WO2022105185A1 - Fibre de verre à faible constante diélectrique et son procédé de préparation, produit en fibre de verre, matériau composite et application correspondante - Google Patents

Fibre de verre à faible constante diélectrique et son procédé de préparation, produit en fibre de verre, matériau composite et application correspondante Download PDF

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WO2022105185A1
WO2022105185A1 PCT/CN2021/097748 CN2021097748W WO2022105185A1 WO 2022105185 A1 WO2022105185 A1 WO 2022105185A1 CN 2021097748 W CN2021097748 W CN 2021097748W WO 2022105185 A1 WO2022105185 A1 WO 2022105185A1
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glass fiber
glass
dielectric
low
mass percentage
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PCT/CN2021/097748
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English (en)
Chinese (zh)
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郭仁贤
黄三喜
黄松林
祖群
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南京玻璃纤维研究设计院有限公司
中材科技股份有限公司
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Publication of WO2022105185A1 publication Critical patent/WO2022105185A1/fr

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    • 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
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/16—Yarns or threads made from mineral substances
    • D02G3/18—Yarns or threads made from mineral substances from glass or the like
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4218—Glass fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/002—Inorganic yarns or filaments
    • D04H3/004—Glass yarns or filaments
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H5/00—Non woven fabrics formed of mixtures of relatively short fibres and yarns or like filamentary material of substantial length
    • D04H5/12—Glass fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
    • H01B3/087—Chemical composition of glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K5/00—Casings, cabinets or drawers for electric apparatus
    • H05K5/02—Details
    • H05K5/0217—Mechanical details of casings
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
    • D10B2101/06—Glass

Definitions

  • the application belongs to the technical field of glass fibers, and in particular relates to a low-dielectric glass fiber and a preparation method, glass fiber products, composite materials and applications.
  • Modern electronic devices often include printed circuit boards reinforced with fiberglass.
  • Two types of glass fibers commonly used to strengthen printed circuit boards are E-glass and D-glass.
  • E-glass and D-glass are the most widely used, and the production and preparation are simple, and the price is low.
  • E glass has a relatively high dielectric constant of about 6.1 and a relatively high dissipation factor of about 38 ⁇ 10 -4 , which can no longer meet the application requirements in the field of high-performance, high-integrated electronic circuits.
  • D glass fiber Compared with E glass fiber, D glass fiber has excellent dielectric properties, the dielectric constant is less than 4.2, but its production processability is poor due to its high silica content, and the glass has high viscosity, high clarification temperature and Bubble is difficult to eliminate, so there are usually streaks and bubble-like defects, the product performance is unstable, the production cost is high, and the interface with epoxy resin is weak; in addition, quartz glass fiber has the lowest dielectric properties, with a dielectric constant of 3.8 , but the production process is more complicated, the yield is low, and the price is expensive.
  • Chinese patent document CN110139841A discloses a low dielectric glass composition, fiber and product, which improves fiber melting by introducing more Al 2 O 3 , introducing more SiO 2 and B 2 O 3 and part of P 2 O 5 is used to obtain lower dielectric constant and dielectric loss, but due to the large amount of Al 2 O 3 , the viscosity during the melting process is too large, the glass is difficult to bubble, and the molding temperature and liquidus temperature are high. This leads to high energy consumption for melting and high operating temperature of the bushing, which leads to the deterioration of the performance of the drawing process and the reduction of the continuous performance of the fiber products.
  • Chinese patent document CN110171929A discloses a method for preparing low-bubble and low-dielectric glass fibers.
  • the method adds ZrO 2 , which can reduce the dielectric constant of glass to a certain extent, while avoiding the melting temperature of glass fiber composition and the temperature of fiber forming. increased, and ZrO 2 improved the water resistance of glass fibers.
  • ZrO 2 improves the water resistance of glass fibers.
  • the molding temperature is very high >1385 ° C, and the working temperature of the bushing is high, so it is difficult to realize the production of large bushings.
  • Chinese patent document CN110028249A discloses a low-dielectric glass fiber and its preparation method.
