CN104114747A - Metal material, and surface treatment method and device - Google Patents

Abstract

A metal material is provided with a metal material base (2) and a reforming layer formed on the surface of the metal material base (2), wherein the reforming layer has an average of three or more protrusions (3) in a 10 [mu]m2 range, the protrusions protruding from the surface of the metal material base (2) and having an average diameter of 1 [mu]m or less when viewed from a direction that is perpendicular to the surface of the metal material base (2). Preferably, the reforming layer is provided with an average of one or more of the following protrusions in a 10 [mu]m2 range, that is, a protrusion provided with a base part protruding from the surface of the metal material base (2), and a tip part formed on the end of the base part, and having a constricted structure, in which the outer diameter of the base part is smaller than the outer diameter of the tip part, and an average diameter of 1 [mu]m or less when viewed from a direction that is perpendicular to the surface of the metal material base (2). As a consequence, it is possible to provide a metal material exhibiting new features such as hydrophilic property and light-emitting property.

Description

Metallic substance, surface treatment method and device

[technical field]

The present invention relates to surface treatment method, the manufacture method of the water-proof material using metallic substance as base material, the surface treatment method of the surface processing device of conductive material and conductive material of metallic substance, metallic substance.

[background technology]

In recent years, strong expectation is given new function to metallic substance.Specifically, except original the had beneficial characteristics of the metallic substance of intensity, processibility, solidity to corrosion and so on, with regard to the meaning of new Application Areas of developing metallic substance, also expect very much the new function relevant to metallic surface of water-wet behavior, fire resistance characteristic, characteristics of luminescence and so on.Under such background, the modified layer that the nearest modified layer for coating layer, zone of oxidation, surface cure layer, raising surfaceness etc. forms in metallic surface has been carried out positive research.If enumerate an example, have pair metallic surface carry out anodic oxidation and form microtexture technology (referring to non-patent literature 1), by electrochemical machining, form the technology (referring to non-patent literature 2) of surface fine structure etc.

[prior art document]

[non-patent literature]

Non-patent literature 1: high bridge is wise, slope enters just quick, chrysanthemum earthworm also, ジ ャ ー ヒ メ Application De ラ Biao Mian Ji Intraoperative (JHA Himendra sufacing) Vol.60 (2009) No.3p.14

Non-patent literature 2: Electricity separates the ying of micro-Fine processing へ of processing and manages permanent sufacing Vol.61 (2010) No.4294 of Theory (application of electrochemical machining in microfabrication is with theoretical) summer with と

[summary of the invention]

[inventing problem to be solved]

For metal material surface being given to the new function of water-wet behavior, fire resistance characteristic, characteristics of luminescence and so on, need to the micro-visual angle below 1 μ m under structure and the composition of effects on surface modified layer design.But it is object that functions such as improving processibility, solidity to corrosion is take in research all the time, has carried out the structure of surface reforming layer, the design of composition in micron number magnitude, thereby the embodiment of new function insufficient.For example, as the method that improves surfaceness, proposed to have the method for the roller of hair side (ダ Le) structure in the surface pressure of metallic substance.But, the concavo-convex size having more than micron number magnitude of the metal material surface being formed by the method.Therefore,, although metal material surface has owing to keeping oil make the effect of processibility raising or have the uniform effect of appearance, do not embody the function that makes new advances.In addition,, as the method that improves the coating adaptation of automobile exterior panel, proposed to form at metal material surface the method for phosphate crystal.But the particle diameter of the phosphate crystal being formed by the method has the size of several microns.Therefore, metal material surface does not embody the function that makes new advances.

On the other hand, in the microtexture formation technology of existing report, anodic oxidation is carried out in metallic surface form in the technology of microtexture the technology of being recorded as non-patent literature 1, has formed fine hole, but the function limitation that can give.In addition,, in order to make surface become zone of oxidation, surface physical property is subject to the restriction of oxide compound kind.And, in the method for the use electrochemical machining as the method that non-patent literature 2 is recorded, in order to form surface fine structure, need to make pending surface and very short to the distance between electrode, this control is very difficult.

The present invention proposes in view of above-mentioned problem, and its object is to provide the metallic substance with the new function such as water-wet behavior and the characteristics of luminescence.

In addition, other object of the present invention is to provide the surface treatment method of metallic substance and the manufacture method of the water-proof material using metallic substance as base material that can give high fire resistance characteristic to metal material surface without a large amount of labours and expense in the situation that.

And then, other object of the present invention is to provide can be low-cost and effectively manufacture surface processing device and the surface treatment method of the conductive material of following conductive material, and the big area on the specific position that described conductive material is effects on surface or surface is processed the conductive material that has formed nano level microtexture.

[solving the means of problem]

Metallic substance of the present invention is characterised in that, the modified layer that it possesses metallic substance base material and forms on the surface of above-mentioned metallic substance base material, and above-mentioned modified layer is at 10 μ m ²scope on average possess 3 above from the outstanding jut in the surface of above-mentioned metallic substance base material, when from the surface with respect to above-mentioned metallic substance base material, vertical direction is observed, the mean diameter of this jut is below 1 μ m.

In foregoing invention, metallic substance of the present invention is characterised in that, above-mentioned modified layer is at 10 μ m ²scope on average possess 1 above jut, this jut possesses from the outstanding base portion in the surface of above-mentioned metallic substance base material and the leading section that forms in the end of above-mentioned base portion, when from the surface with respect to above-mentioned metallic substance base material, vertical direction is observed, the mean diameter of this jut is below 1 μ m, and the external diameter that this jut has an above-mentioned base portion is less than constriction (the く び れ) structure of the external diameter of above-mentioned leading section.

In foregoing invention, metallic substance of the present invention is characterised in that, when from the surface with respect to above-mentioned metallic substance base material, vertical direction is observed, the mean diameter of above-mentioned jut is below 500nm.

In foregoing invention, metallic substance of the present invention is characterised in that, the position direction in the face of above-mentioned metallic substance base material that forms above-mentioned jut does not have periodically

In foregoing invention, metallic substance of the present invention is characterised in that, the mean diameter that above-mentioned modified layer possesses the direction vertical from the surface with respect to above-mentioned metallic substance base material while observing is the recess below 500nm.

In foregoing invention, metallic substance of the present invention is characterised in that, above-mentioned metallic substance base material is formed by steel alloy.

In foregoing invention, metallic substance of the present invention is characterised in that, above-mentioned metallic substance base material is formed by steel.

In foregoing invention, metallic substance of the present invention is characterised in that, the composition of above-mentioned metallic substance base material is different from the composition of above-mentioned jut.

In foregoing invention, metallic substance of the present invention is characterised in that, above-mentioned metallic substance base material is connected continuously with above-mentioned jut.

The surface treatment method of the metallic substance of the 1st mode of the present invention is characterised in that, it possesses following step: the pending material as cathode electrode and anode electrode are immersed in to the step in electrolytic solution, and this pending material as cathode electrode is formed by the metallic substance with pending surface; By more than applying 70V between above-mentioned cathode electrode and above-mentioned anode electrode and for the voltage of the scope of oxidation or melting can not occur pending material, thereby on above-mentioned pending surface, form the step of microtexture; Above-mentioned pending material is taken out from above-mentioned electrolytic solution to the step that this pending material is cleaned; And the step of the above-mentioned pending surface of the above-mentioned pending material after cleaning being implemented to WATER REPELLENT.

The surface treatment method of the metallic substance of the 2nd mode of the present invention is characterised in that, it possesses following step: the pending material as cathode electrode and anode electrode are immersed in to the step in electrolytic solution, and this pending material as cathode electrode is formed by the metallic substance with pending surface; By applying the voltage below the above 200V of 70V between above-mentioned cathode electrode and above-mentioned anode electrode, thereby in the above-mentioned pending surperficial step that forms microtexture; Above-mentioned pending material is taken out from above-mentioned electrolytic solution to the step that this pending material is cleaned; And the step of the above-mentioned pending surface of the above-mentioned pending material after cleaning being implemented to WATER REPELLENT.

