CN103864432A - Aluminum chromium zirconium nitride composite ceramic material and preparation method thereof - Google Patents
Aluminum chromium zirconium nitride composite ceramic material and preparation method thereof Download PDFInfo
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- CN103864432A CN103864432A CN201410090355.4A CN201410090355A CN103864432A CN 103864432 A CN103864432 A CN 103864432A CN 201410090355 A CN201410090355 A CN 201410090355A CN 103864432 A CN103864432 A CN 103864432A
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- composite ceramic
- ceramic material
- high temperature
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Abstract
The invention relates to an aluminum chromium zirconium nitride composite ceramic material and a preparation method thereof. The chemical composition (W) of the aluminum chromium zirconium nitride composite ceramic material is as follows: (Al2O3.Cr2O3) is greater than or equal to 40%, ZrN is greater than or equal to 6%, TiN is greater than or equal to 8%, ALN is greater than or equal to 40%, and Fe2O3 is less than or equal to 1.68%. The preparation method comprises steps of firstly smashing raw material chrome corundum, then deironing, magnetic separating and screening, after mixing, ageing for 25 minutes, molding through compressing, pre-nitriding the product, machining, then transmitting into a high temperature kiln, enriching oxygen to 1450DEG C and firing, then stopping enriching the oxygen, inletting ammonia gas, generating high temperature 1950-2000DEG C through nitriding reaction (nitriding while sintering), and finishing the reaction. The material and sectional material thereof are used in multiple high temperature states like high temperature wear resisting porcelain tubes, glass kilns, heavy metal molten pools, oil field hot blast heaters, steel ladle bottom blowing furnaces, electric power, aviation and the like, can greatly prolong the service life.
Description
Technical field
The present invention relates to a kind of high temperature ceramic material and preparation method thereof, particularly relate to a kind of nitrogenize aluminum chromium zirconia composite ceramic material and preparation method thereof.
Background technology
The high-temperature material that these techniques such as industrial ceramics, electric power, aviation, heavy metal smelting, Ladle Bottom blown converter, oil boom wind furnace adopt, over-all properties is poor, and antioxidant property is poor, and refractoriness is low.Be all the improper direct work-ing life that affects of selection, pore is too high, and thermal shock resistance is poor, poor corrosion resistance, and anti-Fe0 slag poor performance, directly affects the performance of enterprises, has also wasted greatly resource.
Summary of the invention
The object of the present invention is to provide a kind of nitrogenize aluminum chromium zirconia composite ceramic material and preparation method thereof, this material is by (Al
2o
3c
r2o
3) eutectic (alloy smelting waste residue) and Z
ro
2, titanium corundum (TiO
2.AL
2o
3), rare earth element, aluminum oxide powder and graphite composition, match grand technology through technique and improve its refractoriness, resistance to fouling, thermal shock resistance, antioxidant property, being applied to the section bars such as high temperature porcelain tube and brick can anti-FeO slag, improves over-all properties.
The object of the invention is to be achieved through the following technical solutions:
A kind of nitrogenize aluminum chromium zirconia composite ceramic material, described its chemical constitution of nitrogenize aluminum chromium zirconia composite ceramic material (w) is:
Al
2O
3.C
r2O
3≥40%； ZrN≥6%；
TiN≥8% ALN≥40%; F
2O
3≤1.68%；
(Al
2o
3.C
r2o
3) coenosarc raw material be alloy smelting waste residue, Z
ro
2adopt and stablize chromic oxide, titanium corundum does stablizer, rare earth element and alumina powder and does together with sintering agent knot burning and form.
A kind of nitrogenize aluminum chromium zirconia composite ceramic material making method, described method comprises following making processes: raw material chromium corundum is crushed to largest particle and is no more than 5 millimeters of particle diameters, then carry out deironing magnetic separation sub-sieve, 0.5-5 millimeters of particle diameters are sent into mixer and zirconium white, titanium corundum (TiO
2.AL
2o
3), rare earth element, aluminum oxide powder and graphite; Bonding agent batch mixing, to be less than 0.5mm particle and be milled to-320 orders, after iron removal by magnetic separation, be stranded compression moulding again in 25 minutes in the lump with after zirconium white, titanium corundum, rare earth element and graphite, bonding agent batch mixing, again by after sending into high temperature kiln oxygen enrichment to 1450 ℃ after pre-goods nitrogenize, machining and firing, stop oxygen enrichment operation, pass into again ammonia, pass through nitrogenizing reaction, nitrogenize limit, limit sintering, produce high temperature to 1950---2000 ℃, reaction, makes oxide compound eutectic be converted into fully nitride, makes material of main part (Al
2o
3.C
r2o
3) eutectic becomes the composite ceramic material of nitride bonded.
Advantage of the present invention and effect are:
1. the present invention (Al
2o
3.C
r2o
3) to adopt alloy smelting waste residue be body material to eutectic, is characterized in that thermal expansivity is little, cost is low, solves residue contamination, saving resource; Z
ro
2adopt stabilizing zirconia; Titanium corundum (TiO
2.AL
2o
3) use alloy smelting waste residue, cost is low, solves residue contamination, saving resource.
