CN107619263A - One kind addition graphene oxide coated Si3N4The Al of composite granule2O3Base ceramic cutting tool material and preparation method thereof - Google Patents
One kind addition graphene oxide coated Si3N4The Al of composite granule2O3Base ceramic cutting tool material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to one kind to add graphene oxide coated Si3N4The Al of composite granule2O3Base ceramic cutting tool material and preparation method thereof.The ceramic cutting tool material is with Al2O3For matrix, graphene oxide coated Si3N4To strengthen phase, MgO, Ni and Mo are sintering aid.The preparation of the ceramic cutting tool material includes graphene oxide coated Si3N4The steps such as powder preparation, the mixing of cutter material powder, drying and screening, the die-filling and hot pressed sintering of cold pressing.The graphene oxide coated Si of the present invention3N4Composite granule is added in nano composite ceramic cutter material, can significantly improve the fracture toughness and bending strength of material.It is of the invention effectively to solve the problems, such as generation stomata that graphene oxide and nano-particle brought by phenomena such as disperseing uneven, particle aggregation in composite ceramics matrix, the defects of microstructure such as not close is combined with matrix, while avoid orientation sex chromosome mosaicism of the graphene in ceramic matrix.
Description
Technical field
The present invention relates to a kind of preparation method of alumina-based composite ceramics cutter material, graphene oxide is particularly added
Coat aluminum oxide base ceramics cutting tool material of silicon nitride composite powder and preparation method thereof.
Background technology
Aluminum oxide base ceramics cutting tool has high hardness, excellent anti-wear performance and mechanical behavior under high temperature, good chemistry
Stability, it is not easy that the advantages that cohesive occurs with metal, is widely used in the cutting of hardworking material, superhigh-speed cutting, high-speed dry
Cutting and hard machining etc..However, aluminum oxide base ceramics cutting tool material, as one kind in ceramic material, fragility limits its conduct
A kind of further development of outstanding ceramic cutting tool material.Therefore, it is the neck alumina tool material to be carried out toughened and reinforced
The focus of domain research.The aluminum oxide based nano complex phase ceramic system developed has Al2O3/ SiC, Al2O3/Si3N4, Al2O3/ TiC,
Al2O3/ Ti (C, N), Al2O3/ diamond, Al2O3/ Fe, Al2O3/ W, Al2O3/ Ni etc..Research shows to add in ceramic matrix
Appropriate enhancing phase, the mechanical property of cutter material can be effectively improved.In addition, ceramic matric composite fiber reinforced at present,
The ceramic material of CNT toughness reinforcing, ceramic cutting tool material of graphene toughness reinforcing etc. turn into the focus of research, and material property obtains
It is obviously improved.Referring to CN104909785A, CN103979942A, CN106145957A.
The each carbon atom of graphene is connected by 3 carbon atoms of very strong σ keys and other, causes it to show excellent
Physical property：Specific surface area 2630m2/ g, Young's modulus 1100GPa, fracture strength 125GPa etc..In view of what graphene protruded
Physical property, the more efficient toughened and reinforced body of ceramic cutting tool material can be turned into.But strong model moral between graphene sheet layer be present
Hua Li, it is difficult to realize between lamella good scattered.Show therefore, mutually serious reunion be present in ceramic material as enhancing
As being combined with matrix not close and causing the faults of construction such as stomata.In addition, graphene lamellar body perpendicular hot pressing direction in the base
Stratiform arrangement, the orientation problem of lamellar body has a strong impact on the performance of its toughened and reinforced performance in matrix material.Meanwhile nanometer increases
Strong scattering problem of the phase particle in matrix material, and complex phase ceramic material cutter material research urgent problem to be solved.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of addition graphene oxide coated Si3N4Composite granule
Al2O3Base ceramic cutting tool material and preparation method thereof.
Term explanation：
Al2O3/Si3N4：It is writing a Chinese character in simplified form for the composite ceramic tool material that substrate nitridation silicon is enhancing phase to refer to aluminum oxide；
Si3N4@GO：Refer to writing a Chinese character in simplified form for graphene oxide cladding silicon nitride composite powder；With graphene oxide coated Si3N4
It is synonymous.
Al2O3(Si3N4@GO)：It is that matrix graphene oxide cladding silicon nitride is the composite ceramics for strengthening phase to refer to aluminum oxide
Cutter material is write a Chinese character in simplified form.
