阅读说明：本技术 一种表面褶皱化纤维类材料及其制备方法 (Surface-wrinkled fiber material and preparation method thereof ) 是由 葛邓腾 解晓雨 郭颖 杨丽丽 徐利云 石建军 于 2020-04-09 设计创作，主要内容包括：本发明涉及一种表面褶皱化纤维类材料及其制备方法,该方法包括步骤：(1)制备由树脂和稀释剂构成的涂布液；(2)将材料浸泡入所述涂布液中后取出干燥,获得表面涂布有涂层的材料；(3)将表面涂布有涂层的材料进行等离子体处理得表面褶皱化材料。制得的具有褶皱状表面的纤维由纤维基体和包覆于所述纤维基体表面的树脂涂布液涂层构成；且褶皱状结构在纤维表面沿纤维长度方向呈环状排列；且由该纤维制得的表面褶皱化纤维织物与水接触角大于150°,滚动角小于10°,表面褶皱化纤维织物具有超疏水性。本发明的方法提高了材料防水防污性；本发明的表面褶皱化纤维类材料在功能性服装、户外用品、军用防护服、光电等领域,具有广阔的应用前景。(The invention relates to a surface-wrinkled fiber material and a preparation method thereof, wherein the method comprises the following steps: (1) preparing a coating liquid composed of a resin and a diluent; (2) soaking the material into the coating liquid, taking out and drying to obtain the material with the surface coated with the coating; (3) and carrying out plasma treatment on the material with the coating coated on the surface to obtain the surface wrinkling material. The prepared fiber with the wrinkled surface consists of a fiber matrix and a resin coating liquid coating layer coated on the surface of the fiber matrix; the fold-shaped structures are annularly arranged on the surface of the fiber along the length direction of the fiber; and the contact angle between the surface-wrinkled fiber fabric prepared from the fiber and water is more than 150 degrees, the rolling angle is less than 10 degrees, and the surface-wrinkled fiber fabric has super-hydrophobicity. The method improves the water resistance and the antifouling property of the material; the surface-wrinkled fiber material has wide application prospect in the fields of functional clothing, outdoor products, military protective clothing, photoelectricity and the like.)

1. A method of making a material having a surface corrugation, comprising the steps of:

(1) preparing a coating liquid;

the coating liquid is composed of resin and diluent; the resin is a liquid oligomer and is a silicone resin, an acrylate resin or a soluble fluororesin; the diluent is a good solvent corresponding to the resin and is more than one of ethanol, acetone, toluene, ethyl acetate, dimethylformamide and perfluorinated solvent;

the preparation of the coating liquid is that resin and diluent are stirred and mixed uniformly, and the weight ratio of the resin in the coating liquid is 0.01-20%;

(2) coating a film on the surface of the material;

material refers to a fiber monofilament, tow, or fabric;

soaking the material into the coating liquid, taking out and drying to obtain a material with a coating coated on the surface;

(3) plasma processing;

and carrying out plasma treatment on the material with the coating coated on the surface to obtain the surface wrinkling material.

2. The method according to claim 1, wherein in step (1): the organic silicon resin is polydimethylsiloxane, poly-1, 1,3, 3-tetramethyl disiloxane, polymethylhydrosiloxane or silicone resin; the diluent corresponding to the organic silicon resin is more than one of toluene, ethanol, xylene and acetone;

the acrylate resin is polyethyl methacrylate or poly-2-methyl methacrylate; the diluent corresponding to the acrylate resin is more than one of acetone, toluene and ethyl acetate;

the soluble fluororesin is poly (2-trifluoromethyl-3, 3, 3-trifluoropropyl methacrylate), Teflon AF1600, Teflon AF2400, THV 220A, fluorinated ethylene propylene copolymer or perfluoro-1-butenyl vinyl ether polymer; the diluent corresponding to the soluble fluororesin is perfluoro dialkyl ether and/or perfluoro trialkylamine;

in the coating liquid, the weight ratio of the resin is 0.01-5%.

