A glass fiber and a method for producing and using the same

Abstract

The application discloses a kind of glass fiber and its preparation method and application, belong to the technical field of new material production of chemical industry.The glass fiber is prepared by SiO2, Al2O3, MgO, CaO, SrO, ZnO, NiO and TiO2 reaction.The glass fiber simultaneously introduces five divalent metal oxides MgO, CaO, SrO, ZnO, NiO as reaction raw material, and SiO2, Al2O3, TiO2 Synergistic reaction makes that the high temperature viscosity of glass liquid significantly reduces, and then reduces the forming temperature of glass filament to 1365~1383 DEG C.Moreover, by controlling the molar ratio of MgO, CaO, SrO, ZnO, NiO is 1:1:1:1:1, can simultaneously reduce the forming temperature and crystallization temperature of glass filament, ensure that the window temperature difference of drawing operation is not less than 50 DEG C, more conducive to the industrial production and practical application of glass fiber.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of new chemical material production, and in particular to a glass fiber and a preparation method and application thereof. BACKGROUND

[0002] With the development of 5G technology, people have developed integrated circuits installed on ceramic chip carriers. Such circuits include glass fiber filled laminates with integrated circuit chips attached thereto.

[0003] The characteristics of 5G communication are high frequency, high speed, low delay, and high definition, which require the circuit board to have a low dielectric constant. In addition, 5G electronic equipment has a large communication power and a high heat generation, so the thermal expansion coefficient of the circuit board and the thermal expansion coefficient of the chip cannot differ too much to prevent separation of the two during the manufacturing process. Moreover, 5G electronic equipment is small in size and high in processing precision, so the circuit board must have a high elastic modulus.

[0004] In order to meet the above requirements, the glass fiber used in the circuit board of the 5G electronic equipment integrated circuit should have a thermal expansion coefficient (CTE) of less than about 3.5 ppm / ℃, a dielectric constant of less than 6 (1 GHz), and a Young's modulus of more than 90 GPa. In addition, the forming temperature (temperature at which the glass viscosity is 10 3 6 poise) during the production of the glass fiber should be less than 1400℃, and the liquidus temperature (upper limit of crystallization temperature) should be no less than 50℃ below the forming temperature.

[0005] At present, the commonly used glass fiber for circuit boards in the industry is E-glass, L-glass, and S-glass, which generally have the following characteristics:

[0006] Parameters E-glass L-glass S-glass CTE (ppm / °C) 5.0 3.9 2.2 Elastic modulus (GPa) 73.5 62 91 Molding temperature (°C) 1316 1350 1588 Liquidus temperature (°C) 1100 1200 1482 Dielectric constant (1 GHz) 7 4.8 5.3

[0007] Each of the above glass fibers fails to meet all the requirements in some important aspects. For example, the forming temperature and the liquidus temperature of E glass are low, but the CTE and the dielectric constant are unacceptable. The dielectric constant of L glass is low, but the CTE is unacceptable. The thermal expansion coefficient, elastic modulus, and dielectric constant of S glass fiber all meet the requirements, but the forming temperature and the liquidus temperature are very high, making production difficult.

[0008] Therefore, it is an urgent need to develop a glass fiber with a thermal expansion coefficient (CTE) of less than 3.5 ppm / ℃, a dielectric constant of less than 6 (1 GHz), a Young's modulus of more than 90 GPa, a forming temperature of less than 1400℃ during the production of the glass fiber, and a liquidus temperature of less than 50℃ below the forming temperature.

[0009] However, it is difficult to obtain a composition that satisfies both the physical properties and the forming properties of the glass fiber. For example, although increasing the content of SiO2 and Al2O3 in the composition can reduce the thermal expansion coefficient, the forming temperature is increased too high, and increasing the content of MgO and TiO2 can reduce the forming temperature, but the operation window (the difference between the forming temperature and the crystallization temperature) is less than 50℃, and the glass is very easy to crystallize during the drawing operation, causing the drawing operation to be unable to proceed normally. In order to solve the problem of crystallization, a certain amount of B2O3 is generally added to the formula, such as patent CN202110010612.9, but B2O3 is easy to cause environmental pollution.

