Titanium product, separator, and proton exchange membrane fuel cell, and method for producing titanium product

Abstract

A titanium product for a separator of a proton exchange membrane fuel cell according to the present invention includes: a base material that consists of commercially pure titanium; a first oxide layer that is formed in a surface layer of the titanium product, consists of TiO.sub.2 of a rutile crystallinity, and has a thickness of 0.1 to 1.5 nm; and a second oxide layer that is formed between the base material and the first oxide layer, consists of TiO.sub.x (1<x<2), and has a thickness of 3 to 20 nm. This titanium product is suitable to be used as a separator of a proton exchange membrane fuel cell that has a high corrosion resistance in an environment in a fuel cell, is capable of keeping a low contact resistance with an electrode consisting of carbon fiber and the like, and is inexpensive.

Claims

1. A titanium product for a separator of a proton exchange membrane fuel cell, the titanium product comprising: a base material, a first oxide layer, and a second oxide layer, wherein the base material consists of a commercially pure titanium selected from type 1 to 4 specified in JIS H 4600:2014, the first oxide layer is formed in a surface layer of the titanium product, consists of TiO.sub.2 of a rutile crystallinity, and has a thickness of 0.3 to 1.5 nm, and the second oxide layer is formed between the base material and the first oxide layer, consists of TiO.sub.x (1<x<2), and has a thickness of 3 to 20 nm.

2. The titanium product according to claim 1, further comprising at least one of a noble metal layer and a conductive carbon material layer formed on the first oxide layer.

3. A separator for a proton exchange membrane fuel cell, the separator comprising the titanium product according to claim 1.

4. A proton exchange membrane fuel cell comprising the separator according to claim 3.

5. A method for producing a titanium product, the method comprising the steps: a solution treatment step which is treating a substrate consists of commercially pure titanium selected from type 1 to 4 specified in JIS H 4600:2014 using an aqueous solution containing fluoride ions; a first heat treatment step which is subjecting the substrate treated in the solution treatment step to heat treatment under a low-oxygen-partial-pressure atmosphere having an oxygen partial pressure of 0.1 Pa or less, at 200 to 550 C., for 10 to 300 minutes; and a second heat treatment step which is subjecting the substrate treated in the first heat treatment step to heat treatment under a high-oxygen-partial-pressure atmosphere having an oxygen partial pressure of 10000 Pa or more, at 200 to 500 C., for 2 to 30 minutes.

6. The method for producing a titanium product according to claim 5, further comprising a noble metal layer forming step which is, after performing the first and second heat treatment steps, supplying a noble metal to a surface of the titanium product to form a noble metal layer.

7. The method for producing a titanium product according to claim 5, further comprising a conductive carbon material layer forming step which is, after performing the first and second heat treatment steps, supplying carbon to a surface of the substrate to form a conductive carbon material layer.

8. A separator for a proton exchange membrane fuel cell, the separator comprising the titanium product according to claim 2.

9. A proton exchange membrane fuel cell comprising the separator according to claim 8.

10. The method for producing a titanium product according to claim 6, further comprising a conductive carbon material layer forming step which is, after performing the first and second heat treatment steps, supplying carbon to a surface of the substrate to form a conductive carbon material layer.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1A is a perspective view of a proton exchange membrane fuel cells.

(2) FIG. 1B is an exploded perspective view illustrating the structure of a single cell constituting the proton exchange membrane fuel cell.

(3) FIG. 2A is a graph illustrating an example of the relationship between depth from the surface of a titanium product, and shifted energy value at the L.sub.2 edge of Ti.

(4) FIG. 2B is a graph illustrating an example of the relationship between depth from the surface of a titanium product before a second heat treatment step, and shifted energy value at the L.sub.2 edge of Ti.

(5) FIG. 3A is a picture illustrating an example of an X-ray diffraction pattern obtained by TEM observation on the surface of the titanium product before the second heat treatment step.

(6) FIG. 3B is a picture illustrating an example of an X-ray diffraction pattern obtained by TEM observation on the surface of the titanium product after the second heat treatment step.

(7) FIG. 4 is a diagram illustrating the configuration of an apparatus for measuring the contact resistance of a titanium product.

DESCRIPTION OF EMBODIMENTS

(8) 1. Titanium Product According to Present Invention

(9) <Relationship Between Shifted Energy Value by EELS and Conductivity>

(10) The present inventors calculated shifted energy value at the L.sub.2 edge of Ti (hereinafter, simply referred to as shifted energy value) for a surface layer of a titanium product including an oxide film, by the electron energy loss spectroscopy (EELS) using a spectral device supplied with a transmission electron microscope (TEM). The shifted energy value is calculated with reference to the energy of metallic titanium and has a correlation with x of TiO.sub.x (1<x2).

