JP2000178783A - Galvanized steel sheet with exposed photocatalyst and its production - Google Patents
Galvanized steel sheet with exposed photocatalyst and its productionInfo
- Publication number
- JP2000178783A JP2000178783A JP10355708A JP35570898A JP2000178783A JP 2000178783 A JP2000178783 A JP 2000178783A JP 10355708 A JP10355708 A JP 10355708A JP 35570898 A JP35570898 A JP 35570898A JP 2000178783 A JP2000178783 A JP 2000178783A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- exposed
- photocatalyst
- tio
- powder
- 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.)
- Withdrawn
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 title abstract 3
- 239000008397 galvanized steel Substances 0.000 title abstract 3
- 239000000843 powder Substances 0.000 claims abstract description 37
- 238000007747 plating Methods 0.000 claims abstract description 34
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 23
- 239000010959 steel Substances 0.000 claims abstract description 23
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 102000035195 Peptidases Human genes 0.000 claims description 4
- 108091005804 Peptidases Proteins 0.000 claims description 4
- 235000019833 protease Nutrition 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 8
- -1 nitrate compound Chemical class 0.000 description 6
- 239000000809 air pollutant Substances 0.000 description 5
- 231100001243 air pollutant Toxicity 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 102100033040 Carbonic anhydrase 12 Human genes 0.000 description 1
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 229910000532 Deoxidized steel Inorganic materials 0.000 description 1
- 101000867855 Homo sapiens Carbonic anhydrase 12 Proteins 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000021 stimulant Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 210000004127 vitreous body Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光触媒のアナタ−ゼ型
ＴｉＯ2粒子をＺｎ系めっき層表面に露出した状態で担
持しているＺｎ系めっき鋼板およびその製造方法に関す
る。The present invention relates to a photocatalytic anatase - related Zn alloy coated steel sheet and a manufacturing method thereof are supported in a state where the zero-type TiO 2 particles were exposed to the Zn-based plating layer surface.
【０００２】[0002]
【従来技術】ＴｉＯ2は、バンドギャップ以上のエネル
ギ−を有する波長の光を照射すると、光励起により励起
電子と正孔を生じ、その正孔が強い酸化力を有するの
で、従来より光触媒として用いられている。とくに、こ
の光触媒作用はアナタ−ゼ型のものが大きく、その粉末
は従来よりＮＯxやＳＯxなどのような大気汚染物質の分
解やアセトアルデヒドなどのような刺激物質の分解に使
用されている。 2. Description of the Related Art When TiO 2 is irradiated with light having a wavelength having an energy greater than the band gap, excited electrons and holes are generated by photoexcitation, and the holes have a strong oxidizing power. ing. In particular, the photocatalytic action you - the large ones peptidase type, the powder is used in the decomposition of stimulants such as decomposition and acetaldehyde air pollutants such as conventionally NO x and SO x.
【０００３】ＴｉＯ2粉末を光触媒として使用する場
合、基体に担持させる必要があるが、その担持は（Ａ）
粉末を合成樹脂と混合して、シ−ト状に成形する方法、
（Ｂ）粉末をセメントと混練して、基板上に塗布し、硬
化させる方法、（Ｃ）粉末をアルコキシシランに添加し
て、ゾルゲル法により基板に塗布する方法などにより行
われていた。When TiO 2 powder is used as a photocatalyst, it must be supported on a substrate.
A method in which powder is mixed with a synthetic resin to form a sheet;
(B) a method in which the powder is kneaded with cement, applied on a substrate and cured, and (C) a method in which the powder is added to alkoxysilane and applied to the substrate by a sol-gel method, and the like.
【０００４】しかし、これらの方法で担持させた材料
は、表面に存在するものでも、ＴｉＯ 2粉末が担体の樹
脂やセメントなどにより被覆され、露出して大気汚染物
質と接触するものの割合が少ないため、大気汚染物質の
ような分解対象成分とあまり接触しない。また、使用Ｔ
ｉＯ2粉末のうち、光触媒として作用するのは表面の部
分に存在するものだけで、内部に存在するものは光触媒
として作用しないので、光触媒の無駄が多い。さらに、
材料の加工性を高めるために、担体に樹脂のような加工
性の良好なものを用いると、担持力が弱くなり、逆に、
ゾルゲル法により形成されるガラス質体のように担持力
の大きな担体にすると、加工性が低下し、加工性と担持
力の調和した材料が存在しなかった。However, the materials supported by these methods
Is TiO 2 even if it exists on the surface TwoPowder is the carrier tree
Covered with grease or cement, exposed to air pollutants
Low rate of contact with air quality
Does not come into contact with such components to be decomposed. Also, use T
iOTwoOf the powder, the part on the surface that acts as a photocatalyst
Only those that exist in the minute, those that exist inside are photocatalysts
Because it does not act as a photocatalyst, there is much waste of photocatalyst. further,
To improve the workability of the material, the carrier is processed like resin.