  • the method introduces a small amount of Zr and Ti to improve the water resistance of the glass; a small amount of Bi is introduced to appropriately reduce the degree of network connection of the structure and improve the melting temperature;
  • the ratio of CaO ⁇ MgO ⁇ ZnO is adjusted to strengthen the ternary mixed alkaline earth metal effect to improve the melting effect, reduce the phase separation of the glass and relatively low glass dielectric constant and dielectric loss; however, the metal oxide content is high , and Zn and Bi are transition metal elements, the ionic field strength is low, and the dielectric constant and dielectric loss of glass are high.
  • Zn and Zr as a nucleating agent, will lead to the growth of crystal nuclei during the drawing process and lead to wire breakage; In addition, the Mg and Ca contents are low, so the mechanical properties of the fibers are poor.
  • the low-dielectric glass fiber formulation in the prior art, it is still difficult to make the glass fiber formulation have the properties of low dielectric constant and dielectric loss, simple melting, and high mechanical strength.
  • the technical problem to be solved by the present application is to overcome the defects in the prior art that the glass fiber cannot have the properties of low dielectric constant and dielectric loss, simple melting and high mechanical strength at the same time, so as to provide a low dielectric Glass fiber and preparation method, glass fiber product, composite material and application.
  • the present application provides a low dielectric glass fiber, comprising the following raw materials by weight:
  • SiO 2 is the main network former, and the irregular network structure formed by silicon-oxygen tetrahedra is used as the structural skeleton of the glass, which affects the performance and other indicators of the glass.
  • the content of SiO2 is less than 50%, due to weak glass network connection, poor fiber-forming ability of glass and mechanical properties of fibers, etc., its corrosion resistance will also be reduced, and it will also lead to the dielectric constant and dielectric loss of glass fibers. increase, it is not conducive to the improvement of the dielectric properties of the glass; but when the SiO 2 content exceeds 58%, the viscosity of the glass increases relatively, so the melting temperature needs to be greatly increased, on the one hand, it will cause the refractory in the production of glass furnaces.
  • the service life is greatly reduced; on the other hand, due to the increase in viscosity, it is difficult to clarify the glass, and the tiny bubbles in the glass melt are difficult to escape and remain in the glass fiber, resulting in increased dielectric loss and unstable performance of the glass fiber, which is not conducive to low Manufacture of dielectric glass fibers.
  • the present application therefore defines the SiO 2 content to be 50-58%.
  • B 2 O 3 exists as an intermediate in the glass structure.
  • the network exosomes provide enough free oxygen, a part of [BO 4 ] tetrahedral structure is formed into the glass silica network structure, which plays a role in reinforcing the network.
  • the BO bond energy is larger than the Si-O bond energy, which can effectively suppress the ion polarization in the glass structure, thereby reducing the dielectric constant and dielectric loss, and at the same time helping to improve the mechanical properties of the glass; on the other hand, in the low dielectric glass
  • the content of B 2 O 3 is relatively large, and more B 3+ exists in the form of [BO 3 ] triangle, which is a layered structure, and the coupling of the network structure is weak, so it can reduce the high temperature viscosity of the glass. Helps to clarify glass melting.
  • the present application defines the B 2 O 3 content to be 20-28%.
  • SiO 2 and B 2 O 3 are the most significant for reducing dielectric constant and dielectric loss and improving dielectric properties. Increasing the proportion of SiO 2 and B 2 O 3 in the glass component can significantly improve the dielectric properties of the glass, but the excessively high content of SiO 2 and B 2 O 3 will cause the viscosity to be too large, making it difficult for bubbles to escape in the glass melt. It is difficult to solve the process problems such as the forming of glass fiber by adjusting the ratio of SiO 2 and B 2 O 3 .
  • Al 2 O 3 also exists in the form of intermediates in the glass structure.
  • a small amount of [AlO 4 ] tetrahedron enters the glass network structure to strengthen and improve the dielectric and mechanical properties of the glass; on the other hand, it forms [AlO 5 ] Coordinated with [AlO 6 ] polyhedron as the outer body structure of the network, which reduces the phase separation tendency of the glass, inhibits the formation of devitrified phase and improves the forming ability of the fiber.
