CN102701749A - Preparation method for cubic zirconia-beta phase silicon carbide complex phase high temperature resistance powder material - Google Patents
Preparation method for cubic zirconia-beta phase silicon carbide complex phase high temperature resistance powder material Download PDFInfo
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Abstract
The invention relates to a preparation method for a cubic zirconia-beta phase silicon carbide complex phase high temperature resistance powder material, belonging to the technical field of the preparation of the high temperature resistance powder material. The preparation method is characterized by comprising the following steps of: using zirconia, zircon sand or zirconium silicate as main raw materials, carbon black, coke, graphite or activated carbon as reducing agents, magnesium oxide, calcium oxide, yttrium oxide or cerium oxide as additives, mixing the materials according to certain proportions, and then preparing the cubic zirconia-beta phase silicon carbide complex phase high temperature resistance powder material by adopting technological processes such as ball-milling, drying, molding and carbon thermal reduction. The preparation method for the cubic zirconia-beta phase silicon carbide complex phase high temperature resistance powder material has the advantages of short technological process, non-pollution, low energy consumption, lower cost and the like.
Description
Technical field:
The preparation method of a kind of cubic zirconia-β phase silicon carbide complex phase high-temperature resistant powder body material belongs to high temperature resistant technical field of powdered material preparation.
Background technology:
Zirconia material has excellent machinery, calorifics, electricity and optical property, is widely used in numerous areas such as high-temperature structural material, dielectric materials, transmitter high temperature optics, fuel cell.Cubic phase zircite is owing to have very excellent physicals; Comprise rare HMP, high heat conductance, high elastic coefficient; And can at high temperature keep very HS; Also have good heat-shock resistance and moderate coefficient of thermal expansion simultaneously, be considered to following high temperature field one of the most promising material.Carbofrax material has that hardness is big, fusing point is high, anti-erosion, wear-resistant, excellent properties such as thermal shock resistance good, high-temperature oxidation resistance is strong, thermal expansivity is low, chemicalstability is good, heat-conductivity conducting property is good, is used widely in fields such as metallurgy, chemical industry, electronics, aerospace and building materials.
The shortcoming of zirconia ceramics material is that toughness is not high, the high and low safety of cost and low repeatability, and these deficiencies have had a strong impact on the range of application of zirconia ceramics material.Therefore, have only the fracture toughness property of improving pottery, realize the material highly malleablized, improve its safety and work-ing life, just can make it become a kind of type material of widespread use veritably.The thermal shock resistance of β phase silicon carbide, antioxidant property excellence, and fibrous β phase silicon carbide often is used as the matrix phase of structural ceramics.The zirconium oxide-silicon carbide composite diphase material combines the advantage performance of zirconium white and carbofrax material, has improved the intensity and the toughness of zirconia ceramics material effectively, aspect high temperature material, has great exploitation value and application prospect.Common zirconium oxide-silicon carbide composite diphase material is through the mechanically mixing powder raw material, obtains the high-performance diphase ceramic material through technologies such as moulding, drying and high temperature sinterings then.The uniform distribution between the very difficult acquisition of this mechanically mixing technology differing materials and the grain composition of optimization; Also cause simultaneously the cohesion and the chain interlock of fibrous carbonization silicon materials easily; And zirconium white and carbofrax material all belong to the high energy consumption product; Its Industrial processes not only energy consumption are big, and wasting of resources degree is high, thereby cause the cost of zirconium oxide-silicon carbide matrix material higher.
At present, domestic and international preparation method about the cubic zirconia powder mainly comprises hydrolysis method, the precipitator method, hydrothermal method, sol-gel processing, spray pyrolysis, freeze-drying and high-energy ball milling method etc.These preparing method's synthetic cubic zirconia powders have defective such as be prone to reunite, purity is low, and its complex process, cost is high, energy consumption is big, realize that therefore the low cost preparation and energy-saving and cost-reducing of cubic zirconia raw material has crucial meaning.
