CN112981931B - Method for improving performance of organic-inorganic composite material - Google Patents

Method for improving performance of organic-inorganic composite material Download PDF

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CN112981931B
CN112981931B CN202110205813.4A CN202110205813A CN112981931B CN 112981931 B CN112981931 B CN 112981931B CN 202110205813 A CN202110205813 A CN 202110205813A CN 112981931 B CN112981931 B CN 112981931B
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plasma
composite material
nano particles
inorganic
micro
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CN112981931A (en
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张菁
尚晓冉
田立轩
徐雨
王超梁
张宇
王天舒
杨宝敬
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Donghua University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
    • D06M10/025—Corona discharge or low temperature plasma
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

Abstract

The invention relates to a method for improving the performance of an organic-inorganic composite material, which is characterized in that organic polymers covered on the surfaces of micro-nano particles in the composite material are selectively etched and removed, so that the inorganic micro-nano particles loaded on the surfaces are partially exposed on the surfaces of polymers and fibers, the surface roughness is deepened, and the functionality of the inorganic micro-nano particles is really exerted. Meanwhile, due to the improvement of the permeability of the plasma, the inside of the fiber fabric can be fully treated and etched, the exposure proportion of the micro-nano particles is improved, and the performance of the composite material is further improved. The high specific surface area of the fiber fabric and the fully exposed inorganic micro-nano particles inside and outside can fully endow the composite material with greatly improved functional characteristics. The invention is based on the inorganic-organic composite material and the product prepared by large-scale industrial blending, the blending preparation and the plasma etching process are environment-friendly and efficient, and the technical process is mature and easy to implement.

Description

Method for improving performance of organic-inorganic composite material
Technical Field
The invention belongs to the field of preparation of composite materials, and particularly relates to a method for improving the performance of an organic-inorganic composite material.
Background
Inorganic micro-nano particles such as TiO2、Si，SiO2、MnO2、ZnO、Al2O3、CaCO3、Fe2O3,Fe3O4,BaSO4,WO3The micro-nano particles have the special functional characteristics of various catalysis, chemistry, light, force, heat, sound, electricity, magnetism and the like, have small unit size, large specific surface area and high surface activity, and can cause remarkable influence on the performance of a load medium material when being blended with other medium materials.
The polymer or polymer fiber aggregate and fabric material such as polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polypropylene (PP), Polyethylene (PE), Polytetrafluoroethylene (PVDF), Polyimide (PI), Polyurethane (PU), regenerated cellulose, Polystyrene (PS) and the like has low production cost and excellent comprehensive performance, and is widely applied to the wide fields of information industry, biomedicine, textile processing, mechanical equipment, food packaging, optical materials, traffic, health, environment, information and the like. Inorganic micro-nano particles and the polymers are blended and compounded to prepare various functional fibers or fabrics. Such as TiO2Micro-nano particles are blended into polyester PET to control TiO2The proportion of the components can be spun and formed to obtain full-dull polyester PET, semi-dull polyester PET and the like, and can also be endowed with the characteristics of ultraviolet shielding and the like. The method utilizes the functionality of inorganic micro-nano particles and the easy processability of polymers, leads the inorganic micro-nano particles which are not easy to form composite materials such as one-dimensional fibers, two-dimensional fabrics and the like by blending processing, simultaneously has additional special functions such as high specific surface area, amphipathy, amphiphobicity, high toughness, high strength, conductivity, flame retardance, photocatalysis, sensing, optics, filtration, separation or magnetism and the like, and can recycle because the inorganic micro-nano particles are loaded on the surface of a fiber aggregate, thereby expanding the application field of polymer composite materials.
The blending processing of the inorganic micro-nano particle polymer composite material is a physical process, and has the advantages of environmental protection, simplicity, convenience and easiness, and the micro-nano particles are mixed into the surface layer of a polymer or a product by virtue of the bonding action of a polymer body without adding auxiliary agents such as a binder and the like. However, the main problem of the blending method is that the inorganic micro-nano particles are inevitably covered with organic polymer layers with different thicknesses in the blending process, which greatly reduces the performance of the functionality of the inorganic nano particles, because some functions of the micro-nano particles must be brought into play by direct contact with external reactants, and the functions cannot be reflected after being covered by the polymer.