The manufacture method of the water-proof material using metallic substance as base material of the present invention is characterised in that, it possesses following step:

Metallic substance and anode electrode are immersed in to the step in electrolytic solution, and this metallic substance is the pending material as cathode electrode with pending surface;

By applying the voltage below the above 200V of 70V between above-mentioned cathode electrode and above-mentioned anode electrode, thereby at metal material surface as above-mentioned pending material, form the step of microtexture;

Above-mentioned metallic substance is taken out from above-mentioned electrolytic solution to the step that this metallic substance is cleaned; And

The above-mentioned pending surface of the above-mentioned metallic substance after cleaning is implemented to the step of WATER REPELLENT.

The surface processing device of conductive material of the present invention is characterised in that, it possesses: the cathode electrode that is mutually immersed in isolator the anode electrode in electrolytic solution and is formed by conductive material; Be present between above-mentioned anode electrode and above-mentioned cathode electrode and there is the hovel of the peristome of the pending part that limits above-mentioned cathode electrode; And execute alive power supply between above-mentioned anode electrode and above-mentioned cathode electrode.

In foregoing invention, the surface processing device of conductive material of the present invention is characterised in that, it possesses the mechanism that the position of above-mentioned peristome and/or the relative position of above-mentioned anode electrode and above-mentioned cathode electrode are changed.

In foregoing invention, the surface processing device of conductive material of the present invention is characterised in that, the voltage of above-mentioned power supply more than applying 60V between anode electrode and cathode electrode, below 300V.

In foregoing invention, the surface processing device of conductive material of the present invention is characterised in that, above-mentioned hovel is for being overlayed on the surperficial insulativity heat-stable material with above-mentioned peristome of cathode electrode.

In foregoing invention, the surface processing device of conductive material of the present invention is characterised in that, above-mentioned conductive material is metallic substance.

The surface treatment method of conductive material of the present invention is characterised in that, it utilizes the surface processing device of conductive material of the present invention to process the surface of conductive material.

[effect of invention]

Utilize metallic substance of the present invention, the metallic substance with the new function such as water-wet behavior and the characteristics of luminescence can be provided.

Utilize the manufacture method of surface treatment method and the water-proof material using metallic substance as base material of metallic substance of the present invention, can without a large amount of labours and expense in the situation that, to metal material surface, give high fire resistance characteristic.

Utilize surface processing device and the surface treatment method of conductive material of the present invention, can be low-cost and the big area that is effectively manufactured on surperficial specific position or surface formed the conductive material of nano level microtexture.

[accompanying drawing explanation]

Figure 1A is the vertical view of formation that the metallic substance of an embodiment of the invention is shown.

Figure 1B is the A-A line sectional view of Figure 1A.

Fig. 2 is the SEM photo that is illustrated in an example of the jut that the surface of cold-rolled steel sheet forms.

Fig. 3 is for the schematic diagram of the external diameter method of calculation of jut is described.

Fig. 4 is for the schematic diagram of the necked configuration of jut is described.

Fig. 5 is the SEM photo that is illustrated in an example of the jut with necked configuration that cold-rolled steel sheet forms.

Fig. 6 is the cross section TEM photo that is illustrated in an example of the jut with necked configuration that cold-rolled steel sheet forms.

Fig. 7 is the SEM photo that is illustrated in an example of the stainless surperficial recess forming.

Fig. 8 is the SEM photo that is illustrated in an example of the stainless surperficial recess forming.

Fig. 9 illustrates the cross section TEM photo that forms an example of the jut with different compositions from base material.

Figure 10 is illustrated in the cross section TEM photo that cold-rolled steel sheet forms the situation of jut continuously.

Figure 11 is the schema of surface-treated flow process that the metallic substance of one embodiment of the present invention is shown.

Figure 12 is the schematic diagram that a configuration example of equipment therefor in the surface treatment method of metallic substance of one embodiment of the present invention is shown.

Figure 13 is the SEM photo that the stainless surface of SUS316L after surface treatment is shown.

Figure 14 is for implementing stainless steel surface shown in Figure 13 after WATER REPELLENT from laterally for distilled water being dropped to the figure that surperficial state is observed.

Figure 15 is the schematic diagram of formation of surface processing device that the conductive material of an embodiment of the invention is shown.

Figure 16 is the schematic diagram that the variation of the surface processing device shown in Figure 15 is shown.

Figure 17 is the schematic diagram that the variation of the surface processing device shown in Figure 15 is shown.

Figure 18 is the figure that the formation of peristome is shown.

Figure 19 A is the figure of secondary electron image of left part that is illustrated in the length direction of the peristome while applying 150V between anode electrode and cathode electrode.

Figure 19 B is the figure of secondary electron image of central part that is illustrated in the length direction of the peristome while applying 150V between anode electrode and cathode electrode.

Figure 19 C is the figure of secondary electron image of right part that is illustrated in the length direction of the peristome while applying 150V between anode electrode and cathode electrode.

Figure 20 be illustrate by the size of peristome be made as 5mm * 5mm and the figure of the outward appearance of the cathode electrode after processing.

Figure 21 illustrates the size of peristome to be made as the figure of the SEM picture of the cathode electrode surface after processing.

Figure 22 is the figure that the SEM picture that does not carry out surface-treated cathode electrode surface is shown.

[embodiment]

[metallic substance]

Figure 1A, Figure 1B are respectively the vertical view of formation and the A-A line sectional view of Figure 1A of the metallic substance that an embodiment of the invention are shown.As shown in Figure 1A, Figure 1B, the jut 3 as modified layer that possesses base material 2 and form on the surface of base material 2 as the metallic substance 1 of one embodiment of the present invention.Base material 2 is formed by metallic substance.As metallic substance, can exemplify: comprise stainless steel alloy; The steel such as cold-rolled steel sheet of the trace alloying element that contains Fe, C and the following degree of 3 quality % if desired; Soft steel plate, tensile strength are the high tensile steel plate of 2GPa level; Hot-rolled steel sheet etc.The shape of base material 2 is not particularly limited, and can use the shapes such as tabular, bar-shaped, wire or pipe shape.In addition the base material that, base material 2 can be welded for more than 2 parts.And base material 2 is in tabular situation, its thickness of slab indefinite, can be to the tinsel from below 100 μ m until thickness is more than 3mm Plate Steel is used.

Jut 3 is formed by following microtexture: in this microtexture, when from the surface with respect to base material 2, vertical direction is observed, the mean diameter R of jut 3 is 1 μ m, is preferably below 500nm, and it is from the outstanding microtexture in the surface of base material 2.Fig. 2 is scanning electronic microscope (the Scanning Electron Microscope:SEM) photo that is illustrated in an example of the jut that the surface of cold-rolled steel sheet forms.In figure, by the part shown in arrow, be jut 3.This jut 3 is by using cold-rolled steel sheet and the platinum electrode K at concentration 0.3mol/L as cathode electrode and anode electrode respectively ₂cO ₃in the aqueous solution, with 135V energising 30 minutes, form.In this case, as shown in Figure 3, the mean diameter R of the jut 3 when vertical direction is observed from the surface with respect to cold-rolled steel sheet tries to achieve as follows: suppose that an area impaling with profile by jut 3 has round C of the same area, calculate the diameter R of this circle C, obtain thus the mean diameter R of jut 3.By at 10 μ m ²scope in average form 3 above such juts 3, can give the characteristics of luminescence, water-wet behavior to the surface of base material 2.By improving water-wet behavior, in metallic surface, be difficult for forming drop, its result, has the purifying effect that is difficult for adhering to the dirts such as organism, can expect that reflection strength is difficult for the various uses such as light reflecting board that reduce.In the face of jut 3, distribute and indefinite, do not have special periodicity, this is favourable on manufacturing.For example, in order to manufacture jut 3, there is the periodic surface of row shape, need excessive operation, unfavorable on manufacturing.

As shown in Figure 4, the external diameter Lrmin that jut 3 has a base portion 3a be less than the external diameter Lrmax of leading section 3b structure, have in the situation of necked configuration, compare with the situation without necked configuration, the specific surface area of base material 2 and inner space get up to increase on the surface.Therefore, can further improve the water-wet behavior etc. that is subject to specific surface area impact.In addition the jut 3 that, has a necked configuration can expect the surface of base material 2 to give the effect of the adaptation of the thin film layer forming on the surface of surperficial chemical reaction or its promotion functions or raising and base material 2.Therefore, preferably at 10 μ m ²scope in average form the jut 3 of necked configuration that 1 above external diameter Lrmin with base portion 3a is less than the external diameter Lrmax of leading section 3b.Due to specific surface area, more water-wet behavior is higher, thereby projection size is little, mostly bump count is favourable; And because the surface ratio surface-area having the raised structures of constriction further increases, thereby water-wet behavior further improves.

