CN114059347A - Surface modification method for improving binding property of ultrahigh molecular weight polyethylene fiber and matrix resin - Google Patents
Surface modification method for improving binding property of ultrahigh molecular weight polyethylene fiber and matrix resin Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 130
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 73
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 73
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title claims abstract description 21
- 238000002715 modification method Methods 0.000 title claims abstract description 16
- 239000011159 matrix material Substances 0.000 title claims abstract description 15
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- 230000004048 modification Effects 0.000 claims abstract description 20
- 238000012986 modification Methods 0.000 claims abstract description 20
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- 239000011259 mixed solution Substances 0.000 claims description 25
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- 239000007788 liquid Substances 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
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- 238000002791 soaking Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 8
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- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000009832 plasma treatment Methods 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 description 13
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- 229910021641 deionized water Inorganic materials 0.000 description 6
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- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
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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
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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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
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
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- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention relates to the field of high polymer materials, and discloses a surface modification method for improving the binding property of ultrahigh molecular weight polyethylene fibers and matrix resin. The invention combines the plasma technology and the inorganic nano particle doping technology to carry out surface modification on the ultra-high molecular weight polyethylene fiber. The surface of UHMWPE fiber is activated by plasma, then reacts with silane coupling agent to introduce active groups on the surface, and then reacts with inorganic nano particles treated by silane coupling agent, so that the roughness of the fiber surface can be greatly increased without affecting the characteristics of the UHMWPE fiber, and the interface bonding strength of the fiber and other resin matrixes in composite use is improved.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a surface modification method for improving the binding property of ultrahigh molecular weight polyethylene fibers and matrix resin.
Background
Ultra-high molecular weight polyethylene (UHMWPE) fiber is a high-performance fiber with high strength and high modulus which appears after carbon fiber and aramid fiber. The material is prepared from ultra-high molecular weight polyethylene by high-pressure solid extrusion, plasticizing melt spinning, surface crystallization growing, super-stretching or local super-stretching, gel spinning-hot stretching, etc. The UHMWPE has the relative molecular mass of 100-600 ten thousand, the molecular shape is a linear extended chain structure, the orientation degree is close to 100%, the strength is about 15 times that of high-quality steel, 2 times higher than that of carbon fiber and 40 times higher than that of aramid fiber, and the UHMWPE also has the excellent performances of ultraviolet radiation resistance, chemical corrosion resistance, high specific energy absorption, low dielectric constant, high electromagnetic wave transmittance, low friction coefficient, outstanding impact resistance, cutting resistance and the like. Therefore, the UHMWPE fiber is an ideal material for manufacturing soft bulletproof clothes, stab-resistant clothes, light bulletproof helmets, armor plates of cash carriers, armor plates of helicopters, light high-pressure containers, aerospace structures, fishing nets, racing boats, sailing ships and the like.
However, since UHMWPE fibers themselves are linear long chains formed by nonpolar methylene groups, there are no strong intermolecular forces between fiber molecules, and the fiber surface is chemically inert, it is difficult to form chemical bonds with the resin, and the high degree of crystallinity and high degree of orientation produced by high-power drawing in production makes the fiber surface very smooth. All these factors combine to make the surface energy of the fiber very small, and it is difficult to form a good interfacial bond when used in combination with other materials, which greatly limits the application of UHMWPE fibers in the field of composite materials, particularly lightweight structural materials. Therefore, surface modification of UHMWPE fibers is essential.
Disclosure of Invention
In order to solve the technical problems, the invention provides a surface modification method for improving the bonding property of ultrahigh molecular weight polyethylene fibers and matrix resin. The invention combines the plasma technology and the inorganic nano particle doping technology to carry out surface modification on the ultra-high molecular weight polyethylene fiber. The surface of UHMWPE fiber is activated by plasma, then reacts with silane coupling agent to introduce active groups on the surface, and then reacts with inorganic nano particles treated by silane coupling agent, so that the roughness of the fiber surface can be greatly increased without affecting the characteristics of the UHMWPE fiber, and the interface bonding strength of the fiber and other resin matrixes in composite use is improved.
