CN113185297A - Ceramic material for electric heating and application thereof - Google Patents
Ceramic material for electric heating and application thereof Download PDFInfo
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- CN113185297A CN113185297A CN202110457284.7A CN202110457284A CN113185297A CN 113185297 A CN113185297 A CN 113185297A CN 202110457284 A CN202110457284 A CN 202110457284A CN 113185297 A CN113185297 A CN 113185297A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 41
- 238000005485 electric heating Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 40
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 230000008595 infiltration Effects 0.000 claims abstract description 28
- 238000001764 infiltration Methods 0.000 claims abstract description 28
- 239000000919 ceramic Substances 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910000676 Si alloy Inorganic materials 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 8
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 19
- 229920002451 polyvinyl alcohol Polymers 0.000 description 19
- 239000005011 phenolic resin Substances 0.000 description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 13
- 229920001568 phenolic resin Polymers 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- 239000003292 glue Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 235000015895 biscuits Nutrition 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000010000 carbonizing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 239000011363 dried mixture Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003571 electronic cigarette Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021471 metal-silicon alloy Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 235000019505 tobacco product Nutrition 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1068—Making hard metals based on borides, carbides, nitrides, oxides or silicides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1084—Alloys containing non-metals by mechanical alloying (blending, milling)
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/065—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on SiC
-
- 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
- C04B2235/428—Silicon
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/616—Liquid infiltration of green bodies or pre-forms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
Abstract
The application discloses a ceramic material for electric heating and application thereof. The ceramic material for electric heating is prepared by the method comprising the following steps: (A) providing a green body based on silicon carbide, wherein the amount of the silicon carbide accounts for more than 80wt% of the total mass of raw materials of the green body; (B) and sintering the green body under the condition of adding an infiltration material until the infiltration material is dissolved and infiltrated into the main phase of the green body, wherein the infiltration material is a silicon material obtained by infiltrating a silicon simple substance and a silicon alloy into the main phase of the silicon carbide ceramic, the electrical conductivity of the ceramic material is greatly improved, and the mechanical strength of the ceramic material can be maintained at the common level of the silicon carbide ceramic.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a ceramic material for electric heating and application thereof.
Background
Electric heaters are an important component of new tobacco products. From the traditional metal material (metal alloy heating wire) to the non-metal material (PTC thermal sensitive ceramic) and finally to the metal ceramic composite material (MCH metal ceramic heating element), the development of the electric heating material inherits the advantages of the previous generation and abandons the disadvantages, but still has certain disadvantages. For example, the traditional electrothermal material metal alloy wires are easy to oxidize and have poor heating effect; PTC thermal sensitive ceramic is difficult to sinter due to poor conductivity and low Curie temperature; the best choice of MCH substrate material and overcomes the difficulty of co-firing metal and ceramic.
Chinese patent CN110200331A discloses an electronic cigarette heater, which uses ZTA of zirconia toughened alumina as a ceramic substrate, and a bottom insulating layer, an upper electrode layer, a lower electrode layer, a solderable layer and a surface insulating layer are sequentially printed on the surface of the ceramic substrate, but there are still many process difficulties such as atmosphere, temperature and system during cofiring after printing the solder layer when the metal and the ceramic are cofired.
It is known that the ceramic material used for the ceramic heating element has low conductivity, and therefore, a conductive member needs to be separately disposed on the ceramic heating element, which increases the difficulty in manufacturing the ceramic heating element.
Disclosure of Invention
In view of the above, the present application provides a ceramic material for electric heating and an application thereof, which greatly improve electrical conductivity while ensuring mechanical strength without being damaged.
According to the level of common knowledge of those skilled in the art, the ceramic material of the ceramic heat-generating body is so weak in electrical conductivity as to be regarded as an insulating material, which is a basic well-known property of the ceramic material. In order to improve the conductivity of ceramic materials, it is a mainstream to dope conductive substances therein. The doping of the conductive substance is difficult to avoid the difficulty of ceramic sintering, so that the sintering density of the ceramic is not enough, and the mechanical strength of the ceramic is sharply reduced. That is, there appears to be an irreconcilable conflict between the electrical conductivity and the mechanical strength of the ceramic material.
