CN116789454A - Silicon carbide ceramic and preparation method thereof - Google Patents
Silicon carbide ceramic and preparation method thereof Download PDFInfo
- Publication number
- CN116789454A CN116789454A CN202310812352.6A CN202310812352A CN116789454A CN 116789454 A CN116789454 A CN 116789454A CN 202310812352 A CN202310812352 A CN 202310812352A CN 116789454 A CN116789454 A CN 116789454A
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- carbide ceramic
- ceramic
- polyethylene
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000000919 ceramic Substances 0.000 title claims abstract description 130
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000004698 Polyethylene Substances 0.000 claims abstract description 65
- -1 polyethylene Polymers 0.000 claims abstract description 65
- 229920000573 polyethylene Polymers 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006229 carbon black Substances 0.000 claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 22
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 21
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 5
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005011 phenolic resin Substances 0.000 claims abstract description 5
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 5
- 238000007493 shaping process Methods 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims description 26
- 239000011231 conductive filler Substances 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 4
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 45
- 238000005336 cracking Methods 0.000 description 14
- 238000001514 detection method Methods 0.000 description 10
- 238000005452 bending Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/638—Removal thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3821—Boron carbides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/408—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/425—Graphite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
- C04B2235/5248—Carbon, e.g. graphite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Products (AREA)
Abstract
The application relates to the technical field of ceramic materials, and particularly discloses silicon carbide ceramic and a preparation method thereof. The preparation method of the silicon carbide ceramic comprises the following steps: granulating; shaping; coating; sintering; in the granulating step: uniformly mixing 95-97 parts of silicon carbide micro powder, 1-1.5 parts of high-purity phenolic resin, 0.2-1.3 parts of heat conducting filler and 0.5-1 part of boron carbide, and granulating to obtain silicon carbide powder particles; the purity of the silicon carbide micro powder is more than 95 percent; in the heat conduction material, the weight ratio of graphene to carbon nano-tube to carbon black to silver powder is (0.2-2): (0.4-1.8): (0.5-3.5): (0.1-1.2); and in the coating step, the formed ceramic blank is coated with a polyethylene layer. According to the application, the heat conducting filler and the wrapping polyethylene film are added in the preparation method, so that the prepared silicon carbide ceramic has low cracks and better product quality and stability.
Description
Technical Field
The application relates to the technical field of ceramic materials, in particular to silicon carbide ceramic and a preparation method thereof.
Background
Silicon carbide ceramics not only have excellent normal temperature mechanical properties, for example, silicon carbide ceramics have the characteristics of high flexural strength, excellent oxidation resistance, good corrosion resistance, high abrasion resistance, low friction coefficient, and the like, but also the high temperature mechanical properties (e.g., strength, creep resistance, and the like) of silicon carbide ceramics are the best among known ceramic materials. Silicon carbide ceramics have been increasingly used in the fields of automobiles, machining, environmental protection, space technology, information electronics, energy sources and the like, and have become an irreplaceable structural ceramic with excellent performance in a plurality of industrial fields.
The high temperature sintering step is typically involved in the silicon carbide ceramic preparation process. However, after high temperature sintering, the silicon carbide ceramic inevitably generates cracks. Silicon carbide ceramic products with obvious cracks on the surface cannot be used, so that high-temperature sintering can lead to low yield of silicon carbide ceramic. In addition, the inside of the silicon carbide ceramic product after high-temperature sintering is also provided with a plurality of microcracks which cannot be distinguished by naked eyes, and the quality of the silicon carbide ceramic product can be seriously affected by the existence of the microcracks, so that the stability of the silicon carbide ceramic product can not be ensured.
The related art generally improves the uniformity of the internal and external temperatures of the silicon carbide ceramic by adjusting and controlling the temperature in the high-temperature sintering step in order to reduce cracking of the silicon carbide ceramic product. However, the above-described method results in an extended production cycle of silicon carbide ceramics, reduced production efficiency, increased production costs, and higher requirements for temperature uniformity within the equipment temperature zone, so that the above-described method is not an optimal choice from the standpoint of cost, efficiency, and availability.
Therefore, there is an urgent need to develop a method to solve the problem of cracking of silicon carbide ceramic products.
Disclosure of Invention
In order to obtain the low-crack silicon carbide ceramic, the application provides the silicon carbide ceramic and a preparation method thereof.
