CN101307406A - Molybdenum free Ti(C, N)-based cermet and method for preparing same - Google Patents

Molybdenum free Ti(C, N)-based cermet and method for preparing same Download PDF

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CN101307406A
CN101307406A CNA2008100482742A CN200810048274A CN101307406A CN 101307406 A CN101307406 A CN 101307406A CN A2008100482742 A CNA2008100482742 A CN A2008100482742A CN 200810048274 A CN200810048274 A CN 200810048274A CN 101307406 A CN101307406 A CN 101307406A
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based ceramic
ceramic metal
sintering
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熊惟皓
李永涛
杨青青
瞿峻
叶大萌
姚振华
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Huazhong University of Science and Technology
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Abstract

The invention relates to a molybdenum-free Ti(C, N) base cermet and a method for preparing the same, belonging to a cermet material. The invention adopts W as a sintering auxiliary phase to substitute Mo and aims to reducing raw material cost and densely sintering without a complicated pre-solid solution method. A final generated phase of the cermet is a Ti(C,N) Ni17W3 sosoloid, wherein, W is solidly dissolved in Ni; the sosoloid comprises the following elements in percentage by mass: more than or equal to 31 percent and less than or equal to 39 percent of Ti, more than or equal to 8 percent and less than or equal to 10.5 percent of C, more than or equal to 2 percent and less than or equal to 3 percent of N, more than or equal to 23 percent and less than or equal to 32 percent of Ni, and more than or equal to 25 percent and less than or equal to 30 percent of W. The preparation method comprises the steps of raw material mixing, compression molding and forming, degreasing and vacuum sintering. The cermet has dense tissue, fine, even and regular hard phase crystal grains; a phase of the cermet comprises Ti(C, N) and Ni17W3; the phase has a hardness more than or equal to 88HRA and a bending strength more than or equal to 1700 MPa, good shock resistance and long service life. The preparation method does not need to adopt a pre-solid solution technology to prepare TiCN particles firstly, does not need to improve equipment and process and has simple implementation and economy.

