CN114988887B - Ceramic cutter material based on core-shell nanocomposite powder modification and preparation method thereof - Google Patents
Ceramic cutter material based on core-shell nanocomposite powder modification and preparation method thereof Download PDFInfo
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Abstract
The application discloses a ceramic cutter material based on modification of core-shell nano composite powder, which comprises the following components in percentage by volume: 0.1-4.5vol% of core-shell nano composite powder, 0.1-2.0vol% of magnesia, 0.1-1.5vol% of yttrium oxide, 0-1.5vol% of molybdenum, 0-1.5vol% of nickel and the balance of ceramic matrix; the sum of the volume percentages of the components is 100 percent; the core-shell type nano composite powder is prepared by modifying graphene through a cationic dispersing agent and coating the modified nano ceramic powder on the surface of the modified nano ceramic powder through an anionic surfactant; the cationic dispersant is prepared by reacting perylene-3, 4,9, 10-tetracarboxylic dianhydride with vinylamine and then carrying out protonation treatment. The application also discloses a preparation method of the ceramic cutter material, and the ceramic cutter material prepared by the method has excellent performance.
Description
Technical Field
The application relates to the technical field of ceramic composite materials, in particular to a ceramic cutter material based on modification of core-shell nano composite powder and a preparation method thereof.
Background
The ceramic cutter material has the advantages of high hardness, good wear resistance, high temperature resistance, stable chemical property, low affinity with metal and the like, so that the ceramic cutter material has incomparable advantages with other cutter materials in the aspect of high-speed cutting processing. Furthermore, ceramic tool materials exhibit better cutting performance in hard cutting than conventional tool materials and are therefore considered to be potential tool materials. However, the inherent brittleness of ceramic tool materials has greatly limited their development as an excellent tool material. Therefore, the toughening and reinforcement of ceramic cutter materials is one of the hot spots in the research field. In recent years, nanocomposite ceramic materials have received extensive attention from numerous researchers. The mechanical property of the composite material can be improved by adding a proper amount of nano particles into the ceramic matrix.
Graphene is an ideal two-dimensional crystal with a regular hexagonal symmetrical structure, which is formed by combining single-layer carbon atoms through covalent bonds. Due to the unique two-dimensional structure and excellent crystal quality, graphene possesses many excellent properties such as extremely high electron mobility, extremely large specific surface area, and extremely high thermal conductivity. The theoretical thickness of the single-layer graphene is only 0.335nm, and the single-layer graphene is the thinnest and strongest material in the world, and the strength and Young's modulus of the single-layer graphene reach 125GPa and 1100GPa respectively. The high modulus, high strength and other properties of graphene make it an ideal reinforcement for ceramic materials. However, due to the fact that graphene has large specific surface area and high surface energy, graphene cannot be uniformly dispersed in a ceramic matrix by traditional methods such as ball milling mixing and the like, structural defects such as air holes and the like can be caused by aggregation of graphene, good contact interfaces cannot be formed between the graphene and the ceramic matrix, and therefore the reinforcing effect of the graphene is reduced. Therefore, improving the dispersion uniformity of graphene in a ceramic matrix becomes a precondition for preparing high-performance graphene/ceramic composite materials.
Disclosure of Invention
One of the technical problems to be solved by the application is as follows: aiming at the defects existing in the prior art, a ceramic cutter material based on core-shell type nano composite powder modification is provided, and the material utilizes the interaction electrostatic interaction to uniformly coat modified graphene with positive charges on the surface of modified nano ceramic powder with negative charges, and then the modified graphene is added into a ceramic matrix for modification, so that the problems of easy aggregation and poor dispersibility of graphene in the existing graphene ceramic composite material are solved; in addition, the self-made dispersing agent is adopted to modify graphene, and under the mutual synergistic effect of electrostatic attraction and steric hindrance, the prepared core-shell composite powder can be well dispersed in a ceramic matrix, so that the modified ceramic composite material has excellent performance.
Aiming at the defects of the prior art, the application provides a preparation method of the ceramic cutter material modified by the core-shell type nano composite powder, which is simple to operate, and the prepared ceramic cutter material has excellent performance by effectively controlling the preparation process conditions.
In order to solve the technical problems, the technical scheme of the application is as follows:
the ceramic cutter material based on the modification of the core-shell nanocomposite powder comprises the following components in percentage by volume:
0.1-4.5vol% of core-shell nano composite powder, 0.1-2.0vol% of magnesia, 0.1-1.5vol% of yttrium oxide, 0-1.5vol% of molybdenum, 0-1.5vol% of nickel and the balance of ceramic matrix; the sum of the volume percentages of the components is 100 percent;
the core-shell type nano composite powder is prepared by modifying graphene through a cationic dispersing agent and coating the modified nano ceramic powder on the surface of the modified nano ceramic powder through an anionic surfactant; the cationic dispersant is prepared by reacting perylene-3, 4,9, 10-tetracarboxylic dianhydride with vinylamine and then carrying out protonation treatment.