Technical scheme is as follows：
It is a kind of add graphene oxide cladding silicon nitride composite powder alumina-based composite ceramics cutter material, be by with
The raw material of lower mass percent forms through hot pressed sintering：
Graphene oxide cladding silicon nitride 5~30%, magnesia 0.25~5%, molybdenum 0.5~5%, nickel 0.5~5%, its
Remaining is Al2O3；
Wherein, the graphene oxide cladding silicon nitride is prepared as follows：
By Si3N4Powder is added in hydrogen peroxide, in 60~100 DEG C of oxidation processes, is subsequently dispersed water mixed alkoxide solution
In, coupling agent hydrating solution is added, coupling agent dosage is Si after oxidation processes3N4The 2.5%~10% of powder quality；It is warming up to
60~90 DEG C, regulation pH value is 8~10, and stirring reaction obtains the Si of coupling agent surface modification3N4Suspension；Then described in regulation
Si3N4Suspension pH value is 3~5, is added in the graphene oxide aqueous dispersions that pH value is 8~10 and mixes, quiet after ultrasonic agitation
Put, until coating particles all precipitate, separation, dry, obtain graphene oxide cladding silicon nitride (Si3N4@GO) powder.
The coupling agent is selected from 3- aminopropyl triethoxysilanes (KH550), 3- aminopropyl trimethoxysilanes
(KH540), N-2 (aminoethyl) 3- aminopropyl triethoxysilanes (KH910) or N-2 (aminoethyl) 3- aminopropyltriethoxy dimethoxies
Any one of the coupling agents such as base silane (KH602).The coupling agent hydrating solution is silane coupler in water mixed alkoxide solution
Middle ultrasonic hydrolysis is made.
, according to the invention it is preferred to, in the graphene oxide cladding silicon nitride, graphene oxide clad average thickness
In 2~8nm, Si3N4The average grain diameter of particle is 100~300nm.Further preferred graphene oxide clad average thickness
In 3~5nm, Si3N4The average grain diameter of particle is 100~200nm.
According to the present invention, it is further preferred that the raw material components mass percent of the composite ceramic tool material is：Oxygen
Graphite alkene coats silicon nitride 10~30%, and magnesia 0.25~2%, molybdenum 0.5~3%, nickel 1~3%, remaining is Al2O3。
Further, the raw material components mass percent of most preferably described composite ceramic tool material is：Graphite oxide
Alkene coats silicon nitride 20~21%, and magnesia 0.5~0.8%, molybdenum 1~1.5%, nickel 1.2~1.5%, remaining is Al2O3。
, according to the invention it is preferred to, magnesia (sintering aid) average grain diameter is 0.5~5 μm, further preferred oxygen
It is 0.5~2 μm to change magnesium average grain diameter；The average grain diameter of molybdenum is 10~50 μm, and the average grain diameter of nickel is 10~50 μm.It is further excellent
Choosing, nickel and molybdenum average grain diameter are respectively 15~45 μm.
, according to the invention it is preferred to, the Al2O3Average grain diameter is 100~500nm, further preferably, the Al2O3It is flat
Equal particle diameter is 200~300nm.Further preferably, the Al2O3For α-Al2O3。
According to the present invention, the alumina-based composite ceramics cutter of the addition graphene oxide cladding silicon nitride composite powder
The preparation method of material, raw material components ratio is as it was previously stated, including step：
A. by Si3N4Powder is added in hydrogen peroxide, make it is fully dispersed, then in 60~100 DEG C of temperature, magnetic agitation bar
Oxidation processes under part；The Si of surface oxidation is made3N4Powder, it is standby.
It is another to take coupling agent to add in water mixed alkoxide solution, ultrasonic hydrolysis, coupling agent hydrating solution is obtained, it is standby.
B. the Si of surface oxidation made from step a is taken3N4Powder is distributed in water mixed alkoxide solution, ultrasonic disperse, Zhi Houtian
Add coupling agent hydrating solution, coupling agent dosage is the Si of surface oxidation3N4The 2.5%~10% of powder quality；Continue to be stirred by ultrasonic
Make to be well mixed；60~90 DEG C are warming up to, regulation pH value is 8~10, is reacted 2~4 hours under magnetic stirring；Obtain coupling agent
The Si that surface is modified3N4Suspension；Then the Si is adjusted3N4Suspension pH value is 3~5, the acid Si that will be obtained3N4Suspension
It is added drop-wise in the graphene oxide aqueous dispersions that pH value is 8~10, is stood after ultrasonic agitation, until coating particles all precipitate,
Separation, dry, obtain graphene oxide cladding silicon nitride (Si3N4@GO) composite granule.