Description

Molybdenum free Ti (C, N) based ceramic metal and preparation method thereof
Technical field
The invention belongs to cermet material, (C, N) based ceramic metal and preparation method thereof do not need to adopt pre-solid solution technology to prepare the TiCN particle in advance to be specifically related to a kind of molybdenum free Ti.
Background technology
Initial TiC based ceramic metal is because the wettability of TiC and Ni is bad, and the TiC particle aggregation is grown up during sintering, the strength of materials and toughness inequality, and its application is restricted.1956, TiC-Mo invented in Henry Ford 2The C-Ni sintering metal.In TiC and Ni powder, add Mo or Mo 2Behind the C, can improve the wettability of Ni to TiC, and in the alloy sintering process, around the TiC hard-phase particles, form (Ti, Mo) C coats phase, and inhibition TiC particulate is grown up, and ceramic-metallic intensity is greatly improved.The Mo of adding 10% 2C can make liquid phase Ni that the wetting angle of TiC is reduced to zero.(C, N) development of based ceramic metal has epoch making significance, just makes this material move towards practical application widely just because of the introducing of Mo to Ti in the introducing of Mo.Mo also is considered to Ti (C, N) the indispensable interpolation element of based ceramic metal.On the existing Japanese market on sintering metal commonly used and the Chinese market several sintering metals on probation all contain Mo, see Table 1 and table 2.Existing contain molybdenum Ti (C, N) scanning electron photomicrograph of based ceramic metal is seen Fig. 1.
Mo is mainly used in and produces low alloy steel, stainless steel, tool steel, carbon steel, steel alloy and superalloy; The Mo chemical is used to produce petroleum refinement, catalyst of ammoxidation for propylene and aluminium lubricant etc.The output of oil increased owing to stainless steel demand increase in the world in 2004, and the price of Mo ore in sand form has increased by 50%.Domestic, because the defeated engineering of Xi Qidong, and the influence of Huludao City, Liaoning molybdenum ore stopping production, the price of Mo also continues high.Before 2005 10 months, because global economy sustainable growth, particularly steel industry keep prosperous, the price of Mo was high for a long time, the height of its price, and the length of time length is historical rare.Mainly be that (C, N) based ceramic metal, Mo are that (seek more cheap raw material becomes the active demand that Market Situation changes to present Ti for C, the N) important source material of base metal-ceramic material to the Ti that contains molybdenum at present on the China market.Along with the improvement of material preparation technology in recent years, adopt the TiMCN sosoloid (M is Ta, W, Nb etc.) of preparing TiCN sosoloid earlier or having added elements such as Ta, Nb, through pulverizing, mix with WC, Ni/Co more again, sintering is prepared molybdenum free Ti (C, N) based ceramic metal.When adopting this production technique, Mo no longer is the composition that does not lack, but makes preparation section complicated.
The ceramic-metallic trade mark and the performance used always on table 1 Japanese market
The trade mark N302 N308 N310 N350
Form TiCN-WC-TaC TiCN-WC-TaC TiCN-WC-TaC (Ti，W，Ta)CN
Hardness (HRA) 91.0～94.0 91.0～92.0 91.0～92.0 92.5
Bending strength/MPa 1200～1400 1600～1800 1700～1900 1700～1900
Proportion 6.4 7.0 7.0 7.0
Several ceramic-metallic trade mark and the performance of trying out on table 2 Chinese market
The trade mark TN10 TN20 TN30
Form Ti(CN)-Ni-Mo Ti(CN)-Ni-Mo Ti(CN)-Ni-Mo
Hardness (HRA) ≥92.5 ≥91.5 ≥90.5
Bending strength/MPa 1200 ≥1400 ≥1550
Proportion ≥6.5 ≥6.8 ≥6.8
Summary of the invention
(C, N) base metal-ceramic material and preparation method thereof adopt W to substitute Mo as the attached phase that helps of sintering, and purpose is to reduce raw materials cost, does not need complicated pre-solid dissolving method to get final product densified sintering product to the invention provides a kind of molybdenum free Ti.
A kind of molybdenum free Ti of the present invention (C, N) based ceramic metal are made TiC, TiN, Ni, W, WC and powdered graphite through ball mill mixing, moulding, degreasing and sintering, final generate be mutually Ti (C, N), Ni 17W 3Sosoloid, wherein the W solid solution is in Ni, and each element wt per-cent is: 31≤Ti≤39,8≤C≤10.5,2≤N≤3,23≤Ni≤32,25≤W≤30.
(C, N) based ceramic metal is characterized in that in its composition element wt per-cent: 0≤Nb≤2,0≤Ta≤2 described molybdenum free Ti.
(C, N) preparation method of based ceramic metal comprises the steps: molybdenum free Ti of the present invention
1) raw material mixes: (the employing ball mill carries out wet-milling for C, N) TiC of based ceramic metal composition weight percent, TiN, Ni, W, WC and powdered graphite mixing to satisfy described molybdenum free Ti;
2) compression molding: add forming agent polyvinyl alcohol or the SBS of 3wt%-8wt%, compression molding, pressure is 150～350MPa;
