CN103409984A - Method for low-temperature preparation of anatase titanium dioxide film on surface of cotton fabric - Google Patents
Method for low-temperature preparation of anatase titanium dioxide film on surface of cotton fabric Download PDFInfo
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- CN103409984A CN103409984A CN2013102958966A CN201310295896A CN103409984A CN 103409984 A CN103409984 A CN 103409984A CN 2013102958966 A CN2013102958966 A CN 2013102958966A CN 201310295896 A CN201310295896 A CN 201310295896A CN 103409984 A CN103409984 A CN 103409984A
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Abstract
The invention relates to a method for low-temperature preparation of an anatase titanium dioxide film on the surface of cotton fabric, which comprises the following steps: (1) mixing absolute ethyl alcohol, glacial acetic acid and n-tetrabutyl titanate, then slowly dropwise adding the mixture into a mixed solution of acetic acid with a pH value of 2.5-3 and water for hydrolysis, and severely stirring to form titanium dioxide sol; and (2) soaking the cotton fabric in the titanium dioxide sol for 2-3 minutes, soaking twice and rolling twice; pre-drying at 70-90 DEG C for 3-5 minutes; and steaming at 80-100 DEG C for 2-3 hours. The preparation method provided by the invention is simple and does not need an adhesive or high-temperature curing treatment; through a conventional soaking-rolling-steaming technology, an anatase film with good binding strength, high crystallinity and excellent photocatalytic performance is formed on the surface of the cotton fabric; and the method can be applied to the purification of in-car and indoor air, self-cleaning of fabric and the like.
Description
Technical field
The invention belongs to the preparation field of titanium deoxid film, particularly a kind of method for preparing anatase titanium dioxide film at surface of cotton fabric low temperature.
Background technology
Raising along with expanding economy and living standards of the people, people not only rest on the most basic wearability to the functional requirement of textiles, those have automatically cleaning, and antibacterial and deodouring, the textiles of the functions such as uvioresistant often more easily are subject to people's favor.For textile printing and dyeing enterprises, give the special function of textiles to improving product quality, improve added value of product and have vital effect.Catalysis material TiO
2(especially anatase crystal type) photocatalytic activity is high, stability and good heat resistance, to the advantages such as human body is nontoxic and inexpensive widely known to, nano-photocatalyst material is applied in textiles, can give the functions such as fabric photocatalytic self-cleaning, uvioresistant, degraded VOC, have very large application potential.With the nano-titanium dioxide powder material, be applied in fabric, poor because of itself and organic textile raw material compatibility, need the auxiliary of adhesive; Disperse inhomogeneously, easily reunion is even separated out, even if can not thoroughly solve agglomeration traits through finishing, so the application of the method is very restricted.The inorganic oxide finish fabric of filming is the new way of improving fabric property, the method can form at fabric face the film of one deck continuous whole, this film has the advantage such as is combined firmly, surface area is large with fabric, but the method for preparing at present titanium dioxide is difficult to obtain at low temperatures the anatase titanium dioxide of high-crystallinity.
Chinese patent CN1757444A discloses a kind of method that forms coating of titanium dioxide at article surface, and it does not need the auxiliary of adhesive, does not need the hot setting process yet, can facilitate, at article surface, form simply the coating of titanium dioxide of good endurance.But this preparation method does not obtain the titanium dioxide of specific crystal formation, high-crystallinity at low temperatures, do not bring into play the most excellent photo-catalysis capability.
Chinese patent CN101073768A discloses the film formation at low temp method of optically catalytic TiO 2 film, prepares TiO 2 sol with sol-gal process, adopts the method for high-frequency electric field microwave irradiation to form uniform film after coating thin film of titanium oxide on base material.But the method high-frequency electric field heating cost is higher, be not suitable for the large-scale production of factory.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method for preparing anatase titanium dioxide film at surface of cotton fabric low temperature, the method does not need adhesive, do not need hot setting to process yet, at surface of cotton fabric, form the anatase titanium dioxide film that binding strength is good, degree of crystallinity is high, photocatalysis performance is excellent by the soaking-roll of routine-Steaming.
A kind of method for preparing anatase titanium dioxide film at surface of cotton fabric low temperature of the present invention comprises:
(1) preparation of TiO 2 sol
Absolute ethyl alcohol, glacial acetic acid and tetra-n-butyl titanate are mixed, then slowly be added drop-wise in the mixed solution of pH value for the acetic acid of 2.5-3 and water and be hydrolyzed, the faint yellow transparent TiO 2 sol of formation after vigorous stirring;
(2) preparation of titanium deoxid film
COTTON FABRIC is immersed in to 2-3min in above-mentioned TiO 2 sol, and two soak two rolls, and then at 70-90 ℃ of lower preliminary drying 3-5min, then is placed in 80-100 ℃ of decatize 2-3h and gets final product.