(11) FIG. 2A illustrates an example of the relationship between depth from the surface of a titanium product and shifted energy value. FIG. 2B is a graph illustrating an example of the relationship between depth from the surface of a titanium product before a second heat treatment step, which will be described later, and shifted energy value at the L.sub.2 edge of Ti. The titanium product of the example has the following features. The titanium product includes neither noble metal layer nor conductive carbon material layer formed on the titanium product. (i) The shifted energy value shown in an outermost layer of the titanium product is that of TiO.sub.2. (ii) From the surface, the shifted energy value starts to decrease toward a deep portion up to 1.5 nm. (iii) From the start of the decrease in shifted energy value up to a base material, the shifted energy value shows that of TiO.sub.x (1<x<2), where the value of x of TiO.sub.x corresponding to the shifted energy value approaches two as coming close to an outer layer side and approaches one as coming close to a base material side.

(12) The present inventors have found that the titanium product having the features (i) to (iii) shows a low contact resistance.

(13) The conductivity of TiO.sub.x varies in proportion to the value of x and therefore varies in proportion to the shifted energy value. When the shifted energy value of TiO.sub.x (1<x<2) falls below 90% of the shifted energy value of TiO.sub.2 in the outermost layer, a loss amount of oxygen increases, which results in a high conductivity. The smaller the value of x is, the smaller the value of n of a Magneli phase becomes, which is expressed as Ti.sub.nO.sub.2n1 (n: an integer not less than one), and the conductivity increases. The reason that the titanium product having the features (i) to (iii) shows a low contact resistance is supposed to be attributable to such a relationship between an oxygen loss amount and conductivity.

(14) The present invention is completed based on the aforementioned findings. The titanium product according to the present invention includes a base material, a first oxide layer that is formed in a surface layer of the titanium product, and a second oxide layer that is formed between the base material and the first oxidized layer. The titanium product may further include at least one of a noble metal layer and a conductive carbon material layer that are formed on the first oxide layer.

(15) [Base Material]

(16) The base material consists of commercially pure titanium. Examples of the commercially pure titanium include Type 1 to 4 titaniums that are specified in JIS H 4600:2014. Hereinafter, the commercially pure titanium will be simply referred to as pure titanium.

(17) [First Oxide Layer]

(18) Where neither noble metal layer nor conductive carbon material layer is formed, the first oxide layer is located in the outermost-layer portion of the titanium product.

(19) The first oxide layer has a thickness of 0.1 to 1.5 nm and consists of a titanium oxide of a rutile crystallinity the chemical formula of which is expressed as TiO.sub.2. When the ratio of TiO.sub.2 in the first oxide layer is lowered, the first oxide layer becomes unable to exert an expected effect (described later). Consequently, the ratio is preferably 90% by mass or more, more preferably 95% by mass or more.

(20) A reduced thickness of the first oxide layer results in a low corrosion resistance and a failure to sufficiently inhibiting the second oxide layer, which is a lower layer, from advancing in oxidation to turn into TiO.sub.2. For this reason, the thickness of the first oxide layer is set at 0.1 nm or more, and is preferably 0.3 nm or more.

(21) An increased thickness of the first oxide layer results in a low conductivity between an electrode to come in contact with the surface of the titanium product, and the second oxide layer. Consequently, the thickness of the first oxide layer is set at 1.5 nm or less, and is preferably 1.3 nm or less.

(22) The surface of the first oxide layer (the surface of the titanium product) may be flat or may be provided with projections, for example, those which are 1.5 m or less in height. Where projections are provided on the surface, even if a layer having no conductivity is formed on the first oxide layer, such projections help the first oxide layer with obtaining electrical contact with an electrode (a conductive member constituting an anode and a cathode).

(23) The first oxide layer is formed in the second heat treatment step. The first oxide layer is a layer that is a crystallized surface of an amorphous coating film layer formed in a first heat treatment step. For this reason, the interface between the first oxide layer and the second oxide layer can be recognized as an X-ray diffraction pattern by TEM observation. Forming the crystallized first oxide layer in such a manner improves a corrosion resistance in a fuel cell environment.

(24) [Second Oxide Layer]

(25) The second oxide layer has a thickness of 3 to 20 nm and consists of a titanium oxide the chemical formula of which is expressed as TiO.sub.x (1<x<2). When the ratio of TiO.sub.x in the second oxide layer is lowered, the conductivity of the second oxide layer becomes low with some component of the balance of TiO.sub.x. Consequently, the ratio is preferably 90% by mass or more, more preferably 95% by mass or more.

