High magnesium, high specific modulus glass fiber composition and glass fiber

Abstract

The present invention belongs to the technical field of glass fibers, and specifically relates to a high-magnesium, high-specific modulus glass fiber composition and glass fibers. The mass percentages of the components are SiO2: 58.5-63.0%, Al2O3: 15.0-20.0%, CaO: 0.3-2.5%, MgO: 16.0-19.5%, Fe2O3: 0.2-0.6%, Y2O3+B2O3: 1.0-3.5%, B2O3: 0.1-1.0%, and K2O+Na2O: 0.3-0.8%. The present invention significantly increases the MgO content, increases the SiO2 content, reduces the Al2O3 and CaO contents, and adjusts the usage ratio of MgO / Al2O3, thereby achieving a density of the glass fiber composition of 2.610 g / cm. 3 The elastic modulus of the glass fiber is ≧94.0GPa, and the specific elastic modulus is ≧3.67*10 6 m.

Description

[Technical Field]

[0001] This invention belongs to the technical field of glass fibers, and more specifically, relates to a high-magnesium, high-specific-modulus glass fiber composition and glass fibers. [Background technology]

[0002] In recent years, with the continuous advancements in wind power generation technology, wind power generation has progressed to large megawatts and larger blades, resulting in higher demands on the mechanical properties of glass fibers used in wind turbine blades, such as high modulus of elasticity, low density, fatigue resistance, and corrosion resistance. Glass fiber manufacturers are also keeping up with market needs and repeatedly updating their high modulus glass formulations.

[0003] The specific modulus of elasticity is the modulus of elasticity per unit density. Large wind turbine blades made of glass fiber with a high specific modulus of elasticity can effectively reduce blade weight, increase power generation efficiency, and be applicable to low wind speed areas. This represents a direction for the development of the glass fiber industry and has become a hot spot in glass fiber industry research in recent years.

[0004] Chinese patent CN111217531A discloses a high-performance fiberglass composition with improved specific modulus of elasticity, having 58.0-68.0% SiO2, 18.0-23.0% Al2O3, 1.0-9.0% CaO, 9.0-14.0% MgO, and 0.0-4.0% Li2O, 0.0-4.0% TiO2, 0-10.0% Y2O3, 0-10.0% La2O3, 0-2.5% Ce2O3, and 0-4.0% Sc2O3. However, the glass fibers in this patent have a relatively low modulus of elasticity and contain relatively high amounts of rare earth heavy elements, resulting in a relatively high density of the glass, making it difficult to achieve weight reduction in large blades.

[0005] Most existing high-modulus formulations primarily use the SiO2-Al2O3-MgO ternary system, improving the modulus of elasticity by increasing the Al2O3 content (18.0-25%) and MgO content (8.0-14.0%). However, this formulation has a significant drawback: the glass crystallization ability is strong, the crystallization rate is fast, and the precipitated crystals are cordierite. Corgielite has a hexagonal ring composed of silicon-oxygen tetrahedra as its basic structural unit, with Al and Mg connecting the rings. It belongs to the biconic crystal class, has a very stable crystal structure, and once formed, it melts very easily and is difficult to extinguish. Corgielite crystals are a major production concern in the glass fiber production process, and their occurrence is difficult to avoid, making it very disadvantageous for tank kiln and large-scale production of glass fibers. [Overview of the project] [Problems that the invention aims to solve]

[0006] The object of the present invention is to provide a glass fiber composition with a low density (ρ ≤ 2.61 g / cm³). 3 The present invention provides a high-magnesium, high-specific-modulus glass fiber composition that has a high elastic modulus (E≧94.0GPa), excellent fatigue performance as a composite material, avoids the crystallization region of cordierite by adjusting the glass component content and converts it to easily soluble enstatite, and effectively suppresses glass crystallization by adding B2O3 and Y2O3. The present invention also provides glass fibers made from this high-magnesium, high-specific-modulus glass fiber composition. [Means for solving the problem]

[0007] The high magnesium, high specific modulus glass fiber composition described in the present invention has the following mass percentages of each component: The composition is as follows: SiO2: 58.5-63.0%, Al2O3: 15.0-20.0%, CaO: 0.3-2.5%, MgO: 16.0-19.5%, Fe2O3: 0.2-0.6%, Y2O3 + B2O3: 1.0-3.5%, B2O3: 0.1-1.0%, K2O + Na2O: 0.3-0.8%, and other unavoidable impurities.

