CN104326748A - Method for self propagating high temperature synthesis of titanium-sulfur-carbon powder material - Google Patents

Method for self propagating high temperature synthesis of titanium-sulfur-carbon powder material Download PDF

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CN104326748A
CN104326748A CN201410460797.3A CN201410460797A CN104326748A CN 104326748 A CN104326748 A CN 104326748A CN 201410460797 A CN201410460797 A CN 201410460797A CN 104326748 A CN104326748 A CN 104326748A
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powder
body material
shs process
ball milling
powder body
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CN104326748B (en
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朱春城
姚磊
孙和鑫
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Harbin Shinkansen Rail Transit Technology Co., Ltd.
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Harbin Normal University
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Abstract

The invention relates to a method for self propagating high temperature synthesis of a titanium-sulfur-carbon powder material, and concretely relates to a preparation method of a ternary carbide ceramic powder material. The technical problems of complex technology, high cost and low efficiency of present Ti2SC preparation methods are solved. The method comprises the following steps: 1, putting Ti powder, S powder and C powder in a resin ball milling pot, carrying out ball milling in a planetary ball mill with anhydrous ethanol as a dispersant to obtain a mixture, drying the mixture in a vacuum drying box, grinding, and sieving to obtain uniformly mixed powder; 2, putting the uniformly mixed powder in a die, applying a pressure, maintaining the pressuring, and compacting to form a preform; and 3, putting the preform in a vacuum reactor, igniting the center of the upper surface of the preform to initiate a self propagating combustion reaction, and grinding the obtained sintered loose small blocks to obtain the titanium-sulfur-carbon powder material. The method is applied to the field of preparation of ternary carbide ceramic powder materials.

