CN109338193A - A kind of centreless-ring structure cermet and preparation method thereof - Google Patents
A kind of centreless-ring structure cermet and preparation method thereof Download PDFInfo
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- CN109338193A CN109338193A CN201810473746.2A CN201810473746A CN109338193A CN 109338193 A CN109338193 A CN 109338193A CN 201810473746 A CN201810473746 A CN 201810473746A CN 109338193 A CN109338193 A CN 109338193A
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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
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
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- 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
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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
- C22C29/005—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
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Abstract
The present invention relates to cermet material preparation technical field, it is related to a kind of centreless-ring structure cermet and preparation method thereof.Centreless of the invention-ring structure cermet is by weight percentage, its ingredient is 10~55%Ti (C, N) micron powder, 10~55% (Ti, M) (C, N) micron powder, 10~55%Ti (C, N) 10~55% (Ti of sub-micron or/and nanometer powder, M) (C, N) sub-micron/and nanometer powder, 5~20%WC, 0~30%TiC, 0~30%TiN, 0~20%Co, 0~20%Ni, 0~10%Cr, 0~15%Mo2C, 0~10%TaC/NbC, 0~2.5%VC, 0~5%Cr2C3, 0~1.2% carbon black is made into mixture by a certain percentage, blank is made through ball milling, sieving and molding, centreless-ring structure cermet material can be made in sintering cooling.The present invention is prepared for a kind of cermet of centreless-ring structure, microstructure core-ring thickness uppity technological difficulties when it overcomes conventional core-ring structure cermet preparation process using powder metallurgy process.
Description
Technical field
The invention belongs to cermet material preparation technical field, specially a kind of centreless-ring structure cermet
And preparation method thereof.
Background technique
Ti (C, N) based ceramic metal alloy has unique performance advantage, has at 700~1100 DEG C excellent wear-resisting
Property, the high hardness of high temperature, thermal stability, inoxidizability and the features such as Adhesion Resistance, be high temperature, the main cutting tool selection of high speed
One of basis material.Since such alloy is also equipped with stable elevated temperature strength, good frictional behaviour and acid-alkali-corrosive-resisting performance,
It is widely used in a variety of industries and the fields such as high-temperature component, petrochemical industry and the chemical fibre of engine.With traditional WC-Co hard alloy phase
Than such material has filled up the blank between the materials demand such as hard alloy and sintex, and effectively saves common hard
The valuable rare metal such as Co necessary to matter alloy cutter, Ta and W.Developing high-performance, (high rigidity, high intensity, high synthesis are resistance to
Grinding performance, abbreviation " three high ") long-life Ti (C, N) based ceramic metal alloy material becomes Ti (C, N) based ceramic metal in recent years
The focus of research.
Currently, this field mainly has typical core-ring structure Ti (C, N) based ceramic metal for main method with preparation,
Core-annular the shell being made of (Ti, M) (C, N) composite solid solution, but the annular shell can be formed when sintering on hard phase
It is usual and imperfect, so that Ti (C, N) and bonding phase metal a part of in hard phase can be contacted directly, cause hard phase decarburization
The problems such as, make the fracture toughness and bending strength decline of cermet.Microcosmic core-ring structure thickness is to preparing the hard of alloy simultaneously
Degree, the influence of fracture toughness and bending strength are very big, formed during the preparation process alloy microcosmic core-ring structure it is blocked up or
Core-ring structure is excessively thin to be all unfavorable for final comprehensive performance.Therefore, microcosmic core-ring structure thickness control technology difficulty is very big, leads
Material property stability is caused to be not easy to guarantee.
Summary of the invention
In view of the above-mentioned problems, the first object of the present invention is to provide a kind of centreless-ring structure cermet to solve
Certainly annular shell is imperfect, so that Ti (C, N) and bonding phase metal a part of in hard phase can be contacted directly, causes hard phase
Decarburization, cause cermet fracture toughness and bending strength decline the problem of；The second object of the present invention is to provide one kind
Centreless-ring structure cermet preparation method is to solve the problems, such as that core-ring structure thickness is difficult to control.
A kind of centreless-ring structure cermet, cermet by weight percentage, ingredient be 10~
55%Ti (C, N) micron powder, 10~55% (Ti, M) (C, N) micron powder or/and are received 10~55%Ti (C, N) sub-micron
Rice flour end, 10~55% (Ti, M) (C, N) sub-micron/and nanometer powder, 5~20%WC, 0~30%TiC, 0~30%TiN, 0
~20%Co, 0~20%Ni, 0~10%Cr, 0~15%Mo2C, 0~10%TaC/NbC, 0~2%VC, 0~5%Cr2C3, 0
~1.2% carbon black.Herein it should be noted that TiN, Co, Ni, Cr, Mo may be selected in component2C、TaC/NbC、VC、Cr2C3, charcoal
In black any one, it is several or whole.
