CN101181996A - Preparation of nano titanium carbide by liquid alkane backflow carbon packaging process - Google Patents
Preparation of nano titanium carbide by liquid alkane backflow carbon packaging process Download PDFInfo
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- CN101181996A CN101181996A CNA2007100507497A CN200710050749A CN101181996A CN 101181996 A CN101181996 A CN 101181996A CN A2007100507497 A CNA2007100507497 A CN A2007100507497A CN 200710050749 A CN200710050749 A CN 200710050749A CN 101181996 A CN101181996 A CN 101181996A
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Abstract
The invention relates to a method for preparing nano-titanium carbide powder by coated carbon of liquid alkane reflux, and uses low-cost hydrated titanium carbide as a titanium source and liquid alkane mixture (C11-C16) as a carbon source. The processing steps in sequence are preparing materials, refluxing, drying, feeding the materials, high temperature heat treatment and sampling. Precursor powder with different carbon contents can be prepared by controlling the refluxing time and temperature of raw materials; carbon content that organic carbon is transferred into inorganic carbon can be controlled by different heat treatment processes so as to prepare highly pure nano-titanium carbide powder. The nano-titanium carbide powder prepared with the method has good decentrality, and the average particle size is 20 to 40nm and the average grain size is 10 to 20nm. The method has simple technique and low cost, compared with a common carbothermic method, the invention is more energy-saving and easy for realizing scale preparation.
Description
Technical field
The invention belongs to high-temperature structural ceramics powder body material preparation field, being specifically related to organic carbon skeleton coated titanium source is the preparation method that precursor prepares the TiC ceramic nano-powder body.
Background technology
In recent years, transition metal carbides is because its important scientific value and potential huge applications prospect thereof have caused the great interest of researchist, and the different thinking of people's employing is competitively synthesized this type of carbide.
TiC is one of most important function structured material in the transition metal carbide, have series of advantages such as high strength, high rigidity, high temperature resistant, acid and alkali-resistance, wear-resistant, low work function and favorable conductive, thermal conductivity, be commonly used to prepare the TiC base cemented carbide or make the high strength of wild phase, the metal-base composites of high conductivity with TiC.Be widely used in sintering metal, mechanical workout, metallurgical mineral products, space flight and aviation, fields such as microelectronics.
Present stage, WC is the most frequently used a kind of metallic carbide, studies show that TiC is better than WC at aspects such as molten point, hardness, oxidation-resistances; In addition in recent years, the W shortage of resources makes the cost of WC significantly rise, and TiC compares WC more cost advantage, and this has also promoted application and the research of people to TiC from the side.Enjoy people's attention about TiC is synthetic in recent years with the research of using, the organism that especially uses wide material sources and cheapness prepares this phase TiC pottery as carbon source and studies focus in the focus especially.
At present, divide from the angle of reaction mechanism, the main method of preparation TiC has following several: 1) carbothermic reduction reaction method.With inorganic carbon dust and titanium dioxide powder is that the method that the carbothermic reduction reaction of raw material prepares titanium carbide is unique industrialized method, and this method adopts mechanical ball milling batch mixing, and temperature of reaction is generally up to 1700 ℃.2) inorganic polymer cracking process.Research adopts this method to prepare the more of SiC, BC, TiN, TiCN, even the research for preparing TiC for this method of employing is in the exploratory stage at initial stage.3) simple substance carbon and titanium metal direct reaction method.When using this method to prepare titanium carbide, the cost of raw material is higher, product needs further ball grinder graded.4) magnesiothermic reduction reaction method.This method displaces Ti and C atom with liquid metal muriate and liquid magnesium reaction by the magnesium reduction metal chloride, forms TiC by thermopositive reaction, when using this method to prepare titanium carbide, is difficult to obtain purified product.5) calciothermic reduction reaction method etc.