The jut 3 with necked configuration can be confirmed by following method: (1) is by the cross section sample of the making metal material surfaces such as FIB (focused ion beam) method, the method for utilizing SEM or transmission electron microscope (Transmission Electron Microscope:TEM) to observe this cross section sample; (2) metallic substance is tilted, the method for utilizing SEM to observe; Etc..Fig. 5 is the SEM photo that is illustrated in an example of the jut with necked configuration 3 forming on cold-rolled steel sheet.It is to make sample inclination 70 degree take the image obtaining.Fig. 6 is the cross section TEM photo that is illustrated in an example of the jut with necked configuration 3 forming on cold-rolled steel sheet.The jut with necked configuration refers to that the external diameter Lrmin of the base portion 3a shown in the mathematical expression (1) illustrating is as follows the structure below 90% of size of the external diameter Lrmax of leading section 3b, and the external diameter Lrmin that preferably refers to the base portion 3a shown in the mathematical expression (2) illustrating is as follows the structure below 80% of size of the external diameter Lrmax of leading section 3b.In the example depicted in fig. 5, the value of Lrmin/Lrmax is 0.38; In the example depicted in fig. 6, the value of Lrmin/Lrmax is 0.62.The external diameter Lrmin of base portion 3a is the minimum outer diameter of the direction vertical from the surface with respect to the metallic substance base material base portion 3a while observing base portion 3a, the maximum outside diameter of the leading section 3b when external diameter Lrmax of leading section 3b be the direction observation vertical from the surface with respect to metallic substance base material.

[several 1]

Lr min/Lr max≤0.9 …(1)

[several 2]

Lr min/Lr max≤0.8 …(2)

On the surface of base material 2, except jut 3, the mean diameter when being preferably also formed with the direction vertical from the surface with respect to base material 2 and observing is below 1 μ m, be preferably the recess below 500nm.By also form recess except forming jut 3, can further increase the surface-area of metallic substance, thereby can further improve the characteristics of luminescence and the water-wet behavior of metal material surface.In addition,, by also there is recess except protuberance, can keep more and more muchly lubricating oil or functional liquid, thereby can give new function to the surface of base material 2.

Fig. 7 and Fig. 8 are the SEM photo that is illustrated in an example of the stainless surperficial recess forming.Fig. 7 shows the situation from observing metallic substance directly over metal material surface, and Fig. 8 shows metallic substance is tilted situation that 60 degree observe metallic substance.Recess shown in Fig. 7 and Fig. 8 is by using SUS430 stainless steel and the platinum electrode K at concentration 0.1mol/L as cathode electrode and anode electrode respectively ₂cO ₃in the aqueous solution, with 115V energising 30 minutes, form.Arrow in figure represents recess.As clear and definite by Fig. 7 and Fig. 8 institute, there is the position that the recess of 200nm～500nm side-to-side dimensions spreads all at stainless steel surface and form.

The material that forms jut 3 can have same composition, also can be different compositions from base material 2, can distinguish and use according to object.Fig. 9 illustrates the cross section TEM photo of an example from the composition of base material 2 with the jut 3 of different compositions.In the example depicted in fig. 9, base material 2 is formed by SUS316 stainless steel, but Cr concentration in jut 3 is less than the Cr concentration in base material 2.Utilize such structure, can expect when effectively utilizing the stainless advantage of SUS316, more effectively to utilize the catalyst function of Ni.If enumerate an example, having can be as take the possibility that steam reforming catalyzer that Ni is effective constituent is directly used.In this case, known Cr can make catalyst performance reduce, thereby can expect to reduce the impact of Cr.And because specific surface area is large, thereby the heat exchange of raised structures of the present invention is excellent.This point is also favourable as catalyst reaction base material.

Preferred substrates 2 is continuum with jut 3.By making base material 2 and jut 3, be continuum, can improve the intensity of jut 3.Figure 10 is illustrated in the cross section TEM photo that forms continuously the situation of jut on cold-rolled steel sheet.Although not shown, when the region R2 of the region R1 to jut 3 and base material 2 carries out crystalline orientation parsing, jut 3 is monocrystalline, has the crystalline orientation roughly the same with base material 2.Such continuous structure is stable for mechanical effect and chemical action, jut 3 difficult drop-offs, in addition, even be also effective in the situation that of not wanting to use dissimilar substances or xenogenesis element in jut 3.And such continuous structure can for example, by forming the poor steel of the alloying element of easily oxidizable (Cr) or metal as base material 2.

As the example of manufacture method with the metallic substance 1 of such structure, can be by utilizing the electric discharge in electrolytic solution to manufacture.Specifically, the inert metals such as pending material and platinum, respectively as cathode electrode and anode electrode, are applied to the volts DS of 60V～140V degree in electrolytic solution to electrode.Execute alive scope according to the difference of pending material and difference, but can be in the situation that utilize SEM to confirm that the surface tissue of pending material is easily definite.Can, by changing the treatment time in suitable scope, applying voltage, the mean diameter of jut be controlled.Specifically, in the situation that being same material, apply that voltage is larger, the treatment time is longer, be more the position darker apart from electrolytic solution liquid level, more can increase the mean diameter of jut.

But, applying voltage, be while being the value of stripped plasma state, at iron or stainless steel surface, can occur excessively melt or be oxidized.Be difficult for forming fine raised structures.In order to make it to there is necked configuration, in the scope that need to can excessively not melt or be oxidized on surface, select the condition that discharge energy density is high.As an example, compared with highland, set and to apply voltage or to reduce to process subject area so that electric field is concentrated is effective.In this situation, also can be by comparing and determine suitable condition utilizing SEM to observe the result of treat surface and treatment condition.In addition the raised structures that the Ni enrichment shown in Fig. 9,, Cr lack can form by setting sparking voltage compared with highland.In addition,, when making raised structures, can to surface, give new element by continuing to supply with element in solution." stripped plasma state " refers to the state that is mixed with the orange luminous or orange luminous covered cathode electrode surface for main body when electric discharge.

[embodiment 1]

Flexible cold-rolled plate (CRS, size 2mm * 20mm * 0.7mm) and Pt are immersed in respectively to the K of concentration 0.3mol/L as cathode electrode and anode electrode ₂cO ₃in the aqueous solution, for cathode electrode and anode electrode, carry out the energising of different energising voltage and make sample.And by SEM, the surface of the flexible cold-rolled plate after switching on is observed, for mean diameter and the density of the jut forming on surface, evaluated.Now, in order to observe according to the difference of the degree of depth apart from aqueous solution liquid level to have which kind of different processing, for a part of sample, in the degree of depth distinct portions apart from liquid level, by flexible cold-rolled plate, cut out sample, carry out surface observation.The mean diameter of jut is the mean value of the diameter of optional 20 juts in the scope of 12 arbitrarily selected μ m * 9 μ m, density for by the number of jut that is positioned at above-mentioned scope divided by 108 μ m ²(=12 μ m * 9 μ m) is also multiplied by 10 μ m ²and the every 10 μ m that obtain ²the result of number of jut.Evaluation result is listed in the table below 1.The sample of experiment No.1-7 shown in table 1 is the flexible cold-rolled plate before switching in the above-mentioned aqueous solution.As clear and definite in the sample of experiment No.1-1～1-6 and the comparison institute of the sample of experiment No.1-7 as shown in Table 1, confirm by energising and process the modified layer that has obtained having jut of the present invention.In addition confirm, by reducing to apply voltage, can reduce the mean diameter of jut, and can increase the density of jut.In addition, as the sample of experiment No.1-6, confirmed, even if shorten the distance from liquid level to treat surface, also can reduce the mean diameter of jut, and can increase the density of jut.

