A kind of preparation method of zinc oxide nano-rod film on fibre productTechnical field
The invention belongs to low-dimension nano material film preparation field, particularly a kind of preparation method of zinc oxide nano-rod film on fibre product.
Background technology
Along with the raising of people's living standard, people are also more and more higher to the requirement of clothes in recent years.High-grade, comfortable, textiles that have functions such as uvioresistant, antibiotic, automatically cleaning more and more is subjected to consumer's favor.ZnO is a kind of multi-functional semi-conducting material, and ultraviolet ray is had good shielding protection effect.When the particle size of these materials and light wave quite or more hour because small-size effect causes light absorption significantly to strengthen.Therefore can decay ultraviolet ray, especially wavelength of zinc oxide nano-powder is the ultraviolet ray of 280nm-320nm; Nano granular of zinc oxide has visible light transmissive effect preferably simultaneously, compare with traditional organic uv absorbers, nano zine oxide is an inorganic constituents, effective acting time is long, wave band to the light radiation shielding is long, very high chemical stability and thermally-stabilised structure are arranged, nontoxic, nonirritant, safe and reliable.Therefore by these characteristics of nano zine oxide can develop have antibiotic, deodorizing, the textile product of radiation proof function, now formed industrialization product have antibacterial underwear, operation dress, nurse's clothes, the smelly dressing that disappears, deodorizing bandage, lavatory with textiles and Summer care adorn, summer cap, daylight umbrella, sportswear etc.
It is main that tradition utilizes the ZnO superfine powder to give the approach of textile material specific functionality: the one, nanoparticle directly is added in the initial reaction liquid of chemical fibre.Adopt conventional polymerisation complex functionality fiber.Make nanoparticle be uniformly distributed in fibrous inside; The 2nd, adopt the back finishing technique to be applied on the fabric, carry out function modified to fabric.
But above-mentioned these two kinds of methods all must at first prepare the ZnO superfine powder, nano level superfine powder preparation process complexity, and preparation process needs high-temperature process, energy consumption height, cost height; Secondly nano particle diameter is little, specific area and surface energy are very big, be very easy to assemble, the lost original superior function of nano particle, though nano zine oxide is carried out surface modification by esterification reaction method, surperficial coupling grafting method or radiation graft process, can certain improvement be arranged to above problem, can not fundamentally solve the problems referred to above of superfine powder, superfine powder agglomeration after the modification still exists, and cost increases; If employing first method, superfine powder mostly are wrapped in fibrous inside, powder can not contact with moisture with oxygen, and photocatalysis can not take place, and functions such as it is antibiotic, deodorizing also just can not get performance, utilize the method that equipment is had relatively high expectations.If agglomeration appears in superfine powder, there is bigger aggregation, may stop up spinning nozzle, and it can not be processed as natural fabrics such as cotton, fiber crops, silk, hairs; If the employing second method, promptly finishing method is added to powder on the textiles, because the effect of adhesive can cause the powder skewness.And adhesive meeting coated powder, making it and can not contact with moisture with oxygen, photocatalysis can not take place, and functions such as it is antibiotic, deodorizing also just can not get performance.In addition, utilizing the back arrangement of adhesive to add trade union influences performances such as the feel of fabric, intensity, elasticity, and the washing fastness and the function durability of processing back functional fabric are also very poor.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of zinc oxide nano-rod film on fibre product, this method is simple, and cost is low, but film formation at low temp is fit to suitability for industrialized production.
The preparation method of a kind of zinc oxide nano-rod film on fibre product that the present invention proposes comprises the following steps:
(1) by Prepared by Sol Gel Method ZnO nanocrystal and in a large amount of ZnO crystal seeds of fibre surface deposition
A.. at 50～100 ℃, under the strong agitation condition, zinc salt is dissolved in the organic solvent, forms zinc solution; The alkaline agent that is dissolved in the organic solvent slowly is added dropwise in the above-mentioned zinc solution, adds the back that finishes and under this temperature conditions, continue to stir 30～180min; Make ZnO colloidal sol.The molar concentration of zinc salt and alkaline agent is all between 0.001M～0.75M;
B. the fibre with cleaning soaks 1～5min, 1.75～3.50kg/cm in ZnO colloidal sol2The roll compacting condition under two soak two and roll;
C. the fibre that padded is dry 30～180min under 20～60 ℃ of conditions.Under 100～150 ℃ of conditions, bake 5～60min then.At fibre surface deposition ZnO nanocrystal.
