CN111635231B - Preparation method of polycrystalline diamond transparent ceramic - Google Patents
Preparation method of polycrystalline diamond transparent ceramic Download PDFInfo
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Abstract
The invention provides a preparation method of polycrystalline diamond transparent ceramic, which takes diamond micro powder as a raw material and comprises the following process steps: (1) the carbon-containing purity requirement of the raw material diamond micro powder is more than 99 percent, the diamond micro powder with the carbon-containing purity not meeting the requirement is firstly subjected to impurity removal treatment and then subjected to vacuum heat treatment, and the diamond micro powder with the carbon-containing purity meeting the requirement is directly subjected to vacuum heat treatment to remove oxygen, nitrogen or water vapor adsorbed on the surface of the diamond micro powder; (2) putting the diamond micro powder subjected to vacuum heat treatment into a cleaned metal foil for prepressing and forming; (3) and sintering the parison wrapped by the metal foil for 10-2000 s at the pressure of 10-30 GPa and the temperature of 1500-3000 ℃, reducing the pressure and the temperature to the room temperature at normal pressure after the sintering time is up, and removing the metal foil by using inorganic acid to obtain the polycrystalline diamond transparent ceramic. The invention provides a new technical scheme for preparing the polycrystalline diamond transparent ceramic.
Description
Technical Field
The invention belongs to the field of polycrystalline diamond transparent ceramics, and relates to a preparation method of polycrystalline diamond transparent ceramics.
Background
Transparent ceramics can be broadly classified into two types according to application characteristics: the transparent ceramic with light/wave permeability is mainly transparent to visible light or infrared wave, and the transparent ceramic with special light function characteristic is embodied in the aspect of high-power all-solid-state laser. Compared with common optical materials, the transparent ceramic has the performances of high melting point, high strength, high insulation, corrosion resistance, high temperature resistance and the like shared by ceramic materials, and also has good light transmission, so that the transparent ceramic can be made into electric-optical, electric-mechanical and military dual-purpose devices with multiple purposes. The transparent ceramic has wide application prospect in the aspects of national defense, space science, medicine, laser, infrared detection, novel light source, detection, exploration and the like. For example, transparent ceramics are often used in civilian fields such as infrared detection windows, high-pressure sodium light tubes, substitutes for platinum crucibles, substrates for integrated circuits, high-frequency insulating materials, high-temperature lenses, infrared elements, flat panel displays, laser materials and the like, and also used in military fields such as new-generation armed helicopters, armored vehicles and the like, which have sighting windows, and missile fairings, photoelectric radar fairings, infrared alarms, photoelectric countermeasures and the like.
Diamond is the hardest known material at present, has the properties of high melting point, high heat conduction, high insulation, high light transmittance, high refractive index, corrosion resistance and the like, is an ideal special transparent ceramic material, and has great significance for national safety and national economic sustainable development. Diamond is mainly classified into single crystal diamond and polycrystalline diamond transparent ceramic, and researchers mainly focus on the preparation and application of polycrystalline diamond transparent ceramic at present in view of the reasons of single crystal diamond anisotropy, difficulty in preparation and the like. The polycrystalline diamond transparent ceramic has the advantages of isotropy, high hardness, good toughness, high insulation, high heat conduction, high visible light transmittance, high guided wave (infrared, X-ray, neutron and the like) rate and the like. The existing preparation method of block polycrystalline diamond transparent ceramics is mainly a high-temperature high-pressure phase-change method.
The high-temperature high-pressure phase transformation method is a method for directly converting graphite or other non-diamond carbon (such as carbon nano tube, glassy carbon, onion carbon, graphene and the like) into diamond under the extreme conditions of high temperature and high pressure, and has the following problems: (1) the polycrystalline diamond transparent ceramic prepared by the high-temperature high-pressure phase change method has great technical difficulty and high cost, and the technical implementation difficulty is great because the polycrystalline diamond transparent ceramic is collapsed along with the volume of a sintered sample of more than 20 percent in the sintering process, so that the high-temperature high-pressure cavity is easy to be unstable and stress of an anvil cell (a key part of high-pressure equipment) is easy to concentrate; meanwhile, the service life of the anvil can be seriously shortened due to the stress concentration of the anvil and the sealing failure (commonly called blasting in the high-pressure research field) of the high-pressure cavity caused by the instability of the high-temperature high-pressure cavity, and further, the production cost is greatly increased. (2) Because of the characteristics of high melting point and high recrystallization temperature of diamond, the grain size of the transparent polycrystalline diamond prepared by the high-temperature high-pressure phase-change method is difficult to regulate and control and is mostly nano-scale, the mechanism for preparing the polycrystalline diamond transparent ceramic by the high-pressure phase-change method is the phase change of graphite or other non-diamond carbon, the sintering temperature needs to be increased to be higher than the recrystallization temperature after the formation of diamond grains to promote the growth of the grains, but the existing high-temperature high-pressure experimental technology cannot reach the temperature for regulating and controlling the grain size sufficiently. (3) Because the sintered sample has serious volume collapse in the high-temperature high-pressure phase-change method sintering process, the pressure field and the temperature field in the high-temperature high-pressure cavity are easy to be uneven, and the prepared polycrystalline diamond transparent ceramic block has the defects of large residual stress, poor uniformity and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of polycrystalline diamond transparent ceramic, so as to conveniently regulate and control the grain size of the transparent polycrystalline diamond and avoid the sealing failure of a high-pressure cavity caused by the instability of a high-temperature high-pressure cavity and the stress concentration of an anvil during sintering or the non-uniformity of a pressure field and a temperature field in the high-temperature high-pressure cavity.
