阅读说明：本技术 一种掺杂聚合物管状纤维的高温结构陶瓷材料 (High-temperature structural ceramic material doped with polymer tubular fibers ) 是由 李连地 陈健 杨红鑫 潘勇 黄裕娥 于 2021-01-23 设计创作，主要内容包括：本发明公开了一种掺杂聚合物管状纤维的高温结构陶瓷材料,涉及陶瓷技术领域。一种掺杂聚合物管状纤维的高温结构陶瓷材料,包括下列重量份的原料：80份Al-2O-3-SiO-2-MgO骨料颗粒、40份Al-2O-3-SiO-2-MgO细粉、45份氧化铝微粉、45份氧化硅微粉、20份复合添加剂、20份结合剂和20份聚合物管状纤维。本发明的高温结构陶瓷材料,可以应用在铸造热工设备中,并实现快速热处理、缩短停炉时间的掺杂聚合物管状纤维的高温结构陶瓷材料产品,确保高温结构陶瓷材料具有良好的透气性能,并在高温热处理过程中不产生裂纹或剥落,以实现良好的工作性能、强度和耐久性,且节约成本。(The invention discloses a high-temperature structural ceramic material doped with polymer tubular fibers, and relates to the technical field of ceramics. A high-temperature structural ceramic material doped with polymer tubular fibers comprises the following raw materials in parts by weight: 80 parts of Al 2 O 3 ‑SiO 2 -MgO aggregate particles, 40 parts of Al 2 O 3 ‑SiO 2 Fine MgO powder, 45 parts of alumina micro powder, 45 parts of silica micro powder, 20 parts of composite additive, 20 parts of binder and 20 parts of polymer tubular fiber. The high-temperature structural ceramic material can be applied to casting thermal equipment and is practicalThe high-temperature structural ceramic material product doped with the polymer tubular fiber is subjected to rapid heat treatment, the furnace shutdown time is shortened, the high-temperature structural ceramic material is ensured to have good air permeability, cracks or peeling are not generated in the high-temperature heat treatment process, so that good working performance, strength and durability are realized, and the cost is saved.)

1. A high-temperature structural ceramic material doped with polymer tubular fibers is characterized by comprising the following raw materials in parts by weight: 30-80 parts of Al₂O₃-SiO₂-MgO aggregate particles, 2-40 parts of Al₂O₃-SiO₂Fine MgO powder, 3-45 parts of alumina micro powder, 3-45 parts of silica micro powder, 0.1-20 parts of composite additive, 0.2-20 parts of binder and 0.2-20 parts of polymer tubular fiber.

2. The high temperature structural ceramic material of claim 1, wherein the Al is doped with a polymer tubular fiber₂O₃-SiO₂The MgO aggregate particles are at least one of alumina, corundum, mullite and spinel (Al)₂O₃)_m：(SiO₂)_n：(MgO)_xWherein m is 0 to 25, n is 0 to 25, and x is 0 to 25.

3. The high temperature structural ceramic material of claim 1, wherein the Al is doped with a polymer tubular fiber₂O₃-SiO₂The average particle size of the fine MgO powder is 100 mesh.

4. The high temperature structural ceramic material of claim 3, wherein said Al is selected from the group consisting of Al, Cu₂O₃-SiO₂The fine MgO powder is at least one of alumina, corundum, mullite and spinel₂O₃)_m：(SiO₂)_n：(MgO)_xWherein m is 0 to 25, n is 0 to 25, and x is 0 to 25.

5. The polymer tubular fiber doped high temperature structural ceramic material of claim 1, wherein the alumina micropowder has an alumina content of greater than 90%; the content of silicon oxide in the silicon oxide micro powder is more than 80 percent.

