CN114538783A - High-strength low-expansion coefficient glass fiber and composite material - Google Patents
High-strength low-expansion coefficient glass fiber and composite material Download PDFInfo
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 23
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 23
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 23
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 polypropylene Polymers 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920001187 thermosetting polymer Polymers 0.000 claims description 8
- 229920005992 thermoplastic resin Polymers 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims 1
- 239000004416 thermosoftening plastic Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 description 57
- 239000000395 magnesium oxide Substances 0.000 description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 15
- 235000012245 magnesium oxide Nutrition 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000005491 wire drawing Methods 0.000 description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 210000001635 urinary tract Anatomy 0.000 description 1
- 208000019206 urinary tract infection Diseases 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Structural Engineering (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a high-strength low-expansion-coefficient glass fiber which comprises the following components in percentage by mass: 60-66.5% SiO2(ii) a 18-22% of Al2O3(ii) a 0-3.0% CaO; 10-15% MgO; 0.3-3% of P2O5(ii) a 0-0.9% of Na2O+K2O; 0-0.6% Fe2O3(ii) a 0.4-2% TiO2(ii) a 0.2-3% of Y2O3(ii) a The contents of the components are mass percent, and SiO2Content and P2O5The sum of the contents is 61.4-68%, TiO2Content and Y2O3The sum of the contents is 1-4.5%, Y2O3content/TiO2The content is 0.1-7.5. The invention provides a high strength, low expansion systemThe glass fiber is easy to draw and form, and has higher strength and lower expansion coefficient.
Description
Technical Field
The invention relates to the field of glass fiber production, in particular to a high-strength low-expansion-coefficient glass fiber and a composite material.
Background
The glass fiber has the advantages of high tensile strength, high temperature resistance, good corrosion resistance, heat insulation, sound insulation and non-combustion, and can be widely applied to various fields of national economy such as electronics, electricity, automobiles, aviation, ships, environmental protection, chemical engineering, buildings and the like. The electronic grade glass fiber is a high-end product in the glass fiber, electronic cloth woven by the electronic grade glass fiber is compounded with epoxy resin, and then the copper foil is coated on the electronic cloth to obtain the copper-clad plate, which is an indispensable part of all electronic equipment, and the quality of the electronic equipment is directly influenced by the performance of the electronic grade glass fiber. With the advent of the 5G era, the communication power of electronic equipment is higher, the heat productivity of the equipment is higher, and meanwhile, the size of the electronic equipment is smaller, the precision is higher, and higher requirements are put forward on the thermal expansion coefficient of electronic materials. The electronic grade glass fiber is a main reinforcing material of various circuit boards (PCBs), and the thermal stability of electronic components is directly influenced by the thermal expansion coefficient. At present, the conventional electronic grade glass fibers are E glass, and the Coefficient of Thermal Expansion (CTE) of the E glass exceeds 8 x 10-6,The temperature is gradually difficult to meet the high requirement of the 5G era, and the high-performance electronic grade glass fiber with lower thermal expansion coefficient is urgently needed in the future.
At present, the glass with a large coefficient of thermal expansion is researched and is microcrystalline glass, but the microcrystalline glass can only be used as a substrate and a cover plate of electronic equipment and is difficult to be drawn into glass fibers. Some glass must be drawn into glass fiber by specific equipment and process, for example, Chinese patent 201811022023.7 discloses a microcrystalline glass optical fiber with low thermal expansion coefficient, which is prepared by raw materials of Li2CO3, Al2O3, SiO2, ZrO2, TiO2, BaCO3, Na2CO3, K2CO3, MgO and ZnO, wherein the molar ratio of Li2CO3: SiO2: Al2O3: TiO2: ZrO2: BaCO3: Na2CO3: K2CO3: MgO: ZnO is (5-7): 55-58): 20-23): 2-3: (2-3): 2-3: (1-3): 1-3); the microcrystalline glass fiber has a coefficient of thermal expansion of 0-1 × 10-7However, the temperature is high because only the wire drawing tower wire drawing method can be adopted for production, the production difficulty is high, and the cost is high. US patent US4582748 discloses a low expansion coefficient low dielectric constant glass fiber comprising: 50-65% of SiO 2; 10-25% Al2O 3; 5-15% B2O 3; 0-15% MgO; 0-5% TiO 2; 0-5% ZnO; al2O3/MgO 2-2.5. The inventive glass has a low coefficient of thermal expansion of 1-2.3X 10-6,But the production difficulty is too high, the high-temperature viscosity of 102.5 corresponds to the temperature of 2790 DEG and 2830 DEG F, and obviously exceeds the conventional production capacity of the glass fiber.
