CN109158405A - A kind of preparation method of functionalization building castoff material and its resource utilization - Google Patents
A kind of preparation method of functionalization building castoff material and its resource utilization Download PDFInfo
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- CN109158405A CN109158405A CN201810985433.5A CN201810985433A CN109158405A CN 109158405 A CN109158405 A CN 109158405A CN 201810985433 A CN201810985433 A CN 201810985433A CN 109158405 A CN109158405 A CN 109158405A
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- China
- Prior art keywords
- building castoff
- functionalization
- cladding
- resource utilization
- titanium
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/58—Construction or demolition [C&D] waste
Abstract
The invention belongs to waste reutilization technology fields, it is related to the recycling of building castoff, more particularly to a kind of functionalization building castoff material, using building castoff particle as basis material, its partial size is at 50~500 μm, by combining the seed law, hydro-thermal reaction and heat treatment process, one layer of the growth in situ TiO with multistage micro nano structure on the building castoff particle2Nanometer sheet coating carries out functionalization to building castoff.The invention also discloses the resource utilization preparation methods of the functionalization building castoff material.The present invention constructs the TiO of one layer of micro nano structure with many good characteristics by in-situ growth technology2Nanometer sheet coating, assign useless or even harmful building castoff material new characteristic, realize resource utilization, obtained new material has unexpected technical effect, such as will have very big application potential and wide application prospect in fields such as photocatalysis, battery material or special surface wetability materials.
Description
Technical field
The invention belongs to waste reutilization technology field, be related to building castoff recycling more particularly to a kind of function
The preparation method of building castoff material and its resource utilization can be changed.
Background technique
With the rapid development of global economy and science and technology and the quickening of city process, construction industry is constantly in the economic hair of drive
The industry of taking the lead in race of exhibition.But at the same time, construction industry is well-known to produce environmentally harmful waste, accounts for the very big by one of waste stream
Part, being effectively treated for building castoff is a urgent need to solve the problem.Traditional and most common processing method is landfill, this
Kind traditional processing method cause material resources and in material manufacture the energy and cost consumption.In addition, selection landfill side
Formula will increase additional disposal costs, and easily reach maximum landfill capacity, and greatly reduce the use longevity of refuse landfill
Life, brings more economy and ecological problem.Therefore, the management of building castoff needs to send out towards the direction of sustainable development
Exhibition, wherein building castoff recycling is that have a kind of mode of development potentiality and prospect.So-called " recycling " is exactly to building
Waste is recycled as far as possible, is reprocessed, and is realized waste resource and is recycled.Building castoff includes architecture sediment, useless brick, gives up
Watt, waste concrete, the mortar that is scattered, steel, timber, glass and plastics etc., wherein because of architecture sediment, useless brick, useless watt and useless coagulation
Soil etc. is difficult to handle and recovery value is very low, and resource utilization is carried out mainly for this few class waste.
Nano titanium dioxide has excellent chemical stability, thermal stability, Superhydrophilic, high-specific surface area and thermal conductivity
It the features such as property, is widely used in photocatalysis field, anti-ultraviolet material, self-cleaning material, sensor, battery raw material photovoltaic
The fields such as device, because its various functions and advantage have obtained extensive research in worldwide.Its physical and chemical performance is not only
It is influenced by inherent electronic structure, also has close relationship with its size, pattern and surface texture and property.Nanoscale two
Titanium oxide utilizes the unique physical chemistry of Nano titanium dioxide since the limitation of size often loads together with other materials
Matter is applied to it in various fields from different basis material collective effects, raising practicability.
The present invention constructs the nanometer two with good characteristic using reluctant building castoff as basis material on it
Titanium oxide assigns building castoff new performance, realizes functionalization, becomes useless or even harmful building castoff rubbish
For valuable significant new material, the industrialization for " recycling → processing → reproduction → recycling " of building castoff is provided
New direction.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is disclose a kind of functionalization building castoff material
The method of material and its resource utilization.The material is to be existed using building castoff particle as basis material by in-situ growth technology
The TiO with micro/nano level is constructed thereon2Nanometer sheet coating assigns building castoff new characteristic, realizes to building castoff
Innoxious and resource utilization.
