CN107353017B - Graphene-coated aluminum oxide ceramic powder and preparation method and application thereof - Google Patents
Graphene-coated aluminum oxide ceramic powder and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to graphene-coated alumina ceramic powder and a preparation method and application thereof. The preparation method comprises the following steps: (1) preparing an amino surface modified alumina suspension; (2) preparing a graphene oxide dispersion liquid; (3) preparing the graphene-coated alumina ceramic powder. The method can simply and quickly obtain the graphene-coated alumina ceramic powder, so that the graphene is uniformly coated on the surface of the alumina powder, the dispersity between the graphene and the alumina powder and the mixing uniformity of the graphene and the alumina powder are improved, the problems of easy agglomeration and poor dispersity of the graphene in the alumina-based ceramic material are solved, and meanwhile, the method has the advantages of wide raw material source, low price, production cost reduction, simple process, easily controlled parameters, safe and environment-friendly production process and suitability for large-scale industrial production.
Description
Technical Field
The invention relates to graphene-coated alumina ceramic powder and a preparation method and application thereof, belonging to the technical field of ceramic composite materials.
Background
Graphene (Graphene) is an ideal two-dimensional crystal having a regular hexagonal symmetric structure, which is formed by bonding a single layer of carbon atoms by covalent bonds. Due to the unique two-dimensional crystal structure and the excellent crystal quality, the graphene has excellent mechanical, electric and heat conducting properties and is widely applied to the field of composite materials. For example, CN104538639A provides a graphene-coated alumina for lithium ion batteries and a preparation method thereof, LPAN is used as a carbon source, and a metal dopant or a non-metal dopant is added, the graphene-coated and modified alumina material prepared by the method has dual properties of heat conduction and electric conduction, the powder can be well infiltrated with the electrolyte of the lithium ion battery, the internal resistance of the lithium ion battery can be greatly reduced, and the capacity and cycle performance of the battery are stable.
Graphene is a novel nano material which is thinnest, high in strength and good in heat conducting property in the natural world at present and has excellent lubricating property, but the graphene is easy to oxidize when being added into a ceramic matrix as a lubricant, and in order to improve the oxidation resistance of the graphene, a layer of aluminum oxide is reported to be coated on the surface of the graphene, for example, CN106431361A discloses a self-lubricating ceramic cutter material added with aluminum oxide coated graphene, wherein the material takes micron-scale aluminum oxide as a matrix, micron-scale silicon nitride reinforcement, nano-scale aluminum oxide toughening reinforcement and aluminum oxide coated graphene lubricating property are combined, yttrium oxide is taken as a sintering aid, and the ceramic composite material is prepared through vacuum hot-pressing sintering.
On the other hand, graphene is also a good reinforcement for ceramic materials. For example, CN106007762A discloses a graphene nanosheet toughened alumina ceramic cutting tool and a hot-pressing sintering preparation process thereof, wherein the ceramic cutting tool is made of Al2O3The graphene nano-sheet is taken as a matrix, a graphene nano-sheet is taken as a reinforcing phase, a certain amount of metal binder and sintering aid are added, and the graphene nano-sheet is prepared by adopting a hot-pressing technology. In terms of mechanical properties: graphene-added Al2O3The fracture toughness and the bending strength of the nano composite ceramic cutter material in the direction perpendicular to the hot pressing direction are respectively improved by 38 percent and 39 percent compared with the fracture toughness and the bending strength in the direction parallel to the hot pressing direction. Thus, graphene-toughened Al2O3Anisotropy of mechanical properties occurs in the nano composite ceramic cutting tool material.
However, since graphene has a large specific surface area and a high surface energy, graphene cannot be uniformly dispersed in a ceramic matrix by using conventional methods such as ball milling and mixing, and the agglomeration of graphene causes structural defects such as pores, so that a good contact interface cannot be formed between graphene and the ceramic matrix, the microstructure of graphene is damaged, and the improvement of the performance of the composite material is affected. Therefore, improving the dispersion uniformity of graphene in the ceramic matrix becomes a prerequisite for preparing the graphene toughened ceramic material.