(26) A reduced thickness of the second oxide layer results in a high conductivity (a low electric resistance) between the first oxide layer and the base material. Consequently, the thickness of the second oxide layer is set at 20 nm or less. The thickness of the second oxide layer is preferably 17 nm or less, more preferably 15 nm or less. The smaller the thickness of the second oxide layer, the better. However, it is difficult to make the thickness of the second oxide layer less than 3 nm in the presence of the first oxide layer. The thickness of the second oxide layer may be 5 nm or more.

(27) [Noble Metal Layer]

(28) The noble metal layer need not be formed. The noble metal layer contains one, or two or more kinds of gold (Au), silver (Ag), and the platinum group elements (ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt)), as main components. The ratio of these elements to the noble metal layer is preferably 80% by mass or more, more preferably 90% by mass or more.

(29) Assume here that, with respect to the area of the surface of the first oxide layer, a coverage of the noble metal layer is defined as the ratio of the area of a portion that is of the surface of the first oxide layer and covered with the noble metal layer. When the coverage of the noble metal layer is intended to be set at 98% or more, a large quantity of noble metals is to be used, which leads to a rise in cost as well as the risk that, in an environment in a fuel cell, corrosion occurs concentratedly in a portion of the surface of the first oxide layer that is not covered with the noble metal layer. To inhibit the rise in cost and the concentrated corrosion of the first oxide layer, the coverage is set at less than 98% when the noble metal layer is to be formed. The coverage of the noble metal layer may be 50% or less, for example, 2%.

(30) [Conductive Carbon Material Layer]

(31) The conductive carbon material layer need not be formed. The conductive carbon material layer contains a carbon material having conductivity, as a main component. Examples of the conductive carbon material include graphite and amorphous carbon. The conductive carbon material is preferably graphite. This is because a surface that shows a good conductivity with graphite particles is likely to be oriented in a certain direction, and the conductive carbon material layer shows a good conductivity in the direction. In addition, a graphite having a C-plane distance d002 of 3.38 or less has a high purity of carbon, providing a good conductivity. For this reason, a graphite having such a plane distance is suitable as a substance that makes up the conductive carbon material layer.

(32) The ratio of carbon to the conductive carbon material layer is preferably 80% by mass or more, more preferably 90% by mass or more.

(33) Assume here that, with respect to the area of the surface of the first oxide layer, a coverage of the conductive carbon material layer is defined as the ratio of the area of a portion that is of the surface of the first oxide layer and covered with the conductive carbon material layer. When the coverage of the conductive carbon material layer is intended to be set at 98% or more, there is the risk that, in an environment in a fuel cell, corrosion occurs concentratedly in a portion of the surface of the first oxide layer that is not covered with the conductive carbon material layer. To inhibit the concentrated corrosion of the first oxide layer, the coverage of the conductive carbon material layer is set at less than 98%. The coverage of the conductive carbon material layer may be 50% or less, for example, 2%.

(34) On the first oxide layer, both of the noble metal layer and the conductive carbon material layer may be formed. In this case, to the area of the surface of the first oxide layer, the ratio (coverage) of the area of a portion that is of this surface covered with at least one of the noble metal layer and the conductive carbon material layer is set at less than 98%. This coverage may be 50% or less, for example, 2%.

(35) [Effect of Titanium Product according to Present Invention]

(36) Corrosion resistance is obtained by forming the first oxide layer in the surface layer of the base material (pure titanium), the first oxide layer consisted of TiO.sub.2 of a rutile crystallinity, and by causing the first oxide layer to have a thickness of 0.1 nm or more.

(37) A passivation film that is formed on the surface of the base material (pure titanium) as a natural oxide film consists of TiO.sub.2, and a pure titanium with this film formed thereon has a high contact resistance. One of the reasons of this is that the thickness of the passivation film is as large as 5 to 10 nm. In contrast, the thickness of the first oxide layer in the present invention is as small as 1.5 nm or smaller. Therefore, due to the tunnel effect and the like, a high conductivity is obtained between an electrode in contact with the surface of the first oxide layer, and the second oxide layer.

(38) FIG. 3A is a picture illustrating an example of an electron beam diffraction pattern obtained by TEM observation on the surface of the titanium product before the second heat treatment step.

(39) FIG. 3B is a picture illustrating an example of an electron beam diffraction pattern obtained by TEM observation on the surface of the titanium product after the second heat treatment step.