The specific technical scheme of the invention is as follows: a surface modification method for improving the binding property of ultra-high molecular weight polyethylene fibers and matrix resin comprises the following steps:
(1) soaking ultrahigh molecular weight polyethylene (UHMWPE) fibers in ethanol, ultrasonically cleaning, and drying.
This step is mainly intended to clean the UHMWPE fibers of impurities.
(2) Carrying out plasma treatment on the fiber obtained in the step (1), wherein the treatment conditions are as follows: the power is 10-200W, the gas flux is 0.5-5L/min, the pressure is 15-30 Pa, and the processing time is 0.5-5 min.
(3) And (3) soaking the fiber obtained in the step (2) in an ethanol/water mixed solution containing a silane coupling agent, reacting for 1-5 h, taking out, and performing dehydration condensation reaction at 90-130 ℃ for 0.5-3 h.
(4) Ultrasonically dispersing large-particle-size inorganic nanoparticles into a mixed solution of water and absolute ethyl alcohol, and dropwise adding the obtained dispersion into an ethanol/water mixed solution containing a silane coupling agent for modification treatment to obtain a large-particle-size inorganic nanoparticle modification solution.
(5) And (4) adding the fibers obtained in the step (3) into the large-particle-size inorganic nanoparticle modification liquid obtained in the step (4), stirring for reaction, taking out and drying after the reaction.
(6) Ultrasonically dispersing small-particle-size inorganic nanoparticles into a mixed solution of water and absolute ethyl alcohol, and dropwise adding the obtained dispersion liquid into an ethanol/water mixed solution containing a silane coupling agent for modification treatment to obtain a small-particle-size inorganic nanoparticle modified solution.
(7) And (3) adding the fiber obtained in the step (5) into the small-particle-size inorganic nanoparticle modification liquid obtained in the step (6), stirring for reaction, taking out after the reaction, and drying to obtain the surface-modified ultrahigh molecular weight polyethylene fiber.
In the surface modification process, the surface of UHMWPE fiber is activated by plasma to generate active groups such as hydroxyl, carboxyl and the like on the surface of inert fiber; then grafting the active groups and a silane coupling agent, further introducing silane coupling groups, and finally, reacting the fiber with inorganic nanoparticles treated by the silane coupling agent to graft the inorganic nanoparticles. The inorganic nano particles are distributed on the surface of the fiber to form a rough surface, so that the surface roughness of the fiber is greatly improved, and when the fiber is compounded with matrix resin, the interface bonding strength between the fiber and the matrix resin can be obviously improved on the premise of keeping the mechanical property of the original fiber due to the 'meshing' effect of the inorganic particles and the chemical bond effect of the silane coupling agent.
Preferably, in step (1): the mass ratio of the ultra-high molecular weight polyethylene fiber to the ethanol is 1: 20-1: 50.
Preferably, in step (1): the ultrasonic cleaning time is 20-40 min; the drying temperature is 50-70 ℃.
Preferably, in step (2): the atmosphere in which the plasma treatment is performed contains at least oxygen, and the content of oxygen is more than 15% by volume. The technical effect is better under the oxygen content, and if the oxygen content is too low, the plasma treatment mode generates less active groups such as hydroxyl, carboxyl and the like on the surface of the fiber, so that the reaction degree with the silane coupling agent in the subsequent step is influenced. Preferably, in steps (3), (4) and (6): the silane coupling agent is one or more of KH550, KH560 and KH 570; the concentration of the silane coupling agent is 1-10 wt%.
Preferably, in steps (3), (4) and (6): the mass ratio of the ethanol to the water in the ethanol/water mixed solution is 1:0-0: 1.
Preferably, in steps (4) and (6): the particle size of the large-particle-size inorganic nanoparticles is 200-500 nm; the particle size of the small-particle-size inorganic nanoparticles is 10-100 nm.