In numerous preparation methods, TiO
2Advantages such as the carbothermic reduction reaction method has abundant raw material, and technology is simple, and cost is lower and obtained widely using, current paper have been reported some development of this method or to the improvement of this method also morely.A large amount of documents shows that the researchist is preparating mechanism with the carbothermic reduction reaction, attempts using the carbon source of new cheapness, adopts new hybrid mode (collosol and gel, gaseous state cracking coating etc.) preparation titanium carbide.Because the introducing of new carbon source, dramatic shift has taken place in the hybrid mode between the raw material, impels that the contact area between the titanium source and carbon source significantly improves in the presoma, thereby significantly reduces the actual temperature of carrying out of carbothermic reduction reaction, prepares the high-purity Ti C of whole ratio.For example: Yasuo Gotoha, people (J.Materials Research Bulletin 36 (2001) 2263-2275) such as Kensaku Fujimura are with TiO
2Colloidal sol and the mixture that makes of methocel solution combination drying be raw material, under the protection of argon gas, prepare TiC by carbothermic reduction reaction.The methylcellulose gum effect is that pyrolysis provides carbon source, and preparation TiC (the content 0.60-2.32wt% of oxygen) temperature can drop to 1300 ℃; Yongsoon shin, people (AdvancedMaterials 16 (2004) 1212-1214) such as Xiaohong S. with filter paper as carbon source, Tyzor-LA ((NH
4)
2Ti (OH)
2(C
3H
5O
2)
2, 2.23M in Ti) and as the titanium source, by the TiC of carbothermic reduction reaction system, preparation temperature can be reduced to 1350 ℃, and oxygen level can reduce to 0.24%; Koc, people such as Rasit (Journal ofmaterials science 34 (1999) 3083-3093) are with nano-TiO
2Powder is a raw material, by thermolysis propylene (C
3H
6) the inorganic C of simple substance is deposited on TiO
2Increase the contact area of reactant on the powder, thereby the carbothermic reduction reaction temperature is reduced to 1300 ℃.
At present, study morely, based on carbothermic reduction reaction, the method for preparing TiC mainly contains following two kinds: 1. sol-gel method, and the hybrid mode by collosol and gel provides organic carbon source and titanium source; 2. gaseous hydrocarbon cracking bag carbon method, the cracking bag carbon by the gaseous hydrocarbon molecule provides carbon source.More than two kinds of methods all in various degree have many defectives, for example: sol-gel method, raw material than facile hydrolysis, cost height, productive rate is low, product purity is lower, technology is loaded down with trivial details; Gaseous alkanes cracking bag carbon method, precursor can not realize nano-TiO
2Particle wraps carbon under monodisperse status, prepared TiC crystal grain is bigger than normal, equipment requirements is high, power consumption is big, product purity is lower etc., has therefore also just limited these two kinds of methods in industrial application.
The objective of the invention is in order to overcome above-mentioned sol-gel method and gaseous state alkane cracking bag carbon method existing defective when carbothermic reduction prepares nano titanium carbide, provide a kind of new organic carbon source and new mixing to coat the method that legal system is equipped with nano TiC powder.
Basic design of the present invention is: the alkane with liquid state is carbon source, hydrated titanium dioxide is the titanium source, in two kinds of long-time at a certain temperature reflux courses of raw material, utilize the extremely strong adsorptive power of titanium dioxide network chain shape skeleton structure, with the liquid alkane carbochain progressively firmly adsorption and enrichment be coated on the monodisperse nano-titanium dioxide particle surface or be embedded in the interlayer or layer of particulate network chain shape skeleton structure, thereby realize that carbon source fully closely contacts with the titanium source, and then reduce the temperature that carbothermic reduction reaction carries out significantly, finally make nano TiC powder.
Summary of the invention
The liquid-phase reflux method of utilizing that the invention provides a kind of novelty obtains the nano-TiO that organic carbochain coats
2The nucleocapsid powder is a precursor, and the thermal treatment through follow-up different paths makes the novel method of nano TiC powder and new technological line.
Specifically the present invention is the titanium source with the hydrated titanium dioxide, with liquid alkane mixture (C
11-C
16) be carbon source, both prepare the alkane carbochain through refluxing and coat anatase crystal type TiO
2The nucleocapsid composite precursor powder of particle, this precursor powder are realized the sufficient inorganicization transformation and the carbothermic reduction reaction of organic carbon again through subsequent heat treatment, finally prepare nano TiC powder.