(40) [Thicknesses of First and Second Oxide Layers]

(41) The thicknesses of the first and second oxide layers can be determined based on the relationship between depth from the surface of the titanium product and shifted energy value measured by the EELS (see FIG. 2A), and based on a TEM image. It is assumed that the shifted energy value is measured by the EELS in a portion where neither noble metal layer nor conductive carbon material layer is present. It is noted that the first oxide layer is not formed before the second heat treatment step, as illustrated in FIG. 2B.

(42) In the present invention, the boundary between the first oxide layer and the second oxide layer is set at a depth position at which the shifted energy value is 95% of the shifted energy value of TiO.sub.2 (hereinafter, referred to as a first boundary, illustrated by a broken line B1 in FIG. 2). Meanwhile, the second oxide layer and the base material can be discriminated from each other on a TEM image because their crystalline structures are different from each other. In other words, since the second oxide layer and the base material differ in contrast (shade of gray) on a TEM image, the boundary between the second oxide layer and the base material (hereinafter, referred to as a second boundary) can be determined based on the TEM image. The second boundary is also a depth position at which the shifted energy value comes down, from the surface side, to zero (illustrated by a broken line B2 in FIG. 2).

(43) The thickness of the first oxide layer is defined as the distance between the surface of the titanium product and the first boundary. The thickness of the second oxide layer is defined as the distance between the first boundary and the second boundary.

(44) 2. Method for Producing Titanium Product According to Present Invention

(45) The present inventors have found that removing an oxide film of a substrate consisted of pure titanium using a hydrochloric acid aqueous solution or a fluonitric acid aqueous solution, which is used in usual pickling for titanium, and thereafter treating a titanium oxide film that is formed (recovered) on a surface of this substrate using an aqueous solution containing fluoride ions (passivation treatment) make the titanium oxide film have conductivity. The method for producing a titanium product according to the present invention is completed based on this finding.

(46) The method for producing a titanium product according to the present invention includes a solution treatment step, the first heat treatment step, and the second heat treatment step. In the case of producing a titanium product that includes the noble metal layer, the method for producing a titanium product according to the present invention includes a noble metal layer forming step. In the case of producing a titanium product that includes the conductive carbon material layer, the method for producing a titanium product according to the present invention includes a conductive carbon material forming step. Each step will be described below in detail.

(47) [Solution Treatment Step]

(48) In this step, a substrate consisted of pure titanium is treated by an aqueous solution containing fluoride ions.

(49) As the aqueous solution containing fluoride ions, use can be made of an aqueous solution having a concentration of fluoride ions within a range of, for example, 0.05 to 1.5% by mass (if the aqueous solution contains a plurality of kinds of fluoride ions, the concentration of the kinds of fluoride ions is 0.05 to 1.5% by mass). The temperature of the treatment can be set at, for example, 20 to 40 C. The time period of the treatment can be set at, for example, 2 to 30 minutes. The treatment under such conditions can impart conductivity to a titanium oxide film.

(50) The aqueous solution containing fluoride ions may contain a component other than the fluoride ions. This aqueous solution may be an aqueous solution in which, for example, 0.5% by mass of HF, 0.5% by mass of NaF, 0.5% by mass of NaCl, and 0.5% by mass of HNO.sub.3 are dissolved.

(51) In the case of forming projections on the surface of the titanium product to be produced (the surface of the first oxide layer), such projections can be formed by, in the solution treatment step, extending the time period of the treatment using the aqueous solution containing fluoride ions within an appropriate range, for example.

(52) The substrate to be treated in the solution treatment step may be, for example, subjected to rolling processing. In this case, it is preferable to, prior to the solution treatment step, subject this substrate to pickling for removing an oxide film formed in the rolling, for example, using a HF aqueous solution or a HNO.sub.3 aqueous solution at a high concentration (e.g., 3% by mass or more).

(53) [Noble Metal Layer Forming Step]

(54) In the case of producing a titanium product that includes the noble metal layer, the performance of the first arid second heat treatment steps is followed by the performance of the noble metal layer forming step in which noble metals is supplied on the surface of the substrate to form a noble metal layer. The method for forming the noble metal is not limited in particular, and methods such as plating and vapor deposition can be employed. In any of the methods, it is preferable to shorten the time period of the treatment to reduce a weight per unit area so that the coverage of the noble metal layer is less than 98%. This allows cost reduction. In the case of producing a titanium product that includes no noble metal layer, the noble metal layer forming step is not performed.