(2) by the hydro-thermal method or the chemical solution liquid pool precipitation method, growing zinc oxide nanorod film on sewing work
A. after molar concentration being 0.001M～0.05M zinc solution and enveloping agent solution and evenly mixing, put into stainless steel cauldron or uncovered flask all can;
The fibre that b. will preset a large amount of ZnO crystal seeds is put in reactor or the uncovered flask, behind 40～170 ℃ of insulation 0.5～6h, take out, spend deionised water to remove remaining reactant, dry under 30～80 ℃ of conditions at last, on fibre, grow into oriented growth, the nano-stick array thin film of better crystallinity degree.
The molar concentration of described step 1 zinc salt and alkaline agent is all between 0.001M～0.75M;
Described step 1 zinc salt is any in zinc acetate, zinc nitrate, the zinc chloride zinc salt;
Described step 1 alkaline agent is lithium hydroxide, hydrazine hydrate, NaOH, potassium hydroxide, ammoniacal liquor, triethylamine, monoethanolamine, diethanol amine etc.;
Described step 1 organic solvent is absolute ethyl alcohol, methyl alcohol, isopropyl alcohol, EGME etc.
Described step 2 zinc salt is a zinc nitrate, zinc chloride, zinc acetate, zinc citrate, a kind of in the zinc gluconate zinc salt.
Described step 2 complexing agent is hexamethylenetetramine, urea, ammoniacal liquor, triethylamine, inorganic ammonium salt and OH-etc.
Because the present invention adopts Prepared by Sol Gel Method ZnO colloidal sol, products therefrom is stable, and Dispersion of Particles is good, and the ZnO grain graininess is little, purity is high, narrow particle size distribution, and sol-gel technique also has advantages such as the equipment requirement is low, the easy control of condition in addition; The hydro-thermal low temperature deposition method, products therefrom has fine crystallinity, synthetic zinc oxide nano-rod film, directionality is good, the nanometer rods size is even, to be fixed on the fibre surface by the simple operations of padding baking by the nano-ZnO colloidal solid of sol-gel technique preparation, with set the fibre of ZnO crystal seed being arranged then is deposition substrate, obtain the good ZnO nano-rod film of all even directionality in surface, at the synthetic zinc oxide nano-rod film that aligns of low temperature, equipment needed thereby is simple, and cost is low, and it is thin to be suitable for the zinc oxide nano rod that large-scale production aligns.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.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 institute restricted portion equally.
Embodiment 1
The 0.88g zinc acetate is dissolved in the 40ml absolute ethyl alcohol, stirs 30min at 70 ℃ of condition lower magnetic forces, simultaneously, the 0.232g lithium hydroxide is dissolved in the 40ml absolute ethyl alcohol, the room temperature lower magnetic force stirs 30min; Lithium hydroxide solution is poured in the ethanolic solution of zinc acetate, and under this temperature, stirred 120min, prepare stable ZnO colloidal sol.The cotton poplin fabric of cleaning is flooded 2min in prepared ZnO colloidal sol, at 2.8kg/cm2Two soak two and roll under the roll compacting condition, the dry at ambient temperature 150min of the fabric after padding, bake 60min again under 150 ℃ of conditions.With molar concentration is after the zinc nitrate solution of 0.015M and hexamethylenetetramine solution that molar concentration is 0.015M evenly mix, put into stainless steel cauldron, the cotton poplin fabric that will preset the ZnO crystal seed simultaneously takes out behind 95 ℃ of insulation 120min, clean up with deionized water, oven dry, on the cotton poplin fabric, grow into oriented growth at last, the ZnO nano-stick array thin film of better crystallinity degree, the UPF value of arrangement back cotton poplin increases to 415.3 (general UPF＞50 think that the uvioresistant effect is good) rapidly by original 4.3.