3. The method according to claim 1, wherein the fiber monofilaments are polymer fibers or inorganic fibers; the polymer fiber is terylene, nylon, acrylon, polypropylene fiber or aramid fiber; the inorganic fiber is glass fiber, carbon fiber, quartz fiber, alumina fiber or basalt fiber; the fiber monofilament refers to a solid fiber or a porous fiber; the section of the solid fiber is round, square, triangular or cross-shaped or the section of the solid fiber is a fiber with a skin-core structure;

the tows are polymer fiber tows or inorganic fiber tows;

the tows refer to tows formed by 2-1000 fiber monofilaments;

by fabric is meant a fabric made wholly or partially of the fibre filaments.

4. The method according to claim 1, wherein the material surface is cleaned before being coated with the film, and the method comprises the following specific steps: soaking the material in a solvent for 1-10 min, and removing the solvent through a drying process;

the solvent is ethanol or ethyl acetate;

the drying temperature is 50-70 ℃, and the drying time is 5-20 min.

5. The method according to claim 1, wherein the material is soaked in the coating liquid for 1-120 s at 15-35 ℃; the drying is natural airing for 30-60 min or drying for 5-20 min at 50-70 ℃;

the plasma treatment adopts radio frequency capacitance coupling plasma treatment, and the treatment parameters are as follows: 13.56MHz radio frequency or 40kHz radio frequency, 10-300W of power, 50-800 mTorr of air pressure, 20-80 ℃ of temperature, 1-2000 s of time, and argon and/or oxygen as gas.

6. The method of claim 5, wherein the parameters of the plasma process are: the power is 13.56MHz radio frequency, the power is 90W, the air pressure is 200mTorr, the processing time is 60s, and the gas is argon;

or, the parameters of the plasma treatment are as follows: the power is 40MHz radio frequency, the power is 50W, the gas pressure is 150mTorr, the processing time is 60s, and the gas is argon.

7. The method of claim 1, wherein the plasma treatment is selected to treat the material in areas where a corrugated surface is desired;

and (4) when the material is a fabric with the thickness of more than or equal to 0.3 mm, repeatedly treating the front side and the back side of the fabric for 2-5 times according to the step (3).

8. A fiber having a convoluted surface characterized by: the fiber with the wrinkled surface consists of a fiber matrix and a resin coating liquid coating layer coated on the surface of the fiber matrix;

the corrugated structures are annularly arranged on the surface of the fiber along the length direction of the fiber, the distance between the protrusions of the adjacent corrugated structures is 100 nm-5 mu m, and the height of the annular protrusions is 20-500 nm; the thickness of the resin coating liquid coating is 100 nm-2 mu m.

9. Surface-wrinkled fiber fabric, which is characterized in that: the surface-wrinkled fiber fabric is formed by weaving all or part of fiber monofilaments, and the surfaces of the fiber monofilaments in the surface-wrinkled fiber fabric are provided with resin coating liquid coatings with wrinkled structures annularly arranged along the axial direction;

the corrugated structures are annularly arranged on the surface of the fiber along the length direction of the fiber, the distance between the protrusions of the adjacent corrugated structures is 100 nm-5 mu m, and the height of the annular protrusions is 20-500 nm; the thickness of the resin coating liquid coating is 100 nm-2 mu m.

10. The surface-creped fiber fabric according to claim 9, wherein the surface-creped fiber fabric has a contact angle with water of more than 150 ° and a rolling angle with water of less than 10 °, and is superhydrophobic.

Technical Field

The invention belongs to the technical field of material surface modification, relates to a surface-wrinkled fiber material and a preparation method thereof, and particularly relates to a method for preparing micro-nano scale patterns on the surfaces of fibers and fabrics.

Background

The wrinkling and buckling phenomena of the material have been studied for decades, and the phenomenon can be used for producing a micro-nano structure with definite geometric shape and size, endowing the material with excellent optical, electromagnetic, super-hydrophobic, intelligent adhesion and other characteristics, and being widely applied to the fields of biology, nano-metrology, optics, electronics and the like.

Scientists create wrinkles by altering the material surface microstructure to impart superior properties to fibers. However, most methods treat the resulting wrinkles in a disordered state. One typical approach is to use a "two-layer" system of hard skin and elastomer matrix, which induces wrinkle formation due to internal stresses created by the mismatch of modulus and thermal expansion between the layers. The method is simple and convenient, but the appearance of the fold structure cannot be accurately regulated and controlled, and most of the generated folds are disordered and maze-shaped folds. Therefore, it is necessary to develop a method for forming a material surface having periodic wrinkles.