The inventor abandons the improved idea of trying to add conductive substances in the prior art. Surprisingly, the electrical conductivity of the ceramic material is greatly improved after the silicon material of the silicon simple substance and the silicon alloy is soaked into the main phase of the silicon carbide ceramic, and more surprisingly, the mechanical strength of the ceramic material can be basically maintained at the common level of the silicon carbide ceramic. Based on this, the present application was created.
In a first aspect, the present application provides a ceramic material for electric heating, which is prepared by a method comprising the steps of:
(A) providing a green body based on silicon carbide, the silicon carbide accounting for more than 80wt% of the total mass of the raw materials of the green body;
(B) and sintering the green body under the condition of adding an infiltration material until the infiltration material is dissolved and infiltrated into the main phase of the green body, wherein the infiltration material is a silicon simple substance and/or a silicon alloy.
Green body
The green body is based on silicon carbide, and means that the green body contains silicon carbide as a main component. Specifically, the amount of silicon carbide is 80wt% or more of the total mass of the green body raw material. Namely, the raw material of the green body takes silicon carbide as a main material and some additives such as bonding resin, sintered filler and the like added in the conventional technology, or the material after the green body is sintered and formed takes silicon carbide as a main phase.
The silicon carbide used as the main material of the raw material of the green body accounts for more than 80wt percent based on 100wt percent of the total mass of the raw material of the green body. Thus, the hardness, high temperature resistance, oxidation resistance and the like of the ceramic material can be better achieved.
Note that, as a raw material of the green compact of the present application, it is not necessary to add elemental carbon. Because of the free form carbon that is typically required in the ceramic material after sintering, this free form carbon maintains the toughness of the material. The free carbon is not dependent only on the elemental carbon added. The raw material of the green compact is generally carbonized by the addition of a binder or other high molecular resins during high-temperature sintering to produce free carbon.
In order to increase the conductivity of the ceramic material, nano carbon black can be optionally added to the raw material of the green compact, preferably the amount of nano carbon black is less than 15 wt%. If the amount of nano carbon black is too large, it may directly result in too much free form carbon in the ceramic material, which may reduce the oxidation resistance and stability of the ceramic part, and may also result in a lower density. If the content is too small, it is obviously difficult to achieve a significant change in conductivity.
It is known that the raw materials of the green body are usually supplemented with a binder to bind the main material to the functional filler which may be added. The binder may be any of organic materials such as phenol resin, polyvinyl alcohol, furan resin, polyimide, cellulose, starch, sugar, pitch, Polyacrylonitrile (PAN), and inorganic materials such as silicate and silicon-containing polymer. Not weirs repeat that the organic form of the binder carbonizes during sintering to provide the ceramic material with free form carbon.
The binder is preferably used in an amount to give a green body having a desired shape, and if the amount is too large, the amount inevitably results in an excessively large free carbon content. Taking phenolic resin and PVA as examples of the adhesive, the dosage of the phenolic resin is less than 10wt% of the total green body mass, and the dosage of the PVA is less than 10wt% of the total green body mass.
The manner of making green bodies is well known to those skilled in the art, for example:
a. mixing raw materials: wet mixing the components of the green raw material in a ball mill (anhydrous ethanol can be used as a ball milling medium), and placing the mixed raw material in an oven (for example, 80 ℃) for drying for later use.
b. Granulation and staling: pouring the dried mixture into a mortar, adding part of binder into the mixture to granulate and form, uniformly mixing the materials, granulating, and placing in a closed environment for staleness.
c. Forming a blank body: and filling the powder into a mold by adopting a semi-dry pressing method for molding, and pressing and molding by using a pressure mold.
d. Drying the blank: the shaped sample is placed in an oven at a temperature of, for example, 80 ℃.