Forming TiO on the surface of the fiber aggregate material by chemical reaction by sol-gel method, chemical vapor deposition method or plasma chemical vapor deposition method2、SiO2And the inorganic micro-nano particles endow various micro-nano morphological structures on the surface of the fiber aggregate with the functions of hydrophilicity, catalysis, sterilization, deodorization, ultraviolet resistance, self-cleaning and the like. CN101575798A discloses a method for modifying Kevlar fiber by plasma treatment of nano sol, which comprises the steps of mixing inorganic nano particles with organic solvent or macromolecular nano particles, preparing sol solution by ultrasonic oscillation reaction, spraying or padding the sol solution on the surface of Kevlar fiber, drying and collecting organic solvent at a certain temperature, and reducing the water contact angle of the Kevlar fiber surface by plasma treatment. However, the sol-gel method has the problems of secondary generation and collection of organic solvents at a certain temperature, and common plasmas are difficult to permeate into the inside of an aggregate due to the low Debye length of the fabric formed by tightly aggregating micro-nano diameter fibers, so that the treatment is insufficient. The current patent article focuses on introducing polar groups or roughening fibers on the surface of a fabric by plasma treatment to improve the hydrophilicity of the fabric, and no report is found on how to improve the permeability of plasma in the fabric so as to fully expose inorganic micro-nano particles in a large proportion and improve the functionality of a composite material.
Disclosure of Invention
The invention aims to provide a method for improving the performance of an organic-inorganic composite material, which improves the sufficiency of the internal treatment of inorganic micro-nano particle fiber aggregates, the exposure of inorganic micro-nano particles on the surfaces of fiber polymers and the functional characteristics of the organic-inorganic fiber aggregates. The method solves the problems of insufficient treatment on the interior of the fiber aggregate and insufficient exposure on the inorganic nano-particles in the prior art, removes complicated process, and has the advantages of simplicity, environmental protection, effectiveness and wide application range.
The invention relates to a method for improving the functions of an organic-inorganic composite material, which comprises the following steps:
based on organic polymer and inorganic micro-nano particle composite materials (such as fiber fabrics, films, plates and the like) obtained by processing through various blending forming methods, high-permeability plasma selective etching is carried out according to the difference of the reaction etching characteristics of the organic polymer and inorganic matters to various plasma gas-phase reactive particles, so that fibers inside and outside an organic-inorganic fiber aggregate are fully selectively etched, and meanwhile, the inorganic micro-nano particles are fully exposed on the surface of the fibers.
The preferred mode of the above preparation method is as follows:
Preferably, the average particle size of the inorganic micro-nano particles is 5.0nm-1.5 μm, or the average particle size is 5.0nm-1.5 μm, the length-diameter ratio is 300: 1.
the mass percentage of the inorganic micro-nano particles in the organic polymer and inorganic micro-nano particle composite material is 0.2-3%.
Preferably, the inorganic micro-nano particles are TiO2、Si、SiO2、MnO2、ZnO、Al2O3、CaCO3、Fe2O3、Fe3O4、BaSO4、WO3And one or more micro-nano particles.
Preferably, the inorganic micro-nano particles are TiO2、Si、SiO2、MnO2、ZnO、Al2O3、CaCO3、Fe2O3、Fe3O4、BaSO4、WO3The shape of the micro-nano particles is various geometric shapes.
Preferably, the polymer is one or more of polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polypropylene (PP), Polyethylene (PE), Polytetrafluoroethylene (PVDF), Polyimide (PI), Polyurethane (PU), regenerated cellulose and Polystyrene (PS).
Preferably, the forming mode is one or more of melt spinning, flow edge, blow molding film forming, electrostatic spinning and melt blowing.
Preferably, the organic polymer and inorganic micro-nano particle composite material is a film or a plate or a fiber aggregate; wherein the fiber aggregate is one of fiber, fabric, non-woven fabric and woven fabric.
Preferably, the plasma selective etching specifically includes: the composite material is a film or a plate, and selective plasma etching is directly carried out; the composite material is fiber aggregate and is etched by permeable plasma.
The selective plasma etching specifically comprises the following steps: the plasma power frequency is 1 MHz-20 MHz, the atmosphere is Ar, O2、N2、H2One or more of (1-1X 10) air pressure5Pa, the power is 100-1000W, the film or the plate passes through a parallel plate plasma discharge area, the electrode spacing is 3-2 cm, an insulating medium with the thickness of 0.1-1 mm covers the electrode, and the etching time is 0.2-10 min; the upper electrode of the selective plasma is a flat plate electrode, and the lower electrode can be a flat plate electrode or two groups of grid-shaped flat plates which are arranged in parallel as used in the permeable plasma.