In order to improve the periodicity of the material wrinkles, scientists utilize a crack experimental device to apply stress on the surface of the material through a blade to generate periodic cracks perpendicular to the machining direction, so that the mechanical properties and the optical properties of the material are changed. Although this method can give new properties to the material, the inside of the crack is composed of voids and holes, and is not a true wrinkle structure. And the requirement on experimental instruments is high, only local areas of materials can be treated, and the integral treatment cannot be realized. In addition, the material surface is subjected to crosslinking treatment by utilizing ultraviolet light, so that the integral treatment of the material surface is realized, and the ordered wrinkle appearance can be generated with the help of a mask; however, the ultraviolet light penetration effect is poor, only the surface area of the material can be processed, and if the material is a multi-layer material, the processing process cannot be realized at one time, so that the efficiency is low; and the folds generated under the condition of no mask are still in a disordered state, and cannot spontaneously form ordered folds, so that the application of the folds is limited. Therefore, for materials with periodic surface wrinkling, how to integrally prepare the materials remains a challenge.

In addition, the generation of wrinkles on the surface of a single long fiber has attracted the interest of scientists. For example: the irregular fiber generates uneven annular wrinkles after being processed, the porous fiber generates a rough porous surface structure after being processed, and the fiber with a sheath-core structure generates annular wrinkles in a local area after being processed, so that the material generates a plurality of morphological structures along the axial direction of the fiber after being processed, but generates ordered wrinkles only in a small area, the appearances of the wrinkles are not consistent, and the wrinkles cannot penetrate through the whole long fiber; or the ring has periodicity only, so that the hydrophobic property and the optical performance of the ring are far from the requirements. And the single fiber is usually required to be pre-stretched before being treated, and the process is complex and difficult to control.

Disclosure of Invention

In order to solve the technical problems, the resin coating liquid coating layer consisting of resin and diluent is formed on the material matrix, and the plasma of argon or oxygen is utilized for processing, so that not only can single fiber or tows be processed, but also the fabric material with certain thickness can be processed in a penetrating way due to the strong penetrability of the plasma; further utilization of high energy particles in the plasma causes the coating to crosslink in situ and to develop a gradient modulus in the thickness direction of the coating, thereby spontaneously forming annularly arranged wrinkles in the axial direction of the fiber.

One of the objects of the present invention is to provide a method for preparing a material having surface wrinkles, in particular, by forming a coating layer of a resin coating liquid composed of a resin and a diluent on a material substrate and performing a treatment using a plasma of argon or oxygen to generate a gradient modulus in the direction of the thickness of the coating layer, thereby spontaneously forming wrinkles in a ring-like arrangement in the axial direction of the fiber;

the second purpose of the present invention is to provide a fiber having a wrinkled surface, which comprises a fiber base and a resin coating liquid coating layer coated on the surface of the fiber base; the fold-shaped structures are annularly arranged on the surface of the fiber along the length direction of the fiber;

the invention also provides a surface-wrinkled fiber fabric, wherein the fiber surface adopted by the fabric weaving is coated with a resin coating liquid coating layer with a wrinkle structure annularly arranged along the axial direction, and the wrinkle structure is annularly arranged on the fiber surface along the length direction of the fiber.

In order to achieve the purpose, the invention adopts the following scheme:

a method of making a material having a surface corrugation, comprising the steps of:

(1) preparing a coating liquid;

the coating liquid is composed of resin and diluent; the resin is a liquid oligomer and is a silicone resin, an acrylate resin or a soluble fluororesin; the diluent is a good solvent corresponding to the resin and is more than one of ethanol, acetone, toluene, ethyl acetate, dimethylformamide and perfluorinated solvent;

the preparation of the coating liquid is that resin and diluent are stirred and mixed evenly, and the weight of the resin in the coating liquid accounts for 0.01-20%;

(2) coating a film on the surface of the material;

material refers to a fiber monofilament, tow, or fabric;

soaking the material into the coating liquid, taking out and drying to obtain a material with a coating coated on the surface;

(3) plasma processing;

and carrying out plasma treatment on the material with the coating coated on the surface to obtain the surface wrinkling material.

