A kind of multistage composite ceramic metal, its preparation method and shield cutter
Technical field
The invention belongs to hard alloy technical field, particularly relate to a kind of multistage composite ceramic metal, its preparation method and
Shield cutter.
Background technology
In China, traditionally the tunneler being used for soft soil layer is referred to as shield machine, carries out tunnel with shield machine and execute
Instrument has that automaticity is high, saves manpower, speed of application is fast, cavitation, weatherproof, an excavation time controllably face
Sedimentation, reduce on the impact of above ground structure and under water excavation time do not affect the features such as water surface traffic, longer at tunnel line,
In the case of buried depth is relatively big, with shield machine construction more economical rationality.
For shield machine, digging system has conclusive impact, digging system for the construction effect of shield machine
Including digging cutterhead and drive system thereof, digging cutterhead is the plate-like digging device that can rotate or shake, by shield cutter, face
Plate, be unearthed notch, drive mechanism and Bearning mechanism etc. are constituted.Wherein, shield cutter as excavation stratum direct functional component,
Its performance directly affects the cutting effect of shield machine, situation of being unearthed and driving speed.
Shield cutter is generally made up of hard alloy, compared with the hard alloy application in metal machining field, and hard
Alloy is routinely subjected to high abrasion and high impact shock the working condition 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 caused 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 the conventional rigid alloy of coarse grained homogeneous texture, although fracture toughness is higher, but wearability is very
Low, become the basic reason that rock drilling cutter life is short.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of multistage composite ceramic metal, its preparation method and shield cutter
Tool, the multistage composite ceramic metal that the present invention provides has high wearability and higher fracture toughness simultaneously.
The invention provides a kind of multistage composite ceramic metal, including some groups that matrix phase is internal mutually with being distributed in matrix
Grain,
Described granule includes wear-resisting phase and is coated on wear-resisting n-layer transitional face outside mutually, n >=1;
The hardness of described n-layer transitional face is gradually lowered, and the transitional face hardness contacting wear-resisting phase is the highest;
The hardness of described transitional face is more than the hardness of matrix phase less than the hardness of wear-resisting phase.
Preferably, described matrix includes WC-Co alloy, pure Co, pure Ni, Ni base intermetallic compound, high-strength steel, high temperature mutually
One or more in alloy, marmem, acid bronze alloy, acieral and enhancing composite.
Preferably, described wear-resisting phase is WC or WC-Co alloy, and described WC-Co alloy includes:
The Co of A wt%, 0 < A≤10;
Surplus is WC.
Preferably, in described WC-Co alloy, the granularity of WC is 20nm~2000nm.
Preferably, described transitional face is WC-Co alloy, and described WC-Co alloy includes:
The Co of 6wt%~20wt%;
Surplus is WC.
Preferably, the granularity of described WC is 300nm~5000nm.
Preferably, the volume ratio of described wear-resisting phase, transitional face and matrix phase is (30~80): (2~40): (10~68).
The invention provides a kind of ceramic-metallic preparation method of multistage composite, comprise the following steps:
A) in wear-resisting phase external sheath n-layer transitional face, granule, n >=1 are obtained;
B) being mixed mutually with matrix by granule, be sintered, obtain multistage composite ceramic metal, wherein, some granules are distributed
Internal mutually in matrix;
The hardness of described n-layer transitional face is gradually lowered, and the transitional face hardness contacting wear-resisting phase is the highest;
The hardness of described transitional face is more than the hardness of matrix phase less than the hardness of wear-resisting phase.
Preferably, the temperature of described sintering is 500~1450 DEG C;
Temperature retention time in described sintering is 2 minutes~120 minutes.
The invention provides a kind of shield cutter, including the multistage composite ceramic metal or above-mentioned described in technique scheme
The multistage composite ceramic metal that preparation method described in technical scheme prepares.