As a preferable mode of the technical scheme, the ceramic matrix is micron-sized ceramic powder, and the micron-sized ceramic powder is one or two of alumina, titanium carbide, silicon nitride, titanium boride, tungsten carbide and silicon carbide; the nano ceramic powder is one or more of aluminum oxide, zirconium oxide, silicon carbide, titanium carbide, tungsten carbide, titanium boride, titanium carbonitride and silicon nitride; the average grain size of the nano ceramic powder is 50-200nm; the average grain size of the ceramic matrix is 0.1-2 mu m.
In the application, the particle size of the magnesium oxide is 1-3 mu m, the particle size of the yttrium oxide is 1-3 mu m, the particle size of the molybdenum is 5-25 mu m, and the particle size of the nickel is 25-50 mu m.
In the application, the graphene is high-quality graphene prepared by chemical vapor deposition, mechanical stripping and other methods, the diameter of the graphene is 1-5 mu m, the thickness of the graphene is 3-20nm, and the purity of the graphene is not less than 95%.
Further, the application also discloses a preparation method of the cationic dispersing agent, which comprises the following steps: dispersing perylene-3, 4,9, 10-tetracarboxylic dianhydride in toluene by ultrasonic, adding vinylamine, heating and refluxing for reaction, cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing the filtered precipitate, adding the washed precipitate into potassium hydroxide solution, stirring at room temperature, filtering the mixture, washing the precipitate, drying, completely dissolving the dried solid in formic acid, adding isopropanol for precipitation, and finally drying the precipitate to obtain the cationic dispersing agent.
As a preferable choice of the above technical scheme, the vinylamine is one of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the molar ratio of the perylene-3, 4,9, 10-tetracarboxylic dianhydride to the vinylamine is (5-20): 1.
as the preferable choice of the technical proposal, the temperature of the reflux reaction is 40-65 ℃ and the time of the reflux reaction is 6-36h; the concentration of the potassium hydroxide solution is 10wt%, and the stirring treatment time is 5-7h.
In order to better solve the technical problems, the application also discloses a preparation method of the ceramic cutter material, which comprises the following steps:
(1) Ultrasonically dispersing a cationic dispersing agent in deionized water, then adding graphene, and performing ultrasonic treatment under ice bath conditions to obtain modified graphene dispersion;
(2) Dissolving an anionic surfactant in a mixed solution of deionized water, adding nano ceramic powder, regulating the pH of the solution to 6, performing ultrasonic stirring reaction, filtering the reaction solution, drying the obtained precipitate, and dispersing the dried precipitate in the deionized water to obtain a modified nano ceramic powder dispersion;
(3) Slowly dripping the modified nano ceramic powder dispersion liquid into the modified graphene dispersion liquid under the ultrasonic stirring condition, continuing stirring treatment after dripping, standing, filtering, washing the precipitate, and performing vacuum drying treatment to obtain core-shell nano composite powder;
(4) Weighing the raw materials according to the volume percentage, adding the weighed ceramic matrix into absolute ethyl alcohol, mechanically stirring to prepare ceramic matrix suspension, adding magnesium oxide, yttrium oxide, molybdenum and nickel, continuously mechanically stirring to prepare mixed suspension, pouring the prepared mixed suspension into a ball grinding tank, filling protective gas, adding ball grinding balls made of hard alloy materials, and performing ball grinding for the first time; adding core-shell nano composite powder, performing ball milling for the second time to obtain ceramic slurry, vacuum drying the ceramic slurry, sieving with 100-200 mesh sieve to obtain ceramic composite powder, and sealing for use;
(5) And placing the prepared ceramic composite powder into a graphite die for cold press molding treatment to obtain a ceramic block, and placing the prepared ceramic block into a hot press sintering furnace for sintering treatment to obtain the ceramic cutter material.
As a preferable mode of the above technical solution, in step (1), the mass ratio of the cationic dispersant to the graphene is 1: (1-5); the concentration of the modified graphene dispersion liquid is 0.1-1.2mg/ml.
In the step (1), the power of the ultrasonic treatment is 500W, and intermittent ultrasonic is adopted in ultrasonic treatment, and the total ultrasonic time is 0.5-1.5h after 5s of ultrasonic treatment.
As a preferable mode of the above technical scheme, in the step (2), the anionic surfactant is any one of dodecylbenzene sulfonate, dodecylsulfate, sodium polyacrylate and fatty acid salt; the mass ratio of the anionic surfactant to the nano ceramic powder is (0.5-2): 1.
as the preferable choice of the technical scheme, in the step (2), the concentration of the modified nano ceramic powder dispersion liquid is 0.5-2wt%, and the ultrasonic stirring reaction time is 1-3h.
