CN102941020A - Preparation method of high-flux chip type TiO2 nanofiltration membrane - Google Patents
Preparation method of high-flux chip type TiO2 nanofiltration membrane Download PDFInfo
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- CN102941020A CN102941020A CN2012104386115A CN201210438611A CN102941020A CN 102941020 A CN102941020 A CN 102941020A CN 2012104386115 A CN2012104386115 A CN 2012104386115A CN 201210438611 A CN201210438611 A CN 201210438611A CN 102941020 A CN102941020 A CN 102941020A
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- 239000012528 membrane Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000001728 nano-filtration Methods 0.000 title abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract 14
- 230000004907 flux Effects 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 239000006193 liquid solution Substances 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- -1 titanium alkoxide Chemical class 0.000 abstract description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 abstract 2
- 230000014759 maintenance of location Effects 0.000 abstract 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 abstract 1
- 239000011592 zinc chloride Substances 0.000 abstract 1
- 235000005074 zinc chloride Nutrition 0.000 abstract 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- KXCPAUWIRBMTET-SOFGYWHQSA-N (6e)-8-methyl-5-propan-2-ylnona-6,8-dien-2-ol Chemical compound CC(O)CCC(C(C)C)\C=C\C(C)=C KXCPAUWIRBMTET-SOFGYWHQSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of a high-flux chip type TiO2 nanofiltration membrane, which comprises the following steps that a titanium alkoxide is used as a precursor, a sol-gel method is adopted, process parameters are strictly controlled, TiO2 polymerization sol with appropriate performance is prepared, a membrane is coated on a chip type carrier, and then the chip type TiO2 nanofiltration membrane is obtained. The flux of the chip type TiO2 nanofiltration membrane is higher, and the processing capacity of the nanofiltration membrane can be increased, thereby reducing the operating cost in the process of application. Additionally, the nanofiltration membrane has excellent nanofiltration performance, the molecular weight cut off (MWCO) of the TiO2 nanofiltration membrane is less than 1000 Da, the retention rate of the membrane on heavy metal ions Cu(NO3)2, Ni(NO3)2 and ZnCl2 with the concentration of 200 mg/L can reach 80 to 90%, and therefore, the foundation is laid for the application of the TiO2 nanofiltration membrane in the industrial process.
Description
Technical field:
The present invention relates to a kind of high flux chip TiO
2The preparation method of NF membrane.This TiO
2NF membrane will be with a wide range of applications in the industrial applications such as water treatment, dyestuff, food and medicine.
Background technology:
Membrane separation technique have process simple, without chemical change and phase transformation, need not heating and the advantage such as environmentally friendly, be widely used in that various in water treatment, dyestuff, food, medicine and the chemical industry separate, in the refining and concentration process, and NF membrane is owing to having higher rejection to small organic molecule and high valence ion, thereby obtains using very widely.
Difference according to membrane material character, NF membrane can be divided into two kinds of organic nanofiltration membrane and Inorganic Nanofiltration Membranes, wherein, the organic film preparation method is comparatively simple, and preparation cost is low, thereby industrialization and be widely applied in fields such as process industrial and water treatments of organic nanofiltration membrane (such as polysulfones, cellulose acetate, polyamide etc.), yet because organic nanofiltration membrane exists bearing temperature lower, the shortcomings such as the narrower and solvent resistance of acid and alkali-resistance scope is relatively poor are so that its application under some harsh systems is restricted.Nanofiltration membrane is compared with organic nanofiltration membrane has good heat, chemistry and mechanical stability, can be used in high temperature, harsh system and the organic solvent system, therefore is with a wide range of applications.The more nanofiltration membrane of research mainly contains γ-Al at present
2O
3, TiO
2, ZrO
2, SiO
2, HfO
2And the composite membrane between them etc., wherein γ-Al
2O
3The pH tolerance range of NF membrane is narrow, SiO
2NF membrane is alkali-proof medium corrosion etc. not, and TiO
2NF membrane is owing to having the advantages such as thermally-stabilised good (can anti-more than 100 ℃ high temperature), acid-alkali-corrosive-resisting strong (applicable in pH 0 ~ 14 scope), be one of nanofiltration membrane material of at present tool prospect, realized industrialization in companies such as German Inopor, French Tami and U.S. Pall.