The invention provides a kind of multistage composite ceramic metal, including some groups that matrix phase is interior mutually with being distributed in matrix
Grain, described granule includes wear-resisting phase and is coated on wear-resisting n-layer transitional face outside mutually, n >=1;The hardness of n-layer transitional face gradually drops
Low, the transitional face hardness contacting wear-resisting phase is the highest, and the hardness of described transitional face is more than the hard of matrix phase less than the hardness of wear-resisting phase
Degree.The present invention uses transitional face to be coated with wear-resisting phase, forms superhard composite hard alloy granule, this composite ganoine is closed granule uniform
Be distributed in the preferable matrix of toughness mutually in, obtain the multistage composite ceramic metal with special construction, it is multistage that the present invention provides
Composite cermet has higher wearability and higher fracture toughness simultaneously, test result indicate that, the present invention provides many
The hardness of level composite cermet is 6GPa~15GPa, and fracture toughness is 12MPa m1/2~45MPa m1/2。
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
In having technology to describe, the required accompanying drawing used is briefly described, it should be apparent that, the accompanying drawing in describing below is only this
Inventive embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to according to
The accompanying drawing provided obtains other accompanying drawing.
The ceramic-metallic structural representation of multistage composite that Fig. 1 provides for the present invention.
Detailed description of the invention
The invention provides a kind of multistage composite ceramic metal, including some groups that matrix phase is internal mutually with being distributed in matrix
Grain,
Described granule includes wear-resisting phase and is coated on wear-resisting n-layer transitional face outside mutually, n >=1;
The hardness of described n-layer transitional face is gradually lowered, and the transitional face hardness contacting wear-resisting phase is the highest;
The hardness of described transitional face is more than the hardness of matrix phase less than the hardness of wear-resisting phase.
Multistage composite ceramic metal in the present invention has higher wearability and higher fracture toughness simultaneously.
The present invention alloy that toughness is higher so that hardness is relatively low preferably includes as matrix phase, the material of described matrix phase
WC-Co alloy, pure Co, pure Ni, Ni base intermetallic compound, high-strength steel, high temperature alloy, marmem, acid bronze alloy, aluminum
One or more in base alloy and enhancing composite.In the present invention, the enhancing of described enhancing composite is the most preferably wrapped
Include ceramic particle, whisker or fiber.In the present invention, the matrix of described enhancing composite preferably includes WC-Co alloy, 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 is WC-Co alloy mutually, described WC-Co alloy preferably includes the Co of 15wt%~95wt%, and surplus is
WC.In the present invention, in described matrix phase WC-Co alloy, the content of Co is preferably 25wt%~85wt%, more preferably
35wt%~75wt%, most preferably 45wt%~70wt%.In the present invention, the grain of WC in described matrix phase WC-Co alloy
Degree is preferably 20nm~5000nm, more preferably 200nm~2000nm, more preferably 500nm~1500nm, most preferably
800nm~1200nm.The present invention does not has special restriction to the source of described WC-Co alloy, can be bought by market and obtain, it is possible to
WC powder and Co powder are mixed with and obtain by the preparation method using WC-Co hard alloy well known to those skilled in the art.
In the present invention, described Ni base intermetallic compound preferably includes NiAl or Ni3Al.In the present invention, described height
Strong steel preferably includes Fe-17.9Ni-14.8Co-6.69Mo-1.1Ti.In the present invention, described high temperature alloy preferably includes Ni-
Co-Cr-Mo alloy.In the present invention, described marmem preferably includes Ni55/Ti45.In the present invention, described cuprio
Alloy preferably includes 9Al-81Cu-4Fe-1Ni-5Mo.In the present invention, described acieral preferably includes Al-1Cu-2.5Mg-
11.5Zn.The present invention is to described Ni base intermetallic compound, high-strength steel, high temperature alloy, marmem, acid bronze alloy and aluminum
The source of base alloy does not has special restriction, uses Ni base intermetallic compound well known to those skilled in the art, high-strength steel, height
Temperature alloy, marmem, acid bronze alloy and acieral, can be bought by market and obtain, it is possible to according to this area skill
Method known to art personnel prepares.
In the present invention, described matrix is used for improving the ceramic-metallic overall fracture toughness of multistage composite mutually.
