JP6485967B2 - Titanium-based porous body and method for producing the same - Google Patents
Titanium-based porous body and method for producing the same Download PDFInfo
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- JP6485967B2 JP6485967B2 JP2016216121A JP2016216121A JP6485967B2 JP 6485967 B2 JP6485967 B2 JP 6485967B2 JP 2016216121 A JP2016216121 A JP 2016216121A JP 2016216121 A JP2016216121 A JP 2016216121A JP 6485967 B2 JP6485967 B2 JP 6485967B2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 173
- 239000010936 titanium Substances 0.000 title claims description 147
- 229910052719 titanium Inorganic materials 0.000 title claims description 147
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000002245 particle Substances 0.000 claims description 40
- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 description 64
- 230000003746 surface roughness Effects 0.000 description 27
- 238000000034 method Methods 0.000 description 17
- 238000005452 bending Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 238000005245 sintering Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229910001069 Ti alloy Inorganic materials 0.000 description 10
- 230000035699 permeability Effects 0.000 description 10
- 238000009826 distribution Methods 0.000 description 8
- 230000001788 irregular Effects 0.000 description 8
- 238000011049 filling Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 229910021341 titanium silicide Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 208000024705 pituitary adenoma 3 Diseases 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Powder Metallurgy (AREA)
Description
本発明は、二次電池や燃料電池の電極または、フィルター等に利用されるチタン系粉末を原料としたチタン系多孔体とその製造方法に関する。 The present invention relates to a titanium-based porous body made of a titanium-based powder used as an electrode or a filter for a secondary battery or a fuel cell, and a method for producing the same.
最近では、チタン系多孔体は二次電池用の電極や燃料電池の電極としての利用が検討されている。電池の電極として要求されている性能として、高い空隙率や導電率を備えたチタン系多孔体の製造方法が望まれている。
従来、チタン繊維を焼結し、高い空隙率を有するチタン系多孔体を製造する方法が知られている（例えば、特許文献１参照）。しかしながら、繊維を焼結したチタン系多孔体は７０〜９０％の高い空隙率を有するものの、比表面積が小さく、また、繊維同士の焼結面積が小さいため、チタン系多孔体の導電率が低いという問題点がある。例えば、比表面積が小さいことは、チタン系多孔体上に触媒を担持し、チタン系多孔体表面近傍でガスや液を反応させる担体として用いた時、チタン系多孔体と反応溶液や反応ガスとの反応場が少なくなるため、反応効率が低下するという問題へ繋がる。
また、チタン粉末にペースト状のバインダーを混練し、焼結することで、貫通孔を有し、液状物質を一面側から他面側にむけて流通することが可能なチタン系多孔体を得る方法も知られている（例えば、特許文献２参照）。しかしながら、バインダーを混練し、焼結する方法は、製造工程が複雑な上に、焼結体のカーボン含有量が高くなるおそれがある。また、空隙率が１０〜５０％と低く、通気性、通水性が悪いという問題点がある。
更に、ペーストを用いずに、ガスアトマイズチタン粉末を焼結することで、製造されるチタン系多孔体が知られている（例えば、特許文献３参照）。しかしながら、嵩密度が高いチタン粉を使用するため５５％以上の空隙率のチタン系多孔体を製造することができず、通気性、通水性が悪いという問題点がある。
Recently, the use of titanium-based porous bodies as electrodes for secondary batteries and electrodes for fuel cells has been studied. As a performance required as an electrode of a battery, a method for producing a titanium-based porous body having high porosity and electrical conductivity is desired.
Conventionally, a method for producing a titanium-based porous body by sintering titanium fibers and having a high porosity is known (for example, see Patent Document 1). However, although the titanium-based porous body obtained by sintering the fiber has a high porosity of 70 to 90%, the specific surface area is small and the sintered area between the fibers is small, so the conductivity of the titanium-based porous body is low. There is a problem. For example, a small specific surface area means that when a catalyst is supported on a titanium-based porous body and used as a carrier for reacting a gas or liquid near the surface of the titanium-based porous body, the titanium-based porous body and the reaction solution or reaction gas This leads to a problem that the reaction efficiency is lowered because the reaction field is reduced.
Also, a method for obtaining a titanium-based porous body having a through-hole and capable of flowing a liquid substance from one side to the other side by kneading and sintering a paste-like binder in titanium powder Is also known (see, for example, Patent Document 2). However, the method of kneading and sintering the binder involves a complicated manufacturing process and may increase the carbon content of the sintered body. Further, there are problems that the porosity is as low as 10 to 50%, and the air permeability and water permeability are poor.
Furthermore, a titanium-based porous body manufactured by sintering gas atomized titanium powder without using a paste is known (see, for example, Patent Document 3). However, since titanium powder having a high bulk density is used, a titanium-based porous body having a porosity of 55% or more cannot be produced, and there is a problem that air permeability and water permeability are poor.
本発明は、上記のような事情に鑑みなされたものであって、本発明が解決する課題は、優れた反応効率を示すために高い比表面積を有し、かつ、通気性、通水性を確保するための高い空隙率を有したチタン系多孔体を提供することにある。 The present invention has been made in view of the above circumstances, and the problem to be solved by the present invention is to have a high specific surface area in order to exhibit excellent reaction efficiency, and to ensure air permeability and water permeability. An object of the present invention is to provide a titanium-based porous body having a high porosity for the purpose.
本発明者らは、前記課題を解決するために鋭意検討を進めた結果、以下の発明を完成するに至った。
［１］比表面積が４．５×１０−２〜１．５×１０−１ｍ２／ｇ、空隙率が５０〜７０％、厚さが４．０×１０−１〜１．６ｍｍ、少なくとも片面の 表面粗さが８．０μｍ以下であることを特徴とするシート状チタン系多孔体。
［２］平均粒径１０〜５０μｍ、Ｄ９０が７５μｍ未満、平均円形度０．５０〜０．９０の異形チタン系粉を、乾式かつ、無加圧でセッター上に載置後、８００〜１１００℃で焼結させることを特徴とするシート状チタン系多孔体の製造方法。
［３］セッターの材質が、石英であることを特徴とする［２］に記載のシート状チタン系多孔体の製造方法。
［４］［１］に記載のシート状チタン系多孔体を用いた電極。
As a result of diligent investigations to solve the above problems, the present inventors have completed the following invention.
[1] Specific surface area is 4.5 × 10 −2 to 1.5 × 10 −1 m 2 / g, porosity is 50 to 70%, thickness is 4.0 × 10 −1 to 1.6 mm, at least A sheet-like titanium-based porous body having a surface roughness of one side of 8.0 μm or less.
[2] After placing a deformed titanium-based powder having an average particle diameter of 10 to 50 μm, D90 of less than 75 μm, and an average circularity of 0.50 to 0.90 on a setter in a dry and non-pressurized state, 800 to 1100 ° C. A method for producing a sheet-like titanium-based porous body, characterized in that sintering is carried out.
[3] The method for producing a sheet-like titanium porous body according to [2], wherein the setter is made of quartz.
[4] An electrode using the sheet-like titanium-based porous material according to [1].
