CN106011580B - A kind of multistage composite cermet, its preparation method and shield cutter - Google Patents
A kind of multistage composite cermet, its preparation method and shield cutter Download PDFInfo
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- CN106011580B CN106011580B CN201610395182.6A CN201610395182A CN106011580B CN 106011580 B CN106011580 B CN 106011580B CN 201610395182 A CN201610395182 A CN 201610395182A CN 106011580 B CN106011580 B CN 106011580B
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- 239000011195 cermet Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000008187 granular material Substances 0.000 claims abstract description 66
- 239000011159 matrix material Substances 0.000 claims abstract description 47
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 42
- 239000000956 alloy Substances 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims description 29
- 238000005245 sintering Methods 0.000 claims description 28
- 229910009043 WC-Co Inorganic materials 0.000 claims description 23
- 238000002791 soaking Methods 0.000 claims description 4
- 229910001005 Ni3Al Inorganic materials 0.000 abstract description 13
- 238000010276 construction Methods 0.000 abstract description 6
- QFUKUPZJJSMEGE-UHFFFAOYSA-N 5-(hydroxymethyl)-1-(3-methylbutyl)pyrrole-2-carbaldehyde Chemical compound CC(C)CCN1C(CO)=CC=C1C=O QFUKUPZJJSMEGE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 128
- 239000000843 powder Substances 0.000 description 39
- 239000000203 mixture Substances 0.000 description 25
- 238000005469 granulation Methods 0.000 description 17
- 230000003179 granulation Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910002111 aluminum magnesium boride Inorganic materials 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000011812 mixed powder Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000001238 wet grinding Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002362 mulch Substances 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000011435 rock Substances 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002490 spark plasma sintering Methods 0.000 description 4
- 229910000906 Bronze Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000009412 basement excavation Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 marmem Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002970 Calcium lactobionate Substances 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 206010011376 Crepitations Diseases 0.000 description 1
- 208000025599 Heat Stress disease Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21D—SHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
- E21D9/00—Tunnels or galleries, with or without linings; Methods or apparatus for making thereof; Layout of tunnels or galleries
- E21D9/06—Making by using a driving shield, i.e. advanced by pushing means bearing against the already placed lining
- E21D9/08—Making by using a driving shield, i.e. advanced by pushing means bearing against the already placed lining with additional boring or cutting means other than the conventional cutting edge of the shield
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mining & Mineral Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a kind of multistage composite cermet, including matrix phase and some granules for being distributed in matrix phase, the granule include wear-resisting phase and the n-layer transitional face being coated on outside wear-resisting phase, n >=1；The hardness of the n-layer transitional face gradually reduces, and contacts the transitional face layer hardness highest of wear-resisting phase；The wear-resisting phase includes AlMgB14‑Ni3Al SiC alloys.The present invention is with AlMgB14‑Ni3Al SiC alloys are as superhard wear phase, centre is enclosed in by transitional face, form superhard composite cermet granule, composite ganoine conjunction granule is evenly distributed in toughened matrix phase, obtain the multistage composite cermet with special construction, multistage composite cermet in the present invention has higher wearability and higher fracture toughness simultaneously, and present invention also offers a kind of preparation method of multistage composite cermet and a kind of shield cutter.
Description
Technical field
The invention belongs to metallurgical processing technical field, more particularly to a kind of multistage composite cermet, its preparation method and
Shield cutter.
Background technology
In China, the rock tunnel(ling) machine for soft soil layer is traditionally referred to as shield machine, carrying out tunnel with shield machine applies
Controllable ground when instrument has fast high automaticity, saving manpower, speed of application, a cavitation, weatherproof, excavation
Sedimentation, the features such as reducing influence to above ground structure and not influenceing water surface traffic when excavating under water, tunnel line it is longer,
In the case that buried depth is larger, with shield machine construction more economical rationality.
For shield machine, digging system has conclusive influence, digging system for the construction effect of shield machine
Including digging cutterhead and its drive system, digging cutterhead is the plate-like digging device that can be rotated or shake, by shield cutter, face
Plate, be unearthed notch, drive mechanism and Bearning mechanism etc. are formed.Wherein, direct functional component of the shield cutter as excavation stratum,
Its performance directly affects cutting effect, situation of being unearthed and the driving speed of shield machine.
