CN103449435A - Method for producing micro-nanoscale carbide ceramics by carbon coating - Google Patents
Method for producing micro-nanoscale carbide ceramics by carbon coating Download PDFInfo
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- CN103449435A CN103449435A CN2013103789471A CN201310378947A CN103449435A CN 103449435 A CN103449435 A CN 103449435A CN 2013103789471 A CN2013103789471 A CN 2013103789471A CN 201310378947 A CN201310378947 A CN 201310378947A CN 103449435 A CN103449435 A CN 103449435A
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Abstract
The invention discloses a method for producing micro-nanoscale carbide ceramics by carbon coating, relates to a method for generating the carbide ceramics by carbon thermal reduction reaction and aims at solving the problems of high reaction temperature and low production efficiency of the existing production method of the carbide ceramics. The production method of the carbide ceramics comprises the following steps: (1) fully mixing oxide raw materials with resin, performing ball milling in an alcohol type solvent, drying, and then pressing and curing to form a mixture; (2) placing the mixture into a carbonization furnace, performing heating reaction, and carbonizing and decomposing the resin to get carbon-coated oxide powder; (3) performing solid phase carbonization reaction under the protection of inert gas; (4) performing oxidation treatment on carbide powder obtained in the step (3); (5) performing acid washing treatment on the carbide powder obtained in the step (4), and then drying to get the micro-nanoscale carbide ceramics. The method for producing the micro-nanoscale carbide ceramics, disclosed by the invention, has the advantages of high reaction efficiency and lower reaction temperature, and the scale of the obtained carbide powder is uniform and controllable.
Description
Technical field
The present invention relates to a kind of method that carbothermic reduction reaction generates carbide ceramics.
Background technology
Carbide ceramics series, as titanium carbide, wolfram varbide, the characteristics such as the materials such as norbide have Stability Analysis of Structures, fusing point is high, hardness is high, chemical stability is good, be mainly used to manufacture ceramic-metal composite, refractory alloy and Wimet.It is good that common carbide ceramics has wear resistance, and heat-conductive characteristic is good, and thermal shock resistance is high, and chemically stable is good, be not hydrolyzed, high-temperature oxidation resistance good and at normal temperatures not with the characteristics such as acid reacts, be widely used as cutting tool, rubbing paste, grinding tool, the reinforcement of antifatigue material and matrix material.As added the TiC of 6%-30% in the WC-Co series hard metal, form TiC-WC sosoloid with WC, can obviously put forward the performances such as heavy alloyed red heat, wear resistance, oxidation-resistance erosion resistance, than WC-Co Wimet, be more suitable in working steel products.Can also mutually form binary, ternary, quaternary compound Solid solution between carbide ceramics, be applied to the fields such as spray material, welding material, hard thin film material, military aviation material, Wimet and gold pottery reason.
The production technology ubiquity of carbide ceramics is utilized the carbothermic reduction solid state reaction, makes this oxide powder and carbon black, the full and uniform mixing in end of the carbon raw material powders such as bone carbon, and then at high temperature reaction: XO+2C->XC+CO as follows occurs in (more than 1100 ℃); Wherein XO is corresponding metal oxide, and XC is this metallic carbide pottery.
Existing carbide ceramics powder adopts the solid carbon thermal reduction reaction to prepare, and wherein requires metal oxide repeatedly to mix with the carbon raw material.Industrial production carbide powder main method is at present: under the protection of inert gas atmospheric condition; obtain carbide powder with carbon black reduced oxide powder in tube furnace or resistance furnace; this method generally needs the temperature of reaction of 1100 ℃ to 2000 ℃ and very long reaction times (10～24h), and can produce a certain amount of waste gas CO.Therefore this method is because different solid-phase reactant powder Contact areas are limited, and reaction efficiency is low, is prone to that bulk is reunited, particle shape is inhomogeneous, causes in product that unreacted raw material is arranged.
Summary of the invention
The objective of the invention is to solve the problem that the production method temperature of reaction is high and production efficiency is low of existing carbide ceramics, and provide carbon to coat the method for producing the micro nanometer level carbide pottery.
