KR101007887B1 - METHOD FOR PREPARING SiO2-TiO2-BASED COMPOSITE INORGANIC FIBERS USING TWO-STEP HEAT-TREATMENT - Google Patents
METHOD FOR PREPARING SiO2-TiO2-BASED COMPOSITE INORGANIC FIBERS USING TWO-STEP HEAT-TREATMENT Download PDFInfo
- Publication number
- KR101007887B1 KR101007887B1 KR1020080117300A KR20080117300A KR101007887B1 KR 101007887 B1 KR101007887 B1 KR 101007887B1 KR 1020080117300 A KR1020080117300 A KR 1020080117300A KR 20080117300 A KR20080117300 A KR 20080117300A KR 101007887 B1 KR101007887 B1 KR 101007887B1
- Authority
- KR
- South Korea
- Prior art keywords
- tio
- sio
- inorganic fiber
- composite inorganic
- heat treatment
- Prior art date
Links
- 239000012784 inorganic fiber Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000010438 heat treatment Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 39
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001523 electrospinning Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- -1 alkoxide compound Chemical class 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- PPJYSSNKSXAVDB-UHFFFAOYSA-N 3,3',5,5'-tetraiodothyroacetic acid Chemical compound IC1=CC(CC(=O)O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 PPJYSSNKSXAVDB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000035800 maturation Effects 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000000356 contaminant Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 25
- 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 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 229920001410 Microfiber Polymers 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/58—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
Abstract
본 발명은 전기방사를 이용한 SiO2-TiO2계 복합무기섬유의 제조방법에 관한 것으로, 본 발명의 방법은 (1) 실리콘-함유 알콕사이드 화합물 및 티타늄-함유 유기화합물을 포함하는 전구체 용액을 숙성시켜 실리카/티타니아 졸 용액을 제조하는 단계; (2) 상기 실리카/티타니아 졸 용액을 상온에서 전기방사하여 무기섬유를 제조하는 단계; 및 (3) 상기 무기섬유를 100∼400℃에서 1∼48시간 동안 1차 열처리한 후 300∼1200℃에서 1∼6시간 동안 2차 열처리하되, 상기 2차 열처리를 1차 열처리에 비해 100℃ 이상 높은 온도에서 수행하는 단계를 포함하는 것을 특징으로 하며, 이러한 방법에 의해 제조된 SiO2-TiO2계 복합무기섬유는 우수한 열안정성 및 광촉매 활성을 나타내므로, 수처리, 공기필터 및 오염물의 처리에 유용하게 사용될 수 있다. The present invention relates to a method for producing SiO 2 -TiO 2 based inorganic inorganic fibers using electrospinning, the method of the present invention (1) by the aging of a precursor solution containing a silicon-containing alkoxide compound and a titanium-containing organic compound Preparing a silica / titania sol solution; (2) preparing an inorganic fiber by electrospinning the silica / titania sol solution at room temperature; And (3) primary heat treatment of the inorganic fiber at 100 to 400 ° C. for 1 to 48 hours, and secondary heat treatment at 300 to 1200 ° C. for 1 to 6 hours, wherein the secondary heat treatment is 100 ° C. compared with the primary heat treatment. It characterized in that it comprises a step carried out at a high temperature above, the SiO 2 -TiO 2 composite inorganic fiber produced by this method shows excellent thermal stability and photocatalytic activity, so it is used for the treatment of water treatment, air filters and contaminants It can be usefully used.
Description
본 발명은 우수한 광촉매 활성을 갖는 나노 내지는 서브마이크로(submicro) 크기의 SiO2-TiO2계 복합무기섬유를 2단계 열처리를 이용하여 제조하는 방법에 관한 것이다.The present invention relates to a method for producing nano- or submicro-sized SiO 2 -TiO 2 -based composite inorganic fibers having excellent photocatalytic activity using a two -step heat treatment.
나노 내지는 서브마이크로미터 단위의 지름을 갖는 초극세 무기섬유의 제조에 전기방사 기술이 이용될 수 있다. 전기방사 기술은, 고전압을 고분자 용액 혹은 용융물의 방사 도프(dope)와 포집판에 적용하여 나노 내지는 서브마이크로미터 단위 직경으로 방사된 초극세 섬유가 포집판에 집속되도록 하여 웹을 형성시키는 방법이다. 전기방사는 단위 중량당 큰 비표면적을 갖는 초극세 섬유의 제조가 가능할 뿐 아니라 용액 및 용융물을 형성하는 모든 고분자 소재에 적용이 가능하여 다양한 용도로 활용할 수 있다는 장점을 갖는다.Electrospinning techniques may be used to prepare ultrafine inorganic fibers having a diameter in the nano or submicron units. Electrospinning technology is a method of forming a web by applying a high voltage to the spinning dope and the collecting plate of the polymer solution or melt so that the ultra-fine fibers spun at nano or submicron unit diameter is concentrated on the collecting plate. Electrospinning not only enables the production of ultra-fine fibers having a large specific surface area per unit weight, but also has the advantage of being applicable to various polymer materials forming solutions and melts.