Disclosure of Invention
In order to avoid the defects in the prior art, the invention provides graphene-coated alumina ceramic powder for preparing an alumina-based ceramic cutting tool material and a preparation method thereof, and the problems of easy agglomeration and poor dispersibility of graphene in the existing graphene ceramic composite material are solved by utilizing the mutual electrostatic interaction between graphene oxide and aminated alumina powder.
Description of terms:
room temperature: have the meaning well known in the art; typically 25. + -. 3 ℃.
The technical scheme of the invention is as follows:
a preparation method of graphene-coated alumina ceramic powder comprises the following steps:
(1) preparation of amino surface-modified alumina suspensions
Roasting the alumina powder at 500-1000 ℃ for 6-12 h, cooling to room temperature, adding into hydrogen peroxide, carrying out oxidation treatment, ultrasonically stirring for 35-55 min, centrifugally washing with absolute ethyl alcohol, and vacuum drying; adding oxidized aluminum oxide powder into a mixed solution of absolute ethyl alcohol and deionized water, slowly dropwise adding an aminosilane coupling agent into the mixed solution, and dropwise adding a pH regulator to regulate the pH value of a system, wherein the mass-to-volume ratio of the oxidized aluminum powder to the aminosilane coupling agent is (0.1-0.5 g): 2-6 mL; after the dropwise addition is finished, performing ultrasonic treatment for 10-30 min, then stirring at the temperature of 60-120 ℃ for 5-12 h, performing centrifugal washing with absolute ethyl alcohol, and performing vacuum drying to obtain amino surface modified alumina powder;
adding the prepared amino surface modified alumina powder into deionized water, performing ultrasonic dispersion for 10-30 min to obtain an amino surface modified alumina suspension, and dropwise adding a dilute hydrochloric acid solution to adjust the pH value of the suspension so that the suspension is electropositive;
(2) preparation of graphene oxide Dispersion
Under the condition of ice-water bath, adding graphite and sodium nitrate into concentrated sulfuric acid, stirring uniformly, then slowly adding an oxidant potassium permanganate, continuously stirring for 30-60 min, heating the mixture to 40-60 ℃, stirring for 8-12 h, diluting the obtained reactant with deionized water, heating to above 98 ℃, stirring for 30-60 min, cooling to 45-65 ℃, adding hydrogen peroxide, wherein the volume ratio of the diluted deionized water to the hydrogen peroxide is 120-400: 10-30, washing the obtained product with dilute hydrochloric acid, repeatedly washing the product with deionized water to be neutral, and performing centrifugal separation to obtain graphene oxide;
adding graphene oxide into deionized water, performing ultrasonic dispersion for 60-120 min to obtain a graphene oxide dispersion liquid, and dropwise adding an ammonia water solution to adjust the pH value of the graphene oxide dispersion liquid so that the graphene oxide dispersion liquid is electronegative;
(3) preparation of graphene-coated alumina ceramic powder
Slowly dropping the amino surface modified alumina suspension prepared in the step (1) into the graphene oxide dispersion prepared in the step (2) under the conditions of ultrasound and stirring, wherein the mass ratio of the amino surface modified alumina to the graphene oxide is 10-30: 1, centrifuging and drying after dripping to obtain graphene oxide coated alumina ceramic powder; and carrying out high-temperature reduction treatment on the obtained graphene oxide-coated aluminum oxide composite powder at the temperature of 300-800 ℃ in a protective atmosphere to obtain graphene-coated aluminum oxide ceramic powder.
According to the invention, in the step (1), alpha-Al with the average grain diameter of 100-500 nm is preferably adopted as the alumina powder2O3(ii) a The mass fraction of the hydrogen peroxide solution is 10-30%. Further preferably, in the mixed solution of absolute ethyl alcohol and deionized water, the volume ratio of absolute ethyl alcohol to deionized water is 1: 1, the pH value regulator is glacial acetic acid or ammonia water.
According to the invention, in the step (1), the mass volume ratio of the alumina to the absolute ethyl alcohol is 0.1-0.5 g: 100-200 mL;
according to the invention, in the step (1), the mass volume ratio of the alumina to the aminosilane coupling agent is 0.1-0.3 g: 2-5 mL; further preferably, the pH value of the system is adjusted to 4-10, so that the hydrolysis of the aminosilane coupling agent is facilitated. Further preferably, the aminosilane coupling agent is selected from the group consisting of lambda-aminopropyltriethoxysilane (KH550), lambda-aminopropyl-trimethoxysilane (APS) or N- (beta-aminoethyl) -lambda-aminopropyltrimethoxysilane (A1120).