(55) [Conductive Carbon Material Layer Forming Step]

(56) In the case of producing a titanium product that includes the conductive carbon material layer, the performance of the first and second heat treatment steps is followed by the performance of the conductive carbon material layer forming step in which carbon is supplied on the surface of the substrate to form a conductive carbon material layer. The method for forming the conductive carbon material layer is not limited in particular, and methods such as adhesion by sliding and application can be employed. In any of the methods, the time period of the treatment can be shortened by setting the coverage of the conductive carbon material layer at less than 98%. In the case of producing a titanium product that includes no conductive carbon material layer, the conductive carbon material layer forming step is not performed.

(57) As the method for forming the conductive carbon material layer, adhesion by sliding is preferably employed. In the adhesion by sliding, when a conductive carbon material is graphite particles, these particles are normally scale-like and oriented in a given direction efficiently. For this reason, a good adhesiveness of these particles to the substrate is obtained, and a resultant titanium product is likely to have a low contact resistance. The formation of the carbon material layer by the adhesion by sliding can be performed by bringing the substrate and the conductive carbon material into contact with each other, and moving at least one of the substrate and the conductive carbon material with the contact therebetween kept.

(58) [First Heat Treatment Step]

(59) In this step, the substrate treated in the solution treatment step is subjected to heat treatment under a low-oxygen-partial-pressure atmosphere having an oxygen partial pressure of 0.1 Pa or less, at 200 to 550 C., for 10 to 300 minutes. This step increases the loss amount of oxygen in the titanium oxide film, further increasing the conductivity of the titanium oxide film. As will be described later, the second oxide layer is formed mainly through the first heat treatment step. For this reason, it is preferable that the oxygen loss amount in the titanium oxide film substantially satisfies TiO.sub.x (1<x<2) after the performance of the first heat treatment step.

(60) The low-oxygen-partial-pressure atmosphere can be, for example, what is called an oxygen-free atmosphere, namely a vacuum (reduced-pressure) atmosphere, or an inert gas atmosphere such as argon atmosphere.

(61) The first oxide layer is formed in the second heat treatment step. The first oxide layer is a layer that is a crystallized surface of an amorphous coating film layer formed in a first heat treatment step. For this reason, the interface between the first oxide layer and the second oxide layer can be recognized as an electron beam diffraction pattern by TEM observation. Forming the crystallized first oxide layer in such a manner improves a corrosion resistance in a fuel cell environment.

(62) The heat treatment time period is set within a range of 10 to 300 minutes, although depending on the heat treatment temperature. An excessively short heat treatment time period fails to increase the oxygen loss amount in the titanium oxide film sufficiently. On the other hand, an excessively long heat treatment time period results in a saturated effect of increasing the conductivity. The higher the heat treatment temperature is, the shorter the heat treatment time period can be. The lower the heat treatment temperature is, the longer the heat treatment time period needs to be. When the heat treatment temperature is 200 C., the heat treatment time period can be, for example, set at 200 to 300 minutes. When the heat treatment temperature is 550 C., the heat treatment time period can be, for example, set at 10 to 30 minutes.

(63) [Second Heat Treatment Step]

(64) In this step, the substrate treated in the first heat treatment step is subjected to heat treatment under a high-oxygen-partial-pressure atmosphere having an oxygen partial pressure of 10000 Pa or more, at 200 to 500 C., for 2 to 30 minutes. The high-oxygen-partial-pressure atmosphere can be, for example, air atmosphere. This step forms the first oxide layer consisting of TiO.sub.2 of a rutile crystallinity, on the surface layer of the titanium oxide film that is present after the performance of the first heat treatment step. The rest of the titanium oxide film serves as the second oxide layer. Since TiO.sub.2 of a rutile crystallinity is formed in this producing method, the first oxide layer is dense, has high mechanical strength, and has high resistance to corrosion in an environment in which fluorine ions are present and in an environment in which voltage is applied.

(65) The known titanium oxides are anatase, rutile, and brookite, and in general, when heated to 650 to 900 C. or more, turn into rutile titanium oxide, which is the most stable. Although the second heat treatment according to the present application is performed at 200 to 500 C., the surface of the titanium oxide turns into the rutile titanium oxide. The reason for this is unclear, but it is speculated that the rutile-crystallinity titanium oxide is generated because the formed rutile titanium oxide has a thickness as small as 1.5 nm.

(66) A heat treatment temperature of less than 200 C. results in a failure to form a sufficiently oxidized film. For this reason, the heat treatment is supposed to be performed at 200 C. or more, preferably 300 C. or more. On the other hand, a heat treatment temperature of more than 500 C. results in an excessively advanced oxidation, as well as a loss of density of the titanium oxide film. Consequently, the heat treatment is supposed to be performed at 500 C. or less, preferably 450 C. or less.

