CN107353017A - A kind of graphene coated alumina ceramic powder and preparation method and application - Google Patents
A kind of graphene coated alumina ceramic powder and preparation method and application Download PDFInfo
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- CN107353017A CN107353017A CN201710642029.3A CN201710642029A CN107353017A CN 107353017 A CN107353017 A CN 107353017A CN 201710642029 A CN201710642029 A CN 201710642029A CN 107353017 A CN107353017 A CN 107353017A
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Abstract
The present invention relates to a kind of graphene coated alumina ceramic powder and preparation method and application.The preparation method includes：(1) aluminum oxide suspension of amino surface modification is prepared；(2) graphene oxide dispersion is prepared；(3) graphene coated alumina ceramic powder is prepared.The inventive method can simply and rapidly obtain graphene coated alumina ceramic powder, it is coated on the surface of alumina powder with making graphene uniform, improve dispersiveness between graphene and alumina powder and both the uniformity that mixes, solve the problems, such as graphene in alumina-based ceramic material easily reunite, bad dispersibility, simultaneously, the method raw material sources are extensive and cheap, reduce production cost, technique is simple, parameter is easy to control and production process safety and environmental protection, suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of graphene coated alumina ceramic powder and preparation method and application, belong to Ceramic Composite
Field of material technology.
Background technology
Graphene (Graphene) is that have regular six side's symmetrical junctions by what Covalent bonding together formed by single layer of carbon atom
The preferable two dimensional crystal of structure.Because the two dimensional crystal structure and excellent crystal quality, graphene of uniqueness have excellent power
And electrical and thermal conductivity performance performance, are widely applied to field of compound material.For example, CN104538639A, which provides one kind, is used for lithium
Graphene coated aluminum oxide of ion battery and preparation method thereof, as carbon source and metalic contamination or nonmetallic is added by the use of LPAN
Dopant, there is the dual property of heat conduction and conduction, the powder through the modified alumina material of this method graphene coated
Can be well be mutually infiltrated with lithium-ion battery electrolytes, can be greatly lowered the internal resistance of lithium ion battery, and cause battery
Capacity and stable cycle performance.
Graphene as current nature is most thin, intensity is high, a kind of novel nano-material of good heat conductivity, and its have it is excellent
Greasy property more, but be added to as lubricant in ceramic matrix and be oxidized easily, in order to improve the anti-oxidant of graphene
Performance, it has been reported that one layer of aluminum oxide is coated in graphenic surface, for example, CN106431361A discloses a kind of addition aluminum oxide
The self-lubrication ceramic cutter material of coated graphite alkene, the material are using the aluminum oxide of micro-meter scale as matrix, by micro-meter scale
Silicon nitride enhancing, the aluminum oxide of nanoscale is toughened and reinforced and the greasy property of alumina-coated graphene is combined, with oxidation
Yttrium is sintering aid, through ceramic composite made of vacuum heating-press sintering.
On the other hand, graphene or the good reinforcing body of ceramic material.For example, CN106007762A discloses a kind of stone
The alumina tool and its hot pressed sintering preparation technology of black alkene nanometer sheet toughness reinforcing, described sintex is with Al2O3For base
Body, using graphene nanometer sheet as enhancing phase, and a certain amount of metal adhesive and sintering aid are added, prepared using sinter technology
Obtain.In terms of mechanical property：Add the Al of graphene2O3Nano composite ceramic cutter material is on hot pressing direction
38% and 39% has been respectively increased parallel to the fracture toughness on hot pressing direction and bending strength in fracture toughness and bending strength ratio.
Thus, graphene toughness reinforcing Al2O3Occurs the anisotropy of mechanical property in nano composite ceramic cutter material.
But because graphene specific surface area is big and surface energy is high, the conventional method such as ball milling mixing can not make graphene exist
It is dispersed in ceramic matrix, and the reunion of graphene causes the faults of construction such as stomata, makes graphene and ceramic matrix not
Good contact interface can be formed, the heterogeneous microstructure of graphene is destroyed, have impact on the raising of composite property.Therefore,
Improving dispersing uniformity of the graphene in ceramic matrix turns into the premise for preparing graphene toughened ceramic material.
