CN102992644A - Method for keeping anatase nmTiO2 crystal form at 800 DEG C and application of anatase nmTiO2 crystal form on glass brick - Google Patents
Method for keeping anatase nmTiO2 crystal form at 800 DEG C and application of anatase nmTiO2 crystal form on glass brick Download PDFInfo
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- CN102992644A CN102992644A CN2012102342998A CN201210234299A CN102992644A CN 102992644 A CN102992644 A CN 102992644A CN 2012102342998 A CN2012102342998 A CN 2012102342998A CN 201210234299 A CN201210234299 A CN 201210234299A CN 102992644 A CN102992644 A CN 102992644A
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- titanium dioxide
- anatase titanium
- powder
- anatase
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000013078 crystal Substances 0.000 title claims abstract description 22
- 239000011521 glass Substances 0.000 title abstract description 12
- 239000011449 brick Substances 0.000 title abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000007650 screen-printing Methods 0.000 claims abstract description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 4
- 239000005357 flat glass Substances 0.000 claims description 49
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 238000007639 printing Methods 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 235000009508 confectionery Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
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- 230000008030 elimination Effects 0.000 claims description 3
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- 238000010792 warming Methods 0.000 claims description 3
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- 239000000203 mixture Substances 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000000354 decomposition reaction Methods 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000010998 test method Methods 0.000 abstract description 2
- 238000002441 X-ray diffraction Methods 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000011990 functional testing Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- 238000005755 formation reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 4
- 241000191940 Staphylococcus Species 0.000 description 4
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- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- 241000345998 Calamus manan Species 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 235000012950 rattan cane Nutrition 0.000 description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000009631 Broth culture Methods 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000721 bacterilogical effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
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- 208000014674 injury Diseases 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention relates to a method for keeping anatase nmTiO2 crystal form at the temperature of 800 DEG C, and a technology for coating an anatase nmTiO2 film on a glass brick. The method comprises the following steps: preparing a 0.10mol phosphoric solution; slowly adding 25.000g of anatase nmTiO2 powder with the grain size of 20-25 nanometers into a 150ml solution containing 26.90ml 0.10 Mol phosphoric acid under the full stirring, further stirring for 15minutes; completely pouring the phosphoric solution containing anatase nmTiO2 powder into a porcelain crucible, putting the crucible in a muffle, heating up slowly to 800 DEG C and carrying out heat preservation for half hour; cooling to room temperature of 20-30DEG C naturally to obtain anatase nmTiO2 powder containing phosphorus oxide; and coating the anatase nmTiO2 powder on the glass brick by using a screen printing technique. A test method for testing the photocatalytic function of the anatase nmTiO2 membrane on the glass brick is set, and the functional test is carried out through XRD (X-Ray Diffraction), electron microscope, photocatalytic decomposition organism, bacteriostasis and super hydrophilicity.
Description
Technical field
The present invention relates to a kind of at 800 ℃ of maintenance nanometer anatase titania (nmTiO
2) method of crystal formation.Particularly disperse anatase titanium dioxide nmTiO on the building and ornament materials surface
2After, make it keep anatase titanium dioxide nmTiO at 800 ℃
2The method of crystal formation and the application on plate glass thereof.
Background technology
Anatase titanium dioxide nmTiO
2A kind of environment-friendly materials with performances such as photocatalysis Decomposition organism, antibacterial, Superhydrophilics.
Utilize optical excitation anatase titanium dioxide nmTiO
2What the generation photocatalysis promoted chemical reaction is to come from Tokyo University's engineering research in last century professor of section, Doctor of engineering rattan Mr. island, is referred to as at that time " rattan island effect ".From finding to spend for four more than ten years so far, countries in the world are to anatase titanium dioxide nmTiO
2The research of photocatalytic applications also further deep.
Result of study is found anatase titanium dioxide nmTiO
2Photocatalyst is under near-ultraviolet light (sunlight or luminescent lamp etc.) irradiation, electronics in the molecule is excited, generate electron-hole pair, because the hole of positively charged has very strong oxidation capacity, can make airborne water molecules generate the strong oxidizer of hydroxyl free radical (OH); Electronegative electronic energy makes airborne oxygen (O
2) reduction, generate another kind of strong living radical O
2-OH and O
2-The contained energy equivalence of living radical is enough to make most of organic substances " burning " decomposition in the energy that the heat energy of 3600K high temperature produces.So the organic molecules such as its can Decomposition of benzene, formaldehyde, anti-bacteria, and to human body without injury.
