CN115595653B - Titanium boride whisker and preparation method thereof - Google Patents
Titanium boride whisker and preparation method thereof Download PDFInfo
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- CN115595653B CN115595653B CN202211339729.2A CN202211339729A CN115595653B CN 115595653 B CN115595653 B CN 115595653B CN 202211339729 A CN202211339729 A CN 202211339729A CN 115595653 B CN115595653 B CN 115595653B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000010936 titanium Substances 0.000 title claims abstract description 74
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 121
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 61
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 61
- -1 titanium hydride Chemical compound 0.000 claims abstract description 49
- 229910000048 titanium hydride Inorganic materials 0.000 claims abstract description 48
- 238000005245 sintering Methods 0.000 claims abstract description 41
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004327 boric acid Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 44
- 238000000498 ball milling Methods 0.000 claims description 41
- 238000005554 pickling Methods 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 23
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 4
- 230000002787 reinforcement Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 8
- 125000006850 spacer group Chemical group 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910033181 TiB2 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention provides a titanium boride whisker and a preparation method thereof, wherein the preparation method of the titanium boride whisker comprises the following steps: boron oxide powder or boric acid powder is placed at the bottom of the crucible; placing titanium hydride powder or titanium powder on a separator with micropores in the crucible, wherein the titanium hydride powder or the titanium powder is not in direct contact with the boron oxide powder or the boric acid powder; and placing the crucible in an inert atmosphere, and performing high-temperature sintering to generate titanium boride whiskers. The preparation method of the titanium boride whisker provided by the invention has the advantages of cheap and easily available raw materials, simple preparation process, low equipment requirement, convenient operation and short growth period, is suitable for large-scale industrial production, has good size and shape controllability, high length-diameter ratio and low production cost, can be used as a whisker reinforcement for the fields of metal, ceramic, polymer and the like, and also can be used for the fields of superhard ceramic, wear-resistant materials, electrode materials and the like.
Description
Technical Field
The invention relates to the technical field of whisker material preparation, in particular to a titanium boride whisker and a preparation method thereof.
Background
The titanium boride ceramic whisker material has wide application scenes in the fields of high-temperature structural materials, super-hard ceramics, wear-resistant materials, electrode materials, nuclear power materials and the like by virtue of the high melting point, high strength, high hardness, high modulus, corrosion resistance, high electric conduction and high heat conduction of the titanium boride ceramic whisker material. In addition, the titanium boride ceramic whisker material can greatly improve the comprehensive mechanical property of the matrix material by virtue of the characteristics of high length-diameter ratio and good wettability with the matrix, and is widely applied to ceramic matrix, metal matrix and resin matrix composite materials as an ideal ceramic reinforcement.
In the prior artThe titanium boride ceramic whisker is formed by one or more boron-containing ceramics (such as TiB 2 、B 4 C. B) in-situ reaction with metal titanium particles, which belongs to a solid-solid reaction mechanism. However, the titanium boride whisker generated by the method has the advantages of smaller size, lower length-diameter ratio, uncontrollable morphology, higher production cost and lower yield.
Disclosure of Invention
The invention solves the problem of providing a preparation method of titanium boride whisker with controllable size and morphology, simple production process, lower cost, higher yield and short production period.
In order to solve the problems, the invention provides a preparation method of titanium boride whisker, which comprises the following steps:
s1, placing boron oxide powder or boric acid powder at the bottom of a crucible;
s2, placing titanium hydride powder or titanium powder on a separator with micropores in the crucible, wherein the titanium hydride powder or the titanium powder is not in direct contact with the boron oxide powder or the boric acid powder;
and step S3, placing the crucible in an inert atmosphere, and performing high-temperature sintering to generate titanium boride whiskers.
Preferably, in the step S1, the boron oxide powder is placed at the bottom of the crucible.
Preferably, in the step S2, the titanium hydride powder is placed on a separator having micropores in the crucible, and the titanium hydride powder is not in direct contact with the boron oxide powder.
Preferably, in the step S1, the boron oxide powder or the boric acid powder is ball-milled and then placed at the bottom of the crucible, the ball-to-material ratio is 3-5:1, the ball-milling rotation speed is 50-200r/min, and the ball-milling time is 10-20h.