유기고분자와 무기재료를 혼합하면, 무기재료의 특성인 고강도, 고내열성, 열안정성, 내화학성 등과 유기재료의 특성인 가변성을 동시에 가짐으로써 형태 제어가 가능하고 제조가 간단한 유-무기 하이브리드 재료를 만들 수 있다. 이러한 유-무기 하이브리드 재료를 전기방사하면 상대적으로 높은 표면적을 갖는 초극세 유-무기 하이브리드 복합무기섬유를 얻을 수 있다.When organic polymers and inorganic materials are mixed, they have both high strength, high heat resistance, thermal stability, chemical resistance, and variability, which are characteristics of organic materials, to form organic-inorganic hybrid materials that can be controlled in form and are simple to manufacture. Can be. Electrospinning such organic-inorganic hybrid materials can yield ultra-fine organic-inorganic hybrid composite inorganic fibers having a relatively high surface area.
이러한 유-무기 하이브리드 복합무기섬유를 고온에서 열처리하면 유기고분자는 분해되어 사라지고 무기 나노섬유가 얻어지게 된다. 통상적인 방법으로는 섬유화할 수 없는 무기재료를 섬유화하였다는 점에서 이 무기 나노섬유에 많은 관심이 집중되고 있다. 하지만, 아직은 평가단계에 불과하고 실험실 규모로 연구가 진행되고 있기 때문에 상업화까지는 상당한 연구가 필요한 실정이다.When the organic-inorganic hybrid composite inorganic fiber is heat-treated at high temperature, the organic polymer is decomposed and disappeared to obtain inorganic nanofibers. Much attention has been focused on this inorganic nanofiber in that the inorganic material cannot be fiberized by a conventional method. However, it is still only in the evaluation stage and research is being carried out on a laboratory scale, which requires considerable research until commercialization.
한편, 반도성 물질인 광촉매 TiO2를 이용하여 액상, 기상 및 고상 오염물질을 광산화 처리하는 기술은 2차 오염을 유발하지 않고, 슬러리를 발생시키지 않으며, 생물학적으로 난분해성인 유기염소화합물에 대한 광분해 효과가 높아서, 기존의 환경 처리기술의 난점을 보완할 수 있는 유망한 방법으로 기대되고 있다.On the other hand, the technology for photooxidizing liquid, gaseous and solid contaminants using the photocatalyst TiO 2 , which is a semiconducting material, does not cause secondary pollution, does not generate slurry, and photodecomposes organic biologically decomposable organic chlorine compounds. It is highly effective and is expected to be a promising way to supplement the difficulties of existing environmental treatment technologies.
이러한 맥락에서, 극대화된 성능을 갖는 오염물질 처리용 광촉매 물질에 대한 연구가 환경, 에너지 및 신물질 개발의 영역에서 절실히 요구되고 있다.In this context, research on pollutant treatment photocatalytic materials with maximum performance is urgently needed in the area of environment, energy and new material development.
따라서, 본 발명의 목적은 오염물질의 처리에 유용한, 우수한 활성을 갖는 TiO2가 함유된 Si를 기초로 한 섬유상 무기 광촉매를 제조하는 방법을 제공하는 것이다.Accordingly, it is an object of the present invention to provide a method for preparing a fibrous inorganic photocatalyst based on Si containing TiO 2 having good activity, which is useful for the treatment of contaminants.
