CN100519479C - Method for preparing high-temperature-resisting, oxidation-resisting zirconium-aluminium ceramic powder - Google Patents
Method for preparing high-temperature-resisting, oxidation-resisting zirconium-aluminium ceramic powder Download PDFInfo
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- CN100519479C CN100519479C CNB2006100458814A CN200610045881A CN100519479C CN 100519479 C CN100519479 C CN 100519479C CN B2006100458814 A CNB2006100458814 A CN B2006100458814A CN 200610045881 A CN200610045881 A CN 200610045881A CN 100519479 C CN100519479 C CN 100519479C
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- powder
- zirconium
- high temperature
- raw material
- resisting
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- 239000000843 powder Substances 0.000 title claims abstract description 46
- 239000000919 ceramic Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 10
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 title claims description 7
- 239000002994 raw material Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 235000006708 antioxidants Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000010301 surface-oxidation reaction Methods 0.000 abstract description 2
- 238000007731 hot pressing Methods 0.000 abstract 3
- 239000007791 liquid phase Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910052756 noble gas Inorganic materials 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- -1 zirconium aluminum carbon Chemical compound 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 description 19
- 239000007789 gas Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 8
- 229910026551 ZrC Inorganic materials 0.000 description 6
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910007880 ZrAl Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 101150032953 ins1 gene Proteins 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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Abstract
The invention relates to a manufacturing technology for high temperature endurable and oxidation resisting ceramic. The feature is that it uses Zr-Al alloy powder, and C powder as raw material, taking ball milling for 10-30 hours, pressing to cake shape under 10-20MPa, encasing into graphite mold, heating to 1200-1500 degree centigrade in hot-pressing furnace at 2-50 degree centigrade per minutes under protection of noble gas, taking home position hot pressing/ solid-liquid phase reacting for 0.1-1 hours, the hot pressing pressure is 20-40MPa. The invention could compound high purity, high intension, and corrosion proof zirconium aluminum carbon block material at low temperature and in short tie. The material could be used to make surface oxidation resisting coating.
Description
Technical field
The present invention relates to technology of preparing high temperature resistant, oxidation-resistant ceramic, a kind of zirconium aluminium carbon (Zr is provided especially
3Al
3C
5And Zr
2Al
3C
4) preparation method of ceramic powder.
Background technology
Zirconium aluminium carbon (Zr
3Al
3C
5, Zr
2Al
3C
4) pottery is a kind of ternary material of novel fire resistant.It combines the pottery and the plurality of advantages of metal, the high-modulus of existing ceramic aspect, high rigidity, anti-oxidant, corrosion-resistant etc.; The performance that metallic substance is arranged again simultaneously, high conductivity, thermal conductivity, stronger destruction tolerance etc.All have wide practical use at high-technology fields such as Aeronautics and Astronautics, nuclear industry, fuel cell, electronic information, ultrahigh-temperature structural parts.Although zirconium aluminium carbon (Zr
3Al
3C
5, Zr
2Al
3C
4) stupalith has excellent properties like this, but the difficulty in the preparation has limited the research of its performance and its application.The middle U.Leela-adisom of document 1 (Key Eng.Mater. (priority project material) 280-283 (2005) 1379) etc. uses the Al powder, and C powder, ZrC powder are heated to 1500-1600 ℃ in vacuum oven, react to obtain Zr in 1 hour
3Al
3C
5Powder.This method temperature of reaction is higher relatively, and unnecessary simple substance Al volatilizees in vacuum oven, and graphite heater is caused disadvantageous effect.Up to now, about also there not being zirconium aluminium carbon (Zr
3Al
3C
5, Zr
2Al
3C
4) report of aspect of performance of ceramic powder.
Summary of the invention
The present invention has proposed a kind ofly to prepare one-component ceramic zirconium aluminium carbon (Zr with alloy cpd first
3Al
3C
5And Zr
2Al
3C
4) method of powder body material.This method is a raw material with Zr-Al alloy powder and C powder, and the simple substance Al that utilizes reaction to generate is fusing assistant, has synthesized monophasic zirconium aluminium carbon (Zr at lesser temps, in the short period of time
3Al
3C
5And Zr
2Al
3C
4) ceramic powder.
Technical scheme of the present invention is as follows:
A kind of preparation method of zirconium-aluminium ceramic powder, this method feature is:
1) raw material is formed and composition range:
Single-phase Zr
3Al
3C
5, Zr
2Al
3C
4Stoichiometric ratio (being mol ratio) be respectively Zr:Al:C=3:(3-6): (4-6) and Zr:Al:C=2:(3-5): (3-5).