The volume ratio of absolute ethyl alcohol, glacial acetic acid, tetra-n-butyl titanate and the mixed solution described in step (1) is 3-6:6-10:10-15:120-150.
It is 60-80% that described in step (2) two soaked two pick-up rates in rolling.
COTTON FABRIC described in step (2) is pretreated COTTON FABRIC, and pretreatment operation is: COTTON FABRIC, under 60-90 ℃, is processed to 10-30min with the nonionic cleaning agent, clean dry for standby with deionized water.
Above-mentioned nonionic cleaning agent is detergent 6501 or fatty alcohol-polyoxyethylene ether 9(paregal O-9) (peaking work Co., Ltd of river section).
The film forming of COTTON FABRIC of the present invention characterizes by scanning electron microscope (SEM) photograph, the crystal property of titanium dioxide characterizes by X-ray diffractogram, the photocatalysis performance of titanium deoxid film utilizes organic substance decomposing to determine, in gas phase, the COTTON FABRIC of preparation is placed in to airtight container, in container, pass into a small amount of organic gas, after time, organic matter is decomposed through certain irradiation.In liquid phase, utilize red wine, coffee to spread upon on the film of preparation, after the time, red wine, coffee spot are degraded and become colorless through certain irradiation.Due to organic gas and red wine, coffee, be not subjected to the impact of ultraviolet light, so their degraded can be thought the light-catalysed effect of film.
The present invention is by sol-gal process, selects butyl titanate as presoma, prepares anatase titanium dioxide colloidal sol, using this colloidal sol as finishing agent through soaking-roll-after decatize processes, form anatase titanium dioxide film in COTTON FABRIC.
Beneficial effect:
(1) cost of material is cheap, method is simple, preparation temperature is low, be applicable to industrial applications, applying the present invention to fabric face prepares in thin-film process, because dehydration of the present invention is carried out at surface of cotton fabric, the hydroxyl of titanium dioxide and the hydroxyl of COTTON FABRIC easily form covalent bonds, titanium dioxide firmly can be combined in to fabric face, thereby do not need adhesive, titanium deoxid film can anti-50 standards wash;
(2) the film continuous whole for preparing of the present invention, do not ftracture, it is the anatase titanium dioxide film of high-crystallinity, photocatalysis performance is high, under the irradiation that contains the light of ultraviolet light, sunshine, film surface generates electronics, the hole with very strong redox ability, airborne organic pernicious gas, bacterium etc. are had to decomposition, the spot on fabric is had to the effect of degraded;
(3) titanium deoxid film that obtains of the present invention can apply with car in, indoor air cleaning, and the automatically cleaning of fabric etc.
The accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of surface of cotton fabric titanium deoxid film after modification in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the forward and backward surface of cotton fabric of modification in embodiment 2; Wherein: a is unmodified COTTON FABRIC, and b is the COTTON FABRIC after modification.
Fig. 3 is the degradation curve figure of the titanium deoxid film of the forward and backward surface of cotton fabric of modification in embodiment 3 to organic gas; Wherein: a is unmodified COTTON FABRIC, and b is the COTTON FABRIC after modification.
Fig. 4 is the degradation effect figure of the titanium deoxid film of the forward and backward surface of cotton fabric of modification in embodiment 4 to the red wine stain; Wherein: a is unmodified COTTON FABRIC, and b is the COTTON FABRIC after modification.
Fig. 5 is the degradation effect figure of the titanium deoxid film of the forward and backward surface of cotton fabric of modification in embodiment 4 to coffee stain; Wherein: a is unmodified COTTON FABRIC, and b is the COTTON FABRIC after modification.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention be used to the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
The tetra-n-butyl titanate of the glacial acetic acid of the absolute ethyl alcohol of 3mL, 6mL and 10mL is mixed, then it slowly is added drop-wise to 120mL, pH is hydrolyzed in the mixed solution of 2.5 acetic acid and water, after vigorous stirring, forms faint yellow vitreosol.
Pretreated COTTON FABRIC is immersed in to 3min in TiO 2 sol, and two soak two rolls (pick-up rate is 80%), preliminary drying 3min under 80 ℃ of conditions, and 100 ℃ of decatize 3h, complete the process for preparing titanium deoxid film at surface of cotton fabric in steaming box.
According to standard GB/T/T8629-2001 " textiles test with home washings and drying program ", the COTTON FABRIC after titania modified is washed and drying (is selected A type washing machine, the 5A washing procedure, A type drying program), after 50 washings, XRD figure to film characterizes, and sees Fig. 1.Test result shows, film crystalline structure prepared by surface of cotton fabric is the titanium dioxide of anatase titanium dioxide, and degree of crystallinity is higher.