[0010] Therefore, it is an urgent problem to develop a glass fiber formula with low thermal expansion coefficient, high elastic modulus, which is not easy to crystallize and does not contain B2O3, while meeting the requirements of various physical properties and forming properties. SUMMARY

[0011] Therefore, the technical problem to be solved by the present application is to provide a glass fiber and a preparation method and application thereof. The glass fiber has a lower forming temperature and a good temperature difference of drawing operation window.

[0012] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0013] The present application provides a kind of glass fiber, by SiO2, Al2O3, MgO, CaO, SrO, ZnO, NiO and TiO2 Reaction preparation obtains.

[0014] Preferably, the molar ratio of MgO, CaO, SrO, ZnO and NiO is 1:1:1:1:1.

[0015] Preferably, the sum of MgO, CaO, SrO, ZnO and NiO is 12mol% to 13mol%.

[0016] Preferably, the molar ratio of SiO2, Al2O3 and MgO is (67-68):(14-15):(2.4-2.6); more preferably, the molar ratio of SiO2, Al2O3 and MgO is (67.3-68):(14.5-15):(2.4-2.6).

[0017] In some embodiments of the present application, the molar ratio of SiO2, Al2O3 and 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.

[0018] Preferably, the molar ratio of SiO2 to TiO2 is (67-68):(3.5-4); more preferably, the molar ratio of SiO2 to TiO2 is (67.3-68):(3.5-4).

[0019] In some embodiments of the present application, the molar ratio of SiO2 to TiO2 is 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 present application, the molar ratio of SiO2 to MgO is preferably (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.

[0020] The forming temperature of the glass fiber of the present application is preferably 1365-1383°C.

[0021] This is because the present application simultaneously introduces five divalent metal oxides (MgO, CaO, SrO, ZnO, NiO) in the reaction raw material of the glass fiber, and the high-temperature viscosity of the glass liquid is significantly reduced under the synergistic reaction of MgO, CaO, SrO, ZnO, NiO and SiO2, Al2O3, TiO2, thereby reducing the forming temperature of the glass fiber.

[0022] However, if the proportions of the above-mentioned five oxides MgO, CaO, SrO, ZnO, NiO are not appropriate, the operation window temperature difference of the glass fiber in the drawing operation will be less than 50°C, resulting in crystallization, and in severe cases, the drawing operation cannot be carried out normally.

[0023] In the reaction raw material of the glass fiber of the present application, B2O3 does not need to be added additionally, and the drawing operation window temperature difference can also be controlled.

[0024] Preferably, the present application controls MgO:CaO:SrO:ZnO:NiO=1:1:1:1:1, so that in the preparation process of the glass fiber, both the forming temperature and the crystallization temperature can be reduced, thereby ensuring that the operation window temperature difference in the drawing operation is not less than 50°C.

[0025] In addition, the total amount of the five metal oxides of MgO, CaO, SrO, ZnO and NiO is controlled in the range of 12mol% to 13mol% at the same time, so that the coefficient of thermal expansion (CTE) of the prepared glass fiber is 3.37 to 3.49 ppm / ℃, the dielectric constant is 5.5 to 5.6 (1GHz), and the Young's elastic modulus is 91.4 to 92.8 GPa. In the main reaction raw materials of the glass fiber of the present application, strontium oxide belongs to the glass structure network outer oxide, which has the effect of reducing the high temperature viscosity of the glass, but at the same time can also increase the dielectric constant, the coefficient of thermal expansion and the elastic modulus.

[0026] In some embodiments of the present application, the content of strontium oxide is preferably 2.4mol% to 2.6mol%.

[0027] Zinc oxide belongs to the glass structure network outer oxide, which has the effect of reducing the high temperature viscosity and the coefficient of thermal expansion of the glass, but at the same time can also increase the dielectric constant and the elastic modulus. However, if the content of ZnO is too high, crystallization will occur during the glass forming, and if the content is too low, it will not be able to play a role in inhibiting crystallization.

