High-performance glass fiber composition and preparation method therefor

Abstract

The present invention provides a high-performance glass fiber composition and a method for preparing glass fibers by using same. The high-performance glass fiber composition comprises the following components in molar percentages: 61-67% of SiO2, 7.0-16.0% of B2O3, 0.1-16.0% of Al2O3, 3.0-12.5% of MgO, 0.02-9.0% of CaO, 0.01-5.0% of ZnO, 0.1-5.0% of ZrO2, 0.1-4.0% of TiO2, 0-3.0% of F2, and 0-4.0% of P2O5, wherein the contents of F2 and P2O5 are not both 0. In the present invention, a plurality of specific component oxides havinga high ionic field strength and a low polarizability are combined, and the proportion and addition amount of each component are controlled. In this way, the elastic modulus of the glass fibers is improved without increasing the dielectric constant and dielectric loss, while the processability of the glass fibers is maintained. Experiments have shown that the glass fibers have a dielectric constant of not more than 4.75, a dielectric loss of not more than 0.0035, and an elastic modulus of not less than 75 GPa.

Description

A high-performance glass fiber composition and its preparation method Technical Field

[0001] This invention relates to the field of glass fiber preparation technology, and in particular to a high-performance glass fiber composition and a method for preparing glass fibers using the same. Background Technology

[0002] Glass fiber possesses excellent electrical insulation and electromagnetic transparency. As a reinforcement in composite materials, it should also exhibit good mechanical properties to meet the stiffness design requirements of composite materials. Thin-walled radomes and printed circuit board substrates for high-frequency wave transmission require glass fiber with low dielectric constant and loss, while also demanding certain strength and modulus.

[0003] Currently, wave-transparent covers or substrates are commonly made of alkali-free (E), low-dielectric (D), high-strength (S), and quartz (Q) glass fibers. Among them, S glass fiber (silicon-aluminum-magnesium oxide system) has the highest mechanical properties, with an elastic modulus of 92 GPa. However, its dielectric constant and loss are relatively high. Under 10 GHz testing conditions, S-2 glass has a dielectric constant of 5.2, a dielectric loss of 0.0068, and an elastic modulus of 92 GPa. Low-dielectric glass fiber (silicon-boron-aluminum oxide system) has lower dielectric constant and loss. The dielectric constants are 4.8 and 0.0035, but the elastic modulus of glass is less than 70 GPa. Currently, the most widely used E glass fiber (silica-alkaline-alumina-boron oxide system) has a tensile modulus of 78 GPa for its fiber impregnated yarn, but its dielectric constant and loss are relatively high, at 6.2 and 0.0039, respectively. Quartz glass fiber (SiO2>99.98%) has the best dielectric properties among all glass fibers, with a dielectric constant and loss of 4.0 and 0.002, and an elastic modulus of 76 GPa, but quartz fiber is expensive.

[0004] Therefore, there is an urgent need to provide a high-performance glass fiber composition and a method for preparing glass fibers using the same. Summary of the Invention

[0005] This invention provides a high-performance glass fiber composition and a method for preparing glass fibers using the same, which can provide a multi-component glass fiber with excellent mechanical and dielectric properties, good operability, and suitability for large-scale production.

[0006] In a first aspect, the present invention provides a high-performance glass fiber composition, wherein, in molar percentage, the high-performance glass fiber composition comprises the following components: SiO2: 61-67%, B2O3: 7.0-16.0%, Al2O3: 0.1-16.0%, MgO: 3.0-12.5%, CaO: 0.02-9.0%, ZnO: 0-5.0%, ZrO2: 0.1-5.0%, TiO2: 0.1-4.0%, F2: 0-3.0%, and P2O5: 0-4.0%; wherein ZnO, F2, and P2O5 are not simultaneously 0.

[0007] Preferably, the high-performance glass fiber composition further comprises, by molar percentage: BaO: 0.01–4.0% and SrO: 0.01–5.0%.

[0008] Preferably, the high-performance glass fiber composition further comprises, by molar percentage, the following components: LiO2: 0.01-3% and Y2O3: 0.01-0.8%.

