Novel glass fiber cotton and preparation process thereof

Abstract

The invention belongs to the field of inorganic materials, and particularly relates to novel glass fiber cotton and a preparation process thereof. The novel glass fiber cotton provided by the invention is prepared from the following substances in percentage by mass: 70-85% of a glass component, 10-20% of a functional additive and 3-14% of a structural stabilizer. The preparation process comprises the following steps: S1, raw material pretreatment; s2, melting; s3, spinning; s4, forming; and S5, carrying out post-treatment. The glass fiber cotton prepared by the invention has the following beneficial effects: (1) the heat insulation performance is improved: the heat conductivity coefficient is lower than 0.030 W / (m.K); (2) the mechanical strength is high, and the tensile strength reaches 50-80 MPa; and (3) the high temperature resistance is good, and the use temperature can reach 600 DEG C or above.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of inorganic materials, and particularly relates to a new type of glass fiber cotton and a preparation process thereof. BACKGROUND

[0002] Glass fiber cotton is an inorganic non-metallic material with excellent performance, which belongs to a category of glass fibers. It is made of glass balls or waste glass as raw materials through high-temperature melting, wire drawing, winding, weaving and other processes. Its single filament diameter is extremely fine, only a few microns to twenty microns.

[0003] From the chemical composition, glass fiber cotton is mainly silica-based, with a content of about 50-60%, and contains various metal oxides such as calcium, boron, sodium, aluminum and iron. According to the composition, glass fiber cotton can be mainly divided into different types such as alkali-free glass, medium alkali glass and high alkali glass.

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

[0005] Glass fiber cotton is mainly applied to the following technical fields: (1) Building field In the building field, glass fiber cotton is mainly used for thermal insulation and sound absorption. As the best material for thermal insulation and sound absorption of steel structure buildings, glass fiber cotton can be used for external wall insulation, roof insulation, indoor partition and other parts. Its large number of tiny air pores can effectively block heat conduction. Its application advantages include: maintaining the original structure of the building, especially suitable for complex structures and special-shaped structure surfaces; having the characteristics of no joints, good airtightness, and improving the overall energy saving effect; convenient construction, high efficiency, saving labor and time.

[0006] (2) Industrial field In the industrial field, glass fiber cotton is widely used in various industrial facilities due to its heat resistance, fireproof performance and chemical stability. Specific applications include: industrial pipeline insulation: preventing heat loss of pipelines and improving energy utilization efficiency. Equipment insulation: reducing the surface temperature of industrial equipment and improving the working environment. Electrical insulation materials: using its excellent electrical insulation performance for electrical equipment protection. Industrial filtration: superfine glass fiber cotton has strong filtration and adsorption performance due to its large surface area, which can be used in filtration processes in chemical, electronic and other industries.

[0007] (3) Transportation field Glass fiber insulation is also widely used in the transportation sector, including thermal and acoustic insulation for train cars, thermal and fire protection for ships, and sound and thermal insulation for automobiles. In these applications, glass fiber insulation not only provides good thermal and acoustic performance, but also improves the fire safety of vehicles due to its non-combustible properties.

[0008] (4) Safety and protection field Glass fibers are increasingly used in safety and protective textiles. With their high modulus and strength, high elongation at break, and hook strength, as well as excellent impact resistance such as lateral compression and bending stiffness, glass fibers are used in mechanical injury protection textiles, thermal protection textiles, electromagnetic protection, and nuclear and biochemical protection textiles.

[0009] CN108503240B discloses a high-silica glass fiber insulation with low thermal conductivity and its preparation method. The disclosed acid leaching and heating process is carried out at a constant and slow speed, which allows the acid solution to dissolve the non-silicon components in the fiber body at a relatively slow rate. After the heating is completed, a holding stage is set to allow the reaction materials to contact more fully, thereby achieving complete dissolution of the fibers and reducing the blocky dissolution phenomenon on the fiber surface. This better preserves the columnar morphology of the fibers, which is beneficial to the formation of a porous structure after acid leaching, thereby improving the thermal insulation performance of the fiber product. At the same time, the initial temperature of the acid leaching process is relatively low, the reaction rate is slow, and the contact speed between the fiber and the acid solution is moderate, which does not cause a large amount of reaction products to accumulate on the fiber surface, and is beneficial to the migration of impurity ions in the fiber, further improving the content of silicon dioxide in the glass fiber.