Its concrete process is as follows:
(1) get the raw materials ready: the volume ratio of dehydrated alcohol and liquid alkane mixture 4: 1～6: 1, every 500ml liquid alkane mixture is with 25～100g hydrated titanium dioxide.
(1) reflux: the formed suspension of dehydrated alcohol and hydrated titanium dioxide is at 40～100 ℃ of 1～10h that reflux down; Then with the paraffins mixture (C of liquid state
11-C
16) mix with precipitation powder with gained behind the alcohol reflux, and refluxed 6～12 days down at 100～250 ℃, till forming the aterrimus precipitation, filter, obtain black precipitate; The alkane filtrate of filtering gained is through water collection (removal ethanol), anhydrous CaCl
2After dry (dewatering), recycle.
(2) drying: the high alumina porcelain boat or the container that will carry black precipitate are put in the airtight tubular type atmosphere furnace, feed the mobile argon gas then, and time 1～3h under the protection of the argon gas that flows, is warming up to 80～120 ℃, insulation 0.5～2h; Cool to room temperature then; Take out sample, what obtain black is coated anatase crystal type TiO by the alkane carbochain
2The nucleocapsid composite precursor powder of particle, this moment precursor powder grain fineness number 4～9nm, the huge (300～400m of specific surface area
2/ g) and have a cellular structure of non-material self.
(3) charging: pack into black precursor powder in high alumina porcelain boat or the container and compress, it is airtight to put into the tubular type atmosphere furnace;
(4) high-temperature heat treatment: under argon gas atmosphere or vacuum condition, can adopt following several heat treatment mode respectively, all can obtain nano TiC powder.
1. two sections thermal treatments.
The alundum tube reaction chamber of tube furnace is extracted into-0.08～-feed argon gas during 0.1MPa vacuum tightness, fill to being a bit larger tham a standard atmospheric pressure, feed the argon gas that flows again, flowing time is 1～2h, close source of the gas then, the water seal production well makes to be in argon gas normal pressure nature conservation state in the alundum tube reaction chamber, heat temperature raising to 500～800 ℃ then, insulation 1～4h; Next feed high-purity mobile argon gas, and be warming up to 1200～1500 ℃, insulation 1～4h; Naturally cool to room temperature then.
2. the static argon shield thermal treatment of single hop.
To be full of argon gas in the tube furnace alundum tube reaction chamber to being a bit larger tham 1 standard atmospheric pressure, through-flow more moving argon gas, time 1～3h, close source of the gas then, the water seal production well makes to be in argon gas normal pressure nature conservation state in the alundum tube, heat temperature raising to 1200～1500 ℃ then, insulation 1～4h; Naturally cool to room temperature then.
3. the mobile argon shield thermal treatment of single hop.
To be full of argon gas in the tube furnace alundum tube reaction chamber to being a bit larger tham 1 standard atmospheric pressure, through-flow more moving argon gas, time 1～3h, then alundum tube under high-purity mobile argon shield, heat temperature raising to 1200～1500 ℃, insulation 1～4h; Feed argon gas then until cool to room temperature.
4. vacuum condition thermal treatment
The alundum tube reaction chamber of tube furnace is extracted into-0.09～-0.1MPa vacuum tightness, close vacuum pump then.Heat temperature raising to 1200～1500 ℃, insulation 1～4h.Then, feed argon gas then until cool to room temperature.
(5) sampling: the thermal treatment process that the precursor powder approach of different carbon content is different is handled the back and take out product in the porcelain boat of reaction chamber, thereby obtains pure nano TiC powder, grain fineness number: 10-20nm, particle diameter: 20-40nm.
Reaction process of the present invention can be summed up as the alkane carbochain and coat TiO
2The transformation of inorganicization of organic carbon and the carbothermic reduction reaction of the composite precursor powder of core-shell particles.Under the hot conditions by the alkane carbochain of TiO 2 particles strong adsorption also not desorption with regard to thermolysis, the nucleocapsid powder of the titanium dioxide that formation is coated by unbodied inorganic carbon, then along with the inorganic carbon of the further rising shell of thermal treatment temp and the titanium dioxide generation carbothermic reduction reaction in nuclear district, thereby make nano TiC powder.Entire reaction course relates to two kinds of nucleocapsid composite granules: the titanium dioxide core-shell composite granule that the titanium dioxide core-shell powder that the alkane carbochain coats, inorganic carbon coat; The nucleocapsid powder that is coated by organic carbon has than bigger serface and has vesicular structure, active higher, in heat treatment process, be difficult for producing reuniting, this particle growth for the nucleocapsid powder that inorganic carbon coats has the effect of significant inhibition particle diameter, therefore is easy to obtain the TiO 2 particles that the inorganic carbon of nano-scale particle coats; To the nano-TiO that is coated by inorganic carbon
2The nucleocapsid powder is reunited because the iris action of carbon is difficult for producing in follow-up heat treatment process, for the growth of final product TiC particle significant inhibitory effect is arranged, and therefore prepares the TiC powder of nano-scale particle easily.
What the present invention was prepared is high-purity nano TiC powder.Return time and reflux temperature when preparing by adjusting precursor can prepare the nano level nucleocapsid composite precursor powder of different carbon content (organic carbon); Can adjust the carbon amount of inorganicization of organic carbon transformation by different thermal treatment process; Therefore the preparation condition (reflux temperature, return time) of precursor need mate with corresponding thermal treatment process, just can prepare high-purity nano TiC powder (as described in example 2-5).
It is simple and cheap that precursor required for the present invention prepares device, mainly is made up of two portions: reflux whipping appts, condensing works.Effect and mutual relationship between two portions are as follows: 1. reflux whipping appts is used to take up raw material, realizes the adjustment and the material of reflux temperature are stirred; 2. condensing works utilizes it can realize the backflow repeatedly of liquid alkane or dehydrated alcohol.Two portions coordinate operation guarantees thorough mixing between the raw material.
Precursor thermal treatment unit required for the present invention is simple and easy to operate, mainly is made up of three parts: body of heater, gas distributing system, vacuum system.Effect and mutual relationship between three parts are as follows: 1. the alundum tube reaction chamber places in the tube furnace, is used to carry the high alumina crucible of precursor or the center that container places the alundum tube reaction chamber; 2. vacuum system, by decompression cut down, gas circuit and gas meter form, and is connected to an end of alundum tube reaction chamber, utilize it can the conditioned reaction chamber in kind, flow and the proportioning of shielding gas; 3. vacuum system; utilize it can be before presoma thermal treatment; extracting vacuum repeatedly, be full of inert protective gas; air in the eliminating alundum tube reaction chamber is to prevent that airborne oxygen is to the oxidation of reactant under the hot conditions; the vacuum tightness that simultaneously also can regulate reaction chamber, the assurance reaction chamber is heat-treated under the condition of certain vacuum tightness.
The present invention compares with existing technology of preparing and synthetic route, has following advantage and beneficial effect:
1. adopt new carbon source and new bag carbon mode, this makes the precursor particle be monodisperse status, and grain fineness number is little, and specific surface area is huge and have a porousness, the reactive behavior height of precursor.Since the iris action of carbon coated, nano TiC crystal grain and the particulate size that the present invention prepares little (all less than 50nm), and the actual temperature of carrying out of carbothermic reduction reaction can be reduced to 1300 ℃.
2. precursor powder carbon content (organic carbon) is controlled, and the carbon amount of inorganicization of organic carbon transformation is controlled in the precursor powder, is difficult for producing the enrichment or the deficiency of decolorizing carbon, the whole ratio of this nano TiC stoichiometry that makes present method prepare and high-purity.
The carbon content that reflux temperature when preparing by adjusting precursor and time can be controlled the precursor powder; Thermal treatment process by control precursor powder can realize the control to inorganicization of organic carbon transformation amount.
3. technology of the present invention is simple, is easy to realize industrialization.
Do not need strict dosage relation between this preparation method raw material, so technological operation is simple; Preparation simultaneously, Equipment for Heating Processing is simple, and alkane filtrate reclaiming clean reclaim equiment is simple, is convenient to the industrialization operation.
4. titanium source of using among the present invention and organic carbon source cheapness and organic carbon source can recycle repeatedly.
The liquid alkane mixture carbon chain lengths that the present invention uses is about 11-16 C atom, and after paraffins mixture refluxed, the alkane filtrate of filtering gained can be changed the liquid alkane mixture that can be recycled into.
Specific embodiments
Example one
(1) gets the raw materials ready: liquid alkane mixture (C
11-C
16) 1000ml, dehydrated alcohol 5000ml, hydrated titanium dioxide 100g.
(2) reflux: the dehydrated alcohol of 100g hydrated titanium dioxide and 1000ml refluxed one hour down at 70 ℃, filtered then; Gained precipitates with the dehydrated alcohol of fresh 1000ml and mixes, and refluxes one hour down at 70 ℃ once more, and above reflux course repeats 5 times; To filter the throw out and the 1000ml liquid alkane mixture (C of gained then
11-C
16) at first refluxed 48 hours down at 120 ℃, then powder is filtered out, extract ethanol in the alkane filtrate repeatedly with distilled water, next in filtrate, add an amount of anhydrous CaCl
2The water that removal left behind, obtain reusable paraffins mixture, regenerated liquid alkane mixture is mixed with the powder that filters out again 150 ℃ of following backflows 48 hours, the paraffins mixture that obtains recycling with above-mentioned same method, next successively at 180 ℃, respectively refluxed under 210 ℃ 48 hours, and filtered out the black powder at last, and with liquid alkane mixture repetitive scrubbing 5 times.
(3) drying: put into wet black precipitate in the high alumina porcelain boat and compress, place the tubular type atmosphere furnace airtight.Feed the mobile argon gas then, time 1h under the protection of the argon gas that flows, is warming up to 80 ℃, insulation 1h; Naturally cool to room temperature then; Sampling obtains the precursor powder of superfine black.
(4) sampling: take out sample in the porcelain boat from the alundum tube reaction chamber, obtain the huge (300～400m of superfine specific surface area
2/ g) and have the nanometer precursor powder of the cellular structure of non-material self, the evaluation of precursor powder sees Table one.
Example two
(1) gets the raw materials ready: liquid alkane mixture (C
11-C
16) 1000ml, dehydrated alcohol 5000ml, hydrated titanium dioxide 200g.
(2) reflux: the dehydrated alcohol of 200g hydrated titanium dioxide and 1000ml refluxed one hour down at 85 ℃, filtered then; Gained precipitates with the dehydrated alcohol of fresh 1000ml and mixes, and refluxes one hour down at 85 ℃ once more, and above reflux course repeats 5 times; To filter the throw out and the 1000ml liquid alkane mixture (C of gained then
11-C
16) at first refluxed 24 hours down at 120 ℃, then powder is filtered out, extract ethanol in the alkane filtrate repeatedly with distilled water, next in filtrate, add an amount of anhydrous CaCl
2The water that removal left behind, obtain reusable paraffins mixture, regenerated liquid alkane mixture is mixed with the powder that filters out again 150 ℃ of following backflows 48 hours, the paraffins mixture that obtains recycling with above-mentioned same method, next successively at 180 ℃, respectively refluxed under 210 ℃ 48 hours, and filtered out the black powder at last, and with liquid alkane mixture washing repeatedly 5 times.
(3) drying: put into wet black precipitate in the high alumina porcelain boat and compress, place the tubular type atmosphere furnace airtight.Feed the mobile argon gas then, time 1h under the protection of the argon gas that flows, is warming up to 80 ℃, insulation 1h; Naturally cool to room temperature then; Sampling obtains the precursor powder of superfine black.
(4) charging: put into black precursor powder in the high alumina porcelain boat and compress, place the tubular type atmosphere furnace airtight.
(5) high-temperature heat treatment:
Two sections thermal treatment is extracted into-0.08 with the alundum tube of tube furnace～-feed argon gas during 0.1MPa vacuum tightness, fill to being a bit larger tham a standard atmospheric pressure, feed the argon gas that flows again, flowing time is 1h, close source of the gas then, the water seal production well makes to be in argon gas normal pressure nature conservation state in the alundum tube, heat temperature raising to 700 ℃ then, insulation 1h; Next feed high-purity mobile argon gas, and under the argon shield of flowing, be warming up to 1300 ℃, insulation 1h; Feed argon gas then until cool to room temperature.