(67) The heat treatment time period is set within a range of 2 to 30 minutes, although depending on the beat treatment temperature. An excessively short heat treatment time period fails to secure a thickness of the first oxide layer of 0.1 nm or more. An excessively long heat treatment time period results in an excessively advanced oxidation, failing to suppress the thickness of the first oxide layer to 1.5 nm or less. The higher the heat treatment temperature is, the shorter the heat treatment time period can be. The lower the heat treatment temperature is, the longer the heat treatment time period needs to be. When the heat treatment temperature is 200 C., the heat treatment time period can b; for example, set at 20 to 30 minutes. When the heat treatment temperature is 500 C., the heat treatment time period can be, for example, set at 2 to 10 minutes.

(68) As seen from the above, by two-stage heating: heating under the low-oxygen-partial-pressure atmosphere and heating under the high-oxygen-partial-pressure atmosphere, it is possible to form the first oxide layer that is thin to the extent that the thinness does not inhibit the conductivity (a thickness of 1.5 nm or less), and that has high corrosion resistance.

(69) The second heat treatment step may be performed on the substrate treated in the first heat treatment step and comes to a temperature of less than 200 C. (e.g., room temperature) and performed, for example, in a different furnace to which the substrate is conveyed. In addition, the second heat treatment step may be performed on the substrate treated in the first heat treatment step and comes to a temperature of 200 C. or more, and performed without temperature drop, for example, in the same furnace at the atmosphere of which is changed to different one.

EXAMPLE

(70) To confirm the effect of the present invention, samples of titanium products were fabricated by the following method and were evaluated.

(71) 1. Fabrication of Titanium Products

(72) Prepared titanium plates (foils) were those which had been rolled to a thickness of 0.1 mm and thereafter annealed. Each of the titanium plates was subjected to press working so as to include groove-shaped gas channels having a width of 2 mm and a depth of 1 mm formed on both surfaces (an anode side and a cathode side) thereof, and thereby became ready to be used as a separator.

(73) After the press working, every titanium product was subjected to the surface treatment using acid, the heat treatment under the low-oxygen-partial-pressure atmosphere, and the heat treatment under the high-oxygen-partial-pressure atmosphere. Table 1 shows materials used (types of titanium products as base materials (types specified in JIS H 4600)) and heat treatment conditions.

(74) TABLE-US-00001 TABLE 1 First Second Noble metal Coverage of Types oxide oxide kind/coverage conductive Heat treatment under Heat treatment under specified layer layer of noble carbon low-oxygen-partial-pressure high-oxygen-partial-pressure Initial in JIS thickness thickness metal layer material atmosphere atmosphere resistance Post-power-generation Number H 4600 (nm) (nm) (%) layer (%) Temperature ( C.) Time (min) Temperature ( C.) Time (min) (m .Math. cm.sup.2) resistance property *.sup.1 Inventive example 1 1 0.12 18 500 60 200 20 3.8 Inventive example 2 2 1.2 8 400 60 350 10 3.8 Inventive example 3 1 0.8 9 500 30 300 10 3.3 Inventive example 4 1 1 6 300 60 300 15 3.6 Inventive example 5 2 0.5 11 200 300 500 2 3.5 Inventive example 6 17 0.8 8 500 30 250 20 3.6 Inventive example 7 1 0.2 6 450 20 300 5 3.5 Inventive example 8 1 1.2 15 350 180 250 30 4 Inventive example 9 2 1.1 12 250 240 300 20 4.1 Inventive example 10 16 1.2 10 500 30 300 25 4.3 Inventive example 11 17 1.2 16 300 180 250 30 4 Inventive example 12 1 1.4 12 400 150 400 20 4.3 Inventive example 13 2 0.9 8 550 15 300 20 4 Inventive example 14 1 1.3 4 200 30 300 25 4.5 Inventive example 15 1 0.9 9 300 90 300 20 3.7 Inventive example 16 1 0.4 14 250 240 300 10 3.4 Inventive example 17 1 1.2 12 Au/2 400 15 300 10 3.1 Inventive example 18 1 1.4 15 Ru/20 300 30 250 15 3.2 Inventive example 19 1 1 15 Rh/5 500 20 400 5 3.3 Inventive example 20 1 1.3 13 3 400 20 300 10 3.3 Inventive example 21 1 1.4 16 40 300 40 250 15 3.4 Inventive example 22 2 1.1 14 10 500 30 400 5 3.8 Comparative example 1 1 <0.1 8 500 30 300 1 3.5 X Comparative example 2 1 <0.1 9 400 120 200 1 3.6 X Comparative example 3 1 <0.1 15 300 180 180 10 3.8 X Comparative example 4 2 5 8 400 60 400 40 30 Comparative example 5 1 10 9 500 30 600 10 85 Comparative example 6 1 10 <0.1 400 240 600 1 20 Comparative example 7 1 100 <0.1 400 240 600 60 500 Comparative example 8 1 15 <0.1 400 5 400 60 30 Comparative example 9 1 100 <0.1 200 300 550 90 600 Comparative example 10 1 7 <0.1 150 360 400 50 50 Comparative example 11 1 1 2 600 10 300 20 4 X Comparative example 12 1 0.9 <0.1 300 5 300 20 3.9 X Comparative example 13 1 1.3 1 300 10 6 X *.sup.1 The resistance properties were measured for separators having initial resistances of 12 m cm.sup.2 or less after power generation. : 8 m .Math. cm.sup.2, : 8-12 m .Math. cm.sup.2, X: >12 m .Math. cm.sup.2

