CN108589273B - Modified quartz fiber and surface modification method thereof - Google Patents
Modified quartz fiber and surface modification method thereof Download PDFInfo
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- CN108589273B CN108589273B CN201810345812.8A CN201810345812A CN108589273B CN 108589273 B CN108589273 B CN 108589273B CN 201810345812 A CN201810345812 A CN 201810345812A CN 108589273 B CN108589273 B CN 108589273B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 239000000835 fiber Substances 0.000 title claims abstract description 214
- 239000010453 quartz Substances 0.000 title claims abstract description 138
- 238000002715 modification method Methods 0.000 title claims abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 171
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000077 silane Inorganic materials 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 230000004048 modification Effects 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 13
- 238000004873 anchoring Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000005501 phase interface Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000003746 surface roughness Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229930006711 bornane-2,3-dione Natural products 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- AYCYRSRSYYUTCT-UHFFFAOYSA-N 2,3-dihydroxypropanoic acid;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(O)C(O)=O AYCYRSRSYYUTCT-UHFFFAOYSA-N 0.000 description 1
- FOWLFMDRZGRPAG-UHFFFAOYSA-N 2-(dimethylamino)-4-ethylbenzoic acid Chemical compound CCC1=CC=C(C(O)=O)C(N(C)C)=C1 FOWLFMDRZGRPAG-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
- D06M13/5135—Unsaturated compounds containing silicon atoms
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention provides a modified quartz fiber and a surface modification method thereof. The modified quartz fiber is characterized by comprising a quartz fiber body, wherein spherical nano silicon dioxide grows on the surface of the quartz fiber body. The surface modification method of the invention enables a layer of spherical nano-silica to grow on the surface of the quartz fiber, and the shape of the nano-silica layer is controllable. The nano silicon dioxide layer effectively improves the surface roughness, the specific surface area and the silane grafting rate of the fiber, improves the bonding strength of an organic-inorganic phase interface in the fiber pile through the double effects of physical anchoring and chemical bonds of the two-phase interface, and improves the mechanical strength, the water resistance and the service life of the composite material.
Description
Technical Field
The invention belongs to the technical field of interface modification of composite materials, and particularly relates to a modified quartz fiber for a dental fiber pile and a surface modification method thereof.
Background
The composite fiber pile gradually replaces cast metal piles due to the advantages of moderate elastic modulus, good aesthetic property, good biocompatibility, simple and convenient clinical operation and the like, becomes an important repair material for treating large-area tooth defects at present, and is particularly widely applied to transparent or semitransparent glass and quartz fiber piles. The fiber pile is essentially a fiber reinforced composite material, and as with most composite materials, the performance of the fiber pile is mainly determined by the performance of an organic-inorganic phase interface, namely the interaction between a reinforcing phase and a continuous phase is obviously influenced by the surface modification of the fiber, and further the mechanical property and the service life of the composite fiber pile are influenced. The fiber with the rough surface morphology can effectively improve the physical anchoring performance of a two-phase interface, thereby improving the mechanical property and the service performance of the material, and simultaneously, the physical anchoring effect can avoid the hydrolysis reaction of a silane modified interface, thereby becoming a research hotspot in the field of surface modification treatment of composite materials. At present, aiming at quartz and glass fiber reinforced composite materials, the fiber surface treatment mainly comprises a silane coupling agent method and a fiber surface organic molecule grafting method, for example, a patent with the publication number of CN105776895A, a grafting polymer is utilized to improve the fiber surface roughness, but the grafting rate is lower, the reaction is uncontrollable, the uniformity is poor, a silane modified interface is easily damaged by water, and the materials are easily damaged if the materials are used in a humid environment for a long time. Patent publication No. CN103121800B discloses a method for improving the specific surface area of a fiber by adding nanoparticles to a sizing agent and then coating the nanoparticles on the surface of the fiber, but the nanoparticles in this method have poor interaction with the fiber, and the particles are adhered to the surface of the fiber only by the sizing agent, so that the particles are easily detached, thereby having a limitation in improving the interface bonding. Considering that the fiber pile for dentistry needs to be used in a moist environment of the oral cavity for a long time and is frequently subjected to the action of external force, a fiber surface modification method with good water resistance needs to be provided, and the purpose of prolonging the service life of the fiber pile is achieved.
Disclosure of Invention
The invention aims to provide a modified quartz fiber and a surface modification method thereof, which are used for improving water resistance.
In order to achieve the purpose, the invention provides a modified quartz fiber which is characterized by comprising a quartz fiber body, wherein spherical nano silicon dioxide grows on the surface of the quartz fiber body.
Preferably, the particle size of the nano-silica is 100-800 nm.
