CN109112330B - Nano onion carbon reinforced titanium-based composite material and preparation method thereof - Google Patents
Nano onion carbon reinforced titanium-based composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano onion carbon reinforced titanium-based composite material and a preparation method thereof, wherein the composite material mainly comprises nano onion carbon and matrix titanium, wherein the nano onion carbon is used as a reinforcing phase and is uniformly distributed in the matrix of the metal titanium to play a role in dispersion strengthening; aiming at the defects in the prior art, the invention synthesizes nano onion carbon by using nano diamond as a raw material, the nano onion carbon is added into a titanium matrix to obtain uniform distribution, and the compact titanium matrix composite is obtained by sintering and molding.
Description
Technical Field
The invention relates to a nano onion carbon reinforced titanium-based composite material and a preparation method thereof, belonging to the technical field of metal-based composite materials.
Background
Titanium and titanium alloy are new metals rising after steel and aluminum, and have the characteristics of low density, high strength, high and low temperature resistance, corrosion resistance, good biocompatibility and the like. The outstanding characteristics promote titanium and titanium alloy to become ideal materials in the industries of aviation, spacecraft, oceans, petrochemical industry, biomedicine and the like. Meanwhile, titanium and titanium alloy also have the main problems of poor wear resistance, low hardness and the like. New ideas and methods are urgently needed to further improve the comprehensive mechanical properties of the titanium alloy and meet the requirements of various related industries.
The nano onion-like carbon is called as onion carbon for short, the size of the nano onion-like carbon is about 3-50nm, and is called as secondary carbon60Carbon nanotubes, a new member of the fullerene family, is a new allotrope of carbon. The onion carbon has a multi-layer spherical structure formed by curling concentric graphite layers and is sp of carbon atoms2Zero-dimensional carbon materials exist in a hybrid manner. Compared with nanodiamond, it differs from nanodiamond strongly due to its unique structural features (carbon atoms sp)3Hybridization) carbon atom hybridization mode, so that the nano onion carbon has many excellent properties. For example, large specific surface area, nano-size effects, high electrical conductivity and thermal stability, and closed stable structures. The nano onion carbon has good application prospect in catalysis, friction, supercapacitors, electromagnetic shielding and composite materials. The preparation method of nano onion carbon is divided into physical method and chemical methodThe method is divided into two types. The physical methods mainly include arc discharge, electron beam irradiation, plasma and the like; the chemical method mainly comprises chemical vapor deposition, heat treatment of the nano-diamond and the like. For example: the patent "high-temperature high-pressure preparation method of nano onion carbon" (CN105833797A), but high pressure is required, and the single operation period is long; the patent "a preparation method of in-situ generated nano onion carbon" (CN108220910A) has high requirements on a matrix and low yield. The production of the nano-diamond is industrialized, wherein the method for preparing the nano-onion carbon by heat treatment of the nano-diamond has more research and simple operation, but the conventional furnace needs high temperature (1500 ℃ and above), long heat preservation time (2-5hs) and high energy consumption.
Like most carbon materials, the nano onion carbon can also be applied to composite material additives to improve the comprehensive performance of the composite material. At present, the research in the aspect mainly aims at improving the friction and wear performance, the wave absorbing performance and the electrical performance of the composite material; such as: the patent discloses a carbon structure film and graphene additive solid-liquid composite friction-reducing and wear-resisting method (CN108048160A), the patent discloses a preparation method of an onion carbon/MXene layered wave-absorbing composite material (CN107645065A), the patent discloses an organic solar cell based on an onion carbon nano particle/Ag composite electrode and a preparation method thereof (CN106449996A) and the like. It is worth noting that the research on the mechanical properties of the metal matrix composite material with nano onion carbon as an additive is less, and only a few relevant documents exist; such as: the nano onion Carbon reinforcing phase (Carbon 129(2018)631) is synthesized by the nano diamond in the nickel (Ni) based composite material by an in-situ self-generation method. In recent years, with the continuous discovery of nano structures such as nano diamond, carbon nano tube and graphene, the nano structure is widely applied to titanium-based alloy materials as a reinforcing phase, and simultaneously, good effects are obtained. However, the metal matrix composite reinforced with carbon nanotubes and graphene sheets suffers from a series of problems in preparation, such as easy entanglement of carbon nanotubes and easy agglomeration of graphene sheets.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a nano onion carbon reinforced titanium-based composite material which mainly comprises nano onion carbon and matrix titanium; wherein, the nano onion carbon is used as a reinforcing phase and is uniformly dispersed in the titanium matrix.
