CN100584747C - Method for preparing nano-titanium nitride with mesoporous organic-inorganic composite precursors - Google Patents
Method for preparing nano-titanium nitride with mesoporous organic-inorganic composite precursors Download PDFInfo
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- CN100584747C CN100584747C CN200810045566A CN200810045566A CN100584747C CN 100584747 C CN100584747 C CN 100584747C CN 200810045566 A CN200810045566 A CN 200810045566A CN 200810045566 A CN200810045566 A CN 200810045566A CN 100584747 C CN100584747 C CN 100584747C
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Abstract
The invention provides a new method for preparing a TiN nanometer powder by adopting ammonia gas atmosphere heat treatment and using organic and inorganic mesoporous composites as precursors. Cheap hydrated titanium dioxide powder is used as the titanium source, and a liquid alkane mixture (C11-C16) is used as the carbon source, carbon coating is realized by stepwise gradual temperature rise and refluxing, and the precursors with mesoporous structure are prepared in virtue of volume contraction caused by the partial crystallization of titanic dioxide in the process of refluxing. The high-purity titanium nitride nano-powder is prepared by adopting ammonia gas atmosphere heat treatment with the precursors at a relatively low temperature (700 DEG C-900 DEG C). The titanium carbide powder prepared by the method is of spherical shape, has an average particle size of 20-40nm, and an average grain size of 10-20nm. The method has the advantages of simple technology, low cost and energy saving compared with the common preparation methods, and feasibility for large-scale industrial production.
Description
Technical field
The invention belongs to high-temperature structural ceramics powder body material preparation field, being specifically related to a kind of novel mesoporous organic-inorganic composite body is the method that the thermal treatment of precursor ammonia atmosphere prepares the titanium nitride ceramic nano-powder.
Background technology
In recent years, the magnesium-yttrium-transition metal nitride 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 nitride.
Titanium nitride is one of most important function structured material in the transition metal nitride, 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 titanium nitride base cemented carbide or make the high strength of wild phase, the metal-base composites of high conductivity with titanium nitride.Be widely used in sintering metal, mechanical workout, metallurgical mineral products, space flight and aviation, fields such as microelectronics.
At present, the main method of preparation titanium nitride has following several:
(1) metallic titanium powder or TiH
2Direct nitridation method
Under nitrogen or hydrogen atmosphere, nitrogenize 1～4h under 1273～1673K, product pulverize back repetitive operation several times, can obtain stoichiometric nitrogenize titanium valve with titanium valve.
2Ti+N
2＝2TiN
Also can use metal hydride TiH
2Carry out nitrogenize, can below 1273K, react:
2TiH
2+N
2＝2TiN+2H
2
The advantage of this method is easy and simple to handle, can obtain high-quality titanium nitride powder, but that shortcoming is a cost of material is too high, be difficult to produce in batches, and this technology is easy to generate powder sintered phenomenon, so that causes damage.
(2) TiO
2The carbon reduction nitriding
TiO
2The carbothermal reduction-nitridation method be with TiO
2Be raw material, when having carbonaceous reducing agent to exist, with N
2Reaction generates TiN, and synthesis temperature is 1380～1800 ℃, and the reaction times is about 15h.The general purity of the TiN of gained is not high in this way, and O, C content are higher, in order to obtain O, TiN that C content is on the low side, needs higher temperature of reaction and longer reaction times.
(3) chemical Vapor deposition process
This method is with gasiform TiCl
4Be raw material, hydrogen is reductive agent and N
2Effect generates TiN, and synthesis temperature is 1100～1500 ℃.This method synthetic TiN purity height, but production unit is required height, suitable preparation TiN coated material.
(4) self propagating high temperature synthesis method
The self propagating high temperature synthesis method is to utilize the titanium valve pressed compact to light in the nitrogen of certain pressure, and titanium valve obtains the TiN product after burning in nitrogen.This technology has obtained extensive studies and commercialization in Russia, the U.S., Japan, and domestic research report in this respect is less.
(5) microwave carbothermic method
People such as Liu Bing sea (the microwave carbothermic method prepares the TiN. Acta Metallurgica Sinica, and 1996,32 (2): 921-924) adopted microwave heating technique, at 1200 ℃ of carbothermic reduction TiO
2Only having used 1h just to prepare high purity, mean particle size is the TiN powder of 1～2 μ m, compares with conventional carbothermic method, and the microwave carbothermic method makes the titanium nitride synthesis temperature reduce by 100～200 ℃, and synthesis cycle shortens, and is 1/15 of conventional method.
At present a large amount of documents shows that it is raw material that the researchist just more attempts with new presoma, prepares nano TiN through ammonia atmosphere thermal treatment.For example: people (Chem.Mater.1991 such as Zhiping Jiang and Wendell E.Rhine, 3,1132-1137) prepare polymer precursor by hydrolysis Ti (O-n-Bu) 4/furfury alcohol mixture, with this polymer precursor is that raw material prepares TiN through ammonia atmosphere thermal treatment, and its preparation temperature can drop to 1000 ℃; Mariusz Drygas, people such as CezaryCzosnek (Chem.Mater.2006,18, be that presoma obtains spheric TiN powder through ammonia atmosphere thermal treatment with the aerosol 3122-3129), preparation temperature can be reduced to 1000 ℃, and oxygen level can be reduced to less than 2% in the product.Though with above two kinds of novel precursors (polymkeric substance, colloidal sol) is feedstock production TiN, can significantly reduce preparation temperature, obtain nano level more purified product, but all in various degree have many defectives, for example: raw material than facile hydrolysis, cost height, productive rate is low, product purity is lower, technology is loaded down with trivial details.
