Glass composition and glass fiber

Abstract

The present invention provides a glass composition that can impart a high Young's modulus to glass fibers and has a wide window for glass fiber spinning and molding operations. [Solution] The glass composition, with a total amount of 100 wt%, contains 56-66 wt% SiO2, 15-22 wt% Al2O3, 0.1-3.5 wt% CaO, 10-18 wt% MgO, more than 0 wt% and less than 2.5 wt% ZnO, more than 0 wt% and less than 1 wt% CuO, and 4-6 wt% B2O3, and [(CaO content + MgO content) / SiO2 content] + {[(CaO content) 2 [+MgO content] / [Al2O3 content+(ZnO content)] 2 The ratio is 0.70 to 1.35. The present invention also provides glass fibers containing the glass composition. The glass composition of the present invention can impart a high Young's modulus property to glass fibers and has a wide glass fiber spinning and molding work window.

Description

Technical Field

[0001] The present invention relates to a glass composition and glass fiber, and particularly to a glass composition having a high Young's modulus and a wide range of glass fiber spinning and forming operation windows, and glass fiber containing the glass composition.

Background Art

[0002] Chinese Patent Publication No. 103339076 discloses a glass fiber suitable for a reinforcing material of a printed circuit board and a glass fiber fabric composed of the glass fiber. The glass fiber contains 56.0 to 62.5 wt% of SiO2, 15.5 to 24.5 wt% of Al2O3, 0.1 to 4.0 wt% of CaO, 6.0 to 14.0 wt% of MgO, 3.0 to 9.0 wt% of ZnO, and 0.5 to 4.5 wt% of B2O3. The total content of SiO2, Al2O3, CaO, MgO, ZnO, and B2O3 is 99.0 wt% or more, and the total content of ZnO and B2O3 is 4.5 to 13.0 wt%, and the weight ratio of MgO / CaO is 3.0 or more. In the design of the above components and contents, the glass fiber has a high elastic modulus and a low thermal expansion coefficient.

[0003] Although the glass fiber has the characteristics of a high elastic modulus and a low thermal expansion coefficient, when manufacturing a glass fiber having a high elastic modulus, the temperature at which the melt viscosity of the glass composition used to manufacture the glass fiber is 1000 poise is excessively high, there are problems such as rapid equipment wear, short equipment service life, and high energy consumption. In addition, there are problems such as an excessively narrow glass fiber spinning and forming operation window, easy crystallization, and poor glass fiber quality, and the work operability and production capacity are limited.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

[0005] Therefore, one object of the present invention is to provide a glass composition that can impart the property of a high Young's modulus to glass fibers and has a wide window for glass fiber spinning and molding operations. [Means for solving the problem]

[0006] The glass composition of the present invention, with the total amount of the glass composition being 100 wt%, contains 56-66 wt% SiO2, 15-22 wt% Al2O3, 0.1-3.5 wt% CaO, 10-18 wt% MgO, more than 0 wt% and less than 2.5 wt% ZnO, more than 0 wt% and less than 1 wt% CuO, and 4-6 wt% B2O3, and [(CaO content + MgO content) / SiO2 content] + {[(CaO content) 2 [+MgO content] / [Al2O3 content+(ZnO content)] 2 The value of ]} is between 0.70 and 1.35.

[0007] Another object of the present invention is to provide glass fibers having a high Young's modulus.

