阅读说明：本技术 一种碳纤维编织布负载羟基氧化铁纳米颗粒复合结构色的方法及得到的碳纤维编织布 (Method for loading hydroxyl iron oxide nano particle composite structural color on carbon fiber woven cloth and obtained carbon fiber woven cloth ) 是由 宋浩杰 蔺哲 杨进 贾晓华 李永 于 2019-10-15 设计创作，主要内容包括：本发明公开一种碳纤维编织布负载羟基氧化铁纳米颗粒复合结构色的方法及得到的碳纤维编织布,制备包括以下步骤：第一步,将三氯化铁粉末超声分散到去离子水中,室温下搅拌,溶液由无色变为橙色,随后向溶液中加入氟化铵粉末并搅拌,得到透明澄清溶液,随后将混合溶液转入反应釜中；第二步,将经过丙酮和乙醇的混合溶液清洗过的碳纤维编织布裁剪成一定尺寸,浸入反应釜中；第三部,在高温烘箱中水热反应使羟基氧化铁纳米颗粒以不同密度和厚度负载到碳纤维编织布表面,并最终获得不同的结构色的碳纤维编织布；解决了碳纤维编织布表面沉积结构色的技术难题,制备方法简单易行,重复性强,且所用原料环保安全无毒,易于实现工业化。(The invention discloses a method for loading hydroxyl ferric oxide nano-particle composite structural color on carbon fiber woven cloth and the obtained carbon fiber woven cloth, wherein the preparation method comprises the following steps: firstly, ultrasonically dispersing ferric trichloride powder into deionized water, stirring at room temperature to change the solution from colorless to orange, then adding ammonium fluoride powder into the solution, stirring to obtain a transparent clear solution, and then transferring the mixed solution into a reaction kettle; secondly, cutting the carbon fiber woven cloth cleaned by the mixed solution of acetone and ethanol into a certain size, and immersing the carbon fiber woven cloth into a reaction kettle; thirdly, carrying out hydrothermal reaction in a high-temperature oven to load iron oxyhydroxide nanoparticles onto the surface of the carbon fiber woven cloth in different densities and thicknesses, and finally obtaining the carbon fiber woven cloth with different structural colors; the technical problem of structural color deposition on the surface of the carbon fiber woven cloth is solved, the preparation method is simple and easy to implement, the repeatability is strong, the used raw materials are environment-friendly, safe and nontoxic, and the industrialization is easy to realize.)

1. A method for loading hydroxyl iron oxide nano particle composite structural color on carbon fiber woven cloth is characterized by comprising the following steps:

step 1: preparing a ferric chloride-ammonium fluoride mixed solution: uniformly mixing ferric trichloride powder and deionized water, fully and uniformly stirring, performing ultrasonic dispersion, adding ammonium fluoride, and uniformly stirring to obtain a clear and transparent mixed solution;

step 2: pretreating carbon fiber woven cloth: treating commercial carbon fiber weaving to remove industrial sizing agent on the surface of the carbon fiber woven cloth, then improving the roughness of the surface of the carbon fiber by adopting plasma etching, and introducing active groups;

and step 3: coating the hydroxyl ferric oxide nano-particle structure: and (2) placing the mixed solution prepared in the step (1) into a reaction kettle, then soaking the carbon fiber woven cloth treated in the step (2) into the mixed solution, carrying out hydrothermal reaction in a drying oven, wherein the hydrothermal reaction temperature is 50-100 ℃, the reaction time is 8-16h, taking out the carbon fiber woven cloth after the reaction is finished, cleaning the surface of the carbon fiber woven cloth by using ethanol, and drying at low temperature to obtain the carbon fiber woven cloth loaded with the iron oxyhydroxide nanoparticle composite structural color.

2. The method for loading the iron oxyhydroxide nanoparticle composite structural color on the carbon fiber woven cloth according to claim 1, characterized in that: in the step 1, the dosage ratio of the ferric trichloride to the deionized water to the ammonium fluoride is 4-6 g to 50-70 ml to 1-1.5 g.

3. The method for loading the iron oxyhydroxide nanoparticle composite structural color on the carbon fiber woven cloth according to claim 1, characterized in that: and 2, putting the commercial carbon fiber woven cloth into a mixed solution of ethanol and acetone, and ultrasonically cleaning to remove the industrial sizing agent on the surface of the carbon fiber woven cloth.

4. The method for loading the iron oxyhydroxide nanoparticle composite structural color on the carbon fiber woven cloth according to claim 3, characterized in that: the ultrasonic cleaning time is 2 h.

5. The method for loading the iron oxyhydroxide nanoparticle composite structural color on the carbon fiber woven cloth according to claim 1, characterized in that: in the step 1, ferric trichloride powder is added into deionized water, and a magnetic stirrer is adopted to stir at room temperature for 30min, so that the solution is fully and uniformly stirred.