本発明は、チタン系多孔体の比表面積および空隙率を制御することにより、実用上必要な曲げ強度を維持しつつ、導電性及び通気性並びに通水性を良好に保つことができるチタン系多孔体を提供することができる。 The present invention controls a specific surface area and porosity of a titanium-based porous body, thereby maintaining good electrical conductivity, air permeability, and water permeability while maintaining practically required bending strength. Can be provided.
以下では、本発明を実施するための具体的形態を詳細に説明する。
≪比表面積・空隙率・表面粗さについて≫
本発明のチタン系多孔体は、４．５×１０−２〜１．５×１０−１ｍ２／ｇの比表面積、５０〜７０％の空隙率、片面が８．０μｍ以下の表面粗さを有する。
まず、チタン系多孔体の比表面積は、５．０×１０−２〜１．３×１０−１ｍ２／ｇ及び５５〜６８％の空隙率であることが好ましく、さらに好ましくは、７．０×１０−２〜１．１×１０−１ｍ２／ｇ及び６０〜６６％の空隙率である。この範囲に設定することで、実用上必要な曲げ強度を維持しつつ、導電性及び通気性並びに通水性を良好に保つことができる。本発明の比表面積は、ＪＩＳ Ｚ ８８３１：２０１３に準拠したＢＥＴ法で測定したものである。測定ガスにはクリプトンを使用した。
次に、少なくとも片面の 表面粗さは８．０μｍ以下であり、表面粗さの下限の限定はないが、好ましくは、０．１μｍ以上である。本発明の表面粗さは、ＪＩＳ Ｂ ０６０１−２００１に準拠して測定した値であり、算術平均粗さＲａのことである。
また、本発明の空隙率は、チタン系多孔体の単位体積あたりの空隙の割合を百分率で示したものであり、チタン系多孔体の体積Ｖ（ｃｍ３）と、チタン系多孔体の質量Ｍ（ｇ）と、チタン系材料の真密度Ｄ（ｇ／ｃｍ３）（例えば純チタンの場合は真密度４．５１ｇ／ｃｍ３）から算出した値のことであり、以下の式で算出することができる。
空隙率（％）＝（（Ｍ／Ｖ）／Ｄ）×１００ ・・・（Ａ）
Below, the concrete form for implementing this invention is demonstrated in detail.
≪About specific surface area, porosity, surface roughness≫
The titanium-based porous body of the present invention has a specific surface area of 4.5 × 10 −2 to 1.5 × 10 −1 m 2 / g, a porosity of 50 to 70%, and a surface roughness of one side of 8.0 μm or less. Have
First, the specific surface area of the titanium-based porous body is preferably 5.0 × 10 −2 to 1.3 × 10 −1 m 2 / g and a porosity of 55 to 68%, more preferably 7. 0 × 10 −2 to 1.1 × 10 −1 m 2 / g and a porosity of 60 to 66%. By setting to this range, it is possible to maintain good conductivity, air permeability, and water permeability while maintaining practically required bending strength. The specific surface area of the present invention is measured by the BET method based on JIS Z 8831: 2013. Krypton was used as the measurement gas.
Next, the surface roughness of at least one surface is 8.0 μm or less, and there is no limitation on the lower limit of the surface roughness, but it is preferably 0.1 μm or more. The surface roughness of the present invention is a value measured according to JIS B 0601-2001, and is an arithmetic average roughness Ra.
The porosity of the present invention is the percentage of voids per unit volume of the titanium-based porous body, expressed as a percentage. The volume V (cm 3 ) of the titanium-based porous body and the mass M of the titanium-based porous body. and (g), (in the case of for example pure titanium true density 4.51 g / cm 3) true density D (g / cm 3) of the titanium-based material is that the calculated value from that calculated by the following formula Can do.
Porosity (%) = ((M / V) / D) × 100 (A)
≪炭素濃度について≫
本発明のチタン系多孔体の炭素濃度は、０．０５重量％以下、より好ましくは０．０３重量％以下である。本発明のチタン系多孔体は、多孔体中の炭素濃度が低いので、不純物による汚染の影響で強度が低下したり電気抵抗が大きくなる恐れがない、という利点を有する 。
≪About carbon concentration≫
The carbon concentration of the titanium-based porous material of the present invention is 0.05% by weight or less, more preferably 0.03% by weight or less. The titanium-based porous body of the present invention has an advantage that the strength is not lowered and the electric resistance is not increased due to the influence of contamination by impurities because the carbon concentration in the porous body is low.
≪厚さについて≫
本発明のチタン系多孔体は、４．０×１０−１〜１．６ｍｍの厚さを有する。より好ましくは、４．０×１０−１〜１．０ｍｍであり、さらに好ましくは４．０×１０−１〜６．０×１０−１ｍｍである。この範囲にすることで実用上必要な曲げ強度を維持しつつ、最終製品を小型化することができる。チタン系多孔体の厚さが、４．０×１０−１ｍｍ未満だとチタン系多孔体の空隙の均一性が低くなり、チタン系多孔体の曲げ強度が低くなる。チタン系多孔体の厚さが１．６ｍｍよりも厚くなると、小型化が進んでいる二次電池に使用することが難しくなる。
≪About thickness≫
The titanium-based porous body of the present invention has a thickness of 4.0 × 10 −1 to 1.6 mm. More preferably from 4.0 × 10 -1 1.0 mm, more preferably from 4.0 × 10 -1 ~6.0 × 10 -1 mm. By making it in this range, the final product can be miniaturized while maintaining the bending strength necessary for practical use. When the thickness of the titanium-based porous body is less than 4.0 × 10 −1 mm, the uniformity of the voids in the titanium-based porous body is lowered, and the bending strength of the titanium-based porous body is lowered. When the thickness of the titanium-based porous body is thicker than 1.6 mm, it becomes difficult to use it for a secondary battery whose size has been reduced.
