CN111559871A - Low cost high performance glass fiber compositions and glass fibers and composites therefor - Google Patents

Abstract

A preferred solution of the low-cost high-performance glass fiber composition is: the glass fiber composition includes the following components: 55.2-59.2wt% SiO ₂ ; 11.6-13.6wt% Al ₂ O ₃ ; 21.5 ‑23.3wt% CaO; 0‑0.9wt% MgO; 4.1‑4.9wt% _Y2O3 ; 0.1‑0.5wt% ZrO2 _; 0‑0.3wt% _{Fe2O3 ; 0‑0.4wt} % % of TiO ₂ ; 0-1.0 wt % of Li ₂ O; the sum of the mass percentages of Li ₂ O, Na ₂ O and K ₂ O is 0.3-1.5 wt %. The low-cost high-performance glass fiber has a refractive index of 1.580-1.590, has good matching with the refractive index of the polycarbonate resin, and has a lighter color; the low-cost high-performance glass fiber dipped yarn drawing die The amount is greater than 87GPa and has good dimensional stability. The molding temperature of the low-cost high-performance glass fiber does not exceed 1210°C, and the upper limit temperature of crystallization does not exceed 1150°C. It not only has excellent mechanical properties, but also has very good light transmittance. It can be widely used in fields with high requirements on mechanical properties and transparency. It also reduces the content of precious metal Y ₂ O ₃ and greatly reduces the Cost of production.

Description

Low cost high performance glass fiber compositions and glass fibers and composites therefor

technical field

The invention belongs to the technical field of polymer material modification, in particular to a low-cost high-performance glass fiber composition, glass fiber and composite material thereof.

Background technique

Glass fiber is an inorganic non-metallic material with excellent performance. It has the advantages of high tensile strength, high strength, temperature resistance, good corrosion resistance, heat insulation, sound insulation, non-combustibility, etc. It is widely used in electronics, electrical, automotive, Aviation, ships, environmental protection, chemical industry, construction and other fields.

As a thermoplastic resin, polycarbonate (PC) has good transparency, non-toxicity, weather resistance, heat resistance, impact resistance, fatigue resistance and electrical properties. It is the fastest-growing general engineering plastics in the five major engineering plastics. Plastics are widely used in glass assembly industry, automobile industry and electronics, electrical industry, industrial machinery parts, optical discs, packaging, computers and other office equipment, medical and health care, film, leisure and protective equipment and other fields. With the further expansion of the application range of PC resin, in order to make up for its lack of mechanical strength, people began to use glass fiber to enhance its mechanical properties and dimensional stability. However, the refractive index of PC resin is relatively high, usually greater than 1.58, while the refractive index of ordinary glass fiber is generally 1.54-1.56. With the increase of glass fiber content, the light transmittance of its products decreases more and more obviously.

In the development process of E-glass fiber, people mostly consider improving the mechanical properties of glass fiber, and there are not many researches on improving the refractive index and transparency of glass fiber.

Japanese Patent Laid-Open No. 5-155638 discloses a glass fiber composition for strengthening polycarbonate resin, the composition of which includes (by weight percentage): SiO ₂ 54-62%, Al ₂ O ₃ 8-12%, CaO 18-22%, TiO ₂ 0.5-1.9%, MgO 0-5%, ZnO 0-5%, BaO 0-5%, ZrO ₂ 0.6-5%, Li ₂ O+Na ₂ O+K ₂ O 0- 1%, the refractive index of this glass fiber is 1.5700-1.6000, adding 0.5-1.9% TiO ₂ can improve the refractive index of the glass fiber, but when the TiO ₂ content is higher than 0.5%, it will make the glass fiber products appear weak Yellow, not very transparent.

Chinese patent _{CN200580015038.5} discloses a polycarbonate resin reinforced glass fiber, which includes _two types _of B2O3 and B2O3 _- free. The glass fiber components containing B ₂ O ₃ include (weight percent): SiO ₂ 50-60%, Al ₂ O ₃ 10-15%, CaO 15-25%, TiO ₂ 2-10%, B ₂ O ₃ 2-8%, MgO 0-5%, ZnO 0-5%, BaO 0-5%, ZrO ₂ 0-5%, Li ₂ O+Na ₂ O+K ₂ O 0-2%, the glass fiber The refractive index is 1.580-1.590. B2O3 _- free glass fiber components include (by weight percent): _SiO2 50-60%, _Al2O3 10-15 _% , CaO 15-25%, _TiO2 4.1-5%, MgO ₀ -5%, ZnO 0-5%, BaO 0-5%, ZrO ₂ 0-5%, Li ₂ O+Na ₂ O+K ₂ O 0-2%, ZnO+Y ₂ O ₃ 1-5%, TiO ₂ +ZnO+BaO+ZrO ₂ 6-8%, the refractive index of this glass fiber is 1.583-1.586, but the TiO ₂ content is obviously high, making the glass fiber product bright yellow, and the transparency is seriously affected.

Chinese patent CN200910002941.8 discloses a similar glass fiber for polycarbonate resin reinforcement, the main components of which include (by weight percentage): SiO ₂ 50-60%, Al ₂ O ₃ 10-15%, CaO 15 -25%, TiO ₂ 3-5%, MgO 0-5%, ZnO 0-5%, BaO 0-5%, ZrO ₂ 0-5%, Li ₂ O+Na ₂ O+K ₂ O 0-2 %, ZrO ₂ 2-5%, the refractive index of this glass fiber can reach 1.583-1.586, although the refractive index of the glass fiber can be increased, but due to the large amount of TiO2, the color of glass products is obviously yellowish, which is difficult to produce. It is too large, which also limits its application range.