The content of the invention
In order to avoid the weak point present in above-mentioned prior art, the present invention provides a kind of for preparing alumina base pottery
Graphene coated alumina ceramic powder of porcelain cutter material and preparation method thereof, utilize graphene oxide and amination aluminum oxide
Mutual electrostatic interaction between powder, to overcome graphene in existing graphene ceramic composite easily to reunite, bad dispersibility
Problem.
Term explanation：
Room temperature：With implication well known in the art；Generally refer to 25 ± 3 DEG C.
Technical scheme is as follows：
A kind of preparation method of graphene coated alumina ceramic powder, including step：
(1) aluminum oxide suspension of amino surface modification is prepared
Alumina powder is calcined 6~12h at 500~1000 DEG C, is added in hydrogen peroxide, enters after being cooled to room temperature
Row oxidation processes, 35~55min is stirred by ultrasonic, with absolute ethyl alcohol centrifuge washing, vacuum drying；By oxidation-treated aluminum oxide
Powder is added in absolute ethyl alcohol and the mixed solution of deionized water, and amino silicane coupling agent is slowly added dropwise thereto, drips simultaneously
Add the pH value of pH adjusting agent regulation system, the mass volume ratio of the alumina powder and amino silicane coupling agent for 0.1~
0.5g：2~6mL；10~30min of ultrasound after being added dropwise to complete, then 5~12h of stir process at 60~120 DEG C of temperature, with nothing
Water-ethanol centrifuge washing, vacuum drying obtain the alumina powder of amino surface modification；
The alumina powder that obtained amino surface is modified is added in deionized water, 10~30min of ultrasonic disperse, obtained
The aluminum oxide suspension being modified to amino surface, the pH value of dilute hydrochloric acid solution regulation suspension is added dropwise thereto, makes above-mentioned suspension
Liquid is in electropositive；
(2) graphene oxide dispersion is prepared
Under the conditions of ice-water bath, graphite and sodium nitrate are added into the concentrated sulfuric acid, stirs, is then slow added into oxidation
Agent potassium permanganate, 30~60min is persistently stirred, mixture is heated up and is maintained at 40~60 DEG C, 8~12h of stirring, by what is obtained
Reactant adds deionized water to dilute, and is heated to more than 98 DEG C, stirs 30~60min, is subsequently cooled to 45~65 DEG C, adds
Hydrogen peroxide, the deionized water of the dilution and the volume ratio of hydrogen peroxide are 120~400：10~30, products therefrom watery hydrochloric acid
Washing, then cleaned repeatedly to neutrality with deionized water, it is centrifugally separating to obtain graphene oxide；
Add graphene oxide into deionized water, 60~120min of ultrasonic disperse, obtain graphene oxide dispersion,
The pH value of ammonia spirit regulation graphene oxide dispersion is added dropwise thereto so that graphene oxide dispersion is in elecrtonegativity；
(3) graphene coated alumina ceramic powder is prepared
The aluminum oxide suspension that obtained amino surface is modified in step (1) is slowly dropped under ultrasound and stirring condition
In step (2) in obtained graphene oxide dispersion, the mass ratio of the amino surface modified aluminas and graphene oxide
For 10~30：1, centrifuged after dripping, dry, that is, obtain graphene oxide coated aluminum oxide ceramic powder；The oxidation that will be obtained
Graphene coated alumina composite powders carry out high temperature reduction processing under protective atmosphere in 300~800 DEG C, obtain graphene coated
Alumina ceramic powder.
According to currently preferred, in the step (1), alumina powder use average grain diameter for 100~500nm α-
Al2O3；The mass fraction of hydrogen peroxide solution is 10~30%.It is further preferred that the mixing of the absolute ethyl alcohol and deionized water
In solution, absolute ethyl alcohol is 1 with deionized water volume ratio：1, the pH value regulator is glacial acetic acid or ammoniacal liquor.
According to currently preferred, in the step (1), the mass volume ratio of the aluminum oxide and absolute ethyl alcohol is 0.1
~0.5g：100~200mL；
According to currently preferred, in the step (1), the mass volume ratio of the aluminum oxide and amino silicane coupling agent
For 0.1~0.3g：2~5mL；It is further preferred that regulation system pH value is to 4~10, in favor of the water of amino silicane coupling agent
Solution.It is further preferred that the amino silicane coupling agent is selected from λ-aminopropyl triethoxysilane (KH550), λ-aminopropyl
One trimethoxy silane (APS) or N-(β-aminoethyl)-λ-aminopropyl trimethoxysilane (A1120).
