CN105836718A - Sol-gel method for preparing submicron-order titanium nitride powdery material - Google Patents
Sol-gel method for preparing submicron-order titanium nitride powdery material Download PDFInfo
- Publication number
- CN105836718A CN105836718A CN201610273665.9A CN201610273665A CN105836718A CN 105836718 A CN105836718 A CN 105836718A CN 201610273665 A CN201610273665 A CN 201610273665A CN 105836718 A CN105836718 A CN 105836718A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- sol
- phenolic resin
- nitride powder
- titanium nitride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
- C01B21/0765—Preparation by carboreductive nitridation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Products (AREA)
Abstract
The invention relates to a sol-gel method for preparing a submicron-order titanium nitride powdery material .The method comprises the steps of evenly mixing and stirring ordinary titanium dioxide, phenolic resin and methyl alcohol according to the molar ratio of 1:(0.3-0.6):(1.2-2.3) at normal temperature, and conducting heat insulation at 70-110 DEG C for 2-4 h to obtain a titanium dioxide/phenolic resin precursor; placing the precursor in a high-temperature furnace to be heated, and conducting heat insulation for 1-4 h at 1200-1500 DEG C in the nitrogen atmosphere, so that submicron-order (ranging from 200 nanometers to 1 micron) titanium nitride powder is obtained finally .During reaction, high-activity amorphous carbon is generated through phenolic resin pyrolysis to wrap titanium dioxide powder inside, so that a spherical shell microstructure is formed, the contact area between reactants is increased greatly, and carbon thermal reduction can proceed more smoothly .The cost of adopted raw materials is low, sintering time is short, technology is simple, and industrial production can be achieved easily.
Description
Technical field
The invention belongs to field of ceramic material preparation, particularly relate to a kind of method that sol-gal process prepares nitride powder material.
Background technology
Titanium nitride has typical NaCl type structure, belongs to face-centered cubic lattice, lattice paprmeter a=0.4241nm.Titanium nitride has the most excellent machinery and physical and chemical performance, demonstrates great application prospect in fields such as ganoine thin film, optical thin film, integrated circuit and conduction of heat coatings.Along with market is more and more big to its quality and quantity demand, improving titanium nitride production technology is an important problem.The method preparing titanium nitride at present both at home and abroad mainly has metallic titanium powder or titantium hydride direct nitridation method, nitridation in situ method, mechanical alloying method, magnesium reduction process, plasma method and self-propagating high-temperature synthesis etc..
Although titanium nitride synthesis technique is through the development of decades, industrial had a set of fairly perfect production method, but still leave over problem to be solved in its production technology, such as: cumbersome, be difficult to produce in a large number, raw materials used costliness, production cost are high, the cycle is slow.The raw material utilizing low cost effectively and rapidly prepares high-purity high thin high-quality titanium nitride becomes the focus that various countries' researcher is paid close attention to.Patent CN104498982A discloses a kind of method preparing titanium nitride, during titanium soluble anode electrolytic preparation Titanium, being passed through nitrogen at negative electrode, the titanium that nitrogen and negative electrode produce reacts generation titanium nitride, separate electrolyte and titanium nitride, obtain titanium nitride product.Need to control vacuum during separating electrolyte and be less than 10Pa, and need to use the chlorohydric acid pickling of concentration 0.5 ~ 2wt%.This technique is limited by vacuum condition, can produce waste liquid simultaneously, cause environmental pollution.Patent CN104928656A discloses the preparation method of a kind of titanium nitride membrane, utilize the organic precursor colloidal sol of titaniferous, impregnated substrate at normal temperatures, carry out after drying being thermally treated resulting in thin film of titanium oxide, under ammonia atmosphere, thin film of titanium oxide is carried out high-temperature ammonolysis process subsequently, it is thus achieved that titanium nitride membrane.During obtaining thin film of titanium oxide, needing to repeat to process 3 ~ 15 times, technique is loaded down with trivial details, although finally given titanium nitride membrane, but its size and dimension is affected by operational characteristic and is very limited.Patent CN102659087A discloses a kind of method that original position CRN method prepares titanium nitride; in conjunction with the nitridation technology of preparing under alcohol full-boiled process and protection of ammonia; the titanium nitride presoma of different-shape structure is prepared by changing the alcohol heat time; carry out carbothermal reduction-nitridation, obtain the titanium nitride of the special appearance structure of bigger serface.Preparation process needs to use the titanyl sulfate acid solution of 1.2 ~ 1.3mol/L, spent acid can be produced during preparing presoma, cause environmental pollution.