During the research process, the team of the invention finds that if the inorganic nanoparticles are only introduced on the surface of the UHMWPE fiber, the improvement degree of the combination of the fiber and the matrix resin still has certain limitation. Therefore, two types of nanoparticles with different particle size ranges are attached to the surface of the UHMWPE fiber in sequence, so that anchor points with different particle size distribution can be formed, and compared with inorganic nanoparticles with single particle size distribution, the roughness of the surface of the fiber can be further improved. Meanwhile, the size of the large-particle-size inorganic nanoparticles is not suitable to be too large, otherwise the large-particle-size inorganic nanoparticles are poor in stability on fibers and are easy to fall off, and the interface bonding strength is influenced.
Preferably, in steps (4) and (6): the large-particle-size inorganic nanoparticles or the small-particle-size inorganic nanoparticles comprise one or more of silica nanoparticles, titanium dioxide nanoparticles, zirconia nanoparticles, alumina nanoparticles, calcium carbonate nanoparticles, montmorillonite, graphene and carbon nanotubes.
Preferably, in steps (4) and (6): the dropping speed of the dispersion liquid is 1-10 mL/min; the modification conditions are as follows: the temperature is 40-60 ℃, and the stirring speed is 100-1000 r/min.
Preferably, in steps (5) and (7): the reaction temperature is 40-60 ℃, and the reaction time is 1-12 h; the drying temperature is 90-130 ℃, and the drying time is 0.5-3 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) firstly, activating the surface of UHMWPE fiber by using plasma to enable the surface of the fiber to have a large number of active groups; grafting the active groups with a silane coupling agent, further introducing the active groups, and finally, reacting the fiber with inorganic nanoparticles treated by the silane coupling agent to graft the inorganic nanoparticles. The inorganic nano particles are distributed on the surface of the fiber to form a rough surface, so that the surface roughness of the fiber is greatly improved, and when the fiber is compounded with matrix resin, the interface bonding strength between the fiber and the matrix resin can be obviously improved on the premise of keeping the mechanical property of the original fiber due to the 'meshing' effect of the inorganic particles and the chemical bond effect of the silane coupling agent.
(2) The invention further adopts two types of nano particles with different particle size ranges to be attached to the surface of the UHMWPE fiber in sequence, so that anchoring points with staggered distribution can be formed, and compared with inorganic nano particles with single particle size distribution, the roughness of the surface of the fiber can be further improved.
Drawings
FIG. 1 is an electron microscope image of UHMWPE fiber surface treated by different treatment modes; wherein: fig. 1(a) is an untreated UHMWPE fiber; fig. 1(b) shows UHMWPE fibers treated in step (3) of example 1; fig. 1(c) shows the UHMWPE fibers treated in step (7) of example 1.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Soaking 10g of UHMWPE fiber in 200ml of ethanol, ultrasonically cleaning for 30min, and drying in a drying oven at 60 ℃;
(2) plasma treating the washed UHMWPE fibers of step (1) under the following treatment conditions: the power is 30W, the processing gas is air, the gas flux is 1.5L/min, the pressure is 25Pa, and the processing is carried out for 3 min;
(3) putting the UHMWPE fiber treated in the step (2) into an ethanol solution containing 3 wt% of KH550, reacting for 3h, taking out, washing with deionized water, and putting into a 110 ℃ drying oven for dehydration condensation reaction for 1 h;
(4) ultrasonically dispersing 1.2g of large-particle-size silica nanoparticles with the particle size of 300 +/-30 nm in 50ml of ethanol/water mixed solution (v: v is 9: 1), dropwise adding the solution into 5 wt% KH550 ethanol/water mixed solution (v: v is 9: 1) at the speed of 1ml/min, and stirring for reaction for 12 hours at the reaction temperature of 55 ℃;
(5) putting the fiber obtained in the step (3) into the inorganic nanoparticle dispersion liquid obtained in the step (4), stirring and reacting for 6h at 50 ℃, taking out, and then putting into a drying oven at 110 ℃ for drying for 1 h;
(6) ultrasonically dispersing 1.2g of large-particle-size silica nanoparticles with the particle size of 30 +/-10 nm in 50ml of ethanol/water mixed solution (v: v is 9: 1), dropwise adding the solution into 5 wt% KH550 ethanol/water mixed solution (v: v is 9: 1) at the speed of 1ml/min, and stirring for reaction for 12 hours at the reaction temperature of 55 ℃;
(7) and (3) putting the fiber obtained in the step (5) into the inorganic nanoparticle dispersion liquid obtained in the step (6), stirring and reacting for 6h at 50 ℃, taking out, putting into a 110 ℃ oven, and drying for 2h to obtain the surface modified UHMWPE fiber.
