CN1935742A - High-temperature carbonitriding preparation method of nano crystal titanium carbonitride ceramic ultrafine powder - Google Patents
High-temperature carbonitriding preparation method of nano crystal titanium carbonitride ceramic ultrafine powder Download PDFInfo
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- CN1935742A CN1935742A CN 200510021718 CN200510021718A CN1935742A CN 1935742 A CN1935742 A CN 1935742A CN 200510021718 CN200510021718 CN 200510021718 CN 200510021718 A CN200510021718 A CN 200510021718A CN 1935742 A CN1935742 A CN 1935742A
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- pyrocarbon
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- ball milling
- titanium carbonitride
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- 239000000843 powder Substances 0.000 title claims abstract description 17
- 239000010936 titanium Substances 0.000 title claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 8
- 239000000919 ceramic Substances 0.000 title claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000005256 carbonitriding Methods 0.000 title abstract 3
- 238000002360 preparation method Methods 0.000 title description 4
- 239000002159 nanocrystal Substances 0.000 title 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000005121 nitriding Methods 0.000 claims description 7
- 238000001238 wet grinding Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 229910021392 nanocarbon Inorganic materials 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000209456 Plumbago Species 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- -1 titanium hydride Chemical compound 0.000 description 2
- 229910000048 titanium hydride Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention is a method for preparing nano-crystalline titanium carbonitride ceramic superfine powder by high temperature carbonitriding reaction, using nano titanium oxide and nano carbon black, and comprising the steps of batching, mixing, drying, charging, high temperature carbonitriding, ball-milling, and screening. And it has simple process, lower cost, saves energy sources as compared with common carbon reduction, and easily implements scale industrialized production. By controlling reaction temperature, heat preserving time, nitrogen gas pressure (or flow), C-Ti ratio and other process factors, it can synthesize titanium carbonitride nano-crystalline superfine powders of various N contents. And the prepared powder is ball-shaped, has good dispersivity, and average grain size of 100-200nm, average crystal grain size of 20-50 nm and purity up to above 99%.
Description
One, technical field
The present invention relates to a kind of pyrocarbon nitrogenizing reaction preparation method of nanocrystalline TiCN ceramic ultrafine powder.
Two, background technology
At present, the known TiCN method ultra-fine and nano powder for preparing has plasma method, for example: the paper of Ceng Daquan etc. " plasma method synthesizing superfine titanium carbonitride sosoloid micro mist " (see " chemical journal ", 49 phases, 1991,1103-1106); The high energy mechanical ball milled, for example: the paper of Kerr.A etc. " Low temperature mechanochemical formation of titanium carbonitride " (see NanoStructured Materials, 1999,11 (2), 233-239)); Sol-gel method, for example, paper " Synthesis of Ti (C, N) the ultrafine powders bycarbothermal reduction of TiO of Xiang Junhui etc.
2Derived from sol-gel process " (see Journal of the European Ceramic Society, 20 (2000), 933-938); Cryochem process, for example: the paper " A simple route to prepare nanocrystalline titaniumcarbonitride " of Shen Guozhen etc. (see Materials Research Bulletin, 37 (2002), 1207-1211); Starch reduction titanium hydride method, for example: the paper of Li Xikun etc. " starch reduction titanium hydride prepare Ti (C, N) nano powder " (see " Northeastern University's journal (natural science edition) ", 24 volumes, the 3rd phase, in March, 2003,272-275) or the like.
Analyze aforesaid method, can find they generally have raw materials cost height, technology loaded down with trivial details, yield poorly, synthetic product is impure, one or more shortcomings of apparatus expensive or the like, has therefore limited it in industrial large-scale production.
Three, summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of method of simple synthesizing nanocrystalline TiCN ultrafine powder, this method not only technology is simple, and cost is lower, general carbothermic method save energy, and realize large-scale industrial production easily.
Principle of the present invention is: solid that raw material powder particle size has a strong impact on is solid-, solid-solid/liquid/gas reactions speed speed and reaction after product globule size.The titanium source and the carbon source particle of preparation TiCN are more little, specific surface area is big more, and the contact area between them is just big more, so not only can make speeding up of the hot nitrogenizing reaction of carbon, and reduced temperature of reaction, therefore also just reduced the chance of reaction product grain growth.
Method provided by the invention is a raw material with nano-titanium oxide and nanometer carbon black, and processing step is as follows:
1, batching
C, Ti mol ratio are 2.2～2.8;
2, batch mixing
Nano-titanium oxide, the nanometer carbon black ball milling (wet-milling or dry grinding) that will meet proportioning mix, till evenly;
3, drying
The wet-milling material needs 60～90 ℃ of oven dry;
4, charging
A certain amount of combination drying material is put into the carbon tube furnace crucible and compress;
5, pyrocarbon nitrogenize
(1) closed system
Begin heating when certain vacuum is spent with being extracted in the carbon tube furnace, to 300～600 ℃ of insulation 30～60min, logical nitrogen was to certain pressure intensity when insulation finished.The pyrocarbon nitriding temperature is 1300～1600 ℃, and the time is 1～4h;
(2) open system
To be full of nitrogen in the carbon tube furnace to being a bit larger tham 1 standard atmospheric pressure, the through-flow more moving nitrogen and the heating that heats up simultaneously.The pyrocarbon nitriding temperature is 1300～1600 ℃, and the time is 1～4h;
6, ball milling
Pyrocarbon nitrogenize products therefrom is carried out ball milling;
7, sieve
With the ball milling after product sieve product.
Method synthetic product provided by the invention is the TiCN solid-solution powder, and its particle is spherical, and better dispersed, mean particle size is 100～200nm, and mean grain size is 20～50nm, and purity reaches (the XRD figure spectrum goes up the inclusion-free peak) more than 99%.
The present invention has following advantage;
1, owing to used the nanometer powder raw material, so temperature of reaction is lower, soaking time is shorter, has also reduced the chance of product grain growth in save energy.
2, technological factors such as the temperature of reaction by control pyrocarbon nitrogenize, soaking time, nitrogen pressure (or flow), C-Ti ratio can synthesize the TiCN manocrystalline powders of various nitrogen contents;
3, synthetic TiCN powder purity is higher, and particle is thin, and particle size distribution range is narrower;
4, raw material is cheap, and domestic manufacturer can supply in batches;
5, technology is simple, is convenient to operation;
6, realize industrial scale production easily.
Four, description of drawings
Fig. 1 is a kind of process flow sheet according to the pyrocarbon nitriding method for preparing of nanocrystalline TiCN ceramic ultrafine powder provided by the present invention.
Five, embodiment
Embodiment 1:
In the present embodiment, raw material is nano titanium oxide and nanometer carbon black, by technical process Fig. 1 following processing step is arranged:
(1) batching
The mol ratio of nanometer carbon black and titanium dioxide is 2.5;
(2) batch mixing
With the confected materials wet-milling batch mixing that rolls, ball material weight ratio is 5: 1, and medium is a dehydrated alcohol, and drum's speed of rotation is 60 rev/mins, and the ball milling time is 8h;
(3) drying
Material after the wet-milling is 70 ℃ of oven dry, and the time is 24h;
(4) charging
The mixed raw material of weighing 100g is put into the carbon tube furnace plumbago crucible and is compressed;
(5) pyrocarbon nitrogenize
With being extracted into vacuum tightness in the carbon tube furnace is 1.5 * 10
-2Begin the heating with 20 ℃/min during MPa, to 400 ℃ of insulation 30min, logical nitrogen to pressure was 0.005MPa when insulation finished.The pyrocarbon nitriding temperature is 1500 ℃, and the time is 3.5h;
(6) ball milling
Pyrocarbon nitrogenize product is carried out ball milling;
(7) sieve
With the ball milling after product sieve the TiCN powder.
Embodiment 2:
In the present embodiment, raw material is nano titanium oxide and nanometer carbon black, by technical process Fig. 1 following processing step is arranged:
(1) batching
The mol ratio of nanometer carbon black and titanium dioxide is 2.7;
(2) batch mixing
With the confected materials wet-milling batch mixing that rolls, ball material weight ratio is 5: 1, and medium is a dehydrated alcohol, and drum's speed of rotation is 60 rev/mins, and the ball milling time is 8h;
(3) drying
Material after the wet-milling is 80 ℃ of oven dry in baking oven, and the time is 24h;
(4) charging
The mixed raw material of weighing 200g is put into the carbon tube furnace plumbago crucible and is compressed;
(5) pyrocarbon nitrogenize
To be full of nitrogen in the carbon tube furnace to being a bit larger tham 1 standard atmospheric pressure, through-flow more moving nitrogen and simultaneously with the 15 ℃/min heating that heats up is incubated 3h after 1450 ℃;
(6) ball milling
Pyrocarbon nitrogenize product is carried out ball milling;
(7) sieve
With the ball milling after product sieve the TiCN powder.
Claims (1)
1, a kind of pyrocarbon nitriding method for preparing of nanocrystalline TiCN ceramic ultrafine powder is characterized in that with nano-titanium oxide and nanometer carbon black be raw material, and its processing step is as follows:
(1) batching
C, Ti mol ratio are 2.2～2.8;
(2) batch mixing
To meet proportion raw material and carry out ball mill mixing, till evenly;
(3) drying
The wet-milling material is 60～90 ℃ of oven dry;
(4) charging
The combination drying material is put into the carbon tube furnace crucible and compress;
(5) pyrocarbon nitrogenize
1. closed system
Begin heating when certain vacuum is spent with being extracted in the carbon tube furnace, to 300～600 ℃ of insulation 30～60min, logical nitrogen was to certain pressure intensity when insulation finished.The pyrocarbon nitriding temperature is 1300～1600 ℃, and the time is 1～4h;
2. open system
To be full of nitrogen in the carbon tube furnace to being a bit larger tham 1 standard atmospheric pressure, the through-flow more moving nitrogen and the heating that heats up simultaneously.The pyrocarbon nitriding temperature is 1300～1600 ℃, and the time is 1～4h;
(6) ball milling
Ball milling pyrocarbon nitrogenize product;
(7) sieve
With the ball milling after product sieve product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510021718XA CN100503509C (en) | 2005-09-23 | 2005-09-23 | High-temperature carbonitriding preparation method of nano crystal titanium carbonitride ceramic ultrafine powder |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510021718XA CN100503509C (en) | 2005-09-23 | 2005-09-23 | High-temperature carbonitriding preparation method of nano crystal titanium carbonitride ceramic ultrafine powder |
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| Publication Number | Publication Date |
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| CN1935742A true CN1935742A (en) | 2007-03-28 |
| CN100503509C CN100503509C (en) | 2009-06-24 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021461A (en) * | 2010-11-08 | 2011-04-20 | 株洲德丰硬质合金有限公司 | Method for manufacturing titanium carbonitride hard alloy material |
| CN102718214A (en) * | 2011-03-29 | 2012-10-10 | 厦门钨业股份有限公司 | A high-uniformity titanium carbonitride Ti (C, N) powder preparation method |
| CN102976759A (en) * | 2012-12-17 | 2013-03-20 | 长沙伟徽高科技新材料股份有限公司 | Method for preparing titanium carbonitride by use of vacuum reduction nitriding method |
| CN107433333A (en) * | 2017-07-03 | 2017-12-05 | 厦门理工学院 | A kind of solid-solution type (Ti, Mo, Ta, Me) (C, N) nanometer powder and preparation method thereof |
| CN110980667A (en) * | 2019-12-25 | 2020-04-10 | 株洲鸿达实业有限公司 | Micro-nano TiCN powder and preparation method and application thereof |
-
2005
- 2005-09-23 CN CNB200510021718XA patent/CN100503509C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021461A (en) * | 2010-11-08 | 2011-04-20 | 株洲德丰硬质合金有限公司 | Method for manufacturing titanium carbonitride hard alloy material |
| CN102021461B (en) * | 2010-11-08 | 2013-03-13 | 株洲德丰硬质合金有限公司 | Method for manufacturing titanium carbonitride hard alloy material |
| CN102718214A (en) * | 2011-03-29 | 2012-10-10 | 厦门钨业股份有限公司 | A high-uniformity titanium carbonitride Ti (C, N) powder preparation method |
| CN102976759A (en) * | 2012-12-17 | 2013-03-20 | 长沙伟徽高科技新材料股份有限公司 | Method for preparing titanium carbonitride by use of vacuum reduction nitriding method |
| CN107433333A (en) * | 2017-07-03 | 2017-12-05 | 厦门理工学院 | A kind of solid-solution type (Ti, Mo, Ta, Me) (C, N) nanometer powder and preparation method thereof |
| CN107433333B (en) * | 2017-07-03 | 2019-08-02 | 厦门理工学院 | A kind of solid-solution type (Ti, Mo, Ta, Me) (C, N) nanometer powder and preparation method thereof |
| CN110980667A (en) * | 2019-12-25 | 2020-04-10 | 株洲鸿达实业有限公司 | Micro-nano TiCN powder and preparation method and application thereof |
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| CN100503509C (en) | 2009-06-24 |
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