Coating processes – With post-treatment of coating or coating material – Heating or drying
Reexamination Certificate
2003-04-30
2004-10-12
Barr, Michael (Department: 1762)
Coating processes
With post-treatment of coating or coating material
Heating or drying
C427S376100, C427S430100, C427S443200
Reexamination Certificate
active
06803077
ABSTRACT:
CROSS-REFERENCE TO RELATED APPLICATIONS
Priority is claimed from Chinese application Serial No. CN02119304.5 filed Apr. 30, 2002. The entire specification and all the claims of this application are hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to a method for preparing mesoporous TiO
2
thin films with high photocatalytic and antibacterial activities, and to use of the mesoporous TiO
2
thin films as described in sterilizing and purifying seawater, tap water and water coming from other sources.
TECHNICAL BACKGROUND OF THE INVENTION
In the food industry and medical field, sterilization is always an important issue. Bacteria and viruses not only come from piscinas, kitchens and operation rooms of the hospital, but also can be derived from many other places. Once they adapt themselves the environment, they will propagate in a significantly vital speed. Recently, many kinds of bacteria such as
E
-
coli,
comma bacillus, and protoblast with viruses have been found in the fish tank water (for live seafood) of some restaurants in Hong Kong. This kind of contamination is harmful to human health.
A solution for this problem is to use the TiO
2
photocatalysis technology. However, the application of powdered TiO
2
as a photocatalyst for killing bacteria and viruses has the drawback of post-separation in a slurry system after photoreaction. Therefore, great efforts have been made to immobilize photocatalyst TiO
2
on different substrates such as glass, stainless steel and ceramic. Conventional methods for the preparation of a TiO
2
thin film on a substrate include chemical vapor deposition, magnetic spraying and pyrolysis. Although these methods can produce TiO
2
thin films on solid substrates, these TiO
2
films exhibit very poor photocatalytic and antibacterial activities because of poor crystallinity, small surface area and low anatase content.
The inventor has developed a method for preparing TiO
2
thin films by a modified sol-gel method. This method has many significant advantages including: 1) it does not require special apparatus; 2) it allows simultaneous doping of transition metal ions to TiO
2
; 3) it facilitates the optimization of TiO
2
phase constitution; 4) it can control the porous structure, specific surface area and surface hydroxyl groups using an organic template containing a polymer or a surfactant.
It is known that the photocatalytic and antibacterial activities of a TiO
2
thin film are significantly influenced by its phase constitution, specific surface area, porous size and distribution, and surface hydroxyl groups. Therefore, the invention is hereby provided.
SUMMARY OF THE INVENTION
The invention provides a simple and efficient method for preparing a mesoporous TiO
2
thin film with high photocatalytic and antibacterial activities. The TiO
2
thin film prepared by this method can be used to photo-catalytically kill bacteria and viruses in aqueous solutions. This invention is particularly useful for fish tank water disinfection.
Mesoporous materials have a pore size in the range of 2 to 50 nm. These materials can be in different forms such as spherical, thin film, block, and fiber. Materials with pore size of less than 2nm are called microporous materials, and large than 50 nm are classified as macroporous materials.
The method according to the invention for preparing a photocatalytic mesoporous TiO
2
thin film involves the utilization of a TiO
2
sol-gel solution prepared by controlled hydrolysis and condensation of a titanium alkoxide in the presence of a stabilizer. Specifically, the method of the present invention includes the following steps of: a) producing a TiO
2
sol-gel by hydrolysis-condensation of titanium alkoxide in a solution in the presence of a stabilizer; b) coating the TiO
2
sol-gel on a substrate; and c) thermally treating the TiO
2
gel-coated substrate at a temperature ranging from 400° C. to 800° C.
The stabilizer used in the invention acts as a complexing agent to react with titanium alkoxide. Suitable stabilizers include triethanolamine, diethanolamine, acetyl acetone, diethylene glycol, acetic acid, trifluoroacetic acid, and a combination of two or more of them. One or a combination of two stabilizers is preferable. The TiO
2
sol-gel solutions can effectively produce a TiO
2
thin film on a substrate even after being stored for more than two months.