As a preferable mode of the above technical solution, in the step (3), the mass ratio of the modified nano ceramic powder to the modified graphene is (10-40): 1, a step of; the dripping speed of the modified nano ceramic powder dispersion liquid is 5-20ml/min, the stirring treatment time is 20-50min, and the standing treatment is carried out for 1-20h after the stirring.
As a preferable mode of the above technical scheme, in the step (4), the shielding gas is one of argon and nitrogen; ball material ratio in ball milling treatment is (10-20): 1, a step of; the time of the first ball milling treatment is 45-50h, and the time of the second ball milling treatment is 1-3h.
As a preferable mode of the above technical solution, in the step (5), the conditions of the sintering treatment are: sintering temperature is 1600-2000 ℃, hot pressing pressure is 25-35MPa, heating rate is 10-20 ℃/min, and heat preservation time is 10-30min.
Due to the adoption of the technical scheme, the application has the beneficial effects that:
according to the application, a self-made cationic dispersing agent is adopted to modify graphene to obtain graphene with positive charges on the surface, then an anionic surfactant is adopted to modify nano ceramic particles to obtain nano ceramic particles with negative charges on the surface, the graphene is uniformly coated on the surfaces of the nano ceramic particles through electrostatic attraction to obtain core-shell type nano composite powder, the obtained core-shell type nano composite powder is used as a reinforcing phase to be added into a ceramic cutter material, micron-sized ceramic powder is used as a matrix, and magnesium oxide, yttrium oxide, molybdenum and nickel are used as sintering aids, and the ceramic cutter material is prepared through hot press sintering. The graphene can be uniformly dispersed in the ceramic matrix, and a graphene three-dimensional network structure is formed under the action of inter-grain stress. Correspondingly, the mechanical properties of the ceramic cutter material added with the core-shell composite powder of the graphene coated nano particles are greatly improved compared with those of the ceramic cutter material without the composite powder.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the core-shell nanocomposite powder obtained in example 5;
FIG. 2 is a test specimen fracture surface SEM of the ceramic tool material prepared in example 5;
fig. 3 is an XRD pattern of a test sample of the ceramic tool material prepared in example 5.
Detailed Description
The application is further illustrated below with reference to examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application.
The graphene adopted in the embodiment and the comparative example has the diameter of 2 mu m, the thickness of 10nm and the purity of 99 percent;
the particle size of the magnesium oxide used in the examples and comparative examples of the present application was 1. Mu.m, the particle size of yttrium oxide was 2. Mu.m, the particle size of molybdenum was 10. Mu.m, and the particle size of nickel was 12. Mu.m.
Example 1
S1: dispersing 5mmol of perylene-3, 4,9, 10-tetracarboxylic dianhydride in 100ml of toluene by ultrasonic, adding 0.3mmol of triethylene tetramine, heating to 55 ℃, carrying out reflux reaction for 25 hours, cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing the filtered precipitate by adopting toluene and ethanol, adding the washed precipitate into 10wt% potassium hydroxide solution, stirring at room temperature for 6 hours, filtering the mixture, washing the precipitate by adopting deionized water, drying, completely dissolving the dried solid in formic acid, adding isopropanol for precipitation treatment, and finally drying the precipitate in a vacuum oven for 24 hours to prepare the cationic dispersing agent;
s2: ultrasonically dispersing the prepared cationic dispersing agent in deionized water, and then adding graphene, wherein the mass ratio of the cationic dispersing agent to the graphene is adjusted to be 1:3, carrying out ultrasonic treatment under ice bath condition and 500W power, wherein intermittent ultrasonic treatment is adopted during ultrasonic treatment, each ultrasonic treatment is carried out for 5 seconds, the total ultrasonic treatment time is 1h, and modified graphene dispersion liquid with the concentration of 1mg/ml is prepared;
s3: 3g of sodium dodecyl sulfate is dissolved in 100ml of deionized water to form a mixed solution, 5g of zirconia with the particle size of 100nm is added, the pH value of the solution is regulated to 6, the solution is subjected to ultrasonic stirring reaction for 2 hours, then the reaction solution is filtered, and the obtained precipitate after filtration is dried and dispersed in deionized water to prepare a modified zirconia powder dispersion with the concentration of 1 wt%;
s4: under the condition of ultrasonic stirring, dripping the modified zirconia powder dispersion liquid into the modified graphene dispersion liquid at a dripping speed of 15ml/min, and controlling the mass ratio of the modified zirconia powder to the modified graphene to be 20:1, after the dripping is finished, continuing stirring treatment for 40min, standing for 5h, filtering, washing the precipitate, and performing vacuum drying treatment to obtain core-shell type nano composite powder;
s5: according to the volume percentage, 3.5vol% of core-shell nano composite powder, 1.0vol% of magnesia, 0.5vol% of yttrium oxide, 1.0vol% of molybdenum, 1.0vol% of nickel and the balance of alumina with the particle size of 0.2 mu m are weighed; adding the weighed aluminum oxide into absolute ethyl alcohol, mechanically stirring to prepare ceramic matrix suspension, adding magnesium oxide, yttrium oxide, molybdenum and nickel, continuously mechanically stirring to prepare mixed suspension, pouring the prepared mixed suspension into a ball mill tank, filling nitrogen, and adding ball mill balls made of hard alloy materials, wherein the ball material ratio is 10:1, performing first ball milling treatment for 48 hours; then adding core-shell nano composite powder, continuing to perform ball milling for 2 hours for the second time to obtain ceramic slurry, and finally vacuum drying the prepared ceramic slurry, sieving with a 100-mesh sieve to obtain ceramic composite powder, and sealing for later use;
s6: and (3) placing the prepared ceramic composite powder into a graphite die for cold press molding treatment to obtain a ceramic block, placing the prepared ceramic block into a hot press sintering furnace, heating to 1650 ℃ at a heating rate of 15 ℃/min, controlling the hot press pressure to be 30MPa, and performing sintering treatment for 10min to obtain the ceramic cutter material.