FIG. 1 is a scanning electron microscope image of UHMWPE fiber surface treated by different treatment modes; wherein: fig. 1(a) is an untreated UHMWPE fiber; fig. 1(b) shows UHMWPE fibers treated in step (3) of example 1; fig. 1(c) shows the UHMWPE fibers treated in step (7) of example 1. As can be seen from the figure, the surface of the untreated UHMWPE fiber is very smooth, so that the action of the untreated UHMWPE fiber with other resin matrixes in the preparation process of the composite material is weak, the roughness of the fiber surface is slightly increased after the plasma treatment in the step (3), the roughness of the fiber surface is greatly increased after the plasma treatment in the step (7), and the UHMWPE fiber has fine granular modification points and also has sheet-shaped modification areas, so that the action strength of the UHMWPE fiber with other resin matrixes is greatly improved.
Example 2
(1) Soaking 10g of UHMWPE fiber in 350ml of ethanol, ultrasonically cleaning for 30min, and drying in a drying oven at 60 ℃;
(2) plasma treating the washed UHMWPE fibers of step (1) under the following treatment conditions: the power is 200W, the processing gas is air, the gas flux is 5L/min, the pressure is 30Pa, and the processing time is 0.5 min;
(3) putting the UHMWPE fiber treated in the step (2) into an aqueous solution containing 10wt% of KH550, reacting for 5h, taking out, washing with deionized water, and putting into a 110 ℃ oven for dehydration condensation reaction for 2 h;
(4) ultrasonically dispersing 1.2g of titanium dioxide nano particles with large particle size of 250 +/-20 nm in 50ml of aqueous solution, dropwise adding the solution into 10wt% of KH550 aqueous solution at the speed of 5ml/min, and stirring for reacting for 3 hours at the reaction temperature of 55 ℃;
(5) putting the fiber obtained in the step (3) into the inorganic nanoparticle dispersion liquid obtained in the step (4), stirring and reacting at 45 ℃ for 12 hours, taking out, and then putting into a 120 ℃ oven for drying for 1 hour;
(6) ultrasonically dispersing 1.2g of large-particle-size silica nanoparticles with the particle size of 15 +/-5 nm in 50ml of aqueous solution, dropwise adding the solution into 10wt% of KH550 aqueous solution at the speed of 6ml/min, and stirring for reaction for 12 hours at the reaction temperature of 55 ℃;
(7) and (3) putting the fiber obtained in the step (5) into the inorganic nanoparticle dispersion liquid obtained in the step (6), stirring and reacting for 8h at 55 ℃, taking out, putting into a 110 ℃ oven, and drying for 2h to obtain the surface modified UHMWPE fiber.
Example 3
(1) Soaking 10g of UHMWPE fiber in 500ml of ethanol, ultrasonically cleaning for 30min, and drying in a drying oven at 60 ℃;
(2) plasma treating the washed UHMWPE fibers of step (1) under the following treatment conditions: the power is 10W, the processing gas is the mixed gas of oxygen and nitrogen, wherein the volume of the oxygen accounts for 60%, the gas flux is 0.5L/min, the pressure is 15Pa, and the processing is carried out for 5 min;
(3) putting the UHMWPE fiber treated in the step (2) into an ethanol solution containing 1 wt% of KH550, reacting for 5h, taking out, washing with deionized water, and putting into a 110 ℃ drying oven for dehydration condensation reaction for 3 h;
(4) ultrasonically dispersing 1.2g of large-particle-size titanium dioxide nano particles with the particle size of 450 +/-50 nm in 50ml of ethanol solution, dropwise adding the solution into 1 wt% KH550 ethanol solution at the speed of 3ml/min, and stirring for reaction for 12 hours at the reaction temperature of 40 ℃;
(5) putting the fiber obtained in the step (3) into the inorganic nanoparticle dispersion liquid obtained in the step (4), stirring and reacting for 12 hours at 40 ℃, taking out, and then putting into a 90 ℃ oven for drying for 3 hours;
(6) ultrasonically dispersing 1.2g of titanium dioxide nano particles with small particle size of 80 +/-15 nm in 50ml of ethanol solution, dropwise adding the solution into 10wt% KH550 ethanol solution at the speed of 10ml/min, and stirring for reacting for 1h at the reaction temperature of 55 ℃;
(7) and (3) putting the fiber obtained in the step (5) into the inorganic nanoparticle dispersion liquid obtained in the step (6), stirring and reacting for 1h at 60 ℃, taking out, putting into a 110 ℃ oven, and drying for 2h to obtain the surface modified UHMWPE fiber.