The permeable plasma etching specifically comprises the following steps: the lower electrodes of the permeable plasma are two groups of grid electrodes which are arranged in parallel at intervals, the width of the grid electrodes is 1-10 mm, the distance between the grid electrodes is 1-5 mm, the electrodes are covered with an insulating medium with the thickness of 0.1-0.5 mm, and the atmosphere is Ar and O2、N2、H2One or more of them, the air pressure is stabilized to 1-1 x 105After Pa, applying a 1 MHz-20 MHz radio frequency source between an upper flat plate electrode and a certain group of lower grid electrodes with the power of 100-1000W, modulating the radio frequency plasma by using a pulse switch to enable the radio frequency plasma to be between on and off, wherein the frequency of the pulse switch is 1-100 kHz, the width of the pulse switch is 1 us-100 us and the pulse switch accounts for 1 us-100 us The space ratio is 1-99%. In the gap of pulse radio frequency off, positive or negative high-voltage pulses are applied to the other group of grid electrodes to form coplanar enhanced permeability discharge, the frequency of the high-voltage pulses is 1-100 kHz, the voltage is 5000-15000V or-5000-15000V, the pulse width is 1 ns-100 us, the duty ratio is 1-99%, the fiber aggregate passes through a plasma discharge area in a roll-to-roll mode, and the etching time is 0.2-10 min.
The number of the electrodes in each group of grid-shaped electrodes is at least 3-5.
The atmospheres are all, Ar/O2The volume ratio of Ar to N is 1 (0.1-0.5)2The volume ratio of Ar to N is 1 (0.1-0.6)2/O2Is 1: (0.1-0.6): (0.1 to 0.8) or Ar/N2/H2All volume ratios of (1): (0.1-0.6): (0.1-0.8) and a total flow rate of 100-1000 sccm.
The invention relates to an organic and inorganic micro-nano particle fiber composite material prepared by the method.
The invention provides an application of the organic-inorganic micro-nano particle fiber composite material, such as application in hydrophilic, catalytic, bactericidal, deodorant, self-cleaning, sensing characteristics, high specific surface area, amphipathy, amphiphobic, high toughness, high strength, conductivity, flame retardance, sensing, optical, filtering, separating or magnetic materials.
The invention firstly focuses on that the improvement of the functionality of the organic-inorganic blended composite fiber or fabric is closely related to the surface exposure of the inorganic micro-nano particles, such as hydrophilicity, catalysis, sterilization, deodorization, self-cleaning, sensing characteristics and the like, but can not be greatly improved by simple blending; secondly, under the condition of focusing the same plasma, the organic/inorganic material has different etching characteristics, the organic polymer covered on the surface of the micro-nano particles is selectively removed, the inorganic particles are partially exposed out of the surface, the inorganic micro-nano particles and the substrate polymer are still well bonded, and meanwhile, the inorganic particles can be in direct contact with reactants to play the functions. More importantly, the sufficiency and effect of selective etching are improved by improving the penetration of plasma in the fabric. Therefore, the invention can overcome the defects of the prior art, and greatly improves the direct contact area of the inorganic micro-nano particles and the reactant by utilizing the fiber aggregate which is fully treated inside and outside and exposed by the inorganic micro-nano particles, thereby greatly improving the function exertion of the organic-inorganic composite fiber aggregate. Moreover, the organic-inorganic blended composite fiber or fabric is a bulk commodity, has wide application atmosphere, relatively simple and environment-friendly preparation process and larger practical application prospect.
Advantageous effects
The invention prepares inorganic TiO by2、Si，SiO2、MnO2、ZnO、Al2O3、CaCO3、Fe2O3,Fe3O4,BaSO4,WO3After the micro-nano particles are blended with high polymers or polymers such as polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polypropylene (PP), Polyethylene (PE), Polytetrafluoroethylene (PVDF), Polyimide (PI), Polyurethane (PU), regenerated cellulose, Polystyrene (PS), and the like, the composite material of fibers, fabrics, non-woven fabrics, braided fabrics, films, plates and the like, which are compounded with inorganic micro-nano particles in a certain thickness of the surface layer of the fibers or polymers, is obtained by various polymer forming methods such as melt spinning, flow edge, blow molding film forming, electrostatic spinning, melt blowing and the like; and then selectively etching the composite material containing the inorganic micro-nano particles by glow discharge plasma with high permeability under low pressure or normal pressure, fully treating fibers in the aggregate, exposing the inorganic micro-nano particles on the surfaces of the fibers, simultaneously well bonding the inorganic particles with the substrate, and increasing the surface etching depth to obtain the organic-inorganic composite material with fully exposed micro-nano particles inside and outside the aggregate. Depending on the characteristics of the addition of inorganic micro-nano particles, the product may have enhanced functionality due to the fully exposed inorganic particles and the high specific surface area organic aggregates. Such as exposed TiO 2The micro-nano particles have lasting super-hydrophilicity, self-cleaning property, enhanced photocatalysis and filtering property and the like, are loaded on the surface of the fiber aggregate, and are fully exposed inside and outside the aggregate, so that the micro-nano particles cannot be dispersed into a solution in the using process, and are easy to use and recover for multiple times.
