CN117447086A - Glass fiber and preparation method and application thereof - Google Patents
Glass fiber and preparation method and application thereof Download PDFInfo
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- CN117447086A CN117447086A CN202311517506.5A CN202311517506A CN117447086A CN 117447086 A CN117447086 A CN 117447086A CN 202311517506 A CN202311517506 A CN 202311517506A CN 117447086 A CN117447086 A CN 117447086A
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 27
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 26
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 49
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 44
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 23
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 abstract description 37
- 238000005491 wire drawing Methods 0.000 abstract description 17
- 238000002425 crystallisation Methods 0.000 abstract description 13
- 230000008025 crystallization Effects 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000011787 zinc oxide Substances 0.000 description 24
- 238000001816 cooling Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000009941 weaving Methods 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
- C03B37/022—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from molten glass in which the resultant product consists of different sorts of glass or is characterised by shape, e.g. hollow fibres, undulated fibres, fibres presenting a rough surface
-
- 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
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- 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
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
Abstract
The invention discloses glass fiber, a preparation method and application thereof, and belongs to the technical field of new chemical material production. The glass fiber is made of SiO 2 、Al 2 O 3 MgO, caO, srO, znO, niO and TiO 2 And (3) reacting to obtain the product. The glass fiber simultaneously introduces five divalent metal oxides MgO, caO, srO, znO, niO as reaction raw materials and SiO 2 、Al 2 O 3 、TiO 2 The high-temperature viscosity of the glass liquid is obviously reduced by the synergistic reaction, and the forming temperature of the glass fiber is further reduced to 1365-1383 ℃. In addition, the forming temperature and crystallization temperature of the glass fiber can be reduced simultaneously by controlling the molar ratio of MgO, caO, srO, znO, niO to be 1:1:1:1, so that the temperature difference of a wire drawing operation window is not less than 50 ℃, and the industrial production and the crystallization of the glass fiber are facilitated morePractical application.
Description
Technical Field
The invention relates to the technical field of new chemical material production, in particular to a glass fiber and a preparation method and application thereof.
Background
With the development of 5G technology, integrated circuits mounted on ceramic chip carriers have been developed. Such circuits include glass fiber filled laminates with integrated circuit chips attached thereto.
5G communications are characterized by high frequency, high rate, low delay, high definition, which requires a circuit board with a low dielectric constant. In addition, the 5G electronic equipment has high communication power and high equipment heat, so the thermal expansion coefficient of the circuit board and the thermal expansion coefficient of the chip cannot be too different, and the circuit board and the chip are prevented from being separated in the manufacturing process. In addition, the 5G electronic device has small size and high processing precision, so the circuit board must have high elastic modulus.
To meet the above requirements, the glass fibers used in circuit boards for 5G electronic integrated circuits should have a Coefficient of Thermal Expansion (CTE) of less than about 3.5 ppm/DEG C, a dielectric constant of less than 6 (1 GHz), and a Young's modulus of elasticity of greater than 90GPa. In addition, the molding temperature (glass viscosity 10) 3 The temperature at poise) should be less than 1400 ℃, and the liquid phase temperature (crystallization upper limit temperature) should be not lower than 50 ℃ below the molding temperature.
Currently, the glass fibers commonly used in the industry for circuit boards are E-glass, L-glass, and S-glass, which generally have the following characteristics:
| parameters (parameters) | E-glass | L-glass | S-glass |
| CTE(ppm/℃) | 5.0 | 3.9 | 2.2 |
| Elastic modulus (GPa) | 73.5 | 62 | 91 |
| Forming temperature (. Degree. C.) | 1316 | 1350 | 1588 |
| Liquid phase temperature (. Degree. C.) | 1100 | 1200 | 1482 |
| Dielectric constant (1 GHz) | 7 | 4.8 | 5.3 |
Each of the above glass fibers fails to meet all the requirements in some important aspects. For example, E-glass has a lower forming temperature and liquidus temperature, but an unacceptable CTE and dielectric constant. L-glass has a low dielectric constant but an unacceptable CTE. The S glass fiber has the advantages that the thermal expansion coefficient, the elastic modulus and the dielectric constant meet the requirements, but the forming temperature and the liquefying temperature are high, and the production difficulty is high.
