JPH11100695A - Production of titanium material having photocatalytic activity - Google Patents
Production of titanium material having photocatalytic activityInfo
- Publication number
- JPH11100695A JPH11100695A JP9261606A JP26160697A JPH11100695A JP H11100695 A JPH11100695 A JP H11100695A JP 9261606 A JP9261606 A JP 9261606A JP 26160697 A JP26160697 A JP 26160697A JP H11100695 A JPH11100695 A JP H11100695A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalytic activity
- titanium material
- titanium
- oxide film
- anodic oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 62
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000010936 titanium Substances 0.000 title claims abstract description 46
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000007743 anodising Methods 0.000 claims abstract description 10
- 239000010419 fine particle Substances 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000010407 anodic oxide Substances 0.000 abstract description 41
- 238000000034 method Methods 0.000 abstract description 15
- 239000004566 building material Substances 0.000 abstract description 5
- 238000007598 dipping method Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 14
- 239000011941 photocatalyst Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- RCYJPSGNXVLIBO-UHFFFAOYSA-N sulfanylidenetitanium Chemical compound [S].[Ti] RCYJPSGNXVLIBO-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高い光触媒活性を
安定して備えたチタン材を簡易に得ることができる方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for easily obtaining a titanium material stably having high photocatalytic activity.
【０００２】[0002]
【従来技術及びその課題】触媒による反応促進効果は、
一般には、触媒の表面積が大きいほど大きい。それ故、
触媒は、微粒子、更には超微粒子で用いるのが好まし
い。しかし、微粒子状の触媒を用いると、触媒の回収や
生成物との分離等の取り扱いにおいて問題となる場合が
生じる。例えば、特開平４−２４４２９３に示されるよ
うに、過酸化水素及び鉄塩を用いた廃液処理において、
光触媒である酸化チタン粉末を用いると、処理後、酸化
チタンを濾過等によって処理液と分離する必要がある。
従って、通常、触媒は、成形体や多孔質粉体に固定化し
て用いられている。2. Description of the Related Art The reaction promoting effect of a catalyst is as follows.
In general, the larger the surface area of the catalyst, the larger. Therefore,
The catalyst is preferably used in the form of fine particles, more preferably ultrafine particles. However, when a particulate catalyst is used, problems may occur in handling such as recovery of the catalyst and separation from the product. For example, as shown in JP-A-4-244293, in wastewater treatment using hydrogen peroxide and iron salt,
When a titanium oxide powder as a photocatalyst is used, it is necessary to separate the titanium oxide from the treatment liquid by filtration or the like after the treatment.
Therefore, the catalyst is usually used by being immobilized on a compact or a porous powder.
【０００３】ところで、近年、廃液処理や大気の浄化，
脱臭，殺菌を光触媒を用いて行う研究が盛んに行われて
おり、種々の光触媒を、板，ファイバー等の成形体やゼ
オライト，活性炭等の多孔質粉体に固定化する方法が検
討されている。その方法としては、例えば、(i)ゾルゲ
ル法、(ii)ＣＶＤ法、(iii)酢酸セルロース，ポリビニ
ルアルコール，フッ素樹脂等に混合してコーティングす
る方法（特開平１−１３５８４２，特開平６−３１５６
１４）、(iv)セラミックス粉体と共に焼結する方法等が
ある。しかし、上記(i)，(ii)では、大規模化や価格の
点に問題があり、特に一度に大きな面積を処理するのが
困難であった。また、光触媒が固定化された材料を建築
材として用いる場合において、上記(i),(ii)で得られた
膜では強度及び密着性に問題があった。また、上記(ii
i)では、光触媒自身が膜に覆われて作用しなくなった
り、光触媒の効果によって有機物である膜自身が劣化し
たりするという問題があった。また、上記(iv)では、大
規模化の点で問題があった。[0003] In recent years, wastewater treatment, air purification,
Research on deodorization and sterilization using photocatalysts has been actively conducted, and methods for immobilizing various photocatalysts on molded bodies such as plates and fibers and porous powders such as zeolite and activated carbon have been studied. . Examples of the method include (i) a sol-gel method, (ii) a CVD method, and (iii) a method in which cellulose acetate, polyvinyl alcohol, a fluororesin, etc. are mixed and coated (JP-A-1-135842, JP-A-6-3156).
14) and (iv) a method of sintering with ceramic powder. However, in the above (i) and (ii), there is a problem in terms of enlargement and price, and it is particularly difficult to process a large area at a time. Further, when a material on which a photocatalyst is fixed is used as a building material, the films obtained in the above (i) and (ii) have problems in strength and adhesion. In addition, (ii)
In the case of i), there is a problem that the photocatalyst itself is covered by the film and does not work, or the organic film itself is deteriorated by the effect of the photocatalyst. Also, in the above (iv), there was a problem in increasing the scale.