At present, chip TiO
2NF membrane is normally with macropore α-Al
2O
3Be carrier, prepare γ-Al by the particle colloidal sols route
2O
3, TiO
2Or ZrO
2Particle colloidal sols transition multilayer on carrier reaches the ultrafiltration scope, prepares TiO by polymerization colloidal sol route again
2Polymerization colloidal sol is coated with one deck and then reaches the nanofiltration stage at milipore filter.Because stable TiO
2Polymerization colloidal sol and TiO
2The preparation process of NF membrane is complicated, preparation condition is harsh, thereby so that TiO
2The preparation difficulty of NF membrane is very large.Simultaneously, because TiO
2Transition is prepared from TiO to NF membrane through multilayer
2The coupling of polymerization colloidal sol and carrier hole structure can directly have influence on TiO
2The performance of NF membrane.For example,
Prepare chip TiO with people such as Zaspalis
2NF membrane, the nanofiltration of these NF membrane is functional, but flux is lower, thus and operation cost big or small closely related in the treating capacity that the height of flux will be directly connected to NF membrane and the application process.
Summary of the invention:
The objective of the invention is to provide in order to improve the deficiencies in the prior art a kind of high flux chip TiO
2The preparation method of NF membrane.
Technical scheme of the present invention is: a kind of high flux chip TiO
2The preparation method of NF membrane, its concrete steps are:
A:TiO
2Synthesizing of polymerization colloidal sol
With titanium precursor body and solvent 1:(10 ~ 80 in molar ratio) ratio mix and stir to the titanium precursor liquid solution, then with inorganic acid and deionized water with mol ratio 1:(1 ~ 20) ratio be mixed with acid solution, take the mol ratio of acid solution and titanium precursor liquid solution as 1:(5 ~ 20) ratio acid solution is added in the titanium precursor liquid solution, place ice bath to stir, at last this solution being placed temperature is that 0 ~ 90 ℃ water bath with thermostatic control is reacted, behind reaction 1 ~ 6h, obtain the TiO of appearance transparent
2Polymerization colloidal sol;
B: be coated with membrane process
With TiO
2Polymerization colloidal sol and solvent be 1:(5 ~ 20 by volume) dilution proportion be mixed with preparation liquid, preparation liquid is filmed at carrier surface;
C: drying and sintering process
To apply the carrier drying of preparation liquid, and be warming up in 300 ~ 600 ℃ the scope and naturally lower the temperature behind insulation 1 ~ 6h, make high flux chip TiO
2NF membrane.
Titanium precursor body among the preferred steps a is tetraethyl titanate, tetraisopropyl titanate or butyl titanate; Solvent among step a and the b is and the corresponding female alcohol of presoma, is preferably ethanol, isopropyl alcohol or n-butanol; Inorganic acid among the preferred steps a is hydrochloric acid, nitric acid or sulfuric acid; Mixing time among the preferred steps a is 5 ~ 20min; Ice bath temperature among the preferred steps a is-20 ~ 0 ℃; The water bath with thermostatic control reaction time among the preferred steps a is 2 ~ 5h.Carrier among the preferential step b is the γ-Al of chip
2O
3The TiO of film, chip
2The ZrO of film or chip
2Film.Heating rate among the preferred steps c is 0.2 ~ 2 ℃/min.
In step a, can obtain appearance transparent and stable TiO
2Can polymerization colloidal sol be to be related to finally prepare high flux TiO
2One of key factor of NF membrane.Because the hydrolysis rate of titanium precursor body is very fast, the present invention has carried out a large amount of research and probes, by strict control procedure parameter, finally successfully prepares appearance transparent and stable TiO
2Polymerization colloidal sol.In being coated with membrane process, can the viscosity of preparation liquid to obtaining perfect sunken TiO
2The NF membrane impact is very large.
Beneficial effect:
The present invention's polymerisation that is hydrolyzed take the titanium alkoxide as presoma adopts sol-gel process, by accurate control procedure parameter, prepares the colloidal sol of suitable performance and films at the chip carrier, finally prepares chip TiO
2NF membrane.Through characterizing this TiO
2The flux of NF membrane is higher, thereby the treating capacity that can improve NF membrane reduces the operation cost in the application process.Simultaneously, this material has showed comparatively excellent nanofiltration performance, the molecular cut off MWCO＜1000Da of film, and higher to the rejection of ion, this lays a good foundation for its application in industrial process.