C. a certain amount of polyethylene glycol is added in absolute ethyl alcohol, is completely dissolved it；Add Al2O3, ultrasonic disperse is simultaneously
Mechanical agitation, magnesia, molybdenum and nickel are added, continue ultrasonic disperse and mechanical agitation, obtain well mixed suspension.
D. obtained suspension in step c is poured into ball milling to fill, is filled with nitrogen as protective gas, continuous ball milling 24~
48h。
E. by obtained Si in step b3N4@GO composite granules and ball milling ball are added in step d ball grinder together, after
2~4h of continuous ball milling, the material of the alumina-based composite ceramics cutter material of graphene oxide cladding silicon nitride composite powder must be added
Slurry.
F. slurry drying, sieving made from step e are obtained into mixed powder, sealing is standby.
G. the mixed powder dried obtained by step f is encased in the mould that material is graphite and carries out hot pressed sintering, obtained
Add the alumina-based composite ceramics cutter material of graphene oxide cladding silicon nitride composite powder.
, according to the invention it is preferred to, in step a, based on every liter of hydrogen peroxide, Si3N4The addition of powder is 10~20g/L.
Preferably, Si3N4The temperature of surface oxidation treatment is 70~90 DEG C.
, according to the invention it is preferred to, in step a, the ratio between the coupling agent quality and water mixed alkoxide solution volume are：1~
2g：600~1200mL；The water mixed alkoxide solution is absolute ethyl alcohol and water volume ratio 1~1.5:1~1.5 mixed solution.
, according to the invention it is preferred to, in step a, the Si3N4Powder average grain diameter is 100~200nm；The particle diameter for
Particle is uniformly and cladding is completely more important.Because lamellar body structure, Si is presented in graphene oxide in dispersion liquid3N4Grain diameter
Excessive cladding completely difficult to realize；Si3N4Grain diameter is too small, then surface energy is larger, easily reunites between particle, easily occurs same
When have more Si3N4Agglomerated particles are oxidized the phenomenon of graphene coated together, and powder granule is uneven after causing cladding.
According to currently preferred, in step b, the Si of the surface oxidation3N4Powder quality and the water-alcohol solution volume
The ratio between be 1~2g:200~300mL；Preferably, the water-alcohol solution is water and absolute ethyl alcohol volume ratio 1~1.5:1~1.5
Solution.According to currently preferred, in step b, graphene oxide dispersion concentration is 0.3~0.6mg/mL；Ammoniacal liquor is added dropwise to adjust
Save pH=8~10 of graphene oxide dispersion.Preferably, the coupling agent quality is the Si of surface oxidation3N4The 4 of quality~
6%；Preferably, it is 8.5~9.5 to adjust suspension pH, and reaction temperature is 75~85 DEG C.
According to currently preferred, in step b, the Si of the surface oxidation3N4The mass ratio of powder and graphene oxide is
15~35:1~1.5；Most preferably, the Si of surface oxidation3N4The mass ratio of powder and graphene oxide is 20:1.
According to currently preferred, in step c, described molecular weight polyethylene glycol is especially excellent between 2000~10000
Select Macrogol 4000；The quality of described polyethylene glycol is Al2O3The 1~5% of quality.In step c, described ultrasonic disperse
And the churned mechanically time is 15~30min；The described continuation ultrasonic disperse and churned mechanically time is 15~30min.
According to currently preferred, in step d, described ball milling, the ball milling ball of hard alloy material, ball material quality are added
Than for 10~20：1.Most preferably, continuous ball milling time 30-40h.
According to currently preferred, in step e, the addition Si3N4The ball material mass ratio of@GO composite granules and ball milling ball
For 10~20：1；Most preferably, 2~3h of Ball-milling Time is continued.Nitrogen is as protective gas.
According to currently preferred, in step f, the slurry continuous drying 12 at 80~120 DEG C of vacuum drying chamber~
24h.Dried powder crosses 200 mesh sieves.
According to currently preferred, in step g, the hot pressed sintering condition is：1400~1700 DEG C of sintering temperature, hot pressing
20~35MPa of pressure, 10~30min of soaking time, 10~25 DEG C/min of programming rate.