[0010] Glass fiber insulation is a multifunctional material that plays an important role in the fields of construction, industry, transportation, and others. Despite the health risks and insufficient high-temperature resistance, product innovation, process upgrading, and application expansion are continuously overcoming these limitations. SUMMARY

[0011] The purpose of the present application is to provide a new type of glass fiber insulation and its preparation process, which is composed of the following mass percentages of substances: glass component 70-85%, functional additive 10-20%, and structure stabilizer 3-14%, wherein the glass component is composed of silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, and boron oxide, the functional additive is composed of zirconium oxide, strontium oxide, and bio-based adhesive, and the structure stabilizer is composed of lithium lanthanum zirconium oxide nanoparticles and graphene precursor polymer.

[0012] Further, the content of the silicon dioxide is 40-60% of the mass of the new glass fiber cotton, the content of the aluminum oxide is 10-20% of the mass of the new glass fiber cotton, the content of the calcium oxide is 5-15% of the mass of the new glass fiber cotton, the content of the magnesium oxide is 3-8% of the mass of the new glass fiber cotton, and the content of the boron oxide is 2-5% of the mass of the new glass fiber cotton. The silicon dioxide as the main network former provides the basic skeletal structure of the glass fiber, gives the product high melting point and chemical stability, and the principle is to form a three-dimensional network through silicon-oxygen bonds to enhance the mechanical strength and corrosion resistance of the fiber. The aluminum oxide as the network intermediate partially replaces the silicon-oxygen bond to improve the chemical stability and mechanical strength of the glass fiber, and the aluminum ion enters the silicon-oxygen network to inhibit the crystallization of the fiber at high temperature. The calcium oxide as the network modifier can reduce the glass melting temperature and improve the processing fluidity, and the calcium ion reduces the melt viscosity, but excessive amount will cause brittleness, so the amount needs to be controlled. The magnesium oxide as an auxiliary network modifier cooperates with the calcium oxide to further reduce the melting temperature, and at the same time improve the toughness and thermal shock resistance of the fiber, and the magnesium ion has high field strength and can stabilize the glass structure. The boron oxide as a fluxing agent and stabilizer can reduce the thermal expansion coefficient and improve the stability of the fiber under temperature change, and the boron-oxygen bond forms a flexible network to compensate for the rigidity of the silicon-oxygen network.

[0013] Further, the content of the zirconium oxide is 5-10% of the mass of the new glass fiber cotton, the content of the strontium oxide is 0.5-1% of the mass of the new glass fiber cotton, and the content of the bio-based adhesive is 4.5-9.5% of the mass of the new glass fiber cotton. The zirconium oxide as a high-temperature-resistant additive improves the high-temperature resistance and mechanical strength of the fiber, and the zirconium ion has a high melting point and a phase transition toughening effect, which inhibits the softening of the fiber at high temperature and cooperates with the aluminum oxide to form a stable crystal phase. The bio-based adhesive as an environmentally friendly binder replaces synthetic resin to improve the formability and environmental friendliness of the fiber, the hydroxyl groups in the starch molecules form hydrogen bonds with the glass surface to realize the bonding between the fibers, and the biodegradability is good. After adding strontium oxide, a magnesium-calcium-strontium alkaline earth metal oxide system is formed, which forms a multi-alkaline earth metal effect in the glass network. The magnesium ion mainly enters the network interstitial sites due to its small ionic radius and high field strength, which improves the network density, and the calcium ion acts as a network modifier to effectively reduce the melt viscosity. The ionic radius of strontium is larger, which can fill the network cavities and reduce ion migration at high temperature. When the three ions coexist in a specific proportion, the strontium ion forms a gradient filling effect with calcium and magnesium ions, which adjusts the size of the network cavities through the difference in ionic radius, reduces the melt viscosity, and at the same time inhibits ion diffusion at high temperature. It can reduce the melting temperature while significantly improving the elastic modulus of the fiber.