If a material having good properties is used, the supporting force will be weak, and conversely,
Carrying force like vitreous body formed by sol-gel method
If the carrier has a large size, the processability will decrease,
There was no harmonious material.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、多くのＴｉ
Ｏ2光触媒が表面に露出した状態で強固に担持され、し
かも、加工性を有する材料およびその製造方法を提供す
るものである。SUMMARY OF THE INVENTION The present invention relates to a method for producing a large number of Ti.
An object of the present invention is to provide a material having an O 2 photocatalyst firmly supported in a state of being exposed on the surface and having processability, and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明の第１発明は、鋼
板の表面にＺｎ系めっき層が形成され、そのＺｎ系めっ
き層の表面に光触媒のアナタ−ゼ型ＴｉＯ2の粒子が露
出した状態に担持されていて、露出ＴｉＯ2粒子がＺｎ
系めっき層全表面の３０％以上を占めていることを特徴
とする光触媒露出Ｚｎ系めっき鋼板であり、第２発明は
塩化物系電気Ｚｎめっき浴に硝酸化合物とアナタ−ゼ型
ＴｉＯ2粉末とを添加して、硝酸イオン濃度を１.２５×
１０-3ｍｏｌ／Ｌ〜２.５×１０-2ｍｏｌ／Ｌにした状
態で鋼板の表面に電気Ｚｎ系めっきを施すことを特徴と
する光触媒露出Ｚｎ系めっき鋼板の製造方法である。According to a first aspect the invention of the present invention, Zn-based plating layer is formed on the surface of the steel sheet, ANATA photocatalyst on the surface of the Zn-based plating layer - peptidase type TiO 2 particles are exposed State and the exposed TiO 2 particles are Zn
A photocatalyst exposed Zn-plated steel sheet, characterized in that account for more than 30 percent of the system plating layer entire surface, the second invention is a nitrate compound in chloride-based electro Zn plating bath anatase - and peptidase type TiO 2 powder And add nitrate ion concentration to 1.25 ×
A method for producing a photocatalyst-exposed Zn-based plated steel sheet, characterized in that a surface of a steel sheet is subjected to electro-Zn plating in a state of 10 −3 mol / L to 2.5 × 10 −2 mol / L.
【０００７】[0007]
【作用】一般に、光触媒を担体に担持させて、大気汚染
物質などを効率的に浄化させるには、光触媒が大気汚染
物質と接触する比表面積を大きくする必要がある。ま
た、光触媒使用量を少なくして、担持光触媒の大部分が
光触媒として作用するようにするには、光触媒が担体表
面に集中するように担持させる必要がある。さらに、担
持させた光触媒が長期間浄化作用を発揮するためには担
体が光触媒を強固に長期間保持できるものにする必要が
ある。また、光触媒を担持させた大気浄化材料は建築部
材や道路関連資材などに加工して、太陽光線により光励
起されるので、加工性の良好なものであることが必要で
ある。In general, in order for a photocatalyst to be carried on a carrier to efficiently purify air pollutants, it is necessary to increase the specific surface area of the photocatalyst in contact with the air pollutants. Further, in order to reduce the amount of the photocatalyst to be used and to make most of the supported photocatalyst act as a photocatalyst, the photocatalyst needs to be supported so as to be concentrated on the surface of the carrier. Furthermore, in order for the supported photocatalyst to exhibit a purifying action for a long period of time, it is necessary that the carrier can firmly hold the photocatalyst for a long period of time. In addition, the air purification material supporting the photocatalyst is processed into a building material or a road-related material and is light-excited by sunlight, so that it is necessary to have good workability.