The preparation method of the polycrystalline diamond transparent ceramic provided by the invention takes diamond micro powder with the granularity of 5 nm-100 mu m as a raw material, and comprises the following process steps:
(1) pretreatment of diamond micropowder
The carbon-containing purity requirement of the raw material diamond micro powder is more than 99 percent, the diamond micro powder with the carbon-containing purity not meeting the requirement is firstly subjected to impurity removal treatment and then subjected to vacuum heat treatment, and the diamond micro powder with the carbon-containing purity meeting the requirement is directly subjected to vacuum heat treatment to remove oxygen, nitrogen or water vapor adsorbed on the surface of the diamond micro powder;
(2) prepressing for shaping
Putting the diamond micro powder subjected to vacuum heat treatment into a cleaned metal foil for prepressing and forming, wherein the compactness of the obtained parison is not less than 30%;
(3) sintering and removal of metal foil
And (3) placing the parison wrapped by the metal foil into a large-cavity static high-pressure device, sintering for 10-2000 s under the conditions that the pressure is 10-30 GPa and the temperature is 1500-3000 ℃, reducing the pressure and cooling to normal pressure and room temperature after the sintering time is up, and removing the metal foil by using inorganic acid to obtain the polycrystalline diamond transparent ceramic.
It should be noted that: the matching relation between the pressure and the temperature during sintering is that the temperature is low when the pressure is high, namely, in the range of the sintering temperature and the sintering pressure, if the sintering pressure is high, the sintering temperature is low, and if the sintering pressure is low, the sintering temperature is high (see the embodiment).
According to the preparation method of the polycrystalline diamond transparent ceramic, the raw material diamond micro powder can be micro powder with single granularity or mixed granularity according to the requirements of the prepared polycrystalline diamond transparent ceramic.
The preparation method of the polycrystalline diamond transparent ceramic comprises the steps of preparing raw material diamond micro powder by a detonation method or an impact method, a static high pressure method, a large-particle diamond crushing method and a chemical vapor deposition method, wherein the diamond micro powder prepared by the methods is commercially available and can be purchased in the market. Wherein, the chemical vapor deposition method can obtain the diamond micro powder with the carbon content purity of more than 99 percent, and the diamond micro powder prepared by other methods can not meet the requirement of the carbon content purity of more than 99 percent and needs to be subjected to impurity removal treatment.
As for the impurity removal of the diamond fine powder, at least one of an acid washing method, an electrolytic method or an alkali washing method can be adopted, and the acid washing method adopted in the invention is operated as follows: adding diamond micro powder and inorganic acid into a purification kettle according to the weight ratio of 1: 2-4, stirring and heating to 60-70 ℃ in a water bath, then continuously stirring for at least 24h at the temperature, and then drying after the powder is settled to remove liquid and washed to be neutral by deionized water; the inorganic acid is at least one of hydrofluoric acid and hydrochloric acid, and the mass concentration of the inorganic acid is 20-40%.
In the preparation method of the polycrystalline diamond transparent ceramic, the vacuum heat treatment in the step (1) is used for removing oxygen, nitrogen or water vapor adsorbed on the surface of the diamond micro powder, and the specific operation is: putting the diamond micropowder with carbon-containing purity meeting the requirement in a vacuum degree of 1 x 10-1Pa～1×10-5Pa, and the temperature is 500-1200 ℃ and the temperature is kept for 0.1-6 h.
In the preparation method of the polycrystalline diamond transparent ceramic, in the step (2), the adopted metal foil is tantalum foil, rhenium foil or platinum foil, and cleaning treatment is required before use, and the cleaning treatment operation comprises the following steps: and sequentially polishing, deoiling, ultrasonically cleaning and infrared drying the metal foil.
In the preparation method of the polycrystalline diamond transparent ceramic, in the step (2), the pressure intensity of the pre-pressing forming is 400 MPa-700 MPa, and the pressing time is determined by the compactness of the obtained parison.
Researches show that the heating rate, the cooling rate, the boosting rate and the depressurizing rate all affect the microstructure and the macroscopic performance of a final sample, and stress can be effectively released by regulating and controlling the heating rate, the cooling rate, the boosting rate and the depressurizing rate, microcracks in the sample are reduced, and the uniformity of the sample is improved. In the invention, the pressure increasing rate of increasing the pressure from normal pressure to sintering pressure and the pressure decreasing rate of decreasing the pressure from the sintering pressure to normal pressure are 0.5 GPa/h-60 GPa/h, and the temperature increasing rate of increasing the temperature from room temperature to sintering temperature and the temperature decreasing rate of decreasing the temperature from the sintering temperature to room temperature are 1 ℃/min-1000 ℃/min.