According to currently preferred, in the step (1), amino in the aluminum oxide suspension that described amino surface is modified
The concentration of modified aluminum oxide is 1~5mg/mL；The pH value of suspension is adjusted to 3~5；The watery hydrochloric acid mass percent is
1%~5%.
According to currently preferred, in the step (1), it is described with absolute ethyl alcohol centrifuge washing three times.
Further technical scheme is, in the step (2), the mass ratio of graphite and sodium nitrate is 1~3：1~3, graphite
Mass ratio with potassium permanganate is 1~3：2~6, the mass volume ratio of graphite and the concentrated sulfuric acid is 1~3g：60~360mL；It is described
The mass fraction of the concentrated sulfuric acid is 90~98%.
Further technical scheme is, in the step (2), the mass fraction of hydrogen peroxide is 15%~30%, deionization
The volume ratio of water and hydrogen peroxide is 120~400：10~30；The mass fraction of watery hydrochloric acid is 2%~6%.
Further technical scheme is, in the step (2), time of ultrasonic disperse is 60~120min, graphite oxide
The concentration of graphene oxide is 0.5~2mg/mL in alkene dispersion liquid；The pH value of graphene oxide dispersion is adjusted to 8~10；It is logical
Cross the pH value that ammonia spirit regulation graphene oxide dispersion is added dropwise.Preferable ph regulation is with the mass fraction of ammonia spirit
15-25%.
It is further preferred that the mass ratio of amino surface modified aluminas and graphene oxide described in step (3) is (15
~25)：1.
Further technical scheme is, in the step (3), the temperature of the high temperature reduction processing is 500~600 DEG C.
Processing time is 1~24h.The protective atmosphere of high temperature reduction processing is one of nitrogen, argon gas or combination.
Based on above-mentioned preparation method, the present invention also provides a kind of graphene coated alumina ceramic powder.It is used as above
Described preparation method is made.
Graphene coated alumina ceramic powder of the present invention is used to prepare aluminum oxide base ceramics cutting tool material.
The technical characterstic and excellent results of the present invention：
The present invention prepares graphene coated alumina ceramic powder using electrostatic self-assembled method, compared with prior art, this
The advantage of invention is：
1st, the present invention is first calcined to go deoxygenation before graphene coated alumina powder is prepared to alumina powder
Change the impurity of aluminium powder surface, the inventors discovered that surface amino groups silicon of the alumina powder surface impurity to subsequent oxidation aluminium powder body
Alkanisation has larger adverse effect.Oxidation processes are carried out to alumina powder surface with hydrogen peroxide again after calcination process, pass through this
Mode causes the surface of alumina powder to obtain more sufficient activity hydroxy, is advantageous to amino silicane coupling agent to alumina powder
The Aminosilylation on surface.On the other hand, the hydrolysis of amino silicane coupling agent is that amino silicane coupling agent enters to alumina powder
The basis of row Aminosilylation effect, the present invention is before amino silicane coupling agent is to alumina powder surface modification, to influenceing
Improvement is optimized in the influence factor of amino silicane coupling agent hydrolysis, to be advantageous to amino silicane coupling agent to alumina powder
The Aminosilylation on surface.
2nd, the present invention has been surprisingly found that oxidation graphite alkene and amino table during graphene coated alumina powder is prepared
The mass ratio for the aluminum oxide that face is modified is one of key factor for influenceing composite granule performance.When the aluminum oxide that amino surface is modified
It is more than 30 with the mass ratio of graphene oxide：When 1, cause alumina powder can not be by oxygen because the amount of graphene oxide is fewer
Graphite alkene is fully wrapped around；When the aluminum oxide and the mass ratio of graphene oxide that amino surface is modified are 20:When 1 or so, oxidation
Aluminium powder body is almost completely covered by graphene oxide in uniform thickness；When the aluminum oxide and graphene oxide that amino surface is modified
Mass ratio is less than 10：When 1, although alumina powder can be oxidized, graphene is fully wrapped around, causes excessive oxidation stone
Black alkene can not be adhered to the surface of alumina powder, nonadherent graphene oxide because the effect of Van der Waals force causes reunion,
The effect of dispersed graphite alkene can not be realized.