Comparative example 1 (modified with only a single large particle size inorganic nanoparticle)
(1) Soaking 10g of UHMWPE fiber in 200ml of ethanol, ultrasonically cleaning for 30min, and drying in a drying oven at 60 ℃;
(2) plasma treating the washed UHMWPE fibers of step (1) under the following treatment conditions: the power is 30W, the processing gas is air, the gas flux is 1.5L/min, the pressure is 25Pa, and the processing is carried out for 3 min;
(3) putting the UHMWPE fiber treated in the step (2) into an ethanol solution containing 3 wt% of KH550, reacting for 3h, taking out, washing with deionized water, and putting into a 110 ℃ drying oven for dehydration condensation reaction for 1 h;
(4) ultrasonically dispersing 2.4g of large-particle-size silica nanoparticles with the particle size of 300 +/-30 nm in 50ml of ethanol/water mixed solution (v: v is 9: 1), dropwise adding the solution into 5 wt% KH550 ethanol/water mixed solution (v: v is 9: 1) at the speed of 1ml/min, and stirring for reaction for 12 hours at the reaction temperature of 55 ℃;
(5) and (4) putting the fiber obtained in the step (3) into the inorganic nanoparticle dispersion liquid obtained in the step (4), stirring and reacting for 12h at 50 ℃, taking out, putting into a 110 ℃ oven, and drying for 2h to obtain the surface modified UHMWPE fiber.
Comparative example 2 (modification with only inorganic nanoparticles of a Single Small particle size)
(1) Soaking 10g of UHMWPE fiber in 200ml of ethanol, ultrasonically cleaning for 30min, and drying in a drying oven at 60 ℃;
(2) plasma treating the washed UHMWPE fibers of step (1) under the following treatment conditions: the power is 30W, the processing gas is air, the gas flux is 1.5L/min, the pressure is 25Pa, and the processing is carried out for 3 min;
(3) putting the UHMWPE fiber treated in the step (2) into an ethanol solution containing 3 wt% of KH550, reacting for 3h, taking out, washing with deionized water, and putting into a 110 ℃ drying oven for dehydration condensation reaction for 1 h;
(4) ultrasonically dispersing 2.4g of small-particle-size silica nanoparticles with the particle size of 30 +/-10 nm in 50ml of ethanol/water mixed solution (v: v is 9: 1), dropwise adding the solution into 5 wt% KH550 ethanol/water mixed solution (v: v is 9: 1) at the speed of 1ml/min, and stirring for reaction for 12 hours at the reaction temperature of 55 ℃;
(5) and (4) putting the fiber obtained in the step (5) into the inorganic nanoparticle dispersion liquid obtained in the step (4), stirring and reacting for 12h at 50 ℃, taking out, putting into a 110 ℃ oven, and drying for 2h to obtain the surface modified UHMWPE fiber.