(75) Every titanium product was subjected to treatment using fluonitric acid as the surface treatment using acid, and thereafter treated using an aqueous solution at 30 C. in which 0.5% by mass of HF, 0.5% by mass of NaF, 0.5% by mass of NaCl, and 0.5% by mass of HNO.sub.3 are dissolved, for 10 minutes. In other words, every sample was subjected to the treatment that satisfies the requirements on the solution treatment step in the method for producing a titanium product according to the present invention. Through this treatment, an oxide film having conductivity was formed on the surface of each titanium product.

(76) Afterward, these titanium products were subjected to the heat treatment under the low-oxygen-partial-pressure atmosphere, and the heat treatment under the high-oxygen-partial-pressure atmosphere, under the conditions shown in Table 1. For the samples in inventive examples, both the heat treatment under the low-oxygen-partial-pressure atmosphere and the heat treatment under the high-oxygen-partial-pressure atmosphere satisfied the requirements on the first and second heat treatment steps in the method for producing a titanium product according to the present invention, whereas those for the samples in comparative examples did not satisfy any of these requirements.

(77) For the sample in each inventive example, the film of formed through the first heat treatment step and the film formed through the second heat treatment step were checked. FIG. 3A and FIG. 3B illustrate an example of electron beam diffraction patterns obtained by TEM observation. The film formed through the first heat treatment step displays a ring-shaped pattern because the film is in an amorphous form, and the surface of the film was then crystallized through the second heat treatment step, displaying a spot-shaped pattern. This can explain that a layer formed through the second heat treatment step (the first oxide layer) consists of the crystal of TiO.sub.2.

(78) Some other samples (Inventive examples 17 to 19) were subjected to the noble metal layer forming step after subjected to the heat treatment under the high-oxygen-partial-pressure atmosphere. Specifically, a noble metal was supplied to the surface of each titanium product by plating to form a noble metal layer. In addition, still other some samples (Inventive examples 20 to 22) were subjected to the conductive carbon material layer forming step after subjected to the heat treatment under the high-oxygen-partial-pressure atmosphere. Specifically, graphite particles were supplied to the surface of each titanium product by the adhesion by sliding to form a graphite layer as the conductive carbon material layer. The adhesion by sliding was performed by rubbing block graphite from Mechanical Carbon Industry Co., Ltd. against the surface of each titanium product.

(79) 2. Evaluation of Titanium Products

(80) 2-1. Measurement of Thicknesses of First and Second Oxide Layers

(81) By the aforementioned method, the boundary between the first oxide layer and the second oxide layer was identified from the relationship between depth from the surface of a titanium product and shifted energy value by the EELS, and the thickness of the first oxide layer was determined. For titanium products each including a noble metal layer or a conductive carbon material layer formed thereon, their shifted energy value were measured by the EELS in a portion where these layers are absent.

(82) In addition, by the aforementioned method, the boundary between the second oxide layer and the base material was identified from a TEM image, and from this boundary and the boundary between the first oxide layer and the second oxide layer determined by the method described above, the thickness of the second oxide layer was determined.

(83) Table 1 also shows the thickness of the first oxide layer and the thickness of the second oxide layers for each sample. All the samples in inventive examples satisfied the requirements on the thicknesses of the first and second oxide layers in the titanium product according to the present invention, whereas no sample in comparative examples satisfied all of these requirements.

(84) 2-2. Measurement of Contact Resistance

(85) According to the method described in Non-Patent Document 1, the measurement of contact resistance was conducted on each sample using the apparatus schematically illustrated in FIG. 4. Specifically, a fabricated titanium product (hereinafter, referred to as a titanium separator) 11 was first sandwiched between a pair of sheets of carbon paper (TGP-H-90 from Toray Industries, Inc.) 12 used in gas diffusion layers (the anode 3 and the cathode 4 in FIG. 1), which is sandwiched between a pair of gold-plated electrodes 13. Each sheet of carbon paper had an area of 1 cm.sup.2.