(6) sampling: take out sample in the porcelain boat from the alundum tube reaction chamber, thereby obtain nano TiC powder, the evaluation of powder sees Table one.
Example three:
(1) gets the raw materials ready: liquid alkane mixture (C
11-C
16) 1000ml, dehydrated alcohol 5000ml, hydrated titanium dioxide 50g.
(2) reflux: the dehydrated alcohol of 50g hydrated titanium dioxide and 1000ml refluxed one hour down at 60 ℃, filtered then; Gained precipitates with the dehydrated alcohol of fresh 1000ml and mixes, and refluxes one hour down at 60 ℃ once more, and above reflux course repeats 5 times; To filter the throw out and the 1000ml liquid alkane mixture (C of gained then
11-C
16) at first refluxed 48 hours down at 120 ℃, then powder is filtered out, extract alcohol in the alkane filtrate repeatedly with distilled water, next in filtrate, add an amount of anhydrous CaCl
2The water that removal left behind, obtain reusable paraffins mixture, regenerated liquid alkane mixture is mixed with the powder that filters out again 150 ℃ of following backflows 24 hours, the paraffins mixture that obtains recycling with above-mentioned same method, next successively at 180 ℃, respectively refluxed under 210 ℃ 48 hours, and filtered out the black powder at last, and with liquid alkane mixture washing repeatedly 5 times.
(3) drying: put into wet black precipitate in the high alumina porcelain boat and compress, place the tubular type atmosphere furnace airtight.Feed the mobile argon gas then, time 1h under the protection of the argon gas that flows, is warming up to 80 ℃, insulation 1h; Naturally cool to room temperature then; Sampling obtains the precursor powder of superfine black.
(4) charging: put into black precursor powder in the high alumina porcelain boat and compress, place the tubular type atmosphere furnace airtight.
(5) high-temperature heat treatment
The static argon shield thermal treatment of single hop will be full of argon gas to being a bit larger tham 1 standard atmospheric pressure, through-flow more moving argon gas, time 1h in the tube furnace alundum tube, close source of the gas then, the water seal production well makes to be in argon gas normal pressure nature conservation state in the alundum tube, heat temperature raising to 1300 ℃ then, insulation 2h; Feed argon gas then until cool to room temperature.
(6) sampling: take out sample in the porcelain boat from the alundum tube reaction chamber, thereby obtain nano TiC powder, the evaluation of powder sees Table one.
Example four:
(1) gets the raw materials ready: liquid alkane mixture (C
11-C
16) 1000ml, dehydrated alcohol 5000ml, hydrated titanium dioxide 100g.
(2) reflux: the dehydrated alcohol of 100g hydrated titanium dioxide and 1000ml refluxed one hour down at 90 ℃, filtered then; Gained precipitates with the dehydrated alcohol of fresh 1000ml and mixes, and refluxes one hour down at 90 ℃ once more, and above reflux course repeats 5 times; To filter the throw out and the 1000ml liquid alkane mixture (C of gained then
11-C
16) at first refluxed 48 hours down at 120 ℃, then powder is filtered out, extract alcohol in the alkane filtrate repeatedly with distilled water, next in filtrate, add an amount of anhydrous CaCl
2The water that removal left behind, obtain reusable paraffins mixture, regenerated liquid alkane mixture is mixed with the powder that filters out again 150 ℃ of following backflows 48 hours, the paraffins mixture that obtains recycling with above-mentioned same method, next successively at 180 ℃, respectively refluxed under 210 ℃ 24 hours, and filtered out the black powder at last, and with liquid alkane mixture washing repeatedly 5 times.
(3) drying: put into wet black precipitate in the high alumina porcelain boat and compress, place the tubular type atmosphere furnace airtight.Feed the mobile argon gas then, time 1h under the protection of the argon gas that flows, is warming up to 80 ℃, insulation 1h; Naturally cool to room temperature then; Sampling obtains the precursor powder of superfine black.
(4) charging: put into black precursor powder in the high alumina porcelain boat and compress, place the tubular type atmosphere furnace airtight.
(5) high-temperature heat treatment:
The single hop argon shield thermal treatment of flowing will be full of argon gas to being a bit larger tham 1 standard atmospheric pressure in the tube furnace alundum tube, through-flow more moving argon gas, time 1h, heat temperature raising to 1300 ℃ under the argon shield of flowing then, insulation 2.5h; Feed argon gas then until cool to room temperature.