Wherein, the M element in (Ti, M) (C, N) micron powder, (Ti, M) (C, N) sub-micron or/and nanometer powder is Mo,
Any one or a few in the solid-solution powders such as W, Ta, Nb, Zr, Cr, V；Ti (C, N), (Ti, M) (C, N) micron powder and institute
The C in Ti (C, N), (Ti, M) (C, N) sub-micron or/and nano-scale powders is stated, N is all made of C/N atomic ratio 7/3,6/4 or 5/
One of 5, preferred mass score is 5/5.Herein it should be noted that sub-micron or/and nanometer powder herein refer to
The submicron powder of (Ti, M) (C, N), the nanometer powder or (Ti, M) of (Ti, M) (C, N) can be selected during specific experiment
The submicron powder of (C, N) and any one in the nanometer powder mixed-powder of (Ti, M) (C, N).
Specifically, hard phase is mainly selected Ti (C, N) herein, and (Ti, M) (C, N) powder additionally includes WC, TiC,
One or more of TiN, TaC powder, wherein the M element in (Ti, M) (C, N) powder is selected as Mo, W, Ta, Nb, Zr, Cr, V
Deng.Binder Phase selects the one or more such as Co, Ni, Cr, Fe.Mo is mutually selected in addition2C, any one in TaC, NbC；Strengthen
Mutually select VC, Mn2C, ZrC, Cr2C3And any several in hydrocarbon black powder or all as preparation raw material.
Preferably, by weight percentage, ingredient is 15~45%Ti (C, N), 15~45% (Ti, M) (C, N) microns
Powder, 6~15%Ti (C, N) micron or/and nanometer powder, 7~15% (Ti, M) (C, N) sub-micron or/and nanometer powder, 12
~18%WC, 0.5~15%TiC, 0.5~15%TiN, 8~15%Co, 3~8%Ni, 1~5%Cr, 5~12%Mo2C, 2
~10%TaC/NbC, 0.3~1.0%VC, 0.5~1.2%Cr2C3, 0.0~1.0% carbon black.
A kind of preparation method of centreless-ring structure cermet, comprising the following steps:
(1) above-mentioned cited raw material is weighed in proportion to be mixed, and abrasive media, dispersing agent and forming agent is added, mixes
Preparing material is obtained after closing uniformly.
(2) preparing material is packed into the grinding hard alloy ball grinder of ball mill, carries out ball milling and obtains mixed material.
(3) mixed material is crossed into 150~250 mesh screens or spraying granulation.
(4) mixed material after sieving is directly loadable into mold and is pressed into blank.
(5) first the blank of compression molding is packed into high vacuum degreasing positive pressure sintering rapid cooling furnace, extracts gas in furnace body out
Body makes it in vacuum, and vacuum degree is no more than 15Pa, restarts sintering furnace power supply, and sequentially enters heating degreasing stage, solid phase burning
It knot stage, liquid-phase sintering stage and rapid cooling stage, then comes out of the stove and takes out cermet.
Further, abrasive media is hexane or dehydrated alcohol in step (1), and the mass fraction for accounting for addition total amount is
0.5~1.8%；Dispersing agent is detergent alkylate semi-annular jade pendant acid, stearic acid or second Suo Min, and mass fraction is 0.1~0.5%；Molding
It is solute, quality point that agent, which is one or more of in gasoline and rubber, paraffin, polyvinyl alcohol, synthetic rubber, ethylene glycol or SBS,
Number is 2~5%.
Further, the ball mill in step (2) is roll type ball mill or planetary ball mill, the ball of sintered carbide ball
Diameter is 6.25~10mm, and ratio of grinding media to material is 8~15:l；The rotational speed of ball-mill of the ball mill is 70~120 revs/min, Ball-milling Time
For 48~144h, the preferred time is 72~116h.
Further, the pressure in mold is 150~450MPa, and the dwell time is 15~300s, preferably 15~30s.