3rd, the present invention uses high temperature reduction graphene oxide, and virose chemical reagent is used also relative in prior art
Former graphene oxide, this method have more security and the feature of environmental protection.
4th, graphene coated alumina ceramic powder prepared by the present invention is used to prepare alumina tool material, can make
Graphene uniform is scattered in alumina-based ceramic, and the combination property of the alumina-based ceramic of preparation, which obtains, greatly to be carried
Height, particularly bending resistance slightly and fracture toughness than pure alumina ceramic cutting tool material raising 0.5-1 times and more than.
Brief description of the drawings
Fig. 1 is the low power transmission electron microscope picture of obtained graphene coated alumina ceramic powder in embodiment 1.
Fig. 2 is the high power transmission electron microscope picture of obtained graphene coated alumina ceramic powder in embodiment 1.
Fig. 3 is the XRD diffraction patterns of obtained graphene coated alumina ceramic powder in embodiment 2.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
A kind of preparation method of graphene coated alumina ceramic powder, its step are as follows：
(1) aluminum oxide suspension of amino surface modification is prepared
The alumina powder of selection is the α-Al that average grain diameter is 100nm2O3, the alumina powder is roasted at 500 DEG C
6h is burnt, to remove the impurity on alumina powder surface, is added in the hydrogen peroxide of mass fraction 10%, enters after being cooled to room temperature
Row oxidation processes, 35min is stirred by ultrasonic, with absolute ethyl alcohol centrifuge washing three times, vacuum drying；By oxidation-treated aluminum oxide
It is 1 that powder, which is added to absolute ethyl alcohol with deionized water volume ratio,：In 1 mixed solution, the matter of the aluminum oxide and absolute ethyl alcohol
Amount volume ratio is 0.1g：100mL；Amino silicane coupling agent is slowly added dropwise thereto, the amino silicane coupling agent is λ-ammonia third
Ethyl triethoxy silicane alkane (KH550)；The mass volume ratio of the aluminum oxide and amino silicane coupling agent is 0.1g：2mL, drip simultaneously
Adding the pH value of pH adjusting agent regulation system, the pH value regulator is glacial acetic acid to 4.It is added dropwise to complete rear ultrasonic 10min, Ran Hou
Stir process 5h under temperature 60 C, vacuum drying obtain the aluminum oxide of amino surface modification with absolute ethyl alcohol centrifuge washing three times
Powder；
The alumina powder that obtained amino surface is modified is added in deionized water, ultrasonic disperse 10min, obtains ammonia
Primary surface be modified aluminum oxide suspension, described amino surface be modified aluminum oxide suspension in amino surface modified aluminas
Concentration be 1mg/mL；The pH value of dilute hydrochloric acid solution regulation suspension of mass percent 1% is added dropwise thereto to 3, makes above-mentioned
Suspension is in electropositive；
(2) graphene oxide dispersion is prepared
Under conditions of ice-water bath, graphite and sodium nitrate, graphite and nitre are added into the concentrated sulfuric acid that mass fraction is 90%
The mass ratio of sour sodium is 1：1, the mass volume ratio of graphite and the concentrated sulfuric acid is 1g：60mL, stir, be then slow added into oxygen
The mass ratio of agent potassium permanganate, graphite and potassium permanganate is 1：2,30min is persistently stirred, mixture is heated up and is maintained at 40
DEG C, 8h is stirred, adds deionized water to dilute obtained reactant, is heated to more than 98 DEG C, 30min is stirred, then cools down
To 45 DEG C, the hydrogen peroxide of mass fraction 15%, the deionized water of dilution and the volume of the hydrogen peroxide are added after stable reaction
Than for 120：10, products therefrom is washed with the watery hydrochloric acid of mass fraction 2%, then is cleaned repeatedly to neutrality, centrifugation with deionized water
Isolated graphene oxide；
Add graphene oxide into deionized water, ultrasonic disperse 60min, obtain graphene oxide dispersion, aoxidize
The concentration of graphene oxide is 0.5mg/mL in graphene dispersing solution；The ammonia spirit that mass fraction is 15% is added dropwise thereto to adjust
The pH value of graphene oxide dispersion is saved to 8 so that graphene oxide dispersion is in elecrtonegativity；
(3) graphene coated alumina ceramic powder is prepared
The aluminum oxide suspension that obtained amino surface is modified in step (1) is slowly dropped under ultrasound and stirring condition
In step (2) in obtained graphene oxide dispersion, the mass ratio of the amino surface modified aluminas and graphene oxide
For 30：1.Centrifuged after dripping, dry, that is, obtain graphene oxide coated aluminum oxide ceramic powder；The graphite oxide that will be obtained
Alkene coated aluminum oxide composite granule carries out high temperature reduction processing under nitrogen protection atmosphere, and treatment temperature is 300 DEG C, and the time is
1h, obtain graphene coated alumina ceramic powder.