Preferably, in the step S2, the particle size of the titanium hydride or the titanium is 1 to 10 μm.
Preferably, in the step S2, the mass ratio of the titanium hydride powder to the boron oxide powder is 1-10:1.
Preferably, in the step S3, the high-temperature sintering temperature is 1100-1400 ℃ and the sintering time is 0.5-2h.
Preferably, in the step S3, after the high-temperature sintering, acid washing and drying are performed to obtain the titanium boride whisker with high purity.
Preferably, in the pickling process, a mixed solution of hydrofluoric acid, nitric acid and water is used for pickling, wherein the volume ratio of the hydrofluoric acid to the nitric acid to the water is 5-10:15-20:70-80, and the pickling time is 5-10h.
According to the invention, boron oxide powder or boric acid powder is used as a boron source, titanium hydride powder or titanium powder is used as a titanium source, under the condition of no direct contact, the boron oxide powder or the boric acid powder is formed into steam through high-temperature sintering in an inert atmosphere, and the steam is fully contacted with the titanium hydride powder or the titanium powder after passing through a separator with micropores, so that gas-solid reaction is realized, and thus, the titanium boride whisker with high length-diameter ratio is prepared through anisotropic growth. The preparation method of the titanium boride whisker provided by the invention has the advantages of cheap and easily available raw materials, simple preparation process, low equipment requirement, convenient operation and short growth period, is suitable for large-scale industrial production, has good size and shape controllability, high length-diameter ratio and low production cost, can be used as a whisker reinforcement for the fields of metal, ceramic, polymer and the like, and also can be used for the fields of superhard ceramic, wear-resistant materials, electrode materials and the like.
On the other hand, the invention also provides a titanium boride whisker, which is prepared by adopting the preparation method of the titanium boride whisker.
Compared with the prior art, the titanium boride whisker provided by the invention has the beneficial effects that the titanium boride whisker is the same as the preparation method of the titanium boride whisker, and is not repeated here.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing titanium boride whiskers according to an embodiment of the invention;
FIG. 2 is a schematic diagram of the preparation principle of titanium boride whisker in the embodiment of the invention;
FIG. 3 is an SEM image of titanium boride whiskers of example 5 of the invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of embodiments of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
It should be noted that, without conflict, features in the embodiments of the present invention may be combined with each other. The terms "comprising," "including," "containing," and "having" are intended to be non-limiting, as other steps and other ingredients not affecting the result may be added. The above terms encompass the terms "consisting of … …" and "consisting essentially of … …". Materials, equipment, reagents are commercially available unless otherwise specified.
The embodiment of the invention provides a preparation method of titanium boride whisker, as shown in figure 1, comprising the following steps:
s1, placing boron oxide powder or boric acid powder at the bottom of a crucible;
s2, placing titanium hydride powder or titanium powder on a separator with micropores in the crucible, wherein the titanium hydride powder or the titanium powder is not in direct contact with the boron oxide powder or the boric acid powder;
and step S3, placing the crucible in an inert atmosphere, and performing high-temperature sintering to generate titanium boride whiskers.
In step S1, the boron oxide powder is preferably placed on the bottom of the crucible, and in step S2, the titanium hydride powder is preferably placed on a separator having micropores in the crucible, and the titanium hydride powder is not in direct contact with the boron oxide powder.
In the prior art, whisker growth by a gas-solid (VS) growth mechanism is mainly concentrated in the production process of SiC whiskers, siO steam is generated under the oxidation condition by utilizing different silicon sources, and carbon thermal reduction reaction is carried out with a C simple substance, but the silicon dioxide crystal whisker has no application in the preparation of titanium boride whiskers.
Preferably, titanium hydride powder and boron oxide powder are subjected to titanium boride whisker growth through VS growth, on one hand, boron oxide has a lower melting point and a lower boiling point, can form steam at a lower temperature, is contacted with the titanium hydride powder for reaction after volatilization, on the other hand, titanium hydride has stronger reducibility, smaller granularity and low price, can be decomposed into titanium particles and hydrogen with reducibility at a lower temperature, and the generated small-size titanium particles have higher reaction activation energy, are favorable for reaction, can form high-concentration hydrogen in a relatively closed environment, are favorable for contact of boron oxide steam and the titanium particles, and the hydrogen can also participate in the reaction process, so that the reaction is facilitated and the purity of the whisker is improved.