6. The method for loading the iron oxyhydroxide nanoparticle composite structural color on the carbon fiber woven cloth according to claim 1, characterized in that: the ultrasonic dispersion time in the step 1 is 60 min.

7. The method for loading the iron oxyhydroxide nanoparticle composite structural color on the carbon fiber woven cloth according to claim 1, characterized in that: the plasma etching time in the step 2 is 10 min.

8. The method for loading the iron oxyhydroxide nanoparticle composite structural color on the carbon fiber woven cloth according to claim 1, characterized in that: and in the step 3, the low-temperature drying time is 60 min.

9. A carbon fiber woven cloth loaded with a composite structural color of iron oxyhydroxide nanoparticles prepared according to the method of claims 1 to 8.

Technical Field

The invention belongs to the field of preparation of nano composite materials, and particularly relates to a method for loading iron oxyhydroxide nano particle composite structural color on carbon fiber woven cloth and the obtained carbon fiber woven cloth.

Background

The rich color world gives people an attractive visual experience. Chemical and structural (also called physical) colors are two broad classes of colors. Chemical color refers to color generation by pigmentation, and although these chemicals are colorful and simple in color, they are liable to cause resource waste and environmental pollution. The structural color is presented by grating diffraction, interference and refraction of the white light and the special tissue structure of the object. The structural color is not pigmentation, is physical coloring, has the advantages of stable color, no fading, environmental friendliness, short preparation period and the like, and is widely applied to the fields of anti-counterfeiting, painting, stealth, decoration and the like. Carbon fiber, a high-performance fiber, has excellent properties such as high specific strength, high specific modulus, small coefficient of thermal expansion, and low coefficient of friction, and is one of the most widely used reinforcing materials in recent years. And through combining with the color forming technology of structural color, the carbon fiber can present different colors, thereby the application of the carbon fiber is wider.

The chinese patent application No. 201910071203.2 discloses a method for preparing a structural color based on atomic layer deposition, which includes three processes of providing a sample, depositing a material, and depositing a gas. Atomic layer deposition can only plate a thin film at a time with extremely uniform thickness and excellent conformality, but on the other hand, this method has low deposition rate, is time and labor consuming, and has high deposition cost. The Chinese patent application No. 201510604482.6 discloses a purple photonic crystal structure color film and a preparation method thereof, the method adopts a uniform deposition method to prepare zinc sulfide microspheres, and then adopts a vertical deposition method to self-assemble the zinc sulfide microspheres into the purple photonic crystal structure color film on the surface of a glass substrate, the structure color purple film has bright color and is not easy to fade, but the method has complex preparation process and more required raw materials, thereby improving the preparation cost.

Although a great amount of Chinese patent inventions about structural color generation, a preparation method for coloring the surface of the carbon fiber woven cloth is rarely reported, and particularly, a composite structural color material of the carbon fiber woven cloth loaded with iron oxyhydroxide nanoparticles is not reported.

Disclosure of Invention

The invention aims to provide a method for loading hydroxyl iron oxide nano particle composite structural color on carbon fiber woven cloth and the obtained carbon fiber woven cloth, wherein the method has the advantages of strong repeatability, simple and convenient preparation process and short preparation period; the iron oxyhydroxide nanoparticles prepared by the method have the advantages of uniform particle size and single appearance, and the presented structural color has the advantages of bright color, fastness and no change along with the change of an observation angle.

In order to achieve the above object, the present invention adopts the following technical solutions.

A method for loading hydroxyl iron oxide nano particle composite structural color on carbon fiber woven cloth comprises the following steps:

step 1: preparing a ferric chloride-ammonium fluoride mixed solution: uniformly mixing ferric trichloride powder and deionized water, fully and uniformly stirring, performing ultrasonic dispersion, adding ammonium fluoride, and uniformly stirring to obtain a clear and transparent mixed solution;

step 2: pretreating carbon fiber woven cloth: treating commercial carbon fiber weaving to remove industrial sizing agent on the surface of the carbon fiber woven cloth, then improving the roughness of the surface of the carbon fiber by adopting plasma etching, and introducing active groups;

and step 3: coating the hydroxyl ferric oxide nano-particle structure: and (2) placing the mixed solution prepared in the step (1) into a reaction kettle, then soaking the carbon fiber woven cloth treated in the step (2) into the mixed solution, carrying out hydrothermal reaction in a drying oven, wherein the hydrothermal reaction temperature is 50-100 ℃, the reaction time is 8-16h, taking out the carbon fiber woven cloth after the reaction is finished, cleaning the surface of the carbon fiber woven cloth by using ethanol, and drying at low temperature to obtain the carbon fiber woven cloth loaded with the iron oxyhydroxide nanoparticle composite structural color.

Further, the using amount ratio of the ferric trichloride, the deionized water and the ammonium fluoride in the step 1 is 4-6 g, 50-70 ml and 1-1.5 g.

Further, in the step 2, the commercial carbon fiber woven cloth is placed into a mixed solution of ethanol and acetone for ultrasonic cleaning to remove the industrial sizing agent on the surface of the carbon fiber woven cloth.