Example 2
S1: dispersing 5mmol of perylene-3, 4,9, 10-tetracarboxylic dianhydride in 100ml of toluene by ultrasonic, then adding 0.5mmol of tetraethylenepentamine, heating to 50 ℃, carrying out reflux reaction for 25 hours, cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing the filtered precipitate by adopting toluene and ethanol, adding the washed precipitate into 10wt% potassium hydroxide solution, stirring at room temperature for 6 hours, filtering the mixture, washing the precipitate by adopting deionized water, drying, completely dissolving the dried solid in formic acid, adding isopropanol for precipitation treatment, and finally drying the precipitate in a vacuum oven for 24 hours to prepare the cationic dispersing agent;
s2: ultrasonically dispersing the prepared cationic dispersing agent in deionized water, and then adding graphene, wherein the mass ratio of the cationic dispersing agent to the graphene is adjusted to be 1:2.5, carrying out ultrasonic treatment under ice bath condition and 500W power, wherein intermittent ultrasonic treatment is adopted during ultrasonic treatment, each ultrasonic treatment is carried out for 5 seconds, the total ultrasonic treatment time is 1h, and the modified graphene dispersion liquid with the concentration of 0.8mg/ml is prepared;
s3: dissolving 5g of sodium dodecyl sulfate in a mixed solution consisting of 100ml of deionized water, adding 5g of aluminum oxide with the particle size of 100nm, regulating the pH value of the solution to 6, carrying out ultrasonic stirring reaction for 2 hours, filtering the reaction solution, drying the obtained precipitate after filtration, and dispersing the precipitate in the deionized water to prepare a modified aluminum oxide powder dispersion with the concentration of 0.8 wt%;
s4: under the condition of ultrasonic stirring, dripping the modified alumina powder dispersion liquid into the modified graphene dispersion liquid at a dripping speed of 15ml/min, and controlling the mass ratio of the modified nano ceramic powder to the graphene to be 21:1, after the dripping is finished, continuing stirring treatment for 40min, standing for 5h, filtering, washing the precipitate, and performing vacuum drying treatment to obtain core-shell type nano composite powder;
s5: according to the volume percentage, 3.5 volume percent of core-shell nano composite powder, 0.8 volume percent of magnesia, 0.5 volume percent of yttrium oxide, 1.0 volume percent of molybdenum, 1.0 volume percent of nickel and the balance of alumina/titanium carbide with the average grain diameter of 0.2 mu m are weighed; adding the weighed aluminum oxide/titanium carbide into absolute ethyl alcohol, mechanically stirring to prepare ceramic matrix suspension, adding magnesium oxide, yttrium oxide, molybdenum and nickel, continuously mechanically stirring to prepare mixed suspension, pouring the prepared mixed suspension into a ball mill tank, filling nitrogen, and adding ball mill balls made of hard alloy, wherein the ball material ratio is 10:1, performing first ball milling treatment for 48 hours; then adding core-shell nano composite powder, continuing to perform ball milling for 2 hours for the second time to obtain ceramic slurry, and finally vacuum drying the prepared ceramic slurry, sieving with a 100-mesh sieve to obtain ceramic composite powder, and sealing for later use;
s6: and (3) placing the prepared ceramic composite powder into a graphite die for cold press molding treatment to obtain a ceramic block, placing the prepared ceramic block into a hot press sintering furnace, heating to 1650 ℃ at a heating rate of 15 ℃/min, controlling the hot press pressure to be 30MPa, and performing sintering treatment for 15min to obtain the ceramic cutter material.