The tetra-n-butyl titanate of the glacial acetic acid of the absolute ethyl alcohol of 3mL, 6mL and 10mL is mixed, then it slowly is added drop-wise to 120mL, pH is hydrolyzed in the mixed solution of 2.5 acetic acid and water, after vigorous stirring, forms faint yellow vitreosol.
Pretreated COTTON FABRIC is immersed in to 3min in TiO 2 sol, and two soak two rolls (pick-up rate is 80%), preliminary drying 3min under 80 ℃ of conditions, and 100 ℃ of decatize 3h, complete the process for preparing titanium deoxid film at surface of cotton fabric in steaming box.
According to standard GB/T/T8629-2001 " textiles test with home washings and drying program ", the COTTON FABRIC after titania modified is washed and drying (is selected A type washing machine, the 5A washing procedure, A type drying program), after 50 washings, by ESEM (SEM), become membrane stage to characterize to fabric face, see accompanying drawing 2.Test result shows that film continuous whole prepared by surface of cotton fabric does not produce cracking.
The tetra-n-butyl titanate of the glacial acetic acid of the absolute ethyl alcohol of 3mL, 6mL and 10mL is mixed, then it slowly is added drop-wise to 120mL, pH is hydrolyzed in the mixed solution of 2.5 acetic acid and water, after vigorous stirring, forms faint yellow vitreosol.
Pretreated COTTON FABRIC is immersed in to 3min in TiO 2 sol, and two soak two rolls (pick-up rate is 80%), preliminary drying 3min under 80 ℃ of conditions, and 100 ℃ of decatize 3h, complete the process for preparing titanium deoxid film at surface of cotton fabric in steaming box.
According to standard GB/T/T8629-2001 " textiles test with home washings and drying program ", the COTTON FABRIC after titania modified is washed and drying (is selected A type washing machine, the 5A washing procedure, A type drying program), after 50 washings, the fabric that is prepared with titanium deoxid film is placed in to airtight container, in container, pass into a small amount of formaldehyde gas, ultraviolet light illumination is 1.5mW/cm
2± 0.05mW/cm
2, after the UV-irradiation of 5h, organic matter be decomposed (Fig. 3).Result shows that the titanium deoxid film on fabric has good photocatalytic Degradation to organic gas.
Embodiment 4
The tetra-n-butyl titanate of the glacial acetic acid of the absolute ethyl alcohol of 3mL, 6mL and 10mL is mixed, then it slowly is added drop-wise to 120mL, pH is hydrolyzed in the mixed solution of 2.5 acetic acid and water, after vigorous stirring, forms faint yellow vitreosol.
Pretreated COTTON FABRIC is immersed in to 3min in TiO 2 sol, and two soak two rolls (pick-up rate is 80%), preliminary drying 3min under 80 ℃ of conditions, and 100 ℃ of decatize 3h, complete the process for preparing titanium deoxid film at surface of cotton fabric in steaming box.
According to standard GB/T/T8629-2001 " textiles test with home washings and drying program ", the COTTON FABRIC after titania modified is washed and drying (is selected A type washing machine, the 5A washing procedure, A type drying program), after 50 washings, utilize red wine, coffee to spread upon on the film of preparation, ultraviolet light illumination is 1.5mW/cm
2± 0.05mW/cm
2, after the UV-irradiation of 8h, red wine, coffee are degraded to colourless (Fig. 4, Fig. 5).Result shows that the titanium deoxid film on fabric has good photocatalytic Degradation to greasy filth.
Claims (5)
1. method for preparing anatase titanium dioxide film at surface of cotton fabric low temperature comprises:
(1) absolute ethyl alcohol, glacial acetic acid and tetra-n-butyl titanate are mixed, then slowly be added drop-wise in the mixed solution of acetic acid that pH value is 2.5-3 and water and be hydrolyzed, after vigorous stirring, form TiO 2 sol;
(2) COTTON FABRIC is immersed in to 2-3min in above-mentioned TiO 2 sol, two soak two rolls, and then at 70-90 ℃ of lower preliminary drying 3-5min, then is placed in 80-100 ℃ of decatize 2-3h and gets final product.
2. a kind of method for preparing anatase titanium dioxide film at surface of cotton fabric low temperature according to claim 1, it is characterized in that: the volume ratio of absolute ethyl alcohol, glacial acetic acid, tetra-n-butyl titanate and the mixed solution described in step (1) is 3-6:6-10:10-15:120-150.
3. a kind of method for preparing anatase titanium dioxide film at surface of cotton fabric low temperature according to claim 1 is characterized in that: it is 60-80% that two described in step (2) soaked two pick-up rates in rolling.
4. a kind of method for preparing anatase titanium dioxide film at surface of cotton fabric low temperature according to claim 1, it is characterized in that: the COTTON FABRIC described in step (2) is pretreated COTTON FABRIC, pretreatment operation is: by COTTON FABRIC under 60-90 ℃, with the nonionic cleaning agent, process 10-30min, clean dry for standby with deionized water.