【０００４】このような中で、酸化亜鉛や酸化チタンが
光触媒活性を有していることに着目し、亜鉛やチタン又
はそれらの合金を陽極酸化処理して、強度及び密着性が
良好な酸化亜鉛や酸化チタンからなる陽極酸化皮膜を形
成する方法が、検討されている。しかし、特開平６−１
９８１６に示されるように、チタンを陽極酸化処理する
方法では、光触媒活性を向上させるために必要な金属を
予め基材中に合金化させておく必要があり、また、陽極
酸化皮膜中に必ず金属チタン成分や電解浴の液成分であ
るリン等が含まれるために触媒活性が低下するという問
題があった。また、特開平７−２８９９１３に示される
ように、亜鉛を陽極酸化処理する方法では、チタンの場
合と同じく触媒活性が低下するという問題の他に、亜鉛
という金属自身の耐食性の点で建築材として利用するの
に不適であるという問題があった。[0004] Under these circumstances, focusing on the fact that zinc oxide and titanium oxide have photocatalytic activity, zinc oxide and titanium or an alloy thereof are subjected to anodizing treatment to obtain zinc oxide having good strength and adhesion. A method of forming an anodic oxide film made of titanium or titanium oxide has been studied. However, Japanese Patent Laid-Open No. 6-1
As shown in 9816, in the method of anodizing titanium, it is necessary to previously alloy a metal necessary for improving the photocatalytic activity in the base material, and the metal is necessarily contained in the anodized film. There is a problem that the catalytic activity is reduced due to the inclusion of a titanium component and phosphorus as a liquid component of the electrolytic bath. Further, as shown in JP-A-7-289913, in the method of anodizing zinc, in addition to the problem of reduced catalytic activity as in the case of titanium, in addition to the problem of corrosion resistance of zinc itself, as a building material, There was a problem that it was unsuitable for use.
【０００５】本発明は、上記問題点に鑑みてなされたも
のであり、高い光触媒活性を安定して備えたチタン材を
簡易に得ることができる方法を提供することを目的とす
る。The present invention has been made in view of the above problems, and has as its object to provide a method for easily obtaining a titanium material having high photocatalytic activity stably.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するた
め、本願の請求項１記載の発明は、無機酸及び有機酸の
少なくともいずれか１種を含み、且つ光触媒活性を有す
る微粒子が添加されている電解浴中に、チタン材を浸漬
し、火花放電発生電圧以上の電圧を印加して陽極酸化処
理を行うことを特徴とする光触媒活性を有するチタン材
の製造方法である。Means for Solving the Problems In order to achieve the above object, the invention according to claim 1 of the present application is directed to a method in which fine particles containing at least one of an inorganic acid and an organic acid and having photocatalytic activity are added. A method for producing a titanium material having photocatalytic activity, characterized by immersing a titanium material in an electrolytic bath and applying an anodizing treatment by applying a voltage higher than a spark discharge generating voltage.
【０００７】無機酸としては、硫酸、硝酸、リン酸、ク
ロム酸、ピロリン酸等を用いることができる。[0007] As the inorganic acid, sulfuric acid, nitric acid, phosphoric acid, chromic acid, pyrophosphoric acid and the like can be used.
【０００８】有機酸としては、ナフタレンジスルホン
酸、シュウ酸、スルホサリチル酸、酒石酸、酢酸、クエ
ン酸、ギ酸、マレイン酸等を用いることができる。As the organic acid, naphthalenedisulfonic acid, oxalic acid, sulfosalicylic acid, tartaric acid, acetic acid, citric acid, formic acid, maleic acid and the like can be used.
【０００９】光触媒活性を有する微粒子としては、次の
化合物を用いることができる。即ち、酸化チタン，硫化
チタン，チタン酸ストロンチウム等のチタン化合物、二
三酸化鉄，酸化錫，酸化銀，酸化銅，酸化亜鉛，酸化セ
リウム，酸化タングステン，酸化モリブデン，酸化ニッ
ケル等の酸化物、硫化亜鉛，硫化カドミウム等の硫化物
等。As the fine particles having photocatalytic activity, the following compounds can be used. That is, titanium compounds such as titanium oxide, titanium sulfide, and strontium titanate; oxides such as iron trioxide, tin oxide, silver oxide, copper oxide, zinc oxide, cerium oxide, tungsten oxide, molybdenum oxide, and nickel oxide; Sulfides such as zinc and cadmium sulfide.
【００１０】電解浴は、無機酸を１種以上、又は有機酸
を１種以上、又は無機酸及び有機酸をそれぞれ１種以上
含んでいる。なお、電解浴中には、過酸化水素を添加し
てもよい。The electrolytic bath contains at least one inorganic acid, at least one organic acid, or at least one inorganic acid and at least one organic acid. Note that hydrogen peroxide may be added to the electrolytic bath.
