CN101012621A - Preparation method of zinc oxide nano-rod film on fibre product - Google Patents

Abstract

The invention relates to a method for preparing a zinc oxide nanorod film on a fiber product, comprising steps: (1) preparing ZnO nano crystal grains by a sol-gel method and depositing a large amount of ZnO crystal seeds, zinc salt and alkali agent on the surface of the fiber product The molar concentration is between 0.001M and 0.75M; (2) By hydrothermal method or chemical solution pool precipitation method, zinc oxide nanorod film is grown on the fiber fabric, and the molar concentration of zinc salt solution and complexing agent solution are both 0.001M ～0.05M; a ZnO nanorod thin film with uniform surface and good orientation can be obtained, which can be formed at low temperature. The preparation method is simple and low in cost, and is suitable for industrial production.

Description

A kind of preparation method of zinc oxide nanorod film on fiber product

technical field

The invention belongs to the field of preparation of low-dimensional nanometer material films, in particular to a preparation method of zinc oxide nanorod films on fiber products.

Background technique

In recent years, with the improvement of people's living standards, people's requirements for clothing are getting higher and higher. High-grade, comfortable, textiles with anti-ultraviolet, antibacterial, self-cleaning and other functions are more and more favored by consumers. ZnO is a multifunctional semiconductor material with excellent shielding effect on ultraviolet rays. When the particle size of these materials is comparable to or smaller than that of light waves, the light absorption is significantly enhanced due to the small size effect. Therefore, zinc oxide nanopowder can attenuate ultraviolet rays, especially ultraviolet rays with a wavelength of 280nm-320nm; at the same time, nano-zinc oxide particles have better visible light transmission effect. Compared with traditional organic ultraviolet absorbers, nano-zinc oxide is an inorganic component. It has a long effective action time, a long wavelength band for optical radiation shielding, high chemical stability and thermal stability structure, non-toxic, non-irritating, safe and reliable to use. Therefore, with the help of these properties of nano-zinc oxide, textile products with antibacterial, deodorizing, and radiation-proof functions can be developed. Industrialized products include antibacterial underwear, surgical gowns, nurse uniforms, deodorant dressings, deodorant bandages, and toilet textiles. And summer sunscreen clothing, summer hats, sun umbrellas, sportswear, etc.

The traditional ways of using ZnO ultrafine powder to endow textile materials with special functions are as follows: one is to directly add nanoparticles to the initial reaction liquid of chemical fibers. The functional fiber is synthesized by conventional polymerization reaction. The nanoparticles are evenly distributed inside the fiber; the second is to apply the post-finishing technology to the fabric to modify the function of the fabric.

But above-mentioned these two kinds of methods all must at first prepare ZnO ultrafine powder, the preparation process of nanoscale ultrafine powder is complicated, and preparation process needs high-temperature treatment, and energy consumption is high, and cost is high; The surface energy is very large, it is very easy to aggregate, and the original superior properties of nanoparticles are lost. Although the surface modification of nano-zinc oxide by esterification reaction method, surface coupling grafting method or radiation grafting method can effectively solve the above problems It must be improved, but it cannot fundamentally solve the above-mentioned problems of ultrafine powders. The phenomenon of agglomeration of ultrafine powders after modification still exists, and the cost increases; Inside, the powder cannot be in contact with oxygen and moisture, photocatalysis cannot occur, and its antibacterial and deodorizing functions cannot be exerted. Using this method requires high equipment. If the superfine powder is agglomerated, there are larger aggregates, which may block the spinneret, and it cannot be processed such as cotton, hemp, silk, wool and other natural textiles; if the second method is used, that is, the post-finishing method , when the powder is added to the textile, the powder will be unevenly distributed due to the action of the binder. Moreover, the adhesive will cover the powder so that it cannot be in contact with oxygen and moisture, photocatalysis cannot occur, and its antibacterial, deodorizing and other functions cannot be exerted. In addition, the post-finishing process using adhesives will affect the fabric's feel, strength, elasticity and other properties, and the washing fastness and functional durability of the processed functional fabrics are also very poor.

Contents of the invention

The purpose of the present invention is to provide a preparation method of zinc oxide nanorod film on fiber products, the method is simple, low in cost, can form a film at low temperature, and is suitable for industrial production.

A kind of preparation method of zinc oxide nanorod film on the fiber product that the present invention proposes comprises the following steps:

(1) Prepare ZnO nanocrystals by sol-gel method and deposit a large number of ZnO seeds on the surface of fiber products

a. Dissolve the zinc salt in the organic solvent under strong stirring at 50-100°C to form a zinc salt solution; slowly add the alkali agent dissolved in the organic solvent into the above zinc salt solution dropwise, and the addition is complete After that, the stirring is continued for 30-180 min under the temperature condition; ZnO sol is obtained. The molar concentrations of zinc salt and alkali agent are both between 0.001M and 0.75M;

b. Soak the clean fiber products in ZnO sol for 1-5min, and double-dip and double-roll under the rolling condition of 1.75-3.50kg/ ^cm2 ;

c. The padded fiber product is dried at 20-60°C for 30-180 minutes. Then bake at 100-150°C for 5-60 minutes. ZnO nano crystals are deposited on the surface of fiber products.