SUMMARY OF THE INVENTION

The invention provides a low-cost and high-performance glass fiber composition, glass fiber and composite material thereof, which not only have excellent mechanical properties, but also have very good light transmittance, and can be widely used in both mechanical properties and transparency. It is suitable for high-demand fields, and the content of precious metal Y ₂ O ₃ is reduced, which greatly reduces the production cost.

The technical scheme of the present invention is as follows:

A low-cost high-performance glass fiber composition, comprising the following components, the content of each component is expressed as follows in terms of mass percentage:

Wherein the TiO ₂ , Na ₂ O and K ₂ O are introduced in the form of impurities, not added separately, and the sum of the mass percentages of the Li ₂ O, Na ₂ O and K ₂ O does not exceed 1.5wt% .

Preferably, the mass percentage of the Y ₂ O is 4.1-4.9 wt %.

Preferably, the mass percentage content of the ZrO ₂ is 0.1-0.5 wt %.

Preferably, the mass percentage content of the TiO ₂ introduced in the form of impurities should be controlled at 0-0.4 wt %.

Preferably, the mass percentage content of the Fe ₂ O ₃ should be controlled at 0-0.3 wt %.

Preferably, the sum of the mass percentages of Li ₂ O, Na ₂ O and K ₂ O should be controlled at 0.3-1.5wt%

Preferably, the mass percentage content of the SiO ₂ should be controlled at 55.2-59.2 wt %.

Preferably, the mass percentage content of the Al ₂ O ₃ should be controlled at 11.6-15.6 wt %.

Preferably, the mass percentage content of the CaO should be controlled at 21.5-23.3 wt%.

Preferably, the mass percentage content of the MgO should be controlled at 0-0.9 wt%.

Preferably, in the low-cost and high-performance glass fiber composition of the present invention, the content of each component is expressed as a mass percentage as follows:

Wherein the TiO ₂ , Na ₂ O and K ₂ O are introduced in the form of impurities, not added separately, and the sum of the mass percentages of the Li ₂ O, Na ₂ O and K ₂ O is 0.3-1.5wt% %.

A low-cost high-performance glass fiber is made from the above-mentioned low-cost high-performance glass fiber composition, and the low-cost high-performance glass fiber has a refractive index of 1.580-1.590.

A low-cost high-performance glass fiber reinforced composite material includes the above-mentioned low-cost high-performance glass fiber.

In the present invention, silicon dioxide (SiO ₂ ) is one of the main oxides forming the glass fiber network structure, and it mainly plays the role of improving the mechanical strength, chemical stability and thermal stability of the glass fiber. Within a certain range, the higher the SiO ₂ content in the glass, the better the mechanical strength of the glass fiber, but at the same time, the higher the melting temperature of the glass fiber stock solution and the fiber forming temperature, the greater the production difficulty. Considering comprehensively, the mass percentage content of SiO ₂ in the present invention is 55-60 wt %, preferably 55.2-59.2 wt %.

In the present invention, alumina (Al ₂ O ₃ ) and SiO ₂ together form a glass fiber network structure. The higher the content thereof, the better the mechanical strength of the glass fiber, especially the elastic modulus, but at the same time, the high temperature viscosity of the glass fiber will also increase significantly. Generally, if the content of Al ₂ O ₃ exceeds 16%, the viscosity of the glass liquid will be too large, the glass fiber will be difficult to form, and the problem of crystallization will easily occur. Therefore, the content of Al ₂ O ₃ in the present invention is 10-16 wt %, preferably 11.6-15.6 wt %.

In the present invention, both calcium oxide (CaO) and magnesium oxide (MgO) are alkaline earth metal oxides, which have the functions of adjusting the high temperature viscosity of the glass and improving the crystallization tendency of the glass. The effect of increasing the refractive index of glass fiber is more significant. Meanwhile, in the alkali-free glass system, the total amount of CaO+MgO should generally not exceed 25%, preferably below 24%. In the present invention, in order to ensure a higher refractive index, CaO is preferably selected to be added, and MgO is generally not specially added, but considering the cost of mineral raw materials, the present invention allows the introduction of a small amount of MgO in the form of mineral raw material impurities. Experiments show that, in the present invention, when the CaO content is controlled at 20-24 wt % and the MgO content is controlled at 0-1.5 wt %, the comprehensive effect is the best. The mass percentage content of the CaO is preferably 21.5-23.3 wt %, and the mass percentage content of the MgO is preferably 0-0.5 wt %.

Yttrium oxide (Y ₂ O ₃ ) is specifically added to the low-cost high-performance glass fiber composition of the present invention. A large number of experiments have found that adding a certain amount of Y ₂ O ₃ has an obvious effect on improving the refractive index of glass fibers, and it has no coloring effect and will not affect the color of the glass itself. But because Y ₂ O ₃ is expensive, and the addition of too much will increase the tendency of glass crystallization. Zirconium oxide (ZrO ₂ ) is an oxide with a large atomic weight and a high field strength. When a small amount is added to the glass, it can compete with Y ₂ O ₃ and CaO for oxygen atoms, thereby inhibiting devitrification. However, its content must be strictly controlled. Once the limit is exceeded, the crystallization tendency of zircon will increase sharply. It has been proved by repeated experiments that when Y ₂ O ₃ is 3.5-4.95 wt % and ZrO ₂ is 0-1 wt %, the comprehensive effect is better. Preferably, the mass percent content of Y ₂ O ₃ is 4.1-4.9 wt %, and the mass percent content of ZrO ₂ is 0.1-0.5 wt %.