In the step S1, the boron oxide powder or the boric acid powder is placed at the bottom of the crucible after ball milling, the ball-material ratio is 3-5:1, the ball milling rotating speed is 50-200r/min, and the ball milling time is 10-20h. The boron oxide powder or boric acid powder with uniform dispersion and smaller size can be obtained through the ball grinding process, the particles are easily connected together to form new agglomeration due to the fact that the rotating speed is too high or the ball milling time is too long, and the particles are easily unevenly dispersed and larger in particle size due to the fact that the rotating speed is too low or the time is too short.
In step S2, the particle size of the titanium hydride or the titanium is 1-10 μm. The particle size is 1-10 mu m, which is helpful to improve the reducibility of titanium hydride or titanium, has higher specific surface area and is helpful to form titanium boride whisker by contacting boron oxide or boric acid steam.
In addition, in the step S2, the mass ratio of the titanium hydride powder to the boron oxide powder is 1-10:1. The selection of a suitable mass ratio can increase the efficiency of the reaction and can increase the aspect ratio of the titanium boride whisker.
In the step S3, the crucible is placed in an inert atmosphere for high-temperature sintering, and titanium boride whiskers are generated. In the high-temperature sintering process, boron oxide powder or boric acid powder at the bottom of the crucible can form boron oxide or boric acid steam, and after passing through a separator with micropores, the boron oxide powder or boric acid steam contacts with titanium hydride powder or titanium powder on the separator, and gas-solid reaction occurs to generate titanium boride whiskers.
It should be noted that, the crucible is selected from a high temperature resistant crucible, such as an alumina crucible, a zirconia crucible or a boron nitride crucible, and correspondingly, the spacer is also made of a high temperature resistant material, so that the damage of the crucible and the spacer in the high temperature sintering process or the influence of precipitated substances on the generation of titanium boride whiskers is avoided.
Wherein the high-temperature sintering temperature is preferably set to 1100-1400 ℃ and the sintering time is 0.5-2h. In the temperature range of 1100-1400 ℃, the vapor pressure of the boron oxide or boric acid vapor can be ensured, so that the reaction is smoothly carried out, if the sintering temperature is too low, the vapor content is easy to be low, the reaction is difficult to carry out, and if the sintering temperature is too high, on one hand, the energy waste is caused, and on the other hand, the vapor is quickly volatilized and separated from the inside of the crucible, and on the contrary, the vapor concentration in the crucible is reduced, so that the titanium boride whisker production is low.
It should be noted that the sintering temperature and the sintering time of the high-temperature sintering may be adjusted according to the reaction substrate selected for use.
In order to remove impurities in the titanium boride whisker, the purity of the titanium boride whisker is improved, and after high-temperature sintering is completed, acid washing and drying are carried out. In the pickling process, a mixed solution of hydrofluoric acid, nitric acid and water is used for pickling, wherein the volume ratio of the hydrofluoric acid to the nitric acid to the water is 5-10:15-20:70-80, and the pickling time is 5-10h. The acid with the proportion is selected for acid washing, so that the impurity removal effect can be ensured, and the problems of danger and cost improvement caused by overhigh concentration of acid can be avoided.
According to the embodiment of the invention, the boron oxide powder or the boric acid powder is used as a boron source, the titanium hydride powder or the titanium powder is used as a titanium source, under the condition of no direct contact, the boron oxide powder or the boric acid powder is formed into steam through high-temperature sintering in an inert atmosphere, and the steam is fully contacted with the titanium hydride powder or the titanium powder after passing through the isolating sheet with micropores, so that the gas-solid reaction is realized, and the titanium boride whisker with high length-diameter ratio is prepared through anisotropic growth. The preparation method of the titanium boride whisker provided by the embodiment of the invention has the advantages of cheap and easily obtained raw materials, simple preparation process, low equipment requirement, convenient operation and short growth period, is suitable for large-scale industrial production, has good size and shape controllability, high length-diameter ratio and low production cost, can be used as a whisker reinforcement in the fields of metal, ceramic, polymer and the like, and also can be used in the fields of super-hard ceramic, wear-resistant materials, electrode materials and the like.