The composite hard alloy that the present invention provides includes being distributed in some granules that matrix is internal mutually, and described granule includes resistance to
Mill phase and the n-layer transitional face being coated on wear-resisting outside mutually, n >=1.In the present invention, wear-resisting phase outer surface can be coated with one layer of mistake
Cross and can also be coated with mutually multilamellar transitional face, form granule, described granule be evenly distributed on matrix mutually in, as it is shown in figure 1, Fig. 1 is
The ceramic-metallic structural representation of multistage composite that the present invention provides, wherein, 1 is wear-resisting phase, and 2 is transitional face, and 3 is matrix phase, 1
It is granule with 2 spherical powders formed.In the present invention, described granule is preferably spherical, and the particle diameter of described granule is preferably 10 μ
M~1000 μm, more preferably 20 μm~800 μm, most preferably 100 μm~180 μm.In the present invention, described granule is multistage
Volume fraction in composite cermet is preferably 32%~90%, more preferably 40%~80%, most preferably 50%~
70%.
In the present invention, the hardness of described transitional face is higher than the hardness of matrix phase less than the hardness of wear-resisting phase.In the present invention
In, described wear-resisting phase has higher hardness, and the granule dispersion formed with transitional face has preferable anti-wear performance in the base.
In the present invention, the material of described wear-resisting phase is preferably WC or WC-Co alloy, and described WC-Co alloy includes the Co of A%, 0 < A
≤10;Surplus is WC.In the present invention, in described wear-resisting phase WC-Co alloy, the content of Co is preferably 1wt%~5wt%, more excellent
Elect 2wt%~4wt% as, most preferably 2.5wt%~3.5wt%.In the present invention, WC in described wear-resisting phase WC-Co alloy
Granularity be preferably 20nm~2000nm, more preferably 100nm~750nm, more preferably 180nm~220nm, most preferably
200nm.In the present invention, described wear-resisting phase and the total particle diameter of transitional face are preferably 10 μm~1000 μm, more preferably 20 μm~
800 μm, most preferably 100 μm~300 μm.
In the present invention, the preparation method of described wear-resisting phase WC-Co alloy is preferably:
Co, WC and forming agent are mixed, obtains mixture;
Described mixture is carried out successively wet grinding, be dried, sieve, pelletize after dewax and sinter, obtain wear-resisting phase.
In the present invention, the usage ratio of Co and WC with described in technique scheme the Co in wear-resisting phase WC-Co alloy and
The usage ratio of WC is consistent, does not repeats them here.In the present invention, described forming agent is preferably paraffin, PEG or rubber.At this
In invention, the Functionality, quality and appealing design of described forming agent elects the 1%~4% of described mixture quality as, more preferably 1.2%~2.8%,
It is preferably 1.8%~2.2%.
In the present invention, the ball milling speed of described wet grinding 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 described wet grinding is preferably 1 hour
~48 hours, more preferably 20 hours~40 hours, most preferably 25 hours~35 hours.In the present invention, described dry
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 or nitrogen.In the present invention, described 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 described dewaxing is preferably
0.5 hour~2 hours, more preferably 1 hour~1.5 hours.In the present invention, described sintering is preferably at hydrogen, argon, nitrogen
Or vacuum is carried out.In the present invention, the temperature of described sintering is preferably 1100 DEG C~1600 DEG C, more preferably 1300 DEG C~
1400℃。
The present invention does not has special restriction to the method for described pelletize, and spraying well known to those skilled in the art can be used to make
Grain or cylinder pelletize.In the present invention, the particle diameter of the wear-resisting phase after the sintering obtained after described pelletize and technique scheme institute
The particle diameter stating wear-resisting phase is consistent, does not repeats them here.
In the present invention, described wear-resisting volume fraction in granule is preferably 60%~98%, more preferably 65%
~95%, most preferably 75%~85%.In the present invention, described wear-resisting volume fraction in multistage composite ceramic metal
For preferably 30%~80%, more preferably 40%~70%, most preferably 50%~60%.
