CN105734387B - A kind of TiB2Based ceramic metal and preparation method thereof - Google Patents

A kind of TiB2Based ceramic metal and preparation method thereof Download PDF

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Publication number
CN105734387B
CN105734387B CN201610152927.6A CN201610152927A CN105734387B CN 105734387 B CN105734387 B CN 105734387B CN 201610152927 A CN201610152927 A CN 201610152927A CN 105734387 B CN105734387 B CN 105734387B
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tib
powder
warming
incubated
ceramic metal
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CN105734387A (en
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阮建明
吴宁
杨海林
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Central South University
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/14—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/01—Reducing atmosphere
    • B22F2201/013—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/20—Use of vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Abstract

A kind of TiB of the present invention2Based ceramic metal, it includes the component of following percent by volume：TiB265%~90%；Fe and Ni 10%~35%；In the Fe and Ni, Fe, Ni mass ratio are 3:7 to 8:2.The TiB2Based ceramic metal has high-flexural strength and high-fracture toughness, and bending strength is 600MPa~1100Mpa, fracture toughness 15MPam1/2~21MPam1/2。

Description

A kind of TiB2Based ceramic metal and preparation method thereof
Technical field
The present invention relates to a kind of high-compactness high-strength and high ductility TiB2 based ceramic metals and preparation method thereof.
Background technology
Titanium diboride (TiB2) there is excellent combination property, fusing point and hardness are high, heat endurance, inoxidizability, anti-corruption Corrosion and anti-wear performance are good, are acknowledged as excellent hard phase in field of new materials such as composite, cermets great The new and high technology material of promotional value and application prospect.In recent years, vast researcher to addition metal sintering by adding TiB prepared by agent2The research of based ceramic metal shows, TiB2Based ceramic metal has high red hardness, good fracture tough Property, thermal fatigue resistance, thermal shock resistance, hardness --- fracture toughness combination is better than in general hard alloy, and has anti-crescent moon Hollow and antisticking ability.Compared with other ceramic materials, when processing ferroalloy, there is good thermal conductivity, do not closed with iron Gold reacts, and is suitable for high speed processing, in finishing medium carbon steel, spheroidal graphite cast-iron, alusil alloy and processing ferroalloy etc. Aspect, have a good application prospect.In addition, TiB2Based ceramic metal has outstanding corrosion resistance and anti-wear performance, and it is more Adding to be widely applied still has to be developed and explores.
The TiB currently prepared2Based ceramic metal, because the content of the metallic addition of addition is usually no more than gross mass 10% so that TiB2Although based ceramic metal possesses high rigidity, but bending strength and fracture toughness are relatively low.Therefore, one is sought Kind sinter additives, by increasing its content so that the TiB of preparation2While based ceramic metal possesses higher hardness, its bending resistance Intensity and fracture toughness also greatly improve, and just become particularly important.Fe and Ni are to TiB2Particle has good wetability, with Fe, Ni are single sinter additives or the TiB prepared with the polynary sinter additives containing Fe or Ni2Based ceramic metal is more next It is studied more, but using Fe-Ni as binary sinter additives, sintering is especially used as using the Fe-Ni of high volume content TiB prepared by additive2The research of Base Metal pottery is not seen in document report also.Therefore, the present invention is with high volume content Fe-Ni prepares TiB as sinter additives2Base Metal is made pottery, and probes into its performance and application, has highly important scientific research and practice Meaning.
The content of the invention
A kind of it is contemplated that overcome the deficiencies in the prior art, there is provided TiB2Base Metal pottery its preparation method.
In order to achieve the above object, technical scheme provided by the invention is：
The TiB2Based ceramic metal includes the component of following percent by volume：
TiB265%~90%；
Fe and Ni 10%~35%；
In the Fe and Ni, Fe, Ni mass ratio are 3:7 to 8:2.
Wherein, the TiB2Particle mean size be 1 μm~6 μm..The TiB2Based ceramic metal has high-compactness, height anti- Curved intensity, high-fracture toughness, its consistency are 92.48%~99.50%, and bending strength is 600MPa~1100Mpa, and fracture is tough Property is 15MPam1/2~21MPam1/2。
Above-mentioned TiB2The preparation method of based ceramic metal comprises the following steps：
(1) TiB is prepared in the ratio described in claim 12Powder, Fe powder, Ni powder；By TiB2Powder is well mixed with forming agent, The Fe powder and Ni powder as sinter additives are added, then through planetary ball mill batch mixing, obtains mixed-powder；Per 100g mixed powders 0.5~3g forming agents are added in end；
(2) mixed-powder is molded to obtain cuboid pressed compact using steel mold pressing, then with cold isostatic press pressurize 1~ 5min；
(3) in atmosphere of hydrogen, cuboid pressed compact is warming up to 500 DEG C~600 DEG C and is incubated 1.5~2h to carry out degreasing Processing, forming agent is removed, then proceed to be warming up to 800 DEG C and be incubated 0.5~1h to carry out reduction treatment, after obtaining degreasing reduction Pressed compact；
(4) pressed compact after degreasing is reduced carries out vacuum-sintering, obtains TiB2Based ceramic metal.