(86) Next, a load was applied across the pair of gold-plated electrodes 13 to generate a pressure of 10 kgf/cm.sup.2 (9.8110.sup.5 Pa). In this state, a constant current is caused to flow between the electrodes, and a voltage drop occurring then between the sheets of carbon paper 12 and the titanium separator 11 was measured, and based on the result of the measurement, a resistance value was determined. The resultant resistance value is a value being the sum of the contact resistances of both surfaces of the titanium separator 11, and thus the value was divided by two, which was regarded as a contact resistance value (initial contact resistance) per single surface of the titanium separator.

(87) Next, using the titanium separator after being measured its initial contact resistance, a proton exchange membrane fuel cell was fabricated in a single cell form. The reason for employing the single cell form is that, in a multi-cell form in which single cells are stacked, the result of evaluation reflects the state of stacking. As a proton exchange membrane, FC50-MEA (membrane electrode assembly (MEA)), a standard MEA for PFECs (Nafion(R)-1135 based) from Toyo Corporation, was used.

(88) To this fuel cell, a hydrogen gas having a purity of 99.9999% was caused to flow as an anode-side fuel gas, and air was caused to flow as a cathode-side gas. The introduction gas pressures of the hydrogen gas and the air to the fuel cell were set at 0.04 to 0.20 bar (4000 to 20000 Pa). The entire body of the fuel cell was maintained at a temperature of 702 C., and the humidity inside the fuel cell was controlled by setting a dew point at a gas introduction portion at 70 C. The pressure inside the cell was about one atmosphere.

(89) This fuel cell was operated at a constant current density of 0.5 A/cm.sup.2. The output voltage of the fuel cell reached its highest after a lapse of 20 to 50 hours from the start of the operation. After the output voltage had reached the highest voltage, the operation was continued for 500 hours. Afterward, a contact resistance was measured by the aforementioned method, which was regarded as a post-power-generation resistance property. Then, from the initial resistance and the post-power-generation resistance property, the corrosion resistance of the titanium separator was evaluated.

(90) For the measurement of the contact resistance, and the measurement of the current and the voltage in the operation of the fuel cell, use was made of a digital multimeter (KEITHLEY2001 from Toyo Corporation).

(91) Table 1 also shows the value of an initial resistance and a post-power-generation resistance property for each sample.

(92) In Inventive examples 1 to 22, the initial resistances of the samples were all as low as 12 m cm.sup.2 or less. However, in the comparative examples, the initial resistances of some samples (Comparative examples 4 to 10) were as high as more than 12 m cm.sup.2. In the samples in Comparative examples 4 to 10, the thicknesses of the first oxide layers were more than 1.5 nm, and in some of these samples (Comparative examples 6 to 10), the thicknesses of the second oxide layers were less than 3 nm. This is considered to be a cause of high initial resistances of the samples in Comparative examples 4 to 10.

(93) In Inventive examples 1 to 22, the post-power-generation resistance properties of the samples were all good, that is, equal to or less than 12 m cm.sup.2 at most, the samples in the comparative examples the post-power-generation resistance properties of which were measured (Comparative examples 1 to 3 and 11 to 13) were all more than 12 m cm.sup.2. Therefore, the samples in Inventive examples 1 to 22 had higher corrosion resistance than the samples in Comparative examples 1 to 3 and 11 to 13.

(94) The fabrication conditions of the samples in Comparative examples 1 to 3 and II to 13 each included any one of the following conditions (a) to (d). (a) The time period of the heat treatment under the low-oxygen-partial-pressure atmosphere was less than 10 minutes. (b) The heat treatment under the low-oxygen-partial-pressure atmosphere was not performed. (c) The treatment temperature in the heat treatment under the high-oxygen-concentration atmosphere was less than 200 C. (d) The treatment time period in the heat treatment under the high-oxygen-concentration atmosphere was less than two minutes.

(95) It is considered that, due to such conditions, the thicknesses of the first oxide layers became less than 0.1 nm, or even when they are 0.1 nm or more, the densities of the first oxide layers were poor. In addition, it is considered that such first oxide layers results in low corrosion resistances of the samples in Comparative examples 1 to 3 and 11 to 13.

REFERENCE SIGNS LIST

(96) 1: proton exchange membrane fuel cell 2: proton exchange membrane 3: anode 4: cathode 5a, 5b: separator