【０００８】本発明者らは、上記条件を満足させる担
体、担持方法を検討した結果、Ｚｎ系めっき鋼板表面に
アナタ−ゼ型ＴｉＯ2粉末をそれがめっき層より露出す
るように担持させればよいことを見いだした。そして、
Ｚｎ系めっき鋼板にアナタ−ゼ型ＴｉＯ2粉末が露出す
るように担持させるには、塩化物系電気Ｚｎめっき浴に
硝酸化合物とアナタ−ゼ型ＴｉＯ2粉末とを添加して、
硝酸イオン濃度を１.２５×１０-3ｍｏｌ／Ｌ〜２.５×
１０-2ｍｏｌ／Ｌ、好ましくは２.５×１０-3ｍｏｌ／
Ｌ〜１.８８×１０-2ｍｏｌ／Ｌにすると、ＴｉＯ2粉末
がＺｎ系めっき層表面に効率よく析出し、大部分が露出
することを見いだしたのである。Ｚｎ系めっき鋼板にＴ
ｉＯ2粉末がめっき層表面より露出するように担持させ
ると、担体は加工性のよいＺｎ系めっき鋼板であるの
で、加工性が良好で、建築部材や道路関連資材などに容
易に加工できる。また、製造の際には、ＴｉＯ2粉末は
Ｚｎ粒子と同時に共析するので、Ｚｎ系めっき層表面に
も露出させることができる。The present inventors have studied a carrier and a supporting method satisfying the above conditions. As a result, if the anatase-type TiO 2 powder is supported on the surface of the Zn-based plated steel sheet so that it is exposed from the plating layer, I found something good. And
In order to support the Zn-based plated steel sheet so that the anatase-type TiO 2 powder is exposed, a nitrate compound and an anatase-type TiO 2 powder are added to a chloride-based electric Zn plating bath,
The nitrate ion concentration is 1.25 × 10 −3 mol / L to 2.5 ×
10 −2 mol / L, preferably 2.5 × 10 −3 mol / L
It was found that when L was set to 1.88 × 10 −2 mol / L, the TiO 2 powder was efficiently deposited on the surface of the Zn-based plating layer, and most of the TiO 2 powder was exposed. T for Zn-based plated steel sheet
When the iO 2 powder is supported so as to be exposed from the surface of the plating layer, the support is a Zn-based plated steel sheet having good workability, so that the workability is good, and the work can be easily processed into building members and road-related materials. In the production, the TiO 2 powder is co-deposited with the Zn particles, so that it can be exposed to the surface of the Zn-based plating layer.
【０００９】ここで、製造の際に用いる塩化物系電気Ｚ
ｎめっき浴とは、ＺｎＣｌ2を主成分とするもので、酸
性浴、中性浴のいずれでもよい。添加する硝酸化合物は
硝酸イオン濃度が１.２５×１０-3ｍｏｌ／Ｌより低い
と、ＴｉＯ2粉末の析出が劣り、Ｚｎ系めっき層全表面
に占めるＴｉＯ2粉末の露出面積合計が３０％以上にな
らない。一方、硝酸イオン濃度が２.５×１０-2ｍｏｌ
／Ｌより高くなると、Ｚｎの析出が少なくなり、Ｚｎ系
めっき層の形成が阻害される。添加する硝酸化合物は水
溶性のものであればとくに制限はなく、例えば、硝酸ア
ンモニウム、硝酸カリウム、硝酸カルシウム、硝酸銀、
硝酸ジルコニウム、硝酸鉄、硝酸銅、硝酸ナトリウム、
硝酸鉛、硝酸ニッケル、硝酸マンガンなどを使用すれば
よい。Here, chloride-based electricity Z used in the production
The n-plating bath contains ZnCl 2 as a main component, and may be an acidic bath or a neutral bath. If the nitrate compound to be added has a nitrate ion concentration lower than 1.25 × 10 −3 mol / L, the deposition of the TiO 2 powder is inferior, and the total exposed area of the TiO 2 powder on the entire surface of the Zn-based plating layer is 30% or more. do not become. On the other hand, the nitrate ion concentration is 2.5 × 10 -2 mol
If it is higher than / L, the precipitation of Zn is reduced, and the formation of a Zn-based plating layer is hindered. The nitric acid compound to be added is not particularly limited as long as it is a water-soluble one.For example, ammonium nitrate, potassium nitrate, calcium nitrate, silver nitrate,
Zirconium nitrate, iron nitrate, copper nitrate, sodium nitrate,
Lead nitrate, nickel nitrate, manganese nitrate or the like may be used.