Embodiment 2
Take by weighing certain zinc acetate powder, at 60 ℃, under the strong agitation condition it is dissolved in the EGME organic solvent, forming molar concentration is the zinc acetate solution of 0.1M, monoethanolamine is added in the above-mentioned zinc acetate solution slowly, the molar concentration of monoethanolamine also is 0.1M, continues to stir 30min, prepares stable ZnO colloidal sol.The cotton thin plain cloth of cleaning is flooded 2min in above-mentioned prepared ZnO colloidal sol, at 3.0kg/cm2Two soak two and roll under the roll compacting condition, the dry 90min under 50 ℃ of conditions of the fabric after padding, bake 60min again under 150 ℃ of conditions.With molar concentration is after the zinc nitrate solution of 0.01M and sodium hydroxide solution that molar concentration is 0.4M evenly mix, put into stainless steel cauldron, the cotton thin plain cloth that will preset the ZnO crystal seed simultaneously takes out behind 75 ℃ of insulation 90min, clean up with deionized water, dry under 80 ℃ of conditions, on the thin plain cloth of cotton, grow into oriented growth at last, the ZnO nano-stick array thin film of better crystallinity degree, the UPF value of arrangement back cotton poplin increases to 495.1 (general UPF＞50 think that the uvioresistant effect is good) rapidly by original 8.4.
Embodiment 3
Take by weighing 12.2g zinc acetate powder and be dissolved in the 100ml isopropyl alcohol, the powerful 30min that stirs under 85 ℃ of conditions, the 5.6g triethylamine dropwise adds in the above-mentioned zinc acetate solution, continues to stir 30min under these 85 ℃ of conditions, forms the ZnO colloidal sol of transparent and stable.The cotton poplin fabric of cleaning is flooded 2min in prepared ZnO colloidal sol, at 2.8kg/cm2Two soak two and roll under the roll compacting condition, the dry 120min under 40 ℃ of conditions of the fabric after padding, bake 45min again under 150 ℃ of conditions.With molar concentration is after the zinc acetate solution of 0.025M and triethylamine solution that molar concentration is 0.025M evenly mix, put into uncovered flask, the cotton poplin fabric that will preset the ZnO crystal seed simultaneously takes out behind 50 ℃ of insulation 120min, clean up with deionized water, dry under 60 ℃ of conditions, on the cotton poplin fabric, grow into oriented growth at last, the ZnO nano-stick array thin film of better crystallinity degree, the UPF value of arrangement back cotton poplin increases to 386.3 (generally UPF＞50 think that the uvioresistant effect is good) rapidly by original 4.2.
Embodiment 4
0.270g the zinc acetate powder is dissolved in the 60ml methanol solution under 60 ℃ of strong agitation conditions, the 65ml methanol solution that will be dissolved with 0.21g potassium hydroxide then dropwise joins in the above-mentioned zinc acetate solution, continue to stir 180min, preparation ZnO crystal seed, the crystal seed of above-mentioned preparation is anchored at surface of cotton fabric by the mode of padding baking, with molar concentration is after the liquor zinci chloridi of 0.017M and cyclodextrin one hexamethylenetetramine solution that molar concentration is 0.025M evenly mix, put into stainless steel cauldron, to preset the COTTON FABRIC of ZnO crystal seed simultaneously takes out behind 120 ℃ of insulation 120min, clean up with deionized water, dry under 60 ℃ of conditions, on COTTON FABRIC, grow into oriented growth at last, the ZnO nano-stick array thin film of better crystallinity degree, the UPF value of arrangement back COTTON FABRIC increases to 326.3 (generally UPF＞50 think that the uvioresistant effect is good) rapidly by original 5.8.