Further, heat skimming processes in by preheat, be passed through gas, heating, heat preservation temperature control process carry out, heating, vacuum
Skimming temp is warming up to 450~800 DEG C, and preferable temperature is 500 DEG C, and the heat preservation temperature control time is 50~100min, and temperature is inclined
Difference control is at ± 0.50 DEG C.Herein it should be noted that the gas being passed through is pure nitrogen gas, nitrogen and hydrogen, nitrogen and argon gas, first
Any one group of gas in alkane and argon gas.
Further, heating temperature by 450~800 DEG C is warming up to 1280~1350 DEG C in the solid-phase sintering stage, heating speed
Rate is no more than 5 DEG C/min, is 850~950 DEG C, 1220~1280 DEG C and 1280~1350 DEG C in sintering temperature and heat preservation is respectively set
The temperature control time is 45~90min, and temperature deviation is controlled at ± 0.50 DEG C.Herein it should be noted that sintering temperature herein
It is that a certain actual temp value reached in each phase range can be kept the temperature, then the control of this actual temp deviation is ± 0.50
In DEG C.
Further, when entering the liquid-phase sintering stage after the completion of the solid-phase sintering stage, with the heating rate of 2~5 DEG C/min
1430~1470 DEG C are raised the temperature to, the soaking time in liquid-phase sintering stage is 45~90min, while being passed through 1~10MPa's
Argon gas, argon gas purity are greater than 99.995%, and air pressure preferably 2~5MPa, temperature deviation controls in ± 0.50 DEG C.
Further, enter the rapid cooling stage after the completion of the liquid-phase sintering stage, temperature first progressively cooled to 1200 DEG C,
Argon gas is filled with as cooling medium and carries out rapid cooling until room temperature, argon gas purity is greater than 99.995%, cooling
Rate is greater than 35 DEG C/min and reaches room temperature.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) cermet provided by the invention using multi-element alloyed element optimization cermet material hard phase,
Wet phase and hardening constituent, mutually regulate and control modification by effective substance of the alloying element to metal phase or ceramic phase, reduce its coefficient of expansion,
Coupling matching matrix hard phase and Binder Phase；
(2) the solid solution diffusion reaction of (Ti, M) (C, N) each element is promoted to form by solid phase, the sintering of liquid-phase sintering stage
Transition object phase, thus realize between the metallic binding phases such as the black core phase of Ti (C, N) and Co (Ni, Cr, Mn, Fe) without obvious core-
The controlled micro crystallization interface cohesion method of ring transition；
(3) alloy fracture toughness and raising alloy rigidity are increased using sub-micron or nano-powder particles optimization and bending resistance is strong
It dissolves in Binder Phase formation multielement completely or partially in the liquid-phase sintering stage for comprehensive performances, sub-micron or the nano particles such as degree
Transition object phase, while the presence of not molten sub-micron and nano particle has conducive to stress is eliminated；
(4) preparation method provided by the invention has formulated pressure sintering process system in the liquid-phase sintering stage, forms gold
The complete densification technology of cermet low pressure sintering effectively inhibits the denitrogenation phenomenon of alloy sintering process and optimizes C, O effect；
Constitutional supercooling technology is used in cooling stage, alloy approach is prepared by being filled with high prefect dielectric argon gas rapid cooling, promotes hard
Stable phase interface is mutually formed between binding metal, is realized alloy element component even transition, is formed the homogeneous of microstructure
Property.
To sum up, the present invention can be good at the heterogeneous microstructure that control prepares cermet, prepare metal pottery
Porcelain alloy can provide good initial tissu state and Good All-around Property matrix for widely applied cutter material and device, together
When be greatly saved W, the use of the strategy alloying element such as Co, Ta significantly reduces the production cost of alloy.
Detailed description of the invention:
The present invention is described in further detail with reference to the accompanying drawings and examples.
Fig. 1 is the micro-organization chart under 5000 times of scanning electron microscope of the cermet of embodiment 2 in the present invention；
Fig. 2 is 20000 times of scanning electron microscope offline scan element distributions of the cermet of embodiment 2 in the present invention
Figure；
Fig. 3 is the micro-organization chart under 20000 times of scanning electron microscope of the cermet of embodiment 2 in the present invention；
Fig. 4 is the ?core hard phase EDS energy spectrum diagram of A point position detection in Fig. 3 of embodiment 2 in the present invention；
Fig. 5 is the alloying component even transition solid solution phase EDS energy of B point position detection in Fig. 3 of embodiment 2 in the present invention
Spectrogram；
Fig. 6 is the metallic binding phase EDS energy spectrum diagram of C point position detection in Fig. 3 of embodiment 2 in the present invention；
Fig. 7 is the object phase distribution map that the XRD ray of the cermet of embodiment 2 in the present invention spreads out.