The invention also aims to provide a preparation method of the nano onion carbon reinforced titanium-based composite material, which utilizes nano diamond powder as a raw material to obtain nano onion carbon through a discharge plasma sintering furnace under specific parameters, and the process method has the advantages of low temperature requirement, short heat preservation time, low energy consumption, high conversion rate of the obtained nano onion carbon, low impurity content and complete structure; then the nano onion carbon is added into a titanium matrix to prepare the titanium matrix composite, and the nano onion carbon is uniformly distributed in the titanium matrix and keeps the complete shape, so that the composite has good comprehensive mechanical properties.
The technical scheme is as follows: in order to achieve the purpose, the invention is realized by the following technical scheme:
a nanometer onion carbon reinforced titanium-based composite material mainly comprises nanometer onion carbon and matrix titanium, and is characterized in that nanometer onion carbon particles are taken as a reinforcing phase and are introduced into a metal titanium matrix; the nano onion carbon particles are uniformly dispersed in the titanium matrix, so that the dispersion strengthening effect can be achieved, and the comprehensive mechanical property of titanium is improved;
the addition proportion of the nano onion carbon is 0.1-3.0% of the mass of the matrix titanium, and the addition proportion of the alcohol dispersant is 10-30% of the mass of the nano onion carbon, wherein the mass of the matrix titanium in the nano onion carbon reinforced titanium-based composite material is 100%.
The nano onion carbon reinforcing phase is prepared from nano diamond (with the size of 3-50nm) synthesized by an explosion method as a raw material, is synthesized by a discharge plasma sintering furnace under specific technological parameters, has high conversion rate, regular shape, less defects and complete structure, and can be used for nano onion carbon powder of a composite material reinforcing phase.
The particle size of the nano onion carbon powder is 3-50nm, and the particle size of the matrix titanium is 0.1-800 mu m.
The density of the nano onion carbon reinforced titanium-based composite material is up to 98-99.9%.
The matrix titanium is pure titanium, titanium-aluminum-vanadium (Ti6Al4V), titanium-molybdenum (TiMo), titanium-nickel (TiNi), titanium-tantalum (TiTa) or titanium-niobium-zirconium (TiNbZr).
The preparation method of the nano onion carbon reinforced titanium-based composite material comprises the following steps:
(1) preparation of raw materials: taking nano diamond powder, filling the nano diamond powder into a graphite mold, and then carrying out discharge plasma sintering on the mold, wherein the set sintering parameters are as follows: the temperature rising speed is 20-100 ℃/min, the temperature is 1300-1450 ℃, the heat preservation time is 10-30 min, the pressure is non-pressure or low pressure (1-3kN), the sintering atmosphere is vacuum, and the cooling time is 10-30 min, so that the nano onion carbon is obtained;
(2) weighing raw materials: weighing the nano onion carbon, the matrix titanium and the alcohol dispersant;
(3) liquid phase chemical mixing: firstly, mixing nano onion carbon powder and a dispersing agent, dispersing the nano onion carbon powder and the dispersing agent into an absolute ethyl alcohol solution, simultaneously dispersing titanium powder into the absolute ethyl alcohol solution, then uniformly mixing the two solutions, and finally ball-milling the solution, wherein the ball-to-material ratio is 8: 1-15: 1, rotating at a speed of 100-300 r/min, alternately rotating positively and negatively, and ball-milling for 5-10 h;
(4) and (3) drying: vacuumizing and drying the mixed powder ball-milled in the step (3) for 1-10 hours at the drying temperature of 40-100 ℃, and sieving the powder through a 200-400-mesh sieve after complete drying;
(5) sintering and forming: and (4) according to the size parameters of the required product, taking the product obtained in the step (4), and performing discharge plasma sintering, hot-pressing sintering or vacuum pressureless sintering to obtain the required nano onion carbon reinforced titanium-based composite material.
The adding proportion of the nano onion carbon is 0.1-3.0% of the mass of the matrix titanium in percentage by mass; the adding proportion of the alcohol dispersant is 10-30% of the mass of the nano onion carbon in percentage by weight of the nano onion carbon.
The prepared titanium-based composite material can be regulated and controlled to be added with nano onion carbon with different contents according to the mechanical strength requirements of materials with different purposes so as to prepare the titanium-based composite material with different strong plasticity.
Preferably, the preparation method of the nano onion carbon reinforced titanium-based composite material comprises the following specific steps:
(1) preparation of raw materials: taking nano diamond powder (with the particle size of 3-50nm), putting the nano diamond powder into a graphite die with graphite paper on the periphery and the upper and lower surfaces, and ensuring that the upper and lower graphite pressure heads can contact the nano diamond powder; then the filled mould is loaded into a discharge plasma sintering furnace (SPS), and sintering parameters are set as follows: the temperature rising speed is 20-100 ℃/min, the temperature is 1300-1450 ℃, the heat preservation time is 10-30 min, the pressure is non-pressure or low pressure (1-3kN), the sintering atmosphere is vacuum, and the cooling time is 10-30 min, so that the nano onion carbon with high shape regularity and conversion rate is obtained.