Disclosure of Invention
The invention provides a high-strength low-expansion-coefficient glass fiber which is easy to draw, and has higher strength and lower expansion coefficient.
The high-strength low-expansion-coefficient glass fiber comprises the following components in percentage by mass:
60-66.5% SiO2；
18-22% of Al2O3；
0-3.0% CaO;
10-15% MgO;
0.3-3% of P2O5；
0-0.9% of Na2O+K2O；
0-0.6% Fe2O3；
0.4-2% TiO2；
0.2-3% of Y2O3；
The contents of the components are mass percent, and SiO2Content and P2O5The sum of the contents is 61.4-68%, TiO2Content and Y2O3The sum of the contents is 1-4.5%, Y2O3content/TiO2The content is 0.1-7.5.
Preferably, wherein SiO2The content of (B) is 61.4-64.4%.
Preferably, wherein Al2O3The content of (A) is 19-21.5%.
Preferably, the MgO content is 10 to 14%.
Preferably, the content of CaO is 0.5 to 2.6%.
Preferably, wherein P2O5The content of (B) is 0.6-2.6%.
Preferably, wherein TiO2The content of (B) is 0.5-1.6%.
Preferably, wherein Y is2O3The content of (B) is 0.4-2.4%.
Preferably, wherein Na2O content and K2The sum of the O content is 0.1-0.5%, and Na2O content/K2The content of O is more than or equal to 2.0.
Preferably, wherein SiO2+P2O5TiO with content of 62.5-66.8%2Content and Y2O3The sum of the contents is 1.2-4%, Y2O3content/TiO2The content is 1-4.
Preferably, the following ingredients are included: 61.4-64.4% SiO2(ii) a 19-21.5% of Al2O3(ii) a 10-14% MgO; 0.5-2.6% CaO; 0.6-2.6% of P2O5(ii) a 0.5-1.6% TiO2(ii) a 0.4-2.4% of Y2O3(ii) a And SiO2And P2O5The sum of the contents of the components is 62.5 to 66.8 percent, and the TiO2Content and Y2O3The sum of the contents is 1.2-4%; na (Na)2O content and K2The sum of the O content is 0.1-0.5%, and Na2O content/K2The content of O is more than or equal to 2.0; y is2O3content/TiO2Content of 1-4, Fe2O3The content is 0-0.4%.
The invention also provides a composite material, which is obtained by combining thermosetting resin or thermoplastic resin or both thermosetting resin and thermoplastic resin with glass fiber, wherein the glass fiber is the glass fiber.
Preferably, the thermosetting resin is one or more of epoxy resin, unsaturated polyester resin and polyurethane resin.
Preferably, the thermoplastic resin is one or more of polycarbonate, polypropylene, polyamide, polybutylene terephthalate, polyethylene terephthalate, polystyrene, polyphenylene sulfide, polyoxymethylene, and polymethyl methacrylate.
Compared with the prior art, the high-strength low-expansion-coefficient glass fiber and the composite material have the following beneficial effects:
the high-strength low-expansion-coefficient glass fiber adopts SiO with the most compact glass network structure2-Al2O3MgO system, by TiO2And Y2O3To further reinforce the network structure and thereby increase the strength of the glass fibers. Adding P into glass fiber2O5Can obviously reduce the high-temperature viscosity of the glass and improve the melting and forming performance of the glass, and the temperature P is low2O5Can enter into a glass network structure and has a positive effect on reducing the thermal expansion coefficient of the glass fiber. The glass fiber of the invention obtains high strength (tensile strength is more than 3200MPa) and low expansion coefficient (less than 3.0 multiplied by 10) by accurately regulating and controlling the component design and the content and the proportion of each component-6/° c) high performance glass fibers. Meanwhile, the composition has good fiber forming performance, the forming temperature is not more than 1350 ℃, the upper limit temperature of crystallization is not more than 1250 ℃, and large-scale production can be realized under the prior art condition.
Detailed Description
The invention provides a high-strength low-expansion-coefficient glass fiber, which comprises the following components:
60-66.5% SiO2(ii) a 18-22% of Al2O3(ii) a 0-3.0% of CaO; 10-15% MgO; 0.3-3% of P2O5(ii) a 0-0.9% of Na2O+K2O; 0-0.6% Fe2O3(ii) a 0.4-2% TiO2(ii) a 0.2-3% of Y2O3(ii) a And SiO2+P2O5TiO 61.4-68 wt%2+Y2O3Content of 1-4.5%, Y2O3/TiO2The ratio is 0.1-7.5, and the content of each component in the invention is mass percent.