5. a kind of method for preparing anatase titanium dioxide film at surface of cotton fabric low temperature according to claim 4, it is characterized in that: described nonionic cleaning agent is detergent 6501 or aliphatic alcohol polyethenoxy.
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Cited By (9)
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|---|---|---|---|---|
| CN103882681A (en) * | 2014-02-21 | 2014-06-25 | 宁波天河生态水景科技有限公司 | Method for preparing titanium dioxide loaded high polymer fiber through hydrothermal injection |
| CN104294592A (en) * | 2014-10-16 | 2015-01-21 | 苏州大学 | Preparation method of special-infiltration functional fabric surface with self-cleaning and oil-water separation functions |
| CN104631094A (en) * | 2015-01-28 | 2015-05-20 | 东华大学 | Preparation method of long-acting photocatalytic self-cleaning fabric |
| WO2016115980A1 (en) * | 2015-01-21 | 2016-07-28 | 南通纺织丝绸产业技术研究院 | Method for constructing surface of fabric with ultraviolet protection and wash-resistant special wetting functions |
| CN106219664A (en) * | 2016-08-10 | 2016-12-14 | 佛山科学技术学院 | The method of the cotton base optic catalytic TREATMENT OF DYEING WASTEWATER WITH of polyester cotton one-bath dyeing |
| CN108931872A (en) * | 2018-06-13 | 2018-12-04 | 上海大学 | Zinc titanyl composite film material, its application and preparation method with electrochromic effect |
| CN109295697A (en) * | 2018-09-12 | 2019-02-01 | 武汉纺织大学 | A kind of method that silver sulfide quantum dot composite titanium dioxide colloidal sol handles cotton fabric automatically cleaning |
| CN112411176A (en) * | 2020-10-19 | 2021-02-26 | 山东魏桥特宽幅印染有限公司 | Odor-removing fabric and printing and dyeing process and application thereof |
| CN113914003A (en) * | 2021-09-29 | 2022-01-11 | 浙江理工大学象山针织研究院有限公司 | Manufacturing method of ultraviolet-proof cool fabric |
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Cited By (13)
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| CN103882681A (en) * | 2014-02-21 | 2014-06-25 | 宁波天河生态水景科技有限公司 | Method for preparing titanium dioxide loaded high polymer fiber through hydrothermal injection |
| CN103882681B (en) * | 2014-02-21 | 2016-09-14 | 宁波天河生态水景科技有限公司 | A kind of method that titanium dichloride load macromolecular fibre is prepared in hydro-thermal injection |
| CN104294592A (en) * | 2014-10-16 | 2015-01-21 | 苏州大学 | Preparation method of special-infiltration functional fabric surface with self-cleaning and oil-water separation functions |
| WO2016115980A1 (en) * | 2015-01-21 | 2016-07-28 | 南通纺织丝绸产业技术研究院 | Method for constructing surface of fabric with ultraviolet protection and wash-resistant special wetting functions |
| CN104631094A (en) * | 2015-01-28 | 2015-05-20 | 东华大学 | Preparation method of long-acting photocatalytic self-cleaning fabric |
| CN104631094B (en) * | 2015-01-28 | 2016-10-12 | 东华大学 | A kind of preparation method of long-acting photocatalytic self-cleaning fabric |
| CN106219664A (en) * | 2016-08-10 | 2016-12-14 | 佛山科学技术学院 | The method of the cotton base optic catalytic TREATMENT OF DYEING WASTEWATER WITH of polyester cotton one-bath dyeing |
| CN108931872A (en) * | 2018-06-13 | 2018-12-04 | 上海大学 | Zinc titanyl composite film material, its application and preparation method with electrochromic effect |
| CN108931872B (en) * | 2018-06-13 | 2020-11-24 | 上海大学 | Zinc-titanium-oxygen composite film material with electrochromic effect, application and preparation method thereof |
| CN109295697A (en) * | 2018-09-12 | 2019-02-01 | 武汉纺织大学 | A kind of method that silver sulfide quantum dot composite titanium dioxide colloidal sol handles cotton fabric automatically cleaning |
| CN109295697B (en) * | 2018-09-12 | 2020-09-08 | 烟台明远智能家居科技有限公司 | Method for self-cleaning treatment of cotton fabric by silver sulfide quantum dot composite titanium dioxide sol |
| CN112411176A (en) * | 2020-10-19 | 2021-02-26 | 山东魏桥特宽幅印染有限公司 | Odor-removing fabric and printing and dyeing process and application thereof |
| CN113914003A (en) * | 2021-09-29 | 2022-01-11 | 浙江理工大学象山针织研究院有限公司 | Manufacturing method of ultraviolet-proof cool fabric |
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