[0009] Preferably, M1 = SiO2 + B2O3, wherein, in molar percentage, 73% ≤ M1 ≤ 80%.

[0010] Preferably, M2 = MgO + CaO + BaO + SrO, wherein, in molar percentage, 8.0% ≤ M2 ≤ 16.0%.

[0011] Preferably, the ratio of B2O3 content to M2 content is 0.5 to 2.0 in molar percentage.

[0012] Preferably, M3 = (Al2O3 + M2) / M1, wherein, in molar percentage, 0.1% ≤ M3 ≤ 0.4%.

[0013] Preferably, M4 = ZrO2 + Y2O3 + TiO2, wherein, in molar percentage, 0.3% ≤ M4 ≤ 7.5%.

[0014] Preferably, M5 = P2O5 + F2, wherein, in molar percentage, 0.7% ≤ M5 ≤ 7.0%.

[0015] Preferably, the high-performance glass fiber composition comprises, by molar percentage, the following components: SiO2: 54–65.5%, B2O3: 8.0–16.0%, Al2O3: 0.1–10.5%, MgO: 3.0–12.0%, CaO: 0.05–8.5%, ZnO: 0.01%–3.8%, ZrO2: 0.5–4.5%, TiO2: 0.3–3.5%, F2: 0.5–4.0%, P2O5: 0.05–3.0%, BaO: 0.01–3.5%, SrO: 0.01–3.4%, LiO2: 0.01–2.0%, and Y2O3: 0.01–0.75%.

[0016] In a second aspect, the present invention provides a method for preparing high-performance glass fibers from the high-performance glass fiber composition described in any one of the first aspects above, the method comprising the following steps:

[0017] (1) Mix each component according to the molar percentage to obtain a high-performance glass fiber composition;

[0018] (2) The high-performance glass fiber composition is melted to obtain homogeneous glass;

[0019] (3) The homogeneous glass is drawn into fibers to obtain the high-performance glass fiber.

[0020] Compared with the prior art, the present invention has at least the following beneficial effects:

[0021] In this invention, a combination of various specific component oxides with high ionic field strength and low polarizability is used, and the proportion and amount of each component are controlled. In this way, the elastic modulus of glass fiber is improved without increasing the dielectric constant and dielectric loss, and the processing performance of glass fiber is guaranteed. Experiments show that the dielectric constant of glass fiber is not greater than 4.75, the dielectric loss is not greater than 0.0035, and the elastic modulus of glass is not less than 75 GPa. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] This invention provides a high-performance glass fiber composition, comprising the following components by molar percentage: SiO2: 61-67% (e.g., 61%, 62%, 63%, 64%, 65%, 66%, or 67%), B2O3: 7.0-16.0% (e.g., 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, or 16%), and Al2O3: 0.1-16.0% (e.g., 0.1%, 0.5%, or 1%). 0%, 2.0%, 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 11.0%, 12.0%, 13.0%, 14.0%, 15.0%, or 16.0%); MgO: 3.0–12.5% ​​(e.g., 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 11.0%, 12.0%, or 12.5%); CaO: 0.02–9.0% (e.g., 0.02%). 0.05%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 9%), ZnO: 0.01%–5.0% (e.g., 0.01%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, or 5.0%), ZrO2: 0.1%–5.0% (e.g., 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, or 5.0%), T iO2: 0.1–4.0% (e.g., 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, or 4.0%), F2: 0–3.0% (e.g., 0%, 0.01%, 0.5%, 1%, 1.5%, 2%, 2.5%, or 3%), P2O5: 0–4.0% (e.g., 0%, 0.01%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, or 4.0%); wherein, F 2 It is not 0 at the same time as P2O5.

[0024] In this embodiment of the invention, a combination of various specific component oxides with high ionic field strength and low polarizability is used, and the proportion and amount of each component are controlled. In this way, the elastic modulus of glass fiber is improved without increasing the dielectric constant and dielectric loss, and the processing performance of glass fiber is guaranteed. Experiments show that the dielectric constant of glass fiber is not greater than 4.75, the dielectric loss is not greater than 0.0035, and the elastic modulus of glass is not less than 75 GPa.