In a first aspect, the present application provides a method for preparing silicon carbide ceramic, which adopts the following technical scheme:
the preparation method of the silicon carbide ceramic is characterized by comprising the following steps of:
granulating; shaping; coating; sintering;
wherein, in the granulating step: uniformly mixing 95-97 parts of silicon carbide micro powder, 1-1.5 parts of high-purity phenolic resin, 0.5-2.5 parts of heat conducting filler and 0.5-1 part of boron carbide, and granulating to obtain silicon carbide powder particles;
the purity of the silicon carbide micro powder is more than 95%;
the heat conduction material comprises graphene, carbon nanotubes, carbon black and silver powder; the weight ratio of the graphene to the carbon nanotubes to the carbon black to the silver powder is (0.2-2): (0.4-1.6): (0.5-3.5): (0.1-1.2);
and in the coating step, the ceramic blank obtained after the molding is coated with a polyethylene layer.
According to the application, the heat conducting filler is added to form a heat conducting net chain in the silicon carbide ceramic, so that the temperature uniformity of the inside and the outside of the silicon carbide ceramic is improved, the temperature difference between the inside and the outside of the silicon carbide ceramic is reduced, and the cracks after sintering are reduced. Meanwhile, compared with a silicon carbide ceramic product (the internal and external temperatures of the ceramic are not uniform, internal water vapor is easy to stay, and dark deposition exists on the surface of the sintered product) without the heat conducting filler, the silicon carbide ceramic prepared by the preparation method provided by the application has the advantages that the internal and external temperatures are uniform, the internal water of the silicon carbide ceramic is easier to be led out, and the surface color of the sintered silicon carbide product is more uniform. According to the application, the polyethylene film is wrapped around the ceramic body, and the polyethylene film interacts with silicon carbide after being heated and decomposed, so that cracks of the ceramic after sintering are reduced.
According to the application, the heat conducting filler and the wrapping polyethylene film are added in the preparation method, so that the prepared silicon carbide ceramic has low cracks and better product quality and stability.
Preferably, the weight ratio of the graphene, the carbon nanotubes, the carbon black and the silver powder is (0.5-1.5): (0.8-1.2): (1-3): (0.3-0.8).
In one specific embodiment, the weight ratio of the graphene, the carbon nanotubes, the carbon black, and the silver powder is 0.2:1:2:0.5, 0.5:1:2:0.5, 1:1:2:0.5, 1.5:1:2:0.5, 2:1:2:0.5, 1:0.4:0.5, 1:0.8:2:0.5, 1:1.2:2:0.5, 1:1.6:2:0.5, 1:1:0.5, 1:1:1:0.5, 1:1:3:0.5, 1:1:3.5:0.5, 1:1:2:0.1, 1:1:2:0.3, 1:1:2:0.8, 1:1:2:1.2.
In some specific embodiments, the weight ratio of the graphene, the carbon nanotubes, the carbon black, and the silver powder includes, but is not limited to, the weight ratio formed between any of the above points or ranges of any of the above point compositions.
According to the application, the heat conduction filler composed of graphene, carbon nanotubes, carbon black and silver powder is added, and the addition proportion of the graphene, the carbon black and the silver powder is controlled, so that the quality of the prepared silicon carbide ceramic is improved, and the silicon carbide ceramic has low cracking rate and good stability.
Preferably, the heat conductive filler is added in an amount of 1 to 2 parts.
In a specific embodiment, the heat conductive filler may be added in an amount of 0.5 part, 1 part, 2 parts, 3 parts, 3.5 parts.
In some embodiments, the thermally conductive filler may be added in an amount of 0.5-1 part, 0.5-2 parts, 0.5-3 parts, 0.5-3.5 parts, 1-2 parts, 1-3 parts, 1-3.5 parts, 2-3 parts, 2-3.5 parts, 3-3.5 parts.
The application controls the addition amount of the heat conductive filler in the range, can further improve the quality of the prepared silicon carbide ceramic, has low crack and better stability.
Preferably, the purity of the silicon carbide micropowder is 97% or more.
Preferably, the silicon carbide micropowder is a high-purity silicon carbide micropowder.
In a specific embodiment, the purity of the silicon carbide micropowder may be 95%, 97%, 99%.
In some embodiments, the silicon carbide micropowder may have a purity of 95-97%, 95-99%, 97-99%.
The purity of the silicon carbide micro powder is controlled within the range, so that the quality of the prepared silicon carbide ceramic can be further improved, and the silicon carbide micro powder has low cracking and better stability.
Preferably, the polyethylene layer has a thickness of 0.3-1.5mm.