2. the present invention adopts the grand technology of advanced match to produce pottery.By (TiO
2.AL
2o
3) eutectic does stablizer, rare earth element and alumina powder by titanium corundum and do sintering agent, be sintered together down to 1450 ℃ in oxygen enrichment hot conditions, stop oxygen enrichment operation, pass into again ammonia, produce by nitrogenizing reaction (nitrogenize limit, limit sintering) under the effect of high temperature, make four kinds of oxide compounds be converted into fully nitride, make (Al
2o
3c
r2o
3) eutectic becomes the composite ceramic material of nitride bonded; Refractoriness, anti-thermal shock stability, the antioxidant property of its material have been improved widely by matching grand technology.
3. the present invention (Al
2o
3.C
r2o
3) eutectic is alloy smelting waste residue body material, meets country's " comprehensive utilization of resources " industry policy, solved the problem (+6 valency Cr) of waste residue utilization.
4. the Z that the present invention adds
ro
2raw material, finally converts ZrN high-melting-point nitride to; Aluminum oxide fractional conversion becomes high-melting-point nitride ALN, and titanium corundum fractional conversion becomes high-melting-point stupalith TiN, forms a kind of microtexture of relative porous in stupalith, has improved refractoriness, improves again the thermal shock resistance of material.
5. the present invention adopts the grand technical ceramics production technique of match to develop nitrogenize aluminum chromium zirconia composite ceramic material and brick, improve the work-ing life (30-40 months) of industrial high temperature stupalith, solve a core difficult problem for refractory materials, expand the use range of stupalith, increase the performance of enterprises, reduce the environmental pollution that each stopping production causes, reduced financial loss, the waste of the energy that also having reduced stops production simultaneously causes.Solved the problem (+6 valency Cr) of industrial residue pollution discharge, saved resource, utilizing fully airborne nitrogen, oxygen is fuel, has saved again the energy.Accomplish widely effect of energy-saving and emission-reduction.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of wood invention.
Embodiment
Below in conjunction with accompanying drawing illustrated embodiment, the invention will be further described.
Nitrogenize aluminum chromium zirconia composite ceramic material of the present invention is by (Al
2o
3.C
r2o
3) (alloy smelting waste residue) and Z
ro
2, titanium corundum, rare earth element, aluminum oxide powder and graphite and form, making the section bars such as refractory brick can improve refractoriness, resistance to fouling, thermal shock resistance, antioxidant property and anti-Fe0 slag performance.
Its chemical constitution (w) is: (aluminum oxide. chromic oxide) (Al
2o
3c
r2o
3)>=40%; Zirconium nitride Z
rn>=6%; Titanium nitride TiN>=8%; Aluminium nitride ALN>=40%; Ferric oxide Fe
2o
3≤ 1.68%; The present invention and existing same type of material ratio, raw material microstructure is different from it.
Making method of the present invention: (Al
2o
3c
r2o
3) employing alloy smelting waste residue eutectic raw material, Z
ro
2adopt stabilizing zirconia, titanium corundum (TiO
2.AL
2o
3) (alloy smelting waste residue) make inhibitor; Rare earth element and alumina powder do sintering agent.
Adopt again the grand technology of advanced match (thermo-negative reaction) to produce pottery, by (Al
2o
3c
r2o
3) eutectic and by titanium corundum (TiO
2.AL
2o
3) make stablizer; Rare earth element and alumina powder do sintering agent.Batch mixing compression moulding, pre-nitrogenize, machining, be sintered together down to 1450 ℃ in oxygen enrichment hot conditions, stop oxygen enrichment operation, pass into again ammonia, under effect by nitrogenizing reaction (nitrogenize limit, limit sintering) generation high temperature, use four kinds of oxide compounds to be total to solution and be converted to fully nitride, thereby the mechanical property raising anti-thermal shock stability of material is also embodied.
(Al
2o
3.C
r2o
3) eutectic raw material, solve the problem of waste residue utilization.
The listed three kinds of gas permeable brick analysis comparisons of table 1:
Table 1
Visible, original I type is containing C
r2o
3) corundum material, this material contains SiO
2element, SiO
2existence, reduced (Al
2o
3.C
r2o
3) refractoriness of eutectic, increase the fragility of material, be unfavorable for thermal shock resistance.
In this case, scientific worker has added Z again in this raw material
ro
2,c
r2o
3raw material, utilize Z
ro
2hinder the expansion of crackle, utilize C
r2o
3increase its refractoriness.In stupalith, form a kind of microtexture of relative porous, improve the heat-shock resistance of material.Develop II type aluminium chromium zirconium composite material.
The present invention proves by application in practice, adopt the grand technical ceramics production technique of match, nitrogenize aluminum chromium zirconia composite ceramic material and brick are developed, product is applied in multiple industries such as industrial ceramics, heavy metal smelting, electric power, aviation, oil field hotblast stove, Ladle Bottom blown converters, expand the space of application, improve greatly the work-ing life of material, increase the performance of enterprises, reduce the environmental pollution that each stopping production causes, reduce financial loss, the waste of the energy that also having reduced stops production simultaneously causes.