Specific embodiment
The present invention is further explained combined with specific embodiments below.It will be appreciated that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.It should also be understood that be, after reading the content taught by the present invention, this field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within range defined herein.
Wherein in (Ti, M) (C, N) solid-solution powder, each component content is mass percentage, for example, (Ti, W8,
Mo5)(C0.5,N0.5) indicating that W accounts for the 8% of total content, 5%, the C/N atomic ratio for indicating that Mo accounts for total content is 0.5/0.5.Above-mentioned powder
Last component uses differential electronic balance weighing.
Embodiment 1
Ti(C0.5,N0.5) micron powder size be FSSS1.8 weigh 400g, (Ti, W8, Mo5, Ta2.5, Zr0.35)
(C0.5,N0.5) micron powder size be FSSS1.5 weigh 1000g, Ti (C0.5,N0.5) submicron powder granularity claims for FSSS0.8
Weight 960g, (Ti, W8, Mo5) (C0.5,N0.5) nanometer powder granularity is that FSSS0.1 weighs 840g, powder size is FSSS0.8
WC powder weighing 800g.Ball-milling medium dehydrated alcohol weighs 3500ml, and forming agent is used using polyvinyl alcohol weighing 90g, dispersing agent
Second Suo Min weighing 6g.
(1) it ball mill mixing: is put by the raw material powder that step (1) is equipped with diameter as the YG6X alloying pellet of 10mm and anhydrous
Ethyl alcohol is ball-milling medium, while dispersing agent second Suo Min 6g is added and forming agent polyvinyl alcohol 90g is placed in clean stainless steel ball-milling
In tank, then the ball milling 144h on roll-type ball mill, ratio of grinding media to material 8:1, rotational speed of ball-mill 70r/min.In vacuum after the taking-up of wet-milling material
80 DEG C of dry 4h in drying box, homogenization is broken, be sieved powder using the screen in 150 mesh holes, is formed with certain ingredients and grain
Spend desired pellet.
(2) being directly loadable into the mixture powder after step (1) sieving will be equal after mold suppresses 15s under 450MPa pressure
Blank is made in even mixed powder.
(3) the blank body that step (2) suppresses is put into sintering furnace and is carried out by preheating, heating, heat preservation temperature control process, added
Thermal vacuum skimming temp is warming up to 450 DEG C, and the heat preservation temperature control time is 50min, and temperature deviation is controlled at ± 0.50 DEG C.
(4) the solid-phase sintering stage: its heating temperature is warming up to 1300 DEG C by 450 DEG C, and the rate of heat addition is no more than 5 DEG C/min,
Being in sintering temperature is 90min 880 DEG C of heat preservation temperature control times, and 1230 DEG C of heat preservation temperature control times are 90min and 1310 DEG C of heat preservation control
The warm time is 90min, and temperature deviation is controlled at ± 0.50 DEG C；
The liquid-phase sintering stage: its heating temperature is warming up to 1470 DEG C by 1330 DEG C, and heating rate is set as in 5 DEG C/min,
It is passed through high-purity 99.9995% argon gas of 1MPa simultaneously, is 1470 DEG C of setting heat preservation temperature control periods to be in sintering temperature
45min, temperature deviation are controlled at ± 0.50 DEG C.
Cooling stage: after its temperature progressively cools to 1200 ± 0.5 DEG C, rapid cooling to room temperature, cooling medium is height
Pure 99.9995% argon gas reaches room temperature with 37 DEG C/min cooling rate, then comes out of the stove and take out cermet.
Embodiment 2
Ti(C0.5,N0.5) micron powder size be FSSS1.5 weigh 830g, (Ti, W8, Mo5, Ta2.5, Zr0.35)
(C0.5,N0.5) micron powder size be FSSS1.5 weigh 360g, Ti (C0.5,N0.5) submicron powder granularity be FSSS0.8 weighing
820g, (Ti, W8, Mo5) (C0.5,N0.5) nanometer powder granularity be FSSS0.15 weigh 390g, powder size be FSSS1.5 Ni
Powder weighing 320g, the Co powder weighing 320g that powder size is FSSS1.2, the WC powder weighing 600g that powder size is FSSS0.8, powder
Last granularity is the Mo of FSSS1.52C powder weighing 360g；Ball-milling medium hexane weighs 3500ml, and forming agent is weighed using paraffin
160g, dispersing agent is using stearic acid weighing 8g.