Preferably, the polyethylene layer has a thickness of 0.5 to 1mm.
In a specific embodiment, the polyethylene layer may have a thickness of 0.3mm, 0.5mm, 0.8mm, 1mm, 1.5mm.
In some embodiments, the polyethylene layer may have a thickness of 0.3 to 0.5mm, 0.3 to 0.8mm, 0.3 to 1mm, 0.3 to 1.5mm, 0.5 to 0.8mm, 0.5 to 1mm, 0.5 to 1.5mm, 0.8 to 1mm, 0.8 to 1.5mm, 1 to 1.5mm.
The application controls the thickness of the polyethylene layer in the range, can further improve the quality of the prepared silicon carbide ceramic, has low crack and better stability.
Preferably, the polyethylene in the polyethylene layer is high pressure polyethylene.
The application compares the quality of silicon carbide ceramics prepared when high-pressure polyethylene, low-pressure polyethylene and linear low-density polyethylene are used as materials of polyethylene layers. As shown by test results, the high-pressure polyethylene is used as the material of the polyethylene layer, so that the quality of the prepared silicon carbide ceramic can be further improved, and the silicon carbide ceramic has low cracking and better stability.
Preferably, the polyethylene layer is obtained by wrapping and winding a plurality of polyethylene films.
Preferably, the molding step includes a primary molding step and a secondary molding step.
Preferably, in the primary molding step, the silicon carbide powder obtained by granulation is dry-pressed to obtain a primary molded product.
Preferably, in the secondary molding step, the product after the primary molding is die-cast and molded, and the product after the secondary molding, namely the ceramic blank, is obtained.
Preferably, in the sintering step, the sintering temperature is 1800-2200 ℃.
In a second aspect, the present application provides a silicon carbide ceramic prepared by the above-described preparation method.
According to the application, the heat conducting filler and the wrapping polyethylene film are added in the preparation method, so that the prepared silicon carbide ceramic has low cracks and better product quality and stability.
In summary, the application has the following beneficial effects:
1. according to the application, the heat conducting filler is added to form a heat conducting net chain in the silicon carbide ceramic, so that the temperature uniformity of the inside and the outside of the silicon carbide ceramic is improved, the temperature difference between the inside and the outside of the silicon carbide ceramic is reduced, and the cracks after sintering are reduced. Meanwhile, compared with a silicon carbide ceramic product (the internal and external temperatures of the ceramic are not uniform, internal water vapor is easy to stay, and dark deposition exists on the surface of the sintered product) without the heat conducting filler, the silicon carbide ceramic prepared by the preparation method provided by the application has the advantages that the internal and external temperatures are uniform, the internal water of the silicon carbide ceramic is easier to be led out, and the surface color of the sintered silicon carbide product is more uniform.
2. According to the application, the polyethylene film is wrapped around the ceramic body, and the polyethylene film interacts with silicon carbide after being heated and decomposed, so that cracks of the ceramic after sintering are reduced.
3. According to the application, the heat conducting filler and the wrapping polyethylene film are added in the preparation method, so that the prepared silicon carbide ceramic has low cracks and better product quality and stability.
Drawings
FIG. 1 is a surface observation of the case of cracks on the surface of the ceramic after sintering in example 3 of the present application.
FIG. 2 is a surface observation of the case of cracks on the surface of the ceramic after sintering according to comparative example 1 of the present application.
FIG. 3 is a scanning electron microscope observation of the case of cracks on the surface of the ceramic after sintering in example 1 of the present application.
FIG. 4 is a scanning electron microscope observation of the surface crack condition of the ceramic after sintering of comparative example 1 of the present application.
Detailed Description
The application provides a preparation method of silicon carbide ceramic, which specifically comprises the following steps:
(1) Granulating;
mixing evenly 95-97 parts of silicon carbide micro powder, 1-1.5 parts of high-purity phenolic resin, 0.5-2.5 parts of heat conducting filler and 0.5-1 part of boron carbide, and granulating to obtain silicon carbide powder particles. Preferably, the heat conductive filler is added in an amount of 1 to 2 parts.
Wherein the purity of the silicon carbide micro powder is more than 95 percent. Preferably, 97% or more of the fine silicon carbide powder.
The heat conduction material comprises graphene, carbon nanotubes, carbon black and silver powder; the weight ratio of the graphene, the carbon nano-tube, the carbon black and the silver powder is (0.2-2): (0.4-1.6): (0.5-3.5): (0.1-1.2), preferably, the weight ratio of graphene, carbon nanotubes, carbon black and silver powder is (0.5-1.5): (0.8-1.2): (1-3): (0.3-0.8).
