CN109824369A - High thermal conductivity wearing-proof refractory material and preparation method thereof - Google Patents
High thermal conductivity wearing-proof refractory material and preparation method thereof Download PDFInfo
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- CN109824369A CN109824369A CN201910194885.6A CN201910194885A CN109824369A CN 109824369 A CN109824369 A CN 109824369A CN 201910194885 A CN201910194885 A CN 201910194885A CN 109824369 A CN109824369 A CN 109824369A
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Abstract
The present invention relates to high thermal conductivity wearing-proof refractory materials and preparation method thereof, the high thermal conductivity wearing-proof refractory material is the high thermal conductivity wearing-proof refractory material that the heat passage of continuous phase is formed in the silicon carbide as matrix, its porosity≤8%, thermal coefficient is 30~40/ (m.k) at 1000 DEG C, refractoriness under load >=1700 DEG C, abrasion resistance index≤2.In preparation method of the invention, by later period oxidizing atmosphere product surface is quickly aoxidized, sealed porosity forms protective film, to improve antioxygenic property.
Description
Technical field
The invention belongs to high thermal conductivity wearing-proof refractory material fields, and in particular, to suitable for muffle heat industrial kiln
The high thermal conductivity wearing-proof refractory material used.
Background technique
The main body refractory material multiselect of the Industrial Stoves of the muffle such as reduction furnace, coke oven, petroleum coke calciners heating at present is used
High-alumina brick, silica brick etc..The wear-resisting property of the main body refractory material material of industrial kiln depends on the materials and compactness of material
Energy.But the Refractory Thermal Conductivity that is made using high-alumina brick, silica brick as raw material is low, wears no resistance, so as to cause production efficiency
It is low, the problems such as service life is short.
In addition, non-in the industrial kiln main body refractory material of the muffle such as reduction furnace, coke oven, petroleum coke calciners heating
The problem of oxide is aoxidized there is also the oxidizing atmosphere used when being heated.
From the point of view of material producing process, for Industrial Stoves such as the reduction shaft furnaces of muffle heat transfer, thermal conductivity is higher, heat transfer effect
Rate is higher, and production efficiency is higher.Currently on the market, the thermal conductivity relative good of silicon carbide articles, existing silicon carbide articles are logical
The carbon that the silicon carbide articles or silicon carbide often obtained for silicon carbide with oxide, nitride bonded obtain in conjunction with oxide
SiClx product is mutually oxide due to combining, and thermal conductivity is relatively low, and 1000 degree of thermal conductivitys are about 12w/m.k, nitride bonded
Silicon carbide articles thermal conductivity and wear-resisting property with increasing, thermal conductivity is about 16w/m.k, but is not able to satisfy to life still
Produce the higher demand of efficiency.
Summary of the invention
In view of the deficiencies of the prior art, the inventors of the present invention conduct in-depth research, and find high thermal conductivity through the invention
Wearing-proof refractory material and its manufacturing method are able to solve at least one problem existing in the prior art, so as to complete this hair
It is bright.
It is an object of the present invention to provide a kind of high thermal conductivity wearing-proof refractory materials, also, the high thermal conductivity abrasion-proof and refractory
Material also has high antioxygenic property, so as to extend the service life of muffle heat industrial kiln, promotes related fields
The raising of production efficiency.
Another object of the present invention is to provide the preparation methods of high thermal conductivity wearing-proof refractory material of the invention, by adopting
With the preparation method of high thermal conductivity wearing-proof refractory material of the invention, it can obtain that heating conduction is high, wear-resisting and antioxygenic property
High refractory material.
In order to reach the purpose of the present invention, The technical solution adopted by the invention is as follows:
A kind of high thermal conductivity wearing-proof refractory material is the type of thermal communication that continuous phase is formed in the silicon carbide as matrix
The high thermal conductivity wearing-proof refractory material in road, thermal coefficient is 30~40/ (m.k), loading softening at porosity≤8%, 1000 DEG C
Temperature >=1700 DEG C, abrasion resistance index≤2.
On the other hand, the present invention also provides a kind of preparation method of high thermal conductivity wearing-proof refractory material, which includes
Following steps:
Stock: addition is selected from one of aluminium nitride, boron nitride, molybdenum silicide, molybdenum, silicon or a variety of thermally conductive in silicon carbide
Material；
Mix base: by the silicon carbide prepared in material preparation step above-mentioned, Heat Conduction Material mix, be added bonding agent make its at
Then type is dried, blank is obtained；
Fire: the blank for obtaining aforementioned mixing base step is burnt under 1300~1600 degree of firing temperature,
Firing is changed to carry out 2~8 hours under oxidizing atmosphere after carrying out 12~24 hours in a nitrogen atmosphere.