The average grain diameter of gained graphene coated alumina ceramic powder is about 105nm, and alumina powder is by graphene bag
Wrap up in, well dispersed, crystallinity is high.Products obtained therefrom transmission electron microscope picture is as illustrated in fig. 1 and 2.
Embodiment 2
A kind of preparation method of graphene coated alumina ceramic powder, its step are as follows：
(1) aluminum oxide suspension of amino surface modification is prepared
The alumina powder of selection is the α-Al that average grain diameter is 200nm2O3, the alumina powder is roasted at 750 DEG C
9h is burnt, to remove the impurity on alumina powder surface, is added in the hydrogen peroxide of mass fraction 20%, enters after being cooled to room temperature
Row oxidation processes, 45min is stirred by ultrasonic, with absolute ethyl alcohol centrifuge washing three times, vacuum drying；By oxidation-treated aluminum oxide
It is 1 that powder, which is added to absolute ethyl alcohol with deionized water volume ratio,：In 1 mixed solution, the matter of the aluminum oxide and absolute ethyl alcohol
Amount volume ratio is 0.3g：150mL；Amino silicane coupling agent is slowly added dropwise thereto, the amino silicane coupling agent is λ-ammonia third
The trimethoxy silane of base one (APS)；The mass volume ratio of the aluminum oxide and amino silicane coupling agent is 0.1g：2mL, drip simultaneously
Adding the pH value of pH adjusting agent regulation system, the pH value regulator is glacial acetic acid to 7.It is added dropwise to complete rear ultrasonic 20min, Ran Hou
Stir process 8.5h at 90 DEG C of temperature, vacuum drying obtain the oxidation of amino surface modification with absolute ethyl alcohol centrifuge washing three times
Aluminium powder body；
The alumina powder that obtained amino surface is modified is added in deionized water, ultrasonic disperse 10min, obtains ammonia
Primary surface be modified aluminum oxide suspension, described amino surface be modified aluminum oxide suspension in amino surface modified aluminas
Concentration be 1mg/mL；The pH value of dilute hydrochloric acid solution regulation suspension of mass percent 3% is added dropwise thereto to 4, makes above-mentioned
Suspension is in electropositive；
(2) graphene oxide dispersion is prepared
Under conditions of ice-water bath, graphite and sodium nitrate, graphite and nitre are added into the concentrated sulfuric acid that mass fraction is 95%
The mass ratio of sour sodium is 2：2, the mass volume ratio of graphite and the concentrated sulfuric acid is 2g：240mL, stir, be then slow added into
The mass ratio of oxidant potassium permanganate, graphite and potassium permanganate is 2：4,45min is persistently stirred, mixture is heated up and is maintained at
55 DEG C, 10h is stirred, adds deionized water to dilute obtained reactant, be heated to more than 98 DEG C, stir 45min, Ran Houleng
But to 55 DEG C, the hydrogen peroxide of mass fraction 20%, the deionized water of dilution and the body of the hydrogen peroxide are added after stable reaction
Product is than being 260：20, products therefrom is washed with the watery hydrochloric acid of mass fraction 4%, then is cleaned repeatedly to neutrality with deionized water, from
The isolated graphene oxide of the heart；
Add graphene oxide into deionized water, ultrasonic disperse 60min, obtain graphene oxide dispersion, aoxidize
The concentration of graphene oxide is 1.25mg/mL in graphene dispersing solution；The ammonia spirit that mass fraction is 20% is added dropwise thereto
The pH value of graphene oxide dispersion is adjusted to 9 so that graphene oxide dispersion is in elecrtonegativity；
(3) graphene coated alumina ceramic powder is prepared
The aluminum oxide suspension that obtained amino surface is modified in step (1) is slowly dropped under ultrasound and stirring condition
In step (2) in obtained graphene oxide dispersion, the mass ratio of the amino surface modified aluminas and graphene oxide
For 20：1.Centrifuged after dripping, dry, that is, obtain graphene oxide coated aluminum oxide ceramic powder；The graphite oxide that will be obtained
Alkene coated aluminum oxide composite granule carries out high temperature reduction processing under argon atmosphere, and treatment temperature is 550 DEG C, and the time is
12h, obtain graphene coated alumina ceramic powder.