(2) Shaping;
and (3) one-step molding: and (3) dry-pressing the silicon carbide powder particles obtained by granulation to obtain a one-step molded product.
And (5) secondary forming: and (3) die-casting the product after the one-time molding to obtain a product after the two-time molding, namely a ceramic blank.
(3) Coating;
and wrapping the polyethylene layer with the ceramic blank obtained after molding to obtain the ceramic blank wrapped with the polyethylene layer.
Wherein the polyethylene in the polyethylene layer is high pressure polyethylene.
Wherein the polyethylene layer is obtained by wrapping and winding a plurality of layers of polyethylene films.
Wherein the thickness of the polyethylene layer is 0.3-1.5mm. Preferably, the polyethylene film has a thickness of 0.5 to 1mm.
(4) Sintering;
and sintering the ceramic blank coated with the polyethylene layer at 1800-2200 ℃ to obtain the sintered silicon carbide ceramic.
The application also provides the silicon carbide ceramic prepared by the preparation method. According to the application, the heat conducting filler and the wrapping polyethylene film are added in the preparation method, so that the prepared silicon carbide ceramic has low cracks and better product quality and stability.
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application.
The present application will be described in further detail with reference to examples, comparative examples, drawings and performance test results.
Examples
Example 1
The present embodiment provides a silicon carbide ceramic.
The preparation method of the silicon carbide ceramic comprises the following steps:
(1) Granulating;
uniformly mixing silicon carbide micro powder, high-purity phenolic resin, heat conducting filler and boron carbide, and then sending the mixture into a granulator for granulation to obtain silicon carbide powder particles. The amounts of the components added are shown in Table 1.
Wherein the silicon carbide micro powder is high-purity silicon carbide micro powder, the purity is 99%, and the particle size distribution is in the range of 0.1-1 mu m. In the heat conduction material, the weight ratio of graphene to carbon nano-tube to carbon black to silver powder is 1:1:2:0.5. the heat conducting filler is evenly mixed according to the proportion of each component, and then is granulated according to the corresponding amount of the heat conducting filler added into the ceramic.
(2) Shaping;
and (3) one-step molding: and (3) putting the silicon carbide powder particles obtained by granulation into a dry press forming machine for dry press forming to obtain a one-step formed product.
And (5) secondary forming: and (3) placing the product (cake shape) after the one-time molding into a vacuum bag for vacuumizing, and then placing the vacuum bag into an isostatic pressing machine for secondary die casting molding to obtain a product, namely a ceramic blank body, after the two-time molding.
(3) Coating;
and wrapping and winding the ceramic blank (cake shape) obtained after molding by using a plurality of layers of polyethylene films to obtain a polyethylene layer, and obtaining the ceramic blank wrapped with the polyethylene layer. The thickness of the polyethylene layer was 0.8mm, wherein the polyethylene was high pressure polyethylene.
(4) Sintering;
and (3) placing the ceramic blank coated with the polyethylene layer into a degreasing sintering furnace for sintering at 2100 ℃ to obtain the sintered silicon carbide ceramic.
And (3) carrying out finish machining on the sintered silicon carbide ceramic to obtain the silicon carbide ceramic with the required size.
Examples 2 to 21
Examples 2-21 provide a silicon carbide ceramic, respectively.
The preparation method of the above example is the same as that of example 1, except that the addition of each component is as shown in Table 1.
The differences between the above embodiments are as follows:
examples 1 to 5 differ in the amount of graphene added.
Examples 3 and 6 to 9 differ in the amount of carbon nanotubes added.
Examples 3 and 10 to 13 differ in the amount of carbon black added.
Examples 3, 14-17 differ in the amount of silver powder added.
Examples 3, 18-21 differ in the amount of thermally conductive filler added.
Examples 22 to 30
Examples 22-30 each provide a silicon carbide ceramic.
The preparation method of the above example is the same as that of example 1, except that the purity of the silicon carbide fine powder, the type of material of the polyethylene layer, and the thickness of the polyethylene layer are as shown in table 1.
The differences between the above embodiments are as follows:
examples 3, 22-24 differ in the purity of the silicon carbide micropowder.
Examples 3, 25-26 differ in the type of material of the polyethylene layer.