[0008] More preferably, The mass percentage content of Y2O3 and B2O3 satisfies the conditions that Y2O3 + B2O3: 1.0 to 3.2%, and B2O3 / Y2O3 = 0.2 to 0.5.

[0009] The mass percentage content of Al2O3 to MgO satisfies MgO / Al2O3 = 0.8 to 1.2, preferably MgO / Al2O3 = 0.85 to 1.15.

[0010] The density of the high-magnesium, high-specific-modulus glass fiber composition is ≤2.61 g / cm³. 3 That is the case.

[0011] The high-magnesium, high-specific-modulus glass fiber composition described in the present invention has the following mass percentage content of each component: SiO2: 59.0-62.5%, Al2O3: 16.5-19.0%, CaO: 0.5-2.5%, MgO: 16.0-19.0%, Fe2O3: 0.2-0.5%, Y2O3+B2O3: 1.0-3.0%, B2O3: 0.2-0.9%, K2O+Na2O: 0.3-0.6%, and other unavoidable impurities.

[0012] The specific modulus of the glass fibers produced from the high-magnesium, high-specific-modulus glass fiber composition of the present invention is ≥3.67*10 6 The coefficient of elasticity of the glass fiber is m, the elastic modulus of the glass fiber is ≥ 94.0 GPa, the molding temperature of the glass fiber is between 1290 and 1320°C, and the liquidus temperature of the glass fiber is between 1260 and 1280°C.

[0013] The high-magnesium, high-specific-modulus glass fiber composition described in the present invention is manufactured using quartz powder, calcined kaolin, quicklime, talc powder, yttrium oxide, magnesium oxide, and calcium borate mineral as raw materials. Here, the particle size of the quartz powder is 40-50 μm, the particle size of the calcined kaolin is 50-100 μm, the particle size of the quicklime is 100-200 μm, the particle size of the talc powder is 50-100 μm, the particle size of the yttrium oxide is 30-75 μm, the particle size of the magnesium oxide is 50-80 μm, and the particle size of the calcium borate mineral is 40-75 μm.

[0014] SiO2 is the main oxide that forms the glass skeletal structure, and in glass, [SiO4] tetrahedra constitute a three-dimensional continuous framework, which can improve the strength and chemical stability of the glass. In order to adjust and stabilize other components and optimize the fiber-forming properties, elastic modulus, and density of the glass fibers, the present invention limits the SiO2 content to a range of 58.5 to 63.0%, preferably 59.0 to 62.5%.

[0015] MgO is a relatively special alkaline earth metal element, and within the glass network structure, Mg 2+ There are multiple types of coordination, and polyhedra with different coordinations such as [MgO4], [MgO5], and [MgO6] exist, and usually [MgO n The polyhedra are located outside the network framework and, depending on the glass composition, play a role in disrupting the network, supplying free oxygen, or balancing the ionic value around [AlO4], either by disrupting the network or by acting as a regulator. Very rarely, they enter the network structure in the form of four-coordinate [MgO4], and when [MgO4] appears, the glass network structure becomes more complete, the structure becomes tighter, and the glass has a relatively low density and a relatively high modulus of elasticity. The present invention achieves the objective of strengthening the glass network structure and improving the modulus of elasticity by mainly increasing the MgO content, adjusting the content and usage ratio of SiO2, CaO, Al2O3, and R2O, increasing the number of [MgO4] to increase the number of glass network frameworks, and suppressing the conversion from four-coordinate [AlO4] to five-coordinate [AlO5] and six-coordinate [AlO6], while also suppressing the formation of cordierite crystallization, which is one of the main innovations of the present invention. In the glass system of the present invention, the MgO content is limited to being controlled between 16.0 and 19.5%, preferably between 16.0 and 19.0%.