[0008] The glass fiber of the present invention comprises the glass composition described above. [Effects of the Invention]

[0009] The effects of the present invention are that, by combining the above-mentioned components and their content, the glass composition has a Young's modulus of 90 GPa or higher, and at the same time, when manufacturing the glass fibers, the temperature at which the melt viscosity of the glass composition is 1000 poise is 1360°C or lower, thereby reducing equipment wear and energy consumption. Furthermore, because the difference between the temperature at which the melt viscosity of the glass composition is 1000 poise and the devitrification temperature is 100°C or higher, the glass fiber spinning and molding work window is wider, resulting in improved production capacity, reduced crystallization of the glass fibers, and the ability to manufacture high-quality glass fibers. [Modes for carrying out the invention]

[0010] The glass composition of the present invention, with a total amount of 100 wt% of the glass composition, contains 56-66 wt% SiO2, 15-22 wt% Al2O3, 0.1-3.5 wt% CaO, 10-18 wt% MgO, more than 0 wt% and less than 2.5 wt% ZnO, more than 0 wt% and less than 1 wt% CuO, and 4-6 wt% B2O3, where [(CaO content + MgO content) / SiO2 content] + {[(CaO content) 2 [+MgO content] / [Al2O3 content+(ZnO content)] 2 The value of ]} is between 0.70 and 1.35.

[0011] The present invention will be described in detail below. In some embodiments of the present invention, [(CaO content + MgO content) / SiO2 content] + {[(CaO content) 2 [+MgO content] / [Al2O3 content+(ZnO content)] 2 ]} is between 0.75 and 1.24.

[0012] SiO2 is the main component of the glass composition. The SiO2 has a three-dimensional network structure, and the basic structural unit of the three-dimensional network structure is a lattice structure of a tetrahedral skeleton of SiO4. SiO2 contributes to improving the mechanical strength (e.g., Young's modulus) of the glass composition, but if the SiO2 content exceeds 66%, the glass composition will have an excessively high viscosity, leading to increased production costs. In some embodiments of the present invention, the SiO2 content is 60-66 wt% when the total amount of the glass composition is 100 wt%. In some embodiments of the present invention, the SiO2 content is 60-64 wt% when the total amount of the glass composition is 100 wt%.

[0013] Al2O3 can bond with some of the oxygen atoms in the three-dimensional network structure of SiO2 to form bridging oxygen, improving the thermal stability and viscosity of the glass composition. However, if the aluminum oxide content exceeds 22 wt%, the glass composition will have an excessively high viscosity, requiring the glass fiber to be manufactured at a higher temperature, leading to increased production costs. In some embodiments of the present invention, the Al2O3 content is 16-22 wt% when the total amount of the glass composition is 100 wt%. In some embodiments of the present invention, the Al2O3 content is 16-20 wt% when the total amount of the glass composition is 100 wt%.

[0014] MgO can reduce the viscosity of the glass composition, contribute to the sufficient melting of the glass composition during the thermal process, and contribute to improving the mechanical strength of the glass fibers formed by the glass composition. In some embodiments of the present invention, the MgO content is 12-18 wt% when the total amount of the glass composition is 100 wt%. In some embodiments of the present invention, the MgO content is 12-14 wt% when the total amount of the glass composition is 100 wt%.

[0015] CaO can reduce the viscosity of the glass composition and contribute to the complete melting of the glass composition during the thermal process. In some embodiments of the present invention, the CaO content is 0.1 to 2.5 wt% when the total amount of the glass composition is 100 wt%. In some embodiments of the present invention, the CaO content is 0.4 to 2.5 wt% when the total amount of the glass composition is 100 wt%.

[0016] ZnO contributes to reducing the viscosity of the glass composition, which is advantageous for melting the glass composition, and also makes the glass composition less susceptible to crystallization during the glass fiber manufacturing process, thereby providing good spinnability. In some embodiments of the present invention, the ZnO content is 0.1 to 2 wt% when the total amount of the glass composition is 100 wt%.

[0017] CuO contributes to making the glass composition less susceptible to crystallization during the manufacturing process of the glass fibers, thereby providing good spinnability. In some embodiments of the present invention, the CuO content is greater than 0 wt% and less than or equal to 0.1 wt%, with the total amount of the glass composition being 100 wt%.