Wherein, step (1) described forming agent is solid paraffin.During step (1) the planetary ball mill batch mixing, ratio of grinding media to material is (0.5~3)：1.The sheath material that step (2) described cold isostatic press uses is rubber finger sleeve, and cold isostatic press dwell pressure is 150~200MPa.Step (3) is described to be warming up to 500 DEG C~600 DEG C by cuboid pressed compact and is incubated 1.5~2h, and preferably 2h is to enter Row ungrease treatment, then proceed to be warming up to 800 DEG C and be incubated 0.5~1h, be by cuboid when preferably 1h is to carry out reduction treatment Pressed compact with 2 DEG C/min~5 DEG C/min speed be warming up to 500 DEG C~600 DEG C insulation 1.5~2h, then proceed to 4 DEG C/min~ 6 DEG C/min speed is warming up to 800 DEG C and is incubated 0.5~1h.
9th, method as claimed in claim 5, it is characterised in that step (4) described vacuum-sintering is 10-2~10-1Pa Vacuum under, pressed compact after degreasing is reduced is warming up to 600 DEG C~800 DEG C with 4 DEG C/min~6 DEG C/min speed, insulation 0.5h~1h；Then 10-3~10-2Under Pa vacuum, with 5 DEG C/min~7 DEG C/min speed be warming up to 1400 DEG C~ 1500 DEG C, it is incubated 0h~0.5h；Then 10-2~10-1Under Pa vacuum, heated up with 4 DEG C/min~7 DEG C/min speed To 1600 DEG C~1800 DEG C, 0.5h~1h is incubated；1300 DEG C~1400 DEG C are cooled to, is incubated 0h~0.5h；It is finally cooled to 800 DEG C~900 DEG C, after being incubated 0h~0.5h, continue cool to room temperature.
The invention will be further described below：
The present invention is prepared for a kind of with higher hardness bending strength and fracture simultaneously using Fe-Ni as sinter additives Toughness also higher TiB2Base Metal is made pottery.
Below to preparing TiB2Four steps of based ceramic metal are described in detail：
Step (1)：The addition 100g titanium diborides of forming agent, iron, nickel mixed-powder is often prepared to comprise the following steps that：
(a) 50ml gasoline is measured in 500ml beakers and beaker is placed in heating water bath pot and is heated, by 0.5~3g's Forming agent is dissolved in gasoline；
(b) by 49.80~68.93g titanium diborides (TiB2) powder poured into beaker, and with magnetic stirrer 10~ 15min, then beaker is put into air dry oven and is dried, drying temperature is set to 80 DEG C；
(c) by the titanium diboride (TiB of drying2) powder crosses 80 mesh sieves, it is subsequently poured into ball grinder, then by 12.75~ 34.48g iron (Fe) powder and 9.32~30.12g nickel (Ni) powder are added in ball grinder, add 50~80g stainless steel ball；
(d) will be put into after ball grinder applying argon gas on planetary ball mill and carry out ball mill mixing, rotate clockwise 15~30min with Rotate counterclockwise 15~30min alternate rotations, 4~6h；
(e) mixed powder is crossed into 80 mesh sieve, finally gives well mixed mixed-powder.
Preferably, step (a) forming agent is solid paraffin.
Step (2)：Mixed-powder is molded to obtain cuboid pressed compact using steel mold pressing, then with cold isostatic press pressurize, Make what green density further improved to comprise the following steps that：
(a) it is fitted into electronic balance weighing 3~5g mixed-powders in mould, long 24~25mm is made using Bidirectional pressure, Wide 6~7mm, high 5~7mm cuboid pressed compact；
(b) cuboid pressed compact is fitted into rubber finger sleeve (the corresponding fingerstall of a pressed compact) sealing, then entered with isostatic cool pressing One step is compressing；
(c) remove rubber finger sleeve and obtain the pressed compact after isostatic cool pressing.
Preferably, the pressure of step (a) the two-way compacting is 3~5MPa, and the dwell time is 10~60 seconds.