[0016] Al2O3 has a relatively large and complex coordination number in glass, with transitions between multiple coordination numbers such as [AlO6], [AlO5], and [AlO4]. In the absence of free oxygen, Al 3+It is located in the network void as an [AlO6] octahedron, and in the presence of free oxygen, Al 3+ Al2O3 forms [AlO4] and enters the glass framework, and at this time, Al2O3 plays a role in complementing the network, improving the elastic modulus of the glass and enhancing its chemical stability. Too much free oxygen satisfies intermediate ion removal, and if it is in excess, the network framework structure is destroyed, the degree of bonding of the glass framework decreases, the elastic modulus decreases, and stability decreases. The present invention cleverly controls the number of free oxygen atoms according to the content and proportion of SiO2, MgO, and other elements, increasing the number of [AlO4] as much as possible and improving the elastic modulus of the glass. However, too high an Al2O3 content increases the ability to precipitate cordierite crystals in the glass, which is disadvantageous for large-scale tank kiln production. In the glass system of the present invention, the Al2O3 content is limited to a range of 15.0 to 20.0%, preferably 16.5 to 19.0%.

[0017] SiO2-Al2O3-MgO is the main system of this invention and is the primary element that improves the modulus of elasticity and reduces density. For high modulus glass formulations, it is necessary to have high bonding strength between ions in the network, and at the same time, the network must have sufficient deformability to adapt to deformation by external forces. The SiO2-Al2O3-MgO system is a good choice, and is almost always selected as a high-strength, high-modulus system. However, this formulation has a significant drawback: the glass has a strong crystallization ability, a fast crystallization rate, and the precipitated crystals are mainly "cordierite." The decomposition temperature of cordierite is 1540°C, and once crystal nuclei appear in cordierite, the growth rate is very fast. The crystal structure of cordierite is orthorhombic bipyramidal and dense. In tank kiln production, once formed, it is difficult to melt, and the potential risk is extremely high. This is one of the difficulties encountered in the tank kiln production process of high modulus formulations.

[0018] In the case of high elastic modulus formulation, it is common to generate multiple crystal phases, compete the crystal phases, and suppress the cordierite of the main crystal phase by improving CaO and adding other transition metal oxides. However, this technical solution increases the density of the glass fiber composition while improving the elastic modulus. The present invention reduces the Al2O3 content, improves the MgO content, adjusts the usage amount of SiO2, sets the SiO2 content ≥ 58.5% and the MgO content ≥ 16.0%, controls the usage ratio of MgO and Al2O3, and sets MgO / Al2O3 = 0.8 to 1.2, thereby ensuring a high elastic modulus and low density, adjusting the crystallization type of the glass to enstatite, with the growth rate of this crystal being slow, the compactness being poor, the melting temperature being low, and the crystallization risk during tank furnace production being small.

[0019] CaO is an external network body oxide that can reduce the high-temperature viscosity of the glass. CaO's contribution to the elastic modulus is not obvious, and it can significantly increase the glass density. At the same time, since the present invention has a relatively high content of MgO and a relatively high number of free oxygen in the glass, it is necessary to control CaO that can supply free oxygen. The introduction of a small amount of CaO adjusts the glass frit property and is advantageous for the forming of glass fibers. In the present invention, the range of the CaO content is limited to 0.3 to 2.5%, preferably 0.5 to 2.5%.