Preferably, in the step (1), the concentration of the amino surface modified alumina in the amino surface modified alumina suspension is 1-5 mg/mL; adjusting the pH value of the suspension to 3-5; the mass percentage of the dilute hydrochloric acid is 1-5%.
According to the invention, in the step (1), the washing is performed by centrifugation with absolute ethyl alcohol three times.
The further technical scheme is that in the step (2), the mass ratio of graphite to sodium nitrate is 1-3: 1-3, wherein the mass ratio of graphite to potassium permanganate is 1-3: 2-6, wherein the mass-to-volume ratio of the graphite to the concentrated sulfuric acid is 1-3 g: 60-360 mL; the mass fraction of the concentrated sulfuric acid is 90-98%.
The further technical scheme is that in the step (2), the mass fraction of the hydrogen peroxide is 15% -30%, and the volume ratio of the deionized water to the hydrogen peroxide is 120-400: 10-30; the mass fraction of the dilute hydrochloric acid is 2-6%.
The further technical scheme is that in the step (2), the ultrasonic dispersion time is 60-120 min, and the concentration of graphene oxide in the graphene oxide dispersion liquid is 0.5-2 mg/mL; adjusting the pH value of the graphene oxide dispersion liquid to 8-10; and (3) dropwise adding an ammonia water solution to adjust the pH value of the graphene oxide dispersion liquid. The mass fraction of the ammonia aqueous solution for pH adjustment is preferably 15 to 25%.
Further preferably, the mass ratio of the amino surface modified alumina to the graphene oxide in the step (3) is (15-25): 1.
the further technical scheme is that in the step (3), the temperature of the high-temperature reduction treatment is 500-600 ℃. The treatment time is 1-24 h. The protective atmosphere of the high-temperature reduction treatment is one or a combination of nitrogen and argon.
Based on the preparation method, the invention also provides the graphene-coated aluminum oxide ceramic powder. It is prepared by the preparation method.
The graphene-coated alumina ceramic powder is used for preparing an alumina-based ceramic cutter material.
The invention has the technical characteristics and excellent effects that:
compared with the prior art, the method for preparing the graphene-coated alumina ceramic powder by adopting the electrostatic self-assembly method has the advantages that:
1. according to the invention, before the graphene-coated alumina powder is prepared, the alumina powder is roasted to remove impurities on the surface of the alumina powder, and the inventors find that the impurities on the surface of the alumina powder have a great adverse effect on the surface amino silanization of the subsequent alumina powder. And oxidizing the surface of the alumina powder by using hydrogen peroxide after roasting treatment, so that the surface of the alumina powder obtains more sufficient active hydroxyl groups, and amino silanization of the amino silane coupling agent on the surface of the alumina powder is facilitated. On the other hand, the hydrolysis of the aminosilane coupling agent is the basis of the aminosilane coupling agent for performing aminosilane action on the alumina powder, and the influence factors influencing the hydrolysis of the aminosilane coupling agent are optimized and improved before the aminosilane coupling agent modifies the surface of the alumina powder, so that the aminosilane coupling agent is favorable for performing aminosilane action on the surface of the alumina powder.
2. In the process of preparing the graphene-coated alumina powder, the invention unexpectedly discovers that the mass ratio of the oxidized graphene to the amino surface modified alumina is one of the key factors influencing the performance of the composite powder. When the mass ratio of the amino surface modified alumina to the graphene oxide is more than 30: 1, the alumina powder cannot be completely wrapped by the graphene oxide due to the small amount of the graphene oxide; when the mass ratio of the amino surface modified alumina to the graphene oxide is about 20:1, the alumina powder is almost completely covered by the graphene oxide with uniform thickness; when the mass ratio of the amino surface modified alumina to the graphene oxide is less than 10: in case 1, the alumina powder can be completely wrapped with graphene oxide, but excessive graphene oxide cannot adhere to the surface of the alumina powder, and the unadhered graphene oxide is agglomerated due to van der waals' force, so that the effect of dispersing graphene cannot be achieved.