The invention also provides a surface modification method of the quartz fiber, which is characterized by comprising the following steps: pretreating the quartz fiber or the quartz fiber yarn to remove the surface sizing agent, growing spherical nano silicon dioxide on the surface of the quartz fiber or the quartz fiber yarn, and performing silane modification to obtain the modified quartz fiber.
Preferably, the method for pretreating quartz fiber or quartz fiber yarn comprises the following steps: and (2) putting the quartz fiber or the quartz fiber yarn into a sulfuric acid solution with the mass concentration of 20-40%, heating to 80-100 ℃, treating for 2-4h, and washing to be neutral to obtain the quartz fiber or the quartz fiber yarn with the surface treating compound removed.
Preferably, the method for growing spherical nano silica on the surface of the quartz fiber or the quartz fiber yarn comprises the following steps: mixing ethanol and water, adding a catalyst or the catalyst and a surfactant, adding quartz fiber or quartz fiber yarn, stirring for 10-30min, dropwise adding a silicon source, stirring for 4-18h at room temperature, washing, and drying at 70-110 ℃ to obtain the quartz fiber or quartz fiber yarn with spherical nano silicon dioxide growing on the surface.
More preferably, the volume ratio of ethanol to water is: 3: 1-1: 1.
More preferably, the catalyst is ammonia water with the concentration of 25-28%, and the dosage of the catalyst is 0.5-2% of the mass of the system.
More preferably, the surfactant is quaternary ammonium salt cationic surfactant, and the dosage of the surfactant is 0-1% of the mass of the system.
More preferably, the silicon source is at least one of tetraethoxysilane, methyl orthosilicate and water glass, and the dosage of the silicon source is 0.2-2% of the mass of the system.
More preferably, the stirring speed is 100-800 r/min.
Preferably, the silane modification method comprises: preparing cyclohexane solution of methacryloxypropyltrimethoxysilane (gamma-MPS), dripping catalyst n-propylamine, activating for 10-30min, adding the quartz fiber or quartz fiber yarn, reacting at 40-70 ℃ for 1-4h, washing residual solution with ethanol, and drying at 80-120 ℃ to obtain the silane modified quartz fiber.
Preferably, the shape of the spherical nano silicon dioxide layer grown on the fiber surface is controlled by changing the adding amount of the silicon source and the surfactant and adjusting the conditions of stirring speed, reaction time and the like.
The invention provides a surface modification method of quartz fiber, which grows a modification layer with spherical nano silicon dioxide on the surface of the quartz fiber by a template method, carries out silane modification on the modification layer, and improves the organic-inorganic phase interface bonding force between the quartz fiber and an organic matrix by double functions of physical anchoring and chemical bond. The silicon source in the solution directly grows the spherical nano silicon dioxide layer on the surface of the fiber through a hydrolysis-condensation process, so that the layer has excellent compatibility with the fiber. In addition, the spherical nano silicon dioxide layer effectively improves the grafting rate of the silane coupling agent while improving the surface roughness of the fiber, thereby improving the interface bonding force. The modification method provided by the invention can be applied to the field of composite materials, in particular dental repair composite materials.
The nano silicon dioxide layer effectively improves the surface roughness, the specific surface area and the silane grafting rate of the fiber, improves the bonding strength of an organic-inorganic phase interface in a fiber pile through the double effects of physical anchoring and chemical bonds of the two-phase interface, and improves the mechanical strength, the water resistance and the service life of the composite material.
Compared with the prior art, the invention has the beneficial effects that:
the surface of the quartz fiber obtained by the surface modification method of the invention grows a nano silicon dioxide layer with controllable appearance, the nano silicon dioxide layer is firmly combined with the fiber, the nano protrusion structure improves the roughness of the surface of the fiber, provides effective physical anchoring effect for a composite material phase interface, simultaneously improves the grafting rate of silane on the surface of the fiber, further effectively improves the mechanical property of the composite material through the double effects of physical anchoring and chemical bonds, and simultaneously can prevent water from damaging the composite material interface in a moist environment, thereby improving the water resistance of the material and prolonging the service life.
Drawings
FIG. 1 is a scanning electron microscope image of quartz fiber before and after surface modification by a nano-silica coating in the invention, (a) is an unmodified quartz fiber surface, (b) (c) (d) is a quartz fiber surface morphology modified by different nano-silica coatings; (e) and (f) is a scanning electron microscope image of the cross section shape of the fiber pile made of the quartz fibers before and after modification.
FIG. 2 shows the mechanical strength of the sample strip of the fiber pile before and after modification.