[0020] The present invention simultaneously adds B2O3, which is the most ingenious point of the present invention. It has the following three advantages. 1) Silicate glass has B 3+ with a coordination number of 3, forming a layered structure of [BO3] triangular bodies, belonging to the external network body, and having an unstable structure. However, B 3+When it obtains free oxygen, it can form [BO4] tetrahedrons. The [BO4] tetrahedrons can form a network structure. The purpose of adding B2O3 in the present invention is to neutralize the excessive free oxygen supplied by MgO in the glass structure, form [BO4], and together with [SiO4], [AlO4], and [MgO4], form a glass network structure, improve the elastic modulus, and reduce the density. 2) The addition of B2O3 can effectively improve crystallization, especially has a very good synergistic effect with Y2O3, and not only can reduce the crystallization temperature, but also can reduce the crystallization rate. 3) B2O3 has a melting assistant effect, effectively reduces the melting temperature of the blending materials. In the present invention, the SiO2 content is relatively high, and quartz powder is the most difficult-to-melt mineral. Therefore, the addition of B2O3 can effectively solve this problem. Of course, if the B2O3 content is too high, B 3+ will form a triangular body and then destroy [SiO4], exerting a reverse effect, so it must be controlled within an appropriate range. Therefore, the present invention limits the range of the B2O3 content to 0.1 - 1.0%, preferably 0.2 - 0.9%.

[0021] Y2O3 is a rare earth oxide with a high coordination number and high electric field strength. In the present invention, a small amount of Y2O3 is added to effectively suppress crystallization together with B2O3, reduce the liquidus temperature of the glass, and without reducing the fiber forming temperature of the glass, increase △T, and reduce the risk of crystallization in the wire drawing operation, which is particularly advantageous during the production of tank furnaces. Y2O3 belongs to heavy elements. When the added content is excessive, it will affect the density of the glass fiber composition, deviating from the low density of the present invention. Therefore, in order to balance the glass fiber forming temperature, liquidus temperature, and the density of the glass fiber composition, in the present invention, the range of the Y2O3 + B2O3 content is limited to 1.0 - 3.5%, preferably 1.0 - 3.0%.

[0022] The present invention simultaneously adds Y2O3 and B2O3 to increase the crystallization activation energy of this glass system and increase the crystallization potential barrier. When converting this glass system into a crystalline state, more energy - activation energy is required to overcome the rearrangement potential barrier of the structural units. The higher the potential barrier, the greater the required crystallization activation energy, and the smaller the crystallization tendency of the glass. During the production in a tank furnace, crystallization is less likely to occur during the temperature - lowering process of the passage, which is advantageous for the production operation. The present invention reasonably controls the usage ratio of B2O3 and Y2O3, and the effect is the best when B2O3 / Y2O3 = 0.2 - 0.5.

[0023] Na2O and K2O can reduce the resistivity of the glass. During the production in a tank furnace, the utilization rate of the electric melting auxiliary system can be improved, which is advantageous for improving the melting quality of the glass liquid. However, if the introduction amount is too large, it is disadvantageous for improving the elastic modulus of the glass composition. In the present invention, the Na2O + K2O content is limited to be between 0.3% and 0.8%, more preferably between 0.3% and 0.6%.

[0024] The present invention does not contain Li2O, which is one of the technical points differentiating it from other high - elastic - modulus formulations. Li2O can effectively assist melting, and due to its small ionic radius and strong accumulation ability, it can accumulate network intermediate ions and play a role in improving stability. However, the present invention has already significantly improved the number of [BO4], [SiO4], [AlO4], and [MgO4] tetrahedrons by technical means, and it is more effective to improve the elastic modulus by increasing the network structure. Li2O is too costly and has no obvious meaning for the present invention.

[0025] The high - magnesium and high - specific - elastic - modulus glass fiber composition described in the present invention is manufactured using quartz powder, calcined kaolin, quicklime, talc powder, yttrium oxide, magnesium oxide, and calcium borate minerals as raw materials.