Therefore, there is a strong need to develop glass fibers having a Coefficient of Thermal Expansion (CTE) of less than 3.5ppm/°C, a dielectric constant of less than 6 (1 GHz), a Young's modulus of elasticity of greater than 90GPa, a forming temperature of less than 1400 ℃ during glass fiber production, and a liquidus temperature of less than 50 ℃ below the forming temperature.
However, it is difficult to obtain a composition satisfying both physical properties and moldability of glass fibers. For example, although SiO in the composition is improved 2 、Al 2 O 3 The content of (2) can reduce the thermal expansion coefficient, but the molding temperature is increased too high, and MgO and TiO are improved 2 The content of (2) can be reduced to a forming temperature, but the operation window (the difference between the forming temperature and the crystallization temperature) is less than 50 ℃, so that the glass is easy to crystallize in the wire drawing operation process, and the wire drawing operation cannot be normally performed. To solve the crystallization problem, a certain amount of B is generally added into the formula 2 O 3 As in patent CN202110010612.9, but B 2 O 3 Is easy to cause environmental pollution.
Therefore, development of the composition is difficult to crystallize and contains no B 2 O 3 Meanwhile, the glass fiber formula with low thermal expansion coefficient and high elastic modulus, wherein the physical properties and the forming properties meet the requirements, becomes a difficult problem to be solved urgently.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a glass fiber and a preparation method and application thereof. The glass fiber has lower forming temperature and good wiredrawing operation window temperature difference.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a glass fiber, which is prepared from SiO 2 、Al 2 O 3 MgO, caO, srO, znO, niO and TiO 2 And (3) reacting to obtain the product.
Preferably, the molar ratio of MgO, caO, srO, znO, niO is 1:1:1:1:1.
In the present invention, the sum of MgO, caO, srO, znO, niO is preferably 12 to 13mol%.
Preferably, the SiO is as follows 2 、Al 2 O 3 The mol ratio of MgO is (67-68): (14-15): (2.4-2.6); more preferably, the SiO 2 、Al 2 O 3 The mol ratio of MgO is (67.3-68): (14.5-15): (2.4-2.6).
In some embodiments of the invention, the SiO 2 、Al 2 O 3 The molar ratio of MgO is preferably 67.3:15:2.5 or 68:15:2.4 or 67:15:2.6 or 68:14.5:2.5 or 67.5:14.5:2.6 or 68:15:2.5 or 68:14:2.56 or 68:14.5:2.6 or 67.8:14.8:2.5 or 67.3:14.8:2.6.
preferably, the SiO is as follows 2 With TiO 2 The molar ratio of (1) is (67-68): (3.5-4); more preferably, the SiO 2 With TiO 2 The molar ratio of (67.3-68): (3.5-4).
In some embodiments of the invention, the SiO 2 With TiO 2 Preferably 67.3:4 or 68:4 or 67:4 or 67.5:4 or 68:3.5 or 67.8:3.9 or 67.3:3.9. in some embodiments of the invention, preferably, the SiO 2 And MgO in a molar ratio of (67-68): 2.4 or (67-68): 2.5 or (67-68): 2.6, and the molar ratio of MgO, caO, srO, znO, niO is 1:1:1:1:1.
The glass fiber forming temperature is preferably 1365-1383 ℃.
This is because the invention introduces five kinds of divalent metal oxides (MgO, caO, srO, znO, niO) into the reaction raw materials of the glass fiber, mgO, caO, srO, znO, niO and SiO 2 、Al 2 O 3 、TiO 2 Under the synergistic reaction of the glass fiber, the high-temperature viscosity of the glass liquid is obviously reduced, and the forming temperature of the glass fiber is further reduced.
However, the improper proportion of the five oxides MgO, caO, srO, znO, niO may cause a temperature difference of a working window of the glass fiber to be less than 50 ℃ during the drawing operation, and a crystallization phenomenon may occur, so that the drawing operation may not be performed normally in severe cases.