≪材料について≫
なお、本発明のチタン系多孔体は、純チタン、チタン合金、窒化チタンやチタンシリサイドでコーティングされた純チタンまたはチタン合金、あるいはこれらを組み合わせた複合材料等から構成される。純チタンは、金属チタンとその他不可避不純物からなるチタンである。チタン合金は、チタンとＦｅ，Ｓｎ，Ｃｒ，Ａｌ，Ｖ，Ｍｎ，Ｚｒ，Ｍｏ等の金属との合金であり、具体例としては、Ｔｉ−６−４（Ｔｉ−６Ａｌ−４Ｖ）、Ｔｉ−５Ａｌ−２．５Ｓｎ、Ｔｉ−８−１−１（Ｔｉ−８Ａｌ−１Ｍｏ−１Ｖ）、Ｔｉ−６−２−４−２（Ｔｉ−６Ａｌ−２Ｓｎ−４Ｚｒ−２Ｍｏ−０．１Ｓｉ）、Ｔｉ−６−６−２（Ｔｉ−６Ａｌ−６Ｖ−２Ｓｎ−０．７Ｆｅ−０．７Ｃｕ）、Ｔｉ−６−２−４−６（Ｔｉ−６Ａｌ−２Ｓｎ−４Ｚｒ−６Ｍｏ）、ＳＰ７００（Ｔｉ−４．５Ａｌ−３Ｖ−２Ｆｅ−２Ｍｏ）、Ｔｉ−１７（Ｔｉ−５Ａｌ−２Ｓｎ−２Ｚｒ−４Ｍｏ−４Ｃｒ）、β−ＣＥＺ（Ｔｉ−５Ａｌ−２Ｓｎ−４Ｚｒ−４Ｍｏ−２Ｃｒ−１Ｆｅ）、ＴＩＭＥＴＡＬ５５５、Ｔｉ−５５５３（Ｔｉ−５Ａｌ−５Ｍｏ−５Ｖ−３Ｃｒ−０．５Ｆｅ）、ＴＩＭＥＴＡＬ２１Ｓ（Ｔｉ−１５Ｍｏ−２．７Ｎｂ−３Ａｌ−０．２Ｓｉ）、ＴＩＭＥＴＡＬ ＬＣＢ（Ｔｉ−４．５Ｆｅ−６．８Ｍｏ−１．５Ａｌ）、１０−２−３（Ｔｉ−１０Ｖ−２Ｆｅ−３Ａｌ）、Ｂｅｔａ Ｃ（Ｔｉ−３Ａｌ−８Ｖ−６Ｃｒ−４Ｍｏ−４Ｃｒ）、Ｔｉ−８８２３（Ｔｉ−８Ｍｏ−８Ｖ−２Ｆｅ−３Ａｌ）、１５−３（Ｔｉ−１５Ｖ−３Ｃｒ−３Ａｌ−３Ｓｎ）、ＢｅｔａIII（Ｔｉ−１１．５Ｍｏ−６Ｚｒ−４．５Ｓｎ）、Ｔｉ−１３Ｖ−１１Ｃｒ−３Ａｌ等が挙げられる。
特に、純チタン、窒化チタンやチタンシリサイドでコーティングされた純チタン、あるいはこれらを組み合わせた複合材料から構成されたチタン系多孔体が、電極に用いた際の電気抵抗を下げることができるため好ましく、より好ましくは純チタンで構成されるチタン系多孔体である。
≪About material≫
The titanium-based porous body of the present invention is composed of pure titanium, a titanium alloy, pure titanium or a titanium alloy coated with titanium nitride or titanium silicide, or a composite material combining these. Pure titanium is titanium composed of metallic titanium and other inevitable impurities. The titanium alloy is an alloy of titanium and a metal such as Fe, Sn, Cr, Al, V, Mn, Zr, and Mo. Specific examples include Ti-6-4 (Ti-6Al-4V), Ti— 5Al-2.5Sn, Ti-8-1-1 (Ti-8Al-1Mo-1V), Ti-6-2-4-2 (Ti-6Al-2Sn-4Zr-2Mo-0.1Si), Ti- 6-6-2 (Ti-6Al-6V-2Sn-0.7Fe-0.7Cu), Ti-6-2-4-6 (Ti-6Al-2Sn-4Zr-6Mo), SP700 (Ti-4. 5Al-3V-2Fe-2Mo), Ti-17 (Ti-5Al-2Sn-2Zr-4Mo-4Cr), β-CEZ (Ti-5Al-2Sn-4Zr-4Mo-2Cr-1Fe), TIMETAL 555, Ti-5553 (Ti-5Al-5Mo- V-3Cr-0.5Fe), TIMETAL21S (Ti-15Mo-2.7Nb-3Al-0.2Si), TIMETAL LCB (Ti-4.5Fe-6.8Mo-1.5Al), 10-2-3 ( Ti-10V-2Fe-3Al), Beta C (Ti-3Al-8V-6Cr-4Mo-4Cr), Ti-8823 (Ti-8Mo-8V-2Fe-3Al), 15-3 (Ti-15V-3Cr-) 3Al-3Sn), BetaIII (Ti-11.5Mo-6Zr-4.5Sn), Ti-13V-11Cr-3Al, and the like.
In particular, a titanium-based porous body composed of pure titanium, pure titanium coated with titanium nitride or titanium silicide, or a composite material in combination of these, is preferable because it can reduce the electrical resistance when used for an electrode, A titanium-based porous body composed of pure titanium is more preferable.
≪チタン系多孔体の製造方法≫
≪チタン粉の性質について≫
本発明のチタン系多孔体を製造する際に使用するチタン系粉は、(1)平均粒径（Ｄ５０体積基準）１０〜５０μｍ、(2)Ｄ９０が７５μｍ未満、(3)平均円形度が０．５０〜０．９０の異形チタン系粉である。以下、それぞれの特性について説明する。
（１）平均粒径（Ｄ５０）について
平均粒径が５０μｍより大きいと、焼結体の比表面積が４．５×１０−２ｍ２／ｇ未満となる。一方、１０μｍ未満の場合には、チタン系粉のハンドリングが困難である。なお、ここでいう平均粒径は、レーザー回折散乱法によって得られた粒度分布（体積基準）の粒子径Ｄ５０（メジアン径）の値を指す。
（２）Ｄ９０について
粒度分布（体積基準）の粒子径Ｄ９０が７５μｍ未満の異形チタン系粉が好ましい。
Ｄ９０を７５μｍ未満にすることで、強度が高い焼結体を製造することができる。
また、チタン系多孔体の表面粗さは、粒子径Ｄ９０に依存し、Ｄ９０が小さくなるほど表面粗さの値も小さくなり、チタン系多孔体の強度が良好となる。Ｄ９０とはレーザー回析散乱法による粒度分布測定における体積分布の積算値が９０％に相当する粒子径を指す。
（３）平均円形度が０．５０〜０．９０の異形チタン系粉について
異形チタン系粉とは、真球あるいは真球形の形状を有しない一次粒子を含み、一次粒子の平均円形度が、０．５０〜０．９０のチタン系粉を意味する。異形チタン系粉の例としては、ＨＤＨ法で製造されたチタン系粉及び粉砕法で製造されたチタン系粉、並びにこれらを混合してなるチタン系粉が挙げられる。これらの製法で得られるチタン系粉の形状は、不定形であり非球形である。一次粒子の平均円形度が、０．９０より大きいチタン系粉を用いた場合、シート状チタン系多孔体の比表面積は４．５×１０−２ｍ２／ｇ未満、空隙率は５０％未満となる。
ここで、円形度は、電子顕微鏡や原子顕微鏡から粒子の投影面積の周囲長（Ａ）を測定し、前記投影面積と等しい面積の円の周囲長を（Ｂ）とした場合のＢ／Ａとして定義される。また、平均円形度は、例えば、セル内にキャリア液とともに粒子を流し、ＣＣＤカメラで多量の粒子の画像を撮り込み、１０００〜１５００個の個々の粒子画像から、各粒子の投影面積の周囲長（Ａ）と投影面積と等しい面積の円の周囲長（Ｂ）を測定して円形度を算出し、各粒子の円形度の平均値として求めることができる。上記円形度の数値は粒子の形状が真球に近くなるほど大きくなり、完全な真球の形状を有する粒子の円形度は１となる。逆に、粒子の形状が真球から離れるにつれて円形度の数値は小さくなる。
≪Titanium-based porous body production method≫
≪About the properties of titanium powder≫
The titanium-based powder used for producing the titanium-based porous body of the present invention has (1) an average particle diameter (D50 volume basis) of 10 to 50 μm, (2) D90 of less than 75 μm, and (3) an average circularity of 0. .50-0.90 deformed titanium-based powder. Hereinafter, each characteristic will be described.