【００１１】チタン材としては、チタン又はチタン合金
を用いる。チタン合金としては、種々のものを用いるこ
とができる。チタン材の形状は、特に限定するものでは
なく、板状、網状、繊維状、粉体や繊維を圧縮加工して
なる成形体等を用いることができる。As the titanium material, titanium or a titanium alloy is used. Various titanium alloys can be used. The shape of the titanium material is not particularly limited, and a plate-like, mesh-like, fibrous, compact or the like obtained by compressing powder or fiber can be used.
【００１２】陽極酸化処理は、直流、交直重畳、又はパ
ルス波を印加して行う。又は、サイリスタ方式による直
流電源を用いて、単相半波、三相半波、六相半波を印加
して行う。いずれの波形でも、火花放電が発生する電圧
以上で行い、一般には、ピーク電圧が１００Ｖ以上で行
う。The anodic oxidation treatment is performed by applying direct current, AC / DC superposition, or pulse wave. Alternatively, a single-phase half-wave, a three-phase half-wave, and a six-phase half-wave are applied by using a thyristor-type DC power supply. Regardless of the waveform, the operation is performed at a voltage higher than the voltage at which spark discharge occurs, and is generally performed at a peak voltage of 100 V or higher.
【００１３】請求項１記載の発明においては、陽極酸化
皮膜の形成過程において、火花発生と同時に局部的な発
熱が生じ、その箇所に、電解浴中に添加されている光触
媒活性を有する微粒子が入り込み、融着する。これによ
り、光触媒活性を有する微粒子が陽極酸化皮膜中に分散
して存在することとなり、チタン材表面の陽極酸化皮膜
は光触媒活性を有することとなる。陽極酸化皮膜は強度
及びチタン材に対する密着性が良好であるので、上記の
ようにして得られたチタン材では光触媒活性が安定して
発揮され、該チタン材は建築材としても良好に用い得
る。しかも、請求項１記載の方法は、光触媒活性を有す
る微粒子を電解浴中に添加しておき、チタン材を電解処
理するだけであるので、簡易に実施できる。According to the first aspect of the present invention, in the process of forming the anodic oxide film, local heat is generated at the same time as the generation of sparks, and fine particles having photocatalytic activity added to the electrolytic bath enter the location. , Fusing. As a result, the fine particles having photocatalytic activity are dispersed and present in the anodic oxide film, and the anodic oxide film on the surface of the titanium material has photocatalytic activity. Since the anodized film has good strength and good adhesion to a titanium material, the titanium material obtained as described above exhibits a stable photocatalytic activity and can be used well as a building material. In addition, the method according to the first aspect can be easily carried out because only fine particles having photocatalytic activity are added to the electrolytic bath and the titanium material is subjected to electrolytic treatment.
【００１４】請求項２記載の発明は、請求項１記載の発
明に加えて、陽極酸化処理後のチタン材を、空気又は酸
素雰囲気下、２００℃以上９００℃以下で熱処理するも
のである。According to a second aspect of the present invention, in addition to the first aspect, the titanium material after the anodic oxidation treatment is heat-treated at 200 ° C. or more and 900 ° C. or less in an air or oxygen atmosphere.
【００１５】熱処理の温度が、２００℃より低いと、陽
極酸化皮膜中の不純物の除去が不十分となり、９００℃
より高いと、陽極酸化皮膜の結晶構造がアナターゼ型か
らルチル型へ変化し、皮膜自身の光触媒活性が著しく低
下する。熱処理は、好ましくは４００℃以上８００℃以
下で行う。When the temperature of the heat treatment is lower than 200 ° C., the removal of impurities in the anodic oxide film becomes insufficient,
If it is higher, the crystal structure of the anodic oxide film changes from the anatase type to the rutile type, and the photocatalytic activity of the film itself is significantly reduced. The heat treatment is preferably performed at 400 ° C. or higher and 800 ° C. or lower.
【００１６】請求項２記載の発明においては、熱処理に
より、陽極酸化皮膜中の金属チタン成分が酸化されて酸
化チタンとなり、また、陽極酸化皮膜中に混入した電解
浴の液成分が酸化除去されるので、陽極酸化皮膜中に光
触媒の妨げとなるものは無くなる。しかも、陽極酸化皮
膜がアナターゼ型の結晶構造を有することとなるので、
それ自身も光触媒活性を有することとなる。従って、陽
極酸化皮膜の光触媒活性は向上する。According to the second aspect of the invention, the metal titanium component in the anodic oxide film is oxidized to titanium oxide by the heat treatment, and the liquid component of the electrolytic bath mixed in the anodic oxide film is oxidized and removed. Therefore, there is no obstruction of the photocatalyst in the anodic oxide film. Moreover, since the anodized film has an anatase type crystal structure,
As such, it will have photocatalytic activity. Therefore, the photocatalytic activity of the anodic oxide film is improved.