The invention utilizes the mature blending processing method and the advantages of low cost and easy obtaining of the inorganic micro-nano particle polymer fiber composite material, and fully treats the fibers in the aggregate by improving the permeability of plasma; according to the etching rate difference of the organic polymer and the inorganic particles, part of the polymer covered in the blending process of the inorganic micro-nano particle surface is selectively removed, so that the loaded inorganic micro-nano particle part is exposed and tightly combined on the fiber surface. The specific surface area of aggregates such as fiber fabrics and the like is large, and after the aggregates are fully treated in vivo and in vitro, the functionality of the inorganic micro-nano particles is further improved, and the performance of the composite material is further improved. The process is environment-friendly, efficient and easy to implement.
Drawings
FIG. 1 shows the full dull polyester PET/TiO resin of example 12EDS spectra before and after plasma treatment, (a) before plasma treatment; (b) after plasma treatment;
FIG. 2 shows a fully dull polyester PET/TiO finish-coated with a water repellent in example 22Fabric static contact angle versus number of washes (sample F, no plasma treatment, sample PF plasma treatment);
FIG. 3 is the semi-dull polyester PET/TiO plasma treated and disperse blue printed in example 42And the staining test result of pure polyester PET fabric, wherein (a) and (b) are respectively semi-matt polyester PET/TiO after the staining test2Photographs of fabrics and stained cotton; (c) (d) photos of the pure PET fabric and the stained cotton cloth after staining experiments respectively;
FIG. 4 shows pure polyester PET and semi-dull polyester PET/TiO before and after plasma treatment in example 52Fabric (a) optical photograph of antibacterial test; (b) counting the number of colonies of the corresponding samples;
FIG. 5 is a schematic diagram of a permeable plasma device used in the embodiment.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. 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.
The pure PET polyester fabric is made of pure FDY polyester filament yarn and is full dull polyester PET/TiO2The fabric is made of TiO-containing2The FDY polyester filament yarn of (1), wherein TiO2Average particle size of 400nm, TiO2The mass content is 2-3%. Semi-dull polyester PET/TiO2The fabric is made of TiO-containing2The FDY polyester filament yarn of (1), wherein TiO2Average particle size of 400nm, TiO2The mass content is 0.2-0.3%. .
The polytetrafluoroethylene powder is FR102 resin from Shanghai Sanai Rich New materials, Inc., and has an average particle size of 425 +/-100 um. SiO 22The nano powder is purchased from Nanjing Baokett New Material Co., Ltd, and has an average particle size of 20 nm. The perfluorinated methacrylate waterproof finishing agent with the main chain of 6 carbon atoms is provided by Kyoto chemical technology (Shanghai) Co.
The fabric hydrophobicity test adopts an AATCC 20 spray test method, the antibacterial property adopts GB/T20944.3-2008 and a direct contact method GB/T20944.1-2007 standard test method, and the staining property adopts GB/T32598-.