Researches show that the selection of the time points of starting loading and starting unloading under the two conditions of temperature and pressure and the combined action time of the temperature and the pressure can also influence the microstructure and the macroscopic property of a final sample, so that the modes of temperature rise and pressure rise and temperature fall and pressure drop are as follows:
firstly, increasing the pressure from normal pressure to sintering pressure and keeping the sintering pressure, then increasing the temperature from room temperature to sintering temperature, and after the sintering time is up, firstly reducing the temperature from the sintering temperature to the room temperature, and then reducing the pressure from the sintering pressure to the normal pressure;
or firstly increasing the pressure from normal pressure to sintering pressure and keeping the sintering pressure, then increasing the temperature from room temperature to sintering temperature, after the sintering time is up, simultaneously starting cooling and pressure reduction to reduce the temperature from the sintering temperature to the room temperature and reduce the pressure from the sintering pressure to the normal pressure;
or firstly increasing the pressure from normal pressure to the pressure which can stably exist in the diamond and keeping the pressure, then increasing the temperature from room temperature to sintering temperature, then increasing the pressure to sintering pressure, and after the sintering time is up, firstly reducing the temperature from the sintering temperature to the room temperature, and then reducing the pressure from the sintering pressure to the normal pressure;
or firstly increasing the pressure from normal pressure to the pressure which can stably exist in the diamond and keeping the pressure, then increasing the temperature from room temperature to the sintering temperature, then increasing the pressure to the sintering pressure, and after the sintering time is up, simultaneously starting cooling and pressure reduction to reduce the temperature from the sintering temperature to the room temperature and reduce the pressure from the sintering pressure to the normal pressure.
The pressure at which the diamond can exist stably is related to the sintering temperature, and the following documents can be referred to for the temperature and pressure interval at which the diamond can exist stably:
Ghiringhelli L M,Los J H,Meijer E J,et al.Modeling the phase diagram of carbon[J].Physical review letters,2005,94(14):145701.
Khaliullin R Z,Eshet H,Kühne T D,et al.Graphite-diamond phase coexistence study employing a neural-network mapping of the ab initio potential energy surface[J].Physical Review B,2010,81(10):100103.
in the preparation method of the polycrystalline diamond transparent ceramic, the inorganic acid used for removing the coating material in the step (3) is at least one of hydrofluoric acid and nitric acid, and the mass concentration of the inorganic acid is 30-50%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method of the invention takes the diamond micro powder as the raw material, and no sintering aid with non-carbon components is added, thus providing a new technical scheme for the preparation of the polycrystalline diamond transparent ceramic.
(2) Because the method takes the diamond micro powder as the raw material, the raw material does not generate phase change in the sintering process, and the selection of the sintering temperature and the sintering pressure does not cause the crystal grains to obviously grow, the method is convenient for regulating and controlling the crystal grain size of the prepared polycrystalline diamond transparent ceramic by regulating and controlling the crystal grain size of the raw material diamond micro powder.
(3) According to the method, the diamond micro powder is used as the raw material, and the phase change of the raw material does not occur in the sintering process, so that the volume collapse of a sintered sample does not occur during sintering, the root cause of instability of a high-temperature high-pressure cavity and stress concentration of an anvil is effectively eliminated, the smooth sintering is ensured, and the increase of the preparation cost caused by equipment damage is avoided.
(4) The method of the invention takes the diamond micro powder as the raw material, can lead the pressure field and the temperature field in the high-temperature high-pressure cavity to be uniform, and simultaneously optimizes the speed and the mode of temperature rise, pressure rise, temperature drop and pressure drop, so that the prepared polycrystalline diamond transparent ceramic block has good uniformity and small residual stress, and can obtain the polycrystalline diamond transparent ceramic with large size and no crack (see the embodiment)
(5) The method is convenient for regulating and controlling the grain size of the prepared polycrystalline diamond transparent ceramic, thereby being beneficial to regulating and controlling the visible light transmittance, the hardness and the toughness of the polycrystalline diamond transparent ceramic and preparing the polycrystalline diamond transparent ceramic with various light transmission properties (the visible light transmittance is 5-95 percent) and different hardness and toughness.
(6) The polycrystalline diamond transparent ceramic prepared by the method has wide application prospects in the fields of national defense and civil use, for example, the polycrystalline diamond transparent ceramic has excellent light transmission and wave transmission performance, high hardness, certain toughness, high thermal conductivity and high electrical insulation, and can be used for manufacturing various window materials; secondly, the coating has extremely high decorative and surface scratch and scratch resistance due to the visible light transmission, high refractive index and high wear resistance, and can be used for manufacturing luxuries such as high-grade watch cases, glasses and the like; the cutter has ultrahigh wear resistance, can be used for manufacturing various cutters, and is convenient for detecting defects such as microcracks and the like in the cutter by an optical means; and fourthly, the diamond anvil block can be used for preparing the diamond anvil block due to excellent light transmission and wave transmission performance, high strength and high hardness, replaces the existing single crystal diamond anvil block, and has the advantages of low use cost, large size and the like.