Description

A kind of method of SHS process titanium sulphur toner body material
Technical field
The present invention relates to a kind of preparation method of double carbide ceramic powder material.
Background technology
In recent years, a class has the new ceramic material ternary M of laminate structure n+1aX n(M is transition metal, and A is main group element, and X is C or N, n=1 ~ 3) phase compound obtains the favor of vast Materials science worker, becomes study hotspot.Ti 2sC ternary ceramics is M n+1aX nin 211 phases, by the people such as Frick.C (Arch.Eisenhuttenwes Metall, 31 (1960) 419) in nineteen sixty reported first.This material has many advantages of metal and pottery, such as high-melting-point, good electroconductibility and thermal conductivity, excellent oxidation-resistance and heat-shock resistance, and low friction coefficient and processability etc.At all M n+1aX nti in phase material 2the lattice parameter of SC is more minimum than the value of c/a, makes Ti 2sC has and is different from other M n+1aX nthe special performance of compounds of group, Ti 2sC has the highest hardness (Vickers' hardness 8 ± 2GPa), the highest thermal conductivity (60Wm -1k -1) and best wear resistance (all showing stronger friction resistant performance in the temperature range of room temperature to 550 DEG C).Therefore, Ti 2sC gets a good chance of the novel texture/functions formed material that can become the fields such as aerospace.
At present about Ti 2the report of SC synthesis is few.The people such as S.Amini, M.W.Barsoum (J.Am.Ceram.Soc, 90 (2007) 3953) are with Ti 2sC powder is raw material, is incubated 5h obtains Ti by the method for hot pressed sintering under 1500 DEG C of pressure with 45MPa 2sC block materials.Virtue (Wuhan: Wuhan University of Technology, 2010) adopts two step synthesis Ti incomparably 2sC, first by Ti powder and S powder with 1: 2 mixed in molar ratio, in vacuum, be incubated 10 hours at 650 DEG C of temperature TiS 2powder, and then by Ti powder, TiS 2powder, C powder are with Ti:TiS 2: the mixed in molar ratio of C=31.2: 2, is incubated 2h with at the temperature of hot pressing sintering method 30MPa pressure and 1600 DEG C in vacuum, or is incubated 10min at temperature with discharge plasma sintering method 30MPa pressure and 1450 DEG C in vacuum and obtains Ti 2sC block materials.Adopt hot isostatic pressing technique, required equipment is expensive, and complicated operation, and adopt two step synthesis Ti 2sC, with high costs, technique is more loaded down with trivial details consuming time.
Summary of the invention
The present invention will solve existing Ti 2the technical problem of the complex process that the preparation method of SC exists, with high costs, inefficiency, thus provide one SHS process Ti 2the method of SC powder body material.
One SHS process Ti of the present invention 2the method of SC powder body material is carried out according to the following steps:
One, Ti powder, S powder and C powder are put into resin balls grinding jar, using dehydrated alcohol as dispersion agent in planetary ball mill with the rotating speed ball milling 5 ~ 10h of 150 ~ 200r/min, obtain batch mixing, then batch mixing is put into vacuum drying oven, dry at temperature is 30 ~ 40 DEG C, then grind, cross 80 ~ 100 mesh sieves, the powder that must mix; Wherein, the liquid level of described dehydrated alcohol did not have Ti powder, S powder and C powder mixture 5 ~ 10mm; The mol ratio of described Ti powder, S powder and C powder is (1 ~ 2): (1 ~ 1.2): 1;
Two, the powder mixed step one obtained is put into mould in, apply the pressure of 5 ~ 12MPa, pressurize 2 ~ 5min, is pressed into the precast billet that relative density is 40% ~ 60%;
Three, precast billet is put into vacuum reactor, then in the upper surface centerfire of precast billet, cause self-propagating combustion reaction, finally the loose small blocks after sintering is ground powdered, namely obtain titanium sulphur toner body material.
The present invention includes following beneficial effect:
The present invention utilizes self-propagating high-temperature synthesis with the Ti powder of low cost, S powder and C powder for the Ti of higher degree (90.2%) prepared by raw material 2sC powder body material, this process costs is low, simple to operate, and energy consumption is low, and efficiency is high, advantages, and the use of this technology will have obvious social and economic benefits.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of titanium sulphur toner body material prepared by test one; Wherein, ◆ be Ti 2sC, ◇ are TiC.
Embodiment
Embodiment one: the one SHS process Ti of present embodiment 2the method of SC powder body material is carried out according to the following steps:
One, Ti powder, S powder and C powder are put into resin balls grinding jar, using dehydrated alcohol as dispersion agent in planetary ball mill with the rotating speed ball milling 5 ~ 10h of 150 ~ 200r/min, obtain batch mixing, then batch mixing is put into vacuum drying oven, dry at temperature is 30 ~ 40 DEG C, then grind, cross 80 ~ 100 mesh sieves, the powder that must mix; Wherein, the liquid level of described dehydrated alcohol did not have Ti powder, S powder and C powder mixture 5 ~ 10mm; The mol ratio of described Ti powder, S powder and C powder is (1 ~ 2): (1 ~ 1.2): 1;
Two, the powder mixed step one obtained is put into mould in, apply the pressure of 5 ~ 12MPa, pressurize 2 ~ 5min, is pressed into the precast billet that relative density is 40% ~ 60%;
Three, precast billet is put into vacuum combustion synthesis reaction device, then in the upper surface centerfire of precast billet, cause self-propagating combustion reaction, finally the loose small blocks after sintering is ground powdered, namely obtain titanium sulphur toner body material.
Present embodiment comprises following beneficial effect:
Present embodiment utilizes self-propagating high-temperature synthesis with the Ti powder of low cost, S powder and C powder for the Ti of higher degree (90.2%) prepared by raw material 2sC powder body material, this process costs is low, simple to operate, and energy consumption is low, and efficiency is high, advantages, and the use of this technology will have obvious social and economic benefits.
Embodiment two: present embodiment and embodiment one unlike: in step one, the massfraction of Ti powder, S powder and C powder is 99% ~ 100%.Other is identical with embodiment one.
Embodiment three: present embodiment and specifically mode one or two unlike: in step one ball milling used for diameter be the agate ball of 10mm, and ratio of grinding media to material is 10: 1.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: with the rotating speed ball milling 10h of 150r/min in step one.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: in step one at temperature is 35 DEG C dry.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the liquid level of the dehydrated alcohol described in step one did not have Ti powder, S powder and C powder mixture 10mm.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: the mol ratio of the Ti powder described in step one, S powder and C powder is 2: (1 ~ 1.2): 1.Other is identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: apply the pressure of 5 ~ 10MPa in step 2.Other is identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight are unlike pressurize 2min in step 2.Other is identical with one of embodiment one to eight.
By following verification experimental verification beneficial effect of the present invention:
