CN109437968A - A kind of stone slab and preparation method thereof loading multifunctional ecological film - Google Patents
A kind of stone slab and preparation method thereof loading multifunctional ecological film Download PDFInfo
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- CN109437968A CN109437968A CN201811540972.4A CN201811540972A CN109437968A CN 109437968 A CN109437968 A CN 109437968A CN 201811540972 A CN201811540972 A CN 201811540972A CN 109437968 A CN109437968 A CN 109437968A
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- stone slab
- multifunctional ecological
- film
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- organic titanium
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00025—Aspects relating to the protection of the health, e.g. materials containing special additives to afford skin protection
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2038—Resistance against physical degradation
- C04B2111/2061—Materials containing photocatalysts, e.g. TiO2, for avoiding staining by air pollutants or the like
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of stone slabs and preparation method thereof for loading multifunctional ecological film, are related to buildings decoration field of material technology.Production method of the invention is the following steps are included: plated film: after organic titanium solution evaporation, being vapor-deposited on plate；Roasting: heating roasts above-mentioned plate to get the stone slab of load multifunctional ecological film is arrived.The load multifunctional ecological diaphragm plate material that production method of the invention is prepared, energy responding to visible light, has photocatalytic activity, has the function of well to purify the visible light catalytics such as air, decontamination, sterilization and excellent weather resistance；The production method is simple, has significant economic and social benefit.
Description
Technical field
The present invention relates to buildings decoration field of material technology, more particularly to a kind of stone for loading multifunctional ecological film
Plate and preparation method thereof.
Background technique
With the fast development of architectural decoration, demand sustainable growth of the market to architectural decorative and fitting materials, building
Decorating and renovating material is in gold developing period.Stone material is a kind of common large decorating and renovating material, can be divided into natural stone and
Artificial stone.All the time, welcomed by the people due to the special decorative effect of stone material and extensive use.However, being natural
Stone material or inorganic artificial stone, itself all have certain defect, such as have a single function, detergency ability it is poor, shadow to a certain extent
Ring its popularization and use.
In recent years, with nano-TiO2It is widely used for the photocatalysis technology of catalyst in field of environmental improvement, light
Catalysis technique achieves tremendous development to the photocatalytic degradation aspect of the organic and inorganic pollutant in water and air, and people start
By nano-TiO2Plate is loaded to by various methods, makes it have photo-catalysis function, but due to traditional nano-TiO2Forbidden band
Wider width (3.2eV), is only capable of by ultraviolet excitation, cannot effectively utilize visible light or sunlight, photocatalytic activity and effect
Rate is lower.
Summary of the invention
Based on this, it is necessary to had a single function for existing plate, dirt-removing power it is poor, can not utilize visible light carry out photocatalysis
The problem of, a kind of production method of plate loading multifunctional ecological film is provided.
A kind of production method for the stone slab loading multifunctional ecological film, comprising the following steps:
1) it plated film: after organic titanium solution evaporation, is vapor-deposited on stone slab；
2) roast: heating roasts above-mentioned plate to get the stone slab of load multifunctional ecological film is arrived.
Above-mentioned production method, by plating more function on stone slab surface on organic titanium Evaporation precipitation into aqueous solution to stone slab
Energy ecological film, the carbon content of the titania-doped multifunctional ecological film of the carbon are 1%-10%, TiO2Content is 90%-99%,
The multifunctional ecological film absorbs threshold value and is reduced to 350nm, corresponding forbidden bandwidth since the doping of carbons substance generates impurity energy level
For 2.95eV, lower than traditional nano-TiO2Forbidden bandwidth 3.2eV, energy responding to visible light have photocatalytic activity, effectively degrade
Pollutant；Multifunctional ecological film is pure transparent, does not influence the glossiness, color and feel on stone slab surface, and and stone slab
Substrate associativity is good, has the function of well to purify the visible light catalytics such as air, decontamination, sterilization and excellent weather resistance；As
When indoor wall finishing material, to the volatile organic compounds such as indoor formaldehyde, benzene (volatile organic
Compounds, VOCs) gas have decompose and purification function；When as outdoor wall decorating and renovating material, can play sterilization and
The effect of sterilizing, while there are good decomposition and dirt-removing functions to the pollutant of adherency.In addition, the production method is simple, tool
There is significant economic and social benefit.