The average grain diameter of gained graphene coated alumina ceramic powder is about 208nm, and alumina powder is oxidized graphite
Alkene is fully wrapped around.Product XRD diffraction patterns are as shown in Figure 3.
The average grain diameter of gained graphene coated alumina ceramic powder is about 208nm, and alumina powder is complete by graphene
Full parcel, well dispersed, crystallinity is high.Products obtained therefrom XRD diffraction patterns are as shown in Figure 3.
Embodiment 3：As described in Example 2, except that changing aluminum oxide and the oxidation graphite that amino surface is modified
The mass ratio of alkene is 15:1.Gained graphene coated alumina ceramic powder average grain diameter is about 205nm, well dispersed, crystallization
Degree is high.Alumina powder is wrapped up by graphene.
Embodiment 4：As described in Example 2, except that changing aluminum oxide and the oxidation graphite that amino surface is modified
The mass ratio of alkene is 25:1.Gained graphene coated alumina ceramic powder average grain diameter is about 210nm, well dispersed, crystallization
Degree is high.It is fully wrapped around that alumina powder is oxidized graphene.
Embodiment 5
A kind of preparation method of graphene coated alumina ceramic powder, its step are as follows：
(1) aluminum oxide suspension of amino surface modification is prepared
The alumina powder of selection is the α-Al that average grain diameter is 500nm2O3, by the alumina powder at 1000 DEG C
9h is calcined, to remove the impurity on alumina powder surface, is added to after being cooled to room temperature in the hydrogen peroxide of mass fraction 30%,
Oxidation processes are carried out, 55min is stirred by ultrasonic, with absolute ethyl alcohol centrifuge washing three times, vacuum drying；By oxidation-treated oxidation
It is 1 that aluminium powder body, which is added to absolute ethyl alcohol with deionized water volume ratio,：In 1 mixed solution, the aluminum oxide and absolute ethyl alcohol
Mass volume ratio is 0.5g：200mL；Be slowly added dropwise amino silicane coupling agent thereto, the amino silicane coupling agent be N-
(β-aminoethyl)-λ-aminopropyl trimethoxysilane (A1120)；The mass body of the aluminum oxide and amino silicane coupling agent
Product ratio is 0.5g：6mL, while the pH value of pH adjusting agent regulation system is added dropwise to 10, the pH value regulator is ammoniacal liquor.Drip
Into rear ultrasonic 30min, then the stir process 12h at 120 DEG C of temperature, is dried in vacuo with absolute ethyl alcohol centrifuge washing three times
The alumina powder being modified to amino surface；
The alumina powder that obtained amino surface is modified is added in deionized water, ultrasonic disperse 30min, obtains ammonia
Primary surface be modified aluminum oxide suspension, described amino surface be modified aluminum oxide suspension in amino surface modified aluminas
Concentration be 5mg/mL；The pH value of dilute hydrochloric acid solution regulation suspension of mass percent 5% is added dropwise thereto to 5, makes above-mentioned
Suspension is in electropositive；
(2) graphene oxide dispersion is prepared
Under conditions of ice-water bath, graphite and sodium nitrate, graphite and nitre are added into the concentrated sulfuric acid that mass fraction is 98%
The mass ratio of sour sodium is 3：3, the mass volume ratio of graphite and the concentrated sulfuric acid is 3g：360mL, stir, be then slow added into
The mass ratio of oxidant potassium permanganate, graphite and potassium permanganate is 2：6,60min is persistently stirred, mixture is heated up and is maintained at
60 DEG C, 12h is stirred, adds deionized water to dilute obtained reactant, be heated to more than 98 DEG C, stir 60min, Ran Houleng
But to 65 DEG C, the hydrogen peroxide of mass fraction 30%, the deionized water of dilution and the body of the hydrogen peroxide are added after stable reaction
Product is than being 400：30, products therefrom is washed with the watery hydrochloric acid of mass fraction 6%, then is cleaned repeatedly to neutrality with deionized water, from
The isolated graphene oxide of the heart；
Add graphene oxide into deionized water, ultrasonic disperse 60min, obtain graphene oxide dispersion, aoxidize
