Glass fiber wool and process for its preparation

Abstract

This invention belongs to the field of inorganic materials, specifically relating to a glass fiber cotton and its preparation process. The glass fiber cotton provided is composed of the following substances in mass percentage: 70-85% glass component, 10-20% functional additives and 3-14% structural stabilizer. Its preparation process includes the following steps: S1. raw material pretreatment; S2. melting; S3. spinning; S4. molding; S5. post-treatment. The glass fiber cotton prepared by this invention has the following beneficial effects: (1) improved thermal insulation performance: thermal conductivity is less than 0.030W / (m·K); (2) high mechanical strength: tensile strength reaches 50-80MPa; (3) good high temperature resistance: the service temperature can reach above 600℃.

Description

Technical Field

[0001] This invention belongs to the field of inorganic materials, specifically relating to a glass fiber cotton and its preparation process. Background Technology

[0002] Glass fiber wool is a high-performance inorganic non-metallic material, belonging to a category of glass fibers. It is made from glass spheres or waste glass through processes such as high-temperature melting, drawing, winding, and weaving. Its single filament diameter is extremely fine, ranging from a few micrometers to over twenty micrometers.

[0003] From a chemical composition perspective, glass fiber wool is mainly based on silicon dioxide, with a content of approximately 50-60%, and also contains various metal oxides such as calcium, boron, sodium, aluminum, and iron. Depending on its composition, glass fiber wool can be mainly classified into different types, including alkali-free glass, medium-alkali glass, and high-alkali glass.

[0004] Glass fiber wool has many excellent properties: good insulation, strong heat resistance, good corrosion resistance, and high mechanical strength. However, it also has disadvantages such as brittleness and poor wear resistance.

[0005] Glass fiber cotton is mainly used in the following technical fields:

[0006] (1) Construction field

[0007] In the construction industry, fiberglass wool is mainly used for thermal insulation and sound absorption. As the best material for thermal insulation and sound absorption in steel structure buildings, fiberglass wool can be used for exterior wall insulation, roof insulation, and interior partitions. Its numerous tiny air pores enable it to effectively block heat conduction. Its advantages include: maintaining the original building structure, especially suitable for complex and irregularly shaped surfaces; seamless construction with good airtightness, improving overall energy efficiency; and convenient and efficient construction, saving labor and time.

[0008] (2) Industrial sector

[0009] In the industrial sector, glass fiber wool is widely used in various industrial facilities due to its heat resistance, fire resistance, and chemical stability. Specific applications include: industrial pipeline insulation: preventing heat loss from pipelines and improving energy efficiency; equipment insulation: reducing the surface temperature of industrial equipment and improving the working environment; electrical insulation material: utilizing its excellent electrical insulation properties for the protection of electrical equipment; industrial filtration: due to its large surface area, ultrafine glass fiber wool has strong filtration and adsorption properties, and can be used in filtration processes in industries such as chemical and electronics.

[0010] (3) Transportation sector

[0011] Fiberglass insulation also has wide applications in the transportation sector, including thermal and sound insulation of train carriages, heat insulation and fireproofing of ships, and sound and heat insulation of automobiles. In these applications, fiberglass insulation not only provides excellent thermal and acoustic properties, but also improves the fire safety of vehicles due to its non-combustible nature.

[0012] (4) Safety protection field

[0013] The application of glass fiber in safety and protective textiles is becoming increasingly widespread. Due to its high modulus and strength, high elongation at break and hook strength, as well as its excellent impact resistance properties such as transverse compression and bending stiffness, glass fiber is used in fields such as mechanical injury protection textiles, thermal protection textiles, electromagnetic protection, and nuclear and biochemical protection textiles.

[0014] CN108503240B discloses a high-silica glass fiber cotton with low thermal conductivity and its preparation method. The disclosed acid leaching heating process is carried out at a uniform and slow rate, allowing the acid to dissolve the non-silica components within the fiber cotton at a relatively slow rate. After the heating is completed, a heat preservation stage is set to ensure more sufficient contact between the reaction materials to achieve complete fiber dissolution, thereby reducing blocky dissolution on the fiber surface and better preserving the columnar morphology of the fiber. This is beneficial for the formation of a porous structure in the fiber after acid leaching, thus improving the thermal insulation performance of the fiber product. Simultaneously, the disclosed acid leaching treatment has a low initial reaction temperature and a slow reaction rate, resulting in a moderate contact speed between the fiber and the acid, preventing the excessive accumulation of reaction products on the fiber surface. This facilitates the migration of impurity ions within the fiber, further increasing the silica content in the glass fiber.