[0014] Further, the content of the lithium lanthanum zirconium oxide nanoparticles is 3-10% of the mass of the new glass fiber cotton, and the content of the graphene precursor polymer is 0-4% of the mass of the new glass fiber cotton, and the graphene precursor polymer is a polyimide. The lithium lanthanum zirconium oxide nanoparticles serve as a structure stabilizer, the crystal lattice structure of which can guide the uniform deposition of lithium ions, improve the interface stability of the fibers, and at the same time, the lithium lanthanum zirconium oxide nanoparticles form a composite phase with the glass components to inhibit crack propagation. The graphene precursor polymer serves as a precursor of the electrothermal functional layer, which is converted into graphene under laser induction to form a conductive network, endow the glass fiber cotton with electrothermal function, and at the same time, enhance the flexibility and surface hardness of the fibers.

[0015] Further, the bio-based adhesive is a starch-based adhesive, and the starch is corn starch or potato starch. The starch-based adhesive serves as an environmentally friendly binder to replace synthetic resins, improve the formability and environmental friendliness of the fibers, and the hydroxyl groups in the starch molecules form hydrogen bonds with the glass surface to achieve fiber bonding and good biodegradability.

[0016] The mutual synergy among the components in the application mainly has the following points: (1) Synergy of glass components and functional additives: Silicon dioxide and aluminum oxide form a main network to reduce defects through interface bonding, and the bio-based adhesive wraps the fibers during the forming process and forms hydrogen bonds with the base components to improve the bonding strength without compromising environmental friendliness.

[0017] (2) Synergy of boron oxide and magnesium oxide: Boron oxide reduces thermal expansion, and magnesium oxide improves toughness, and the two work together to improve the durability of the fibers under thermal cycling.

[0018] (3) Synergy of bio-based adhesive and graphene precursor polymer: The bio-based adhesive preliminarily shapes the fibers at low temperature to provide a stable substrate for subsequent coating and laser treatment. The graphene precursor polymer coated subsequently is converted into a graphene conductive layer under laser induction, which is tightly combined with the fiber network bonded by the bio-based adhesive, endowing the material with electrothermal function, and at the same time, the bio-based adhesive ensures the environmental friendliness of the preparation process.

[0019] The application also provides a preparation process of the new glass fiber cotton. S1. Raw material pretreatment: ultrasonic dispersion of lithium lanthanum zirconium oxide nanoparticles, mixing and pulverizing silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, boron oxide, zirconium oxide, and strontium oxide to a particle size of less than 50 μm, and then mixing with the ultrasonically dispersed lithium lanthanum zirconium oxide nanoparticles; S2. Melting: heating the mixture obtained in step S1 to 1500-1600℃ under a nitrogen atmosphere for 2-4 hours; S3. Spinning: melt into fibers by centrifugal blowing method, centrifugal speed is 3000-5000 rpm; S4. Forming: mix fibers with bio-based adhesive, dry and solidify at 100-180℃, and coat graphene precursor polymer solution; S5. Post-processing: laser scanning with preset pattern, convert graphene precursor polymer into graphene layer, then surface treatment and cutting.

[0020] Further, the melting step adopts segmented temperature rise: first rise to 1000℃ at 10℃ / min, then rise to target 1500℃ at 5℃ / min.

[0021] Further, the laser power of the laser scanning is 8-12W, and the scanning speed is 5-10mm / s.

[0022] Further, the bio-based adhesive is added in the form of aqueous solution before forming, the concentration is 10-20%, and the graphene precursor polymer solution is coated by immersion method, the concentration of graphene precursor polymer is 5-15%.