Preferably, the pressure of the pressurize of step (b) cold isostatic press is 150~200MPa, the dwell time is 1~ 5min。
Step (3)：In atmosphere of hydrogen, pressed compact is warming up to 500 DEG C~600 DEG C insulation 2h and carries out ungrease treatment, it is follow-up It is continuous to be warming up to 800 DEG C of insulation 1h and reduced, obtain comprising the following steps that for the pressed compact after degreasing reduction：
(a) the layer overlay Al in stainless steel sintering boat2O3Powder, the pressed compact after isostatic pressed is put into sintering boat, then used Al2O3Powder all covers pressed compact；
(b) sintering boat is put into the heating furnace of atmosphere of hydrogen protection, is first passed through 1~2min of hydrogen to drive the sky in stove away Gas, 500 DEG C~600 DEG C insulation 2h are then warming up to 2 DEG C/min~5 DEG C/min speed, it is rear continue with 4 DEG C/min~6 DEG C/ Min speed is warming up to 800 DEG C, and closing power supply is cooled to room temperature after being incubated 1h；
(c) by the Al on pressed compact surface2O3Powder is cleaned out, and obtains the pressed compact after degreasing reduction.
Preferably, in step (b) cooling procedure, logical hydrogen is stopped again after sample cooling terminates.Hydrogen is also Originality gas, it can prevent sample in temperature-rise period by the dioxygen oxidation in air, while at a temperature of 800 DEG C, can be to sample In oxidized iron reduced.
Wherein, degreasing refers to making paraffin remove from sample, paraffin can be decomposed between 500~600 degree gas with Hydrogen stream and run away.1~2h of insulation is in order that paraffin is completely decomposed into gas and is removed, and makes degreasing more complete.Al2O3 Powder covering sample has two big effects, and one acts as the medium of heat transfer, is heated evenly sample, thus ensure that institute as far as possible There is sample to be among same temperature；Second, when hydrogen flows through sample surfaces also raw sample, regulation hydrogen is played The effect of stream, so that sample reduction is more abundant.Reduction is realized by using the thermal reduction of hydrogen.Due to the gold For the Fe added with high level as sinter additives, iron is easily oxidized to iron oxide, iron oxide in atmosphere in category ceramics Could be in order that the reduction of iron oxide is more thorough by hydrogen reducing, insulation under 800 DEG C of high temperature.
Step (4)：Pressed compact after degreasing is reduced carries out vacuum-sintering, obtains TiB2The specific steps of based ceramic metal are such as Under：
(a) pressed compact after degreasing is reduced is put into tungsten crucible, and is filled sample with thin Zirconium oxide powder, after by sample It is put into vacuum sintering furnace and is sintered；
(b) vacuum of vacuum drying oven is first extracted into 10-2~10-1Pa, then heated up with 4 DEG C/min~6 DEG C/min speed To 600 DEG C~800 DEG C, 0.5h~1h is incubated；10-3~10-2Under Pa vacuum, continue with 5 DEG C/min~7 DEG C/min's Speed is warming up to 1400 DEG C~1500 DEG C, is incubated 0h~0.5h；101~10-1Under Pa vacuum, then with 4 DEG C/min~7 DEG C/min speed is warming up to 1600 DEG C~1800 DEG C, it is incubated 0.5h~1h；Cooled down again with 5 DEG C/min~8 DEG C/min speed To 1300 DEG C~1400 DEG C, 0h~0.5h is incubated；Finally 800 DEG C~900 are cooled to 7 DEG C/min~10 DEG C/min speed DEG C, after being incubated 0h~0.5h, continue cool to room temperature.
(c) sample after sintering is taken out, the Zirconium oxide powder for being bonded at sintered sample surface is cleaned out, after obtaining sintering TiB2Based ceramic metal.
Preferably, step (b) the vacuum-sintering process, it is 10 in vacuum-2~10-1Pa with 4 DEG C/min~6 DEG C/ Min speed is warming up to 600 DEG C~800 DEG C insulation 0.5h~1h, and the forming agent for being advantageous to remain in sample further removes Totally.
Preferably, step (b) the vacuum-sintering process, 1600 DEG C~1800 DEG C insulation 0.5h~1h processes are being warming up to In, vacuum is adjusted to 101~10-1Pa, vapored away too much in order to avoid the iron Ni binder of liquid at high temperature.
During vacuum-sintering, sintering temperature-rise period uses multistage more slow heating rate, may be such that in sample The exclusion of the impurity such as carbon, oxygen is more thorough, while makes sample sintering more abundant.In cooling procedure, the more slow rank of use Section property rate of temperature fall, can avoid sintered sample because of temperature shock gross distortion.