High pressure polyethylene: polymerization grade ethylene is used as a raw material, oxygen or organic peroxide is used as a catalyst, and the catalyst is polymerized in a tubular reactor cargo tank reactor by using an ultrahigh pressure of 130-280Mpa and a high temperature process of about 300 ℃; i.e.Low Density Polyethylene (LDPE) having a density of less than 0.925g/cm 3 。
Low pressure polyethylene: taking high-purity ethylene as a raw material, propylene or 1-butene and the like as comonomers, taking alkane as a solvent, carrying out solution polymerization at a certain temperature and under a certain pressure in the presence of a high-activity catalyst, and separating, drying, mixing and granulating to obtain the catalyst; i.e., high Density Polyethylene (HDPE) having a density greater than 0.94g/cm 3 。
Linear Low Density Polyethylene (LLDPE): is a copolymer obtained by polymerizing ethylene and a small amount of higher alpha-olefin (such as butene-1, hexene-1, octene-1, tetramethylpentene-1, etc.) under the action of a catalyst and high pressure or low pressure. The molecular structure of conventional LLDPE is characterized by its linear backbone with little or no long chain branching, but contains some short chain branching. The absence of long chain branches results in a higher crystallinity of the polymer. The density is 0.915-0.935g/cm 3 Between them. Compared with LDPE, LLDPE has the advantages of high strength, good toughness, strong rigidity, heat resistance, cold resistance and the like, has good performances of environmental stress cracking resistance, tearing strength resistance and the like, and can resist acid, alkali, organic solvents and the like.
Examples 3, 27-30 differ in the thickness of the polyethylene layer.
Comparative example
Comparative example 1
Comparative example 1 provides a silicon carbide ceramic. This comparative example differs from example 3 in that: in this comparative example, no thermally conductive filler was added. The addition of the other components is shown in Table 1.
Comparative example 2
Comparative example 2 provides a silicon carbide ceramic. This comparative example differs from example 3 in that: carbon black and silver powder were not added to the heat conductive filler of this comparative example. The addition of the other components is shown in Table 1.
Comparative example 3
Comparative example 3 provides a silicon carbide ceramic. This comparative example differs from example 3 in that: silver powder was not added to the heat conductive filler of this comparative example. The addition of the other components is shown in Table 1.
Comparative example 4
Comparative example 4 provides a silicon carbide ceramic. This comparative example differs from example 3 in that: carbon black was not added to the heat conductive filler of this comparative example. The addition of the other components is shown in Table 1.
Comparative example 5
Comparative example 5 provides a silicon carbide ceramic. This comparative example differs from example 3 in that: the polyethylene film was not wrapped in this comparative example. The addition of the other components is shown in Table 1.
TABLE 1 addition of the components in examples 1 to 30 and comparative examples 1 to 5
Performance test-detection of silicon carbide ceramics
The silicon carbide ceramics prepared in examples 1 to 30 and comparative examples 1 to 5 of the present application were examined.
When the surface or subsurface of the ceramic product has cracks of 10-60 mu m, the ceramic product can be damaged during working. For example, silicon carbide ceramics can be subject to material failure when subjected to loading stresses of 686-980N/mm, such as those having cracks on the order of 30-50um in surface. Therefore, it is important to detect ceramic cracks.
The application adopts bending strength and compressive strength to indirectly evaluate the crack condition of the prepared silicon carbide ceramic, and has small size, small quantity of ceramic cracks and high bending strength and compressive strength.
In the application, the method for detecting the bending strength adopts a three-point bending strength detection method in the detection of the mechanical properties of the ceramic material in the related technology. The compressive strength detection method adopts the compressive strength detection method in the mechanical property detection of the ceramic material in the related technology.
The test results are shown in Table 2.
TABLE 2 detection results for examples 1-30 and comparative examples 1-5
As can be seen from table 2, the possibility of cracking of the silicon carbide ceramic can be effectively reduced by using the preparation method of the present application, and thus a low-cracking silicon carbide ceramic can be obtained.
Example 3 differs from comparative example 1 in the presence or absence of the addition of a thermally conductive filler. From the test results of comparative example 3 and comparative example 1, it is evident that the flexural strength and compressive strength of example 3 are much greater than those of comparative example 1, and that the risk of cracking of silicon carbide ceramic can be effectively reduced by heating the heat conductive filler in the preparation method of the present application.