【００１７】請求項３記載の発明は、請求項１記載の発
明に加えて、電解浴中に、光触媒活性を向上させる金属
の微粒子も添加しておくものである。光触媒活性を向上
させる金属としては、Ｐｔ，Ｐｄ，Ｒｕ，Ｒｅ，Ｏｓ，
Ａｕ，Ａｇ等を用いることができる。According to a third aspect of the present invention, in addition to the first aspect of the present invention, fine particles of a metal for improving photocatalytic activity are added to the electrolytic bath. Examples of metals that improve photocatalytic activity include Pt, Pd, Ru, Re, Os,
Au, Ag, etc. can be used.
【００１８】請求項３記載の発明においては、光触媒活
性を向上させる金属が、陽極酸化皮膜中に含まれ、しか
も、一部は光触媒活性を有する微粒子と接触して存在す
るので、陽極酸化皮膜自身の光触媒活性が向上するとと
もに、光触媒活性を有する微粒子も良好に活性を呈する
こととなる。According to the third aspect of the present invention, since the metal for improving the photocatalytic activity is contained in the anodic oxide film and a part of the metal is present in contact with the fine particles having the photocatalytic activity, the anodic oxide film itself is not present. As a result, the fine particles having the photocatalytic activity exhibit good activity.
【００１９】[0019]
（実施形態１）３％リン酸と１％過酸化水素水との混合
浴１Ｌ中に、光触媒である酸化チタンの微粒子（粒径７
ｎｍ，比表面積３００ｍ2／ｇ）５ｇを添加し、その浴
中に純チタン板（５ｃｍ×５ｃｍ）を浸漬し、これを直
流４００Ｖで５分間陽極酸化処理した。これにより、純
チタン板表面に厚さ１３μｍの陽極酸化皮膜が得られ
た。(Embodiment 1) In a mixed bath of 3% phosphoric acid and 1% hydrogen peroxide solution, 1 L of titanium oxide fine particles (particle size: 7
nm, specific surface area: 300 m 2 / g), and a pure titanium plate (5 cm × 5 cm) was immersed in the bath and subjected to anodizing treatment at 400 V DC for 5 minutes. As a result, an anodized film having a thickness of 13 μm was obtained on the surface of the pure titanium plate.
【００２０】得られた陽極酸化皮膜を、５ｍｍｏｌの酢
酸水溶液３０ｍｌ中に浸漬し、上方からブラックライト
（１ｍＷ／ｃｍ2）を２時間照射した。照射後、酢酸の
分解量をイオンクロマトグラフ法により測定した。酢酸
は８５μｍｏｌ（５６％）分解されていた。このことか
ら、得られた陽極酸化皮膜が光触媒活性を備えているこ
とがわかる。The obtained anodized film was immersed in 30 ml of a 5 mmol aqueous acetic acid solution, and irradiated with black light (1 mW / cm 2 ) from above for 2 hours. After the irradiation, the amount of acetic acid decomposed was measured by ion chromatography. Acetic acid was degraded by 85 μmol (56%). This indicates that the obtained anodized film has photocatalytic activity.
【００２１】（比較形態１）光触媒である酸化チタンを
添加せず、その他は実施形態１と同様に行った。そし
て、得られた陽極酸化皮膜による酢酸分解量を実施形態
１と同様に測定したところ、酢酸は分解されていなかっ
た。Comparative Example 1 The same operation as in Example 1 was performed except that titanium oxide as a photocatalyst was not added. When the amount of acetic acid decomposed by the obtained anodic oxide film was measured in the same manner as in Embodiment 1, acetic acid was not decomposed.
【００２２】（実施形態２）実施形態１で得られた陽極
酸化皮膜を９００℃で４５分間熱処理した。そして、熱
処理後の陽極酸化皮膜による酢酸分解量を、実施形態１
と同様に測定した。酢酸は１２０μｍｏｌ（８０％）分
解されていた。このことから、熱処理により光触媒活性
が向上したことがわかる。(Embodiment 2) The anodic oxide film obtained in Embodiment 1 was heat-treated at 900 ° C for 45 minutes. Then, the amount of acetic acid decomposed by the anodic oxide film after the heat treatment was measured according to the first embodiment.
It measured similarly to. Acetic acid had been degraded by 120 μmol (80%). This shows that the heat treatment improved the photocatalytic activity.