Shield cutter is generally made up of cermet, compared with application of the cermet in metal machining field, metal
Ceramics are routinely subjected to high abrasion and high impact shock and the condition of work deposited, its failure mechanism bag in the application in shield field
Include abrasive wear, erosive wear, heat fatigue cracking, stress, impact fatigue crackle, and the fracture triggered by these crackles
Deng therefore, the cermet for shield cutter need to be provided simultaneously with high wearability and high fracture toughness.Shield field at present
Cermet be mainly coarse grained homogeneous texture conventional cermets, its WC grain be more than 10 μm, although fracture toughness
It is higher, but wearability is very low, turns into the short basic reason of rock drilling cutter life.
The content of the invention
It is an object of the invention to provide a kind of multistage composite cermet, its preparation method and shield cutter, the present invention
In multistage composite cermet simultaneously there is high wearability and higher fracture toughness.
The present invention provides a kind of multistage composite cermet, including matrix phase and some groups for being distributed in inside matrix phase
Grain,
The granule includes wear-resisting phase and the n-layer transitional face being coated on outside wear-resisting phase, n >=1；
The hardness of the n-layer transitional face gradually reduces, and contacts the transitional face layer hardness highest of wear-resisting phase；
The wear-resisting phase includes AlMgB14-Ni3Al-SiC alloys.
Preferably, the transitional face includes WC-Co alloys.
Preferably, described matrix mutually includes WC-Co alloys, pure Co bases, pure Ni bases, Ni base toughened matrix phase, Ni3Al, height
One or more in Qiang Gang, high temperature alloy, marmem, acid bronze alloy, acieral and enhancing composite.
Preferably, the overall volume fraction in the multistage composite cermet of the granule is 32~90%.
Preferably, volume fraction of the wear-resisting phase in the granule is 60~98%.
Preferably, the particle diameter of the granule is 10~1000 μm.
Preferably, the particle diameter of the wear-resisting phase is 2~996 μm；
The thickness of the transitional face is 2~50 μm.
A kind of preparation method of multistage composite cermet of the present invention, comprises the following steps：
A) in wear-resisting phase external sheath n-layer transitional face, granule, n >=1 are obtained；
The hardness of the n-layer transitional face gradually reduces, and contacts the transitional face layer hardness highest of wear-resisting phase；
The wear-resisting phase includes AlMgB14-Ni3Al-SiC alloys；
B) granule and matrix are mixed, are sintered, obtains multistage composite cermet, wherein, some granule distributions
Inside matrix phase.
Preferably, the temperature of the sintering is 600~1600 DEG C；
Soaking time in the sintering is 0.02~3 hour.
The present invention also provides a kind of shield cutter, including above-mentioned multistage composite cermet.
The invention provides a kind of multistage composite cermet, including matrix phase and some groups for being distributed in matrix phase
Grain, the granule include wear-resisting phase and the n-layer transitional face being coated on outside wear-resisting phase, n >=1；The wear-resisting phase includes AlMgB14-
Ni3Al-SiC alloys.The hardness of the n-layer transitional face gradually reduces, and contacts the transitional face hardness highest of wear-resisting phase；The transition
The hardness of phase is less than hardness of the hardness more than matrix phase of wear-resisting phase.The present invention is with AlMgB14-Ni3Al-SiC alloys are as superhard
Wear-resisting phase, centre is enclosed in by transitional face, forms superhard composite cermet granule, the composite cermet granule is uniformly divided
Cloth obtains the multistage composite cermet with special construction in toughened matrix phase, the multistage composite metal pottery in the present invention
Porcelain has higher wearability and higher fracture toughness simultaneously, test result indicates that, the multistage composite metal pottery in the present invention
The hardness of porcelain is 9~20GPa, and fracture toughness is 8~20MPam1/2。
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is the structural representation of multistage composite cermet in the present invention.
Embodiment
The invention provides a kind of multistage composite cermet, including matrix phase and some groups for being distributed in matrix phase
Grain,
The granule includes wear-resisting phase and the n-layer transitional face being coated on outside wear-resisting phase, n >=1；
The hardness of the n-layer transitional face gradually reduces, and contacts the transitional face hardness highest of wear-resisting phase；
The wear-resisting phase includes AlMgB14-Ni3Al-SiC alloys.
Multistage composite cermet in the present invention has higher wearability and higher fracture toughness simultaneously.