[0026] This invention selects calcined kaolin as the raw material for introducing Al2O3 into the glass component in order to reduce production costs. The first advantage is that, instead of introducing Al2O3 using industrial alumina, the cost of glass per ton can be significantly reduced. Second, the main purpose of calcined kaolin is that it can effectively adjust the COD and gas ratio of the compounding material. Furthermore, calcined kaolin mainly consists of the mullite phase, has a lower melting point than industrial alumina, reduces the melting energy consumption of the compounding material, and is very beneficial in saving the production cost of glass per ton.

[0027] The glass system of the present invention has a high SiO2 content and a low CaO content, resulting in a decrease in calcium raw materials in the compounding material and an increase in quartz powder, which is a silicon raw material. The quartz powder consists of a pure quartz phase and has a high theoretical melting temperature of 1750°C. This results in a relatively high melting temperature for the compounding material, which is unfavorable for melting in a tank furnace. The present invention reduces the amount of quartz powder used by introducing talc powder to replace part of the quartz powder. Since talc powder is a silicate raw material, it readily eutectic at low temperatures in the compounding material, further lowering the melting temperature of the compounding material.

[0028] This invention controls the particle size range of the talc powder raw material between 50 and 100 μm. If the particle size is too fine, it affects the thickness of the foam layer in the tank furnace, affects the absorption of heat radiation, and increases energy consumption. If the particle size is too coarse, it causes poor melting of the glass liquid. Preferably, the particle size distribution of the other raw materials is 50 to 100 μm for calcined kaolin, 40 to 50 μm for quartz powder, 100 to 200 μm for quicklime, 30 to 75 μm for yttrium oxide, 50 to 80 μm for magnesium oxide, and 40 to 75 μm for calcium borate mineral. This invention ensures the quality of the molten glass liquid of this glass system through rational raw material selection and particle size control, while simultaneously reducing the melting temperature and energy consumption of the furnace, and reducing the erosion of the glass liquid into the refractory material in the furnace at high temperatures. [Effects of the Invention]

[0029] The beneficial effects of the present invention are as follows:

[0030] This invention significantly increases the MgO content and SiO2 content, reduces the Al2O3 and CaO content, and adjusts the MgO / Al2O3 usage ratio in the SiO2, Al2O3, and MgO ternary system, thereby converting the glass crystallization type from cordierite to enstatite. The [SiO4], [AlO4], [MgO4], and [BO4] elements of this invention jointly constitute the glass framework structure. By utilizing elements that can be converted into network structures such as B2O3, the free oxygen content and the ratio of each component are adjusted to increase the number of glass networks, improve the elastic modulus, and reduce density. Furthermore, this invention skillfully adds Y2O3 and B2O3 content and controls the B2O3 / Y2O3 ratio within a range of 0.2 to 0.5 to adjust the crystallization activation energy and reduce the risk of crystallization during the production process. The density of the high-magnesium, high-specific-modulus glass fiber composition of this invention is ≤2.610 g / cm³. 3 The glass fibers made from this high-magnesium, high-specific-modulus glass fiber composition have an elastic modulus of ≥94.0 GPa and a specific modulus of ≥3.67 * 10 6 It has a relatively high modulus of elasticity, a relatively low density, and a relatively weak crystallization ability, and is also relatively inexpensive, making it suitable for use in large wind turbine blades and significantly reducing the mass of glass fiber composite materials.

[0031] The glass fibers produced from the high-magnesium, high-specific-modulus glass fiber composition of the present invention have a molding temperature not exceeding 1320°C and a crystallization upper limit temperature not exceeding 1280°C. By adjusting the crystallization type, crystallization rate, and crystallization potential barrier, crystallization is less likely to occur during the glass fiber production process, meeting the requirements of the wire drawing process. Furthermore, rational raw material selection and particle size control further reduce costs, making this system advantageous for tank kiln kiln production and mass production of glass compounds. [Brief explanation of the drawing]

[0032] [Figure 1] This is a graph of the SN curve of the fatigue test of the glass fiber push-pull plates of Example 1, Example 2, and Comparative Example 3 of the present invention. [Modes for carrying out the invention]

[0033] The present invention will be further described below with reference to examples.