3. Compared with the prior art in which the graphene oxide is reduced by using a toxic chemical reagent, the method has the advantages of higher safety and environmental friendliness.
4. The graphene-coated alumina ceramic powder prepared by the invention is used for preparing an alumina ceramic cutter material, and can uniformly disperse graphene in alumina-based ceramic, so that the comprehensive performance of the prepared alumina-based ceramic is greatly improved, and particularly, the bending strength and the fracture toughness of the prepared alumina-based ceramic are improved by 0.5-1 time and more than that of a pure alumina ceramic cutter material.
Drawings
Fig. 1 is a low power transmission electron micrograph of the graphene-coated alumina ceramic powder obtained in example 1.
Fig. 2 is a high-power transmission electron micrograph of the graphene-coated alumina ceramic powder obtained in example 1.
Fig. 3 is an XRD diffractogram of the graphene-coated alumina ceramic powder prepared in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of graphene-coated alumina ceramic powder comprises the following steps:
(1) preparation of amino surface-modified alumina suspensions
The selected alumina powder is alpha-Al with the average grain diameter of 100nm2O3Roasting the alumina powder at 500 ℃ for 6h to remove impurities on the surface of the alumina powder, cooling to room temperature, adding the cooled alumina powder into hydrogen peroxide with the mass fraction of 10%, carrying out oxidation treatment, carrying out ultrasonic stirring for 35min, carrying out centrifugal washing with absolute ethyl alcohol for three times, and carrying out vacuum drying; adding the oxidized alumina powder into the mixture of absolute ethyl alcohol and deionized water according to the volume ratio of 1: 1, the mass volume ratio of the alumina to the absolute ethyl alcohol is 0.1 g: 100 mL; slowly dripping an aminosilane coupling agent into the aqueous solution, wherein the aminosilane coupling agent is lambda-aminopropyl triethoxysilane (KH 550);the mass volume ratio of the alumina to the aminosilane coupling agent is 0.1 g: 2mL, and simultaneously dropwise adding a pH regulator to regulate the pH value of the system to 4, wherein the pH regulator is glacial acetic acid. Performing ultrasonic treatment for 10min after the dropwise addition is finished, then stirring and treating for 5h at the temperature of 60 ℃, performing centrifugal washing for three times by using absolute ethyl alcohol, and performing vacuum drying to obtain amino surface modified alumina powder;
adding the prepared amino surface modified alumina powder into deionized water, and performing ultrasonic dispersion for 10min to obtain amino surface modified alumina suspension, wherein the concentration of amino surface modified alumina in the amino surface modified alumina suspension is 1 mg/mL; dropwise adding a dilute hydrochloric acid solution with the mass percent of 1% to adjust the pH value of the suspension to 3, so that the suspension is electropositive;
(2) preparation of graphene oxide Dispersion
Under the condition of ice-water bath, adding graphite and sodium nitrate into concentrated sulfuric acid with the mass fraction of 90%, wherein the mass ratio of the graphite to the sodium nitrate is 1: 1, the mass-to-volume ratio of graphite to concentrated sulfuric acid is 1 g: 60mL, stirring evenly, then slowly adding an oxidant potassium permanganate, wherein the mass ratio of graphite to potassium permanganate is 1: 2, continuously stirring for 30min, heating the mixture to 40 ℃, stirring for 8h, adding deionized water to dilute the obtained reactant, heating to above 98 ℃, stirring for 30min, cooling to 45 ℃, adding hydrogen peroxide with the mass fraction of 15% after the reaction is stable, wherein the volume ratio of the deionized water for dilution to the hydrogen peroxide is 120: washing the obtained product with dilute hydrochloric acid with the mass fraction of 2%, repeatedly washing the product with deionized water to be neutral, and performing centrifugal separation to obtain graphene oxide;
adding graphene oxide into deionized water, and performing ultrasonic dispersion for 60min to obtain a graphene oxide dispersion liquid, wherein the concentration of the graphene oxide in the graphene oxide dispersion liquid is 0.5 mg/mL; dropwise adding an ammonia water solution with the mass fraction of 15% to adjust the pH value of the graphene oxide dispersion liquid to 8, so that the graphene oxide dispersion liquid is electronegative;
(3) preparation of graphene-coated alumina ceramic powder
Slowly dropping the amino surface modified alumina suspension prepared in the step (1) into the graphene oxide dispersion prepared in the step (2) under the conditions of ultrasound and stirring, wherein the mass ratio of the amino surface modified alumina to the graphene oxide is 30: 1. centrifuging and drying after the dripping is finished to obtain graphene oxide coated alumina ceramic powder; and carrying out high-temperature reduction treatment on the obtained graphene oxide-coated alumina composite powder under the nitrogen protection atmosphere, wherein the treatment temperature is 300 ℃ and the treatment time is 1h, so as to obtain the graphene-coated alumina ceramic powder.
