CN1324155C - Titatium material and method for manufacturing the same - Google Patents

Titatium material and method for manufacturing the same Download PDF

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CN1324155C
CN1324155C CNB2005100818016A CN200510081801A CN1324155C CN 1324155 C CN1324155 C CN 1324155C CN B2005100818016 A CNB2005100818016 A CN B2005100818016A CN 200510081801 A CN200510081801 A CN 200510081801A CN 1324155 C CN1324155 C CN 1324155C
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titanium
enriched layer
titanium alloy
contact resistance
acid
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CN1715431A (en
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屋敷贵司
阪下真司
佐藤俊树
福田正人
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Kobe Steel Ltd
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Kobe Steel Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

A titanium material of the present invention includes a base material composed of a titanium alloy containing at least one alloying element selected from the group consisting of gold, silver, and platinum group elements; and a concentrated layer integrally disposed as a layer on the surface of the base material. In the concentrated layer, the alloying elements are concentrated by elution of Ti from the surface of the base material. The average thickness of the concentrated layer is 2.5 nm or more. The total alloying element concentration in the concentrated layer is 40 to 100 atomic percent. The total content of the alloying element in the base material is 0.01 to 1.0 percent by mass. Electrodes composed of the titanium material of the present invention are suitable for use in separators of fuel cells, and can readily be produced, so that the cost can be reduced.

Description

Titanium material and preparation method thereof
Technical field
The present invention relates to the method for a kind of titanium material and this titanium material of preparation.Particularly, the present invention relates in a kind of electrode that is adapted at fuel cell titanium material that for example in dividing plate, uses and preparation method thereof.
Background technology
Titanium and alloy thereof have fabulous erosion resistance, and titanium itself has fabulous electroconductibility.Therefore, these materials promise to be the material that is used for electrode, for example are used for the electrode and the solid polymer type fuel battery dividing plate of electrolytic industry, and these material requirements have electroconductibility and erosion resistance.
But,, when letting alone to place simply, can form the oxide film that is known as passive film on the material surface because pure titanium and alloy thereof are the active metals.Passive film has increased resistance, thereby causes current loss.So, in many cases, be not suitable for use in electrode materials without the titanium material of handling.
Therefore, the open 2003-105523 of Japanese unexamined patent discloses a kind of titanium electrode material, wherein the passive film on the titanium material surface is removed, and by plating, silk screen printing etc., the noble metal film that resulting surface-coated last layer is formed by platinum group precious metal and/or its oxide compound, thus guarantee its electroconductibility.
Solid polymer type fuel battery is by a plurality of elementary cells (unit cell) are piled up, between them, there is the electrode that is called dividing plate (perhaps bipolar plates) to construct, wherein elementary cell has a kind of like this structure, and wherein solid polymer dielectric film is clipped in the middle by anode and negative electrode.This dividing plate requires to have low contact resistance, and the application of metallic substance, and for example the application of aluminium alloy, stainless steel, nickelalloy and titanium alloy was studied by the people.But the problem of these metallic substance is: in environment for use rust form or the corrosion product deposition from the teeth outwards, and contact resistance increases in time, causes the decline and the current loss of electroconductibility.
In order to prevent such contact resistance increase and to keep electroconductibility; the someone has proposed the technology that forms one deck electroconductibility ceramic membrane on the metallic surface (below be called known technology A); and at metallic surface formation one deck noble metal film layer; carry out processed compressed, in active gas atmosphere, carry out the technology that corrosion protection handles (below be called known technology B) (open 11-162479 of Japanese unexamined patent and the open 2003-105523 of Japanese unexamined patent) then.
But above-mentioned noble metal film coating is handled, and except using expensive titanium material as the starting material, has also caused the further increase of cost, and therefore, because the production cost height, in actual production, this technology is not widely used in the preparation of electrode materials.
Particularly, the dividing plate of fuel cell is constructed by battery (elementary cell) is clipped between a plurality of dividing plates, and wherein elementary cell has a kind of like this structure, and wherein polymer dielectric film is between porous fuel electrode and air electrode.Owing to used a large amount of dividing plates, the requirement that reduces cost becomes stronger.Under existing conditions, from cost consideration, the first-selected use provides the starting material of the stainless steel of electroconductibility as dividing plate, although its erosion resistance is not always satisfactory.
According to above-mentioned known technology A and B, can guarantee the weather resistance of dividing plate to a certain extent.But keeping of electroconductibility is also unsatisfactory.To be described in detail this point below.
In known technology A (wherein on the metallic surface, forming one deck electroconductibility ceramic membrane),, wait certain class former thereby the crack in ceramic membrane, occurs because of collision easily because pottery is frangible.When the crack occurring in the ceramic membrane, caustic material enters by the crack and corrodes base material (metal).Therefore, the problem below existing: coming off of ceramic membrane promptly occur, thereby contact resistance is increased, to such an extent as to reduce electroconductibility.
In known technology B (wherein form one deck noble metal film layer, carry out processed compressed, in active gas atmosphere, carry out corrosion protection then and handle) in the metallic surface, exist the noble metal film layer local shedding to occur, thus the problem that electroconductibility is descended.Promptly, because dividing plate has surfaceness (asperity) usually, be difficult in the processed compressed after forming the noble metal film layer noble metal film layer be carried out even processed compressed, and can not avoid of the variation of the unrelieved stress of noble metal film layer at the different positions place.Therefore, the local shedding of noble metal film layer can occur, thereby contact resistance is increased, to such an extent as to electroconductibility reduces.
Summary of the invention
Summary of the invention
The present invention considers the problems referred to above and carries out.Therefore, an object of the present invention is to overcome the problems referred to above and a kind of titanium material that is adapted at using in the electrode and preparation method thereof is provided.That is, the present invention aims to provide a kind of titanium material, wherein produces easily, can reduce cost, and be difficult to occur owing to contact resistance increases the phenomenon that electroconductibility is descended.
Known packets contains platinum group etc. and is higher than pure titanium as the erosion resistance of the titanium alloy of alloying element.But the present inventor finds: even the content of above-mentioned alloying element is very little, by wash-out Ti from titanium alloy, therefore above-mentioned alloying element, forms the conduction enriched layer continuously also by enrichment on titanium alloy base material surface.Thereby finished the present invention.
The titanium material of one aspect of the present invention comprises the base material that is made of titanium alloy, and described titanium alloy comprises at least a alloying element that is selected from gold and silver and the platinum group (Pd, Pt, Ir, Ru, Rh and Os) that total amount is 0.01 to 1.0 mass percent; And on above-mentioned substrate surface the complete enriched layer that is arranged in one deck, wherein the mean thickness of above-mentioned enriched layer is more than or equal to 2.5nm, the total concn of above-mentioned alloying element is 40 to 100 atomic percents in the enriched layer.
The thickness of above-mentioned enriched layer is meant until alloy element concentration is reduced to the degree of depth of the alloying element enriched layer at half place of peak concentration, this concentration of sentencing alloying element in the base material is as reference, and compositional analysis carries out along the base material degree of depth (thickness) direction with Auger electron spectrum (AES).The mean thickness of preferred above-mentioned enriched layer is more than or equal to 6.0nm.
The total content of above-mentioned alloying element is 0.01 to 1.0 mass percent in the preferred above-mentioned base material.When using by when substrate surface wash-out Ti forms the method for enriched layer, if content less than 0.01 mass percent, then will increase the elution amount of Ti, it is time-consuming too many to form enriched layer.On the other hand, even content surpasses 1.0 mass percents,, do not promote the formation of enriched layer though material cost has increased.Therefore, this is uneconomic.
The titanium material of one aspect of the present invention can be formed on and comprise the structure that a thickness is 10 to 40nm oxide film between above-mentioned enriched layer and the above-mentioned base material.Above-mentioned oxide film can comprise the titanium dioxide with Detitanium-ore-type crystalline structure.
Electrode that the titanium material of each above-mentioned aspect of free the present invention constitutes and fuel cell separator plate are also within the scope of the invention.
The method of the above-mentioned titanium material of the present invention's preparation on the other hand comprises the steps: to be that the base material that at least a titanium alloy that is selected from the alloying element in gold and silver and the platinum group (Pd, Pt, Ir, Ru, Rh and Os) of 0.01 to 1.0 mass percent is formed is immersed in the solution that comprises non-oxide acid by comprising total amount, wash-out titanium from the above-mentioned substrate surface is 40 to 100 atomic percents and the mean thickness enriched layer more than or equal to 2.5nm thereby form above-mentioned element total concn on titanium alloy surface.