[0015] Fiberglass wool, as a multifunctional material, plays an important role in construction, industry, transportation, and other fields. Although it has drawbacks such as health risks and insufficient high-temperature resistance, these limitations are being continuously overcome through product innovation, process upgrades, and application expansion. Summary of the Invention

[0016] The purpose of this invention is to provide a glass fiber cotton and its preparation process, which is composed of the following substances in mass percentage: 70-85% glass component, 10-20% functional additives and 3-14% structural stabilizer, wherein the glass component is composed of silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide and boron oxide, the functional additives are composed of zirconium oxide, strontium oxide and bio-based binder, and the structural stabilizer is composed of lithium lanthanum zirconium oxide nanoparticles and graphene precursor polymer.

[0017] Further, the content of silica is 40-60% of the mass of the glass fiber wool, the content of alumina is 10-20% of the mass of the glass fiber wool, the content of calcium oxide is 5-15% of the mass of the glass fiber wool, the content of magnesium oxide is 3-8% of the mass of the glass fiber wool, and the content of boron oxide is 2-5% of the mass of the glass fiber wool. Silica, as the main network former, provides the basic skeletal structure of the glass fiber, giving the product a high melting point and chemical stability. Its principle is to form a three-dimensional network through silicon-oxygen bonds, enhancing the mechanical strength and corrosion resistance of the fiber. Alumina, as a network intermediate, partially replaces silicon-oxygen bonds, improving the chemical stability and mechanical strength of the glass fiber. Aluminum ions enter the silicon-oxygen network, inhibiting the crystallization phenomenon of the fiber at high temperatures. Calcium oxide, as a network modifier, can lower the glass melting temperature and improve processing fluidity. Calcium ions reduce melt viscosity, but excessive amounts can lead to brittleness; therefore, its usage needs to be controlled. Magnesium oxide, as an auxiliary network modifier, works synergistically with calcium oxide to further lower the melting temperature while improving the fiber's toughness and thermal shock resistance. Magnesium ions possess a high field strength, which helps stabilize the glass structure. Boron oxide, as a flux and stabilizer, reduces the coefficient of thermal expansion, improving the fiber's stability under temperature changes. Boron-oxygen bonds form a flexible network, compensating for the rigidity of the silicon-oxygen network.

[0018] Furthermore, the zirconium oxide content is 5-10% of the glass fiber cotton's mass, the strontium oxide content is 0.5-1% of the glass fiber cotton's mass, and the bio-based adhesive content is 4.5-9.5% of the glass fiber cotton's mass. Zirconium oxide, as a high-temperature resistant additive, improves the fiber's high-temperature resistance and mechanical strength. Zirconium ions have a high melting point and a phase transformation toughening effect, inhibiting fiber softening at high temperatures and synergistically forming a stable crystalline phase with alumina. The bio-based adhesive, as an environmentally friendly binder, replaces synthetic resins, improving the fiber's formability and environmental friendliness. The hydroxyl groups in starch molecules form hydrogen bonds with the glass surface, achieving inter-fiber bonding, and exhibiting good biodegradability. The addition of strontium oxide forms a magnesium-calcium-strontium alkaline earth metal oxide system, creating a multi-alkaline earth metal effect in the glass network. Due to its smaller ionic radius and higher field strength, magnesium ions mainly enter the interstitial sites of the glass network, improving the network density. Calcium ions act as a network modifier, effectively reducing melt viscosity. Strontium ions have a larger ionic radius and can fill network voids, reducing ion migration at high temperatures. When the three ions coexist in a specific ratio, strontium ions form a gradient filling effect with calcium and magnesium ions. By adjusting the network void size through the difference in ionic radii, the melt viscosity is reduced while inhibiting high-temperature ion diffusion. This significantly improves the elastic modulus of the fiber while lowering the melting temperature.