The glass fiber reaction raw material does not need to be additionally added with B 2 O 3 Also, itThe temperature difference of the wiredrawing operation window can be controlled.
According to the invention, preferably, mgO, caO, srO, znO and NiO=1:1:1:1:1 are controlled, so that the forming temperature and crystallization temperature can be reduced in the preparation process of the glass fiber, and the temperature difference of an operation window in the wire drawing operation is not less than 50 ℃.
In addition, the total doping amount of the five metal oxides of MgO, caO, srO, znO, niO is controlled within the range of 12-13 mol%, so that the thermal expansion Coefficient (CTE) of the prepared glass fiber is 3.37-3.49 ppm/DEG C, the dielectric constant is 5.5-5.6 (1 GHz), and the Young's elastic modulus is 91.4-92.8 GPa. In the main reaction raw materials of the glass fiber, the strontium oxide belongs to the external oxide of the glass structure network, has the function of reducing the high-temperature viscosity of the glass, and can increase the dielectric constant, the thermal expansion coefficient and the elastic modulus.
In some embodiments of the invention, the strontium oxide is preferably present in an amount of 2.4mol% to 2.6mol%.
Zinc oxide belongs to an external oxide of a glass structure network, has the function of reducing the high-temperature viscosity and the thermal expansion coefficient of glass, and can increase the dielectric constant and the elastic modulus. However, if the ZnO content is too high, crystallization occurs during glass molding, and if the ZnO content is too low, crystallization cannot be suppressed.
In some embodiments of the invention, the zinc oxide content is preferably 2.4mol% to 2.6mol%.
Nickel oxide belongs to an external oxide of a glass structure network, has the function of reducing the high-temperature viscosity and the thermal expansion coefficient of glass, and can increase the dielectric constant and the elastic modulus. However, if the NiO content is too high, crystallization occurs during glass molding, and if the NiO content is too low, crystallization cannot be suppressed.
In some embodiments of the invention, the nickel oxide is preferably present in an amount of 2.4mol% to 2.6mol%.
In some embodiments of the invention, preferably, the SiO 2 The content of (C) is selected from 67mol% or 67.3mol% or 67.5mol% or 67.8mol% or 68mol%.
Preferably, in some embodiments of the invention, the Al 2 O 3 The content of (2) is selected from 14mol% or 14.5mol% or 14.8mol% or 15mol%.
Preferably, in some embodiments of the present invention, the content of MgO, caO, srO, znO and NiO is selected from 2.4mol% or 2.5mol% or 2.6mol% or 2.56mol%, and the molar ratio of MgO, caO, srO, znO to NiO is 1:1:1:1, and the sum of the masses is 12mol% to 13mol%.
Preferably, in some embodiments of the invention, the TiO 2 The content of (2) is selected from 3.5mol% or 3.9mol% or 4mol%.
Preferably, the glass fiber further comprises impurities in an amount of not more than 1 mol%.
The impurities are introduced from the main reaction raw materials of the glass fiber, and have no decisive influence on the performance of the glass fiber.
The impurities may be trace elements such as Fe, ti, zn, pb, zr, sr, but are very low (ppm level), so the components and properties are not affected.