The average particle size of the obtained graphene-coated alumina ceramic powder is about 105nm, and the alumina powder is coated by the graphene, so that the dispersion is good, and the crystallinity is high. The transmission electron micrographs of the resulting product are shown in FIGS. 1 and 2.
Example 2
A preparation method of graphene-coated alumina ceramic powder comprises the following steps:
(1) preparation of amino surface-modified alumina suspensions
The selected alumina powder is alpha-Al with the average grain diameter of 200nm2O3Roasting the alumina powder at 750 ℃ for 9h to remove impurities on the surface of the alumina powder, cooling to room temperature, adding the alumina powder into hydrogen peroxide with the mass fraction of 20%, carrying out oxidation treatment, carrying out ultrasonic stirring for 45min, carrying out centrifugal washing with absolute ethyl alcohol for three times, and carrying out vacuum drying; adding the oxidized alumina powder into the mixture of absolute ethyl alcohol and deionized water according to the volume ratio of 1: 1, the mass volume ratio of the alumina to the absolute ethyl alcohol is 0.3 g: 150 mL; slowly dripping an aminosilane coupling agent into the solution, wherein the aminosilane coupling agent is lambda-aminopropyl-trimethoxysilane (APS); the mass volume ratio of the alumina to the aminosilane coupling agent is 0.1 g: 2mL, and simultaneously dropwise adding a pH regulator to regulate the pH value of the system to 7, wherein the pH regulator is glacial acetic acid. Performing ultrasonic treatment for 20min after the dropwise addition is finished, then stirring and treating for 8.5h at the temperature of 90 ℃, performing centrifugal washing for three times by using absolute ethyl alcohol, and performing vacuum drying to obtain amino surface modified alumina powder;
adding the prepared amino surface modified alumina powder into deionized water, and performing ultrasonic dispersion for 10min to obtain amino surface modified alumina suspension, wherein the concentration of amino surface modified alumina in the amino surface modified alumina suspension is 1 mg/mL; dropwise adding a dilute hydrochloric acid solution with the mass percentage of 3% into the suspension to adjust the pH value of the suspension to 4, so that the suspension is electropositive;
(2) preparation of graphene oxide Dispersion
Under the condition of ice-water bath, adding graphite and sodium nitrate into concentrated sulfuric acid with the mass fraction of 95%, wherein the mass ratio of the graphite to the sodium nitrate is 2: 2, the mass-to-volume ratio of the graphite to the concentrated sulfuric acid is 2 g: 240mL, stirring uniformly, and then slowly adding an oxidant potassium permanganate, wherein the mass ratio of the graphite to the potassium permanganate is 2: and 4, continuously stirring for 45min, heating the mixture to 55 ℃, stirring for 10h, adding deionized water to dilute the obtained reactant, heating to 98 ℃ or above, stirring for 45min, cooling to 55 ℃, adding hydrogen peroxide with the mass fraction of 20% after the reaction is stable, wherein the volume ratio of the deionized water for dilution to the hydrogen peroxide is 260: 20, washing the obtained product with dilute hydrochloric acid with the mass fraction of 4%, repeatedly washing the product with deionized water to be neutral, and performing centrifugal separation to obtain graphene oxide;
adding graphene oxide into deionized water, and performing ultrasonic dispersion for 60min to obtain a graphene oxide dispersion liquid, wherein the concentration of the graphene oxide in the graphene oxide dispersion liquid is 1.25 mg/mL; dropwise adding an ammonia water solution with the mass fraction of 20% into the solution to adjust the pH value of the graphene oxide dispersion liquid to 9, so that the graphene oxide dispersion liquid is electronegative;
(3) preparation of graphene-coated alumina ceramic powder
Slowly dropping the amino surface modified alumina suspension prepared in the step (1) into the graphene oxide dispersion prepared in the step (2) under the conditions of ultrasound and stirring, wherein the mass ratio of the amino surface modified alumina to the graphene oxide is 20: 1. centrifuging and drying after the dripping is finished to obtain graphene oxide coated alumina ceramic powder; and carrying out high-temperature reduction treatment on the obtained graphene oxide-coated alumina composite powder under the argon protective atmosphere, wherein the treatment temperature is 550 ℃ and the treatment time is 12 hours, so as to obtain the graphene-coated alumina ceramic powder.