(1) it ball mill mixing: is put by the raw material powder that step (1) is equipped with diameter as the YG6X alloying pellet of 6.25mm and oneself
Alkane is ball-milling medium, while dispersing agent stearic acid 8g is added and forming agent paraffin 160g is placed in clean stainless steel jar mill,
Then the ball milling 96h on roll-type ball mill, ratio of grinding media to material 10:1, rotational speed of ball-mill 75r/min.In vacuum oven after the taking-up of wet-milling material
In 80 DEG C of dry 4h, homogenization is broken, be sieved powder using the screen in 200 mesh holes, is formed with certain ingredients and granularity requirements
Pellet.
(2) being directly loadable into the mixture powder after step (1) sieving will be equal after mold suppresses 20s under 350MPa pressure
Blank is made in even mixed powder.
(3) the blank body that step (2) suppresses is put into sintering furnace and is carried out by preheating, heating, heat preservation temperature control process, added
Thermal vacuum skimming temp is warming up to 500 DEG C, and the heat preservation temperature control time is 80min, and temperature deviation is controlled at ± 0.50 DEG C.
(4) the solid-phase sintering stage: its heating temperature is warming up to 1330 DEG C by 500 DEG C, and the rate of heat addition is no more than 5 DEG C/min,
Being in sintering temperature is 45min 900 DEG C of heat preservation temperature control times, and 1220 DEG C of heat preservation temperature control times are 60min and 1330 DEG C of heat preservation control
The warm time is 60min, and temperature deviation is controlled at ± 0.50 DEG C；
The liquid-phase sintering stage: its heating temperature is warming up to 1470 DEG C by 1330 DEG C, and heating rate is set as in 3 DEG C/min,
It is passed through high-purity 99.9995% argon gas of 5MPa simultaneously, is 1470 DEG C of setting heat preservation temperature control periods to be in sintering temperature
90min, temperature deviation are controlled at ± 0.50 DEG C.
Cooling stage: after its temperature progressively cools to 1200 ± 0.5 DEG C, rapid cooling to room temperature, cooling medium is height
Pure 99.9995% argon gas reaches room temperature with 36 DEG C/min cooling rate, then comes out of the stove and take out cermet.
Embodiment 3
Ti(C0.5,N0.5) micron powder size be FSSS1.2 weigh 760g, (Ti, W8, Mo5) (C0.5,N0.5) micron powder
Granularity is FSSS1.5 weighing 240g, Ti (C0.5,N0.5) submicron powder granularity be FSSS0.7 weigh 760g, (Ti, W8, Mo5)
(C0.5,N0.5) nanometer powder granularity be FSSS0.1 weigh 240g, powder size be FSSS1.5 Ni powder weigh 200g, powder grain
The Cr powder weighing 120g that degree is FSSS1.5, the Co powder weighing 650g that powder size is FSSS1.2, powder size is FSSS0.8's
WC powder weighing 600g, powder size are the Mo of FSSS1.52C powder weighing 49g, powder size are the Cr of FSSS1.52C3Powder claims
Weight 60g；Ball-milling medium hexane weighs 3500ml, and forming agent is using paraffin weighing 160g, and dispersing agent is using stearic acid weighing 40g.
(1) YG6X alloying pellet and hexane with diameter for 8mm ball mill mixing: are put by the raw material powder that step (1) is equipped with
For ball-milling medium, while dispersing agent stearic acid 4g is added and forming agent paraffin 16g is placed in clean stainless steel jar mill, then
Ball milling 72h, ratio of grinding media to material 11:1, rotational speed of ball-mill 80r/min on roll-type ball mill.Wet-milling material take out after in a vacuum drying oven 80
DEG C dry 4h, homogenization is broken, be sieved powder using the screen in 150 mesh holes, is formed with the grain of certain ingredients and granularity requirements
Material.
(2) being directly loadable into the mixture powder after step (1) sieving will be equal after mold suppresses 20s under 150MPa pressure
Blank is made in even mixed powder.
(3) the blank body that step (2) suppresses is put into sintering furnace and is carried out by preheating, heating, heat preservation temperature control process, added
Thermal vacuum skimming temp is warming up to 500 DEG C, and the heat preservation temperature control time is 90min, and temperature deviation is controlled at ± 0.50 DEG C.