As is clear from the test results of comparative example 3 and comparative examples 2 to 4, the flexural strength and tensile strength of the silicon carbide ceramics obtained when the used thermally conductive filler components were only graphene and carbon nanotubes (comparative example 2), only graphene, carbon nanotubes and carbon black (comparative example 3), only graphene, carbon nanotubes and silver powder (comparative example 4) were inferior to those of the silicon carbide ceramics obtained when the thermally conductive filler components were graphene, carbon nanotubes, carbon black and silver powder in example 3. Therefore, when the heat conducting filler is composed of the four components, the risk of cracking of the silicon carbide ceramic can be effectively reduced, and the low-cracking silicon carbide ceramic is obtained.
As can be seen from the detection results of comparative examples 1 to 17, the weight ratio of graphene, carbon nanotubes, carbon black and silver powder in the heat conductive material is defined as (0.2 to 2): (0.4-1.6): (0.5-3.5): (0.1-1.2), the risk of cracking of the silicon carbide ceramic can be further effectively reduced. Preferably, the weight ratio of graphene, carbon nanotubes, carbon black and silver powder in the heat conductive material is defined as (0.5-1.5): (0.8-1.2): (1-3): (0.3-0.8).
As can be seen from the test results of comparative examples 3 and 18-21, the application controls the addition amount of the heat conductive filler in the granulating step to be 0.5-2.5 parts, and the prepared silicon carbide ceramic has higher bending strength and compressive strength, and can further effectively reduce the risk of cracking of the silicon carbide ceramic. Preferably, the addition amount of the heat conductive filler is controlled to 1-2 parts.
As is clear from the detection results of comparative examples 2 and 22-24, the purity of the silicon carbide micro powder is controlled to be more than 95%, and the prepared silicon carbide ceramic has higher bending strength and compressive strength. Preferably, the purity of the silicon carbide micro powder is controlled to be more than 97%.
As is clear from the test results of comparative examples 2 and 25 to 26, the silicon carbide ceramic obtained by using high-pressure polyethylene for the polyethylene in the polyethylene layer has higher flexural strength and compressive strength than those obtained by using low-pressure polyethylene and linear low-density polyethylene.
As is clear from the test results of comparative examples 2 and 27 to 30, the thickness of the polyethylene layer is controlled to be 0.3 to 1.5mm, and the prepared silicon carbide ceramic has higher bending strength and compressive strength, so that the low-crack silicon carbide ceramic is obtained. Preferably, the thickness of the polyethylene layer is controlled to be 0.5-1mm,
2. surface cracking conditions of silicon carbide ceramics
The crack conditions of the surfaces of the silicon carbide ceramics prepared in example 3 of the present application and comparative example 1 were compared. The surface observations are shown in figures 1-2, respectively. The scanning electron microscope observation results are shown in fig. 3-4 respectively.
FIGS. 1 and 3 show the silicon carbide ceramic prepared in example 3 of the present application, which has a good quality and almost no cracks as shown in FIGS. 1 and 3. While fig. 2 and 4 show the silicon carbide ceramics prepared in comparative example 1, it is understood from fig. 2 and 4 that the silicon carbide ceramics prepared by the preparation method provided in comparative example 1 have cracks of different degrees and have poor quality. The difference between example 3 and comparative example 1 is whether or not the heat conductive filler is added, and it is understood from the above-described detection result that heating the heat conductive filler in the production method of the present application can effectively reduce the possibility of occurrence of cracks in the silicon carbide ceramic, thereby enabling to obtain a low-crack silicon carbide ceramic.
In conclusion, by utilizing the preparation method provided by the application, the prepared silicon carbide ceramic has low cracks and better product quality and stability by simultaneously adding the heat conducting filler and wrapping the polyethylene film.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and are not limiting; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. The preparation method of the silicon carbide ceramic is characterized by comprising the following steps of:
granulating; shaping; coating; sintering;
wherein, in the granulating step: uniformly mixing 95-97 parts of silicon carbide micro powder, 1-1.5 parts of high-purity phenolic resin, 0.5-2.5 parts of heat conducting filler and 0.5-1 part of boron carbide, and granulating to obtain silicon carbide powder particles;
the purity of the silicon carbide micro powder is more than 95%;
the heat conduction material comprises graphene, carbon nanotubes, carbon black and silver powder; the weight ratio of the graphene to the carbon nanotubes to the carbon black to the silver powder is (0.2-2): (0.4-1.6): (0.5-3.5): (0.1-1.2);
and in the coating step, the ceramic blank obtained after the molding is coated with a polyethylene layer.
