CN1152091C - Process for preparing superfine powder of ZrB2 or TiB2 - Google Patents
Process for preparing superfine powder of ZrB2 or TiB2 Download PDFInfo
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- CN1152091C CN1152091C CNB011101415A CN01110141A CN1152091C CN 1152091 C CN1152091 C CN 1152091C CN B011101415 A CNB011101415 A CN B011101415A CN 01110141 A CN01110141 A CN 01110141A CN 1152091 C CN1152091 C CN 1152091C
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- Prior art keywords
- ball milling
- powder
- preparation
- ultrafine powder
- tib2
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- 239000000843 powder Substances 0.000 title claims abstract description 45
- 229910007948 ZrB2 Inorganic materials 0.000 title claims abstract description 26
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910033181 TiB2 Inorganic materials 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000498 ball milling Methods 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 titanium hydride Chemical compound 0.000 claims abstract description 11
- 229910000048 titanium hydride Inorganic materials 0.000 claims abstract description 11
- 229910052786 argon Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 13
- 150000004678 hydrides Chemical class 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 9
- 238000005245 sintering Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 229910052796 boron Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 abstract 1
- 229910000568 zirconium hydride Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 239000000077 insect repellent Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Ceramic Products (AREA)
Abstract
The present invention relates to a method for preparing superfine powder of zirconium diboride or titanium diboride. The method uses the principle of a self spreading synthesis method, and proposes a new raw material system and a new preparation technique. Zirconium hydride (or titanium hydride) and simple substance boron are used as raw materials. After ball milling, mixing and pressed compact, the raw materials are treated through vacuum pumping preheating and heat preservation, and then react through argon charge and ignition. Ball milling is carried out to reactants, and the superfine powder of zirconium diboride or titanium diboride is obtained. The superfine powder of zirconium diboride or titanium diboride, which is prepared with the method has the product granularity smaller than 1 mu m, has the product purity which can reach 99%wt, and has good formability and sintering performance. When the superfine powder is sintered in vacuum at 1860 DEG C for 3 hours, the sintered density reached the theoretical density higher than 95 %.
Description
Technical field
The invention belongs to material synthesis method, be specifically related to the preparation method of zirconium diboride or TiB2 ultrafine powder.
Background technology
The new terminology that uses after the eighties in last century of ultrafine powder, English is Ultra-finePowder.Ultrafine powder is meant that the mean particle size of powder is less than 1 μ m.The granularity of powder depends on the time of the temperature and the building-up reactions experience of powder building-up reactions.Preparation zirconium diboride and titanium diboride powder carbothermic method commonly used, this method is a raw material with zirconium white or titanium oxide, norbide or boron oxide or boric acid and graphite, carry out ball milling again through ball milling mixing, pressed compact, applying argon gas igniting reaction, product, make zirconium diboride or TiB2 powder.Because reaction is to carry out for a long time under 1400～1600 ℃ of high temperature, the powder size of preparation is greater than 4～5 μ m, and sintering activity is poor.A kind of material preparation new technology that after the method for spreading is 1980, grows up, the English SHS that is called for short.From the principle that spreads synthetic method for spreading certainly synthetic in, the base substrate that the synthesis material mixture is pressed into strings, from an end (as left end) igniting, then building-up reactions resembles Poona's sample and propagates (as mosquito-repellent incense) from a left side.The back of ripple is product (as the mosquito-repellent incense ash), the front of ripple is raw material base substrate (mosquito-repellent incense that does not also have combustion), the zone that ripple is passing through is reaction zone (that section mosquito-repellent incense that is just burning and smoldering), compares with traditional synthetic method, spreads the synthetic characteristics certainly and is: (1) reaction times is short; (2) the product cooling is fast; (3) product is easy to fragmentation; (4) energy-conservation.The new legal system that spreads certainly is equipped with zirconium diboride or titanium diboride powder (" burning is synthetic " Beijing metallurgical industry press 1999.6), the material system that adopts has two kinds, the first is with zirconium white, boron oxide and magnesium are made raw material, the product of combustion reactions need carry out pickling and remove magnesium oxide, also has the oxide impurity that can not remove; It two is to make raw material with metal zirconium and pure boron, and for fear of zirconium and the aerial oxidation of titanium, the powder size of zirconium and titanium is bigger, and the granularity of synthetic zirconium diboride and titanium diboride powder is also thick, and sintering activity is very low.
Summary of the invention
The object of the present invention is to provide a kind of synthetic purity height, powder size is little, is easy to the preparation method of agglomerating zirconium diboride or TiB2 ultrafine powder.