(2) Weighing raw materials: firstly, weighing appropriate 325-mesh titanium powder, weighing the nano onion carbon powder in the step (1) according to 0.1-3.0% of the titanium powder by mass fraction, and weighing an alcohol-based dispersing agent with the weight of 10-30% of the nano onion carbon powder by mass fraction.
(3) Liquid phase chemical mixing: putting the nano onion carbon powder weighed in the step (2) and a dispersing agent into a beaker, adding a proper amount of absolute ethyl alcohol solution, and carrying out ultrasonic oscillation for 30-40 min; meanwhile, putting the weighed titanium powder into another beaker, adding a proper amount of absolute ethyl alcohol solution, and carrying out ultrasonic treatment for 30-40 min; transferring the two ultrasonic solutions into the same beaker, and then carrying out ultrasonic treatment for 30-40 min; and finally pouring the solution into a ball milling tank, wherein the ball-material ratio is 8: 1-15: 1, alternately rotating the ball mill in a positive and negative direction at a rotating speed of 100-300 r/min for 5-10 h.
(4) And (3) drying: and (4) vacuumizing and drying the mixed powder ball-milled in the step (3) for 1-10 hours at the drying temperature of 40-100 ℃, and sieving the powder through a 200-400-mesh sieve after complete drying.
(5) Sintering and forming: and (4) according to the size parameters of the required product, taking the product in the step (4), and performing spark plasma sintering, hot-pressing sintering and vacuum pressureless sintering to obtain the required nano onion carbon reinforced titanium-based composite material.
Preferably, in step 5:
the pressure used for sintering the discharge plasma is 20-100 MPa, the temperature is 800-1000 ℃, the temperature rising speed is 20-150 ℃/min, the heat preservation time at the highest sintering temperature is 1-60 min, and the sintering atmosphere is high-purity argon or vacuum;
the hot-pressing sintering is carried out under the protection of vacuum or inert atmosphere, the pressure is 10-80 MPa, the temperature is 1000-1400 ℃, the temperature rising speed is 10-100 ℃/min, and the heat preservation time at the highest sintering temperature is 10-180 min;
the sintering temperature for the vacuum pressureless sintering is 1100-1500 ℃, the heating rate is 10-80 ℃/min, and the heat preservation time is 30-240 min;
according to the nano onion carbon reinforced titanium-based composite material, the nano onion carbon reinforced phase is the nano onion carbon powder which is searched and synthesized continuously through the exploration and synthesis process and is used for the reinforced phase of the composite material, the nano onion carbon is finally successfully synthesized, the nano onion carbon powder is complete in structure, high in conversion rate and few in defects, and can be used for the reinforced phase of the composite material, so that the excellent toughening effect of the zero-dimensional nano material reinforced titanium and titanium alloy with excellent performance of the nano onion carbon is realized, and the result also shows that the nano onion carbon reinforced titanium-based composite material has good comprehensive mechanical properties, and the application range of the titanium alloy is widened.
The technical effects are as follows: compared with the prior art, the method takes the nano-diamond as the raw material, and utilizes the discharge plasma sintering to successfully synthesize the nano-onion carbon powder with complete structure and high conversion rate; meanwhile, the problems of poor mechanical property of the traditional pure titanium and easy entanglement of the carbon nano tube and easy agglomeration of the graphene when the carbon nano tube or the graphene is used as a reinforcing phase of the titanium-based composite material are solved, and in the nano onion carbon reinforced titanium-based composite material prepared by the invention, the nano onion carbon is uniformly distributed, the impurity content is low, and the nano onion carbon reinforced titanium-based composite material has higher hardness, strength and plasticity levels, and is a titanium-based composite material with excellent comprehensive mechanical property.
Drawings
FIG. 1 is a transmission electron microscope picture of nano onion carbon powder prepared by spark plasma sintering technique using nano diamond as raw material;
FIG. 2 is an X-ray diffractometer spectrum of nano onion carbon powder prepared by spark plasma sintering technique using nano diamond as raw material;
FIG. 3 is a scanning electron microscope picture of the distribution of nano onion carbon in the ball milled raw material on the surface of titanium powder;
FIG. 4 is an X-ray diffractometer spectra of nano onion carbon reinforced titanium matrix composites of different nano onion carbon content and pure titanium;
FIG. 5 is a graph of the microhardness trends of nano onion carbon reinforced titanium matrix composites of different nano onion carbon content and pure titanium;
FIG. 6 is a graph of the trend of compressive strength of nano-onion carbon reinforced titanium matrix composites of different nano-onion carbon content and pure titanium;
FIG. 7 is a scanning electron microscope topography of a compressive fracture of a nano onion carbon reinforced titanium matrix composite article with a content of 1.0%.