[0034] The present invention provides a method for producing high-magnesium, high-specific modulus glass fibers. Step (1) involves calculating the mass of various raw materials required based on the content of each component, weighing each raw material and mixing them uniformly using gaseous force, then transporting them to the material storage at the head of the kiln to obtain the blended material, and then feeding the blended material at a constant speed into the large tank kiln furnace using a feeding machine. Step (2) involves melting the mixed materials in a tank furnace at 1450-1550°C and clarifying them into a homogeneous glass liquid. Step (3) involves drawing a glass liquid through a leak nozzle on a platinum-rhodium leak plate at 1290-1320°C to form glass fibers, The process includes (4) applying a wetting agent to glass fibers via an oiling device, pulling them in a wire drawing machine, and forming a yarn product through high-speed wire drawing.

[0035] The components and specifications of each raw material used are shown in Table 1.

[0036] [Table 1]

[0037] This invention employs raw materials of different particle sizes to ensure uniformity in raw material mixing, while reducing the introduction of ultrafine powders and facilitating the removal of air bubbles from the glass liquid. This invention is applicable to large tank kilns and is advantageous for improving production efficiency.

[0038] Manufacturing method for push-pull plates: Glass fiber threads are neatly and uniformly aligned using guides and thread handling devices, uniformly immersed in a resin tank, then initial shaping is performed using a pre-molding device, excess resin is extruded, then the material is placed in a mold and heat-cured, and finally pulled out of the mold using a pulling device to form a composite material plate.

[0039] Fatigue Life SN Curve: When a glass fiber reinforced composite material is subjected to a fatigue load, some of the work done forms defects within the material. As the number of load cycles increases, these defects continuously accumulate. When the number of load cycles reaches the material's lifespan, the cracks expand to a critical point, causing the material to fracture. The load-fatigue life curve (SN curve) of the material is a monotonically decreasing curve, meaning that the fatigue life of the material decreases monotonically as the applied load increases.

[0040] When verifying the overall properties of the glass fibers in the examples and comparative examples, the following parameters were selected.

[0041] 1) The molding temperature, i.e., the temperature at which the viscosity of the glass is 1000 Poise, can characterize the molding temperature for fiber formation, and the high-temperature viscosity of the glass is obtained using a high-temperature viscometer.

[0042] 2) The liquidus temperature, i.e., the critical temperature at which glass begins to crystallize, is generally the upper limit of the glass crystallization temperature, and this upper limit is obtained using a crystallization furnace.

[0043] 3) ΔT is the difference between the molding temperature and the liquidus temperature.

[0044] 4) Crystallization type: A polarizing microscope and an X-ray diffractometer are used.

[0045] 5) Glass density shall be tested according to the standard test method for measuring glass density by buoyancy, ASTM C693.

[0046] 6) The modulus of elasticity shall be tested according to the ASTM D2343 standard.

[0047] 7) The specific modulus of elasticity is the ratio of the material's elastic modulus to its density (specific modulus of elasticity = elastic modulus / (density * 9.8)), unit: 10 6 It is m.

[0048] 8) Crystallization activation energy: This is obtained by reading the temperature parameter from the DSC curves at heating rates of 5°C / min, 10°C / min, 15°C / min, and 20°C / min using the non-isothermal DSC method and calculating it.

[0049] 9) Fatigue performance will be tested in accordance with the ISO 13003 (2003) standard test, using an Instron 8802-250 / 100KN fatigue testing machine to perform dynamic fatigue performance tests on continuous fiber-reinforced plastic extrusion and tensile plates.

[0050] Examples 1-8 Table 2 shows the composition and glass fiber performance data of the high-magnesium, high-specific modulus glass fiber compositions in Examples 1 to 8.

[0051] Comparative Examples 1-8 Table 3 shows the composition and glass fiber performance data of the glass fiber compositions in Comparative Examples 1 to 8.