The present invention using hardness is relatively low and cermet that toughness is higher preferably wraps as matrix phase, the material of described matrix phase
Include WC-Co alloys, pure Co bases, pure Ni bases, Ni base toughened matrix phase, Ni3Al, high-strength steel, high temperature alloy, marmem,
One or more in acid bronze alloy, acieral enhancing composite；The enhancing composite is preferably to be closed with WC-Co
Golden, pure Co bases, pure Ni bases, Ni base toughened matrix phase, Ni3Al, high-strength steel, high temperature alloy, marmem, acid bronze alloy
With ceramic particle, whisker and the fibre-reinforced composite that acieral is matrix.Described matrix is mutually in multistage composite metal
Volume fraction in ceramics is preferably 10~68%, more preferably 15~60%, most preferably 20~55%.In the present invention,
Co content is higher in the WC-Co alloys, and Co mass fraction is preferably 25~85%, and more preferably 35~75%, it is optimal
Elect 45~70%, surplus WC as, this causes the mean free path of WC grain in toughened matrix phase to be improved significantly, ensure that
The high tenacity of multistage composite cermet.
In the present invention, wear-resisting phase outer surface cladding n-layer transitional face, n >=1 form granule, and the granule is evenly distributed on
In matrix phase, as shown in figure 1, Fig. 1 is the structural representation of multistage composite cermet in the present invention, wherein, 1 is wear-resisting phase, 2
It is matrix phase for transitional face, 3,1 and 2 spherical powders formed are granule.In the present invention, the granule is preferably spherical, institute
The particle diameter for stating granule is preferably 10~1000 μm, more preferably 20~800 μm, most preferably 100~180 μm, specifically,
It can be 100 μm in embodiments of the invention.Volume fraction of the granule in multistage composite cermet be preferably 32~
90%, more preferably 40~80%, most preferably 60~75%, specifically, can be 70% in an embodiment of the present invention.
In the present invention, the transitional face can strengthen heat between matrix phase and superhard wear phase, mechanical matching, reduce
Internal stress, improve the overall fracture toughness of multistage composite cermet.In the present invention, 1 layer of transitional face can be used, can also
Using multilayer transitional face；When using multilayer transitional face, the hardness of multilayer transitional face gradually reduces, and contacts the transitional face of wear-resisting phase
Layer hardness highest, contacts that the transitional face hardness of matrix phase is minimum, the first layer transitional face of wear-resisting phase is contacted in multilayer transitional face
Hardness can with it is wear-resisting it is mutually identical can also be different.In the present invention, the material of the transitional face preferably includes WC-Co alloys,
Wherein, Co is preferably 6~20% in the mass fraction of WC-Co alloys, more preferably 10~15%, surplus WC.In the present invention
In, hardness can be used gradually to increase WC-Co alloys as 3 layers of transitional face, contact the composition of the first layer transitional face of wear-resisting phase
Can be 92wt.%WC-8wt.%Co (this layer of hardness highest), the composition of middle second layer transitional face can be 85wt.%
WC-15wt.%Co (this layer of hardness is placed in the middle), the composition for contacting the third layer transitional face of matrix phase can be 70wt.%WC-
30wt.%Co (this layer of hardness hardness in three layers of transitional face is minimum).
In the present invention, the thickness of the transitional face is preferably (if the gross thickness that multilayer transitional face is multilayer transitional face)
2~50 μm, more preferably 3~40 μm, most preferably 5~20 μm；Volume of the transitional face in multistage composite cermet
Fraction is preferably 2~40%, more preferably 5~35%, most preferably 10~30%.
In the present invention, the wear-resisting phase has higher hardness, disperses to have in the base with the granule that transitional face is formed
There is preferable anti-wear performance.The material of the wear-resisting phase preferably includes AlMgB14-Ni3Al-SiC alloys, the wear-resisting phase are being rolled into a ball
Volume fraction in grain is preferably 60~98%, and more preferably 65~90%, most preferably 70~85%, the wear-resisting phase is more
Volume fraction in level composite cermet for preferably 30~80%, more preferably 40~70%, most preferably 50~
60%, specifically, can be 52.5% in an embodiment of the present invention.The particle diameter of the wear-resisting phase is preferably 2~996 μm, more
Preferably 20~450 μm, most preferably 50~400 μm, specifically, can be 150 μm in an embodiment of the present invention.
In the present invention, the AlMgB14-Ni3In Al-SiC alloys, AlMgB14Mass fraction be preferably 70~90%,
More preferably 75~85%, more preferably 80%；Ni3Al mass fraction is preferably 0.5~20%, more preferably 3~
15%, most preferably 4~10%；SiC mass fraction is preferably 0.2~10%, more preferably 1~8%, most preferably 2~
4%.It is AlMgB that material, which is preferably prepared, in the present invention in accordance with the following methods14-Ni3The wear-resisting phase of Al-SiC alloys：
(1) by aluminium powder, magnesium powder and boron powder Al in molar ratio：Mg：B=1:1:14 are well mixed to obtain mixture, then will be mixed
Compound, which is placed under 20MPa, to be heated to 1350~1450 DEG C and is incubated 90min, and AlMgB is made after cooling14, by AlMgB14After grinding
Obtain AlMgB14Pre-reaction powder.