Example 1
1. A permeable low-pressure plasma reactor (shown in figure 5) is adopted, a flat plate electrode is arranged on the upper part, two groups of grid electrodes are arranged on the lower part, the width of each grid electrode is 8-10 mm, and the distance between every two grid electrodes is 1-2 mm. The distance between the upper electrode and the lower electrode is 2cm, and insulating media with the thickness of 0.1-0.2 mm are covered on the electrodes. Vacuumizing the cavity until the background air pressure is 5Pa, opening the flowmeter and introducing Ar/O into the discharge cavity 2Mixed gas, Ar/O2The volume ratio is 1 (0.1-0.2), the total flow is 100-300 sccm, and after the pressure in the discharge chamber is stabilized to be 30-100 Pa, the parameters of plasma discharge are set as follows: and a 10 MHz-13.56 MHz radio frequency source is applied between the upper plate electrode and the lower grid electrode, and the power is 300-400W. By pulsing onAnd (3) turning off the discharge regulation and control, wherein the frequency of the pulse switch is 80-100 kHz, the width is 80 us-100 us, and the duty ratio is 1% -5%. And in the gap of the pulse radio frequency off, applying pulse negative bias to the other group of grid electrodes, wherein the frequency of the pulse negative bias is 1-2 kHz, the voltage is-5000 to-8000V, the pulse width is 1 us-2 us, and the duty ratio is 1-20%, so that coplanar enhanced permeability discharge is formed. Full dull polyester PET/TiO2The fiber fabric passes through the plasma discharge area in a roll-to-roll mode, and the etching time of the fiber fabric passing through the plasma discharge area is 3 min.
2. After the etching is finished, closing the power supply and the gas source, opening the vacuum pump and the air release valve, opening the discharge chamber after the pressure in the discharge chamber is recovered to a standard atmospheric pressure, taking out the sample, and obtaining the full-dull polyester PET/TiO treated by plasma etching2A fabric.
3. Full dull polyester PET/TiO2EDS before and after plasma treatment of the fabric is shown in figure 1, the Ti content of the surface after treatment is 2.6 times that before treatment, and the O content of the surface is 1.6 times that before treatment.
Example 2
1. The untreated and plasma treated full gloss polyester PET/TiO of example 12Dipping and coating the mixture for 10min at room temperature by 30 weight percent of perfluoro methacrylate waterproof finishing agent, and drying the mixture for 90s at 160 ℃. Then, the hydrophobic and oleophobic performance test of the fabric is carried out.
2. According to AATCC20 standard method for testing the spraying hydrophobicity of the fabric, a standard soap solution is prepared to be washed for 10 cycles at room temperature continuously, the static contact angle and the spraying characteristic are tested after 1, 5 and 10 cycles, and the test result of the change of the static water contact angle along with the washing times is shown in figure 2.
3. Full dull polyester PET/TiO coated without plasma treatment2(sample F), the static contact angle to water is 160 degrees, the spraying grade is 90 degrees, after 10 times of circular washing, the static contact angle to water is reduced to 40 degrees, and the spraying grade to water is 0 degrees.
4. Full dull polyester PET/TiO selectively etched and coated by permeable plasma2(sample PF) a static contact angle for water of 170 ° or more and a spray rating of 100 °. After 10 times of circulation washingThe water static contact angle hardly drops, still at 170 °, water spray rating 80 °.
Example 3
1. The selective plasma etching treatment specifically comprises the following steps: a low-pressure plasma reactor is adopted, a flat plate electrode is arranged on the upper portion, two groups of grid-shaped electrodes are arranged on the lower portion, the distance between the upper electrode and the lower electrode is 1cm, the width of the lower grid-shaped electrode is 6 mm-7 mm, and insulating media with the thickness of 0.4-0.5 mm are covered on the electrodes with the distance of 2 mm-3 mm. Vacuumizing the cavity until the background air pressure is 5Pa, opening the flowmeter and introducing Ar/O into the discharge cavity 2Mixed gas, Ar/O2The volume ratio is 1 (0.3-0.5), the total flow is 130-150 sccm, after the pressure in the discharge chamber is stabilized to 50-80 Pa, plasma with the frequency of 2-5 MHz and the power of 100-300W is applied to the upper parallel plate electrode and the lower group of grid electrodes, and pure PET polyester fabric and semi-dull polyester PET/TiO are mixed2The fabric is processed through the plasma discharge area in a roll-to-roll mode, and the etching time is 4 min.