Carry out the nmTiO of anatase crystal type in the prior art
2The crystalline transformation temperature is following attempts its technology that is scattered in ceramic tile surface klining typing, referring to " ceramic tile glaze TiO in " Shanghai Institute Of Technology's journal "
2Material preparation and structure and morphology research thereof "; With Chinese patent CN101143763B.
Plate glass (glass Mosaic) is as finishing material, and it has abundant color and comprises that gold and silver etc. show the pattern of metal quality.Pattern on the plate glass all is to print on the thick plate glass of 8mm by the method monochrome of silk screen printing or chromatography, by 800 ℃ of (glass softening point temperature) klining typings, adheres to and becomes a useful person again.Because anatase crystal type nmTiO
2The limitation of thermostability, it can be transformed into the nmTiO of rutile-type when temperature surpasses 600 ℃
2Thereby, lose photocatalysis characteristic.If reduce the klining temperature, then form the metallic substance such as the pigment of pattern color and gold and silver and can not adhere to thick on glass of 8mm, certainly can not make needed plate glass.The character of glass is not reburned once in 500-600 ℃ after not allowing 800 ℃ of burnings once yet.Namely first the temperature of plate glass pattern at 800 ℃ formed by a firing, again at plate glass surface coverage anatase crystal type nmTiO
2Film, and again under 500-600 ℃ temperature, this plate glass is carried out klining again.
Have good pattern, shape and optical characteristics if guarantee the plate glass (glass Mosaic) of making, make simultaneously the nmTiO of dispersion
2The film water white transparency also has photocatalysis performance, just must make the anatase titanium dioxide nmTiO that covers on the plate glass
2Finish with the pattern klining, simultaneously anatase titanium dioxide nmTiO
2In the time of 800 ℃, must keep crystal formation constant.
Can together stand 800 ℃ of klining techniques with plate glass in the urgent need to a kind of now, guarantee anatase titanium dioxide nmTiO
2In the constant method of 800 ℃ of crystal formations and the technique that applies at plate glass thereof.
Summary of the invention
The purpose of this invention is to provide a kind of assurance anatase titanium dioxide nmTiO
2Keep the method for crystal formations and the application on plate glass thereof at 800 ℃, namely select a kind of can be prior to anatase titanium dioxide nmTiO
2The energy of absorbing radiation and shielding protection anatase titanium dioxide nmTiO
2The material of crystal formation makes anatase titanium dioxide nmTiO
2When finalizing the design, the plate glass klining can keep crystal formation constant.
Can select the suitable shielding protection anatase titanium dioxide nmTiO of being used for from the physicochemical property of compound
2About 800 ℃, do not change the material of crystal formation.The present invention selects the oxide compound of phosphorus as anatase titanium dioxide nmTiO by many experiments
2The shielding protection material.
The anatase titanium dioxide nmTiO that contains phosphorous oxides
2The preparation method of powder: with distilled water, AR level phosphoric acid preparation 0.10mol phosphoric acid solution, the volume that contains the 0.10Mol concentration of 26.90ml is in the phosphate aqueous solution of 150ml, and slowly adding particle diameter under abundant agitation condition is the anatase titanium dioxide nmTiO of 20-25nm
2Powder 25.000g stirred 15 minutes until all adding rear continuation, will contain anatase titanium dioxide nmTiO
2The phosphate aqueous solution of powder is all poured in the sweet pot of porcelain, puts into retort furnace, slowly is warming up to 800 ℃, is incubated half an hour, naturally is down to room temperature 20-30 ℃, makes the anatase titanium dioxide nmTiO that contains phosphorous oxides
2Powder.
Every gram anatase titanium dioxide nmTiO
2In the content of corresponding phosphorus reach 3.05-3.33mg and can guarantee nmTiO
2Crystal formation can not change rutile-type into by anatase titanium dioxide in the time of 800 ℃.