Summary of the invention
It is an object of the invention to provide a kind of method using sol-gal process to prepare submicron order nitride powder material.The present invention uses ordinary titanium dioxide, phenolic resin, methanol as raw material, reduces preparation cost；And it is prepared for titanium dioxide/novolak resin precursor body by sol-gal process, increase the contact area between reactant；The method technique is simple, can prepare high-purity, submicron order nitride powder granule.
The present invention uses ordinary titanium dioxide, phenolic resin, methanol as raw material, and is prepared for titanium dioxide/novolak resin precursor body by sol-gal process.
The present invention specifically comprises the following steps that
(1) it is 1:(0.3 ~ 0.6 by titanium dioxide, phenolic resin and methanol according to mol ratio): (1.2 ~ 2.3) mix, and form mixed liquor；
(2) mixed solution is dried 2 ~ 4 hours at 70 ~ 110 DEG C, obtain titanium dioxide/novolak resin precursor body；
(3) presoma is put in high temperature furnace and heats, 1200 ~ 1500 DEG C, under argon gas atmosphere, be incubated 1 ~ 4 hour, phenolic resin pyrolysis generation amorphous carbon, by carbothermic reduction reaction, finally give submicron order nitride powder material.
In above-mentioned steps (1), titanium dioxide and phenolic resin are stirred for uniformly by electromagnetic agitation in methanol solution, and speed of agitator is 100 ~ 400rpm, mixing time 1 ~ 3 hour.
The technique of described carbothermic reduction reaction is, with the ramp of 5 ~ 15 DEG C/min to 1200 ~ 1500 DEG C, is incubated 1 ~ 4 hour, is then down to room temperature with the speed of 5 ~ 15 DEG C/min.
The invention still further relates to titanium nitride prepared by above-mentioned technique, the purity of described titanium nitride is more than 99.5%, and granularity is 200nm ~ 1 μm.
The present invention compared with prior art, possesses advantages below:
1, the present invention uses titanium dioxide, phenolic resin and methanol to be raw material, cheaper compared to other preparation method costs, and preparation temperature is relatively low, and technological process is simple, and is prone to industrialized production；
2, the present invention uses sol-gal process to prepare titanium dioxide/novolak resin precursor body, two kinds of reactant mix homogeneously, the amorphous carbon that phenolic resin pyrolysis produces forms spherical shell structure with titanium dioxide granule, increase the contact area between reactant, and the amorphous carbon activity height produced, beneficially the carrying out of carbothermic reduction reaction；
3, the titanium nitride particles purity that the present invention obtains is high, and is submicron order powder body material.
Accompanying drawing explanation
Fig. 1 is embodiment 1 carbon thermal reduction temperature X-ray diffractogram (XRD) of titanium nitride when being 1500 DEG C.
Fig. 2 is embodiment 2 carbon thermal reduction temperature X-ray diffractogram (XRD) of titanium nitride when being 1400 DEG C.
Fig. 3 is embodiment 3 carbon thermal reduction temperature X-ray diffractogram (XRD) of titanium nitride when being 1300 DEG C.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment
1:
By titanium dioxide, phenolic resin and methanol according to mol ratio be 1:0.5:1.9 mixing, utilize electromagnetic agitation to be stirred for uniformly, speed of agitator is 300rpm, mixing time 3 hours.Mixed solution is dried 2 hours at 110 DEG C, obtains titanium dioxide/novolak resin precursor body.Being put into by presoma in alumina crucible, under nitrogen protection atmosphere, with the ramp of 5 DEG C/min to 1500 DEG C, be incubated 4 hours, be then down to room temperature with the speed of 5 DEG C/min, finally given the purity nitride powder more than 99.5%, granularity is 200nm ~ 1 μm.
Fig. 1 is carbon thermal reduction temperature X-ray diffractogram (XRD) of product when being 1500 DEG C, it was demonstrated that product is titanium nitride, and there are not other dephasigns.
Embodiment
2:
By titanium dioxide, phenolic resin and methanol according to mol ratio be 1:0.6:2.3 mixing, utilize electromagnetic agitation to be stirred for uniformly, speed of agitator is 300rpm, mixing time 3 hours.Mixed solution is dried 2 hours at 110 DEG C, obtains titanium dioxide/novolak resin precursor body.Being put into by presoma in alumina crucible, under nitrogen protection atmosphere, with the ramp of 5 DEG C/min to 1400 DEG C, be incubated 4 hours, be then down to room temperature with the speed of 5 DEG C/min, finally given the purity nitride powder more than 99.5%, granularity is 200nm ~ 1 μm.