Carbon of the present invention coats the method for producing the micro nanometer level carbide pottery and follows these steps to realize:
One, oxide raw material and mixed with resin is even, be placed in alcoholic solvent ball milling 2～3h, then put into rotatory evaporator with 65～75 ℃ of oven dry, press curing obtains mixture;
Two, mixture step 1 obtained is placed in charring furnace, is heated to 600～700 ℃ with 10～50 ℃ of heat-up rates hourly, and is incubated 1～2h, obtains the oxide powder of carbon coated;
Three, the oxide powder of carbon coated is transferred in the operation stove, be heated to 1100～2000 ℃ under protection of inert gas, be incubated 4～8h and carry out the solid phase carburizing reagent, obtain carbide powder;
Four, carbide powder step 3 obtained carries out oxide treatment and removes unreacted carbon raw material, obtains the carbide powder after oxide treatment;
Five, the carbide powder after oxide treatment step 4 obtained carries out cleanup acid treatment and removes oxide compound, after the oven dry classification, obtains the micro nanometer level carbide pottery;
Wherein the described oxide raw material of step 1 is titanium oxide, Tungsten oxide 99.999, aluminum oxide, tantalum oxide or boron oxide; Described resin is furane resin, resol or epoxy resin.
It is the improvement to general carbothermic reduction reaction that carbon of the present invention coats the method for producing the micro nanometer level carbide pottery, by the resin-coated process, carbon is coated on around the metal oxide powder of question response, assurance carbon contacts fully with metal oxide surface, finally carry out the high temperature cabonization reaction, the temperature that temperature of reaction generates higher than RESEARCH OF PYROCARBON, finally obtain the micro nanometer level carbide pottery.
The method that to sum up the micro nanometer level carbide pottery is produced in carbon coating of the present invention has the following advantages:
1, the reaction efficiency of carbon coating production micro nanometer level carbide pottery is high, the nano level carbonization titanium Production of Ceramics of take is example, 1400 ℃ its percent weight loss of thermotonus of take is 50.1%, approach theoretical weightless ratio 48.3%, reaction is only about 5 hours the rise time, lower than routine, produces required more than 10 hours;
2, oxide compound and carbon can react at 600～700 ℃, and temperature of reaction is lower;
3,, because reactant powders is evenly coated, the carbide powder yardstick that therefore reaction generates is evenly controlled, with the oxide raw material powder, has very large cognation.
The accompanying drawing explanation
Fig. 1 is low power scanning electron microscope (SEM) figure of the micro nanometer level carbide pottery that obtains of embodiment mono-;
Fig. 2 is high power scanning electron microscope (SEM) figure of the micro nanometer level carbide pottery that obtains of embodiment mono-.
Embodiment
Embodiment one: present embodiment carbon coats the method for producing the micro nanometer level carbide pottery and follows these steps to implement:
One, oxide raw material and mixed with resin is even, be placed in alcoholic solvent ball milling 2～3h, then put into rotatory evaporator with 65～75 ℃ of oven dry, press curing obtains mixture;
Two, mixture step 1 obtained is placed in charring furnace, is heated to 600～700 ℃ with 10～50 ℃ of heat-up rates hourly, and is incubated 1～2h, obtains the oxide powder of carbon coated;
Three, the oxide powder of carbon coated is transferred in the operation stove, be heated to 1100～2000 ℃ under protection of inert gas, be incubated 4～8h and carry out the solid phase carburizing reagent, obtain carbide powder;
Four, carbide powder step 3 obtained carries out oxide treatment and removes unreacted carbon raw material, obtains the carbide powder after oxide treatment;
Five, the carbide powder after oxide treatment step 4 obtained carries out cleanup acid treatment and removes oxide compound, after the oven dry classification, obtains the micro nanometer level carbide pottery;
Wherein the described oxide raw material of step 1 is titanium oxide, Tungsten oxide 99.999, aluminum oxide, tantalum oxide or boron oxide; Described resin is furane resin, resol or epoxy resin.
Present embodiment is produced the micro nanometer level carbide pottery obtained and is of a size of 80～100nm.
The method that present embodiment is produced the micro nanometer level carbide pottery is in order to realize high efficiency carbothermic reduction reaction, the carbon raw material is contacted fully with reactive material, generation polycondensation polymerization is decomposed in the liquid resin carbonization, form hole and be coated on the powder raw material surface, pyrolysis again after coating, make coating and be wrapped by thing solid state reaction fully occurs, reduce temperature of reaction, improved reaction efficiency.
Embodiment two: present embodiment is different from embodiment one is metal oxide in the described oxide raw material of step 1 and the ratio of resin, according to metal in metal oxide, with the mol ratio of carbon in resin, is 1:(2.5～4.5) mix.Other step and parameter are identical with embodiment one.
In present embodiment, metal oxide is titanium oxide, Tungsten oxide 99.999, aluminum oxide or tantalum oxide, when the oxide raw material nonmetal oxide such as be boron oxide, according to nonoxygen element in oxide raw material, with the mol ratio of carbon in resin, be 1:(2.5～4.5) mix.
Embodiment three: the step 1 that present embodiment is different from embodiment one or two is described is that the particle size of oxide raw material is 20～30nm.Other step and parameter are identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is that step 3 is heated to 1350～1650 ℃ under protection of inert gas.Other step and parameter are identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four is that the described oxide treatment of step 4 is that carbide powder that step 3 is obtained is put into retort furnace and calcined with the temperature of 300 ° under the environment ventilated.Other step and parameter are identical with one of embodiment one to four.
The oxide treatment of present embodiment is in order to make unreacted carbon raw material carry out abundant oxidation, the carbon monoxide of formation and metal oxide volatilization.
Embodiment six: what present embodiment was different from one of embodiment one to five is that the described pickling of step 5 is that the hydrochloric acid that functional quality concentration is 3% carries out pickling.Other step and parameter are identical with one of embodiment one to four.
Embodiment mono-: the present embodiment carbon coats the method for producing the micro nanometer level carbide pottery and follows these steps to realize:
One, the mol ratio according to carbon in titanium metal and furane resin in the oxide raw material nano titanium oxide is that 1:3 is even by oxide raw material and mixed with resin, be placed in methanol solvate ball milling 2h, then put into rotatory evaporator with 70 ℃ of oven dry, press curing obtains mixture;
Two, mixture step 1 obtained is placed in charring furnace, with 25 ℃ of heat-up rates hourly, is heated to 700 ℃, and insulation 2h, obtains the oxide powder of carbon coated;
Three, the oxide powder of carbon coated is transferred in the operation stove, be heated to 1400 ℃ under protection of inert gas, insulation 5h carries out the solid phase carburizing reagent, obtains carbide powder;
Four, carbide powder step 3 obtained carries out oxide treatment and removes unreacted carbon raw material, obtains the carbide powder after oxide treatment;
Five, the carbide powder after oxide treatment step 4 obtained carries out cleanup acid treatment and removes oxide compound, after the oven dry classification, obtains the micro nanometer level carbide pottery.
The present embodiment oxide raw material used adopts the P-25 type TiO of Degussa company
2, this type TiO
2average particle size particle size be 20 nanometers, the specific surface value that BET measures is 64m
2g
-1, mostly be the sharp titanium phase that is easy to reaction.
The present embodiment is according to TiO
2gu ()+3C(is solid) → TiC(is solid)+2CO(gas) chemical formula reacted, weight minimizing before and after carbothermic reduction reaction compares, discovery approaches 50.1% with its percent weight loss of thermotonus of 1400 ℃, approach very much the theoretical value 48.3% of carbonizing reduction reaction, thereby illustrate that reaction efficiency of the present invention is high, react completely.
Embodiment bis-: the present embodiment carbon coats the method for producing the micro nanometer level carbide pottery and follows these steps to realize:
One, according to tungsten metal in oxide raw material oxidation tungsten powder and the mol ratio of carbon in epoxy resin E44, be that 1:4 mixes the 1380g Tungsten oxide 99.999 with 450g epoxy resin E44, be placed in methanol solvate ball milling 3h, then put into rotatory evaporator with 70 ℃ of oven dry, press curing obtains mixture;
Two, mixture step 1 obtained is placed in charring furnace, with 25 ℃ of heat-up rates hourly, is heated to 700 ℃, and insulation 2h, obtains the oxide powder of carbon coated;
Three, the oxide powder of carbon coated is transferred in tube furnace, be heated to 1500 ℃ under protection of inert gas, insulation 8h carries out the solid phase carburizing reagent, obtains carbide powder;
Four, carbide powder step 3 obtained carries out oxide treatment and removes unreacted carbon raw material, obtains the carbide powder after oxide treatment;
Five, the carbide powder after oxide treatment step 4 obtained carries out cleanup acid treatment and removes oxide compound, after the oven dry classification, obtains the micro nanometer level carbide pottery.