In some embodiments of the invention, the glass fiber raw material comprises any one of the following groups:
SiO 2 67.5mol％、Al 2 O 3 15wt％、MgO 2.5mol％、CaO 2.5mol％、SrO 2.5mol％、ZnO 2.5mol％、NiO 2.5mol％、MgO:CaO:SrO:ZnO:NiO＝1:1:1:1:1、TiO 2 4mol% and the balance of impurities;
SiO 2 68mol％、Al 2 O 3 15wt％、MgO 2.4mol％、CaO 2.4mol％、SrO 2.4mol％、ZnO 2.4mol％、NiO 2.4mol％、MgO:CaO:SrO:ZnO:NiO＝1:1:1:1:1、TiO 2 4mol% and the balance of impurities;
SiO 2 67mol％、Al 2 O 3 15wt％、MgO 2.6mol％、CaO 2.6mol％、SrO 2.6mol％、ZnO 2.6mol％、NiO 2.56mol％、MgO:CaO:SrO:ZnO:NiO＝1:1:1:1:1、TiO 2 4mol% and the balance of impurities;
SiO 2 68mol％、Al 2 O 3 14.5wt％、MgO 2.5mol％、CaO 2.5mol％、SrO 2.5mol％、ZnO 2.5mol％、NiO 2.5mol％、MgO:CaO:SrO:ZnO:NiO＝1:1:1:1:1、TiO 2 4mol% and the balance of impurities;
SiO 2 67.5mol％、Al 2 O 3 14.5wt％、MgO 2.6mol％、CaO 2.6mol％、SrO2.6mol％、ZnO 2.6mol％、NiO 2.6mol％、MgO:CaO:SrO:ZnO:NiO＝1:1:1:1:1、TiO 2 4mol% and the balance of impurities;
SiO 2 68mol％、Al 2 O 3 15wt％、、MgO 2.5mol％、CaO 2.5mol％、SrO 2.5mol％、ZnO 2.5mol％、NiO 2.5mol％、MgO:CaO:SrO:ZnO:NiO＝1:1:1:1:1、TiO 2 3.5mol% of impurities;
SiO 2 68mol％、Al 2 O 3 14wt％、MgO 2.56mol％、CaO 2.6mol％、SrO 2.6mol％、ZnO 2.6mol％、NiO 2.6mol％、MgO:CaO:SrO:ZnO:NiO＝1:1:1:1:1、TiO 2 4mol% and the balance of impurities;
SiO 2 68mol％、Al 2 O 3 14.5wt％、MgO 2.6mol％、CaO 2.6mol％、SrO 2.6mol％、ZnO 2.6mol％、NiO 2.6mol％、MgO:CaO:SrO:ZnO:NiO＝1:1:1:1:1、TiO 2 3.5mol% of impurities;
SiO 2 67.8mol％、Al 2 O 3 14.8wt％、MgO 2.5mol％、CaO 2.5mol％、SrO 2.5mol％、ZnO 2.5mol％、NiO 2.5mol％、MgO:CaO:SrO:ZnO:NiO＝1:1:1:1:1、TiO 2 3.9mol% of impurities;
SiO 2 67.3mol％、Al 2 O 3 14.8wt％、、MgO 2.6mol％、CaO 2.6mol％、SrO2.6mol％、ZnO 2.6mol％、NiO 2.6mol％、MgO:CaO:SrO:ZnO:NiO＝1:1:1:1:1、TiO 2 3.9mol percent and the balance of impurities. The invention also provides a preparation method of the glass fiber, and the glass fiber is prepared by mixing raw materials and then adopting a tank furnace method.
In the above preparation method, the raw material comprises SiO 2 、Al 2 O 3 MgO, caO, srO, znO, niO and TiO 2 ToAnd impurities in an amount of not more than 1 mol%.
In the present invention, preferably, the tank furnace method specifically includes the steps of:
1) After the raw materials are uniformly mixed, melting, clarifying and homogenizing in a tank furnace to obtain glass liquid;
2) Cooling the glass liquid obtained in the step 1) to be molded, and preparing glass fiber;
3) Drawing the glass fiber into glass fiber with fixed diameter;
4) Winding the glass fiber with the fixed diameter into a cake, and performing a post-treatment process to prepare the glass fiber.
Preferably, in the above preparation method, the raw materials are first fed into the tank furnace through a tank furnace silo. Preferably, the melting temperature of the raw materials in the tank furnace method is 1500-1700 ℃.
And then, cooling, flowing out and drawing the molten glass obtained after melting, clarifying and homogenizing to obtain the glass fiber.
The cooling treatment refers to cooling to molding.
The molding temperature is 1365-1383 ℃.
In the outflow treatment, the glass fiber is preferably formed by flowing out the glass liquid after cooling molding through a platinum-rhodium alloy bushing.
The raw materials and the proportion are adopted to prepare the glass fiber, so that the glass fiber with lower forming temperature and good wiredrawing operation window temperature difference can be obtained, the cost is obviously reduced, and the industrialized production of the glass fiber is facilitated.