Preferably, will first be used to prepare AlMgB14The boron powder of pre-reaction powder is placed in 1 × 10-3In Pa vacuum drying oven, by room temperature
It is heated to 1500 DEG C and is incubated 2h, is then cooled to room temperature with stove；Then boron powder, magnesium powder and aluminium powder are mixed in proportion again.
Preferably, the particle diameter of the aluminium powder is 1~2 μm, and the particle diameter of magnesium powder is 60~80 μm, and the particle diameter of boron powder is 2~5 μ
m。
(2) in proportion by AlMgB14Pre-reaction powder and SiC whiskers are well mixed, and obtain compound material.Preferably, in proportion will
AlMgB14Pre-reaction powder, SiC whiskers and Ni3Al mixed powders are well mixed, and obtain compound material.Preferably, gained compound material
Cross 80~200 mesh sieves.
Above-mentioned Ni3Al mixed powders are made by following steps：In terms of mass fraction, by 19~20% Al, 9.0~
9.5% Cr, 0.6~0.65% Zr, 0.6~0.65% Y, 0.6~0.65% V, 0.95~1% B and surplus
Ni is mixed, and obtains mixed powder；Ball milling mixing powder 50h under an inert atmosphere, obtains Ni3Al mixed powders.
(3) it is AlMgB compound material to be prepared into material14-Ni3The spherical wear-resisting phase of Al-SiC alloys.It is of the invention preferred
In compound material：AlMgB14-Ni31-4wt% binder is added in Al-SiC mixed powders, the mixture is carried out successively wet
Mill, dry, sieve, granulation, obtaining wear-resisting phase.Wear-resisting phase particle can also be by carrying out wet-milling, mist successively by the mixture
Change dry, sieving and obtain wear-resisting phase.Resulting wear-resisting phase needs further to be dewaxed and sintered.
In the present invention, the forming agent is preferably paraffin, PEG or rubber.In the present invention, the quality of the forming agent
The 1%~4% of preferably described compound material quality, more preferably 1.2%~2.8%, most preferably 1.8%~2.2%.
In the present invention, the ball milling speed of the wet-milling is preferably 100r/min~250r/min, more preferably 150r/
Min~200r/min, most preferably 160r/min~180r/min.In the present invention, the time of the wet-milling is preferably 1 hour
~48 hours, more preferably 20 hours~40 hours, most preferably 25 hours~35 hours.In the present invention, the drying
Temperature is preferably 50 DEG C~70 DEG C, more preferably 55 DEG C~65 DEG C, most preferably 60 DEG C.
In the present invention, described dewaxing can be carried out in hydrogen, argon gas, nitrogen, 400-600 DEG C of dewaxing temperature, be taken off
0.5-2 hours wax time, sintering can be carried out in hydrogen, argon gas, nitrogen, vacuum, and 1100~1600 DEG C of sintering temperature is more excellent
Elect 1200~1500 DEG C as.
The present invention does not have special limitation to the method for the granulation, and spraying well known to those skilled in the art can be used to make
Grain or roller are granulated.In the present invention, the particle diameter of the wear-resisting phase after the sintering obtained after the granulation and above-mentioned technical proposal institute
It is consistent to state the particle diameter of wear-resisting phase, will not be repeated here.
The multistage composite structural metal ceramics of the present invention, wherein the combination of superhard phase and transitional face is as composite cermet
Granule, hardness is relatively low and cermet that toughness is high is as matrix, due to the composite cermet group of superhard phase-transition phase composition
Grain has higher hardness, therefore wearability is good, and the low toughness of the hardness of matrix is high, so as to reach high-wearing feature and high tenacity
Unification, applied to the ceramic tool and instrument for making the fields such as mining, agricultural, capital construction, the energy, solve conventional metals pottery
The limitation that porcelain wearability and fracture toughness can not improve simultaneously.
Present invention also offers a kind of preparation method of multistage composite cermet, comprise the following steps：
A) in wear-resisting phase external sheath n-layer transitional face, granule, n >=1 are obtained；
The hardness of the n-layer transitional face gradually reduces, and contacts the transitional face layer hardness highest of wear-resisting phase；
The wear-resisting phase includes AlMgB14-Ni3Al-SiC alloys；
B) granule and matrix are mixed, are sintered, obtains multistage composite cermet.