[0028] In some embodiments of the present application, the content of zinc oxide is preferably 2.4mol% to 2.6mol%.

[0029] Nickel oxide belongs to the glass structure network outer oxide, which has the effect of reducing the high temperature viscosity and the coefficient of thermal expansion of the glass, but at the same time can also increase the dielectric constant and the elastic modulus. However, if the content of NiO is too high, crystallization will occur during the glass forming, and if the content is too low, it will not be able to play a role in inhibiting crystallization.

[0030] In some embodiments of the present application, the content of nickel oxide is preferably 2.4mol% to 2.6mol%.

[0031] In some embodiments of the present application, preferably, the content of SiO2 is selected from 67mol% or 67.3mol% or 67.5mol% or 67.8mol% or 68mol%.

[0032] Preferably, in some embodiments of the present application, the content of Al2O3 is selected from 14mol% or 14.5mol% or 14.8mol% or 15mol%.

[0033] Preferably, in some embodiments of the present application, 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 and NiO is 1:1:1:1:1, and the total amount of mass is 12mol% to 13mol%.

[0034] Preferably, in some embodiments of the present application, the content of TiO2 is selected from 3.5 mol% or 3.9 mol% or 4 mol%.

[0035] Preferably, in the present application, the glass fiber further comprises an impurity with a content of not more than 1 mol%.

[0036] The impurity is introduced by the main raw materials of the glass fiber, and has no decisive influence on the performance of the glass fiber.

[0037] The impurity can be trace elements such as Fe, Ti, Zn, Pb, Zr, Sr, etc., only with very low content (ppm level), so it does not affect the composition and performance.

[0038] In some embodiments of the present application, the raw materials of the glass fiber include any one of the following groups:

[0039] SiO2 67.5mol%, Al2O3 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, TiO2 4mol%, the balance being impurities;

[0040] SiO2 68mol%, Al2O3 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, TiO2 4mol%, the balance being impurities;

[0041] SiO2 67mol%, Al2O3 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, TiO2 4mol%, the balance being impurities;

[0042] SiO2 68mol%, Al2O3 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, TiO2 4mol%, the balance being impurities;

[0043] SiO2 67.5mol%, Al2O3 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, TiO2 4mol%, the balance being impurities;

[0044] SiO2 68mol%, Al2O3 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, TiO2 3.5mol%, the balance being impurities;

[0045] SiO2 68mol%, Al2O3 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, TiO2 4mol%, the balance being impurities;

[0046] SiO2 68mol%, Al2O3 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, TiO2 3.5mol%, the balance being impurities;

[0047] SiO2 67.8mol%, Al2O3 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, TiO2 3.9mol%, the balance being impurities;

[0048] SiO2 67.3mol%, Al2O3 14.8wt%, 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, TiO2 3.9mol%, the balance being impurities. The application also provides a method for preparing the above glass fiber, which comprises mixing raw materials and then preparing the glass fiber by a pool kiln method.

[0049] In the above preparation method, the raw materials include SiO2, Al2O3, MgO, CaO, SrO, ZnO, NiO and TiO2, and impurities with a content of no more than 1 mol%.

[0050] In the present application, preferably, the pool kiln method specifically comprises the following steps:

[0051] 1) After the raw materials are uniformly mixed, melting, refining and homogenizing are carried out in a pool kiln to obtain a glass liquid;

[0052] 2) The glass liquid obtained in step 1) is cooled to form a shape, and then glass filaments are prepared;

[0053] 3) The above glass filaments are drawn into glass filaments with a fixed diameter;

[0054] 4) The above glass filaments with a fixed diameter are wound into a cake, and after a post-processing procedure, glass fibers are prepared.

[0055] Preferably, in the above preparation method, the raw materials are first put into the pool kiln through a pool kiln bin. Preferably, the temperature for melting the raw materials in the pool kiln method is 1500-1700°C.

[0056] Then, the glass liquid obtained after melting, refining and homogenizing is cooled, flowed out, and subjected to a drawing treatment to obtain glass fibers.