In glass fiber, titanium dioxide (TiO ₂ ) has a very obvious effect of improving the refractive index. Many glass products with high refractive index contain high TiO ₂ , but at the same time, TiO ₂ also has obvious coloring effect. When its content exceeds 0.5 When the content is more than 1 wt%, the glass will appear light yellow, and when the content exceeds 1 wt%, the glass will have a very obvious bright yellow color. Therefore, in order to avoid the influence of TiO ₂ on the glass color, the present invention basically does not contain TiO ₂ , but in order to reduce the cost of raw materials, the present invention allows a small amount of TiO ₂ to be introduced into the mineral raw materials in the form of impurities. The mass percentage content of TiO ₂ in the glass fiber of the present invention is limited to 0-1 wt %, preferably 0-0.4 wt %.

In glass fibers, a small amount of Fe ₂ O ₃ has little effect on performance, but a high content can cause the glass to turn yellow or green. Usually, in order to reduce the cost of mineral raw materials, a small amount of introduction is generally allowed. In the present invention, Fe ₂ O ₃ is not specially added, it is mainly introduced in the form of mineral raw material impurities. But in order to control the color of the glass, the mass percentage content of Fe ₂ O ₃ in the glass fiber of the present invention is limited to 0-0.6wt%, preferably 0-0.3wt%.

In order to reduce the melting temperature of the glass fiber and improve the difficulty of fiber forming, a small amount of Li ₂ O can be added to the glass fiber of the present invention, and its mass percentage content is 0-1 wt %. The glass fiber of the present invention also contains a small amount of alkali metal oxides Na ₂ O and K ₂ O, which also help to reduce the difficulty of glass fiber production. The total content of Na ₂ O and K ₂ O in the glass composition of the present invention is controlled at 0-0.8 wt %. At the same time, the sum of the mass percentages of Li ₂ O, Na ₂ O and K ₂ O does not exceed 1.5wt%, preferably 0.3-1.5wt%.

In the present invention, a preferred solution of the low-cost high-performance glass fiber composition is: the glass fiber composition includes the following components: 55.2-59.2 wt % SiO ₂ ; 11.6-13.6 wt % Al ₂ O ₃ ; 21.5-23.3 wt % CaO; 0-0.9 wt % MgO; 4.1-4.9 wt % Y ₂ O ₃ ; 0.1-0.5 wt % ZrO ₂ ; 0-0.3 wt % Fe ₂ O ₃ 0-0.4wt% of TiO ₂ ; 0-1.0wt% of Li ₂ O; the sum of the mass percentages of Li ₂ O, Na ₂ O and K ₂ O is 0.3-1.5wt%. The low-cost high-performance glass fiber has a refractive index of 1.580-1.590, has good matching with the refractive index of the polycarbonate resin, and has a lighter color; the low-cost high-performance glass fiber dipped yarn drawing die The amount is greater than 87GPa and has good dimensional stability. The molding temperature of the low-cost high-performance glass fiber does not exceed 1210°C, and the upper limit temperature of crystallization does not exceed 1150°C.

The present invention has no special limitation on the preparation method of the glass fiber, and the preparation can be carried out according to the kiln method well known to those skilled in the art.

The tank kiln method is specifically as follows: according to the actual formulation of the glass, the required proportion of raw materials is calculated; according to the proportion, various raw materials are quantitatively transported to the mixing bin, fully mixed evenly to obtain qualified batch materials; and the batch materials are transported to the tank The kiln head silo of the kiln is fed to the pool kiln at a constant speed by the feeder; the batches are heated, melted, clarified and homogenized at a high temperature of 1300-1500 ℃ in the pool kiln to form a qualified glass liquid; the glass liquid passes through the working channel Cool to the forming temperature, and then flow out through the platinum bushing to form glass filaments; the glass filaments are rapidly drawn into glass fibers with a set diameter under the high-speed traction of the wire drawing machine, and are then wound into filaments by the wire drawing machine after spray cooling, coating with sizing agent, and bundling. Cake; in the programmed automatic drying oven, the silk cake is dried to obtain dry low-cost high-performance glass fiber raw yarn, that is, untwisted direct yarn. Alternatively, the wound cake is chopped into chopped strands of a certain length, and then granulated, dried, and screened to obtain dry, low-cost, high-performance glass fiber chopped strands.

Compared with the prior art, the present invention has the following advantages:

1. The low-cost and high-performance glass fiber composition of the present invention can reduce the content of TiO ₂ to the greatest extent on the basis of ensuring that the refractive index of the glass fiber product is maintained at 1.580-1.590, even without TiO ₂ , so The low-cost high-performance glass fiber made of it has excellent transparency, and the composite material reinforced with the low-cost high-performance glass fiber also has good transparency, especially the glass fiber reinforced PC composite material, the low-cost high-performance glass fiber. It will not affect the true color of PC resin, so it can be widely used in occasions with high requirements on color, especially transparency.

2. The low-cost and high-performance glass fiber made of the low-cost and high-performance glass fiber composition has good mechanical properties. It is beneficial to maintain the structural strength and dimensional stability of glass fiber reinforced composite materials, especially glass fiber reinforced PC composite materials.