Detailed Description
The invention is further explained below with reference to the drawings and the specific embodiments;
example 1
A preparation method of nanometer onion carbon reinforced titanium matrix composite material comprises the steps of firstly, taking nanometer diamond (with the size of about 5 nm) as a raw material, and sintering by utilizing discharge plasma to synthesize nanometer onion carbon powder capable of being used as a reinforcing phase; nano onion carbon powder and pure titanium powder (with the purity of 99%) are used as raw materials, wherein the grain size of the nano onion carbon is 5-10 nm, the grain size of the pure titanium powder is 45 microns (325 meshes), and the nano onion carbon powder and the pure titanium powder are nano powder and micron powder respectively; a cylindrical composite sintered body having a diameter of 20mm and a height of 12mm was produced using a graphite mold having a diameter of 20 mm.
The method comprises the following specific steps:
(1) weighing 2g (according to requirements) of nano-diamond powder produced by an explosion method, wherein the average size is 5nm, putting the nano-diamond powder into a graphite die with graphite paper on the periphery and the upper and lower surfaces, and ensuring that the upper and lower graphite pressure heads can contact the nano-diamond powder; then the filled die is loaded into a plasma sintering furnace, and the sintering parameters are set as follows: the heating speed is 25 ℃/min, the temperature is 1400 ℃, the heat preservation time is 15min, the pressure is non-pressure, and the cooling time is 10 min; and observing the prepared raw materials by using a transmission electron microscope to find out the nano onion carbon with regular shape and high conversion rate.
(2) Weighing 50g of 325-mesh titanium powder (with the purity of 99%), weighing the nano onion carbon powder in the step (1) according to 0.25% of the mass of the titanium powder by mass fraction, and simultaneously weighing an alcohol-based dispersing agent with the mass fraction of 30% of the mass of the nano onion carbon powder.
(3) Putting the nano onion carbon powder weighed in the step (2) and the alcohol-based dispersing agent into the same beaker, adding a proper amount of absolute ethyl alcohol solution, and carrying out ultrasonic oscillation for 30 min; meanwhile, putting the weighed titanium powder into another beaker, adding a proper amount of absolute ethyl alcohol solution, and carrying out ultrasonic treatment for 30 min; transferring the two ultrasonic solutions into the same beaker, and then carrying out ultrasonic treatment for 30 min; and finally pouring the mixed solution into a ball milling tank, wherein the ball-material ratio is 8: 1, alternately rotating the ball mill in a positive and negative way at the rotating speed of 250r/min for 6 hours.
(4) Placing the mixed powder ball-milled in the step (3) in a vacuum drying oven, vacuumizing and drying for 8 hours at the drying temperature of 100 ℃, and sieving by using a 300-mesh sieve after completely drying; determining the size parameters of the sintered product: phi 20mm, h 12mm, the mass of the powder required was calculated to be 16.99g according to the density formula.
(5) Weighing 16.99g of sieved powder, pouring the powder into a graphite mold, and ensuring that graphite sheets are filled around, on the upper surface and on the lower surface of the graphite mold, and an upper pressure head and a lower pressure head can contact with a sample; placing the mixture into a discharge plasma sintering furnace for sintering and forming, under the protection of vacuum or high-purity argon, at the pressure of 70MPa and the temperature of 900 ℃, measuring the temperature by using a thermocouple or infrared temperature measuring mode, wherein the heating speed is 100 ℃/min, the heat preservation time at the highest sintering temperature is 10min, cooling the mixture by using cooling water for 10min, and demolding to obtain a product;
the relative density of the sintered product is measured by an Archimedes method, and the calculated density is as high as 99.9%.
Characterization of the samples: observing the dispersion degree of the nano onion carbon on the matrix of the powder subjected to ball milling and drying by using a scanning electron microscope, respectively carrying out phase analysis on the sample by using an X-ray diffractometer, measuring microhardness by using a microhardness meter, carrying out a compression test by using a microcomputer-controlled electronic universal testing machine, and finally observing and analyzing the fracture morphology by using the scanning electron microscope.
