CN106011579B - 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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- CN106011579B CN106011579B CN201610392118.2A CN201610392118A CN106011579B CN 106011579 B CN106011579 B CN 106011579B CN 201610392118 A CN201610392118 A CN 201610392118A CN 106011579 B CN106011579 B CN 106011579B
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- 239000002131 composite material Substances 0.000 title claims abstract description 94
- 239000011195 cermet Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 77
- 239000008187 granular material Substances 0.000 claims abstract description 70
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 69
- 239000000956 alloy Substances 0.000 claims abstract description 69
- 239000010432 diamond Substances 0.000 claims abstract description 19
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 18
- 229910052582 BN Inorganic materials 0.000 claims abstract description 12
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims description 26
- 229910009043 WC-Co Inorganic materials 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 229910000765 intermetallic Inorganic materials 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 229910000906 Bronze Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- -1 marmem Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 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 6
- 238000010276 construction Methods 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 149
- 239000000203 mixture Substances 0.000 description 47
- 238000005469 granulation Methods 0.000 description 26
- 230000003179 granulation Effects 0.000 description 26
- 238000000034 method Methods 0.000 description 18
- 238000001238 wet grinding Methods 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 239000012188 paraffin wax Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 235000013339 cereals Nutrition 0.000 description 13
- 238000000498 ball milling Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000011435 rock Substances 0.000 description 7
- 229910000531 Co alloy Inorganic materials 0.000 description 6
- 230000002708 enhancing effect Effects 0.000 description 5
- 239000002362 mulch Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 238000002490 spark plasma sintering Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000009412 basement excavation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000009768 microwave sintering Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000010998 test method Methods 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010011376 Crepitations Diseases 0.000 description 1
- 208000025599 Heat Stress disease Diseases 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910001005 Ni3Al Inorganic materials 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001960 triggered effect Effects 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 hardness highest of wear-resisting phase；The wear-resisting phase is diamond or boron nitride；The hardness of the transitional face is more than hardness of the hardness less than wear-resisting phase of matrix phase.The present invention coats wear-resisting phase using transitional face, form composite hard alloy granule, composite ganoine conjunction granule is evenly distributed in tough matrix phase, the multistage composite cermet with special construction is obtained, multistage composite cermet provided by the invention has higher wearability and higher fracture toughness simultaneously.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 hard alloy 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 hard alloy, compared with application of the hard alloy in metal machining field, hard
Alloy is 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 hard alloy for shield cutter need to be provided simultaneously with high wearability and high fracture toughness.Shield field at present
Hard alloy be mainly coarse grained homogeneous texture conventional rigid alloy, although fracture toughness is higher, wearability is very
It is low, turn into the short basic reason of rock drilling cutter life.
The content of the invention
In view of this, it is an object of the invention to provide a kind of multistage composite cermet, its preparation method and shield knife
Tool, multistage composite cermet provided by the invention have high wearability and higher fracture toughness simultaneously.
The 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 hardness highest of wear-resisting phase；
The wear-resisting phase includes diamond or boron nitride；
The hardness of the transitional face is less than hardness of the hardness more than matrix phase of wear-resisting phase.
Preferably, described matrix mutually includes WC-Co alloys, pure Co, pure Ni, Ni base intermetallic compound, high-strength steel, high temperature
One or more in alloy, marmem, acid bronze alloy, acieral and enhancing composite.
Preferably, the granularity of the wear-resisting phase is 5 microns~500 microns.
Preferably, percent by volume of the wear-resisting phase in the granule is 40%~98%.
Preferably, the transitional face is WC-Co alloys, and the WC-Co alloys include：
6wt%~20wt% Co；
Surplus is WC.
Preferably, percent by volume of the granule in the multistage composite cermet is 32%~90%.
The invention provides 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 hardness highest of wear-resisting phase；
The wear-resisting phase includes diamond or boron nitride；
B) granule and matrix are mixed, are sintered, obtains multistage composite cermet, wherein, some granule distributions
Inside matrix phase；
The hardness of the transitional face is less than hardness of the hardness more than matrix phase of wear-resisting phase.