상기 목적을 달성하기 위하여 본 발명은, The present invention to achieve the above object,
(1) 실리콘-함유 알콕사이드 화합물 및 티타늄-함유 유기화합물을 포함하는 전구체 용액을 숙성시켜 실리카/티타니아 졸 용액을 제조하는 단계;(1) aging a precursor solution comprising a silicon-containing alkoxide compound and a titanium-containing organic compound to produce a silica / titania sol solution;
(2) 상기 실리카/티타니아 졸 용액을 상온에서 전기방사하여 무기섬유를 제조하는 단계; 및(2) preparing an inorganic fiber by electrospinning the silica / titania sol solution at room temperature; And
(3) 상기 무기섬유를 100∼400℃에서 1∼48시간 동안 1차 열처리한 후 300∼1200℃에서 1∼6시간 동안 2차 열처리하되, 상기 2차 열처리를 1차 열처리에 비해 100℃ 이상 높은 온도에서 수행하는 단계(3) heat treatment of the inorganic fiber for 1 to 48 hours at 100 to 400 ° C., followed by secondary heat treatment at 300 to 1200 ° C. for 1 to 6 hours, wherein the secondary heat treatment is 100 ° C. or more compared to the first heat treatment. Steps to Perform at High Temperature
를 포함하는, SiO2-TiO2계 복합무기섬유의 제조방법을 제공한다.It provides a method for producing a SiO 2 -TiO 2 -based composite inorganic fiber comprising a.
본 발명의 방법에 의해 제조된 SiO2-TiO2계 복합무기섬유는 섬유 표면에 균 일하게 분포된 TiO2를 다량으로 포함하고 있어 우수한 열안정성 및 광촉매 활성을 나타내므로, 수처리, 공기필터 및 오염물의 처리에 유용하게 사용될 수 있다. SiO 2 -TiO 2 composite inorganic fiber prepared by the method of the present invention contains a large amount of TiO 2 uniformly distributed on the surface of the fiber, showing excellent thermal stability and photocatalytic activity, so that water treatment, air filters and contaminants It can be usefully used for the treatment of.
본 발명에 따른 SiO2-TiO2계 복합무기섬유는, (1) 실리콘-함유 알콕사이드 화합물 및 티타늄-함유 유기화합물을 포함하는 전구체 용액을 숙성시켜 실리카/티타니아 졸 용액을 형성한 후, (2) 이를 상온에서 전기방사하여 무기섬유를 제조한 다음, (3) 이를 2단계 열처리함으로써 제조된다.The SiO 2 -TiO 2 -based composite inorganic fiber according to the present invention is prepared by (1) aging a precursor solution containing a silicon-containing alkoxide compound and a titanium-containing organic compound to form a silica / titania sol solution, followed by (2) This is electrospun at room temperature to prepare an inorganic fiber, and then (3) it is prepared by heat treatment in two steps.
본 발명에 사용되는 실리콘-함유 알콕사이드 화합물의 예로는 테트라C1-4알킬오르소실리케이트, 1 내지 3개의 알콕시기를 갖는 실란계 화합물 및 이들의 혼합물을 들 수 있으며, 티타늄-함유 유기화합물로는 티타늄 C1-4알콕사이드를 비롯한 다양한 티타늄-함유 유기착체를 사용할 수 있다. 상기 실리콘-함유 알콕사이드 화합물을 티타늄-함유 유기화합물 1 중량부를 기준으로 1 내지 100 중량부, 바람직하게는 1 내지 10 중량부의 양으로 사용할 수 있다. Examples of silicon-containing alkoxide compounds used in the present invention include tetraC 1-4 alkylorthosilicates, silane compounds having 1 to 3 alkoxy groups, and mixtures thereof, and titanium-containing organic compounds include titanium Various titanium-containing organic complexes can be used including C 1-4 alkoxides. The silicon-containing alkoxide compound may be used in an amount of 1 to 100 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of the titanium-containing organic compound.
본 발명에 따른 전구체 용액에 사용되는 용매로는 물과 알콜의 혼합물이 적합하며, 바람직하게는 1:1 중량비의 물과 알콜의 혼합물일 수 있고, 상기 알콜로는 에탄올 및 이소프로판올 (i-PrOH)과 같은 저급 알콜을 사용할 수 있다.As a solvent used in the precursor solution according to the present invention, a mixture of water and alcohol is suitable, preferably a mixture of water and alcohol in a 1: 1 weight ratio, and the alcohol is ethanol and isopropanol ( i -PrOH). Lower alcohols such as these may be used.
상기 실리콘-함유 알콕사이드 화합물 및 티타늄-함유 유기화합물 각각의 가수분해와 고분자화를 촉진시키기 위해, 전구체 용액에 염산 또는 암모니아수를 추 가로 첨가하는 것이 바람직하며, 이때 염산 또는 암모니아수를 티타늄-함유 유기화합물 1 중량부를 기준으로 0.1 내지 5 중량부의 양으로 사용할 수 있다.In order to promote hydrolysis and polymerization of each of the silicon-containing alkoxide compound and the titanium-containing organic compound, it is preferable to further add hydrochloric acid or ammonia water to the precursor solution, wherein hydrochloric acid or ammonia water is added to the titanium-containing organic compound 1 It can be used in an amount of 0.1 to 5 parts by weight based on parts by weight.