The present invention preferably includes n-layer transitional face in wear-resisting phase spherical powder particle outer layer, obtains granule, n >=1, the present invention
It is preferred that in wear-resisting phase spherical powder particle external sheath n-layer transitional face, granule is obtained, specifically, can be by wear-resisting phase spherical powder
Body particle, which is placed on, to be added in the transitional face powder of forming agent, carries out mixing granulation, by pre-burning, obtain it is internal for wear-resisting phase,
External sheath has the spherical nodule of transitional face.In the present invention, can be successively when in wear-resisting phase external sheath multilayer transitional face
Coated, wear-resisting phase spherical powder particle is placed in first layer transitional face powder and carries out mixing granulation；The particle that will be obtained
It is placed in second layer transitional face powder and carries out mixing granulation；Obtained particle is placed in third layer transitional face powder and mixed
Granulation, the rest may be inferred, and it is wear-resisting phase to obtain inside, and external sheath has the spheric granules of multilayer transitional face.
In the present invention, the material of the wear-resisting phase, the material of dosage and wear-resisting phase in preparation method and above-mentioned technical proposal
Matter, dosage are consistent with preparation method, will not be repeated here；The material of the transitional face and dosage and transition in above-mentioned technical proposal
The material of phase is consistent with dosage, will not be repeated here；The forming agent is consistent with the forming agent species in above-mentioned technical proposal,
This is repeated no more.
In the present invention, the mixing granulation technique can use mist projection granulating well known to those skilled in the art or roller to make
Grain.In the present invention, the particle diameter of the wear-resisting phase after the sintering obtained after the granulation and wear-resisting phase-mistake described in above-mentioned technical proposal
It is consistent to cross the particle diameter of phase granule, can also be adjusted according to the actual requirements, the present invention does not do special restriction.
Obtained granule is preferably carried out pre-burning by the present invention, obtains the granule of pre-burning, in the present invention, the pre-burning includes
Dewaxing and sintering, described dewaxing can be carried out in hydrogen, argon gas, nitrogen, 400-600 DEG C of dewaxing temperature, be dewaxed the time
0.5-2 hours, sintering can be carried out in hydrogen, argon gas, nitrogen, vacuum, 1100~1600 DEG C of sintering temperature.
After the pre-burning for completing granule, the present invention mixes granule and matrix, is sintered, and obtains multistage composite metal pottery
Porcelain.In the present invention, the sintering processing such as hot pressed sintering, discharge plasma sintering, microwave sintering or HIP sintering can be used,
It is preferred that discharge plasma sintering (Spark Plasma Sintering, SPS) prepares multistage composite cermet.SPS technologies profit
Plasma is produced between powder particle with discharge pulse, while Joule heat is produced in powder face, it is net greatly to accelerate powder
Change, sinter the sintering densification mechanism such as big neck length, body diffusion, grain boundary decision and evaporation-cohesion, can be than conventional liquid phase
Realized at a temperature of sintering Di Ji Baidu fast densified.With SPS technologies can relatively low sintering temperature, very short soaking time,
Ultra-fine or even nanostructured the cermet that grain structure is more uniform, consistency is high is prepared under controllable sintering pressure, and
And mechanical property produces unusual " double high (hardness and fracture toughnesses) " characteristic.With conventional cermets liquid sintering technology ratio
Compared with discharge plasma sintering has quick densifying and the advantage for preventing crystal grain from growing up, and the multistage composite that is particularly suitable for use in etc. is non-
The preparation of even structural metal ceramics.
In the present invention, the temperature of the sintering is preferably 500~1600 DEG C, more preferably 800~1400 DEG C；The burning
Soaking time during knot is preferably 0.02~3 hour, more preferably 0.1~2 hour, most preferably 0.5~1.5 hour.
Present invention also offers a kind of shield cutter, including the multistage composite cermet in above-mentioned technical proposal.This hair
Multistage composite cermet in bright belongs to heterogeneous texture cermet, suitably to soil, the driving of rock and cutting, by this
Its wearability of shield cutter and service life can carry than ceramic tool made of multistage composite cermet in invention
High by more than 50%, hardness is more than 85HRA.