(1) About average particle diameter (D50) When an average particle diameter is larger than 50 micrometers, the specific surface area of a sintered compact will be less than 4.5 * 10 <-2 > m < 2 > / g. On the other hand, when it is less than 10 μm, it is difficult to handle the titanium-based powder. In addition, the average particle diameter here refers to the value of the particle diameter D50 (median diameter) of the particle size distribution (volume basis) obtained by the laser diffraction scattering method.
(2) About D90 Deformed titanium powder having a particle size distribution (volume basis) particle size D90 of less than 75 μm is preferred.
By setting D90 to less than 75 μm, a sintered body having high strength can be manufactured.
In addition, the surface roughness of the titanium-based porous body depends on the particle diameter D90, and the smaller the D90, the smaller the surface roughness value and the better the strength of the titanium-based porous body. D90 refers to the particle diameter corresponding to 90% of the integrated volume distribution in the particle size distribution measurement by the laser diffraction scattering method.
(3) About deformed titanium-based powder having an average circularity of 0.50 to 0.90 The deformed titanium-based powder includes primary particles that do not have a true spherical shape or a true spherical shape, and the average circularity of the primary particles is It means 0.50 to 0.90 titanium-based powder. Examples of the deformed titanium-based powder include titanium-based powder manufactured by the HDH method, titanium-based powder manufactured by the pulverization method, and titanium-based powder obtained by mixing these. The shape of the titanium-based powder obtained by these production methods is irregular and non-spherical. When a titanium-based powder having an average primary circularity of greater than 0.90 is used, the specific surface area of the sheet-like titanium-based porous body is less than 4.5 × 10 −2 m 2 / g, and the porosity is less than 50%. It becomes.
Here, the circularity is B / A when the circumference (A) of the projected area of the particle is measured from an electron microscope or an atomic microscope and the circumference of a circle having the same area as the projected area is (B). Defined. The average circularity can be calculated by, for example, flowing particles together with a carrier liquid in a cell, taking a large number of particle images with a CCD camera, and calculating the perimeter of the projected area of each particle from 1000 to 1500 individual particle images. The circularity can be calculated by measuring the circumference (B) of a circle having the same area as (A) and the projected area, and can be obtained as an average value of the circularity of each particle. The numerical value of the circularity increases as the particle shape approaches a true sphere, and the circularity of a particle having a complete true sphere shape becomes 1. Conversely, the numerical value of circularity decreases as the particle shape moves away from the true sphere.
本発明のチタン系粉とは、純チタン粉、チタン合金粉、水素化した純チタン粉またはチタン合金粉、または窒化チタンやチタンシリサイドでコーティングした純チタン粉あるいはチタン合金粉である。なお、純チタン粉は、金属チタンとその他不可避不純物からなるチタン粉である。チタン合金粉のチタン合金の一例としては、上述した例示と同様である。特に、純チタン粉、水素化した純チタン粉、窒化チタンやチタンシリサイドでコーティングされた純チタン粉、あるいはこれらを組み合わせた複合材料が好ましく、純チタン粉が特に好ましい。 The titanium-based powder of the present invention is pure titanium powder, titanium alloy powder, hydrogenated pure titanium powder or titanium alloy powder, or pure titanium powder or titanium alloy powder coated with titanium nitride or titanium silicide. The pure titanium powder is a titanium powder composed of metallic titanium and other inevitable impurities. An example of the titanium alloy powder titanium alloy is the same as that described above. In particular, pure titanium powder, hydrogenated pure titanium powder, pure titanium powder coated with titanium nitride or titanium silicide, or a composite material combining these is preferable, and pure titanium powder is particularly preferable.
本発明のチタン系多孔体の製造方法では、平均粒径１０〜５０μｍ、Ｄ９０が７５μｍ未満、平均円形度が０．５０〜０．９０の異形チタン系粉を乾式かつ、無加圧でセッター上に載置する。粉末を自重のみより密に充填するため、空隙率が７０％より大きいチタン系多孔体を製造することは困難になる。
セッターは、石英やＢＮなどチタン系多孔体と反応しにくい材質であれば良い。形状は、平面の板状のもの、ザグリ部を設けた平面の板状のものを使用することができ、特にザグリ部を設けた平面の板状のものが好ましい。ここでいうザグリ部とは、まわりに縁があり、板に貫通しないまでの穴が開いているものや、仕切りで周りを囲っているものを指す。ザグリの底が平らになっていても良く、また、ザグリの形状は、最終製品の形状と同様であるとより好ましい。
In the method for producing a titanium-based porous body of the present invention, a deformed titanium-based powder having an average particle diameter of 10 to 50 μm, D90 of less than 75 μm, and an average circularity of 0.50 to 0.90 is dry-type and applied without pressure on a setter. Placed on. Since the powder is packed more densely than only its own weight, it becomes difficult to produce a titanium-based porous body having a porosity of more than 70%.
The setter should just be a material which does not react easily with titanium-type porous bodies, such as quartz and BN. As the shape, a flat plate-like shape or a flat plate-like shape provided with a counterbore portion can be used, and a flat plate-like shape provided with a counterbore portion is particularly preferable. The counterbore part here refers to one having an edge around it and having a hole until it does not penetrate the plate, or one surrounded by a partition. The bottom of the counterbore may be flat, and the shape of the counterbore is more preferably the same as the shape of the final product.
チタン系異形粉の載置方法は、平面の板状のセッターを用いる場合には、
（１）セッター上方から、異形チタン系粉を自然落下させ、セッター上に載置する方法
（２）セッター上に製品寸法の枠状の粉末充填用治具を載置したのち、セッター上方から、異形チタン系粉を自然落下させ、異形チタン系粉を加圧することなく、粉末充填用治具のすりきり一杯まで充填する方法、などがある。
ザグリ部を設けたセッターを用いる場合には、
（３）ザグリ部にチタン系異形粉を自然落下により投入した後、チタン系異形粉を加圧することなく、板状の治具でザグリ部から溢れた粉末を擦切る方法、などがある。
特に（２）、（３）の方法は、治具内またはザグリ部に残存する粉末がそのまま製品寸法とする方法となり好ましい。
チタン系異形粉を載置される場所（セッターの表面またはザグリ部の底面）の表面粗さは１．５μｍ以下が好ましい。この範囲とすることで、シート状チタン系多孔体の少なくとも片面の表面粗さを８．０μｍ以下とすることができる。
When using a flat plate-shaped setter, the method for placing titanium-based deformed powder is
(1) A method of naturally dropping a deformed titanium-based powder from above the setter and placing it on the setter (2) After placing a frame-shaped powder filling jig of product dimensions on the setter, from above the setter, There is a method in which the irregular titanium-based powder is naturally dropped, and the powder-filling jig is filled up to the full without pressing the irregular titanium-based powder.