본 발명에서는, 상기 전구체 용액을 바람직하게는 40 내지 100℃, 더욱 바람직하게는 60 내지 80℃의 온도에서 1 내지 5시간 동안 유지(숙성)시키는데, 상기 숙성공정 동안 전구체 용액 중의 실리콘-함유 알콕사이드 화합물과 티타늄-함유 유기화합물은 가수분해된 후 축중합되어 엉킴을 일으킬 수 있는 분자의 크기로 충분히 성장하게 되고, 이로써 용액의 점도가 증가하면서 전기방사에 적합한 점도를 갖는 실리카/티타니아 졸 용액이 형성된다. 숙성시간이 상기 범위값 보다 길어지게 되면, 용액의 점도가 과도하게 높아져 용액의 겔화가 일어나 전기방사가 불가능해질 수 있다. 전기방사에 적합한 실리카/티타니아 졸 용액의 점도는 60 내지 100 센티포이즈(25℃에서) 범위이다.In the present invention, the precursor solution is preferably maintained (matured) for 1 to 5 hours at a temperature of 40 to 100 ° C, more preferably 60 to 80 ° C, wherein the silicon-containing alkoxide compound in the precursor solution during the aging process And titanium-containing organic compounds are sufficiently hydrolyzed and condensed to grow to the size of molecules that can cause entanglement, thereby increasing the viscosity of the solution to form a silica / titania sol solution having a viscosity suitable for electrospinning. . If the aging time is longer than the above range value, the viscosity of the solution may be excessively high and gelation of the solution may occur, thereby making electrospinning impossible. Silica / titania sol solutions suitable for electrospinning range from 60 to 100 centipoise (at 25 ° C.).
또한, 상기 전구체 용액 또는 상기 형성된 졸 용액에 Fe, Zn, Co, Ni 등 전이금속 및 이들의 합금, 또는 이의 산화물 또는 유기착체를 첨가함으로써 추후 도핑된 SiO2-TiO2계 복합무기섬유를 제조할 수 있다.In addition, a doped SiO 2 -TiO 2 based inorganic inorganic fiber may be prepared by adding a transition metal such as Fe, Zn, Co, Ni, an alloy thereof, or an oxide or an organic complex thereof to the precursor solution or the formed sol solution. Can be.
이와 같이 형성된 실리카/티타니아 졸 용액을 상온에서 통상적인 방법에 따라 전기방사함으로써 나노 내지는 서브마이크론 크기의 무기섬유를 제조하는데, 이에 사용되는 전기방사 장치는 주사기(실린지 펌프)와 주사바늘, 바닥전극(회전 속도를 조절할 수 있는 스테인레스 강판의 드럼) 및 방사전압 공급장치로 구성된다. 이때, 주사바늘의 끝과 드럼 사이의 거리는 5 내지 30 cm 범위일 수 있으며, 방사 전압은 15 kV 이상, 바람직하게는 20 내지 30 kV일 수 있고, 실린지 펌프의 방사용액의 유량은 1 내지 20 ml/hr일 수 있다.The thus formed silica / titania sol solution is electrospun at room temperature according to a conventional method to produce nano- or submicron-sized inorganic fibers. The electrospinning apparatus used in this method includes a syringe (syringe pump), a needle, and a bottom electrode. (Drum of stainless steel plate with adjustable rotation speed) and radiation voltage supply device. At this time, the distance between the end of the needle and the drum may be in the range of 5 to 30 cm, the radiation voltage may be 15 kV or more, preferably 20 to 30 kV, the flow rate of the spinning solution of the syringe pump is 1 to 20 may be ml / hr.
이와 같이 제조된 무기섬유를 100∼400℃에서 1∼48시간 동안 1차 열처리한 후 300∼1200℃에서 1∼6시간 동안 2차 열처리하되, 상기 2차 열처리를 1차 열처리에 비해 100℃ 이상, 바람직하게는 300∼700℃ 정도 높은 온도에서 수행하여 소성시킴으로써 목적하는 SiO2-TiO2계 복합무기섬유를 얻을 수 있다.The inorganic fiber prepared as described above was subjected to the first heat treatment at 100 to 400 ° C. for 1 to 48 hours and then to the second heat treatment at 300 to 1200 ° C. for 1 to 6 hours. Preferably, the desired SiO 2 -TiO 2 -based composite inorganic fiber can be obtained by performing baking at a high temperature of about 300 to 700 ° C.