3. The low-cost and high-performance glass fiber composition of the present invention has good fiber-forming properties when preparing low-cost and high-performance glass fibers. The difficulty is comparable to that of general boron-free and fluorine-free alkali-free glass fibers, and large-scale production can be realized under the existing kiln process conditions.

4. The low-cost and high-performance glass fiber composition of the present invention can maintain a high refractive index while reducing the amount of the more expensive Y ₂ O ₃ through formula optimization, thereby greatly reducing the production cost.

Detailed ways

In order to facilitate understanding of the present invention, the present invention will be described in more detail below with reference to specific embodiments and comparative examples.

In the examples and comparative examples of the present invention, the high temperature viscosity of glass fibers is detected by BROOKFIELD high temperature viscometer produced by ORTON; the liquidus temperature of glass is detected by Orton Model gradient furnace; the refractive index of glass fibers is detected by GB/T7962.1-2010 standard The tensile modulus was measured by ASTM D2343-03 standard.

T _logη=3 represents the temperature at which the glass viscosity is 1000 poise, which corresponds to the temperature of the glass liquid during glass fiber molding, and is also referred to as "glass fiber molding temperature".

_Liquid T represents the liquidus temperature of the glass, which is equivalent to the temperature when the glass crystallization rate is 0, which is equivalent to the upper limit of the glass crystallization temperature, and is often referred to as "glass fiber crystallization temperature".

In addition, the components of the compounds in Examples 1-20 are glass formulation components. For the components of the compounds in Comparative Examples 1 and 2, please refer to pages 53-54 of the Complete Book of Glass Fiber and Mineral Wool, and the values are weight percentages. Due to factors such as detection errors, trace impurities not included in the analysis, decimal places and other factors, the total percentage content of the components described in the table may not be completely 100%.

Example 1

In mass percentage, 60wt% _SiO2 , 10.8wt% _Al2O3 , _22.4wt % CaO, 0.3wt% MgO, 0.3wt% _TiO2 , _4.6wt % _Y2O3 , 0.4wt% wt% ZrO ₂ , 0.4 Li ₂ O, 0.7 Na ₂ O+K ₂ O, 0.1 wt % Fe ₂ O ₃ , calculate the addition ratio of the required raw materials according to its formula, and quantify various raw materials according to the ratio It is transported to the mixing silo and fully mixed to obtain qualified batches; the batches are transported to the kiln head silo of the pool kiln, and fed to the pool kiln at a uniform speed by the feeder; After high-temperature heating, melting, clarification, and homogenization, a qualified low-cost high-performance glass liquid 1 is formed; the low-cost high-performance glass liquid 1 is cooled to the forming temperature through the working channel, and then flows out through the platinum leakage plate to form low-cost high-performance glass fiber 1 ; The glass fiber 1 is quickly drawn into a low-cost high-performance glass fiber 1 with a set diameter (11±1um) under the high-speed traction of the drawing machine. Performance silk cake 1; in the programmed automatic chopped production line, low-cost high-performance silk cake 1 is chopped and dried to obtain dry glass fiber chopped yarn 1, that is, low-cost high-performance chopped yarn 1 .

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber 1 is 1209°C, the upper limit of the crystallization temperature of the glass _liquid T is 1118°C, and the refractive index nD/20°C of the glass fiber strand 1 is 1.584. The tensile modulus was 87.1 GPa.

Example 2

In terms of mass percentage, 59.2wt% SiO ₂ , 11.6wt% Al ₂ O ₃ , 22.4wt% CaO, 0.3wt% MgO, 0.3wt% TiO ₂ , 4.6wt% Y ₂ O ₃ , 0.4 wt% ZrO ₂ , 0.4 wt % Li ₂ O, 0.7 wt % Na ₂ O+K ₂ O, 0.1 wt % Fe ₂ O ₃ , calculate the addition ratio of the required raw materials according to the formula, and mix the various raw materials according to the ratio. Quantitatively transported to the mixing silo, fully mixed and evenly mixed to obtain qualified batching materials; the batching materials are transported to the kiln head silo of the pool kiln, and the feeder is uniformly sent to the pool kiln; After high temperature heating, melting, clarification and homogenization, qualified low-cost and high-performance glass melt 2 is formed; low-cost high-performance glass melt 2 is cooled to the forming temperature through the working channel, and then flows out through the platinum leakage plate to form low-cost high-performance glass filaments 2; The glass fiber 2 is quickly drawn into a low-cost high-performance glass fiber 2 with a set diameter (13±1um) under the high-speed traction of the drawing machine. The high-performance silk cake 2; the low-cost high-performance silk cake 2 is dried in the programmed automatic drying furnace to obtain the dried glass fiber precursor 2, that is, the low-cost high-performance untwisted direct yarn 2 is obtained.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber 2 is 1205°C, the upper limit of the crystallization temperature of the glass _liquid is 1122°C, and the refractive index nD/20°C of the glass fiber strand 2 is 1.585. The elongation modulus was 87.5 GPa.