The invention provides a kind of multistage composite cermet, including matrix phase and some groups for being distributed in matrix phase
Grain, the granule include wear-resisting phase and the n-layer transitional face being coated on outside wear-resisting phase, n >=1；The hardness of the n-layer transitional face by
Gradually reduce, contact the transitional face layer hardness highest of wear-resisting phase；The wear-resisting phase includes AlMgB14-Ni3Al-SiC alloys.The present invention
With AlMgB14-Ni3Al-SiC alloys are enclosed in centre by transitional face, form superhard composite cermet as superhard wear phase
Granule, this kind of almost spherical and the thicker composite ganoine of particle diameter are closed granule and are evenly distributed in continuous toughened matrix phase,
Obtain the multistage composite cermet with special construction, the multistage composite cermet in the present invention has higher resistance to simultaneously
Mill property and higher fracture toughness, test result indicates that, the hardness of the multistage composite cermet in the present invention is 9~20GPa,
Fracture toughness is 8~20MPam1/2。
The present invention tests the fracture toughness of multistage composite cermet in the present invention according to ASTM E399, the results showed that,
The fracture toughness of multistage composite cermet in the present invention is up to 20MPam1/2。
The present invention tests the wearability of multistage composite cermet in the present invention according to ASTM B611, the results showed that, this
The wearability of multistage composite cermet in invention improves 15-30% than the conventional cermets of even structure.
The present invention tests the Vickers hardness of multistage composite cermet in the present invention, the results showed that, it is more in the present invention
The hardness of level composite cermet is up to 20GPa.
The present invention tests the associated lifetime that multistage composite cermet in the present invention digs rock, the results showed that, dig
The associated lifetime of rock is up to 300min.
In order to further illustrate the present invention, a kind of multistage composite metal provided by the invention is made pottery with reference to embodiments
Porcelain, its preparation method and shield cutter are described in detail, but can not be understood as limiting the scope of the present invention.
In the examples below, boron powder footpath is 2~5 μm, and the particle diameter of aluminium powder is 1~2 μm, and the particle diameter of magnesium powder is 60~80
μm,
Embodiment 1
Boron powder is placed in 1 × 10-3In Pa vacuum drying oven, it is heated to 1500 DEG C by room temperature and is incubated 2h, then cool with stove
To room temperature；By aluminium powder, magnesium powder and boron powder Al in molar ratio：Mg：B=1:1:14 are well mixed to obtain mixture, then by mixture
It is placed under 20MPa and is heated to 1450 DEG C and is incubated 90min, AlMgB is made after cooling14, by AlMgB14AlMgB is obtained after grinding14
Pre-reaction powder.
In terms of mass fraction, by 19% Al, 9.0% Cr, 0.65% Zr, 0.6% Y, 0.6% V, 1% B
Mixed with the Ni of surplus, obtain mixed powder；Ball milling mixing powder 50h under an inert atmosphere, obtains Ni3Al mixed powders.
In terms of mass fraction, by 2% SiC whiskers, 4% Ni3Al and 94% AlMgB14Pre-reaction powder is well mixed
100 mesh sieves are crossed afterwards, and AlMgB is prepared after added binder, wet-milling, atomization drying granulation, sieving, dewaxing, sintering14-
Ni3The wear-resisting phase of Al-SiC alloy sphericals.The average grain diameter of wear-resisting phase is 100 μm.
By AlMgB14-Ni3The wear-resisting phase of Al-SiC alloy sphericals is placed on mixing granulation in the WC-Co powders containing 85%WC,
Wear-resisting one layer of WC-Co powder of phase Surface mulch is transitional face, obtains cermet granule, the average grain of obtained cermet granule
Footpath is 110 μm.
55.7g cermets granule is mixed to (Co mass fractions are 70%) with 44.3gWC-Co cermets, mixing is equal
Compressing, the plasma agglomeration at 1200 DEG C after even, 5min is incubated, obtains multistage composite cermet.Multistage composite metal
In ceramics, with volume fraction, wear-resisting phase 57.7%, transitional face 12.3%, matrix phase 30%.
Embodiment 2
Boron powder is placed in 1 × 10-3In Pa vacuum drying oven, it is heated to 1500 DEG C by room temperature and is incubated 2h, then cool with stove
To room temperature；By aluminium powder, magnesium powder and boron powder Al in molar ratio：Mg：B=1:1:14 are well mixed to obtain mixture, then by mixture
It is placed under 20MPa and is heated to 1450 DEG C and is incubated 90min, AlMgB is made after cooling14, by AlMgB14AlMgB is obtained after grinding14
Pre-reaction powder.
In terms of mass fraction, by 19% Al, 9.0% Cr, 0.65% Zr, 0.6% Y, 0.6% V, 1% B
Mixed with the Ni of surplus, obtain mixed powder；Ball milling mixing powder 50h under an inert atmosphere, obtains Ni3Al mixed powders.