The magnitude of the glass thermal expansion coefficient depends on the attractive forces (R — O bonding forces) between various cations and oxygen ions in the glass, and the stronger the attractive forces, the smaller the glass thermal expansion coefficient. Therefore, the improvement of the compactness of the glass network structure and the addition of the extra-network ions with higher field intensity are beneficial to reducing the thermal expansibility of the glass. However, too high an R-O bond force also increases the melting temperature of the glass fiber and the difficulty of production. The glass fiber adopts SiO with the most compact glass network structure2-Al2O3MgO system, and a certain amount of TiO with high coordination and high field strength is introduced2And Y2O3To further reinforce the network structure. The inventors have found that a certain amount of P is incorporated into the glass of the system2O5Can obviously reduce the high-temperature viscosity of the glass and improve the melting and forming performance of the glass fiber, and the temperature is P at low temperature2O5Can enter a glass network structure and has positive effect on reducing the thermal expansion coefficient of the glass fiber; k is2O and CaO belong to network exosomatic ions with large ionic radius and small field intensity, the thermal expansion coefficient of the glass is easily increased, and K is2O and Na2O may be added without special care, present as an impurity, or strictly controlled to keep the content low. And controlling the glass fiber to be substantially free of BaO, ZnO, PbO, etc., or to be present as impurities.
According to the invention, through the component design of the glass fiber and the accurate regulation and control of the content and the proportion of each component, the high strength (the tensile strength is greater than that of the glass fiber) can be obtained through drawing the glass fiber3200MPa), low expansion coefficient (less than 3.0 × 10)-6/° c). Meanwhile, the composition has good fiber forming performance, the forming temperature is not more than 1350 ℃, the upper limit crystallization temperature is not more than 1250 ℃, and large-scale production can be realized under the condition of the prior art.
In the glass fiber of the present invention, SiO2Is the main oxide forming the glass network structure, has the functions of adjusting the glass drawing performance and reducing the thermal expansion coefficient of the glass, and endows the glass with certain mechanical strength and chemical stability. In a certain range, SiO in the glass2The higher the content, the better the mechanical strength of the glass, and the lower the thermal expansion coefficient, but at the same time, the higher the melting temperature and the fiber forming temperature of the glass, and the greater the production difficulty. SiO in the invention2The mass percentage content is preferably 60 to 66.5 percent, and more preferably 61.4 to 64.4 percent.
Al2O3It is also one of the main oxides forming the glass network structure, and enters the glass network structure in the form of alundum tetrahedron at a certain content, which is helpful for improving the elastic modulus of the glass fiber and reducing the thermal expansion coefficient of the glass fiber. But if Al is present2O3If the content is too high, the glass crystallization temperature can be obviously increased, which is not beneficial to the stable wire drawing and forming of the glass fiber. Al of the composition of the invention2O3The mass percent is preferably 18 to 22%, more preferably 19 to 21.5%.
The composition of the invention is added with P2O5Composition, the phosphorus atoms can enter the glass network structure in the form of phosphorus-oxygen tetrahedra. However, since an asymmetric center is formed due to the presence of a double bond in the phosphorus-oxygen tetrahedron, it has both a layered structure and a framework structure in the glass network. The inventors have found that by controlling the content and ratio, P2O5Has the functions of reducing the high-temperature viscosity of the glass and improving the low-temperature thermal expansion performance of the glass. P in the glass fiber of the present invention2O5The mass percentage content is 0.3-3%, and the preferable content range is 0.6-2.6%. Meanwhile, in order to give consideration to both the thermal expansion property and the drawing formability of the glass fiber, SiO2+P2O5The total content is limited to61.4-68%, preferably 62.5-66.8%.
Li2O、Na2O and K2As an alkali metal oxide, O plays a role in fluxing and reducing the drawing forming difficulty in the glass, but the increase of the alkali content also has negative influence on the thermal expansion coefficient of the glass. Therefore, the content and proportion of Na in the composition of the present invention are strictly controlled2O and K2The sum of the contents of O is defined to be 0.1-0.9%, preferably 0.1-0.5%, and Na2Content of O/K2The content of O being greater than 1, i.e. Na2Content of O and K2The ratio of the contents of O is greater than 1, preferably greater than or equal to 2. In addition, due to Li2O is too costly and the invention is essentially free of Li2O, i.e. without addition of Li2O, which can reduce the cost of the glass fiber.