[table 1]

[embodiment 2]

SUS316 stainless steel (size 25mm * 2.5mm * 0.8mm) and Pt are immersed in respectively to the K of concentration 0.3mol/L as cathode electrode and anode electrode ₂cO ₃in the aqueous solution, for cathode electrode and anode electrode, carry out the energising of different energising voltage and make sample.And by SEM, the stainless surface of SUS316 after switching on is observed, for mean diameter and the density of the jut forming on surface, evaluated similarly to Example 1.Now, in order to observe according to the difference of the degree of depth apart from aqueous solution liquid level to have which kind of different processing, for a part of sample, in the degree of depth distinct portions apart from liquid level, by flexible cold-rolled plate, cut out sample, carry out surface observation.And the photoluminescence of the SUS316 stainless steel surface after energising is measured.The FP6200 that device is used Japan Spectroscopy Corporation to manufacture measures under initial wavelength 350nm, termination wavelength 600nm, excitation wavelength 435nm.Specifically, in the photoluminescence spectra that obtains of stainless steel surface by after energising, confirm near unobservable glow peak centered by wavelength 430nm in the photoluminescence spectra obtaining at the stainless steel surface by before energising.Therefore, in the present embodiment, for the intensity of this glow peak in photoluminescence determination, measure.In the present embodiment, the height of glow peak that obtains the experiment No.2-5 of maximum emission intensity is made as to 10, the height of the glow peak of the untreated experiment No.2-7 that cannot observe corresponding luminescence peak is made as to 0 evaluates.Evaluation result is listed in the table below 2.As shown in table 2 confirming, the sample that far surpasses the experiment No.2-6 of 1000nm with the untreated stainless steel surface without jut (sample of experiment No.2-7) or projection is compared, and the stainless steel surface (sample of experiment No.2-1～2-5) with jut of the present invention has the high characteristics of luminescence.The size of jut is less, and the characteristics of luminescence is larger, and the mean diameter of jut is 500nm when following, obtains the extra high characteristics of luminescence.According to this result, expectation can be using the stainless steel with jut of the present invention as display element or is utilized the metallic substance of element of the light of visible region to be used.

[table 2]

[embodiment 3]

Use SUS316 stainless steel (thickness 1mm * width 2.5mm * length 30mm).Utilize DIA-WLAPML-150P effects on surface to carry out mirror ultrafinish.This stainless steel and Pt are immersed in respectively to the K of concentration 0.1mol/L as cathode electrode and anode electrode ₂cO ₃aqueous solution 300cm ³in, with different energising voltage anticathode electrodes and anode electrode, switch on 15 minutes, make thus sample.Electrode (SUS316 stainless steel) after experiment is utilized after the abundant rinse of distilled water, be fully dried, for the part at the degree of depth 30mm apart from liquid level, 28mm, this 3 place of 26mm, carry out surperficial contact angle determination experiment.Utilize micropipet to drip 1 μ L distilled water (manufacturing with the pure pharmaceutical worker's industry of light society), utilize photographic camera (Canon society manufactures EOS Kiss X2) from positive side, each water droplet to be taken, by photo, determined height (h), the contact length (l) of drop, by θ _r=2tan ^-1(2h/l) obtain each contact angle (θ _r), calculate mean value, as the contact angle of the part of the degree of depth 30mm apart from liquid level.

After contact angle determination experiment finishes, be fully dried, for mean diameter and the density of the jut forming on surface, evaluate similarly to Example 1.In addition, in order to evaluate the surface-area of resulting sample, have the increase of which kind of degree with respect to level and smooth surface, the surface-area that the surface-area of establishing smooth-flat-surface is established to 1 o'clock sample, as specific surface area, calculates based on following supposition.That is, suppose the hemispheric projection with above-mentioned mean diameter of trying to achieve is present on smooth-flat-surface according to above-mentioned density of trying to achieve, and calculates as how many times with respect to smooth-flat-surface.The results are shown in following table 3.As shown in Table 3, with unprocessed and do not have the sample (experiment No.3-6) that the sample (experiment No.3-1) of modified layer of the present invention or the proterties of modified layer exceed the scope of the invention and compare, the contact angle of the embodiment in the scope of the invention is little, water-wet behavior improves.

[table 3]

[embodiment 4]

Flexible cold-rolled plate (size 1.5mm * 20mm * 0.7mm) and Pt are immersed in respectively to the K of concentration 0.3mol/L as cathode electrode and anode electrode ₂cO ₃in the aqueous solution, energising voltage is made as to 110V, sample is made in anticathode electrode and anode electrode energising for 30 minutes.In the present embodiment, for electric field is concentrated, the width of sample is made as to the 1.0mm different from embodiment 1,2.And, after energising, for the part apart from level 15mm, utilize the method identical with embodiment 3 to measure the contact angle at 1 place.Result contact angle is 45 °.In addition, after contact angle determination, be dried, by SEM, the surface of same section observed, for mean diameter and the density of the jut forming on surface, evaluate similarly to Example 1.Fig. 5 is shown in by representational SEM photo.The result of evaluating is that the mean diameter of the projection of observing from top is 350nm.And evaluate thering is the density of the projection of necked configuration.The density with the projection of necked configuration is obtained as follows: for counting in the projection number with necked configuration of same section with carrying out the part (scope) that the mean diameter of jut and density evaluates, similarly calculate every 10 μ m with the density of jut ²mean number, obtain thus the density that this has the projection of necked configuration.Its results verification arrives, and on average has 3.

[embodiment 5]

Flexible cold-rolled plate (size 1.5mm * 20mm * 0.7mm) and Pt are immersed in respectively to the K of concentration 0.3mol/L as cathode electrode and anode electrode ₂cO ₃in the aqueous solution, establishing energising voltage is 95V, and sample is made in anticathode electrode and anode electrode energising for 10 minutes.And, after energising, for the part apart from level 15mm, utilize the method identical with embodiment 3 to measure the contact angle at 1 place.Result contact angle is 60 °.In addition, after contact angle determination, be dried, by SEM, the surface of same section observed, for mean diameter and the density of the jut forming on surface and the density with the projection of necked configuration, evaluate similarly to Example 1.Evaluation result confirms, and the projection that the mean diameter of the projection of observing from top is 350nm, have necked configuration is at 10 μ m ²1 of interior average existence.

[embodiment 6]

6 quality %C-2 quality %Si-2 quality %Cr steel are rolled to processing, and pair cross-section carries out the evaluation of 25g Vickers intensity, and result is 900, confirms as the ultrahigh-strength steel of 2GPa level.These steel are cut into and are of a size of 1mm * 20mm * 0.7mm, the steel that cut out and Pt, respectively as cathode electrode and anode electrode, are immersed in to the K of concentration 0.1mol/L ₂cO ₃in the aqueous solution, establishing energising voltage is 110V, anticathode electrode and anode electrode energising 30 minutes.And, after energising, by SEM, for the surface of the flexible cold-rolled plate of the part apart from level 18mm, observe, for mean diameter and the density with the projection of necked configuration of the jut forming on surface, evaluate.Evaluation result confirms, and the projection that the mean diameter of the projection of observing from top is 400nm, have necked configuration is at 10 μ m ²2 of interior average existence.

[surface treatment method of metallic substance]

Figure 11 is the schema of surface-treated flow process that the metallic substance of an embodiment of the invention is shown.Figure 12 is the schematic diagram that a configuration example of equipment therefor in the surface treatment method of metallic substance of an embodiment of the invention is shown.As shown in figure 11, in the surface treatment of the metallic substance of an embodiment of the invention, first pending material and anode electrode as cathode electrode (it is metallic substance) are immersed in electrolytic solution, between cathode electrode and anode electrode, apply voltage, thereby form microtexture (step S1) on the surface of pending material.Specifically, as shown in figure 12, anode electrode 13 and pending material 14 are immersed in the electrolytic solution 12 in container 11, by the wires such as copper cash 15, by power supply 16 antianode electrodes 13 and pending material 14, apply voltage, thereby form microtexture on the surface of pending material 14.

Electrolytic solution 12 is not particularly limited, it is following solution: this solution has electrical conductivity, and when carrying out the surface treatment of pending material 14, be not easy the surperficial over etching of pending material 14, be difficult in the surface attachment of anode electrode 13 and pending material 14 or separate out, be difficult for forming throw out.As the ionogen of such electrolytic solution 12, can exemplify salt of wormwood (K ₂cO ₃), sodium carbonate (Na ₂cO ₃), sodium bicarbonate (NaHCO ₃), volatile salt ((NH ₄) ₂cO ₃), lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH ₄oH), sodium-chlor (NaCl), Repone K (KCl), ammonium chloride (NH ₄cl), the sodium salt of sulfuric acid, the ammonium salt of the sylvite of sulfuric acid, sulfuric acid, the sylvite of the sodium salt of nitric acid, nitric acid, the ammonium salt of nitric acid, Trisodium Citrate (NaH ₂(C ₃h ₅o (COO) ₃)) etc. the sodium salt of citric acid, the ammonium salt of the sylvite of citric acid, citric acid, nitric acid and hydrochloric acid etc.