As a preferred technical scheme:

the method as described above, wherein in the step (1): the organic silicon resin is polydimethylsiloxane, poly-1, 1,3, 3-tetramethyl disiloxane, polymethylhydrosiloxane or silicone resin (Japanese triple bond TB 1206C); the diluent corresponding to the organic silicon resin is more than one of toluene, ethanol, xylene and acetone;

the acrylate resin is polyethyl methacrylate or poly-2-methyl methacrylate; the diluent corresponding to the acrylate resin is more than one of acetone, toluene and ethyl acetate;

the soluble fluororesin is poly (2-trifluoromethyl-3, 3, 3-trifluoropropyl methacrylate), Teflon AF1600 (DuPont), Teflon AF2400 (DuPont), THV 220A (3M), fluorinated ethylene propylene copolymer or perfluoro 1-butenyl vinyl ether polymer; the diluent corresponding to the soluble fluororesin is perfluoro dialkyl ether and/or perfluoro trialkylamine;

in the coating liquid, the weight ratio of the resin is 0.01-5%.

The method as described above, the fiber monofilaments are polymer fibers or inorganic fibers; the polymer fiber is terylene, nylon, acrylon, polypropylene fiber or aramid fiber; the inorganic fiber is glass fiber, carbon fiber, quartz fiber, alumina fiber or basalt fiber; the fiber monofilament refers to a solid fiber or a porous fiber; the section of the solid fiber is round, square, triangular or cross-shaped or the section of the solid fiber is a fiber with a skin-core structure;

the tows are polymer fiber tows or inorganic fiber tows;

the tows refer to tows formed by 2-1000 fiber monofilaments;

by fabric is meant a fabric made wholly or partially of the fibre filaments.

According to the method, the surface of the material is cleaned before being coated with the film, and the method comprises the following specific steps: soaking the material in a solvent for 1-10 min, and removing the solvent through a drying process;

the solvent is ethanol or ethyl acetate;

the drying temperature is 50-70 ℃, and the drying time is 5-20 min.

The method comprises the steps of soaking the material into the coating liquid for 1-120 s at 15-35 ℃; the drying is natural airing for 30-60 min or drying for 5-20 min at 50-70 ℃;

the plasma treatment adopts radio frequency capacitance coupling plasma treatment, and the treatment parameters are as follows: 13.56MHz radio frequency or 40kHz radio frequency, 10-300W of power, 50-800 mTorr of air pressure, 20-80 ℃ of temperature, 1-2000 s of time, and argon and/or oxygen as gas.

In the method, the parameters of the plasma treatment are as follows: the power is 13.56MHz radio frequency, the power is 90W, the air pressure is 200mTorr, the processing time is 60s, and the gas is argon;

or, the parameters of the plasma treatment are as follows: the power is 40MHz radio frequency, the power is 50W, the gas pressure is 150mTorr, the processing time is 60s, and the gas is argon.

As mentioned above, the plasma treatment refers to the treatment of selecting the area of the material that needs to have a corrugated surface; the method is characterized in that wrinkles can be simultaneously prepared on local parts of fibers by a method of localized coating or localized plasma treatment; the whole can be processed and the fold structure is generated; and during treatment, the single side of the fabric can be treated, and the front side and the back side of the fabric can be simultaneously treated.

When the material is a fabric with the thickness of more than or equal to 0.3 mm, in order to ensure uniform treatment, the front side and the back side of the fabric need to be repeatedly treated for 2-5 times according to the step (3).

The invention also provides a fiber with a corrugated surface, which is composed of a fiber matrix and a resin coating liquid coating layer coated on the surface of the fiber matrix;

the corrugated structures are annularly arranged on the surface of the fiber along the length direction of the fiber, the distance between the protrusions of the adjacent corrugated structures is 100 nm-5 mu m, and the height of the annular protrusions is 20-500 nm; the thickness of the resin coating liquid coating is 100 nm-2 mu m.

The invention also provides a surface-wrinkled fiber fabric, wherein the surface-wrinkled fiber fabric is formed by weaving all or part of fiber monofilaments, and the surfaces of the fiber monofilaments in the surface-wrinkled fiber fabric are provided with resin coating liquid coatings with wrinkled structures which are annularly arranged along the axial direction;

the corrugated structures are annularly arranged on the surface of the fiber along the length direction of the fiber, the distance between the protrusions of the adjacent corrugated structures is 100 nm-5 mu m, and the height of the annular protrusions is 20-500 nm; the thickness of the resin coating liquid coating is 100 nm-2 mu m.