[0025] Meanwhile, in this embodiment of the invention, SiO2 and B2O3 are used as the main glass components. SiO2 can act as a network former for the glass structure. On the one hand, some B2O3 can form [BO4] tetrahedral structures and enter the glass silicon-oxygen network structure, thereby playing a role in network reinforcement. On the other hand, B2O3 can effectively suppress ion polarization, thereby reducing the dielectric constant and dielectric loss of the glass fiber. By adding specific types of oxides with high ion field strength and low polarizability, such as Al2O3, MgO, CaO, ZnO, ZrO2, TiO2, and F, 2 Along with P2O5, ZrO2 and TiO2, they form a network exosome in the glass structure. ZrO2 can increase the high-temperature viscosity of glass, improve its density and elastic modulus. ZrO2 has a lower polarizability than Al2O3, and its addition to glass helps to further reduce the dielectric constant and losses of glass fibers. Simultaneously, a certain amount of TiO2 can increase the density and modulus of glass fibers, and its increase in the dielectric constant of glass fibers is relatively slow compared to alkaline earth oxides. However, excessive amounts of TiO2 and ZrO2 not only increase costs but also result in excessively high glass viscosity, thereby reducing the glass's processing properties. Although Zn... 2+ The mass is greater than Mg 2+ and Ca 2+ However, due to its outermost shell having 18 electrons, its electron binding energy is high and its electron displacement polarization is small, which is beneficial for further reducing the dielectric constant and dielectric loss of glass fibers. Furthermore, in the embodiments of this invention, it was found that when Mg... 2+ Ca 2+ and Zn 2+ When incorporated into glass, these composites exhibit a synergistic effect, further reducing the dielectric constant and dielectric loss of the glass fibers. When there are sufficient ions in the glass, the Al in Al₂O₃... 3+ [AlO4] tetrahedra can enter the glass network structure, which can enhance the densification of the glass network structure, reduce the phase separation tendency of the glass, inhibit the formation of crystal nuclei and improve the forming process performance of the fiber, as well as improve the mechanical properties, dielectric properties and chemical corrosion resistance of the glass fiber. However, excessive Al2O3 introduction will not only lead to a large number of network exosomes, resulting in excessively high glass melting temperature and enhanced crystallization tendency, but also lead to problems such as increased dielectric constant and dielectric loss of glass fiber.

[0026] In this embodiment of the invention, by synergistically controlling the various components, it is not only beneficial to enhance the processing performance of the glass and make the glass fiber have better drawing stability, but also to improve the elastic modulus of the glass without increasing the dielectric constant and dielectric loss, so that the prepared glass fiber has both excellent dielectric and mechanical properties.

[0027] According to some preferred embodiments, the high-performance glass fiber composition further comprises, in molar percentage, the following components: BaO: 0.01 to 4.0% (e.g., 0.01%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, or 4.0%), and SrO: 0.01 to 5.0% (e.g., 0.01%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 4%, or 5.0%).

[0028] In this embodiment of the invention, the inventors discovered that adding Mg alone... 2+ Ca 2+ Ba 2+ 、Sr 2+ The content of alkaline earth metal oxides increases the dielectric constant, ionic polarizability, and dielectric constant of glass fibers. However, when multiple alkaline earth ions are present, a blocking effect similar to the mixed alkali effect hinders ion vibration or relaxation, slowing down and decreasing the increase in dielectric loss. Therefore, in this embodiment of the invention, BaO and SrO are added to CaO and MgO to form multiple alkaline earth metal oxides, which not only helps to further reduce the dielectric constant of glass fibers but also improves their elastic modulus. Furthermore, the inventors have found that increasing the content of alkaline earth metal oxides is beneficial to increasing the elastic modulus of glass fibers, and MgO has a more significant effect on the elastic modulus. Therefore, controlling the molar percentage of MgO to be greater than the sum of the molar percentages of the other three alkaline earth metal oxides helps to ensure good elastic modulus and processing performance of glass fibers while maintaining low dielectric loss and dielectric constant.