When envrionment temperature is room temperature 20-25 ℃, (diameter is Φ 1mm and Φ 2mm to add the zirconium pearl in 2000-2500ml silk screen printing solution, ratio is 4: 6) 50g, use the sand milling dispersion machine slowly to add the anatase titanium dioxide nmTiO that contains phosphorous oxides under the stirring velocity of 2500-3000r/min
2Powder 20-25g (± 0.000g), and continuously stirring 30 minutes, elimination zirconium pearl generates the anatase titanium dioxide nmTiO that contains phosphorous oxides
2Silk screen printing colloidal sol, the plate glass of 8mm thickness is carried out the oil removing dust removal process, with screen printer print anatase titanium dioxide nmTiO
2Colloidal sol, thickness is 5 μ m approximately, can select 165T or 200T silk screen according to print speed, treat after the printing that the film surface drying can advance 800 ℃ klining system and pattern one co-shaping on plate glass surface.
Anatase titanium dioxide nmTiO
2The crystal formation of powder is to be determined by X-ray diffracting spectrum (XRD).
The present invention has overcome anatase titanium dioxide nmTiO
2When the klining typing of plate glass surface, because the klining temperature makes anatase titanium dioxide nmTiO up to 800 ℃
2Be transformed into rutile-type nmTiO
2Cause the problem that loses photocatalysis performance, and complete processing is easy, the processed finished products rate is high, does not produce the three wastes in the production process, and is with low cost.
Description of drawings
Fig. 1 is anatase titanium dioxide nmTiO
2Plate glass X-ray diffracting spectrum (XRD) detected result;
Fig. 2 is anatase titanium dioxide nmTiO
2Plate glass electron microscope collection of illustrative plates;
Fig. 3 is anatase titanium dioxide nmTiO
2Plate glass benzene decomposition curve;
Fig. 4 is anatase titanium dioxide nmTiO
2The plate glass bacteriostatic test.
Fig. 5 measures nmTiO with contact angle measurement
2Water droplet contact angle on the plate glass;
Fig. 6 is nmTiO
2Plate glass Superhydrophilic experimental result.
Embodiment
One, preparation contains the anatase titanium dioxide nmTiO of phosphorous oxides
2Powder.
1. the anatase titanium dioxide nmTiO that the material that adopts and equipment particle diameter are 20-25nm
2Powder, XRD determines nmTiO by X ray diffracting spectrum
2Crystal formation is by specific surface area 104-120m
2/ g proves particle diameter;
Phosphoric acid: analytical pure level (AR);
Distilled water;
Retort furnace;
Electronic balance: ± 0.001g;
Volumetric flask;
Transfer pipet.
2. implementation step
With distilled water configuration 0.10mol phosphoric acid solution, dilute again as required during use.
In the phosphoric acid solution of different concns, (press every gram anatase titanium dioxide nmTiO
2The phosphorus content meter Pmg/nmTiO that needs
2G) fully slowly adding anatase titanium dioxide nmTiO under the agitation condition
2Powder stirred 15 minutes until all adding rear continuation.To contain anatase titanium dioxide nmTiO
2The phosphoric acid solution of powder is all poured in the sweet pot of porcelain, puts into retort furnace.Slowly be warming up to 800 ℃, be incubated half an hour.Naturally be down to room temperature 20-30 ℃, take out product and carry out respectively the detection of XRD and specific surface.
Experimental Comparison one
By the implementation step operation, in the phosphate aqueous solution 150ml of the 0.10mol that contains 12.60ml, add 25.000g anatase titanium dioxide nmTiO
2Powder (P1.56mg/nmTiO
2G), after 800 ℃ of roasting half an hour, detect to have an appointment with XRD and 5% change into rutile-type nmTiO
2, specific surface 37.2m
2/ g.
Experimental Comparison two
By the implementation step operation, in the phosphate aqueous solution 150ml of the 0.10mol that contains 14.20ml, add 25.000g anatase titanium dioxide nmTiO
2Powder (P1.76mg/nmTiO
2G), after 800 ℃ of roasting half an hour, detect to have an appointment with XRD and 5% change into rutile-type nmTiO
2, specific surface 53.8m
2/ g.
Experimental Comparison three
By the implementation step operation, in the phosphate aqueous solution 150ml of the 0.10Mol that contains 24.60ml, add 25.000g anatase titanium dioxide nmTiO
2Powder (P3.05mg/nmTiO
2G), after 800 ℃ of roasting half an hour, detect with XRD and not find rutile nmTiO
2, specific surface 104m
2/ g-110m
2/ g.
