CN103147281A - Super-hydrophobic fabric preparation method and super-hydrophobic functional fabric - Google Patents
Super-hydrophobic fabric preparation method and super-hydrophobic functional fabric Download PDFInfo
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- CN103147281A CN103147281A CN201310074491XA CN201310074491A CN103147281A CN 103147281 A CN103147281 A CN 103147281A CN 201310074491X A CN201310074491X A CN 201310074491XA CN 201310074491 A CN201310074491 A CN 201310074491A CN 103147281 A CN103147281 A CN 103147281A
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- 239000004744 fabric Substances 0.000 title claims abstract description 70
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims abstract description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 2
- 150000001282 organosilanes Chemical class 0.000 abstract 2
- 230000001680 brushing effect Effects 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 229920000742 Cotton Polymers 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 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 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
The invention relates to a super-hydrophobic fabric preparation method and a super-hydrophobic functional fabric. The preparation method comprises the following steps: I. preparing stable silicic acid and titanium dioxide mixed sol; II. applying the mixed sol obtained in step I onto a clean fabric through steps of soaking, membrane brushing and drying, and firmly bonding nanoscale silicon dioxide and titanium dioxide particles on the fiber surface of the fabric; and III. modifying the surfaces of the silicon dioxide and titanium dioxide particles, obtained in step II, with organosilane through the steps of soaking and drying, so as to realize the super-hydrophobic property, wherein the organosilane at least comprises hexadecyltrimethoxysilane. The invention provides a preparation method of super-hydrophobic fabric with stronger adhesive force and environment friendliness, and the super-hydrophobic fabric obtained by adopting the preparation method has the functions of ultraviolet irradiation resistance and washing resistance.
Description
Technical field
The present invention relates to preparation method and the corresponding fabric of fabric in a kind of light industry field, particularly relate to a kind of preparation method and super hydrophobic functional fabric of superhydrophobic fabric.
Background technology
The animals and plants of occurring in nature have a lot of peculiar phenomenons, and super hydrophobic surface is wherein a kind of.Vegeto-animal super hydrophobic surface is to be caused by the rough surface structure that wax is wrapped up.Wax can so that the surface have lower surface can, thereby increase contact angle, and coarse surface texture also can further increase this hydrophobic effect.Because super hydrophobic surface has the properties such as waterproof, anti-pollution, automatically cleaning, thereby enjoys people to pay close attention to.
In prior art, the technology of preparation super hydrophobic surface mainly can be divided into following a few class: the etching method on silicon materials surfaces, sol-gal process, chemical vapour deposition technique, the mechanical stretching method, polymerisation becomes embrane method, template, Electrospinning Method, electrochemical deposition method, and the corroding metal method etc.The common characteristics of these methods are that the surface of preparation has lower surface energy, have again larger roughness simultaneously, thereby cause it to have super-hydrophobic characteristic.But the shortcomings such as above-mentioned prior art also exists the equipment complexity, cost is expensive, preparation condition is harsh, unstable properties.
Summary of the invention
The objective of the invention is to propose that a kind of technique is simple, cost is lower, utilize eco-friendly material to prepare the method with ultra-hydrophobicity fabric, make fabric have uvioresistant irradiation and wash durability.
For achieving the above object, the invention provides a kind of preparation method of superhydrophobic fabric, described preparation method comprises the steps: step 1, stable silicic acid and the titanium dioxide mixed sols of preparation: under continuous stirring condition, be dropwise to add butyl titanate in 1～3 acid solution to PH, it is muddy that solution becomes gradually, dirty solution is put into the water bath heating of 70～90 ° of C until become translucent TiO 2 sol, and in colloidal sol, the content of titanium dioxide is controlled between 5～25g/L; With concentration be the sodium silicate solution of 10～25g/L and above-mentioned preparation TiO 2 sol under agitation by volume ratio be that 0.2～5 ratio is mixed, be 7～9 with the PH of acid adjusting mixed liquor, obtain silicic acid and titanium dioxide mixed sols; Step 2, with the mixed sols of gained in step 1 by soak～step of brush film～oven dry is applied on fabric via the cleaning after washed with de-ionized water, nano level silica and titanium dioxide granule on the fiber surface strong bonded of fabric; Step 3, by soaking～silica and the titanium dioxide granule finishing organosilan of step gained in step 2 of oven dry, realize ultra-hydrophobicity; Described organosilan comprises the cetyl trimethoxy silane at least.