When using a setter with a counterbore,
(3) There is a method of scraping off the powder overflowing from the counterbore part with a plate-shaped jig without applying pressure to the titanium-base irregular powder after the titanium-base irregular powder is introduced into the counterbore part by natural dropping.
In particular, the methods (2) and (3) are preferable because the powder remaining in the jig or the counterbore part is used as the product dimensions as it is.
The surface roughness of the place (the surface of the setter or the bottom surface of the counterbore) where the titanium-based irregular shaped powder is placed is preferably 1.5 μm or less. By setting it as this range, the surface roughness of at least one surface of the sheet-like titanium-based porous body can be set to 8.0 μm or less.
≪チタン系粉末の載置≫
チタン系粉末を加圧することなく（無加圧で）載置することによって、チタン粉末同士が自然な状態でブリッジし、空隙率５０〜７０％のチタン系多孔体の焼結体を得ることができる。ここでいう無加圧とは、意図的に充填したチタン粉末面に向かって応力を加えない状態を指し、充填時にチタン粉末面に加わる応力は、セッターと平行方向に粉末を擦切る際に付随するもののみになる。また、ここでいうブリッジとは粉末がアーチ状の空洞を形成することを指す。
さらにチタン系粉末の充填は乾式で行うことが好ましい。乾式で粉末を充填することによって、粉末同士が自然な状態でブリッジし、高い空隙率を持つ焼結体を得ることができる。ここでいう乾式とは、意図的に粉末と水分や有機溶剤を混合しない状態を指す。湿式でチタン系粉末を充填すると、流体の抵抗によりチタン系粉末が異方性を持って堆積し、高い空隙率を得ることが困難になる。また、有機溶媒を用いた場合は炭素濃度が０．１重量％以上と高くなり、不純物のコンタミによりチタン系多孔体の焼結品の強度が低下したり電気抵抗が大きくなるおそれがある。
≪Placement of titanium-based powder≫
By placing the titanium-based powder without applying pressure (without applying pressure), the titanium powders can be bridged in a natural state to obtain a sintered body of a titanium-based porous body having a porosity of 50 to 70%. it can. The term "no pressure" refers to a state in which no stress is applied toward the intentionally filled titanium powder surface. The stress applied to the titanium powder surface during filling accompanies when the powder is scraped in a direction parallel to the setter. It will be only what you do. Further, the bridge here means that the powder forms an arched cavity.
Furthermore, it is preferable to fill the titanium-based powder by a dry method. By filling the powder with a dry method, the powders can be naturally bridged to obtain a sintered body having a high porosity. The dry type here refers to a state in which powder and moisture or an organic solvent are not intentionally mixed. When the titanium-based powder is filled in a wet process, the titanium-based powder is deposited with anisotropy due to fluid resistance, and it becomes difficult to obtain a high porosity. Further, when an organic solvent is used, the carbon concentration becomes as high as 0.1% by weight or more, and the strength of the sintered product of the titanium-based porous body may be reduced or the electrical resistance may be increased due to impurity contamination.
≪チタン系粉末の焼結≫
得られたチタン系粉末の堆積体は、８００〜１１００℃で焼結する。石英セッターを使用する場合は８００〜１０００℃で焼結することが好ましい。この範囲の温度で焼結を行うことで、実用上必要な強度を持ち、表面の平滑な焼結体を製造することができる。焼結時間は１〜３時間が好ましい。
なお、原料の異形チタン系粉として、水素化した純チタン粉またはチタン合金粉を用いる場合は、焼結工程の前に一旦４００〜６００℃で保持することにより粉末に含まれる水素を抜きとる脱水素工程をはさむことで、より曲げ強度の高いＨＤＨ粉を原料としたものと同等の多孔体を製造する方法なども挙げられる。
≪Sintering of titanium-based powder≫
The obtained titanium-based powder deposit is sintered at 800 to 1100 ° C. When using a quartz setter, it is preferable to sinter at 800-1000 degreeC. By performing sintering at a temperature in this range, a sintered body having a practically necessary strength and a smooth surface can be produced. The sintering time is preferably 1 to 3 hours.
In addition, when hydrogenated pure titanium powder or titanium alloy powder is used as the raw material irregular titanium-based powder, it is dehydrated to remove hydrogen contained in the powder by holding at 400 to 600 ° C. once before the sintering step. A method of producing a porous body equivalent to that using HDH powder with higher bending strength as a raw material by sandwiching the elementary process is also included.
≪チタン系粉末の製造方法まとめ≫
上述したように、平均粒径、形状が特定のチタン系粉を用い、特定の条件で成型、焼成することにより、本発明のシート状チタン系多孔体を得ることができる。
例えば、チタン系粉の平均粒径が大きくなると、シート状チタン系多孔体の比表面積、は小さくなり、空隙率は大きくなる。また、チタン系粉の円形度は大きくなると、シート状チタン系多孔体の空隙率は小さくなる。チタン系粉の円形度のシート状チタン系多孔体の比表面積に対する傾向は、ある値で極大を有する変化を示す。焼成温度は高温になると、シート状チタン系多孔体の比表面積、空隙率は小さくなる。これらのパラメータを制御することで、シート状チタン系多孔体の比表面積、空隙率を調整することができる。
シート状チタン系多孔体の厚さは、チタン系異形粉の載置した厚さ、治具の高さまたはサグリ部の深さにより調整することができる。また、シート状チタン系多孔体の片面の表面粗さは、チタン系粉を載置するセッターまたはザグリ部の底面の表面粗さにより調整できる。
≪Titanium-based powder manufacturing method summary≫
As described above, the sheet-like titanium-based porous body of the present invention can be obtained by using a titanium-based powder having a specific average particle size and shape and molding and firing under specific conditions.
For example, when the average particle diameter of the titanium-based powder is increased, the specific surface area of the sheet-like titanium-based porous body is decreased, and the porosity is increased. Moreover, when the circularity of the titanium-based powder increases, the porosity of the sheet-like titanium-based porous body decreases. The tendency of the circularity of the titanium-based powder to the specific surface area of the sheet-like titanium-based porous body shows a change having a maximum at a certain value. When the firing temperature is increased, the specific surface area and porosity of the sheet-like titanium porous body are reduced. By controlling these parameters, the specific surface area and porosity of the sheet-like titanium porous body can be adjusted.
The thickness of the sheet-like titanium-based porous body can be adjusted by the thickness of the titanium-based irregular shaped powder, the height of the jig, or the depth of the sagging portion. Moreover, the surface roughness of the single side | surface of a sheet-like titanium-type porous body can be adjusted with the surface roughness of the bottom surface of the setter or counterbore part which mounts titanium type powder.