FIG. 3 shows the mechanical strength of fiber pile sample strips obtained by different modified fibers after being soaked in water for different times.
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.
Example 1
A surface modification method of quartz fiber comprises the following steps:
(1) pretreating the quartz fiber: 500mL of sulfuric acid solution with the mass concentration of 30% is prepared, about 1g of quartz fiber is placed into the sulfuric acid solution and heated to 80 ℃, the quartz fiber is taken out after being treated for 4 hours, and the quartz fiber is washed for 3 times by deionized water until the quartz fiber is neutral, so that the quartz fiber with the surface size removed is obtained.
(2) Growing spherical nano silicon dioxide on the surface of quartz fiber or quartz fiber yarn: mixing 125ml of water and 125ml of ethanol at room temperature, adding 1.25ml of ammonia water with the mass concentration of 25-28% (accounting for 0.5% of the mass of the system), adjusting the stirring speed to 300r/min, putting the fiber bundle obtained in the step (1) into the solution, stirring for 10min, slowly dropwise adding 0.5ml of ethyl orthosilicate (accounting for 0.2% of the mass of the system), and continuously stirring for 4h at room temperature; and (3) taking out the fiber, washing the fiber for 3 times by using deionized water and ethanol until no obvious particles exist on the surface of the fiber, and drying the fiber in an oven at 100 ℃ to obtain the quartz fiber with the spherical nano silicon dioxide growing on the surface.
(3) Silane modification: preparing 10ml of 10% gamma-MPS cyclohexane solution, slowly dropwise adding 0.1ml of catalyst n-propylamine, stirring and activating for 20min, then adding the quartz fiber obtained in the step (2), reacting for 4h at 40 ℃, then taking out, washing off residual solution by using ethanol, and drying at 110 ℃ to obtain the silane modified quartz fiber, wherein the silane modified quartz fiber comprises a quartz fiber body, and spherical nano silicon dioxide grows on the surface of the quartz fiber body. The particle size of the nano silicon dioxide is 100-800 nm.
Example 2
A surface modification method of quartz fiber comprises the following steps:
(1) pretreating the quartz fiber: 500mL of 40% sulfuric acid solution is prepared, 1g of quartz fiber is put into the sulfuric acid solution and heated to 95 ℃, the quartz fiber is taken out after being treated for 2 hours, and the quartz fiber is washed for 3 times by deionized water until the quartz fiber is neutral, so that the quartz fiber with the surface size removed is obtained.
(2) Growing spherical nano silicon dioxide on the surface of quartz fiber or quartz fiber yarn: mixing 150ml of water and 100ml of ethanol at room temperature, adding 2ml of ammonia water with the mass concentration of 25-28% (accounting for 0.8% of the mass of the system) and 1.5g of hexadecyl trimethyl ammonium bromide (accounting for 0.6% of the mass of the system), adjusting the stirring speed to be 200r/min, putting the fiber bundle obtained in the step (1) into the solution, stirring for 20min, slowly dropwise adding 1ml of ethyl orthosilicate (accounting for 0.4% of the mass of the system), and continuously stirring at room temperature for 12 h; and (3) taking out the fiber, washing the fiber for 3 times by using deionized water and ethanol until no obvious particles exist on the surface of the fiber, and drying the fiber in an oven at 110 ℃ to obtain the quartz fiber with the spherical nano silicon dioxide growing on the surface.
(3) Silane modification: preparing 10ml of 10% gamma-MPS cyclohexane solution, slowly dropwise adding 0.05ml of catalyst n-propylamine, stirring and activating for 30min, then putting the quartz fiber obtained in the step (2), reacting for 3h at 60 ℃, then taking out, washing off residual solution by using ethanol, and drying at 100 ℃ to obtain the silane modified quartz fiber, wherein the silane modified quartz fiber comprises a quartz fiber body, and spherical nano silicon dioxide grows on the surface of the quartz fiber body. The particle size of the nano silicon dioxide is 100-800 nm.
Example 3
A surface modification method of quartz fiber comprises the following steps:
(1) pretreating the quartz fiber: 500mL of 35% sulfuric acid solution is prepared, 1g of quartz fiber is put into the sulfuric acid solution and heated to 90 ℃, the quartz fiber is taken out after being treated for 2.5 hours, and the quartz fiber is washed for 3 times by deionized water until the quartz fiber is neutral, so that the quartz fiber with the surface size removed is obtained.