It further include in one of the embodiments, pre-treatment step before the plating steps, the pre-treatment step is will
Stone slab cleans drying；It further include post-processing step after the calcination steps, the post-processing step is the slabstone after roasting
Material cleans drying, and the stone slab of load multifunctional ecological film is obtained after cooling.
The plating steps carry out in atmosphere furnace in one of the embodiments, and organic titanium solution is put into atmosphere furnace
In, stone slab is placed on organic titanium superjacent, refills atmosphere gas, heat temperature raising；The heat temperature raising includes program
The rate of heating step and incubation step, described program heating is 2-5 DEG C/min, is kept the temperature after being warming up to 100-150 DEG C, the guarantor
The time of warm step is 1.5-2h.
In one of the embodiments, the atmosphere gas be air, nitrogen, oxygen, high pure nitrogen, in high-purity argon gas extremely
A kind of few gas.It is protected in atmosphere furnace full of atmosphere gas, the life to the ratio for forming carbon and titanium dioxide of the present invention
State film is most important.When atmosphere gas is mixed gas, using different air supply systems, gas flow range be 1 to
99mL/mim。
The heating rate in the calcination steps is 2-5 DEG C/min in one of the embodiments, is warming up to 300-500
DEG C, and cool down after maintaining this temperature 1.5-2h.It is roasted at such a temperature, is conducive to organic titanium and is deposited on stone slab surface,
And it is titania-doped that carbon is generated under the protection of atmosphere gas.
The stone slab is granite plates, marble slabs or inorganic artificial stone slab in one of the embodiments,.
The solute of organic titanium solution is tetraethyl titanate, titanium propanolate and butyl titanate in one of the embodiments,
One of or it is a variety of, not only can be used as titanium source but also can be used as carbon source, and can evaporate to form steaming at 200 DEG C or less
Vapour requires coating temperature lower.The solvent of organic titanium solution is dehydrated alcohol, propyl alcohol, butanol, polyethylene glycol and the third three
One of alcohol is a variety of.
The weight percent of organic titanium solute is 70%-95% in organic titanium solution in one of the embodiments,.
The weight percent of carbon is 1%-10%, TiO in the ecological film in one of the embodiments,2Weight hundred
Score is 90%-99%.
A kind of stone slab of the load multifunctional ecological film obtained by above-mentioned production method.
The stone slab of the load multifunctional ecological film, using common stone slab, by organic titanium Evaporation precipitation into aqueous solution in plate
Surface, forms multifunctional ecological film, and the carbon content of the titania-doped multifunctional ecological film of the carbon is 1%-10%, TiO2Content
For 90%-99%, which absorbs threshold value and is reduced to 350nm since the doping of carbons substance generates impurity energy level, right
The forbidden bandwidth answered is 2.95eV, lower than traditional nano-TiO2Forbidden bandwidth 3.2eV, energy responding to visible light, has photocatalysis
Activity, effective degradation of contaminant；Multifunctional ecological film is pure transparent, does not influence the glossiness, color and feel of plate surface, and
And it is good with plate substrate associativity, have the function of well to purify the visible light catalytics such as air, decontamination, sterilization and excellent weatherability
Energy；When as indoor wall finishing material, has to the volatile organic compounds gas such as indoor formaldehyde, benzene and decompose and purify
Function；When as outdoor wall decorating and renovating material, sterilization and sterilizing can be played the role of, while having to the pollutant of adherency
Good decomposition and dirt-removing functions.
Compared with prior art, the invention has the following advantages:
The production method of load multifunctional ecological film stone slab of the invention, by by organic titanium Evaporation precipitation into aqueous solution to plate
On material, multifunctional ecological film is plated in plate surface, the carbon content of the titania-doped multifunctional ecological film of the carbon is 1%-
10%, TiO2Content is 90%-99%, which absorbs threshold since the doping of carbons substance generates impurity energy level
Value is reduced to 350nm, and corresponding forbidden bandwidth is 2.95eV, lower than traditional nano-TiO2Forbidden bandwidth 3.2eV can be responded visible
Light has photocatalytic activity, effective degradation of contaminant；In addition, the production method is simple, there is significant economy and society effect
Benefit.