(2) Grow zinc oxide nanorod films on fiber fabrics by hydrothermal method or chemical solution pool precipitation method

a. Evenly mix the zinc salt solution and the complexing agent solution with a molar concentration of 0.001M to 0.05M, and then put it into a stainless steel reaction kettle or an open flask;

b. Put the fiber product pre-prepared with a large number of ZnO seeds in a reaction kettle or an open flask, take it out after keeping it at 40-170°C for 0.5-6h, wash it with deionized water to remove the remaining reactants, and finally dry it at 30 It is dried under the condition of ~80°C, and grows on the fiber product to form a nanorod array film with directional growth and good crystallinity.

The molar concentrations of the zinc salt and the alkali agent in the step 1 are both between 0.001M and 0.75M;

Described step 1 zinc salt is any one in zinc acetate, zinc nitrate, zinc chloride zinc salt;

The alkaline agent in step 1 is lithium hydroxide, hydrazine hydrate, sodium hydroxide, potassium hydroxide, ammonia water, triethylamine, ethanolamine, diethanolamine, etc.;

The organic solvent in step 1 is absolute ethanol, methanol, isopropanol, ethylene glycol methyl ether and the like.

The zinc salt in the step 2 is one of zinc nitrate, zinc chloride, zinc acetate, zinc citrate, and zinc gluconate.

The complexing agent in step 2 is hexamethylenetetramine, urea, ammonia water, triethylamine, inorganic ammonium salt and OH-, etc.

Since the present invention adopts the sol-gel method to prepare ZnO sol, the obtained product is stable, the particle dispersibility is good, the ZnO particle size is small, the purity is high, and the particle size distribution is narrow. In addition, the sol-gel technology also has the advantages of low equipment requirements and easy control of conditions; Hydrothermal low-temperature deposition method, the resulting product has very good crystallinity, the synthesized zinc oxide nanorod film has good orientation, and the size of the nanorod is uniform. The nano-ZnO colloidal particles prepared by sol-gel technology are simply operated by padding Fix on the surface of fiber products, and then use the fiber products with fixed ZnO seeds as the deposition substrate to obtain ZnO nanorod films with uniform surface and good orientation, and synthesize oriented ZnO nanorod films at low temperature, the required equipment is simple , low cost, and suitable for large-scale production of aligned thin ZnO nanorods.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

Dissolve 0.88g of zinc acetate in 40ml of absolute ethanol, and stir magnetically for 30min at 70°C. At the same time, dissolve 0.232g of lithium hydroxide in 40ml of absolute ethanol, and stir magnetically for 30min at room temperature; pour the lithium hydroxide solution into an ethanol solution of zinc acetate and stirred at this temperature for 120 min to prepare a stable ZnO sol. Immerse the clean cotton poplin fabric in the prepared ZnO sol for 2 minutes, dip twice and twice under the condition of 2.8kg/cm ² rolling, dry the soaked fabric at room temperature for 150 minutes, and then dry it at 150°C Bake for 60min. After uniformly mixing the zinc nitrate solution with a molar concentration of 0.015M and the hexamethylenetetramine solution with a molar concentration of 0.015M, put it into a stainless steel reaction kettle, and at the same time, put the cotton poplin fabric pre-prepared with ZnO crystal seeds at 95°C After heat preservation for 120 minutes, take it out, clean it with deionized water, dry it, and finally grow it on the cotton poplin fabric into a directional growth, ZnO nanorod array film with good crystallinity, and the UPF value of the cotton poplin after finishing is rapidly increased from 4.3 to 415.3 (generally UPF>50 is considered to have excellent anti-ultraviolet effect).

Example 2

Weigh a certain amount of zinc acetate powder, and dissolve it in an organic solvent of ethylene glycol methyl ether under strong stirring at 60°C to form a zinc acetate solution with a molar concentration of 0.1M, and slowly add ethanolamine to the above zinc acetate solution, The molar concentration of ethanolamine was also 0.1 M, and the stirring was continued for 30 min to prepare a stable ZnO sol. Immerse the clean cotton fine plain weave fabric in the ZnO sol prepared above for 2 minutes, dip twice and roll twice under the condition of 3.0kg/cm ² rolling, dry the soaked fabric at 50°C for 90 minutes, and then dry it at 150 Bake at ℃ for 60min. After uniformly mixing the zinc nitrate solution with a molar concentration of 0.01M and the sodium hydroxide solution with a molar concentration of 0.4M, put it into a stainless steel reaction kettle, and at the same time, keep the cotton fine plain weave fabric with ZnO crystal seeds at 75°C for 90min Finally, take it out, clean it with deionized water, dry it at 80°C, and finally grow a directional growth film on the cotton fine plain weave fabric with good crystallinity. Increase to 495.1 (generally UPF>50 is considered to have excellent anti-ultraviolet effect).