2. The method for producing silicon carbide ceramic according to claim 1, wherein the weight ratio of the graphene, the carbon nanotubes, the carbon black and the silver powder is (0.5 to 1.5): (0.8-1.2): (1-3): (0.3-0.8).
3. The method for producing silicon carbide ceramic according to claim 1, wherein the amount of the heat conductive filler added is 1 to 2 parts.
4. The method for producing a silicon carbide ceramic according to claim 1, wherein the purity of the fine silicon carbide powder is 97% or more.
5. The method for producing silicon carbide ceramic according to claim 1, wherein the polyethylene layer has a thickness of 0.3 to 1.5mm;
preferably, the polyethylene layer has a thickness of 0.5 to 1mm.
6. The method of producing silicon carbide ceramic according to claim 1, wherein the polyethylene in the polyethylene layer is high pressure polyethylene.
7. The method for producing silicon carbide ceramic according to claim 1, wherein the polyethylene layer is obtained by wrapping and winding a plurality of polyethylene films.
8. The method for producing a silicon carbide ceramic according to claim 1, wherein the molding step includes a primary molding step and a secondary molding step;
preferably, in the step of one-step molding, the silicon carbide powder obtained by granulation is subjected to dry press molding to obtain a one-step molded product;
preferably, in the secondary molding step, the product after the primary molding is die-cast and molded, and the product after the secondary molding, namely the ceramic blank, is obtained.
9. The method for producing a silicon carbide ceramic according to claim 8, wherein in the sintering step, the sintering temperature is 1800 to 2200 ℃.
10. A silicon carbide ceramic produced by the production method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310812352.6A CN116789454B (en) | 2023-07-04 | 2023-07-04 | Silicon carbide ceramic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310812352.6A CN116789454B (en) | 2023-07-04 | 2023-07-04 | Silicon carbide ceramic and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116789454A true CN116789454A (en) | 2023-09-22 |
| CN116789454B CN116789454B (en) | 2024-01-02 |
Family
ID=88036423
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310812352.6A Active CN116789454B (en) | 2023-07-04 | 2023-07-04 | Silicon carbide ceramic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116789454B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020041959A1 (en) * | 2000-06-23 | 2002-04-11 | Chihiro Kawai | High thermal conductivity composite material, and method for producing the same |
| JP2010195668A (en) * | 2008-04-04 | 2010-09-09 | Toto Ltd | Boron carbide silicon carbide silicon composite material |
| CN104926312A (en) * | 2015-06-29 | 2015-09-23 | 莱芜亚赛陶瓷技术有限公司 | High-thermal-conductivity pressurelessly-sintered silicon carbide ceramic material and preparation method thereof |
| US20150313041A1 (en) * | 2014-04-29 | 2015-10-29 | Enerage Inc. | Graphene dissipation structure |
| CN105722375A (en) * | 2016-01-29 | 2016-06-29 | 白德旭 | Graphene radiating apparatus and preparation method therefor |
| CN107021768A (en) * | 2017-04-18 | 2017-08-08 | 扬州北方三山工业陶瓷有限公司 | A kind of high-performance silicon carbide ceramic dewatering element and preparation method thereof |
| CN107176838A (en) * | 2017-06-20 | 2017-09-19 | 安徽省含山瓷业股份有限公司 | A kind of preparation method of the silicon carbide ceramics pot of graphene enhancing thermal conductivity |
| CN111099898A (en) * | 2020-01-03 | 2020-05-05 | 常州市申鑫新材料科技有限公司 | Aluminum-based silicon carbide high-density packaged semiconductor composite material |
| CN112279648A (en) * | 2020-10-21 | 2021-01-29 | 上海德宝密封件有限公司 | Pressureless sintering high-toughness silicon carbide and preparation method thereof |
| CN112592188A (en) * | 2020-12-15 | 2021-04-02 | 新沂市锡沂高新材料产业技术研究院有限公司 | Preparation method of graphene composite silicon carbide ceramic material |
| CN115010497A (en) * | 2022-03-22 | 2022-09-06 | 南通三责精密陶瓷有限公司 | Preparation method of high-purity silicon carbide ceramic |
-
2023
- 2023-07-04 CN CN202310812352.6A patent/CN116789454B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020041959A1 (en) * | 2000-06-23 | 2002-04-11 | Chihiro Kawai | High thermal conductivity composite material, and method for producing the same |