The technical characterstic and beneficial effect of the present invention：
The present invention provides a kind of new mechanical property good aluminum oxide base ceramics cutting tool material.First by electrostatic from group
Graphene oxide is carried out Surface coating by dress technology to the beta-silicon nitride powder being modified by silane coupler surface.By coated powder
It is added in aluminium oxide ceramics matrix, by vacuum heating-press sintering, obtains graphene coated Si3N4The Al of toughness reinforcing2O3Base composite ceramic
Porcelain cutter material, because graphene oxide is the growth of graphene, under vacuum heating-press sintering, graphene oxide oxy radical point
Solution is changed into graphene, while effectively solving the problems, such as graphene nano powder reuniting, realizes the coordination of graphene nano phase
Toughness reinforcing.
The present invention successfully solve graphene as enhancing mutually present in ceramic material reunite combined with matrix it is not tight
It is close and the problem of cause the faults of construction such as stomata, and Si3N4Low, environmental pollution of caused controllability etc. in improving particle surface
Problem, while avoid orientation sex chromosome mosaicism of the graphene in ceramic matrix.
Graphene oxide cladding silicon nitride composite powder is added in aluminium oxide ceramics matrix material by the present invention, with oxidation
Graphene coated silicon nitride is enhancing phase, and magnesia, molybdenum and nickel are sintering aid, and Al is prepared through vacuum heating-press sintering2O3
(Si3N4@GO) composite ceramic tool material.The material has good mechanical property.From the microcosmic knot of composite ceramic tool material
It has been observed that graphene uniform is scattered in alumina substrate in structure, it is tightly combined with matrix material.Accordingly, with addition
Graphene oxide coats the increase of silicon nitride composite powder, and the mechanical property of ceramic cutting tool material improves therewith.Work as graphite oxide
When the mass fraction of alkene cladding silicon nitride is 21%, the alumina-based ceramic of addition graphene oxide cladding silicon nitride composite powder
The mechanical property of cutter material is optimal, hardness 18.4GPa, fracture toughness 7.6MPam1/2, bending strength 628MPa.
Brief description of the drawings
Fig. 1 is Si3N4The SEM photograph of@GO composite granules.
Fig. 2 is that embodiment 2 adds the aluminum oxide base ceramics cutting tool material that graphene oxide coats silicon nitride composite powder
Test sample plane of disruption SEM shape appearance figures.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited in following implementation
Example.Methods described is conventional method unless otherwise instructed.
Graphene oxide cladding silicon nitride composite powder is prepared as follows used in each embodiment：
(1) the raw material Si that average grain diameter is 200nm is weighed3N4Powder 2g, it is water-soluble to add the dioxygen that 200mL concentration is 20%
Liquid, magnetic agitation, 80 DEG C are warming up to, react 20min.Room temperature is cooled to, is centrifuged, and is cleaned 2~3 times with distilled water, is put
8 hours of 220 DEG C of high temperature dryings in drying box, obtain the Si of surface oxidation3N4Powder.
(2) 3- aminopropyl triethoxysilanes (KH-550) silane coupler hydrolyzate is prepared, silane coupler dosage is
0.1g, it is added drop-wise to 80mL absolute ethyl alcohols:Distilled water=1:In the solution of 1 volume ratio, ultrasonic hydrolysis 40min is standby.
(3) Si of the surface oxidation of step (1) preparation is taken3N4Powder 2g, it is placed in 200mL absolute ethyl alcohols:Distilled water=1:1
0.5h is stirred by ultrasonic in the solution of volume ratio, 3- aminopropyl triethoxysilanes (KH-550) silane that will be prepared in step (2)
Coupling agent hydrolyzate is added in silicon nitride suspension, and the ammonia spirit for being then 10% with mass fraction regulation pH value is 9, is put
In the three-necked flask with reflux, magnetic agitation, heating-up temperature reacts 3h to 80 DEG C, and the dilute of mass fraction 10% is added dropwise
Hydrochloric acid solution, regulation system pH to 4, obtain acid Si3N4Suspension.
(4) 100mg graphene oxides (GO) are weighed and are placed in (concentration 0.5mg/mL) ultrasonic 1.5h in 200mL distilled water,
PH value is adjusted to 9 with the ammoniacal liquor that mass fraction is 10%, obtains graphene oxide aqueous dispersions.
(5) by the acid Si of step (3)3N4Graphene oxide moisture under the conditions of suspension ultrasonic agitation with step (4) dissipates
Liquid mixes, and 40min is stirred by ultrasonic, and stands, precipitation, removes supernatant, be placed in vacuum drying chamber, and 70 DEG C of vacuum drying 12 are small
When, obtain Si after drying3N4@GO composite granules.Si3N4@GO mean particle sizes are 208nm, are coated on Si3N4Particle surface
Graphene oxide coating thickness is good in 3~5nm or so, covered effect.As shown in Figure 1.