Drawings
FIG. 1 is an optical microscope photograph of a polycrystalline diamond transparent ceramic prepared in example 1;
FIG. 2 is an optical microscope photograph of the polycrystalline diamond transparent ceramic prepared in example 2;
FIG. 3 is an optical microscope photograph of the polycrystalline diamond transparent ceramic prepared in example 3;
FIG. 4 is an optical microscope photograph of the polycrystalline diamond transparent ceramic prepared in example 4;
FIG. 5 is an optical microscope photograph of the polycrystalline diamond transparent ceramic prepared in example 5;
FIG. 6 is an optical microscope photograph of the polycrystalline diamond transparent ceramic prepared in example 6;
FIG. 7 is an optical photograph of the polycrystalline diamond transparent ceramic prepared in example 7;
FIG. 8 is an X-ray diffraction pattern of the polycrystalline diamond transparent ceramic prepared in example 2;
FIG. 9 is a Raman spectrum of the polycrystalline diamond transparent ceramic prepared in example 2;
FIG. 10 is a scanning electron micrograph (magnification: 10000 times) of a polycrystalline diamond transparent ceramic prepared in example 2;
FIG. 11 is a scanning electron micrograph (magnification 20000 times) of the polycrystalline diamond transparent ceramic prepared in example 4.
Detailed Description
The method for preparing the polycrystalline diamond transparent ceramic according to the present invention will be further described by way of examples with reference to the accompanying drawings. It is to be understood that the described embodiments are merely a few embodiments of the invention and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following embodiments, the large-cavity static high-pressure device is a domestic hinge type cubic press with a model of DS 6 × 8MN, and the manufacturing enterprise: zhang Jiakou prospecting mechanical plant; all the raw materials are purchased from the market.
Example 1
This example prepares a polycrystalline diamond transparent ceramic by the following steps:
(1) pretreatment of diamond micropowder
The method comprises the following steps of taking single crystal diamond micro powder with the granularity range of 10 nm-50 nm prepared by a commercially available detonation method as a raw material, firstly removing impurities: adding raw diamond micro powder and hydrofluoric acid (mass concentration is 20%) into a purification kettle according to the weight ratio of 1: 3, stirring and heating to 60 ℃ in a water bath, then continuing to stir for 48 hours at the temperature, then pouring out liquid after the powder is settled, washing the powder with deionized water to be neutral, then adding the diamond micro powder after water washing and hydrochloric acid (mass concentration is 25%) into the purification kettle according to the weight ratio of 1: 3, stirring and heating to 60 ℃ in the water bath, then continuing to stir for 48 hours at the temperature, then pouring out the liquid after the powder is settled, washing the powder with deionized water to be neutral, repeating the step of acid dissolution and impurity removal for 2 times, and then drying the treated diamond micro powder;
drying the diamond micropowder at vacuum degree of 5 × 10-4Pa, the temperature is 700 ℃ for 3h to remove impurities such as oxygen, nitrogen, water vapor and the like adsorbed on the surface of the diamond micro powder;
(2) prepressing for shaping
Taking tantalum foil as a wrapping material, and performing conventional polishing, deoiling, ultrasonic cleaning and infrared drying on the surface of the tantalum foil of the wrapping material; then, filling the diamond micro powder pretreated in the step (1) into wrapping material tantalum foil, maintaining the pressure at 500MPa for 1min, and performing pre-pressing forming to obtain a parison with the compactness of 45%;
(3) sintering and removal of metal foil
And (3) placing the parison wrapped by the metal foil into a large-cavity static high-pressure device, and sintering for 600s under the conditions that the pressure is 15GPa and the temperature is 2200 ℃. The temperature and pressure loading mode, the unloading mode and the process conditions are as follows: increasing the pressure by 10GPa at the pressure increasing rate of 3GPa/h, keeping the pressure unchanged, then increasing the temperature to 2200 ℃ at the temperature increasing rate of 100 ℃/min, keeping the temperature unchanged, increasing the pressure to 15GPa at the pressure increasing rate of 20GPa/h, keeping the pressure unchanged, sintering for 600s at the temperature of 15GPa and 2200 ℃, simultaneously starting temperature reduction and pressure reduction after the sintering time is up, reducing the temperature to room temperature at the temperature reducing rate of 3 ℃/min, and reducing the pressure to normal pressure at the pressure reducing rate of 1 GPa/h.
And (3) putting the obtained sample into mixed acid (the volume ratio of hydrofluoric acid to nitric acid is 1:1) consisting of hydrofluoric acid with the mass concentration of 30% and nitric acid with the mass concentration of 40% to remove the tantalum serving as a wrapping material, and polishing the sample to be bright by using a grinding disc to obtain the polycrystalline diamond transparent ceramic.
