CN116730725A - Silicon nitride composite ceramic material for lift tube, preparation method and application - Google Patents

Silicon nitride composite ceramic material for lift tube, preparation method and application Download PDF

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CN116730725A
CN116730725A CN202310656129.7A CN202310656129A CN116730725A CN 116730725 A CN116730725 A CN 116730725A CN 202310656129 A CN202310656129 A CN 202310656129A CN 116730725 A CN116730725 A CN 116730725A
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ceramic material
silicon nitride
parts
lift tube
composite ceramic
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朱福林
肖立
崔辉
谭皓文
汤娜
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Hengyang Kaixin Special Materials Technology Co ltd
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Hengyang Kaixin Special Materials Technology Co ltd
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Abstract

The silicon nitride composite ceramic material for the lift tube comprises the following raw materials in parts by weight: 60-80 parts of silicon carbide, 4-12 parts of silicon nitride, 3-10 parts of metal oxide, 2-6 parts of rare earth oxide and 1-10 parts of high molecular polymer. According to the invention, the silicon carbide materials, the silicon nitride and other raw materials with different particle sizes are used together and matched with specific high molecular polymers and rare earth oxides, and the specific sintering temperature is adopted, so that powder particles are dispersed more uniformly in a system, the mixing is uniform, the bonding effect among the raw materials is enhanced, and the prepared ceramic material has good compactness, low thermal expansion coefficient, good thermal shock resistance, excellent bending strength and wear resistance, is particularly suitable for being used as a preparation material of a lift tube, can effectively prolong the service life of a product, and can reach more than 7 months.

Description

Silicon nitride composite ceramic material for lift tube, preparation method and application
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a silicon nitride composite ceramic material for a lift tube, a preparation method and application thereof.
Background
Silicon nitride ceramic is a special ceramic material with the best comprehensive performance, and has the characteristics of high strength, high hardness, high fracture toughness, thermal shock resistance and low friction coefficient, and is widely applied to various fields of photovoltaics, automobiles, metallurgy, chemical industry, energy sources, environmental protection, aerospace and the like.
The liquid lifting pipe is one of key components in the low-pressure casting process, and is required to have good high-temperature strength, excellent thermal shock resistance, high-temperature corrosion resistance and the like. The development of lift tubes has undergone the stages of cast iron lift tubes, stainless steel lift tubes, quartz lift tubes, and aluminum titanate lift tubes. At present, the high-performance ceramic lift tube is made of silicon nitride, and the lift tube made of the material has the characteristics of no infiltration, no reaction and the like with aluminum solution, and has the characteristics of high strength, strong thermal shock resistance and the like, and has the defects of high price and large one-time investment.
Chinese patent CN105906348A discloses a dense silicon nitride ceramic lift tube, and preparation method and application thereof, prepared from raw materials comprising 85-95 parts of silicon nitride and 5-15 parts of sintering aid; the sintering aid is one or more selected from aluminum oxide, magnesium oxide, yttrium oxide, cerium oxide and titanium carbide. The prepared silicon nitride ceramic lift tube has the characteristics of high density, high hardness, high bending strength, strong fracture toughness and the like, has long service life, and can be continuously used for more than one year on a conventional low-pressure aluminum casting machine. But its production cost is high.
The main defects of the prior art are that the performance is low, the service life is short, and the method can only be used in the low-end field; the price meeting the performance requirement is high, and the market acceptance is weak. The lift tube made of silicon nitride combined with silicon carbide materials produced by the current Jin Haihong, hong Yuan and other companies accounts for most of domestic markets, and the product of the type is positioned at the low end, but has short service life (about 2 months) due to poor compactness and low strength, and has low added value; while the market of high-end silicon nitride lift tubes is firmly controlled by Japanese company.