Example 3

In terms of mass percentage, 57.2wt% SiO ₂ , 13.6wt% Al ₂ O ₃ , 22.4wt% CaO, 0.3wt% MgO, 0.3wt% TiO ₂ , 4.6wt% Y ₂ O ₃ , 0.4 wt% ZrO ₂ , 0.4 wt % Li ₂ O, 0.7 wt % Na ₂ O+K ₂ O, 0.1 wt % Fe ₂ O ₃ , calculate the addition ratio of the required raw materials according to the formula, and mix the various raw materials according to the ratio. Quantitatively transported to the mixing silo, fully mixed and evenly mixed to obtain qualified batching materials; the batching materials are transported to the kiln head silo of the pool kiln, and the feeder is uniformly sent to the pool kiln; After high temperature heating, melting, clarification and homogenization, qualified low-cost and high-performance glass melt 3 is formed; low-cost high-performance glass melt 3 is cooled to the forming temperature through the working channel, and then flows out through the platinum leakage plate to form low-cost high-performance glass filaments 3; The glass fiber 3 is quickly drawn into a low-cost high-performance glass fiber 3 with a set diameter (16±1um) under the high-speed traction of the drawing machine. The high-performance silk cake 3; the low-cost high-performance silk cake 3 is dried in the programmed automatic drying furnace to obtain the dried glass fiber precursor, that is, the low-cost high-performance untwisted direct yarn 3 is obtained.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber 3 is 1196°C, the upper limit of the crystallization temperature of the glass _liquid is 1129°C, the refractive index nD/20°C of the untwisted direct yarn 3 is 1.587, and the tensile The elongation modulus was 88.5 GPa.

Example 4

In terms of mass percentage, 55.2wt% SiO ₂ , 15.6wt% Al ₂ O ₃ , 22.4wt% CaO, 0.3wt% MgO, 0.3wt% TiO ₂ , 4.6wt% Y ₂ O ₃ , 0.4 wt% ZrO ₂ , 0.4 wt % Li ₂ O, 0.7 wt % Na ₂ O+K ₂ O, 0.1 wt % Fe ₂ O ₃ , calculate the addition ratio of the required raw materials according to the formula, and mix the various raw materials according to the ratio. Quantitatively transported to the mixing silo, fully mixed and evenly mixed to obtain qualified batching materials; the batching materials are transported to the kiln head silo of the pool kiln, and the feeder is uniformly sent to the pool kiln; After high temperature heating, melting, clarification and homogenization, qualified low-cost and high-performance glass melt 4 is formed; low-cost and high-performance glass melt 4 is cooled to the forming temperature through the working channel, and then flows out through the platinum leakage plate to form low-cost high-performance glass filaments 4; Glass fiber 4 is quickly drawn into low-cost and high-performance glass fiber 4 with a set diameter (17±1um) under the high-speed traction of the drawing machine. The high-performance silk cake 4; the low-cost high-performance silk cake 4 is dried in the programmed automatic drying furnace to obtain the dried glass fiber precursor, that is, the low-cost high-performance untwisted direct yarn 4 is obtained.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber 4 is 1188°C, the upper limit of the crystallization temperature of the glass _liquid is 1138°C, the refractive index nD/20°C of the untwisted direct yarn 4 is 1.587, and the tensile strength is 1.587. The elongation modulus was 87.8 GPa.

_The above examples 1-4 are the experimental verification of the variation range of _{SiO 2} and Al ₂ O ₃ , and the test results are analyzed. _{= 3} is also higher, and the higher the component content of Al ₂ O ₃ , the higher the crystallization temperature of the glass liquid, the upper limit T _liquid , the higher the refractive index nD/20℃ of the untwisted direct yarn, and the tensile modulus will increase. increase.

Example 5

In terms of mass percentage, 58.2wt% SiO ₂ , 14.4wt% Al ₂ O ₃ , 20.6wt% CaO, 0.3wt% MgO, 0.3wt% TiO ₂ , 4.6wt% Y ₂ O ₃ , 0.4 wt% ZrO ₂ , 0.4 wt % Li ₂ O, 0.7 wt % Na ₂ O+K ₂ O, 0.1 wt % Fe ₂ O ₃ , calculate the addition ratio of the required raw materials according to the formula, and mix the various raw materials according to the ratio. Quantitatively transported to the mixing silo, fully mixed and evenly mixed to obtain qualified batching materials; the batching materials are transported to the kiln head silo of the pool kiln, and the feeder is uniformly sent to the pool kiln; After high temperature heating, melting, clarification and homogenization, qualified low-cost and high-performance glass liquid 5 is formed; low-cost high-performance glass liquid 5 is cooled to the forming temperature through the working channel, and then flows out through the platinum leakage plate to form low-cost high-performance glass filaments 5; The glass fiber 5 is quickly drawn into a low-cost high-performance glass fiber 5 with a set diameter (13±1um) under the high-speed traction of the drawing machine. High-performance silk cake 5; in the programmed automatic chopped production line, low-cost high-performance silk cake 1 is chopped and dried to obtain dry glass fiber chopped yarn 5, that is, low-cost high-performance chopped yarn 5.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber 5 is 1201 °C, the upper limit of the crystallization temperature of the glass _liquid T is 1135 °C, the refractive index nD/20 °C of the untwisted direct yarn 5 is 1.575, and the tensile strength is 1.575. The elongation modulus was 88.6 GPa.