(6) sampling: take out sample in the porcelain boat from the alundum tube reaction chamber, thereby obtain nano TiC powder, the evaluation of powder sees Table one.
Example five:
(1) gets the raw materials ready: liquid alkane mixture (C
11-C
16) 1000ml, dehydrated alcohol 5000ml, hydrated titanium dioxide 150g.
(2) reflux: the dehydrated alcohol of 150g hydrated titanium dioxide and 1000ml refluxed one hour down at 70 ℃, filtered then; Gained precipitates with the dehydrated alcohol of fresh 1000ml and mixes, and refluxes one hour down at 70 ℃ once more, and above reflux course repeats 5 times; To filter the throw out and the 1000ml liquid alkane mixture (C of gained then
11-C
16) at first refluxed 24 hours down at 120 ℃, then powder is filtered out, extract alcohol in the alkane filtrate repeatedly with distilled water, next in filtrate, add an amount of anhydrous CaCl
2The water that removal left behind, obtain reusable paraffins mixture, regenerated liquid alkane mixture is mixed with the powder that filters out again 150 ℃ of following backflows 36 hours, the paraffins mixture that obtains recycling with above-mentioned same method, next successively at 180 ℃, respectively refluxed under 210 ℃ 48 hours, and filtered out the black powder at last, and with liquid alkane mixture washing repeatedly 5 times.
(3) drying: put into wet black precipitate in the high alumina porcelain boat and compress, place the tubular type atmosphere furnace airtight.Feed the mobile argon gas then, time 1h under the protection of the argon gas that flows, is warming up to 80 ℃, insulation 1h; Naturally cool to room temperature then; Sampling obtains the precursor powder of superfine black.
(4) charging: put into black precursor powder in the high alumina porcelain boat and compress, place the tubular type atmosphere furnace airtight.
(5) high-temperature heat treatment:
Vacuum condition thermal treatment is extracted into-0.09 with the alundum tube of tube furnace～-0.1MPa vacuum tightness, close vacuum pump then.Heat temperature raising to 1300 ℃, insulation 2.5h, the logical argon gas of reaction chamber is until cool to room temperature.
(6) sampling: take out sample in the porcelain boat from the alundum tube reaction chamber, thereby obtain nano TiC powder, the evaluation of powder sees Table one.
The evaluation of precursor powder and TiC product in each example of table one
| Embodiment | Precursor specific surface area (BET) (m 2/g) | Precursor grain fineness number (nm) | Product TiC total carbon (wt%) | Product TiC uncombined carbon amount (wt%) | Product TiC grain fineness number (XRD) (nm) | Product TiC granularity (TEM) (nm) |
| Example one example two examples three examples four examples five | 378 319 350 323 318 | 4-7 5-7 5-8 5-7 6-9 | - 20.04 20.05 20.03 20.04 | - 0.014 0.021 0.020 0.019 | - 14-17 15-19 13-18 15-20 | - 20-30 20-40 20-40 20-35 |
Claims (6)
1. nano TiC powder preparation method is characterized in that comprising following process:
(1) gets the raw materials ready: the volume ratio of dehydrated alcohol and liquid alkane mixture 4: 1～6: 1, every 500ml liquid alkane mixture 25～200g hydrated titanium dioxide.
(2) reflux: the formed suspension of dehydrated alcohol and hydrated titanium dioxide is at 40～100 ℃ of 1～10h that reflux down; Then the paraffins mixture of liquid state is mixed with precipitation powder with gained behind the alcohol reflux, and refluxed 6～12 days down, till forming the aterrimus precipitation, filter, obtain black precipitate at 100～250 ℃; The alkane filtrate of filtering gained is through water collection (removal ethanol), anhydrous CaCl
2After dry (dewatering), recycle.
(3) drying: the high alumina porcelain boat or the container that will carry black precipitate are put in the airtight tubular type atmosphere furnace, feed the mobile argon gas then, and time 1～3h under the protection of the argon gas that flows, is warming up to 80～120 ℃, insulation 0.5～2h; Cool to room temperature then; Take out sample, obtain the anatase crystal type TiO of the alkane carbochain coating of black
2The precursor powder.