High thermal conductivity wearing-proof refractory material of the invention be formed in matrix continuous phase as continuous heat passage to
Performance with high thermal conductivity and high abrasion, in addition, inoxidizability is also largely increased.
High thermal conductivity wearing-proof refractory material of the invention is obtained due to firing at high temperature, by high temperature firing, as
The waterless resin that bonding agent uses burns at high temperature and is converted into gas to remove from blank, uses nitridation as raw material
The materials such as aluminium, molybdenum silicide, molybdenum, silicon, so as to form the heat passage as continuous phase.Here heat passage refers to that height is led
Hot material is scattered in continuous phase under microscopic state, as having interted many conductors in a material.
In firing at a high temperature of aforementioned, firing atmosphere is switched into oxidizing atmosphere from nitrogen atmosphere in the later period of firing,
So that the surface of high thermal conductivity wearing-proof refractory material of the invention quickly aoxidizes, sealed porosity forms protective film, to improve material
Antioxygenic property.Here " oxidizing atmosphere " refers to oxygen containing atmosphere, can be such as oxygen atmosphere, also can be used containing
The atmosphere of oxygen, such as air.
Detailed description of the invention
Fig. 1 is the schematic diagram of the preparation method of high thermal conductivity wearing-proof refractory material of the invention.
Specific embodiment
[high thermal conductivity wearing-proof refractory material]
High thermal conductivity wearing-proof refractory material of the invention is the hot-fluid that continuous phase is formed in the silicon carbide as matrix
The high thermal conductivity wearing-proof refractory material in channel, thermal coefficient is 30~40/ (m.k) at porosity≤8%, 1000 DEG C, and loading is soft
Change temperature >=1700 DEG C, abrasion resistance index≤2.
In high thermal conductivity wearing-proof refractory material of the invention, continuous phase above-mentioned contains selected from aluminium nitride, boron nitride, silication
At least one of molybdenum, molybdenum, silicon nitride.Preferably, aforementioned continuous phase contains silicon nitride, and optionally containing selected from selected from nitridation
The ingredient in group that aluminium, boron nitride, molybdenum silicide, molybdenum form.
As the raw material for forming high thermal conductivity wearing-proof refractory material of the invention, using silicon carbide as matrix, on this basis,
Also containing the raw material and bonding agent for being used to form the heat passage as continuous phase.
The raw material of the heat passage as continuous phase is formed as being previously described for, can be enumerated, for example, selected from nitridation
One of aluminium, molybdenum silicide, molybdenum, silicon or a variety of Heat Conduction Materials.Can be used, for example, individual aluminium nitride, molybdenum silicide, molybdenum or
As Heat Conduction Material such as metallic silicon also can be used and selected from one or more of molybdenum, molybdenum silicide, aluminium nitride in person's silicon materials
As Heat Conduction Material.
As bonding agent, waterless resin can be enumerated.As such waterless resin, such as silicone resin can be enumerated
Deng.
High thermal conductivity wearing-proof refractory material of the invention is by carborundum substrate, Heat Conduction Material and bonding agent together through excessively high
Temperature burns at high temperature as the waterless resin that bonding agent uses and is converted into gas to remove from blank.
[preparation method of high thermal conductivity wearing-proof refractory material]
As shown in the schematic diagram of the preparation method of the high thermal conductivity wearing-proof refractory material of the invention of Fig. 1 comprising Xia Shubu
It is rapid:
Stock: addition is selected from one of aluminium nitride, boron nitride, molybdenum silicide, molybdenum, silicon or a variety of thermally conductive in silicon carbide
Material；
Mix base: by the silicon carbide prepared in material preparation step above-mentioned, Heat Conduction Material mix, be added bonding agent make its at
Then type is dried, blank is obtained；
Fire: the blank for obtaining aforementioned mixing base step is burnt under 1300~1600 degree of firing temperature,
Firing is changed to carry out 2~8 hours under oxidizing atmosphere after carrying out 12~24 hours in a nitrogen atmosphere.