[0019] Furthermore, the content of the lithium lanthanum zirconium oxide nanoparticles is 3-10% of the mass of the glass fiber cotton, and the content of the graphene precursor polymer is 0.01-4% of the mass of the glass fiber cotton. The graphene precursor polymer is polyimide. The lithium lanthanum zirconium oxide nanoparticles act as a structural stabilizer; their lattice structure guides the uniform deposition of lithium ions, improving the interfacial stability of the fiber. Simultaneously, the lithium lanthanum zirconium oxide nanoparticles form a composite phase with the glass components, inhibiting crack propagation. The graphene precursor polymer, as a precursor to the electrothermal functional layer, transforms into graphene under laser induction, forming a conductive network that endows the glass fiber cotton with electrothermal functionality while simultaneously enhancing the fiber's flexibility and surface hardness.

[0020] Furthermore, the bio-based adhesive is a starch-based adhesive, and the starch is corn starch or potato starch. As an environmentally friendly binder, the starch-based adhesive replaces synthetic resins, improving the formability and environmental friendliness of the fibers. The hydroxyl groups in the starch molecules form hydrogen bonds with the glass surface, achieving inter-fiber bonding, and it also exhibits good biodegradability.

[0021] The synergistic effects between the components in this invention are mainly as follows:

[0022] (1) Synergy between glass components and functional additives: Silica and alumina form the main network, reducing defects through interfacial bonding. Bio-based adhesives encapsulate fibers during molding, forming hydrogen bonds with the base components, thereby improving bonding strength without compromising environmental friendliness.

[0023] (2) Synergistic effect of boron oxide and magnesium oxide: boron oxide reduces thermal expansion and magnesium oxide increases toughness. The two work together to improve the durability of fibers under thermal cycling.

[0024] (3) Synergy between bio-based adhesive and graphene precursor polymer: The bio-based adhesive initially shapes the fibers at low temperature, providing a stable substrate for subsequent coating and laser treatment. The coated graphene precursor polymer is then transformed into a graphene conductive layer under laser induction. This layer is tightly bonded to the fiber network bonded by the bio-based adhesive, giving the material electrothermal function. At the same time, the bio-based adhesive ensures the environmental friendliness of the preparation process.

[0025] The present invention also provides a preparation process for the above-mentioned glass fiber cotton, comprising the following steps:

[0026] S1. Raw material pretreatment: Lithium lanthanum zirconium oxide nanoparticles are ultrasonically dispersed, and silica, alumina, calcium oxide, magnesium oxide, boron oxide, zirconium oxide and strontium oxide are mixed and pulverized to a particle size of less than 50 μm, and then mixed with the ultrasonically dispersed lithium lanthanum zirconium oxide nanoparticles.

[0027] S2. Melting: Melt the mixture obtained in step S1 at a temperature of 1500-1600℃ for 2-4 hours under a nitrogen atmosphere;

[0028] S3. Spinning: The melt is spun into fibers using a centrifugal blowing method at a speed of 3000-5000 rpm;

[0029] S4. Molding: The fiber is mixed with the bio-based adhesive, dried and cured at 100-180℃, and coated with a graphene precursor polymer solution;

[0030] S5. Post-processing: Laser scanning is performed along a preset graphic path to convert the graphene precursor polymer into a graphene layer, followed by surface treatment and cutting.

[0031] Furthermore, the melting step employs a segmented heating method: first, the temperature is increased to 1000°C at a rate of 10°C / min, and then increased to the target temperature of 1500°C at a rate of 5°C / min.

[0032] Furthermore, the laser power of the laser scanning is 8-12W, and the scanning speed is 5-10mm / s.

[0033] Furthermore, the bio-based adhesive is added in the form of an aqueous solution with a concentration of 10-20% before molding, and the graphene precursor polymer solution is coated by impregnation with a graphene precursor polymer concentration of 5-15%.

[0034] The glass fiber cotton prepared above can be used in building insulation, industrial insulation, energy storage device diaphragms, or smart electric heating materials.