【００１０】ＴｉＯ2粉末は、粒径が平均粒径で０.００
５μｍより小さいと、浴中で凝集して、析出しにくくな
り、０.１μｍより大きいと、比表面積が小さくなり、
光触媒作用が低下するので、０.００５〜０.１μｍにす
るのが好ましい。また、ＴｉＯ2粉末の濃度は２５ｇ／
Ｌより低いと、析出ＴｉＯ2粉末のうち、露出している
ものの面積合計が少なく、Ｚｎ系めっき層全表面の３０
％以上にするのが困難になり、２００ｇ／Ｌより高くし
ても、析出ＴｉＯ2粉末の露出面積合計は２００ｇ／Ｌ
の場合とほとんど多くならず、しかも、めっき浴の撹拌
も困難になるので、２５〜２００ｇ／Ｌにするのが好ま
しい。なお、Ｚｎ系めっき層全表面に占めるＴｉＯ2粉
末の露出面積合計はめっき鋼板表面を顕微鏡などの拡大
具で目視観察して、露出しているＴｉＯ2粉末の面積を
合計する。The TiO 2 powder has an average particle diameter of 0.00.
If it is less than 5 μm, it will be difficult to precipitate in the bath, and if it is more than 0.1 μm, the specific surface area will be small,
Since the photocatalytic action is reduced, the thickness is preferably set to 0.005 to 0.1 μm. The concentration of the TiO 2 powder was 25 g /
If it is lower than L, the total area of the exposed TiO 2 powder is small, and the total surface area of the Zn-based plating layer is 30%.
% Or more, and even if it is higher than 200 g / L, the total exposed area of the precipitated TiO 2 powder is 200 g / L.
And the stirring of the plating bath becomes difficult, so that the amount is preferably 25 to 200 g / L. The total exposed area of the TiO 2 powder occupying the entire surface of the Zn-based plating layer is obtained by visually observing the surface of the plated steel sheet with a magnifying tool such as a microscope, and summing the area of the exposed TiO 2 powder.
【００１１】ＴｉＯ2粉末は、Ｚｎ系めっき層の内部に
も分散されているが、この内部に分散されたＴｉＯ2粉
末は光触媒作用を発揮しない。しかし、めっき層はＴｉ
Ｏ2粉末含有により耐食性が向上するため、耐久性が長
くなる。The TiO 2 powder is also dispersed inside the Zn-based plating layer, but the TiO 2 powder dispersed inside does not exhibit a photocatalytic action. However, the plating layer is Ti
Since the corrosion resistance is improved by the inclusion of the O 2 powder, the durability is increased.
【００１２】[0012]
【実施例】実施例１ 板厚０.８ｍｍの鋼板（弱脱酸鋼、長さ７５ｍｍ、幅２
５ｍｍ）をホメザリン浴中で電解脱脂した後、濃度２０
％の硫酸水溶液で酸洗して、下記組成の酸性塩化物浴で
陽極をＺｎ板にして、電気Ｚｎめっきを施し、試験片を
作製した。 成分 濃度 ＺｎＣｌ2 １２０ｇ／Ｌ ＮＨ4Ｃｌ １８０ｇ／Ｌ ＴｉＯ2粉末 ７５ｇ／Ｌ ＮＨ4ＮＯ3 ０〜２.５ｇ／Ｌ 浴温 ３０℃ 電流密度 ４Ａ／ｄｍ2 電解時間 ７２０秒 その後試験片表面を走査型電子顕微鏡で観察して、５０
００倍に拡大して画像より露出しているＴｉＯ2粉末の
合計面積がめっき層全表面積に占める割合を算出した。
この結果を表１に示す。また、表１のＮｏ.４の試験片
めっき層深さをグロ−放電分光分析法（ＧＤＳ）で分析
したところ、ＴｉＯ2粉末の濃度は図１に示すようにＺ
ｎめっき層の内部より表面で最大になっていた。EXAMPLES Example 1 A steel plate having a thickness of 0.8 mm (weakly deoxidized steel, length 75 mm, width 2)
5 mm) in a homezalin bath after electrolytic defatting,
The sample was pickled with an aqueous solution of sulfuric acid at 10%, and the anode was made into a Zn plate in an acidic chloride bath having the following composition, and electro-Zn plating was performed to prepare a test piece. Component concentration ZnCl 2 120 g / L NH 4 Cl 180 g / L TiO 2 powder 75 g / L NH 4 NO 3 0-2.5 g / L Bath temperature 30 ° C. Current density 4 A / dm 2 Electrolysis time 720 seconds Then scan the specimen surface Observed with a scanning electron microscope, 50
The ratio of the total area of the TiO 2 powder exposed from the image magnified 00 times to the total surface area of the plating layer was calculated.