In terms of mass fraction, by 4% SiC whiskers, 6% Ni3Al and 90% AlMgB14The addition shaping of pre-reaction powder
100 mesh sieves are crossed after agent is well mixed, through spraying granulation, sieves, dewaxing, is prepared after pre-burning.The average grain diameter of wear-resisting phase is
150μm。
By AlMgB14-Ni3The wear-resisting phase of Al-SiC alloy sphericals is placed on mixing granulation in the WC-Co powders containing 85%WC,
Wear-resisting one layer of WC-Co powder of phase Surface mulch is transitional face, obtains cermet granule, the average grain of obtained cermet granule
Footpath is 160 μm.
51.6g cermet granules are mixed to (Co mass fractions are 70%) with 48.4gWC-Co, suppressed after well mixed
Shaping, the discharge plasma sintering at 1200 DEG C, 5min is incubated, obtains multistage composite cermet.Multistage composite cermet
In, with volume fraction, wear-resisting phase 57.7%, transitional face 12.3%, matrix phase 30%.
Embodiment 3
Using the AlMgB in embodiment 114-Ni3The wear-resisting phase of Al-SiC alloy sphericals.
By AlMgB14-Ni3The wear-resisting phase of Al-SiC alloy sphericals, which is placed in the WC-Co powders containing 85%WC, to be rotated, wear-resisting
One layer of WC-Co powder of phase Surface mulch is transitional face, obtains cermet granule, and obtained cermet granule average grain diameter is
310μm。
46.1g cermet granules are mixed to (Co mass fractions are 70%) with 53.9gWC-Co, suppressed after well mixed
Shaping, the plasma agglomeration at 1200 DEG C, 5min is incubated, obtains multistage composite cermet.In multistage composite cermet, with
Volume fraction, wear-resisting phase 63.4%, transitional face 6.6%, matrix phase 30%.
Embodiment 4
The AlMgB that particle diameter is 300 μm is prepared according to the method in embodiment 214-Ni3Al-SiC alloy sphericals are wear-resisting
Phase.
By AlMgB14-Ni3The wear-resisting phase of Al-SiC alloy sphericals is placed on the WC-Ni containing 85%WC3Rotated in Al powders, resistance to
It is transitional face to grind phase one layer of WC-Co powder of Surface mulch, obtains cermet granule, obtained cermet granule average grain diameter
For 310 μm.
48.4g cermets granule is mixed with 51.6gWC-Co (Co mass fractions are 90%), suppressed after well mixed
Shaping, the discharge plasma sintering at 1200 DEG C, 5min is incubated, obtains multistage composite cermet.Multistage composite cermet
In, with volume fraction, wear-resisting phase 63.4%, transitional face 6.6%, matrix phase 30%.
Embodiment 5
The AlMgB that particle diameter is 300 μm is prepared according to the method in embodiment 114-Ni3Al-SiC alloy sphericals are wear-resisting
Phase.
By AlMgB14-Ni3The wear-resisting phase of Al-SiC alloy sphericals, which is placed in the WC-Co powders containing 85%WC, to be rotated, wear-resisting
One layer of WC-Co powder of phase Surface mulch is transitional face, obtains cermet granule, and obtained cermet granule average grain diameter is
320μm。
51.6g cermets granule is mixed with 48.4gWC-Co (Co mass fractions are 70%), suppressed after well mixed
Shaping, the discharge plasma sintering at 1200 DEG C, 1.5 hours are incubated, obtains multistage composite cermet.Multistage composite metal is made pottery
In porcelain, with volume fraction, wear-resisting phase 57.7%, transitional face 12.3%, matrix phase 30%.
Embodiment 6
The AlMgB that particle diameter is 300 μm is prepared according to the method in embodiment 114-Ni3Al-SiC alloy sphericals are wear-resisting
Phase；
First layer transitional face is prepared by the following method：
92wt.%WC-8wt.%Co and paraffin are mixed, obtain mixture；
21.5 grams of mixtures and 37.7 grams of wear-resisting phase particles are subjected to wet-milling in 48 hours, at 60 DEG C under 200r/min
Dry, sieve, granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 0.5 hour, then in 600 DEG C of vacuum bars at 400 DEG C
It is sintered under part, obtains wear-resisting phase and the granule of first layer transition phase composition.
Second layer transitional face is prepared by the following method：
85wt.%WC-15wt.%Co and paraffin are mixed, obtain mixture；
By the granule of 21.9 grams of mixtures and 52.9 grams of wear-resisting phase and first layer transition phase composition in 200r/min
Lower progress wet-milling in 48 hours, dry at 60 DEG C, sieving, granulation；Obtained spherolite is carried out 2 hours in hydrogen at 400 DEG C
Dewaxing, is then sintered under 600 DEG C of vacuum conditions, obtains wear-resisting phase and the granule of first layer+second layer transition phase composition.