Disclosure of Invention
Aiming at the problems, the silicon nitride composite ceramic material for the lift tube provided by the invention has the advantages that the prepared ceramic material has good compactness, low thermal expansion coefficient, good thermal shock resistance, excellent bending strength and wear resistance, is particularly suitable for being used as a preparation material of the lift tube, and can effectively prolong the service life of a product by more than 5 months.
The invention provides a silicon nitride composite ceramic material for a lift tube, which comprises the following raw materials in parts by weight: 60-80 parts of silicon carbide, 4-12 parts of silicon nitride, 3-10 parts of metal oxide, 2-6 parts of rare earth oxide and 1-10 parts of high molecular polymer.
Preferably, the mass ratio of the 10-20 meshes of silicon carbide to the 50-70 meshes of silicon carbide to the 150-200 meshes of silicon carbide is 0.2-0.5:1:0.1-0.3.
The inventor finds in experiments that when silicon carbide materials with different particle sizes are used, the compactness of the ceramic material can be effectively improved, and the anti-seismic effect of the ceramic material is enhanced. The inventor analyzes that the silicon nitride materials with different granulas can be used together, so that other components in the system can be better mixed and dispersed, and the powder particles can be more uniformly covered by matching with a specific high polymer material, so that the bonding force among the particles is enhanced, and the ceramic material is more uniform and compact.
Preferably, the purity of the silicon nitride is more than or equal to 99.5 percent, and the grain diameter is 1 mu m.
Preferably, the metal oxide is one of iron oxide, nickel oxide and calcium oxide.
Further preferably, the metal oxide is nickel oxide.
Preferably, the rare earth oxide is one of lanthanum oxide and cerium oxide.
Further preferably, the rare earth oxide is cerium oxide.
Preferably, the high molecular polymer is one or more of epoxy resin or acrylic resin.
Further preferably, the high molecular polymer further contains at least one of polyethylene and polyvinyl alcohol. The polyethylene is a linear low density polyethylene.
The silicon nitride composite ceramic material further comprises at least one of carnauba wax, microcrystalline wax and polyethylene wax.
Further preferably, the mass ratio of the carnauba wax, the linear low density polyethylene and the epoxy resin is 1.5-2:1-1.5:0.1.
further preferably, the epoxy resin is epoxy resin E51.
When carnauba wax, linear low density polyethylene, epoxy resin are used, especially when the mass ratio of the three is 1.5-2:1-1.5: at 0.1, the prepared ceramic material has excellent wear resistance, heat resistance and anti-seismic effect, and has high yield and difficult crack generation. The inventor analyzes that the carnauba wax can effectively improve the fluidity and the permeability of raw materials by using several high molecular polymers together, is easier for other components to disperse in a system, can ensure that powder particles are covered by the high molecular polymers as much as possible, ensures that the mixing is uniform, effectively enhances the stability of the material, and the carnauba wax is alkyl acid ester, has strong polarity, can possibly form hydrogen bonds with metal powder and enhances the bonding effect; the linear low-density polyethylene and the epoxy resin have longer or larger skeleton structure and higher strength, are uniformly dispersed in the system, and can effectively reduce the agglomeration tendency of the powder. In the firing process of the product, the carnauba wax is easier to remove, and meanwhile, the linear low-density polyethylene and the epoxy resin can be kept for a long time to avoid cracking caused by the fact that the high polymer leaves the blank, and pores generated during the removal of the carnauba wax are convenient for the subsequent removal of the linear low-density polyethylene and the epoxy resin. Therefore, the prepared ceramic material has excellent stability, uniform dispersion of raw materials in the system, strong acting force among the raw materials, and higher density, so that the ceramic material has excellent wear resistance, heat resistance and earthquake resistance.
However, the inventors found that too much of the carnauba wax or too much of the epoxy resin may cause cracking. The inventors analyzed, probably because carnauba wax is of low molecular weight, has a low strength, and if too many pores are formed, would affect the strength and wear resistance of the ceramic material; and epoxy resin is too much, and has more cyclic groups, so that the internal stress of the molecule is strong, and cracks are easily formed.