  • the introduction of an appropriate amount of Al 2 O 3 not only improves the mechanical properties and dielectric properties of the glass, but also helps to improve the chemical resistance stability; however, excessive introduction of Al 2 O 3 will lead to problems such as difficulty in glass melting, increase in dielectric constant and dielectric loss.
  • Alkaline earth metal oxides are network exosomes that can provide free oxygen. On the one hand, it reduces the density of the Si-O tetrahedral network structure in the glass network, thereby reducing the viscosity of the glass and helping to improve the melting point of the glass.
  • free oxygen can promote the formation of network intermediates such as B 2 O 3 and Al 2 O 3 [BO 4 ]- and [ AlO 4 ]-tetrahedral structure, so as to complement the network structure of the glass, help to reduce the dielectric constant and dielectric loss, improve the dielectric properties, and also help to improve the modulus and chemical resistance of the glass fiber ;
  • the ionic polarizability of alkaline earth metal oxides is larger than that of Si/B, and the greater the polarizability is, the more unfavorable the dielectric properties of glass fibers are.
  • Metal oxides such as (Na 2 O/K 2 O) have a much lower polarizability.
  • the ionic field strength of alkaline earth metal oxides is relatively large, which can play a role in aggregation in the glass network structure, thereby reducing structural breaks and defects, improving the strength and modulus of glass fibers, and helping to improve the chemical corrosion resistance of glass fibers. performance.
  • the influence mechanisms of alkaline earth metal ions on the dielectric constant and dielectric loss are different. The weaker the ion field, the easier the ion migration and the slower the influence of polarization. Therefore, the effect on the dielectric constant is more significant than that of the dielectric loss.
  • the field strength is stronger, so the ion force is stronger in the network structure, the ion migration is weaker and the polarization is more sensitive, which has a more significant effect on the dielectric loss.
  • the contribution of alkaline earth metal oxides to the increase in dielectric constant is as follows BaO>SrO>CaO>MgO>BeO, while its contribution to the dielectric loss is opposite. Therefore, how to adjust the dielectric constant and dielectric loss requires reasonable adjustment of the addition amount of each alkaline earth oxide.
  • alkaline earth metal oxides promotes the transformation of intermediates to formers, thereby enhancing the structure of the glass network; on the other hand, metal ions with high field strength help to improve the polymerization of the network structure, thereby improving the mechanical properties of glass.
  • SiO 2 , B 2 O 3 , MgO, CaO, TiO 2 , CeO 2 Component adjustment has the following designs:
  • a is the mass percentage of SiO 2 in the component formula for preparing glass fibers; if the formula contains 53% SiO 2 , then a is 0.53;
  • b is the mass percentage of B 2 O 3 in the component formula for preparing glass fiber
  • c is the mass percentage of MgO in the component formula for preparing glass fiber
  • d is the mass percentage of CaO in the component formula for preparing glass fiber
  • e is the mass percentage of TiO 2 in the component formula for preparing glass fibers
  • f is the mass percentage of CeO 2 in the component formula for preparing glass fiber; when the CeO 2 content is 0, it should be excluded from the formula.
  • X ⁇ 0.15 preferably, when X is less than or equal to 0.09, the glass fiber has low dielectric constant and dielectric loss, and the dielectric constant is less than or equal to 4.40 and the dielectric loss is less than or equal to 4.0 at a frequency of 10MHz ⁇ 10 -3 , and the temperature range of the wire drawing process is greater than or equal to 30°C, the modulus is greater than or equal to 52GPa, and the single-filament strength is greater than or equal to 2500MPa.
  • the glass fiber when X is less than or equal to 0.07, the glass fiber has a lower liquidus temperature, the drawing process range is greater than or equal to 40°C, and the monofilament strength is greater than or equal to 2600MPa.
  • the glass fiber when X is less than or equal to 0.025, the glass fiber has better dielectric properties.
  • the dielectric constant is less than or equal to 4.32, the dielectric loss is less than or equal to 3.6 ⁇ 10 -3 , and the bubble content is less than or equal to 0.01/g.
  • the mass ratio of MgO, CaO and TiO 2 is 3-11:2-10:1. Adjusting the ratio of magnesium oxide, calcium oxide and titanium oxide, on the one hand, the mechanical strength of the glass is significantly improved, and on the other hand, its dielectric constant and dielectric loss are also reduced.