열처리 후에도 섬유 형태가 거의 유지되므로, 전기방사에 의해 얻어진 섬유는 열처리 전과 후 모두 50 내지 2,500 nm 범위의 직경을 가질 수 있으며, 이 직경은 TiO2의 농도가 증가함에 따라 증가하는 경향이 있다.Since the fiber shape is almost maintained even after the heat treatment, the fiber obtained by electrospinning may have a diameter in the range of 50 to 2,500 nm both before and after the heat treatment, and the diameter tends to increase as the concentration of TiO 2 increases.
본 발명에 따른 SiO2-TiO2계 복합무기섬유는 우수한 열안정성 및 광촉매 활성을 나타내는데, 이는, 열처리 후에도 고르게 분산되어 있는 SiO2가 TiO2 입자 및 분자의 이동을 방해하여 TiO2가 응집하는 것을 방지함으로써 입자 크기가 증가하는 것을 억제하기 때문이다. 특히 적어도 SiO2의 함량이 TiO2의 함량 보다 많을 경우 그 결정구조가 아나타제(anatase)상에서 루타일(rutile)상으로 상전이되는 것이 억제될 수 있다. 나아가, 본 발명에 따른 2단계 열처리는 SiO2-TiO2 입자에서 TiO2의 입자 표면으로의 확산(bleed-out)을 유도하므로, 본 발명에 따른 복합무기섬유는 섬유 표면에 균일하게 분포된 TiO2를 다량으로 포함함으로써 광활성에 적합한 자외선 흡수가 가능하여 우수한 광촉매 활성을 나타내며, 이러한 효과는 단일 열처리를 통해서는 달성될 수 없는 것이다.The SiO 2 -TiO 2 based inorganic inorganic fiber according to the present invention exhibits excellent thermal stability and photocatalytic activity, which indicates that evenly dispersed SiO 2 prevents TiO 2 particles and molecules from agglomerating and aggregates TiO 2. This is because it prevents the particle size from increasing. In particular, when the content of at least SiO 2 is greater than the content of TiO 2 , the phase transition of the crystal structure from the anatase to the rutile phase can be suppressed. Furthermore, the two stage heat treatment according to the present invention is derived because the diffusion (bleed-out) to the surface of the TiO 2 particles in the SiO 2 -TiO 2 particles, composite inorganic fibers according to the invention is uniformly distributed on the fiber surface TiO By containing a large amount of 2 , it is possible to absorb ultraviolet rays suitable for photoactivity and thus exhibit excellent photocatalytic activity. Such an effect cannot be achieved through a single heat treatment.
이와 같이, 본 발명에 따라 제조된 SiO2-TiO2계 복합무기섬유는 우수한 열안정성 및 광촉매 활성을 나타내므로, 수처리, 공기필터 및 오염물의 처리에 유용하게 사용될 수 있다.As described above, since the SiO 2 -TiO 2 -based composite inorganic fiber prepared according to the present invention shows excellent thermal stability and photocatalytic activity, it can be usefully used for water treatment, air filter and contaminant treatment.
이하, 본 발명을 하기 실시예에 의거하여 좀더 상세하게 설명하고자 한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위가 이들만으로 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
<SiO<SiO 22 -TiO-TiO 22 계 복합무기섬유의 제조>Manufacturing of Compound Inorganic Fiber>
실시예 1Example 1
실리카/티타니아 졸 용액의 제조에 사용되는 원료로서, 아크로스(Acros)사 제품인 98% 이상의 순도를 갖는 테트라에틸오르소실리케이트(TEOS), 티타늄 이소프로폭사이드(TiP) 및 이소프로필알코올(i-PrOH)을 구입하여 사용하였다.Tetraethylorthosilicate (TEOS), titanium isopropoxide (TiP) and isopropyl alcohol ( i -having a purity of 98% or more, manufactured by Acros, as a raw material for the preparation of the silica / titania sol solution. PrOH) was purchased and used.
먼저, i-PrOH, TEOS, 물 및 HCl을 혼합한 후, 여기에 TiP를 서서히 첨가하면서 격렬하게 교반하였다. 이때, i-PrOH, TEOS, 물, HCl 및 TiP의 중량비는 1.0 : 0.5 : 1.0 : 0.3 : 0.5 이었다. 이 전구체 용액을 70℃에서 3시간 동안 숙성시켜 약 70 센티포이즈(25℃에서)의 점도를 갖는 실리카/티타니아 졸 용액을 제조하였다.First, i- PrOH, TEOS, water and HCl were mixed and then stirred vigorously while TiP was slowly added thereto. At this time, the weight ratio of i- PrOH, TEOS, water, HCl and TiP was 1.0: 0.5: 1.0: 0.3: 0.5. This precursor solution was aged at 70 ° C. for 3 hours to produce a silica / titania sol solution having a viscosity of about 70 centipoise (at 25 ° C.).