Example 2
This example prepares a polycrystalline diamond transparent ceramic by the following steps:
(1) pretreatment of diamond micropowder
The method comprises the following steps of taking single crystal diamond micro powder with the average particle size of about 500nm prepared by a commercially available detonation method as a raw material, firstly, removing impurities: adding raw diamond micro powder and hydrofluoric acid (mass concentration is 40%) into a purification kettle according to the weight ratio of 1: 2, stirring and heating to 70 ℃ in a water bath, then continuing to stir for 72 hours at the temperature, then pouring out liquid after the powder is settled, washing the powder with deionized water to be neutral, then adding the diamond micro powder after water washing and hydrochloric acid (mass concentration is 35%) into the purification kettle according to the weight ratio of 1: 2, stirring and heating to 70 ℃ in the water bath, then continuing to stir for 72 hours at the temperature, then pouring out liquid after the powder is settled, washing the powder with deionized water to be neutral, repeating the step of acid dissolution and impurity removal for 3 times, and then drying the treated diamond micro powder;
drying the diamond micropowder at vacuum degree of 4 × 10-3Pa, at 800 ℃ for 5h to remove impurities such as oxygen, nitrogen, water vapor and the like adsorbed by the micro powder on the surface of the diamond;
(2) prepressing for shaping
Taking a rhenium foil as a wrapping material, and carrying out conventional polishing, deoiling, ultrasonic cleaning and infrared drying on the surface of the rhenium foil of the wrapping material; then, putting the diamond micro powder pretreated in the step (1) into a rhenium foil wrapping material, maintaining the pressure at 700MPa for 5min, and performing pre-pressing forming to obtain a parison with the compactness of 55%;
(3) sintering and removal of metal foil
And (3) placing the parison wrapped by the metal foil into a large-cavity static high-pressure device, and sintering for 1800s under the conditions of the pressure of 16GPa and the temperature of 2200 ℃. The temperature and pressure loading mode, the unloading mode and the process conditions are as follows: increasing the pressure by 16GPa at the pressure increasing rate of 10GPa/h, keeping the pressure unchanged, then increasing the temperature to 2200 ℃ at the temperature increasing rate of 200 ℃/min, carrying out heat preservation sintering for 1800s, starting temperature reduction and pressure reduction at the same time after the sintering time is reached, reducing the temperature to room temperature at the temperature reducing rate of 1.5 ℃/min, and reducing the pressure to the normal pressure at the pressure reducing rate of 0.5 GPa/h.
And putting the obtained sample into nitric acid with the mass concentration of 50% to remove the rhenium of the wrapping material, and polishing the sample to be bright by using a grinding disc to obtain the polycrystalline diamond transparent ceramic.
Example 3
This example prepares a polycrystalline diamond transparent ceramic by the following steps:
(1) pretreatment of diamond micropowder
The method comprises the following steps of taking single crystal diamond micro powder with the average particle size of 500nm prepared by a commercially available detonation method and single crystal diamond micro powder with the average particle size of 5 microns prepared by a commercially available large-particle diamond crushing method as raw materials, wherein the weight ratio of the single crystal diamond micro powder to the single crystal diamond micro powder is 1:1, uniformly mixing the raw materials, and then removing impurities: adding raw diamond micro powder and hydrofluoric acid (mass concentration is 30%) into a purification kettle according to the weight ratio of 1: 2, stirring and heating to 60 ℃ in a water bath, then continuing to stir for 48 hours at the temperature, then pouring out liquid after the powder is settled, washing the powder with deionized water to be neutral, then adding the diamond micro powder after water washing and hydrochloric acid (mass concentration is 25%) into the purification kettle according to the weight ratio of 1: 2, stirring and heating to 60 ℃ in the water bath, then continuing to stir for 48 hours at the temperature, then pouring out the liquid after the powder is settled, washing the powder with deionized water to be neutral, repeating the step of acid dissolution and impurity removal for 4 times, and then drying the treated diamond micro powder.
Drying the diamond micropowder under vacuum degree of 1 × 10-5Pa, at the temperature of 500 ℃ for 6h to remove impurities such as oxygen, nitrogen, water vapor and the like adsorbed on the surface of the diamond micro powder;
(2) prepressing for shaping
Taking tantalum foil as a wrapping material, and performing conventional polishing, deoiling, ultrasonic cleaning and infrared drying on the surface of the tantalum foil of the wrapping material; then, filling the diamond micro powder pretreated in the step (1) into wrapping material tantalum foil, maintaining the pressure at 400MPa for 1min, and performing pre-pressing forming treatment to obtain a parison with the compactness of 35%;
(3) sintering and removal of metal foil
And (3) placing the parison wrapped by the metal foil into a large-cavity static high-pressure device, and sintering for 900s under the conditions of 16GPa of pressure and 2300 ℃. The temperature and pressure loading mode, the unloading mode and the process conditions are as follows: increasing the pressure by 16GPa at the pressure increasing rate of 20GPa/h, keeping the pressure unchanged, then increasing the temperature to 2300 ℃ at the temperature increasing rate of 10 ℃/min, carrying out heat preservation sintering for 900s, cooling to room temperature at the temperature decreasing rate of 1000 ℃/min after the sintering time is finished, and reducing the pressure to normal pressure at the pressure reducing rate of 0.5GPa/h after the temperature is finished.
And (3) putting the obtained sample into mixed acid (the volume ratio of hydrofluoric acid to nitric acid is 1:1) consisting of hydrofluoric acid with the mass concentration of 40% and nitric acid with the mass concentration of 40% to remove the wrapping material tantalum, and polishing the sample to be bright by using a grinding disc to obtain the polycrystalline diamond transparent ceramic.