Technical solution:
A kind of functionalization building castoff material, using building castoff particle as basis material, partial size leads at 50~500 μm
It crosses and combines the seed law, hydro-thermal reaction and heat treatment process, there is multistage one layer of growth in situ on the building castoff particle
The TiO of micro nano structure2Nanometer sheet coating carries out functionalization to building castoff.
Building castoff of the present invention derives from inorganic building castoff, such as glass waste, brick waste, stone
Masonry waste, concrete debris etc..
Building castoff basis material of the present invention, building castoff is classified, chosen, cleaned, be crushed, is ground
With after sieving to obtain the final product.
The above-mentioned resource utilization preparation method based on functionalization building castoff material, specifically includes the following steps:
A) building castoff basis material water and ethanol solution are washed 3~5 times, in 60~100 DEG C of dry 3~6 h, preferably
80 DEG C of 4 h of drying；
B) it is 1:2~10:1, preferably 5:1 by basis material and the mass ratio of titanium source, titanium source is added drop-wise in basis material sufficiently
Mixing, natural drying at room temperature obtain the basis material of titanium precursors seed cladding；
C) 0.5~2 mol/L inorganic alkali solution and 30 wt% H are pressed2O2Volume ratio be 20:1~160:1, preferably inorganic base
Solution is 1mol/L, and and H2O2Volume ratio be 50:1, inorganic base/H is obtained after being sufficiently mixed2O2Mixed solution；
D) inorganic base/H of 10~30 mL is added in the basis material coated by the titanium precursors of every 1 g2O2Mixed solution, it is excellent
15 mL are selected, by the basis material and inorganic base/H of titanium precursors cladding2O2Mixed solution is added to polytetrafluoroethyllining lining reaction
In kettle, 120~180 DEG C of 18~24 h of hydro-thermal reaction, preferably 140 DEG C of 20 h of hydro-thermal reaction；Gained crude product uses water and ethyl alcohol respectively
Washing 3~5 times, is dried in vacuo 3~7h at 40~80 DEG C, and preferably 60 DEG C vacuum drying 5h obtain the titanium with multilevel structure
The building castoff material of presoma cladding；
E) the building castoff material of the titanium precursors cladding with multilevel structure is placed in tube furnace, 200~600 DEG C are forged
2~5h is burnt, preferably 400 DEG C calcining 3h are obtained with multilevel structure TiO2The functionalization building castoff material of nanometer sheet cladding.
In the more excellent disclosed example of the present invention, titanium source described in step b) is butyl titanate, four isopropyl of tetraethyl titanate and metatitanic acid
One of ester etc. or multiple combinations, preferably butyl titanate.
In the more excellent disclosed example of the present invention, inorganic base described in step c) is NaOH or KOH, preferably NaOH.
Beneficial effect
The invention discloses a kind of resource utilization methods of building castoff, significant to drop using building castoff as basis material
Low building castoff processing cost, avoids difficult to degrade, intractable building castoff and breaks after landfill to ecological environment
It is bad.For the present invention on building castoff basis material, constructing one layer by in-situ growth technology has the micro- of many good characteristics
The TiO of nanostructure2Nanometer sheet coating assigns useless or even harmful building castoff material new characteristic, realizes recycling
It utilizes, obtained new material has very big application latent in fields such as photocatalysis, battery material and special surface wetability materials
Power and wide application prospect；Building castoff functionalization method proposed by the invention, processing, change including raw material
The processes such as reaction and heat treatment are learned, technique is relatively easy, does not need expensive equipment and rare raw material, it is easy to accomplish industry
Change.