[0023] The new type of glass fiber cotton prepared above can be applied in building thermal insulation, industrial thermal insulation, energy storage device separator or intelligent electrothermal material.

[0024] The preparation method of the application realizes uniform distribution of fiber diameter through multi-stage temperature control and high-speed spinning, uses bio-based adhesive to avoid environmental pollution, introduces laser-induced graphene technology to realize in-situ generation of graphene layer, endows electrothermal function, and maintains fiber flexibility.

[0025] The glass fiber cotton prepared by the application has the following beneficial effects: (1) Improved thermal insulation performance: thermal conductivity is lower than 0.030W / (m·K); (2) High mechanical strength: tensile strength reaches 50-80MPa; (3) Good high temperature resistance: service temperature can reach more than 600℃. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the application will be described below in conjunction with the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, not all embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the application.

[0027] Example 1 A new type of glass fiber cotton, consisting of: a glass component of 74 kg, a functional additive of 18 kg and a structure stabilizer of 8 kg, the glass component consisting 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 additive consisting of 9 kg of zirconium oxide, 0.6 kg of strontium oxide and 8.4 kg of a bio-based binder, the structure stabilizer including 6 kg of lithium lanthanum zirconium oxide nanoparticles and 2 kg of a graphene precursor polymer, the graphene precursor polymer being a polyimide, the bio-based binder being corn starch.

[0028] The present application also provides a preparation process of the above-mentioned new type of glass fiber cotton, comprising the following steps: S1. Raw material pretreatment: ultrasonic dispersion of lithium lanthanum zirconium oxide nanoparticles, mixing and crushing of silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, boron oxide, zirconium oxide, strontium oxide to a particle size of less than 50 μm, and then mixing with the ultrasonic dispersed lithium lanthanum zirconium oxide nanoparticles; S2. Melting: heating the mixture obtained in step S1 to 1500-1600℃ under nitrogen atmosphere for 2-4 hours; S3. Spinning: fiberizing the melt by centrifugal blowing method, with a centrifugal speed of 4000 rpm; S4. Shaping: mixing the fibers with the bio-based binder, drying and curing at 140-160℃, and coating with a graphene precursor polymer solution; S5. Post-treatment: laser scanning with a preset pattern to convert the graphene precursor polymer into a graphene layer, and then surface treatment and cutting.

[0029] The melting step uses a segmented temperature rise: first rise to 1000℃ at 10℃ / min, and then rise to the target 1500℃ at 5℃ / min, the laser power of the laser scanning is 10W, the scanning speed is 8mm / s, the bio-based binder is added in the form of an aqueous solution before shaping, with a concentration of 15%, the graphene precursor polymer solution is coated by immersion, with a graphene precursor polymer concentration of 10%.

[0030] The above-mentioned new type of glass fiber cotton is applied in building insulation, industrial insulation, energy storage device separator or intelligent electrothermal material.

[0031] Example 2 A new type of glass fiber cotton, consisting of: a glass component of 74 kg, a functional additive of 18 kg and a structure stabilizer of 8 kg, the glass component consisting 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 additive consisting of 9 kg of zirconium oxide, 0.6 kg of strontium oxide and 8.4 kg of a bio-based binder, the structure stabilizer including 7.9 kg of lithium lanthanum zirconium oxide nanoparticles and 0.1 kg of a graphene precursor polymer consisting of a polyimide, the bio-based binder being corn starch.

[0032] The present application also provides a preparation process of the above-mentioned new type of glass fiber cotton, comprising the following steps: S1. Raw material pretreatment: ultrasonic dispersion of lithium lanthanum zirconium oxide nanoparticles, mixing and crushing of silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, boron oxide, zirconium oxide, strontium oxide to a particle size of less than 50 μm, and then mixing with the ultrasonic dispersed lithium lanthanum zirconium oxide nanoparticles; S2. Melting: heating the mixture obtained in step S1 to 1500-1600℃ under nitrogen atmosphere for 2-4 hours; S3. Spinning: fiberizing the melt by centrifugal blowing method with a centrifugal speed of 4000 rpm; S4. Shaping: mixing the fibers with the bio-based binder, drying and curing at 140-160℃, and coating with a graphene precursor polymer solution; S5. Post-treatment: laser scanning with a preset pattern to convert the graphene precursor polymer into a graphene layer, and then surface treatment and cutting.