Example 3
S1: dispersing 5mmol of perylene-3, 4,9, 10-tetracarboxylic dianhydride in 100ml of toluene by ultrasonic, adding 0.5mmol of triethylene tetramine, heating to 55 ℃, carrying out reflux reaction for 26 hours, cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing the filtered precipitate by adopting toluene and ethanol, adding the washed precipitate into 10wt% potassium hydroxide solution, stirring at room temperature for 5 hours, filtering the mixture, washing the precipitate by adopting deionized water, drying, completely dissolving the dried solid in formic acid, adding isopropanol for precipitation treatment, and finally drying the precipitate in a vacuum oven for 24 hours to prepare the cationic dispersing agent;
s2: ultrasonically dispersing the prepared cationic dispersing agent in deionized water, and then adding graphene, wherein the mass ratio of the cationic dispersing agent to the graphene is adjusted to be 1:2.5, carrying out ultrasonic treatment under ice bath conditions and 500W power, wherein intermittent ultrasonic treatment is adopted during ultrasonic treatment, each ultrasonic treatment is carried out for 5 seconds, the total ultrasonic treatment time is 1h, and the modified graphene dispersion liquid with the concentration of 1mg/ml is prepared;
s3: dissolving 5g of sodium dodecyl benzene sulfonate in a mixed solution consisting of 100ml of deionized water, adding 5g of zirconia with the particle size of 100nm, regulating the pH value of the solution to 6, carrying out ultrasonic stirring reaction for 2 hours, filtering the reaction solution, drying the filtered precipitate, and dispersing the dried precipitate in the deionized water to prepare a modified zirconia powder dispersion with the concentration of 0.9 wt%;
s4: under the condition of ultrasonic stirring, dripping the modified zirconia powder dispersion liquid into the modified graphene dispersion liquid at the dripping speed of 16ml/min, and controlling the mass ratio of the modified nano ceramic powder to the graphene to be 20:1, after the dripping is finished, continuing stirring for 45min, standing for 5h, filtering, washing the precipitate, and performing vacuum drying treatment to obtain core-shell type nano composite powder;
s5: according to the volume percentage, 3.5vol% of core-shell nano composite powder, 1.0vol% of magnesia, 0.5vol% of yttrium oxide, 1.0vol% of molybdenum, 1.0vol% of nickel and the balance of alumina/titanium carbide are weighed; adding the weighed ceramic matrix into absolute ethyl alcohol, mechanically stirring to obtain ceramic matrix suspension, adding magnesium oxide, yttrium oxide, molybdenum and nickel, continuously mechanically stirring to obtain mixed suspension, pouring the prepared mixed suspension into a ball mill tank, filling nitrogen, and adding ball mill balls made of hard alloy materials, wherein the ball material ratio is 10:1, performing first ball milling treatment for 48 hours; then adding core-shell nano composite powder, continuing to perform ball milling for 2 hours for the second time to obtain ceramic slurry, and finally vacuum drying the prepared ceramic slurry, sieving with a 100-mesh sieve to obtain ceramic composite powder, and sealing for later use;
s6: and (3) placing the prepared ceramic composite powder into a graphite die for cold press molding treatment to obtain a ceramic block, placing the prepared ceramic block into a hot press sintering furnace, heating to 1650 ℃ at a heating rate of 15 ℃/min, controlling the hot press pressure to be 30MPa, and performing sintering treatment for 15min to obtain the ceramic cutter material.
Example 4
S1: dispersing 5mmol of perylene-3, 4,9, 10-tetracarboxylic dianhydride in 100ml of toluene by ultrasonic, adding 0.5mmol of triethylene tetramine, heating to 55 ℃, carrying out reflux reaction for 25 hours, cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing the filtered precipitate by adopting toluene and ethanol, adding the washed precipitate into 10wt% potassium hydroxide solution, stirring at room temperature for 6 hours, filtering the mixture, washing the precipitate by adopting deionized water, drying, completely dissolving the dried solid in formic acid, adding isopropanol for precipitation treatment, and finally drying the precipitate in a vacuum oven for 24 hours to prepare the cationic dispersing agent;
s2: ultrasonically dispersing the prepared cationic dispersing agent in deionized water, and then adding graphene, wherein the mass ratio of the cationic dispersing agent to the graphene is adjusted to be 1:3, carrying out ultrasonic treatment under ice bath conditions and 500W power, wherein intermittent ultrasonic treatment is adopted during ultrasonic treatment, each ultrasonic treatment is carried out for 5 seconds, the total ultrasonic treatment time is 1h, and the modified graphene dispersion liquid with the concentration is prepared;
s3: dissolving 5g of sodium dodecyl benzene sulfonate in a mixed solution consisting of 100ml of deionized water, adding 5g of aluminum oxide with the average particle size of 100nm, regulating the pH value of the solution to 6, carrying out ultrasonic stirring reaction for 2 hours, filtering the reaction solution, drying the obtained precipitate after filtration, and dispersing the precipitate in the deionized water to prepare a modified aluminum oxide powder dispersion with the concentration of 1.1 wt%;