As a preferred technical scheme:

the surface-wrinkled fiber fabric has a contact angle with water of more than 150 degrees and a rolling angle with water of less than 10 degrees, and has super-hydrophobicity.

The principle of the invention is as follows:

capacitively Coupled Plasma (CCP) is a non-equilibrium process with high electron density and high power density, with radicals, excited molecules, neutral molecules, ions, energetic photons and uv/visible light simultaneously existing and colliding with each other. And after the treatment of argon or oxygen plasma, the structure of the material is not obviously changed. Since the plasma can diffuse in the direction of the thickness of the coating, the coating of the resin coating liquid has a controlled gradual cross-linking according to the gradient concentration (gradually decreasing from the outside to the inside concentration) of the high-energy particles diffusing into the coating.

The invention adopts plasma to treat the material with the coating on the surface, the high-energy particles can generate small thermal deformation to cause the temperature of a material system to rise, so that the resin coating liquid coating with gradual change crosslinking expands when undergoing plasma treatment, the temperature of the system drops after the completion, the resin coating liquid coating expanding when being heated contracts when meeting cold, and the invention has unstable mechanics, and concretely comprises the following steps: firstly, due to local uneven heating, the thermal expansion volume of the material is changed differently, so that local buckling instability is caused, flattening wrinkles are formed, then plasma treatment is carried out, the coating generates gradual cross-linking along the thickness direction, the cross-linking degree on the surface of the coating is high, the internal cross-linking degree is gradually reduced, so that hardening is generated on the surface layer of the material, the flattening wrinkles are connected and grow around the fiber matrix, and due to the self-restraint of the fibers and the movable interface of the resin coating liquid coating, the flattening wrinkles annularly arranged along the axial direction of the fibers appear.

Two conditions are required to achieve a superhydrophobic surface: has certain surface roughness and hydrophobic surface. The surface of ordinary fibers and fabrics has roughness but cannot meet the hydrophobic requirement. According to the invention, the hydrophobic coating is formed on the surface of the material by coating the hydrophobic coating liquid, and the circularly arranged folds are formed after plasma treatment, so that the structure of the hydrophobic coating is not damaged while the surface roughness is improved, and the super-hydrophobic surface is realized.

The hydrophobic coating is coated on the surface of the material to construct a hydrophobic surface, and then the annular arranged fold structure is generated on the surface of the material by plasma treatment to generate roughness with micro-nano scale, so that the hydrophobic property of the surface of the material is further improved, and the super-hydrophobic surface is realized.

With the nanoindentation technique, the indentation modulus of the resin coating liquid coating layer in its thickness direction was found to be high at the top and low at the bottom of the coating layer, thus forming a hard outer shell and a soft inner layer. The structural color formed by optical coherence due to different thicknesses of the folded coating can be observed through an optical microscope, and particularly for the dyed material, the light scattering degree is reduced, and the structural color is more obvious.

Advantageous effects

(1) The method for preparing the material with surface folds endows the material with excellent performance, improves the waterproof and antifouling performance of the material, and simultaneously keeps good air permeability and flexibility;

(2) the method for preparing the material with surface wrinkles can promote the development of high-performance fibers and fabrics;

(3) the fiber with the wrinkled surface and the surface wrinkled fiber fabric can be used for manufacturing military camouflage color equipment due to the structural color formed by optical coherence caused by different thicknesses of coating films;

(4) the fiber with the wrinkled surface and the surface wrinkled fiber fabric have wide application prospect in the fields of functional clothing, outdoor products, military protective clothing, photoelectricity and the like.

Drawings

FIG. 1 is a schematic flow diagram of the present invention for preparing fibers having a convoluted surface;

FIG. 2 is an electron microscope photograph of the present invention showing periodic wrinkles formed on the surface of polyester fibers;

FIG. 3 is an optical microscope photograph of the present invention showing periodic wrinkles formed on the surface of polyester fibers;

FIG. 4 is a schematic view of a process for forming local folds in the surface of a coated fiber according to the present invention;

FIG. 5 is a schematic flow chart of the present invention for producing local wrinkles on the surface of partially coated fibers;

fig. 6 is a photograph of a polyester fabric treated with dyed water drops in fiber wrinkling.

Detailed Description

The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

A schematic flow diagram of the process of the present invention for making fibers having a convoluted surface is shown in fig. 1.