Embodiment 1, a kind of alumina-based composite ceramics cutter material for adding graphene oxide cladding silicon nitride composite powder
Material, is to be formed by the raw material of following mass percent through hot pressed sintering：
Graphene oxide coats silicon nitride 10.5%, and magnesia 0.25%, molybdenum 0.5%, nickel 1%, remaining is Al2O3。
Preparation process is as follows：
1. it is Al by quality2O31% polyethylene glycol of quality is added in absolute ethyl alcohol, is completely dissolved it, ultrasound point
Dissipate simultaneously mechanical agitation 15min；Add the Al that mean radius is 200nm2O3Powder, continue ultrasonic disperse and mechanical agitation 15min,
Obtain Al2O3Dispersion liquid.
2. addition sintering aid MgO average grain diameters are 0.5 μm and W metal, Mo average grain diameters are 15 μm and arrived described in step 1
Al2O3In dispersion liquid, then ultrasonic disperse and mechanical agitation 15min, obtain well mixed suspension.
3. obtained suspension in step 2 is poured into ball milling to fill, nitrogen is filled with as protective gas, adds hard alloy material
The ball milling ball of matter, ball material mass ratio are 10:1, continuous ball milling 24h.
4. by obtained Si3N4@GO composite granules and ball milling ball are added in ball grinder by step 3 ball material mass ratio, its
In, Si3N4The addition of@GO composite granules is that 10.5% (addition of graphene oxide is 0.5%) continues ball milling 2h, is obtained
Add the slurry of the alumina-based composite ceramics cutter material of graphene oxide cladding silicon nitride composite powder.
5. by the alumina-based composite ceramics cutter material of gained addition graphene oxide cladding silicon nitride composite powder
Slurry continuous drying 12h at 80 DEG C of vacuum drying chamber, then sieving obtain mixed powder, and sealing is standby.
6. the mixed powder dried obtained by step 5 is encased in the mould that material is graphite and carries out hot pressed sintering, sinter
1450 DEG C, hot pressing pressure 20MPa, soaking time 15min, 10 DEG C/min of programming rate of temperature, that is, obtain adding graphene oxide
Coat the alumina-based composite ceramics cutter material of silicon nitride composite powder.
The aluminum oxide base ceramics cutting tool material of obtained addition graphene oxide cladding silicon nitride composite powder is cleaved
The steps such as processing, corase grind, fine grinding, grinding and polishing are prepared into 3mm × 4mm × 30mm ceramic batten, measure its mechanical property
For：Hardness 18.2GPa, fracture toughness 5.2MPam1/2, bending strength 502MPa.Test sample plane of disruption SEM shape appearance figures are as schemed
Shown in 2.
Embodiment 2, a kind of alumina-based composite ceramics cutter material for adding graphene oxide cladding silicon nitride composite powder
Material, is to be formed by the raw material of following mass percent through hot pressed sintering：
Graphene coated silicon nitride 21%, magnesia 0.5%, molybdenum 1%, nickel 1.25%, remaining is Al2O3。
1. it is Al by quality2O32% polyethylene glycol of quality is added in absolute ethyl alcohol, is completely dissolved it, ultrasound point
Dissipate simultaneously mechanical agitation 25min；Add the Al that mean radius is 200nm2O3, continue ultrasonic disperse and mechanical agitation 30min, obtain
Al2O3Dispersion liquid.
2. addition sintering aid MgO average grain diameters are 1 μm and W metal, Mo average grain diameters are 20 μm and arrived described in step 1
Al2O3In dispersion liquid, then ultrasonic disperse and mechanical agitation 20min, obtain well mixed suspension.
3. obtained suspension in step 2 is poured into ball milling to fill, nitrogen is filled with as protective gas, adds hard alloy material
The ball milling ball of matter, ball material mass ratio are 15:1, continuous ball milling 36h.
4. by obtained Si3N4@GO composite granules and ball milling ball are added in ball grinder by step 3 ball material mass ratio, its
In, Si3N4The addition of@GO composite granules is 21% (addition of graphene oxide is 1%), and ball milling 3h, is added again
The slurry of the alumina-based composite ceramics cutter material of graphene oxide cladding silicon nitride composite powder.
