High-temperature resistant fiberglass and associated manufacturing process

Abstract

High-temperature resistant glass fiber comprising the following components and mass fractions: SiO2 62-66%; Al2O3 14-19%; CaO 15-20%; MgO 0-2%; Fe2O 30-3%; TiO 20-1.2%; Total content of Na2O and K2O 0.1-0.8%; BaO 0.05-1.5%.

Description

[0001] The present application claims priority over Chinese patent application No. 201710463953.5 entitled “A high temperature resistant glass fiber and an associated manufacturing process”, which was filed with the Chinese Patent Office on June 19, 2017 and the entire content of which is incorporated by reference as part of this application. Technical field

[0002] The present invention relates to the technical field of non-metallic materials and in particular to a high-temperature resistant glass fiber and an associated manufacturing process. State of the art

[0003] Glass fiber is an inorganic, non-metallic material with outstanding performance characteristics, exhibiting many advantageous properties such as high specific strength, high specific stiffness, good electrical insulation, high heat resistance, good corrosion resistance, etc. With over 90%, glass fiber is currently the most widely used reinforcing substrate in the field of resin-based composites.

[0004] The main components of glass fiber are silicon dioxide, aluminum oxide, calcium oxide, boron oxide, magnesium oxide, sodium oxide, etc. Glass fiber can be divided according to its alkali content into alkali-free glass fiber (sodium oxide 0%-2%, belonging to aluminum-boron silicate glass), medium-alkali glass fiber (sodium oxide 8%-12%, belonging to soda-calcium silicate glass with or without boron), and high-alkali glass fiber (more than 13% sodium oxide, belonging to soda-lime silicate glass), with alkali-free glass fiber, also known as E-glass fiber, being the most widely used.

[0005] As the application area of ​​glass fiber composites continues to evolve, the performance requirements for E-glass fibers in industry are also continuously increasing, particularly in the fields of aerospace, the military, the automotive industry, etc., and stricter requirements apply regarding high-temperature resistance and the formability of the materials; however, existing E-glass fibers generally have problems with low softening temperature and excessively high forming temperature. Summary of the invention

[0006] In this context, one object of the present invention is to provide a high-temperature-resistant glass fiber and an associated manufacturing process. The high-temperature-resistant glass fiber provided in the present invention has a high softening temperature and good formability properties.

[0007] The present invention provides for a high-temperature resistant glass fiber comprising the following components: SiO2 62-66 %; Al2O3 14-19 %; CaO 15-20 %; MgO 0-2 %; Fe2O3 0-3 %; TiO2 0-1,2 %; Total content of Na2O and K2O 0,1-0,8 %.

[0008] Preferably, it comprises a mass fraction of 63-65% SiO2.

[0009] Preferably it comprises a mass fraction of 16-18% Al2O3.

[0010] Preferably, it comprises a mass fraction of 16-19% CaO.

[0011] Preferably, it comprises a mass fraction of 0-1% MgO.

[0012] Preferably it comprises a mass fraction of 0.1-2% Fe2O3.

[0013] Preferably it comprises a mass fraction of 0.1-0.8% TiO2.

[0014] The total content of Na2O and K2O is preferably a mass fraction of 0.1-0.4%.

[0015] Preferably, it also includes ZrO2 and / or BaO with a total mass fraction of no more than 2%.

[0016] The present invention provides a manufacturing process for the high-temperature resistant glass fiber according to the above-mentioned technical solution comprising the following steps: a) Selecting glass raw materials according to the components of the high-temperature resistant glass fiber and calculating the respective quantity of raw materials used; b) Mixing all raw materials and then melting them into liquid glass; and c) Drawing the liquid glass into a glass filament through a wire drawing machine and subsequent cooling to obtain the high-temperature resistant glass fiber.

