CN103979567A - Method for preparing CrB or CrB2 powder at low temperature - Google Patents

Method for preparing CrB or CrB2 powder at low temperature Download PDF

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CN103979567A
CN103979567A CN201410219062.1A CN201410219062A CN103979567A CN 103979567 A CN103979567 A CN 103979567A CN 201410219062 A CN201410219062 A CN 201410219062A CN 103979567 A CN103979567 A CN 103979567A
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powder
crb
fused salt
described step
mixture
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CN103979567B (en
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冉松林
周黎明
魏雅男
李�杰
林新媛
孙朔
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Anhui University of Technology AHUT
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Anhui University of Technology AHUT
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Abstract

The invention discloses a preparation method of CrB or CrB2 powder, belonging to the technical field of ceramic powder preparation. The preparation method is characterized by uniformly mixing chromium oxide, amorphous boron powder and a certain amount of molten salt and then carrying out heat treatment on the mixture at 800-1100 DEG C for 0.5-2 hours under the protection of an inert gas, thus obtaining the CrB or CrB2 powder, wherein the mole ratio of chromium oxide to amorphous boron powder is 1:4 or 1:6; the byproducts generated after reaction, namely diboron trioxide and molten salt, can be removed by soaking the byproducts in hot water to dissolve the byproducts. The method has the technical effects that the method is low in synthesis temperature, short in synthesis cycle, simple in adopted production process and low in cost and is suitable for volume production; and the prepared CrB or CrB2 powder can be used for preparing structural ceramics, wear and high-temperature oxidation resistant coatings and the like.