The present invention is with 1 μm~6 μm of TiB2For hard phase, TiB is prepared by binding agent of Fe, Ni2Based ceramic metal, wherein Hard phase TiB2Volume content be 65vol.%~90vol.%, Binder Phase Fe-Ni volume content for 10vol.%~ 35vol.%, according to iron nickel binary alloy phase diagram, the ratio of iron nickel is preferably Fe:Ni=8:2~3:7.Compared with prior art, TiB prepared by the present invention2Based ceramic metal has the following advantages that：
(1) in the TiB2In based ceramic metal, Fe-Ni is in hard phase TiB2Distributed very evenly between particle, and Fe- Ni forms the network structure of connection in whole material, enhances adhesion between Binder Phase and hard phase, substantially increases material The mechanical performance of material.
(2) TiB2Based ceramic metal, while higher hardness is kept, bending strength reached 600MPa~ 1100Mpa, fracture toughness have reached 15MPa m1/2~21MPa m1/2, this is the TiB than other systems2Based ceramic metal will height Much.
(3) TiB produced by the invention2Based ceramic metal has technological process simple, and equipment is simple, low cost and other advantages.
In a word, the TiB that prepared by the present invention2The TiB that based ceramic metal is prepared with other method2Based ceramic metal is compared, maximum Be particular in that:The present invention uses the iron nickel of high volume content to reach as binding agent, its percent by volume first Between 10vol.%~35vol.%, and set according to iron nickel binary alloy phase diagram, the additive of each group of volumn concentration The iron nickel weight ratio put is Fe:Ni=8:2~3:7 totally 6 kinds of ratios seek its influence to material structure and performance.The present invention The TiB of preparation2Based ceramic metal has high-compactness, high intensity and high-fracture toughness, and its preparation technology and equipment are simple, into This is low, has a good application prospect.
Brief description of the drawings
Fig. 1 is TiB prepared by the invention2The XRD thing phase spectral lines of-(Fe-Ni) cermets；
Fig. 2 is TiB prepared by the invention2The surface polishing pattern photo of-(Fe-Ni) cermets；
Fig. 3 is TiB prepared by the invention2The fractograph pattern photo of-(Fe-Ni) cermets.
Embodiment
Embodiment 1
TiB2(iron nickel weight ratio is Fe to -35vol.% (Fe-Ni) cermet in Binder Phase:Ni=6:4)
1. weighing 1g solid paraffins, it is put into the beaker equipped with 50ml gasoline, beaker is put into heating water bath in water bath And stir and accelerate paraffin dissolving.Weigh 50.43g TiB2Powder is poured into beaker, and makes TiB with magnetic stirrer 10min2 The gasoline solution of powder and paraffin fully mixes.Afterwards by mixed TiB2Powder slurries are put into air dry oven and done Dry, drying temperature is set as 80 DEG C, dries 1.5h and is dried completely to powder.The powder of drying is crossed into 80 mesh mesh screens, obtains TiB2 With the mixed-powder of paraffin.
2. by TiB2Poured into the mixed-powder of paraffin in stainless steel jar mill, and weigh 29.74g iron powders, 19.83g nickel Powder is added in ball grinder together, makes TiB with spoon stirring 1min2, iron powder, nickel powder tentatively mix.50g stainless steel balls are weighed to add Enter in ball grinder, tightly cover ball grinder, be then put on planetary ball mill and carry out ball mill mixing.Drum's speed of rotation is set to 350r/min, rotating alternate run, often rotate 15min and change a rotation direction, altogether ball mill mixing 3h.Batch mixing will after terminating Mixed-powder crosses 80 mesh mesh screens, obtains TiB2, iron, nickel mixed-powder.
3. from interior stamping length and the punching block mould that wide size is 25mm × 7mm, weighing 4.97g mixed-powders are die-filling, after Bidirectional pressure system is carried out on press with 4MPa pressure, dwell time 5s, small cuboid pressed compact is obtained after the demoulding.By small cuboid It is fitted into latex finger cot and seals fingerstall with tenacity viscose, cold etc. press is carried out after allowing.It is 200MPa from isostatic cool pressing pressure, Dwell time 3min, isostatic cool pressing remove latex finger cot after terminating, and obtain the pressed compact that consistency greatly improves.
4. the layer overlay Al into stainless steel sintering boat2O3Powder, the pressed compact after isostatic cool pressing is put into sintering boat week, and Use Al2O3Powder is by pressed compact all standing.Then sintering boat is put into ungrease treatment in the heating furnace of nitrogen atmosphere protection, burnt being put into First lead to hydrogen 1min by the complete emptying of air in stove before tying boat.Temperature in stove is heated up from room temperature with 4 DEG C/min speed To 500 DEG C, insulation 1h carries out degreasing.Continue to be warming up to 800 DEG C with 7 DEG C/min speed after insulation terminates, insulation 1h is carried out Reduction, closing power supply is cooled to room temperature after insulation terminates, and is then shut off hydrogen.Pressed compact is taken out to the Al for cleaning out surface2O3 Powder, obtain the pressed compact after degreasing reduction.