Example 4
This example prepares a polycrystalline diamond transparent ceramic by the following steps:
(1) pretreatment of diamond micropowder
The method comprises the following steps of taking single crystal diamond micro powder with the average particle size of about 1 mu m prepared by a commercially available large-particle diamond crushing method as a raw material, and firstly carrying out impurity removal treatment: adding raw diamond micro powder and hydrofluoric acid (mass concentration is 20%) into a purification kettle according to the weight ratio of 1: 3, stirring and heating to 60 ℃ in a water bath, then continuing to stir for 24 hours at the temperature, then pouring out liquid after the powder is settled, washing the powder with deionized water to be neutral, then adding the diamond micro powder after water washing and hydrochloric acid (mass concentration is 25%) into the purification kettle according to the weight ratio of 1: 3, stirring and heating to 60 ℃ in the water bath, then continuing to stir for 24 hours at the temperature, then pouring out liquid after the powder is settled, washing the powder with deionized water to be neutral, repeating the steps of acid dissolution and impurity removal for 3 times, and then drying the treated diamond micro powder;
drying the diamond micropowder at vacuum degree of 5 × 10-4Processing at 1000 deg.C under Pa for 0.5h to remove oxygen, nitrogen and water vapor adsorbed on the surface of the diamond micropowderAnd the like;
(2) prepressing for shaping
Taking a rhenium foil as a wrapping material, and carrying out conventional polishing, deoiling, ultrasonic cleaning and infrared drying on the surface of the rhenium foil of the wrapping material; then, putting the diamond micro powder pretreated in the step (1) into a rhenium foil wrapping material, maintaining the pressure for 2min at 600MPa, and performing pre-pressing forming to obtain a parison with the compactness of 50%;
(3) sintering and removal of metal foil
And (3) placing the parison wrapped by the metal foil into a large-cavity static high-pressure device, and sintering for 10s under the conditions of the pressure of 12GPa and the temperature of 2800 ℃. The temperature and pressure loading mode, the unloading mode and the process conditions are as follows: increasing the pressure by 12GPa at the pressure increasing rate of 60GPa/h, keeping the pressure unchanged, then increasing the temperature to 2800 ℃ at the temperature increasing rate of 500 ℃/min, carrying out heat preservation sintering for 10s, cooling to room temperature at the temperature decreasing rate of 1000 ℃/min after the sintering time is finished, and reducing the pressure to the normal pressure at the pressure reducing rate of 30GPa/h after the temperature is reduced for 10 min.
And putting the obtained sample into hydrofluoric acid with the mass concentration of 50% to remove the rhenium of the wrapping material, and polishing the sample to be bright by using a grinding disc to obtain the polycrystalline diamond transparent ceramic.
Example 5
This example prepares a polycrystalline diamond transparent ceramic by the following steps:
(1) pretreatment of diamond micropowder
The single crystal diamond micropowder with average particle size of about 500nm prepared by chemical vapor deposition method is used as raw material, its carbon-containing purity is greater than 99%, and it is directly placed in vacuum degree of 5X 10-3Pa, at 1200 deg.C for 0.5h to remove impurities such as oxygen, nitrogen, water vapor, etc. adsorbed on the surface of the diamond micropowder;
(2) prepressing for shaping
Taking tantalum foil as a wrapping material, and performing conventional polishing, deoiling, ultrasonic cleaning and infrared drying on the surface of the tantalum foil of the wrapping material; then, filling the diamond micro powder pretreated in the step (1) into wrapping material tantalum foil, maintaining the pressure at 500MPa for 1min, and performing pre-pressing forming to obtain a parison with the compactness of 45%;
(3) sintering and removal of metal foil
And (3) placing the parison wrapped by the metal foil into a large-cavity static high-pressure device, and sintering for 300s under the conditions of pressure of 15GPa and temperature of 2300 ℃. The temperature and pressure loading mode, the unloading mode and the process conditions are as follows: increasing the pressure by 15GPa at the pressure increasing rate of 25GPa/h, keeping the pressure unchanged, then increasing the temperature to 2300 ℃ at the temperature increasing rate of 500 ℃/min, carrying out heat preservation sintering for 300s, cooling to room temperature at the temperature decreasing rate of 20 ℃/min after the sintering time is finished, and reducing the pressure to normal pressure at the pressure reducing rate of 3GPa/h after the temperature is reduced for 10 min.
And (3) putting the obtained sample into mixed acid (the volume ratio of hydrofluoric acid to nitric acid is 1:1) consisting of hydrofluoric acid with the mass concentration of 30% and nitric acid with the mass concentration of 30% to remove the wrapping material tantalum, and polishing the sample to be bright by using a grinding disc to obtain the polycrystalline diamond transparent ceramic.
Example 6
This example prepares a polycrystalline diamond transparent ceramic by the following steps:
(1) pretreatment of diamond micropowder
The method comprises the following steps of taking single crystal diamond micro powder with the average particle size of about 10 mu m prepared by a commercially available static high pressure method as a raw material, and firstly carrying out impurity removal treatment: adding raw diamond micro powder and hydrofluoric acid (mass concentration is 30%) into a purification kettle according to the weight ratio of 1: 4, stirring and heating to 60 ℃ in a water bath, then continuing to stir for 48 hours at the temperature, then pouring out liquid after the powder is settled, washing the powder with deionized water to be neutral, then adding the diamond micro powder after water washing and hydrochloric acid (mass concentration is 35%) into the purification kettle according to the weight ratio of 1: 3, stirring and heating to 60 ℃ in the water bath, then continuing to stir for 48 hours at the temperature, then pouring out the liquid after the powder is settled, washing the powder with deionized water to be neutral, repeating the step of acid dissolution and impurity removal for 2 times, and then drying the treated diamond micro powder.