Prepare in the method for above-mentioned titanium material in the present invention, the above-mentioned solution that is used to flood base material can also comprise oxidizing acid except non-oxide acid.Herein, above-mentioned oxidizing acid can comprise the nitric acid of 0.1 to 40 mass percent.
Prepare in the method for above-mentioned titanium material in the present invention, the above-mentioned solution that is used for flooding titanium alloy can comprise at least a acid of oxalic acid of the formic acid of phosphoric acid, 10 to 40 mass percents of sulfuric acid, 10 to 50 mass percents of hydrochloric acid, 1.0 to 30 mass percents of the hydrogen fluoride that is selected from 0.01 to 3.0 mass percent, 1.0 to 30 mass percents and 10 to 30 mass percents as non-oxide acid.
The method that the present invention prepares above-mentioned titanium material also is included in floods the step that heat the back with titanium alloy under 350 ℃ to 600 ℃ temperature in above-mentioned solution.
Therefore above-mentioned titanium material not only has fabulous erosion resistance but also fabulous electroconductibility is arranged, and is adapted at using in the dividing plate of fuel cell.The method of the present invention's use titanium material on the other hand comprises uses above-mentioned titanium material as the raw-material step of titanium alloy, and described titanium alloy is to prepare by dissolving under the situation of not removing titanium material enriched layer.The enriched layer of above-mentioned titanium material is to be formed by the alloying element that constitutes the titanium alloy that serves as base material at first, and therefore, its waste material has fabulous recycling efficient.
The titanium material of producing with the inventive method has enriched layer, and this enriched layer has preset thickness, and wherein alloying element is by from substrate surface wash-out Ti and enrichment, and described base material is made by the titanium alloy that comprises alloying element such as platinum group.Therefore, this titanium material can have erosion resistance that is demonstrated by titanium alloy and the fabulous electroconductibility that is demonstrated by enriched layer simultaneously.Titanium material of the present invention can use the titanium alloy that comprises a small amount of alloying element to produce by the technology of simple relatively wash-out Ti.Therefore, can also reduce production costs.According to preparation method of the present invention, can produce prevention the titanium material that electroconductibility descends takes place because of contact resistance increases.Therefore, titanium material of the present invention is suitable for electrode materials, for example is used for the electrode of electrolysis treatment and the dividing plate of fuel cell.
Description of drawings
Fig. 1 shows the graphic representation that concerns between the mean thickness of enriched layer and the contact resistance.
Fig. 2 shows the Ti that measures with Auger electron spectrum (AES) and the synoptic diagram of the concentration profile of precious metal on depth direction.
Preferred embodiment is described
The titanium material of one embodiment of the invention will be described below.
This titanium material comprises a kind of base material that is made of titanium alloy and the complete enriched layer that is arranged in one deck on substrate surface, described titanium alloy comprises at least a alloying element that is selected from platinum group (Pd, Pt, Ir, Ru, Rh and Os), gold and the silver that total amount is 0.01 to 1.0 mass percent, and all the other comprise Ti and incidental impurity.Above-mentioned enriched layer is by forming above-mentioned alloying element enrichment from substrate surface wash-out Ti, and part comprises the oxide compound of alloying element.The electroconductibility of platinum group oxide compound is similar to the single matrix of platinum group.The platinum group oxide compound partly is eluted in the following Ti-caustic soln.But, think that oxide compound can be deposited on the substrate surface again because the solubleness of oxide compound is little.
As the result of selective corrosion and Ti wash-out, thereby above-mentioned alloying element forms enriched layer in the substrate surface enrichment.Therefore, even the content of alloying element very hour in the titanium alloy that constitutes base material,, also can form the enriched layer of effective reduction contact resistance in time along with the increase of Ti elution amount.On the other hand, when increasing as alloying element content, the elution amount of Ti can reduce.But because alloying element is very expensive, the increase of material cost is opposite with the purpose that will reach.Therefore, consider cost and the required elution time of the effective enriched layer of formation of the Ti of wash-out, the content that is preferably alloying element is about 0.01 to 1.0 mass percent, more preferably about 0.05 to 0.5 mass percent, also more preferably about 0.05 to 0.3 mass percent.Except above-mentioned alloying element, can also add Cr smaller or equal to about 0.2 mass percent, smaller or equal to the Ni of about 1.0 mass percents, smaller or equal to the Co of about 0.5 mass percent and smaller or equal to the Mo of about 0.5 mass percent as auxiliary element, with further raising erosion resistance and intensity.
In general titanium alloy, be suitable for titanium alloy example of the present invention (amount of alloying element by mass percentage) and can comprise Ti-0.15Pd (JIS 11 classes, 12 classes, 13 classes), Ti-0.4Ni-0.015Pd-0.025Ru-0.14Cr (JIS 14 classes, 15 classes), Ti-0.05Pd (JIS 17 classes, 18 classes), Ti-0.05Pd-0.3Co (JIS 19 classes, 20 classes), Ti-0.05Ru-0.5Ni (JIS 21 classes, 22 classes, 23 classes) and Ti-0.1Ru (26 grades, 27 grades of ASTM).
Form under the situation of above-mentioned enriched layer at the Ti that serves as matrix by wash-out, as in the present invention, the surface film of enrichment alloying element forms one deck on substrate surface.Therefore, the thickness of enriched layer is defined as until alloy element concentration is reduced to the alloying element enriched layer thickness at half place of peak concentration, this concentration of sentencing alloying element in the base material is as reference, and compositional analysis carries out along the base material depth direction with Auger electron spectrum (AES).If the mean thickness of enriched layer is less than 2.5nm, because solute segregation etc. and the zone that do not form enriched layer increases on substrate surface form the passive film of Ti, thereby whole electroconductibility is descended in this zone.Therefore, the mean thickness that it is desirable to enriched layer is more than or equal to 2.5nm, is preferably greater than to equal 6.0nm, more preferably greater than equaling 12.5nm.
Clear now, when the total concn of precious metal element in this enriched layer was 40 to 100 atomic percents, initial contact resistance was low, demonstrate fabulous erosion resistance and height weather resistance, therefore, contact resistance is difficult to increase in long-time, thereby electroconductibility is difficult to reduce.
The reason that the total concn of precious metal element in the precious metal element enriched layer is defined in 40 to 100 atomic percents is: if this concentration is less than 40 atomic percents, initial contact resistance increases, and contact resistance increases along with the passage of operating time, causes electroconductibility to be reduced to unsafty level.The concentration of precious metal element is the ratio of amount (total amount) sum of the amount of amount (total amount) and Ti of precious metal element in the precious metal element enriched layer and precious metal element in the precious metal element enriched layer.That is, the amount of Ti is A in hypothesis precious metal element enriched layer, and when the amount of precious metal element (total amount) was B, the concentration of precious metal element (atomic percent) was expressed as 100 * B/ (A+B) in the precious metal element enriched layer.Be assumed to be respectively under the situation of B1 and B2 including two kinds of precious metal elements and their amount, equation B=B1+B2 is effectively, and the concentration (atomic percent) of precious metal element is expressed as 100 * (B1+B2)/(A+B1+B2) in the precious metal element enriched layer.Be assumed to be respectively under the situation of B1, B2 and B3 including three kinds of precious metal elements and their amount, equation B=B1+B2+B3 is effectively, and the concentration (atomic percent) of precious metal element is expressed as 100 * (B1+B2+B3)/(A+B1+B2+B3) in the precious metal element enriched layer.
According to the method for preparing the titanium material, wherein by forming enriched layer from substrate surface wash-out Ti, can form the precious metal element enriched layer that the precious metal element total concn is 40 to 100 atomic percents at titanium alloy surface, in addition, can also between precious metal element enriched layer and titanium alloy, form oxide film.Therefore, the precious metal element total concn that the titanium material of producing with this preparation titanium material method is included in titanium alloy surface is the precious metal element enriched layer of 40 to 100 atomic percents, in addition, the titanium material can also provide oxide film between this enriched layer and titanium alloy.Although the unclear mechanism that forms above-mentioned oxide film thinks that the precious metal element enriched layer works to this mechanism.
When being formed on oxide thickness between precious metal element enriched layer and the titanium alloy, can improve erosion resistance when above-mentioned more than or equal to 10nm.But if the thickness of this oxide film surpasses 40nm, then contact resistance increases to unsafty level.From the above point of view, the thickness piece of oxide film being decided to be 10 to 40nm is ideal.This point will be discussed in more detail below.
Form because above-mentioned precious metal element enriched layer is the selective dissolution by Ti, may contain micropore.Therefore, in environment for use, caustic material for example chlorion enters in the hole, thereby the titanium alloy of base material may be corroded.When the titanium alloy of base material is corroded, because of volumetric expansion appears in corrosion product.Therefore, above-mentioned enriched layer may come off, and contact resistance may increase because of the resistance of corrosion product itself, thereby electroconductibility is reduced.