Example 2
A preparation method of nanometer onion carbon reinforced titanium matrix composite material comprises the steps of firstly, sintering nanometer diamond (with the size of about 10 nm) serving as a raw material by utilizing discharge plasma to synthesize nanometer onion carbon powder serving as a reinforcing phase; nano onion carbon powder and Ti6Al4V titanium alloy powder (with the purity of 99%) are used as raw materials, wherein the particle size of the nano onion carbon is 10nm, the grain size of the pure titanium powder is 38 mu m (400 meshes), and the nano onion carbon powder and the pure titanium powder are nano powder and micron powder respectively; a cylindrical composite sintered body having a diameter of 20mm and a height of 12mm was produced using a graphite mold having a diameter of 20 mm. The method comprises the following specific steps:
(1) weighing 2g (according to requirements) of nano-diamond powder produced by an explosion method, wherein the average size is 10nm, putting the nano-diamond powder into a graphite die with graphite paper on the periphery and the upper and lower surfaces, and ensuring that the upper and lower graphite pressure heads can contact the nano-diamond powder; then the filled die is loaded into a plasma sintering furnace, and the sintering parameters are set as follows: the heating rate is 50 ℃/min, the temperature is 1450 ℃, the heat preservation time is 20min, the pressure is non-pressure, and the cooling time is 10 min; and observing the prepared raw materials by using a transmission electron microscope to find out the nano onion carbon with regular shape and high conversion rate.
(2) Weighing 50g of 400-mesh Ti6Al4V powder, weighing the nano onion carbon powder in the step (1) according to 0.7% of the mass of the titanium powder by mass fraction, and weighing an alcohol-based dispersing agent with the mass fraction of 30% of the mass of the nano onion carbon powder.
(3) Putting the nano onion carbon powder weighed in the step (2) and the alcohol-based dispersing agent into the same beaker, adding a proper amount of absolute ethyl alcohol solution, and carrying out ultrasonic oscillation for 30 min; meanwhile, putting the weighed titanium powder into another beaker, adding a proper amount of absolute ethyl alcohol solution, and carrying out ultrasonic treatment for 30 min; transferring the two ultrasonic solutions into the same beaker, and then carrying out ultrasonic treatment for 30 min; and finally pouring the mixed solution into a ball milling tank, wherein the ball-material ratio is 8: 1, alternately rotating the ball mill in a positive and negative way at the rotating speed of 250r/min for 6 hours.
(4) Placing the mixed powder ball-milled in the step (3) in a vacuum drying oven, vacuumizing and drying for 8 hours at the drying temperature of 100 ℃, and sieving by using a 300-mesh sieve after completely drying; determining the size parameters of the sintered product: phi 20mm, h 12mm, the mass of the powder required was calculated to be 16.99g according to the density formula.
(5) Weighing 16.99g of sieved powder, pouring the powder into a graphite mold, and ensuring that graphite sheets are filled around, on the upper surface and on the lower surface of the graphite mold, and an upper pressure head and a lower pressure head can contact with a sample; placing the mixture into a discharge plasma sintering furnace for sintering and molding, under the protection of vacuum or high-purity argon, at the pressure of 70MPa and the temperature of 900 ℃, measuring the temperature by using a thermocouple or infrared temperature measuring mode, wherein the heating speed is 100 ℃/min, the heat preservation time at the highest sintering temperature is 10min, cooling the mixture by using cooling water for 10min, and demolding to obtain a product;
the relative density of the sintered product is measured by an Archimedes method, and the calculated density is as high as 99.9%.
Characterization of the samples: observing the dispersion degree of the nano onion carbon on the matrix of the powder subjected to ball milling and drying by using a scanning electron microscope, respectively carrying out phase analysis on the sample by using an X-ray diffractometer, measuring microhardness by using a microhardness meter, carrying out a compression test by using a microcomputer-controlled electronic universal testing machine, and finally observing and analyzing the fracture morphology by using the scanning electron microscope.
Example 3
A preparation method of nanometer onion carbon reinforced titanium matrix composite material comprises sintering nanometer diamond (about 20nm in size) as raw material with discharge plasma to synthesize nanometer onion carbon powder as reinforcing phase; adopting nano onion carbon powder and titanium nickel powder as raw materials, wherein the grain size of the nano onion carbon is 20nm, the grain size of the pure titanium powder is 106 microns (150 meshes), and the nano onion carbon powder and the titanium nickel powder are nano powder and micron powder respectively; a cylindrical composite sintered body having a diameter of 30mm and a height of 10mm was produced using a graphite mold having a diameter of 30 mm.
The method comprises the following specific steps:
(1) weighing 2g (according to requirements) of nano-diamond powder produced by an explosion method, wherein the average size is 20nm, putting the nano-diamond powder into a graphite die with graphite paper on the periphery and the upper and lower surfaces, and ensuring that the upper and lower graphite pressure heads can contact the nano-diamond powder; then the filled die is loaded into a plasma sintering furnace, and the sintering parameters are set as follows: the heating speed is 100 ℃/min, the temperature is 1300 ℃, the heat preservation time is 30min, the pressure is non-pressure, the cooling time is 10min, and the vacuum protection is carried out; and observing the prepared raw materials by using a transmission electron microscope to find out the nano onion carbon with regular shape and high conversion rate.