Preferably, in described step 2, first soak 5～30min in the mixed sols with the gained in step 1 of the fabric after washed with de-ionized water, then take out and dry 5～30min at 60～100 ° of C temperature; Repeat aforesaid operations at least one times, at last at 60～100 ° of C oven dry 4～6h.
Preferably, in described step 3, it is 6～12h in 2～4% cetyl trimethoxy silane ethanolic solution that the fabric that obtains in step 2 is immersed in volume fraction, dry 6～12h at 60～100 ° of C temperature then, the fabric that obtains having the floride-free super-hydrophobic function.
Preferably, in described step 1, the acid that is used for regulating mixed liquor PH is nitric acid, hydrochloric acid or sulfuric acid.
Another object of the present invention is to provide a kind of super hydrophobic functional fabric, described fabric is to be made by above-mentioned preparation method.
Based on technique scheme, advantage of the present invention is:
The invention provides the preparation method of the stronger and eco-friendly superhydrophobic fabric of a kind of adhesive force, the super hydrophobic functional fabric that namely makes by preparation method of the present invention, be not only a kind of floride-free super-hydrophobic function fabric, and, function and the wash fast function of ultraviolet radiation resisting had; Meanwhile, the present invention selects sodium metasilicate as raw material in the fabric processing procedure, has reduced widely production cost, makes application of the present invention stronger.
Description of drawings
Accompanying drawing described herein is used to provide a further understanding of the present invention, consists of the application's a part, and illustrative examples of the present invention and explanation thereof are used for explaining the present invention, do not consist of improper restriction of the present invention.In the accompanying drawings:
Fig. 1 is the SEM photo of the prepared super hydrophobic functional fabric face of the present invention;
Fig. 2-1st, the droplet morphology on the prepared super hydrophobic functional fabric of the present invention;
Fig. 2-2nd, the top view of Fig. 2-1;
Fig. 2-3rd, the liquid-drop contact angle on the prepared super hydrophobic functional fabric of the present invention;
Fig. 3 is the ultraviolet radiation resisting performance schematic diagram of the prepared super hydrophobic functional fabric of the present invention;
Fig. 4 is the washing durability schematic diagram of the prepared super hydrophobic functional fabric of the present invention.
The specific embodiment
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
The preparation method of a kind of superhydrophobic fabric provided by the invention, operation principle of the present invention is: utilize the bionic principle of " lotus leaf effect ", first fabric is carried out surface treatment, make nano particle evenly firmly be combined in fabric face, make its surface roughening; Long chain silane with low-surface-energy is applied on fabric again, prepares floride-free super-hydrophobic uvioresistant irradiation water-wash resistance fabric.
Preparation method of the present invention mainly comprises at least three steps, that is: preparation silica and titanium dioxide mixed sols, mixed sols be applied to form nano-scale particle on fabric and at the nano-scale particle finishing organosilan of fabric, concrete technical scheme sees also following embodiment.
Embodiment 1:
The 17mL butyl titanate is dropwise added in the nitric acid of 0.1mol/L of 200mL, and constantly stir, it is muddy that solution becomes gradually; Dirty solution is put into constant temperature water bath, heating water bath 3～4h under 85 ° of C, white precipitate gradually becomes translucent colloidal sol, and in colloidal sol, the content of titanium dioxide is 20g/L.
The 7.52g sodium metasilicate is added in the 400ml deionized water, the preparation sodium silicate solution, and with above-mentioned TiO 2 sol by volume ratio be that 0.6 ratio under agitation mixes, then adjust PH=9(with nitric acid and can certainly use sulfuric acid and hydrochloric acid etc.), obtain milky silicic acid and titanium dioxide mixed sols.
COTTON FABRIC is immersed in mixing water colloidal sol after 10min, at 80 ° of C oven dry 15min, repeats aforesaid operations 2 times, at last at 80 ° of C oven dry 6h.It is 12h in 4% cetyl trimethoxy silane ethanolic solution that the COTTON FABRIC of above-mentioned processing is immersed in volume fraction, dries 12h under 80 ° of C, obtains the floride-free super-hydrophobic function fabric.