Impregnating material
The infiltration of the infiltration material into the green body being sintered in the present application is such that, upon heating of the sintering, the infiltration material changes from a solid state to a liquid molten state, while the green body being sintered remains substantially solid, the infiltration material in the molten state generates a solid-liquid interfacial tension at the surface of the green body, and the structure of the green body being sintered contains pores (which are partly a result of carbonization of the binder during sintering, and partly inherent to silicon carbide itself). Driven by the interfacial tension and under the blank, the infiltrated material generates a capillary effect to the pores, forming an internal driving force for infiltration.
As a result of the infiltration of the impregnating material, not only the pores are directly filled; but also can react with free carbon to obtain silicon carbide so as to bond the original silicon carbide together, thereby improving the sintering compactness of the ceramic material and ensuring the mechanical strength. More importantly, the pores of the blank body are filled with silicon simple substance and/or silicon alloy components, and the components can stably exist in the pores, namely the positions of the components are relatively fixed, excessive aggregation is avoided, and the conductive effect is stably exerted. Thus, the electrical conductivity of the ceramic material of the impregnated material is greatly improved, and the mechanical strength thereof can be maintained at substantially the level of that of silicon carbide ceramics.
The infiltration material of the present application is preferably a silicon alloy composed of silicon and a metal selected from one or at least two of molybdenum, boron, nickel, aluminum, and iron. Compared with the infiltration material in the form of pure silicon simple substance, the silicon alloy can reduce the content of free silicon in the ceramic material, and the excessive content of silicon can cause the free silicon to excessively react with free carbon to excessively consume the free carbon, thereby intensifying brittleness and damaging mechanical strength.
In this regard, the content of non-silicon elements in the silicon alloy in the present application is preferably 0.1 to 30wt%, such as 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.5 wt%, 1 wt%, 5wt%, 8wt%, 10wt%, 15wt%, 18 wt%, 20 wt%, 25 wt%, 28 wt%, 30wt%, etc., in order to maintain the free silicon content in the ceramic material at a more suitable level.
The infiltration material of the present application is added in an amount of 5 to 15wt%, for example, 5wt%, 5.5wt%, 6 wt%, 7 wt%, 8wt%, 10wt%, 12 wt%, 13 wt%, 14 wt%, 15wt%, etc., based on 100wt% of silicon carbide, to maintain the free silicon content in the ceramic material at a suitable level.
The impregnating material of the present application may have a particle diameter of 1 to 3mm, for example, 1mm, 1.5mm, 1.8mm, 2mm, 2.5mm, or 3 mm. Unsuitable particle sizes can cause the effect of leaching the leaching material into the green body. Specifically, if the particle size is too large, the resistance to infiltration of the impregnated material may be too large; if the particle size is too small, a large possibility of agglomeration may exist during infiltration into the green body.
Sintering
The sintering temperature may be 1530 to 1600 ℃, for example 1530 ℃, 1540 ℃, 1550 ℃, 1570 ℃, 1580 ℃, 1590 ℃ and 1600 ℃. If the temperature is not proper, the infiltration effect can be affected.
The heating mode of sintering can be stepped temperature rise heating, which is beneficial to ensuring the uniformity of the temperature in the furnace. For example, at 0-900 deg.C at 5 deg.C/min; at 900-1400 deg.C at 3 deg.C/min; after the temperature is 1400 ℃, the temperature is raised at 2 ℃/min.
Glue discharging
The binder is used for binder resin and other organic components to be cracked and carbonized in advance, so that the sintering compactness of a sintered body is prevented from being too low and the mechanical strength of the sintered body is prevented from being reduced due to uncontrollable carbonization in the sintering process. More importantly, the carbonization caused by the binder removal can generate pores, which provides better conditions for the subsequent infiltration of the infiltration material.