5. by the alumina-based composite ceramics cutter material of gained addition graphene oxide cladding silicon nitride composite powder
Slurry continuous drying 18h at 90 DEG C of vacuum drying chamber, then sieving obtain mixed powder, and sealing is standby.
6. the mixed powder dried obtained by step 5 is encased in the mould that material is graphite and carries out hot pressed sintering, sinter
1600 DEG C, hot pressing pressure 30MPa, soaking time 30min, 15 DEG C/min of programming rate of temperature, that is, obtain adding graphene oxide
Coat the alumina-based composite ceramics cutter material of silicon nitride composite powder.
By it is obtained addition graphene coated alumina composite powders aluminum oxide base ceramics cutting tool material it is cleaved processing,
The steps such as corase grind, fine grinding, grinding and polishing are prepared into 3mm × 4mm × 30mm ceramic batten, and measuring its mechanical property is：Firmly
Spend 18.4GPa, fracture toughness 7.6MPam1/2, bending strength 628MPa.
Embodiment 3, a kind of alumina-based composite ceramics cutter material for adding graphene oxide cladding silicon nitride composite powder
Material, is to be formed by the raw material of following mass percent through hot pressed sintering：
Graphene coated silicon nitride 26.25%, magnesia 0.75%, molybdenum 2%, nickel 2.5%, remaining is Al2O3。
1. it is Al by quality2O35% polyethylene glycol of quality is added in absolute ethyl alcohol, is completely dissolved it, ultrasound point
Dissipate simultaneously mechanical agitation 30min；Add the Al that mean radius is 200nm2O3, continue ultrasonic disperse and mechanical agitation 30min, obtain
Al2O3Dispersion liquid.
2. addition sintering aid MgO average grain diameters are 2 μm and W metal, Mo average grain diameters are 30 μm and arrived described in step 1
Al2O3In dispersion liquid, then ultrasonic disperse and mechanical agitation 30min, obtain well mixed suspension.
3. obtained suspension in step 2 is poured into ball milling to fill, nitrogen is filled with as protective gas, adds hard alloy material
The ball milling ball of matter, ball material mass ratio are 20:1, continuous ball milling 48h.
4. by obtained Si3N4@GO composite granules and ball milling ball are added in ball grinder by step 3 ball material mass ratio, its
In, Si3N4The addition of@GO composite granules is 26.25% (addition of graphene oxide is 1.25%), and ball milling 3h, is obtained again
The slurry of the alumina-based composite ceramics cutter material of graphene oxide cladding silicon nitride composite powder must be added.
5. by the alumina-based composite ceramics cutter material of gained addition graphene oxide cladding silicon nitride composite powder
Slurry continuous drying 24h at 100 DEG C of vacuum drying chamber, then sieving obtain mixed powder.
6. the mixed powder dried obtained by step 5 is encased in the mould that material is graphite and carries out hot pressed sintering, sinter
1700 DEG C, hot pressing pressure 30MPa, soaking time 30min, 15 DEG C/min of programming rate of temperature, that is, obtain adding graphene oxide
Coat the alumina-based composite ceramics cutter material of silicon nitride composite powder.
By it is obtained addition graphene coated alumina composite powders aluminum oxide base ceramics cutting tool material it is cleaved processing,
The steps such as corase grind, fine grinding, grinding and polishing are prepared into 3mm × 4mm × 30mm ceramic batten, and measuring its mechanical property is：Firmly
Spend 18.1GPa, fracture toughness 6.8MPam1/2, bending strength 526MPa.
Comparative example 1.
1. it is Al by quality2O32% polyethylene glycol of quality is added in absolute ethyl alcohol, is completely dissolved it, ultrasound point
Dissipate simultaneously mechanical agitation 25min；Add the Al that mean radius is 200nm2O3, continue ultrasonic disperse and mechanical agitation 30min, obtain
Al2O3Dispersion liquid.
2. addition sintering aid MgO average grain diameters are 1 μm and W metal, Mo average grain diameters are 20 μm and arrived described in step 1
Al2O3In dispersion liquid, then ultrasonic disperse and mechanical agitation 20min, obtain well mixed suspension.
3. obtained suspension in step 2 is poured into ball milling to fill, nitrogen is filled with as protective gas, adds hard alloy material
The ball milling ball of matter, ball material mass ratio are 15:1, continuous ball milling 36h.