[0029] According to some preferred embodiments, the high-performance glass fiber composition further comprises, in molar percentage, the following components: LiO2: 0.01-3% (e.g., 0.01%, 0.05%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, or 3%), Y2O3: 0.01-0.8% (e.g., 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, or 0.8%).

[0030] In this embodiment of the invention, the high-performance glass fiber composition further includes a certain amount of LiO2 and Y2O3. Li2O can lower the melting temperature of the glass and the forming temperature of the fiber, improving the thermal stability of the glass. Simultaneously, Li2O can act as a flux, lowering the melting temperature of the glass, improving production efficiency, and aiding in the formation of the desired glass structure. Furthermore, the addition of an appropriate amount of Li2O can further reduce the dielectric constant of the glass, improving its dielectric properties. Meanwhile, the addition of Y2O3 can aggregate the non-bridging oxygen in the Si-O bonds, making the network structure more compact. At the same time, an appropriate amount of Y2O3 also helps to reduce the dielectric constant and dielectric loss of the glass fiber; excessive introduction not only increases costs but also reduces its effect on optimizing the dielectric properties of the glass.

[0031] According to some preferred embodiments, M1 = SiO2 + B2O3, wherein, in molar percentage, 73% ≤ M1 ≤ 80%.

[0032] In this embodiment of the invention, considering that SiO2 can form a network structure of glass using silicon-oxygen tetrahedra, this network structure has strong mechanical strength and high bond strength, making it less prone to polarization under an external electric field. Consequently, it exhibits low conductivity and relaxation losses at high frequencies. Therefore, increasing the SiO2 content can reduce the dielectric constant and dielectric loss of the glass fiber. However, excessively high SiO2 content leads to excessively high glass viscosity, making glass melting and fiber forming difficult. It also results in a larger network space volume that is easily deformed, thus reducing the elastic modulus of the glass.

[0033] A certain amount of B2O3 can lower the liquidus temperature of glass, which helps to increase the forming temperature range of glass fibers. When there is sufficient free oxygen, some B2O3 forms a [BO4] tetrahedral structure and enters the glass silicon-oxygen network structure, thus playing a role in network reinforcement. Simultaneously, on the one hand, the BO bond energy is larger than the Si-O bond energy, which can effectively suppress ion polarization in the glass structure, thereby reducing the dielectric constant and dielectric loss of the glass fibers; on the other hand, the presence of B2O3 allows more B... 3+ B2O3 exists in the form of [BO3] triangles, forming a layered structure. This structure has weak coupling, which can reduce the high-temperature viscosity of glass, thus benefiting glass melting and refining. However, the addition of B2O3 can reduce the rigidity of the glass network, thereby reducing the elastic modulus of the glass. Therefore, the content of B2O3 needs to be precisely controlled.

[0034] Furthermore, experimental verification revealed that the dielectric constant of glass fiber is mainly affected by the total ionic polarizability and the number of ions per unit volume. Generally, the dielectric constant increases with the increase of the total polarizability of positive and negative ions in the glass, and decreases with the increase of the molar volume. SiO2 and B2O3 have lower polarizability and higher molar volume; increasing the concentration of SiO2 and B2O3 helps to reduce the dielectric constant of the glass. However, the elastic modulus of the glass increases with the increase of the ionic field strength and the molar volume, showing the opposite trend to the dielectric constant. Therefore, in this embodiment of the invention, controlling the total molar percentage of SiO2 and B2O3 within a reasonable range is beneficial for balancing the dielectric and mechanical properties of the glass fiber while ensuring good processability.

[0035] According to some preferred embodiments, M2 = MgO + CaO + BaO + SrO, wherein, in molar percentage, 8.0% ≤ M2 ≤ 16.0%.