Test one: the one SHS process Ti of this test 2the method of SC powder body material realizes according to the following steps:
One, agate ball Ti powder, S powder and C powder and diameter being about 10mm puts into resin balls grinding jar by the ratio of grinding media to material of 10: 1, using dehydrated alcohol as dispersion agent in planetary ball mill with the rotating speed ball milling 10h of 150r/min, obtain batch mixing, then batch mixing is put into vacuum drying oven, dry at temperature is 35 DEG C, then grind, cross 80 mesh sieves, the powder that must mix; Wherein, the liquid level of described dehydrated alcohol did not have Ti powder, S powder and C powder mixture 10mm; The mol ratio of described Ti powder, S powder and C powder is 2: 1: 1; The massfraction of described Ti powder, S powder and C powder is 99%;
Two, the powder mixed step one obtained is put into mould in, apply the pressure of 10MPa, pressurize 2min, is pressed into the precast billet that relative density is 60%;
Three, precast billet is put into vacuum combustion synthesis reaction device, then in the upper surface centerfire of precast billet, cause self-propagating combustion reaction, finally the loose small blocks after sintering is ground powdered, namely obtain titanium sulphur toner body material.
The X ray diffracting spectrum of the titanium sulphur toner body material of this test preparation as shown in Figure 1; Wherein, ◆ be Ti 2sC, ◇ are TiC, as can be seen from Figure 1, and prepared Ti 2sC powder body material purity is higher, only containing a small amount of impurity phase TiC.
According to the proportioning of the raw material of this test and the relative density of precast billet, gained Ti 2in SC powder body material, Ti 2the content of SC is 85.4%.
Test two: the one SHS process Ti of this test 2the method of SC powder body material realizes according to the following steps:
One, agate ball Ti powder, S powder and C powder and diameter being about 10mm puts into resin balls grinding jar by the ratio of grinding media to material of 10: 1, using dehydrated alcohol as dispersion agent in planetary ball mill with the rotating speed ball milling 10h of 150r/min, obtain batch mixing, then batch mixing is put into vacuum drying oven, dry at temperature is 35 DEG C, then grind, cross 80 mesh sieves, the powder that must mix; Wherein, the liquid level of described dehydrated alcohol did not have Ti powder, S powder and C powder mixture 10mm; The mol ratio of described Ti powder, S powder and C powder is 2: 1.1: 1; The massfraction of described Ti powder, S powder and C powder is 99%;
Two, the powder mixed step one obtained is put into mould in, apply the pressure of 10MPa, pressurize 2min, is pressed into the precast billet that relative density is 60%;
Three, precast billet is put into vacuum combustion synthesis reaction device, then in the upper surface centerfire of precast billet, cause self-propagating combustion reaction, finally the loose small blocks after sintering is ground powdered, namely obtain titanium sulphur toner body material.
According to the proportioning of the raw material of this test and the relative density of precast billet, gained Ti 2in SC powder body material, Ti 2the content of SC is 87.3%.
Test three: the one SHS process Ti of this test 2the method of SC powder body material realizes according to the following steps:
One, agate ball Ti powder, S powder and C powder and diameter being about 10mm puts into resin balls grinding jar by the ratio of grinding media to material of 10: 1, using dehydrated alcohol as dispersion agent in planetary ball mill with the rotating speed ball milling 10h of 150r/min, obtain batch mixing, then batch mixing is put into vacuum drying oven, dry at temperature is 35 DEG C, then grind, cross 80 mesh sieves, the powder that must mix; Wherein, the liquid level of described dehydrated alcohol did not have Ti powder, S powder and C powder mixture 10mm; The mol ratio of described Ti powder, S powder and C powder is 2: 1.2: 1; The massfraction of described Ti powder, S powder and C powder is 99%;
Two, the powder mixed step one obtained is put into mould in, apply the pressure of 10MPa, pressurize 2min, is pressed into the precast billet that relative density is 60%;
Three, precast billet is put into vacuum combustion synthesis reaction device, then in the upper surface centerfire of precast billet, cause self-propagating combustion reaction, finally the loose small blocks after sintering is ground powdered, namely obtain titanium sulphur toner body material.
According to the proportioning of the raw material of this test and the relative density of precast billet, gained Ti 2in SC powder body material, Ti 2the content of SC is 90.2%.
Test four: the one SHS process Ti of this test 2the method of SC powder body material realizes according to the following steps:
One, agate ball Ti powder, S powder and C powder and diameter being about 10mm puts into resin balls grinding jar by the ratio of grinding media to material of 10: 1, using dehydrated alcohol as dispersion agent in planetary ball mill with the rotating speed ball milling 10h of 150r/min, obtain batch mixing, then batch mixing is put into vacuum drying oven, dry at temperature is 35 DEG C, then grind, cross 80 mesh sieves, the powder that must mix; Wherein, the liquid level of described dehydrated alcohol did not have Ti powder, S powder and C powder mixture 10mm; The mol ratio of described Ti powder, S powder and C powder is 2: 1.2: 1; The massfraction of described Ti powder, S powder and C powder is 99%;
Two, the powder mixed step one obtained is put into mould in, apply the pressure of 6MPa, pressurize 2min, is pressed into the precast billet that relative density is 50%;
Three, precast billet is put into vacuum combustion synthesis reaction device, then in the upper surface centerfire of precast billet, cause self-propagating combustion reaction, finally the loose small blocks after sintering is ground powdered, namely obtain titanium sulphur toner body material.
According to the proportioning of the raw material of this test and the relative density of precast billet, gained Ti 2in SC powder body material, Ti 2the content of SC is 86.1%.
Test five: the one SHS process Ti of this test 2the method of SC powder body material realizes according to the following steps:
One, agate ball Ti powder, S powder and C powder and diameter being about 10mm puts into resin balls grinding jar by the ratio of grinding media to material of 10: 1, using dehydrated alcohol as dispersion agent in planetary ball mill with the rotating speed ball milling 10h of 150r/min, obtain batch mixing, then batch mixing is put into vacuum drying oven, dry at temperature is 35 DEG C, then grind, cross 80 mesh sieves, the powder that must mix; Wherein, the liquid level of described dehydrated alcohol did not have Ti powder, S powder and C powder mixture 10mm; The mol ratio of described Ti powder, S powder and C powder is 2: 1.2: 1; The massfraction of described Ti powder, S powder and C powder is 99%;
Two, the powder mixed step one obtained is put into mould in, apply the pressure of 5MPa, pressurize 2min, is pressed into the precast billet that relative density is 40%;
Three, precast billet is put into vacuum combustion synthesis reaction device, then in the upper surface centerfire of precast billet, cause self-propagating combustion reaction, finally the loose small blocks after sintering is ground powdered, namely obtain titanium sulphur toner body material.
According to the proportioning of the raw material of this test and the relative density of precast billet, gained Ti 2in SC powder body material, Ti 2the content of SC is 79.7%.