以下、本発明の内容を実施例および比較例によってさらに具体的に説明するが、本発明はこれらの例によって何ら限定されるものではない。
実施例で使用した設備および条件を以下に示す。
１．原料チタン系粉末
１）製造方法：水素化脱水素法
２）平均粒径・粒度分布の測定方法：ＬＭＳ−３５０（セイシン企業社製）を用いて、ＪＩＳ Ｚ ８８２５：２０１３に準拠し測定した。得られた粒度分布（体積基準）より体積分布の積算値が５０％及び９０％に相当する粒子径Ｄ５０、Ｄ９０を求めた。
３）平均円形度の測定方法：セイシン企業社製のＰＩＴＡ３を用いて測定を行った。具体的には、セル内にキャリア液とともに粒子を流し、ＣＣＤカメラで多量の粒子の画像を撮り込み、個々の粒子画像から、粒子の投影面積の周囲長（Ａ）と投影面積と等しい面積の円の周囲長を（Ｂ）を測定し、投影面積の周囲長（Ａ）と、前記投影面積と等しい面積の円の周囲長を（Ｂ）とした場合のＢ／Ａを円形度として求めた。１０００〜１５００個の各粒子を対象とし、円形度を測定し、その個数平均値を平均円形度とした。
Hereinafter, the content of the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
The equipment and conditions used in the examples are shown below.
1. Raw material titanium-based powder 1) Production method: hydrodehydrogenation method 2) Measurement method of average particle size / particle size distribution: LMS-350 (manufactured by Seishin Enterprise Co., Ltd.) was used for measurement according to JIS Z 8825: 2013. From the obtained particle size distribution (volume basis), particle diameters D50 and D90 corresponding to 50% and 90% of the integrated value of the volume distribution were obtained.
3) Measurement method of average circularity: Measurement was performed using PITA3 manufactured by Seishin Enterprise Co., Ltd. Specifically, the particles are flowed together with the carrier liquid in the cell, and a large number of particle images are taken with a CCD camera. From the individual particle images, the perimeter of the projected area of the particles (A) and the area equal to the projected area are taken. The circumference of the circle was measured as (B), and B / A was calculated as the circularity when the circumference of the projected area (A) and the circumference of the circle having the same area as the projected area were (B). . The circularity was measured for 1000 to 1500 particles, and the number average value was defined as the average circularity.
２．焼結条件
１）セッター：ザグリ付石英セッター（ザグリ寸法：６０×６０×０．５ｔｍｍ，サグリ部底面の表面粗さ：０．７６μｍ）
２）真空度：３．０×１０−３Ｐａ
３）昇温速度：１５℃／ｍｉｎ
４）到達温度：９００℃（保持時間１Ｈｒ）
５）冷却方法：９００℃から１００℃まで炉冷
2. Sintering condition 1) Setter: Quartz setter with counterbore (Counterbore size: 60 × 60 × 0.5tmm, Surface roughness of the bottom surface of the sagittal portion: 0.76 μm)
2) Degree of vacuum: 3.0 × 10 −3 Pa
3) Temperature increase rate: 15 ° C / min
4) Achieving temperature: 900 ° C. (holding time 1 Hr)
5) Cooling method: furnace cooling from 900 ° C to 100 ° C
３．分析方法
１）空隙率：上記（Ａ）式を用いて算出
２）比表面積：ＡＳＡＰ２４６０（マイクロメリティックス社製）を用い、ＪＩＳ Ｚ ８８３１：２０１３に準拠したＢＥＴ法にて測定。
吸着ガスはクリプトン。前処理条件はＮ２流通法（１２０℃×１Ｈｒ）。測定温度は―１９６℃。
３）導電率：ＭＣＰ―Ｔ６１０（三菱化学社製）を用い、ＪＩＳ Ｋ ７１９４に準拠して測定。
４）表面粗さ：サーフテストＳＪ−３１０（株式会社ミツトヨ製）を用い、ＪＩＳ Ｂ ０６０１−２００１に準拠して測定。
５）曲げ強さ：５５８２型万能試験機（インストロン社製）を用い、ＪＩＳ Ｚ ２４８に準拠し、測定。試験条件は、押し子直径５ｍｍ、受け３Ｒエッジ、外部支点間距離４０ｍｍ、試験速度４ｍｍ／ｍｉｎで行ったときの最大荷重（Ｎ）で評価した。
６）炭素濃度の測定方法：株式会社堀場製作所製ＥＭＩＡ−９２０Ｖ２を使用して、燃焼−赤外線吸収法により測定した。試料０．５ｇと金属錫および金属タングステンをアルミナるつぼに入れ、酸素気流中で高周波電流によって加熱、燃焼させ、発生したＣＯ２を赤外線により検出、定量し、試料中の炭素濃度とした。
3. Analysis method 1) Porosity: calculated using the above formula (A) 2) Specific surface area: Measured by BET method based on JIS Z 8831: 2013 using ASAP2460 (manufactured by Micromeritics).
Adsorbed gas is krypton. Pretreatment conditions are N 2 flow method (120 ° C. × 1 Hr). The measurement temperature is -196 ° C.
3) Conductivity: Measured according to JIS K 7194 using MCP-T610 (Mitsubishi Chemical Corporation).
4) Surface roughness: Measured according to JIS B 0601-2001 using Surf Test SJ-310 (manufactured by Mitutoyo Corporation).
5) Bending strength: Measured according to JIS Z 248 using a 5582 type universal testing machine (Instron). The test conditions were evaluated by the maximum load (N) when the pusher diameter was 5 mm, the receiving 3R edge, the distance between external fulcrums was 40 mm, and the test speed was 4 mm / min.
6) Measurement method of carbon concentration: Measured by combustion-infrared absorption method using EMIA-920V2 manufactured by Horiba, Ltd. 0.5 g of a sample, metal tin and metal tungsten were placed in an alumina crucible, heated and burned with a high-frequency current in an oxygen stream, and the generated CO 2 was detected and quantified by infrared rays to obtain the carbon concentration in the sample.