In the present invention, described transitional face can strengthen the heat between matrix phase with superhard wear phase, mechanical matching, reduces
Internal stress, improves the ceramic-metallic overall fracture toughness of multistage composite.In the present invention, 1 layer of transitional face can be used, it is also possible to
Use multilamellar transitional face;When using multilamellar transitional face, the hardness of multilamellar transitional face is gradually lowered, and contacts the transitional face of wear-resisting phase
Hardness is the highest, and the transitional face hardness of contact matrix phase is minimum, contacts ground floor transitional face hard of wear-resisting phase in multilamellar transitional face
Degree can with wear-resisting mutually identical can also be different.In the present invention, the material of described transitional face is preferably WC-Co alloy, described
WC-Co alloy preferably includes the Co of 6wt%~20wt%, and surplus is WC.In the present invention, Co in described transitional face WC-Co
Content is preferably 7wt%~15wt%, more preferably 8wt%~10wt%.In the present invention, described transitional face WC-Co alloy
The granularity of middle WC is preferably 300nm~5000nm, more preferably 800nm~3000nm, more preferably 1000nm~2000nm,
It is preferably 1200nm~1600nm.In the present invention, hardness can be used to be gradually increased WC-Co alloy as 3 layers of transitional face, connect
The composition of the ground floor transitional face touching wear-resisting phase can be 92wt.%WC-8wt.%Co, the composition of middle second layer transitional face
Can be 85wt.%WC-15wt.%Co, the composition of the third layer transitional face of contact matrix phase can be 70wt.%WC-
30wt.%Co.The present invention does not has special restriction to the preparation method of described transitional face WC-Co alloy, uses art technology
The method that WC powder and Co powder are mixed with WC-Co alloy known to personnel prepares.
In the present invention, the thickness (if gross thickness that multilamellar transitional face is multilamellar transitional face) of described transitional face is preferably
2 μm~50 μm, more preferably 5 μm~40 μm, most preferably 10 μm~30 μm.In the present invention, described transitional face is multistage multiple
Close the volume fraction in ceramic metal and be preferably 2%~40%, more preferably 5%~30%, most preferably 10%~20%.
In the present invention, the volume ratio of described wear-resisting phase, transitional face and matrix phase is preferably (30~80): (2~40):
(10~68), more preferably (40~75): (10~30): (17~58), most preferably (60~70): (15~25): (24~
38)。
The combination of the multistage composite ceramic metal that the present invention provides, the most wear-resisting phase and transitional face is as composite hard alloy
Granule, hardness is relatively low and hard alloy that toughness is high as matrix, due to the composite hard alloy group of wear-resisting phase-transitional face composition
Grain has higher hardness, and therefore wearability is good, and the low toughness of the hardness of matrix is high, thus has reached high-wearing feature and high tenacity
Unification, be applied to make carbide tool and the instrument in the fields such as mining, agricultural, capital construction, the energy, solve conventional rigid and close
The limitation that gold wearability and fracture toughness can not improve simultaneously.
Present invention also offers a kind of ceramic-metallic preparation method of multistage composite, comprise the following steps:
A) in wear-resisting phase external sheath n-layer transitional face, granule, n >=1 are obtained;
The hardness of described n-layer transitional face is gradually lowered, and the transitional face hardness contacting wear-resisting phase is the highest;
B) being mixed mutually with matrix by granule, be sintered, obtain multistage composite ceramic metal, wherein, some granules are distributed
Internal mutually in matrix;
The hardness of described transitional face is more than the hardness of matrix phase less than the hardness of wear-resisting phase.
The present invention, in wear-resisting phase external sheath n-layer transitional face, obtains granule, n >=1.The present invention is preferably wear-resisting mutually spherical
Powder granule external sheath n-layer transitional face, obtains granule, concrete, wear-resisting phase spherical powder granule can be placed on transitional face
In powder body, carry out mixing granulation, obtain the internal spherical nodule having transitional face for wear-resisting phase, external sheath.In the present invention, when
When wear-resisting phase external sheath multilamellar transitional face, can successively be coated with, wear-resisting phase spherical powder granule is placed on ground floor
Transitional face powder body carries out mixing granulation;The granule obtained is placed in second layer transitional face powder body and carries out mixing granulation;Will
To granule be placed in third layer transitional face powder body and carry out mixing granulation, the rest may be inferred, obtains internal for wear-resisting phase, external sheath
There is the spheroidal particle of multilamellar transitional face.In the present invention, the material of described wear-resisting phase, consumption and preparation method and above-mentioned technical side
The material of wear-resisting phase in case, consumption are consistent with preparation method, do not repeat them here;The material of described transitional face, consumption and preparation
Method is consistent with the material of transitional face, consumption and preparation method in technique scheme, does not repeats them here.