[0035] The preparation method of this invention achieves uniform fiber diameter distribution through multi-stage temperature control and high-speed spinning, uses bio-based adhesives to avoid environmental pollution, and introduces laser-induced graphene technology to achieve in-situ generation of graphene layers, imparting electrothermal function while maintaining fiber flexibility.

[0036] The glass fiber cotton prepared by this invention has the following beneficial effects:

[0037] (1) Improved thermal insulation performance: thermal conductivity is less than 0.030 W / (m·K);

[0038] (2) High mechanical strength: tensile strength reaches 50-80MPa;

[0039] (3) Good high temperature resistance: the operating temperature can reach over 600℃. Detailed Implementation

[0040] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0041] Example 1

[0042] A type of glass fiber cotton is composed of the following substances: 74 kg of glass component, 18 kg of functional additives, and 8 kg of structural stabilizer. The glass component consists of 44 kg of silicon dioxide, 12 kg of aluminum oxide, 10 kg of calcium oxide, 5 kg of magnesium oxide, and 3 kg of boron oxide. The functional additives consist of 9 kg of zirconium oxide, 0.6 kg of strontium oxide, and 8.4 kg of bio-based binder. The structural stabilizer consists of 6 kg of lithium lanthanum zirconium oxide nanoparticles and 2 kg of graphene precursor polymer, wherein the graphene precursor polymer is polyimide, and the bio-based binder is corn starch.

[0043] The present invention also provides a preparation process for the above-mentioned glass fiber cotton, comprising the following steps:

[0044] S1. Raw material pretreatment: Lithium lanthanum zirconium oxide nanoparticles are ultrasonically dispersed, and silica, alumina, calcium oxide, magnesium oxide, boron oxide, zirconium oxide and strontium oxide are mixed and pulverized to a particle size of less than 50 μm, and then mixed with the ultrasonically dispersed lithium lanthanum zirconium oxide nanoparticles.

[0045] S2. Melting: Melt the mixture obtained in step S1 at a temperature of 1500-1600℃ for 2-4 hours under a nitrogen atmosphere;

[0046] S3. Spinning: The melt is spun into fibers using a centrifugal blowing method at a speed of 4000 rpm;

[0047] S4. Molding: The fiber is mixed with the bio-based adhesive, dried and cured at 140-160℃, and coated with a graphene precursor polymer solution;

[0048] S5. Post-processing: Laser scanning is performed along a preset graphic path to convert the graphene precursor polymer into a graphene layer, followed by surface treatment and cutting.

[0049] The melting step employs a segmented heating method: first, the temperature is increased to 1000℃ at a rate of 10℃ / min, and then increased to the target temperature of 1500℃ at a rate of 5℃ / min. The laser power for the laser scanning is 10W, and the scanning speed is 8mm / s. The bio-based adhesive is added in the form of an aqueous solution with a concentration of 15% before molding. The graphene precursor polymer solution is coated by impregnation, and the graphene precursor polymer concentration is 10%.

[0050] The aforementioned glass fiber cotton is used in building insulation, industrial insulation, energy storage device diaphragms, or smart electric heating materials.

[0051] Example 2

[0052] A type of glass fiber cotton comprises: 74 kg of glass component, 18 kg of functional additives, and 8 kg of structural stabilizer. The glass component consists of 44 kg of silicon dioxide, 12 kg of aluminum oxide, 10 kg of calcium oxide, 5 kg of magnesium oxide, and 3 kg of boron oxide. The functional additives consist of 9 kg of zirconium oxide, 0.6 kg of strontium oxide, and 8.4 kg of bio-based binder. The structural stabilizer comprises 7.9 kg of lithium lanthanum zirconium oxide nanoparticles and 0.1 kg of graphene precursor polymer, wherein the graphene precursor polymer is polyimide, and the bio-based binder is corn starch.

[0053] The present invention also provides a preparation process for the above-mentioned glass fiber cotton, comprising the following steps:

[0054] S1. Raw material pretreatment: Lithium lanthanum zirconium oxide nanoparticles are ultrasonically dispersed, and silica, alumina, calcium oxide, magnesium oxide, boron oxide, zirconium oxide and strontium oxide are mixed and pulverized to a particle size of less than 50 μm, and then mixed with the ultrasonically dispersed lithium lanthanum zirconium oxide nanoparticles.