Fig. 2 is carbon thermal reduction temperature X-ray diffractogram (XRD) of product when being 1400 DEG C, it was demonstrated that product is titanium nitride, and there are not other dephasigns.
Embodiment
3:
By titanium dioxide, phenolic resin and methanol according to mol ratio be 1:0.5:1.9 mixing, utilize electromagnetic agitation to be stirred for uniformly, speed of agitator is 300rpm, mixing time 3 hours.Mixed solution is dried 2 hours at 110 DEG C, obtains titanium dioxide/novolak resin precursor body.Being put into by presoma in alumina crucible, under nitrogen protection atmosphere, with the ramp of 5 DEG C/min to 1300 DEG C, be incubated 4 hours, be then down to room temperature with the speed of 5 DEG C/min, finally given the purity nitride powder more than 99.5%, granularity is 200nm ~ 1 μm.
Fig. 3 is carbon thermal reduction temperature X-ray diffractogram (XRD) of product when being 1300 DEG C, it was demonstrated that product is titanium nitride, and there are not other dephasigns.
Embodiment
4:
By titanium dioxide, phenolic resin and methanol according to mol ratio be 1:0.6:2.3 mixing, utilize electromagnetic agitation to be stirred for uniformly, speed of agitator is 400rpm, mixing time 1 hour.Mixed solution is dried 4 hours at 110 DEG C, obtains titanium dioxide/novolak resin precursor body.Presoma is put in alumina crucible, under nitrogen protection atmosphere, with the ramp of 15 DEG C/min to 1200 DEG C; it is incubated 4 hours; then being down to room temperature with the speed of 15 DEG C/min, finally given the purity nitride powder more than 99.5%, granularity is 200nm ~ 500nm.
Embodiment
5:
By titanium dioxide, phenolic resin and methanol according to mol ratio be 1:0.3:1.2 mixing, utilize electromagnetic agitation to be stirred for uniformly, speed of agitator is 100rpm, mixing time 4 hours.Mixed solution is dried 4 hours at 110 DEG C, obtains titanium dioxide/novolak resin precursor body.Being put into by presoma in alumina crucible, under nitrogen protection atmosphere, with the ramp of 15 DEG C/min to 1500 DEG C, be incubated 1 hour, be then down to room temperature with the speed of 15 DEG C/min, finally given the purity nitride powder more than 99.5%, granularity is 200nm ~ 1nm.
Claims (5)
1. the method that a sol-gal process prepares submicron order nitride powder material, it is characterised in that employing ordinary titanium dioxide, phenolic resin, methanol are as raw material, and are prepared for titanium dioxide/novolak resin precursor body by sol-gal process.
2. the method that sol-gal process as claimed in claim 1 prepares submicron order nitride powder material, it is characterised in that specifically comprise the following steps that
1) it is 1:(0.3 ~ 0.6 by titanium dioxide, phenolic resin and methanol according to mol ratio): (1.2 ~ 2.3) mix, and form mixed liquor；
2) mixed solution is dried 2 ~ 4 hours at 70 ~ 110 DEG C, obtain titanium dioxide/novolak resin precursor body；
3) presoma is put in high temperature furnace and heats, 1200 ~ 1500 DEG C, under argon gas atmosphere, be incubated 1 ~ 4 hour, phenolic resin pyrolysis generation amorphous carbon, by carbothermic reduction reaction, finally give submicron order nitride powder material.
3. the method that sol-gal process as claimed in claim 1 prepares submicron order nitride powder material, it is characterized in that, above-mentioned steps 1) in, titanium dioxide and phenolic resin are stirred for uniformly by electromagnetic agitation in methanol solution, speed of agitator is 100 ~ 400rpm, mixing time 1 ~ 3 hour.
4. the method that sol-gal process as claimed in claim 1 prepares submicron order nitride powder material, it is characterized in that, the technique of described carbothermic reduction reaction is, with the ramp of 5 ~ 15 DEG C/min to 1200 ~ 1500 DEG C, it is incubated 1 ~ 4 hour, is then down to room temperature with the speed of 5 ~ 15 DEG C/min.