Except for specific indication, the term of “titanium alkoxide(s)” used herein means titanic acid ester(s). In the invention, it is preferably one or more selected from titanium butoxide, titanium isopropoxide and titanium ethoxide, more preferably one or a combination of two compounds.
The molar ratio of the stabilizer and titanium alkoxide used in the invention may be 0.05-3:1, preferably 1-1.5:1. Molar concentration of the used titanium alkoxide in the solution may be 0.01-3M, preferably 0.3-1M.
In the invention, the titanium alkoxide solution may comprise one or more solvents such as ethanol, isopropanol and propanol, besides water, and isopropanol or propanol or a mixture of both is preferably used as the solvent.
Materials such as glass, quartz glass, borosilicate glass, soda-lime glass pre-coated with a SiO
2
film, stainless steel and ceramic can be used as substrates for the TiO
2
thin film coating.
In order to form desired mesoporous TiO
2
films, it is preferable to add a template during the preparation of the TiO
2
sol-gel to aid the formation of the desired mesoporous TiO
2
films. The template used in the invention may be certain polymers or surfactants.
A typical polymer used as a template in the invention is an amphipathic three-block copolymer such as polyoxyethylene ether (PEO)-polyoxypropenyl ether (PPO)-polyoxyethylene ether (PEO) ((HO)CH
2
CH
2
)x(CH
2
CH(CH
3
)Oy(CH
2
CH
2
O)zH, P123, product of Aldrich, USA) with an average molecular weight of 1,000-10,000. In the invention, P123 with an average molecular weight of 3,300-5,800 is preferable. The porous size and size distribution can be controlled by adjusting the molecular weight and the amount of the used polymer. In general, the amount of the polymer used as a template in the TiO
2
sol-gel solution may be 5-35% by weight, preferably 9-20% by weight.
Surfactants used as templates in the invention may include cetyltrimethyl ammonium bromide, cetyltrimethyl ammonium chloride, dodecyltrimethyl ammonium bromide, and a combination thereof. The amount added may preferably account for 10-15% by weight in the TiO
2
sol-gel solution.
TiO
2
thin films may be thermally treated at a temperature ranging a temperature from 400° C. to 800° C. for 0.5-4 hours. Preferably, the thin film is calcined at a temperature ranging from 500° C. to 700° C. for 1-2 hours.
According to the invention, the procedure for the formation of the TiO
2
sol-gel solution can be divided into the following three steps: 1) dissolving a titanium alkoxide in an organic solvent; 2) adding a stabilizer to the above solution with continuous agitation; and 3) controlling hydrolysis and condensation of the titanium alkoxide by adding an excess of water.
The invention also provides a mesoporous TiO
2
thin film having high photocatalytic and antibacterial activities prepared according to the method of the invention.
The invention still provides use of the mesoporous TiO
2
thin film described herein in sterilizing and purifying water of the fish tank, seawater, and tap water or water from other sources.
To produce a good affinity between the TiO
2
thin film and substrate, the surface of the substrate has to be pre-treated. The TiO
2
gel film is coated onto a substrate by a dip coating technique (1. R. Reisfeld and C. K. Jorgensen, 77 Structure and Bonding: Chemistry, Spectroscopy and Applications of Sol-Gel Glass, Springer-Verlag, 1992, Berlin, pp91-95; 2. C. I. Brinker and G. W. Scherer, Sol-Gel Science, Academic Press, 1990, San Diego, pp788). Generally, the withdrawal speed can be controlled at 1-6 mm/s. The TiO
2
gel film formed on a substrate is dried at around 100° C. for 10-60 mins, and then calcined a
Barr Michael
Insight Intellectual Property Limited
McAndrews Held & Malloy Ltd.
LandOfFree
Method for preparing mesoporous TiO2 thin films with high... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Method for preparing mesoporous TiO2 thin films with high..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Method for preparing mesoporous TiO2 thin films with high... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3286649