Another embodiment of the present invention provides a titanium diboride whisker prepared by the method of preparing a titanium diboride whisker as described above.
Compared with the prior art, the titanium boride whisker provided by the invention has the beneficial effects that the titanium boride whisker is the same as the preparation method of the titanium boride whisker, and is not repeated here.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, which do not address specific conditions in the following examples, are generally in accordance with the conditions recommended by the manufacturer.
Example 1
1.1, ball milling is carried out on boron oxide powder, the ball-material ratio is 3:1, the ball milling rotating speed is 200r/min, the ball milling time is 20h, and the boron oxide powder after ball milling is placed at the bottom of an alumina crucible;
1.2, placing titanium hydride powder with the average diameter of 1 μm on a separator with micropores in the middle of a crucible, wherein the titanium hydride powder is not in direct contact with boron oxide powder, and the mass ratio of the titanium hydride powder to the boron oxide powder is 1:1;
1.3, placing the alumina crucible in a gas pressure furnace, adopting argon as a protective gas, setting the sintering temperature to 1100 ℃ and setting the sintering time to 0.5h;
and 1.4, pickling the mixed substance generated above the spacer, wherein in the pickling process, a mixed solution of hydrofluoric acid, nitric acid and water is used for pickling, the volume ratio of the hydrofluoric acid to the nitric acid to the water is 10:20:70, and the pickling time is 10 hours, so that the titanium boride whisker is obtained.
FIG. 2 is a schematic diagram showing a high temperature sintering reaction process, wherein boron oxide powder is positioned at the bottom of a crucible, titanium hydride powder is positioned on an aluminum oxide sheet with micropores in the middle of the crucible, boron oxide vapor is formed by the boron oxide powder after high temperature sintering, the boron oxide vapor is volatilized to the middle of the crucible through the micropores on a separator with the micropores, and the boron oxide vapor contacts with the titanium hydride powder and undergoes a gas-solid reaction to obtain titanium boride whisker, and the whole reaction is carried out under the protection atmosphere of argon.
Example 2
2.1, ball milling is carried out on the boron oxide powder, the ball-material ratio is 4:1, the ball milling rotating speed is 100r/min, the ball milling time is 15h, and the boron oxide powder after ball milling is placed at the bottom of an alumina crucible;
2.2, placing titanium hydride powder with the average diameter of 5 mu m on a separator with micropores in the middle of a crucible, wherein the titanium hydride powder is not in direct contact with boron oxide powder, and the mass ratio of the titanium hydride powder to the boron oxide powder is 5:1;
2.3, placing the alumina crucible in a gas pressure furnace, adopting argon as a protective gas, setting the sintering temperature to 1200 ℃ and setting the sintering time to 0.5h;
2.4, pickling the mixed substance generated above the isolating sheet, wherein in the pickling process, a mixed solution of hydrofluoric acid, nitric acid and water is used for pickling, the volume ratio of the hydrofluoric acid to the nitric acid to the water is 5:15:80, and the pickling time is 5 hours, so that the titanium boride whisker is obtained.
Example 3
3.1, ball milling is carried out on the boron oxide powder, the ball-material ratio is 4:1, the ball milling rotating speed is 100r/min, the ball milling time is 15h, and the boron oxide powder after ball milling is placed at the bottom of an alumina crucible;
3.2, placing titanium hydride powder with the average diameter of 10 mu m on a separator with micropores in the middle of a crucible, wherein the titanium hydride powder is not in direct contact with boron oxide powder, and the mass ratio of the titanium hydride powder to the boron oxide powder is 10:1;
3.3, placing the alumina crucible in a gas pressure furnace, adopting argon as a protective gas, setting the sintering temperature to 1200 ℃ and setting the sintering time to 0.5h;
and 3.4, pickling the mixed substance generated above the spacer, wherein in the pickling process, a mixed solution of hydrofluoric acid, nitric acid and water is used for pickling, the volume ratio of the hydrofluoric acid to the nitric acid to the water is 5:15:80, and the pickling time is 5 hours, so that the titanium boride whisker is obtained.