6. The polymer tube fiber doped high temperature structural ceramic material as claimed in claim 1, wherein the composite additive is at least one of barium sulfate, strontium sulfate, chromium oxide, magnesium oxide, cerium oxide, calcium fluoride, aluminum phosphate, magnesium phosphate, silicon nitride, boron nitride, silicon carbide, boron carbide, kyanite, aluminum titanate, andalusite, sillimanite, polyphosphate, metaphosphate, polycarboxylic acid, lignin water reducer, naphthalene water reducer, or dispersed alumina superplasticizer.

7. The polymer tubular fiber-doped high-temperature structural ceramic material as claimed in claim 1, wherein the binder is at least one of water, silica sol, water glass, phosphoric acid, aluminum dihydrogen phosphate, high silica alumina sol, hydrated alumina micropowder, silica alumina sol powder, aluminate cement, resin and asphalt.

8. The polymer tubular fiber doped high-temperature structural ceramic material as claimed in claim 1, wherein the cross section of the polymer tubular fiber has an outer diameter of 1-200 μm, an inner diameter of 0.1-190 μm, and a wall thickness of 0.9-180 μm.

9. The polymeric tubular fiber doped high temperature structural ceramic material of claim 1, wherein the polymeric tubular fiber is a pre-blend of at least one of polyethylene, polypropylene, polyester, polyolefin, polyacrylonitrile fiber with at least one of one-dimensional, two-dimensional or three-dimensional nanocarbon materials, or at least one of polyethylene, polypropylene, polyester, polyolefin, polyacrylonitrile fiber.

10. The method for preparing a high-temperature structural ceramic material doped with polymer tubular fibers according to any one of claims 1 to 9, which is characterized by comprising the following steps: mixing the weight part of Al₂O₃-SiO₂-MgO aggregate particles, Al₂O₃-SiO₂Fine powder of MgO,Mixing the alumina micro powder, the silica micro powder and the composite additive, adding the bonding agent in parts by weight, stirring and mixing, then constructing and molding, and naturally drying; then baking and preserving heat at the temperature of more than 50 ℃ to obtain the ceramic material.

Technical Field

The invention relates to the technical field of ceramics, in particular to a high-temperature structural ceramic material doped with polymer tubular fibers.

Background

The lining body material of the smelting thermal equipment is constructed and manufactured by high-temperature structural ceramic materials, but a certain content of moisture or volatile components can exist in the manufactured lining body material, on one hand, part of the high-temperature structural ceramic materials are formed by adding water or the volatile components through mixing, on the other hand, the material can absorb environmental moisture to form free water, crystal water and compound water, the moisture or the volatile components in the lining body material can be converted from liquid state into gaseous state along with the rise of temperature when being subjected to heat treatment or used for a long time under the high-temperature environment during smelting, and gradually dissipate outwards through each channel in a lining body material matrix, but the lining body material is compact and has discontinuous pore passages, so that water or volatile component steam cannot be rapidly dissipated, and larger steam pressure is formed in the lining body material, if the air permeability of the lining body material is not enough to rapidly discharge the internal water or volatile component steam, the rapid increase of internal pressure and thermal stress can cause the damage of a matrix structure, a great amount of cracks, even peeling and bursting are generated, high-temperature melt in smelting thermal equipment is further caused to leak and overflow to the outside, the damage of lining materials is aggravated, and even a great safety problem is caused. Therefore, in order to ensure the stable and safe production of the smelting thermal equipment and prolong the service life of the smelting thermal equipment, effective measures are needed to realize the heat treatment of lining materials or the effective and quick discharge of moisture or volatile components in a high-temperature environment.

At present, there are two main measures for improving the anti-explosion performance of the high-temperature structural ceramic material, namely, reasonably controlling a heat treatment procedure and using an anti-explosion additive, but because the production conditions of various thermal equipment are different, it is difficult to make a uniform and reasonable heat treatment procedure, and therefore, the mode of adding the anti-explosion additive is the most effective method for improving the anti-explosion performance of the high-temperature structural ceramic material.