| JP2010195668A (en) * | 2008-04-04 | 2010-09-09 | Toto Ltd | Boron carbide silicon carbide silicon composite material |
| US20150313041A1 (en) * | 2014-04-29 | 2015-10-29 | Enerage Inc. | Graphene dissipation structure |
| CN104926312A (en) * | 2015-06-29 | 2015-09-23 | 莱芜亚赛陶瓷技术有限公司 | High-thermal-conductivity pressurelessly-sintered silicon carbide ceramic material and preparation method thereof |
| CN105722375A (en) * | 2016-01-29 | 2016-06-29 | 白德旭 | Graphene radiating apparatus and preparation method therefor |
| CN107021768A (en) * | 2017-04-18 | 2017-08-08 | 扬州北方三山工业陶瓷有限公司 | A kind of high-performance silicon carbide ceramic dewatering element and preparation method thereof |
| CN107176838A (en) * | 2017-06-20 | 2017-09-19 | 安徽省含山瓷业股份有限公司 | A kind of preparation method of the silicon carbide ceramics pot of graphene enhancing thermal conductivity |
| CN111099898A (en) * | 2020-01-03 | 2020-05-05 | 常州市申鑫新材料科技有限公司 | Aluminum-based silicon carbide high-density packaged semiconductor composite material |
| CN112279648A (en) * | 2020-10-21 | 2021-01-29 | 上海德宝密封件有限公司 | Pressureless sintering high-toughness silicon carbide and preparation method thereof |
| CN112592188A (en) * | 2020-12-15 | 2021-04-02 | 新沂市锡沂高新材料产业技术研究院有限公司 | Preparation method of graphene composite silicon carbide ceramic material |
| CN115010497A (en) * | 2022-03-22 | 2022-09-06 | 南通三责精密陶瓷有限公司 | Preparation method of high-purity silicon carbide ceramic |
Non-Patent Citations (3)
| Title |
|---|
| LIU FU 等: "Mechanical properties and microstructure of reaction sintering SiC ceramics reinforced with graphene-based fillers", APPLIED PHYSICS A, vol. 125, pages 1 - 7, XP036879026, DOI: 10.1007/s00339-019-2975-0 * |
| 叶纯麟 等: "加工工艺对纳米SiC/超高分子量聚乙烯复合材料力学性能的影响", 化学世界, no. 12, pages 730 - 735 * |
| 徐彬桓 等: "石墨烯添加量对无压烧结石墨烯/碳化硅陶瓷复合材料性能的影响", 机械工程材料, no. 8, pages 29 - 32 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116789454B (en) | 2024-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1107084C (en) | Propylene terpolymers and process for production thereof | |
| CA2620825C (en) | Polymer composition | |
| KR101367688B1 (en) | Polyolefin powder | |
| CA2479704C (en) | High density homopolymer blends | |
| EP1655337B1 (en) | Multimodal polyethylene composition with improved homogeneity | |
| JP5169262B2 (en) | Propylene-based copolymer material, film comprising the same, and method for producing propylene-based copolymer material | |
| JP4925593B2 (en) | Polyethylene polymer composition | |
| CN100424105C (en) | Preparation method of high density polyethylene communication cable insulating material | |
| CN116789454B (en) | Silicon carbide ceramic and preparation method thereof | |
| CN101724205B (en) | High-rigidity high impact polypropylene composition and preparation method thereof | |
| CA2881702C (en) | Ethylene-based polymer compositions, and articles prepared from the same | |
| CN109535532B (en) | Production method of 1-hexene copolymerized linear polyethylene resin | |
| CN115710394A (en) | Antistatic polyethylene composite material and preparation method and application thereof | |
| KR101831530B1 (en) | Resin composition of polyethylene for extrusion coating and lamination coating and the molded article by using the same | |
| JP4596510B2 (en) | Polyethylene composition | |
| JP2014019806A (en) | Polyethylene resin composition | |
| JPS631327B2 (en) | ||
| CN105602067A (en) | High-strength HDPE high-voltage electric power cable material and preparation method thereof | |
| CN105985561B (en) | Drinking water is packed for PE Hollow Containers material and preparation method thereof | |
| CN105694332A (en) | HDPE cable material and preparation method thereof | |
| CN110172206B (en) | Polyethylene composition for rotational molding and preparation method thereof | |
| CN104098818B (en) | A kind of high-density polyethylene composition and preparation thereof and application | |
| CN117794997A (en) | Polyethylene copolymer composition for film layers | |
| KR101840126B1 (en) | The polyethylene resin with excellent chemical resistance for medium blow molding | |
| CN116656052A (en) | CPP aluminized casting film special material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |