CN101863663A - Preparation of Submicron Titanium Carbide Polycrystalline Powder by Combustion Method - Google Patents
Preparation of Submicron Titanium Carbide Polycrystalline Powder by Combustion Method Download PDFInfo
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000000843 powder Substances 0.000 title claims abstract description 50
- 238000009841 combustion method Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 57
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002485 combustion reaction Methods 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 21
- 239000012265 solid product Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 11
- 229930006000 Sucrose Natural products 0.000 claims description 11
- 239000005720 sucrose Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 22
- 239000002245 particle Substances 0.000 abstract description 16
- 238000002156 mixing Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 23
- 238000006722 reduction reaction Methods 0.000 description 11
- 239000010936 titanium Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000007405 data analysis Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000003936 Plumbago auriculata Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
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- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910000753 refractory alloy Inorganic materials 0.000 description 1
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- 230000035939 shock Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- 238000001149 thermolysis Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及一种燃烧法制备亚微米级碳化钛多晶粉末，将只含碳氢氧的有机碳源、二氧化钛和金属镁粉混合，混合物料经过燃烧反应，所得固体产物再经酸洗、水洗、分离和干燥，即可得到亚微米级碳化钛多晶粉末。本发明的有益效果在于：(1)可以调控整个反应体系的热效应，一方面可以节能，另一方面可以控制自蔓延反应的温度，抑制TiC产物晶粒生长；(2)能够很好地抑制TiC晶粒烧结和结构团聚，而且可以用来隔离产物粒子，有利于形成细小均匀的TiC晶粒，产率高，耗能少，成本低，适合规模化工业生产；(3)碳化钛收率大于90％，碳化钛多晶颗粒直径为50～250nm，平均约为150nm。The invention relates to a combustion method for preparing submicron titanium carbide polycrystalline powder, mixing an organic carbon source containing only carbon, hydrogen and oxygen, titanium dioxide and metal magnesium powder, and the mixed material undergoes a combustion reaction, and the obtained solid product is then acid-washed and water-washed , separation and drying to obtain submicron titanium carbide polycrystalline powder. The beneficial effects of the present invention are: (1) the thermal effect of the entire reaction system can be regulated, on the one hand, energy can be saved, on the other hand, the temperature of the self-propagating reaction can be controlled, and the grain growth of the TiC product can be suppressed; (2) the TiC can be well suppressed Grain sintering and structural reunion, and can be used to isolate product particles, which is conducive to the formation of fine and uniform TiC grains, high yield, low energy consumption, low cost, and suitable for large-scale industrial production; (3) The yield of titanium carbide is greater than 90%, the diameter of titanium carbide polycrystalline particles is 50-250nm, with an average of about 150nm.
Description
Technical field
The present invention relates to field of ceramic material preparation, concrete relate to a kind of combustion method for preparing submicron grade titanium carbide polycrystal powder.
Background technology
Titanium carbide (TiC) belongs to sodium-chlor type isometric system, its chemistry and physical properties are stable, have high-melting-point, high rigidity, high strength, high-wearing feature and characteristics such as erosion resistance, high-heat resistance shock resistant, also has good electroconductibility, and since TiC have lower reaction free energy of formation, thereby be a kind of very potential be the hard phase [1] of the particles reiforced metal-base composition of target with wear-resistant grinding abrasion.The mill capacity of TiC can compare favourably with man-made diamond, its high-wearing feature, low wear rate and have higher intermiscibility with other carbide, make its application in high-abrasive material particularly outstanding, and in each field, be widely used as new high-abrasive material.TiC is mainly used to make sintering metal, refractory alloy and Wimet, and the composite diphase material for preparing with it has a wide range of applications in fields such as mechanical workout, metallurgical mineral products, space industry, fusion reactors.
The method for preparing at present the TiC powder mainly contains carbothermic method, self-propagating high-temperature synthesis method, chemical Vapor deposition process, sol-gel method, microwave process for synthesizing or the like.Li Ciying etc. [2] are raw material with titanium slag, carbon black, the batching of certain proportioning is put plumbago crucible in vertical pyrocarbon pipe furnace and good seal, carry out carbonization test, made the TiC powder, long reaction time, owing to be subjected to the influence of diffusion gradient to make the synthetic powder usually pure inadequately, contain unreacted charcoal and TiO in the product in the reaction
2Li Maoxiang [3] is a raw material with tetrabutyl titanate and resol, and ethylene glycol monomethyl ether is a solvent, and glacial acetic acid is a stablizer, prepares Gel Precursor under the catalysis of nitric acid, again the presoma that makes is obtained TiC through the pyrocarbon thermal reduction in the ar gas environment of circulation.Liu Yang etc. [4] are raw material with nano titanium oxide and carbon black, with microwave heating synthesis of nano TiC powder.R.Koc etc. [5] are with nano-TiO
2Powder is a raw material, by the thermolysis propylene simple substance inorganic carbon is deposited on TiO
2Increase the contact area of reactant on the powder, thereby the carbothermic reduction reaction temperature is reduced to 1300 ℃, synthesized submicron order high-purity Ti C powder.Li Jingfeng etc. [6] utilize the self-propagating high-temperature synthesis method to prepare the TiC powder in metallic titanium powder-Graphite Powder 99 system, and the self-propagating high-temperature speed of reaction is exceedingly fast, remaining Ti and C simple substance among the TiC.Zhu Xinkun etc. [7] adopt ball milled, are that 1: 1 batching is carried out ball milling by Ti powder and carbon dust mol ratio, with purity greater than 99.9% Ar as shielding gas, made nanocrystal TiC, degree of purity of production is not high yet.After Liu Junbo [8] mixed sphere of powder mill, oven dry with titanium valve and sucrose, carbonization in ebullient oil, generation is deoiled, lighted to oven dry from the synthetic TiC of climing combustion reaction etc. again.
Reference
[1]I.N.Mihailescu，M.L.DeGiorge，C.H.Boulmer-Leborgne，S.Udrea.Direct?carbidesynthesis?by?multipulse?exciter?laser?treatment?of?Ti?sample?in?ambient?CH
4?gas?atsuperatmospheric?Pressure[J]J.APPL.Phys，1994，75：5286-5294
[2] Li Ciying, Li Yawei, Gao Yunming, etc. the research [J] that titanium carbonitride is got in the titanium slag proposition. steel vanadium titanium, 2006,27 (3): 5-9.
[3] Li Maoxiang, Su Guojun. so-gel and carbothermic method prepare the research [J] of titanium carbide. inorganic chemicals industry, 2007,39 (7): 36-38.
[4] Liu Yang, Ceng Keling, Hu Xiaoli, etc. the dynamics research [J] of microwave synthetizing nano titanium carbide powder. Chinese pottery industry, 2003,10 (5): 6-8.
[5]R.Koc，Chang?Meng?and?G.A.Swift.Sintering?properties?of?submieron?TiC?powders?fromcarbon?coated?titania?precursor[J].J.Mater.Sci，2000，35(12)：3131-3141.
[6] Li Jingfeng, Zhang Zhao, Zheng Ziqiao, etc. burning synthetic (TiC, W) forming process of C [J]. rare metal and Wimet, 2001,147:1-6.
[7] Zhu Xinkun, Cheng Baochang, Zhang Xiuqing, etc. solid state reaction synthesizes TiC[J]. powder metallurgy technology, 2001,19 (6): 335-338
[8] Liu Junbo. a kind of preparation method of titanium carbide micro powder [P], Chinese invention patent application 200910014446.9, publication number CN101486462. day for announcing 2009.07.22
[9] Xiang Lunqiang. the mensuration of total carbon, uncombined carbon [J] titanium industrial progress in the carbonized titanium powder, 2004,21 (1): 45-47.
Summary of the invention
Problem to be solved by this invention is to propose a kind of combustion method for preparing submicron grade titanium carbide polycrystal powder at above-mentioned prior art, and its preparation technology is simple, energy consumption is low, is applicable to industrial production.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: combustion method for preparing submicron grade titanium carbide polycrystal powder, it is characterized in that organic carbon source, titanium dioxide and the metal magnesium powder of a carbon containing hydrogen-oxygen are mixed, organic carbon source, the metal magnesium powder mole proportioning of titanium dioxide, a carbon containing hydrogen-oxygen are TiO
2: C: Mg=1: (0.5～6): (0.5～5), wherein C is corresponding to carbonaceous mole number in the organic carbon source of carbon containing hydrogen-oxygen, mixture is through combustion reactions, and the gained solid product can obtain submicron grade titanium carbide polycrystal powder again through pickling, washing, separation and drying.
Press such scheme, the organic carbon source of described titanium dioxide, a carbon containing hydrogen-oxygen and metal magnesium powder mole proportion optimization scope are TiO
2: C: Mg=1: (1～4): (0.75～3), wherein C is corresponding to carbonaceous mole number in the organic carbon source of carbon containing hydrogen-oxygen.
Press such scheme, the organic carbon source of described carbon containing hydrogen-oxygen is sucrose, glucose, starch or citric acid.
Press such scheme, organic carbon source the best of described carbon containing hydrogen-oxygen is a sucrose.
Press such scheme, the organic carbon source of described carbon containing hydrogen-oxygen, titanium dioxide and metal magnesium powder are 100～300 order pressed powders.
Press such scheme, described combustion reactions is with mixture direct heating to 700～850 ℃ and the combustion reactions that causes.
Press such scheme, described combustion reactions is that mixture is passed through briquetting, and making the gained block reach density is 1.00～1.15g/cm
3, light block and the reaction of the self-propagating combustion that causes with the hot tungsten filament of energising at normal temperatures then.
Press such scheme, described pickling, washing, separation and dry concrete steps are: with the 100g solid product, 35～38wt% the concentrated hydrochloric acid that adds 450～800ml stirred 12～24 hours down at 50～80 ℃, suction filtration then, be washed with distilled water to neutrality, filter cake was in 80 ℃ of following vacuum-dryings 12～24 hours.
Press such scheme, described submicron grade titanium carbide polycrystal powder diameter is 50～250nm.
Among the present invention, the organic carbon source of a metal magnesium powder and a carbon containing hydrogen-oxygen is (with sucrose (C
12H
22O
11) be example), TiO
2The reaction process of magnesiothermic reduction reaction synthesizing submicron TiC powder be exothermic process, as the formula (1).Organic carbon source raw material and TiO
2The synthetic TiC of carbothermic reduction reaction be endothermic process, as the formula (2).The above-mentioned two reactions net reaction comprehensive by generating equivalent TiC be as the formula (3):
1/12C
12H
22O
11+TiO
2+2Mg＝TiC+2MgO+11/12H
2O↑ (1)
1/6C
12H
22O
11+TiO
2＝TiC+11/6H
2O↑+CO↑ (2)
1/4C
12H
22O
11+2TiO
2+2Mg＝2TiC+2MgO+11/12H
2O↑+CO↑ (3)
To above-mentioned reaction formula (1)～(3) calculate the mark condition under reaction heat be respectively Δ
rH
θ 1=-525.6kJ/mol, Δ
rH
θ 2=291.7kJ/mol, Δ
rH
θ=-116.9kJ/mol. this shows that a large amount of heat is emitted in magnesiothermic reduction reaction (formula (1)), and carbothermic reduction reaction (formula (2)) is thermo-negative reaction, and two reactions then are thermopositive reaction by generating the comprehensive net reaction (formula (3)) of equivalent TiC.
Generating TiC according to reaction is benchmark, supposes that carbothermic reduction thermo-negative reaction percentage is x% in the whole reaction system, and then magnesiothermic reduction thermopositive reaction percentage is (100-x) %, in the whole reaction system heat effect is so:
Δ
rH
θ＝(100-x)％Δ
rH
θ 1+x％Δ
rH
θ 2 (4)
By equation (4) as seen, calculate when x=64.31 Δ in theory
rH
θ=0, promptly under adiabatic condition, carbothermic reduction thermo-negative reaction mark is 64.31% o'clock, whole combustion reactions meeting reaches thermal equilibrium, promptly do not having under the external energy condition, the heat that thermopositive reaction (formula (1)) liberated heat and thermo-negative reaction (formula (2)) absorb equates that the exothermic heat of reaction and the heat absorption of above-mentioned pair of reaction system reach balance.
Can regulate the combustion reactions heat effect by control proportioning raw materials example, even to reach energy-conservation, regulate and control temperature of reaction and more to help the TiC grain refining.
Accompanying drawing 1 provides between different thermo-negative reaction percentage and the total reaction system heat effect and concerns.By accompanying drawing 1 as can be known, under adiabatic condition, the thermo-negative reaction percentage was less than 64.31% o'clock, and the total reaction system is the heat release system, i.e. Δ H＜0.
Subordinate list 1 is a combustion method synthesizing submicron titanium carbide product feature table look-up.Be to be example for the organic carbon source raw material with sucrose.The data such as severe degree, TiC product purity of thermo-negative reaction percentage and real reaction have been provided.The thermo-negative reaction percentage is the 0%, the 30%th, the result that self-propagating reaction obtains behind the mixing raw material briquetting, and the thermo-negative reaction percentage is a rate the 0%, 10%, 20%, 30%, the 40%th, the result that the raw material powder combustion reactions obtains.
Table 1. combustion method synthesizing submicron titanium carbide product feature table look-up
Fig. 2 is the XRD spectra of submicron order TiC powder, adopt XD-5A type x-ray powder diffraction instrument (30kV, 20mA go into=1.5406
), 2 θ are 10-80 ° of scope).The X-ray diffraction peak of product is consistent with TiC standard diffraction card PDF#89-3828.With thermo-negative reaction percentage in scheming is 0%, and the XRD figure spectrum that the mixing raw material dust-firing reacts resultant TiC sample is 2.4820,2.1494,1.5222,1.2972,1.2433 in the d value
There is diffraction peak at the place, correspond respectively to (111), (200), (220), (311), (222) crystal face of cube TiC, by each crystal face d value of XRD, calculating the product lattice constant is a=0.4304nm, with standard card a=0.4317nm basically identical, show that product is a cube TiC.With mixing raw material powder self-propagating combustion reaction pair ratio, the obvious broadening of TiC diffraction peak that mixing raw material briquetting self-propagating reaction obtains, and in the reaction of mixing raw material powder self-propagating combustion, increase with the thermo-negative reaction percentage, the phenomenon of obvious broadening also appears in the TiC diffraction peak, and this explanation mixing raw material briquetting self-propagating reaction and the thermo-negative reaction large percentage synthetic TiC of time institute sample particle are littler.
Beneficial effect of the present invention is: (1) adopts magnesiothermic reduction thermopositive reaction and carbothermic reduction thermo-negative reaction to carry out suitable proportioning, can regulate and control the heat effect of whole reaction system, on the one hand can be energy-conservation, can control the temperature of self-propagating reaction on the other hand, suppress the grain growing of TiC product; (2) can discharge a large amount of water vapour and CO gas in the reaction process, can take away heat, reduce the combustion system temperature, can suppress the grained sintered and structure of TiC well and reunite, and can be used for the isolating product particle, help forming tiny and uniform TiC crystal grain, the productive rate height, power consumption is few, and cost is low, is fit to large-scale industrial production; (3) titanium carbide yield of the present invention contains uncombined carbon less than 2.75wt% greater than 90% in the described titanium carbide, contains Mg, O and is not higher than 0.5wt%, and the titanium carbide polycrystal particle diameter is 50～250nm, on average is about 150nm.
Description of drawings
Fig. 1 concerns between reaction system heat effect and the thermo-negative reaction percentage;
Fig. 2 is the XRD spectra of all submicron grade titanium carbide powder sample correspondences in the table 1;
Fig. 3 is a solid product pictorial diagram behind embodiment 1 and embodiment 2 mixing raw material dust-firings and the briquetting self-propagating reaction; Wherein Fig. 3 (a) is a solid product pictorial diagram behind the embodiment 1 mixing raw material dust-firing; Fig. 3 (b) is a solid product pictorial diagram behind the embodiment 2 mixing raw material powder compact self-propagating reactions;
Fig. 4 is that embodiment 1 thermo-negative reaction percentage is 0% o'clock TiC sample SEM photo and EDS spectrum;
Fig. 5 is that embodiment 2 thermo-negative reaction percentage are 30% o'clock TiC sample SEM photo.
Embodiment
Further introduce the present invention below by embodiment, but embodiment can not be construed as limiting the invention.Each cited in technical solution of the present invention raw material can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of processing parameter of the present invention (as temperature, time and rotating speed etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Embodiment 1
By the thermo-negative reaction percentage is 0%, gets 33.35 gram titanium dioxide, 11.91 gram sucrose (C
12H
22O
11), 20.30 gram magnesium powder, mol ratio is TiO
2: C: Mg=1: 1: 2, wherein C was carbonaceous amount in the organic carbon source raw material, and sucrose, titanium dioxide and magnesium powder are 100～300 order pressed powders.Mixing and stirring, direct heating to 800 ℃ generation combustion reactions cools to room temperature with the furnace, and the product after the burning is shown in accompanying drawing 3 (a).Solid product after the burning is with excessive 35wt% salt acid soak (100g solid product add 650ml hydrochloric acid), in 80 ℃ of following heated and stirred 14 hours, again through suction filtration with repeatedly be washed to neutrality, filter cake was in 80 ℃ of vacuum-dryings 12 hours, obtaining black TiC powder 22.88 gram, is that to calculate its yield be 91.53% to benchmark with titanium dioxide.
Accompanying drawing 4 is electron scanning micrograph (SEM) and corresponding energy spectrum analysis figure (EDS) of resultant TiC sample, adopt the S-4800 of Hitachi, Ltd type sem observation granule-morphology and yardstick, characterize elementary composition and content with Horiba 250 model energy spectrometer.Scale length is represented 0.5 μ m in the SEM photo.By photo as seen, the TiC particle fine particle that is obtained is less than 250nm, and the particle mean size is about 150nm.But the TiC sample has tangible sintering and agglomeration, and may be that temperature of reaction is too high causes, because the thermo-negative reaction rate is 0%.The massfraction of product titaniferous, carbon is respectively 78.40%, 21.01% as can be seen from the EDS spectrogram, contains oxygen and is not higher than 0.16%, contains magnesium and is not higher than 0.43%.Can draw atomic ratio C/Ti=1.07 from figure, cause that with theoretical value very little reasons of error to be arranged mainly may be to contain small-amount free carbon in the sample.Adopt chemical separation and high frequency-infrared absorption carbon and sulfur analytical instrument to combine and measure the method [9] of the uncombined carbon in the TiC powder, obtain containing in the sample uncombined carbon 1.25%.
Embodiment 2
According to the thermo-negative reaction percentage is 30%, gets 33.35 gram titanium dioxide, 19.06 gram sucrose (C
12H
22O
11), 14.21 gram magnesium powder, mol ratio is TiO
2: C: Mg=1: 1.6: 1.4, wherein C was carbonaceous amount in the organic carbon source raw material, and sucrose, titanium dioxide and magnesium powder are 100～300 order pressed powders.Mixing and stirring, then with the mixture briquetting, it is 1.08g/cm that block reaches density
3, light block and the reaction of the self-propagating combustion that causes with the hot tungsten filament of energising at normal temperatures again, the solid product after the burning is shown in accompanying drawing 3 (b).Solid product is with excessive 35wt.% salt acid soak (100g solid product add 600ml hydrochloric acid), in 60 ℃ of following heated and stirred 20 hours, again through suction filtration with repeatedly be washed to neutrality, filter cake was in 80 ℃ of vacuum-dryings 12 hours, obtain black TiC powder 23.76 grams, with titanium dioxide is that benchmark calculates scanning electronic microscope (SEM) the observation pattern that its yield is a 95.04%. usefulness JSM-5510LV model, and accompanying drawing 5 is SEM photos of resultant TiC sample, and scale length is represented 1 μ m in the photo.The TiC uniform crystal particles, particle diameter 20～100nm, average out to 50nm does not have tangible sintering and aggregation phenomenon.EDS analyzes the massfraction that obtains titaniferous, carbon and is respectively 77.50%, 21.91%, contains oxygen 0.23%, contains magnesium 0.36%, and atomic ratio C/Ti=1.12 records uncombined carbon 1.64%.
Embodiment 3
Get 66.85 gram titanium dioxide, 35.62 gram starch (C
6H
12O
6), 34.63 gram magnesium powder, its mol ratio is TiO
2: C: Mg=1: 1.5: 1.7, wherein C was carbonaceous amount in the organic carbon source raw material, and titanium dioxide, starch and magnesium powder are 100～300 order pressed powders.Mixing and stirring, direct heating to 800 ℃ generation combustion reactions cools to room temperature with the furnace.Product product after the burning is with excessive 35wt% salt acid soak (100g solid product add 700ml hydrochloric acid), in 70 ℃ of following heated and stirred 18 hours, again through suction filtration with repeatedly be washed to neutrality, filter cake was in 80 ℃ of vacuum-dryings 12 hours, obtaining black titanium carbide powder 45.52 gram, is that to calculate its yield be 91.04% to benchmark with titanium dioxide.Product is analyzed through XRD, SEM, EDS, proves that product is the very high submicron grade titanium carbide polycrystal powder of purity, and particle is less than 250nm, and the particle mean size is 150nm, and particle is thin and even.From the data analysis that EDS provides, the massfraction of product titaniferous, carbon is respectively 77.21%, 22.21%, contains oxygen 0.37%, contains magnesium 0.22%, and atomic ratio C/Ti=1.14 records uncombined carbon 1.75%.
Embodiment 4
Get 50.10 gram titanium dioxide, 22.08 gram citric acid (C
6H
8O
7), 42.67 gram magnesium powder, mol ratio is TiO
2: C: Mg=1: 2.2: 2.8, wherein C was carbonaceous amount in the organic carbon source raw material, and titanium dioxide, citric acid and magnesium powder are 100～300 order pressed powders.Mixing and stirring, then with the mixture briquetting, it is 1.15g/cm that block reaches density
3, light block and the reaction of the self-propagating combustion that causes with the hot tungsten filament of energising at normal temperatures again.Solid product after the burning is with excessive 35wt% salt acid soak (100g solid product add 800ml hydrochloric acid), in 80 ℃ of following heated and stirred 12 hours, again through suction filtration with repeatedly be washed to neutrality, filter cake was in 80 ℃ of vacuum-dryings 12 hours, obtaining black titanium carbide powder 34.26 gram, is that to calculate its yield be 91.36% to benchmark with titanium dioxide.Product is analyzed through XRD, SEM, EDS, proves that product is the very high submicron grade titanium carbide polycrystal powder of purity, and particle is less than 250nm, and the particle mean size is 150nm, and particle is thin and even.From the data analysis that EDS provides, the massfraction of product titaniferous, carbon is respectively 77.99%, 21.61%, contains oxygen 0.16%, contains magnesium 0.24%, and atomic ratio C/Ti=1.10 gets uncombined carbon 1.43%.
Claims (9)
1. combustion method for preparing submicron grade titanium carbide polycrystal powder is characterized in that an organic carbon source of carbon containing hydrogen-oxygen, titanium dioxide and metal magnesium powder are mixed, and organic carbon source, the metal magnesium powder mole proportioning of titanium dioxide, a carbon containing hydrogen-oxygen are TiO
2: C: Mg=1 (0.5～6): (0.5～5), wherein C is corresponding to carbonaceous mole number in the organic carbon source of carbon containing hydrogen-oxygen, mixture is through combustion reactions, and the gained solid product can obtain submicron grade titanium carbide polycrystal powder again through pickling, washing, separation and drying.
2. by the described combustion method for preparing submicron grade titanium carbide polycrystal powder of claim 1, it is characterized in that the organic carbon source of described titanium dioxide, a carbon containing hydrogen-oxygen and metal magnesium powder mole ratio range are TiO
2: C: Mg=1: (1～4): (0.75～3), wherein C is corresponding to carbonaceous mole number in the organic carbon source of carbon containing hydrogen-oxygen.
3. by the described combustion method for preparing submicron grade titanium carbide polycrystal powder of claim 1, the organic carbon source that it is characterized in that described carbon containing hydrogen-oxygen is sucrose, glucose, starch or citric acid.
4. by the described combustion method for preparing submicron grade titanium carbide polycrystal powder of claim 3, the organic carbon source that it is characterized in that described carbon containing hydrogen-oxygen is a sucrose.
5. by claim 1 or 3 described combustion method for preparing submicron grade titanium carbide polycrystal powder, it is characterized in that organic carbon source, titanium dioxide and the metal magnesium powder of described carbon containing hydrogen-oxygen is 100～300 order pressed powders.
6. by the described combustion method for preparing submicron grade titanium carbide polycrystal powder of claim 1, it is characterized in that described combustion reactions is the combustion reactions that mixture direct heating to 700～850 ℃ are caused.
7. by the described combustion method for preparing submicron grade titanium carbide polycrystal powder of claim 1, it is characterized in that described combustion reactions is that mixture is passed through briquetting, making the gained block reach density is 1.00～1.15g/cm
3, light block and the reaction of the self-propagating combustion that causes with the hot tungsten filament of energising at normal temperatures then.
8. by the described combustion method for preparing submicron grade titanium carbide polycrystal powder of claim 1, it is characterized in that described pickling, washing, separation and dry concrete steps are: with the 100g solid product, 35～38wt% the concentrated hydrochloric acid that adds 450～800ml stirred 12～24 hours down at 50～80 ℃, suction filtration then, be washed with distilled water to neutrality, filter cake was in 80 ℃ of following vacuum-dryings 12～24 hours.
9. by the described combustion method for preparing submicron grade titanium carbide polycrystal powder of claim 1, it is characterized in that described submicron grade titanium carbide polycrystal powder diameter is 50～250nm.
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| CN103387216A (en) * | 2013-07-28 | 2013-11-13 | 桂林理工大学 | The method for preparing TiCN powder with TiOSO4 and starch as titanium source and carbon source respectively |
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