(2) Weighing 100g of 150-mesh titanium nickel powder, weighing the nano onion carbon powder in the step (1) according to 0.5% of the mass of the titanium powder by mass fraction, and weighing an alcohol-based dispersing agent with the mass fraction of 30% of the mass of the nano onion carbon powder.
(3) Putting the nano onion carbon powder weighed in the step (2) and the alcohol-based dispersing agent into the same beaker, adding a proper amount of absolute ethyl alcohol solution, and carrying out ultrasonic oscillation for 30 min; meanwhile, putting the weighed titanium powder into another beaker, adding a proper amount of absolute ethyl alcohol solution, and carrying out ultrasonic treatment for 30 min; transferring the two ultrasonic solutions into the same beaker, and then carrying out ultrasonic treatment for 30 min; and finally pouring the mixed solution into a ball milling tank, wherein the ball-material ratio is 10: 1, alternately rotating the ball mill in a positive and negative way at the rotating speed of 300r/min, and carrying out ball milling for 6 h.
(4) Placing the mixed powder ball-milled in the step (3) in a vacuum drying oven for vacuum drying for 8 hours at the drying temperature of 100 ℃, and sieving the powder by using a 200-mesh sieve after completely drying; determining the size parameters of the sintered product: phi 20mm, h 10mm, the mass of powder required calculated according to the density formula is 14.13 g.
(5) Weighing 14.13g of sieved powder, pouring the powder into a steel mould, performing compression molding under the pressure of 200-500 MPa, demolding to obtain a cold pressed blank, then placing the cold pressed blank in a vacuum sintering furnace for sintering molding, performing pressureless sintering molding under the protection of vacuum, wherein the heating rate is 10 ℃/min, performing heat preservation for 120min at the highest temperature of 1300 ℃, and performing natural cooling and demolding to obtain the nano onion carbon reinforced titanium-based composite material;
the sintered product has a relative density as high as 99.9% as measured by Archimedes' method.
Characterization of the samples: observing the dispersion degree of the nano onion carbon on the matrix of the powder subjected to ball milling and drying by using a scanning electron microscope, respectively carrying out phase analysis on the sample by using an X-ray diffractometer, measuring microhardness by using a microhardness meter, carrying out a compression test by using a microcomputer-controlled electronic universal testing machine, and finally observing and analyzing the fracture morphology by using the scanning electron microscope.
Example 4
A preparation method of nanometer onion carbon reinforced titanium matrix composite material comprises sintering nanometer diamond (about 50nm in size) as raw material with discharge plasma to synthesize nanometer onion carbon powder as reinforcing phase; adopting nano onion carbon powder and TiTa titanium alloy powder as raw materials, wherein the particle size of the nano onion carbon is 50nm, the size of the TiTa powder is 13 mu m (1000 meshes), and the nano onion carbon powder and the TiTa powder are respectively nano powder and micron powder; a cylindrical composite sintered body having a diameter of 30mm and a height of 25mm was produced.
The method comprises the following specific steps:
(1) weighing 2g (according to requirements) of nano-diamond powder produced by an explosion method, wherein the average size is 50nm, putting the nano-diamond powder into a graphite die with graphite paper on the periphery and the upper and lower surfaces, and ensuring that the upper and lower graphite pressure heads can contact the nano-diamond powder; then the filled mold is put into a plasma sintering furnace (sintering parameters are set as the temperature rising speed is 80 ℃/min, the temperature is 1400 ℃, the heat preservation time is 20min, the pressure is non-pressure, and the cooling time is 10 min), and the prepared raw materials are observed by using a transmission electron microscope to find out the nano onion carbon with regular shape and high conversion rate.
(2) Weighing 100g of 600-mesh TiTa alloy powder, weighing the nano onion carbon powder in the step (1) according to 2.5% of the mass of TiTa, and simultaneously weighing an alcohol-based dispersing agent with the mass fraction of 30% of the mass of the nano onion carbon powder.
(3) Putting the nano onion carbon powder weighed in the step (2) and the alcohol-based dispersing agent into the same beaker, adding a proper amount of absolute ethyl alcohol solution, and carrying out ultrasonic oscillation for 30 min; meanwhile, putting the weighed TiTa powder into another beaker, adding a proper absolute ethyl alcohol solution, and carrying out ultrasonic treatment for 30 min; transferring the two ultrasonic solutions into the same beaker, and then carrying out ultrasonic treatment for 30 min; and finally pouring the mixed solution into a ball milling tank, wherein the ball-material ratio is 15: 1, alternately rotating the ball mill in a positive and negative way at the rotating speed of 350r/min for 5 hours.