Preferably, the silicon nitride composite ceramic material further contains 20-50 parts by weight of silicon micropowder.
Preferably, the mesh number of the silicon micro powder is 15-250 mesh.
More preferably, the mesh number of the fine silica powder is 200 mesh, and the purity of the fine silica powder is more than 99%.
The second aspect of the invention provides a preparation process of a silicon nitride composite ceramic material for a lift tube, which comprises the following specific steps:
s1, mixing: adding raw materials except high molecular polymers into ethanol, performing ball milling, and drying slurry obtained by ball milling to obtain a mixture;
s2, forming: adding the mixture and the high polymer into ethanol, mixing, and stirring to obtain mixed slurry; injecting the mixed slurry into a mold, airing and demolding to obtain a ceramic material green body;
s3, sintering: and (3) placing the green body to be sintered into a sintering furnace, heating to 1800-1900 ℃, preserving heat for 2-3h, and cooling to obtain the ceramic material.
Preferably, the preparation process of the ceramic material comprises the following specific steps:
s1, mixing: adding the raw materials except the high polymer into ethanol, and performing ball milling for 4-5h at the rotating speed of 300r/min; drying slurry obtained by ball milling to obtain a mixture; sieving the mixture with 40-150 mesh sieve;
s2, forming: adding the mixture and the high polymer into ethanol, mixing, and stirring to obtain mixed slurry; injecting the mixed slurry into a mold, airing and demolding to obtain a ceramic material green body;
s3, sintering: placing the green compact to be sintered into a sintering furnace, closing the furnace, vacuumizing to a temperature below 20pa for starting heating, and preserving heat for 2-3 hours when the temperature reaches 700-800 ℃ and the heating rate is 100 ℃/h; after 2MPa nitrogen is introduced, continuously heating to 1000-1300 ℃, preserving heat for 2-3h, continuously heating to 1800-1900 ℃, preserving heat for 2-3h, and heating at a speed of 80 ℃/h; cooling to 1400-1500 ℃ at a cooling rate of 100 ℃/h; and finally cooling along with the furnace to obtain the ceramic material.
The third aspect of the invention provides an application of the silicon nitride composite ceramic material for the lift tube in preparation of raw materials for the lift tube.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the silicon carbide materials, the silicon nitride and other raw materials with different particle sizes are used together and matched with specific high molecular polymers and rare earth oxides, and the specific sintering temperature is adopted, so that powder particles are dispersed more uniformly in a system, the mixing is uniform, the bonding effect among the raw materials is enhanced, and the prepared ceramic material has good compactness, low thermal expansion coefficient, good thermal shock resistance, excellent bending strength and wear resistance, is particularly suitable for being used as a preparation material of a lift tube, can effectively prolong the service life of a product, and can reach more than 7 months.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be noted that the following examples are further illustrative of the present invention and are not intended to be limiting.
Examples
Example 1
In one aspect, the embodiment provides a silicon nitride composite ceramic material for a lift tube, which comprises the following raw materials in parts by weight: 70 parts of silicon carbide, 8 parts of silicon nitride, 6 parts of metal oxide, 3 parts of rare earth oxide, 8 parts of high polymer and carnauba wax, and 15 parts of silicon micropowder.
The silicon carbide is 20 meshes of silicon carbide, 60 meshes of silicon carbide and 200 meshes of silicon carbide with the mass ratio of 0.35:1:0.2, and is purchased from metal materials of Ruijiang Co., ltd.
The purity of the silicon nitride is more than or equal to 99.5%, the grain diameter is 1 mu m, and the silicon nitride is purchased from Fosman technology (Beijing) Co.
The metal oxide is nickel oxide; the rare earth oxide is zirconia.