[0033] The melting step uses a segmented temperature rise: first rise to 1000℃ at 10℃ / min, and then rise to the target 1500℃ at 5℃ / min, the laser power of the laser scanning is 10W, the scanning speed is 8mm / s, the bio-based binder is added in the form of an aqueous solution before shaping, the concentration is 15%, the graphene precursor polymer solution is coated by immersion, the concentration of graphene precursor polymer is 10%.

[0034] The above-mentioned new type of glass fiber cotton is applied in building insulation, industrial insulation, energy storage device separator or intelligent electrothermal material.

[0035] Example 3 A new type of glass fiber cotton, consisting of: a glass component 76 kg, a functional additive 17 kg and a structure stabilizer 7 kg, the glass component consisting 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 additive consisting of 8 kg of zirconium oxide, 0.6 kg of strontium oxide and 8.4 kg of a bio-based binder, the structure stabilizer including 5.2 kg of lithium lanthanum zirconium oxide nanoparticles and 1.8 kg of a graphene precursor polymer consisting of a polyimide, the bio-based binder being corn starch.

[0036] The present application also provides a preparation process of the above-mentioned new type of glass fiber cotton, comprising the following steps: S1. Raw material pretreatment: ultrasonic dispersion of lithium lanthanum zirconium oxide nanoparticles, mixing and crushing silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, boron oxide, zirconium oxide, strontium oxide to a particle size of less than 50 μm, and then mixing with the ultrasonic dispersed lithium lanthanum zirconium oxide nanoparticles; S2. Melting: heating the mixture obtained in step S1 to 1500-1600℃ under nitrogen atmosphere for 2-4 hours; S3. Spinning: centrifugal blowing method is used to form fibers from the melt, with a centrifugal speed of 4000 rpm; S4. Molding: mixing the fibers with a bio-based binder, drying and curing at 140-160℃, and coating a graphene precursor polymer solution; S5. Post-processing: laser scanning with a preset pattern to convert the graphene precursor polymer into a graphene layer, and then surface treatment and cutting.

[0037] The melting step uses a segmented temperature rise: first rise to 1000℃ at 10℃ / min, and then rise to the target 1500℃ at 5℃ / min, the laser power of the laser scanning is 10W, the scanning speed is 8mm / s, the bio-based binder is added in the form of an aqueous solution before molding, with a concentration of 15%, the graphene precursor polymer solution is coated by immersion, with a graphene precursor polymer concentration of 10%.

[0038] The above-mentioned new type of glass fiber cotton is applied in building insulation, industrial insulation, energy storage device separator or intelligent electrothermal material.

[0039] Comparative Example 1 The strontium oxide component in Example 1 is removed, and the others are the same as in Example 1, which will not be repeated.

[0040] Comparative Example 2 The lithium lanthanum zirconium oxide nanoparticle component in Example 1 is removed, and the others are the same as in Example 1, which will not be repeated.

[0041] The new type glass fiber cotton prepared in the above examples and comparative examples was subjected to performance test, and the test results are shown in Table 1.