(4) the solid-phase sintering stage: its heating temperature is warming up to 1300 DEG C by 500 DEG C, and the rate of heat addition is no more than 3 DEG C/min,
Being in sintering temperature is 50min 920 DEG C of heat preservation temperature control times, and 1270 DEG C of heat preservation temperature control times are 60min and 1350 DEG C of heat preservation control
The warm time is 50min, and temperature deviation is controlled at ± 0.50 DEG C；
The liquid-phase sintering stage: its heating temperature is warming up to 1430 DEG C by 1330 DEG C, and heating rate is set as in 3 DEG C/min,
It is passed through high-purity 99.9995% argon gas of 6MPa simultaneously, is 1450 DEG C of setting heat preservation temperature control periods to be in sintering temperature
90min, temperature deviation are controlled at ± 0.50 DEG C.
Cooling stage: after its temperature progressively cools to 1200 ± 0.5 DEG C, rapid cooling to room temperature, cooling medium is height
Pure 99.9995% argon gas reaches room temperature with 37 DEG C/min cooling rate, then comes out of the stove and takes out cermet.
Embodiment 4
Ti(C0.5,N0.5) micron powder size be FSSS1.8 weigh 1000g, (Ti, W8, Mo5) (C0.5,N0.5) powder and micron
Last granularity is FSSS1.5 weighing 120g, Ti (C0.5,N0.5) submicron powder granularity be FSSS0.8 weigh 1080g, (Ti, W8,
Mo5)(C0.5,N0.5) nanometer powder granularity be FSSS0.05 weigh 80g, powder size be FSSS1.5 Mo2C powder weighing 200g,
The Cr powder weighing 120g that powder size is FSSS1.5, the Co powder weighing 580g that powder size is FSSS1.2, powder size are
The WC powder weighing 380g of FSSS0.8, powder size is the Mo of FSSS1.52C powder weighing 320g, powder size are FSSS1.5's
TiN powder weighing 60g, the TiC powder weighing 60g that powder size is FSSS1.5.Ball-milling medium hexane weighs 3500ml, molding
Agent is using paraffin weighing 160g, and dispersing agent is using detergent alkylate semi-annular jade pendant acid weighing 20g.
(1) YG6X alloying pellet and hexane with diameter for 9mm ball mill mixing: are put by the raw material powder that step (1) is equipped with
For ball-milling medium, while dispersing agent detergent alkylate semi-annular jade pendant acid 20g is added and forming agent paraffin 200g is placed in clean stainless steel ball
In grinding jar, then the ball milling 116h on roll-type ball mill, ratio of grinding media to material 13:1, rotational speed of ball-mill 100r/min.Wet-milling material take out after
80 DEG C of dry 4h in vacuum oven, homogenization is broken, be sieved powder using the screen in 250 mesh holes, is formed with certain ingredients
With the pellet of granularity requirements.
(2) being directly loadable into the mixture powder after step (1) sieving will be equal after mold suppresses 30s under 200MPa pressure
Blank is made in even mixed powder.
(3) the blank body that step (2) suppresses is put into sintering furnace and is carried out by preheating, heating, heat preservation temperature control process, added
Thermal vacuum skimming temp is warming up to 600 DEG C, and the heat preservation temperature control time is 90min, and temperature deviation is controlled at ± 0.50 DEG C.
(4) the solid-phase sintering stage: its heating temperature is warming up to 1300 DEG C by 600 DEG C, and the rate of heat addition is no more than 5 DEG C/min,
Being in sintering temperature is 70min 920 DEG C of heat preservation temperature control times, and 1270 DEG C of heat preservation temperature control times are 60min and 1350 DEG C of heat preservation control
The warm time is 50min, and temperature deviation is controlled at ± 0.50 DEG C；
The liquid-phase sintering stage: its heating temperature is warming up to 1430 DEG C by 1330 DEG C, and heating rate is set as in 4 DEG C/min,
It is passed through high-purity 99.9995% argon gas of 8MPa simultaneously, is 1460 DEG C of setting heat preservation temperature control periods to be in sintering temperature
70min, temperature deviation are controlled at ± 0.50 DEG C.
Cooling stage: after its temperature progressively cools to 1200 ± 0.5 DEG C, rapid cooling to room temperature, cooling medium is height
Pure 99.9995% argon gas reaches room temperature with 38 DEG C/min cooling rate, then comes out of the stove and take out cermet
Embodiment 5
Ti(C0.5,N0.5) micron powder size be FSSS1.8 weigh 1200g, (Ti, W8, Mo5) (C0.5,N0.5) powder and micron
Last granularity is FSSS1.8 weighing 120g, Ti (C0.5,N0.5) submicron powder granularity be FSSS1.0 weigh 1000g, (Ti, W8,
Mo5)(C0.5,N0.5) nanometer powder granularity be FSSS0.05 weigh 80g, powder size be FSSS1.5 Mo2C powder weighing 200g,
The TaC/NbC powder weighing 120g that powder size is FSSS1.5, the Co powder weighing 580g that powder size is FSSS1.2, powder size
For the WC powder weighing 380g of FSSS0.8, powder size is the VC 20g of FSSS1.2, and powder size is the Cr 300g of FSSS1.2.