The high molecular polymer is linear low density polyethylene and epoxy resin;
carnauba wax (CAS number 8015-86-9), linear low density polyethylene, epoxy resin mass ratio 1.5:1: 0.1; linear low density polyethylene is purchased from Shanghai bridge micro chemical technology Co., ltd, and has the trade name LL0230AT; the epoxy resin is epoxy resin E51.
The mesh number of the silicon micro powder is 200 meshes, the purity of the silicon micro powder is more than 99%, and the silicon micro powder is purchased from Hebei Mimeni mineral products limited company.
In another aspect, the present embodiment provides a method for preparing a silicon nitride composite ceramic material for a lift tube, which specifically includes the following steps:
s1, mixing: adding raw materials except high molecular polymers into 100 parts of ethanol, and performing ball milling for 4 hours at the rotating speed of 300r/min; drying slurry obtained by ball milling to obtain a mixture; sieving the mixture with a 100-mesh sieve;
s2, forming: adding the mixture and the high polymer into 50 parts of ethanol, mixing, and stirring to obtain mixed slurry; injecting the mixed slurry into a mold, airing and demolding to obtain a ceramic material green body;
s3, sintering: placing the green compact to be sintered into a sintering furnace, closing the furnace, vacuumizing to a temperature below 20pa for starting heating, and preserving heat for 2 hours when the temperature reaches 800 ℃ and the heating rate is 100 ℃/h; after 2MPa nitrogen is introduced, the temperature is continuously raised to 1200 ℃, the heat is preserved for 2 hours, the temperature is continuously raised to 1800 ℃, the heat is preserved for 2 hours, and the temperature raising rate is 80 ℃/h; then cooling to 1500 ℃ at a cooling rate of 100 ℃/h; and finally cooling along with the furnace to obtain the ceramic material.
Example 2
In one aspect, the present embodiment provides a silicon nitride composite ceramic material for a lift tube, which includes the following raw materials in parts by weight: 60 parts of silicon carbide, 4 parts of silicon nitride, 3 parts of metal oxide, 2 parts of rare earth oxide, 5 parts of high molecular polymer, carnauba wax and 10 parts of silicon micropowder.
The specific raw materials are the same as in example 1.
In another aspect of this embodiment, a method for preparing a silicon nitride composite ceramic material for a lift tube is provided, which includes the same steps as in embodiment 1.
Example 3
In one aspect, the present embodiment provides a silicon nitride composite ceramic material for a lift tube, which includes the following raw materials in parts by weight: 80 parts of silicon carbide, 12 parts of silicon nitride, 10 parts of metal oxide, 6 parts of rare earth oxide, 10 parts of high polymer and carnauba wax and 20 parts of silicon micropowder.
The specific raw materials are the same as in example 1.
In another aspect of this embodiment, a method for preparing a silicon nitride composite ceramic material for a lift tube is provided, which includes the same steps as in embodiment 1.
Comparative example 1
This example provides a silicon nitride composite ceramic material for a lift tube, which has the same steps as those of example 1, and differs from example 1 in that the silicon carbide content is 0 parts.
Comparative example 2
The embodiment provides a silicon nitride composite ceramic material for a lift tube, which has the specific implementation steps similar to those of embodiment 1, and is different from embodiment 1 in that the high molecular polymer is epoxy resin E51.
Comparative example 3
This embodiment provides a silicon nitride composite ceramic material for a lift tube, which has the same specific implementation steps as those of embodiment 1, and is different from embodiment 1 in that the silicon carbide is 50-70 mesh silicon carbide.
Comparative example 4
The embodiment provides a silicon nitride composite ceramic material for a lift tube, which has the specific implementation steps same as those of embodiment 1, and is different from embodiment 1 in that in the preparation method, step S3 is directly heated to 1800 ℃, and is kept for 2 hours, and the heating rate is 80 ℃/h.