[0017] Compared to the prior art, the present invention provides a high-temperature-resistant glass fiber and an associated manufacturing process. The high-temperature-resistant glass fiber provided by the present invention comprises a mass fraction of 62-66% SiO2; 14-19% Al2O3; 15-20% CaO; 0-2% MgO; 0-3% Fe2O3; 0-1.2% TiO2; and 0.1-0.8% total content of Na2O and K2O. The present invention ensures that the glass fiber has high temperature resistance and good dimensional properties by precisely controlling the proportions of all components. In particular, the high softening point of the glass is significantly improved. ZrO2 and / or BaO can be added to the glass fiber composition of the present invention as required, with a total mass fraction of no more than 2%, the inclusion of these components further improving the high-temperature resistance of the glass fiber.The test results show that the forming temperature of the glass fiber of the present invention is at most 1380 °C, the upper temperature limit for crystallization is below 1280 °C and the high-temperature softening temperature of the glass fiber is above 950 °C. Detailed description of the embodiments

[0018] The technical solutions from the examples of the present invention are clearly and completely described below. It is evident that the described examples represent only a part and not the entirety of all examples of the present invention. Based on the examples of the present invention, all other examples obtained by skilled workers without creative activity fall within the scope of the present invention.

[0019] The present invention provides a high-temperature resistant glass fiber comprising the following components and mass fractions: SiO2 62-66 %; Al2O3 14-19 %; CaO 15-20 %; Fe2O3 0,1-3 %; MgO 0-2 %; TiO2 0-1,2 %; Total content of Na2O and K2O 0,1-0,8 %.

[0020] The high-temperature resistant glass fiber provided by the present invention comprises SiO2, Al2O3, CaO, Fe2O3, MgO, TiO2, Na2O, and K2O. Among these components, silicon dioxide (SiO2) is one of the oxides primarily responsible for the formation of a glass network and mainly serves to improve the mechanical properties, chemical stability, and thermal stability of the glass. In the present invention, the mass fraction of SiO2 is 62–66%, preferably 63–65%, and particularly 62%, 63%, 64%, 65%, or 66%.

[0021] In the present invention, aluminum oxide (Al₂O₃) is also one of the oxides primarily responsible for the formation of a glass network, thus reducing the tendency to crystallize and improving the structure of the glass network. In the present invention, the mass fraction of Al₂O₃ is 14–19%, preferably 16–18%, and particularly 14.7%, 16%, 16.7%, 17.8%, or 18.5%.

[0022] In the present invention, both calcium oxide (CaO) and magnesium oxide (MgO) are included as outer oxides of the glass structure network, thus reducing the high-temperature viscosity of the glass and improving the glass frit. Simultaneously, the appropriate mass fraction and ratio also contribute to improving the stability of the glass network structure. In the present invention, the mass fraction of CaO is 15-20%, preferably 16-19%, particularly 15%, 16.3%, 17.5%, 18%, or 19.1%; the mass fraction of MgO is 0-2%, preferably 0-1%, particularly 0.3% or 1%.

[0023] In the present invention, iron oxide (Fe₂O₃) promotes heat transfer in the tank furnace, is heat-resistant and creep-resistant in the glass fiber, and improving or increasing the iron oxide content can significantly raise the high-temperature softening point of the glass. In the present invention, the mass fraction of iron oxide is 0–3%, preferably 0.1–2%, and particularly 0.5%, 0.9%, 1.5%, or 2.3%.

[0024] In the present invention, the addition of titanium dioxide (TiO2) improves the flow and crystallization tendency of the glass at high temperatures, as well as the tensile modulus and corrosion resistance of the glass fiber. In the present invention, the mass fraction of TiO2 is 0-1.2%, preferably 0.1-0.8%, and particularly 0.1%, 0.2%, or 0.4%.

[0025] In the present invention, Na₂O and K₂O, which reduce the viscosity of the glass and improve its tendency to crystallize, are added to the glass fiber composition. In the present invention, the mass fraction of Na₂O + K₂O is 0.1–0.8%, preferably 0.1–0.4%, and particularly 0.3%, 0.4%, or 0.5%.

[0026] In a preferred embodiment, the glass fiber composition of the present invention may further comprise ZrO2 and / or BaO with a total mass fraction of at most 2%, without impairing the formability of the glass fiber, the addition of these components being able to further improve the high-temperature softening point of the glass fiber. In an example of the present invention, the mass fraction of ZrO2 is preferably 0.05–1.5%, more particularly 0.1% or 0.6%; the mass fraction of BaO is preferably 0.05–1.5%, more particularly 0.1% or 0.2%.

[0027] The present invention presents a manufacturing process for producing the high-temperature resistant glass fiber according to the above-mentioned technical solution, comprising the following steps: a) Selecting glass raw materials according to the components of the high-temperature resistant glass fiber and calculating the respective quantity of raw materials used; b) Mixing all raw materials and then melting them into liquid glass; and c) Drawing the liquid glass into a glass filament through a wire drawing machine and subsequent cooling to obtain the high-temperature resistant glass fiber.

