CN103409984B - A kind of method at surface of cotton fabric low-temperature growth anatase titanium dioxide film - Google Patents

Abstract

The invention relates to a method for preparing anatase titanium dioxide film on the surface of cotton fabric at low temperature, comprising: (1) mixing absolute ethanol, glacial acetic acid and tetra-n-butyl titanate, and then slowly adding them dropwise until the pH value is 2.5- 3. Hydrolyze in a mixed solution of acetic acid and water, and form a titanium dioxide sol after vigorous stirring; (2) Soak the cotton fabric in the above titanium dioxide sol for 2-3 minutes, two dipping and two rolling, and then pre-dry at 70-90°C for 3- 5min, and steam at 80-100°C for 2-3h. The preparation method of the present invention is simple, does not require adhesives, and does not require high-temperature curing treatment, and forms a sharp bond fastness, high crystallinity, and excellent photocatalytic performance on the surface of cotton fabrics through a conventional dipping-rolling-steaming process. Titanium film; it can be used in car and indoor air purification, as well as self-cleaning of fabrics, etc.

Description

A method for preparing anatase titanium dioxide thin film on the surface of cotton fabric at low temperature

technical field

The invention belongs to the field of preparation of titanium dioxide thin films, in particular to a method for preparing anatase titanium dioxide thin films on the surface of cotton fabrics at low temperature.

Background technique

With the development of the economy and the improvement of people's living standards, people's functional requirements for textiles are not limited to the most basic wearable performance. favor. For textile printing and dyeing enterprises, endowing textiles with special functions plays a vital role in improving product quality and increasing product added value. The photocatalytic material TiO ₂ (especially the anatase crystal form) has high photocatalytic activity, good stability and heat resistance, is non-toxic to the human body and cheap, and has been widely known. The application of nano photocatalytic materials in textiles Among them, it can endow the fabric with functions such as photocatalytic self-cleaning, UV resistance, and VOC degradation, and has great application potential. The use of nano-titanium dioxide powder materials in fabrics requires the assistance of adhesives because of their poor affinity with organic textile materials; the dispersion is uneven, easy to agglomerate or even precipitate, and even after surface modification cannot completely solve the agglomeration problem, so this The application of the method is very limited. Finishing fabrics with inorganic oxide coating is a new way to improve the performance of fabrics. This method can form a continuous and complete film on the surface of the fabric. The film has the advantages of firm bonding with the fabric and large surface area. It is difficult to obtain anatase titanium dioxide with high crystallinity at low temperature.

Chinese patent CN1757444A discloses a method for forming a titanium dioxide coating on the surface of an article, which does not require the assistance of an adhesive or a high-temperature curing process, and can easily and simply form a durable titanium dioxide coating on the surface of an article. However, this preparation method does not obtain titanium dioxide with a specific crystal form and high crystallinity at low temperature, and does not exert the most excellent photocatalytic ability.

Chinese patent CN101073768A discloses a low-temperature film-forming method of titanium dioxide photocatalytic thin film. The titanium dioxide sol is prepared by the sol-gel method. After coating the titanium oxide thin film on the substrate, a uniform thin film is formed by high-frequency electric field microwave irradiation. However, the high-frequency electric field heating cost of this method is relatively high, and it is not suitable for large-scale production in factories.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for preparing anatase titanium dioxide film at low temperature on the surface of cotton fabric. An anatase film with good bonding fastness, high crystallinity and excellent photocatalytic performance is formed on the surface of cotton fabric.

A method for preparing anatase titanium dioxide film at low temperature on the surface of cotton fabric of the present invention, comprising:

(1) Preparation of titania sol

Mix absolute ethanol, glacial acetic acid and tetra-n-butyl titanate, then slowly drop them into a mixed solution of acetic acid and water with a pH value of 2.5-3 for hydrolysis, and form a light yellow transparent titanium dioxide sol after vigorous stirring;

(2) Preparation of titanium dioxide thin film

Soak the cotton fabric in the above-mentioned titanium dioxide sol for 2-3 minutes, dip twice and pad twice, then pre-dry at 70-90°C for 3-5 minutes, and steam at 80-100°C for 2-3 hours.

The volume ratio of absolute ethanol, glacial acetic acid, tetra-n-butyl titanate and the mixed solution in step (1) is 3-6:6-10:10-15:120-150.

The squeeze rate in the second dipping and second rolling described in step (2) is 60-80%.

The cotton fabric described in step (2) is a pretreated cotton fabric, and the pretreatment operation is as follows: the cotton fabric is treated with a non-ionic cleaning agent at 60-90°C for 10-30min, washed with deionized water and dried. Dry and set aside.