[0057] The cooling treatment refers to cooling to form a shape.

[0058] The temperature for forming a shape is 1365-1383°C.

[0059] The flowing-out treatment preferably refers to flowing out the glass liquid after cooling to form a shape through a platinum-rhodium alloy bushing to form glass filaments.

[0060] Using the raw materials and the ratio according to the present application to prepare glass filaments can obtain glass filaments with a lower forming temperature and a good drawing operation window temperature difference, significantly reduce the cost, and be conducive to the industrialized production of glass fibers.

[0061] The drawing treatment preferably refers to drawing into glass filaments with a set diameter under the traction of a drawing machine.

[0062] Preferably, the diameter of the glass filaments in the pool kiln method is 3.5-25 μm.

[0063] Then, the prepared glass filaments are subjected to a post-processing to obtain a cake.

[0064] The post-processing includes spray cooling, coating with an infiltrant, bundling and then being wound by a drawing machine, etc.

[0065] Finally, the cake is processed to obtain the glass fibers according to the present application.

[0066] The processing includes twisting, weaving, surface treatment and the like.

[0067] The preparation method has good processability and operability, and the prepared glass fiber has good performance.

[0068] The application also provides the application of the glass fiber prepared by the preparation method in printed circuit boards and information technology parts.

[0069] The application also provides a composite material comprising the glass fiber prepared by the preparation method.

[0070] Compared with the prior art, the glass fiber prepared by the application is prepared by the reaction of SiO2, Al2O3, MgO, CaO, SrO, ZnO, NiO and TiO2. The five divalent metal oxides MgO, CaO, SrO, ZnO and NiO are introduced as reaction raw materials, and are cooperatively reacted with SiO2, Al2O3 and TiO2, so that the high-temperature viscosity of the glass liquid is significantly reduced, and the forming temperature of the glass fiber is reduced to 1365-1383 DEG C. Moreover, by controlling the molar ratio of MgO, CaO, SrO, ZnO and NiO to be 1:1:1:1:1, the forming temperature and the crystallization temperature of the glass fiber can be simultaneously reduced, the temperature difference of the drawing operation window is not less than 50 DEG C, and the industrial production and practical application of the glass fiber are more beneficial. DETAILED DESCRIPTION

[0071] In order to further illustrate the application, the glass fiber, the preparation method and the application thereof provided by the application are described in detail below in combination with examples.

[0072] The performance of the glass fiber is tested according to the following method:

[0073] After the raw materials of the glass fiber are uniformly mixed, they are loaded into a platinum crucible and placed in a high-temperature resistance furnace, and are kept at 1550-1600 DEG C for heat preservation. After being fully melted and clarified, the glass is quickly poured into a mold to form a circular glass sheet. The glass sheet is polished on both sides to obtain a test sample.

[0074] The dielectric constant of the sample is detected at room temperature at a frequency of 1GHz;

[0075] A high-temperature viscometer is used to detect the forming temperature;

[0076] A gradient crystallization furnace is used to test the liquidus temperature;

[0077] A thermal dilatometer is used to detect the thermal expansion coefficient between room temperature and 300 DEG C;

[0078] The elastic modulus is tested by a universal electronic testing machine. Examples 1-10

[0079] The raw materials are transported to a mixing tank, and after being mixed uniformly, the mixture is transported to a tank furnace bin. The content of each raw material is shown in Table 1.

[0080] The mixture in the tank furnace bin is put into the tank furnace. In the tank furnace, the mixture gradually melts into glass liquid at a high temperature of more than 1550°C, and after being clarified and homogenized, the stable and high-quality glass liquid enters a fiber drawing operation channel.

[0081] After the glass liquid in the fiber drawing operation channel is cooled to a forming temperature, it flows out through a platinum gauze, and is quickly pulled by a fiber drawing machine into glass filaments with a diameter of 3.5-25 μm. The glass filaments are sprayed and cooled, coated with an immersion agent, and bundled, and then are wound into a cake on the fiber drawing machine, which is a glass fiber precursor.