Preferably, the temperature of the sintering is 500~1450 DEG C；
Soaking time in the sintering is 2 minutes~120 minutes.
The invention provides a kind of shield cutter, including the multistage composite cermet or above-mentioned described in above-mentioned technical proposal
Multistage composite cermet made from preparation method described in technical scheme.
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 diamond
Or boron nitride；The hardness of the n-layer transitional face gradually reduces, and contacts the transitional face hardness highest of wear-resisting phase；The transitional face
Hardness is less than hardness of the hardness more than matrix phase of wear-resisting phase.The present invention uses diamond or boron nitride, transitional face is coated resistance to
Phase is ground, forms superhard composite hard alloy granule, composite ganoine conjunction granule is evenly distributed in the preferable matrix phase of toughness,
The multistage composite cermet with special construction is obtained, multistage composite cermet provided by the invention has higher simultaneously
Wearability and higher fracture toughness, test result indicates that, the hardness ＞ of multistage composite cermet provided by the invention
85HRA, fracture toughness 15-40MPam1/2。
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 provided by the invention.
Embodiment
The 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 hardness highest of wear-resisting phase；
The wear-resisting phase includes diamond or boron nitride；
The hardness of the transitional face is less than hardness of the hardness more than matrix phase of wear-resisting phase.
Multistage composite cermet in the present invention has higher wearability and higher fracture toughness simultaneously.
The present invention using hardness is relatively low and alloy that toughness is higher preferably includes as matrix phase, the material of described matrix phase
WC-Co alloys, pure Co, pure Ni, Ni base intermetallic compound, high-strength steel, high temperature alloy, marmem, acid bronze alloy, aluminium
One or more in based alloy and enhancing composite.In the present invention, the enhancing of the enhancing composite is mutually preferred wraps
Include ceramic particle, whisker or fiber.In the present invention, the matrix of the enhancing composite preferably includes WC-Co alloys, pure
Co, pure Ni, Ni base intermetallic compound, high-strength steel, high temperature alloy, marmem, acid bronze alloy or acieral.At this
In invention, when matrix phase is WC-Co alloys, the WC-Co alloys preferably include 15wt%~95wt% Co, and surplus is
WC.In the present invention, Co content is preferably 25wt%~85wt% in described matrix phase WC-Co alloys, more preferably
35wt%~75wt%, most preferably 45wt%~70wt%.In the present invention, in described matrix phase WC-Co alloys WC grain
Degree is preferably 20nm~5000nm, more preferably more preferably 200nm~2000nm, 500nm~1500nm, is most preferably
800nm~1200nm.The present invention does not have special limitation to the source of the WC-Co alloys, can be bought and obtained by market, may be used yet
It is mixed with using the preparation method of WC-Co hard alloy well known to those skilled in the art using WC powder and Co powder
Arrive.
In the present invention, the Ni base intermetallic compounds preferably include NiAl or Ni3Al.In the present invention, the height
Strong steel preferably includes Fe-17.9Ni-14.8Co-6.69Mo-1.1Ti.In the present invention, the high temperature alloy preferably includes Ni-
Co-Cr-Mo alloys.In the present invention, the marmem preferably includes Ni55/Ti45.In the present invention, it is described copper-based
Alloy preferably includes 9Al-81Cu-4Fe-1Ni-5Mo.In the present invention, the acieral preferably includes Al-1Cu-2.5Mg-
11.5Zn.The present invention is to Ni base intermetallic compounds, high-strength steel, high temperature alloy, marmem, acid bronze alloy and the aluminium
The source of based alloy does not have special limitation, using Ni base intermetallic compounds well known to those skilled in the art, high-strength steel, height
Temperature alloy, marmem, acid bronze alloy and acieral, it can be bought and obtained by market, also can be according to this area skill
Method known to art personnel is prepared.
In the present invention, described matrix is mutually used for the overall fracture toughness for improving multistage composite cermet.