In aforementioned material preparation step, as Heat Conduction Material, it can be used in aluminium nitride, boron nitride, molybdenum silicide, molybdenum, silicon
Independent one kind, or also can be used therein two or more.Preferably, in material preparation step, silicon is added in silicon carbide
And optional it is selected from one of aluminium nitride, boron nitride, molybdenum silicide, molybdenum or a variety of Heat Conduction Materials；
In aforementioned mixing base step, as aforementioned bonding agents, such as waterless resin can be enumerated, as no water tree
Rouge has silicone resin etc..
In aforementioned the firing step, aforementioned firing temperature can be such as 1400~1500 degree, preferably 1450~1500 degree.
Under firing temperature above-mentioned, the waterless resin used as bonding agent burn at high temperature and be converted into gas from
And it is removed from blank.The materials such as aluminium nitride, molybdenum silicide, molybdenum, silicon are used as raw material, so as to form the heat as continuous phase
Circulation road.
By the way that firing atmosphere is switched to oxic gas from nitrogen atmosphere in the later period of firing in the firing at a high temperature of aforementioned
Atmosphere, so that the surface of high thermal conductivity wearing-proof refractory material of the invention quickly aoxidizes, sealed porosity forms protective film, to improve
The antioxygenic property of material.
Embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
Embodiment 1:
Stock: adding aluminium nitride in silicon carbide, and the mass percent of silicon carbide and aluminium nitride is 2:1；
Mixing base: in the raw material that aforementioned material preparation step is prepared be added 2~3% silicone resin make bonding agent, will before
The raw material mixing for stating preparation, forms base, 8 hours dry at 80-200 DEG C.
It fires: being fired under nitriding atmosphere, temperature is 1300 degrees Celsius, and heat preservation switched to oxic gas after 12 hours
Atmosphere is warming up to 1450 degree, keeps the temperature 4 hours.
According to the highly heat-conductive material that the above method is formed, the porosity 6%, thermal coefficient is 38w/ (m.k) at 1000 DEG C,
Refractoriness under load is 1700 DEG C, abrasion resistance index 1.5.
Embodiment 2:
Stock: adding silicon in silicon carbide, and the mass percent of silicon carbide and silicon is 2:1；
Mixing base: in the raw material that aforementioned material preparation step is prepared be added 2~3% silicone resin make bonding agent, will before
The raw material mixing for stating preparation, forms base, 8 hours dry at 80-200 DEG C.
It fires: being fired under nitriding atmosphere, temperature is 1300 degrees Celsius, and heat preservation switched to oxic gas after 12 hours
Atmosphere is warming up to 1450 degree, keeps the temperature 4 hours.
According to the highly heat-conductive material that the above method is formed, the porosity 5%, thermal coefficient is 37w/ (m.k) at 1000 DEG C,
Refractoriness under load is 1650 DEG C, abrasion resistance index 1.3.
Embodiment 3:
Stock: adding silicon in silicon carbide, and the mass percent of silicon carbide and silicon, molybdenum silicide is 2:0.5:0.5；
Mixing base: in the raw material that aforementioned material preparation step is prepared be added 2~3% silicone resin make bonding agent, will before
The raw material mixing for stating preparation, forms base, 8 hours dry at 80-200 DEG C.
It fires: being fired under nitriding atmosphere, temperature is 1300 degrees Celsius, and heat preservation switched to oxic gas after 12 hours
Atmosphere is warming up to 1450 degree, keeps the temperature 4 hours.
According to the highly heat-conductive material that the above method is formed, the porosity 5%, thermal coefficient is 37w/ (m.k) at 1000 DEG C,
Refractoriness under load is 1650 DEG C, abrasion resistance index 1.3.
Embodiment 4:
Stock: adding silicon in silicon carbide, and the mass percent of silicon carbide and silicon, aluminium nitride is 2:0.5:0.5；
Mixing base: in the raw material that aforementioned material preparation step is prepared be added 2~3% silicone resin make bonding agent, will before
The raw material mixing for stating preparation, forms base, 8 hours dry at 80-200 DEG C.
It fires: being fired under nitriding atmosphere, temperature is 1300 degrees Celsius, and heat preservation switched to oxic gas after 12 hours
Atmosphere is warming up to 1450 degree, keeps the temperature 4 hours.
According to the highly heat-conductive material that the above method is formed, the porosity 5%, thermal coefficient is 37w/ (m.k) at 1000 DEG C,
Refractoriness under load is 1650 DEG C, abrasion resistance index 1.3.