The concentration of graphene oxide is 2mg/mL in graphene dispersing solution；The ammonia spirit that mass fraction is 25% is added dropwise thereto to adjust
The pH value of graphene oxide dispersion is to 10 so that graphene oxide dispersion is in elecrtonegativity；
(3) graphene coated alumina ceramic powder is prepared
The aluminum oxide suspension that obtained amino surface is modified in step (1) is slowly dropped under ultrasound and stirring condition
In step (2) in obtained graphene oxide dispersion, the mass ratio of the amino surface modified aluminas and graphene oxide
For 20：1.Centrifuged after dripping, dry, that is, obtain graphene oxide coated aluminum oxide ceramic powder；The graphite oxide that will be obtained
Alkene coated aluminum oxide composite granule carries out high temperature reduction processing, treatment temperature 800 under nitrogen and argon gas hybrid protection atmosphere
DEG C, time 24h, obtain graphene coated alumina ceramic powder.
Application examples：
The graphene coated alumina ceramic powder prepared in embodiment 1,2,3,4,5 is added to alumina-based ceramic knife
Have in material, accordingly, be designated as application examples 1,2,3,4,5, sintex mass percent formula is graphene coated aluminum oxide
20%, magnesia 0.25%, molybdenum 1.05%, nickel 1.5%, remaining is micrometer alumina；Hot-pressing sintering technique condition：Sintering temperature
For 1550 ± 20 DEG C, soaking time 25min, pressure 25MPa.The mechanical property of gained ceramic cutting tool material is as shown in table 1.
Comparative example：Change the graphene coated aluminum oxide of addition into the graphene (specification of graphene：0.5~5 μm of piece footpath,
Thickness 0.8-1.2nm), formula is same as above with sintering process conditions, is designated as application examples 6.The mechanical property of gained ceramic cutting tool material
As shown in table 2.
The aluminum oxide base ceramics cutting tool mechanical property inspection of the application examples 1-5 of table 1 addition graphene coated alumina ceramic powders
Survey result
Table 2 directly adds the aluminum oxide base ceramics cutting tool mechanics properties testing result of graphene
Hardness, fracture toughness, the bending strength of above cutter material are perpendicular on hot pressing direction.
Claims (10)
1. a kind of preparation method of graphene coated alumina ceramic powder, including step：
(1) aluminum oxide suspension of amino surface modification is prepared
Alumina powder is calcined 6~12h at 500~1000 DEG C, is added to after being cooled to room temperature in hydrogen peroxide, carries out oxygen
Change is handled, and 35~55min is stirred by ultrasonic, with absolute ethyl alcohol centrifuge washing, vacuum drying；By oxidation-treated alumina powder
It is added in absolute ethyl alcohol and the mixed solution of deionized water, amino silicane coupling agent is slowly added dropwise thereto, while pH is added dropwise
The pH value of conditioning agent regulation system, the mass volume ratio of the alumina powder and amino silicane coupling agent is 0.1~0.5g：2
~6mL；10~30min of ultrasound after being added dropwise to complete, then 5~12h of stir process at 60~120 DEG C of temperature, uses absolute ethyl alcohol
Centrifuge washing, vacuum drying obtain the alumina powder of amino surface modification；
The alumina powder that obtained amino surface is modified is added in deionized water, 10~30min of ultrasonic disperse, obtains ammonia
The aluminum oxide suspension that primary surface is modified, the pH value of dilute hydrochloric acid solution regulation suspension is added dropwise thereto, makes the above-mentioned suspension be in
Electropositive；
(2) graphene oxide dispersion is prepared
Under the conditions of ice-water bath, graphite and sodium nitrate are added into the concentrated sulfuric acid, stirs, is then slow added into oxidant height
Potassium manganate, 30~60min is persistently stirred, mixture is heated up and is maintained at 40~60 DEG C, 8~12h of stirring, the reaction that will be obtained
Thing adds deionized water to dilute, and is heated to more than 98 DEG C, stirs 30~60min, is subsequently cooled to 45~65 DEG C, adds dioxygen