Table 1 shows the results. Further, when the test piece plating layer depth of No. 4 in Table 1 was analyzed by glow-discharge spectroscopy (GDS), the concentration of the TiO 2 powder was Z as shown in FIG.
It was maximum on the surface from the inside of the n-plated layer.
【００１３】[0013]
【表１】 [Table 1]
【００１４】実施例２ 実施例１のＮｏ.５において、ＴｉＯ2粉末濃度を１０〜
１５０ｇ／Ｌに変更して、めっき層全表面積に占めるＴ
ｉＯ2粉末の合計面積の割合を算出した。この結果を表
２に示す。また、ＴｉＯ2粉末合計面積割合の算出後、
一部の各試験片を個々に容量１Ｌの密閉容器に入れ、次
に示す要領の順序でアセトアルデヒド分解速度定数（Ｋ
ｔ）を算出した。その値を表３に示す。 （１）容器を１３３.３Ｐａまで減圧して、アセトアル
デヒド濃度が５００ｐｐｍの標準ガスを３９,９９０Ｐ
ａになるまで導入する。 （２）常圧になるまで空気を導入した。 （３）容器内のアセトアルデヒドが均一になった頃を見
計らってキセノンランプを所定時間照射する。 （４）次式によりアセトアルデヒド分解速度定数（Ｋ
ｔ）を算出する。 Ｋｔ＝Ｉｎ（Ｃ０／Ｃｔ） Ｃ０； キセノンランプの照射前のアセトアルデヒド濃
度 Ｃｔ； キセノンランプの照射ｔ分後のアセトアルデヒ
ド濃度 Ｋ ； 速度定数 ｔ ； キセノンランプ照射時間Example 2 In Example No. 5, the TiO 2 powder concentration was changed from 10 to
Changed to 150 g / L, T
The ratio of the total area of the iO 2 powder was calculated. Table 2 shows the results. After calculating the total area ratio of the TiO 2 powder,
A part of each test piece is individually placed in a closed container having a capacity of 1 L, and the acetaldehyde decomposition rate constant (K
t) was calculated. Table 3 shows the values. (1) The pressure of the container was reduced to 133.3 Pa, and a standard gas having an acetaldehyde concentration of 500 ppm was supplied to 39,990 P
Introduce until a. (2) Air was introduced until normal pressure was reached. (3) The xenon lamp is irradiated for a predetermined time when the acetaldehyde in the container becomes uniform. (4) Acetaldehyde decomposition rate constant (K
Calculate t). Kt = In (C0 / Ct) C0; acetaldehyde concentration before irradiation with xenon lamp Ct; acetaldehyde concentration after t minutes from irradiation with xenon lamp K; rate constant t; xenon lamp irradiation time
【００１５】[0015]
【表２】 [Table 2]
【００１６】[0016]
【表３】 （注）比較例１２はめっき浴に硝酸イオンを添加せずに
電気めっきしたものである。[Table 3] (Note) In Comparative Example 12, electroplating was performed without adding nitrate ions to the plating bath.
【００１７】[0017]
【発明の効果】以上のように、本発明のＺｎ系めっき鋼
板は、Ｚｎ系めっき鋼板の表面に光触媒のＴｉＯ2がＺ
ｎ系めっき層全表面の３０％以上を占めるように露出し
た状態で担持されているので、大気汚染物質のような分
解対象成分との接触が良好である。また、表面にＴｉＯ
2粉末が多量に露出したＺｎ系めっき鋼板は塩化物系電
気Ｚｎめっき浴に硝酸化合物とＴｉＯ2粉末とを添加す
れば製造できるので、製造は容易である。As described above, in the Zn-based plated steel sheet of the present invention, the surface of the Zn-based plated steel sheet has TiO 2 of photocatalyst on the surface thereof.
Since it is supported in an exposed state so as to occupy 30% or more of the entire surface of the n-type plating layer, good contact with components to be decomposed such as air pollutants is obtained. In addition, TiO
(2) A Zn-based plated steel sheet in which a large amount of powder is exposed can be manufactured by adding a nitric acid compound and TiO 2 powder to a chloride-based electro-Zn plating bath, so that the manufacture is easy.