The object of the present invention is achieved like this:
The preparation method of a kind of zirconium diboride or TiB2 ultrafine powder uses the self-spread synthesizing method principle, and adopting zircoium hydride or titanium hydride and amorphous boron powder is raw material, synthetic zirconium diboride or TiB2 ultrafine powder; Processing step comprises:
(1) be that zircoium hydride below the 100 μ m or titanium hydride and noncrystal pure boron powder are raw material with granularity, mix in the ratio ball milling of 1: 2 weight quota ratio that ratio of grinding media to material is 10～30: 1, the ball milling time is 2～6 hours;
(2) powder behind the ball milling is made the cylindrical base substrate of 20～40mm, blank density 50%～60%T.D. theoretical density;
(3) base substrate is placed the self-propagating reaction chamber vacuumize, vacuum tightness is better than 5 * 10
-2Pa, and to give heat to 500～750 ℃, soaking time be 0.5～4 hour;
(4) after insulation finished, applying argon gas was to normal pressure, and the igniting reaction obtains reaction product zirconium diboride or TiB2;
(5) again with the reaction product ball milling, the time is 8～10 hours, makes the zirconium diboride or the TiB2 ultrafine powder of certain particle size.
The zirconium diboride that the present invention proposes or the preparation method of TiB2 ultrafine powder, because the chemical stability of zircoium hydride and titanium hydride is good, can in air, operate, carry out spheroidal graphite energy thorough mixing with the pure boron powder, both improved the degree of mixing, reduced the granularity of zircoium hydride or titanium hydride again, reduced the reaction field energy of zircoium hydride or titanium hydride and boron by vacuum preheating dehydrogenation, make combustion reaction products purity height, oxide-free impurity, ball milling through the short period of time can obtain the ultrafine powder of mean particle size less than 1 μ m at last, and the processability of product and sintering character are good.The zirconium diboride and the ultra-fine end of Er Pengization TA of the preparation of this method, product purity be up to 99%Wt, and in 1860 ℃ of sintering 3 hours, sintered density reached more than 95% theoretical density in the vacuum.
Embodiment
Embodiment 1.
(1) be that zircoium hydride or the titanium hydride raw material powder of 70～100 μ m mixes with the ratio ball milling of non-crystalline state pure boron powder in 1: 2 with granularity, ratio of grinding media to material is 30: 1, and the ball milling time is 2 hours;
(2) with the pressed compact on press of the powder behind the ball milling, base substrate is the 20mm right cylinder, and blank density is the 50%T.D theoretical density;
(3) base substrate is placed the self-propagating reaction chamber vacuumize, and give heat to 500 ℃, vacuum tightness is 5 * 10
-2Pa, soaking time is 0.5 hour;
(4) after insulation finished, applying argon gas was to normal pressure, and the igniting reaction gets reaction product zirconium diboride or TiB2;
(5) the reactant ball milling after 8 hours, is obtained zirconium diboride or the TiB2 ultrafine powder of powder mean particle sizes less than 1 μ m.
Embodiment 2.
(1) be that titanium hydride or the zircoium hydride raw material powder of 70～100 μ m mixes with the ratio ball milling of non-crystalline state pure boron powder in 1: 2 with granularity, ratio of grinding media to material is 20: 1, and the ball milling time is 4 hours;
(2) with the pressed compact on press of the powder behind the ball milling, base substrate is the 30mm right cylinder, and blank density is the 55%T.D theoretical density;
(3) base substrate is placed the self-propagating reaction chamber vacuumize, and give heat to 600 ℃, vacuum tightness is 2 * 10
-2Pa, soaking time is 2 hours;
(4) after insulation finished, applying argon gas was to normal pressure, and the igniting reaction gets reaction product Er Pengization TA or zirconium diboride;
(5) the reactant ball milling after 8 hours, is obtained TiB2 or the zirconium diboride ultrafine powder of powder mean particle sizes less than 1 μ m.
Embodiment 3.
(1) be that zircoium hydride or the titanium hydride raw material powder of 70～100 μ m mixes with the ratio ball milling of non-crystalline state pure boron powder in 1: 2 with granularity, ratio of grinding media to material is 10: 1, and the ball milling time is 6 hours;
(2) with the pressed compact on common press of the powder behind the ball milling, base substrate is the 40mm right cylinder, and blank density is the 60%T.D theoretical density;
(3) base substrate is placed the self-propagating reaction chamber vacuumize, and give heat to 650 ℃, vacuum tightness is 1 * 10
-2Pa, soaking time is 4 hours;
(4) after insulation finished, applying argon gas was to normal pressure, and the igniting reaction gets reaction product zirconium diboride or Er Pengization TA;
(5) the reactant ball milling after 8 hours, is obtained zirconium diboride or the Er Pengization TA ultrafine powder of powder mean particle sizes less than 1 μ m.
