CN1176847C - Preparation method of titanium diboride nanopowder - Google Patents
Preparation method of titanium diboride nanopowderInfo
- Publication number
- CN1176847C CN1176847C CNB021156646A CN02115664A CN1176847C CN 1176847 C CN1176847 C CN 1176847C CN B021156646 A CNB021156646 A CN B021156646A CN 02115664 A CN02115664 A CN 02115664A CN 1176847 C CN1176847 C CN 1176847C
- Authority
- CN
- China
- Prior art keywords
- powder
- titanium diboride
- water
- preparation
- tib
- 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.)
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- 229910033181 TiB2 Inorganic materials 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000011858 nanopowder Substances 0.000 title claims description 13
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000003929 acidic solution Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000000713 high-energy ball milling Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 239000002253 acid Substances 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000000265 homogenisation Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000005554 pickling Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 238000005551 mechanical alloying Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
The present invention relates to a method for preparing titanium diboride nanometer powder, which has the technical scheme that titanium diboride nanometer powder of which the average grain size is 5mm is milleed in a ball way firstly, certain activation energy and intracrystalline imperfection od a grain surface are provided, and the titanium diboride powder with nonuniform submicron order grain sizes is obtained; then, the powder is processed with secondary thinning and homogenization in an acidic solution, and the titanium diboride nanometer powder of which the average grain size is about 50 nanometers can be obtained after acid cleaning treatment. The present invention has the advantages of simple manufacturing process and uniform powder grain sizes; furthermore, the present invention is suitable for large-scale powder preparation.
Description
Technical field
The present invention relates to the preparation method of nano powder.
Background technology
TiB2 (TiB
2) ceramic powder is a class important engineering ceramic raw material, has high-melting-point, high rigidity, high chemical stability and good heat conduction, conductivity.Be mainly used in: hard tool material, high temperature corrosion-resisting electrode, large-scale integrated circuit high strength blaster fuse frame material etc.Use more titanium diboride ceramic powder at present and utilize the preparation of self propagating high temperature synthetic technology, the about 5um of its median size.In order further to improve material property, need preparation nano level titanium boride powder.Nineteen ninety-five, the Susan E.Bates of U.S. Washington University has delivered the paper of " Synthesis of titanium boride nanocrystallites bysolution-phase processing " by name in periodical " Journal ofMaterial Research ", use NaBH
4And TiCl
4Be raw material, in trimethylbenzene solution, 164 ℃ are reacted synthetic unbodied TiB down
2Precursor powder then 900～1100 ℃ of annealing down, makes the TiB of particle size range 5～100nm
2Nano powder.This preparing technique process complexity, product component are difficult to control, need carry out aftertreatment, are difficult for realizing large batch of industrial production.1996, " Journal of Material Research " delivered the paper " Gas-phase combustion synthesis of titanium boridenanocrystallites " of the R.L.Axelbam of WashingtonUniversity again, reported employing TiCl
4, BCl
3, Na is raw material, by the reaction of the gaseous combustion in the Na gas atmosphere, prepared the TiB of particle diameter less than 15nm
2Nanometer powder.This technology can be prepared the TiB that particle diameter is little, purity is higher
2Nano powder, but the technology content of its requirement and cost are all than higher.
The technology of preparing of nano powder mainly comprises at present: chemical gas-phase method, chemical coprecipitation, mechanical alloying method, sol-gel method, spray pyrolysis and fluidization method etc.The chemical gas-phase method processing condition are strict, and cost is higher; Chemical coprecipitation need select can be in basic solution the dissolved presoma, bigger to preparation boride difficulty; The nano powder particle diameter of mechanical alloying method preparation is inhomogeneous; Sol-gel method cost of material height, organic solvent have toxicity, when at high temperature doing thermal treatment simultaneously particle are reunited fast; Spray method needs high temperature and vacuum condition, and is higher to equipment and operational requirement; Fluidization method Processes and apparatus complexity, preparation cost height in enormous quantities.
Summary of the invention
The objective of the invention is: utilize a kind of more easy method, prepare the uniform TiB of particle diameter in enormous quantities
2Nano powder.
The technical solution adopted for the present invention to solve the technical problems is: (1) is at micron-sized TiB
2Powder utilizes the first crystal grain thinning of mechanochemistry method, obtains the submicron order powder of granularity inequality, produces lattice distortion to a certain degree simultaneously, the activation particle surface; (2) by the further crystal grain thinning of cleanup acid treatment, utilize the laminate structure of boride and inhale hydrogen, obtain the uniform nanometer TiB of particle diameter
2Powder.
Details are as follows for specific implementation process of the present invention:
1. with median size the purity 98% above TiB of 5um
2Powder carries out high-energy ball milling and handles ratio of grinding media to material 20: 1, ball milling 40～50 hours.Obtain the powder of particle diameter 0.1～0.3um.