The present embodiment is according to WO
3gu ()+4C(is solid) → WC(is solid)+3CO(gas) chemical formula reacted, due to the existence of oxygen element in epoxy resin E44, a small amount of resin does not resolve into carbon simple substance fully, and with carbon monoxide (CO), the gaseous form such as methane (CH4) are escaped.Finally obtain 1136g micro nanometer level carbide pottery, calculate to obtain weightless than being 32.4%.Theoretical Calculation opinion value is 30%, demonstrates the reaction efficiency that the present invention is higher.
Claims (6)
1. carbon coats the method for producing the micro nanometer level carbide pottery, it is characterized in that carbon coats the method for producing the micro nanometer level carbide pottery and follows these steps to realize:
One, oxide raw material and mixed with resin is even, be placed in alcoholic solvent ball milling 2～3h, then put into rotatory evaporator with 65～75 ℃ of oven dry, press curing obtains mixture;
Two, mixture step 1 obtained is placed in charring furnace, is heated to 600～700 ℃ with 10～50 ℃ of heat-up rates hourly, and is incubated 1～2h, obtains the oxide powder of carbon coated;
Three, the oxide powder of carbon coated is transferred in the operation stove, be heated to 1100～2000 ℃ under protection of inert gas, be incubated 4～8h and carry out the solid phase carburizing reagent, obtain carbide powder;
Four, carbide powder step 3 obtained carries out oxide treatment and removes unreacted carbon raw material, obtains the carbide powder after oxide treatment;
Five, the carbide powder after oxide treatment step 4 obtained carries out cleanup acid treatment and removes oxide compound, after the oven dry classification, obtains the micro nanometer level carbide pottery;
Wherein the described oxide raw material of step 1 is titanium oxide, Tungsten oxide 99.999, aluminum oxide, tantalum oxide or boron oxide; Described resin is furane resin, resol or epoxy resin.
2. carbon according to claim 1 coats the method for producing the micro nanometer level carbide pottery, it is characterized in that metal oxide in the described oxide raw material of step 1 and the ratio of resin, is 1:(2.5～4.5 according to metal in metal oxide with the mol ratio of carbon in resin) mix.
3. carbon according to claim 1 coats the method for producing the micro nanometer level carbide pottery, it is characterized in that step 1 described be that the particle size of oxide raw material is 20～30nm.
4. carbon according to claim 1 coats the method for producing the micro nanometer level carbide pottery, it is characterized in that step 3 is being heated to 1350 ℃～1650 ℃ under protection of inert gas.
5. carbon according to claim 1 coats the method for producing the micro nanometer level carbide pottery, it is characterized in that the described oxide treatment of step 4 is that carbide powder that step 3 is obtained is put into retort furnace and calcined with the temperature of 300 ° under the environment ventilated.
6. carbon according to claim 1 coats the method for producing the micro nanometer level carbide pottery, it is characterized in that the described pickling of step 5 is that the hydrochloric acid that functional quality concentration is 3% carries out pickling.
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| CN108793970A (en) * | 2018-06-12 | 2018-11-13 | 佛山市华强协兴陶瓷有限公司 | A kind of preparation method of gypsum mill ceramic grinding body |
| CN108840681A (en) * | 2018-08-16 | 2018-11-20 | 景德镇陶瓷大学 | A kind of nano boron carbide and preparation method thereof |
| CN113113602A (en) * | 2021-04-06 | 2021-07-13 | 常德速碳新能源科技有限公司 | Hard carbon negative electrode material for lithium ion secondary battery and preparation method thereof |
| CN114605170A (en) * | 2022-04-13 | 2022-06-10 | 北航（四川）西部国际创新港科技有限公司 | Infiltration agent with multilayer coating structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108793970A (en) * | 2018-06-12 | 2018-11-13 | 佛山市华强协兴陶瓷有限公司 | A kind of preparation method of gypsum mill ceramic grinding body |
| CN108840681A (en) * | 2018-08-16 | 2018-11-20 | 景德镇陶瓷大学 | A kind of nano boron carbide and preparation method thereof |
| CN108840681B (en) * | 2018-08-16 | 2022-01-14 | 景德镇陶瓷大学 | Nano boron carbide and preparation method thereof |
| CN113113602A (en) * | 2021-04-06 | 2021-07-13 | 常德速碳新能源科技有限公司 | Hard carbon negative electrode material for lithium ion secondary battery and preparation method thereof |
| CN114605170A (en) * | 2022-04-13 | 2022-06-10 | 北航（四川）西部国际创新港科技有限公司 | Infiltration agent with multilayer coating structure and preparation method thereof |
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Application publication date: 20131218 |