Description of drawings:
Fig. 1 is the chip TiO that burns till under 300 ℃ among the embodiment 1
2The pure water flux figure of NF membrane;
Fig. 2 is the high flux chip TiO that burns till under 300 ℃ among the embodiment 1
2NF membrane is to the cutoff performance figure of PEG;
Fig. 3 is the high flux chip TiO that burns till under 300 ℃ among the embodiment 1
2NF membrane under different operating pressure to the cutoff performance figure of ion, wherein
Be Cu (NO
3)
2 
Be Ni (NO
3)
2 
Be ZnCl
2 
Be CdCl
2
The chip TiO that burns till under 300 ℃ in Fig. 4 comparative example 1
2The pure water flux figure of NF membrane.
The specific embodiment:
Embodiment 1:
2.1ml (0.01mol) tetraethyl titanate mixed with 8ml (0.14mol) ethanol and stir 15min after obtain mixed liquor M1.With 0.9mL (0.012mol) hydrochloric acid and 0.27mL (0.015mol) H
2O obtains mixed liquor M2 after mixing.Mixed liquor M1 placed 0 ℃ ice bath, under the condition that stirs, add mixed liquor M2.After mixing 15min, place rapidly 0 ℃ water bath with thermostatic control to react 2h.After finishing, reaction obtains the TiO of appearance transparent
2Polymerization colloidal sol.Be placed on-20 ℃ of lower preservations stand-by.Ratio take volume ratio as 1:5 is mixed to get preparation liquid with colloidal sol and ethanol, with preparation liquid at chip γ-Al
2O
3Carrier surface is filmed, and with 2 ℃ of min
-1The heating rate sintering, reach 300 ℃ after the insulation 2h more naturally the cooling, obtain TiO
2NF membrane.The pure water flux of this film is higher, as shown in Figure 1, is about 1.63Lm
-2h
-1Bar
-1, to holding back as shown in Figure 2 of PEG, molecular cut off MWCO＜1000Da is about 545Da.Fig. 3 is TiO
2NF membrane under different pressures to the cutoff performance of ion, as can be seen from the figure, TiO
2NF membrane is the heavy metal ion Cu (NO of 200mg/L to concentration
3)
2, Ni (NO
3)
2And ZnCl
2Rejection can reach 80 ~ 90%.
Comparative example 1:
Document (Journal of Sol-Gel Science and Technology 31 (2004) 201-204) has been reported TiO
2The preparation of NF membrane.
Take tetraethyl titanate as presoma, promote TiO take nitric acid as catalyst
2The formation of polymerization colloidal sol, control H
2The mol ratio of O and tetraethyl titanate＜2, the mol ratio of nitric acid and tetraethyl titanate〉0.02, through obtaining TiO after hydrolysis and the polymerisation
2Colloidal sol.Adopt the laminar film instrument of filming, by cement-dipping method, with TiO
2Colloidal sol is at chip γ-Al
2O
3Carrier or TiO
2After carrier surface applies 1 time, be warmed up to 300 ℃ after insulation 3h lower the temperature again, obtain TiO
2Film.Fig. 4 is the TiO that burns till under 300 ℃
2The pure water flux of film.As can be seen from the figure, TiO
2The pure water flux of film only is 0.38L m
-2h
-1Bar
-1
Embodiment 2:
3ml (0.01mol) tetraisopropyl titanate mixed with 40ml (0.52mol) isopropyl alcohol and stir 8min after obtain mixed liquor M1.With 0.2mL (0.003mol) nitric acid and 1mL (0.056mol) H
2O obtains mixed liquor M2 after mixing.Mixed liquor M1 placed-20 ℃ ice bath, under the condition that stirs, add mixed liquor M2.After mixing 8min, place rapidly 80 ℃ water bath with thermostatic control to react 3h.After finishing, reaction obtains the TiO of appearance transparent
2Polymerization colloidal sol.Be placed on-20 ℃ of lower preservations stand-by.Ratio take volume ratio as 1:12 is mixed to get preparation liquid with colloidal sol and isopropyl alcohol, with preparation liquid at chip TiO
2Carrier surface is filmed, and with 1 ℃ of min
-1The heating rate sintering, reach 450 ℃ after the insulation 5h more naturally the cooling, obtain TiO
2NF membrane.Through characterizing TiO
2The pure water flux of NF membrane is about 1.88L m
-2h
-1Bar
-1, molecular cut off MWCO＜1000Da has the nanofiltration performance.