The drawing treatment is preferably a glass fiber drawn into a set diameter under the traction of a drawing machine.
Preferably, the diameter of the glass filaments in the tank furnace method is 3.5-25 mu m.
And then, carrying out post-treatment on the prepared glass yarn to obtain a yarn cake.
The post-treatment comprises spray cooling, impregnating compound coating, bundling, winding by a wire drawing machine and the like.
And finally, processing the spinning cake to obtain the glass fiber.
The treatment comprises the procedures of twisting, weaving, surface treatment and the like.
The preparation method has better manufacturability and operability, and the prepared glass fiber has good performance.
The invention also provides application of the glass fiber or the glass fiber prepared by the preparation method in printed circuit boards and information technology parts.
The invention also provides a composite material, which comprises the glass fiber or the glass fiber prepared by the preparation method.
Compared with the prior art, the glass fiber provided by the invention is prepared from SiO 2 、Al 2 O 3 MgO, caO, srO, znO, niO and TiO 2 And (3) reacting to obtain the product. The glass fiber simultaneously introduces five divalent metal oxides MgO, caO, srO, znO, niO as reaction raw materials and SiO 2 、Al 2 O 3 、TiO 2 The high-temperature viscosity of the glass liquid is obviously reduced by the synergistic reaction, and the forming temperature of the glass fiber is further reduced to 1365-1383 ℃. And the forming temperature and crystallization temperature of the glass fiber can be reduced simultaneously by controlling the molar ratio of MgO, caO, srO, znO, niO to be 1:1:1:1, so that the temperature difference of a wire drawing operation window is not less than 50 ℃, and the industrial production and practical application of the glass fiber are facilitated.
Detailed Description
In order to further illustrate the present invention, the glass fiber provided by the present invention, and the preparation method and application thereof are described in detail with reference to the following examples.
The glass fiber of the invention was tested for performance as follows:
and (3) uniformly mixing various raw materials of glass fibers, then placing the glass fibers into a platinum crucible, placing the platinum crucible into a high-temperature resistance furnace, preserving heat at 1550-1600 ℃, fully melting and clarifying, then rapidly pouring the glass fibers into a mold to prepare a round glass sheet, and polishing both sides of the glass sheet to obtain a test sample.
Detecting the dielectric constant of the sample at the frequency of 1GHz at room temperature;
detecting the molding temperature by adopting a high-temperature viscosimeter;
testing the liquid phase temperature by using a gradient crystallization furnace;
detecting the thermal expansion coefficient between room temperature and 300 ℃ by using a thermal expansion instrument;
the modulus of elasticity was measured with a universal electronic tester. Examples 1 to 10
Conveying all raw materials to a mixing tank, uniformly mixing, and conveying the mixed materials to a tank furnace bin, wherein the content of all the raw materials is shown in table 1;
putting the mixture in a tank furnace bin into the tank furnace, melting the mixture into glass liquid by a high Wen Zhujian with the temperature of 1550 ℃ or higher in the tank furnace, clarifying and homogenizing the glass liquid, and then enabling the stable high-quality glass liquid to enter a wire drawing operation channel;
cooling glass liquid in a wire drawing operation channel to a forming temperature, flowing out through a platinum bushing, rapidly drawing into glass filaments with the diameter of 3.5-25 mu m by a wire drawing machine, spraying cooling, impregnating compound coating and bundling, and winding into a filament cake on the wire drawing machine to obtain glass fiber precursor;
and (3) performing procedures such as twisting, weaving, surface treatment and the like on the spinning cake to obtain a glass fiber product.
The glass fibers were subjected to performance testing, and the results are shown in table 1, and table 1 shows the formulation and performance testing results of the glass fibers prepared in the examples of the present invention.
Table 1 formulation and performance parameters of examples 1-10 glass fibers
Comparative examples 1 to 10
According to the formula shown in Table 2, various raw materials are conveyed to a mixing tank, after being uniformly mixed, the mixture is conveyed to a tank furnace bin, and the content of each raw material is shown in Table 2.