Another object of the present invention is to provide a kind of super hydrophobic functional fabric, described fabric is to be made by above-mentioned preparation method.Described fabric can be the various fabrics such as cotton fiber, polyster fibre.In the present embodiment, employing be cotton fiber.
The SEM photo of the super hydrophobic functional fabric face that shown in Fig. 1, said method makes; Liquid in the form of this super hydrophobic functional fabric face and contact angle value as shown in Fig. 2-1, Fig. 2-2 and Fig. 2-3.
By in above-mentioned test accompanying drawing as can be known, cotton fiber surface coverage of the present invention the particle of size at 50～500nm, form certain roughness.Obtain good super-hydrophobic effect after further modifying by organosilan, contact angle reaches 159.2 °, and can hinder and refuse the methylene blue drop.
Fig. 3 and Fig. 4 are ultraviolet radiation resisting performance and the washing durabilitys of prepared super hydrophobic functional fabric.
As seen from the figure, super hydrophobic functional fabric of the present invention still can keep the contact angle of water more than 140 ° at ultraviolet ray irradiation 6h; Clean 10 times in the family expenses washing machine, and after cleaning 30min, still can keep the contact angle of water more than 155 ° at every turn.
To sum up, the super hydrophobic functional fabric that uses preparation method of the present invention to make is compared with other superhydrophobic fabrics of the prior art, mainly has the following advantages:
(1) the super hydrophobic functional fabric of the inventive method preparation has the function of ultraviolet radiation resisting.Its contact angle that still can keep water after ultraviolet ray is shone more than 6h is more than 140 °, and irradiation is 40 days under natural sunshine, still can keep the contact angle of water more than 150 °.
(2) the super hydrophobic functional fabric of the inventive method preparation has wash fast function.Washing machine cleans more than 10 times, cleans 30min at every turn, still can keep the contact angle of water more than 155 °.
(3) after the fabric that makes of super hydrophobic functional fabric of the present invention has ultraviolet radiation resisting and wash fast function, can adapt to the long-time irradiation of strong sunshine, also can resist washing away for a long time of rainwater, more can adapt to abominable natural environment.And can waterproof and dustproof, automatically cleaning, saved a large amount of cleanings and repaired expense, manpower and the time of cost, also reduced the pollution of washing agent to environment.
(4) the present invention has selected without silicon fluoride and has carried out surface treatment, and this organosilan good biocompatibility can not cause the allergic reaction of skin, and can welding (as Ozone in Atmosphere layer etc.).
(5) the floride-free super-hydrophobic function fabric of the present invention's preparation, can be widely used in high-grade fabric, home decoration, outdoor tent and various waterproof cloth, have the opposing adverse circumstances, permanent durable, super-hydrophobic effect keeps permanent effect, has wide market application foreground.
Should be noted that at last: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; Although with reference to preferred embodiment, the present invention is had been described in detail, those of ordinary skill in the field are to be understood that: still can modify or the part technical characterictic is equal to replacement the specific embodiment of the present invention; And not breaking away from the spirit of technical solution of the present invention, it all should be encompassed in the middle of the technical scheme scope that the present invention asks for protection.
Claims (4)
1. the preparation method of a superhydrophobic fabric, it is characterized in that: described preparation method comprises the steps:
Step 1, stable silicic acid and the titanium dioxide mixed sols of preparation: under continuous stirring condition, be that dropwise to add concentration in 1～3 acid solution be the butyl titanate solution of 50～100mL/L to PH, it is muddy that solution becomes gradually, dirty solution is put into the water bath heating of 70～90 ° of C until become translucent TiO 2 sol, and in colloidal sol, the content of titanium dioxide is controlled between 5～25g/L;
With concentration be the sodium silicate solution of 10～25g/L and above-mentioned preparation TiO 2 sol under agitation by volume ratio be that 0.2～5 ratio is mixed, be 7～9 with the PH of acid adjusting mixed liquor, obtain silicic acid and titanium dioxide mixed sols;
Step 2, with the mixed sols of gained in step 1 by soak～step of brush film～oven dry is applied on the fabric of cleaning, nano level silica and titanium dioxide granule on the fiber surface strong bonded of fabric;
Step 3, by soaking～silica and the titanium dioxide granule finishing organosilan of step gained in step 2 of oven dry, realize ultra-hydrophobicity; Described organosilan comprises the cetyl trimethoxy silane at least.