Composite hard alloy provided by the invention includes being distributed in some granules inside matrix phase, and the granule includes resistance to
Mill phase and the n-layer transitional face being coated on outside wear-resisting phase, n >=1.In the present invention, wear-resisting phase outer surface can coat one layer of mistake
Multilayer transitional face can also mutually be coated by crossing, and form granule, the granule is evenly distributed in matrix phase, as shown in figure 1, Fig. 1 is
The structural representation of multistage composite cermet provided by the invention, wherein, 1 is wear-resisting phase, and 2 be transitional face, and 3 be matrix phase, 1
It is granule with 2 spherical powders formed.In the present invention, the granule is preferably spherical, and the particle diameter of the granule is preferably 20 μ
M~1000 μm, it is more preferably 50 μm~900 μm, more preferably 100 μm~800 μm, more preferably 200 μm~600 μm, optimal
Elect 300 μm~500 μm as.In the present invention, volume fraction of the granule in multistage composite cermet is preferably 32%
~90%, more preferably 40%~80%, most preferably 50%~70%.
In the present invention, the hardness of the transitional face is higher than the hardness of matrix phase less than the hardness of wear-resisting phase.In the present invention
In, the wear-resisting phase has higher hardness, disperses have preferable anti-wear performance in the base with the granule that transitional face is formed.
In the present invention, the preferred diamond of material or boron nitride of the wear-resisting phase.In the present invention, the diamond or boron nitride can
It can also be glomerocryst particle to think single crystal grain.In the present invention, the granularity of the wear-resisting phase is preferably 5 microns~1000 micro-
Rice, more preferably 20 microns~800 microns, more preferably 50 microns~600 microns, most preferably 100 microns~500 microns.
In the present invention, volume fraction of the wear-resisting phase in granule is preferably 40%~98%, and more preferably 40%~80%, more
Preferably 50%~70%, most preferably 50%~60%.In the present invention, the wear-resisting phase is in multistage composite cermet
Volume fraction be preferably 30%~80, more preferably 40%~70%, most preferably 50%~60%.
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
Hardness highest, contacts that the transitional face hardness of matrix phase is minimum, contacted in multilayer transitional face wear-resisting phase first layer transitional face it is hard
Degree can with it is wear-resisting it is mutually identical can also be different.In the present invention, the material of the transitional face is preferably WC-Co alloys, described
WC-Co alloys preferably include 6wt%~20wt% Co, surplus WC.In the present invention, Co in the transitional face WC-Co
Content is preferably 6wt%~15wt%, more preferably 7wt%~8wt%.In the present invention, in the transitional face WC-Co alloys
WC granularity is preferably 0.2 micron~5 microns, and more preferably 2.5 microns~3.5 microns, most preferably 2.8 microns~3.2 is micro-
Rice.In the present invention, hardness can be used gradually to increase WC-Co alloys as 3 layers of transitional face, contacts the first layer mistake of wear-resisting phase
The composition for crossing phase can be 92wt.%WC-8wt.%Co, and the composition of middle second layer transitional face can be 85wt.%WC-
15wt.%Co, the composition for contacting the third layer transitional face of matrix phase can be 70wt.%WC-30wt.%Co.
In the present invention, the preparation method of the transitional face WC-Co alloys is preferably：
Co, WC and forming agent are mixed, obtain mixture；
Dewaxed and sintered after the mixture is carried out into wet-milling, drying, sieving, granulation successively, obtain transitional face.
In the present invention, the Co in transitional face WC-Co alloys described in Co and WC usage ratio and above-mentioned technical proposal and
WC usage ratio is consistent, will not be repeated here.In the present invention, the forming agent is preferably paraffin, PEG or rubber.At this
In invention, the quality of the forming agent is preferably the 1%~4% of the mixture quality, and 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 is preferably carried out in hydrogen, argon gas or nitrogen.In the present invention, the dewaxing
Temperature be preferably 400 DEG C~600 DEG C, more preferably 450 DEG C~550 DEG C.In the present invention, the time of the dewaxing is preferably
0.5 hour~2 hours, more preferably 1 hour~1.5 hours.In the present invention, the sintering is preferably in hydrogen, argon gas, nitrogen
Or carried out in vacuum.In the present invention, the temperature of the sintering is preferably 600 DEG C~1600 DEG C, more preferably 800 DEG C~1400
DEG C, most preferably 1000 DEG C~1200 DEG C.