3) degreasing: adopt vacuum sintering furnace to carry out degreasing, when forming agent was polyvinyl alcohol, degreasing process was: 200 ℃～400 ℃, and soaking time 4～8h; When forming agent was SBS, degreasing process was: 300 ℃～500 ℃ soaking time 4～8h;
4) vacuum sintering: 1410 ℃～1450 ℃ of sintering temperatures, soaking time 40～90min.
(C, the N) preparation method of based ceramic metal is characterized in that adding NbC, TaC in the described raw material mixing step described molybdenum free Ti, account for the total composition element wt of final product per-cent to be: 0≤Nb≤2,0≤Ta≤2.
(C, the N) preparation method of based ceramic metal is characterized in that adopting planetary ball mill in the described raw material mixing step described molybdenum free Ti, and rotating speed is 100～200rpm, and the time is 10～36h.
The present invention adopts W to substitute Mo as the sintering auxiliary phase, does not need to get final product densified sintering product by pre-solid dissolving method.W and Mo are same gangs, all are body-centered cubic structures, have similar character, can improve wettability between TiC and metallographic phase.Mo can Mo 2The form of C or Mo is added, and W also can simple substance and two kinds of forms interpolations of carbide.The density of tungsten is 19.3g/cm 3, 3410 ℃ of fusing points are all than the density 10.2g/cm of Mo 3, 2917 ℃ high of fusing points are a lot.The price of Mo is about 3 times of W price, and (C, N) addition of Mo is 10～25wt% to preparation Ti during based ceramic metal, adopts W to replace Mo that raw materials cost is obviously reduced, and does not bring any negative impact to preparation technology.Raw-material variation more helps Ti, and (C, N) based ceramic metal further develops.
Because Ni is a W agglomerating activating element,, adds 0.13%Ni and just can then will add 0.2%～0.5% Ni powder for thinner powder among the present invention at 1300 ℃ of densified sintering products for the W powder of 3.3 μ m, just can densified sintering product.Molybdenum free Ti (C, N) based ceramic metal can be in lower sintering temperature densification, and (C, N) based ceramic metal is low 20 ℃～30 ℃ than the molybdenum Ti that contains of similar chemical ingredients.Because W is easy and the Ni reaction generates Ni 17W 3, help the raising of phase intensity that bonds, thereby the over-all properties of material further improved.
Molybdenum free Ti of the present invention (C, N) based ceramic metal tissue signature:
(1) hard phase homogeneous grain size, regular shape, as shown in Figure 3.
(2) microstructure presents typical core-ring structure, by the bonding phase of white, the hard core phase and the gray annular phase composite of black.Outer shroud is thicker, and interior ring is not sufficiently complete, and sees Fig. 2 and Fig. 4, and its EDAX results sees Table 10.
(3) behind the sintering thing phase composite be Ti (C, N) and Ni 17W 3Sosoloid, wherein the W solid solution is in Ni, as shown in Figure 5.
Molybdenum free Ti of the present invention (C, N) its hardness 〉=88.0HRA of based ceramic metal, bending strength 〉=1700MPa, its hardness contains molybdenum Ti (C a little less than similar chemical ingredients, N) based ceramic metal, its bending strength then contain molybdenum Ti (C, N) based ceramic metal a little more than similar chemical ingredients.This material with its higher hardness and bending strength, chemical stability, with advantages such as the intermetallic frictional coefficient is little, what can be used in any similar chemical ingredients contains molybdenum Ti (C, N) the applied place of based ceramic metal.And since this material than similar chemical ingredients contain molybdenum Ti (C, N) the based ceramic metal agglomerating is fine and close more, defective still less, shock resistance is better, longer service life.
Molybdenum free Ti (C of the present invention, N) preparation method of based ceramic metal, need not to adopt pre-solid solution technology preparation TiCN particle earlier, but after directly adopting TiC, TiN, Ni, W, WC and the powdered graphite of market sale to prepare, adopt usual way just can prepare by certain chemical ratios; Need not to improve equipment and technology, implement simple, economical, if add NbC again, TaC can further improve material property.
Description of drawings
Fig. 1 is existing molybdenum Ti (C, the N) scanning electron photomicrograph of based ceramic metal, the magnification 5000 of containing;
Fig. 2 is C13 group molybdenum free Ti (C, N) based ceramic metal scanning electron photomicrograph, a magnification 5000 in the embodiment of the invention 3;
Fig. 3 is C13 group molybdenum free Ti (C, N) the fracture apperance SEM of based ceramic metal, a magnification 2000 in the embodiment of the invention 3;
Fig. 4 be C13 group molybdenum free Ti in the embodiment of the invention 3 (C, N) hard in the based ceramic metal mutually and annular energy spectrum analysis figure EDS mutually, magnification 5000, its analytical results sees Table 10;
Fig. 5 is C13 group molybdenum free Ti (C, N) X-ray analysis of based ceramic metal in the embodiment of the invention 3.
Embodiment