(2) Growing spherical nano silicon dioxide on the surface of quartz fiber or quartz fiber yarn: mixing 180ml of water and 70ml of ethanol at room temperature, adding 4.5ml of ammonia water with the mass concentration of 25-28% (accounting for 1.8% of the mass of the system) and 2.5g of octadecyl trimethyl ammonium bromide (accounting for 1% of the mass of the system), adjusting the stirring speed to be 800r/min, putting the fiber bundle obtained in the step (1) into the solution, stirring for 20min, slowly dropwise adding 2.5ml of ethyl orthosilicate (accounting for 1% of the mass of the system), and continuously stirring for 6h at room temperature; and (3) taking out the fiber, washing the fiber for 3 times by using deionized water and ethanol until no obvious particles exist on the surface of the fiber, and drying the fiber in an oven at 80 ℃ to obtain the quartz fiber with the spherical nano silicon dioxide growing on the surface.
(3) Silane modification: preparing 10ml of 10% gamma-MPS cyclohexane solution, slowly dropwise adding 0.25ml of catalyst n-propylamine, stirring and activating for 10min, then putting the quartz fiber obtained in the step (2), reacting at 70 ℃ for 2h, then taking out, washing off residual solution by using ethanol, and drying at 120 ℃ to obtain the silane modified quartz fiber, wherein the silane modified quartz fiber comprises a quartz fiber body, and spherical nano silicon dioxide grows on the surface of the quartz fiber body. The particle size of the nano silicon dioxide is 100-800 nm.
Example 4
A surface modification method of quartz fiber comprises the following steps:
(1) pretreating the quartz fiber: 500mL of 35% sulfuric acid solution is prepared, 1g of quartz fiber is put into the sulfuric acid solution and heated to 100 ℃, the quartz fiber is taken out after being treated for 2 hours, and the quartz fiber is washed for 3 times to be neutral by water and ethanol respectively, so that the quartz fiber with the surface size removed is obtained.
(2) Growing spherical nano silicon dioxide on the surface of quartz fiber or quartz fiber yarn: mixing 140ml of water and 110ml of ethanol at room temperature, adding 3ml of ammonia water with the mass concentration of 25-28% (accounting for 1.2% of the mass of the system) and 2.25g of hexadecyl trimethyl ammonium bromide (accounting for 0.9% of the mass of the system), adjusting the stirring speed to be 100r/min, putting the fiber bundle obtained in the step (1) into the solution, stirring for 10min, slowly dropwise adding 5ml of ethyl orthosilicate (accounting for 2% of the mass of the system), and continuously stirring for 10h at room temperature; and (3) taking out the fiber, washing the fiber for 3 times by using deionized water and ethanol until no obvious particles exist on the surface of the fiber, and drying the fiber in an oven at 70 ℃ to obtain the quartz fiber with the spherical nano silicon dioxide growing on the surface.
(3) Silane modification: preparing 10ml of 10% gamma-MPS cyclohexane solution, slowly dropwise adding 0.4ml of catalyst n-propylamine, stirring and activating for 10min, then putting the quartz fiber obtained in the step (2), reacting for 2h at 65 ℃, then taking out, washing off residual solution by using ethanol, and drying at 95 ℃ to obtain the silane modified quartz fiber, wherein the silane modified quartz fiber comprises a quartz fiber body, and spherical nano silicon dioxide grows on the surface of the quartz fiber body. The particle size of the nano silicon dioxide is 100-800 nm.
Example 5
A surface modification method of quartz fiber comprises the following steps:
(1) pretreating the quartz fiber: 500mL of 20% sulfuric acid solution is prepared, 1g of quartz fiber is put into the sulfuric acid solution and heated to 85 ℃, the quartz fiber is taken out after being treated for 3 hours, and the quartz fiber is washed for 3 times to be neutral by water and ethanol respectively, so that the quartz fiber with the surface size removed is obtained.
(2) Growing spherical nano silicon dioxide on the surface of quartz fiber or quartz fiber yarn: mixing 125ml of water and 125ml of ethanol at room temperature, adding 5ml of ammonia water with the mass concentration of 25-28% (accounting for 2% of the mass of the system) and 1g of hexadecyl trimethyl ammonium bromide (accounting for 0.4% of the mass of the system), adjusting the stirring speed to be 600r/min, putting the fiber bundle obtained in the step (1) into the solution, stirring for 10min, slowly dropwise adding 2.5ml of water glass (accounting for 1% of the mass of the system), and continuously stirring at room temperature for 8 h; and (3) taking out the fiber, washing the fiber for 3 times by using deionized water and ethanol until no obvious particles exist on the surface of the fiber, and drying the fiber in an oven at 80 ℃ to obtain the quartz fiber with the spherical nano silicon dioxide growing on the surface.