The average particle size of the obtained graphene-coated alumina ceramic powder is about 208nm, and the alumina powder is completely coated by the graphene oxide. The XRD diffraction pattern of the product is shown in figure 3.
The average particle size of the obtained graphene-coated alumina ceramic powder is about 208nm, and the alumina powder is completely coated by the graphene, so that the dispersion is good, and the crystallinity is high. The XRD diffraction pattern of the obtained product is shown in figure 3.
Example 3: as described in example 2, except that the mass ratio of the amino surface modified alumina to the oxidized graphene was changed to 15: 1. The average grain diameter of the obtained graphene-coated alumina ceramic powder is about 205nm, the dispersion is good, and the crystallinity is high. The alumina powder is wrapped with graphene.
Example 4: as described in example 2, except that the mass ratio of the amino surface modified alumina to the oxidized graphene was changed to 25: 1. The average grain diameter of the obtained graphene-coated alumina ceramic powder is about 210nm, the dispersion is good, and the crystallinity is high. The alumina powder is completely wrapped by the graphene oxide.
Example 5
A preparation method of graphene-coated alumina ceramic powder comprises the following steps:
(1) preparation of amino surface-modified alumina suspensions
The selected alumina powder is alpha-Al with the average grain diameter of 500nm2O3Roasting the alumina powder at 1000 ℃ for 9h to remove impurities on the surface of the alumina powder, cooling to room temperature, adding the alumina powder into hydrogen peroxide with the mass fraction of 30%, carrying out oxidation treatment, carrying out ultrasonic stirring for 55min, carrying out centrifugal washing for three times by using absolute ethyl alcohol, and carrying out vacuum drying; adding the oxidized alumina powder into the mixture of absolute ethyl alcohol and deionized water according to the volume ratio of 1: 1, the mass volume ratio of the alumina to the absolute ethyl alcohol is 0.5 g: 200 mL; slowly dripping an aminosilane coupling agent into the solution, wherein the aminosilane coupling agent is N- (beta-aminoethyl) -lambda-aminopropyltrimethoxysilane (A1120); the mass volume ratio of the alumina to the aminosilane coupling agent is 0.5 g: 6mL, and simultaneously dropwise adding a pH regulator to regulate the pH value of the system to 10, wherein the pH regulatorIs ammonia water. Performing ultrasonic treatment for 30min after the dropwise addition is finished, then stirring and treating for 12h at the temperature of 120 ℃, performing centrifugal washing for three times by using absolute ethyl alcohol, and performing vacuum drying to obtain amino surface modified alumina powder;
adding the prepared amino surface modified alumina powder into deionized water, and performing ultrasonic dispersion for 30min to obtain amino surface modified alumina suspension, wherein the concentration of amino surface modified alumina in the amino surface modified alumina suspension is 5 mg/mL; dropwise adding a dilute hydrochloric acid solution with the mass percent of 5% to adjust the pH value of the suspension to 5, so that the suspension is electropositive;
(2) preparation of graphene oxide Dispersion