4. by the Si that average grain diameter is 200nm3N4Composite granule and ball milling ball are added to ball milling by step 3 ball material mass ratio
In tank, wherein, Si3N4The addition of powder is 21%, again ball milling 3h, and the alumina base for obtaining addition beta-silicon nitride powder is compound
The slurry of ceramic cutting tool material.
5. gained is added to the slurry of the alumina-based composite ceramics cutter material of beta-silicon nitride powder in vacuum drying chamber 90
Continuous drying 18h at DEG C, then sieving obtain mixed powder, and sealing is standby.
6. the mixed powder dried obtained by step 5 is encased in the mould that material is graphite and carries out hot pressed sintering, sinter
1600 DEG C, hot pressing pressure 30MPa, soaking time 30min, 15 DEG C/min of programming rate of temperature, that is, obtain adding beta-silicon nitride powder
Alumina-based composite ceramics cutter material.
It is prepared by the steps such as the cleaved processing of obtained aluminum oxide base ceramics cutting tool material, corase grind, fine grinding, grinding and polishing
Into 3mm × 4mm × 30mm ceramic batten, measuring its mechanical property is：Hardness 17.6GPa, fracture toughness 4.6MPam1/2、
Bending strength 432MPa.
Claims (10)
1. a kind of alumina-based composite ceramics cutter material for adding graphene oxide cladding silicon nitride composite powder, its feature exist
Then formed by the raw material of following mass percent through hot pressed sintering：
Graphene oxide coats silicon nitride 5~30%, and magnesia 0.25~5%, molybdenum 0.5~5%, nickel 0.5~5%, remaining is
Al2O3；
Wherein, the graphene oxide cladding silicon nitride is prepared as follows：
By Si3N4Powder is added in hydrogen peroxide, in 60~100 DEG C of oxidation processes, is subsequently dispersed in water mixed alkoxide solution, is added
Add coupling agent hydrating solution, coupling agent dosage is Si after oxidation processes3N4The 2.5%~10% of powder quality；It is warming up to 60~90
DEG C, regulation pH value is 8~10, and stirring reaction obtains the Si of coupling agent surface modification3N4Suspension；Then the Si is adjusted3N4It is outstanding
Turbid pH value is 3~5, is added in the graphene oxide aqueous dispersions that pH value is 8~10 and mixes, is stood after ultrasonic agitation, directly
All precipitate, separation, dry to coating particles, obtain graphene oxide cladding silicon nitride (Si3N4@GO) powder.
2. the alumina-based composite ceramics cutter of addition graphene oxide cladding silicon nitride composite powder as claimed in claim 1
Material, it is characterised in that the graphene oxide coated Si3N4Composite granule, graphene oxide clad average thickness 2~
8nm, Si3N4The average grain diameter of particle is 100~300nm.
3. the alumina-based composite ceramics cutter of addition graphene oxide cladding silicon nitride composite powder as claimed in claim 1
Material, it is characterised in that the raw material components mass percent of the composite ceramic tool material is：Graphene oxide cladding nitridation
Silicon 10~30%, magnesia 0.25~2%, molybdenum 0.5~3%, nickel 1~3%, remaining is Al2O3；Preferably, the composite ceramics
The raw material components mass percent of cutter material is：Graphene oxide cladding silicon nitride 20~21%, magnesia 0.5~0.8%,
Molybdenum 1~1.5%, nickel 1.2~1.5%, remaining is Al2O3。
4. the alumina base of the addition graphene oxide cladding silicon nitride composite powder as described in claim any one of 1-3 is compound
Ceramic cutting tool material, it is characterised in that the magnesia average grain diameter is 0.5~5 μm, and the average grain diameter of molybdenum is 10~50 μm,
The average grain diameter of nickel is 10~50 μm；Preferably, the Al2O3Average grain diameter is 100~500nm.