  • the mass ratio of MgO, CaO and TiO 2 is 5-9:4-7:1.
  • the magnesium oxide, calcium oxide and titanium oxide in this proportion can further improve the mechanical properties of the glass and improve the drawing temperature and liquidus temperature of the glass.
  • the amount of Li 2 O+Na 2 O+K 2 O is 0.3-1.6% of the total amount of raw materials.
  • the glass fiber raw materials include Li 2 O+Na 2 O+K 2 O ⁇ 1.0%, 0-0.8% CeO 2 , and 0.2-0.7% SnO 2 .
  • the present application improves the melting and clarifying effect of glass fibers by adding multiple alkali metal oxides for composite melting.
  • Alkali metal oxides have a significant effect on reducing viscosity, but at the same time are not conducive to improving dielectric properties.
  • a small amount of Li 2 O+Na 2 O+K 2 O is set to be introduced. Due to the mixed alkali effect, the high temperature viscosity of the glass is Significant reduction but little change in dielectric properties.
  • the mixed alkali effect means that, under the premise of the same amount of introduction, the chemical corrosion resistance and dielectric properties of the glass are reduced by the use of mixed alkali metal oxides, which is much weaker than that of a single alkali metal oxide.
  • alkali metal ions mainly fill in the gaps of the glass network to neutralize and depolymerize anion groups to achieve charge balance.
  • the ionic radius of alkali metal ions increases gradually, and the ionic polarizability also increases gradually.
  • mixed alkali metal ions due to the significantly different ion radii, the internal structure of the glass is more disordered, and ions with larger radii are filled in the smaller structural gaps, blocking the migration of ions with smaller radii, so that the ions in the glass structure are more disordered.
  • the migration ability is significantly reduced, and the dielectric properties are improved; while the alkali metal with a large ionic radius is simply reused, although the ion migration ability is weakened, its polarizability is significantly increased, and the dielectric properties are also reduced. Therefore, the use of mixed alkali effect to formulate alkali metal ions is of great significance for reducing viscosity and maintaining dielectric properties.
  • the mixed alkali effect is not simply a mix and match.
  • the effect of mixed alkali on performance also needs to comprehensively consider the basic composition of glass.
  • the basic composition of glass determines the densification of the glass network structure, the size of network gaps and defects, etc. Therefore, according to the different composition of the glass itself, many experiments are needed to adjust and match, in order to obtain better performance improvement.
  • Li 2 O or Na 2 O or K 2 O When the content of Li 2 O or Na 2 O or K 2 O is less than 0.05%, it has little effect on improving the glass melting and forming properties, and it is very difficult to form textile-grade fibers in particular.
  • Li 2 O content exceeds 0.5% or Na 2 O exceeds 0.6% or K 2 O exceeds 0.8% or Li 2 O+NaO 2 +K 2 O exceeds 0.8%, the dielectric constant and dielectric loss of the glass will increase more than big.
  • CeO 2 and SnO 2 can generate oxygen during high temperature heating, on the one hand, adjust the gas partial pressure in the glass melt; On the other hand, it can combine with microbubbles to form large bubbles, thereby promoting the growth and escape of microbubbles in the glass melt.
  • the number of air bubbles in the glass fiber is less than or equal to 0.05/g.
  • the diameter of the glass fiber is 4-10um.
  • the dielectric constant is 4.2-4.5, and the dielectric loss is 2.5 ⁇ 10 -3 -4.4 ⁇ 10 -3 .
  • liquidus temperature of the glass fiber is lower than 1315°C
  • the temperature at which the viscosity is 1000 poise is lower than 1370°C
  • the molding process temperature is higher than 30°C.
  • the modulus of the glass fiber is 55-62GPa, and the strength is 2500-3100MPa.
  • the present application also provides a method for preparing a low dielectric glass fiber, comprising the following steps:
  • the glass fiber raw material is melted, heated to above the liquidus temperature, clarified and homogenized, and then drawn and formed.
  • the glass composition (such as the above-mentioned glass components provided in this application) is transported into a glass melter (such as a furnace equipment), and the composition is heated to a forming temperature above the liquidus temperature through the melting zone, and the clarification is uniform.