Zircon, zircon sand or zirconium silicate can a step be realized synthetic zirconium white and carbofrax material through the zirconium oxide-silicon carbide complex phase powder body material of carbo-thermal process preparation.This complex phase powder raw material can be used for preparing high-performance zirconia-β phase silicon carbide composite diphase material.The zirconia material of zircon carbothermic reduction preparation mainly exists with the form of monocline phase; Nonoclinic phase zirconium oxide material is accompanied by the volume change about 7% in high-temperature sintering process; Cause the cracking of goods and the intensity of goods also will descend significantly easily, this defective is fatefulue to the influence of zirconia-based ceramics material.Patented claim of the present invention proposes to prepare in the technological process of zirconium oxide-silicon carbide composite diphase material in zircon, zircon sand or zirconium silicate carbothermic reduction based on solving this critical defect, suitably introduces certain amount of stabilizer, like MgO, CaO, Y
2O
3Or CeO
2Deng, through the temperature and the reaction process of control zircon, zircon sand or zirconium silicate carbothermic reduction reaction, the step preparation that realizes zirconium oxide-silicon carbide complex phase powder body material simultaneously makes the transition with the monocline phase zircite and is the purpose of cubic phase zircite.The present invention has that technical process is short, production process is polluted little, many advantages such as energy consumption is low, cost is lower, added value of product height, and the efficient increment utilization of non-metallic mineralss such as the production cost that reduces high-performance zirconia-β phase silicon carbide composite diphase material and zircon, zircon sand is had crucial meaning.
Summary of the invention:
Patented claim of the present invention is to prepare in the technological process of zirconium white-β phase silicon carbide composite diphase material in zircon, zircon sand or zirconium silicate carbothermic reduction, suitably introduces certain amount of stabilizer, like MgO, CaO, Y
2O
3Or CeO
2Deng, and temperature and reaction process through control zircon, zircon sand or zirconium silicate carbothermic reduction reaction, a step realizes that simultaneously preparation and the monocline phase zircite of zirconium oxide-silicon carbide complex phase high-temperature resistant powder body material are the purpose of cubic phase zircite transition.The present invention has that technical process is short, production process is polluted little, many advantages such as cost is lower, energy consumption is low, added value of product height, and the efficient increment utilization of non-metallic mineralss such as the production cost that reduces high-performance cubic zirconia-β phase silicon carbide composite diphase material and zircon, zircon sand is had crucial meaning.
The preparation method of a kind of cubic zirconia-β phase silicon carbide complex phase high-temperature resistant powder body material that the present invention proposes; It is characterized in that: in total batching quality 0.1%～99.0% zircon, zircon sand or zirconium silicate; And 0.1%～99.0% carbon black, coke, graphite or gac be raw material, in total batching quality 0.1%～99.0%MgO, CaO, Y
2O
3Or CeO
2Be stablizer; Prepare the sample green compact through technological processs such as batching batch mixing, ball milling, drying, moulding; In being selected from the airtight reducing atmosphere that coke buries or be selected from the rare gas element of argon shield; 0.1 hour～100 hours 1400 ℃～1800 ℃ following reaction times, prepare cubic zirconia-silit complex phase high-temperature resistant powder body material.
Zircon, zircon sand or the zirconium silicate described in the preparation method of above-mentioned cubic zirconia-β phase silicon carbide complex phase high-temperature resistant powder body material in mass its purity be not less than 80%; Carbon black, coke, graphite or gac its carbon content in mass are not less than 60%, MgO, CaO, Y
2O
3Or CeO
2Its purity is not less than 90% in mass.
Inert gas pressure described in the preparation method of a kind of cubic zirconia-β phase silicon carbide complex phase high-temperature resistant powder body material is 0.1Pa～10.0MPa.
The airtight reducing atmosphere that coke described in the preparation method of a kind of cubic zirconia-β phase silicon carbide complex phase high-temperature resistant powder body material is buried be through bury with coke place can be anti-the sample green compact of high temperature saggar container more than 1800 ℃, and seal the reducing atmosphere environment that high temperature resistant saggar container produces sample and coke air-isolation.
Zirconium white mainly mainly exists with β phase form with a cube phase, silit in the complex phase high-temperature resistant powder body material that the preparation method of a kind of cubic zirconia-β phase silicon carbide complex phase high-temperature resistant powder body material obtains.