Detailed description of the invention
The SEM of Fig. 1 functionalization building castoff material of the present invention schemes,
Wherein, the SEM figure of (a) useless brick basis material；(b) TiO with multistage micro nano structure of low magnification2Nanometer
The SEM figure of the useless brick of piece cladding；(c) TiO with multistage micro nano structure of high-amplification-factor2Nanometer sheet cladding
The SEM figure of useless brick.
Specific embodiment
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited to following embodiments.
Embodiment 1
A kind of resource utilization method of functionalization brick building castoff material, the specific steps are as follows:
A) selected useless brick basis material water and ethanol solution are washed 4 times, and dry 4 h at 80 DEG C；
B) it is 5:1 by the mass ratio of useless brick basis material and butyl titanate, butyl titanate is added drop-wise to useless brick basis material
On, and it is sufficiently mixed the two.It is then placed at room temperature, spontaneously dries, obtain the useless brick matrix of titanium precursors seed cladding
Material；
C) by 1 mol/L NaOH solution and 30 wt% H2O2Volume ratio be 50:1, by NaOH solution and H2O2It is sufficiently mixed,
Obtain NaOH/H2O2Mixed solution；
D) NaOH/H of 15 mL is added in the basis material coated by the titanium precursors of every 1 g2O2Mixed solution, by titanium precursor
The basis material and NaOH/H of body cladding2O2Mixed solution is added in polytetrafluoroethyllining lining reaction kettle, reacts 20 at 140 DEG C
H, gained crude product use water and ethanol washing 4 times respectively, 5 h are dried in vacuo at 60 DEG C, obtain the titanium precursor with multilevel structure
The useless brick of body cladding；
E) the useless brick of the titanium precursors cladding with multilevel structure is placed in tube furnace, 3 h is calcined at 400 DEG C,
It obtains with multilevel structure TiO2The useless brick of the functionalization of nanometer sheet cladding.
Embodiment 2
A kind of resource utilization method of the useless brick of functionalization, the specific steps are as follows:
A) selected useless brick basis material water and ethanol solution are washed 3 times, and dry 6 h at 60 DEG C；
B) it is 10:1 by the mass ratio of useless brick basis material and butyl titanate, butyl titanate is added drop-wise to useless brick matrix material
On material, and it is sufficiently mixed the two.It is then placed at room temperature, spontaneously dries, obtain the useless brick base of titanium precursors seed cladding
Body material；
C) by 2 mol/L KOH solutions and 30 wt% H2O2Volume ratio be 100:1, by NaOH solution and H2O2It is sufficiently mixed,
Obtain KOH/H2O2Mixed solution；
D) NaOH/H of 10 mL is added in the basis material coated by the titanium precursors of every 1 g2O2Mixed solution, by titanium precursor
The basis material and NaOH/H of body cladding2O2Mixed solution is added in polytetrafluoroethyllining lining reaction kettle, reacts 24 at 120 DEG C
H, gained crude product use water and ethanol washing 3 times respectively, 8 h are dried in vacuo at 40 DEG C, obtain the titanium precursor with multilevel structure
The useless brick of body cladding；
E) the useless brick of the titanium precursors cladding with multilevel structure is placed in tube furnace, 6 h is calcined at 200 DEG C,
It obtains with multilevel structure TiO2The useless brick of the functionalization of nanometer sheet cladding.