(4) Placing the mixed powder ball-milled in the step (3) in a vacuum drying oven for vacuum drying for 6 hours at the drying temperature of 100 ℃, and sieving by using a 300-mesh sieve after complete drying; determining the size parameters of the sintered product: phi 30mm, h 25mm, and the mass of the powder required was calculated to be 78.60g according to the density formula.
(5) Weighing 78.60g of sieved powder, and filling the powder into a graphite die with the diameter of phi 30 to ensure that graphite sheets are filled around, on the upper surface and on the lower surface in the graphite die, and an upper pressure head and a lower pressure head can contact with a sample; loading into a hot-pressing sintering furnace, keeping the temperature for 60min at the maximum sintering temperature of 1200 ℃ under the vacuum condition and the pressure of 30MPa, naturally cooling, and demolding to obtain a product;
the sintered product has a relative density as high as 99.9% as measured by Archimedes' method.
Performance testing and organizational structure analysis: observing the dispersion degree of the nano onion carbon on the matrix of the powder subjected to ball milling and drying by using a scanning electron microscope, respectively carrying out phase analysis on the sample by using an X-ray diffractometer, measuring microhardness by using a microhardness meter, carrying out a compression test by using a microcomputer-controlled electronic universal testing machine, and finally observing and analyzing the fracture morphology by using the scanning electron microscope.
Example 5
The process is the same as example 1 except that:
the prepared nano onion carbon reinforced titanium-based composite material has the matrix titanium of titanium molybdenum, and the particle size of powder of titanium molybdenum
0.1 μm, wherein the adding proportion of the nano onion carbon is 0.1 percent of the mass of the matrix titanium.
The relative density of the sintered product is measured by an Archimedes method, and the calculated density is as high as 99.7%.
Performance testing and organizational structure analysis: observing the dispersion degree of the nano onion carbon on the matrix of the powder subjected to ball milling and drying by using a scanning electron microscope, respectively carrying out phase analysis on the sample by using an X-ray diffractometer, measuring microhardness by using a microhardness meter, carrying out a compression test by using a microcomputer-controlled electronic universal testing machine, and finally observing and analyzing the fracture morphology by using the scanning electron microscope.
Example 6
The process is the same as example 1 except that:
in the prepared nano onion carbon reinforced titanium-based composite material, the matrix titanium is TiNbZr, the particle size of powder of the TiNbZr is 800 mu m, and the adding proportion of the nano onion carbon is 3.0 percent of the mass of the matrix titanium by mass fraction.
The relative density of the sintered product is measured by an Archimedes method, and the calculated density is as high as 99.9%.
Performance testing and organizational structure analysis: observing the dispersion degree of the nano onion carbon on the matrix of the powder subjected to ball milling and drying by using a scanning electron microscope, respectively carrying out phase analysis on the sample by using an X-ray diffractometer, measuring microhardness by using a microhardness meter, carrying out a compression test by using a microcomputer-controlled electronic universal testing machine, and finally observing and analyzing the fracture morphology by using the scanning electron microscope.
The attached figure 1 of the specification is a high-resolution transmission electron microscope photo of nano onion carbon powder which is synthesized by adopting a blasting method to synthesize nano diamond with the size of 5nm as a raw material and utilizing a discharge plasma sintering instrument successfully through exploring process parameters; the nano diamond synthesized by the process parameters has regular structure and high purity, and meets the requirement of serving as an enhanced phase.
Description figure 2 is an XRD pattern of nano onion carbon powder successfully synthesized by a spark plasma sintering instrument by using nano diamond with the size of 5nm synthesized by an explosion method as a raw material and exploring process parameters.
The attached figure 3 in the specification is a scanning electron microscope picture of mixed powder after ball milling and drying, and the nano onion carbon powder can be found to be uniformly distributed on a titanium powder substrate;
the attached figure 4 in the specification is an XRD (X-ray diffraction) pattern of the nano onion carbon reinforced titanium-based composite material and pure titanium with different contents, and it can be seen that trace titanium carbide (TiC) phase is generated in a certain content along with the increase of the addition amount;
the attached figures 5 and 6 of the specification are respectively a Vickers hardness trend graph and a corresponding stress-strain curve graph of compressive strength of the nano onion carbon reinforced titanium-based composite material and pure titanium with different contents; with the combination of fig. 4 and 5, the hardness and strength of the composite material prepared with the increase of the content of the nano onion carbon are obviously improved compared with those of pure titanium, but the plasticity is also reduced to different degrees, but it can be seen that when the addition amount of the nano onion carbon is below 0.5%, the strength is improved, and simultaneously, the good plasticity can be still maintained; when the carbon carbide phase (TiC) appears in the matrix, the plasticity of the composite material is reduced faster, so that the nano onion carbon content of the optimized nano onion carbon reinforced titanium-based composite material is 0.35 percent; in addition, the nano onion carbon with different contents can be regulated and controlled to be added according to the mechanical strength requirements of materials with different purposes so as to prepare the titanium-based composite materials with different strong plasticity.