5. the pressed compact after degreasing is reduced is put into tungsten crucible, filling Zirconium oxide powder keeps apart each pressed compact, And with Zirconium oxide powder then the tungsten crucible for filling sample is put into vacuum sintering furnace and is sintered by pressed compact all standing.Will Vacuum is extracted into 10-2Pa, the temperature in vacuum drying oven is then warming up to 700 DEG C from room temperature with 5 DEG C/min speed, insulation 0.5h；Vacuum is brought up to 10 again-3Pa, 1450 DEG C are warming up to 7 DEG C/min speed, is incubated 0.5h；Finally by vacuum It is adjusted to 10-1Pa, 1700 DEG C are warming up to 6 DEG C/min speed, is incubated 1h.Insulation is cooled down after terminating with 8 DEG C/min speed To 1300 DEG C, 0h~0.5h is incubated；800 DEG C finally are cooled to 10 DEG C/min speed, after being incubated 0h~0.5h, continues to cool down To room temperature.6. taking out the sample after sintering, the Zirconium oxide powder of surface adhesion, the TiB after being sintered are cleaned out2- 35vol.% (Fe-Ni) cermet.
The TiB prepared using the above method2- 35vol.% (Fe-Ni) cermet, Binder Phase are evenly distributed on hard phase TiB2Between particle, there is excellent comprehensive mechanical performance, the relative density of the cermet is 99.03%, Vickers hardness For 8.56GPa, bending strength 1050.92MPa, fracture toughness is 17.75MPa m1/2。
Embodiment 2
TiB2(iron nickel weight ratio is Fe to -30vol.% (Fe-Ni) cermet in Binder Phase:Ni=7:3)
1. weighing 1.5g solid paraffins, it is put into the beaker equipped with 50ml gasoline, beaker is put into water-bath in water bath adds Heat simultaneously stirs acceleration paraffin dissolving.Weigh 56.40g TiB2Powder is poured into beaker, and is made with magnetic stirrer 15min TiB2The gasoline solution of powder and paraffin fully mixes.Afterwards by mixed TiB2Powder slurries are put into air dry oven and carried out Dry, drying temperature is set as 90 DEG C, dries 2h and is dried completely to powder.The powder of drying is crossed into 80 mesh mesh screens, obtains TiB2 With the mixed-powder of paraffin.
2. by TiB2Poured into the mixed-powder of paraffin in stainless steel jar mill, and weigh 30.52g iron powders, 13.08g nickel Powder is added in ball grinder together, makes TiB with spoon stirring 2min2、Iron powder, nickel powder tentatively mix.40g stainless steel balls are weighed to add In ball grinder, ball grinder is tightly covered, is then put on planetary ball mill and carries out ball mill mixing.Drum's speed of rotation is set to 400r/ Min, rotating alternate run, often rotate 20min and change a rotation direction, altogether ball mill mixing 4h.Batch mixing will mixing after terminating Powder crosses 80 mesh mesh screens, obtains TiB2, iron, nickel mixed-powder.
3. from interior stamping length and the punching block mould that wide size is 25mm × 7mm, weighing 5.07g mixed-powders are die-filling, after Bidirectional pressure system is carried out on press with 5MPa pressure, dwell time 4s, small cuboid pressed compact is obtained after the demoulding.By small cuboid It is fitted into latex finger cot and seals fingerstall with tenacity viscose, cold etc. press is carried out after allowing.It is 190MPa from isostatic cool pressing pressure, Dwell time 4min, isostatic cool pressing remove latex finger cot after terminating, and obtain the pressed compact that consistency greatly improves.
4. the layer overlay Al into stainless steel sintering boat2O3Powder, the pressed compact after isostatic cool pressing is put into sintering boat week, and Use Al2O3Powder is by pressed compact all standing.Then sintering boat is put into ungrease treatment in the heating furnace of nitrogen atmosphere protection, burnt being put into First lead to hydrogen 2min by the complete emptying of air in stove before tying boat.Temperature in stove is heated up from room temperature with 5 DEG C/min speed To 550 DEG C, insulation 1h carries out degreasing.Continue to be warming up to 800 DEG C with 6 DEG C/min speed after insulation terminates, insulation 1h is carried out Reduction, closing power supply is cooled to room temperature after insulation terminates, and is then shut off hydrogen.Pressed compact is taken out to the Al for cleaning out surface2O3 Powder, obtain the pressed compact after degreasing reduction.