Embodiment 3
A kind of resource utilization method of functionalization waste glass material, the specific steps are as follows:
A) selected cullet basis material water and ethanol solution are washed 4 times, and dry 5 h at 70 DEG C；
B) it is 5:1 by the mass ratio of cullet basis material and tetraethyl titanate, tetraethyl titanate is added drop-wise to cullet matrix
On material, and it is sufficiently mixed the two.It is then placed at room temperature, spontaneously dries, obtain the useless glass of titanium precursors seed cladding
Glass basis material；
C) by 1 mol/L NaOH solution and 30 wt% H2O2Volume ratio be 80:1, by NaOH solution and H2O2It is sufficiently mixed,
Obtain NaOH/H2O2Mixed solution；
D) NaOH/H of 15 mL is added in the basis material coated by the titanium precursors of every 1 g2O2Mixed solution, by titanium precursor
The cullet basis material and NaOH/H of body cladding2O2Mixed solution is added in polytetrafluoroethyllining lining reaction kettle, at 160 DEG C
18 h are reacted, gained crude product uses water and ethanol washing 3 times respectively, 5 h are dried in vacuo at 60 DEG C, obtains having more
The waste glass material of the titanium precursors cladding of level structure；
E) waste glass material of the titanium precursors cladding with multilevel structure is placed in tube furnace, calcines 3 at 400 DEG C
H is obtained with multilevel structure TiO2The functionalization waste glass material of nanometer sheet cladding.
Embodiment 4
A kind of resource utilization method of functionalization waste glass material, the specific steps are as follows:
A) selected cullet basis material water and ethanol solution are washed 5 times, and dry 4 h at 80 DEG C；
B) it is 2:1 by the mass ratio of cullet basis material and butyl titanate, butyl titanate is added drop-wise to useless brick matrix material
On material, and it is sufficiently mixed the two.It is then placed at room temperature, spontaneously dries, obtain the useless brick base of titanium precursors seed cladding
Body material；
C) by 2 mol/L NaOH solutions and 30 wt% H2O2Volume ratio be 100:1, by NaOH solution and H2O2It is sufficiently mixed,
Obtain NaOH/H2O2Mixed solution；
D) NaOH/H of 10 mL is added in the basis material coated by the titanium precursors of every 1 g2O2Mixed solution, by titanium precursor
The basis material and NaOH/H of body cladding2O2Mixed solution is added in polytetrafluoroethyllining lining reaction kettle, reacts 24 at 120 DEG C
H, gained crude product use water and ethanol washing 3 times respectively, 8 h are dried in vacuo at 40 DEG C, obtain the titanium precursor with multilevel structure
The useless brick of body cladding；
E) the useless brick of the titanium precursors cladding with multilevel structure is placed in tube furnace, 4 h is calcined at 300 DEG C,
It obtains with multilevel structure TiO2The useless brick of the functionalization of nanometer sheet cladding.
Embodiment 5
A kind of resource utilization method of the useless watt material of functionalization, the specific steps are as follows:
A) selected useless watt basis material water and ethanol solution are washed 4 times, and dry 6 h at 60 DEG C；
B) it is 2:1 by the mass ratio of useless watt basis material and butyl titanate, butyl titanate is added drop-wise to useless watt basis material
On, and it is sufficiently mixed the two.It is then placed at room temperature, spontaneously dries, obtain the useless watt matrix of titanium precursors seed cladding
Material；
C) by 1.5 mol/L KOH solutions and 30 wt% H2O2Volume ratio be 40:1, by NaOH solution and H2O2It is sufficiently mixed,
Obtain KOH/H2O2Mixed solution；
D) NaOH/H of 20 mL is added in the useless watt basis material coated by the titanium precursors of every 1 g2O2Mixed solution, by titanium
The basis material and NaOH/H of presoma cladding2O2Mixed solution is added in polytetrafluoroethyllining lining reaction kettle, anti-at 140 DEG C
20 h are answered, gained crude product uses water and ethanol washing 3 times respectively, 8 h are dried in vacuo at 40 DEG C, obtains having multilevel structure
The useless brick of titanium precursors cladding；
E) a useless watt material for the titanium precursors cladding with multilevel structure is placed in tube furnace, calcines 3h at 400 DEG C,
It obtains with multilevel structure TiO2The useless watt material of the functionalization of nanometer sheet cladding.