[0018] B2O3 contributes to reducing the viscosity of the glass composition, which is advantageous for melting the glass composition, and also makes the glass composition less susceptible to crystallization during the glass fiber manufacturing process, thereby providing good spinnability. In some embodiments of the present invention, the B2O3 content is 4 to 5.8 wt% when the total amount of the glass composition is 100 wt%.

[0019] In some embodiments of the present invention, the glass composition of the present invention further includes a dopant component, and the dopant component includes at least one dopant. The dopant is, for example, sodium oxide, potassium oxide, ferric oxide, titanium dioxide, etc., but is not limited thereto. In some embodiments of the present invention, the dopant component includes at least one dopant selected from the group consisting of sodium oxide, potassium oxide, ferric oxide, and titanium dioxide. In some embodiments of the present invention, with the total amount of the glass composition being 100 wt%, the content of the dopant component is more than 0 wt% and not more than 1.2 wt%.

[0020] The sodium oxide and the potassium oxide improve the acid resistance of the glass fiber obtained from the glass composition, reduce the melting point of the glass composition, and contribute to manufacturing the glass fiber at a lower temperature. However, when the content of the sodium oxide or the potassium oxide is excessive, the chemical stability of the glass fiber is reduced, resulting in a reduction in electrical insulation and mechanical strength. In one embodiment of the present invention, the sodium oxide content relative to 100% by weight of the total amount of the glass composition is greater than 0% by weight and less than 0.5% by weight, and the potassium oxide content is greater than 0% by weight and less than 0.5% by weight.

[0021] The ferric oxide can improve the stability when the glass composition performs manufacturing processes such as melting and spinning. However, when the content of ferric oxide is excessive, a problem of temperature non-uniformity occurs when the glass composition is melted. In one embodiment of the present invention, the content of ferric oxide relative to 100% by weight of the total amount of the glass composition is greater than 0% by weight and less than 1% by weight.

[0022] The titanium dioxide can improve the mechanical strength of the glass composition. However, when the content of the titanium dioxide is excessive, a precipitation crystallization phenomenon occurs in the process of forming the glass fiber from the glass composition, which is disadvantageous to the glass fiber spinning and forming operation. In one embodiment of the present invention, the titanium dioxide content relative to 100% by weight of the total amount of the glass composition is greater than 0% by weight and less than 1.2% by weight.

[0023] <Glass fiber> The glass fiber includes a glass composition. Since the glass composition is as described above, repeated description is omitted.

[0024] The present invention will be further illustrated by the following embodiments, but it should be understood that these embodiments are for illustrative purposes only and should not be construed as limitations on the implementation of the present invention.

[0025] <Example 1> A glass composition is obtained by mixing 60.0 wt% SiO2, 19.1 wt% Al2O3, 0.4 wt% CaO, 12.3 wt% MgO, 2.0 wt% ZnO, 0.1 wt% CuO, 5.0 wt% B2O3, and 1.1 wt% dopant (derived from impurities contained in each of the above components, including Na2O, K2O, Fe2O3, and TiO2). The glass composition is placed in a high-temperature furnace and heated at a temperature of 1500°C to 1600°C for 1 to 4 hours to obtain a completely molten glass liquid. Next, the glass liquid is poured into a graphite crucible with a diameter of 40 mm, and then placed in an annealing furnace preheated to 800°C and cooled to 25°C to obtain a glass block.

[0026] <Examples 2-6 and Comparative Examples 1-10> The manufacturing methods for Examples 2-6 and Comparative Examples 1-10 are generally the same as those for Example 1, with the only difference being the change in the content of each component. Please refer to Tables 1 and 2.

[0027] <Evaluation Criteria> The following tests will be performed on the glass blocks of Examples 1-6 and Comparative Examples 1-10. For clarity, the test procedures for the following test items will be described using the glass block of Example 1 as a representative example.