Performance testing
1. Abrasion resistance test:
adopting an abrasion resistance tester to conduct abrasion resistance testing on fragments of ceramic products, taking 5 fragments of the ceramic products, placing grinding steel balls with certain grain size, no. 80 white corundum and quantitative deionized water or distilled water on the fragments, conducting rotary grinding according to a specified rotation rate, observing and comparing the worn ceramic fragments with unworn ceramic fragments, evaluating the abrasion resistance of the ceramic fragments through the number of grinding revolutions of which abrasion begins to appear on the ceramic fragments, and averaging abrasion resistance testing results of the 5 fragments of the ceramic products to obtain the abrasion resistance testing result of the ceramic products.
Wherein the ceramic wear-resistant grade standard is 1 to 5 grades, the 5 grades are the best 1 grade and the worst, and the judgment standard is as follows
Table 1 shows the results.
2. Coefficient of thermal expansion: the test was carried out according to the GB/T16535-1996 test method.
3. Thermal shock resistance: processing the sintered product into a certain shape, carrying out rapid water cooling circulation for 20 times after heat preservation for 15 minutes at 1150 ℃, observing whether cracking and other phenomena occur on the surface of the material, and if no change occurs, marking the material as qualified; if a cracking phenomenon such as a crack occurs, the test piece is judged as being unqualified.
4. Four-point flexural strength test: according to test standard ISO14704: 2016.
The ceramic materials of examples 1 to 3 and comparative examples 1 to 4 were subjected to the above-mentioned performance test, and the test results are shown in Table 3 below.
TABLE 2

Claims (10)

1. The silicon nitride composite ceramic material for the lift tube is characterized by comprising the following raw materials in parts by weight: 60-80 parts of silicon carbide, 4-12 parts of silicon nitride, 3-10 parts of metal oxide, 2-6 parts of rare earth oxide and 1-10 parts of high molecular polymer.
2. The silicon nitride composite ceramic material for a lift tube according to claim 1, wherein the silicon carbide is 10 to 20 mesh silicon carbide, 50 to 70 mesh silicon carbide, 150 to 200 mesh silicon carbide.
3. The silicon nitride composite ceramic material for a lift tube according to claim 2, wherein the mass ratio of 10-20 mesh silicon carbide, 50-70 mesh silicon carbide, 150-200 mesh silicon carbide is 0.2-0.5:1:0.1-0.3.
4. The silicon nitride composite ceramic material for a lift tube of claim 1, wherein the metal oxide is one of iron oxide, nickel oxide, and calcium oxide.
5. The silicon nitride composite ceramic material for a lift tube according to claim 1, wherein the rare earth oxide is one of lanthanum oxide and cerium oxide.
6. The silicon nitride composite ceramic material for a lift tube according to claim 1, wherein the high molecular polymer is one or more of epoxy resin or acrylic resin.
7. The silicon nitride composite ceramic material for a lift tube according to claim 6, wherein the high molecular polymer further contains at least one of polyethylene and polyvinyl alcohol.
8. The silicon nitride composite ceramic material for a lift tube according to claim 1, further comprising 10-20 parts by weight of fine silica powder.
9. The silicon nitride composite ceramic material for a lift tube of claim 7, further comprising at least one of carnauba wax, microcrystalline wax, polyethylene wax.
10. A process for preparing a silicon nitride composite ceramic material for lift tubes according to any one of claims 1 to 9, characterized by the specific steps of:
s1, mixing: adding raw materials except high molecular polymers into ethanol, performing ball milling, and drying slurry obtained by ball milling to obtain a mixture;
s2, forming: adding the mixture and the high polymer into ethanol, mixing, and stirring to obtain mixed slurry; injecting the mixed slurry into a mold, airing and demolding to obtain a ceramic material green body;
s3, sintering: and (3) placing the green body to be sintered into a sintering furnace, heating to 1800-1900 ℃, preserving heat for 2-3h, and cooling to obtain the ceramic material.
CN202310656129.7A 2023-06-05 2023-06-05 Silicon nitride composite ceramic material for lift tube, preparation method and application Pending CN116730725A (en)

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