[0082] After the cake is twisted, woven, and surface treated, a glass fiber product is obtained.

[0083] The performance of the glass fiber is tested, and the results are shown in Table 1, which is the formula and performance test results of the glass fiber prepared in the examples.

[0084] Table 1 Formula and performance parameters of glass fibers in Examples 1-10

[0085]

[0086]

[0087] Comparative Examples 1-10

[0088] According to the formula shown in Table 2, the various raw materials are transported to a mixing tank, and after being mixed uniformly, the mixture is transported to a tank furnace bin. The content of each raw material is shown in Table 2.

[0089] The mixture in the tank furnace bin is put into the tank furnace. In the tank furnace, the mixture gradually melts into glass liquid at a high temperature of more than 1550°C, and after being clarified and homogenized, the stable and high-quality glass liquid enters a fiber drawing operation channel.

[0090] After the glass liquid in the fiber drawing operation channel is cooled to a forming temperature, it flows out through a platinum gauze, and is quickly pulled by a fiber drawing machine into glass filaments with a diameter of 3.5-25 μm. The glass filaments are sprayed and cooled, coated with an immersion agent, and bundled, and then are wound into a cake on the fiber drawing machine, which is a glass fiber precursor.

[0091] After the cake is twisted, woven, and surface treated, a glass fiber product is obtained, and the performance parameters are tested. Table 2 is the formula and performance parameters of the glass fibers in Comparative Examples 1-10.

[0092] Table 2 Formulation and performance parameters of glass fibers of comparative examples 1-10

[0093]

[0094]

[0095] From the above examples 1-10 and comparative examples 1-10, it can be seen that the glass fibers prepared in examples 1-10 of the present application have good processability, lower dielectric constant and thermal expansion coefficient, and higher elastic modulus. In addition, the drawing forming temperature of the glass fibers prepared in examples 1-10 of the present application is lower than 1383℃, and the difference between the forming temperature of the glass fibers and the liquidus temperature is not less than 50℃, which is beneficial to drawing operation. Therefore, the glass fibers provided by the present application can meet the needs of light and thin circuit boards in 5G communication.

[0096] The above examples are only used to help understand the method of the present application and its core idea. It should be pointed out that for ordinary skilled in the art, without departing from the principles of the present application, the present application can be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present application.

Claims

1. A glass fiber, characterized by, Prepared by reacting SiO2, Al2O3, MgO, CaO, SrO, ZnO, NiO and TiO2; The molar ratio of the MgO, CaO, SrO, ZnO and NiO is 1:1:1:1:1; The content of the MgO, CaO, SrO, ZnO and NiO is 12 mol%~13 mol% in total; The molar ratio of the SiO2, Al2O3 and MgO is (67~68):(14~15):(2.4~2.6); The molar ratio of the SiO2 and TiO2 is (67~68):(3.5~4).

2. The glass fiber according to claim 1, characterized in that The molar ratio of the SiO2, Al2O3 and MgO is (67.3~68):(14.5~15):(2.4~2.6); The molar ratio of the SiO2 and TiO2 is (67.3~68):(3.5~4).

3. The glass fiber of claim 1, wherein, The glass fiber further comprises impurities with content not more than 1 mol%.

4. The process for producing glass fibers according to any one of claims 1 to 3, characterized in that, The raw materials are mixed and then the glass fiber is prepared by a pool kiln method; The raw materials comprise SiO2, Al2O3, MgO, CaO, SrO, ZnO, NiO and TiO2, and impurities with content not more than 1 mol%.

5. The preparation method according to claim 4, characterized in that, The temperature for melting the raw materials in the pool kiln method is 1500℃~1700℃; The diameter of the glass fiber in the pool kiln method is 3.5~25 μm.

6. The application of the glass fiber of any one of claims 1~3 or the glass fiber prepared by the preparation method of any one of claims 4~5 in printed circuit boards, information technology components.

7. A composite material, characterized by The glass fiber of any one of claims 1~3 or the glass fiber prepared by the preparation method of any one of claims 4~5.

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