Ball-milling medium hexane weighs 350ml, and forming agent is using paraffin weighing 160g, and dispersing agent is using stearic acid weighing 40g.
(1) YG6X alloying pellet and hexane with diameter for 8mm ball mill mixing: are put by the raw material powder that step (1) is equipped with
For ball-milling medium, while dispersing agent stearic acid 40g is added and forming agent paraffin 160g is placed in clean stainless steel jar mill, so
The ball milling 48h on roll-type ball mill, ratio of grinding media to material 15:1, rotational speed of ball-mill 120r/min afterwards.In vacuum oven after the taking-up of wet-milling material
In 80 DEG C of dry 4h, homogenization is broken, be sieved powder using the screen in 250 mesh holes, is formed with certain ingredients and granularity requirements
Pellet.
(2) being directly loadable into the mixture powder after step (1) sieving will after mold suppresses 300s under 150MPa pressure
Blank is made in powder after evenly mixing.
(3) the blank body that step (2) suppresses is put into sintering furnace and is carried out by preheating, heating, heat preservation temperature control process, added
Thermal vacuum skimming temp is warming up to 800 DEG C, and the heat preservation temperature control time is 90min, and temperature deviation is controlled at ± 0.50 DEG C.
(4) the solid-phase sintering stage: its heating temperature is warming up to 1300 DEG C by 800 DEG C, and the rate of heat addition is no more than 5 DEG C/min,
Being in sintering temperature is 50min 920 DEG C of heat preservation temperature control times, and 1270 DEG C of heat preservation temperature control times are 50min and 1350 DEG C of heat preservation control
The warm time is 50min, and temperature deviation is controlled at ± 0.50 DEG C；
The liquid-phase sintering stage: its heating temperature is warming up to 1430 DEG C by 1330 DEG C, and heating rate is set as in 2 DEG C/min,
It is passed through high-purity 99.9998% argon gas of 10MPa simultaneously, is 1430 DEG C of setting heat preservation temperature control periods to be in sintering temperature
80min, temperature deviation are controlled at ± 0.50 DEG C.
Cooling stage: after its temperature progressively cools to 1200 ± 0.5 DEG C, rapid cooling to room temperature, cooling medium is height
Pure 99.9998% argon gas reaches room temperature with 40 DEG C/min cooling rate, then comes out of the stove and take out cermet.
The above, only presently preferred embodiments of the present invention, are not intended to limit the invention, patent protection model of the invention
It encloses and is subject to claims, it is all to change with equivalent structure made by description of the invention, similarly should all include
Within the scope of the present invention.
Claims (10)
1. a kind of centreless-ring structure cermet, which is characterized in that by weight percentage, ingredient is 10~55%
Ti (C, N) micron powder, 10~55% (Ti, M) (C, N) micron powder, 10~55%Ti (C, N) sub-micron or/and nano powder
End, 10~55% (Ti, M) (C, N) sub-micron/and nanometer powder, 5~20%WC, 0~30%TiC, 0~30%TiN, 0~
20%Co, 0~20%Ni, 0~10%Cr, 0~15%Mo2C, 0~10%TaC/NbC, 0~2%VC, 0~5%Cr2C3, 0~
1.2% carbon black；
Wherein, the M element in described (Ti, M) (C, N) the micron powder, (Ti, M) (C, N) sub-micron or/and nanometer powder is Mo,
Any one or a few in W, Ta, Nb, Zr, Cr, V solid-solution powder；The Ti (C, N), (Ti, M) (C, N) micron powder with
C in the Ti (C, N), (Ti, M) (C, N) sub-micron or/and nano-scale powders, N be all made of C/N atomic ratio 7/3,6/4 or
One of 5/5.
2. a kind of centreless-ring structure cermet according to claim 1, which is characterized in that by weight percentage
Meter, ingredient be 15~45%Ti (C, N), 15~45% (Ti, M) (C, N) micron powder, 6~15%Ti (C, N) micron or/
And nanometer powder, 7~15% (Ti, M) (C, N) sub-micron or/and nanometer powder, 12~18%WC, 0.5~15%TiC, 0.5
~15%TiN, 8~15%Co, 3~8%Ni, 1~5%Cr, 5~12%Mo2C, 2~10%TaC/NbC, 0.3~1.0%
VC, 0.5~1.2%Cr2C3, 0.0~1.0% carbon black.