As long as the modifying surface that electrolytic solution 12 can be to pending material 14, can be pH and concentration arbitrarily.For example, in situation about wet chemical being used as electrolytic solution 12, its concentration is not particularly limited, can be for more than 0.001mol/L, more preferably more than 0.005mol/L.This be due to, if the concentration of electrolytic solution 12 is too low, while applying voltage between anode electrode 13 and pending material 14, be sometimes difficult to the discharge condition that remains suitable.The upper limit of the concentration of electrolytic solution 12 is not set especially, for example can be for below 0.5mol/L.In addition, only otherwise can cause excessive corrosion or the etching of electrode, the pH of electrolytic solution 12 can be value arbitrarily, for example, can be pH10～12.

The material that anode electrode 13 has thermostability and chemical stability by when electric discharge forms.As such anode electrode 13, can exemplify Pt, Ir, graphite etc.

Pending material 14 is as long as be just not particularly limited for metallic substance, if iron steel can be used cold rolling material, hot rolling material or casting material and machining object (comprising welding etc.) thereof.In addition, steel grade is not particularly limited, and can utilize carbon steel, low alloy steel or stainless steel etc.And also can utilize and take the coated steel sheet that electrogalvanizing steel plate is representative.In addition, the shape of pending material 14 is not particularly limited, and can utilize tabular, wire, bar-shaped, pipe shape or processing component.In addition, pending material 14 need to be immersed in electrolytic solution 12, at least needs than darker apart from liquid level 1mm.

Discharging condition can utilize and from the surface at pending material 14, form concavo-convex part plasmoid to the scope of stripped plasma state.But, need in the low voltage range of the voltage that occurs to melt than pending material 14, implement.Specifically, occur that naked eyes are certifiable luminous when sparking voltage increases in darkroom, it is for to be about to the state red heat from demonstrating the luminous voltage of orange point to material monolithic.In the situation that pending material 14 is of a size of 1mm * 1mm * 20mm, it is suitable applying in the scope that voltage is roughly 70V～200V, more preferably in the scope of 80V～150V.This voltage range is applicable to the most of iron steel that comprises the steel alloys such as stainless steel.But, because this voltage range changes according to the kind of pending material 14 or configuration, thereby can to the surface of the pending material 14 after processing, carry out SEM observation by change voltage conditions and determine.

Sparking voltage is on the surface of iron steel, to form the voltage of micro crowning, and this is prerequisite.If be less than the voltage as lower limit, on surface, fail to form micro crowning, thereby can be by utilizing SEM to confirm to have or not micro crowning to determine this lower voltage limit.If surpass the upper limit, processed can melt.Thereby the form that the upper limit, with surface, the voltage of melting can be occurred to is determined.But more preferably surface is not oxidized.In this case, can study by the voltage that uses energy dispersion type x-ray spectrometry device (EDS) effects on surface appended in SEM and SEM that oxidation occurs, thereby easily determine.In the situation that go out oxygen with the X ray intensity detection of the oxide compound equal extent with pending material 14, can be judged as surface oxidized.In addition, the oxygen in pending material 14 need to be the Fe of the oxide compound (for example referring to the oxide compound of Fe in cold-rolled steel sheet or low alloy steel) of pending material 14 below 1/3 of X ray intensity through the oxygen of the strength criterion of L line through the standardized X ray intensity of Fe-L line strength.Above-mentioned study of surfaces is undertaken by following observation: change voltage and carry out after electric discharge in 30 minutes, pending material 14 is taken out, wash, be dried, import to afterwards in SEM, observe.

The discharge process time need to be for more than 3 seconds.But the discharge process time also can be for waiting the longer time such as 60 minutes, if but discharge process overlong time, may there is loss in pending material 14, thereby preferred 30 minutes above treatment times not.Knownly among preferred voltage range, apply voltage larger, the surperficial fire resistance characteristic after final operation is higher.Thereby most preferred condition is optionally connected is bordering on the voltage that applies of the upper limit in optimum condition scope.

The example of Figure 13 for the SUS316L stainless steel plate of thickness 0.8mm is processed.This SUS316L stainless steel plate is cut into wide 2mm, long 30mm, utilize copper cash to obtain conducting, make cathode electrode.Anode electrode is used and the Pt line of length 50cm to be bent according to the mode not being in contact with one another and is shaped to planar parts.For the connection section of SUS316L stainless steel plate and copper cash, carry out the thermo-compressed that adds of heat stable resin, the mode not contacting with electrolytic solution according to copper cash, the part that the 20mm of electrode is long is immersed in electrolytic solution.The K of electrolytic solution working concentration 0.1mol/L ₂cO ₃the aqueous solution, is made as 130V by voltage and carries out electric discharge in 10 minutes, after finishing, washes immediately.

Its result, as shown in figure 13, confirming and on the surface of SUS316L stainless steel plate, having formed mean diameter is the fine raised structures below 1 μ m.And the surface that confirms SUS316L stainless steel plate by the ultimate analysis based on EDS is not oxidized.In addition, surpass 160V apply voltage time, the front end of SUS316L stainless steel plate fuses.Therefore, tried to achieve that to execute alive higher limit be 160V.In addition, because the surface that applies SUS316L stainless steel plate under voltage that the ultimate analysis utilizing based on EDS confirms below 140V is not oxidized, thereby known, in this experiment condition and test material, executing alive preferred upper limit value is 140V.On the other hand, execute alive lower value and be defined as 80V according to having or not of raised structures.The most preferred voltage that applies is confirmed as 140V.

Get back to Figure 11.While forming microtexture on the surface of pending material 14 as mentioned above, then pending material 14 is taken out from electrolytic solution 12, pending material 14 is cleaned to (step S2).Finally WATER REPELLENT (step 3) is implemented in the pending surface of the pending material 14 after cleaning.Purging method carries out in order to remove surperficial electrolytic solution, can enumerate method that is immersed in pure water or sprays etc.Be not limited to pure water, only otherwise microtexture that can failure surface also can be used weak acid or alkaline solution.Now, also can impose electrolysis.After cleaning, can make it dry, sometimes also can not be dried and enter into subsequent processing according to ensuing WATER REPELLENT.The organic method etc. that method for waterproofing can adopt the method for the anti-water spray of coating or Adsorption of fluoride resinoid etc. has water-proof function in liquid phase or gas phase.In the present embodiment, the Nanopro (composition: fluorocarbons resin, silicone resin) that Collonil society is manufactured blows and sprays to the surface of pending material 14 and carries out more than 12 hours being dried, thereby WATER REPELLENT is implemented in the surface of pending material 14.Thus, a series of surface treatment finishes.

Figure 14 implements WATER REPELLENT to the specimen surface shown in Figure 13, from the result of laterally observing dripping the state of distilled water.The result of observing, the contact angle of water is 152 ° after measured, confirms and has realized super waterproof.The contact angle that does not carry out the water in the sample of WATER REPELLENT is 51 °.In addition, to implementing the material of solution applying plasma electric discharge, do not implement same WATER REPELLENT, the contact angle of result water is 125 °.Thereby confirm, in order to obtain super water-proof surface, need to carry out solution applying plasma electric discharge and WATER REPELLENT the two.