Under the condition of ice-water bath, adding graphite and sodium nitrate into concentrated sulfuric acid with the mass fraction of 98%, wherein the mass ratio of the graphite to the sodium nitrate is 3: 3, the mass-to-volume ratio of the graphite to the concentrated sulfuric acid is 3 g: 360mL, stirring evenly, then slowly adding oxidizing agent potassium permanganate, the mass ratio of graphite to potassium permanganate is 2: and 6, continuously stirring for 60min, heating the mixture to 60 ℃, stirring for 12h, adding deionized water to dilute the obtained reactant, heating to 98 ℃ or higher, stirring for 60min, cooling to 65 ℃, adding hydrogen peroxide with the mass fraction of 30% after the reaction is stable, wherein the volume ratio of the deionized water for dilution to the hydrogen peroxide is 400: 30, washing the obtained product with dilute hydrochloric acid with the mass fraction of 6%, repeatedly washing the product with deionized water to be neutral, and performing centrifugal separation to obtain graphene oxide;
adding graphene oxide into deionized water, and performing ultrasonic dispersion for 60min to obtain a graphene oxide dispersion liquid, wherein the concentration of the graphene oxide in the graphene oxide dispersion liquid is 2 mg/mL; dropwise adding an ammonia water solution with the mass fraction of 25% into the graphene oxide dispersion liquid to adjust the pH value of the graphene oxide dispersion liquid to 10, so that the graphene oxide dispersion liquid is electronegative;
(3) preparation of graphene-coated alumina ceramic powder
Slowly dropping the amino surface modified alumina suspension prepared in the step (1) into the graphene oxide dispersion prepared in the step (2) under the conditions of ultrasound and stirring, wherein the mass ratio of the amino surface modified alumina to the graphene oxide is 20: 1. centrifuging and drying after the dripping is finished to obtain graphene oxide coated alumina ceramic powder; and carrying out high-temperature reduction treatment on the obtained graphene oxide-coated alumina composite powder under the mixed protective atmosphere of nitrogen and argon at the treatment temperature of 800 ℃ for 24 hours to obtain graphene-coated alumina ceramic powder.
Application example:
adding the graphene-coated alumina ceramic powder prepared in the embodiments 1, 2, 3, 4 and 5 into an alumina-based ceramic cutting tool material, and correspondingly marking as application examples 1, 2, 3, 4 and 5, wherein the ceramic cutting tool comprises 20% of graphene-coated alumina, 0.25% of magnesium oxide, 1.05% of molybdenum, 1.5% of nickel and the balance of micron alumina in percentage by mass; the hot-pressing sintering process conditions are as follows: the sintering temperature is 1550 +/-20 ℃, the heat preservation time is 25min, and the pressure is 25 MPa. The mechanical properties of the obtained ceramic cutting tool material are shown in table 1.
Comparative example: the added graphene-coated alumina was replaced with graphene (the specification of graphene: sheet diameter 0.5 to 5 μm, thickness 0.8 to 1.2nm), and the formula and sintering process conditions were the same as above, and the application example 6 was recorded. The mechanical properties of the obtained ceramic cutting tool material are shown in table 2.
Table 1 application examples 1 to 5 mechanical property test results of alumina-based ceramic cutting tools coated with graphene-containing alumina ceramic powder
TABLE 2 detection results of mechanical properties of alumina-based ceramic cutting tools directly added with graphene
The hardness, fracture toughness and bending strength of the above cutter material are perpendicular to the hot pressing direction.