Drying the diamond micropowder at vacuum degree of 5 × 10-2Processing for 1h under the conditions of Pa and the temperature of 900 ℃ to remove impurities such as oxygen, nitrogen, water vapor and the like adsorbed on the surface of the diamond micro powder;
(2) prepressing for shaping
Taking tantalum foil as a wrapping material, and performing conventional polishing, deoiling, ultrasonic cleaning and infrared drying on the surface of the tantalum foil of the wrapping material; then, filling the diamond micro powder pretreated in the step (1) into wrapping material tantalum foil, maintaining the pressure for 3min at 600MPa, and performing pre-pressing forming to obtain a parison with the compactness of 52%;
(3) sintering and removal of metal foil
And (3) placing the parison wrapped by the metal foil into a large-cavity static high-pressure device, and sintering for 1800s under the conditions of 28GPa of pressure and 1800 ℃. The temperature and pressure loading mode, the unloading mode and the process conditions are as follows: increasing the pressure by 22GPa at the pressure increasing rate of 6GPa/h, keeping the pressure unchanged, then increasing the temperature to 1800 ℃ at the temperature increasing rate of 50 ℃/min, keeping the temperature unchanged, increasing the pressure to 28GPa at the pressure increasing rate of 20GPa/h, keeping the pressure unchanged, sintering for 1800s under the pressure and temperature conditions of 28GPa and 1800 ℃, after the sintering time is up, firstly reducing the temperature to the room temperature at the temperature reducing rate of 250 ℃/min, and reducing the pressure to the normal pressure at the pressure reducing rate of 1GPa/h after the temperature reduction is finished.
And (3) putting the obtained sample into mixed acid (the volume ratio of hydrofluoric acid to nitric acid is 1:1) consisting of hydrofluoric acid with the mass concentration of 30% and nitric acid with the mass concentration of 40% to remove the wrapping material tantalum, and polishing the sample to be bright by using a grinding disc to obtain the polycrystalline diamond transparent ceramic.
Example 7
This example prepares a polycrystalline diamond transparent ceramic by the following steps:
(1) pretreatment of diamond micropowder
The method comprises the following steps of taking single crystal diamond micro powder with the average particle size of about 50 mu m prepared by a commercially available static high pressure method as a raw material, and firstly carrying out impurity removal treatment: adding raw diamond micro powder and hydrofluoric acid (mass concentration is 20%) into a purification kettle according to the weight ratio of 1: 3, stirring and heating to 60 ℃ in a water bath, then continuing to stir for 48 hours at the temperature, then pouring out liquid after the powder is settled, washing the powder with deionized water to be neutral, then adding the diamond micro powder after water washing and hydrochloric acid (mass concentration is 25%) into the purification kettle according to the weight ratio of 1: 3, stirring and heating to 60 ℃ in the water bath, then continuing to stir for 48 hours at the temperature, then pouring out the liquid after the powder is settled, washing the powder with deionized water to be neutral, repeating the steps of acid dissolution and impurity removal for 3 times, and then drying the treated diamond micro powder.
Drying the diamond micropowder at vacuum degree of 5 × 10-2Processing for 3 hours at the temperature of 800 ℃ under Pa to remove impurities such as oxygen, nitrogen, water vapor and the like adsorbed on the surface of the diamond micro powder;
(2) prepressing for shaping
Taking tantalum foil as a wrapping material, and performing conventional polishing, deoiling, ultrasonic cleaning and infrared drying on the surface of the tantalum foil of the wrapping material; then, filling the diamond micro powder pretreated in the step (1) into wrapping material tantalum foil, maintaining the pressure at 500MPa for 1min, and performing pre-pressing forming to obtain a parison with the compactness of 45%;
(3) sintering and removal of metal foil
And (3) placing the parison wrapped by the metal foil into a large-cavity static high-pressure device, and sintering for 1800s under the conditions that the pressure is 15GPa and the temperature is 2000 ℃. The temperature and pressure loading mode, the unloading mode and the process conditions are as follows: increasing the pressure by 15GPa at the pressure increasing rate of 3GPa/h, keeping the pressure unchanged, then increasing the temperature to 2000 ℃ at the temperature increasing rate of 100 ℃/min, carrying out heat preservation sintering for 1800s, cooling to room temperature at the temperature decreasing rate of 4 ℃/min after the sintering time is finished, and reducing the pressure to normal pressure at the pressure decreasing rate of 1GPa/h after the temperature is finished.
And (3) putting the obtained sample into mixed acid (the volume ratio of hydrofluoric acid to nitric acid is 1:1) consisting of hydrofluoric acid with the mass concentration of 30% and nitric acid with the mass concentration of 30% to remove the wrapping material tantalum, and polishing the sample to be bright by using a grinding disc to obtain the polycrystalline diamond transparent ceramic.
The polycrystalline diamond transparent ceramic structures prepared in the examples were analyzed as follows.
Optical micrographs (see fig. 1 to 6) of the polycrystalline diamond transparent ceramic samples prepared in examples 1 to 6 were taken by an optical microscope and subjected to light transmission property evaluation, and an optical micrograph (see fig. 7) of the polycrystalline diamond transparent ceramic sample prepared in example 7 was taken and subjected to light transmission property evaluation, and the light transmission property evaluation was shown in table 1. Statistics on the diameter and height of the polycrystalline diamond transparent ceramic samples prepared in examples 1 to 7 were carried out, and the results are shown in Table 1.
