1 Anodized titanium sheets with high photocatalytic ... · © 2014 NIPPON STEEL & SUMITOMO METAL CORPORATION All Rights Reserved . Conclusions . 1) We newly developed anodized titanium

© 2014 NIPPON STEEL & SUMITOMO METAL CORPORATION All Rights Reserved.

Dr. Michio Kaneko Chief Researcher

Steel Research Laboratories Nippon Steel & Sumitomo Metal Corporation

Anodized titanium sheets with high photocatalytic activity under ultra-violet and visible light irradiation

1

1


Background of this Study

Self Cleaning

Antibacterial

Titanium Oxide ・*OH formation ・Superhydrophilicity

Air purification

Water purification

UV Irradiation Application of Titanium

oxides(●） needs binder.

Ｓｕｂｓｔｒａｔｅ

・Less photocatalytic activity

・Degradation of binder

Binder

2


Objective of this Study

・To develop Anodized Titanium Sheets with High Photocatalytic activity under UV or Visible light illumination.

Titanium Sheet

Target ⇒ Titanium Oxides Layer consisted of a), b), c)

a) Anatase type TiO2

b) Rough Surface

c) C, N Doping

3


Experimental Procedure (Material) 1)Sample:

CP titanium sheets with TiC in the surface layer.

2) Anodic Oxidation Condition:

Solution : 0.06M NH4NO3

Applied Voltage: 15V, 24V, 45V, 80V

Temperature : R.T.

3) Heat Treatment: 803K×3600 sec. in Air

4) Reference Sample: P25 “Nano-Titanium Oxide Powder” (Degussa Corp.)

Titanium

Titanium Sheet

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5

Experimental Procedure (Photocatalytic activity Tests) Test Method Test Condition Sample Size Light Source Control

15×25×ｔmm a) Black Light

15×25×ｔmm b)White LED

(2)Antifungal TestAccording to JIS R1705(Aspergillus nigerNBRC 105649)

50×50×ｔmm a) Black Light Glass Sheet

(3)Antivirus Test According to JIS R1705(Influenza A virus)

50×50×ｔmm a) Black Light Glass Sheet

(1) KI Mehod 0.1M KI Solution P-25 TiO2　Powder(Degussa Corp.)

KI Solution Anodized Ti sheet

P-25 TiO2 Powder

Adhesive Tape

*JIS: Japanese Industrial Standard

*JIS: Japanese Industrial Standard

Fig. Schematic Diagram of KI Method.


Experimental Procedure (Surface Analysis)

1)X-ray Diffraction measurement(XRD)

2)Scanning Electron Microscope(ＳＥＭ)

3)Glow Discharge Spectroscopy (GDS) Analysis

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Experimental Results: UV(Black Light Irradiation)

00.20.40.60.8

11.21.41.61.8

2

Blank(No

Sample)

15V 24V 45V 80V P25 Particle

Abs

orba

nce

at 2

87nm

Fig. Photocatalytic activity test results using 0.1M KI solution under black light irradiation..

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2I- + 2OH ⇒ I2 +2OH-

I2 + I- ⇒ I3- （Detected by Absorption spectrophotometer）


Fig. Antifungal Test Results (JIS R1705) after removing the glass sheets and the anodized titanium samples.

Black Light Irradiation with glass sheet

Black Light Irradiation with Anodized Ti sample (45V, 803K)

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*Average Spore Counts of Aspergillus Niger before and after test

(a) (b)

Before Irradiation Black Light Irradiation (Glass sheet)

Black Light Irradiation(Anodized Ti sample)

1.50E+04 1.20E+04 <10


Fig. Antivirus test results (JIS R1702, Influenza A virus )

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0100020003000400050006000700080009000

10000

Glass Sheet(Control)

Ti sheet(45V, 803K)

Undetectable

Infe

ctiv

ity ti

ter o

f viru

sInfluenza A virus

Black Light Irradiation


Fig. X-ray Diffraction of Anodized Titanium Sheets at 45V and Heat Treated.

Anatase TiO2

Rutile TiO2

Titanium

×:Anatase TiO2

× ×

△:Rutile TiO2

△

△

△ ×

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Fig. SEM Photographs of Anodized Ti Sample (45V, 803K).

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00.10.20.30.40.50.60.70.80.9

1

Blank(No Sample)

45V

Abs

orba

nce

at 2

87nm

Fig. Photoactivity Test Results in 0.1M KI Solution under White Color LED Irradiation

Heat treatment: 803K×3600sec.

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Visible Light Irradiation


Fig. GDS analysis of Ti sample anodized at 45V and heat treated.

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0

10

20

30

40

50

60

70

80

90

100

0 0.5 1 1.5 2

Conc

entr

atio

n (a

tom

ic％

）

Depth（μｍ）

C

N

O

Ti

Ti

O

CN


Conclusions 1) We newly developed anodized titanium sheets with high

photocatalytic activity under UV irradiation.

2) Formation of anatase type TiO2 is considered to be attributable to high photocatalytic activity.

3) The anodized Ti sheets showed photocatalytic under white color LED irradiation. Visible light response is considered to be attributable to doping of carbon and nitrogen in titanium oxides.

4) It is believed that it would open up a new field of titanium applications.

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Contact address, phone number and e-mail

Steel Research Laboratories, Nippon Steel and Sumitomo Metal Corporation, 20-1 Shintomi Futtsu 293-8511, Japan

Tel.:+81-439-80-3126; fax:+81-439-80-2752

[email protected]

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1 Anodized titanium sheets with high photocatalytic ... · © 2014 NIPPON STEEL & SUMITOMO METAL CORPORATION All Rights Reserved . Conclusions . 1) We newly developed anodized titanium