  • the molten glass is fiberized by continuous wire drawing through a pulling device, thereby producing glass fibers with low dielectric constant and loss.
  • the application also provides a glass fiber product
  • the glass fiber product is a product obtained by grinding, weaving, heat treatment and/or chemical treatment of the glass fiber, such as glass micropowder, woven fabric (electronic cloth, open cloth, etc.) fiber cloth, etc.), non-woven fabric, unidirectional fabric, chopped yarn, 3D fabric, colored glass fiber cloth, pre-treated cloth, post-treated cloth and/or cotton felt, etc.
  • the present application also provides a composite material comprising the above-mentioned glass fiber product, such as a printed circuit board, an electronic device substrate, and/or an electronic device frame and housing.
  • the present application also provides an application of the above composite material in electronic devices and systems operating at high frequency and/or high speed, the electronic devices and systems include mobile phones, computers, smart wearable devices and electronic products that use high-frequency signal transmission , intelligent driving and computing equipment, etc.
  • the low dielectric glass fiber includes the following raw materials by weight: SiO 2 : 50-58%; Al 2 O 3 : 10-16%; B 2 O 3 : 20-28%; MgO: 1 -4%; CaO: 1-4%; Li2O : 0.05-0.5%; Na2O: 0.05-0.6 % ; K2O: 0.05-0.8% ; TiO2 : 0.2-1.5%; CeO2 : 0-1%; SnO 2 : 0.01-1.5%; Fe 2 O 3 ⁇ 0.1%, the application can reasonably adjust the proportion of each oxide in the glass component to obtain high mechanical strength, good dielectric properties and melting process Low-dielectric glass with excellent comprehensive properties such as simplicity.
  • the glass fiber has lower dielectric constant and dielectric loss, and the glass viscosity is properly adjusted.
  • the dielectric properties and mechanical strength Under the premise, by reasonably setting the dosage of alkaline earth metal oxide, alkali metal oxide, TiO 2 , CeO 2 and SnO 2 , the melting and clarifying properties of glass are further improved, the wire drawing temperature is lower, and the stability and yield are higher. , the density is smaller, and it has excellent working performance.
  • the low-dielectric glass fiber provided by the present application has fewer defects, and the melting process is optimized by adjusting the components, so that the wire drawing process interval is enlarged, which is beneficial to the wire drawing operation.
  • the escape of micro-bubbles is improved to reduce the residual of bubble defects, and the number of bubbles in the glass body is significantly reduced, so the defects in the glass fiber are lower, and the broken wire caused by the hollow fiber in the glass drawing process is less, and the production efficiency is improved.
  • the low-dielectric glass fiber provided by this application has good water resistance, stable mechanical properties, good compatibility with resins, and excellent processing performance, and is especially suitable for use as a reinforced substrate for aircraft radomes, radomes, and electromagnetic windows.
  • the fiber cloth produced by the low-dielectric glass fiber provided by the present application the weaving process is due to the breakage caused by the hollow fiber, and the fly wire is reduced. , Strong tensile damage ability, thus reducing the proportion of splicing silk, improving the yield and product quality.
  • the composite material prepared by using the fiber cloth processed and manufactured by the glass fiber described in the present application has strong mechanical properties and large space for resin preparation according to product performance requirements; at the same time, due to the lower defects of micro-bubble, the defects in the subsequent processing of the composite material are relatively low. less, the performance is more stable, and the efficiency and quality of subsequent product use and processing are improved.
  • Table 1 shows the composition of the low-dielectric glass fiber raw materials in Examples 1-28.
  • Table 1 shows the composition of the low-dielectric glass fiber raw materials in Comparative Examples 1-5.
  • the properties of the glass fibers obtained in the above examples were tested, and the specific testing items included: dielectric properties, bubble content, strength, modulus, liquidus temperature, and forming temperature (drawing temperature).