【図１】実施例で製造した本発明のＺｎ系めっき鋼板の
めっき層深さ方向の元素分布を示すものである。FIG. 1 shows an element distribution in a plating layer depth direction of a Zn-based plated steel sheet of the present invention manufactured in an example.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G069 AA03 AA08 AA12 BA04A BA04B BA17 BA36A BA48A BB02A BB02B BB12C BC35A BC35B CA10 CA12 CA13 CA17 EA07 EB15Y EB18X EB18Y EC22X EC29 FA05 FB06 FB11 FC04 FC08 4K023 AA15 BA08 CA09 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G069 AA03 AA08 AA12 BA04A BA04B BA17 BA36A BA48A BB02A BB02B BB12C BC35A BC35B CA10 CA12 CA13 CA17 EA07 EB15Y EB18X EB18Y EC22X EC29 FA05 FB06 CA03 FC04 FC09 FC04
Claims (4)
れ、そのＺｎ系めっき層の表面に光触媒のアナタ−ゼ型
ＴｉＯ2の粒子が露出した状態に担持されていて、露出
ＴｉＯ2粒子がＺｎ系めっき層全表面の３０％以上を占
めていることを特徴とする光触媒露出Ｚｎ系めっき鋼
板。1. A Zn-based plating layer on the surface of the steel sheet is formed, ANATA photocatalyst on the surface of the Zn-based plating layer - by peptidase type TiO 2 particles are supported on an exposed state, exposed TiO 2 particles A photocatalyst exposed Zn-based plated steel sheet occupying 30% or more of the entire surface of the Zn-based plated layer.
も分散されていることを特徴とする請求項１に記載の光
触媒露出Ｚｎ系めっき鋼板。2. The photocatalyst-exposed Zn-based plated steel sheet according to claim 1, wherein the TiO 2 particles are also dispersed inside the Zn-based plating layer.
物とアナタ−ゼ型ＴｉＯ2粉末とを添加して、硝酸イオ
ン濃度を１.２５×１０-3ｍｏｌ／Ｌ〜２.５×１０-2ｍ
ｏｌ／Ｌにした状態で鋼板の表面に電気Ｚｎ系めっきを
施すことを特徴とする光触媒露出Ｚｎ系めっき鋼板の製
造方法。3. A nitrate compound chloride-based electro Zn plating bath with you - the addition of a zero-type TiO 2 powder, a nitrate ion concentration 1.25 × 10 -3 mol / L~2.5 × 10 - 2 m
A method for producing a photocatalyst-exposed Zn-based plated steel sheet, wherein an electro-Zn-based plating is applied to the surface of the steel sheet in a state of ol / L.
０.１μｍ、濃度を２５〜２００ｇ／Ｌにすることを特
徴とする請求項３に記載の光触媒露出Ｚｎ系めっき鋼板
の製造方法。4. The TiO 2 powder has an average particle diameter of 0.005 to 0.005.
The method for producing a photocatalyst-exposed Zn-based plated steel sheet according to claim 3, wherein the concentration is 0.1 µm and the concentration is 25 to 200 g / L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10355708A JP2000178783A (en) | 1998-12-15 | 1998-12-15 | Galvanized steel sheet with exposed photocatalyst and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10355708A JP2000178783A (en) | 1998-12-15 | 1998-12-15 | Galvanized steel sheet with exposed photocatalyst and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000178783A true JP2000178783A (en) | 2000-06-27 |
Family
ID=18445364
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10355708A Withdrawn JP2000178783A (en) | 1998-12-15 | 1998-12-15 | Galvanized steel sheet with exposed photocatalyst and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000178783A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005334827A (en) * | 2004-05-28 | 2005-12-08 | Mitsui Mining & Smelting Co Ltd | Composite element |
| US8673456B2 (en) | 2005-11-15 | 2014-03-18 | Meisei Industrial Company Limited | Composite plated film and laminated film |
-
1998
- 1998-12-15 JP JP10355708A patent/JP2000178783A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005334827A (en) * | 2004-05-28 | 2005-12-08 | Mitsui Mining & Smelting Co Ltd | Composite element |
| JP4524142B2 (en) * | 2004-05-28 | 2010-08-11 | 三井金属鉱業株式会社 | Composite element |
| US8673456B2 (en) | 2005-11-15 | 2014-03-18 | Meisei Industrial Company Limited | Composite plated film and laminated film |
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