Description

A kind of low temperature is prepared CrB or CrB 2the method of powder
Technical field
The invention belongs to ceramic powder preparing technical field, be specifically related to a kind of CrB or CrB 2the preparation method of powder, it can be used for preparing structural ceramics and wear-resisting, high temperature coatings.
Background technology
CrB and CrB 2it is the stone metallic compound of a class, its wear resistance is fabulous, there is good high temperature oxidation resistance, there is below good thermal shock resistance at 1300 DEG C, resistance to strong acid and have higher neutron-absorption cross-section, is widely used as neutron-absorbing coating in wear-resistant coating, corrosion-resistant finishes, nuclear reactor and the tough phase as metal or ceramic matric composite.
Traditional synthetic method is to utilize excessive boric acid and chromic oxide to add carbon black to react in high temperature hydrogen furnace, and its temperature of reaction is high, energy consumption is large, complex process and products obtained therefrom stable not.Although the self-propagating combustion energy consumption of follow-up developments is little, to pollute greatly, safety coefficient is little, required equipment complexity, quality product is also unstable.Bao is met congruent people, and to adopt norbide, chromium metal and carbon-contained additive be raw material, and the method for smelting by electrofuse in vacuum resistance furnace has been prepared high-purity chromium boride powder, its steady quality (Chinese invention patent application number: 201010606506).But this method temperature, up to 2000-2400 DEG C, has improved its production cost undoubtedly.
From the above analysis, current CrB or CrB 2preparation method's ubiquity some shortcomings of powder, have greatly limited its range of application.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provides that a kind of technique is simple, with low cost, prepares CrB or CrB under low temperature 2the method of powder.
In order to solve above technical problem, the present invention is achieved by the following technical programs.
The invention provides one and prepare CrB or CrB 2the method of powder, the method comprises the following steps:
(1) first by chromic oxide (Cr 2o 3), boron (B) powder and fused salt carry out in proportion proportioning, and put into ball mill for dry grinding and mix; Described fused salt is sodium-chlor (NaCl), Repone K (KCl), magnesium chloride (MgCl 2), one or more mixing in lithium chloride (LiCl); The quality of fused salt is Cr 2o 3with 5～20 times of B powder total mass; In the time of preparation CrB, Cr 2o 3with the mol ratio of B powder be 1:4; As preparation CrB 2time, Cr 2o 3with the mol ratio of B powder be 1:6;
(2) mixed powder step (1) being obtained is put into alumina crucible, and naturally cooling after thermal treatment for some time under protection of inert gas obtains CrB (or CrB 2), B 2o 3mixture with fused salt; Described thermal treatment temp is 800～1100 DEG C, and the treatment time is 0.5～2h;
(3) mixture step (2) being obtained is put into the deionized water of 60～90 DEG C and stirs, as the B of reaction generation 2o 3and after fused salt dissolves, be precipitated thing by filtering separation, this throw out can be obtained to CrB (or CrB through washing, alcohol wash, after dry 2) powder.
In the time of preparation CrB powder, as one optimization, the fused salt in described step (1) be NaCl and KCl in molar ratio 1:1 carry out the mixture that proportioning obtains, the quality of this fused salt is Cr 2o 3with 10 times of B powder total mass, Cr 2o 3with the mol ratio of B powder be 1:4; Described step (2) thermal treatment temp is 900 DEG C, and heat treatment time is 1h; Deionized water temperature in described step (3) is 60 DEG C.
At preparation CrB 2when powder, as one optimization, the fused salt in described step (1) be NaCl and KCl in molar ratio 1:1 carry out the mixture that proportioning obtains, the quality of this fused salt is Cr 2o 3with 10 times of B powder total mass, Cr 2o 3with the mol ratio of B powder be 1:6; Described step (2) thermal treatment temp is 900 DEG C, and heat treatment time is 1h; Deionized water temperature in described step (3) is 60 DEG C.
Compared with prior art, the present invention has following technique effect.
(1) technique of the present invention is simple, without the required moulding process of conventional solid-state method, without specific installation, is applicable to batch production.
(2) the present invention prepares CrB or CrB by improving traditional boron thermal reduction method 2powder.The hot method of traditional boron is solid state reaction, and material rate of diffusion is slower, and general requirement B is excessive could be completely by the Cr in raw material 2o 3react completely.Meanwhile, for obtaining pure phase CrB or CrB 2, must allow excessive B and resultant B in early stage 2o 3reaction generates gas phase B 2o 2, and this needs 1500 DEG C of above pyroprocessing, corresponding reaction equation is 2Cr 2o 3+ 10B=4CrB+3B 2o 2or 2Cr 2o 3+ 14B=4CrB 2+ 3B 2o 2.In the present invention, by adding fused salt that the reaction environment of a liquid phase is provided to solid matter, accelerated the diffusion of material, without B is excessive just can be completely by Cr 2o 3react completely.In the present invention, work as Cr 2o 3while being 1:4 or 1:6 with the mol ratio of B, just can obtain CrB or CrB 2pure phase, corresponding reaction equation is Cr 2o 3+ 4B=2CrB+B 2o 3or Cr 2o 3+ 6B=2CrB 2+ B 2o 3, the B that reaction generates 2o 3the method stripping that can infiltrate by hot water.Compare traditional boron thermal reduction method, B raw materials cost has reduced respectively 20% and 14.3%.In addition, the introducing of fused salt has significantly reduced temperature of reaction, has shortened the reaction times, has effectively reduced production energy consumption.