s4: under the condition of ultrasonic stirring, dripping the modified alumina powder dispersion liquid into the modified graphene dispersion liquid at the dripping speed of 16ml/min, and controlling the mass ratio of the modified nano ceramic powder to the graphene to be 22:1, after the dripping is finished, continuing stirring treatment for 40min, standing for 5h, filtering, washing the precipitate, and performing vacuum drying treatment to obtain core-shell type nano composite powder;
s5: according to the volume percentage, 3.5vol% of core-shell nano composite powder, 0.9vol% of magnesia, 0.6vol% of yttrium oxide, 1.0vol% of molybdenum, 1.0vol% of nickel and the balance of alumina/titanium carbide are weighed; adding the weighed ceramic matrix into absolute ethyl alcohol, mechanically stirring to obtain ceramic matrix suspension, adding magnesium oxide, yttrium oxide, molybdenum and nickel, continuously mechanically stirring to obtain mixed suspension, pouring the prepared mixed suspension into a ball grinding tank, filling argon, and adding ball grinding balls made of hard alloy materials, wherein the ball material ratio is 10:1, performing first ball milling treatment for 48 hours; then adding core-shell nano composite powder, continuing to perform ball milling for 2 hours for the second time to obtain ceramic slurry, and finally vacuum drying the prepared ceramic slurry, sieving with a 100-mesh sieve to obtain ceramic composite powder, and sealing for later use;
s6: and (3) placing the prepared ceramic composite powder into a graphite die for cold press molding treatment to obtain a ceramic block, placing the prepared ceramic block into a hot press sintering furnace, heating to 1650 ℃ at a heating rate of 15 ℃/min, controlling the hot press pressure to be 30MPa, and performing sintering treatment for 20min to obtain the ceramic cutter material.
Example 5
S1: dispersing 5mmol of perylene-3, 4,9, 10-tetracarboxylic dianhydride in 100ml of toluene by ultrasonic, adding 0.5mmol of triethylene tetramine, heating to 55 ℃, carrying out reflux reaction for 25 hours, cooling to room temperature after the reaction is finished, filtering the reaction liquid, washing the filtered precipitate by adopting toluene and ethanol, adding the washed precipitate into 10wt% potassium hydroxide solution, stirring at room temperature for 6 hours, filtering the mixture, washing the precipitate by adopting deionized water, drying, completely dissolving the dried solid in formic acid, adding isopropanol for precipitation treatment, and finally drying the precipitate in a vacuum oven for 24 hours to prepare the cationic dispersing agent;
s2: ultrasonically dispersing the prepared cationic dispersing agent in deionized water, and then adding graphene, wherein the mass ratio of the cationic dispersing agent to the graphene is adjusted to be 1:3, carrying out ultrasonic treatment under ice bath condition and 500W power, wherein intermittent ultrasonic treatment is adopted during ultrasonic treatment, each ultrasonic treatment is carried out for 5 seconds, the total ultrasonic treatment time is 1h, and modified graphene dispersion liquid with the concentration of 1mg/ml is prepared;
s3: dissolving 5g of sodium dodecyl benzene sulfonate in a mixed solution consisting of 100ml of deionized water, adding 5g of aluminum oxide with the average particle size of 100nm, regulating the pH value of the solution to 6, carrying out ultrasonic stirring reaction for 2 hours, filtering the reaction solution, drying the obtained precipitate after filtration, and dispersing the precipitate in the deionized water to prepare a modified aluminum oxide powder dispersion with the concentration of 1 wt%;
s4: under the condition of ultrasonic stirring, dripping the modified nano alumina powder dispersion liquid into the modified graphene dispersion liquid at a dripping speed of 15ml/min, and controlling the mass ratio of the modified alumina powder to the graphene to be 20:1, after the dripping is finished, continuing stirring for 45min, standing for 5h, filtering, washing the precipitate, and performing vacuum drying treatment to obtain core-shell type nano composite powder;
s5: according to the volume percentage, 3.5vol% of core-shell nano composite powder, 1.0vol% of magnesia, 0.5vol% of yttrium oxide, 1.0vol% of molybdenum, 1.0vol% of nickel and the balance of alumina/titanium carbide composite matrix are weighed; adding the weighed aluminum oxide/titanium carbide composite matrix into absolute ethyl alcohol, mechanically stirring for 20min to obtain ceramic matrix suspension, adding magnesium oxide, yttrium oxide, molybdenum and nickel, continuously mechanically stirring for 20min to obtain mixed suspension, pouring the obtained mixed suspension into a ball grinding tank, filling nitrogen, and adding ball grinding balls made of hard alloy materials, wherein the ball material ratio is 10:1, performing first ball milling treatment for 48 hours; adding core-shell nano composite powder, continuing to perform ball milling for 2 hours for the second time to obtain ceramic slurry, finally vacuum drying the prepared ceramic slurry at 60 ℃ for 24 hours, sieving with a 100-mesh sieve to obtain ceramic composite powder, and sealing for later use;
s6: and (3) placing the prepared ceramic composite powder into a graphite die for cold press molding treatment to obtain a ceramic block, placing the prepared ceramic block into a hot press sintering furnace, heating to 1650 ℃ at a heating rate of 20 ℃/min, controlling the hot press pressure to be 30MPa, and sintering for 12min to obtain the ceramic cutter material.