【００２３】（実施形態３）２％硫酸と２％過酸化水素
水との混合浴１Ｌ中に、光触媒である、酸化チタンの微
粒子（粒径９ｎｍ，比表面積２７０ｍ2／ｇ）５ｇ及び
二三酸化鉄の微粒子（粒径１３．２ｎｍ、比表面積１４
９ｍ2／ｇ）５ｇを添加し、その浴中に純チタン板（５
ｃｍ×１０ｃｍ）を浸漬し、これを直流２００Ｖで５分
間陽極酸化処理した。これにより、純チタン板表面に厚
さ１．５μｍの陽極酸化皮膜が得られた。(Embodiment 3) In a mixed bath of 2% sulfuric acid and 2% hydrogen peroxide solution, 5 g of titanium oxide fine particles (particle diameter 9 nm, specific surface area 270 m 2 / g) and 23 Fine particles of iron oxide (particle size 13.2 nm, specific surface area 14
9 m 2 / g) and 5 g of pure titanium plate (5
cm × 10 cm), and anodized at 200 V DC for 5 minutes. As a result, an anodic oxide film having a thickness of 1.5 μm was obtained on the surface of the pure titanium plate.
【００２４】得られた陽極酸化皮膜を、商品名「サノダ
ルレッド(Sanodal Red)Ｂ３ＬＷ」（クラリアントジャ
パン株式会社製）である赤色染料の０．５％溶液１Ｌ中
に浸漬し、更に０．０５％過酸化水素水を添加し、上方
からブラックライト（１ｍＷ／ｃｍ2）を照射したとこ
ろ、１０分で赤色が消失して無色透明となった。The obtained anodic oxide film was immersed in 1 L of a 0.5% solution of a red dye of “Sanodal Red B3LW” (manufactured by Clariant Japan KK), and further dried by 0.05%. Hydrogen oxide water was added and irradiated with black light (1 mW / cm 2 ) from above, and the red color disappeared and became colorless and transparent in 10 minutes.
【００２５】（比較形態２）光触媒である酸化チタン及
び二三酸化鉄を添加せず、その他は実施形態３と同様に
行った。そして、得られた陽極酸化皮膜について、実施
形態３と同様にして染料分解速度を測定したところ、２
時間照射しても赤色は全く変化しなかった。Comparative Example 2 The same operation as in Example 3 was carried out except that titanium oxide and iron trioxide as photocatalysts were not added. Then, the dye decomposition rate of the obtained anodic oxide film was measured in the same manner as in Embodiment 3.
The red color did not change at all after irradiation for hours.
【００２６】（実施形態４）実施形態３で得られた陽極
酸化皮膜を７００℃で１時間３０分熱処理した。そし
て、熱処理後の陽極酸化皮膜について、実施形態３と同
様にして染料分解速度を測定したところ、６分で赤色が
消失して無色透明となった。このことから、熱処理によ
り光触媒活性が向上したことがわかる。(Embodiment 4) The anodic oxide film obtained in Embodiment 3 was heat-treated at 700 ° C for 1 hour and 30 minutes. When the dye decomposition rate of the anodized film after the heat treatment was measured in the same manner as in Embodiment 3, the red color disappeared in 6 minutes and became colorless and transparent. This shows that the heat treatment improved the photocatalytic activity.
【００２７】（実施形態５）２％硫酸と１％スルホサリ
チル酸との混合浴１Ｌ中に、光触媒である酸化チタンの
微粒子（粒径７ｎｍ，比表面積３００ｍ2／ｇ）１０ｇ
を添加し、その浴中に純チタン板（１０ｃｍ×１０ｃ
ｍ）を浸漬し、これを直流２００Ｖで５分間陽極酸化処
理した。これにより、純チタン板表面に厚さ１．３μｍ
の陽極酸化皮膜が得られた。(Embodiment 5) In a mixed bath of 2% sulfuric acid and 1% sulfosalicylic acid, 10 g of titanium oxide fine particles (particle diameter: 7 nm, specific surface area: 300 m 2 / g) as a photocatalyst
And a pure titanium plate (10 cm × 10 c
m) was immersed, and this was subjected to anodizing treatment at DC 200 V for 5 minutes. As a result, the thickness of the pure titanium plate is 1.3 μm
Was obtained.
【００２８】得られた陽極酸化皮膜を１Ｌの反応容器中
に入れ、その容器中に一酸化窒素を注入して濃度を１ｐ
ｐｍとした後、ブラックライト（１ｍＷ／ｃｍ2）を１
時間照射した。照射後、反応容器中の一酸化窒素濃度
を、化学発光式窒素酸化物計により測定した。その結
果、一酸化窒素濃度は０．３ｐｐｍであり、７０％の一
酸化窒素が分解されていた。このことから、得られた陽
極酸化皮膜が光触媒活性を備えていることがわかる。The obtained anodized film is placed in a 1 L reaction vessel, and nitrogen monoxide is injected into the vessel to adjust the concentration to 1 p.
pm, the black light (1 mW / cm 2 )
Irradiated for hours. After irradiation, the concentration of nitric oxide in the reaction vessel was measured with a chemiluminescent nitrogen oxide meter. As a result, the concentration of nitric oxide was 0.3 ppm, and 70% of nitric oxide was decomposed. This indicates that the obtained anodized film has photocatalytic activity.