Further, the ultrasonic cleaning time was 2 hours.

Further, in the step 1, ferric trichloride powder is added into deionized water, and a magnetic stirrer is adopted to stir at room temperature for 30min, so that the solution is fully and uniformly stirred.

Further, the ultrasonic dispersion time in the step 1 is 60 min.

Further, the plasma etching time in the step 2 is 10 min.

Further, the low-temperature drying time in the step 3 is 60 min.

A carbon fiber woven cloth loaded with a hydroxyl ferric oxide nanoparticle composite structural color.

Compared with the prior art, the invention has the following excellent technical effects:

according to the invention, uniform ferric oxyhydroxide nanoparticles with a certain thickness are loaded on the surface of the carbon fiber woven cloth by a simple hydrothermal method, and the uniform ferric oxyhydroxide nanoparticles and light rays have diffraction, interference and other effects, so that the surface of a product generates structural color.

The method of the invention adopts a hydrothermal method for preparation, has no directionality, the loaded iron oxyhydroxide nano particles are uniform and compact, the color of the carbon fiber woven cloth can not change along with the change of an observation angle, the color is stable, the color is not easy to fade, the carbon fiber woven cloth has good chemical stability, the bright color can still be kept after being soaked in acid, alkali and salt solution for a long time, the carbon fiber woven cloth has good color stability, and the technical problem of depositing structural color on the surface of the carbon fiber woven cloth is solved.

The product with bright structural color can be prepared by only needing a small amount of water and the precursor in the preparation process, the reaction precursor is easy to obtain, the raw materials are saved, the preparation cost of the required raw materials is low, and the method is suitable for large-scale industrial production. The density of the loaded iron oxyhydroxide nanoparticles is controlled by adjusting the reaction temperature and time, so that the structural color of the surface of the product is controlled.

Drawings

FIG. 1 is a physical diagram of a product of carbon fiber woven cloth loaded with iron oxyhydroxide nanoparticles prepared by the invention at different hydrothermal temperatures and times

FIG. 2 is SEM of iron oxyhydroxide nanoparticles loaded on carbon fiber woven cloth prepared by the invention

FIG. 3 is an energy spectrum diagram of iron oxyhydroxide nanoparticles loaded on carbon fiber woven cloth prepared by the invention

FIG. 4 is an energy spectrum diagram of iron oxyhydroxide nanoparticles loaded on carbon fiber woven cloth prepared by the invention

FIG. 5 is an XRD of iron oxyhydroxide nanoparticles loaded on carbon fiber woven cloth prepared by the invention

Detailed Description

The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.

The method for loading the hydroxyl ferric oxide nano-particle composite structural color on the carbon fiber woven cloth comprises the following steps of:

1) preparing a ferric chloride-ammonium fluoride mixed solution: uniformly mixing 4-6 g of ferric trichloride powder and 50-70 ml of deionized water, fully stirring uniformly, controlling the magnetic stirring time to be 30min, then placing the solution in ultrasound for dispersing, wherein the ultrasound time is 60min, after the ultrasound is finished, adding 1-1.5 g of ammonium fluoride, and magnetically stirring for 30min to finally obtain a clear and transparent ferric trichloride-ammonium fluoride mixed solution.

2) Pretreating carbon fiber woven cloth: cutting commercial carbon fiber woven cloth into 15 x 15cm²Fixing the size, putting into mixed solution of ethanol and acetone for ultrasonic cleaning for 2h to remove industrial sizing agent on the surface of the carbon fiber woven cloth, then washing with deionized water, drying with a blast drying oven, taking out, and then etching with plasma for 10min to improve the roughness of the surface of the carbon fiber and introduce living mattersA sex group.

3) Coating the hydroxyl ferric oxide nano-particle structure: and (3) placing the mixed solution of ferric trichloride and ammonium fluoride obtained in the step one into a reaction kettle, then soaking the treated carbon fiber woven cloth into the solution, and carrying out hydrothermal reaction in an oven, wherein the reaction temperature is 50-100 ℃, and the reaction time is 8-16 h. And (3) after the reaction is finished, taking out the carbon fiber woven cloth, cleaning the surface of the carbon fiber woven cloth by using deionized water and ethanol, and then drying for 60min at the low temperature of 60 ℃ by using an air blower to obtain the composite structural color material. And the density of the deposited iron oxyhydroxide nanoparticles can be controlled by changing the hydrothermal reaction temperature and the reaction time, and the iron oxyhydroxide nanoparticles with different densities have different diffraction and interference effects, so that the color of the product is controlled. The inventor finds that when the reaction temperature and the reaction time are respectively 50 ℃ and 8 hours through repeated experiments; at 50 ℃, for 16 h; at 70 ℃, for 16 h; at 90 ℃ for 16 h; at 100 ℃ for 16h, the product respectively presents light blue; a dark blue color; purple color; cyan and gold.

The present invention will be described with reference to specific examples.