[0028] In the manufacturing process provided by the present invention, glass raw materials are first selected according to the components of the high-temperature-resistant glass fiber, and the quantity of each raw material is calculated. Then, all raw materials are mixed and subsequently melted to obtain liquid glass, the melting temperature preferably being 1400-1500 °C; and the melting apparatus is preferably a tank furnace. Preferably, the present invention clarifies and homogenizes the molten glass.

[0029] After obtaining the molten glass, it is drawn into a glass filament by a wire drawing machine and then cooled to obtain a high-temperature resistant glass fiber, wherein the preferred cooling method is spray cooling and the diameter of the glass fiber is preferably 5-25 µm. In the present invention, the molten glass is preferably cooled before being drawn through a wire drawing machine, preferably to a temperature of 1300 to 1380 °C. After obtaining the glass fiber, its surface is preferably treated with a sizing agent.

[0030] The present invention ensures that the glass fiber possesses high temperature resistance and good dimensional properties by precisely controlling the proportion of each component. In particular, the high-temperature softening point of the glass is significantly improved. ZrO₂ and / or BaO can be added to the glass fiber composition of the present invention as required, with a total mass fraction of no more than 2%, the inclusion of these components further improving the high-temperature resistance of the glass fiber. Test results show that the dimensional temperature of the glass fiber of the present invention is at most 1380 °C, the upper temperature limit for crystallization is below 1280 °C, and the high-temperature softening point of the glass fiber is above 950 °C.

[0031] For a better understanding of the invention, the optical fiber provided by the present invention is described in detail below with reference to the examples. The scope of the present invention is not limited by the following examples. Examples 1-5

[0032] The glass raw materials were selected according to the glass fiber composition shown in Table 1 and the respective quantity of raw materials was calculated: Table 1 Example glass fiber composition composition Example 1 Example 2 Example 3 Example 4 Example 5 SiO2 62 63 64 65 66 Al2O3 18,5 17,8 16,7 14,7 16 CaO 19,1 18 17,5 16,3 15 Fe2O3 -- 0,5 0,9 1,5 2,3 MgO -- -- 0,3 1 0,3 TiO2 -- 0,2 0,1 0,4 0,1 Na2O+K2O 0,4 0,5 0,3 0,3 0,3 ZrO2 -- -- 0,1 0,6 -- BaO -- -- 0,1 0,2 -- The required raw materials were then weighed proportionally, transported in their entirety into the mixing container, and after uniform mixing, the mixed material was transported into the storage container of the tub furnace; The mixed materials in the storage container of the tank furnace were conveyed into the tank furnace, gradually melted to liquid glass at a high temperature of 1400 °C or higher, and after clarification and homogenization, the stable and high-quality liquid glass was conveyed into the drawing process channel; After the liquid glass was cooled to a suitable temperature in the drawing channel, it flowed out through a platinum perforated plate and was quickly drawn by a wire drawing machine into a glass filament with a diameter of 3-25 µm; The glass filament was spray-cooled and coated with sizing to obtain a glass fiber. Comparative example 1

[0033] The glass raw materials were selected according to the glass fiber composition shown in Table 2 and the respective quantity of raw materials was calculated: Table 2: Comparative example of glass fiber composition composition Comparative example SiO2 65 Al2O3 24 CaO ≤ 1 Fe2O3 10 MgO -- TiO2 track Na2O+K2O < 0,5 ZrO2 -- BaO -- The required raw materials were then weighed proportionally, transported in their entirety into the mixing container, and after uniform mixing, transferred to the storage container of the tank furnace; The mixed materials in the storage container of the tank furnace were conveyed into the tank furnace, gradually melted to liquid glass at a high temperature of 1400 °C or higher, and after clarification and homogenization, the stable and high-quality liquid glass was conveyed into the drawing process channel; After the liquid glass was cooled to a suitable temperature in the drawing channel, it flowed out through a platinum perforated plate and was quickly drawn by a wire drawing machine into a glass filament with a diameter of 3-25 µm; The glass filament was spray-cooled and coated with sizing to obtain a glass fiber. Example 6

[0034] The properties of the glass fibers described above were tested. The results are shown in Table 3. Table 3 shows the formulation and properties of the glass fibers provided by the examples and comparative examples of the present invention, wherein T logη = 3 represents the forming temperature of the fibers, which was determined using a BROOKFIELD high-temperature viscometer; T liquid The upper limit of the glass crystallization temperature, which was determined using an Orton gradient furnace; ΔT represents the difference between the forming temperature of the fibers and the upper limit of the crystallization temperature of the glass; the softening temperature of the glass was measured using an Orton SP-1100 and the heat resistance test procedure was carried out as follows: Rate of weight change

[0035] The length of the test piece was 200 mm and the number of samples was n = 10.