The objective of the invention is in order to overcome above-mentioned is presoma existing defective when ammonia atmosphere thermal treatment prepares the TiN powder with sol-gel and polymkeric substance, and it is the method for feedstock production nanometer TiN powder that a kind of presoma new, that have nanostructure is provided.
Basic design of the present invention is: the alkane with liquid state is carbon source, hydrated titanium dioxide is the titanium source, two kinds of raw materials reflux at a certain temperature for a long time, utilize the extremely strong adsorptive power of titanium dioxide network chain shape skeleton structure, realize that carbon source fully closely contacts with the titanium source, utilize partial crystalline titanium dioxide to shrink the mesoporous presoma that obtains having high specific area simultaneously; With this mesoporous presoma is that raw material prepares nanometer TiN powder through ammonia atmosphere thermal treatment again.
Summary of the invention
The novel mesoporous organic-inorganic composition that utilizes the liquid-phase reflux method to obtain that the invention provides a kind of novelty is presoma, makes the novel method of nanometer TiN powder and new technological line through the thermal treatment of follow-up ammonia atmosphere.
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 mesoporous organic and inorganic composite precursor powder through refluxing, and this precursor powder prepares nanometer TiN powder through follow-up ammonia atmosphere thermal treatment again.
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.
(2) 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.
(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 ammonia then, and time 1～3h under the protection of the ammonia that flows, is warming up to 80～120 ℃, insulation 0.5～2h; Cool to room temperature then; Take out sample, obtain the composite mesoporous precursor powder of black, this moment precursor powder grain fineness number 4～9nm, specific surface area 300～400m2/g, pore volume 0.5～1cm3/g, mean pore size 10-15nm has meso-hole structure.
(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;
(5) high-temperature heat treatment:
To be full of ammonia in the tube furnace alundum tube reaction chamber to being a bit larger tham 1 standard atmospheric pressure, through-flow more moving ammonia, time 1～3h, heat temperature raising to 700～900 ℃ under the ammonia atmosphere that flows then, insulation 0.5～1h; Naturally cool to room temperature then.
(6) sampling: in the porcelain boat of reaction chamber, take out product, thereby obtain pure nano TiN powder, grain fineness number: 10-20nm, particle diameter: 20-40nm.
It is simple to operation 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 utilizes it can be before presoma thermal treatment, extracting vacuum repeatedly, is full of ammonia, gets rid of air in the alundum tube reaction chamber to prevent that airborne oxygen is to the oxidation of reactant under the hot conditions.
The present invention compares with existing technology of preparing and synthetic route, has following advantage and beneficial effect:
1. adopt new source material, and new backflow carbon packaging and hybrid mode, by the staged temperature rising reflux, realizing titanium source and well-mixed while of carbon source, impel local unbodied titanium source crystallization, cause the local volume contraction, obtain having the presoma in mesoporous space, precursor has meso-hole structure simultaneously, and specific surface area is huge, so the reactive behavior height of precursor.Nano TiN crystal grain that the present invention prepares and particulate size little (less than 30nm), the real reaction temperature can be reduced to 900 ℃.
2. 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.
3. 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 ammonia then, time 1h under the protection of the ammonia 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 ultra-fine precursor powder have big specific surface area (300～400m2/g) and pore volume (0.5～1cm3/g), 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 ammonia then, time 1h under the protection of the ammonia that flows, is warming up to 120 ℃, 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 alundum tube 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 ammonia that flows again, flowing time is 1h, heat temperature raising to 900 ℃ under mobile ammonia condition then, insulation 1h; Next under the protection of ammonia that flows, naturally cool to room temperature.
(6) sampling: take out sample in the porcelain boat from the alundum tube reaction chamber, thereby obtain nanometer TiN powder, the evaluation of powder sees Table one.
The evaluation of precursor powder and TiN product in each example of table one
Claims (3)
1, a kind of nanometer TiN 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 is with 25～200g hydrated titanium dioxide, wherein the carbon chain lengths of liquid alkane mixture is between 11 carbon atoms and 16 carbon atoms, 180～250 ℃ of boiling points;
(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 under 100～250 ℃, refluxed 6～12 days, till forming the aterrimus precipitation, filter, obtain black precipitate, filter the paraffins mixture filtrate of gained and after the water collection, remove dehydrated alcohol, use anhydrous CaCl again
2After drying dewaters, recycle;
(3) drying: the high alumina porcelain boat that will carry black precipitate is put in the airtight tubular type atmosphere furnace, feeds the mobile ammonia then, and time～3h under the protection of the ammonia that flows, is warming up to 80～120 ℃, insulation 0.5～2h; Cool to room temperature then; Take out sample, obtain the presoma powder of the high specific area with meso-hole structure of black;
(4) charging: with pack into high alumina porcelain boat and compressing of black presoma powder, it is airtight to put into the tubular type atmosphere furnace;
(5) atmosphere heat treatment: under mobile ammonia atmosphere condition, direct heating is warming up to 700～900 ℃, and insulation 1～2h naturally cools to room temperature then.
2, preparation method by the described TiN nano-powder of claim 1, it is characterized in that preparation by the realization presoma powder that refluxes, wherein, carbon source is provided by the liquid alkane mixture, the titanium source is provided by hydrated titanium dioxide, realizes bag carbon and mixing with liquid-phase reflux, and the volumetric shrinkage that local unbodied titanium dioxide crystallization causes in long-time reflux course makes presoma have mesoporous feature: specific surface 300～400m
2/ g, total pore volume 0.5～1cm
3/ g, mean pore size 10～15nm, average grain size 4-9nm.
3, by the preparation method of the described TiN nano-powder of claim 1, the TiN powder that it is characterized in that preparing is for spherical, and average particle size particle size is 10～30nm, and average grain size is 15～20nm.
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