TABLE 1 polycrystalline diamond transparent ceramic sample size and visible light transmittance test results
| Diameter (mm) | Height (mm) | Visible light transmittance | |
| Example 1 | 3 | 2 | Is preferably used |
| Example 2 | 3.5 | 2.5 | Is excellent in |
| Example 3 | 3.5 | 2 | Is preferably used |
| Example 4 | 4 | 3 | Is preferably used |
| Example 5 | 3 | 2.5 | Is preferably used |
| Example 6 | 5 | 3 | Is poor |
| Example 7 | 10 | 6 | Difference (D) |
As can be seen from Table 1, the method of the present invention can prepare large-size bulk polycrystalline diamond transparent ceramics with different light transmittances.
The X-ray diffraction test and the raman spectrum test were performed on the polycrystalline diamond transparent ceramic samples prepared in examples 1 to 7, wherein the X-ray diffraction spectrum corresponding to example 2 is shown in fig. 8, and the raman spectrum is shown in fig. 9, and the test results show that the polycrystalline diamond transparent ceramic samples prepared by the preparation method provided by the present invention only have a diamond phase.
Scanning electron microscope tests are carried out on the polycrystalline diamond transparent ceramic samples prepared in the examples 1 to 7, wherein the scanning electron microscope images corresponding to the examples 2 and 4 are shown in fig. 10 and 11, and the test results show that the polycrystalline diamond transparent ceramic samples obtained by the preparation method of the invention have high compactness, the grain size is basically consistent with the grain size of the raw material powder, and a large-area and tightly-combined high-strength diamond-diamond bonding interface is formed between diamond grains.
Claims (4)
1. A preparation method of polycrystalline diamond transparent ceramics is characterized in that diamond micro powder with the granularity of 5 nm-100 mu m is used as a raw material, and the process steps are as follows:
(1) pretreatment of diamond micropowder
The carbon-containing purity requirement of the raw material diamond micro powder is more than 99 percent, the diamond micro powder with the carbon-containing purity not meeting the requirement is firstly subjected to impurity removal treatment and then subjected to vacuum heat treatment, and the diamond micro powder with the carbon-containing purity meeting the requirement is directly subjected to vacuum heat treatment to remove oxygen, nitrogen or water vapor adsorbed on the surface of the diamond micro powder;
the vacuum degree of the vacuum heat treatment is 1 × 10-1 Pa～1×10-5 Pa, the temperature is 500-1200 ℃, and the heat preservation time is 0.1-6 h;
(2) prepressing for shaping
Putting the diamond micro powder subjected to vacuum heat treatment into a cleaned metal foil for prepressing and forming, wherein the compactness of the obtained parison is not less than 30%;
(3) sintering and removal of metal foil
Placing the parison wrapped by the metal foil into a large-cavity static high-pressure device, sintering for 10-2000 s under the conditions of pressure of 12-28 GPa and temperature of 1800-2800 ℃, wherein the matching relation of the pressure and the temperature is that the pressure is high and the temperature is low, reducing the pressure and cooling to normal pressure and room temperature after the sintering time is up, and then removing the metal foil by using inorganic acid to obtain the polycrystalline diamond transparent ceramic;
the pressure increasing rate for increasing the pressure from normal pressure to sintering pressure and the pressure decreasing rate for decreasing the pressure from sintering pressure to normal pressure are 0.5 GPa/h-60 GPa/h, and the temperature increasing rate for increasing the temperature from room temperature to sintering temperature and the temperature decreasing rate for decreasing the temperature from sintering temperature to room temperature are 1 ℃/min-1000 ℃/min.
2. The method for preparing a polycrystalline diamond transparent ceramic according to claim 1, wherein the temperature and pressure increase and the temperature and pressure decrease are performed in the following manner:
firstly, increasing the pressure from normal pressure to sintering pressure and keeping the sintering pressure, then increasing the temperature from room temperature to sintering temperature, and after the sintering time is up, firstly reducing the temperature from the sintering temperature to the room temperature, and then reducing the pressure from the sintering pressure to the normal pressure;
or firstly increasing the pressure from normal pressure to sintering pressure and keeping the sintering pressure, then increasing the temperature from room temperature to sintering temperature, after the sintering time is up, simultaneously starting cooling and pressure reduction to reduce the temperature from the sintering temperature to the room temperature and reduce the pressure from the sintering pressure to the normal pressure;
or firstly increasing the pressure from normal pressure to the pressure which can stably exist in the diamond and keeping the pressure, then increasing the temperature from room temperature to sintering temperature, then increasing the pressure to sintering pressure, and after the sintering time is up, firstly reducing the temperature from the sintering temperature to the room temperature, and then reducing the pressure from the sintering pressure to the normal pressure;
or firstly increasing the pressure from normal pressure to the pressure which can stably exist in the diamond and keeping the pressure, then increasing the temperature from room temperature to the sintering temperature, then increasing the pressure to the sintering pressure, and after the sintering time is up, simultaneously starting cooling and pressure reduction to reduce the temperature from the sintering temperature to the room temperature and reduce the pressure from the sintering pressure to the normal pressure.
3. The method for preparing a polycrystalline diamond transparent ceramic according to claim 1, wherein in the step (2), the pressure for the pre-press molding is 400 to 700MPa, and the pressing time is determined by the compactness of the obtained parison.
4. The method for producing a polycrystalline diamond transparent ceramic according to claim 1, wherein the metal foil is tantalum foil, rhenium foil or platinum foil.
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