(3) in the present invention,, on the one hand because synthesis temperature is only 800～1000 DEG C, fused salt is to generated CrB or CrB on the other hand 2particle has certain iris action, and grain growth is suppressed, gained CrB or CrB 2powder median size is less than 0.5 μ m.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the CrB powder that makes of embodiment 1.
Fig. 2 is scanning electronic microscope (SEM) photo of the CrB powder that makes of embodiment 1.
Fig. 3 is the CrB that embodiment 2 makes 2x-ray diffraction (XRD) collection of illustrative plates.
Fig. 4 is the CrB that embodiment 1 makes 2scanning electronic microscope (SEM) photo of powder.
Embodiment
In order further to understand technology contents of the present invention, below in conjunction with drawings and Examples in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Embodiment 1
By chromic oxide (Cr 2o 3) carry out proportioning for the ratio of 1:4 in molar ratio with amorphous B powder and obtain powder 1; NaCl and KCl are carried out to proportioning for the ratio of 1:1 in molar ratio and obtain powder 2; By powder 1 and powder 2 in mass ratio the ratio of 1:10 after ball mill for dry grinding is mixed 1h, obtain powder 3; Powder 3 is placed in to alumina crucible, under the protection of mobile Ar gas, is heated to 900 DEG C and be incubated 1h, obtain powder 4 after naturally cooling to room temperature; Powder 4 immersed in 60 DEG C of distilled water and continue to stir 1h, separating and be precipitated thing through vacuum filtration; By throw out with twice of 60 DEG C of distilled water wash rear with washing with alcohol once, after 60 DEG C of dry 8h, obtain CrB powder.
Fig. 1 is the XRD figure spectrum of the prepared CrB powder of the present embodiment, and this collection of illustrative plates shows, prepared CrB powder is pure phase, does not have other impurity phase.Fig. 2 is the SEM photo of the prepared CrB powder of the present embodiment, can find out, its grain-size is less, and median size is less than 0.5 μ m.
Embodiment 2
By chromic oxide (Cr 2o 3) carry out proportioning for the ratio of 1:6 in molar ratio with amorphous B powder and obtain powder 1; NaCl and KCl are carried out to proportioning for the ratio of 1:1 in molar ratio and obtain powder 2; By powder 1 and powder 2 in mass ratio the ratio of 1:10 after ball mill for dry grinding is mixed 1h, obtain powder 3; Powder 3 is placed in to alumina crucible, under the protection of mobile Ar gas, is heated to 900 DEG C and be incubated 1h, obtain powder 4 after naturally cooling to room temperature; Powder 4 immersed in 60 DEG C of distilled water and continue to stir 1h, separating and be precipitated thing through vacuum filtration; By throw out with twice of 60 DEG C of distilled water wash rear with washing with alcohol once, after 60 DEG C of dry 8h, obtain CrB 2powder.
Fig. 3 is the prepared CrB of the present embodiment 2the XRD figure spectrum of powder, this collection of illustrative plates shows, prepared CrB 2powder is pure phase, does not have other impurity phase.Fig. 4 is the prepared CrB of the present embodiment 2the SEM photo of powder, can find out, its grain-size is less, and median size is less than 0.5 μ m.
Embodiment 3
By chromic oxide (Cr 2o 3) carry out proportioning for the ratio of 1:4 in molar ratio with amorphous B powder and obtain powder 1; By powder 1 and LiCl in mass ratio the ratio of 1:20 after ball mill for dry grinding is mixed 1h, obtain powder 2; Powder 2 is placed in to alumina crucible, under the protection of mobile Ar gas, is heated to 800 DEG C and be incubated 2h, obtain powder 3 after naturally cooling to room temperature; Powder 3 immersed in 80 DEG C of distilled water and continue to stir 1h, separating and be precipitated thing through vacuum filtration; By throw out with twice of 80 DEG C of distilled water wash rear with washing with alcohol once, after 60 DEG C of dry 8h, obtain CrB powder.
Embodiment 4
By chromic oxide (Cr 2o 3) carry out proportioning for the ratio of 1:6 in molar ratio with amorphous B powder and obtain powder 1; By powder 1 and MgCl 2the ratio of 1:20 obtains powder 2 after ball mill for dry grinding is mixed 1h in mass ratio; Powder 2 is placed in to alumina crucible, under the protection of mobile Ar gas, is heated to 800 DEG C and be incubated 2h, obtain powder 3 after naturally cooling to room temperature; Powder 3 immersed in 80 DEG C of distilled water and continue to stir 1h, separating and be precipitated thing through vacuum filtration; By throw out with twice of 80 DEG C of distilled water wash rear with washing with alcohol once, after 60 DEG C of dry 8h, obtain CrB 2powder.
Embodiment 5
By chromic oxide (Cr 2o 3) carry out proportioning for the ratio of 1:4 in molar ratio with amorphous B powder and obtain powder 1; By powder 1 and KCl in mass ratio the ratio of 1:5 after ball mill for dry grinding is mixed 1h, obtain powder 2; Powder 2 is placed in to alumina crucible, under the protection of mobile Ar gas, is heated to 1100 DEG C and be incubated 0.5h, obtain powder 3 after naturally cooling to room temperature; Powder 3 immersed in 90 DEG C of distilled water and continue to stir 1h, separating and be precipitated thing through vacuum filtration; By throw out with twice of 90 DEG C of distilled water wash rear with washing with alcohol once, after 60 DEG C of dry 8h, obtain CrB powder.
Embodiment 6
By chromic oxide (Cr 2o 3) carry out proportioning for the ratio of 1:6 in molar ratio with amorphous B powder and obtain powder 1; By powder 1 and NaCl in mass ratio the ratio of 1:5 after ball mill for dry grinding is mixed 1h, obtain powder 2; Powder 2 is placed in to alumina crucible, under the protection of mobile Ar gas, is heated to 1100 DEG C and be incubated 0.5h, obtain powder 3 after naturally cooling to room temperature; Powder 3 immersed in 90 DEG C of distilled water and continue to stir 1h, separating and be precipitated thing through vacuum filtration; By throw out with twice of 90 DEG C of distilled water wash rear with washing with alcohol once, after 60 DEG C of dry 8h, obtain CrB 2powder.