The above-mentioned non-ionic cleaning agent is cleaning agent 6501 or fatty alcohol polyoxyethylene ether 9 (Pingpingjia O-9) (Jiangkefeng Chemical Co., Ltd.).

The film-forming properties of the cotton fabrics of the present invention are characterized by scanning electron microscope images, the crystallization properties of titanium dioxide are characterized by X-ray diffraction patterns, the photocatalytic properties of titanium dioxide films are determined by the decomposition of organic matter, and the prepared cotton fabrics are placed in an airtight container in the gas phase , A small amount of organic gas is introduced into the container, and after a certain light irradiation time, the organic matter is decomposed. In the liquid phase, red wine and coffee are used to smear on the prepared film. After a certain light irradiation time, the red wine and coffee stains are degraded and become colorless. Since organic gases, red wine, and coffee are not affected by ultraviolet light, their degradation can be considered as the effect of thin film photocatalysis.

The present invention uses butyl titanate as a precursor to prepare anatase-type titanium dioxide sol through a sol-gel method, and uses the sol as a finishing agent to form an anatase-type titanium dioxide film on cotton fabrics after dipping-rolling-steaming treatment .

Beneficial effect:

(1) The cost of raw materials is low, the method is simple, the preparation temperature is low, and it is suitable for industrial applications. When the present invention is applied to the process of preparing a film on the surface of a fabric, since the dehydration reaction of the present invention is carried out on the surface of the cotton fabric, the hydroxyl group of titanium dioxide and the hydroxyl group of the cotton fabric It is easy to form covalent bonds, which can firmly bind titanium dioxide to the surface of the fabric, so that no adhesive is needed, and the titanium dioxide film can withstand 50 standard washings;

(2) The film prepared by the present invention is continuous and complete without cracking, and is an anatase titanium dioxide film with high crystallinity and high photocatalytic performance. Reducing electrons and holes can decompose organic harmful gases and bacteria in the air, and degrade stains on fabrics;

(3) The titanium dioxide thin film obtained by the present invention can be applied to air purification in cars and indoors, and self-cleaning of fabrics, etc.

Description of drawings

Fig. 1 is the X-ray diffraction spectrogram of the modified titanium dioxide film on the surface of cotton fabric in Example 1.

Fig. 2 is the scanning electron microscope picture of the cotton fabric surface before and after modification in embodiment 2; Wherein: a is unmodified cotton fabric, b is the cotton fabric after modification.

Fig. 3 is the degradation curve of the titanium dioxide film on the surface of the cotton fabric before and after modification in Example 3 to organic gas; wherein: a is the unmodified cotton fabric, and b is the modified cotton fabric.

Fig. 4 is the degradation effect diagram of titanium dioxide film on the surface of cotton fabric before and after modification in Example 4 to red wine stains; wherein: a is the unmodified cotton fabric, and b is the modified cotton fabric.

Fig. 5 is the degradation effect diagram of the titanium dioxide film on the surface of the cotton fabric before and after modification in Example 4 to coffee stains; wherein: a is the unmodified cotton fabric, and b is the modified cotton fabric.

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

Mix 3mL of absolute ethanol, 6mL of glacial acetic acid and 10mL of tetra-n-butyl titanate, then slowly add it dropwise to 120mL of a mixed solution of acetic acid and water with a pH of 2.5 for hydrolysis, and form a light yellow color after vigorous stirring transparent sol.

Soak the pretreated cotton fabric in titanium dioxide sol for 3 minutes, dip twice and roll it twice (the liquid rolling rate is 80%), pre-dry it at 80°C for 3 minutes, steam it in a steam box at 100°C for 3 hours, and finish drying the cotton fabric. The process of preparing titanium dioxide film on the surface of fabric.

According to the national standard GB/T8629-2001 "Household Washing and Drying Procedures for Textile Testing", the titanium dioxide modified cotton fabrics were washed and dried (type A washing machine, 5A washing procedure, A-type drying procedure), after 50 times of washing Finally, the XRD pattern of the film was characterized, as shown in Figure 1. The test results show that the crystal structure of the film prepared on the surface of cotton fabric is anatase titanium dioxide with high crystallinity.

Example 2

Mix 3mL of absolute ethanol, 6mL of glacial acetic acid and 10mL of tetra-n-butyl titanate, then slowly add it dropwise to 120mL of a mixed solution of acetic acid and water with a pH of 2.5 for hydrolysis, and form a light yellow color after vigorous stirring transparent sol.

Soak the pretreated cotton fabric in titanium dioxide sol for 3 minutes, dip twice and roll it twice (the liquid rolling rate is 80%), pre-dry it at 80°C for 3 minutes, steam it in a steam box at 100°C for 3 hours, and finish drying the cotton fabric. The process of preparing titanium dioxide film on the surface of fabric.