Comparative example 3 (Small particle size nanoparticle treatment followed by Large particle size nanoparticle treatment)
(1) Soaking 10g of UHMWPE fiber in 200ml of ethanol, ultrasonically cleaning for 30min, and drying in a drying oven at 60 ℃;
(2) plasma treating the washed UHMWPE fibers of step (1) under the following treatment conditions: the power is 30W, the processing gas is air, the gas flux is 1.5L/min, the pressure is 25Pa, and the processing is carried out for 3 min;
(3) putting the UHMWPE fiber treated in the step (2) into an ethanol solution containing 3 wt% of KH550, reacting for 3h, taking out, washing with deionized water, and putting into a 110 ℃ drying oven for dehydration condensation reaction for 1 h;
(4) ultrasonically dispersing 1.2g of large-particle-size silica nanoparticles with the particle size of 30 +/-10 nm in 50ml of ethanol/water mixed solution (v: v is 9: 1), dropwise adding the solution into 5 wt% KH550 ethanol/water mixed solution (v: v is 9: 1) at the speed of 1ml/min, and stirring for reaction for 12 hours at the reaction temperature of 55 ℃;
(5) putting the fiber obtained in the step (3) into the inorganic nanoparticle dispersion liquid obtained in the step (4), stirring and reacting for 6h at 50 ℃, taking out, and then putting into a drying oven at 110 ℃ for drying for 1 h;
(6) ultrasonically dispersing 1.2g of large-particle-size silica nanoparticles with the particle size of 300 +/-30 nm in 50ml of ethanol/water mixed solution (v: v is 9: 1), dropwise adding the solution into 5 wt% KH550 ethanol/water mixed solution (v: v is 9: 1) at the speed of 1ml/min, and stirring for reaction for 12 hours at the reaction temperature of 55 ℃;
(7) and (3) putting the fiber obtained in the step (5) into the inorganic nanoparticle dispersion liquid obtained in the step (6), stirring and reacting for 6h at 50 ℃, taking out, putting into a 110 ℃ oven, and drying for 2h to obtain the surface modified UHMWPE fiber.
Interfacial bond strength test
A bundle of the surface-modified UHMWPE fibers obtained in examples 1-3 and comparative examples 1-2 was vertically embedded in a mixed solution of E51 epoxy resin and a curing agent (resin: curing agent mass ratio: 3: 1) and cured at room temperature for 12 hours, and the resin matrix was clamped by a jig using an Instron Universal Material testing machine, and one end of the fiber was clamped and a force perpendicular to the resin matrix was continuously increased to conduct drawing at a drawing speed of 10mm/min until the fiber was pulled out of the resin matrix, and a force Fd at the moment of fiber debonding was recorded, and the interfacial adhesion strength was calculated according to the following formula:
wherein L is the fiber length and R is the fiber diameter. The results are shown in the following table:
| sample (I) | Interfacial bond strength (MPa/mm)2) |
| UHMWPE fiber | 0.518 |
| Example 1 | 2.169 |
| Example 2 | 1.972 |
| Example 3 | 2.021 |
| Comparative example 1 | 1.213 |
| Comparative example 2 | 1.145 |
| Comparative example 3 | 1.578 |
As can be seen from the above table, the surface of the untreated UHMWPE fiber is very smooth and has low interfacial bonding strength with the epoxy resin, while the surface roughness of the UHMWPE fiber treated by the large and small particle size inorganic nanoparticles is greatly increased and the interfacial bonding strength with the epoxy resin is greatly improved (examples 1-3); while the UHMWPE fibers treated with the large-or small-particle-size inorganic nanoparticles alone (comparative examples 1 and 2) had an increased surface roughness, the roughness was not as high-order as that of the fibers treated with the large-or small-particle-size inorganic nanoparticles, and the interfacial bond strength was not increased as much as that of the fibers treated with the large-or small-particle-size inorganic nanoparticles. It should also be noted that the order of modification of the nanoparticles also affects the interfacial bond strength, and the interfacial bond strength of UHMWPE fibers modified with nanoparticles of a smaller particle size first and then with nanoparticles of a larger particle size is higher than that of fibers modified with nanoparticles of a single size, but is still different from that of fibers modified with nanoparticles of a smaller particle size first and then with nanoparticles of a larger particle size. This is probably because the small-particle-size nanoparticles can be embedded into the unmodified region of the large particle size by the treatment method of the large particle size and then the small particle size, and the staggered roughness is formed on the fiber surface, while if the small particle size and then the large particle size are carried out, the small particle size may occupy most of the space on the fiber surface, so that the large-particle-size nanoparticles can only be distributed on the small particle size, and the interface bonding strength is finally affected.