The SEM image of the core-shell nanocomposite powder prepared in this example, the SEM topography image of the fracture surface of the test sample of the ceramic tool material, and the XRD image of the test sample of the ceramic tool material are shown in FIGS. 1, 2, and 3, respectively, and it can be seen from FIG. 1 that, when Al having a particle size of 100nm 2 O 3 Extremely thin transparent graphene sheets appear at the edges of the particles, indicating nano Al 2 O 3 The particles are uniformly coated inside by the graphene sheets. Furthermore, it is notable that nano Al 2 O 3 No gaps were observed at the interface between the particles and graphene sheets, indicating graphene and nano-Al 2 O 3 The particles have a strong interaction with each other. As can be seen from fig. 2, the fracture of the ceramic tool composite material exhibits the characteristics of close grain bonding and low porosity. In addition, coating nano Al 2 O 3 The graphene sheets on the surfaces of the particles are subjected to stress exerted by adjacent particles in the sintering process, so that the graphene sheets form a three-dimensional graphene network structure penetrating through the whole composite material. The formation of such unique three-dimensional graphene network structures may be due to the difficulty in achieving uniform distribution of such thin and highly flexible graphene sheets in ceramic materials. As can be seen from FIG. 3, in the XRD phase composition of the tool material, al 2 O 3 And TiC is strong and sharp, and is the main crystal phase of the cutter material, and the intensity and position of the diffraction peak in the figure are basically kept stable, which indicates that the addition of the graphene coated nano particle core-shell-type composite powder does not have obvious influence on the phase composition of the cutter material. In addition, a characteristic diffraction peak of the graphene (002) crystal face is shown at 2θ=26° or so, which indicates that graphene can still exist stably in the ceramic tool material during the high-temperature sintering process.
Comparative example
S1: according to the volume percentage, weighing 3.5vol% of graphene, 1.0vol% of magnesium oxide, 0.5vol% of yttrium oxide, 1.0vol% of molybdenum, 1.0vol% of nickel and the balance of aluminum oxide/titanium carbide composite matrix; adding the weighed aluminum oxide/titanium carbide composite matrix into absolute ethyl alcohol, mechanically stirring for 20min to obtain ceramic matrix suspension, adding magnesium oxide, yttrium oxide, molybdenum and nickel, continuously mechanically stirring for 20min to obtain mixed suspension, pouring the obtained mixed suspension into a ball grinding tank, filling nitrogen, and adding ball grinding balls made of hard alloy materials, wherein the ball material ratio is 10:1, performing first ball milling treatment for 48 hours; adding graphene, continuing to perform ball milling for 2 hours for the second time to obtain ceramic slurry, and finally vacuum drying the prepared ceramic slurry at 60 ℃ for 24 hours, sieving with a 100-mesh sieve to obtain ceramic composite powder, and sealing for later use;
s2: and (3) placing the prepared ceramic composite powder into a graphite die for cold press molding treatment to obtain a ceramic block, placing the prepared ceramic block into a hot press sintering furnace, heating to 1650 ℃ at a heating rate of 20 ℃/min, controlling the hot press pressure to be 30MPa, and sintering for 12min to obtain the ceramic cutter material.
The ceramic tool materials prepared as described above were subjected to performance tests, and the test results are shown in table 1.