Example 4
4.1, ball milling is carried out on the boron oxide powder, the ball-material ratio is 4:1, the ball milling rotating speed is 100r/min, the ball milling time is 15h, and the boron oxide powder after ball milling is placed at the bottom of an alumina crucible;
4.2, placing titanium hydride powder with the average diameter of 10 mu m on a separator with micropores in the middle of a crucible, wherein the titanium hydride powder is not in direct contact with boron oxide powder, and the mass ratio of the titanium hydride powder to the boron oxide powder is 10:1;
4.3, placing the alumina crucible in a gas pressure furnace, adopting argon as a protective gas, setting the sintering temperature to 1300 ℃ and setting the sintering time to 1h;
4.4, pickling the mixed substance generated above the isolating sheet, wherein in the pickling process, a mixed solution of hydrofluoric acid, nitric acid and water is used for pickling, the volume ratio of the hydrofluoric acid to the nitric acid to the water is 5:15:80, and the pickling time is 5 hours, so that the titanium boride whisker is obtained.
Example 5
5.1, ball milling is carried out on the boron oxide powder, the ball-material ratio is 4:1, the ball milling rotating speed is 100r/min, the ball milling time is 15h, and the boron oxide powder after ball milling is placed at the bottom of an alumina crucible;
5.2, placing titanium hydride powder with the average diameter of 5 mu m on a separator with micropores in the middle of a crucible, wherein the titanium hydride powder is not in direct contact with boron oxide powder, and the mass ratio of the titanium hydride powder to the boron oxide powder is 5:1;
5.3, placing the alumina crucible in a gas pressure furnace, adopting argon as a protective gas, setting the sintering temperature to 1400 ℃ and setting the sintering time to 0.5h;
and 5.4, pickling the mixed substance generated above the spacer, wherein in the pickling process, a mixed solution of hydrofluoric acid, nitric acid and water is used for pickling, the volume ratio of the hydrofluoric acid to the nitric acid to the water is 10:15:75, and the pickling time is 10 hours, so that the titanium boride whisker is obtained.
FIG. 3 is an SEM image of a titanium boride whisker obtained in example 5 of the present invention, and the titanium boride whisker obtained is 0.8-1.1 μm in diameter and 30-42 μm in length. The titanium boride whisker prepared by the embodiment of the invention is generated by the reaction between boron oxide steam and titanium hydride powder at high temperature, the growth mechanism of the titanium boride whisker belongs to a gas-solid reaction mechanism, and compared with the traditional solid-solid reaction diffusion, the length of the titanium boride whisker prepared by the embodiment of the invention is longer than that of the whisker prepared by the solid-solid reaction diffusion. In addition, the gas-solid reaction is adopted, so that the chemical components of the product are distributed more uniformly, the yield is higher, the process is simple, and the industrial application is facilitated.
Example 6
Ball milling is carried out on boric acid powder, the ball-material ratio is 4:1, the ball milling rotating speed is 100r/min, the ball milling time is 15h, and the boric acid powder after ball milling is placed at the bottom of an alumina crucible;
6.2, placing titanium powder with an average diameter of 5 mu m on a separator with micropores in the middle of a crucible, wherein the titanium powder is not in direct contact with boric acid powder, and the mass ratio of the titanium powder to the boric acid powder is 5:1;
6.3, placing the alumina crucible in a gas pressure furnace, adopting argon as a protective gas, setting the sintering temperature to 1400 ℃ and setting the sintering time to 0.5h;
and 6.4, pickling the mixed substance generated above the spacer, wherein in the pickling process, a mixed solution of hydrofluoric acid, nitric acid and water is used for pickling, the volume ratio of the hydrofluoric acid to the nitric acid to the water is 5:15:80, and the pickling time is 5 hours, so that the titanium boride whisker is obtained.
Example 7
7.1, ball milling is carried out on boric acid powder, the ball-material ratio is 4:1, the ball milling rotating speed is 100r/min, the ball milling time is 15h, and the boric acid powder after ball milling is placed at the bottom of an alumina crucible;
7.2, placing titanium hydride powder with the average diameter of 5 mu m on a separator with micropores in the middle of a crucible, wherein the titanium hydride powder is not in direct contact with boric acid powder, and the mass ratio of the titanium hydride powder to the boric acid powder is 5:1;
7.3, placing the alumina crucible in a gas pressure furnace, adopting argon as a protective gas, setting the sintering temperature to 1400 ℃ and setting the sintering time to 0.5h;
and 7.4, pickling the mixed substance generated above the spacer, wherein in the pickling process, a mixed solution of hydrofluoric acid, nitric acid and water is used for pickling, the volume ratio of the hydrofluoric acid to the nitric acid to the water is 5:15:80, and the pickling time is 5 hours, so that the titanium boride whisker is obtained.