Embodiment 3:
3.4ml (0.01mol) butyl titanate mixed with 65ml (0.71mol) n-butanol and stir 16min after obtain mixed liquor M1.With 0.15mL (0.003mol) sulfuric acid and 0.64mL (0.036mol) H
2O obtains mixed liquor M2 after mixing.Mixed liquor M1 placed-10 ℃ ice bath, under the condition that stirs, add mixed liquor M2.After mixing 16min, place rapidly 40 ℃ water bath with thermostatic control to react 5h.After finishing, reaction obtains the TiO of appearance transparent
2Polymerization colloidal sol.Be placed on-20 ℃ of lower preservations stand-by.Ratio take volume ratio as 1:18 is mixed to get preparation liquid with colloidal sol and n-butanol, with preparation liquid at chip ZrO
2Carrier surface is filmed, and with 0.2 ℃ of min
-1The heating rate sintering, reach 550 ℃ after the insulation 3h more naturally the cooling, obtain TiO
2NF membrane.Through characterizing TiO
2The pure water flux of NF membrane is 1.4L m
-2h
-1Bar
-1, molecular cut off MWCO＜1000Da has the nanofiltration performance.
Claims (9)
1. high flux chip TiO
2The preparation method of NF membrane, its concrete steps are:
A:TiO
2Synthesizing of polymerization colloidal sol
With titanium precursor body and solvent 1:(10 ~ 80 in molar ratio) ratio mix and stir to the titanium precursor liquid solution, then with inorganic acid and deionized water with mol ratio 1:(1 ~ 20) ratio be mixed with acid solution, take the mol ratio of acid solution and titanium precursor liquid solution as 1:(5 ~ 20) ratio acid solution is added in the titanium precursor liquid solution, place ice bath to stir, at last this solution being placed temperature is that 0 ~ 90 ℃ water bath with thermostatic control is reacted, behind reaction 1 ~ 6h, obtain the TiO of appearance transparent
2Polymerization colloidal sol;
B: be coated with membrane process
With TiO
2Polymerization colloidal sol and solvent be 1:(5 ~ 20 by volume) dilution proportion be mixed with preparation liquid, preparation liquid is filmed at carrier surface;
C: drying and sintering process
To apply the carrier drying of preparation liquid, and be warming up in 300 ~ 600 ℃ the scope and naturally lower the temperature behind insulation 1 ~ 6h, make high flux chip TiO
2NF membrane.
2. preparation method according to claim 1 is characterized in that the titanium precursor body among the step a is tetraethyl titanate, tetraisopropyl titanate or butyl titanate.
3. preparation method according to claim 1 is characterized in that the solvent described in step a and the b is ethanol, isopropyl alcohol or n-butanol.
4. preparation method according to claim 1 is characterized in that the inorganic acid among the step a is hydrochloric acid, nitric acid or sulfuric acid.
5. preparation method according to claim 1 is characterized in that the mixing time among the step a is 5 ~ 20min.
6. preparation method according to claim 1 is characterized in that the ice bath temperature among the step a is-20 ~ 0 ℃.
7. preparation method according to claim 1 is characterized in that the water bath with thermostatic control reaction time among the step a is 2 ~ 5h.
8. preparation method according to claim 1 is characterized in that the carrier among the step b is the γ-Al of chip
2O
3The TiO of film, chip
2The ZrO of film or chip
2Film.
9. preparation method according to claim 1 is characterized in that the heating rate among the step c is 0.2 ~ 2 ℃ of min
-1
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|---|---|---|---|
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|---|---|
| CN102941020A true CN102941020A (en) | 2013-02-27 |
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ID=47724065
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|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718543A (en) * | 2012-06-12 | 2012-10-10 | 中材高新材料股份有限公司 | Preparation method of ceramic membrane filter element for treatment of printing and dyeing wastewater |
| CN102744049A (en) * | 2012-07-06 | 2012-10-24 | 长安大学 | Process for preparing TiO2 (titanium dioxide) film on aluminum-oxide foamed ceramic |
-
2012
- 2012-11-06 CN CN2012104386115A patent/CN102941020A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102718543A (en) * | 2012-06-12 | 2012-10-10 | 中材高新材料股份有限公司 | Preparation method of ceramic membrane filter element for treatment of printing and dyeing wastewater |
| CN102744049A (en) * | 2012-07-06 | 2012-10-24 | 长安大学 | Process for preparing TiO2 (titanium dioxide) film on aluminum-oxide foamed ceramic |
Non-Patent Citations (1)
| Title |
|---|
| 漆虹 等: "TiO2纳滤膜的制备及其离子截留性能", 《无机材料学报》 * |
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Application publication date: 20130227 |