2) preparation technology and chemical reaction process:
Raw material process ball milling 10-20 hour; pressure with 10-20MPa is cold-pressed into pie; pack in the graphite jig, (be preferably 5-30 ℃/min) temperature rise rate and rise to 0.1-1 hour (being preferably 0.5-1 hour) of 1200 ℃-1500 ℃ (being preferably 1400 ℃-1500 ℃) reaction with 2-50 ℃/min in as the High Temperature Furnaces Heating Apparatus of protection gas being connected with rare gas element (as argon gas).Use simple substance Al superfluous in 5-20mol% (being preferably 15-20mol%) the hydrochloric acid flush away reaction product then.Main chemical reaction process is the Zr-Al compound at lesser temps through to each other stoichiometry adjustment, reacts rapidly at comparatively high temps and C then to generate zirconium aluminium carbon (Zr
3Al
3C
5And Zr
2Al
3C
4) ternary compound and simple substance A1..
Among the present invention, the granularity of Zr-Al alloy powder and C powder is the 200-400 order; The granularity of the zirconium-aluminium ceramic powder that employing the inventive method obtains is at the 1-20 micron.
Relevant chemical equation is as follows:
4Zr
3Al
2(s)+9ZrAl
3(s)＝7Zr
2Al
3(s)+7ZrAl
2(s) (1)
ZrAl
2(s)+Zr
2Al
3(s)+5C(s)＝Zr
3Al
3C
5(s)+2Al(1) (2)
Characteristics of the present invention are:
1. selecting for use raw material simple, is respectively Zr-Al alloy powder and C powder;
2. utilize the liquid Al of the simple substance that generates in the reaction process to be fusing assistant, promoted the carrying out of mass transfer diffusion process, therefore can be at low temperature (below 1500 ℃), the short period of time (less than 1 hour) is synthesized zirconium-aluminium ceramic powder;
3. the powder that adopts the inventive method to obtain does not contain other impurity, as zirconium carbide etc., can be used to prepare zirconium aluminium carbon block material, zirconium aluminium C-base composte material and as the surface oxidation-resistant coating of C/C matrix material.。
4. the zirconium aluminium toner body that is obtained is than corresponding binary carbide, and the zirconium carbide powder has better high-temperature oxidation resistance, has potential and use in high-temperature structural material.
Description of drawings
Fig. 1 reaction product Zr
3Al
3C
5X-ray diffracting spectrum.
Fig. 2 reaction product Zr
3Al
3C
5The stereoscan photograph of powder.
Fig. 3 reaction product Zr
2Al
3C
4X-ray diffracting spectrum.
The oxidation TGDSC curve of Fig. 4 (a)-(b) powder.Wherein, (a) Zr
3Al
3C
5(b) ZrC.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Raw material employing granularity is ZrAl50 (weight ratio of Zr and Al is 50:50 in the alloy) powder 30.00 grams, ZrAl16 (weight ratio of Zr and Al is 84:16 in the alloy) powder 52.32 grams and C powder 12.64 grams about 300 orders; ball milling 10 hours; under the pressure of 15MPa, be cold-pressed into pie; pack in the graphite jig, the temperature rise rate with 10 ℃/min in the High Temperature Furnaces Heating Apparatus that is connected with rare gas element (argon gas) conduct protection gas rises to 1300 ℃ of reaction ins 0.5 hour.Use simple substance Al superfluous in the 15mol% hydrochloric acid flush away reaction product then, and at room temperature dry 24 hours, the reaction product of acquisition is Zr through the X-ray diffraction analysis
3Al
3C
5Corresponding X-ray diffracting spectrum, stereoscan photograph is listed in respectively on the accompanying drawing 1-2.
Raw material employing granularity is ZrA150 (weight ratio of Zr and Al is 50:50 in the alloy) powder 30.00 grams, ZrAl16 (weight ratio of Zr and Al is 84:16 in the alloy) powder 28.12 grams and C powder 8.35 grams about 200 orders; ball milling 20 hours; under the pressure of 10MMPa, be cold-pressed into pie; pack in the graphite jig, the temperature rise rate with 15 ℃/min in the High Temperature Furnaces Heating Apparatus that is connected with rare gas element (argon gas) conduct protection gas rises to 1500 ℃ of reaction ins 0.2 hour.Use simple substance Al superfluous in the 5mol% hydrochloric acid flush away reaction product then, and at room temperature dry 24 hours, the reaction product of acquisition is Zr through the X-ray diffraction analysis
3Al
3C
5
Embodiment 3
Raw material employing granularity is ZrAl50 (weight ratio of Zr and Al is 50:50 in the alloy) powder 30.00 grams, ZrAl16 (weight ratio of Zr and Al is 84:16 in the alloy) powder 6.50 grams and C powder 5.42 grams about 300 orders; ball milling 10 hours; under the pressure of 15MPa, be cold-pressed into pie; pack in the graphite jig, the temperature rise rate with 15 ℃/min in the High Temperature Furnaces Heating Apparatus that is connected with rare gas element (argon gas) conduct protection gas rises to 1500 ℃ of reaction ins 0.5 hour.Use simple substance Al superfluous in the 20mol% hydrochloric acid flush away reaction product then, and at room temperature dry 24 hours, the principal reaction product of acquisition is Zr through the X-ray diffraction analysis
2Al
3C
4Corresponding X-ray diffracting spectrum is listed on the accompanying drawing 3.