At present, the traditional method is to use solid round or special-shaped polymer fibers as an anti-burst additive, which mainly utilizes that the polymer fibers can be melted after reaching the melting point of the material during high-temperature heat treatment and can be ablated after reaching the ignition point, so that corresponding channels are left in a lining body material to facilitate the dissipation and discharge of moisture or volatile components, but a certain temperature is needed in the initial stage, according to the practical application, the melting temperature of the polymer fibers is within 200 ℃, and the temperature for discharging a large amount of water or volatile component steam is above 50 ℃, so that a certain temperature overlapping area is caused, and if the heat treatment temperature is not well controlled in the overlapping area, the lining body material can still be damaged by large steam pressure and heat stress inside the lining body material.

Disclosure of Invention

Based on the defects, the invention provides a high-temperature structural ceramic material doped with polymer tubular fibers, which is doped into a matrix of the high-temperature structural ceramic material after the polymer tubular fibers are adopted or one-dimensional, two-dimensional or three-dimensional nano carbon materials (including carbon nano tubes, graphene, carbon nano fibers, nano carbon spheres and the like) are adopted for modifying or premixing, the cross section of the tubular fibers is tubular, and the tubular fibers have low melting point and are easy to melt at low temperature because the wall thickness of the tubular fibers is in a micron-scale; because the tube-shaped structure is adopted, the residues after melting and ablation are less, and the blockage of the internal channel can not be caused.

The technical scheme for solving the technical problem is as follows:

a high-temperature structural ceramic material doped with polymer tubular fibers comprises the following raw materials in parts by weight: 30-80 parts of Al₂O₃-SiO₂-MgO aggregate particles, 2-40 parts of Al₂O₃-SiO₂Fine MgO powder, 3-45 parts of alumina micro powder, 3-45 parts of silica micro powder, 0.1-20 parts of composite additive, 0.2-20 parts of binder and 0.2-20 parts of polymer tubular fiber.

Further, the Al₂O₃-SiO₂The MgO aggregate particles are at least one of alumina, corundum, mullite and spinel (Al)₂O₃)_m：(SiO₂)_n：(MgO)_xWherein m is 0 to 25, n is 0 to 25, and x is 0 to 25.

Further, the Al₂O₃-SiO₂The average particle size of the fine MgO powder is 100 mesh.

Further, the Al₂O₃-SiO₂The fine MgO powder is at least one of alumina, corundum, mullite and spinel₂O₃)_m：(SiO₂)_n：(MgO)_xWherein m is 0 to 25, n is 0 to 25, and x is 0 to 25.

Further, the content of alumina in the alumina micro powder is more than 90%; the content of silicon oxide in the silicon oxide micro powder is more than 80 percent.

Further, the composite additive is at least one of barium sulfate, strontium sulfate, chromium oxide, magnesium oxide, cerium oxide, calcium fluoride, aluminum phosphate, magnesium phosphate, silicon nitride, boron nitride, silicon carbide, boron carbide, kyanite, aluminum titanate, andalusite, sillimanite, polyphosphate, metaphosphate, polycarboxylic acid, lignin water reducer, naphthalene water reducer or dispersed alumina high-efficiency water reducer.

Further, the binding agent is at least one of water, silica sol, water glass, phosphoric acid, aluminum dihydrogen phosphate, high silica alumina sol, hydrated alumina micro powder, silica alumina sol powder, aluminate cement, resin and asphalt.

Furthermore, the outer diameter of the cross section of the polymer tubular fiber is 1-200 mu m, the inner diameter is 0.1-190 mu m, and the wall thickness is 0.9-180 mu m.

Further, the polymer tubular fiber is a pre-mixture of at least one of polyethylene, polypropylene, polyester, polyolefin, polyacrylonitrile fiber and at least one of one-dimensional, two-dimensional or three-dimensional nano carbon materials, or at least one of polyethylene, polypropylene, polyester, polyolefin, polyacrylonitrile fiber.