In the present invention, the technique of described mixing granulation can be adjusted according to the actual requirements, and it is special that the present invention does not do
Limit.
The granule obtained preferably is carried out presintering by the present invention, obtains the granule of presintering.In the present invention, described pre-burning
The temperature of knot is preferably 1000 DEG C~1600 DEG C, more preferably 1100 DEG C~1500 DEG C, most preferably 1200 DEG C~1400 DEG C.?
In the present invention, the time of described presintering is preferably 20 minutes~120 minutes, more preferably 30 minutes~90 minutes.
After completing the presintering of granule, granule is mixed mutually by the present invention with matrix, is sintered, and obtains multistage composite metal
Pottery.The present invention carries out microwave sintering after preferably being suppressed with matrix phase mixture by granule.In the present invention, microwave sintering is used
Time, the pressure of compacting of colding pressing before sintering is preferably 250MPa~350MPa, more preferably 280MPa~320MPa, most preferably
For 300MPa.In the present invention, the time of described compacting is preferably 50 seconds~70 seconds, more preferably 55 seconds~65 seconds, most preferably
It it is 60 seconds.In the present invention, the temperature of described sintering is preferably 1200 DEG C~1450 DEG C, more preferably 1250 DEG C~1400 DEG C,
Most preferably 1300 DEG C~1350 DEG C.In the present invention, the temperature retention time in described sintering is preferably 2 minutes~120 minutes.
In the present invention, the sintering such as hot pressed sintering, discharge plasma sintering, microwave sintering or HIP sintering can be used
Mode is sintered, it is preferred to use prepared by microwave sintering or discharge plasma sintering (Spark Plasma Sintering, SPS)
Multistage composite ceramic metal.SPS technology utilizes discharge pulse to produce plasma between powder particle, produces at powder face simultaneously
Green coke is had burning ears, and greatly accelerates the sintering causes such as powder purifies, sinter is grown up, bulk diffusion, grain boundary decision and evaporation-cohesion
Densification mechanism, it is possible to realize fast densified sintering at a temperature of Di Ji Baidu sintering than conventional liquid phase.Can be relatively by SPS technology
Prepare under low sintering temperature, the shortest temperature retention time, controlled sintering pressure that grain structure is more uniform, that consistency is high is super
Thin or even the hard alloy of nanostructured.Comparing with conventional rigid alloy liquid phase sintering process, discharge plasma sintering has soon
Fast densification and the advantage preventing crystal grain from growing up, be particularly suited for the preparation of the hard alloy with nonuniform structure such as multistage composite.
Present invention also offers a kind of shield cutter, including the multistage composite ceramic metal in technique scheme.This
Multistage composite ceramic metal 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 that multistage composite ceramic metal in invention is made and can carrying than carbide tool service life
High by more than 50%, hardness is more than 86HRA.
The present invention is according to ASTM E399's " metal material linear-elastic linear strain fracture toughness K Ic test method "
Standard, tests the ceramic-metallic fracture toughness of multistage composite in the present invention, and the multistage composite in the present invention is ceramic-metallic disconnected
Split toughness and be up to 25MPa m1/2。
The present invention, according to the standard of ASTM B611 " hard alloy wear resistance test method ", tests in the present invention multistage
The wearability of composite cermet, the ceramic-metallic wearability of multistage composite in the present invention is closed than the conventional rigid of even structure
Gold improves 15%~30%.
Testing the ceramic-metallic Vickers hardness of multistage composite in the present invention, result shows, the multistage composite in the present invention
Ceramic-metallic hardness is up to 9.5GPa.
The conventional cemented carbide cutter that in the present invention, multistage composite ceramic metal has than digging now rock preferably breaks
Splitting toughness and wearability, its rock penetration performance can improve 30%, and the rock drilling life-span can improve 50%.