Experimental Comparison four
By the implementation step operation, in the phosphate aqueous solution 150ml of the 0.10Mol that contains 26.90ml, add 25.000g anatase titanium dioxide nmTiO
2Powder (P3.33mg/nmTiO
2G), after 800 ℃ of roasting half an hour, detect with XRD and not find rutile nmTiO
2, specific surface 115m
2/ g-120m
2/ g.
3. conclusion (of pressure testing)
1) testing data that provides according to above Experimental Comparison, as can be known anatase titanium dioxide nmTiO
2Phosphorous oxides in the powder can be prior to anatase titanium dioxide nmTiO
2The energy of absorbing radiation is to anatase titanium dioxide nmTiO
2Play shielding protection.
2) as every gram anatase titanium dioxide nmTiO
2When the content of corresponding phosphorus reaches 3.05-3.33mg, anatase titanium dioxide nmTiO
2Can be to rutile-type nmTiO when 800 ℃ of high temperature
2Change.
Two, with the phosphorous anatase titanium dioxide nmTiO of above-mentioned preparation
2Be dispersed in the plate glass surface, and this plate glass klining finalized the design:
Contain anatase titanium dioxide nmTiO
2The method that the plate glass of film is made of silk screen printing:
1) preparation silk screen printing solution.
Printing solution material proportioning following (by weight, the g of unit):
A) distilled water: 100;
B) hydroxypropyl formaldehyde Mierocrystalline cellulose: food grade, 2.6;
C) Virahol: technical grade, 30;
D) cyclodextrin: analytical pure (AR), 0.5;
E) ethylene glycol monobutyl ether: analytical pure (AR), 0.3;
Print with solution preparation program (work is at room temperature carried out):
Vltra tears is dissolved in the distilled water, be stirred to the rear Virahol that adds of fully dissolving with the sand milling dispersion machine with 2500-3000r/min speed, continue stirring and add one by one cyclodextrin, ethylene glycol monobutyl ether.With the solution left standstill that configures 12 hours, after solution is transparent, can use.
2) preparation contains the anatase titanium dioxide nmTiO of phosphorous oxides
2Silk screen printing colloidal sol.
Material and equipment:
A) contain the anatase titanium dioxide nmTiO of phosphorous oxides
2Powder;
B) the employed solution of silk screen printing;
C) sand milling dispersion machine SDF-400;
D) zirconium pearl mixture (diameter is Φ 1mm and Φ 2mm, and blending ratio is 4: 6);
Preparation contains the anatase titanium dioxide nmTiO of phosphorous oxides
2Silk screen printing colloidal sol
Envrionment temperature is that room temperature (20-25 ℃) adds 50g zirconium pearl in 2000-2500ml silk screen printing solution, uses the sand milling dispersion machine slowly to add the anatase titanium dioxide nmTiO that contains phosphorous oxides under the stirring velocity of 2500-3000r/min
2Powder 20.000-25.000g, continuously stirring 30 minutes, elimination zirconium pearl makes the anatase titanium dioxide nmTiO that contains phosphorous oxides
2Silk screen printing colloidal sol is for silk screen printing.
3) silk screen printing reaches the klining technique to plate glass
A) plate glass to be printed must carry out the oil removing dust removal process, makes the plate glass surface of printing nanometer film dustless without oil.
B) the about 5 μ m of thickness of printing nanometer film select 165T or 200T silk screen according to print speed.
C) can select manual, semi-automatic or the automatic printing machine according to condition.
D) after the printing, treat the film surface drying, plate glass can advance klining system.
Three, the anatase titanium dioxide nmTiO of the plate glass surface coverage of klining typing
2The anatase titanium dioxide nmTiO of Performance Detection plate glass (glass Mosaic) surface coverage of film
2The Performance Detection of film has five of XRD, electron microscope, photocatalysis Decomposition organism-benzene, antibacterial, Superhydrophilics etc.
The preparation of check sample
Five check samples be unified preparation contain anatase titanium dioxide nmTiO
2Printing colloidal sol and typography printing are made the thick plate glass of 8mm through 800 ℃ of klining.Need do different treatment to sample during for the disparity items check.