With concentrated hydrochloric acid and water by 1: 5～8 or concentrated nitric acid, strong phosphoric acid and water make acidic solution by 1: 1: 3～5, the powder of ball-milling processing is put into above-mentioned acidic solution to be stirred 30 minutes, after at room temperature leaving standstill 10 minutes, water cleans 2～3 times, to remove the acidic substance on throw out surface, suction filtration, oven dry, promptly obtaining particle diameter is 46～53nm, uniform, the TiB of purity more than 98%
2Nano-powder,
The invention has the advantages that: compare with other nano powder technology of preparing, technology is simple, and particle diameter is even, is easy to prepare in enormous quantities.
Specific embodiments
Introduce specific embodiments of the present invention in detail below in conjunction with accompanying drawing.
Fig. 1: preparation technology's schema of titanium diboride nano powder.
1: 100 gram of example average grain diameter is 5 microns TiB2Powder mixes with an amount of absolute ethyl alcohol, places carbide alloy Ball milling is 40 hours in the high energy ball mill of material, ratio of grinding media to material 20: 1. Drum's speed of rotation is 200 rev/mins, during ball milling every Added an ethanolic solution in 5～6 hours, in case oxidation and reunion. Powder red fuming nitric acid (RFNA) behind the ball milling: SPA: water=1: 1: 5 mixed acid carries out pickling, suction filtration, oven dry. The powder sample of getting the pickling front and back carries out under transmission electron microscope Observe, find pickling before powder inhomogeneous, bulky grain is about 0.2 micron, such as Fig. 2: the transmission electron microscope of powder before the pickling Shown in the figure. Powder after the pickling is very even, about average grain diameter 50 nanometers, such as Fig. 3: the transmission electron microscope of powder after the pickling Shown in the figure. Utilize the nitrogen adsorption method to measure the specific area of pickling front and back powder, be converted into again the average grain diameter d of powderBET The result is: the powder d before the picklingBET=147nm, the powder d after the picklingBET＝53nm。
Example 2: get the sample of the same ball-milling treatment of 100 grams, at concentrated hydrochloric acid: carry out pickling in the acid solution of water=1: 5 Process, suction filtration is dried subsequently. Utilize the nitrogen adsorption method to measure the specific area of pickling front and back powder, be converted into again powder Average grain diameter dBET The result is: the powder d before the picklingBET=151nm, the powder d after the picklingBET＝46nm。
Claims (1)
1. the preparation method of a titanium diboride nano powder is characterized in that with median size being the TiB of 5um
2Powder carries out high-energy ball milling to be handled, ratio of grinding media to material is 20: 1, ball milling 40～50 hours, obtaining particle diameter is the powder of 0.1～0.3um, this powder is placed concentrated hydrochloric acid and water blended acidic solution, wherein the ratio of concentrated hydrochloric acid and water is 1: 5～8, or this powder placed concentrated nitric acid, strong phosphoric acid and water blended acidic solution, wherein the ratio of concentrated nitric acid, strong phosphoric acid and water is 1: 1: 3～5, stirs after 30 minutes, at room temperature leaves standstill 10 minutes, water cleans 2～3 times, suction filtration, oven dry, promptly obtaining particle diameter is 46～53nm, uniform TiB
2Nano-powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021156646A CN1176847C (en) | 2002-04-01 | 2002-04-01 | Preparation method of titanium diboride nanopowder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021156646A CN1176847C (en) | 2002-04-01 | 2002-04-01 | Preparation method of titanium diboride nanopowder |
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|---|---|
| CN1371863A CN1371863A (en) | 2002-10-02 |
| CN1176847C true CN1176847C (en) | 2004-11-24 |
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|---|---|---|---|
| CNB021156646A Expired - Fee Related CN1176847C (en) | 2002-04-01 | 2002-04-01 | Preparation method of titanium diboride nanopowder |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005028463A1 (en) * | 2005-06-17 | 2006-12-28 | Basf Ag | Process for the preparation of nanoparticulate lanthanoid / boron compounds of nanoparticulate lanthanide / boron compounds containing solid mixtures |
| CN100423873C (en) * | 2006-09-22 | 2008-10-08 | 北京工业大学 | Preparation method of TiB2 nanometer micrometer structure feeding for hot spraying |
| CN103601499A (en) * | 2013-11-04 | 2014-02-26 | 天津大学 | Method for preparing TiB2 (titanium diboride) nano powder by using sol-gel technique |
| CN107572545B (en) * | 2017-08-18 | 2019-10-22 | 山东大学深圳研究院 | Application of titanium boride for chemically trapping polysulfides in lithium-sulfur batteries to prepare cathode materials for lithium-sulfur batteries |
| CN110817896B (en) * | 2019-12-15 | 2022-07-01 | 合肥中航纳米技术发展有限公司 | A kind of preparation method of nanometer titanium diboride powder |
| CN114933311B (en) * | 2022-06-02 | 2023-08-25 | 安阳工学院 | Method for refining hexaboride powder |
-
2002
- 2002-04-01 CN CNB021156646A patent/CN1176847C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1371863A (en) | 2002-10-02 |
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