In order to further illustrate the present invention, the multistage composite ceramic metal that the present invention provided below in conjunction with embodiment, 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
Prepare wear-resisting phase by the following method:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains wear-resisting phase.
The particle diameter of the wear-resisting phase that the embodiment of the present invention 1 prepares is 100 μm, and composition is 94wt.%WC-6wt.%Co.
Prepare transitional face by the following method:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains transitional face.
The transitional face composition that the embodiment of the present invention 1 prepares is 85wt.%WC-15wt.%Co.
Employing 30wt.%WC-70wt.%Co alloy as matrix phase, the preparation method of described matrix phase is:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains matrix phase.
The wear-resisting phase of 76.3 grams is placed on mixing granulation in the transitional face of 23.7 grams, at wear-resisting phase Surface mulch 5 μ m thick
Transitional face, obtain hard alloy granule, the hard alloy granule mean diameter obtained is 110 μm.
The hard alloy granule of 77 grams and the matrix of 23 grams are mixed mutually, at 41MPa, carry out at 1200 DEG C after mix homogeneously
Discharge plasma sintering, is incubated 10 minutes, obtains multistage composite ceramic metal.In multistage composite ceramic metal, with volume fraction
Meter, wear-resisting phase 52.5%, transitional face 17.5%, matrix phase 30%.
The ceramic-metallic microstructure of multistage composite preparing the embodiment of the present invention 1 is observed, its micro-knot
The schematic diagram of structure is as shown in Figure 1.
The multistage composite ceramic metal that the embodiment of the present invention 1 prepares is tested according to the method described in technique scheme
Hardness, fracture toughness and wearability, testing result is as shown in table 1, the multistage composite metal that table 1 provides for the embodiment of the present invention
The performance test results of pottery.
Embodiment 2
Prepare wear-resisting phase by the following method:
Co, WC and paraffin are mixed, obtains mixture;
It is that 200r/min carries out wet grinding in 48 hours, is dried at 60 DEG C, sieves, makes in ball milling speed successively by described mixture
Grain;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, is then sintered under 1200 DEG C of vacuum conditions,
Obtain wear-resisting phase.
The particle diameter of the wear-resisting phase that the embodiment of the present invention 2 prepares is 150 μm, and composition is 94wt.%WC-6wt.%Co.
Prepare transitional face by the following method:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains transitional face.
The composition of the transitional face that the embodiment of the present invention 2 prepares is 85wt.%WC-15wt.%Co.
Employing 30wt.%WC-70wt.%Co alloy as matrix phase, described matrix phase preparation method is:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains matrix phase.
The wear-resisting phase of 82.4 grams is placed on mixing granulation in the transitional face of 17.6 grams, at wear-resisting phase Surface mulch 5 μ m thick
Transitional face, obtain hard alloy granule, the hard alloy granule mean diameter obtained is 160 μm.
The hard alloy granule of 77 grams and the matrix of 23 grams are mixed mutually, suppresses 60 seconds to become under 250MPa after mix homogeneously
Type, plasma agglomeration at 1250 DEG C, it is incubated 10 minutes, obtains multistage composite ceramic metal.In multistage composite ceramic metal, with
Volume fraction, wear-resisting phase 57.7%, transitional face 12.3%, matrix phase 30%.
The multistage composite ceramic metal that the embodiment of the present invention 2 prepares is tested according to the method described in technique scheme
Hardness, fracture toughness and wearability, testing result is as shown in table 1.
Embodiment 3
Prepare wear-resisting phase by the following method:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains wear-resisting phase.
The particle diameter of the wear-resisting phase that the embodiment of the present invention 3 prepares is 300 μm, and composition is 94wt.%WC-6wt.%Co.
Prepare transitional face by the following method:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains transitional face.
The composition of the transitional face that the embodiment of the present invention 3 prepares is 85wt.%WC-15wt.%Co.
Employing 30wt.%WC-70wt.%Co alloy as matrix phase, the preparation method of described matrix phase is:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains matrix phase.