Multifunctional ecological film on load multifunctional ecological film stone slab of the invention is pure transparent, does not influence plate surface
Glossiness, color and feel, and it is good with plate substrate associativity, there are the visible lights such as good purification air, decontamination, sterilization
Catalysis and excellent weather resistance；When as indoor wall finishing material, to volatile organics such as indoor formaldehyde, benzene
Closing object gas has decomposition and purification function；When as outdoor wall decorating and renovating material, sterilization and sterilizing can be played the role of,
There are good decomposition and dirt-removing functions to the pollutant of adherency simultaneously.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.But the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes
It is more thorough and comprehensive to the understanding of the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
Embodiment 1
A kind of production method for the stone slab loading multifunctional ecological film, steps are as follows:
S1, pre-treatment: marble slabs are cleaned up, and are removed the residues such as surface dirt, are put into drying box, 100
DEG C drying 80min；
S2, plated film: taking 75 parts of isopropyl titanate, 20 parts of dehydrated alcohols and 5 parts of polyethylene glycol to stir evenly, and moves into crucible
In, it puts it into atmosphere furnace, then the marble slabs after pre-treatment is placed in above crucible, nitrogen is filled to entire
Atmosphere furnace；150 DEG C are risen to the heating rate of 2 DEG C/min, and maintains this temperature 2h, carries out the vapor deposition processes of organic titanium,
Organic titanium slow evaporation is deposited on stone slab；
S3, roasting: after the completion of plated film, atmosphere furnace rises to 400 DEG C with the heating rate of 3 DEG C/min, and maintains this temperature 2h,
It is roasted；
S4, post-processing: it after roasting, is cooled to room temperature to atmosphere in-furnace temperature, marble slabs is taken out；With distillation
Water cleans up, and is put into baking oven and dries, and takes out, cooled to room temperature, obtains the stone slab of load multifunctional ecological film.
Embodiment 2
A kind of production method for the stone slab loading multifunctional ecological film, steps are as follows:
S1, pre-treatment: marble slabs are cleaned up, and are removed the residues such as surface dirt, are put into drying box, 100
DEG C drying 80min；
S2, plated film: taking 80 parts of isopropyl titanate, 17 parts of propyl alcohol and 3 parts of glycerine to stir evenly, and moves into crucible, will
It is put into atmosphere furnace, and then the marble slabs after pre-treatment are placed in above crucible, high pure nitrogen is filled to entire
Atmosphere furnace；150 DEG C are risen to the heating rate of 2 DEG C/min, and maintains this temperature 2h, carries out the vapor deposition processes of organic titanium,
Organic titanium slow evaporation is deposited on stone slab；
S3, roasting: after the completion of plated film, atmosphere furnace rises to 400 DEG C with the heating rate of 3 DEG C/min, and maintains this temperature 2h,
It is roasted；
S4, post-processing: it after roasting, is cooled to room temperature to atmosphere in-furnace temperature, marble slabs is taken out；With distillation
Water cleans up, and is put into baking oven and dries, and takes out, cooled to room temperature, obtains the stone slab of load multifunctional ecological film.
Embodiment 3
A kind of production method for the stone slab loading multifunctional ecological film, steps are as follows:
S1, pre-treatment: granite plates are cleaned up, and are removed the residues such as surface dirt, are put into drying box, 120
DEG C drying 60min；
S2, plated film: taking 70 parts of tetraethyl titanate, 25 parts of dehydrated alcohols and 5 parts of glycerine to stir evenly, and moves into crucible,
It puts it into atmosphere furnace, then the marble slabs after pre-treatment is placed in above crucible, air is filled to entire gas
Atmosphere furnace；120 DEG C are risen to the heating rate of 2 DEG C/min, and maintains this temperature 2h, carries out the vapor deposition processes of organic titanium, it will
Organic titanium slow evaporation deposits on stone slab；
S3, roasting: after the completion of plated film, atmosphere furnace rises to 350 DEG C with the heating rate of 2 DEG C/min, and maintains this temperature 2h,
It is roasted；
S4, post-processing: it after roasting, is cooled to room temperature to atmosphere in-furnace temperature, granite plates is taken out；With distillation
Water cleans up, and is put into baking oven and dries, and takes out, cooled to room temperature, obtains the stone slab of load multifunctional ecological film.