A preparation method of a high-temperature structural ceramic material doped with polymer tubular fibers comprises the following specific steps: mixing the weight part of Al₂O₃-SiO₂-MgO aggregate particles, Al₂O₃-SiO₂Mixing fine MgO powder, fine alumina powder, fine silica powder and composite additive, adding the bonding agent in parts by weight, stirring and mixing, performing construction molding, and naturally drying; then baking and preserving heat at the temperature of more than 50 ℃ to obtain the ceramic material.

The invention has the beneficial effects that: according to the high-temperature structural ceramic material doped with the polymer tubular fibers, after one-dimensional, two-dimensional or three-dimensional nano carbon materials (comprising carbon nano tubes, graphene, carbon nano fibers, nano carbon spheres and the like) are adopted to modify or premix the polymer tubular fibers, the nano carbon materials have excellent heat conductivity, so that the heat conductivity of the polymer tubular fibers can be remarkably improved, heat can be rapidly transferred in the polymer fibers in the heat treatment process of the high-temperature structural ceramic material, the polymer tubular fibers are integrally and rapidly softened and melted, and the nano carbon materials can be rapidly oxidized and ablated in the heat treatment process due to the size nano effect and do not remain in pores in the material; moreover, the unique tubular cross-sectional structure of the polymeric tubular fibers allows for the passage of moisture or volatile components without melting and burning; in the heat treatment process, the polymer tubular fiber can be softened at a lower temperature before reaching the melting point, and due to the hollow tubular structure, the tube wall can shrink towards the center in the softening process, so that a gap is formed between the polymer fiber and the high-temperature structural ceramic material, the gap is continuously enlarged along with the increase of the temperature, the hollow inner diameter of the tubular fiber is continuously reduced, and a stable conveying channel can still be provided for moisture or volatile components.

The high-temperature structural ceramic material can be applied to casting thermal equipment, and can realize rapid heat treatment and shorten the shutdown time. According to the optimization of the proportion, the components and the size of the polymer tubular fiber, the serialization of products is realized, the high-temperature structural ceramic material is ensured to have good air permeability, no crack or peeling is generated in the high-temperature heat treatment process, so that good working performance, strength and durability are realized, and the cost is saved.

Drawings

FIG. 1 is an electron microscopic scanning pattern of the product obtained in example 1;

FIG. 2 is an electron microscopic scanning pattern of the product obtained in example 3.

Detailed Description

The conception, the specific structure, and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below, so that the objects, the features, and the effects of the present invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.

The first embodiment is as follows:

a high-temperature structural ceramic material doped with polymer tubular fibers comprises the following raw materials in parts by weight: 30 parts of Al₂O₃-SiO₂-MgO aggregate particles, 2 parts of Al₂O₃-SiO₂Fine MgO powder, 3 parts of alumina micropowder, 3 parts of silica micropowder, 0.5 part of composite additive, 0.2 part of binder and 0.2 part of polymer tubular fiber. The Al is₂O₃-SiO₂the-MgO aggregate particles are alumina, mullite and spinel which are composed of (Al)₂O₃)₁₀：(SiO₂)₈：(MgO)₆The material of (a); the Al is₂O₃-SiO₂-the average particle size of the fine MgO powder is 100 mesh; the Al is₂O₃-SiO₂Fine MgO powder comprising alumina, corundum, mullite or spinel₂O₃)₂₀：(SiO₂)₁₈：(MgO)₁₀The material of (a); the alumina content in the alumina micro powder is 90 percent; the content of silicon oxide in the silicon oxide micro powder is 80%. The composite additive is sulfurThe weight ratio of barium sulfate to strontium sulfate is 1: 1. The binding agent is silica sol. The outer diameter of the cross section of the polymer tubular fiber is 1 micrometer, the inner diameter is 0.5 micrometer, and the wall thickness is 1 micrometer; the polymeric tubular fiber is polyethylene.