The temperature for the present application is 750 to 850 ℃, for example, 750 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 840 ℃, 850 ℃ and the like. The temperature rising mode in the glue discharging process is preferably carried out slowly, the temperature rising rate is 2 ℃ per min, and the temperature is kept for 2 h.
In a second aspect, the present application provides use of a ceramic material for electric heating as a ceramic heat-generating body capable of conducting electricity.
Therefore, the conductive ceramic heating element can avoid the additional arrangement of a conductive component, thereby increasing the complexity of the process.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The preparation method of the silicon carbide ceramic material for electric heating in the embodiment comprises the following steps:
the raw materials of the green body are 80wt% of silicon carbide, 10wt% of nano carbon black, 5wt% of phenolic resin as an additional binder and 5wt% of PVA (5 wt% of PVA aqueous solution) as a forming binder.
Mixing raw materials: mixing silicon carbide, nano carbon black and phenolic resin in a ball mill (with absolute ethyl alcohol as a ball milling medium) for 4 hours in a wet method, wherein the mass ratio of the raw materials to the balls to the ethyl alcohol is 1:2:3, and drying the mixed raw materials in an oven at 80 ℃ for 24 hours for later use.
Granulation and staling: pouring the dried mixture into a mortar, taking PVA aqueous solution in the mixture as a forming binder, uniformly mixing the materials, granulating, and placing in a closed environment for ageing for 12 hours to uniformly distribute PVA.
Forming a blank body: and (3) molding by a semi-dry pressing method, filling the powder into a mold, and molding the powder into a square strip with the thickness of 37mm multiplied by 6mm multiplied by 3mm by 120MPa, and maintaining the pressure for 30s after the maximum pressure is reached.
Drying the blank: and (3) placing the formed sample into an oven at 80 ℃ for drying for 12 h.
Discharging glue from the blank body: placing the molded blank into an atmosphere sintering furnace, and sintering at 800 ℃ in an inert atmosphere to obtain a ceramic biscuit after binder removal; wherein 800 ℃ is the temperature for cracking and carbonizing the phenolic resin, and in order to avoid the defects that a green body is cracked and the like due to a large amount of gas generated by carbonizing and cracking organic matters in the sintering process, the glue discharging process is carried out slowly, the temperature rising rate is 2 ℃ per min, and the temperature is kept for 2 hours.
And (3) reaction infiltration: placing the biscuit subjected to binder removal in a BN crucible, and covering pure silicon particles (the particle size is 2 mm) accounting for 10wt% of the using amount of silicon carbide on the upper part and the lower part of the biscuit, wherein the sintering temperature is as follows: 1570 ℃; the highest firing temperature is kept for 3 hours; at 0-900 ℃ and 5 ℃/min; at 900-1400 ℃ and 3 ℃/min; after a high temperature of 1400 ℃ the temperature was raised at 2 ℃ per min.
Example 2
The preparation method of the silicon carbide ceramic material for electric heating in the embodiment comprises the following steps:
the raw material proportion of the green body is 90wt% of silicon carbide, 5wt% of additional binding agent phenolic resin and 5wt% of forming binding agent PVA (PVA aqueous solution with the mass percentage of 5%).
Mixing raw materials: mixing silicon carbide and phenolic resin in a ball mill (with absolute ethyl alcohol as a ball milling medium) for 4 hours in a wet method, wherein the mass ratio of the raw materials to the balls to the ethyl alcohol is 1:2:3, and drying the mixed raw materials in an oven at 80 ℃ for 24 hours for later use.
Granulation and staling: pouring the dried mixture into a mortar, adding 5% by mass of PVA aqueous solution (10 wt% additionally) into the mixture as a forming binder, uniformly mixing the materials, granulating, and placing in a closed environment for ageing for 12h to uniformly distribute the PVA.