5. the pressed compact after degreasing is reduced is put into tungsten crucible, filling Zirconium oxide powder keeps apart each pressed compact, And with Zirconium oxide powder then the tungsten crucible for filling sample is put into vacuum sintering furnace and is sintered by pressed compact all standing.Will Vacuum is extracted into 10-1Pa, the temperature in vacuum drying oven is then warming up to 800 DEG C from room temperature with 6 DEG C/min speed, insulation 0.5h；Vacuum is brought up to 10 again-3Pa, 1500 DEG C are warming up to 6 DEG C/min speed, is incubated 0.5h；Finally by vacuum It is adjusted to 10-1Pa, 1800 DEG C are warming up to 7 DEG C/min speed, is incubated 1h.Insulation is cooled down after terminating with 8 DEG C/min speed To 1400 DEG C, 0.25h is incubated；900 DEG C finally are cooled to 10 DEG C/min speed, after being incubated 0.2h, continues cool to room temperature.
6. taking out the sample after sintering, the Zirconium oxide powder of surface adhesion, the TiB after being sintered are cleaned out2- 30vol.% (Fe-Ni) cermet.
The TiB prepared using the above method2- 30vol.% (Fe-Ni) cermet, Fe-Ni is in hard phase TiB2Particle it Between be evenly distributed, there is good comprehensive mechanical performance, the relative density of the cermet is 96.56%, and Vickers hardness is 9.96GPa, bending strength 829.34MPa, fracture toughness are 18.04MPa m1/2。
Embodiment 3
TiB2(iron nickel weight ratio is Fe to -25vol.% (Fe-Ni) cermet in Binder Phase:Ni=5:5).
1. weighing 2g solid paraffins, it is put into the beaker equipped with 50ml gasoline, beaker is put into heating water bath in water bath And stir and accelerate paraffin dissolving.Weigh 61.88g TiB2Powder is poured into beaker, and makes TiB with magnetic stirrer 5min2 The gasoline solution of powder and paraffin fully mixes.Afterwards by mixed TiB2Powder slurries are put into air dry oven and done Dry, drying temperature is set as 95 DEG C, dries 1.5h and is dried completely to powder.The powder of drying is crossed into 80 mesh mesh screens, obtains TiB2 With the mixed-powder of paraffin.
2. by TiB2Poured into the mixed-powder of paraffin in stainless steel jar mill, and weigh 19.06g iron powders, 19.06g nickel Powder is added in ball grinder together, makes TiB with spoon stirring 3min2、Iron powder, nickel powder tentatively mix.45g stainless steel balls are weighed to add In ball grinder, ball grinder is tightly covered, is then put on planetary ball mill and carries out ball mill mixing.Drum's speed of rotation is set to 300r/ Min, rotating alternate run, often rotate 10min and change a rotation direction, altogether ball mill mixing 4.5h.Batch mixing will be mixed after terminating Close powder and cross 80 mesh mesh screens, obtain TiB2, iron, nickel mixed-powder.
3. from interior stamping length and the punching block mould that wide size is 25mm × 7mm, weighing 5.0g mixed-powders are die-filling, rear to use 3MPa pressure carries out Bidirectional pressure system on press, dwell time 6s, small cuboid pressed compact is obtained after the demoulding.Small cuboid is filled Enter in latex finger cot and seal fingerstall with tenacity viscose, cold etc. press is carried out after allowing.It is 180MPa from isostatic cool pressing pressure, protects Time 3min is pressed, isostatic cool pressing removes latex finger cot after terminating, and obtains the pressed compact that consistency greatly improves.
4. the layer overlay Al into stainless steel sintering boat2O3Powder, the pressed compact after isostatic cool pressing is put into sintering boat week, and Use Al2O3Powder is by pressed compact all standing.Then sintering boat is put into ungrease treatment in the heating furnace of nitrogen atmosphere protection, burnt being put into First lead to hydrogen 1.5min by the complete emptying of air in stove before tying boat.By the temperature in stove from room temperature with 4 DEG C/min speed liter For temperature to 600 DEG C, insulation 1h carries out degreasing.Continue to be warming up to 800 DEG C with 5 DEG C/min speed after insulation terminates, insulation 1h enters Row reduction, closing power supply is cooled to room temperature after insulation terminates, and is then shut off hydrogen.Pressed compact is taken out and cleans out surface Al2O3Powder, obtain the pressed compact after degreasing reduction.