[0028] Measurement of the spinning window (ΔT): A 2.25 gram glass block from Example 1 is placed in a high-temperature furnace, and the furnace is heated to a specific temperature and maintained for 2 hours. Next, the glass block is removed from the high-temperature furnace and allowed to cool to room temperature, and it is observed whether or not crystals are present in the glass block. If they are present, the specific temperature is the devitrification temperature of the glass from Example 1. The spinning window (ΔT, in °C) of the glass composition from Example 1 is obtained by subtracting the devitrification temperature from the temperature at which the viscosity of the glass composition from Example 1 is 1000 poise. A larger spinning window (ΔT) indicates that it is more advantageous for the spinning process during glass fiber production.

[0029] Measurement of Young's modulus (unit: GPa): The glass block from Example 1 is cut and polished to obtain a sample to be measured with dimensions of 1.5 cm × 1.5 cm × 0.5 cm. Next, a positive stress is applied to the sample to be measured using a nanoindenter (manufacturer: Keysight Technologies; model number: The Nano Indenter® XP) to generate a positive strain, from which Young's modulus is calculated.

[0030] [Table 1]

[0031] [Table 2]

[0032] In summary, the present invention, through the above-mentioned combination of components and their content, simultaneously controls the content relationship of CaO, MgO, SiO2, Al2O3, and ZnO to 0.70-1.35, resulting in a glass composition having a Young's modulus of 90 GPa or higher. At the same time, during the production of the glass fibers, the temperature at which the melt viscosity of the glass composition reaches 1000 poise is 1360°C or lower, thereby reducing equipment wear and energy consumption. Furthermore, since the difference between the temperature at which the melt viscosity of the glass composition reaches 1000 poise and the devitrification temperature is 100°C or more, the glass fiber spinning and molding work window is broadened, thereby improving production capacity, making the glass fibers less prone to crystallization, and enabling the production of high-quality glass fibers. Thus, the objectives of the present invention are certainly achieved.

[0033] However, the above descriptions are merely embodiments of the present invention and do not limit the scope of implementation of the present invention. Any simple equivalent modifications and alterations made based on the claims and specifications of the present invention fall within the scope of the claims of the present invention.

Claims

1. Assuming the total amount of the glass composition is 100 wt%, 56-66 wt% SiO ２ and, 15-22 wt% Al2O ３ and, 0.1 to 3.5 wt% CaO, 10-18 wt% MgO, ZnO exceeding 0 wt% and less than 2.5 wt%, CuO exceeding 0 wt% and less than 1 wt%, 4-6 wt% B ２ O ３ and, Includes, [((CaO content) + (MgO content)) / SiO ２ content] + {[(CaO content) ２ + (MgO content)] / [Al ２ O ３ content + (ZnO content) ２} is 0.70 to 1.35, a glass composition.

2. [(CaO content + MgO content) / SiO ２ [Content of] + {[(Content of CaO) ２ [MgO content] / [Al ２ O ３ Content of + (ZnO content) ２ The glass composition according to claim 1, wherein} is 0.75 to 1.

24.

3. The total amount of the glass composition is 100 wt%, SiO ２ The glass composition according to claim 1, wherein the content of is 60 to 66 wt%.

4. With the total amount of the glass composition being 100 wt%, Al ２ O ３ The glass composition according to claim 1, wherein the content of is 16 to 22 wt%.

5. The glass composition according to claim 1, wherein the CaO content is 0.1 to 2.5 wt%, with the total amount of the glass composition being 100 wt%.

6. The glass composition according to claim 1, wherein the total amount of the glass composition is 100 wt%, and the MgO content is 12 to 18 wt%.

7. The glass composition according to claim 1, wherein the ZnO content is 0.1 to 2 wt%, with the total amount of the glass composition being 100 wt%.

8. The glass composition according to claim 1, wherein the CuO content is greater than 0 wt% and less than or equal to 0.1 wt%, with the total amount of the glass composition being 100 wt%.

9. Glass fiber comprising the glass composition according to any one of claims 1 to 8.

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