5. the alumina-based composite ceramics of any one of the claim 1-4 addition graphene oxide cladding silicon nitride composite powders
The preparation method of cutter material, including step：
A. by Si3N4Powder is added in hydrogen peroxide, make it is fully dispersed, then under the conditions of 60~100 DEG C of temperature, magnetic agitation
Oxidation processes；The Si of surface oxidation is made3N4Powder, it is standby；
It is another to take coupling agent to add in water mixed alkoxide solution, ultrasonic hydrolysis, coupling agent hydrating solution is obtained, it is standby；
B. the Si of surface oxidation made from step a is taken3N4Powder is distributed in water mixed alkoxide solution, ultrasonic disperse, and addition is even afterwards
Join agent hydrating solution, coupling agent dosage is the Si of surface oxidation3N4The 2.5%~10% of powder quality；Continuing ultrasonic agitation makes to mix
Close uniform；60~90 DEG C are warming up to, regulation pH value is 8~10, is reacted 2~4 hours under magnetic stirring；Obtain coupling agent surface
Modified Si3N4Suspension；Then the Si is adjusted3N4Suspension pH value is 3~5, the acid Si that will be obtained3N4Suspension is added dropwise
In the graphene oxide aqueous dispersions for being 8~10 to pH value, stood after ultrasonic agitation, until coating particles all precipitate, separation,
Dry, obtain graphene oxide cladding silicon nitride (Si3N4@GO) composite granule；
C. a certain amount of polyethylene glycol is added in absolute ethyl alcohol, is completely dissolved it；Add Al2O3, ultrasonic disperse and machinery
Stirring, magnesia, molybdenum and nickel are added, continue ultrasonic disperse and mechanical agitation, obtain well mixed suspension；
D. obtained suspension in step c is poured into ball milling to fill, is filled with nitrogen as protective gas, 24~48h of continuous ball milling；
E. by obtained Si in step b3N4@GO composite granules and ball milling ball are added in step d ball grinder together, continue ball
2~4h is ground, the slurry of the alumina-based composite ceramics cutter material of graphene oxide cladding silicon nitride composite powder must be added；
F. slurry drying, sieving made from step e are obtained into mixed powder, sealing is standby；
G. the mixed powder dried obtained by step f is encased in the mould that material is graphite and carries out hot pressed sintering, added
Graphene oxide coats the alumina-based composite ceramics cutter material of silicon nitride composite powder.
6. the alumina-based composite ceramics cutter material of addition graphene oxide cladding silicon nitride composite powder as claimed in claim 5
The preparation method of material, it is characterised in that in step a, based on every liter of hydrogen peroxide, Si3N4The addition of powder is 10~20g/L；It is excellent
Choosing, the Si3N4Powder average grain diameter is 100~200nm；Preferably, Si3N4The temperature of surface oxidation treatment is 70~90
℃。
7. the alumina-based composite ceramics cutter material of addition graphene oxide cladding silicon nitride composite powder as claimed in claim 5
The preparation method of material, it is characterised in that in step a, the ratio between the coupling agent quality and water mixed alkoxide solution volume are：1~2g：
600~1200mL；The water mixed alkoxide solution is absolute ethyl alcohol and water volume ratio 1~1.5:1~1.5 mixed solution.
8. the alumina-based composite ceramics cutter material of addition graphene oxide cladding silicon nitride composite powder as claimed in claim 5
The preparation method of material, it is characterised in that in step b, the Si of the surface oxidation3N4Powder quality and the water-alcohol solution volume it
Than for 1~2g:200~300mL；Graphene oxide dispersion concentration is 0.3~0.6mg/mL；Preferably, the coupling agent matter
Measure the Si for surface oxidation3N4The 4~6% of quality；Preferably, it is 8.5~9.5 to adjust suspension pH, and reaction temperature is 75~85
℃。
9. the alumina-based composite ceramics cutter material of addition graphene oxide cladding silicon nitride composite powder as claimed in claim 5
The preparation method of material, it is characterised in that in step b, the Si of the surface oxidation3N4The mass ratio of powder and graphene oxide is 15
~35:1~1.5；Preferably, the Si of surface oxidation3N4The mass ratio of powder and graphene oxide is 20:1.
10. the alumina-based composite ceramics cutter of addition graphene oxide cladding silicon nitride composite powder as claimed in claim 5
The preparation method of material, it is characterised in that：Continue 2~3h of Ball-milling Time in continuous ball milling time 30-40h in step d, step e；
In step f, the slurry continuous drying 12~24h at 80~120 DEG C of vacuum drying chamber；In step g, the hot pressed sintering bar
Part is：1400~1700 DEG C, 20~35MPa of hot pressing pressure, 10~30min of soaking time of sintering temperature, programming rate 10~25
℃/min。
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| CN201710953002.6A CN107619263A (en) | 2017-10-13 | 2017-10-13 | One kind addition graphene oxide coated Si3N4The Al of composite granule2O3Base ceramic cutting tool material and preparation method thereof |
| PCT/CN2017/118231 WO2019071839A1 (en) | 2017-10-13 | 2017-12-25 | Graphene oxide coated silicon nitride composite powder, preparation therefor and application thereof, and al2o3 based ceramic cutter material |
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