Forming a blank body: and (3) molding by a semi-dry pressing method, filling the powder into a mold, and molding the powder into a square strip with the thickness of 37mm multiplied by 6mm multiplied by 3mm by 120MPa, and maintaining the pressure for 30s after the maximum pressure is reached.
Drying the blank: and (3) placing the formed sample into an oven at 80 ℃ for drying for 12 h.
Discharging glue from the blank body: placing the molded blank into an atmosphere sintering furnace, and sintering at 800 ℃ in an inert atmosphere to obtain a ceramic biscuit after binder removal; wherein 800 ℃ is the temperature for cracking and carbonizing the phenolic resin, and in order to avoid the defects that a green body is cracked and the like due to a large amount of gas generated by carbonizing and cracking organic matters in the sintering process, the glue discharging process is carried out slowly, the temperature rising rate is 2 ℃ per min, and the temperature is kept for 2 hours.
And (3) reaction infiltration: placing the biscuit subjected to binder removal in a BN crucible, covering silicon (94.4 wt%) with a grain size of 1mm accounting for 15wt% of the using amount of silicon carbide on the upper part and the lower part of the biscuit, and sintering at a temperature: 1550 ℃; the highest firing temperature and heat preservation time: 3 h; at 0-900 ℃ and 5 ℃/min; at 900-1400 ℃ and 3 ℃/min; after a high temperature of 1400 ℃ the temperature was raised at 2 ℃ per min.
Example 3
The preparation method of the silicon carbide ceramic material for electric heating in the embodiment comprises the following steps:
the raw material proportion of the green body is 90wt% of silicon carbide, 5wt% of additional binding agent phenolic resin and 5wt% of forming binding agent PVA (PVA aqueous solution with the mass percentage of 5%).
Mixing raw materials: mixing silicon carbide and phenolic resin in a ball mill (with absolute ethyl alcohol as a ball milling medium) for 4 hours in a wet method, wherein the mass ratio of the raw materials to the balls to the ethyl alcohol is 1:2:3, and drying the mixed raw materials in an oven at 80 ℃ for 24 hours for later use.
Granulation and staling: pouring the dried mixture into a mortar, adding 5% by mass of PVA aqueous solution (10 wt% additionally) into the mixture as a forming binder, uniformly mixing the materials, granulating, and placing in a closed environment for ageing for 12h to uniformly distribute the PVA.
Forming a blank body: and (3) molding by a semi-dry pressing method, filling the powder into a mold, and molding the powder into a square strip with the thickness of 37mm multiplied by 6mm multiplied by 3mm by 120MPa, and maintaining the pressure for 30s after the maximum pressure is reached.
Drying the blank: and (3) placing the formed sample into an oven at 80 ℃ for drying for 12 h.
Discharging glue from the blank body: placing the formed blank into an atmosphere sintering furnace, and sintering at 800 ℃ in an inert atmosphere to obtain a ceramic biscuit after glue discharging; wherein 800 ℃ is the temperature for cracking and carbonizing the phenolic resin, and in order to avoid the defects that a green body is cracked and the like due to a large amount of gas generated by carbonizing and cracking organic matters in the sintering process, the glue discharging process is carried out slowly, the temperature rising rate is 2 ℃ per min, and the temperature is kept for 2 hours.
And (3) reaction infiltration: the biscuit after the binder removal is placed in a BN crucible, silicon (96.8 wt%) with the grain size of 2mm accounting for 10wt% of the using amount of silicon carbide is covered on the upper part and the lower part of the crucible, and the sintering temperature is as follows: 1530 ℃ C; the highest firing temperature and heat preservation time: 3 h; at 0-900 ℃ and 5 ℃/min; at 900-1400 ℃ and 3 ℃/min; after a high temperature of 1400 ℃ the temperature was raised at 2 ℃ per min.
Example 4
Unlike example 3, where the infiltration material is pure silicon particles (i.e., non-alloyed), the other examples are the same as example 3.