The preparation method of a kind of cubic zirconia-silit complex phase high-temperature resistant powder body material, described technological process is specially:
1) zircon, zircon sand or zirconium silicate and carbon black, coke, graphite or raw materials such as gac and stablizer are prepared burden in proportion and thorough mixing even; Again mixed raw material is packed in the ball grinder; And ball milling 0.1～50 hour to each raw material is uniformly dispersed in ball mill, and the mode of ball milling is selected dry ball milling or wet ball grinding for use; Then the uniform raw material of ball mill mixing is processed blocky sample green compact through dry-pressing formed, half-dried molded or isostatic pressing technological process;
2) put into can anti-high temperature resistant saggar container more than 1800 ℃ for green compact that above-mentioned drying is good; The size that around the sample green compact, distributes is coke or the activated carbon granule of 0.1～1.0mm; Make coke or activated carbon granule fully be wrapped in the sample green compact around; Then high temperature resistant saggar container sealing is guaranteed sample and coke and air insulated, the high temperature resistant saggar container after handling like this can place corresponding thermal kiln furnace heating to burn till, and its synoptic diagram is shown in Figure of description; Or the sample green compact that above-mentioned drying is good directly place the high-temperature atmosphere furnace of protection of inert gas to carry out the pyrocarbon thermal reduction reaction; The sample green compact in normal temperature to synthesis temperature scope in the heat treatment process heat-up rate do not have particular requirement; Under corresponding temperature, can be incubated certain hour respectively; After naturally cooling to room temperature after 1400 ℃～1800 ℃ 0.1 hour～100 hours following reaction times, take out sample and carry out to obtain cubic oxide silicon-β phase silicon carbide complex phase high-temperature resistant powder body material after levigate.
The present invention is through effectively controlling the temperature and the reaction process of zircon, zircon sand or zirconium silicate carbothermic reduction reaction; Next step is realized that the preparation of zirconium white-β phase silicon carbide powder body material makes the transition with the monocline phase zircite and is the purpose of cubic phase zircite in short technical process; Therefore have production process and pollute little, many advantages such as cost is lower, energy consumption is low, added value of product height, the efficient increment utilization of non-metallic mineralss such as the production cost that reduces cubic zirconia-β phase silicon carbide composite diphase material and zircon, zircon sand is had crucial meaning.
Description of drawings:
Accompanying drawing is device synoptic diagram (the 1-high temperature furnace wall for preparing cubic zirconia-β phase silicon carbide complex phase high-temperature resistant material under the coke airtight reducing atmosphere condition of burying; The 2-heating element; The 3-burner hearth; 4-can anti-1800 ℃ of pyritous saggar containers; 5-coke fine powder; The 6-carbon paper; The 7-coke granule; 8-sample green compact; 9-refractory ceramics support)
Embodiment:
Below in conjunction with instance technical scheme of the present invention is further specified:
At first various raw materials and additive are prepared burden in said ratio; Adopt ball mill dry ball milling or wet ball grinding 0.1-50 hour even admixtion then to each raw materials mix; Then the raw material that mixes is processed the sample green compact of definite shape through technological processs such as dry-pressing formed, half-dried molded or isostatic pressings, the carbothermic reduction reaction under the reducing atmosphere condition prepares cubic zirconia-β phase silicon carbide complex phase high-temperature resistant powder body material then.Concrete technical process is:
Carbothermic reduction under raw material → raw materials pretreatment → batching → ball milling → drying → moulding → sample green compact → drying → reducing atmosphere condition → levigate → cubic zirconia-β phase silicon carbide complex phase high-temperature resistant powder body material
Embodiment 1
Raw material and proportioning:
The granularity of zircon raw material and specification of quality are ZrSiO
4Content is in mass greater than 80%, wherein ZrO
2Content is in mass greater than 50%, particle size≤1mm; The employing carbon black is a reductive agent, and the granularity of carbon black reductive agent and specification of quality do, carbon content is in mass greater than 98%, particle size≤1 μ m, and the mass ratio of zircon and carbon black add-on is 5: 1; Adopting the technical pure yttrium oxide is additive, and the add-on of yttrium oxide is in mass for adding 10%.
Technological process:
Above-mentioned various raw materials are processed the sample green compact of Φ 20mm * 20mm through technological processs such as batching, batch mixing, ball milling, drying, moulding; The airtight high temperature resistant saggar container that places coke to bury sample form shown in the drawings to specifications then; The high temperature kiln that this high-temperature resistant container is placed oxidizing atmosphere is isolated the coke around sample and the sample after 1600 ℃ of insulations naturally cooled to room temperature after 4 hours, sample is taken out promptly obtain to contain the cubic phase zircite of stabilized with yttrium oxide and the complex phase high-temperature resistant powder body material of β phase silicon carbide after levigate.
Reaction product characterizes: the main thing that exists is cubic phase zircite and β-SiC mutually in the sample of zircon after the described carbothermic reduction of above-mentioned technological process.
Raw material and proportioning:
The granularity of zircon sand raw material and specification of quality are ZrSiO
4Content is in mass greater than 95%, wherein ZrO
2Content is in mass greater than 60%, particle size≤1mm; Selecting gac for use is reductive agent, and its granularity and specification of quality do, in the gac carbon content in mass greater than 98%, particle size≤1 μ m; The mass ratio of zircon and gac add-on is 5: 1; Adopting technical pure Natural manganese dioxide is additive, and magnesian add-on is in mass for adding 8wt%.