[0042] Table 1 Performance test results

[0043] As can be seen from the data in Table 1, the new type glass fiber cotton prepared in Examples 1-3 has low thermal conductivity, high tensile strength, excellent high temperature resistance, and good sound absorption effect. The thermal conductivity of Example 2 is smaller due to the significant reduction of the graphene precursor polymer component. The reduction of the graphene precursor polymer leads to the decrease of the density of the conductive network on the fiber surface and the reduction of the heat conduction path, so the thermal conductivity is reduced. However, the support of the graphene layer to the high temperature structure is weakened, and the high temperature resistance is slightly decreased. The data of Comparative Example 1 shows that the performance of the product is decreased due to the disappearance of the synergistic effect after the strontium oxide component is removed. The data of Comparative Example 2 shows that the performance of the product is decreased after the lithium lanthanum zirconium oxide nanoparticle component is removed. The lithium lanthanum zirconium oxide nanoparticle has a higher effect on improving the high temperature resistance than the strontium oxide by inhibiting the crystallization and crack propagation of the glass phase at high temperature.

Claims

1. A new glass fiber wool, characterized in that, Consist of the following mass percentage of substances: glass component 70-85%, functional additives 10-20% and structure stabilizer 3-14%, wherein the glass component consists of silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide and boron oxide, the functional additives consist of zirconium oxide, strontium oxide and bio-based binder, and the structure stabilizer consists of lithium lanthanum zirconium oxide nanoparticles and graphene precursor polymer.

2. The novel glass fiber wool according to claim 1, characterized in that, The content of silicon dioxide is 40-60% of the mass of the new glass fiber cotton, the content of aluminum oxide is 10-20% of the mass of the new glass fiber cotton, the content of calcium oxide is 5-15% of the mass of the new glass fiber cotton, the content of magnesium oxide is 3-8% of the mass of the new glass fiber cotton, and the content of boron oxide is 2-5% of the mass of the new glass fiber cotton.

3. The novel glass fiber wool according to claim 1, characterized in that, The content of zirconium oxide is 5-10% of the mass of the new glass fiber cotton, the content of strontium oxide is 0.5-1% of the mass of the new glass fiber cotton, and the content of bio-based binder is 4.5-9.5% of the mass of the new glass fiber cotton.

4. The novel glass fiber wool according to claim 1, characterized in that, The content of lithium lanthanum zirconium oxide nanoparticles is 3-10% of the mass of the new glass fiber cotton, and the content of graphene precursor polymer is 0.01-4% of the mass of the new glass fiber cotton, and the graphene precursor polymer is polyimide.

5. The novel glass fiber wool according to claim 1, characterized in that, The bio-based binder is a starch-based binder, and the starch is corn starch or potato starch.

6. A process for the production of the novel glass fiber wool according to any one of claims 1 to 5, characterized in that, The method comprises the following steps: S1. Raw material pretreatment: ultrasonic dispersion of lithium lanthanum zirconium oxide nanoparticles, mixing and crushing of silicon dioxide, aluminum oxide, calcium oxide, magnesium oxide, boron oxide, zirconium oxide, strontium oxide to a particle size of less than 50μm, and then mixing with the ultrasonic dispersed lithium lanthanum zirconium oxide nanoparticles; S2. Melting: heating the mixture obtained in step S1 to 1500-1600℃ under nitrogen atmosphere for 2-4 hours; S3. Spinning: fiberizing the melt by centrifugal blowing method, with a centrifugal speed of 3000-5000rpm; S4. Forming: mixing the fiber with bio-based binder, drying and curing at 100-180℃, and coating with graphene precursor polymer solution; S5. Post-processing: laser scanning with a preset pattern to convert graphene precursor polymer into graphene layer, and then surface treatment and cutting.

7. The manufacturing process of claim 6, wherein, The melting step adopts segmented heating: first increase to 1000℃ at 10℃ / min, and then increase to the target 1500℃ at 5℃ / min.

8. The manufacturing process of claim 6, wherein, The laser power of the laser scanning is 8-12W, and the scanning speed is 5-10mm / s.

9. The manufacturing process of claim 6, wherein, The bio-based binder is added in the form of aqueous solution before forming, with a concentration of 10-20%, and the graphene precursor polymer solution is coated by immersion, with a graphene precursor polymer concentration of 5-15%.

10. Use of the new glass fiber cotton according to any one of claims 1-5 in building insulation, industrial insulation, energy storage device separator or intelligent electrothermal material.

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