture site for attack metal (Cu) ions (precipitation sites), the peeling-precipitation after deposition of the attack metal (Cu) which is electrolytically deposited on the cathode and, as a result, presumably because by subtracting the attack metal (Cu) supply to objects or electrolyte solution to precipitate a residue as a metal Cu.
[0069]
　Further, the graph shown in (3), the cathode remain Pt electrode, and Mn as measured from the electrolytic residue when the electrolyte in the electrolytic solution obtained by adding 5 vol% triethylenetetramine (4% MS + 5% TETA) It indicates the concentration of Cu.
　In this case, Cu component of the electrolytic residue is decreased to 0.0016 wt% (16 ppm). This, triethylenetetramine (TETA) forms a Cu ion complexes, are replaced with metal (Mn) at the surface of attack metal (Cu) metal compound (MnS) (i.e., Artifact (onomatopoeic)) It is considered to be due to suppressed that.
[0070]
　Further, (4) shows the measurement values when used in combination with fixation of the Cu plates of the electrolytic solution containing TETA and (4% MS + 5% TETA) to Pt-made cathode.
　Cu concentrations measured from the electrolytic residue is reduced to 0.0004 wt% (4 ppm), up to 5ppm or less is the measurement limit Ordinarily analysis, we found that it is possible to reduce the Cu concentration It was.
[0071]
　That is, according to the present invention comprises a member made of attack metal on at least a portion of the cathode, using the electrolyte etching apparatus, if electrolytic metal sample improves the residue chemical analysis accuracy, present in the sample interposed it is possible to accurately identify and quantify goods and precipitated phase.
Industrial Applicability
[0072]
　According to the present invention comprises a member made of attack metal on at least a portion of the cathode, by electrolytic metal sample using electrolytic etching apparatus, the as originally present inclusions and precipitation phase in the sample in the sample together is possible to observe the form, in the chemical analysis of these inclusions and precipitation phase, can eliminate the contamination caused by the contamination by Cu or the like, it is possible to improve the accuracy of the chemical analysis.
DESCRIPTION OF SYMBOLS
[0073]
　4 metal samples
　5 inclusions and precipitation phase particle
　sixth electrode
　(cathode) 7 reference electrode
　8 power
　(potentiostat) 9 electrolytic solution
　10 electrolytic cell
　11 electrolyte residue

WE CLAIM

[Requested item 1]
　Comprising an anode and a cathode, the metal material was electrolytically etched by energizing between the anode and the cathode, an apparatus for electrolytic etching to separate extract metal compound particles in the metal material,
a metal compound M ' x' A y ' the solubility product K sp [M' x ' a y' and,
extraction target metal compound M included in the metal material in x a y the solubility product K sp [M x a y When,
following formula in defined Δ metal M to be 10 or more 'of the member that includes, provided on at least a portion of the cathode,
the metal M' accommodates the electrolyte solution containing the drug and a non-aqueous solvent to form a complex comprising characterized in that it comprises an electrolytic bath, apparatus for electrolytic etching.

= PK delta sp [M ' x' A y ' ] -pK sp [M x A
y ] = (- log 10 K sp [M' x ' A y' ]) - (- log 10 K sp [M x A y ])
here, M and M 'are different metal elements, a is M or M' is a single atom or group to form a compound, x, x ', y, y' is M, M ' represents the composition ratio of the compound depends on the valence of a, said solubility product K sp is the value at 25 ° C. in an aqueous solution
[Requested item 2]
　The extraction target metal compound M x A y is characterized in that it is a one or two MnS or FeS, apparatus for electrolytic etching according to claim 1.
[Requested item 3]
　The metal compound M ' x' A 'y metal M' is, Hg, Ag, Cu, Pb , Cd, Co, Zn, and wherein the at least one of Ni, to claim 1 or 2 electrolytic etching apparatus according.
[Requested item 4]
　It said cathode member provided in the apparatus for electrolytic etching according to any one of claims 1 to 3, characterized in that provided so as to cover the surface of the cathode.
[Requested item 5]
　The cathode, apparatus for electrolytic etching according to any one of claims 1 to 3, characterized in that is made of the metal M '.
[Requested item 6]
　It said cathode member provided in the apparatus for electrolytic etching according to any one of claims 1 to 5, characterized in that it consists of 99.9% of Cu and unavoidable impurities in mass%.
[Requested item 7]
　The non-aqueous solvent, electrolytic etching apparatus according to any one of claims 1 to 6, characterized in that it comprises at least one of methanol or ethanol.
[Requested item 8]
Agent to form a complex containing the metal M 'is selected from the group consisting of polyethylene amines, ethylenediaminetetraacetic acid, according to any one of claims 1 to 7, characterized in that it comprises at least one cyclohexane diamine tetraacetic acid of electrolytic etching apparatus.
[Requested item 9]
　Wherein the agent is characterized in that it comprises triethylenetetramine, electrolytic etching apparatus according to claim 8.
[Requested item 10]
Electrolytic etching apparatus according to any one of claims 1 to 9, further comprising a stirring means of the electrolytic solution.
[Requested item 11]
The bubble generator for irradiating a bubble in the anode surface, the electrolytic etching apparatus of claim 10, further comprising.
[Requested item 12]
　Comprising an anode and a cathode, the metal material was electrolytically etched by energizing between the anode and the cathode, a method of extracting the metal compound particles in the metal material,
a metal compound M ' x' A y ' of the solubility product K sp [M ' x' a y ' and,
the metallic material extraction target metal compound contained in the M x a y solubility product of K sp [M x a y When,
delta is defined by the following formula metal M to be 10 or more 'of the member that includes, provided on at least a portion of the cathode,
the metal M', characterized by using an electrolytic solution containing a drug and a non-aqueous solvent to form a complex containing a metal method of extracting the compound particles.

= PK delta sp [M ' x' A y ' ] -pK sp [M x A
y ] = (- log 10 K sp [M' x ' A y' ]) - (- log 10 K sp [M x A y ])
here, M and M 'are different metal elements, a is M or M' is a single atom or group to form a compound, x, x ', y, y' is M, M ' represents the composition ratio of the compound depends on the valence of a, said solubility product K sp is the value at 25 ° C. in an aqueous solution
[Requested item 13]
Wherein when performing electrolytic etching, method of extracting the metal compound particles according to claim 12, characterized in that the electrolytic etching with stirring electrolyte.
[Requested item 14]
Method of extracting the metal compound particles according to claim 13, characterized in that stirring the electrolyte solution with a magnetic stirrer.
[Requested item 15]
Method of extracting the metal compound particles according to claim 13, wherein the bubbling gas bubbles in the electrolyte.