[0055] S2. Melting: Melt the mixture obtained in step S1 at a temperature of 1500-1600℃ for 2-4 hours under a nitrogen atmosphere;

[0056] S3. Spinning: The melt is spun into fibers using a centrifugal blowing method at a speed of 4000 rpm;

[0057] S4. Molding: The fiber is mixed with the bio-based adhesive, dried and cured at 140-160℃, and coated with a graphene precursor polymer solution;

[0058] S5. Post-processing: Laser scanning is performed along a preset graphic path to convert the graphene precursor polymer into a graphene layer, followed by surface treatment and cutting.

[0059] The melting step employs a segmented heating method: first, the temperature is increased to 1000℃ at a rate of 10℃ / min, and then increased to the target temperature of 1500℃ at a rate of 5℃ / min. The laser power for the laser scanning is 10W, and the scanning speed is 8mm / s. The bio-based adhesive is added in the form of an aqueous solution with a concentration of 15% before molding. The graphene precursor polymer solution is coated by impregnation, and the graphene precursor polymer concentration is 10%.

[0060] The aforementioned glass fiber cotton is used in building insulation, industrial insulation, energy storage device diaphragms, or smart electric heating materials.

[0061] Example 3

[0062] A type of glass fiber cotton comprises: 76 kg of glass component, 17 kg of functional additives, and 7 kg of structural stabilizer. The glass component consists of 46 kg of silicon dioxide, 12 kg of aluminum oxide, 10 kg of calcium oxide, 5 kg of magnesium oxide, and 3 kg of boron oxide. The functional additives consist of 8 kg of zirconium oxide, 0.6 kg of strontium oxide, and 8.4 kg of bio-based binder. The structural stabilizer comprises 5.2 kg of lithium lanthanum zirconium oxide nanoparticles and 1.8 kg of graphene precursor polymer, wherein the graphene precursor polymer is polyimide, and the bio-based binder is corn starch.

[0063] The present invention also provides a preparation process for the above-mentioned glass fiber cotton, comprising the following steps:

[0064] S1. Raw material pretreatment: Lithium lanthanum zirconium oxide nanoparticles are ultrasonically dispersed, and silica, alumina, calcium oxide, magnesium oxide, boron oxide, zirconium oxide and strontium oxide are mixed and pulverized to a particle size of less than 50 μm, and then mixed with the ultrasonically dispersed lithium lanthanum zirconium oxide nanoparticles.

[0065] S2. Melting: Melt the mixture obtained in step S1 at a temperature of 1500-1600℃ for 2-4 hours under a nitrogen atmosphere;

[0066] S3. Spinning: The melt is spun into fibers using a centrifugal blowing method at a speed of 4000 rpm;

[0067] S4. Molding: The fiber is mixed with the bio-based adhesive, dried and cured at 140-160℃, and coated with a graphene precursor polymer solution;

[0068] S5. Post-processing: Laser scanning is performed along a preset graphic path to convert the graphene precursor polymer into a graphene layer, followed by surface treatment and cutting.

[0069] The melting step employs a segmented heating method: first, the temperature is increased to 1000℃ at a rate of 10℃ / min, and then increased to the target temperature of 1500℃ at a rate of 5℃ / min. The laser power for the laser scanning is 10W, and the scanning speed is 8mm / s. The bio-based adhesive is added in the form of an aqueous solution with a concentration of 15% before molding. The graphene precursor polymer solution is coated by impregnation, and the graphene precursor polymer concentration is 10%.

[0070] The aforementioned glass fiber cotton is used in building insulation, industrial insulation, energy storage device diaphragms, or smart electric heating materials.

[0071] Comparative Example 1

[0072] The strontium oxide component in Example 1 was removed, and the rest was the same as in Example 1, so it will not be described again.

[0073] Comparative Example 2

[0074] The lithium lanthanum zirconium oxide nanoparticle component in Example 1 was removed, and the rest was the same as in Example 1, so it will not be described again.

[0075] The glass fiber wool prepared in the above embodiments and comparative examples was subjected to performance tests, and the test results are shown in Table 1.