Example 6

In terms of mass percentage, 57.7wt% SiO ₂ , 14.0wt% Al ₂ O ₃ , 21.5wt% CaO, 0.3wt% MgO, 0.3wt% TiO ₂ , 4.6wt% Y ₂ O ₃ , 0.4 wt% ZrO ₂ , 0.4 wt % Li ₂ O, 0.7 wt % Na ₂ O+K ₂ O, 0.1 wt % Fe ₂ O ₃ , calculate the addition ratio of the required raw materials according to the formula, and mix the various raw materials according to the ratio. Quantitatively transported to the mixing silo, fully mixed and evenly mixed to obtain qualified batching materials; the batching materials are transported to the kiln head silo of the pool kiln, and the feeder is uniformly sent to the pool kiln; After high temperature heating, melting, clarification and homogenization, qualified low-cost and high-performance glass melt 6 is formed; low-cost high-performance glass melt 6 is cooled to the forming temperature through the working channel, and then flows out through the platinum leakage plate to form low-cost high-performance glass filaments 6; The glass fiber 6 is quickly drawn into a low-cost high-performance glass fiber 6 with a set diameter (10±1um) under the high-speed traction of the drawing machine. High-performance silk cake 6; In the programmed automatic chopped production line, low-cost high-performance silk cake 1 is chopped and dried to obtain dry glass fiber chopped yarn 6, that is, low-cost high-performance chopped yarn 6.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber 6 is 1198°C, the upper limit of the crystallization temperature of the glass _liquid T is 1132°C, the refractive index nD/20°C of the untwisted direct yarn 6 is 1.582, and the tensile The elongation modulus was 88.6 GPa.

Example 7

In terms of mass percentage, 56.8wt% SiO ₂ , 13.2wt% Al ₂ O ₃ , 23.3wt% CaO, 0.3wt% MgO, 0.3wt% TiO ₂ , 4.6wt% Y ₂ O ₃ , 0.4 wt% ZrO ₂ , 0.4 wt % Li ₂ O, 0.7 wt % Na ₂ O+K ₂ O, 0.1 wt % Fe ₂ O ₃ , calculate the addition ratio of the required raw materials according to the formula, and mix the various raw materials according to the ratio. Quantitatively transported to the mixing silo, fully mixed and evenly mixed to obtain qualified batching materials; the batching materials are transported to the kiln head silo of the pool kiln, and the feeder is uniformly sent to the pool kiln; After high temperature heating, melting, clarification and homogenization, qualified low-cost and high-performance glass liquid 7 is formed; low-cost high-performance glass liquid 7 is cooled to the forming temperature through the working channel, and then flows out through the platinum leakage plate to form low-cost high-performance glass filaments 7; Glass fiber 7 is quickly drawn into low-cost high-performance glass fiber 7 with a set diameter (16±1um) under the high-speed traction of the drawing machine. The high-performance silk cake 7; the low-cost high-performance silk cake 7 is dried in the programmed automatic drying oven to obtain the dried glass fiber precursor, that is, the low-cost high-performance untwisted direct yarn 7 is obtained.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber 7 is 1193°C, the upper limit of the crystallization temperature of the glass _liquid T is 1130°C, the refractive index nD/20°C of the untwisted direct yarn 7 is 1.588, and the tensile strength is 1.588. The elongation modulus was 88.4 GPa.

Example 8

In terms of mass percentage, 56.4wt% SiO ₂ , 12.9wt% Al ₂ O ₃ , 24.0wt% CaO, 0.3wt% MgO, 0.3wt% TiO ₂ , 4.6wt% Y ₂ O ₃ , 0.4 wt% ZrO ₂ , 0.4 wt % Li ₂ O, 0.7 wt % Na ₂ O+K ₂ O, 0.1 wt % Fe ₂ O ₃ , calculate the addition ratio of the required raw materials according to the formula, and mix the various raw materials according to the ratio. Quantitatively transported to the mixing silo, fully mixed and evenly mixed to obtain qualified batching materials; the batching materials are transported to the kiln head silo of the pool kiln, and the feeder is uniformly sent to the pool kiln; After high temperature heating, melting, clarification and homogenization, qualified low-cost high-performance glass liquid 8 is formed; low-cost high-performance glass liquid 8 is cooled to the forming temperature through the working channel, and then flows out through the platinum leakage plate to form low-cost high-performance glass filaments 8; The glass fiber 8 is quickly drawn into a low-cost high-performance glass fiber 8 with a set diameter (16±1um) under the high-speed traction of the drawing machine. The high-performance silk cake 8; the low-cost high-performance silk cake 8 is dried in the programmed automatic drying furnace to obtain the dried glass fiber precursor, that is, the low-cost high-performance untwisted direct yarn 8 is obtained.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber 8 is 1190 °C, the upper limit of the crystallization temperature of the glass liquid, T _liquid, is 1131 °C, and the refractive index nD/20 °C of the untwisted direct yarn 8 is 1.589. The tensile modulus was 88.1 GPa.

The above-mentioned Examples 5-8 are based on Example 3 to verify the influence of the preferred CaO component content range on the refractive index. With the increase of the CaO component content, the refractive index of the untwisted direct yarn will increase. With the decrease of the total amount of SiO ₂ and Al ₂ O ₃ , the forming temperature T _logη=3 of the low-cost high-performance glass fiber decreases, and the tensile modulus decreases.

Example 9

The difference from Example 3 is that, in terms of mass percentage, the addition amount of MgO is changed to 0 wt %, and the corresponding addition amount of SiO ₂ is 57.5 wt %.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1197 °C, the upper limit of the crystallization temperature of the glass _liquid is 1129 °C, and the refractive index nD/20 °C of the untwisted direct yarn is 1.587. The elongation modulus was 88.2 GPa.

Example 10

Different from Example 3, in terms of mass percentage, the addition amount of MgO is changed to 0.9 wt %, and the corresponding addition amount of SiO ₂ is 56.6 wt %.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1192°C, the upper limit of the crystallization temperature of the glass _liquid is 1134°C, and the refractive index nD/20°C of the untwisted direct yarn is 1.587. The tensile modulus was 88.1 GPa.