Technological process:
Above-mentioned various raw materials are processed the sample green compact of Φ 20mm * 20mm through technological processs such as batching, batch mixing, ball milling, drying, moulding; Sample is placed in the open plumbago crucible; Place the high temperature kiln of argon gas atmosphere protection to naturally cool to room temperature after 6 hours plumbago crucible then through 1650 ℃ of insulations, with sample take out levigate after i.e. acquisition contain the cubic phase zircite of stabilized magnesium hydroxide and the complex phase high-temperature resistant powder body material of silit.
Reaction product characterizes: the main thing that exists is cubic phase zircite and β-SiC mutually in the sample of zircon after the described carbothermic reduction of above-mentioned technological process.
Claims (5)
1. the preparation method of cubic zirconia-β phase silicon carbide complex phase high-temperature resistant powder body material; It is characterized in that: in total batching quality 0.1%～99.0% zircon, zircon sand or zirconium silicate; And 0.1%～99.0% carbon black, coke, graphite or gac be raw material, in total batching quality 0.1%～99.0%MgO, CaO, Y
2O
3Or CeO
2Be stablizer; Prepare the sample green compact through technological processs such as batching batch mixing, ball milling, drying, moulding; In being selected from the airtight reducing atmosphere that coke buries or be selected from the rare gas element of argon shield; 0.1 hour～100 hours 1400 ℃～1800 ℃ following reaction times, prepare cubic zirconia-β phase silicon carbide complex phase high-temperature resistant powder body material.
2. preparation method according to claim 1 is characterized in that: described zircon, zircon sand or zirconium silicate its purity in mass are not less than 80%, and carbon black, coke, graphite or gac its carbon content in mass are not less than 60%, MgO, CaO, Y
2O
3Or CeO
2Its purity is not less than 90% in mass.
3. preparation method according to claim 1; It is characterized in that: the airtight reducing atmosphere that coke is buried be through bury with coke place can be anti-the sample green compact of high temperature saggar container more than 1800 ℃, and seal the reducing atmosphere environment that high temperature resistant saggar container produces sample and coke air-isolation.
4. preparation method according to claim 1 is characterized in that: described inert gas pressure is 0.1Pa～10.0MPa.
5. the complex phase high-temperature resistant powder body material that obtains according to claim 1,2,3 or 4 said preparing methods is characterized in that zirconium white mainly mainly exists with β phase form with a cube phase, silit in this complex phase powder body material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370521A (en) * | 2014-10-28 | 2015-02-25 | 倪娟形 | Cerium-oxide-containing high-temperature-resistant special ceramic and preparation method thereof |
| CN106470958A (en) * | 2014-07-14 | 2017-03-01 | 里弗雷克特里知识产权两合公司 | Refractory product, the purposes of zirconium dioxide, zirconium dioxide, be used for the method manufacturing refractory product and the refractory product being produced from |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919792A (en) * | 2006-09-04 | 2007-02-28 | 青岛大学 | Manufacture method of silicon carbide refractory ceramics material |
| CN101195486A (en) * | 2006-12-04 | 2008-06-11 | 于景坤 | Production method of zirconium oxide-silicon carbide composite powder body |
| CN102320850A (en) * | 2011-09-02 | 2012-01-18 | 郑州大学 | ZrB2-SiC composite powder and preparation method thereof |
-
2012
- 2012-06-14 CN CN201210194570XA patent/CN102701749A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919792A (en) * | 2006-09-04 | 2007-02-28 | 青岛大学 | Manufacture method of silicon carbide refractory ceramics material |
| CN101195486A (en) * | 2006-12-04 | 2008-06-11 | 于景坤 | Production method of zirconium oxide-silicon carbide composite powder body |
| CN102320850A (en) * | 2011-09-02 | 2012-01-18 | 郑州大学 | ZrB2-SiC composite powder and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106470958A (en) * | 2014-07-14 | 2017-03-01 | 里弗雷克特里知识产权两合公司 | Refractory product, the purposes of zirconium dioxide, zirconium dioxide, be used for the method manufacturing refractory product and the refractory product being produced from |
| CN104370521A (en) * | 2014-10-28 | 2015-02-25 | 倪娟形 | Cerium-oxide-containing high-temperature-resistant special ceramic and preparation method thereof |
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Application publication date: 20121003 |