Example 3

Weigh 12.2g of zinc acetate powder and dissolve it in 100ml of isopropanol, stir vigorously at 85°C for 30min, add 5.6g of triethylamine dropwise into the above zinc acetate solution, and continue stirring at 85°C for 30min to form a transparent Stable ZnO sol. Immerse the clean cotton poplin fabric in the prepared ZnO sol for 2min, dip twice and twice under the condition of 2.8kg/cm ² rolling, dry the soaked fabric at 40°C for 120min, and then dry it at 150°C Bake for 45 minutes. After uniformly mixing the zinc acetate solution with a molar concentration of 0.025M and the triethylamine solution with a molar concentration of 0.025M, put it into an open flask, and at the same time, keep the cotton poplin fabric with ZnO seed crystals at 50°C for 120min. Take it out, clean it with deionized water, dry it at 60°C, and finally grow a ZnO nanorod array film with directional growth and good crystallinity on the cotton poplin fabric. After finishing, the UPF value of the cotton poplin increases rapidly from the original 4.2. As large as 386.3 (generally UPF>50 is considered to have excellent anti-ultraviolet effect).

Example 4

Dissolve 0.270g of zinc acetate powder in 60ml of methanol solution under strong stirring at 60°C, then add 65ml of methanol solution containing 0.21g of potassium hydroxide dropwise into the above zinc acetate solution, and continue stirring for 180min to prepare ZnO seed crystals , the above prepared seed crystals are fixed on the surface of cotton fabric by padding and drying, and the zinc chloride solution with a molar concentration of 0.017M and the cyclodextrin-hexamethylenetetramine solution with a molar concentration of 0.025M are uniformly mixed Finally, put it into a stainless steel reaction kettle, and at the same time, take out the cotton fabric preset with ZnO seeds at 120°C for 120min, then take it out, clean it with deionized water, dry it at 60°C, and finally grow on the cotton fabric into a oriented Growth, ZnO nanorod array film with good crystallinity, the UPF value of the cotton fabric after finishing is rapidly increased from 5.8 to 326.3 (generally UPF>50 is considered to have excellent anti-ultraviolet effect).

Claims (8)

1. a preparation method of zinc oxide nanorod film on fiber product, comprises the following steps: (1) Prepare ZnO nanocrystals by sol-gel method and deposit a large number of ZnO seeds on the surface of fiber products a. Under strong stirring at 50-100°C, dissolve the zinc salt in an organic solvent to form a zinc salt solution; slowly add the alkali agent dissolved in the organic solvent dropwise, and continue stirring for 30-180 minutes to obtain ZnO Sol; b. Soak the clean fiber products in ZnO sol for 1-5min, and double-dip and double-roll under the rolling condition of 1.75-3.50kg/ ^cm2 ; c. The padded fiber product is dried at 20-60°C for 30-180 minutes. Then bake at 100-150°C for 5-60 minutes. Deposit ZnO nanocrystals on the surface of fiber products; (2) Grow zinc oxide nanorod films on fiber fabrics by hydrothermal method or chemical solution pool precipitation method a. After uniformly mixing the zinc salt solution and the complexing agent solution with a molar concentration of 0.001M to 0.05M, put them into a reaction kettle or an open flask; b. Put the fiber product pre-prepared with a large number of ZnO seeds in a reaction kettle or an open flask, take it out after keeping it at 40-170°C for 0.5-6h, wash it with deionized water to remove the remaining reactants, and finally dry it at 30 It is dried under the condition of ~80°C, and grows on the fiber product to form a nanorod array film with directional growth and good crystallinity. 2 . The method for preparing a zinc oxide nanorod film on a fiber product according to claim 1 , wherein the molar concentrations of the zinc salt and the alkali agent in the step 1 are both 0.001M-0.75M. 3. the preparation method of zinc oxide nanorod film on a kind of fiber product according to claim 1, it is characterized in that: described step 1 zinc salt is selected from any one in zinc acetate, zinc nitrate, zinc chloride zinc salt kind. 4. the preparation method of zinc oxide nanorod film on a kind of fiber product according to claim 1, is characterized in that: described step 1 alkali agent is lithium hydroxide, hydrazine hydrate, sodium hydroxide, potassium hydroxide, ammoniacal liquor , triethylamine, ethanolamine, or diethanolamine. 5 . The method for preparing a zinc oxide nanorod film on a fiber product according to claim 1 , wherein the organic solvent in step 1 is absolute ethanol, methanol, isopropanol or ethylene glycol methyl ether. 6. the preparation method of zinc oxide nanorod film on a kind of fiber product according to claim 1, it is characterized in that: described step 2 zinc salt is selected from zinc nitrate, zinc chloride, zinc acetate, zinc citrate, glucose One of the acid zinc salts. 7. the preparation method of zinc oxide nanorod film on a kind of fiber product according to claim 1, is characterized in that: described step 2 complexing agent is hexamethylenetetramine, urea, ammoniacal liquor, triethylamine, Inorganic ammonium salt or OH ^- . 8 . The method for preparing a zinc oxide nanorod film on a fiber product according to claim 1 , wherein the molar concentration of the zinc nitrate solution and hexamethylenetetramine in the step 2 is 0.015M.