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 thickness of the transitional face is preferably (if the gross thickness that multilayer transitional face is multilayer transitional face)
2 μm~50 μm, more preferably 5 μm~40 μm, most preferably 10 μm~30 μm.In the present invention, the transitional face is multiple in multistage
The volume fraction closed in cermet is preferably 2%~40%, more preferably 5%~30%, most preferably 10%~20%.
In the present invention, the volume ratio of the wear-resisting phase, transitional face and matrix phase is preferably (30~80):(2~40):
(10~68), more preferably (40~75):(10~30):(17~58), it is most preferably (60~70):(15~25):(24~
38)。
The multistage composite cermet of the present invention, wherein the combination of wear-resisting phase and transitional face is as composite hard alloy group
Grain, hardness is relatively low and hard alloy that toughness is high as matrix, due to the composite hard alloy granule of wear-resisting phase-transition phase composition
With 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
It is unified, applied to the hard alloy cutter and instrument for making the fields such as mining, agricultural, capital construction, the energy, solve conventional rigid alloy
The limitation that 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 hardness highest of wear-resisting phase；
The wear-resisting phase includes diamond or boron nitride；
B) granule and matrix are mixed, are sintered, obtains multistage composite cermet, wherein, some granule distributions
Inside matrix phase；
The hardness of the transitional face is less than hardness of the hardness more than matrix phase of wear-resisting phase.
The present invention obtains granule, n >=1 in wear-resisting phase external sheath n-layer transitional face.The present invention is preferably wear-resisting mutually spherical
Powder granule external sheath n-layer transitional face, obtains granule, specifically, wear-resisting phase spherical powder particle can be placed on into transitional face
In powder, mixing granulation is carried out, obtains the internal spherical nodule for having transitional face for wear-resisting phase, external sheath.In the present invention, when
It in wear-resisting phase external sheath multilayer transitional face, can successively be coated, wear-resisting phase spherical powder particle is placed on first layer
Mixing granulation is carried out in transitional face powder；Obtained particle is placed in second layer transitional face powder and carries out mixing granulation；Will
To particle be placed in third layer transitional face powder and carry out mixing granulation, the rest may be inferred, and it is wear-resisting phase to obtain inside, external sheath
There is the spheric granules of multilayer transitional face.In the present invention, the material of the wear-resisting phase, dosage and wear-resisting phase in above-mentioned technical proposal
Material, dosage it is consistent, will not be repeated here；In the material of the transitional face, dosage and preparation method and above-mentioned technical proposal
Material, the dosage of transitional face are consistent with preparation method, will not be repeated here.
In the present invention, the technique of the mixing granulation can be adjusted according to the actual requirements, and it is special that the present invention is not done
Limit.
Obtained granule is preferably carried out pre-sintering by the present invention, obtains the granule of pre-sintering.In the present invention, the pre-burning
The temperature of knot is preferably 600 DEG C~1200 DEG C, more preferably 700 DEG C~1100 DEG C, most preferably 750 DEG C~1000 DEG C.At this
In invention, the pre-sintered time is preferably 2 minutes~120 minutes, more preferably 10 minutes~100 minutes.
After the pre-sintering for completing granule, the present invention mixes granule and matrix, is sintered, obtains multistage composite metal
Ceramics.The present invention will preferably sinter after granule and the compacting of the mixture of matrix phase.In the present invention, when using microwave sintering,
The pressure of compacting is preferably 250MPa~350MPa before sintering, more preferably 280MPa~320MPa, most preferably 300MPa.