CaO and MgO belong to alkaline earth metal oxides, and in silicate glass, the high-temperature viscosity of the glass can be reduced, and the glass crystallization tendency can be improved. However, since the ionic radius of CaO is larger than that of MgO, the thermal expansion coefficient of the glass is obviously increased when the content of CaO is higher under the same conditions. CaO is not added specially but exists as impurity, or the adding amount is strictly controlled, and the content of CaO is controlled to be 0-3%. The content of MgO is controlled between 10 and 15 percent. Preferably, the CaO accounts for 0.5-2.6% by mass, and the MgO accounts for 10-14% by mass.
TiO2And Y2O3All are high-coordination high-field-strength oxides which have an aggregation effect on a glass network, so that a certain content of TiO2And Y2O3The coefficient of thermal expansion of the glass can be reduced. However, the inventors have found that TiO alone is added2And Y2O3Too high a content of one or more of these substances leads to a high tendency of devitrification of the glass. By controlling the proportion of the two components, a synergistic effect can be generated, and the optimal balance of reducing the thermal expansion coefficient of the glass and controlling the devitrification of the glass is achieved. In the present invention, TiO is limited20.4-2% of Y2O30.2-3% of TiO2Content and Y2O3The sum of the contents being 1.0-4.5%, and Y2O3content/TiO2In an amount of0.1-7.5. Preferably, TiO20.5-1.6% of Y2O30.4-2.4% of TiO2Content and Y2O3The sum of the contents being 1.2-4%, and Y2O3content/TiO2The content is 1-4.
In the present invention, Fe2O3Only exists in the form of mineral raw material impurity, its content is controlled at 0-0.6%, and can prevent glass fibre from yellowing or greening, and Fe2O3More preferably, the content is 0 to 0.4%.
As a preferred embodiment, the composition comprises the following ingredients: 61.4-64.4% SiO2(ii) a 19-21.5% of Al2O3(ii) a 10-14% MgO; 0.5-2.6% CaO; 0.6-2.6% of P2O5(ii) a 0.5-1.6% TiO2(ii) a 0.4-2.4% of Y2O3(ii) a And SiO2And P2O5The sum of the contents of the components is 62.5 to 66.8 percent, and the TiO2And Y2O3The sum of the contents is 1.2-4%; na (Na)2O and K2The sum of the O content is 0.1-0.5%, and Na2O content/K2The content of O is more than or equal to 2.0; y is2O3content/TiO2The content is 1-4%.
The glass fiber of the present invention can be prepared by a well-known tank furnace method or electric melting furnace method. The tank furnace method or the electric melting furnace method specifically comprises the following steps: calculating the required raw material adding proportion according to the actual formula of the glass; quantitatively conveying various raw materials to a mixing bin according to the proportion, and fully and uniformly mixing to obtain qualified batch; conveying the batch to a kiln head bin of the tank furnace or the electric melting furnace, and delivering the batch to the tank furnace or the electric melting furnace by a feeder at a constant speed; the batch materials are heated, melted, clarified and homogenized in a tank furnace at the high temperature of 1300 ℃ and 1500 ℃ to form qualified glass liquid, namely a liquid composition; cooling the molten glass to the molding temperature through the operation channel, and then flowing out through a platinum bushing to form glass filaments; rapidly drawing the glass fiber into glass fiber with a set diameter under the high-speed traction of a wire drawing machine, and winding the glass fiber into a spinning cake by the wire drawing machine after spray cooling, impregnating compound coating and beam collecting; then drying in a drying furnace, and obtaining continuous glass fiber yarns after disintegration and packaging; or the well wound spinning cakes are sent to a short cutting production line, cut into short strands with required length, and subjected to the working procedures of granulation, drying, screening and the like to obtain the short glass fiber yarns.
Table 1, Table 2 and Table 3 show the formulation components and properties of the glass fibers of the present invention according to examples 1 to 22, and the components of the comparative examples are referred to pages 53 to 54 of the book "glass fibers and mineral wool". The values are in mass%. Because of factors such as detection errors, no analysis and counting of trace impurities, decimal place value and the like, the total percentage content of the components in the table may not reach 100%.