【００２９】（比較形態３）光触媒である酸化チタンを
添加せず、その他は実施形態５と同様に行った。そし
て、得られた陽極酸化皮膜による一酸化窒素分解量を実
施形態５と同様に測定したところ、一酸化窒素は分解さ
れていなかった。Comparative Example 3 The same operation as in Example 5 was performed except that titanium oxide as a photocatalyst was not added. Then, the amount of decomposed nitric oxide by the obtained anodic oxide film was measured in the same manner as in Embodiment 5, and it was found that nitric oxide was not decomposed.
【００３０】（実施形態６）実施形態５で得られた陽極
酸化皮膜を２００℃で４時間熱処理した。そして、熱処
理後の陽極酸化皮膜について、実施形態５と同様にして
一酸化窒素分解量を測定したところ、８５％の一酸化窒
素が分解されていた。このことから、熱処理により光触
媒活性が向上したことがわかる。(Embodiment 6) The anodic oxide film obtained in Embodiment 5 was heat-treated at 200 ° C for 4 hours. Then, when the amount of decomposed nitric oxide of the anodized film after the heat treatment was measured in the same manner as in Embodiment 5, 85% of nitric oxide was decomposed. This shows that the heat treatment improved the photocatalytic activity.
【００３１】（実施形態７）２％硫酸と１％スルホサリ
チル酸との混合浴１Ｌ中に、光触媒である酸化チタンの
微粒子（粒径７ｎｍ，比表面積３００ｍ2／ｇ）１０ｇ
と、光触媒活性を向上させる金属であるパラジウム微粒
子（粒径１５．５ｎｍ、比表面積１２６ｍ2／ｇ）０．
１ｇを含むパラジウムのコロイド溶液１０ｍｌとを添加
し、その浴中に純チタン板（１０ｃｍ×１０ｃｍ）を浸
漬し、これを直流２００Ｖで５分間陽極酸化処理した。
これにより、純チタン板表面に厚さ１．３μｍの陽極酸
化皮膜が得られた。(Embodiment 7) 10 g of titanium oxide fine particles (particle diameter: 7 nm, specific surface area: 300 m 2 / g) as a photocatalyst in 1 L of a mixed bath of 2% sulfuric acid and 1% sulfosalicylic acid.
And fine particles of palladium (a particle size of 15.5 nm, a specific surface area of 126 m 2 / g) which are metals for improving the photocatalytic activity.
10 ml of a palladium colloid solution containing 1 g was added, and a pure titanium plate (10 cm × 10 cm) was immersed in the bath, and this was subjected to anodizing treatment at 200 V DC for 5 minutes.
As a result, an anodic oxide film having a thickness of 1.3 μm was obtained on the surface of the pure titanium plate.
【００３２】得られた陽極酸化皮膜による一酸化窒素分
解量を実施形態５と同様にして測定したところ、９０％
の一酸化窒素が分解されていた。このことから、パラジ
ウムにより光触媒活性が向上したことがわかる。The amount of decomposed nitric oxide by the obtained anodic oxide film was measured in the same manner as in the fifth embodiment.
Nitric oxide had been decomposed. This indicates that palladium improved the photocatalytic activity.
【００３３】（実施形態８）実施形態７で得られた陽極
酸化皮膜を２００℃で４時間熱処理した。そして、熱処
理後の陽極酸化皮膜について、実施形態５と同様にして
一酸化窒素分解量を測定したところ、一酸化窒素は１０
０％分解されていた。このことから、熱処理により光触
媒活性が向上したことがわかる。Embodiment 8 The anodic oxide film obtained in Embodiment 7 was heat-treated at 200 ° C. for 4 hours. When the amount of decomposed nitric oxide was measured on the anodized film after the heat treatment in the same manner as in Embodiment 5, the amount of nitric oxide was 10%.
It had been decomposed by 0%. This shows that the heat treatment improved the photocatalytic activity.