[0036] In this embodiment of the invention, the addition of alkaline earth metal oxides is beneficial to improving the dielectric constant and ionic polarizability of glass fibers, thereby increasing the dielectric constant. However, when multiple alkaline earth ions are present, due to the blocking effect similar to the mixed alkali effect, ion vibration or relaxation is hindered, the increase in dielectric loss slows down and shows a decreasing trend. Furthermore, the increase of multiple alkaline earth oxides is beneficial to increasing the elastic modulus of the glass, but excessive alkaline earth oxide content will be detrimental to the reduction of the dielectric constant. Therefore, in this embodiment of the invention, by controlling the total amount of alkaline earth metals, it is beneficial to ensure that the glass fibers have both good dielectric properties and elastic modulus.

[0037] According to some preferred embodiments, the ratio of B2O3 content to M2 content is 0.5 to 2.0 in molar percentage.

[0038] In this embodiment of the invention, a certain amount of B2O3 can lower the liquidus temperature of the glass, which helps to increase the glass fiber forming temperature range. When there is sufficient free oxygen, some B2O3 forms a [BO4] tetrahedral structure and enters the glass silicon-oxygen network structure, thereby playing a role in network reinforcement. Furthermore, the BO bond energy is larger than the Si-O bond energy, which can effectively suppress ion polarization in the glass structure, thereby reducing the dielectric constant and dielectric loss of the glass fiber. However, excessive B2O3 content will lead to a decrease in the elastic modulus of the glass. Therefore, the ratio of B2O3 content to M2 is controlled to be 0.5 to 2.0.

[0039] According to some preferred embodiments, M3 = (Al2O3 + M2) / M1, wherein, in molar percentage, 0.1% ≤ M3 ≤ 0.4%.

[0040] In this embodiment of the invention, Al in Al2O3 3+Al2O3 can enter the glass network structure as [AlO4] tetrahedra, enhancing the densification of the glass network structure, reducing the tendency of glass phase separation, suppressing crystal nucleation and improving the forming process performance of fibers, as well as improving the mechanical properties, dielectric properties and chemical corrosion resistance of glass fibers. However, excessive Al2O3 introduction not only leads to a large number of network exosomes, resulting in excessively high glass melting temperature and enhanced crystallization tendency, but also causes problems such as increased dielectric constant and dielectric loss of glass fibers. The addition of alkaline earth metal oxides is beneficial to improving the dielectric constant and ionic polarizability of glass fibers, thereby increasing the dielectric constant. However, in the embodiments of this invention, it was found that when at least two alkaline earth metal oxides are present, the increase in dielectric constant and dielectric loss of glass fibers can be slowed down and show a decreasing trend. Therefore, in the embodiments of this invention, by adding appropriate amounts of BaO, SrO, CaO and MgO, it is beneficial to further reduce the dielectric loss and dielectric constant of glass fibers. Meanwhile, magnesium oxide has a significant effect on the elastic modulus of glass, but excessive amounts can cause phase separation in the glass. Therefore, it is necessary to adjust the value of (Al2O3+M2) / M1 to relatively increase the elastic modulus of the glass while ensuring low dielectric constant and loss.

[0041] According to some preferred embodiments, M4 = ZrO2 + Y2O3 + TiO2, wherein, in molar percentage, 0.3% ≤ M4 ≤ 7.5%.

[0042] In this embodiment of the invention, since TiO2, ZrO2, and Y2O3 are all network exogenous substances in the glass structure, their addition to the glass composition can enhance the elastic modulus of the glass structure in different ways and reduce the dielectric constant and dielectric loss of the glass fibers. By controlling the total molar percentage of these three substances, it is beneficial to better regulate the elastic modulus and dielectric properties of the glass fibers while ensuring good processing performance. However, if the content of these three substances is too high, it will not only increase the high-temperature viscosity of the glass and reduce its processing performance, but also reduce its effect on optimizing the dielectric properties of the glass.

[0043] According to some preferred embodiments, M5 = P2O5 + F2, wherein, in molar percentage, 0.7% ≤ M5 ≤ 7.0%.