Description figure 7 is a scanning electron microscope image of a compression fracture of a titanium-based composite material added with 1.0 wt% of nano onion carbon, and can show that the nano onion carbon reinforced titanium-based composite material has certain plasticity while improving the strength.
It is to be understood that these examples are intended only for the purpose of illustrating the invention and are not intended to limit the scope of the invention, which is defined in the appended claims to the full extent permitted by those skilled in the art after perusal of this application.
Claims (6)
1. A nano onion carbon reinforced titanium-based composite material is characterized in that the composite material mainly comprises nano onion carbon and matrix titanium; wherein, the nano onion carbon is used as a reinforcing phase and is uniformly dispersed in a titanium matrix;
the preparation method of the nano onion carbon reinforced titanium-based composite material comprises the following steps:
(1) preparation of raw materials: taking nano diamond powder, filling the nano diamond powder into a graphite mold, and then carrying out discharge plasma sintering on the mold, wherein the set sintering parameters are as follows: the temperature rising speed is 20-100 ℃/min, the temperature is 1300-1450 ℃, the heat preservation time is 10-30 min, the pressure is non-pressure or low pressure (1-3kN), the sintering atmosphere is vacuum, and the cooling time is 10-30 min, so that the nano onion carbon is obtained;
(2) weighing raw materials: weighing the nano onion carbon, the matrix titanium and the alcohol dispersant;
(3) liquid phase chemical mixing: mixing nano onion carbon powder and a dispersing agent, dispersing the mixture into an absolute ethyl alcohol solution, dispersing titanium powder into the absolute ethyl alcohol solution, uniformly mixing the two solutions, and finally performing ball milling on the solution, wherein the ball-material ratio is 8: 1-15: 1, the rotating speed is 100-300 r/min, the rotation is alternately performed in a positive and negative way, and the ball milling is performed for 5-10 hours;
(4) and (3) drying: vacuumizing and drying the mixed powder ball-milled in the step (3) for 1-10 hours at the drying temperature of 40-100 ℃, and sieving the powder through a 200-400-mesh sieve after complete drying;
(5) sintering and forming: and (4) according to the size parameters of the required product, taking the product obtained in the step (4), and performing discharge plasma sintering, hot-pressing sintering or vacuum pressureless sintering to obtain the required nano onion carbon reinforced titanium-based composite material.
2. The nano onion carbon-reinforced titanium-based composite material of claim 1, wherein the nano onion carbon has a particle size of 3 to 50nm, and the matrix titanium has a particle size of 0.1 to 800 μm.
3. The nano onion carbon reinforced titanium matrix composite material of claim 1, wherein the density of the nano onion carbon reinforced titanium matrix composite material is up to 98-99.9%.
4. The nano onion carbon reinforced titanium based composite material of claim 1, wherein the matrix titanium is pure titanium, titanium aluminum vanadium (Ti6a14V), titanium molybdenum (TiMo), titanium nickel (TiNi), titanium carbon (TiTa), or titanium niobium zirconium (TiNbZr).
5. The nano onion carbon reinforced titanium-based composite material as claimed in claim 1, wherein the nano onion carbon is added in a proportion of 0.1-3.0% by mass of the matrix titanium; the adding proportion of the alcohol dispersant is 10-30% of the mass of the nano onion carbon in percentage by weight of the nano onion carbon.
6. The nano onion carbon reinforced titanium matrix composite according to claim 1, wherein in step (5):
the pressure used for sintering the discharge plasma is 20-100 MPa, the temperature is 800-1000 ℃, the temperature rising speed is 20-150 ℃/min, the heat preservation time at the highest sintering temperature is 1-60 min, and the sintering atmosphere is high-purity argon or vacuum;
the hot-pressing sintering is carried out under the protection of vacuum or inert atmosphere, the pressure is 10-80 MPa, the temperature is 1000-1400 ℃, the temperature rising speed is 10-100 ℃/min, and the heat preservation time at the highest sintering temperature is 10-180 min;
the sintering temperature for vacuum pressureless sintering is 1100-1500 ℃, the heating rate is 10-80 ℃/min, and the heat preservation time is 30-240 min.
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