[embodiment 1]

The stainless steel SUS316L steel plate of commercially available thickness 0.8mm is cut into wide 2mm, long 30mm, be immersed in dilute hydrochloric acid and carry out, after degreasing, utilizing copper cash to obtain conducting, make cathode electrode.Anode electrode use by length 50cm, pt line according to mutually non-touching mode, bend and be shaped to planar parts.For the connection section of cathode electrode and copper cash, carry out the thermo-compressed that adds of heat stable resin, the mode not contacting with electrolytic solution according to copper cash, the part that the 20mm of electrode is long is immersed in electrolytic solution.Electrolytic solution is the K of concentration 0.1mol/L ₂cO ₃the aqueous solution, is set in the scope of 60V～180V applying voltage, carries out electric discharge in 10 minutes, after finishing, washes immediately with pure water, makes it dry.Thereafter Nanopro Collonil society being manufactured blows and sprays the surface to pending material, carries out 12 hours above dry WATER REPELLENT of implementing, and wettability is studied.Wettability is evaluated as follows: use micropipet, distilled water is equally spaced on and on electrode surface, drips 6 places with every 1 μ m of place, the digital camera EOS Kiss X2 that uses Canon society to manufacture takes from positive side, by resulting photo, measure contact angle, get the mean value at 6 places, carry out thus the evaluation of wettability.The distilled water 049-16787 that distilled water is used and the pure pharmaceutical worker's industry of light society manufactures.Test-results has been shown in table 4.As shown in table 4 confirming, example has all demonstrated the contact angle higher than untreated timber.Confirm especially, in applying the example 3,4,5 that voltage is 120V～140V scope, having realized contact angle is 150 ° of above super waterproof; In applying the example 5 that voltage is 140V, demonstrated the highest contact angle of 153.6 °.

[table 4]

Test number	Plasma body voltage (V)	WATER REPELLENT	Water contact angle (°)	Remarks
					1	0 (untreated)	Nothing	77.2	Comparative example 1
2	0 (untreated)	Have	125.1	Comparative example 2
					3	60	Have	126.9	Comparative example 3
4	80	Have	140.2	Example 1
					5	100	Have	145.8	Example 2
6	120	Have	150.0	Example 3
					7	130	Have	152.0	Example 4
8	140	Nothing	51.6	Comparative example 4
					9	140	Have	153.6	Example 5
10	160	Have	143.0	Example 6
					11	180 (fusing)	-	-	Comparative example 5

[surface processing device of conductive material]

The present inventor is for low-cost and be effectively manufactured on surface and formed the conductive material of nano level microtexture and conducted in-depth research, and wherein also comprised and to thought in the past, can not form the research that utilizes possibility that the liquid applying plasma of nano level microtexture discharges.Its result, the present inventor finds, by conductive material is used as to cathode electrode, causes that part liquid applying plasma discharges, thereby can form on the surface of conductive material nano level microtexture.In addition, the method that the present inventor forms nano level microtexture for the surperficial specific part at conductive material is studied, discovery arranges the hovel with peristome by the pending part of conductive material being immersed in together with anode electrode in electrolytic solution, between conductive material and anode electrode, can form nano level microtexture at the surperficial specific part of conductive material.The present inventor further finds, by the peristome of hovel and/or the relative position of anode electrode and conductive material are changed, can form continuously or discretely nano level microtexture on the surface of conductive material.

Figure 15 is the schematic diagram of formation of surface processing device that the conductive material of one embodiment of the present invention is shown.As shown in figure 15, the surface processing device 21 of the conductive material of one embodiment of the present invention possesses: modification unit 22, store electrolytic solution 23 in modification unit 22, be mutually immersed in isolator the cathode electrode 25 that anode electrode 24 in electrolytic solution 23 forms with pending material by having electroconductibility and the direct supply 26 being connected with cathode electrode 25 with anode electrode 24.The case 27 that cathode electrode 25 is made by insulating material covers, and at case 27, is formed with for limiting the peristome 28 of the pending part of cathode electrode 25.According to top, the position higher than the liquid level of electrolytic solution 23 is configured case 27.The top of case 27 can be opened, and also can have lid, and this covers the hole having for through connecting the wire of cathode electrode 25 and direct supply 26.

As modification unit 22, can use the known unit of being made by the material stable with respect to electrolytic solution 23, the unit that for example can use glass, Teflon (registered trademark) or polytrimethylene ether ketone (PEEK) to manufacture.In addition, as modification unit 22, the unit that also can use pottery to manufacture.In the surface processing device 21 shown in Figure 16 described later, also can use metallic unit.

Electrolytic solution 23 is following solution: this solution has electrical conductivity, and when (surface of cathode electrode 25) forms nano level microtexture on pending surface applying voltage between anode electrode 24 and cathode electrode 25, be difficult for pending surperficial over etching, be difficult in the surface attachment of anode electrode 24 and cathode electrode 25 or separate out, be difficult for forming throw out.As such electrolytic solution 23, for example, can use to contain and select free salt of wormwood (K ₂cO ₃), sodium carbonate (Na ₂cO ₃), sodium bicarbonate (NaHCO ₃), volatile salt ((NH ₄) ₂cO ₃), lithium hydroxide (LiOH), sodium hydroxide (NaOH), magnesium hydroxide (Mg (OH) ₂), potassium hydroxide (KOH), ammonium hydroxide (NH ₄oH), sodium-chlor (NaCl), Repone K (KCl), magnesium chloride (MgCl ₂), ammonium chloride (NH ₄cl), the vitriol of lithium, the vitriol of the vitriol of sodium, magnesium, the vitriol of the vitriol of potassium, ammonium, the nitrate of the nitrate of lithium, sodium, the nitrate of the nitrate of magnesium, potassium, the Citrate trianion of the nitrate of ammonium, lithium, Trisodium Citrate (NaH ₂(C ₃h ₅o (COO) ₃)) etc. the Citrate trianion of sodium, the Citrate trianion of the Citrate trianion of magnesium, potassium, the aqueous solution of at least one in the group that the Citrate trianion of ammonium, sulfuric acid, nitric acid, hydrochloric acid and citric acid form.

About electrolytic solution 23, as long as can implement the surface treatment of cathode electrode 25, can be just pH and concentration arbitrarily, for example by wet chemical as in the situation of electrolytic solution 23, its concentration is not particularly limited, can be for more than 0.001mol/L, more preferably more than 0.005mol/L.This be due to, if concentration is too low, while applying voltage between anode electrode 24 and cathode electrode 25, be sometimes difficult to the discharge condition that remains suitable.The upper limit of concentration is not set especially, for example can be for below 0.5mol/L.In addition, only otherwise can cause excessive corrosion or the etching of electrode, the pH of electrolytic solution 23 can be value arbitrarily, for example, can be pH5～12.

The insoluble anode electrode of anode electrode 24 for being formed by following electrode material: when applying voltage between anode electrode 24 and cathode electrode 25 and form nano level microtexture on pending surface, this electrode material can not dissolve at electrolytic solution 23 intermediate ions, can not separate out on cathode electrode 25 and suppress the formation of nano level microtexture.As such anode electrode 24, for example, can use: platinum (Pt) electrode, palladium (Pd) electrode, iridium (Ir) electrode; Surface-coated has the electrode of Pt, Pd or Ir; Or Graphite Electrodes etc.

The pending material of cathode electrode 25 for modifying surface being processed by applying voltage, the material (conductive material) by metallic substance or alloy material etc. with electroconductibility forms.About the pending material as cathode electrode 25 performance functions, such as enumerating carbon steel material, alloy steel products, stainless steel, nickel material etc.In addition, the shape of cathode electrode 25 (pending material) is not particularly limited, and can be parts tabular, banded, that have conductive material portion.Pending material also can utilize arbitrarily the effects on surfaces such as sand paper to carry out as cathode electrode 25, using after mirror ultrafinish.

Direct supply 26 for apply the needed voltage of surperficial modification as the cathode electrode 25 of pending material between anode electrode 24 and cathode electrode 25, for example, is that 60V is above, the voltage below 300V.As direct supply 26, can use known power supply.

In the present embodiment, cathode electrode 25 is covered by case 27, but also can as shown in figure 16, utilize the case 27 that has formed peristome 28 that anode electrode 24 is covered.And, the case 27 that the pending part of cathode electrode 25 also can not had peristome 28 limits, as shown in figure 17, can by cathode electrode 25 be at least immersed in the heat-stable material coating that surface in electrolytic solution 23 utilizes the insulativity such as heat-resistant resin or glass, in the part of heat-stable material, be formed for limiting the peristome 28 of the pending part of cathode electrode 25.

Shape or the size of peristome 28 are not particularly limited, and case 27 can have 2 above peristomes.Be provided with in the situation of 2 above peristomes 28, peristome 28 is not limited to the same face of cathode electrode 25.For example, can peristome 28 be set in face side and the rear side of cathode electrode 25.In addition, as shown in figure 18, can rake 28a be set in the end of the upside (liquid level side) of peristome 28.By rake 28a is set, the gas being produced by pending part can be emitted in electrolytic solution 23 effectively.