In the present invention, the time of the compacting is preferably 50 seconds~70 seconds, more preferably 55 seconds~65 seconds, most preferably 60 seconds.At this
In invention, the temperature of the sintering is preferably 700 DEG C~1450 DEG C, more preferably 800 DEG C~1300 DEG C, most preferably 900 DEG C
~1200 DEG C.In the present invention, the soaking time in the sintering is preferably 1 minute~120 minutes, more preferably 5 minutes~
100 minutes.
In the present invention, hot pressed sintering, discharge plasma sintering, microwave sintering or HIP sintering etc. can be used to sinter
Mode is sintered, it is preferred to use discharge plasma sintering (Spark Plasma Sintering, SPS) prepares multistage composite gold
Category ceramics.SPS technologies produce plasma using discharge pulse between powder particle, while produce Joule heat in powder face,
The sintering densification mechanism such as powder purification, sinter is grown up, body spreads, grain boundary decision and evaporation-cohesion are greatly accelerated,
Fast densified sintering can be realized at a temperature of than conventional liquid phase sintering Di Ji Baidu.Can be in relatively low sintering with SPS technologies
To prepare that grain structure is more uniform, consistency is high under temperature, very short soaking time, controllable sintering pressure ultra-fine or even receives
The hard alloy of rice structure.Compared with conventional rigid alloy liquid phase sintering process, discharge plasma sintering has quick densifying
With the advantage for preventing crystal grain from growing up, the preparation of the hard alloy with nonuniform structure such as the multistage composite that is particularly suitable for use in.
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 hard alloy with nonuniform structure, suitably to soil, the driving of rock and cutting, by this
Its wearability of shield cutter and service life can carry than hard alloy cutter made of multistage composite cermet in invention
High by more than 50%, hardness is more than 85HRA.
The present invention is according to ASTM E399《Metal material is linear-elastic linear strain fracture toughness K Ic test methods》's
Standard, tests the fracture toughness of multistage composite cermet in the present invention, the multistage composite cermet in the present invention it is disconnected
Split toughness and be up to 25MPam1/2。
The present invention is according to ASTM B611《Hard alloy wear resistance test method》Standard, test in the present invention multistage
The wearability of composite cermet, the present invention in multistage composite cermet wearability than even structure conventional rigid close
Gold improves 15%~30%.
The Vickers hardness of multistage composite cermet in the test present invention, the results showed that, the multistage composite gold in the present invention
The hardness of category ceramics is up to 9.5GPa.
Multistage composite cermet has in the present invention preferably breaks than digging the conventional cemented carbide cutter of rock now
Toughness and wearability are split, its rock penetration performance can improve 30%, and the rock drilling life-span can improve 50%.
In order to further illustrate the present invention, with reference to embodiments to multistage composite cermet provided by the invention, its
Preparation method and shield cutter are described in detail, but can not be understood as limiting the scope of the present invention.
Embodiment 1
Granularity is used as 100 μm of the diamond (gold that the diamond dust of Henan Huanghe Xuanfeng Co., Ltd. provides
Hard rock powder) it is used as wear-resisting phase；
Transitional face is prepared by the following method：
Co, WC and paraffin are mixed, obtain mixture；
The mixture is carried out in the case where ball milling speed is 200r/min successively wet-milling in 48 hours, dry at 60 DEG C, sieve,
Granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 2 hours at 400 DEG C, then burnt under 800 DEG C of vacuum conditions
Knot, obtains transitional face.
The composition for the transitional face that the embodiment of the present invention 1 is prepared is 85wt.%WC-15wt.%Co.
It is as matrix phase, the preparation method of described matrix phase using 30wt.%WC-70wt.%Co alloys：
Co, WC and paraffin are mixed, obtain mixture；
The mixture is carried out in the case where ball milling speed is 200r/min successively wet-milling in 48 hours, dry at 60 DEG C, sieve,
Granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 2 hours at 400 DEG C, then burnt under 1200 DEG C of vacuum conditions
Knot, obtains matrix phase.