At this moment, the oxide film between above-mentioned precious metal element enriched layer and base material titanium alloy plays the titanium alloy corrosive effect that prevents base material, because this oxide film plays the diffusion barrier effect to the caustic material in the environment.If oxidation is lepthymenia, its anticorrosive action effect is insufficient, and caustic material enters by diffusion easily.Consider that it is used as the environment of dividing plate, the thickness of oxide film is ideal more than or equal to 10nm, and is then better more than or equal to 15nm.Consider that from erosion resistance the thickness of this oxide film is bigger to be ideal.But if oxide film is too thick, contact resistance is owing to its resistance increases, thereby electroconductibility is reduced.Consider this point, the thickness of this oxide film is ideal smaller or equal to 40nm, and recommends smaller or equal to 30nm.
It is ideal that oxide film between above-mentioned precious metal element enriched layer and titanium alloy comprises the titanium dioxide with Detitanium-ore-type crystalline structure.Reason is that the titanium dioxide with Detitanium-ore-type crystalline structure demonstrates high-caliber electroconductibility, and therefore, electroconductibility is difficult to reduce because contact resistance increases.Particularly for the electroconductibility that reduces to cause because of oxide film reduces degree, being defined as above-mentioned content with titanium dioxide of Detitanium-ore-type crystalline structure more than or equal to 50 mass percents is ideal.Can prove by methods such as electron diffractions to include the Detitanium-ore-type crystalline structure, with and content.
With the above-mentioned base material dipping of being made by titanium alloy and remain on and carry out corrosion treatment in the caustic soln, forming enriched layer by wash-out Ti from the surface at substrate surface is very easily.Not clearly restriction of type to above-mentioned caustic soln gets final product so long as can corrode the solution of Ti, can use nitric acid and hydrofluoric acid, hydrofluoric acid, hydrochloric acid, sulfuric acid etc.Wherein, nitric acid and hydrofluoric acid, hydrofluoric acid, high-temperature high concentration hydrochloric acid and sulfuric acid or its mixing solutions demonstrate highly corrosive to Ti, are suitable for being embodied as at short notice the surface enrichment of alloying element.
The enriched layer that forms by above-mentioned corrosion treatment wash-out Ti from the substrate surface can not be removed owing to the wearing and tearing that come off or the slight friction in surface causes, because the top coat of enrichment alloying element forms on substrate surface continuously.Therefore, titanium material of the present invention is suitable for electrode materials, for example is used for the electrode materials of electrolysis treatment and fuel cell separator plate, and these materials are used to or remain on statically in the electrolytic solution environment.After forming enriched layer, can improve the sticking power of enriched layer by for example carrying out heat treated in air or in the vacuum.
Below preparation method of the present invention will be described in more detail.
When the titanium alloy of at least a element in will comprising platinum group (Pd, Pt, Ir, Ru, Rh and Os), Au and Ag (below be called precious metal element) is immersed in the solution that comprises non-oxide acid, Ti is optionally dissolved, thereby can form layer with high precious metal element concentration (below be called the precious metal element enriched layer) on the titanium alloy surface.Clear now, by changing treatment condition, immersion condition for example, for example Suan concentration and the solution temperature used of dipping titanium alloy, and dipping time, can change the precious metal element concentration in the enriched layer, and can obtain high density, for example can obtain concentration up to 100 atomic percents.
The present invention is based on that above-mentioned discovery finishes.The method that the present invention prepares the titanium material is characterised in that and comprises following steps: will be immersed in the solution that comprises non-oxide acid by comprising at least a titanium alloy that is selected from the element (precious metal element) among platinum group (Pd, Pt, Ir, Ru, Rh and Os), Au and the Ag, thereby form the layer (concentration of precious metal layer) that above-mentioned element (precious metal element) total concn is 40 to 100 atomic percents on titanium alloy surface.
When above-mentioned titanium alloy being immersed in the solution that comprises non-oxide acid, the precious metal element of trace is dissolved in the solution.Also comprise under the situation of oxidizing acid except non-oxide acid at this solution, the trace noble metal element that is dissolved in the solution deposits once more.Therefore, promoted the enrichment of precious metal element, thereby formed the enriched layer that contains enough high density precious metal elements easily on the surface.
Oxidizing acid refers to the acid with following character: when titanium material or stainless steel being immersed in when comprising in this sour solution, form oxide film on titanium material or stainless steel surface.Non-oxide acid is meant the acid that does not have this character, promptly when titanium material or stainless steel being immersed in when comprising in this sour solution, can not form oxide film on its surface.
The solution that comprises non-oxide acid can be that non-oxide acid is joined in the solvent, for example be added to the water, the solution that mixes subsequently and form, perhaps can be by making it become non-oxide acid in the solvent that salt (for example iron(ic) chloride) is dissolved into water for example, join in the solvent then, for example be added to the water, and make its dissolving and the solution that forms.Each can be used as the solution that comprises non-oxide acid these solution.The solution that comprises oxidizing acid can be that oxidizing acid is joined in the solvent, for example be added to the water, the solution that mixes subsequently and form, perhaps can be by making it become oxidizing acid in the solvent that salt is dissolved into water for example, join in the solvent then, for example be added to the water, and make its dissolving and the solution that forms.Each can be used as the solution that comprises oxidizing acid these solution.This solution is without limits in the aqueous solution, can make acid is dissolved in the non-aqueous solution that forms in the organic solvent etc.
Comprise under the situation of nitric acid as oxidizing acid of 0.1 to 40 mass percent at the above-mentioned solution that is used to flood titanium alloy, above-mentioned precious metal element occurs and deposit again and become more reliable, and can further promote precious metal element enrichment from the teeth outwards.If concentration of nitric acid is less than 0.1 mass percent, the effect of above-mentioned promotion surface enrichment has the trend that reduces.If concentration surpasses 40 mass percents, the passivation of Ti appears, and the selective dissolution of Ti is become be difficult to take place, thereby tend to be difficult to form gratifying precious metal element enriched layer.Therefore, the concentration of nitric acid be 0.1 to 40 mass percent (below to be called concentration be ideal a), 1 to 30 mass percent is better.Consider the sticking power of precious metal element enriched layer, the concentration of nitric acid is that 1 to 20 mass percent is also better.
When the above-mentioned solution that is used to flood titanium alloy comprises the hydrogen fluoride (HF) of 0.01 to 3.0 mass percent, the hydrochloric acid (HCl) of 1.0 to 30 mass percents, the sulfuric acid (H of 1.0 to 30 mass percents 28O 4), the phosphoric acid (H of 10 to 50 mass percents 3PO 4), the oxalic acid of the formic acid (HCOOH) of 10 to 40 mass percents or 10 to 30 mass percents [(COOH) 2] as non-oxide when acid (following these concentration can be generically and collectively referred to as concentration b), can form the enriched layer that contains enough high density precious metal elements more reliably.If these sour concentration are less than separately minimum value in the above-mentioned scope, for example, if concentration of hydrochloric acid is less than 1.0 mass percents, the selective dissolution speed of Ti obviously descends, thereby is difficult to form the enriched layer that contains enough high density precious metal elements in the treatment time of reality scope.On the other hand, if these sour concentration have surpassed in the above-mentioned scope maximum value separately, for example, if the concentration of hydrochloric acid surpasses 30 mass percents, because the selective dissolution speed of Ti obviously improves, even the formation in a single day of precious metal element enriched layer, this layer comes off immediately, and the result is difficult to obtain effective enriched layer.Even obtain the precious metal element enriched layer, its sticking power also trends towards dying down.Therefore, it is ideal that the concentration of non-oxide acid is within the above-mentioned scope, and for example, the concentration of hydrochloric acid is defined as 1.0 to 30 mass percents.In addition, hydrogen fluoride concentration is that 0.05 to 2.0 mass percent, concentration of hydrochloric acid are that 2.0 to 25 mass percents, sulfuric acid concentration are that 2.0 to 25 mass percents, phosphoric acid concentration are that the concentration of 15 to 45 mass percents, formic acid is that the concentration of 15 to 35 mass percents and oxalic acid is that 15 to 25 mass percents are better.More preferably hydrogen fluoride is defined as 0.1 to 1.0 mass percent.Can with in these acid at least two kinds be used in combination.Under the situation that at least two kinds of acid are used in combination, has only a primary condition, that is, each sour concentration in these acid is arranged on and can excessively increases because of the selective dissolution speed of Ti and cause on the concentration that comes off immediately after the formation in a single day of precious metal element enriched layer.