[0044] To avoid the adverse effects of adding alkaline earth metal oxides and high-valence oxides on the dielectric properties of glass fibers, a certain amount of F was added to the glass composition in this embodiment of the invention. 2 (in fluoride form) and P2O5. Due to F - Ions can combine with cations, reducing the ionic radius and polarizability, which helps to further reduce the dielectric constant and dielectric loss of glass fibers. For example, when Li... + or Mg 2+isocations and F - After combining, the polarizability is lower than that of these ions with O. 2- The combined polarizability, with its lower polarizability, helps to further ensure the glass fiber's lower dielectric constant and loss. Furthermore, fluorides can effectively reduce the high-temperature viscosity of the glass melt, thereby lowering the drawing temperature and improving the drawing process performance. Introducing an appropriate amount of P2O5 into silicate glass helps to reduce the non-bridging oxygen number and aggregate the network structure, and also helps to reduce the glass's dielectric constant. Further limiting the total content of both helps to further ensure the glass fiber's good processing performance and dielectric properties.

[0045] It should be noted that, provided that SiO2, B2O3, P2O5, F2, MgO, CaO, BaO, SrO, ZrO2, and Y2O3 are within their respective ranges, the values ​​of M1, M3, M2, and M4 can be any value within the aforementioned range.

[0046] According to some preferred embodiments, the high-performance glass fiber composition comprises the following components in molar percentage:

[0047] SiO2: 61-65.5% (e.g., 61%, 62%, 63%, 64%, 65%, or 65.5%), B2O3: 8.0-16.0% (e.g., 8.0%, 9.0%, 10.0%, 11.0%, 12.0%, 13.0%, 14.0%, 15.0%, or 16.0%), Al2O3: 0.1-10.5% (e.g., 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10.5%), MgO: 3.0-12.0% (e.g., 3.0%, 4.0%, 5.0%, 6.0%). % (7.0%, 8.0%, 9.0%, 10.0%, 11.0%, or 12.0%), CaO: 0.05–8.5% (e.g., 0.02%, 0.05%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, or 8.5%), ZnO: 0.01%–3.8% (e.g., 0.01%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, or 3.8%), ZrO2: 0.5–4.5% (e.g., 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%), 3.5%, 4.0%, or 4.5%), TiO2: 0.3–3.5% (e.g., 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, or 3.5%), F2: 0.5–3.0% (e.g., 0.5%, 1%, 1.5%, 2%, 2.5%, or 3%), P2O5: 0.05–3.0% (e.g., 0.05%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, or 3.0%), BaO: 0.01–3.5% (e.g., 0.01%, 0.1%, 0.5%, 1.0%, 1.5%). 5%, 2.0%, 2.5%, 3.0% or 3.5%); SrO: 0.01 to 3.5% (e.g., 0.01%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0% or 3.5%); LiO2: 0.01 to 2.0% (e.g., 0.01%, 0.05%, 0.1%, 0.5%, 1.0%, 1.5% or 2.0%); Y2O3: 0.01 to 0.75% (e.g., 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7% or 0.75%).

[0048] In this embodiment of the invention, through extensive experimental screening and data summarization, it was found that by using a variety of component oxides with specific types of high ionic field strength and low polarizability and controlling their proportion and addition amount, a suitable positive aggregation effect can be achieved. This is beneficial to enhance the elastic modulus of glass fibers without increasing the dielectric constant and dielectric loss, and the glass fiber drawing process is more stable, exhibiting excellent processing performance.

[0049] It should be noted that the unavoidable impurities in this invention are Na2O, K2O and Fe2O3 introduced from the raw materials, and the total content of such substances should be controlled within 0.3%.

[0050] The present invention also provides a method for preparing low-dielectric glass fibers from the high-performance glass fiber composition described in any one of the above claims, the method comprising the following steps:

[0051] (1) Mix each component according to the molar percentage to obtain a high-performance glass fiber composition;

[0052] (2) The high-performance glass fiber composition is melted to obtain homogeneous glass;

[0053] (3) The homogeneous glass is drawn into fibers to obtain the high-performance glass fiber.