Embodiment 6
A kind of resource utilization method of functionalization waste concrete material, the specific steps are as follows:
A) selected waste concrete basis material water and ethanol solution are washed 3 times, and dry 3 h at 100 DEG C；
B) it is 1:2 by the mass ratio of waste concrete basis material and tetraisopropyl titanate, tetraisopropyl titanate is added drop-wise to useless mixed
On solidifying soil basis material, and it is sufficiently mixed the two.It is then placed at room temperature, spontaneously dries, obtain titanium precursors kind attached bag
The waste concrete basis material covered；
C) by 0.5 mol/L NaOH solution and 30 wt% H2O2Volume ratio be 20:1, by NaOH solution and H2O2It fills
Divide mixing, obtains NaOH/H2O2Mixed solution；
D) NaOH/H of 30 mL is added in the waste concrete basis material coated by the titanium precursors of every 1 g2O2Mixed solution,
The waste concrete basis material and NaOH/H that titanium precursors are coated2O2Mixed solution is added to polytetrafluoroethyllining lining reaction kettle
In, in 180 DEG C of 20 h of reaction, gained crude product uses water and ethanol washing 3 times respectively, 3 h is dried in vacuo at 80 DEG C, are had
There is the waste concrete material of the titanium precursors cladding of multilevel structure；
E) a useless watt material for the titanium precursors cladding with multilevel structure is placed in tube furnace, 2 h is calcined at 600 DEG C,
It obtains with multilevel structure TiO2The functionalization waste concrete material of nanometer sheet cladding.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (10)
1. a kind of functionalization building castoff material, using building castoff particle as basis material, it is characterised in that: its partial size exists
50~500 μm, by combining the seed law, hydro-thermal reaction and heat treatment process, the growth in situ on the building castoff particle
One layer of TiO with multistage micro nano structure2Nanometer sheet coating.
2. functionalization building castoff material according to claim 1, it is characterised in that: the building castoff refers to useless
Brick, useless watt, the raw materials such as architecture sediment, waste concrete or cullet.
3. functionalization building castoff material according to claim 1, it is characterised in that: the building castoff matrix material
Material, be after building castoff is classified, is chosen, is cleaned, is crushed, is ground and sieved to obtain the final product.
4. a kind of resource utilization preparation method of the functionalization building castoff material as described in claim 1-3 is any, special
Sign is, comprising the following steps:
Building castoff basis material water and ethanol solution are washed 3~5 times, in 60~100 DEG C of dry 3~6h；
It is 1:2~10:1 by basis material and the mass ratio of titanium source, titanium source is added drop-wise in basis material and is sufficiently mixed, room temperature is certainly
It is so dry, obtain the basis material of titanium precursors seed cladding；
By 0.5~2 mol/L inorganic alkali solution and 30 wt% H2O2Volume ratio be 20:1~160:1, obtained after being sufficiently mixed
Inorganic base/H2O2Mixed solution；
Inorganic base/H of 10~30 mL is added in the basis material coated by the titanium precursors of every 1 g2O2Mixed solution, before titanium
Drive the basis material and inorganic base/H of body cladding2O2Mixed solution is added in polytetrafluoroethyllining lining reaction kettle, and 120~180 DEG C
18~24 h of hydro-thermal reaction；Gained crude product uses water and ethanol washing 3~5 times respectively, and 3~7h is dried in vacuo at 40~80 DEG C,
Obtain the building castoff material of the titanium precursors cladding with multilevel structure；
The building castoff material of titanium precursors cladding with multilevel structure is placed in tube furnace, 200~600 DEG C of calcinings
2~5h is obtained with multilevel structure TiO2The functionalization building castoff material of nanometer sheet cladding.
5. the resource utilization preparation method of functionalization building castoff material according to claim 4, it is characterised in that: step
In 80 DEG C of dry 4 h after rapid a) the described washing.
6. the resource utilization preparation method of functionalization building castoff material according to claim 4, it is characterised in that: step
Rapid b) the described titanium source is butyl titanate, one of tetraethyl titanate and tetraisopropyl titanate etc. or multiple combinations；By matrix
Material and the mass ratio of titanium source are 5:1.