In the processing of carrying out,,, speed of response forms the precious metal element enriched layer titanium alloy being immersed in the solution owing to needing the cost plenty of time slowly if treatment temp (solution temperature) is too low.If treatment temp is too high, then solubilizing reaction carries out inhomogeneously, thereby occurs the part that precious metal element does not have suitable enrichment easily.Consider this point, it is ideal that temperature of reaction is arranged on 10 ℃ to 80 ℃, and recommends 15 ℃ to 60 ℃.
If the treatment time is too short, be difficult to form gratifying precious metal element enriched layer, and weather resistance and stability descend also.If will extend in the treatment time to a certain degree, the stable upper layer of precious metal element that has been enrichment that then forms, and reaction becomes and is difficult to carry out, so its effect is saturated.Therefore, although can change the treatment time a little according to the composition and the treatment temp of the solution that is used to flood titanium alloy, the treatment time of recommending is about 1 to 60 minute.
If precious metal element content is less than 0.01 mass percent in the titanium alloy of base material, then be difficult to suitably increase the concentration of precious metal element in the enriched layer that forms by dipping in solution, and also may be because the growth of surface film oxide increases according to the environment for use contact resistance.When the content of precious metal element is more than or equal to 0.01 per-cent in the titanium alloy of regulation base material, can suitably increase the concentration of precious metal element in the enriched layer at an easy rate.But if content surpasses 1.0 mass percents, its effect is saturated.Consider this point, recommend the total content of precious metal element in the titanium alloy of base material is defined in 0.01 to 1.0 mass percent.
If desired, except precious metal element, can add other elements in the titanium alloy of base material, for example O, H, Fe and C are to regulate its mechanical property, for example tensile strength.To the not clearly restriction of titanium alloy surface state of base material, can adopt states such as common pickling material, clean annealing material, polished finish material.
After titanium alloy being immersed in the solution, under 350 ℃ to 600 ℃ temperature, heat, can improve the sticking power between precious metal element enriched layer and the titanium alloy.If Heating temperature, can reduce the raising effect to sticking power less than 350 ℃.If temperature surpasses 600 ℃, then the oxide growth owing to the base material titanium alloy significantly increases contact resistance.If heating is carried out in oxidizing atmosphere, contact resistance tends to increase, because the oxide growth of base material titanium alloy is remarkable.Consider this point, in vacuum atmosphere, at rare gas element (Ar, N 2Deng) in the atmosphere or to carry out this heating in the reducing atmosphere be ideal.
Preparing titanium material that the method for titanium material produces with the present invention, the precious metal element total concn is arranged on titanium alloy surface is the precious metal element enriched layer of 40 to 100 atomic percents.This titanium material has low initial contact resistance, fabulous erosion resistance and high-durability, and wherein contact resistance is difficult to increase in the time bar of a prolongation, and electroconductibility is difficult to reduce.
Therefore, this titanium material is adapted at having in the electrode of above-mentioned character and uses.Particularly, this titanium material is suitable for the dividing plate of fuel cell, uses this material, and contact resistance is difficult to increase in the time bar of a prolongation, and can keep its electroconductibility, therefore can improve its weather resistance.
Wherein the titanium alloy titanium material that is coated with precious metal element can have low initial contact resistance, fabulous erosion resistance and high-durability, therefore, descends and may be difficult to appearance because contact resistance increases the electroconductibility that causes.But this method is remarkable, and compares with the method that the present invention prepares the titanium material, and this method is uneconomical because production cost is high.That is, the method that the present invention prepares the titanium material is simple method, wherein only needs to be immersed in titanium alloy in the acidiferous solution of bag and not electroplate, and is therefore simple beyond doubt, and compares with carrying out electric plating method, because production cost is low but economical.
When after titanium alloy being used as electrode, use the titanium material as waste material when (being used for starting material) by the titanium alloy of dissolving preparation, at the titanium material is to be coated with under the situation of titanium alloy of precious metal element, with the titanium material again as starting material by the dissolving prepare titanium alloy before, precious metal element coating and raw-material titanium alloy must be separated.But, produce under the situation of titanium material in the method that adopts the present invention to prepare the titanium material, need not remove the precious metal element enriched layer, just can be used as starting material again by the titanium alloy of dissolving preparation.Therefore, it is simple that the method for preparing the titanium material with the present invention is produced the titanium material, because cost is low and economical, and because with compare above-mentioned advantage arranged by electroplate titanium material that titanium alloy produces with precious metal element, thereby fabulous recycling efficient is arranged.
The method that the present invention prepares the titanium material is not with the acidiferous solution of bag the titanium alloy that comprises precious metal element to be carried out simple acidleach to reach the method for for example removing the scales of skin that peel off (scale) purpose, but optionally Ti is dissolved from the titanium alloy that comprises precious metal element with the acidiferous solution of bag, be the method for the precious metal element enriched layer of 40 to 100 atomic percents on titanium alloy surface, to form precious metal element concentration.Do not use the acidleach of for example removing scales of skin that peel off purpose with improvement if do not add, then be difficult to form above-mentioned precious metal element enriched layer with fabulous sticking power in order to reach.
With reference to embodiment the present invention is done to describe more specifically below.But, can not make an explanation with restrictive one to the present invention according to these embodiment.
Embodiment
Embodiment 1
From the titanium alloy cold-reduced sheet (thickness of slab 2mm) with composition as shown in table 1 below take off 30mm wide * the long sample of 30mm.Sample is immersed in the caustic soln, wherein with the HF aqueous solution of 1 mass percent and the HNO of 10 mass percents 3Aqueous solution, 25 ℃ of following times shown in the dipping tables 1, so that Ti is eluted from the sample substrate surface, and the brown enriched layer of the light brown or duskiness of the platinum group that on substrate surface, formed enrichment and oxide compound thereof.Subsequently, from caustic soln, take out sample, wash with water, dry then.After this, measure the thickness and the contact resistance of enriched layer with following mode.Be shown in the table 1 in its result set.
The thickness of enriched layer is measured with PHI-670 analyser (by the PHI preparation).The compositional analysis of sample (titanium alloy sheet) carries out with following measuring condition on thickness direction with AES.Content with alloying element in the titanium alloy is reference, measures the degree of depth that alloying element content becomes a half of its peak value, and this degree of depth is defined as the thickness of enriched layer.In the zone beyond the part with the outward appearance that demonstrates special surface character, get three different points, carry out thickness measurement, measure its mean value.
Measuring condition:
Primary electron beam: 5kV-50nA;
Measured zone: 10 μ m * 10 μ m squares;
Sputter rate: 4.5nm/min is (with SiO 2Meter).
Two surfaces of said sample all are clipped between the potential electrode (surface in contact size: 20mm * 20mm),, measure the voltage E between two electrodes by the electric current I of 4A, and calculate contact resistance from E/I (I=4A).At this moment, be coated with gold on the surface in contact of potential electrode, and potential electrode applied load its power with 1.0kN is clipped in the middle sample.
Because contact resistance that can the actual electrode materials that uses is smaller or equal to 30% of the contact resistance (No. 11 samples, known materials are 7.5m Ω) of spontaneous passive film, that is, and smaller or equal to 2.25m Ω, so with the evaluation criteria of this numerical value as contact resistance.Nature, contact resistance is low more good more.More preferably contact resistance is smaller or equal to 20% of the contact resistance of spontaneous passive film, promptly smaller or equal to 1.5m Ω.
Table 1
Sample number into spectrum Base material is formed (quality %) Dipping time in caustic soln (second) The mean thickness of enriched layer (nm) Contact resistance (m Ω) Remarks
1 Ti-0.15Pd 30 4.0 2.0 Embodiment
2 Ti-0.15Pd 60 7.0 1.2 Embodiment
3 Ti-0.15Pd 180 13.0 0.8 Embodiment
4 Ti-0.15Pd 300 16.0 0.6 Embodiment
5 Ti-0.15Pd 600 20.0 0.3 Embodiment
6 Ti-0.05Pd 600 15.0 0.5 Embodiment
7 Ti-0.1Ru 600 17.0 0.5 Embodiment
8 Ti-0.1Ir 600 19.0 0.4 Embodiment
9 Ti-0.1Pt 600 18.0 0.5 Embodiment
10 Ti-0.4Ni-0.015Pd- 0.025Ru-0.14Cr 600 17.0 0.6 Embodiment
11 Ti-0.15Pd - (passive film: 8.0) 7.5 Known materials
12 Ti-0.001Pd 600 0.5 7.2 Comparing embodiment
13 Ti-0.15Pd 600 (upper layer comes off back) 8.0 1.1 Embodiment
, set up the relation between its enriched layer thickness and the contact resistance, and be shown among Fig. 1 to No. 9 samples as for 1 shown in the table 1.As being clear that from Fig. 1, when the enriched layer mean thickness became less than 2.5nm, contact resistance sharply increased, and when mean thickness during more than or equal to 2.5nm, contact resistance falls within the scope smaller or equal to 2.25m Ω, thereby demonstrates the electroconductibility that is suitable as electrode materials.When having determined mean thickness more than or equal to 6.0nm, contact resistance becomes smaller or equal to 1.5m Ω, and when mean thickness during more than or equal to 12.5nm, contact resistance becomes smaller or equal to 0.75m Ω, thereby demonstrates fabulous electroconductibility.