[0054] In this embodiment of the invention, the raw materials for low-dielectric glass fibers are obtained by optimizing and controlling the content of each component. During the preparation process, the raw materials can be melted into a glassy state, water-quenched, and then added to a platinum crucible for fiber drawing, thereby preparing high-performance glass fibers. It should be noted that SnO2 or CeO2 can be used as a clarifying agent in the glass melting process, and the content of a single or combined clarifying agent must not exceed 0.5%.

[0055] The low-dielectric glass fiber in this embodiment of the invention has low dielectric properties and high elastic modulus. At 10 GHz, the dielectric loss of the glass fiber is not greater than 0.0035, the dielectric constant is not greater than 4.75, and the elastic modulus is not less than 75 GPa. Furthermore, the composition formed by the above components is easy to form into glass fibers, and the forming window temperature is not less than 50°C.

[0056] It should be noted that, in the embodiments of the present invention, during melting, the furnace can be used for melting in an oxygen-based combustion process, an electric melting process, or a combination of thermal and electric methods to form homogeneous glass. Furthermore, the furnace used for melting the glass can be a melting furnace composed of refractory materials that are resistant to high temperatures and erosion by molten glass, such as electrically fused high-zirconium bricks, dense zirconium bricks, and electrically fused mullite bricks. Simultaneously, a platinum-platinum furnace constructed with refractory materials such as dense zirconium bricks, corundum bricks, electrically fused chromium-zirconium corundum bricks, and mullite can be used for fiber drawing production. That is, glass is first melted using the high-performance glass fiber composition of the present invention, and then glass fibers are drawn from the glass, or a one-step fiber drawing process can be performed using a furnace passage constructed with the aforementioned refractory materials.

[0057] The high-performance glass fiber composition in the embodiments of the present invention has a high melting temperature and fiber forming temperature. Therefore, it is necessary to use a melting furnace and platinum substitute furnace or one-step tank furnace constructed with refractory materials that are resistant to high temperature and glass melt erosion for glass melting and fiber preparation.

[0058] This invention also provides an application in any of the above-described low-dielectric glass fiber high-frequency circuit boards.

[0059] The high-performance glass fiber prepared in this invention can be used in radar domes and in the electronics industry to manufacture copper-clad laminates, printed circuit boards, etc. Due to its low dielectric constant and low dielectric loss, it helps improve signal transmission speed and efficiency in high-speed data transmission and high-frequency circuit boards. In the aerospace field, low-dielectric glass fiber can be used to manufacture lightweight and high-strength structural components. Low-dielectric glass fiber is an indispensable engineering material in high-end communications, aerospace, and other fields.

[0060] To more clearly illustrate the technical solution and advantages of the present invention, the following detailed description of a high-performance glass fiber composition and a method for preparing glass fibers using the same is provided through several embodiments.

[0061] Calculate the required mass percentage of each raw material in Examples 1-13 and Comparative Examples 1-2 according to the raw material composition listed in Table 1. After accurate weighing, mix them evenly to prepare the raw materials. Mix them pneumatically and convey them to the furnace feeding port. Feed them using an automatic feeder. Melt the glass at around 1600℃ in a furnace using either all-electric melting or a combination of thermal and electric melting to obtain clear and homogenized molten glass. Prepare glass spheres from the molten glass. Then, remelt the molten glass spheres at 1550℃. Using a spinneret of 400 or higher, control the glass fiber forming process parameters (liquid level, hot spot temperature, spinneret temperature, drawing machine speed, etc.) to draw them into continuous glass fibers with a diameter of 8-22μm. Perform performance tests on the fibers. The results are shown in Table 1.