A preparation method of a high-temperature structural ceramic material doped with polymer tubular fibers comprises the following specific steps: mixing the weight part of Al₂O₃-SiO₂-MgO aggregate particles, Al₂O₃-SiO₂Mixing fine MgO powder, fine alumina powder, fine silica powder and composite additive, adding the bonding agent in parts by weight, stirring and mixing, performing construction molding, and naturally drying; then baking and preserving heat at the temperature of more than 50 ℃ to obtain a ceramic material; and then the material is used according to the requirements of casting thermal equipment.

Example two:

a high-temperature structural ceramic material doped with polymer tubular fibers comprises the following raw materials in parts by weight: 50 parts of Al₂O₃-SiO₂-MgO aggregate particles, 25 parts of Al₂O₃-SiO₂Fine MgO powder, 28 parts of alumina micro powder, 28 parts of silica micro powder, 10 parts of composite additive, 10 parts of binder and 10 parts of polymer tubular fiber. The Al is₂O₃-SiO₂the-MgO aggregate particles are alumina, mullite and spinel which are composed of (Al)₂O₃)₁₀：(SiO₂)₈：(MgO)₆The material of (a); the Al is₂O₃-SiO₂-the average particle size of the fine MgO powder is 100 mesh; the Al is₂O₃-SiO₂Fine MgO powder comprising alumina, corundum, mullite or spinel₂O₃)₂₀：(SiO₂)₁₈：(MgO)₁₀The material of (a); the alumina content in the alumina micro powder is 93 percent; the content of silicon oxide in the silicon oxide micro powder is 85%. The composite additive is a mixture of barium sulfate and strontium sulfate in a weight ratio of 1: 1. The binding agent is silica sol. The outer diameter of the cross section of the polymer tubular fiber is 100 micrometers, the inner diameter is 150 micrometers, and the wall thickness is 150 micrometers; the polymeric tubular fibers are polypropylene.

A preparation method of a high-temperature structural ceramic material doped with polymer tubular fibers comprises the following specific steps: mixing the weight part of Al₂O₃-SiO₂-MgO aggregate particles, Al₂O₃-SiO₂Mixing fine MgO powder, fine alumina powder, fine silica powder and composite additive, adding the bonding agent in parts by weight, stirring and mixing, performing construction molding, and naturally drying; then baking and preserving heat at the temperature of more than 50 ℃ to obtain a ceramic material; and then the material is used according to the requirements of casting thermal equipment.

Example three:

a high-temperature structural ceramic material doped with polymer tubular fibers comprises the following raw materials in parts by weight: 80 parts of Al₂O₃-SiO₂-MgO aggregate particles, 40 parts of Al₂O₃-SiO₂Fine MgO powder, 45 parts of alumina micro powder, 45 parts of silica micro powder, 20 parts of composite additive, 20 parts of binder and 20 parts of polymer tubular fiber. The Al is₂O₃-SiO₂the-MgO aggregate particles are alumina, mullite and spinel which are composed of (Al)₂O₃)₁₀：(SiO₂)₈：(MgO)₆The material of (a); the Al is₂O₃-SiO₂-the average particle size of the fine MgO powder is 100 mesh; the Al is₂O₃-SiO₂Fine MgO powder comprising alumina, corundum, mullite or spinel₂O₃)₂₀：(SiO₂)₁₈：(MgO)₁₀The material of (a); the content of alumina in the alumina micro powder is 95 percent; the content of silicon oxide in the silicon oxide micro powder is 90%. The composite additive is a mixture of barium sulfate and strontium sulfate in a weight ratio of 1: 1. The binding agent is silica sol. The outer diameter of the cross section of the polymer tubular fiber is 200 mu m, the inner diameter is 190 mu m, and the wall thickness is 180 mu m; the polymer tubular fiber is polyacrylonitrile fiber.