The preparation method of No. 13 samples is as follows: form the enriched layer with suitable thickness (mean thickness 20.0nm), self adhesive tape by being pressed on the sample surfaces, and is forcibly peeled off the upper layer of enriched layer.As a result, the mean thickness of enriched layer has become 8.0nm, even under these circumstances, contact resistance remains gratifying low numerical value.
On the other hand, as for No. 12 samples that are the low alloying element content of 0.001 mass percent, even dipping time is arranged on 600 seconds, the amount of the Ti of wash-out also is inadequate, there is not to form enriched layer with net thickness, titanium alloy has mass part to expose, and contact resistance increases.
The titanium alloy of the base material that constitutes above-mentioned No. 5 samples formed carried out Accurate Analysis.As a result, Pd is 0.15%, and O is 0.049%, and Fe is 0.043%, and N is 0.008%, and C is 0.006%, and H is 0.004%, and all the other are Ti.Formed enriched layer, and prepared 20 samples altogether of No. 5 samples, under the situation of not removing enriched layer, with non-consumble electric arc smelting furnace fusing sample.Form end ingot, carry out compositional analysis.As a result, Pd is 0.13%, and O is 0.055%, and Fe is 0.044%, and N is 0.008%, and C is 0.007%, and H is 0.007%, and all the other are Ti.Therefore, determined that electrode materials of the present invention can utilize the starting material as the titanium alloy for preparing by dissolving satisfactorily again after use, and need not to remove enriched layer.
Embodiment 2
The titanium alloy sheet dry-fine (dry-polish) of 30 * 30 * 1mm size to the SiC#400 level, and is cleaned with acetone.After this, titanium alloy sheet is immersed in comprises in the aqueous acid.Titanium alloy sheet, the aqueous solution, dip treating temperature (aqueous temperature) and the dipping time that use this moment are presented at table 2 in 4.
After above-mentioned dipping, with the precious metal element concentration in Auger electron spectrum (AES) the measurement titanium alloy sheet upper layer (precious metal element enriched layer).Simultaneously, as above-mentioned embodiment 1, measure the thickness of enriched layer.Contact resistance is measured with following mode.That is, getting thickness is the counterpart of the golden plate of 0.1mm as titanium alloy sheet, is applying 2.5N/mm with oil press 2Pressure (in the time of surface in contact: 20mm * 20mm), is measured contact resistance with the four-wire ohm table.In addition, abide by the adhesive tape test method (tape testing method) among the JIS H8504, the sticking power between the titanium alloy of precious metal element enriched layer and base material is assessed with the glassine paper self adhesive tape.
As mentioned above, can use Auger electron spectrum (AES) to measure precious metal element concentration in the precious metal element enriched layer.As for measuring condition, recommend analyzed area to be about 10 μ m * 10 μ m, and to recommend sputtering rate be 1 to 10nm/min (with SiO 2Meter).When with AES when depth direction is measured the concentration of Ti and precious metal element, resulting concentration profile is as shown in Figure 2.Usually, on the surface of metal outermost, often observe C (carbon) etc., this is by attached to lip-deep pollutent, and for example oil causes.Therefore, the Ti on the outermost surface and the concentration of precious metal element become relatively low, thereby, in many cases, can't obtain accurate analytical value.Therefore, in concentration profile, read Ti and precious metal element concentration that precious metal element concentration reaches the degree of depth place of its peak value, and its ratio, promptly 100 * B1/ (A+B1) is defined as the precious metal element concentration in the enriched layer.When the concentration of precious metal element does not have peak value, get precious metal element on outermost surface concentration and the ratio of Ti concentration as the concentration of precious metal element.Measurement is to carry out on any 5 points in the analyzed area of 5mm * 5mm, gets the concentration of its mean value as precious metal element.
Titanium alloy sheet through above-mentioned dip treating is carried out corrosion test.Corrosion test is the dip test in the aqueous sulfuric acid of the pH 2 under 80 ℃, and dipping time is 3,000 hours.
After above-mentioned corrosion test, measure the contact resistance of titanium alloy sheet.The mode of measuring is similar to the above-mentioned measurement to the titanium alloy contact resistance behind dipping.Contact resistance result based on the corrosion test fore-and-aft survey assesses weather resistance.
Measuring contact resistance result between measuring result, precious metal element enriched layer and the titanium alloy of above-mentioned titanium alloy sheet upper layer precious metal element concentration before the measuring result of sticking power, the corrosion test and the measuring contact resistance after the corrosion test the results are shown in table 2 in 5.
Among the embodiment 2, contact resistance is with m Ω cm 2Unit representation.This is that the measuring contact resistance area is 1cm 2The time numerical value.Among the embodiment 1, owing to be to apply to measure contact resistance in the 100kg load on the contact area of 2cm * 2cm, what the contact resistance of embodiment 1 was represented is that surface pressure is 25kg/cm 2And contact area is 4cm 2The time numerical value.On the other hand, in embodiment 2, although measuring condition is identical, applying unit is m Ω cm 2And contact area changed into 1cm 2Numerical value compare.That is, because observed value is that contact area is 4cm 2The time numerical value, divided by 4, be 1cm with observed value thereby change into contact area 2The time numerical value.
Table 2 in 5, aspect sticking power, symbol * represent non-constant, that symbol △ represents is poor (than symbol * expression better), symbol zero is represented (satisfaction), that symbol ⊙ represents is very good (than symbol zero expression also good).As for contact resistance, symbol * expression contact resistance is more than or equal to 100m Ω cm 2(non-constant), symbol △ represent that contact resistance is less than 100m Ω cm 2And more than or equal to 50m Ω cm 2(poor), symbol represents that contact resistance is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(generally), symbol zero expression contact resistance is less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(good: than symbol represent better), symbol ⊙ represents that contact resistance is less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(very good: than symbol zero expression better), and symbol ⊙ ⊙ represents that contact resistance is less than 15m Ω cm 2(fabulous: than symbol ⊙ represent also good).
In the table 2, relate to comparing embodiment No. 1, the titanium alloy sheet that wherein carries out dip treating in the aqueous solution, and is cleaned with acetone to the SiC#400 level by dry-fine.As being clear that from table 2, this titanium alloy sheet demonstrates the cm more than or equal to 50m Ω before corrosion test 2High contact resistance (△), and contact resistance is increased to the cm more than or equal to 100m Ω after corrosion test 2(*) therefore considers from resistance, and it is problematic using as dividing plate.
On the other hand, table 2 to 2 shown in 3 to No. 35 titanium materials are to produce with the method in the inventive embodiments.Their each contact resistances before corrosion test are all less than 50m Ω cm 2(, zero, ⊙ or ⊙ ⊙), and the contact resistance after the corrosion test is equally less than 50m Ω cm 2(, zero, ⊙ or ⊙ ⊙) therefore demonstrates fabulous electrical resistance property.This has satisfied as the required electrical resistance property of dividing plate.In addition, each all has the extraordinary upper layer of sticking power the titanium material of producing with the method in the embodiment of the invention, therefore, it is believed that the problem that pre-determined characteristics can not occur in actual use can not reaching owing to come off.
In 2 to No. 35 titanium materials, under titanium alloy the situation as the titanium alloy of base material of use precious metal element content less than 0.01 mass percent (total concn) (No. 2, No. 3, No. 5 etc.), the contact resistance before and after the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2Level (), perhaps less than 30m Ω cm 2And more than or equal to 20m Ω cm 2Level (zero).
Using precious metal element content more than or equal to 0.01 mass percent and under smaller or equal to the situation of the titanium alloy of 0.1 mass percent (total concn) (No. 12, No. 13 and No. 14), the contact resistance before the corrosion test is less than 15m Ω cm 2(⊙ ⊙) or less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙), be fabulous therefore.But the contact resistance after the corrosion test is less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(zero) or contact resistance less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙), therefore, contact resistance increases slightly owing to corrosion test.