7. the resource utilization preparation method of functionalization building castoff material according to claim 4, it is characterised in that: step
Rapid b) the described titanium source is butyl titanate.
8. the resource utilization preparation method of functionalization building castoff material according to claim 4, it is characterised in that: step
Rapid c) the described inorganic alkali solution is 1mol/L and and H2O2Volume ratio be 50:1, inorganic base/H is obtained after being sufficiently mixed2O2Mixing
Solution.
9. the resource utilization preparation method of functionalization building castoff material according to claim 4, it is characterised in that: step
Inorganic base/H of 15mL is added in the basis material that rapid d) the described titanium precursors by every 1 g coat2O2Mixed solution, before titanium
Drive the basis material and inorganic base/H of body cladding2O2Mixed solution is added in polytetrafluoroethyllining lining reaction kettle, 140 DEG C of hydro-thermals
React 20 h；Gained crude product uses water and ethanol washing 3~5 times respectively, is dried in vacuo 5h at 60 DEG C, obtains with multilevel structure
Titanium precursors cladding building castoff material.
10. the resource utilization preparation method of functionalization building castoff material according to claim 4, it is characterised in that:
Step e) the building castoff material by the titanium precursors cladding with multilevel structure is placed in tube furnace, and 400 DEG C are forged
3h is burnt, is obtained with multilevel structure TiO2The functionalization building castoff material of nanometer sheet cladding.
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| JPS54118652A (en) * | 1978-03-07 | 1979-09-14 | Agency Of Ind Science & Technol | Solidification method of river water sludge |
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| CN103268919A (en) * | 2013-05-13 | 2013-08-28 | 河南师范大学 | Method for preparing TiO2 thin film and method for preparing P3HT/TiO2 organic-inorganic hybrid heterojunction thin film |
| EP2813297A1 (en) * | 2012-02-06 | 2014-12-17 | Tottori Prefecture | Method for separating heavy metal from glass |
| CN104370472A (en) * | 2014-10-09 | 2015-02-25 | 陕西华陆化工环保有限公司 | Preparation method of glass-loaded nano-TiO2 membrane |
| CN105275185A (en) * | 2015-11-06 | 2016-01-27 | 周翠华 | Hollowed out type renewable environmentally friendly sterilization floor and manufacturing method thereof |
| CN107915403A (en) * | 2017-11-27 | 2018-04-17 | 安徽玻扬节能钢化玻璃有限公司 | A kind of energy-saving glass produced using discarded glass as raw material and its production technology |
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2018
- 2018-08-28 CN CN201810985433.5A patent/CN109158405B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS54118652A (en) * | 1978-03-07 | 1979-09-14 | Agency Of Ind Science & Technol | Solidification method of river water sludge |
| CN101559979A (en) * | 2009-05-22 | 2009-10-21 | 东华大学 | Method for preparing extrafine anatase titanium dioxide nano rods |
| EP2813297A1 (en) * | 2012-02-06 | 2014-12-17 | Tottori Prefecture | Method for separating heavy metal from glass |
| CN103268919A (en) * | 2013-05-13 | 2013-08-28 | 河南师范大学 | Method for preparing TiO2 thin film and method for preparing P3HT/TiO2 organic-inorganic hybrid heterojunction thin film |
| CN104370472A (en) * | 2014-10-09 | 2015-02-25 | 陕西华陆化工环保有限公司 | Preparation method of glass-loaded nano-TiO2 membrane |
| CN105275185A (en) * | 2015-11-06 | 2016-01-27 | 周翠华 | Hollowed out type renewable environmentally friendly sterilization floor and manufacturing method thereof |
| CN107915403A (en) * | 2017-11-27 | 2018-04-17 | 安徽玻扬节能钢化玻璃有限公司 | A kind of energy-saving glass produced using discarded glass as raw material and its production technology |
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