[0052] [Table 2]

[0053] [Table 3]

[0054] Comparative Examples 1 and 2 are both well-known SiO2-MgO-Al2O3 ternary high modulus glass fiber components in the art, and both are characterized by high aluminum content and low magnesium content. Comparative Example 1 is a relatively old high modulus glass fiber component, has a relatively high glass fiber molding temperature and liquidus temperature, is relatively difficult to produce, and is difficult to realize tank kiln production. Comparative Example 2 is a currently conventional high modulus glass fiber component, has a relatively low molding temperature and liquidus temperature, and has a relatively high modulus, but fails to achieve the objectives of the present invention and cannot meet higher usage requirements.

[0055] Comparative Example 3 increased the elastic modulus of the glass fiber by increasing the amount of rare earth oxide used, and simultaneously with the increase in elastic modulus, the density of the glass composition increased to 2.675 g / cm³. 3 It reaches a significant increase, limiting the use of composite materials.

[0056] In Comparative Example 4, when the MgO content was adjusted to less than 16.0% compared to Example 1, clear cordierite crystallization occurred, and the elastic modulus and specific modulus of elasticity clearly decreased.

[0057] Comparative Example 5, compared to Example 1, had an MgO content greater than 19.5%, resulting in the presence of cordierite crystallization, a clear decrease in molding temperature, a smaller ΔT, a greater risk of crystallization, and difficulty in meeting tank kiln production requirements. As the drawing process technology for glass fiber tank kilns matures, the demand for fiber formation can be met when ΔT ≥ 35℃, and the difficulty of production gradually increases as ΔT decreases.

[0058] In Comparative Example 6, compared to Example 1, the MgO / Al2O3 ratio exceeds 1.2, resulting in cordierite crystallization and a decrease in elastic modulus.

[0059] In Comparative Example 7, compared to Example 1, the B2O3 / Y2O3 ratio is less than 0.2, the liquidus temperature is higher, and the crystallization activity energy is lower.

[0060] In Comparative Example 8, compared to Example 1, the B2O3 / Y2O3 ratio exceeds 0.5, the liquidus temperature increases, the crystallization activity energy decreases, and the elastic modulus is clearly reduced.

[0061] When glass fibers produced from the glass fiber compositions of Example 1, Example 2, and Comparative Example 3 were made into push-pull plates and subjected to fatigue tests, a comparison of the SN curves is shown in Figure 1. As can be seen from Figure 1, the fatigue data of the push-pull plates in Example 1 and Example 2 are superior to that of Comparative Example 3, indicating that the glass fiber composite material provided by the present invention has excellent fatigue performance. This disclosure includes the following embodiments of the invention: <Aspect 1> A high magnesium, high specific modulus glass fiber composition in which the content of each component by mass percentage is SiO 2 :58.5%~63.0%、Al 2 O 3 :15.0%~20.0%, CaO:0.3%~2.5%, MgO:16.0%~19.5%, Fe 2 O 3 :0.2%~0.6%、Y 2 O 3 +B 2 O 3:1.0%~3.5%、B 2 O 3 :0.1%~1.0%、K 2 O+Na 2 A high-magnesium, high-specific-modulus glass fiber composition characterized by having an O content of 0:0.3% to 0.8%. <Aspect 2> Y 2 O 3 and B 2 O 3 The mass percentage content of is B 2 O 3 / Y 2 O 3 The high magnesium, high specific modulus glass fiber composition according to embodiment 1, characterized in that it satisfies the value of =0.2 to 0.5. <Aspect 3> Al 2 O 3 The mass percentage content of MgO is MgO / Al 2 O 3 A high-magnesium, high-specific-modulus glass fiber composition according to embodiment 1, characterized in that it satisfies the value of =0.8 to 1.2. <Aspect 4> The mass percentage of each component is SiO 2 :59.0%~62.5%、Al 2 O 3 :16.5%~19.0%, CaO:0.5%~2.5%, MgO:16.0%~19.0%, Fe 2 O 3 :0.2%~0.5%、Y 2 O 3 +B 2 O 3 :1.0%~3.0%、B 2 O 3 :0.2%~0.9%、K 2 O+Na 2 The high magnesium, high specific modulus glass fiber composition according to embodiment 1, characterized in that O: 0.3% to 0.6%. <Aspect 5> The density of the high-magnesium, high-specific-modulus glass fiber composition is ≤2.61 g / cm³. 3 A high-magnesium, high-specific-modulus glass fiber composition according to any one of embodiments 1 to 4, characterized in that it is such. <Aspect 6> The specific modulus of glass fiber is ≥ 3.67 * 10 6 Glass fibers produced from a high-magnesium, high-specific modulus glass fiber composition according to any one of embodiments 1 to 5, characterized in that m is present. <Aspect 7> Glass fibers produced from the high-magnesium, high-specific modulus glass fiber composition according to embodiment 6, characterized in that the elastic modulus of the glass fibers is ≥ 94.0 GPa. <Aspect 8> Glass fibers produced from a high-magnesium, high-specific modulus glass fiber composition according to embodiment 6, characterized in that the molding temperature of the glass fibers is between 1290°C and 1320°C. <Pattern 9> Glass fibers produced from the high-magnesium, high-specific-modulus glass fiber composition according to claim 6, characterized in that the liquidus temperature of the glass fibers is between 1260°C and 1280°C.