Use precious metal element content more than or equal to 0.1 mass percent and situation smaller or equal to the titanium alloy of 1.0 mass percents (total concn) under (No. 4, No. 6, No. 7 etc.), the contact resistance before the corrosion test is less than 15m Ω cm 2(⊙ ⊙) is fabulous therefore.In addition, the contact resistance after the corrosion test is also less than 15m Ω cm 2(⊙ ⊙) therefore demonstrates fabulous contact resistance character.
Table 4 has been listed when using the aqueous solution comprise hydrogen fluoride and nitric acid as the solution of dipping titanium alloy, the assay of hydrogen fluoride concentration and concentration of nitric acid role.As being clear that from table 4, when concentration of nitric acid is 0 (when not containing nitric acid) (4-1 number), the precious metal element concentration in the precious metal element enriched layer satisfies the concentration (40 to 100 atomic percent) of the present invention's regulation.But the contact resistance before the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), the contact resistance after the corrosion test also is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2().When concentration of nitric acid during less than 0.1 mass percent (4-2 number), although the concentration of precious metal element is higher than above-mentioned concentration when not containing nitric acid in the precious metal element enriched layer, the contact resistance before the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), the contact resistance after the corrosion test also is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2().
On the other hand, when concentration of nitric acid was 0.1 to 40 mass percent, the contact resistance before the corrosion test was less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(zero), less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙) or less than 15m Ω cm 2(⊙ ⊙), the contact resistance after the corrosion test is less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(zero), less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙) or less than 15m Ω cm 2(⊙ ⊙) therefore, demonstrates fabulous contact resistance character.
When concentration of nitric acid surpassed 40 mass percents (4-8 number), the concentration of precious metal element satisfied the concentration of the present invention's regulation in the precious metal element enriched layer, but was lower than the concentration in the above-mentioned situation.Contact resistance before the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), and the contact resistance after the corrosion test less than 50m Ω cm 2And more than or equal to 30m Ω cm 2().
When hydrofluoric concentration during less than 0.01 mass percent (4-9 number), although the concentration of precious metal element satisfies the concentration of the present invention's regulation in the precious metal element enriched layer, the contact resistance before the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), and the contact resistance after the corrosion test less than 50m Ω cm 2And more than or equal to 30m Ω cm 2().
On the other hand, when hydrogen fluoride concentration was 0.01 to 3.0 mass percent, the contact resistance before the corrosion test was less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(zero), less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙) or less than 15m Ω cm 2(⊙ ⊙), the contact resistance after the corrosion test is less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(zero), less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙) or less than 15m Ω cm 2(⊙ ⊙) therefore, demonstrates fabulous contact resistance character.
When hydrogen fluoride concentration surpasses 3.0 mass percents (4-17 number), although formed the precious metal element enriched layer that satisfies normality condition of the present invention, its less thick, perhaps part comes off.Therefore, the contact resistance before the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), and the contact resistance after the corrosion test less than 50m Ω cm 2And more than or equal to 30m Ω cm 2().
Table 5 has been listed when using the aqueous solution comprise hydrochloric acid and nitric acid as the solution of dipping titanium alloy, the assay of concentration of hydrochloric acid and concentration of nitric acid role.As being clear that from table 5, when not containing nitric acid, the precious metal element concentration in the precious metal element enriched layer satisfies the concentration of the present invention's regulation.But the contact resistance before the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), the contact resistance after the corrosion test also is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2().When concentration of nitric acid during less than 0.1 mass percent, although the concentration of precious metal element is higher than above-mentioned concentration when not containing nitric acid in the precious metal element enriched layer, the contact resistance before the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), the contact resistance after the corrosion test also is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2().
On the other hand, when concentration of nitric acid was 0.1 to 40 mass percent, the contact resistance before the corrosion test was less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(zero), less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙) or less than 15m Ω cm 2(⊙ ⊙), the contact resistance after the corrosion test is less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(zero), less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙) or less than 15m Ω cm 2(⊙ ⊙) therefore, demonstrates fabulous contact resistance character.
When concentration of nitric acid surpassed 40 mass percents, the concentration of precious metal element satisfied the concentration of the present invention's regulation in the precious metal element enriched layer, but was lower than the concentration in the above-mentioned situation.Contact resistance before the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), and the contact resistance after the corrosion test less than 50m Ω cm 2And more than or equal to 30m Ω cm 2().
When the concentration of hydrochloric acid during less than 1.0 mass percents, although the concentration of precious metal element satisfies the concentration of the present invention's regulation in the precious metal element enriched layer, the contact resistance before the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), and the contact resistance after the corrosion test less than 50m Ω cm 2And more than or equal to 30m Ω cm 2().
On the other hand, when concentration of hydrochloric acid was 1.0 to 30 mass percents, the contact resistance before the corrosion test was less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(zero), less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙) or less than 15m Ω cm 2(⊙ ⊙), the contact resistance after the corrosion test is less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(zero), less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙) or less than 15m Ω cm 2(⊙ ⊙) therefore, demonstrates fabulous contact resistance character.
When concentration of hydrochloric acid surpasses 30 mass percents, although formed the precious metal element enriched layer that satisfies normality condition of the present invention, its less thick, perhaps part comes off.Therefore, the contact resistance before the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), and the contact resistance after the corrosion test less than 50m Ω cm 2And more than or equal to 30m Ω cm 2().
As mentioned above, the aqueous solution that comprises hydrogen fluoride and nitric acid in use comprises under the solution both of these case of the aqueous solution as the dipping titanium alloy of hydrochloric acid and nitric acid as solution that floods titanium alloy and use, when its concentration is in above-mentioned concentration range separately (concentration a and b), contact resistance before and after the corrosion test is all low, therefore, demonstrate fabulous contact resistance character.If this concentration is less than concentration a or surpassed concentration b, although the contact resistance before and after the corrosion test is still, contact resistance numerical value is higher than concentration and is in the contact resistance of above-mentioned scope (concentration a and b) when interior.
Replacing with sulfuric acid, phosphoric acid, formic acid or oxalic acid under the situation of above-mentioned hydrogen fluoride or hydrochloric acid, also demonstrate trend similar to the above.That is, when its concentration was in above-mentioned concentration range separately (concentration a and b), the contact resistance before and after the corrosion test was all low, therefore, demonstrates fabulous contact resistance character.If this concentration is less than concentration a or surpassed concentration b, although the contact resistance before and after the corrosion test is still, contact resistance numerical value is higher than concentration and is in the contact resistance of above-mentioned scope (concentration a and b) when interior.
As being clear that from table 4 and 5, when the precious metal element concentration (total concn) in the precious metal element enriched layer during less than 40 atomic percents (4-18 number and 7-15 number), the contact resistance before the corrosion test is less than 100m Ω cm 2And more than or equal to 50m Ω cm 2(△), and the contact resistance after the corrosion test more than or equal to 100m Ω cm 2(*) or less than 100m Ω cm 2And more than or equal to 50m Ω cm 2(△).
On the other hand, when the precious metal element concentration (total concn) in the precious metal element enriched layer was 40 to 100 atomic percents, the contact resistance before the corrosion test was less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(zero), less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙) or less than 15m Ω cm 2(⊙ ⊙), the contact resistance after the corrosion test is less than 50m Ω cm 2And more than or equal to 30m Ω cm 2(), less than 30m Ω cm 2And more than or equal to 20m Ω cm 2(zero), less than 20m Ω cm 2And more than or equal to 15m Ω cm 2(⊙) or less than 15m Ω cm 2(⊙ ⊙) therefore, demonstrates fabulous contact resistance character.
Table 6 is depicted as the assay of the thickness role of the oxide film that is formed between precious metal element enriched layer and the titanium alloy.The thickness of oxide film is the mean value with any 5 positions of the observed cross-section photograph figure of transmission electron microscope (TEM).Observation magnification when oxide thickness is measured is 150,000 times.The thickness of five of film parts is gone up about 700nm in film thickness direction (vertically) in the photo, goes up about 900nm in vertical film thickness direction (level), measures its numerical value and average, thereby determines the thickness of oxide film.As being clear that from table 6, the thickness that is formed at the oxide film between precious metal element enriched layer and the titanium alloy is 10 to 40nm, compare during with thickness less than 10nm, and its high corrosion resistance, weather resistance is also fabulous.Therefore, the contact resistance increase degree that causes owing to corrosion test is little.That is, even contact resistance is in par before the corrosion test, after corrosion test, therefore the contact resistance the when contact resistance of above-mentioned oxide thickness during more than or equal to 10nm will be lower than thickness less than 10nm is fabulous.If above-mentioned oxide thickness surpasses 40nm, even formed the precious metal element enriched layer that contains enough high density precious metal elements, contact resistance also has the trend that becomes big a little before corrosion test, and this is not preferred.If the thickness of above-mentioned oxide film surpasses 60nm, it is big that the contact resistance before the corrosion test obviously becomes, therefore can not be satisfactory.