Embodiment 1:
Adopt TiC, TiN, Ni, W, WC and the powdered graphite of market sale, according to 38.2wt%Ti, 9.5wt%C, 2.3wt%N, 25wt%Ni, 25wt%W batching, be divided into 5 groups, adopt ball mill wet-milling batch mixing, ratio of grinding media to material 5: 1～7: 1, processing parameter is as shown in table 3.
Table 3 milling parameters
Figure A20081004827400081
Figure A20081004827400091
Forming agent polyvinyl alcohol with the powder interpolation 7wt% after grinding well mixes the back granulation, and the unidirectional pressing force of employing compression molding is 150MPa.
Degreasing process is to carry out under the condition of 5Pa in vacuum tightness, and holding temperature is 200 ℃, and soaking time is 4h.
Adopt vacuum sintering, its vacuum tightness is not less than 1.0 * 10 -1Pa.Sintering temperature is 1445 ℃, soaking time 60min; Each ceramic-metallic mechanical property is as shown in table 4.
The various molybdenum free Tis of table 4 (C, N) mechanical property of based ceramic metal
Figure A20081004827400092
Embodiment 2:
Adopt TiC, TiN, Ni, W, WC and the powdered graphite of market sale,, be divided into totally 7 groups of B1～B7 according to 31.9wt%Ti, 8.2wt%C, 2.1wt%N, 28wt%Ni, 29.8wt%W batching.Its preparation technology parameter is as follows:
The ball milling of compound carries out on planetary ball mill, ratio of grinding media to material 5: 1～7: 1, and rotating speed 200rpm, time 24h, the abrasive dust mode is for adding the ethanol wet-milling.
The addition of forming agent, forming parameters and degreasing process are as shown in table 5.
The addition of table 5 forming agent, forming parameters and degreasing process
Figure A20081004827400101
Adopt vacuum sintering, its vacuum tightness is not less than 1.0 * 10 -1Pa.Sintering temperature is 1420 ℃, soaking time 60min;
Each ceramic-metallic mechanical property is as shown in table 6.
The various molybdenum free Tis of table 6 (C, N) mechanical property of based ceramic metal
Figure A20081004827400102
Embodiment 3:
Adopt TiC, TiN, Ni, W, WC and the powdered graphite of market sale, prepare burden according to the proportioning raw materials in the table 7.
The various molybdenum free Tis of table 7 (C, N) moiety of based ceramic metal
Figure A20081004827400111
The ball milling of compound carries out on planetary ball mill, ratio of grinding media to material 5: 1～7: 1, and rotating speed 200rpm, time 24h, the abrasive dust mode is for adding the ethanol wet-milling.
Forming agent SBS with the powder interpolation 7wt% after grinding well mixes the back granulation, and the unidirectional pressing force of employing compression molding is 200MPa.
Degreasing process is to carry out under the condition of 5Pa in vacuum tightness, and holding temperature is 450 ℃, and soaking time is 6h.
Adopt vacuum sintering, its vacuum tightness is not less than 1.0 * 10 -1Pa.Ni content difference, the sintering temperature difference.Its sintering process is as shown in table 8.
Table 8 vacuum sintering technology parameter
Figure A20081004827400121
Each ceramic-metallic mechanical property is as shown in table 9.
The various molybdenum free Tis of table 9 (C, N) mechanical property of based ceramic metal
Figure A20081004827400122
Figure A20081004827400131
Wherein C13 group molybdenum free Ti (C, N) the based ceramic metal scanning electron photomicrograph is seen Fig. 2, fracture apperance SEM sees Fig. 3, hard is seen Fig. 4, W among the figure with annular energy spectrum analysis figure EDS mutually mutually: phase bonds; H: hard phase; R: annular phase; Analytical results sees Table 10; X-ray analysis is seen Fig. 5.
(C, N) the middle mutually element of based ceramic metal thing distributes table 10 molybdenum free Ti
Figure A20081004827400132
Embodiment 4:
Adopt and add TaC/NbC, with further raising performance.Adopt TiC, TiN, Ni, W, WC, TaC, NbC and the powdered graphite of market sale, prepare burden according to the proportioning raw materials in the table 11.
The various molybdenum free Tis of table 11 (C, N) moiety of based ceramic metal
Figure A20081004827400141
The ball milling of compound carries out on planetary ball mill, ratio of grinding media to material 5: 1～7: 1, and rotating speed 200rpm, time 24h, the abrasive dust mode is for adding the ethanol wet-milling.
Forming agent SBS with the powder interpolation 7wt% after grinding well mixes the back granulation, and the unidirectional pressing force of employing compression molding is 200MPa.
Degreasing process is to carry out under the condition of 5Pa in vacuum tightness, and holding temperature is 450 ℃, and soaking time is 6h.
Adopt vacuum sintering, its vacuum tightness is not less than 1.0 * 10 -1Pa.D1, D2, D3 sintering temperature are 1435 ℃, soaking time 60min; The D4 sintering temperature is 1430 ℃, soaking time 60min; D5 and D6 sintering temperature are 1415 ℃, soaking time 60min;
Adopt these compositions and method the preparation Ti (C, N) its mechanical property of based ceramic metal such as table 12 show.
The various molybdenum free Tis of table 12 (C, N) mechanical property of based ceramic metal
Figure A20081004827400151