[0062] Table 1

[0063] Glass density was tested according to GB / T 5432 "Determination of Glass Density - Buoyancy Method". Liquidation temperature was determined using a gradient crystallization temperature test furnace, referencing ASTM C829. The sample was placed in a platinum boat and then in the furnace at 1400℃ for 2 hours. The crystallization location was observed, and the upper limit temperature for crystallization was calculated based on the temperature gradient. High-temperature viscosity was determined using a Brookfield high-temperature viscometer (ASTM C965). Specifically, the sample was placed in a platinum crucible and then in a furnace at 1500℃. The rotor was then immersed in the high-temperature molten glass and held for 1 hour. The high-temperature viscosity of the molten glass was measured by the rotor's torque. Elastic modulus was tested using the ultrasonic echo method on a glass block. By measuring the propagation rate of elastic waves in the solid sample, and based on the theory of elastic wave propagation in solids, the propagation rate of different modes of sound waves in a solid is related to the corresponding elastic modulus and density of the material, thus calculating the elastic modulus of the glass fiber.

[0064] As shown in Table 1, the low-dielectric glass fiber prepared using the optimized raw material composition and content combination in this invention not only has good processing performance, but also has high elastic modulus and good dielectric properties.

[0065] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high-performance glass fiber composition, characterized in that, The high-performance glass fiber composition comprises the following components by molar percentage: SiO2: 61-67%, B2O3: 7.0-16.0%, Al2O3: 0.1-16.0%, MgO: 3.0-12.5%, CaO: 0.02-9.0%, ZnO: 0.01-5.0%, ZrO2: 0.1-5.0%, TiO2: 0.1-4.0%, F2: 0-3.0%, and P2O5: 0-4.0%; wherein F2 and P2O5 are not both 0.

2. The high-performance glass fiber composition according to claim 1, characterized in that, The high-performance glass fiber composition further comprises, by molar percentage: BaO: 0.01–4.0% and SrO: 0.01–5.0%.

3. The high-performance glass fiber composition according to claim 2, characterized in that, The high-performance glass fiber composition further comprises, by molar percentage, the following components: LiO2: 0.01–3% and Y2O3: 0.01–0.8%.

4. The high-performance glass fiber composition according to claim 1, characterized in that, M1 = SiO2 + B2O3, where, in molar percentage, 73% ≤ M1 ≤ 80%.

5. The high-performance glass fiber composition according to claim 2, characterized in that, M2 = MgO + CaO + BaO + SrO, where, in molar percentage, 8.0% ≤ M2 ≤ 16.0%.

6. The high-performance glass fiber composition according to claim 5, characterized in that, The ratio of B2O3 content to M2 is 0.5 to 2.0 in molar percentage.

7. The high-performance glass fiber composition according to claim 6, characterized in that M3 = (Al2O3 + M2) / M1, where, in molar percentage, 0.1% ≤ M3 ≤ 0.4%.

8. The high-performance glass fiber composition according to claim 3, characterized in that, M4 = ZrO2 + Y2O3 + TiO2, where, in molar percentage, 0.3% ≤ M4 ≤ 7.5%.

9. The high-performance glass fiber composition according to claim 1, characterized in that, M5 = P2O5 + F2, where, in molar percentage, 0.7% ≤ M5 ≤ 7.0%.

10. The high-performance glass fiber composition according to any one of claims 1 to 9, characterized in that, The high-performance glass fiber composition comprises, by molar percentage, the following components: SiO2: 54–65.5%, B2O3: 8.0–16.0%, Al2O3: 0.1–10.5%, MgO: 3.0–12.0%, CaO: 0.05–8.5%, ZnO: 0.01%–3.8%, ZrO2: 0.5–4.5%, TiO2: 0.3–3.5%, F 2 : 0.5~4.0%, P2O5: 0.05~3.0%, BaO: 0.01~3.5%, SrO: 0.01~3.4%, LiO2: 0.01~2.0%, Y2O3: 0.01~0.75%.

11. A method for preparing high-performance glass fibers from a high-performance glass fiber composition according to any one of claims 1 to 10, characterized in that, The method includes the following steps: (1) Mix each component according to the molar percentage to obtain a high-performance glass fiber composition; (2) The high-performance glass fiber composition is melted to obtain homogeneous glass; (3) The homogeneous glass is drawn into fibers to obtain the high-performance glass fiber.

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