No. Base material Solution Temperature (℃) Dipping time (min) Precious metal concentration in the enriched layer (weight %) Enriched layer thickness (nm) Sticking power between base material and the enriched layer Contact resistance Remarks
Before the corrosion test After the corrosion test
1 Ti-0.15Pd - - - - 0 - △ × Comparing embodiment
2 Ti-0.009Pd 5％HNO 3+0.05％HF 35 10 45.2 6 ⊙ ○ ○ Inventive embodiments
3 Ti-0.008Pt 5％HNO 3+0.05％HF 35 10 40.1 5 ⊙ ○ □ Inventive embodiments
4 Ti-0.14Pd 5％HNO 3+0.5％HF 35 10 80.4 14 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
5 Ti-0.009Au 15％HNO 3+30％HCl 50 7 49.8 7 ⊙ ○ □ Inventive embodiments
6 Ti-0.21Ir 15％HNO 3+30％HCl 50 7 66.5 10 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
7 Ti-0.53Ru 15％HNO 3+30％HCl 50 7 74.5 12 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
8 Ti-0.48Rh 15％HNO 3+30％HCl 50 7 63.7 10 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
9 Ti-0.008Ag 40％HNO 3+10％H 2SO 4 60 15 52.8 7 ⊙ ○ ○ Inventive embodiments
10 Ti-0.82Os 40％HNO 3+10％H 2SO 4 60 l5 71.0 11 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
11 Ti-0.005Ir- 0.004Rh 1％HNO 3+50％H 3PO 4 45 20 50.1 7 ⊙ ○ ○ Inventive embodiments
12 Ti-0.01Au 1％HNO 3+50％H 3PO 4 45 20 40.3 5 ⊙ ⊙ ○ Inventive embodiments
13 Ti-0.005Pd- 0.006Ir 1％HNO 3+50％H 3PO 4 45 20 58.9 9 ⊙ ⊙⊙ ⊙ Inventive embodiments
14 Ti-0.09Pt 12％HNO 3+40％HCOOH 80 20 51.2 7 ⊙ ⊙ ○ Inventive embodiments
15 Ti-1.02Ru 15％HNO 3+30％(COOH) 2 60 15 99.8 25 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
16 Ti-0.10Pd 18％HNO 3+0.1％HF+2％HCl 40 30 72.1 11 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
17 Ti-0.18Pd- 0.02Os 18％HNO 3+0.1％HF+2％HCl 40 30 69.4 11 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
18 Ti-0.25Ir- 0.12Ru 6％HNO 3+2％HF+1％H 2SO 4 15 5 88.3 17 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
19 Ti-0.25Rh - 0.11Au 6％HNO 3+2％HF+1％H 2SO 4 15 5 77.9 13 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
20 Ti-0.50Au- 0.07Ag 10％HNO 3+0.5％HF+ 10％H 3PO 4 10 15 92.8 19 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
Table 3
No. Base material Solution Temperature (℃) Dipping time (min) Precious metal concentration in the enriched layer (weight %) Enriched layer thickness (nm) Sticking power between base material and the enriched layer Contact resistance Remarks
Before the corrosion test After the corrosion test
21 Ti-0.52Pd-0.03Ag 13％HNO 3+0.8％HF+ 10％HCOOH 25 10 90.2 18 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
22 Ti-0.29Pt-0.01Au 13％HNO 3+0.8％HF+ 10％HCOOH 25 10 84.3 16 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
23 Ti-0.18Pd-0.02Ir 0.5％HNO 3+0.1％HF+ 10％(COOH) 2 30 18 79.5 14 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
24 Ti-0.18Pd-0.06Ru- 0.05Ag 0.5％HNO 3+0.1％HF+ 10％(COOH) 2 30 18 83.2 15 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
25 Ti-0.18Pd-0.02Ir 15％HNO 3+1％HCl+ 2％H 2SO 4 25 20 81.1 14 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
26 Ti-0.20Pt-06Ir- 0.05Au 15％HNO 3+1％HCl+ 2％H 2SO 4 25 20 85.3 16 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
27 Ti-0.20Pt-0.06Ir- 0.05Au 20％HNO 3+5％HCl+ 10％H 3PO 4 30 60 95.5 20 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
28 Ti-0.15Pd 20％HNO 3+5％HCl+ 10％H 3PO 4 30 60 90.1 18 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
29 Ti-0.15Pd 0.1％HNO 3+3％HCl+ 10％(COOH) 2 25 30 84.1 15 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
30 Ti-0.18Pd-0.02Ir 0.1％HNO 3+3％HCl+ 10％(COOH) 2 25 30 89.0 17 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
31 Ti-0.15Pd 3.5％HNO 3+3％HCl+ 10％(COOH) 2 25 30 69.9 11 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
32 Ti-0.20Pt-0.06Ir- 0.05Au 3.5％HNO 3+3％HCl+ 10％(COOH) 2 25 30 76.5 13 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
33 Ti-0.15Pd 5％HNO 3+1 5％HCOOH+ 20％(COOH) 2 60 20 88.2 17 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
35 Ti-0.15Pd-0.05Ru 15％HNO 3+0.1％HF+ 2％HCl+15％HCOOH 55 20 92.5 19 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
Table 4
No. Base material Solution Temperature (℃) Dipping time (min) Precious metal concentration in the upper layer (weight %) Enriched layer thickness (nm) Sticking power between base material and the enriched layer Contact resistance Remarks
Before the corrosion test After the corrosion test
4-1 Ti-0.14Pd 0.5％HF 35 10 40.2 5 ⊙ □ □ Inventive embodiments
4-2 Ti-0.14Pd 0.08％HNO 3+0.5％HF 35 10 43.5 6 ⊙ □ □ Inventive embodiments
4-3 Ti-0.14Pd 0.1％HNO 3+0.5％HF 35 10 44.9 6 ⊙ ⊙ ⊙ ：No.4
4-4 Ti-0.14Pd 1％HNO 3+0.5％HF 35 10 50.2 7 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
4 Ti-0.14Pd 5％HNO 3+0.5％HF 35 10 80.4 14 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
4-5 Ti-0.14Pd 20％HNO 3+0.5％HF 35 10 83.1 15 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
4-6 Ti-0.14Pd 25％HNO 3+0.5％HF 35 10 68.4 11 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
4-7 Ti-0.14Pd 35％HNO 3+0.5％HF 35 10 51.1 7 ○ ⊙ ⊙ Inventive embodiments
4-8 Ti-0.14Pd 45％HNO 3+0.5％HF 35 10 42.5 5 ○ □ □ Inventive embodiments
4-9 Ti-0.14Pd 5％HNO 3+0.005％HF 35 10 40.3 5 ⊙ □ □ Inventive embodiments
4-10 Ti-0.14Pd 5％HNO 3+0.01％HF 35 10 50.7 7 ⊙ ⊙ ⊙ Inventive embodiments
4-11 Ti-0.14Pd 5％HNO 3+0.1％HF 35 10 70.2 11 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
4 Ti-0.14Pd 5％HNO 3+0.5％HF 35 10 80.4 14 ⊙ ⊙⊙ ⊙⊙ ：No.4
4-12 Ti-0.14Pd 5％HNO 3+1.0％HF 35 10 81.1 14 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
4-13 Ti-0.14Pd 5％HNO 3+1.5％HF 35 10 79.7 14 ⊙ ⊙ ⊙ Inventive embodiments
4-14 Ti-0.14Pd 5％HNO 3+2.0％HF 35 10 65.5 10 ⊙ ⊙ ⊙ Inventive embodiments
4-15 Ti-0.14Pd 5％HNO 3+2.5％HF 35 10 60.2 9 ⊙ ○ ○ Inventive embodiments
4-16 Ti-0.14Pd 5％HNO 3+3.0％HF 35 10 52.0 7 ○ ○ ○ Inventive embodiments
4-17 Ti-0.14Pd 5％HNO 3+3.5％HF 35 10 42.8 6 △ □ □ Inventive embodiments
4-18 Ti-0.14Pd 5％HNO 3+3.5％HF 35 15 38.9 4 △ △ △ Comparing embodiment
Table 5
No. Base material Solution Temperature (℃) Dipping time (min) Precious metal concentration in the upper layer (weight %) Enriched layer thickness (nm) Sticking power between base material and the enriched layer Contact resistance Remarks
Before the corrosion test After the corrosion test
7-1 Ti-0.53Ru 30％HCl 50 7 40.1 5 ⊙ □ □ Inventive embodiments
7-2 Ti-0.53Ru 0.08％HNO 3+30％HCl 50 7 42.3 5 ⊙ □ □ Inventive embodiments
7-3 Ti-0.53Ru 0.1％HNO 3+30％HCl 50 7 47.1 6 ⊙ ⊙ ⊙ Inventive embodiments
7-4 Ti-0.53Ru 1％HNO 3+30％HCl 50 7 50.9 7 ⊙ ⊙ ⊙ Inventive embodiments
7-5 Ti-0.53Ru 10％HNO 3+30％HCl 50 7 59.8 9 ⊙ ⊙ ⊙ Inventive embodiments
7 Ti-0.53Ru 15％HNO 3+30％HCl 50 7 74.5 12 ⊙ ⊙⊙ ⊙⊙ ：No.7