Third layer transitional face is prepared by the following method：
70wt.%WC-30wt.%Co and paraffin are mixed, obtain mixture；
21.1 grams of mixtures are existed with 74.8 grams of wear-resisting phase and the granule of first layer+second layer transition phase composition
Carried out under 200r/min wet-milling in 48 hours, dry at 60 DEG C, sieving, granulation；Obtained spherolite is carried out in hydrogen at 400 DEG C
The dewaxing of 2 hours, then it is sintered under 600 DEG C of vacuum conditions, obtains wear-resisting phase and first layer+second layer+third layer mistake
Cross the granule of phase composition.
It is as matrix phase, the preparation method of described matrix phase using 30wt.%WC-70wt.%Co alloys：
30wt.%WC-70wt.%Co and paraffin are mixed, obtain mixture；
82.4 grams of mixtures and 95.9 grams of wear-resisting phases and the granule of three layers of transition phase composition are entered under 200r/min
Row wet-milling in 48 hours, dry at 60 DEG C, sieving, granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 2 hours at 400 DEG C,
Then in 41MPa, 1200 DEG C of progress discharge plasma sinterings, 5 minutes is incubated, obtains final multistage composite cermet.It is more
In level composite cermet, the average grain diameter of wear-resisting phase-transitional face granule is 330 μm, with volume fraction, wear-resisting phase
52.6%, transitional face 17.4%, matrix phase 30%.
The present invention tests the wearability of cermet, fracture toughness and hardness in embodiment 1~6 respectively, as a result such as table 1
Shown, table 1 is the performance parameter of cermet in the embodiment of the present invention 1~6.
The performance parameter of cermet in the embodiment of the present invention 1~6 of table 1
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of multistage composite cermet, including matrix phase and some granules for being distributed in inside matrix phase,
Described matrix mutually includes WC-Co alloys, and Co mass fraction is 25~85% in the WC-Co alloys；
The granule includes wear-resisting phase and the n-layer transitional face being coated on outside wear-resisting phase, n >=1；
The hardness of the n-layer transitional face gradually reduces, and contacts the transitional face layer hardness highest of wear-resisting phase；
The transitional face includes WC-Co alloys；
The wear-resisting phase includes AlMgB14-Ni3Al-SiC alloys.
2. multistage composite cermet according to claim 1, it is characterised in that the granule is overall described multistage multiple
It is 32~90% to close the volume fraction in cermet.
3. multistage composite cermet according to claim 2, it is characterised in that the wear-resisting phase is in the granule
Volume fraction is 60~98%.
4. multistage composite cermet according to claim 1, it is characterised in that the particle diameter of the granule is 10~1000
μm。
5. multistage composite cermet according to claim 4, it is characterised in that the particle diameter of the wear-resisting phase is 2~996
μm；
The thickness of the transitional face is 2~50 μm.
6. a kind of preparation method of multistage composite cermet, comprises the following steps：
A) in wear-resisting phase external sheath n-layer transitional face, granule, n >=1 are obtained；
The wear-resisting phase includes AlMgB14-Ni3Al-SiC alloys；The transitional face includes WC-Co alloys；
The hardness of the n-layer transitional face gradually reduces, and contacts the transitional face hardness highest of wear-resisting phase；
B) granule and matrix are mixed, are sintered, obtains multistage composite cermet, wherein, some granules are distributed in base
Inside body phase；
Described matrix mutually includes WC-Co alloys, and Co mass fraction is 25~85% in the WC-Co alloys.
7. preparation method according to claim 6, it is characterised in that the temperature of the sintering is 600~1600 DEG C；
Soaking time in the sintering is 0.02~3 hour.
8. a kind of shield cutter, including multistage composite cermet or claim 6 described in Claims 1 to 5 any one
Multistage composite cermet made from preparation method described in~7 any one.
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| CN101077644A (en) * | 2006-05-26 | 2007-11-28 | 南京盛润科技有限公司 | Gradient compound material and preparation method |
| CN101487121A (en) * | 2009-02-27 | 2009-07-22 | 中南大学 | Diamond / W-C gradient structure composite coating and preparing method thereof |
| CN102220533A (en) * | 2011-06-09 | 2011-10-19 | 株洲硬质合金集团有限公司 | Net-shaped structure hard alloy brazing sheet and preparation method thereof |
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