Wherein T islogη＝3The temperature at which the glass viscosity is 1000 poise corresponds to the temperature of the glass melt at the time of glass fiber molding, and is also referred to as the glass "glass fiber molding temperature". T isLiquid for treating urinary tract infectionThe liquidus temperature of glass is represented by a temperature at which the glass crystallization rate is 0, i.e., an upper limit of glass crystallization temperature, and is also referred to as "glass fiber crystallization temperature".
The high-temperature viscosity of the glass fiber is detected by a BROOKFIELD high-temperature viscometer produced by ORTON company, the liquidus temperature of the glass is detected by an Orton Model gradient furnace, the thermal expansion coefficient of the glass is measured by GB/T1690-2015 standard, and the tensile strength is measured by ASTM D2343-03 standard.
TABLE 1
TABLE 2
TABLE 3
| Composition of | Example 17 | Example 18 | Example 19 | Example 20 | Example 21 | Example 22 | Comparative example |
| SiO2 | 60.2 | 60.2 | 61.2 | 60.8 | 60.8 | 63.4 | 58.0 |
| Al2O3 | 19.5 | 19.5 | 19.5 | 19.4 | 19.4 | 19.5 | 11.2 |
| P2O5 | 2.3 | 2.3 | 2.3 | 2.3 | 2.3 | 2.3 | 0 |
| SiO2+P2O5 | 62.5 | 62.5 | 63.5 | 63.1 | 63.1 | 65.7 | 58 |
| MgO | 12.4 | 12.4 | 12.4 | 12.4 | 10.4 | 10.4 | 2.7 |
| CaO | 2.6 | 2.6 | 2.6 | 2.6 | 1.7 | 0.8 | 22 |
| Na2O | 0.6 | 0.1 | 0.4 | 0.4 | 0.4 | 0.3 | / |
| K2O | 0.3 | 0 | 0.1 | 0.1 | 0.1 | 0.1 | / |
| Na2O and K2O | 0.9 | 0.1 | 0.5 | 0.5 | 0.5 | 0.4 | <0.5 |
| TiO2 | 0.8 | 0.8 | 0.5 | 0.6 | 1.5 | 1.2 | <2.2 |
| Y2O3 | 1.2 | 1.5 | 0.7 | 1.0 | 3 | 1.8 | / |
| TiO2+Y2O3 | 2 | 2.3 | 1.2 | 1.6 | 4.5 | 3 | <2.2 |
| Y2O3/TiO2 | 1.5 | 1.88 | 1.4 | 1.67 | 2 | 1.5 | / |
| Fe2O3 | 0.1 | 0.6 | 0.3 | 0.4 | 0.4 | 0.2 | 0.3 |
| Tlogη＝3(℃) | 1319 | 1328 | 1331 | 1328 | 1330 | 1340 | 1245 |
| TLiquid for treating urinary tract infection(℃) | 1221 | 1222 | 1220 | 1222 | 1221 | 1220 | 1193 |
| Expansion coefficient x 10-6/℃ | 2.83 | 2.83 | 2.76 | 2.76 | 2.70 | 2.62 | 7.65 |
| Tensile strength MPa | 3360 | 3365 | 3490 | 3430 | 3470 | 3790 | 2520 |
As can be seen from tables 1 to 3, the glass fibers of the present invention have a low coefficient of thermal expansion (not more than 3X 10)-6/° c) and excellent mechanical properties (the tensile strength of the yarn is as high as 3200MPa), and meanwhile, the invention has lower forming difficulty, the forming temperature is not more than 1340 ℃, the crystallization temperature is less than 1250 ℃, and the large-scale production can be realized under the prior art conditions.
The invention also provides a composite material, which is obtained by combining one or more organic materials with the glass fiber, wherein the organic materials are one or more of thermosetting resin such as epoxy resin, unsaturated polyester, polyurethane, vinyl resin and the like, or one or more of thermoplastic resin such as Polycarbonate (PC), polypropylene (PP), Polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), Polystyrene (PS), polyphenylene sulfide (PPS), Polyformaldehyde (POM), polymethyl methacrylate (PMMA) and the like and modified products thereof, and the organic materials can also be formed by compounding one or more of thermosetting resin and one or more of thermoplastic resin. The glass fiber has a low thermal expansion coefficient, so that the dimensional thermal stability of the composite material can be remarkably improved, and the problems of deformation, warping and the like of a product in various occasions with large environmental temperature fluctuation are effectively prevented. Meanwhile, the glass fiber has good mechanical properties, so that the strength, toughness and other properties of the composite material are greatly improved.