The mixed material in the tank furnace bin is put into the tank furnace, and in the tank furnace, the mixed material is melted into glass liquid by the high Wen Zhujian with the temperature of more than 1550 ℃, and after clarification and homogenization, the stable and high-quality glass liquid enters a wire drawing operation channel.
Cooling glass liquid in a wire drawing operation channel to a forming temperature, flowing out through a platinum bushing, rapidly drawing into glass filaments with the diameter of 3.5-25 mu m by a wire drawing machine, spraying cooling, impregnating compound coating and bundling, and winding into a filament cake on the wire drawing machine to obtain the glass fiber precursor.
And (3) performing procedures such as twisting, weaving, surface treatment and the like on the spinning cake to obtain a glass fiber product, and checking performance parameters. Table 2 shows the formulation and performance parameters of the glass fibers of comparative examples 1-10.
Table 2 formulations and performance parameters of comparative examples 1-10 glass fibers
As is clear from the above examples 1 to 10 and comparative examples 1 to 10, the glass fibers prepared in examples 1 to 10 of the present invention have good manufacturability, low dielectric constant and thermal expansion coefficient, and high elastic modulus, and in addition, the glass fibers prepared in examples 1 to 10 of the present invention have a drawing forming temperature of less than 1383 ℃ and a difference between the forming temperature of the glass fibers and the liquid phase temperature of not less than 50 ℃, which is advantageous for drawing operations. Therefore, the glass fiber provided by the invention can meet the requirement of thinning the circuit board in 5G communication.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (10)
1. A glass fiber is characterized by comprising SiO 2 、Al 2 O 3 MgO, caO, srO, znO, niO and TiO 2 And (3) reacting to obtain the product.
2. The glass fiber according to claim 1, wherein the molar ratio of MgO, caO, srO, znO, niO is 1:1:1:1:1.
3. The glass fiber according to claim 2, wherein the sum of the contents of MgO, caO, srO, znO, niO is 12mol% to 13mol%.
4. The glass fiber according to claim 2, wherein the SiO 2 、Al 2 O 3 The mol ratio of MgO is (67-68): (14-15): (2.4-2.6);
the SiO is 2 With TiO 2 The molar ratio of (1) is (67-68): (3.5-4).
5. The glass fiber according to claim 4, wherein the SiO 2 、Al 2 O 3 The mol ratio of MgO is (67.3-68): (14.5-15): (2.4-2.6);
the SiO is 2 With TiO 2 The molar ratio of (67.3-68): (3.5-4).
6. The glass fiber according to claim 1, further comprising an impurity in an amount of no greater than 1 mol%.
7. The method for producing a glass fiber according to any one of claims 1 to 6, wherein the glass fiber is produced by a tank furnace method after mixing the raw materials;
the raw materials comprise SiO 2 、Al 2 O 3 、MgO、CaO、SrO、ZnO、NiO and TiO 2 And impurities in an amount of not more than 1 mol%.
8. The method according to claim 7, wherein the melting temperature of the raw materials in the tank furnace method is 1500 ℃ to 1700 ℃;
the diameter of the glass fiber in the tank furnace method is 3.5-25 mu m.
9. Use of the glass fiber according to any one of claims 1 to 6 or the glass fiber prepared by the preparation method according to any one of claims 7 to 8 in printed circuit boards and information technology parts.
10. A composite material comprising the glass fiber according to any one of claims 1 to 6 or the glass fiber produced by the production method according to any one of claims 7 to 8.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311517506.5A CN117447086A (en) | 2023-11-13 | 2023-11-13 | Glass fiber and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311517506.5A CN117447086A (en) | 2023-11-13 | 2023-11-13 | Glass fiber and preparation method and application thereof |
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| CN117447086A true CN117447086A (en) | 2024-01-26 |
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| CN202311517506.5A Pending CN117447086A (en) | 2023-11-13 | 2023-11-13 | Glass fiber and preparation method and application thereof |
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| Country | Link |
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| CN (1) | CN117447086A (en) |
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