[0036] Weight measurement conditions before heating: Heating 100°C × 1 hr → Drying → Cooling to normal temperature in the oven for 1 hr → Size and weight determination;

[0037] Weight measurement conditions after heating: 805 °C × 4 hrs → Heating → Cooling to normal temperature in the oven for 1 hr → Size and weight determination;

[0038] Comparing the weight change before and after heating, taking 10 samples to obtain an average value; Heat shrink

[0039] The dimensional change before and after heating was compared using the same rate of weight change. Tensile strength

[0040] Test conditions: the heating conditions corresponded to the heating conditions of the weight change rate, the test piece length was 200 mm, the test piece width was 150 mm; number of samples n = 20; The tensile strength of the sample before and after heating was tested and averaged. Table 3 Performance data of the fiber optic cable from the examples and comparison examples composition Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example T logη=3 (°C) 1319 1337 1352 1344 1368 1460 T liquid (°C) 1202 1234 1228 1251 1280 1320 ΔT (°C) 117 103 124 93 88 140 High-temperature softening temperature / °C 950 953 962 955 958 950 Transition temperature crystallization phase / °C 819 821 833 812 825 810 Heat resistance Rate of weight change / % 0,77 0,75 0,74 0,73 0,74 Heat shrinkage / % 0,28 0,34 0,3 0,32 0,38 Tensile strength (N / beam) 45,1 54,8 60,1 58,3 57,8

[0041] As can be seen from Table 3, the glass fiber from the examples of the present invention has better high-temperature resistance and formability compared to the comparison example; the forming temperature is at most 1380 °C, the upper temperature limit of crystallization is below 1280 °C, and the high-temperature softening temperature of the glass fiber is above 950 °C.

[0042] The above description of the examples serves solely to illustrate the process of the present invention and its basic concept. It should be noted that a person skilled in the art can modify and alter the present invention in various ways without departing from its fundamental principle. Such modifications and alterations also fall within the scope of the appended claims. The above description of the disclosed examples enables a person skilled in the art to carry out or use the present invention, and various modifications of these examples are obvious to them. The basic principles defined in this invention can be applied to other examples without departing from the meaning or scope of the present invention.The present invention is therefore not limited to the examples described herein, while at the same time it corresponds to the broadest scope of application within the basic principles described herein and the novel features disclosed herein. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] CN 201710463953

[0001]

Claims

[1] High-temperature resistant glass fiber comprising the following components and mass fractions SiO2 62-66 %; Al2O3 14-19 %; CaO 15-20 %; MgO 0-2 %; Fe2O3 0-3 %; TiO2 0-1,2 %; Total content of Na2O and K2O 0,1-0,8 %. [2] Glass fiber according to claim 1, comprising a mass fraction of 63-65% SiO2. [3] Glass fiber according to claim 1, comprising a mass fraction of 16-18% Al2O3. [4] Glass fiber according to claim 1, comprising a mass fraction of 16-19% CaO. [5] Glass fiber according to claim 1, comprising a mass fraction of 0-1% MgO. [6] Glass fiber according to claim 1, comprising a mass fraction of 0.1-2% Fe2O3. [7] Glass fiber according to claim 1, comprising a mass fraction of 0.1-0.8% TiO2. [8] Glass fiber according to claim 1, wherein the mass fraction of the total content of Na2O and K2O is 0.1-0.4%. [9] Glass fiber according to any one of claims 1 to 8, further comprising ZrO2 and / or BaO with a total mass fraction of not more than 2%. [10] Manufacturing process for the high-temperature resistant glass fiber according to any one of claims 1 to 9, comprising the steps: a) Selecting glass raw materials according to the components of the high-temperature resistant glass fiber and calculating the respective quantity of raw materials used; b) Mixing all raw materials and then melting them into liquid glass; and c) Drawing the liquid glass into a glass filament through a wire drawing machine and subsequent cooling to obtain the high-temperature resistant glass fiber.