Example 11

Different from Example 3, in terms of mass percentage, the addition amount of MgO was changed to 0.9 wt %, and the corresponding addition amount of SiO ₂ was 56.0 wt %.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1189°C, the upper limit of the crystallization temperature of the glass _liquid is 1137°C, and the refractive index nD/20°C of the untwisted direct yarn is 1.587. The modulus is 88.0 GPa.

Examples 9-11 verify the variation range of MgO content on the basis of Example 3. Since it is necessary to ensure the refractive index of untwisted direct yarn, MgO cannot be used to replace CaO. In this experiment, MgO is used to replace part of SiO ₂ . In general, a small amount of MgO has little effect on the performance, but too high a content will lead to a low SiO ₂ content, which in turn will reduce the molding temperature, and the molding interval (T _logη=3 -T _liquid ) will become smaller, which is not conducive to the stability of the glass fiber. brushed.

Example 12

The difference from Example 3 is that, in terms of mass percentage, the addition amount of Li ₂ O is changed to 0 wt %, and the corresponding addition amount of SiO ₂ is 57.6 wt %.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1189°C, the upper limit of the crystallization temperature of the glass _liquid is 1137°C, and the refractive index nD/20°C of the untwisted direct yarn is 1.587. The modulus is 88.0 GPa.

Example 13

The difference from Example 3 is that the addition amount of Li ₂ O is changed to 1wt% in terms of mass percentage, the corresponding addition amount of SiO ₂ is 56.8wt%, and the addition amount of Na ₂ O+K ₂ O is 0.5wt% %.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1189°C, the upper limit of the crystallization temperature of the glass _liquid is 1137°C, and the refractive index nD/20°C of the untwisted direct yarn is 1.587. The modulus is 88.0 GPa.

Example 14

The difference from Example 3 is that the addition amount of Li ₂ O is changed to 1.5wt% in terms of mass percentage, the corresponding addition amount of SiO ₂ is 56.3wt%, and the addition amount of Na ₂ O+K ₂ O is 0.5 wt%.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1189°C, the upper limit of the crystallization temperature of the glass _liquid is 1137°C, and the refractive index nD/20°C of the untwisted direct yarn is 1.587. The modulus is 88.0 GPa.

Examples 12-14 verify the variation range of Li ₂ O content on the basis of Example 3. According to the test results, it can be seen that a small amount of Li ₂ O has an obvious effect on reducing the molding temperature T _logη=3 of low-cost high-performance glass fibers , and has little effect on other performance. However, if the content is too high, the molding temperature will drop too low, and the molding interval (T _logη=3 -T _liquid ) will become smaller, which is not conducive to the stable drawing of the glass fiber.

Example 15

Different from Example 3, in terms of mass percentage, the addition amount of ZrO ₂ was changed to 0.1 wt %, and the corresponding addition amount of SiO ₂ was 57.5 wt %.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1197°C, the upper limit of the crystallization temperature of the glass _liquid is 1137°C, and the refractive index nD/20°C of the untwisted direct yarn is 1.586. The modulus is 88.0 GPa.

Example 16

Different from Example 3, in terms of mass percentage, the addition amount of ZrO ₂ was changed to 0.5 wt %, and the corresponding addition amount of SiO ₂ was 57.1 wt %.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1195°C, the upper limit of the crystallization temperature of the glass _liquid is 1125°C, and the refractive index nD/20°C of the untwisted direct yarn is 1.587. The modulus is 88.2GPa.

Example 17

Different from Example 3, in terms of mass percentage, the addition amount of ZrO ₂ was changed to 1.0 wt %, and the corresponding addition amount of SiO ₂ was 56.6 wt %.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1194°C, the upper limit of the crystallization temperature of the glass _liquid is 1132°C, and the refractive index nD/20°C of the untwisted direct yarn is 1.587. The modulus is 88.0 GPa.

Examples 15-17 verify the variation range of ZrO ₂ content on the basis of Example 3. According to the test results, a small amount of ZrO ₂ can reduce the crystallization temperature T _of low-cost high-performance glass fibers and increase the molding interval (T _logη=3 -T _liquid ), showing the effect of inhibiting glass crystallization, and has no negative impact on other properties. However, if the content is too large, there will be a tendency to increase the crystallization temperature.

Example 18

Different from Example 3, in terms of mass percentage, the addition amount of Y ₂ O ₃ was changed to 4.9 wt %, and the corresponding addition amount of SiO ₂ was 56.9 wt %.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1194°C, the upper limit of the crystallization temperature of the glass _liquid is 1132°C, and the refractive index nD/20°C of the untwisted direct yarn is 1.590. The modulus is 88.6GPa.

Example 19

Different from Example 3, in terms of mass percentage, the addition amount of Y ₂ O ₃ was changed to 4.1 wt %, and the corresponding addition amount of SiO ₂ was 57.7 wt %.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1201 °C, the upper limit of the crystallization temperature of the glass _liquid is 1125 °C, and the refractive index nD/20 °C of the untwisted direct yarn is 1.583. The modulus is 87.6GPa.

Example 20

Different from Example 3, in terms of mass percentage, the addition amount of Y ₂ O ₃ was changed to 3.5 wt %, and the corresponding addition amount of SiO ₂ was 58.3 wt %.

After testing, the molding temperature T _logη=3 of the low-cost high-performance glass fiber is 1205°C, the upper limit of the crystallization temperature of the glass _liquid is 1121°C, and the refractive index nD/20°C of the untwisted direct yarn is 1.578. The modulus is 87.2GPa.