(4) charging: pack into black precursor powder in high alumina porcelain boat or the container and compress, it is airtight to put into the tubular type atmosphere furnace.High-temperature heat treatment: a). under argon gas atmosphere or vacuum condition, direct heating is warming up to 1200～1500 ℃, and insulation 1～4h feeds argon gas then until cool to room temperature.B). under argon gas atmosphere, first heat temperature raising to 500～800 ℃, insulation 1～4h, heat temperature raising to 1200～1500 ℃ then, insulation 1～4h feeds argon gas then until cool to room temperature.
(5) sampling: the precursor powder of different reflux conditionss (reflux temperature, return time) preparation, behind different high-temperature heat treatment process, take out product, thereby obtain nano TiC powder in the porcelain boat of reaction chamber.
2. by the preparation method of the described TiC nano-powder of claim 1, it is characterized in that carbon source is provided by the liquid alkane mixture, the titanium source is provided by hydrated titanium dioxide, realizes that by liquid-phase reflux bag carbon mixes.
3. by the preparation method of the described TiC nano-powder of claim 1, the carbon chain lengths that it is characterized in that the liquid alkane mixture between 11 carbon atoms and 16 carbon atoms, 180～250 ℃ of boiling points.
4. by the preparation method of the described TiC nano-powder of claim 1, it is characterized in that black precursor powder grain size 4-9nm, specific surface 300～400m
2/ g has vesicular structure, total pore volume 0.5～1cm
3/ g, average aperture 10～15nm.
5. by the preparation method of the described TiC nano-powder of claim 1, it is characterized in that the carbon content that reflux temperature when adjusting precursor and prepare and return time can be controlled the precursor powder.
6. by the preparation method of the described TiC nano-powder of claim 1, it is characterized in that the precursor powder of different carbon content, can change the carbon amount control of inorganic carbon to organic carbon into, prepare high-purity nm TiC powder by different thermal treatment process.
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462722B (en) * | 2009-01-09 | 2011-02-16 | 北京科技大学 | Method for preparing titanium carbide ceramic powder |
| CN102717070A (en) * | 2012-07-10 | 2012-10-10 | 四川大学 | Method for preparing carbon-coated copper nano particles through liquid alkane reflux method |
| CN102990075A (en) * | 2012-11-05 | 2013-03-27 | 四川大学 | Method for preparing carbon-coated iron nano particles |
| CN103072987A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Method for preparing metal carbide or carbon coated metal carbide |
| CN103449435A (en) * | 2013-08-27 | 2013-12-18 | 哈尔滨工业大学 | Method for producing micro-nanoscale carbide ceramics by carbon coating |
| CN109231208A (en) * | 2018-11-30 | 2019-01-18 | 长江师范学院 | A kind of preparation method of transition metal carbide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3661523A (en) * | 1970-04-14 | 1972-05-09 | Ppg Industries Inc | Preparation of titanium carbide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462722B (en) * | 2009-01-09 | 2011-02-16 | 北京科技大学 | Method for preparing titanium carbide ceramic powder |
| CN102717070A (en) * | 2012-07-10 | 2012-10-10 | 四川大学 | Method for preparing carbon-coated copper nano particles through liquid alkane reflux method |
| CN102990075A (en) * | 2012-11-05 | 2013-03-27 | 四川大学 | Method for preparing carbon-coated iron nano particles |
| CN103072987A (en) * | 2012-12-20 | 2013-05-01 | 华南理工大学 | Method for preparing metal carbide or carbon coated metal carbide |
| CN103072987B (en) * | 2012-12-20 | 2016-04-13 | 华南理工大学 | A kind of method preparing metallic carbide or carbon-clad metal carbide |
| CN103449435A (en) * | 2013-08-27 | 2013-12-18 | 哈尔滨工业大学 | Method for producing micro-nanoscale carbide ceramics by carbon coating |
| CN109231208A (en) * | 2018-11-30 | 2019-01-18 | 长江师范学院 | A kind of preparation method of transition metal carbide |
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| CN100526218C (en) | 2009-08-12 |
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