Embodiment 1:
First, raw material chromium corundum chemical analysis is carried out to jaw crushing crusher machine again, then be crushed to largest particle through cone crusher and be no more than 5 millimeters of particle diameters, then carry out the magnetic separation of strong magnetic separator deironing, carry out again sub-sieve, the roll crusher of sending into larger particle is pulverized again.The material of 0.5-5 millimeters of particle diameters is sent into mixer and chromic oxide, titanium corundum (TiO
2.AL
2o
3), rare earth element, aluminum oxide powder and graphite, bonding agent batch mixing; To be less than 0.5mm particle and be milled to-320 orders, after iron removal by magnetic separation, tired within 25 minutes, carry out chemical analysis in the lump with after zirconium white, titanium corundum, rare earth element and graphite, bonding agent batch mixing; Wherein 40 kilograms of zirconium whites, 50 kilograms, titanium corundum, 10 kilograms, rare earth element, 200 kilograms of aluminum oxide powders, 150 kilograms, graphite, 40 kilograms of bonding agents (bonding agent is that 85% phosphorus concentration acid solution body does not belong to material content); 450 kilograms of 0.5-5mm particle diameter chromium corundums;-320 200 kilograms of order particle diameter chromium corundums.After fully being stirred, above-mentioned raw materials sends into hydropress moulding, again by after sending into high temperature kiln oxygen enrichment to 1450 ℃ after pre-goods nitrogenize, machining and firing, stop oxygen enrichment operation, pass into again ammonia high temperature, produce high temperature to 1950---2000 ℃ by nitrogenizing reaction (nitrogenize limit, limit sintering), reaction terminating.
Claims (2)
1. a nitrogenize aluminum chromium zirconia composite ceramic material, is characterized in that, described its chemical constitution of nitrogenize aluminum chromium zirconia composite ceramic material (w) is:
Al
2O
3.C
r2O
3≥40%； ZrN≥6%；
TiN≥8% ALN≥40%; F
2O
3≤1.68%；
(Al
2o
3.C
r2o
3) coenosarc raw material be alloy smelting waste residue, Z
ro
2adopt and stablize chromic oxide, titanium corundum does stablizer, rare earth element and alumina powder and does together with sintering agent knot burning and form.
2. a nitrogenize aluminum chromium zirconia composite ceramic material making method, it is characterized in that, described method comprises following making processes: raw material chromium corundum is crushed to largest particle and is no more than 5 millimeters of particle diameters, then carry out deironing magnetic separation sub-sieve, 0.5-5 millimeters of particle diameters are sent into mixer and zirconium white, titanium corundum (TiO
2.AL
2o
3), rare earth element, aluminum oxide powder and graphite; Bonding agent batch mixing, to be less than 0.5mm particle and be milled to-320 orders, after iron removal by magnetic separation, be stranded compression moulding again in 25 minutes in the lump with after zirconium white, titanium corundum, rare earth element and graphite, bonding agent batch mixing, again by after sending into high temperature kiln oxygen enrichment to 1450 ℃ after pre-goods nitrogenize, machining and firing, stop oxygen enrichment operation, pass into again ammonia, pass through nitrogenizing reaction, nitrogenize limit, limit sintering, produce high temperature to 1950---2000 ℃, reaction, makes oxide compound eutectic be converted into fully nitride, makes material of main part (Al
2o
3.C
r2o
3) eutectic becomes the composite ceramic material of nitride bonded.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746180A (en) * | 2019-11-25 | 2020-02-04 | 浙江自立高温科技股份有限公司 | Sintered aluminum-chromium-zirconium sliding plate brick for copper smelting anode furnace and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050245387A1 (en) * | 2004-04-30 | 2005-11-03 | Dexian Zhu | Yttira containing high-density chrome based refractory composites |
| CN1939875A (en) * | 2006-09-07 | 2007-04-04 | 浙江大学 | Thermal-knock resisting diamond spar-spinele refractory materials and its production |
-
2014
- 2014-03-13 CN CN201410090355.4A patent/CN103864432B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050245387A1 (en) * | 2004-04-30 | 2005-11-03 | Dexian Zhu | Yttira containing high-density chrome based refractory composites |
| CN1939875A (en) * | 2006-09-07 | 2007-04-04 | 浙江大学 | Thermal-knock resisting diamond spar-spinele refractory materials and its production |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746180A (en) * | 2019-11-25 | 2020-02-04 | 浙江自立高温科技股份有限公司 | Sintered aluminum-chromium-zirconium sliding plate brick for copper smelting anode furnace and preparation method thereof |
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| CN103864432B (en) | 2015-05-20 |
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Effective date of registration: 20170126 Address after: 121000 Jinzhou City, Liaoning province Guta District No. 71 Zhong Tun Cun Patentee after: Jinzhou Dalong special metal materials Co. Ltd. Address before: 121001 Jinzhou District, Liaoning, Guta people''s livelihood 49-13 Patentee before: Zhao Daxing |