  • the specific detection method is as follows:
  • the test uses glass block glass, which is prepared into glass batches according to the glass ratio, put into a platinum crucible, heated to 1500-1550 ° C in a resistance furnace, clarified for 24 hours, and then poured into the mold. , for annealing. According to the test requirements, the glass is processed into a sample to be tested with a diameter of 60mm ( ⁇ 0.1mm), a thickness of 3mm ( ⁇ 0.1mm), and the surface is ground and polished. According to the standard GB/T 5597, the dielectric constant and dielectric loss of glass samples were measured by the resonant cavity method at a frequency of 10 GHz.
  • Determination of bubble content use glass blocks, prepare glass batches according to the glass composition, put them into platinum crucibles, heat to 1500-1550 ° C in a resistance furnace, clarify for 10 hours, and then pour the glass liquid into the mold (mold size The diameter of the mold is 30-100mm and the thickness is 3-10mm). After the pouring is completed, annealing is carried out. In this experiment, the diameter of the mold is 60mm and the thickness is 3-5mm. Observe the bubbles in the glass sample with a magnifying glass and count the number n, and weigh the weight g of the glass sample. In order to ensure the accuracy of the number of bubbles, it is usually necessary to observe 5 to 10 samples, calculate the bubble content by the formula n/g, and take the average value. Among them, n is the total number of bubbles, and g is the total weight of all samples, wherein the weight of the sample in this example is 40-60 g.
  • Glass drawing temperature According to the ASTM-C 965 standard "Standard Practice for Measureing Viscosity of Glass Above Softening Point", measure the temperature corresponding to glass at 1000 poise, which is glass drawing temperature.
  • Liquidus temperature According to the ASTM C 829 standard "Standard Pratice for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method" (Standard Pratice for Measurement of Liquidus Temperature of Glass by the Gradient Furnace Method), the liquidus temperature of glass is determined, namely Crystallization temperature.
  • the determination of glass fiber modulus requires the preparation of glass fiber thick filaments.
  • the glass batch is prepared according to the glass ratio, put into a platinum crucible, heated to 1500-1550 °C in a resistance furnace, and kept for 2 hours. Then use a quartz glass rod to pick the glass melt, pull the glass wire out and collect fibers with a length of 30-40cm.
  • the fiber diameter is from 100-300um at one end to 700-1000um at the other end.
  • the glass batch is prepared according to the glass ratio, added to the platinum single-hole furnace, heated to near the drawing temperature, about 1280 °C-1380 °C, after 30 minutes of heat preservation, the glass filament is extended from the single-hole leak nozzle, and the wire drawing is adjusted by adjusting The pulling rate of the machine is used to prepare glass fiber monofilaments with a diameter of 8-10um.
  • the glass fiber filaments were collected by the sample strips to prepare the strength test samples. The strength of glass fiber filaments is measured on a microstress strength tester, and at least 50 samples of each glass fiber are tested.

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  • Inorganic Chemistry (AREA)
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  • Mechanical Engineering (AREA)
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  • Glass Compositions (AREA)

Abstract

L'invention concerne une fibre de verre à faible constante diélectrique et son procédé de préparation, un produit de fibre de verre, un matériau composite et une application correspondante. Un verre à faible constante diélectrique présentant d'excellentes propriétés globales telles qu'une résistance mécanique élevée, de bonnes propriétés diélectriques et un procédé de fusion simple peut être obtenu en ajustant raisonnablement les proportions d'oxydes dans une composition de verre. Plus particulièrement, en configurant raisonnablement un rapport d'oxyde de silicium, d'oxyde d'aluminium et d'oxyde de bore, la fibre de verre a une constante diélectrique et une perte diélectrique relativement faibles, et la viscosité du verre est ajustée de manière appropriée ; pendant ce temps, en tenant compte des propriétés diélectriques et de la résistance mécanique, en définissant de manière appropriée les quantités d'oxydes de métaux alcalino-terreux, d'oxydes de métaux alcalins, de TiO2, de CeO2 et de SnO2, les propriétés de fusion et de clarification du verre sont davantage améliorées, la température d'étirage et de formage est plus faible, la stabilité et le rendement sont plus élevés, la masse volumique est plus faible et une excellente performance de travail est obtenue.
PCT/CN2021/097748 2020-11-18 2021-06-01 Fibre de verre à faible constante diélectrique et son procédé de préparation, produit en fibre de verre, matériau composite et application correspondante WO2022105185A1 (fr)

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