Embodiment 4
A kind of production method for the stone slab loading multifunctional ecological film, steps are as follows:
S1, pre-treatment: granite plates are cleaned up, and are removed the residues such as surface dirt, are put into drying box, 120
DEG C drying 60min；
S2, plated film: taking 75 parts of tetraethyl titanate, 20 parts of butanol and 5 parts of polyethylene glycol to stir evenly, and moves into crucible, will
It is put into atmosphere furnace, and then the marble slabs after pre-treatment are placed in above crucible, high-purity argon gas is filled to entire
Atmosphere furnace；120 DEG C are risen to the heating rate of 2 DEG C/min, and maintains this temperature 2h, carries out the vapor deposition processes of organic titanium,
Organic titanium slow evaporation is deposited on stone slab；
S3, roasting: after the completion of plated film, atmosphere furnace rises to 350 DEG C with the heating rate of 2 DEG C/min, and maintains this temperature 2h,
It is roasted；
S4, post-processing: it after roasting, is cooled to room temperature to atmosphere in-furnace temperature, granite plates is taken out；With distillation
Water cleans up, and is put into baking oven and dries, and takes out, cooled to room temperature, obtains the stone slab of load multifunctional ecological film.
In order to be compared with embodiment 1-4, provided with following reference examples:
Reference examples 1
A kind of production method of stone slab, the stone slab of selection is the marble slabs after polishing, with aforementioned implementation
Unlike example 1, there is no plating steps in this reference examples 1.
Reference examples 2
A kind of production method of plate, the plate of selection are the inorganic artificial stone slab after polishing, not with embodiment 3
It is same, there is no plating steps in this reference examples 2.
Reference examples 3
A kind of production method of stone slab, the plate of selection were the granite plates after polishing, and the present embodiment 5 is different
It is there is no plating steps in this reference examples 3.
Reference examples 4
General T iO2Plated film stone slab.
The plate that experimental example 1-4 and reference examples 1-4 are prepared carries out following experiment:
Experimental example 1: air cleaning performance test
Selection formaldehyde is air pollutants, and LED (450nm, 20W) lamp is radiation source, is tested above-mentioned in confined space
The Degradation Formaldehyde rate of plate, initial concentration of formaldehyde 30ppm, test temperature are room temperature, and action time is respectively 6h and 12h, are surveyed
Test result is as shown in table 1.
The degradation rate of the various plate PARA FORMALDEHYDE PRILLS(91,95)s of table 1
As it can be seen from table 1 general T iO of the reference examples 1-3 substantially without detergent power, in reference examples 42Plated film stone slab
Degradation Formaldehyde ability is weaker, and the degradation rate of embodiment 1-4 PARA FORMALDEHYDE PRILLS(91,95) is higher, and with the increase of irradiation time, degradation capability
It increases considerably, illustrates that load multifunctional biological film plate of the invention has good air purification ability, and with the time
Increase degradation capability it is stronger.
Experimental example 2: detergency ability test
Selection rhodamine B is simulating pollution object, and LED (450nm, 20W) lamp is radiation source, and above-mentioned plate is respectively put into
In the rhodamine B solution of 10mg/L, the absorbance of front and back rhodamine B solution is irradiated with spectrophotometric determination LED light, according to suction
Luminosity can calculate the concentration of rhodamine B solution, and then can calculate the palliating degradation degree of rhodamine B, and irradiation time is respectively 4h and 8h.
Test result is as shown in table 2.
Degradation rate of the various plates of table 2 to rhodamine B solution
From table 2 it can be seen that embodiment 1-4 is higher than degradation rate of the reference examples 1-4 to rhodamine B, with irradiation time
Increase, the rhodamine B degradation rate of reference examples has increased slightly, and the rhodamine B degradation rate of embodiment greatly increases, and illustrates the present invention
Load multifunctional biological film stone slab there is the ability of good degradation of contaminant, and degradation capability is got over as time increases
By force.