1. check embodiment one: XRD check
Thick 20 * 50 plate glasss of 8mm are milled to 0.1-0.3mm thick, are broken to powdery with ball mill, for X-ray diffracting spectrum (XRD) check, the results are shown in accompanying drawing 1:
(anatase titanium dioxide nmTiO
2Plate glass XRD detected result)
2. check embodiment two: the scanning electronic microscope check
To apply anatase titanium dioxide nmTiO
2The plate glass of powder is cut into the microscopical determination of 20 * 50mm supplied for electronic, the results are shown in Figure 2:
3. check embodiment three: the check of decomposing organic matter-benzene
According to anatase titanium dioxide nmTiO
2Absorb luminous energy and produce the reaction mechanism that hydroxyl free radical decomposes organic molecule.Can be with this method as scribbling anatase titanium dioxide nmTiO
2The main test method of plate glass product function and quality.
Because benzene has good conjugated structure, decompose the larger energy of its needs.So can use it as the organic target compound of check photocatalysis Decomposition.
This check is the benzene vapour static check, will apply anatase titanium dioxide nmTiO
2Plate glass 150*150*8mm places closed reactor, and (220 * 220 * 30mm), the reactor sensitive surface is silica glass (220 * 220 * 3mm) illumination parameters: wavelength 385nm, light intensity 0.15mW/cm
2
This light-catalyzed reaction is the anatase titanium dioxide nmTiO on the plate glass
2Absorb hydroxyl free radical and benzene molecular reaction that luminous energy produces.Reaction is at anatase titanium dioxide nmTiO
2Carry out at the interface of particle, and when reaction conditions is fixed, then organic molecule is the important factor that the impact reaction is carried out to plate glass surface diffusion speed in the reactor.When benzene molecular begins small molecules after cracking will produce cracking, they and benzene molecular exist simultaneously.At this moment be the gas of a mixing in the reactor, because the benzene molecular quality is relatively large, so and nmTiO
2The interface contact probability must reduce.The decomposition of benzene also must be slow by easing up.Therefore this check can illustrate and apply anatase titanium dioxide nmTiO
2Plate glass has the function of decomposing organic matter.The blank sample removes on the plate glass without anatase titanium dioxide nmTiO
2Outward, other condition for surveyss are identical.Checking procedure: the reactor that plate glass to be tested will be housed places 100 ℃ ± 1 ℃ thermostat, and balance began irradiation after 14 hours.Irradiation 1 hour begins sampling (C0) behind the stabilized intensity, took a sample once every one hour later on (Ct) gets three parallel sample at every turn, analyzes benzene concentration by the GC-9800 gas chromatograph.Check is not to apply anatase titanium dioxide nmTiO
2The blank glass brick compare.The results are shown in Figure 3:
4. check embodiment four: bacteriologic test
Detect with equipment, reagent and bacterial classification: culture dish, magnificent test tube, suction pipe, phosphoric acid buffer, basic medium, soft agar, golden yellow staphylococcus (ATCC), intestinal bacteria (ATCC)
Detection method: golden yellow staphylococcus, 24 hours broth cultures of intestinal bacteria are diluted into about 200 bacterium/plates with phosphoric acid buffer, draw bacterium liquid and soft agar mixing, water through UV-lamp (30w, apart from 48cm) irradiation (be respectively 2 minutes, 4 minutes, 8 minutes, after 16 minutes) scribble anatase titanium dioxide nmTiO
2On glass, culture dish is put in 37 ℃ of constant incubators and was cultivated 24 hours, counting bacterium number.Assay is seen Fig. 4:
Conclusion: after the UV-lamp irradiation, full pattern group plate glass is better to golden yellow staphylococcus, intestinal bacteria fungistatic effect, and shining namely had effect in 2 minutes, and bacteriostasis rate reaches 80%.Shine after 4 minutes effect more obvious; And blank group is relatively poor to golden yellow staphylococcus, intestinal bacteria fungistatic effect, and after irradiation under the UV-lamp, bacterial growth is good, and quantity reduces slightly.