Ａ．原料粉末（異形チタン系粉）の特性の影響
本件発明に係るシート状チタン系多孔体の製造方法では、原料粉末として特定の粒度分布と円形度を有する異形チタン系粉末を使用するが、粒度分布と円形度を変化させて、その影響を調べた。
［実施例１］
平均粒径（Ｄ５０）３０μｍ（Ｄ９０：４７μｍ）、平均円形度０．７８のＨＤＨチタン粉末をザグリ深さ０．５０ｍｍ、ザグリ部の底面の表面粗さ０．７６μｍのザグリ付石英セッター上に充填し、上記焼結条件で焼結し、チタン系多孔体を得た。
得られたチタン系多孔体の厚さは０．４７ｍｍであり、空隙率は６４％であり、比表面積は８．４×１０−２ｍ２／ｇであり、ザグリ付石英セッターに接した面の表面粗さ（以下の実施例で同じ）は３．７μｍであり、導電率は２．９６×１０３Ｓ／ｃｍであり、曲げ試験での最大荷重は５．９Ｎであった。また、チタン系多孔体中の炭素濃度は０．０２％であった。
［実施例２］
平均粒径（Ｄ５０）１２μｍ（Ｄ９０：１９μｍ）、平均円形度０．８８のＨＤＨチタン粉末を原料とした以外、実施例１と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは０．４５ｍｍであり、空隙率は５８％であり、比表面積は１．１×１０−１ｍ２／ｇであり、表面粗さは２．４μｍであり、導電率は３．１５×１０３Ｓ／ｃｍであり、曲げ試験での最大荷重は１４．７Ｎであった。
また、チタン系多孔体中の炭素濃度は０．０１％であった。
［実施例３］
平均粒径（Ｄ５０）５０μｍ（Ｄ９０：７４μｍ）、平均円形度０．８２のＨＤＨチタン粉末を原料とした以外、実施例１と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは０．５２ｍｍであり、空隙率は５９％であり、比表面積は４．９×１０−２ｍ２／ｇであり、表面粗さは６．０μｍであり、導電率は２．０２×１０３Ｓ／ｃｍであり、曲げ試験での最大荷重は４．６Ｎであった。
また、チタン系多孔体中の炭素濃度は０．０３％であった。
［比較例１］
平均粒径（Ｄ５０）３２μｍ（Ｄ９０：４８μｍ）、平均円形度０．９４の球状チタン粉末を原料とした以外、実施例１と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは０．４９ｍｍであり、空隙率は４４％であり、比表面積は４．３×１０−２ｍ２／ｇであり、表面粗さは３．３μｍであり、導電率は５．２８×１０３Ｓ／ｃｍであり、曲げ試験での最大荷重は２２．２Ｎであった。
［比較例２］
平均粒径（Ｄ５０）９０μｍ（Ｄ９０：１０７μｍ）、平均円形度０．８０のＨＤＨチタン粉末を原料とした以外、実施例１と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは０．４７ｍｍであり、空隙率は６３％であり、比表面積は３．３×１０−２ｍ２／ｇであり、表面粗さは８．４μｍであり、導電率は１．３１×１０３Ｓ／ｃｍであり、曲げ試験での最大荷重は１．６Ｎであった。
［比較例３］
寸法φ２０μｍ×２．５ｍｍのチタン繊維（平均円形度は、測定不能）を原料とした以外、実施例１と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは０．５１ｍｍであり、空隙率は８０％であり、比表面積は５．４×１０−２ｍ２／ｇであり、表面粗さは１８μｍであり、導電率は１．２７×１０３Ｓ／ｃｍであり、曲げ試験での最大荷重は３．４Ｎであった。
A. Effect of characteristics of raw material powder (deformed titanium powder) In the method for producing a sheet-like titanium porous body according to the present invention, a deformed titanium powder having a specific particle size distribution and circularity is used as the raw material powder. And the circularity was changed and the influence was investigated.
[Example 1]
HDH titanium powder with an average particle size (D50) of 30 μm (D90: 47 μm) and an average circularity of 0.78 is packed on a countersunk quartz setter with a counterbore depth of 0.50 mm and a bottom surface roughness of the counterbore of 0.76 μm. And it sintered on the said sintering conditions, and obtained the titanium-type porous body.
The thickness of the obtained titanium-based porous body is 0.47 mm, the porosity is 64%, the specific surface area is 8.4 × 10 −2 m 2 / g, and the surface in contact with the counterbore quartz setter The surface roughness (same in the following examples) was 3.7 μm, the conductivity was 2.96 × 10 3 S / cm, and the maximum load in the bending test was 5.9 N. The carbon concentration in the titanium-based porous body was 0.02%.
[Example 2]
A titanium-based porous material was obtained under the same conditions as in Example 1 except that HDH titanium powder having an average particle size (D50) of 12 μm (D90: 19 μm) and an average circularity of 0.88 was used as a raw material.
The obtained titanium-based porous body has a thickness of 0.45 mm, a porosity of 58%, a specific surface area of 1.1 × 10 −1 m 2 / g, and a surface roughness of 2.4 μm. Yes, the conductivity was 3.15 × 10 3 S / cm, and the maximum load in the bending test was 14.7 N.
Moreover, the carbon concentration in the titanium-based porous body was 0.01%.
[Example 3]
A titanium-based porous body was obtained under the same conditions as in Example 1 except that HDH titanium powder having an average particle size (D50) of 50 μm (D90: 74 μm) and an average circularity of 0.82 was used as a raw material.
The obtained titanium-based porous body has a thickness of 0.52 mm, a porosity of 59%, a specific surface area of 4.9 × 10 −2 m 2 / g, and a surface roughness of 6.0 μm. Yes, the conductivity was 2.02 × 10 3 S / cm, and the maximum load in the bending test was 4.6 N.
The carbon concentration in the titanium-based porous body was 0.03%.
[Comparative Example 1]
A titanium-based porous body was obtained under the same conditions as in Example 1 except that spherical titanium powder having an average particle diameter (D50) of 32 μm (D90: 48 μm) and an average circularity of 0.94 was used as a raw material.
The obtained titanium-based porous body has a thickness of 0.49 mm, a porosity of 44%, a specific surface area of 4.3 × 10 −2 m 2 / g, and a surface roughness of 3.3 μm. Yes, the conductivity was 5.28 × 10 3 S / cm, and the maximum load in the bending test was 22.2N.
[Comparative Example 2]
A titanium-based porous material was obtained under the same conditions as in Example 1 except that HDH titanium powder having an average particle size (D50) of 90 μm (D90: 107 μm) and an average circularity of 0.80 was used as a raw material.
The obtained titanium-based porous body has a thickness of 0.47 mm, a porosity of 63%, a specific surface area of 3.3 × 10 −2 m 2 / g, and a surface roughness of 8.4 μm. Yes, the conductivity was 1.31 × 10 3 S / cm, and the maximum load in the bending test was 1.6 N.
[Comparative Example 3]
A titanium-based porous body was obtained under the same conditions as in Example 1 except that titanium fibers having a size of φ20 μm × 2.5 mm (average circularity cannot be measured) were used as raw materials.
The obtained titanium-based porous body has a thickness of 0.51 mm, a porosity of 80%, a specific surface area of 5.4 × 10 −2 m 2 / g, and a surface roughness of 18 μm. The conductivity was 1.27 × 10 3 S / cm, and the maximum load in the bending test was 3.4N.
以上の結果を表に整理してまとめると、次の表１（原料粉末の特性）及び、表２（チタン系多孔体の特性）のとおりとなる。
これらの表１及び表２の結果から明らかなように、本発明に係るシート状チタン系多孔体の製造方法において、原料として使用する異形チタン系粉は、請求項２で特定するようにD50が１０〜５０μｍ、Ｄ９０が７５μｍ未満、平均円形度０．５０〜０．９０のものを使用することにより、請求項１で特定する、好ましい比表面積、空隙率、厚さ及び表面粗さを有するシート状チタン系多孔体が得られ、これは、導電率と強度特性において優れたものとなった。
平均円形度（比較例１）、Ｄ５０及びＤ９０が上記範囲を逸脱するもの（比較例２）、チタン繊維を原料としたもの（比較例３）は、良好なシート状チタン系多孔体を得ることができなかった。
As apparent from the results of Tables 1 and 2, in the method for producing a sheet-like titanium porous body according to the present invention, the deformed titanium-based powder used as a raw material has D50 as specified in claim 2. A sheet having a preferred specific surface area, porosity, thickness and surface roughness specified in claim 1 by using 10 to 50 µm, D90 less than 75 µm, and an average circularity of 0.50 to 0.90. A titanium-like porous body was obtained, which was excellent in conductivity and strength characteristics.