5. the pressed compact after degreasing is reduced is put into tungsten crucible, filling Zirconium oxide powder keeps apart each pressed compact, And with Zirconium oxide powder then the tungsten crucible for filling sample is put into vacuum sintering furnace and is sintered by pressed compact all standing.Will Vacuum is extracted into 10-2Pa, the temperature in vacuum drying oven is then warming up to 600 DEG C with 5 DEG C/min speed from room temperature, is incubated 1h； Vacuum is brought up to 10 again-3Pa, 1400 DEG C are warming up to 7 DEG C/min speed, is incubated 0.5h；Finally vacuum is adjusted to 10-2Pa, 1600 DEG C are warming up to 7 DEG C/min speed, is incubated 1h.It is incubated after terminating and is cooled to 1350 with 6 DEG C/min speed DEG C, it is incubated 0h~0.5h；850 DEG C finally are cooled to 9 DEG C/min speed, after being incubated 0.5h, continues cool to room temperature.
6. taking out the sample after sintering, the Zirconium oxide powder of surface adhesion, the TiB after being sintered are cleaned out2- 25vol.% (Fe-Ni) cermet.
The TiB prepared using the above method2- 25vol.% (Fe-Ni) cermet, Fe-Ni is in hard phase TiB2Particle it Between be evenly distributed, there is good comprehensive mechanical performance, the relative density of the cermet is 94.43%, and Vickers hardness is 10.42GPa, bending strength 724.30MPa, fracture toughness are 16.14MPa m1/2。
Embodiment 4
TiB2(iron nickel weight ratio is Fe to -20vol.% (Fe-Ni) cermet in Binder Phase:Ni=4:6).
1. weighing 2.5g solid paraffins, it is put into the beaker equipped with 50ml gasoline, beaker is put into water-bath in water bath adds Heat simultaneously stirs acceleration paraffin dissolving.Weigh 68.41g TiB2Powder is poured into beaker, and is made with magnetic stirrer 7min TiB2The gasoline solution of powder and paraffin fully mixes.Afterwards by mixed TiB2Powder slurries are put into air dry oven and carried out Dry, drying temperature is set as 100 DEG C, dries 1h and is dried completely to powder.The powder of drying is crossed into 80 mesh mesh screens, obtains TiB2 With the mixed-powder of paraffin.
2. by TiB2Poured into the mixed-powder of paraffin in stainless steel jar mill, and weigh 12.75g iron powders, 19.13g nickel Powder is added in ball grinder together, makes TiB with spoon stirring 4min2、Iron powder, nickel powder tentatively mix.50g stainless steel balls are weighed to add In ball grinder, ball grinder is tightly covered, is then put on planetary ball mill and carries out ball mill mixing.Drum's speed of rotation is set to 400r/ Min, rotating alternate run, often rotate 30min and change a rotation direction, altogether ball mill mixing 5h.Batch mixing will mixing after terminating Powder crosses 80 mesh mesh screens, obtains TiB2, iron, nickel mixed-powder.
3. from interior stamping length and the punching block mould that wide size is 25mm × 7mm, weighing 4.59g mixed-powders are die-filling, after Bidirectional pressure system is carried out on press with 6MPa pressure, dwell time 3s, small cuboid pressed compact is obtained after the demoulding.By small cuboid It is fitted into latex finger cot and seals fingerstall with tenacity viscose, cold etc. press is carried out after allowing.It is 170MPa from isostatic cool pressing pressure, Dwell time 5min, isostatic cool pressing remove latex finger cot after terminating, and obtain the pressed compact that consistency greatly improves.
4. the layer overlay Al into stainless steel sintering boat2O3Powder, the pressed compact after isostatic cool pressing is put into sintering boat week, and Use Al2O3Powder is by pressed compact all standing.Then sintering boat is put into ungrease treatment in the heating furnace of nitrogen atmosphere protection, burnt being put into First lead to hydrogen 2min by the complete emptying of air in stove before tying boat.Temperature in stove is heated up from room temperature with 5 DEG C/min speed To 500 DEG C, insulation 1h carries out degreasing.Continue to be warming up to 800 DEG C with 6 DEG C/min speed after insulation terminates, insulation 1h is carried out Reduction, closing power supply is cooled to room temperature after insulation terminates, and is then shut off hydrogen.Pressed compact is taken out to the Al for cleaning out surface2O3 Powder, obtain the pressed compact after degreasing reduction.
5. the pressed compact after degreasing is reduced is put into tungsten crucible, filling Zirconium oxide powder keeps apart each pressed compact, And with Zirconium oxide powder then the tungsten crucible for filling sample is put into vacuum sintering furnace and is sintered by pressed compact all standing.Will Vacuum is extracted into 10-1Pa, the temperature in vacuum drying oven is then warming up to 700 DEG C with 5 DEG C/min speed from room temperature, is incubated 1h； Vacuum is brought up to 10 again-3Pa, 1450 DEG C are warming up to 6 DEG C/min speed, is incubated 0.5h；Finally vacuum is adjusted to 10-1Pa, 1700 DEG C are warming up to 5 DEG C/min speed, is incubated 1h.It is incubated after terminating and is cooled to 1300 with 8 DEG C/min speed DEG C, it is incubated 0.3h；800 DEG C finally are cooled to 10 DEG C/min speed, after being incubated 0.5h, continues cool to room temperature.