Surface processing device 21 can have heater meanses such as well heater for electrolytic solution 23 is heated and for measuring the thermometer of the temperature of electrolytic solution 23.And the angle that arranges of cathode electrode 25 can be vertical with the liquid level of electrolytic solution 23, but be not limited to this.In addition,, in order to promote the plasma body on cathode electrode 25 surfaces to occur, can be provided for supplying with to the surface of cathode electrode 25 mechanism of the gases such as hydrogen, argon, water vapour.

The following conductive material of manufacturing surface modification of surface processing device 21 with such formation.To utilizing 21 pairs of conductive materials of this surface processing device to carry out surface-treated method, be illustrated below.

[surface treatment method of conductive material]

When utilizing surface processing device 21 to manufacture the conductive material of surface modification, first construct an individual system (surface modification treatment system), in this system, case 27 is immersed in the electrolytic solution 23 storing in modification unit 22, by anode electrode 24 and cathode electrode 25 isolation dippings, anticathode electrode 25 carries out surface modification treatment afterwards.Now, cathode electrode 25 is immersed in case 27, makes to think that part to be processed is from the peristome 28 of case 27.The surface modification treatment of cathode electrode 25 is to implement for the part of exposing in electrolytic solution 23 sides from peristome 28.In the formation of the surface processing device 21 shown in Figure 16, according to anode electrode 24 insert in case 27, the peristome of case 27 28 arranges case 27 with the opposed mode of pending part of cathode electrode 25.Owing to thinking that part to be processed more keeps away oral area 28, processed part is more greater than peristome, thereby peristome 28 is preferably below 5mm, more preferably below 1mm conventionally with the interval of thinking part to be processed (distance) of cathode electrode 25.

Next, between anode electrode 24 and cathode electrode 25, apply specific voltage, the modifying surface of anticathode electrode 25 is processed (surface modification treatment operation).The voltage of specific voltage for being determined by preliminary experiment, can determine by following method.That is, first, in desirable scope, to being applied to voltage and the treatment time of surface modification treatment system, change.In unspecified situation for the treatment of time, carry out 15 minutes.In addition, the variation range of voltage can be the degree of 50V～300V.Next, utilize SEM to observe treat surface, for the situation that forms raised structures below average 1 μ m, surface not oxidized (thickness for the natural oxidizing layer of number nanometer degree except) on surface, do not occur to melt, confirm, carry out thus to determine condition.The surface whether EDS in the oxidized SEM of use is confirmed.

Voltage range slightly changes according to the kind of cathode electrode 25, but in the scope of 60V～300V, be preferably in the scope of 80V～180V.The voltage that lower voltage limit and plasma body occur is corresponding.Upper voltage limit is by for high temperature time surface is oxidized, or surface melting, the disappearance of micro crowning structure are determined.Although can determine above-mentioned preferred voltage range, in the situation that want to carry out short period of time processing in the situation that or want to increase raised structures, also can set the higher voltage that applies.

Concrete example is described.In this concrete example, use stainless steel plate (SUS316) to construct the surface modification treatment system shown in Figure 15 as cathode electrode 25.If peristome 28 is of a size of 25mm * 4mm.And by the salt of wormwood (K of 0.1mol/L ₂cO ₃) aqueous solution as electrolytic solution 23 carry out 15 minutes energising.Utilize SEM to observe the stainless steel plate surface after processing, it is 80V that result is obtained lower voltage limit.And known upper voltage limit is 250V.While applying 150V between anode electrode 24 and cathode electrode 25, (a) left part of the length direction of peristome 28, (b) central part and (c) secondary electron image of right part be shown in Figure 19 A, Figure 19 B, Figure 19 C.

As shown in Figure 19 A, Figure 19 B, Figure 19 C, confirming and on the surface of stainless steel plate, having formed diameter 1 μ m is following micro crowning structure.And, because the left part of the length direction at peristome 28 and right part and central part have been observed same raised structures, thereby confirm at the whole face of peristome and carried out suitable processing.And confirm, in preferred voltage range, voltage is lower, and the size of raised structures more reduces, the number of raised structures more increases.Therefore, can be in conjunction with needed surface property to applying voltage adjustment.For example, in the situation that wanting to obtain the characteristics of luminescence, preferably raised structures is little, thereby can set and apply voltage compared with lowland.

The principle that forms micro crowning is still not clear, and by inference, is to form by near the electric discharge of generating unit separatory applying plasma cathode electrode 25.That is, in the method, if the under voltage lower voltage limit applying between anode electrode 24 and cathode electrode 25, fully generating unit separatory applying plasma discharges, cannot form micro crowning; If more than upper voltage limit,, due to the generation of stripped plasma, the surface of cathode electrode 25 melts, unfavorable for the formation of micro crowning.

The electric discharge of liquid applying plasma it is believed that as follows and causes: by applying voltage, more than near the temperature part of the electrolytic solution 23 cathode electrode 25 reaches boiling point, near cathode electrode 25, during generation gas phase, in gas phase, produce plasma discharge, thereby cause the electric discharge of liquid applying plasma.Therefore, though voltage apply that from room temperature, to start be also possible, if but to make near temperature electrolytic solution 23 integral body or cathode electrode 25 be that to carry out applying of voltage after the scope of 80 ℃ to 100 ℃ more effective.This be due to, can make near the temperature of cathode electrode 25 effectively increase, can effectively cause liquid applying plasma electric discharge.The application time of voltage can be random time, for example, more than can be for 1 second, below 30 minutes.The application time of voltage is shorter, and the size of formed micro crowning is less, thereby the application time of voltage can carry out suitable selection according to desired surface shape and characteristic.

Can be clear and definite by above explanation, utilize this surface treatment method, in the situation that do not use expensive device and senior technology, only by controlling being immersed in anode electrode 24 in electrolytic solution 23 and the voltage that applies between cathode electrode 25, can be low-cost and be effectively manufactured on the conductive material that surface has formed nano level microtexture.The conductive material that has formed nano level microtexture on surface can have been given play to various functions based on this microtexture.By cathode electrode 25 being moved or case 27 is moved by cathode electrode 25 is fixing case 27 being fixing, more big area that can anticathode electrode 25 is carried out surface modification.And, while can move and obtain continuous treat surface by processing continuously.Can make it to there is discrete pattern by stepped movement or by repeatedly moving and discharging in addition.Particularly, in the surface processing device 21 shown in Figure 16, cathode electrode 25 needn't be covered by case 27, thereby can be by making cathode electrode 25 expand to continuous processing apparatus and continous treatment process for large-scale sample or strip specimen.

[embodiment 1]

Be produced on the peristome on the alumina plate of thickness 1.7mm with various size (5mm * 5mm, these 5 kinds of 10mm * 2mm and 20mm * 1mm) case 27.As shown in figure 18, upper surface inclination 30 degree of peristome 28 are processed.The SUS316 stainless steel of used thickness 1mm, as cathode electrode 25, using Pt as anode electrode 24, is immersed in the K of concentration 0.3mol/L ₂cO ₃in the aqueous solution, construct surface modification treatment system as shown in figure 15.At cathode electrode 25 and 24 of anode electrodes, apply voltage.And the stainless surface of SUS316 after utilizing SEM to apply voltage is observed.By the size of peristome 28 be made as 5mm * 5mm and one of the outward appearance photo of the cathode electrode 25 after processing is illustrated in Figure 20.Applying voltage is that 160V, application time are 15 minutes.As shown in figure 20, process with the shape of peristome 28 on the surface that confirms cathode electrode 25.

The size of peristome 28 is made as one of the surperficial SEM picture of the cathode electrode 25 after processing is illustrated in Figure 21.As shown in figure 21, not in order to carry out surface-treated surface (with reference to Figure 22), formed diameter on the surface of cathode electrode 25 be not the micro crowning structure below 1 μ m.In addition known, even if use the shape of other peristome 28, also applying of 90V～200V, under voltage, formed micro crowning structure, but in the situation that 220V is above, micro crowning structure decrease.This is due to due to surperficial melting by inference.In addition, for the whole face of the cathode electrode 25 shown in Figure 20, carry out same WATER REPELLENT, result is not compared with carrying out surface-treated surface, has obtained high water resistance.And, using two sides to have with the case 27 of the peristome 28 of 5mm * 5mm applies in the experiment that 170V (application time is 15 minutes) carries out, according to SEM, observe, on two sides, all formed micro crowning structure, confirm and can implement surface modification treatment in the effects on surface back side simultaneously.