제조된 실리카/티타니아 졸 용액을 상온에서 전기방사하여 무기섬유를 제조 하였는데, 전기방사시 주사기(실린지 펌프)와 주사바늘(바늘 사이즈 : 0.81 mm), 바닥전극(회전 속도를 조절할 수 있는 스테인레스 강판의 드럼, 드럼 직경 : 21.5 cm) 및 방사전압 공급장치로 구성되어 있는 전기방사 장치(CPS-UC2000, CPS 40K03VIT, 청파(주))를 사용하였다. 이때, 주사바늘의 끝과 드럼 사이의 거리는 12 cm이고, 방사전압은 25 kV이며, 실린지 펌프의 방사용액의 유량은 3 ml/hr이었다.Inorganic fibers were prepared by electrospinning the prepared silica / titania sol solution at room temperature.In the case of electrospinning, a syringe (syringe pump), a needle (needle size: 0.81 mm), and a bottom electrode (stainless steel plate with adjustable rotation speed) Electrospinning apparatus (CPS-UC2000, CPS 40K03VIT, Cheongpa Co., Ltd.) consisting of a drum, a drum diameter of 21.5 cm) and a radiation voltage supply device was used. At this time, the distance between the end of the needle and the drum was 12 cm, the radiation voltage was 25 kV, the flow rate of the spinning solution of the syringe pump was 3 ml / hr.
전기방사에 의해 형성된 무기섬유를 300℃에서 2시간 동안 1차 열처리한 후 1,000℃에서 2시간 동안 2차 열처리하여 목적하는 SiO2-TiO2 복합무기섬유를 얻었다.The inorganic fibers formed by electrospinning were subjected to primary heat treatment at 300 ° C. for 2 hours and then secondary heat treatment at 1,000 ° C. for 2 hours to obtain desired SiO 2 -TiO 2 composite inorganic fibers.
실시예 2Example 2
i-PrOH, TEOS, 물, HCl 및 TiP의 중량비를 1.0 : 0.9 : 1.0 : 0.3 : 0.1 로 변화시키고 숙성을 2시간 동안 수행한 것을 제외하고는, 상기 실시예 1과 동일한 방법을 수행하여 목적하는 SiO2-TiO2 복합무기섬유를 얻었다.Except for changing the weight ratio of i- PrOH, TEOS, water, HCl and TiP to 1.0: 0.9: 1.0: 0.3: 0.1 and aging for 2 hours, the same method as in Example 1 SiO 2 -TiO 2 composite inorganic fibers were obtained.
실시예 3Example 3
i-PrOH, TEOS, 물, HCl 및 TiP의 중량비를 1.0 : 0.8 : 1.0 : 0.3 : 0.2 로 변화시키고 숙성을 2시간 동안 수행한 것을 제외하고는, 상기 실시예 1과 동일한 방법을 수행하여 목적하는 SiO2-TiO2 복합무기섬유를 얻었다.Except for changing the weight ratio of i- PrOH, TEOS, water, HCl and TiP to 1.0: 0.8: 1.0: 0.3: 0.2 and aging for 2 hours, the same method as in Example 1 SiO 2 -TiO 2 composite inorganic fibers were obtained.
비교예 1Comparative Example 1
단일 열처리를 1000℃에서 2시간 동안 수행한 것을 제외하고는, 상기 실시예 1과 동일한 방법을 수행하여 SiO2-TiO2 복합무기섬유를 얻었다.Except that the single heat treatment was performed for 2 hours at 1000 ℃, the same method as in Example 1 was carried out to obtain a SiO 2 -TiO 2 composite inorganic fiber.
비교예 2Comparative Example 2
단일 열처리를 1000℃에서 2시간 동안 수행한 것을 제외하고는, 상기 실시예 2와 동일한 방법을 수행하여 SiO2-TiO2 복합무기섬유를 얻었다.Except that the single heat treatment was performed for 2 hours at 1000 ℃, the same method as in Example 2 was carried out to obtain a SiO 2 -TiO 2 composite inorganic fiber.
비교예 3Comparative Example 3
단일 열처리를 1000℃에서 2시간 동안 수행한 것을 제외하고는, 상기 실시예 3과 동일한 방법을 수행하여 SiO2-TiO2 복합무기섬유를 얻었다.Except that the single heat treatment was performed for 2 hours at 1000 ℃, the same method as in Example 3 was carried out to obtain a SiO 2 -TiO 2 composite inorganic fiber.