Example 5
The raw material composition of the green compact, namely 90wt% of silicon carbide, 5wt% of nano carbon black, 2.5wt% of additional binder phenolic resin, 2.5wt% of forming binder PVA (PVA aqueous solution with mass percent of 5%), and the rest are the same as example 3.
Comparative example 1
The raw material mixture ratio of the green body, namely 50wt% of silicon carbide, 40wt% of nano carbon black, 5wt% of additional binder phenolic resin and 5wt% of forming binder PVA (5 wt% of PVA aqueous solution), and the rest is the same as that of the embodiment 3.
Comparative example 2
The sintering step was carried out without adding silicon (96.8 wt%) -boron alloy particles, and the rest was the same as example 3.
Evaluation of
1. Evaluation procedure
The results of the medium volume density and the bending strength are obtained according to the requirements of national standards GB/T25995-; the resistivity is obtained by measuring the resistance of a standard sample (37 mm × 6mm × 3 mm) by an LCR digital bridge (model ET 4510), measuring the actual length, width and height of the sample by a vernier caliper, and calculating.
2. Evaluation results
The evaluation results of the examples and comparative examples are shown in table 1.
TABLE 1 evaluation results of examples and comparative examples
As can be seen from Table 1, the flexural strength and resistivity of comparative example 2 are significantly lower than those of example 3, which illustrates the technical contribution of the addition of the impregnating material;
the flexural strength and resistivity of comparative example 1 are significantly lower than those of example 3, which indicates that the main phase component of the green compact, namely silicon carbide, is a prerequisite for ensuring that the impregnated material can exert the above properties;
the flexural strength and resistivity of example 4 are significantly lower than those of example 3, which illustrates the technical contribution of the silicon metal alloy with respect to pure silicon.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A ceramic material for electric heating, characterized in that it is produced by a method comprising the steps of:
(A) providing a green body based on silicon carbide, wherein the amount of the silicon carbide accounts for more than 80wt% of the total mass of raw materials of the green body;
(B) and sintering the green body under the condition of adding an infiltration material until the infiltration material is dissolved and infiltrated into the main phase of the green body, wherein the infiltration material is a silicon simple substance and/or a silicon alloy.
2. The ceramic material for electric heating according to claim 1, wherein the sintering temperature is 1530 to 1600 ℃.
3. The ceramic material for electric heating according to claim 1, wherein the silicon alloy is an alloy of silicon and a metal selected from one or at least two of molybdenum, boron, nickel, aluminum, and iron.
4. The ceramic material for electric heating according to claim 1, wherein the content of non-silicon element in the silicon alloy is 0.1 to 30 wt%.
5. The ceramic material for electric heating according to claim 1, wherein the infiltration material is added in an amount of 5 to 15wt% based on 100wt% of the silicon carbide.
6. The ceramic material for electric heating according to claim 1, wherein the grain size of the impregnating material is 1 to 3 mm.
7. The ceramic material for electric heating according to claim 1, wherein the amount of silicon carbide in the raw material of the green compact is 90wt% or more.
8. The ceramic material for electric heating according to claim 1, wherein the raw material of the green compact further contains nano carbon black in an amount of 15wt% or less.
9. The ceramic material for electric heating according to claim 1, further comprising binder removal from the green body between the step (A) and the step (B), wherein the binder removal temperature is 750-850 ℃.
10. Use of a ceramic material for electric heating according to any one of claims 1 to 9 as a ceramic heating element capable of conducting electricity.
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| CN116655386A (en) * | 2023-05-18 | 2023-08-29 | 山东鑫亿新材料科技有限公司 | Disposable recrystallized circular silicon carbide heating disc and preparation method thereof |
| CN116655386B (en) * | 2023-05-18 | 2024-04-05 | 山东鑫亿新材料科技有限公司 | Disposable recrystallized circular silicon carbide heating disc and preparation method thereof |
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