42.9 grams of wear-resisting phase is placed on mixing granulation in 57.1 grams of transitional face, in the wear-resisting μ m thick of phase Surface mulch 5
Transitional face, obtain hard alloy granule, obtained hard alloy granule average grain diameter be 110 μm.
58.4 grams of hard alloy granule is mixed with 41.6 grams of matrix, after being well mixed at 41MPa, 1200 DEG C
Discharge plasma sintering, 5 minutes are incubated, obtains multistage composite cermet.In multistage composite cermet, with volume fraction
Meter, wear-resisting phase 52.5%, transitional face 17.5%, matrix phase 30%.
The multistage composite cermet that the embodiment of the present invention 1 is prepared carries out displaing microstructure observing, and observation result is
The microstructure schematic diagram for the multistage composite cermet that the embodiment of the present invention 1 is prepared is as shown in Figure 1.
The multistage composite cermet being prepared according to the method test embodiment of the present invention 1 described in above-mentioned technical proposal
Hardness, fracture toughness and wearability, testing result is as shown in table 1, and table 1 is multistage composite metal provided in an embodiment of the present invention
The performance test results of ceramics.
Embodiment 2
It is 150 μm of diamond as wear-resisting phase to use granularity；
Transitional face is prepared by the following method：
Co, WC and paraffin are mixed, obtain mixture；
The mixture is carried out in the case where ball milling speed is 200r/min successively wet-milling in 48 hours, dry at 60 DEG C, sieve,
Granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 2 hours at 400 DEG C, then burnt under 800 DEG C of vacuum conditions
Knot, obtains transitional face.
The composition for the transitional face that the embodiment of the present invention 2 is prepared is 85wt.%WC-15wt.%Co.
It is as matrix phase, the preparation method of described matrix phase using 30wt.%WC-70wt.%Co alloys：
Co, WC and paraffin are mixed, obtain mixture；
The mixture is carried out in the case where ball milling speed is 200r/min successively wet-milling in 48 hours, dry at 60 DEG C, sieve,
Granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 2 hours at 400 DEG C, then burnt under 1200 DEG C of vacuum conditions
Knot, obtains matrix phase.
54 grams of wear-resisting phase is placed on mixing granulation in 46 grams of transitional face, in the mistake of the wear-resisting μ m thick of phase Surface mulch 5
Phase is crossed, obtains hard alloy granule, obtained hard alloy granule average grain diameter is 160 μm.
55 grams of hard alloy granule is mixed with 45 grams of matrix, discharged after well mixed at 41MPa, 1200 DEG C
Plasma agglomeration, 5 minutes are incubated, obtains multistage composite cermet.It is resistance to volume fraction in multistage composite cermet
Grind phase 57.7%, transitional face 12.3%, matrix phase 30%.
The multistage composite cermet being prepared according to the method test embodiment of the present invention 2 described in above-mentioned technical proposal
Hardness, fracture toughness and wearability, testing result is as shown in table 1.
Embodiment 3
It is 300 μm of diamonds as wear-resisting phase to use granularity；
Transitional face is prepared by the following method：
Co, WC and paraffin are mixed, obtain mixture；
The mixture is carried out in the case where ball milling speed is 200r/min successively wet-milling in 48 hours, dry at 60 DEG C, sieve,
Granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 2 hours at 400 DEG C, then burnt under 800 DEG C of vacuum conditions
Knot, obtains transitional face.
The composition for the transitional face that the embodiment of the present invention 3 is prepared is 85wt.%WC-15wt.%Co.
It is as matrix phase, the preparation method of described matrix phase using 30wt.%WC-70wt.%Co alloys：
Co, WC and paraffin are mixed, obtain mixture；
The mixture is carried out in the case where ball milling speed is 200r/min successively wet-milling in 48 hours, dry at 60 DEG C, sieve,
Granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 2 hours at 400 DEG C, then burnt under 1200 DEG C of vacuum conditions
Knot, obtains matrix phase.