7-6 Ti-0.53Ru 20％HNO 3+30％HCl 50 7 78.2 14 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
7-7 Ti-0.53Ru 25％HNO 3+30％HCl 50 7 67.7 10 ⊙ ⊙ ⊙ Inventive embodiments
7-8 Ti-0.53Ru 35％HNO 3+30％HCl 50 7 53.1 7 ○ ○ ○ Inventive embodiments
7-9 Ti-0.53Ru 45％HNO 3+30％HCl 50 7 44.3 6 ○ □ □ Inventive embodiments
7-10 Ti-0.53Ru 15％HNO 3+0.5％HCl 50 7 40.9 5 ⊙ □ □ Inventive embodiments
7-11 Ti-0.53Ru 15％HNO 3+1.0％HCl 50 7 50.0 7 ⊙ ⊙ ⊙ Inventive embodiments
7-12 Ti-0.53Ru 15％HNO 3+10％HCl 50 7 68.8 11 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
7-13 Ti-0.53Ru 15％HNO 3+20％HCl 50 7 82.5 15 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
7 Ti-0.53Ru 15％HNO 3+30％HCl 50 7 74.5 12 ⊙ ⊙⊙ ⊙⊙ ：No.7
7-14 Ti-0.53Ru 15％HNO 3+3 5％HCl 50 7 45.6 6 △ □ □ Inventive embodiments
7-15 Ti-0.53Ru 15％HNO 3+35％HCl 90 7 37.9 4 △ △ × Comparing embodiment
Table 6
No. Base material Solution Temperature (℃) Dipping time (min) Precious metal concentration in the upper layer (weight %) Oxide thickness (nm) Enriched layer thickness (nm) Sticking power Contact resistance Remarks
Before the corrosion test After the corrosion test
36 Ti-0.28Pd- 0.08Au 3％HNO 3+30％H 3PO 4 15 10 62.1 9.8 9 ⊙ ⊙⊙ ⊙ Inventive embodiments
37 Ti-0.28Pd- 0.08Au 3％HNO 3+30％H 3PO 4 25 15 65.3 10.3 10 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
38 Ti-0.28Pd- 0.08Au 10％HNO 3+30％HCOOH 35 15 72.9 25.6 12 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
39 Ti-0.28Pd- 0.08Au 10％HNO 3+30％HCOOH 50 20 83.8 39.7 15 ⊙ ⊙⊙ ⊙⊙ Inventive embodiments
40 Ti-0.28Pd- 0.08Au 10％HNO 3+12％HCl+ 15％HCOOH 55 25 89.5 40.8 5 ⊙ ⊙ ⊙ Inventive embodiments
41 Ti-0.28Pd- 0.08Au 5％HNO 3+2％HF+ 30％H 3PO 4 50 20 74.5 62.8 13 ⊙ △ △ Inventive embodiments

Claims (12)

1, a kind of titanium material, this titanium material comprises:
By the base material that titanium alloy constitutes, described titanium alloy comprises at least a alloying element that is selected from gold and silver and the platinum group that total amount is 0.01 to 1.0 mass percent; And
The complete enriched layer that is arranged in one deck on substrate surface,
Wherein the mean thickness of enriched layer is more than or equal to 2.5nm, and the total concn of alloying element is 40 to 100 atomic percents in the enriched layer.
2, the titanium material of claim 1, wherein the mean thickness of enriched layer is more than or equal to 6.0nm.
3, the titanium material of claim 1, wherein the total content of alloying element is 0.05 to 0.5 mass percent in the base material.
4, the titanium material of claim 1, this titanium material also comprise a layer thickness between enriched layer and base material be 10 to 40nm oxide film.
5, the titanium material of claim 4, wherein oxide film comprises the titanium dioxide with Detitanium-ore-type crystalline structure.
6, a kind of electrode that comprises the titanium material of claim 1.
7, a kind of fuel cell separator plate that comprises the titanium material of claim 1.
8, a kind of method for preparing the titanium material of claim 1, this method comprises the steps:
Will be by comprising at least a gold that is selected from that total amount is 0.01 to 1.0 mass percent, the base material that titanium alloy in the alloying element of silver and platinum group constitutes is immersed in the solution that comprises non-oxide acid, wash-out titanium from the substrate surface, thereby form enriched layer on substrate surface, wherein said non-oxide acid is selected from the hydrogen fluoride of 0.01 to 3.0 mass percent, 1.0 hydrochloric acid to 30 mass percents, 1.0 sulfuric acid to 30 mass percents, the phosphoric acid of 10 to 50 mass percents, at least a in the oxalic acid of the formic acid of 10 to 40 mass percents and 10 to 30 mass percents.
9, the titanium material preparation method of claim 8, the solution that wherein is used to flood titanium alloy can also comprise oxidizing acid except non-oxide acid.
10, the method for preparing the titanium material of claim 9, the solution that wherein is used to flood titanium alloy comprises the nitric acid of 0.1 to 40 mass percent as oxidizing acid.
11, after the method for preparing the titanium material of claim 8, this method also are included in titanium alloy are flooded in solution, the step that under 350 ℃ to 600 ℃ temperature, heats.
12, a kind of method of using the titanium material of claim 1, this method comprise the titanium material that the uses claim 1 raw-material step as titanium alloy, and described titanium alloy is to prepare by dissolving under the situation of not removing enriched layer.
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JP4981284B2 (en) * 2004-12-09 2012-07-18 株式会社神戸製鋼所 Method for producing titanium material for fuel cell separator
JP4032068B2 (en) * 2005-07-28 2008-01-16 株式会社神戸製鋼所 Titanium material used in fuel cell separators
ITMI20061974A1 (en) * 2006-10-16 2008-04-17 Industrie De Nora Spa ANODE FOR ELECTROLYSIS
JP4823202B2 (en) * 2007-11-15 2011-11-24 株式会社神戸製鋼所 Method for producing titanium substrate for fuel cell separator and method for producing fuel cell separator
CN101824565B (en) * 2010-03-16 2011-11-23 中南大学 Silver powder-containing metallurgic titanium-molybdenum-aluminum-vanadium alloy and preparation method thereof
CN101914781B (en) * 2010-07-02 2013-06-12 波鹰(厦门)科技有限公司 Titanium electrode material coated with nanometre rhodium iridium coatings and preparation method thereof
KR101609077B1 (en) * 2011-08-09 2016-04-05 제이엑스 킨조쿠 가부시키가이샤 Separator material for fuel cells, separator for fuel cells using same, fuel cell stack using same, and method for producing separator material for fuel cells
JP5201256B1 (en) * 2011-11-18 2013-06-05 新日鐵住金株式会社 Titanium material for polymer electrolyte fuel cell separator, production method thereof, and polymer electrolyte fuel cell using the same
JP6258113B2 (en) * 2014-04-18 2018-01-10 株式会社神戸製鋼所 Method for producing antibacterial titanium alloy material
US20180087131A1 (en) * 2015-03-18 2018-03-29 Nippon Steel & Sumitomo Metal Corporation Titanium alloy, separator, and polymer electrolyte fuel cell
JP6620468B2 (en) * 2015-09-01 2019-12-18 日本製鉄株式会社 Titanium material and cell member for polymer electrolyte fuel cell containing the same
JP6542080B2 (en) * 2015-09-11 2019-07-10 田中貴金属工業株式会社 Method for improving the amount of dissolved hydrogen in electrolytic hydrogen water
CN114614020B (en) * 2022-03-21 2023-05-09 合肥国轩高科动力能源有限公司 Preparation method of composite current collector

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