[0076] Table 1 Performance Test Results

[0077]

[0078] Table 1 shows that the glass fiber cotton prepared in Examples 1-3 has low thermal conductivity, high tensile strength, excellent high-temperature resistance, and good sound absorption. In Example 2, the thermal conductivity is even lower due to a significant reduction in the graphene precursor polymer component. This reduction in the graphene precursor polymer leads to a decrease in the density of the conductive network on the fiber surface, reducing the heat conduction path and thus lowering the thermal conductivity. However, the supporting effect of the graphene layer on the high-temperature structure is weakened, resulting in a slight decrease in high-temperature resistance. Comparative Example 1 data shows that removing the strontium oxide component eliminates the synergistic effect and reduces product performance. Comparative Example 2 data shows that removing the lithium lanthanum zirconium oxide nanoparticle component reduces product performance. The lithium lanthanum zirconium oxide nanoparticles, by inhibiting glass phase crystallization and crack propagation at high temperatures, have a greater effect on improving high-temperature resistance than strontium oxide.

Claims

1. A type of glass fiber cotton, characterized in that, It is composed of the following substances by mass percentage: 70-85% glass component, 10-20% functional additives and 3-14% structural stabilizer, wherein the glass component is composed of silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide and boron oxide, the functional additives are composed of zirconium oxide, strontium oxide and bio-based binder, and the structural stabilizer is composed of lithium lanthanum zirconium oxide nanoparticles and graphene precursor polymer; The content of silicon dioxide is 40-60% of the mass of the glass fiber wool, the content of aluminum oxide is 10-20% of the mass of the glass fiber wool, the content of calcium oxide is 5-15% of the mass of the glass fiber wool, the content of magnesium oxide is 3-8% of the mass of the glass fiber wool, and the content of boron oxide is 2-5% of the mass of the glass fiber wool. The zirconium oxide content is 5-10% of the mass of the glass fiber cotton, the strontium oxide content is 0.5-1% of the mass of the glass fiber cotton, and the bio-based adhesive content is 4.5-9.5% of the mass of the glass fiber cotton. The content of the lithium lanthanum zirconium oxide nanoparticles is 3-10% of the mass of the glass fiber cotton, and the content of the graphene precursor polymer is 0.01-4% of the mass of the glass fiber cotton. The graphene precursor polymer is polyimide.

2. The glass fiber cotton according to claim 1, characterized in that, The bio-based adhesive is a starch-based adhesive, and the starch is corn starch or potato starch.

3. A process for preparing glass fiber cotton according to any one of claims 1 to 2, characterized in that, Includes the following steps: S1. Raw material pretreatment: Lithium lanthanum zirconium oxide nanoparticles are ultrasonically dispersed, and silica, alumina, calcium oxide, magnesium oxide, boron oxide, zirconium oxide and strontium oxide are mixed and pulverized to a particle size of less than 50 μm, and then mixed with the ultrasonically dispersed lithium lanthanum zirconium oxide nanoparticles. S2. Melting: Melt the mixture obtained in step S1 at a temperature of 1500-1600℃ for 2-4 hours under a nitrogen atmosphere; S3. Spinning: The melt is spun into fibers using a centrifugal blowing method at a speed of 3000-5000 rpm; S4. Molding: The fiber is mixed with the bio-based adhesive, dried and cured at 100-180℃, and coated with a graphene precursor polymer solution; S5. Post-processing: Laser scanning is performed along a preset graphic path to convert the graphene precursor polymer into a graphene layer, followed by surface treatment and cutting.

4. The preparation process according to claim 3, characterized in that, The melting step employs a segmented heating method: first, the temperature is increased to 1000℃ at a rate of 10℃ / min, and then increased to the target temperature of 1500℃ at a rate of 5℃ / min.

5. The preparation process according to claim 3, characterized in that, The laser power of the laser scanning is 8-12W, and the scanning speed is 5-10mm / s.

6. The preparation process according to claim 3, characterized in that, The bio-based adhesive is added in the form of an aqueous solution with a concentration of 10-20% before molding, and the graphene precursor polymer solution is coated by impregnation with a graphene precursor polymer concentration of 5-15%.

7. The application of the glass fiber cotton according to any one of claims 1-2 in building insulation, industrial insulation, energy storage device diaphragm or smart electric heating material.

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