The wear-resisting phase of 90.6 grams is placed on mixing granulation in the transitional face of 9.6 grams, at wear-resisting phase Surface mulch 5 μ m thick
Transitional face, obtains hard alloy granule, and the hard alloy granule mean diameter obtained is 310 μm.
The hard alloy granule of 77 grams and the matrix of 23 grams are mixed mutually, at 41MPa after mix homogeneously, transfers at 1200 DEG C
Electricity plasma agglomeration, is incubated 5 minutes, obtains multistage composite ceramic metal.In multistage composite ceramic metal, with volume fraction,
Wear-resisting phase 63.4%, transitional face 6.6%, matrix phase 30%.
The multistage composite ceramic metal that the embodiment of the present invention 3 prepares is tested according to the method described in technique scheme
Hardness, fracture toughness and wearability, testing result is as shown in table 1.
Embodiment 4
Prepare wear-resisting phase by the following method:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains wear-resisting phase.
The particle diameter of the wear-resisting phase that the embodiment of the present invention 4 prepares is 300 μm, and composition is 94wt.%WC-6wt.%Co.
Prepare transitional face by the following method:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains transitional face.
The transitional face composition that the embodiment of the present invention 4 prepares is 85wt.%WC-15wt.%Co.
Employing 10wt.%WC-90wt.%Co alloy as matrix phase, described matrix phase preparation method is:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains matrix phase.
The wear-resisting phase of 90.6 grams is placed on mixing granulation in the transitional face of 9.4 grams, at wear-resisting phase Surface mulch 5 μ m thick
Transitional face, obtains hard alloy granule, and the hard alloy granule mean diameter obtained is 310 μm.
The hard alloy granule of 78.5 grams and the matrix of 21.5 grams are mixed mutually, suppress under 41MPa after mix homogeneously,
Discharge plasma sintering at 1200 DEG C, is incubated 5 minutes, obtains multistage composite ceramic metal.In multistage composite ceramic metal, with body
Fraction meter, wear-resisting phase 63.4%, transitional face 6.6%, matrix phase 30%.
The multistage composite ceramic metal that the embodiment of the present invention 4 prepares is tested according to the method described in technique scheme
Hardness, fracture toughness and wearability, testing result is as shown in table 1.
Embodiment 5
Prepare wear-resisting phase by the following method:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains wear-resisting phase.
The particle diameter of the wear-resisting phase that the embodiment of the present invention 5 prepares is 300 μm, and composition is 94wt.%WC-6wt.%Co.
Prepare transitional face by the following method:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains transitional face.
The composition of the transitional face that the embodiment of the present invention 5 prepares is 85wt.%WC-15wt.%Co.
Employing 30wt.%WC-70wt.%Co alloy as matrix phase, described matrix phase preparation method is:
Co, WC and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1200 DEG C of vacuum conditions
Knot, obtains matrix phase.
The wear-resisting phase of 82.4 grams is placed on mixing granulation in the transitional face of 17.6 grams, at wear-resisting phase Surface mulch 10 μ m thick
Transitional face, obtain hard alloy granule, the hard alloy granule mean diameter obtained is 320 μm.
The hard alloy granule of 77 grams and the matrix of 23 grams are mixed mutually, at 41MPa after mix homogeneously, transfers at 1200 DEG C
Electricity plasma agglomeration, is incubated 5 minutes, obtains multistage composite ceramic metal.In multistage composite ceramic metal, with volume fraction,
Wear-resisting phase 57.7%, transitional face 12.3%, matrix phase 30%.
The multistage composite ceramic metal that the embodiment of the present invention 5 prepares is tested according to the method described in technique scheme
Hardness, fracture toughness and wearability, testing result is as shown in table 1.
Embodiment 6
Prepare wear-resisting phase by the following method:
94wt.%WC-6wt.%Co and paraffin are mixed, obtains mixture;
Described mixture is carried out successively under ball milling speed is 200r/min wet grinding in 48 hours, be dried at 60 DEG C, sieve,
Pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen the dewaxing of 2 hours, then burns under 1450 DEG C of vacuum conditions
Knot, obtains wear-resisting phase.