(3) Silane modification: preparing 10ml of 10% gamma-MPS cyclohexane solution, slowly dropwise adding 0.35ml of catalyst n-propylamine, stirring and activating for 10min, then putting the quartz fiber obtained in the step (2), reacting at 70 ℃ for 1.5h, then taking out, washing off residual solution by using ethanol, and drying at 110 ℃ to obtain the silane modified quartz fiber, wherein the silane modified quartz fiber comprises a quartz fiber body, and spherical nano silicon dioxide grows on the surface of the quartz fiber body. The particle size of the nano silicon dioxide is 100-800 nm.
FIG. 1 is a scanning electron microscope image of quartz fiber before and after surface modification by a nano-silica coating in the invention, (a) is an unmodified quartz fiber surface, (b) (c) (d) is a quartz fiber surface morphology modified by different nano-silica coatings; (b), (c) and (d) correspond to examples 1, 3 and 4, respectively)
Mixing bisphenol A glycerate dimethacrylate (Bis-GMA) and Methyl Methacrylate (MMA) in an equal mass ratio (50: 50, wt./wt.) and magnetically stirring at room temperature for 12 h; respectively adding 0.2 wt% of photoinitiator Camphorquinone (CQ) and 0.8 wt% of co-initiator 4-ethyl (dimethylamino) benzoic acid (4-EDMAB) into the solution, and magnetically stirring the solution for 8 hours in a dark environment. Soaking the quartz fiber in the prepared resin, keeping out of the sun, placing in a vacuum oven at 60 ℃, vacuumizing, defoaming, preserving heat for 1h, cooling to room temperature, and taking out. 50 strands of the resin-impregnated fiber bundle are passed through a pultrusion die (the size of a die forming groove is 25mm multiplied by 2mm) under the action of tensile force, and are cured for 2min by blue light. And (5) obtaining a composite material test sample strip after demolding and polishing. (e) And (f) is a scanning electron microscope image of the cross section shape of the fiber pile made of the quartz fibers before and after modification. ((e) fiber pile made of unmodified fiber, (f) fiber pile made of fiber obtained according to example 3)
FIG. 2 shows the mechanical strength of the sample strip of the fiber pile before and after modification.
FIG. 3 shows the mechanical strength of fiber pile sample strips obtained by different modified fibers after being soaked in water for different times.
Claims (8)
1. A surface modification method of a quartz fiber, characterized by comprising: the quartz fiber or the quartz fiber yarn is pretreated to remove the surface sizing agent, spherical nano silicon dioxide grows on the surface of the quartz fiber or the quartz fiber yarn, and silane modification is carried out to obtain the quartz fiber with modified surface.
2. The method for modifying the surface of a silica fiber according to claim 1, wherein the method for pretreating a silica fiber or a silica fiber yarn comprises: and (2) putting the quartz fiber or the quartz fiber yarn into a sulfuric acid solution with the mass concentration of 20-40%, heating to 80-100 ℃, treating for 2-4h, and washing to be neutral to obtain the quartz fiber or the quartz fiber yarn with the surface treating compound removed.
3. The method of modifying the surface of a silica fiber according to claim 1, wherein the method of growing spherical nanosilica on the surface of a silica fiber or a silica fiber yarn comprises: mixing ethanol and water, adding a catalyst or the catalyst and a surfactant, adding quartz fiber or quartz fiber yarn, stirring for 10-30min, dropwise adding a silicon source, stirring for 4-18h at room temperature, washing, and drying at 70-110 ℃ to obtain the quartz fiber or quartz fiber yarn with spherical nano silicon dioxide growing on the surface.
4. A method for modifying the surface of a silica fiber according to claim 3, wherein the volume ratio of ethanol to water is: 3: 1-1: 1.
5. The method for modifying the surface of a silica fiber according to claim 3, wherein the catalyst is ammonia water having a concentration of 25 to 28% in an amount of 0.5 to 2% by mass of the system.
6. The method of modifying the surface of a silica fiber according to claim 3, wherein said surfactant is a quaternary ammonium salt-type cationic surfactant and is used in an amount of 0 to 1% by mass based on the mass of the system.
7. The method for modifying the surface of a silica fiber according to claim 3, wherein the silicon source is at least one of tetraethoxysilane, tetraethoxysilane and water glass, and the amount thereof is 0.2 to 2% by mass of the system.
8. The method of modifying the surface of a silica fiber according to claim 1, wherein said silane modification method comprises: preparing cyclohexane solution of methacryloxypropyl trimethoxy silane, dripping catalyst n-propylamine, activating for 10-30min, adding the quartz fiber or quartz fiber yarn, reacting at 40-70 ℃ for 1-4h, washing residual solution with ethanol, and drying at 80-120 ℃ to obtain the silane modified quartz fiber.
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