[embodiment 2]

Using stainless steel plate (SUS316) as cathode electrode, the case 27 that utilization is provided with aluminum oxide (thickness 1.7mm) manufacture of the peristome 28 of 1mm (longitudinally) * 20mm (laterally) covers anode electrodes 24, constructs surface modification treatment system as shown in figure 16.Face and the cathode electrode 25 with peristome 28 are arranged across 1mm.The interelectrode voltage that applies is made as to 140V and 220V.Between electrode, apply 5 minutes voltage, then, by stainless steel plate (longitudinally) mobile 5mm upward, again apply 5 minutes voltage.Repeatedly carry out applying of 10 movements upward and voltage.Carry out the interelectrode situation and 2 groups of experiments that are the situation of 220V that voltage is 140V that apply.As a result, all obtained thering is the stainless steel plate that has the region of micro crowning structure with 5mm interval.

[embodiment 3]

Using Zn coated steel sheet as cathode electrode, utilize the case 27 of aluminum oxide (thickness 1.7mm) manufacture of the peristome 28 that is provided with 1mm (longitudinally) * 20mm (laterally) to cover anode electrodes 24, construct surface modification treatment system as shown in figure 16.Face and the cathode electrode 25 with peristome 28 are arranged across 1mm.The interelectrode voltage that applies is made as to 120V, between electrode apply voltage on one side, one side makes Zn coated steel sheet (longitudinally) mobile 20mm downwards with the speed of 1mm/ minute.Making has obtained the Zn coated steel sheet that processing area is 20mm * 20mm.For this surface, implement the test of methylene blue color fading reaction, result has obtained being significantly higher than the photocatalysis effect that does not carry out surface-treated surface.

[embodiment 4]

The commercially available cold-rolled steel sheet of thickness 0.8mm is cut off to growth 80mm * wide 6mm, as cathode electrode.By length direction, for axially width being carried out to bending machining, be processed into width cross section and be the arcuation that radius-of-curvature is 10mm.Except the connection section with electrode, at the surface coated heat stable resin of cathode electrode 25, a face after bending machining forms the peristome 28 of length 25mm with width 2mm and 4mm.Between Pt and cathode electrode 25, apply the voltage of 150V.Arbitrary sample has all formed the micro crowning structure below mean diameter 1 μ m on the surface of peristome 28.

[industrial applicibility]

Utilize the present invention, the metallic substance with the new function such as water-wet behavior and the characteristics of luminescence can be provided.

Utilize the present invention, can without a large amount of labours and expense in the situation that, provide and can give at metal material surface the surface treatment method of metallic substance and the manufacture method of the water-proof material using metallic substance as base material of high fire resistance characteristic.

Utilize the present invention, a kind of surface processing device and surface treatment method of conductive material can be provided, and it can be with low-cost and effectively manufacture that the specific position of effects on surface or the big area on surface are processed and the conductive material that formed nano level microtexture.

[explanation of symbol]

1 metallic substance

2 base materials

3 juts

11 containers

12 electrolytic solutions

13 anode electrodes

14 pending materials (cathode electrode)

15 wires

16 power supplys

17 thermometers

21 surface processing devices

22 modification unit

23 electrolytic solutions

24 anode electrodes

25 cathode electrodes (pending material)

26 direct supplys

27 casees

28 peristomes

28a rake

Claims (18)

1. a metallic substance, is characterized in that,

The modified layer that this metallic substance possesses metallic substance base material and forms on the surface of described metallic substance base material,

Described modified layer is at 10 μ m ²scope on average possess 3 above from the outstanding jut in the surface of described metallic substance base material, when from the surface with respect to described metallic substance base material, vertical direction is observed, the mean diameter of this jut is below 1 μ m.

2. metallic substance as claimed in claim 1, is characterized in that, described modified layer is at 10 μ m ²scope on average possess 1 above jut, this jut possesses from the outstanding base portion in the surface of described metallic substance base material and the leading section that forms in the end of described base portion, when from the surface with respect to described metallic substance base material, vertical direction is observed, the mean diameter of this jut is below 1 μ m, and the external diameter that this jut has a described base portion is less than the necked configuration of the external diameter of described leading section.

3. metallic substance as claimed in claim 1 or 2, is characterized in that, while observing from the vertical direction in the surface with respect to described metallic substance base material described in the mean diameter of jut be below 500nm.

4. the metallic substance as described in any one in claim 1～3, is characterized in that, the position direction in the face of described metallic substance base material that forms described jut does not have periodically.

5. the metallic substance as described in any one in claim 1～4, is characterized in that, mean diameter when described modified layer possesses the direction observation vertical from the surface with respect to described metallic substance base material is the recess below 500nm.

6. the metallic substance as described in any one in claim 1～5, is characterized in that, described metallic substance base material is formed by steel alloy.

7. metallic substance as claimed in claim 6, is characterized in that, described metallic substance base material is formed by steel.

8. the metallic substance as described in any one in claim 1～7, is characterized in that, the composition of described metallic substance base material is different from the composition of described jut.

9. the metallic substance as described in any one in claim 1～7, is characterized in that, described metallic substance base material is connected continuously with described jut.

10. a surface treatment method for metallic substance, is characterized in that, this surface treatment method possesses following step:

Pending material as cathode electrode and anode electrode are immersed in to the step in electrolytic solution, and this pending material as cathode electrode is formed by the metallic substance with pending surface;

By more than applying 70V between described cathode electrode and described anode electrode and for the voltage of the scope of oxidation or melting can not occur pending material, thereby on described pending surface, form the step of microtexture;

Described pending material is taken out from described electrolytic solution to the step that this pending material is cleaned; And

The described pending surface of the described pending material after cleaning is implemented to the step of WATER REPELLENT.

The surface treatment method of 11. 1 kinds of metallic substance, is characterized in that, this surface treatment method possesses following step:

Pending material as cathode electrode and anode electrode are immersed in to the step in electrolytic solution, and this pending material as cathode electrode is formed by the metallic substance with pending surface;

By applying the voltage below the above 200V of 70V between described cathode electrode and described anode electrode, thereby in the described pending surperficial step that forms microtexture;

Described pending material is taken out from described electrolytic solution to the step that this pending material is cleaned; And

The described pending surface of the described pending material after cleaning is implemented to the step of WATER REPELLENT.

The manufacture method of 12. 1 kinds of water-proof materials using metallic substance as base material, is characterized in that, this manufacture method possesses following step:

Metallic substance and anode electrode are immersed in to the step in electrolytic solution, and this metallic substance is the pending material as cathode electrode with pending surface;

By applying the voltage below the above 200V of 70V between described cathode electrode and described anode electrode, thereby at the described metal material surface as pending material, form the step of microtexture;

Described metallic substance is taken out from described electrolytic solution to the step that this metallic substance is cleaned; And

The described pending surface of the described metallic substance after cleaning is implemented to the step of WATER REPELLENT.

The surface processing device of 13. 1 kinds of conductive materials, is characterized in that, this surface processing device possesses:

The cathode electrode that is mutually immersed in isolator the anode electrode in electrolytic solution and is formed by conductive material;

Be present between described anode electrode and described cathode electrode and there is the hovel of the peristome of the pending part that limits described cathode electrode; And

Between described anode electrode and described cathode electrode, execute alive power supply.

The surface processing device of 14. conductive materials as claimed in claim 13, is characterized in that, this surface processing device possesses the mechanism that the position of described peristome and/or the relative position of described anode electrode and described cathode electrode are changed.

The surface processing device of 15. conductive materials as described in claim 13 or 14, is characterized in that the voltage of described power supply more than applying 60V between anode electrode and cathode electrode, below 300V.

The surface processing device of 16. conductive materials as described in any one in claim 13～15, is characterized in that, described hovel is the surperficial insulativity heat-stable material with described peristome that covers cathode electrode.

The surface processing device of 17. conductive materials as described in any one in claim 13～16, is characterized in that, described conductive material is metallic substance.

The surface treatment method of 18. 1 kinds of conductive materials, is characterized in that, it utilizes the modifying surface of the surface processing device of the conductive material described in any one in claim 13～17 to conductive material.