Raw material employing granularity is ZrAl50 (weight ratio of Zr and Al is 50:50 in the alloy) powder 50.00 grams, ZrAl16 (weight ratio of Zr and Al is 84:16 in the alloy) powder 10.84 grams and C powder 9.04 grams about 400 orders; ball milling 30 hours; under the pressure of 10MPa, be cold-pressed into pie; pack in the graphite jig, the temperature rise rate with 10 ℃/min in the High Temperature Furnaces Heating Apparatus that is connected with rare gas element (argon gas) conduct protection gas rises to 1400 ℃ of reaction ins 1 hour.Use simple substance Al superfluous in the 10mol% hydrochloric acid flush away reaction product then, and at room temperature dry 24 hours, the principal reaction product of acquisition is Zr through the X-ray diffraction analysis
2Al
3C
4
Comparative example
Zr
3Al
3C
5The TG-DSC curve of powder oxidation shows that the initial oxidation of this powder and termination oxidizing temperature are respectively 400 ℃ and 1200 ℃.And the initial oxidation of ZrC powder on the market (300 order) and termination oxidizing temperature are respectively 300 ℃ and 800 ℃, and Zr is described
3Al
3C
5Powder has better high-temperature oxidation resistance than ZrC powder.Corresponding oxidation curve is listed on the accompanying drawing 4.
Claims (2)
1, a kind of preparation method of high temperature resistant, anti-oxidant zirconium-aluminium ceramic powder, this method feature is:
1) raw material is formed and composition range:
With Zr-Al alloy powder and C powder is raw material, synthetic single-phase Zr
3Al
3C
5, Zr
2Al
3C
4Stoichiometric ratio be respectively Zr:Al:C=3:(3-6): (4-6) and Zr:Al:C=2:(3-5): (3-5);
2) preparation technology:
Raw material is through ball milling 10-30 hour, is cold-pressed into pie with the pressure of 10-20MPa, in the graphite jig of packing into, rises to 1200 ℃-1500 ℃ reactions 0.1-1 hour in being connected with the High Temperature Furnaces Heating Apparatus of rare gas element as protection gas; Use simple substance Al superfluous in the 5-20mol% hydrochloric acid flush away reaction product then.
2, according to the preparation method of described high temperature resistant, the anti-oxidant zirconium-aluminium ceramic powder of claim 1, this method feature is: described step 2), the High Temperature Furnaces Heating Apparatus temperature rise rate is 2-50 ℃/min.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100458814A CN100519479C (en) | 2006-02-22 | 2006-02-22 | Method for preparing high-temperature-resisting, oxidation-resisting zirconium-aluminium ceramic powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100458814A CN100519479C (en) | 2006-02-22 | 2006-02-22 | Method for preparing high-temperature-resisting, oxidation-resisting zirconium-aluminium ceramic powder |
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|---|---|
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| CN100519479C true CN100519479C (en) | 2009-07-29 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443719A (en) * | 2011-12-13 | 2012-05-09 | 广西大学 | In-situ synthesized zirconium-based composite material reinforced by using zirconium carbide particles, and preparation method thereof |
| CN109207786B (en) * | 2018-11-01 | 2020-08-07 | 西北工业大学 | Zr3Al3C5-ZrAlxSiyMethod for preparing composite material |
| CN112592183B (en) * | 2021-01-05 | 2022-04-19 | 中钢南京环境工程技术研究院有限公司 | Preparation method of Zr-Al-C series MAX phase ceramic powder product |
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- 2006-02-22 CN CNB2006100458814A patent/CN100519479C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| The crystal structure of Zr3Al3C5，ScAl3C3，and UAl3C3abd their reaction to the structures of U2Al3C4 and Al4C3. Gesting，TM.JOURNAL OF SOLID STATE CHEMISTRY,Vol.140 No.2. 1998 |
| The crystal structure of Zr3Al3C5，ScAl3C3，and UAl3C3abd their reaction to the structures of U2Al3C4 and Al4C3. Gesting，TM.JOURNAL OF SOLID STATE CHEMISTRY,Vol.140 No.2. 1998 * |
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