The permeable plasma treatment is specifically as follows: on the basis of the plasma reactor, the upper part is a flat plate electrode, the lower part is two groups of grid-shaped electrodes, the distance between the upper electrode and the lower electrode is 1cm, the width of the lower grid-shaped electrode is 6 mm-7 mm, the distance is 2 mm-3 mm, and the electrodes are all covered with insulating media with the thickness of 0.4-0.5 mm. Vacuumizing the cavity until the background air pressure is 5Pa, opening the flowmeter and introducing Ar/O into the discharge cavity2Mixed gas, Ar/O2The volume ratio is 1 (0.3-0.5), the total flow is 130-150 sccm, after the pressure in the discharge chamber is stabilized to 50-80 Pa, plasma with the frequency of 2-5 MHz and the power of 100-300W is applied to the upper parallel plate electrode and the lower group of grid electrodes, discharge is regulated and controlled through a pulse switch, the frequency of the pulse switch is 60-70 kHz, the width is 8 us-10 us, and the duty ratio is 8-10%. In the gap of the RF pulse off, a pulse positive bias is applied to the other group of grid electrodes, the frequency of the pulse negative bias is 70-80 kHz, the voltage is-10000-12000V, the pulse width is 10 us-20 us, and the duty ratio is 30-50%, so that coplanar enhanced permeability discharge is formed. Pure PET polyester fabric and full dull polyester PET/TiO 2The fiber fabric is wound by roll to rollAnd passing through the plasma discharge region, and etching time of the plasma discharge region was 4 min.
2. After the etching is finished, the power supply and the gas source are closed, the chamber is opened, the sample is taken out, and the pure PET polyester fabric and the full-dull PET/TiO polyester fabric which are subjected to selective plasma treatment and permeable plasma treatment are respectively obtained2A fabric.
3. Mixing pure PET polyester fabric and full dull PET/TiO2Respectively testing the static water contact angle of the fabric along with the standing time, and after selective plasma treatment, reducing the static contact angle of the pure polyester PET fabric from 125 degrees at the untreated state to 15 degrees, but increasing the contact angle along with the extension of the standing time, and recovering to 70 degrees after standing for 60 days; full dull polyester PET/TiO2The static contact angle of the fabric is reduced from 110 degrees in the untreated state to 0 degree, the static contact angle of the fabric is kept at about 25 degrees in the first three months, and the hydrophilicity is good; with the prolonging of the standing time to 6 months, the contact angle is only increased to about 55 degrees, and good hydrophilic property and aging property are still shown.
After treatment with penetrating plasma, the static contact angle of the pure polyester PET fabric decreased from 125 ° at the time of non-treatment to 0 °, but with prolonged standing time, the contact angle increased with the increase of 60 ° after standing for 60 days. Full dull polyester PET/TiO 2The static contact angle of the fabric is reduced from 110 degrees to 0 degrees when the fabric is not treated, the static contact angle of the fabric is kept at about 15 degrees in the first three months, and the fabric is good in hydrophilicity; as the standing time is prolonged to 6 months, the contact angle is only increased to about 40 degrees, and better hydrophilicity and timeliness are shown.
Example 4
1. A permeable plasma reactor is adopted, a flat plate electrode is arranged on the upper portion, two groups of grid-shaped electrodes are arranged on the lower portion, the distance between the upper electrode and the lower electrode is 2mm, the width of the lower grid-shaped electrode is 2 mm-3 mm, the distance between the lower grid-shaped electrodes is 1 mm-2 mm, and insulating media with the thickness of 0.2-0.3 mm are covered on the electrodes. Opening the flowmeter to start to introduce Ar/O into the discharge cavity2Mixed gas, Ar/O2The volume ratio of 1 to 0.2 to 0.5, the total flow rate of 800 to 1000sccm, and the pressure stabilized to 105And (6) Pa later. Applying plasma with frequency of 1-2 MHz and power of 800-1000W to the upper parallel plate electrode and the lower grid electrode, and regulating by pulse switchDischarging, wherein the frequency of a pulse switch is 30-50 kHz, the width is 1 us-3 us, and the duty ratio is 28% -40%. And in the gap of the 'off' of the radio frequency pulse, applying pulse negative bias to the other grid electrode, wherein the frequency of the pulse negative bias is 10-20 kHz, the voltage is-30000-5000V, the pulse width is 5 us-7 us, and the duty ratio is 10% -20%, so that coplanar enhanced permeability discharge is formed. Pure polyester PET fabric and semi-dull polyester PET/TiO 2The fabric passes through a plasma discharge area in a roll-to-roll mode, and the etching time is 9 min.
2. After the etching is finished, the power supply and the gas source are closed, the chamber is opened, and the sample is taken out to obtain pure polyester PET and semi-dull polyester PET/TiO treated by plasma etching2A fabric.
3. The plasma treatment of pure polyester PET and semi-dull polyester PET/TiO with disperse blue was carried out by conventional screen printing method2And (4) printing and dyeing the fabric, and then performing a wet-cleaning staining experiment.