Claims (5)

  1. A molybdenum free Ti (C, N) based ceramic metal are made TiC, TiN, Ni, W, WC and powdered graphite through ball mill mixing, moulding, degreasing and sintering, final generate be mutually Ti (C, N), Ni 17W 3Sosoloid, wherein the W solid solution is in Ni, and each element wt per-cent is: 31≤Ti≤39,8≤C≤10.5,2≤N≤3,23≤Ni≤32,25≤W≤30.
  2. 2. (C, N) based ceramic metal is characterized in that in its composition element wt per-cent: 0≤Nb≤2,0≤Ta≤2 molybdenum free Ti as claimed in claim 1.
  3. 3. (C, N) preparation method of based ceramic metal comprises the steps: the described molybdenum free Ti of claim 1
    1) raw material mixes: (the employing ball mill carries out wet-milling for C, N) TiC of based ceramic metal composition weight percent, TiN, Ni, W, WC and powdered graphite mixing to satisfy described molybdenum free Ti;
    2) compression molding: add forming agent polyvinyl alcohol or the SBS of 3wt%-8wt%, compression molding, pressure is 150～350MPa;
    3) degreasing: adopt vacuum sintering furnace to carry out degreasing, when forming agent was polyvinyl alcohol, degreasing process was: 200 ℃～400 ℃, and soaking time 4～8h; When forming agent was SBS, degreasing process was: 300 ℃～500 ℃ soaking time 4～8h;
    4) vacuum sintering: 1410 ℃～1450 ℃ of sintering temperatures, soaking time 40～90min.
  4. 4. (C, the N) preparation method of based ceramic metal is characterized in that adding NbC, TaC in the described raw material mixing step molybdenum free Ti as claimed in claim 3, account for the total composition element wt of final product per-cent to be: 0≤Nb≤2,0≤Ta≤2.
  5. 5. (C, the N) preparation method of based ceramic metal is characterized in that adopting planetary ball mill in the described raw material mixing step, and rotating speed is 100～200rpm, and the time is 10～36h as claim 3 or 4 described molybdenum free Tis.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102828096A (en) * 2012-09-17 2012-12-19 天津瑞克曼德科技发展有限公司 Metal ceramic cutting tool material and preparation method thereof
CN103521770A (en) * 2013-09-22 2014-01-22 成都工具研究所有限公司 TiCN based metal ceramic
CN103774022A (en) * 2012-10-19 2014-05-07 郑汉东 Ti(C,N)-based metal ceramic and its application
CN106944610A (en) * 2017-04-19 2017-07-14 东莞华晶粉末冶金有限公司 A kind of cermet material, preparation method and products thereof
CN112024890A (en) * 2020-11-06 2020-12-04 宁波新宇硬质合金密封有限公司 Hard alloy stop block and compression molding process

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102828096A (en) * 2012-09-17 2012-12-19 天津瑞克曼德科技发展有限公司 Metal ceramic cutting tool material and preparation method thereof
CN102828096B (en) * 2012-09-17 2013-12-11 天津瑞克曼德科技发展有限公司 Metal ceramic cutting tool material and preparation method thereof
CN103774022A (en) * 2012-10-19 2014-05-07 郑汉东 Ti(C,N)-based metal ceramic and its application
CN103774022B (en) * 2012-10-19 2015-11-11 郑汉东 Ti (C, N) based ceramic metal and application thereof
CN103521770A (en) * 2013-09-22 2014-01-22 成都工具研究所有限公司 TiCN based metal ceramic
CN103521770B (en) * 2013-09-22 2015-10-28 成都工具研究所有限公司 TiCN based ceramic metal
CN106944610A (en) * 2017-04-19 2017-07-14 东莞华晶粉末冶金有限公司 A kind of cermet material, preparation method and products thereof
CN112024890A (en) * 2020-11-06 2020-12-04 宁波新宇硬质合金密封有限公司 Hard alloy stop block and compression molding process

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