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A surface modification method for improving the bonding property of ultra-high molecular weight polyethylene fibers and matrix resin is characterized by comprising the following steps:
(1) soaking the ultra-high molecular weight polyethylene fiber in ethanol, ultrasonically cleaning and drying;
(2) carrying out plasma treatment on the fiber obtained in the step (1), wherein the treatment conditions are as follows: the power is 10-200W, the gas flux is 0.5-5L/min, the pressure is 15-30 Pa, and the treatment time is 0.5-5 min;
(3) soaking the fiber obtained in the step (2) in an ethanol/water mixed solution containing a silane coupling agent, reacting for 1-5 h, taking out, and performing dehydration condensation reaction at 90-130 ℃ for 0.5-3 h;
(4) ultrasonically dispersing large-particle-size inorganic nanoparticles into a mixed solution of water and absolute ethyl alcohol, and dropwise adding the obtained dispersion into an ethanol/water mixed solution containing a silane coupling agent for modification treatment to obtain a large-particle-size inorganic nanoparticle modified solution;
(5) adding the fiber obtained in the step (3) into the large-particle-size inorganic nano particle modification liquid obtained in the step (4), stirring for reaction, taking out after the reaction, and drying;
(6) ultrasonically dispersing small-particle-size inorganic nanoparticles into a mixed solution of water and absolute ethyl alcohol, and dropwise adding the obtained dispersion liquid into an ethanol/water mixed solution containing a silane coupling agent for modification treatment to obtain a small-particle-size inorganic nanoparticle modified solution;
(7) and (3) adding the fiber obtained in the step (5) into the small-particle-size inorganic nanoparticle modification liquid obtained in the step (6), stirring for reaction, taking out after the reaction, and drying to obtain the surface-modified ultrahigh molecular weight polyethylene fiber.
2. The surface modification method of claim 1, wherein in step (1): the mass ratio of the ultrahigh molecular weight polyethylene fibers to the ethanol is 1: 20-1:50.
3. The surface modification method of claim 1, wherein in step (1):
the ultrasonic cleaning time is 20-40 min;
the drying temperature is 50-70 ℃.
4. The surface modification method of claim 1, wherein in step (2): the atmosphere in which the plasma treatment is performed contains at least oxygen, and the content of oxygen is more than 15% by volume.
5. The surface modification method of claim 1, wherein in steps (3), (4) and (6):
the silane coupling agent is one or more of KH550, KH560 and KH 570;
the concentration of the silane coupling agent is 1-10 wt%.
6. The surface modification method of claim 1, wherein in steps (3), (4) and (6):
the mass ratio of the ethanol to the water in the ethanol/water mixed solution is 1:0-0: 1.
7. The surface modification method of claim 1, wherein in steps (4) and (6):
the particle size of the large-particle-size inorganic nanoparticles is 200-500 nm;
the particle size of the small-particle-size inorganic nanoparticles is 10-100 nm.
8. The surface modification method of claim 1 or 7, wherein in steps (4) and (6): the large-particle-size inorganic nanoparticles or the small-particle-size inorganic nanoparticles comprise one or more of silica nanoparticles, titanium dioxide nanoparticles, zirconia nanoparticles, alumina nanoparticles, calcium carbonate nanoparticles, montmorillonite, graphene and carbon nanotubes.
9. The surface modification method of claim 1 or 7, wherein in steps (4) and (6):
the dropping speed of the dispersion liquid is 1-10 mL/min; the modification conditions are as follows: the temperature is 40-60 ℃, and the stirring speed is 100-1000 r/min.
10. The surface modification method of claim 1, wherein in steps (5) and (7):
the reaction temperature is 40-60 ℃, and the reaction time is 1-12 h; the drying temperature is 90-130 ℃, and the drying time is 0.5-3 h.
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