Claims (6)
1. the preparation method of zirconium diboride or TiB2 ultrafine powder is characterized in that comprising following processing step:
(1) zircoium hydride or titanium hydride are mixed with the ratio ball milling of pure boron powder stock in 1: 2 weight quota ratio;
(2) make base substrate;
(3) base substrate is placed the self-propagating reaction chamber vacuumize, vacuum tightness is better than 5 * 10
-2Pa also gives 500～750 ℃ of heat, insulation 0.5～4 hour;
(4) after insulation finished, applying argon gas was to normal pressure, and the igniting reaction obtains reaction product zirconium diboride or TiB2;
(5), make the zirconium diboride or the TiB2 ultrafine powder of certain particle size again with the reaction product ball milling.
2. the preparation method of ultrafine powder as claimed in claim 1, the granularity that it is characterized in that zircoium hydride in the step (1) or titanium hydride and pure boron powder stock is below 100 μ m.
3. the preparation method of ultrafine powder as claimed in claim 1 is characterized in that the ball milling in the step (1) mixes, and ratio of grinding media to material is 10～30: 1, and the ball milling time is 2～6 hours.
4. the preparation method of ultrafine powder as claimed in claim 1 is characterized in that the blank density 50%～60%T.D. theoretical density in the step (2).
5. the preparation method of ultrafine powder as claimed in claim 1 is characterized in that the base substrate in the step (2) is the right cylinder of 20～40mm.
6. the preparation method of ultrafine powder as claimed in claim 1 is characterized in that the reaction product ball milling time in the step (5) is 8～10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011101415A CN1152091C (en) | 2001-03-30 | 2001-03-30 | Process for preparing superfine powder of ZrB2 or TiB2 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011101415A CN1152091C (en) | 2001-03-30 | 2001-03-30 | Process for preparing superfine powder of ZrB2 or TiB2 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1317519A CN1317519A (en) | 2001-10-17 |
| CN1152091C true CN1152091C (en) | 2004-06-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011101415A Expired - Lifetime CN1152091C (en) | 2001-03-30 | 2001-03-30 | Process for preparing superfine powder of ZrB2 or TiB2 |
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| Country | Link |
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| CN (1) | CN1152091C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1517858A1 (en) | 2002-03-28 | 2005-03-30 | Council Of Scientific And Industrial Research | Process for the production of zirconium boride powder |
| CN100364016C (en) * | 2004-12-02 | 2008-01-23 | 中国核动力研究设计院 | （U，Gd）O2Mixing process for preparing burnable poison core block |
| CN100336723C (en) * | 2005-05-23 | 2007-09-12 | 哈尔滨工业大学 | Combustion synthesis method of zirconium diboride micro-powder |
| CN100569644C (en) * | 2006-11-10 | 2009-12-16 | 清华大学 | A kind of preparation method of high-purity ultrafine zirconium diboride powder |
| CN101508572B (en) * | 2009-03-27 | 2012-01-11 | 北京工业大学 | Rapid preparation method of highly dense single-phase TiB2 ceramics |
| CN102584242B (en) * | 2012-02-28 | 2013-08-14 | 吉林大学 | High-temperature high-pressure preparation method for titanium diboride |
| CN103253678B (en) * | 2013-05-06 | 2016-01-27 | 南京航空航天大学 | A kind of low-temperature solid-phase synthesis method of diboride ceramic powder |
| CN105986323B (en) * | 2015-01-30 | 2018-08-10 | 中国人民解放军军械工程学院 | It is a kind of to prepare micro/nano level TiB2The method of whisker |
| CN108015291A (en) * | 2017-12-26 | 2018-05-11 | 天钛隆（天津）金属材料有限公司 | A kind of method that powder metallurgy prepares Ti2AlNb based alloys |
| CN111777072B (en) * | 2020-07-23 | 2022-05-20 | 辽宁中色新材科技有限公司 | Production process of hafnium disilicide |
| CN113120915B (en) * | 2021-04-23 | 2023-09-01 | 西北核技术研究所 | Nanometer TiB 2 Method for producing a coating |
| CN114349015A (en) * | 2022-02-28 | 2022-04-15 | 辽宁中色新材科技有限公司 | A low-cost high-purity zirconium diboride or titanium diboride production process |
| CN121044590B (en) * | 2025-11-05 | 2026-01-13 | 山东华元新材料有限公司 | High-purity titanium diboride powder and preparation method thereof |
-
2001
- 2001-03-30 CN CNB011101415A patent/CN1152091C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1317519A (en) | 2001-10-17 |
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