Claims

1. A high-magnesium and high specific elastic modulus glass fiber composition, in terms of mass percentage, the content of each component is SiO ２ : 58.5% to 63.0%, Al ２ O ３ : 15.0% to 20.0%, CaO: 0.3% to 2.5%, MgO: 16.0% to 19.5%, Fe ２ O ３ : 0.2% to 0.6%, Y ２ O ３ +B ２ O ３ : 1.0% to 3.5%, B ２ O ３ : 0.1% to 1.0%, K ２ O + Na ２ O: 0.3% to 0.8%, and The mass percentage content of Y₂O₃ and B₂O₃ satisfies the ratio B₂O₃ / Y₂O₃ = 0.2 to 0.

5. A high-magnesium, high-specific-modulus glass fiber composition characterized by having a mass percentage content of Al₂O₃ and MgO that satisfies MgO / Al₂O₃ = 0.8 to 1.

2.

2. The mass percentage of each component is SiO ２ :59.0%~62.5%, Al ２ O ３ : 16.5% to 19.0%, CaO: 0.5% to 2.5%, MgO: 16.0% to 19.0%, Fe ２ O ３ :0.2%~0.5%, Y ２ O ３ +B ２ O ３ :1.0%~3.0%, B ２ O ３ :0.2%~0.9%, K ２ O + Na ２ The high magnesium, high specific modulus glass fiber composition according to claim 1, characterized in that O: 0.3% to 0.6%.

3. The density of the high-magnesium, high-specific-modulus glass fiber composition is ≤2.61 g / cm³. ３ The high magnesium, high specific modulus glass fiber composition according to claim 1 or 2, characterized in that it is such.

4. The specific modulus of glass fiber is ≥ 3.67 * 10 ６ Glass fiber produced from the high-magnesium, high-specific modulus glass fiber composition according to claim 1 or 2, characterized in that it is m.

5. Glass fibers produced from the high-magnesium, high-specific modulus glass fiber composition according to claim 4, characterized in that the elastic modulus of the glass fibers is ≥ 94.0 GPa.

6. Glass fibers produced from the high-magnesium, high-specific-modulus glass fiber composition according to claim 4, characterized in that the molding temperature of the glass fibers is between 1290°C and 1320°C.

7. Glass fibers produced from the high-magnesium, high-specific-modulus glass fiber composition according to claim 4, characterized in that the liquidus temperature of the glass fibers is between 1260°C and 1280°C.

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