A preparation method of a high-temperature structural ceramic material doped with polymer tubular fibers comprises the following specific steps: mixing the weight part of Al₂O₃-SiO₂-MgO aggregate particles, Al₂O₃-SiO₂Fine powder of-MgO and fine powder of aluminaMixing the powder, the silicon oxide micro powder and the composite additive, adding the bonding agent in parts by weight, stirring and mixing, then constructing and molding, and naturally drying; then baking and preserving heat at the temperature of more than 50 ℃ to obtain a ceramic material; and then the material is used according to the requirements of casting thermal equipment.

Comparative example 1

A high-temperature structural ceramic material doped with polymer tubular fibers comprises the following raw materials in parts by weight: 30 parts of Al₂O₃-SiO₂-MgO aggregate particles, 2 parts of Al₂O₃-SiO₂Fine MgO powder, 3 parts of alumina micropowder, 3 parts of silica micropowder, 0.5 part of composite additive, 0.2 part of binder and 0.2 part of polymer tubular fiber. The Al is₂O₃-SiO₂the-MgO aggregate particles are alumina, mullite and spinel which are composed of (Al)₂O₃)₅：(SiO₂)₃：(MgO)₂The material of (a); the Al is₂O₃-SiO₂-the average particle size of the fine MgO powder is 100 mesh; the Al is₂O₃-SiO₂Fine MgO powder comprising alumina, corundum, mullite or spinel₂O₃)₅：(SiO₂)₃：(MgO)₂The material of (a); the alumina content in the alumina micro powder is 90 percent; the content of silicon oxide in the silicon oxide micro powder is 80%. The composite additive is a mixture of barium sulfate and strontium sulfate in a weight ratio of 1: 1. The binding agent is silica sol. The outer diameter of the cross section of the polymer tubular fiber is 1 micrometer, the inner diameter is 0.5 micrometer, and the wall thickness is 1 micrometer; the polymeric tubular fiber is polyethylene.

A preparation method of a high-temperature structural ceramic material doped with polymer tubular fibers comprises the following specific steps: mixing the weight part of Al₂O₃-SiO₂-MgO aggregate particles, Al₂O₃-SiO₂Mixing fine MgO powder, fine alumina powder, fine silica powder and composite additive, adding the bonding agent in parts by weight, stirring and mixing, performing construction molding, and naturally drying; then baking and preserving heat at the temperature of more than 50 ℃ to obtain a ceramic material; and then the material is used according to the requirements of casting thermal equipment.

Then, carrying out related performance detection on products in the embodiment and the comparative example according to the requirements of the casting thermal equipment; the thermal shock resistance test standard follows GB/T30873-; the flexural strength test standard conforms to GBT 6569-2006); the abrasion resistance test follows GB/T18301-2001; the water absorption test follows GB/T2999-2002. The test results are shown in table 1 below. FIG. 1 is an electron microscopic scanning pattern of the product obtained in example 1; FIG. 2 is an electron microscopic scanning pattern of the product obtained in example 3.

As shown in the figure, FIG. 1 illustrates that the polymer tubular fibers can be uniformly dispersed in the matrix of the high temperature structural ceramic, and FIG. 2 illustrates that the polymer tubular fibers can be connected with each other to form continuous channels in a dispersed state.

Table 1 results of performance testing

Examples	Example 1	Example 2	Example 3	Comparative example 1
					Flexural strength (MPa)	25	5	20	15
Number of thermal shocks	45	40	45	55
					Amount of wear (cm)3)	3.1	6.0	4.2	4.5
Water absorption rate	1.2％	1.00％	1.10％	1.30％

The high temperature structural ceramic material of the doped polymer tubular fiber obtained in example 3 was aged by ultraviolet light at room temperature for 24h, and shrinkage occurred in the cross-sectional dimension of the tubular polymer fiber without temperature increase. The relationship between the amount of ultraviolet radiation energy and the shrinkage of the cross-sectional dimension of the tubular polymer fibers is shown in Table 2 below.

TABLE 2 aging test

While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that the present invention is not limited to the details of the embodiments shown and described, but is capable of numerous equivalents and substitutions without departing from the spirit of the invention as set forth in the claims appended hereto.