Claims (8)
1. a kind of high thermal conductivity wearing-proof refractory material is the heat passage for being formed with continuous phase in the silicon carbide as matrix
High thermal conductivity wearing-proof refractory material, thermal coefficient is 30~40/ (m.k), loading softening temperature at porosity≤8%, 1000 DEG C
>=1700 DEG C of degree, abrasion resistance index≤2.
2. high thermal conductivity wearing-proof refractory material according to claim 1, which is characterized in that the continuous phase contains selected from nitridation
At least one of aluminium, boron nitride, molybdenum silicide, molybdenum, silicon nitride.
3. high thermal conductivity wearing-proof refractory material according to claim 2, which is characterized in that the continuous phase contains silicon nitride,
And optionally containing the ingredient in the group that aluminium nitride, boron nitride, molybdenum silicide, molybdenum form.
4. a kind of preparation method of described in any item high thermal conductivity wearing-proof refractory materials of claims 1 to 3 comprising Xia Shubu
It is rapid:
Stock: addition is selected from one of aluminium nitride, boron nitride, molybdenum silicide, molybdenum, silicon or a variety of heat conduction materials in silicon carbide
Material；
It mixing base: the silicon carbide prepared in material preparation step above-mentioned, Heat Conduction Material is mixed, bonding agent, which is added, makes its molding,
Then it dries, obtains blank；
Fire: the blank for obtaining aforementioned mixing base step is burnt under 1300~1600 degree of firing temperature, is burnt into
It is changed to carry out 2~8 hours under oxidizing atmosphere after carrying out 12~24 hours in a nitrogen atmosphere.
5. the preparation method of high thermal conductivity wearing-proof refractory material according to claim 4, which is characterized in that the material preparation step
In, silicon is added in silicon carbide and optional is selected from one of aluminium nitride, boron nitride, molybdenum silicide, molybdenum or a variety of heat conduction materials
Material.
6. the preparation method of high thermal conductivity wearing-proof refractory material according to claim 4 or 5, which is characterized in that the combination
Agent is waterless resin.
7. the preparation method of high thermal conductivity wearing-proof refractory material according to claim 4 or 5, the firing temperature is 1400~
1500 degree.
8. the preparation method of high thermal conductivity wearing-proof refractory material according to claim 4 or 5, which is characterized in that the firing
Temperature is 1450~1500 degree.
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Citations (3)
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|---|---|---|---|---|
| DE10059990A1 (en) * | 2000-12-02 | 2002-07-04 | Bosch Gmbh Robert | Ceramic heating module used as a cooking hob comprises an electrically insulating ceramic supporting plate and an electrically conducting hot conductor applied as a conducting layer on the plate |
| CN105110795A (en) * | 2015-06-27 | 2015-12-02 | 湖北神雾热能技术有限公司 | Non-metal material tray for garbage pyrolysis furnace rotating bed, and preparation method tehreof |
| CN107324821A (en) * | 2017-07-12 | 2017-11-07 | 瑞泰科技股份有限公司 | It is a kind of that there is high-absorbility, the CFB boiler water-cooling wall carborundum wear-resistant castable of high heat conductance |
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2019
- 2019-03-14 CN CN201910194885.6A patent/CN109824369A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10059990A1 (en) * | 2000-12-02 | 2002-07-04 | Bosch Gmbh Robert | Ceramic heating module used as a cooking hob comprises an electrically insulating ceramic supporting plate and an electrically conducting hot conductor applied as a conducting layer on the plate |
| CN105110795A (en) * | 2015-06-27 | 2015-12-02 | 湖北神雾热能技术有限公司 | Non-metal material tray for garbage pyrolysis furnace rotating bed, and preparation method tehreof |
| CN107324821A (en) * | 2017-07-12 | 2017-11-07 | 瑞泰科技股份有限公司 | It is a kind of that there is high-absorbility, the CFB boiler water-cooling wall carborundum wear-resistant castable of high heat conductance |
Non-Patent Citations (5)
| Title |
|---|
| 王零森: "《特种陶瓷》", 28 February 2018, 冶金工业出版社 * |
| 程卫华等: "SiC含量对AlN-SiC复合材料导热性能的影响", 《山东工业技术》 * |
| 编写组: "《铜铅锌冶炼设计参考资料 下册》", 30 April 1979, 冶金工业出版社 * |
| 胡宝玉等: "《特种耐火材料实用技术手册》", 30 June 2007, 冶金工业出版社 * |
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Application publication date: 20190531 |