According to the national standard GB/T8629-2001 "Household Washing and Drying Procedures for Textile Testing", the titanium dioxide modified cotton fabrics were washed and dried (type A washing machine, 5A washing procedure, A-type drying procedure), after 50 times of washing Finally, the film-forming state on the surface of the fabric was characterized by a scanning electron microscope (SEM), as shown in Figure 2. The test results show that the film prepared on the surface of cotton fabric is continuous and complete without cracking.

Example 3

Mix 3mL of absolute ethanol, 6mL of glacial acetic acid and 10mL of tetra-n-butyl titanate, then slowly add it dropwise to 120mL of a mixed solution of acetic acid and water with a pH of 2.5 for hydrolysis, and form a light yellow color after vigorous stirring transparent sol.

Soak the pretreated cotton fabric in titanium dioxide sol for 3 minutes, dip twice and roll it twice (the liquid rolling rate is 80%), pre-dry it at 80°C for 3 minutes, steam it in a steam box at 100°C for 3 hours, and finish drying the cotton fabric. The process of preparing titanium dioxide film on the surface of fabric.

According to the national standard GB/T8629-2001 "Household Washing and Drying Procedures for Textile Testing", the titanium dioxide modified cotton fabrics were washed and dried (type A washing machine, 5A washing procedure, A-type drying procedure), after 50 times of washing Finally, the fabric prepared with titanium dioxide film was placed in a closed container, a small amount of formaldehyde gas was introduced into the container, and the ultraviolet light intensity was 1.5mW/cm ² ±0.05mW/cm ² . After 5h of ultraviolet light irradiation, the organic matter was Break down (Figure 3). The results show that the titanium dioxide film on the fabric has a good photocatalytic degradation effect on organic gases.

Example 4

Mix 3mL of absolute ethanol, 6mL of glacial acetic acid and 10mL of tetra-n-butyl titanate, then slowly add it dropwise to 120mL of a mixed solution of acetic acid and water with a pH of 2.5 for hydrolysis, and form a light yellow color after vigorous stirring transparent sol.

Soak the pretreated cotton fabric in titanium dioxide sol for 3 minutes, dip twice and roll it twice (the liquid rolling rate is 80%), pre-dry it at 80°C for 3 minutes, steam it in a steam box at 100°C for 3 hours, and finish drying the cotton fabric. The process of preparing titanium dioxide film on the surface of fabric.

According to the national standard GB/T8629-2001 "Household Washing and Drying Procedures for Textile Testing", the titanium dioxide modified cotton fabrics were washed and dried (type A washing machine, 5A washing procedure, A-type drying procedure), after 50 times of washing Finally, use red wine and coffee to smear on the prepared film, and the ultraviolet light intensity is 1.5mW/cm ² ± 0.05mW/cm ² , after 8h of ultraviolet light irradiation, red wine and coffee are degraded into colorless (Fig. 4, Fig. 5 ). The results show that the TiO2 film on the fabric has a good photocatalytic degradation effect on organic stains.

Claims (4)

1. A method for preparing anatase titanium dioxide thin film at low temperature on cotton fabric surface, comprising: (1) Mix absolute ethanol, glacial acetic acid and tetra-n-butyl titanate, then slowly add dropwise to a mixed solution of acetic acid and water with a pH value of 2.5-3 for hydrolysis, and form a titanium dioxide sol after vigorous stirring; (2) Soak the cotton fabric in the above-mentioned titanium dioxide sol for 2-3min, dip twice and pad twice, then pre-bake at 70-90°C for 3-5min, and steam at 80-100°C for 2-3h; , the cotton fabric is a pretreated cotton fabric, and the pretreatment operation is as follows: the cotton fabric is treated with a non-ionic cleaning agent at 60-90°C for 10-30min, washed with deionized water and dried for later use. 2. a kind of method preparing anatase titanium dioxide film at low temperature on cotton fabric surface according to claim 1, is characterized in that: dehydrated alcohol described in step (1), glacial acetic acid, tetra-n-butyl titanate The volume ratio to the mixed solution is 3-6:6-10:10-15:120-150. 3. a kind of method for preparing anatase titanium dioxide thin film at low temperature on cotton fabric surface according to claim 1, is characterized in that: the rolling liquid rate in the two dipping two rollings described in step (2) is 60-80 %. 4. A method for preparing anatase titanium dioxide film at low temperature on the surface of cotton fabric according to claim 1, characterized in that: the non-ionic cleaning agent is cleaning agent 6501 or fatty alcohol polyoxyethylene ether 9.