Water, the deionized water of the dilution and the volume ratio of hydrogen peroxide are 120~400：10~30, products therefrom is washed with watery hydrochloric acid
Wash, then cleaned repeatedly to neutrality with deionized water, be centrifugally separating to obtain graphene oxide；
Add graphene oxide into deionized water, 60~120min of ultrasonic disperse, obtain graphene oxide dispersion, Xiang Qi
The middle pH value that ammonia spirit regulation graphene oxide dispersion is added dropwise so that graphene oxide dispersion is in elecrtonegativity；
(3) graphene coated alumina ceramic powder is prepared
The aluminum oxide suspension that obtained amino surface is modified in step (1) is slowly dropped into step under ultrasound and stirring condition
(2) in obtained graphene oxide dispersion, the mass ratio of the amino surface modified aluminas and graphene oxide is 10
~30：1, centrifuged after dripping, dry, that is, obtain graphene oxide coated aluminum oxide ceramic powder；The graphite oxide that will be obtained
Alkene coated aluminum oxide composite granule carries out high temperature reduction processing under protective atmosphere in 300~800 DEG C, obtains graphene coated oxidation
Aluminium ceramic powder.
2. the preparation method of graphene coated alumina ceramic powder as claimed in claim 1, it is characterised in that step (1)
In, alumina powder uses α-Al of the average grain diameter for 100~500nm2O3；The mass fraction of hydrogen peroxide solution is 10~30%.
3. the preparation method of graphene coated alumina ceramic powder as claimed in claim 1, it is characterised in that step (1)
In, in the mixed solution of the absolute ethyl alcohol and deionized water, absolute ethyl alcohol is 1 with deionized water volume ratio：1；Preferably, institute
It is glacial acetic acid or ammoniacal liquor to state pH value regulator.
4. the preparation method of graphene coated alumina ceramic powder as claimed in claim 1, it is characterised in that step (1)
In, the mass volume ratio of the aluminum oxide and absolute ethyl alcohol is 0.1~0.5g：100~200mL.
5. the preparation method of graphene coated alumina ceramic powder as claimed in claim 1, it is characterised in that step (1)
In, the mass volume ratio of the aluminum oxide and amino silicane coupling agent is 0.1~0.3g：2~5mL；Preferably, the amino silicone
Alkane coupling agent is selected from λ-aminopropyl triethoxysilane, the trimethoxy silane of λ-aminopropyl one) or N-(β-aminoethyl)-
λ-aminopropyl trimethoxysilane.
6. the preparation method of graphene coated alumina ceramic powder as claimed in claim 1, it is characterised in that step (1)
In, the concentration of amino surface modified aluminas is 1~5mg/mL in the aluminum oxide suspension that described amino surface is modified；Regulation
The pH value of suspension is to 3~5.
7. the preparation method of graphene coated alumina ceramic powder as claimed in claim 1, it is characterised in that step (2)
In, the mass ratio of graphite and sodium nitrate is 1~3：1~3, the mass ratio of graphite and potassium permanganate is 1~3：2~6, graphite with it is dense
The mass volume ratio of sulfuric acid is 1~3g：60~360mL.
8. the preparation method of graphene coated alumina ceramic powder as claimed in claim 1, it is characterised in that step (2)
In, the mass fraction of hydrogen peroxide is 15%~30%, and the volume ratio of deionized water and hydrogen peroxide is 120~400：10~30；It is excellent
Choosing, time of ultrasonic disperse is 60~120min, and the concentration of graphene oxide is 0.5~2mg/ in graphene oxide dispersion
mL；The pH value of graphene oxide dispersion is adjusted to 8~10.
9. the preparation method of graphene coated alumina ceramic powder as claimed in claim 1, it is characterised in that step (3)
In, the mass ratio of the amino surface modified aluminas and graphene oxide is 15~25：1.
10. a kind of graphene coated alumina ceramic powder, the preparation method according to any one of claim 1~9 are made；
The graphene coated alumina ceramic powder is used to prepare aluminum oxide base ceramics cutting tool material.
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