2. the preparation method of superhydrophobic fabric according to claim 1, it is characterized in that: in described step 2, first soak 5～30min in the mixed sols with the gained in step 1 of the fabric after washed with de-ionized water, then take out and dry at 60～100 ° of C temperature; Repeat aforesaid operations at least one times, at last at 60～100 ° of C oven dry 4～6h.
3. the preparation method of superhydrophobic fabric according to claim 1 and 2, it is characterized in that: in described step 3, it is 6～12h in 2～4% cetyl trimethoxy silane ethanolic solution that the fabric that obtains in step 2 is immersed in volume fraction, then dry 6～12h at 60～100 ° of C temperature, the fabric that obtains having the floride-free super-hydrophobic function.
4. super hydrophobic functional fabric, it is characterized in that: described fabric is to be made by the described preparation method of above-mentioned any one claim.
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Cited By (18)
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| CN103590236A (en) * | 2013-10-24 | 2014-02-19 | 浙江理工大学 | Preparation method of super-hydrophobic surface of fabric |
| CN103726302A (en) * | 2013-12-06 | 2014-04-16 | 南京工业大学 | Preparation method of multifunctional super-hydrophobic hybrid material |
| CN103806262A (en) * | 2014-01-28 | 2014-05-21 | 东华大学 | Preparation method of self-cleaning wool fabric |
| CN104088147A (en) * | 2014-07-13 | 2014-10-08 | 成都市绿科华通科技有限公司 | Functional woolen fabric with super-hydrophobicity |
| CN104088146A (en) * | 2014-07-13 | 2014-10-08 | 成都市绿科华通科技有限公司 | Preparation method of waterproof and snow-proof wool fabric |
| CN104088148A (en) * | 2014-07-13 | 2014-10-08 | 成都市绿科华通科技有限公司 | Surface-modified functional yak hair/wool fabric |
| CN104745019A (en) * | 2015-03-31 | 2015-07-01 | 华南理工大学 | Preparation method of nano-SiO2/TiO2 modified PVDF superhydrophobic composite membrane with self-cleaning properties |
| CN104746336A (en) * | 2015-04-01 | 2015-07-01 | 江南大学 | Finishing method of chinlon hydrophobic fabric based on butyl titanate |
| CN105316932A (en) * | 2015-11-30 | 2016-02-10 | 无锡新德印染制品有限公司 | Preparation method of fabric with super-hydrophobic function |
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| CN103590236A (en) * | 2013-10-24 | 2014-02-19 | 浙江理工大学 | Preparation method of super-hydrophobic surface of fabric |
| CN103726302A (en) * | 2013-12-06 | 2014-04-16 | 南京工业大学 | Preparation method of multifunctional super-hydrophobic hybrid material |
| CN103726302B (en) * | 2013-12-06 | 2016-01-20 | 南京工业大学 | Preparation method of multifunctional super-hydrophobic hybrid material |
| CN103806262B (en) * | 2014-01-28 | 2016-08-17 | 东华大学 | A kind of preparation method of automatically cleaning wool fabric |
| CN103806262A (en) * | 2014-01-28 | 2014-05-21 | 东华大学 | Preparation method of self-cleaning wool fabric |
| CN104088147A (en) * | 2014-07-13 | 2014-10-08 | 成都市绿科华通科技有限公司 | Functional woolen fabric with super-hydrophobicity |
| CN104088146A (en) * | 2014-07-13 | 2014-10-08 | 成都市绿科华通科技有限公司 | Preparation method of waterproof and snow-proof wool fabric |
| CN104088148A (en) * | 2014-07-13 | 2014-10-08 | 成都市绿科华通科技有限公司 | Surface-modified functional yak hair/wool fabric |
| WO2016074113A1 (en) * | 2014-11-12 | 2016-05-19 | 江南大学 | Method for preparing super-hydrophobic fabric by sol-gel electrochemical deposition |
| CN104745019A (en) * | 2015-03-31 | 2015-07-01 | 华南理工大学 | Preparation method of nano-SiO2/TiO2 modified PVDF superhydrophobic composite membrane with self-cleaning properties |
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