Claims (3)

1. a low temperature is prepared CrB or CrB 2the method of powder, is characterized in that, the method comprises the following steps:
(1) first by Cr 2o 3, B powder and fused salt carry out in proportion proportioning, and put into ball mill for dry grinding and mix; Described fused salt is NaCl, KCl, MgCl 2, one or more mixing in LiCl; The quality of fused salt is Cr 2o 3with 5～20 times of B powder total mass; Cr 2o 3with the mol ratio of B powder be 1:4 or 1:6;
(2) mixed powder step (1) being obtained is put into alumina crucible, and under protection of inert gas, naturally cooling after thermal treatment, obtains B 2o 3, fused salt and CrB or CrB 2mixture; Described thermal treatment temp is 800～1100 DEG C, and heat treatment time is 0.5～2h;
(3) mixture step (2) being obtained is put into the deionized water of 60～90 DEG C and stirs, as the B of reaction generation 2o 3and after fused salt dissolves, be precipitated thing by filtering separation, this throw out can be obtained to CrB or CrB through washing, alcohol wash, after dry 2powder.
2. a kind of low temperature as claimed in claim 1 is prepared the method for CrB powder, it is characterized in that, the fused salt in described step (1) be NaCl and KCl in molar ratio 1:1 carry out the mixture that proportioning obtains, the quality of this fused salt is Cr 2o 3with 10 times of B powder total mass, Cr 2o 3with the mol ratio of B powder be 1:4; Described step (2) thermal treatment temp is 900 DEG C, and heat treatment time is 1h; Deionized water temperature in described step (3) is 60 DEG C.
3. a kind of low temperature as claimed in claim 1 is prepared CrB 2the method of powder, is characterized in that, the fused salt in described step (1) be NaCl and KCl in molar ratio 1:1 carry out the mixture that proportioning obtains, the quality of this fused salt is Cr 2o 3with 10 times of B powder total mass, Cr 2o 3with the mol ratio of B powder be 1:6; Described step (2) thermal treatment temp is 900 DEG C, and heat treatment time is 1h; Deionized water temperature in described step (3) is 60 DEG C.
CN201410219062.1A 2014-05-22 2014-05-22 A kind of low-temperature growth CrB or CrB 2the method of powder Active CN103979567B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017702A (en) * 2015-08-21 2015-11-04 朱明德 High-density rubber sealing gasket containing nano chromium diboride and preparation method of gasket
CN105753005A (en) * 2016-04-02 2016-07-13 上海大学 Method for preparing high-purity quadri-boride manganese (MnB4) with low-temperature solid phase method
CN106882815A (en) * 2017-05-02 2017-06-23 东北大学 A kind of wolfram diboride preparation method
CN108483459A (en) * 2018-02-11 2018-09-04 北京交通大学 A kind of New Two Dimensional CrB nano ceramic materials and preparation method thereof
CN114045546A (en) * 2021-11-22 2022-02-15 安徽工业大学 Method for preparing transition metal boride coating through fused salt in-situ synthesis and electrophoretic deposition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB861743A (en) * 1958-10-29 1961-02-22 United States Borax Chem Method for producing borides
CN102009982A (en) * 2010-12-27 2011-04-13 鲍迎全 Producing method for high-purity chromium boride
CN102689907A (en) * 2012-05-30 2012-09-26 深圳市新星轻合金材料股份有限公司 Preparing method and application of transition metal boride
CN103754871A (en) * 2013-12-10 2014-04-30 西北农林科技大学 Method for preparing Cr7C3/CrB composite powder by utilizing solid-phase reaction diffusion process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB861743A (en) * 1958-10-29 1961-02-22 United States Borax Chem Method for producing borides
CN102009982A (en) * 2010-12-27 2011-04-13 鲍迎全 Producing method for high-purity chromium boride
CN102689907A (en) * 2012-05-30 2012-09-26 深圳市新星轻合金材料股份有限公司 Preparing method and application of transition metal boride
CN103754871A (en) * 2013-12-10 2014-04-30 西北农林科技大学 Method for preparing Cr7C3/CrB composite powder by utilizing solid-phase reaction diffusion process

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017702A (en) * 2015-08-21 2015-11-04 朱明德 High-density rubber sealing gasket containing nano chromium diboride and preparation method of gasket
CN105753005A (en) * 2016-04-02 2016-07-13 上海大学 Method for preparing high-purity quadri-boride manganese (MnB4) with low-temperature solid phase method
CN106882815A (en) * 2017-05-02 2017-06-23 东北大学 A kind of wolfram diboride preparation method
CN108483459A (en) * 2018-02-11 2018-09-04 北京交通大学 A kind of New Two Dimensional CrB nano ceramic materials and preparation method thereof
CN114045546A (en) * 2021-11-22 2022-02-15 安徽工业大学 Method for preparing transition metal boride coating through fused salt in-situ synthesis and electrophoretic deposition
CN114045546B (en) * 2021-11-22 2023-09-12 安徽工业大学 Method for preparing transition metal boride coating by fused salt in-situ synthesis and electrophoretic deposition

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