70.6 grams of wear-resisting phase is placed on mixing granulation in 29.4 grams of transitional face, in the wear-resisting μ m thick of phase Surface mulch 5
Transitional face, obtain hard alloy granule, obtained hard alloy granule average grain diameter be 310 μm.
50.7 grams of hard alloy granule is mixed with 49.3 grams of matrix, after being well mixed at 41MPa, 1200 DEG C
Plasma agglomeration, 5 minutes are incubated, obtains multistage composite cermet.It is resistance to volume fraction in multistage composite cermet
Grind phase 63.4%, transitional face 6.6%, matrix phase 30%.
The multistage composite cermet being prepared according to the method test embodiment of the present invention 3 described in above-mentioned technical proposal
Hardness, fracture toughness and wearability, testing result is as shown in table 1.
Embodiment 4
It is 300 μm of diamond as wear-resisting phase to use granularity；
Transitional face is prepared by the following method：
Co, WC and paraffin are mixed, obtain mixture；
The mixture is carried out in the case where ball milling speed is 200r/min successively wet-milling in 48 hours, dry at 60 DEG C, sieve,
Granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 2 hours at 400 DEG C, then burnt under 800 DEG C of vacuum conditions
Knot, obtains transitional face.
The composition for the transitional face that the embodiment of the present invention 4 is prepared is 85wt.%WC-15wt.%Co.
It is as matrix phase, the preparation method of described matrix phase using 10wt.%WC-90wt.%Co alloys：
Co, WC and paraffin are mixed, obtain mixture；
The mixture is carried out in the case where ball milling speed is 200r/min successively wet-milling in 48 hours, dry at 60 DEG C, sieve,
Granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 2 hours at 400 DEG C, then burnt under 1200 DEG C of vacuum conditions
Knot, obtains matrix phase.
70.6 grams of wear-resisting phase is placed on mixing granulation in 29.4 grams of transitional face, in the wear-resisting μ m thick of phase Surface mulch 5
Transitional face, obtain hard alloy granule, obtained hard alloy granule average grain diameter be 310 μm.
53 grams of hard alloy granule is mixed with 47 grams of matrix, discharged after well mixed at 41MPa, 1200 DEG C
Plasma agglomeration, 5 minutes are incubated, obtains multistage composite cermet.It is resistance to volume fraction in multistage composite cermet
Grind phase 63.4%, transitional face 6.6%, matrix phase 30%.
The multistage composite cermet being prepared according to the method test embodiment of the present invention 4 described in above-mentioned technical proposal
Hardness, fracture toughness and wearability, testing result is as shown in table 1.
Embodiment 5
It is 300 μm of diamond as wear-resisting phase to use granularity；
Transitional face is prepared by the following method：
Co, WC and paraffin are mixed, obtain mixture；
The mixture is carried out in the case where ball milling speed is 200r/min successively wet-milling in 48 hours, dry at 60 DEG C, sieve,
Granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 2 hours at 400 DEG C, then burnt under 800 DEG C of vacuum conditions
Knot, obtains transitional face.
The composition for the transitional face that the embodiment of the present invention 5 is prepared is 85wt.%WC-15wt.%Co.
It is as matrix phase, the preparation method of described matrix phase using 30wt.%WC-70wt.%Co alloys：
Co, WC and paraffin are mixed, obtain mixture；
The mixture is carried out in the case where ball milling speed is 200r/min successively wet-milling in 48 hours, dry at 60 DEG C, sieve,
Granulation；Obtained spherolite is carried out in hydrogen to the dewaxing of 2 hours at 400 DEG C, then burnt under 1200 DEG C of vacuum conditions
Knot, obtains matrix phase.
54 grams of wear-resisting phase is placed on mixing granulation in 46 grams of transitional face, in the mistake of the wear-resisting μ m thick of phase Surface mulch 10
Phase is crossed, obtains hard alloy granule, obtained hard alloy granule average grain diameter is 320 μm.