3. a kind of centreless-ring structure cermet preparation method, which comprises the following steps:
(1) raw material weighed in proportion in claims 1 or 2 is mixed, and abrasive media, dispersing agent and forming agent is added, and is mixed
Preparing material is obtained after closing uniformly；
(2) preparing material is packed into the grinding hard alloy ball grinder of ball mill, carries out ball milling and obtains mixed material；
(3) mixed material is crossed into 150~250 mesh screens or spraying granulation；
(4) mixed material after sieving is directly loadable into mold and is pressed into blank；
(5) first the blank of compression molding is packed into high vacuum degreasing positive pressure sintering rapid cooling furnace, extracting gas in furnace body out makes
It is in vacuum, and vacuum degree is no more than 15Pa, restarts sintering furnace power supply, and sequentially enters the heating degreasing stage, solid-phase sintering rank
It section, liquid-phase sintering stage and rapid cooling stage, then comes out of the stove and takes out cermet.
4. according to the method described in claim 3, it is characterized in that, abrasive media is hexane or anhydrous second in the step (1)
Alcohol, accounting for and the mass fraction of total amount is added is 0.5~1.8%；The dispersing agent is detergent alkylate semi-annular jade pendant acid, stearic acid or second rope
Quick, mass fraction is 0.1~0.5%；The forming agent is gasoline and rubber, paraffin, polyvinyl alcohol, synthetic rubber, second two
One or more of in alcohol or SBS is solute, and mass fraction is 2~5%.
5. according to the method described in claim 3, it is characterized in that, the ball mill in the step (2) is roll type ball mill
Or planetary ball mill, the sphere diameter of the sintered carbide ball are 6.25~10mm, ratio of grinding media to material is 8~15:l；The ball mill
Rotational speed of ball-mill is 70~120 revs/min, and Ball-milling Time is 48~144h.
6. according to the method described in claim 3, it is characterized in that, in the step (4), the pressure in mold is 150~
450MPa, dwell time are 15~300s.
7. according to the method described in claim 3, it is characterized in that, in the heating skimming processes by preheat, be passed through gas, rise
Temperature, heat preservation temperature control process carry out, and heating, vacuum skimming temp is warming up to 450~800 DEG C, then keeps the temperature 50~100min.
8. according to the method described in claim 3, it is characterized in that, heating temperature is by 450~800 in the solid-phase sintering stage
DEG C be warming up to 1280~1350 DEG C, the rate of heat addition is no more than 5 DEG C/min, sintering temperature reach 850~950 DEG C, 1220~
45~90min is kept the temperature respectively when a certain temperature of 1280 DEG C and 1280~1350 DEG C respective ranges.
9. according to the method described in claim 3, it is characterized in that, entering liquid-phase sintering rank after the completion of the solid-phase sintering stage
Duan Shi raises the temperature to 1430~1470 DEG C with the heating rate of 2~5 DEG C/min, and the soaking time in liquid-phase sintering stage is
45~90min, while it being passed through the argon gas of 1~10MPa, argon gas purity is greater than 99.995%.
10. according to the method described in claim 3, it is characterized in that, entering rapid cooling after the completion of the liquid-phase sintering stage
Temperature is first progressively cooled to 1200 DEG C by the stage, is filled with argon gas as cooling medium and is carried out rapid cooling until room temperature, argon gas gas
Body purity is greater than 99.995%, and cooling rate is greater than 35 DEG C/min and reaches room temperature.
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| CN110512131A (en) * | 2019-09-05 | 2019-11-29 | 四川轻化工大学 | A kind of bulk metal ceramal bar and the preparation method and application thereof |
| CN111378888A (en) * | 2020-01-02 | 2020-07-07 | 四川轻化工大学 | Nano particle interface reinforced Ti (C, N) -based metal ceramic material with high nitrogen content and preparation method thereof |
| CN111850373A (en) * | 2020-07-31 | 2020-10-30 | 中南大学 | Ti (C, N) -based metal ceramic with high-entropy ring-phase structure and preparation method thereof |
| CN114729421A (en) * | 2019-11-28 | 2022-07-08 | 瑞典海博恩材料与技术有限公司 | NbC based hard alloy |
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