The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the scope of the present invention is defined by the claims. Various modifications and equivalents may be made by those skilled in the art within the spirit and scope of the invention.
Claims (13)
1. The high-strength low-expansion-coefficient glass fiber is characterized by comprising the following components in percentage by mass:
60-66.5% SiO2；
18-22% of Al2O3；
0-3.0% CaO;
10-15% MgO;
0.3-3% of P2O5；
0-0.9% of Na2O+K2O；
0-0.6% Fe2O3；
0.4-2% TiO2；
0.2-3% of Y2O3；
The contents of the components are mass percent, and SiO2Content and P2O5The sum of the contents is 61.4-68%, TiO2Content and Y2O3The sum of the contents is 1-4.5%, Y2O3content/TiO2The content is 0.1-7.5.
2. The high strength, low expansion glass fiber of claim 1 wherein the SiO2The content of (B) is 61.4-64.4%.
3. The high strength, low expansion glass fiber of claim 1, wherein Al is present2O3The content of (A) is 19-21.5%.
4. A high strength, low expansion coefficient glass fiber as claimed in claim 1, wherein the content of MgO is 10-14%.
5. A high strength, low coefficient of expansion glass fiber as claimed in claim 1, wherein the content of CaO is 0.5-2.6%.
6. The high strength, low expansion glass fiber of claim 1 wherein P is2O5The content of (B) is 0.6-2.6%.
7. The high strength, low expansion glass fiber of claim 1 wherein the TiO is2The content of (B) is 0.5-1.6%.
8. The high strength, low expansion glass fiber of claim 1, wherein Y is2O3The content of (B) is 0.4-2.4%.
9. The high strength, low expansion glass fiber of claim 1 wherein Na2O content and K2The sum of the O content is 0.1-0.5%, and Na2O content/K2The content of O is more than or equal to 2.0.
10. The high strength, low expansion glass fiber of claim 1, wherein the SiO is2+P2O5TiO with content of 62.5-66.8%2Content and Y2O3The sum of the contents being 1.2-4%, Y2O3content/TiO2The content is 1-4.
11. A high strength, low expansion coefficient glass fiber as defined in claim 1, comprising the following composition: 61.4-64.4% SiO2(ii) a 19-21.5% of Al2O3(ii) a 10-14% MgO; 0.5-2.6% CaO; 0.6-2.6% of P2O5(ii) a 0.5-1.6% TiO2(ii) a 0.4-2.4% of Y2O3(ii) a And SiO2And P2O5The sum of the contents of the components is 62.5 to 66.8 percent, and the TiO2Content and Y2O3The sum of the contents is 1.2-4%; na (Na)2O content and K2The sum of the O content is 0.1-0.5%, and Na2O content/K2The content of O is more than or equal to 2.0; y is2O3content/TiO2Content of 1-4, Fe2O3The content is 0-0.4%. A composite material is characterized by comprising a thermosetting resin or a thermoplastic resin or a thermosetting resin and a thermoplastic resinObtained by combining with glass fibers according to any one of claims 1 to 11.
12. The composite material of claim 12, wherein the thermosetting resin is one or more of an epoxy resin, an unsaturated polyester resin, and a polyurethane resin.
13. The composite material of claim 12, wherein the thermoplastic resin is one or more of polycarbonate, polypropylene, polyamide, polybutylene terephthalate, polyethylene terephthalate, polystyrene, polyphenylene sulfide, polyoxymethylene, and polymethyl methacrylate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115093123A (en) * | 2022-06-21 | 2022-09-23 | 重庆国际复合材料股份有限公司 | Low-expansion high-modulus glass fiber composition and glass fiber |
| CN117825378A (en) * | 2024-03-05 | 2024-04-05 | 四川省科源工程技术测试中心有限责任公司 | Basalt ore fiber forming capacity judging method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115093123A (en) * | 2022-06-21 | 2022-09-23 | 重庆国际复合材料股份有限公司 | Low-expansion high-modulus glass fiber composition and glass fiber |
| CN115093123B (en) * | 2022-06-21 | 2024-03-15 | 重庆国际复合材料股份有限公司 | Low-expansion high-modulus glass fiber composition and glass fiber |
| CN117825378A (en) * | 2024-03-05 | 2024-04-05 | 四川省科源工程技术测试中心有限责任公司 | Basalt ore fiber forming capacity judging method |
| CN117825378B (en) * | 2024-03-05 | 2024-06-04 | 四川省科源工程技术测试中心有限责任公司 | Basalt ore fiber forming capacity judging method |
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