55 grams of hard alloy granule is mixed with 45 grams of matrix, after being well mixed 41MPa, 1200 DEG C it is inferior from
Son sintering, is incubated 5 minutes, obtains multistage composite cermet.In multistage composite cermet, with volume fraction, wear-resisting phase
57.7%, transitional face 12.3%, matrix phase 30%.
The multistage composite cermet being prepared according to the method test embodiment of the present invention 5 described in above-mentioned technical proposal
Hardness, fracture toughness and wearability, testing result is as shown in table 1.
Embodiment 6
It is 100 μm of diamond as wear-resisting phase to use granularity；
First layer transitional face is prepared by the following method：
92wt.%WC-8wt.%Co and paraffin are mixed, obtain mixture；
25.5 grams of mixtures and 18.4 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 29.2 grams of mixtures and 43.9 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；
31.3 grams of mixtures are existed with 73.1 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
The granule of phase composition is crossed, the average grain diameter of wear-resisting phase-transitional face granule is 130 μm.
Using 30wt.%WC-70wt.%Co alloys as matrix phase.
30wt.%WC-70wt.%Co and paraffin are mixed, obtain mixture；
50.4 grams of mixtures and 104.4 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, with volume fraction, wear-resisting phase 31.9%, transitional face 38.1%, matrix phase 30%.
The multistage composite cermet being prepared according to the method test embodiment of the present invention 6 described in above-mentioned technical proposal
Hardness, fracture toughness and wearability, testing result is as shown in table 1.
The performance test results for the multistage composite cermet that the embodiment of the present invention of table 1 is prepared
As seen from the above embodiment, the invention provides a kind of multistage composite cermet, including matrix phase and it is distributed in
Some granules 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 n
The hardness of layer transitional face gradually reduces, and contacts the transitional face hardness highest of wear-resisting phase；The wear-resisting phase is diamond or boron nitride；
The hardness of the transitional face is more than hardness of the hardness less than wear-resisting phase of matrix phase.The present invention coats wear-resisting phase using transitional face,
Composite hard alloy granule is formed, composite ganoine conjunction granule is evenly distributed in tough matrix phase, obtains that there is special knot
The multistage composite cermet of structure, multistage composite cermet provided by the invention have higher wearability and higher simultaneously
Fracture toughness.
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 (9)
1. a kind of multistage composite cermet, including matrix phase and some granules for being distributed in inside matrix phase,
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 diamond or boron nitride；
The hardness of the transitional face is less than hardness of the hardness more than matrix phase of wear-resisting phase；
The granularity of the wear-resisting phase is 5 microns~500 microns.
2. multistage composite cermet according to claim 1, it is characterised in that described matrix mutually include WC-Co alloys,
Pure Co, pure Ni, Ni base intermetallic compound, high-strength steel, high temperature alloy, marmem, acid bronze alloy, acieral neutralize
Strengthen the one or more of composite.
3. multistage composite cermet according to claim 2, it is characterised in that the WC-Co alloys include：
15wt%~98wt% Co；
Surplus is WC.
4. multistage composite cermet according to claim 1, it is characterised in that the wear-resisting phase is in the granule
Percent by volume is 20%~90%.
5. multistage composite cermet according to claim 1, it is characterised in that the transitional face is WC-Co alloys, institute
Stating WC-Co alloys includes：
6wt%~30wt% Co；
Surplus is WC.
6. multistage composite cermet according to claim 1, it is characterised in that the granule is in multistage composite gold
Percent by volume in category ceramics is 32%~90%.
7. 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 diamond or boron nitride；
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；
The hardness of the transitional face is less than hardness of the hardness more than matrix phase of wear-resisting phase.
8. preparation method according to claim 7, it is characterised in that the temperature of the sintering is 500~1450 DEG C；
Soaking time in the sintering is 2 minutes~120 minutes.
9. a kind of shield cutter, including multistage composite cermet or claim 7 described in claim 1~6 any one
Multistage composite cermet made from preparation method described in~8 any one.
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