시험예: 복합무기섬유의 물성 측정Test Example: Measurement of Physical Properties of Composite Inorganic Fibers
상기 실시예 1 및 비교예 1에서 제조된 복합무기섬유의 절단면의 투과전자현미경(TEM) 사진을 도 1에 나타내었다 ((a): 실시예 1, (b) 비교예 1).A transmission electron microscope (TEM) photograph of the cut surface of the composite inorganic fiber prepared in Example 1 and Comparative Example 1 is shown in Figure 1 ((a): Example 1, (b) Comparative Example 1).
도 1의 TEM 사진으로부터 알 수 있듯이, 실시예 1의 복합무기섬유의 경우는 검은색으로 나타나는 결정성 TiO2 입자가 섬유의 표면부에서 더 많이 관찰되었는데, 이것은 2단계 열처리를 통해 TiO2 입자가 섬유의 표면으로 확산(bleed-out)되었기 때문이다. 반면에, 비교예 1의 복합무기섬유는 섬유 전체적으로 TiO2 입자가 분산되어 있을 뿐 표면에 특별히 집중되어 있지 않음을 알 수 있다.As can be seen from the TEM photograph of FIG. 1, when the composite inorganic fiber of Example 1 was a crystalline TiO 2 particles that appear as black more observed in the fiber surface portion, which is a TiO 2 particles via a two-step heat treatment This is because it has bleed-out to the surface of the fiber. On the other hand, in the composite inorganic fiber of Comparative Example 1, it can be seen that TiO 2 particles are dispersed in the fiber as a whole and are not particularly concentrated on the surface.
또한, 실시예 2 및 3, 및 비교예 2 및 3에서 제조된 복합무기섬유의 광촉매 활성을 평가하기 위해 메틸렌블루(MB) 분해능(반응시간에 따른 MB의 상대 농도)을 측정하여 도 2에 나타내었다. MB 분해능은, 제조된 섬유 웹(web) 시료를 1 mmol/L의 MB 수용액에 1시간 정도 충분히 화학흡착시키고 건조한 다음 광촉매 측정장치(Photocatalysis evaluation checker, PCC-2)를 이용하여 측정하였다.In addition, in order to evaluate the photocatalytic activity of the composite inorganic fibers prepared in Examples 2 and 3 and Comparative Examples 2 and 3, methylene blue (MB) resolution (relative concentration of MB according to reaction time) was measured and shown in FIG. 2 . It was. The MB resolution was measured by using a photocatalysis evaluation checker (PCC-2), and the resulting fibrous web sample was sufficiently chemisorbed and dried for 1 hour in 1 mmol / L of MB aqueous solution.
도 2의 그래프로부터, 2단계 열처리를 수행한 실시예 2 및 3의 복합무기섬유가 단일 열처리를 수행한 비교예 2 및 3의 경우에 비해 광촉매 활성이 훨씬 우수하고, 특히 0.8SiO2-0.2TiO2 복합무기섬유의 광촉매 활성이 가장 우수함을 알 수 있다.From the graph of FIG. 2, the photocatalytic activity of the composite inorganic fibers of Examples 2 and 3, which performed the two-step heat treatment, was much better than that of Comparative Examples 2 and 3, which performed the single heat treatment, in particular, 0.8SiO 2 -0.2TiO. 2 It can be seen that the photocatalytic activity of the composite inorganic fiber is the best.
도 1은 실시예 1 및 비교예 1에서 제조된 0.5SiO2-0.5TiO2 복합무기섬유의 절단면의 투과전자현미경(TEM) 사진이고,1 is a transmission electron microscope (TEM) photograph of the cut surface of 0.5SiO 2 -0.5TiO 2 composite inorganic fiber prepared in Example 1 and Comparative Example 1,
도 2는 실시예 2 및 비교예 2에서 제조된 0.9SiO2-0.1TiO2 복합무기섬유, 및 실시예 3 및 비교예 3에서 제조된 0.8SiO2-0.2TiO2 복합무기섬유의 메틸렌블루(MB) 분해능(반응시간에 따른 MB의 상대 농도) 측정 그래프이다.Figure 2 Example 2 and Comparative Example 2 The 0.9SiO 2 -0.1TiO second inorganic fiber composite, and Example 3 and Comparative methylene blue (MB of 0.8SiO 2 -0.2TiO 2 composite inorganic fiber produced in Example 3 prepared from ) Resolution (relative concentration of MB according to reaction time).