Experimental example 3: bactericidal property test
Selecting Escherichia coli is test bacterium, and LED (450nm, 20W) lamp is radiation source, under the same conditions by large intestine
Bacillus bacteria suspension pours into the closed container that selected plate surrounds, and after LED light irradiates 6h and 12h respectively, passes through plate bacterium
The survival rate for falling counting method measurement bacterium, then calculates the removal rate of removal Escherichia coli, the results are shown in Table 3.
Bactericidal effect of the various plates of table 3 to Escherichia coli
From table 3 it can be seen that embodiment 1-4 is stronger than the bactericidal properties ability of reference examples 1-4, with the increase of irradiation time,
The sterilizing ability of reference examples slightly enhances, and the sterilizing ability of embodiment greatly enhances, and illustrates the multi-functional life of load of the invention
Object film stone slab has good sterilizing ability, and sterilizing ability is stronger as time increases.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of production method for the stone slab for loading multifunctional ecological film, which comprises the following steps:
1) it plated film: after organic titanium solution evaporation, is vapor-deposited on stone slab；
2) roast: heating roasts above-mentioned plate to get the stone slab of load multifunctional ecological film is arrived.
2. manufacturing method according to claim 1, which is characterized in that it further include pre-treatment step before the plating steps,
The pre-treatment step is that stone slab is cleaned drying；It further include post-processing step after the calcination steps, the post-processing step
The rapid stone slab for after roasting cleans drying, and the stone slab of load multifunctional ecological film is obtained after cooling.
3. manufacturing method according to claim 1, which is characterized in that the plating steps carry out in atmosphere furnace, will have
Machine titanium solution is put into atmosphere furnace, and stone slab is placed on organic titanium superjacent, refills atmosphere gas, heat temperature raising；Institute
Stating heat temperature raising includes temperature programming step and incubation step, and the rate of described program heating is 2-5 DEG C/min, is warming up to 100-
It is kept the temperature after 150 DEG C, the time of the incubation step is 1.5-2h.
4. production method according to claim 3, which is characterized in that the atmosphere gas is air, nitrogen, oxygen, height
At least one of pure nitrogen gas, high-purity argon gas gas.
5. manufacturing method according to claim 1, which is characterized in that heating rate in the calcination steps is 2-5 DEG C/
Min is warming up to 300-500 DEG C, and maintains this temperature 1.5-2h.
6. manufacturing method according to claim 1, which is characterized in that the stone slab is granite plates, marble slab
Material or inorganic artificial stone slab.
7. manufacturing method according to claim 1, which is characterized in that the solute of organic titanium solution be tetraethyl titanate,
One of titanium propanolate and butyl titanate are a variety of；The solvent of organic titanium solution is dehydrated alcohol, propyl alcohol, butanol, gathers
One of ethylene glycol and glycerine are a variety of.
8. production method according to claim 7, which is characterized in that the weight of organic titanium solute in organic titanium solution
Percentage is 70%-95%.
9. production method according to claim 1-8, which is characterized in that the weight percent of carbon in the ecological film
Number is 1%-10%, TiO2Weight percent be 90%-99%.
10. a kind of stone slab of the load multifunctional ecological film obtained by the described in any item production methods of claim 1-9.
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| CN201811540972.4A CN109437968A (en) | 2018-12-17 | 2018-12-17 | A kind of stone slab and preparation method thereof loading multifunctional ecological film |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2868671Y (en) * | 2005-04-11 | 2007-02-14 | 北京安迪克斯家具有限责任公司 | Composite material with internal and external purifying, sterilizing function |
| CN101418437A (en) * | 2008-12-05 | 2009-04-29 | 北京航空航天大学 | Method for preparing carbon doped titanium oxide film |
-
2018
- 2018-12-17 CN CN201811540972.4A patent/CN109437968A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2868671Y (en) * | 2005-04-11 | 2007-02-14 | 北京安迪克斯家具有限责任公司 | Composite material with internal and external purifying, sterilizing function |
| CN101418437A (en) * | 2008-12-05 | 2009-04-29 | 北京航空航天大学 | Method for preparing carbon doped titanium oxide film |
Non-Patent Citations (1)
| Title |
|---|
| 崔玉民等: "《二氧化钛光催化技术》", 31 December 2010, 中国书籍出版社 * |
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Application publication date: 20190308 |