Claims (11)
1. A preparation method of graphene coated alumina ceramic powder for preparing an alumina-based ceramic cutting tool material comprises the following steps:
(1) preparation of amino surface-modified alumina suspensions
Roasting alumina powder at 500-1000 ℃ for 6-12 h, wherein the alumina powder adopts alpha-Al with the average particle size of 100-500 nm2O3After cooling to room temperature, adding the mixture into hydrogen peroxide for oxidation treatment, ultrasonically stirring for 35-55 min, centrifugally washing with absolute ethyl alcohol, and drying in vacuum; adding the oxidized aluminum oxide powder into a mixed solution of absolute ethyl alcohol and deionized water, slowly dropwise adding an aminosilane coupling agent into the mixed solution, and dropwise adding a pH regulator to regulate the pH value of the system to 4-10 so as to be beneficial to hydrolysis of the aminosilane coupling agent; the mass volume ratio of the alumina powder to the aminosilane coupling agent is 0.1-0.5 g: 2-6 mL; after the dropwise addition is finished, performing ultrasonic treatment for 10-30 min, then stirring at the temperature of 60-120 ℃ for 5-12 h, performing centrifugal washing with absolute ethyl alcohol, and performing vacuum drying to obtain amino surface modified alumina powder;
adding the prepared amino surface modified alumina powder into deionized water, and performing ultrasonic dispersion for 10-30 min to obtain an amino surface modified alumina suspension, wherein the concentration of the amino surface modified alumina is 1-5 mg/mL; dropwise adding a dilute hydrochloric acid solution into the suspension to adjust the pH value of the suspension to 3-5, so that the suspension is electropositive;
(2) preparation of graphene oxide Dispersion
Under the condition of ice-water bath, adding graphite and sodium nitrate into concentrated sulfuric acid, stirring uniformly, then slowly adding an oxidant potassium permanganate, continuously stirring for 30-60 min, heating the mixture to 40-60 ℃, stirring for 8-12 h, diluting the obtained reactant with deionized water, heating to above 98 ℃, stirring for 30-60 min, cooling to 45-65 ℃, adding hydrogen peroxide, washing the obtained product with dilute hydrochloric acid, repeatedly washing with deionized water to neutrality, and centrifugally separating to obtain graphene oxide;
adding graphene oxide into deionized water, performing ultrasonic dispersion for 60-120 min to obtain a graphene oxide dispersion liquid, and dropwise adding an ammonia water solution to adjust the pH value of the graphene oxide dispersion liquid to 8-10, so that the graphene oxide dispersion liquid is electronegative;
(3) preparation of graphene-coated alumina ceramic powder
Slowly dropping the amino surface modified alumina suspension prepared in the step (1) into the graphene oxide dispersion prepared in the step (2) under the conditions of ultrasound and stirring, wherein the mass ratio of the amino surface modified alumina to the graphene oxide is 10-30: 1, centrifuging and drying after dripping to obtain graphene oxide coated alumina ceramic powder; and carrying out high-temperature reduction treatment on the obtained graphene oxide-coated alumina composite powder at the temperature of 300-800 ℃ in a protective atmosphere for 1-24 h to obtain graphene-coated alumina ceramic powder.
2. The method for preparing graphene-coated alumina ceramic powder according to claim 1, wherein in the step (1), the mass fraction of the hydrogen peroxide solution is 10-30%.
3. The method for preparing graphene-coated alumina ceramic powder according to claim 1, wherein in the step (1), the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 1 in the mixed solution of the absolute ethyl alcohol and the deionized water.
4. The method for preparing graphene-coated alumina ceramic powder according to claim 1, wherein in the step (1), the pH regulator is glacial acetic acid or ammonia water.
5. The method for preparing graphene-coated alumina ceramic powder according to claim 1, wherein in the step (1), the mass-to-volume ratio of the alumina to the absolute ethyl alcohol is 0.1-0.5 g: 100-200 mL.
6. The method for preparing graphene-coated alumina ceramic powder according to claim 1, wherein in the step (1), the mass-to-volume ratio of the alumina to the aminosilane coupling agent is 0.1-0.3 g: 2-5 mL.
7. The method according to claim 1, wherein in step (1), the aminosilane coupling agent is selected from the group consisting of γ -aminopropyltriethoxysilane, γ -aminopropyl-trimethoxysilane, and N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane.
8. The preparation method of the graphene-coated alumina ceramic powder according to claim 1, wherein in the step (2), the mass ratio of graphite to sodium nitrate is 1-3: 1-3, wherein the mass ratio of graphite to potassium permanganate is 1-3: 2-6, wherein the mass-to-volume ratio of the graphite to the concentrated sulfuric acid is 1-3 g: 60-360 mL.
9. The method for preparing graphene-coated alumina ceramic powder according to claim 1, wherein in the step (2), the mass fraction of hydrogen peroxide is 15-30%.
10. The method for preparing graphene-coated alumina ceramic powder according to claim 1, wherein in the step (2), the ultrasonic dispersion time is 60-120 min, and the concentration of graphene oxide in the graphene oxide dispersion liquid is 0.5-2 mg/mL.
11. The method for preparing graphene-coated alumina ceramic powder according to claim 1, wherein in the step (3), the mass ratio of the amino surface modified alumina to the graphene oxide is 15-25: 1.
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