The particle diameter of the wear-resisting phase that the embodiment of the present invention 6 prepares is 100 μm, and composition is 94wt.%WC-6wt.%Co.
Prepare ground floor transitional face by the following method:
92wt.%WC-8wt.%Co and paraffin are mixed, obtains mixture;
Wear-resisting to 25.5 grams of described mixture and 78.2 grams phase granule is carried out under 200r/min wet grinding in 48 hours, at 60 DEG C
It is dried, sieves, pelletizes;The spherolite obtained is carried out in hydrogen the dewaxing of 2 hours, then at 1200 DEG C of vacuum bars at 400 DEG C
It is sintered under part, obtains the granule that wear-resisting phase is formed with ground floor transitional face.
Prepare second layer transitional face by the following method:
85wt.%WC-15wt.%Co and paraffin are mixed, obtains mixture;
The granule 29.2 grams of described mixture and 103.7 grams of wear-resisting phases and ground floor transitional face formed is at 200r/min
Under carry out wet grinding in 48 hours, be dried at 60 DEG C, sieve, pelletize;The spherolite obtained is carried out at 400 DEG C 2 hours in hydrogen
Dewaxing, is then sintered under 1200 DEG C of vacuum conditions, obtains the group that wear-resisting phase is formed with ground floor+second layer transitional face
Grain.
Prepare third layer transitional face by the following method:
70wt.%WC-30wt.%Co and paraffin are mixed, obtains mixture;
The granule that 31.3 grams of described mixture and 132.9 grams of wear-resisting phases and ground floor+second layer transitional face are formed is existed
Carry out wet grinding in 48 hours under 200r/min, be dried at 60 DEG C, sieve, pelletize;The spherolite obtained is carried out at 400 DEG C in hydrogen
The dewaxing of 2 hours, is then sintered under 1200 DEG C of vacuum conditions, obtains wear-resisting phase and ground floor+second layer+third layer mistake
Crossing the granule that phase is formed, be hard alloy granule, the mean diameter of hard alloy granule is 130 μm.
Use 30wt.%WC-70wt.%Co alloy as matrix phase.
30wt.%WC-70wt.%Co and paraffin are mixed, obtains mixture;
50.4 grams of described mixture and 164.2 grams of wear-resisting phases are formed with ground floor+second layer+third layer transitional face
Granule carries out wet grinding in 48 hours under 200r/min, is dried at 60 DEG C, sieves, pelletizes;By the spherolite that obtains in hydrogen 400 DEG C
Under carry out the dewaxing of 2 hours, then at 41MPa, at 1200 DEG C, carry out discharge plasma sintering, be incubated 5 minutes, obtain final
Multistage composite ceramic metal.In multistage composite ceramic metal, with volume fraction, wear-resisting phase 31.9%, transitional face 38.1%, base
Body phase 30%.
The multistage composite ceramic metal that the embodiment of the present invention 6 prepares is tested according to the method described in technique scheme
Hardness, fracture toughness and wearability, testing result is as shown in table 1.
The ceramic-metallic the performance test results of multistage composite that table 1 embodiment of the present invention prepares
As seen from the above embodiment, the invention provides a kind of multistage composite ceramic metal, including matrix phase be distributed in
Some granules that matrix is interior mutually, described granule includes wear-resisting phase and is coated on wear-resisting n layer transitional face outside mutually, n >=1;Described
The hardness of n-layer transitional face is gradually lowered, and the transitional face hardness contacting wear-resisting phase is the highest;The hardness of described transitional face is more than matrix phase
Hardness less than the hardness of wear-resisting phase.The present invention uses transitional face to be coated with wear-resisting phase, forms composite hard alloy granule, and this is multiple
Close hard close granule be evenly distributed on tough matrix mutually in, obtain the multistage composite ceramic metal with special construction, the present invention
The multistage composite ceramic metal provided has higher wearability and higher fracture toughness simultaneously.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For Yuan, under the premise without departing from the principles of the invention, it is also possible to make some improvements and modifications, these improvements and modifications also should
It is considered as protection scope of the present invention.