Example 8
8.1, ball milling is carried out on the boron oxide powder, the ball-material ratio is 4:1, the ball milling rotating speed is 100r/min, the ball milling time is 15h, and the boron oxide powder after ball milling is placed at the bottom of an alumina crucible;
8.2, placing titanium powder with an average diameter of 5 mu m on a separator with micropores in the middle of a crucible, wherein the titanium powder is not in direct contact with boron oxide powder, and the mass ratio of the titanium powder to the boron oxide powder is 5:1;
8.3, placing the alumina crucible in a gas pressure furnace, adopting argon as a protective gas, setting the sintering temperature to 1400 ℃ and setting the sintering time to 0.5h;
8.4, pickling the mixed substance generated above the spacer, wherein in the pickling process, a mixed solution of hydrofluoric acid, nitric acid and water is used for pickling, the volume ratio of the hydrofluoric acid to the nitric acid to the water is 5:15:80, and the pickling time is 5 hours, so that the titanium boride whisker is obtained.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the invention.
Claims (6)
1. The preparation method of the titanium boride whisker is characterized by comprising the following steps:
s1, placing boron oxide powder or boric acid powder at the bottom of a crucible;
s2, placing titanium hydride powder or titanium powder on a separator with micropores in the crucible, wherein the titanium hydride powder or the titanium powder is not in direct contact with the boron oxide powder or the boric acid powder;
step S3, placing the crucible in an inert atmosphere, and performing high-temperature sintering to generate titanium boride whiskers;
in the step S1, the boron oxide powder or the boric acid powder is placed at the bottom of the crucible after ball milling, the ball-material ratio is 3-5:1, the ball milling rotating speed is 50-200r/min, and the ball milling time is 10-20h;
in the step S2, the particle size of the titanium hydride powder or the titanium powder is 1-10 mu m.
2. The method for preparing titanium boride whiskers according to claim 1, wherein in the step S2, the mass ratio of the titanium hydride powder to the boron oxide powder is 1-10:1.
3. The method for preparing titanium boride whisker according to claim 1, wherein in the step S3, the high-temperature sintering temperature is 1100-1400 ℃ and the sintering time is 0.5-2h.
4. The method for preparing titanium boride whiskers according to claim 1, wherein in said step S3, after said high-temperature sintering, acid washing and drying are performed to obtain high-purity titanium boride whiskers.
5. The method for preparing titanium boride whiskers according to claim 4, wherein in the pickling process, a mixed solution of hydrofluoric acid, nitric acid and water is used for pickling, the volume ratio of the hydrofluoric acid to the nitric acid to the water is 5-10:15-20:70-80, and the pickling time is 5-10h.
6. A titanium boride whisker prepared by a process according to any one of claims 1 to 5.
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| CN1603238A (en) * | 2004-09-27 | 2005-04-06 | 南京大学 | Preparation method of titanium carbide and titanium nitride one dimension nanometer construction material |
| CN101530918A (en) * | 2007-12-13 | 2009-09-16 | 通用汽车环球科技运作公司 | Method for preparing composite component with strengthened TiB based on titanium alloy via powder metallurgy method |
| CN101691671A (en) * | 2009-08-03 | 2010-04-07 | 山东大学 | Titanium diboride whisker material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1603238A (en) * | 2004-09-27 | 2005-04-06 | 南京大学 | Preparation method of titanium carbide and titanium nitride one dimension nanometer construction material |
| CN101530918A (en) * | 2007-12-13 | 2009-09-16 | 通用汽车环球科技运作公司 | Method for preparing composite component with strengthened TiB based on titanium alloy via powder metallurgy method |
| CN101691671A (en) * | 2009-08-03 | 2010-04-07 | 山东大学 | Titanium diboride whisker material and preparation method thereof |
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