4. The pictures of the fabrics after wet wash staining experiments are shown in figure 3. After plasma treatment, semi-dull polyester PET/TiO2The wet cleaning staining grade of the fabric is improved by more than 2 times, the tested cotton cloth is almost free from staining, and the tested cotton cloth has staining phenomenon after the pure PET polyester fabric is subjected to plasma treatment.
Example 5
1. A permeable low-pressure plasma reactor is adopted, a flat plate electrode is arranged on the upper portion, two groups of grid-shaped electrodes are arranged on the lower portion, the distance between the upper electrode and the lower electrode is 2cm, the width of the lower grid-shaped electrode is 2 mm-3 mm, the distance between the lower grid-shaped electrodes is 1 mm-2 mm, and insulating media with the thickness of 0.1-0.2 mm are covered on the electrodes. Opening the flowmeter to start to introduce Ar/O into the discharge cavity2Mixed gas, Ar/O2The volume ratio is 1 (0.1-0.2), the total flow rate is 200-500 sccm, and the pressure in the reactor is maintained at 90-150 Pa. Plasma with frequency of 13.56MHz and power of 200-400W is applied to the upper parallel plate electrode and the lower set of grid electrodes. The discharge is regulated and controlled through a pulse switch, the frequency of the pulse switch is 10-30 kHz, the width of the pulse switch is 1 us-3 us, and the duty ratio of the pulse switch is 28% -40%. In the gap of the RF pulse off, the pulse high voltage is applied to the other group of grid electrodes, the frequency is 1-5 kHz, the voltage is 5000-6000V, the pulse width is 1 us-5 us, and the pulse voltage accounts for 1-6 percent of space ratio, pure polyester PET fabric and semi-dull polyester PET/TiO2The fabric passes through a plasma discharge area in a roll-to-roll mode, and the etching time is 10 min.
2. After the etching is finished, the power supply and the gas source are closed, the chamber is opened, and the sample is taken out to obtain pure polyester PET and semi-dull polyester PET/TiO treated by plasma etching2A fabric.
3. Pure polyester PET fabric and semi-dull polyester PET/TiO before and after plasma treatment2The fabric is subjected to a biological antibacterial treatment experiment, the strains are escherichia coli and staphylococcus aureus, and antibacterial property representation is carried out on the sample. The antibacterial property of pure polyester PET before and after plasma treatment is poor, and the semi-dull polyester PET/TiO2Has higher antibacterial property than pure polyester PET group, and after plasma etching treatment, the semi-dull polyester PET/TiO2The antibacterial property of the sample is obviously improved (as shown in figure 4).
Example 6
1. Mixing 1.6-2.0 wt% SiO2And uniformly mixing with polytetrafluoroethylene PTFE powder, and pressing and molding according to a conventional polytetrafluoroethylene block processing method. To obtain SiO2PTFE sheet material.
2. A low-pressure plasma reactor is adopted, a flat plate electrode is arranged on the upper portion, two groups of grid-shaped electrodes are arranged on the lower portion, the distance between the upper electrode and the lower electrode is 2cm, the width of the lower grid-shaped electrode is 2 mm-3 mm, the distance between the lower grid-shaped electrodes is 1 mm-2 mm, and insulating media with the thickness of 0.3-0.4 mm are covered on the electrodes. Opening the flowmeter to start to introduce Ar/N into the discharge cavity 2/H2The volume ratio of the mixed gas of (1): (0.1-0.2): (0.7-0.8), the total flow rate is 10-40 sccm, and the pressure in the reactor is maintained at 10-20 Pa. Setting parameters of plasma discharge: the frequency is 13.56MHz, and the power is 800-100W. SiO with the thickness of 2mm2The PTFE sheet continuously passes through a plasma discharge area, and the etching time is controlled for 30 s.
After the etching is finished, the power supply and the gas source are closed, the chamber is opened, the sample is taken out, and the Ar/N is obtained2/H2Plasma selective etch treated SiO2PTFE sheet material.
Ar/N2/H2After the selective treatment of the plasma, the plasma is removed,SiO2the contact angle of the surface of the PTFE sheet is reduced from 120 degrees to about 90 degrees, the hydrophilicity is improved, the surface roughness is improved due to the control of the etching time, and the adhesion between the sheet and the metal base is improved.