Examples 15-17 are based on Example 3 to verify the variation range of the content of Y ₂ O _3. According to the test results, it can be seen that the refractive index and elastic tensile modulus of the glass fiber increase significantly when the content of Y ₂ O ₃ is increased. , the crystallization temperature T _liquid will also increase accordingly, and the molding temperature T _logη=3 also decreases due to the relative decrease of the SiO ₂ content. Therefore, if the content of Y ₂ O ₃ continues to increase, on the one hand, the cost will increase, the refractive index will exceed the standard, and on the other hand, the molding interval (T _logη=3 -T _liquid ) will also be too small. Not conducive to drawing production.

Comparative Example 1

In mass percentage, 54.4wt% SiO ₂ , 14.9wt% Al ₂ O ₃ , 16.6wt% CaO, 4.6wt% MgO, <0.5wt% Fe ₂ O ₃ , trace amount of TiO ₂ ,< 0.5 wt % of Na ₂ O+K ₂ O, 8.5 wt % of B, 0.3 wt % of F, ordinary untwisted direct yarns were produced in the same manner as in Examples 1-20.

After testing, the forming temperature T _logη=3 of the glass fiber is 1214°C, the upper limit of the crystallization temperature of the glass _liquid is 1135°C, the refractive index nD/20°C of the untwisted direct yarn is 1.545, and the tensile modulus is 81.9 GPa.

Comparative Example 2

In mass percentage, 58.0wt% SiO ₂ , 11.2wt% Al ₂ O ₃ , 22wt% CaO, 2.7wt% MgO, 0.3wt% Fe ₂ O ₃ ,<2.2wt% TiO ₂ , 0.5 wt% Na ₂ O+K ₂ O, and ordinary untwisted direct yarns were produced in the same manner as in Examples 1-20.

After testing, the forming temperature T _logη=3 of the glass fiber is 1261°C, the upper limit of the crystallization temperature of the glass _liquid is 1173°C, the refractive index nD/20°C of the untwisted direct yarn is 1.576, and the tensile modulus is 83.1 GPa.

Table 1 below is a summary table of components and properties of Examples 1-20 and Comparative Examples 1-2 of the present invention.

The present invention can be used not only to strengthen the transparent PC resin, but also to strengthen the transparent polyamide (PA) resin with a refractive index of about 1.57-1.59.

The glass fiber composition according to the present invention can be combined with one or more organic and/or inorganic materials to prepare composite materials with excellent properties, and the organic materials can include epoxy resins, unsaturated polyesters, vinyl resins and other thermosetting resins Resins and thermoplastic resins such as polycarbonate (PC), polypropylene (PP), polyamide (PA), polybutylene terephthalate (PBT), and polyethylene terephthalate (PET).

Although the embodiments of the present invention have been shown and described above, it should be understood that the above-mentioned embodiments are exemplary and should not be construed as limiting the present invention. Embodiments are subject to variations, modifications, substitutions and variations.

Claims (12)

1. a low-cost high-performance glass fiber composition is characterized in that, comprises the following components, and the content of each component is expressed as follows by mass percentage:

Wherein the TiO ₂ , Na ₂ O and K ₂ O are introduced in the form of impurities, not added separately, and the sum of the mass percentages of the Li ₂ O, Na ₂ O and K ₂ O does not exceed 1.5wt% . 2. The low-cost high-performance glass fiber composition according to claim 1, wherein the mass percentage of the Y ₂ O is 4.1-4.9 wt %. The mass percentage content of the ZrO ₂ is 0.1-0.5 wt %. 3 . The low-cost high-performance glass fiber composition according to claim 1 , wherein the mass percentage of the TiO ₂ introduced in the form of impurities should be controlled at 0-0.4 wt %. 4 . 4 . The low-cost high-performance glass fiber composition according to claim 1 , wherein the mass percentage content of Fe ₂ O ₃ should be controlled at 0-0.3 wt %. 5 . 5 . The low-cost high-performance glass fiber composition according to claim 1 , wherein the sum of the mass percentages of the Li ₂ O, Na ₂ O and K ₂ O should be controlled at 0.3-1.5wt%. 6 . . 6 . The low-cost high-performance glass fiber composition according to claim 1 , wherein the mass percentage content of the SiO ₂ should be controlled at 55.2-59.2 wt %. 7 . 7 . The low-cost high-performance glass fiber composition according to claim 1 , wherein the mass percentage of the Al ₂ O ₃ should be controlled at 11.6-15.6 wt %. 8 . 8 . The low-cost high-performance glass fiber composition according to claim 1 , wherein the mass percentage content of the CaO should be controlled at 21.5-23.3 wt %. 9 . 9 . The low-cost high-performance glass fiber composition according to claim 1 , wherein the mass percentage content of the MgO should be controlled at 0-0.9 wt %. 10 . 10. The low-cost high-performance glass fiber composition according to claim 1, wherein the content of each component is expressed as a mass percentage as follows:

Wherein the TiO ₂ , Na ₂ O and K ₂ O are introduced in the form of impurities, not added separately, and the sum of the mass percentages of the Li ₂ O, Na ₂ O and K ₂ O is 0.3-1.5wt% %. 11. A low-cost high-performance glass fiber, characterized in that it is made from the low-cost high-performance glass fiber composition according to any one of claims 1-11, and the low-cost high-performance glass fiber has a refractive index of 1.580-1.590. 12 . A low-cost high-performance glass fiber reinforced composite material, comprising the low-cost high-performance glass fiber according to claim 12 .