TABLE 1
As can be seen from table 1, compared with the comparative example, the ceramic tool material modified by the graphene coated modified ceramic nano powder has more excellent mechanical properties, mainly because the graphene coated modified ceramic nano powder has more excellent dispersibility in the ceramic tool material matrix.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (5)
1. The ceramic cutter material based on the modification of the core-shell nanocomposite powder is characterized by comprising the following components in percentage by volume:
0.1-3.5vol% of core-shell nano composite powder, 0.1-2.0vol% of magnesia, 0.1-1.5vol% of yttrium oxide, 0-1.5vol% of molybdenum, 0-1.5vol% of nickel and the balance of ceramic matrix; the sum of the volume percentages of the components is 100 percent;
the core-shell type nano composite powder is prepared by modifying graphene through a cationic dispersing agent and coating the modified nano ceramic powder on the surface of the modified nano ceramic powder through an anionic surfactant; the cationic dispersing agent is prepared by reacting perylene-3, 4,9, 10-tetracarboxylic dianhydride with vinylamine and then carrying out protonation treatment, and the specific process is as follows: dispersing perylene-3, 4,9, 10-tetracarboxylic dianhydride in toluene by ultrasonic, adding vinylamine, heating to 40-65 ℃ for reflux reaction for 6-36h, cooling to room temperature after reaction, filtering the reaction liquid, washing the filtered precipitate, adding into 10wt% potassium hydroxide solution, stirring at room temperature for 5-7h, filtering the mixture, washing the precipitate, drying, completely dissolving the dried solid in formic acid, adding isopropanol for precipitation treatment, and finally drying the precipitate to obtain the cationic dispersing agent; the vinylamine is one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine; the molar ratio of the perylene-3, 4,9, 10-tetracarboxylic dianhydride to the vinylamine is (5-20): 1, a step of;
the preparation method of the core-shell type nano composite powder comprises the following steps:
(1) Dispersing a cationic dispersing agent in deionized water by ultrasonic, adding graphene, and performing ultrasonic treatment under ice bath conditions to obtain a modified graphene dispersion liquid with the concentration of 0.1-1.2 mg/ml; wherein, the mass ratio of the cationic dispersing agent to the graphene is 1: (1-5); the power of the ultrasonic treatment is 500W, intermittent ultrasonic is adopted during ultrasonic treatment, each ultrasonic treatment lasts for 5 seconds, the ultrasonic treatment is stopped for 5 seconds, and the total ultrasonic time is 0.5-1.5 hours;
(2) Dissolving an anionic surfactant in a mixed solution of deionized water, adding nano ceramic powder, regulating the pH of the solution to 6, performing ultrasonic stirring reaction for 1-3 hours, filtering the reaction solution, drying the filtered precipitate, and dispersing the dried precipitate in the deionized water to prepare a modified nano ceramic powder dispersion with the concentration of 0.5-2 wt%; wherein the anionic surfactant is any one of dodecyl benzene sulfonate, dodecyl sulfate, sodium polyacrylate and fatty acid salt; the mass ratio of the anionic surfactant to the nano ceramic powder is (0.5-2): 1, a step of;
(3) Under the condition of ultrasonic stirring, dripping the modified nano ceramic powder dispersion liquid into the modified graphene dispersion liquid at the speed of 5-20ml/min, continuing stirring for 20-50min after dripping, standing for 1-20h, filtering, washing the precipitate, and performing vacuum drying treatment to obtain core-shell nano composite powder; wherein, the mass ratio of the modified nano ceramic powder to the modified graphene is (10-40): 1.
2. the ceramic cutter material based on the modification of the core-shell nanocomposite powder according to claim 1, wherein the ceramic matrix is micron-sized ceramic powder, and the micron-sized ceramic powder is one or two of aluminum oxide, titanium carbide, silicon nitride, titanium boride, tungsten carbide and silicon carbide; the nano ceramic powder is one or more of aluminum oxide, zirconium oxide, silicon carbide, titanium carbide, tungsten carbide, titanium boride, titanium carbonitride and silicon nitride; the average grain size of the nano ceramic powder is 50-200nm; the average grain size of the ceramic matrix is 0.1-2 mu m.
3. The method for preparing the ceramic cutter material based on the modification of the core-shell nanocomposite powder according to any one of claims 1 to 2, which is characterized by comprising the following steps:
s1, weighing the raw materials according to the volume percentage, adding the weighed ceramic matrix into absolute ethyl alcohol, mechanically stirring to obtain ceramic matrix suspension, adding magnesium oxide, yttrium oxide, molybdenum and nickel, continuously mechanically stirring to obtain mixed suspension, pouring the prepared mixed suspension into a ball grinding tank, filling protective gas, adding ball grinding balls made of hard alloy materials, and performing ball grinding for the first time; adding core-shell nano composite powder, performing ball milling for the second time to obtain ceramic slurry, vacuum drying the ceramic slurry, sieving with 100-200 mesh sieve to obtain ceramic composite powder, and sealing for use;
and S2, placing the prepared ceramic composite powder into a graphite die for cold press molding treatment to obtain a ceramic block, and placing the prepared ceramic block into a hot press sintering furnace for sintering treatment to obtain the ceramic cutter material.
4. The method for preparing a ceramic tool material based on modification of core-shell nanocomposite powder according to claim 3, wherein in step S1, the shielding gas is one of argon and nitrogen; ball material ratio in ball milling treatment is (10-20): 1, a step of; the time of the first ball milling treatment is 45-50h, and the time of the second ball milling treatment is 1-3h.
5. The method for preparing a ceramic tool material based on modification of core-shell nanocomposite powder according to claim 3, wherein in step S2, the sintering process conditions are as follows: sintering temperature is 1600-2000 ℃, hot pressing pressure is 25-35MPa, heating rate is 10-20 ℃/min, and heat preservation time is 10-30min.
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