3. A low-pressure plasma reactor is adopted, a flat plate electrode is arranged on the upper portion, two groups of grid-shaped electrodes are arranged on the lower portion, the distance between electrodes is 2cm, the width of the lower grid-shaped electrodes is 2 mm-3 mm, the distance is 1 mm-2 mm, and insulating media with the thickness of 0.1-0.2 mm are covered on the electrodes. Opening the flowmeter to start to introduce Ar/H into the discharge cavity2/CF4The volume ratio of the mixed gas of (1): (0.2-0.3): (0.7-0.8), the total flow rate is 10-40 sccm, and the pressure in the reactor is maintained at 10-20 Pa. Setting parameters of plasma discharge: the frequency is 13.56MHz, and the power is 800-100W. Put into a reactor through Ar/N 2/H2Plasma selective etch processing of SiO2PTFE sheet material, etching time 3 min.
After the etching is finished, the power supply and the gas source are closed, the chamber is opened, the sample is taken out, and the Ar/N is obtained2/H2Plasma selective etching treatment and Ar/H treatment2/CF4Plasma non-selective etch treated SiO2PTFE sheet material.
Due to Ar/H2/CF4Plasma on SiO2The etching rate is relatively high, and after two paths of treatment, SiO is obtained2The surface roughness of the PTFE sheet is rather reduced.

Claims (8)

1. A method for improving the function of an organic-inorganic composite material, comprising:
blending and molding inorganic micro-nano particles and polymers to obtain an organic polymer and inorganic micro-nano particle composite material, and then carrying out plasma selective etching to expose the inorganic micro-nano particles on the surface of the material; wherein the organic polymer and inorganic micro-nano particle composite material is a fiber aggregate; the composite material is a fiber aggregate, and is subjected to permeability plasma selective etching, wherein the permeability plasma selective etching specifically comprises the following steps: the lower electrode of the permeable plasma is provided with two groups of grid-shaped electrodes which are arranged at intervals and have the width1 mm-10 mm, 1 mm-5 mm of space, insulating medium with thickness of 0.1-0.5 mm covered on the electrode, Ar and O as atmosphere 2、N2、H2One or more of them, the air pressure is stable to 1 x 105After Pa, applying a 1 MHz-20 MHz radio frequency source between an upper plate electrode and a group of lower grid electrodes, wherein the power is 100-1000W, modulating a radio frequency plasma by using a pulse switch, so that the radio frequency plasma is between 'on' and 'off', the frequency of the pulse switch is 1-100 kHz, the width is 1 us-100 us, and the duty ratio is 1% -99%; and applying positive or negative high-voltage pulses to the other group of grid electrodes in the gap of the pulse radio frequency off to form coplanar enhanced permeability discharge, wherein the high-voltage pulse frequency is 1-100 kHz, the voltage is 5000-15000V or-5000-15000V, the pulse width is 1 ns-100 us, the duty ratio is 1-99%, the fiber aggregate passes through a plasma discharge area in a roll-to-roll mode, and the etching time is 0.2-10 min.
2. The method according to claim 1, wherein the inorganic micro-nano particles have an average particle size of 5.0 nm to 1.5 μm; the mass percentage of the inorganic micro-nano particles in the organic polymer and inorganic micro-nano particle composite material is 0.2-3%.
3. The method according to claim 1, wherein the inorganic micro-nano particles are TiO2、Si、SiO2、MnO2、ZnO、Al2O3、CaCO3、Fe2O3、 Fe3O4、BaSO4、WO3One or more micro-nano particles; the shape of the inorganic micro-nano particles is various geometric shapes.
4. The method according to claim 1, wherein the polymer is one or more of polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polypropylene (PP), Polyethylene (PE), Polytetrafluoroethylene (PVDF), Polyimide (PI), Polyurethane (PU), regenerated cellulose and Polystyrene (PS).
5. The method of claim 1, wherein the forming is one of melt spinning, electrospinning and melt blowing; the fiber aggregate is one of fiber and fabric.
6. The method of claim 1, wherein the atmosphere is Ar/O2The volume ratio of Ar to N is 1 (0.1-0.5)2The volume ratio of Ar to N is 1 (0.1-0.6)2/O2Is 1: (0.1-0.6): (0.1 to 0.8) or Ar/N2/H2All volume ratios of (1): (0.1-0.6): (0.1-0.8) and a total flow rate of 100-1000 sccm.
7. An organic-inorganic micro-nano particle composite material prepared by the method of claim 1.
8. The use of the organic-inorganic micro-nano particle composite material of claim 7 in hydrophilic, catalytic, bactericidal, self-cleaning, amphiphilic, amphiphobic, sensing, optical, filtering or magnetic materials.
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