6. taking out the sample after sintering, the Zirconium oxide powder of surface adhesion, the TiB after being sintered are cleaned out2- 20vol.% (Fe-Ni) cermet.
The TiB prepared using the above method2- 20vol.% (Fe-Ni) cermet, Fe-Ni is in hard phase TiB2Particle it Between be evenly distributed, there is good comprehensive mechanical performance, the relative density of the cermet is 92.86%, and Vickers hardness is 11.21GPa, bending strength 643.71MPa, fracture toughness are 15.19MPa m1/2。

Claims (8)

  1. A kind of 1. TiB2The preparation method of based ceramic metal, the TiB2Based ceramic metal includes the component of following percent by volume：
    TiB265%~90%；
    Fe and Ni 10%~35%；
    In the Fe and Ni, Fe, Ni mass ratio are 3:7 to 8:2；
    It is characterised in that it includes following steps：
    （1）Prepare TiB in proportion2 Powder, Fe powder, Ni powder；By TiB2Powder is well mixed with forming agent, adds Fe powder and Ni powder, Then through planetary ball mill batch mixing, mixed-powder is obtained；0.5~3g forming agents are added in per 100g mixed-powders；
    （2）Mixed-powder is molded to obtain cuboid pressed compact using steel mold pressing, then with 1~5min of cold isostatic press pressurize；
    （3）In atmosphere of hydrogen, cuboid pressed compact is warming up to 500oC~600oC is simultaneously incubated 1.5~2h to carry out at degreasing Reason, forming agent is removed, then proceedes to be warming up to 800oC is simultaneously incubated 0.5~1h to carry out reduction treatment, after obtaining degreasing reduction Pressed compact；
    （4）Pressed compact after degreasing is reduced carries out vacuum-sintering, obtains TiB2Based ceramic metal.
  2. 2. TiB as claimed in claim 12The preparation method of based ceramic metal, it is characterised in that the TiB2Particle mean size For 1 μm~6 μm.
  3. 3. TiB as claimed in claim 1 or 22The preparation method of based ceramic metal, it is characterised in that the TiB2Base Metal is made pottery Porcelain consistency is 92.48%~99.50%；Bending strength is the MPa of 600MPa~1100；Fracture toughness is 15MPam1/2~ 21MPam1/2。
  4. 4. TiB as claimed in claim 12The preparation method of based ceramic metal, it is characterised in that step（1）The forming agent is Solid paraffin.
  5. 5. TiB as claimed in claim 12The preparation method of based ceramic metal, it is characterised in that step（1）The planetary ball mill During batch mixing, ratio of grinding media to material is（0.5~3）：1.
  6. 6. TiB as claimed in claim 12The preparation method of based ceramic metal, it is characterised in that step（2）The isostatic cool pressing Machine dwell pressure is 150~200MPa.
  7. 7. TiB as claimed in claim 12The preparation method of based ceramic metal, it is characterised in that step（3）It is described by cuboid Pressed compact is warming up to 500oC~600oC is simultaneously incubated 1.5~2h to carry out ungrease treatment, then proceedes to be warming up to 800oC is simultaneously incubated It is with 2 by cuboid pressed compact when 0.5~1h is to carry out reduction treatmentoC/min~5oC/min speed is warming up to 500oC~ 600oC is incubated 1.5~2h, then proceedes to 4oC/min~6oC/min speed is warming up to 800oC is simultaneously incubated 0.5~1h.
  8. 8. TiB as claimed in claim 12The preparation method of based ceramic metal, it is characterised in that step（4）The vacuum-sintering It is 10-2~10-1Under Pa vacuum, the pressed compact after degreasing is reduced is with 4oC/min~6oC/min speed is warming up to 600oC~800oC, it is incubated 0.5h~1h；Then 10-3~10-2Under Pa vacuum, with 5oC/min~7oC/min speed It is warming up to 1400oC~1500oC, it is incubated 0h~0.5h；Then 10-2~10-1Under Pa vacuum, with 4oC/min~7oC/ Min speed is warming up to 1600oC~1800oC, it is incubated 0.5h~1h；It is cooled to 1300oC~1400oC, insulation 0h~ 0.5h；It is finally cooled to 800oC~900oC, after being incubated 0h~0.5h, continue cool to room temperature.
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