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US99007307A | 2007-11-26 | 2007-11-26 | |
| US60/990,073 | 2007-11-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20090054385A KR20090054385A (en) | 2009-05-29 |
| KR101007887B1 true KR101007887B1 (en) | 2011-01-14 |
Family
ID=40861545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020080117300A KR101007887B1 (en) | 2007-11-26 | 2008-11-25 | METHOD FOR PREPARING SiO2-TiO2-BASED COMPOSITE INORGANIC FIBERS USING TWO-STEP HEAT-TREATMENT |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101007887B1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101032214B1 (en) | 2009-06-30 | 2011-05-02 | 주식회사 엘지화학 | Method for manufacturing an electrode having a porous coating layer, an electrode formed therefrom and an electrochemical device having the same |
| CN102668172B (en) | 2009-11-23 | 2016-01-06 | 株式会社Lg化学 | Comprise the manufacture method of the barrier film of porous coating, the barrier film manufactured by the method and comprise the electrochemical apparatus of this barrier film |
| WO2013012292A2 (en) | 2011-07-20 | 2013-01-24 | 주식회사 엘지화학 | Separator, manufacturing method thereof, and electrochemical device employing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020049389A (en) * | 2000-12-19 | 2002-06-26 | 윤종용 | Method of manufacturing capacitor of semiconductor memory device by two-step thermal treatment |
-
2008
- 2008-11-25 KR KR1020080117300A patent/KR101007887B1/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020049389A (en) * | 2000-12-19 | 2002-06-26 | 윤종용 | Method of manufacturing capacitor of semiconductor memory device by two-step thermal treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20090054385A (en) | 2009-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Aryal et al. | Multi-walled carbon nanotubes/TiO2 composite nanofiber by electrospinning | |
| US20090208744A1 (en) | Ceramic fiber and process for producing the same | |
| Cacciotti et al. | Synthesis, thermal behaviour and luminescence properties of rare earth-doped titania nanofibers | |
| US20070116640A1 (en) | Titanium dioxide nanorod and preparation method thereof | |
| Lee et al. | Preparation of SiO2/TiO2 composite fibers by sol–gel reaction and electrospinning | |
| UA119753C2 (en) | Titania particles and a process for their production | |
| KR101349293B1 (en) | Nanofiber composite and method for fabricating same | |
| US6191067B1 (en) | Titania fiber, method for producing the fiber and method for using the fiber | |
| KR101172037B1 (en) | Manufacturing method of titanium dioxide fiber added silver | |
| CN108914250B (en) | Preparation method of polyacetylacetonato titanium precursor sol spinning solution, titanium oxide continuous fiber and nano fiber | |
| US7482297B2 (en) | Size controlled fibers, tubes and channels synthesized by heterogeneous deposition via sol-gel processing | |
| CN105126886A (en) | Preparation method of TiO<2>/WO<3>/g-C<3>N<4> thoroughly mesoporous nanofibers | |
| KR101007887B1 (en) | METHOD FOR PREPARING SiO2-TiO2-BASED COMPOSITE INORGANIC FIBERS USING TWO-STEP HEAT-TREATMENT | |
| EP2103722B1 (en) | Ceramic fiber and method for production of ceramic fiber | |
| WO2007123114A1 (en) | Titania fiber and method for producing titania fiber | |
| KR101183745B1 (en) | Fabrication of SnO2 nanoparticle embedded TiO2 nanoifbers by electrospinning and photocatalytic application under UV light | |
| TW201437443A (en) | Photocatalyst composite nano-fiber and its manufacturing method | |
| CN105107548A (en) | Preparation method of porous structure metal/rare earth co-doped inorganic nanofiber photocatalytic material | |
| Zhao et al. | Preparation of Low‐Dimensional Bismuth Tungstate (Bi2WO6) Photocatalyst by Electrospinning | |
| TWI566830B (en) | Preparation of Photocatalyst Composite Nanofibers | |
| Liu et al. | Fabrication and photocatalytic properties of flexible BiOI/SiO2 hybrid membrane by electrospinning method | |
| CN113737395A (en) | Flexible titanium dioxide nanofiber membrane and preparation method and application thereof | |
| Iimura et al. | Preparation of silica fibers and non-woven cloth by electrospinning | |
| Zhang et al. | Influences of acids on morphology and properties of TiO2 grown on electrospun PVDF fibers | |
| CN105126892A (en) | Use of TiO<2>/WO<3>/g-C<3>N<4> thoroughly mesoporenanofiber in high efficiency photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20140107 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20150107 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20160107 Year of fee payment: 6 |
|
| LAPS | Lapse due to unpaid annual fee |