Claims (9)

1. use SHS process Ti for one kind 2the method of SC powder body material, is characterized in that using SHS process Ti 2the method of SC powder body material is carried out according to the following steps:
One, Ti powder, S powder and C powder are put into resin balls grinding jar, using dehydrated alcohol as dispersion agent in planetary ball mill with the rotating speed ball milling 5 ~ 10h of 150 ~ 200r/min, obtain batch mixing, then batch mixing is put into vacuum drying oven, dry at temperature is 30 ~ 40 DEG C, then grind, cross 80 ~ 100 mesh sieves, the powder that must mix; Wherein, the liquid level of described dehydrated alcohol did not have Ti powder, S powder and C powder mixture 5 ~ 10mm; The mol ratio of described Ti powder, S powder and C powder is (1 ~ 2): (1 ~ 1.2): 1;
Two, the powder mixed step one obtained is put into mould in, apply the pressure of 5 ~ 12MPa, pressurize 2 ~ 5min, is pressed into the precast billet that relative density is 40% ~ 60%;
Three, precast billet is put into vacuum combustion synthesis reaction device, then in the upper surface centerfire of precast billet, cause self-propagating combustion reaction, finally the loose small blocks after sintering is ground powdered, namely obtain titanium sulphur toner body material.
2. one SHS process Ti according to claim 1 2the method of SC powder body material, is characterized in that the massfraction of Ti powder in step one, S powder and C powder is 99% ~ 100%.
3. one SHS process Ti according to claim 1 2the method of SC powder body material, to it is characterized in that in step one ball milling used for diameter be the agate ball of 10mm, and ratio of grinding media to material is 10: 1.
4. one SHS process Ti according to claim 1 2the method of SC powder body material, is characterized in that in step one with the rotating speed ball milling 10h of 150r/min.
5. one SHS process Ti according to claim 1 2the method of SC powder body material, is characterized in that drying at temperature is 35 DEG C in step one.
6. one SHS process Ti according to claim 1 2the method of SC powder body material, is characterized in that the liquid level of the dehydrated alcohol described in step one did not have Ti powder, S powder and C powder mixture 10mm.
7. one SHS process Ti according to claim 1 2the method of SC powder body material, is characterized in that the mol ratio of the Ti powder described in step one, S powder and C powder is 2: (1 ~ 1.2): 1.
8. one SHS process Ti according to claim 1 2the method of SC powder body material, is characterized in that the pressure applying 5 ~ 10MPa in step 2.
9. one SHS process Ti according to claim 1 2the method of SC powder body material, is characterized in that pressurize 2min in step 2.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106187194A (en) * 2016-07-20 2016-12-07 哈尔滨师范大学 A kind of Ti2the preparation method of SnC block ceramic
CN112010308A (en) * 2020-08-26 2020-12-01 盐城工学院 Preparation method of surface modified carbon titanium sulfide battery negative electrode material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992112A (en) * 2014-05-19 2014-08-20 河南工业大学 Novel method for synthesizing Ti2SC ceramic

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103992112A (en) * 2014-05-19 2014-08-20 河南工业大学 Novel method for synthesizing Ti2SC ceramic

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
梁宝岩等: "自蔓延高温合成Ti2SC材料", 《粉末冶金材料科学与工程》, vol. 18, no. 5, 31 October 2013 (2013-10-31), pages 675 - 679 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106187194A (en) * 2016-07-20 2016-12-07 哈尔滨师范大学 A kind of Ti2the preparation method of SnC block ceramic
CN112010308A (en) * 2020-08-26 2020-12-01 盐城工学院 Preparation method of surface modified carbon titanium sulfide battery negative electrode material
CN112010308B (en) * 2020-08-26 2023-05-16 盐城工学院 Preparation method of surface modified titanium carbonitride battery negative electrode material

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