【００３４】（実施形態９）パラジウムの代わりに白金
微粒子（粒径１８．１ｎｍ、比表面積１１１ｍ2／ｇ）
０．１ｇを含む白金のコロイド溶液１０ｍｌを用い、そ
の他は実施形態７と同様に行った。これにより、純チタ
ン板表面に厚さ１．４μｍの陽極酸化皮膜が得られた。
得られた陽極酸化皮膜による一酸化窒素分解量を実施形
態５と同様にして測定したところ、８５％の一酸化窒素
が分解されていた。このことから、白金により光触媒活
性が向上したことがわかる。(Embodiment 9) Platinum fine particles (particle diameter 18.1 nm, specific surface area 111 m 2 / g) instead of palladium
The procedure was the same as in Embodiment 7, except that 10 ml of a colloidal platinum solution containing 0.1 g was used. As a result, an anodized film having a thickness of 1.4 μm was obtained on the surface of the pure titanium plate.
When the amount of nitrogen monoxide decomposed by the obtained anodized film was measured in the same manner as in Embodiment 5, 85% of the nitrogen monoxide was decomposed. This indicates that the photocatalytic activity was improved by platinum.
【００３５】（実施形態１０）実施形態９で得られた陽
極酸化皮膜を９００℃で４５分間熱処理した。そして、
熱処理後の陽極酸化皮膜について、実施形態５と同様に
して一酸化窒素分解量を測定したところ、一酸化窒素は
９５％分解されていた。このことから、熱処理により光
触媒活性が向上したことがわかる。(Embodiment 10) The anodic oxide film obtained in Embodiment 9 was heat-treated at 900 ° C for 45 minutes. And
When the amount of decomposed nitric oxide of the anodized film after the heat treatment was measured in the same manner as in Embodiment 5, it was found that nitrogen monoxide was decomposed by 95%. This shows that the heat treatment improved the photocatalytic activity.
【００３６】[0036]
【発明の効果】請求項１記載の発明によれば、次のよう
な効果を発揮できる。 陽極酸化皮膜中に、光触媒活性を有する微粒子を分散
状態で保持させることができるので、陽極酸化皮膜に光
触媒活性を持たせることができる。従って、光触媒活性
を有するチタン材を得ることができる。According to the first aspect of the present invention, the following effects can be obtained. Since fine particles having photocatalytic activity can be held in a dispersed state in the anodic oxide film, the anodic oxide film can have photocatalytic activity. Therefore, a titanium material having photocatalytic activity can be obtained.
【００３７】光触媒活性を有する微粒子を添加した電
解浴にチタン材を浸漬して陽極酸化処理するだけである
ので、簡単な装置で、簡易に行うことができ、しかも、
大規模化も容易である。Since the titanium material is simply immersed in an electrolytic bath containing fine particles having photocatalytic activity and subjected to anodizing treatment, it can be easily carried out with a simple apparatus.
Large scale is also easy.
【００３８】陽極酸化皮膜の凹凸により表面積が増す
ので、光触媒活性を効率良く発揮できる。Since the surface area is increased by the unevenness of the anodic oxide film, the photocatalytic activity can be efficiently exhibited.
【００３９】一般に、光触媒活性を有する化合物は微
粒子であるので、それをそのまま用いることができ、従
って、その取り扱いが容易である。また、光触媒活性を
有する化合物として種々のものを容易に用いることがで
きる。In general, since the compound having photocatalytic activity is fine particles, it can be used as it is, and therefore, its handling is easy. In addition, various compounds having photocatalytic activity can be easily used.
【００４０】陽極酸化皮膜は耐久性が良く、母材であ
るチタン材に対する密着性も良いので、チタン材は陽極
酸化皮膜による光触媒活性を安定して発揮できる。ま
た、該チタン材は、強度が問われる建築材としても良好
に用いることができる。Since the anodic oxide film has good durability and good adhesion to the titanium material as the base material, the titanium material can stably exhibit the photocatalytic activity by the anodic oxide film. Further, the titanium material can be favorably used as a building material for which strength is required.
【００４１】電解浴中で処理するので、複雑な形状の
チタン材であっても均一に処理できる。Since the treatment is performed in the electrolytic bath, even a titanium material having a complicated shape can be treated uniformly.
【００４２】陽極酸化皮膜自身も僅かながら光触媒活
性を呈するものであるので、光触媒活性を有する微粒子
の光触媒作用が陽極酸化皮膜自身によって阻害されるこ
とはなく、従って、光触媒活性の劣化を防止できる。Since the anodic oxide film itself exhibits a slight amount of photocatalytic activity, the photocatalytic action of the fine particles having photocatalytic activity is not hindered by the anodic oxide film itself, so that deterioration of the photocatalytic activity can be prevented.