5. the method that sol-gal process as claimed in claim 1 prepares submicron order nitride powder material, it is characterised in that the purity of titanium nitride prepared by described technique is more than 99.5%, and granularity is 200nm ~ 1 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610273665.9A CN105836718A (en) | 2016-04-27 | 2016-04-27 | Sol-gel method for preparing submicron-order titanium nitride powdery material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610273665.9A CN105836718A (en) | 2016-04-27 | 2016-04-27 | Sol-gel method for preparing submicron-order titanium nitride powdery material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105836718A true CN105836718A (en) | 2016-08-10 |
Family
ID=56590016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610273665.9A Pending CN105836718A (en) | 2016-04-27 | 2016-04-27 | Sol-gel method for preparing submicron-order titanium nitride powdery material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105836718A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467448A (en) * | 2018-10-31 | 2019-03-15 | 武汉科技大学 | A kind of Al4SiC4Refractory material and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103569977A (en) * | 2013-10-16 | 2014-02-12 | 河北联合大学 | Preparation method of TiN powder |
-
2016
- 2016-04-27 CN CN201610273665.9A patent/CN105836718A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103569977A (en) * | 2013-10-16 | 2014-02-12 | 河北联合大学 | Preparation method of TiN powder |
Non-Patent Citations (4)
| Title |
|---|
| HAIJUN ZHANG ET AL;: "Preparation of titanium nitride ultrafine powders by sol–gel and microwave carbothermal reduction nitridation methods", 《CERAMICS INTERNATIONAL》 * |
| HAI-PENG GOU ET AL;: "Formation of submicrometer titanium carbide from a titanium dioxide encapsulated in phenolic resin", 《J MATER SCI》 * |
| 杨保祥等: "《钛基材料制造》", 31 January 2015, 冶金工业出版社 * |
| 裴立宅: "《高技术陶瓷材料》", 30 June 2015, 合肥工业大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467448A (en) * | 2018-10-31 | 2019-03-15 | 武汉科技大学 | A kind of Al4SiC4Refractory material and preparation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Rasaki et al. | Synthesis and application of nano-structured metal nitrides and carbides: A review | |
| Li et al. | Revisiting the preparation progress of nano‐structured Si anodes toward industrial application from the perspective of cost and scalability | |
| CN108269989B (en) | Carbon-coated micron silicon, and preparation method and application thereof | |
| Luo et al. | A review on the synthesis of transition metal nitride nanostructures and their energy related applications | |
| CN106077695B (en) | A kind of preparation method of high-copper tungsten copper nano composite powder | |
| CN104986742A (en) | Bead-chain-like graphitized carbon nitride nano material and preparation method thereof | |
| CN106975489B (en) | Preparation method of nickel oxide in-situ coated graphene nanocomposite | |
| CN103449496A (en) | Nano cerium oxide and preparation method thereof | |
| Ma et al. | Synthesis of nanocrystalline strontium titanate by a sol–gel assisted solid phase method and its formation mechanism and photocatalytic activity | |
| CN106587010B (en) | A kind of carbon nano-tube material and preparation method thereof using carbon-clad metal catalyst preparation | |
| CN103337611A (en) | Preparation method of graphene-titanium dioxide composite material | |
| CN103588216B (en) | The method of a kind of boron/carbothermic method low-temperature growth zirconium boride powder | |
| CN106431418A (en) | Method for preparing nanometer AlN powder through hydrothermal method and intermediate and product produced through method | |
| CN106994517B (en) | A kind of preparation method of high-thermal-conductivity low-expansibility W-Cu encapsulating material | |
| WO2023197682A1 (en) | Method for efficiently preparing boron nitride nanosheet | |
| CN104671245A (en) | Preparation method of hafnium carbide nano-powder | |
| CN103754891A (en) | Method for preparing hafnium boride powder by using boron/carbothermic method | |
| CN103647097B (en) | Sc2o3stablize ZrO2base electrolyte powder body, its preparation method and Sc2o3stablize ZrO2electrolyte ceramics sheet | |
| CN111905796A (en) | Preparation method of superfine metal nanoparticle/carbon nitride nanosheet composite material | |
| CN110184488B (en) | Method for preparing metal dispersion strengthened copper in short process | |
| CN108461725A (en) | Vanadium trioxide hollow microsphere of carbon confinement and its preparation method and application | |
| CN101628812A (en) | Method for preparing compact yttria ceramics | |
| CN111653750A (en) | Preparation method of carbon nitride modified molybdenum disulfide lithium ion battery cathode material | |
| CN109546126A (en) | A kind of transition metal element doped carbon coating lithium titanate, preparation method and application | |
| CN108928822B (en) | Method for preparing molybdenum carbide by gaseous reduction of molybdenum oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160810 |