When the average circularity (Comparative Example 1), D50 and D90 deviate from the above ranges (Comparative Example 2), and those using titanium fibers as a raw material (Comparative Example 3), a good sheet-like titanium-based porous body is obtained. I could not.
Ｂ 焼成温度の影響
本発明に係るシート状チタン系多孔体の製造方法では、焼結の際の到達温度を８００〜１１００℃としているが、その影響を調べた。
［比較例４］
昇温速度１２℃／ｍｉｎ、到達温度７００℃とした以外、実施例１と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは０．４９ｍｍであり、空隙率は７３％であり、比表面積は１．１×１０−１ｍ２／ｇであり、表面粗さは４．５μｍであり、導電率は４．７６×１０２Ｓ／ｃｍであり、曲げ試験での最大荷重は０．５Ｎであった。
［実施例４］
セッター表面（表面粗さ１．１μｍ）から約０．５０ｍｍの高さの枠状の粉末充填用治具を用いて、実施例１のＨＤＨチタン粉末をＢＮセッター上に充填し、真空度３．０×１０−３Ｐａの雰囲気で１０℃／ｍｉｎの速さで昇温し、到達温度１１００℃で１Ｈｒ保持後炉冷することでチタン系多孔体を得た。
得られたチタン系多孔体の厚さは０．４６ｍｍであり、空隙率は５７％であり、比表面積は６．７×１０−２ｍ２／ｇであり、表面粗さは４．３μｍであり、導電率は３．５５×１０３Ｓ／ｃｍであり、曲げ試験での最大荷重は９．８Ｎであった。
また、チタン系多孔体中の炭素濃度は０．０３％であった。
［比較例５］
実施例４の到達温度を１１００℃から１２００℃へ変更した以外、実施例４と同様にチタン系多孔体の製造を試みたが、粉末とセッターが反応し、セッターからチタン系多孔体の剥離不可となり、チタン系多孔体を得ることはできなかった。
B Influence of calcination temperature In the method for producing a sheet-like titanium porous body according to the present invention, the ultimate temperature during sintering is set to 800 to 1100 ° C., but the influence was examined.
[Comparative Example 4]
A titanium-based porous body was obtained under the same conditions as in Example 1 except that the temperature increase rate was 12 ° C./min and the ultimate temperature was 700 ° C.
The obtained titanium-based porous body has a thickness of 0.49 mm, a porosity of 73%, a specific surface area of 1.1 × 10 −1 m 2 / g, and a surface roughness of 4.5 μm. Yes, the conductivity was 4.76 × 10 2 S / cm, and the maximum load in the bending test was 0.5N.
[Example 4]
Using a frame-shaped powder filling jig having a height of about 0.50 mm from the setter surface (surface roughness 1.1 μm), the HDH titanium powder of Example 1 is filled on the BN setter, and the degree of vacuum is 3. The temperature was raised at a rate of 10 ° C./min in an atmosphere of 0 × 10 −3 Pa, and after holding at 1100 ° C. for 1 hour, the reactor was cooled to obtain a titanium-based porous body.
The obtained titanium-based porous body has a thickness of 0.46 mm, a porosity of 57%, a specific surface area of 6.7 × 10 −2 m 2 / g, and a surface roughness of 4.3 μm. Yes, the conductivity was 3.55 × 10 3 S / cm, and the maximum load in the bending test was 9.8 N.
The carbon concentration in the titanium-based porous body was 0.03%.
[Comparative Example 5]
Except for changing the ultimate temperature of Example 4 from 1100 ° C. to 1200 ° C., an attempt was made to produce a titanium-based porous body in the same manner as in Example 4, but the powder and setter reacted, and the titanium-based porous body could not be peeled from the setter. Thus, a titanium-based porous body could not be obtained.
以上の結果を表にまとめると、次の表３（シート状チタン系多孔体の特性と焼成温度との関係）のとおりとなる。
Ｃ シート状チタン系多孔体の厚さの影響
本発明に係るシート状チタン系多孔体は、厚さを４．０×１０−１〜１．６ｍｍと 特定するが、その値を変化させて、特性のシート厚のシート特性に対する影響を調べた。
［実施例５］
ザグリ付石英セッターのザグリ深さを１．５０ｍｍとした以外、実施例１と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは１．５ｍｍであり、空隙率は６２％であり、比表面積は７．３×１０−２ｍ２／ｇであり、表面粗さは４．２μｍであり、導電率は３．０９×１０３Ｓ／ｃｍであり、曲げ試験での最大荷重は５０．２Ｎであった。
また、チタン系多孔体中の炭素濃度は０．０１％であった。
［比較例６］
セッター表面から約０．３０ｍｍの高さの枠状の粉末充填用治具を用いて、ＢＮセッター上に粉末を充填した以外は実施例１と同様の条件でチタン系多孔体を得た。
得られたチタン系多孔体の厚さは０．３０ｍｍであり、空隙率は７４％であり、比表面積は７．４×１０−２ｍ２／ｇであり、表面粗さは９．０μｍであり、導電率は１．２２×１０３Ｓ／ｃｍであり、曲げ試験での最大荷重は０．８Ｎであった。
C Effect of thickness of sheet-like titanium-based porous material
The sheet-like titanium-based porous body according to the present invention has a thickness of 4.0 × 10 −1 to 1.6 mm, but the value is changed to examine the influence of the sheet thickness on the sheet characteristics. .
[Example 5]
A titanium-based porous body was obtained under the same conditions as in Example 1 except that the counterbore depth of the counterbore quartz setter was 1.50 mm.
The obtained titanium-based porous body has a thickness of 1.5 mm, a porosity of 62%, a specific surface area of 7.3 × 10 −2 m 2 / g, and a surface roughness of 4.2 μm. Yes, the conductivity was 3.09 × 10 3 S / cm, and the maximum load in the bending test was 50.2N.
Moreover, the carbon concentration in the titanium-based porous body was 0.01%.
[Comparative Example 6]
A titanium-based porous body was obtained under the same conditions as in Example 1 except that a powder was filled on the BN setter using a frame-shaped powder filling jig having a height of about 0.30 mm from the setter surface.
The obtained titanium-based porous body has a thickness of 0.30 mm, a porosity of 74%, a specific surface area of 7.4 × 10 −2 m 2 / g, and a surface roughness of 9.0 μm. Yes, the conductivity was 1.22 × 10 3 S / cm, and the maximum load in the bending test was 0.8N.
以上の結果を表にまとめると、次の表４（シート状チタン系多孔体の特性と多孔体の厚さの関係）のとおりとなる。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021187228A1 (en) | 2020-03-16 | 2021-09-23 | 三菱マテリアル株式会社 | Sponge titanium sheet material, and water electrolysis electrode and water electrolysis apparatus |
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