【００４３】請求項２記載の発明によれば、熱処理によ
り、陽極酸化皮膜中の金属チタン成分を酸化チタンにす
ることができ、また、陽極酸化皮膜中の電解浴の液成分
を酸化除去でき、更に、陽極酸化皮膜の結晶構造を光触
媒活性を呈するアナターゼ型とすることができるので、
陽極酸化皮膜による光触媒作用を円滑に発揮させること
ができ、従って、陽極酸化皮膜による光触媒活性を向上
させることができる。According to the second aspect of the present invention, the metal titanium component in the anodic oxide film can be changed to titanium oxide by heat treatment, and the liquid component of the electrolytic bath in the anodic oxide film can be removed by oxidation. Furthermore, since the crystal structure of the anodized film can be an anatase type exhibiting photocatalytic activity,
The photocatalytic action of the anodic oxide film can be smoothly exhibited, and therefore, the photocatalytic activity of the anodic oxide film can be improved.
【００４４】請求項３記載の発明によれば、光触媒活性
を向上させる金属により、陽極酸化皮膜自身及び該金属
に接触する光触媒活性を有する微粒子の、光触媒活性を
向上させることができる。According to the third aspect of the present invention, the photocatalytic activity of the anodic oxide film itself and the fine particles having photocatalytic activity in contact with the metal can be improved by the metal that improves the photocatalytic activity.
Claims (3)
１種を含み、且つ光触媒活性を有する微粒子が添加され
ている電解浴中に、チタン材を浸漬し、火花放電発生電
圧以上の電圧を印加して陽極酸化処理を行うことを特徴
とする光触媒活性を有するチタン材の製造方法。1. A titanium material is immersed in an electrolytic bath containing at least one of an inorganic acid and an organic acid and containing fine particles having photocatalytic activity, and a voltage higher than a spark discharge generating voltage is applied. And producing an titanium oxide having photocatalytic activity.
酸素雰囲気下、２００℃以上９００℃以下で熱処理する
請求項１記載の光触媒活性を有するチタン材の製造方
法。2. The method for producing a titanium material having photocatalytic activity according to claim 1, wherein the titanium material after the anodizing treatment is heat-treated at 200 ° C. or more and 900 ° C. or less in an air or oxygen atmosphere.
属の微粒子も添加しておく請求項１記載の光触媒活性を
有するチタン材の製造方法。3. The method for producing a titanium material having photocatalytic activity according to claim 1, wherein metal fine particles for improving photocatalytic activity are also added to the electrolytic bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9261606A JPH11100695A (en) | 1997-09-26 | 1997-09-26 | Production of titanium material having photocatalytic activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9261606A JPH11100695A (en) | 1997-09-26 | 1997-09-26 | Production of titanium material having photocatalytic activity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11100695A true JPH11100695A (en) | 1999-04-13 |
Family
ID=17364250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9261606A Pending JPH11100695A (en) | 1997-09-26 | 1997-09-26 | Production of titanium material having photocatalytic activity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11100695A (en) |
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|---|---|---|---|---|
| JP2000271493A (en) * | 1999-03-25 | 2000-10-03 | Takehisa Ito | Production of photocatalytic material |
| JP2002038298A (en) * | 2000-07-25 | 2002-02-06 | Daiwa House Ind Co Ltd | Method for forming anodic oxide film on titanium for photocatalyst |
| JP2005103504A (en) * | 2003-10-02 | 2005-04-21 | Denka Himaku Kogyo Kk | Magnesium metallic material having photocatalytically active surface and its manufacturing method |
| JP2006116398A (en) * | 2004-10-20 | 2006-05-11 | Norio Shimizu | Method for producing photocatalyst |
| JP2006239483A (en) * | 2005-02-28 | 2006-09-14 | Central Res Inst Of Electric Power Ind | Material and member of apparatus |
| WO2007029602A1 (en) * | 2005-09-08 | 2007-03-15 | Kinki University | Bone substitute material, medical material containing the bone substitute material, and process for producing the bone substitute material |
| JP2007190528A (en) * | 2006-01-23 | 2007-08-02 | Doshisha | Metal particulate fixed photocatalyst substance and its production method |
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| KR100926126B1 (en) | 2008-05-15 | 2009-11-11 | 한국에너지기술연구원 | Method for preparing integral nanotube photocatalyst, apparatus and method for reducing hexavalent chrominum |
| WO2013144660A2 (en) * | 2012-03-30 | 2013-10-03 | Keronite International Limited | Photocatalyst |
| WO2013144660A3 (en) * | 2012-03-30 | 2013-12-12 | Keronite International Limited | Photocatalyst |
| US9492810B2 (en) | 2012-03-30 | 2016-11-15 | Keronite International Limited | Photocatalyst |
| GB2505025B (en) * | 2012-03-30 | 2019-07-17 | Atg R&D Ltd | Method for making assembly for photocatalytic treatment of water |
| CN105121014A (en) * | 2013-04-08 | 2015-12-02 | 日立金属株式会社 | Photocatalyst and production method for same |
| JP2015039674A (en) * | 2013-08-22 | 2015-03-02 | シャープ株式会社 | Photocatalytic fiber structure, and method of producing photocatalytic fiber structure |
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