5. check embodiment five: the Superhydrophilic check
Inspection machine: contact angle measurement-JC2000C1
Measure nmTiO with contact angle measurement
2Water droplet contact angle on the plate glass, referring to Fig. 5:
Checking procedure: get and apply anatase titanium dioxide nmTiO
2Some of plate glass 50 * 50 * 8mm are positioned over respectively wavelength 385nm, light intensity 0.15mW/cm
2Illumination 90 under the condition, 180,270 minutes.Then measure water droplet contact angle on the plate glass with contact angle measurement, the results are shown in Figure 6:
Although the embodiment of the best of the present invention has been described in above-mentioned by way of example explanation, protection scope of the present invention is not limited in above-mentioned explanation, uses method of the present invention to make anatase titanium dioxide nmTiO
2Be attached to the body surface (such as glassware etc.) that to fire and play fungistatic effect; persons skilled in the art are understandable that; under the prerequisite that does not deviate from essence that the present invention instructs and marrow, any modifications and variations all fall into protection scope of the present invention.
Claims (10)
1. one kind keeps anatase titanium dioxide nmTiO at 800 ℃
2The method of crystal formation is characterized in that: anatase titanium dioxide nmTiO
2Have phosphorous oxides in the powder systems, described phosphorous oxides is by with anatase titanium dioxide nmTiO
2Powder places phosphoric acid solution to fire at 800 ℃ and forms, every gram anatase titanium dioxide nmTiO
2Need the content of phosphorus to be not less than 3.05mg.
2. method according to claim 1, described phosphoric acid solution is taken 0.10mol phosphoric acid and is done the basis.
3. described method one of according to claim 1-2, preparation contains the anatase titanium dioxide nmTiO of phosphorous oxides
2In the process, press nmTiO
2Amount calculate the consumption of the required phosphoric acid solution of content of phosphorus.
4. one kind keeps anatase titanium dioxide nmTiO at 800 ℃
2The method of crystal formation is characterized in that: utilize every gram anatase titanium dioxide nmTiO
2The phosphorous oxides of corresponding content keeps anatase titanium dioxide nmTiO in the powder
2Thermostability, use distilled water, AR level phosphoric acid preparation 0.10mol phosphate aqueous solution, in the phosphate aqueous solution of the 0.10Mol concentration that contains 26.90ml, fully slowly add anatase titanium dioxide nmTiO under the agitation condition
2Powder stirred 15 minutes until all adding rear continuation, will contain anatase titanium dioxide nmTiO
2The phosphate aqueous solution of powder is all poured in the sweet pot of porcelain, puts into retort furnace, slowly is warming up to 800 ℃, is incubated half an hour, naturally is down to room temperature 20-30 ℃, makes the anatase titanium dioxide nmTiO that contains phosphorous oxides
2Powder, the described anatase titanium dioxide nmTiO that contains phosphorous oxides
2Powder can keep anatase titanium dioxide nmTiO
2Crystal formation is constant under 800 ℃ of states.
5. method according to claim 4, it is characterized in that: the volume of described phosphate aqueous solution is 150ml, the anatase titanium dioxide nmTiO of described adding
2The quality of powder is 25.000g.
6. one of according to claim 4-5 described method is characterized in that: described anatase titanium dioxide nmTiO
2The particle diameter of powder is 20-25nm, and specific surface area is 104-120m
2/ g.
7. one of according to claim 4-6 described method is characterized in that: described anatase titanium dioxide nmTiO
2The crystal formation of powder is determined by X-ray diffracting spectrum XRD.
8. method according to claim 4, it is characterized in that: the phosphorous oxides of described corresponding content is every gram anatase titanium dioxide nmTiO
2In the content of corresponding phosphorus reach 3.05-3.33mg.
9. anatase titanium dioxide nmTiO who contains phosphorous oxides
2The application of powder on plate glass, it is characterized in that: when envrionment temperature is room temperature 20-25 ℃, in 2000-2500ml silk screen printing solution, add an amount of zirconium pearl, use sand milling dispersion machine slow anatase titanium dioxide nmTiO that contains phosphorous oxides that adds such as the method manufacturing among the claim 4-8 under the stirring velocity of 2500-3000r/min
2Powder, and continue to stir 30 minutes, elimination zirconium pearl forms the anatase titanium dioxide nmTiO that contains phosphorous oxides
2Silk screen printing colloidal sol.Plate glass to 8mm thickness carries out the oil removing dust removal process, and the about 5 μ M of thickness of printing nanometer film select 165T or 200T silk screen according to print speed, treats after the printing that the film surface drying can advance 800 ℃ klining formulation type.
10. application according to claim 9 is characterized in that: described zirconium pearl diameter is Φ 1mm and Φ 2mm, and zirconium pearl usage ratio is 4: 6, and add-on is 50g.
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