CN115634622B - Synthesis process of high-grade artificial diamond - Google Patents
Synthesis process of high-grade artificial diamond Download PDFInfo
- Publication number
- CN115634622B CN115634622B CN202211130313.XA CN202211130313A CN115634622B CN 115634622 B CN115634622 B CN 115634622B CN 202211130313 A CN202211130313 A CN 202211130313A CN 115634622 B CN115634622 B CN 115634622B
- Authority
- CN
- China
- Prior art keywords
- temperature
- synthetic
- pressure
- graphite
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of diamond, and in particular relates to a synthesis process of high-grade artificial diamond, which comprises the following steps: adding sodium chloride into ethanol, stirring uniformly to form slurry, adding graphite and catalyst powder, performing ultrasonic treatment to form suspension slurry, and drying to obtain mixed powder; placing the mixed powder into a mould for pressing and forming to obtain a prefabricated synthetic column; and placing the prefabricated synthetic column into a composite block, drying at constant temperature to obtain the synthetic column, synthesizing the synthetic column at high temperature and high pressure to obtain synthetic diamond, separating the synthetic block, removing the composite block to obtain the prefabricated synthetic column with complete reaction, sequentially placing the prefabricated synthetic column into a nitric acid solution and a sulfuric acid solution, and stirring at constant temperature for 1-2 hours to obtain the artificial diamond. The invention solves the defects of the existing artificial diamond, and utilizes sodium chloride and catalyst powder to form a stable coating barrier system, so as to achieve excellent temperature and pressure balance and ensure the internal balance of a high-temperature high-pressure system.
Description
Technical Field
The invention belongs to the technical field of diamond, and particularly relates to a synthesis process of high-grade artificial diamond.
Background
Diamond is commonly known as "diamond drill", which is a mineral composed of pure carbon and is the most hard substance in nature. Since the 18 th century, it was confirmed that diamond consisted of pure carbon, research into artificial diamond was started, and only in the 50 th century, real success and rapid development were achieved through high pressure research and development of high pressure experimental technology, and artificial diamond was also widely used in various industries, process industries.
The synthetic diamond is mainly made up by adopting static pressure catalyst method, and its principle is that the hydraulic press can be used for producing 5-10GPa pressure, and the electric current can be used for heating to high temp. of 1000-2000 deg.C, and the catalyst (or catalyst) can be used for implementing conversion of graphite into diamond. The catalyst material can not only reduce the high-temperature and high-pressure conditions of diamond and industrialize the diamond synthesis, but also play an important role in optimizing the diamond performance. The catalyst is divided into a metal catalyst and a non-metal catalyst, wherein the metal catalyst is used as a traditional catalyst, the production cost, the synthesis environment and the economic benefit are all superior to those of the non-metal catalyst, the process is mature, and the application is most extensive. However, the static pressure catalyst method is very easy to have poor internal and external temperature balance in high-temperature and high-pressure treatment, so that the internal and external quality of the diamond is unbalanced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a synthesis process of high-grade artificial diamond, which solves the defects of the existing artificial diamond, and utilizes sodium chloride and catalyst powder to form a stable coating barrier system, so as to achieve excellent temperature and pressure balance and ensure the internal balance of a high-temperature high-pressure system.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a synthesis process of high-grade artificial diamond, comprising the following steps:
step 1, adding sodium chloride into ethanol, uniformly stirring to form slurry, then adding graphite and catalyst powder, performing ultrasonic treatment to form suspension slurry, and drying to obtain mixed powder; the concentration of the sodium chloride in the ethanol is 200-500g/L, the mass ratio of the sodium chloride to the graphite to the catalyst powder is 1:3:5-7, the ultrasonic frequency of the ultrasonic wave is 50-70kHz, and the temperature is 10-20 ℃; the drying is carried out under the nitrogen atmosphere; the method comprises the steps of utilizing sodium chloride to be insoluble in ethanol, dispersing the sodium chloride into fine particles, integrally forming a colloid state, adding graphite and catalyst powder into the whole system, and performing ultrasonic treatment to form a sizing material of a dispersion system, wherein the catalyst powder and the graphite form uniform dispersion in the sizing material; further, the graphite and the catalyst powder adopt micron-sized particles with the particle size of 50-500 mu m, the catalyst powder consists of micron-sized iron powder, micron-sized nickel powder and micron-sized cobalt powder, the mass ratio of the iron powder to the nickel to the cobalt powder is 5-8:10-14:1, the micron-sized graphite and the catalyst powder are fully fused, the catalyst powder can be ensured to be in uniform contact with the graphite, excellent wrapping property is achieved, sodium chloride is matched to be uniformly embedded between the catalyst powder, and gaps of the catalyst powder are filled;
further, in the drying process, ethanol in the slurry is gradually dried and removed, but the residual property of the ethanol and the adsorptivity of graphite are gradually removed, ethanol is remained in the mixed powder, the ethanol is used as a residual, impurities are generated in subsequent treatment, and poor purity of diamond is caused, therefore, the drying comprises the following steps of a1, carrying out reduced pressure distillation on the suspension slurry in a nitrogen environment for 40-60min to obtain a semi-dry material, wherein the pressure of the reduced pressure distillation is 80-90% of atmospheric pressure, the temperature is 55-65 ℃, the step is carried out in the nitrogen environment, the influence caused by oxygen is prevented, simultaneously, the reduced pressure distillation can be removed under the condition of low temperature to form a semi-dry material, a2, adding diethyl ether into the semi-dry material, stirring uniformly, carrying out ultrasonic treatment for 30-40min to obtain diethyl ether slurry, then carrying out reduced pressure distillation until drying, repeating for 2-3 times to obtain a dried mixed powder, the concentration of the semi-dry material in diethyl ether is 600-900g/L, the ultrasonic treatment temperature is 10-20 ℃, the ultrasonic frequency is 50-70kHz, the step utilizes the diethyl ether to dissolve the mixed powder and the ethanol, the ethanol can be completely dissolved in the mixed powder, and the ethanol is completely dissolved in the ethanol, and the surface is completely dissolved in the ethanol, and the ethanol is completely dissolved by using the ethanol, and the ethanol is completely dissolved in the mixed system, the surface is formed; the temperature of the reduced pressure distillation is 60-70 ℃, the pressure is 80-90% of the atmospheric pressure, and the reduced pressure distillation atmosphere is nitrogen atmosphere. According to the method, the insolubility of the mixed powder and the mutual solubility of the ethyl alcohol and the ethyl ether are utilized, so that the ethanol can be stably dissolved to realize the replacement effect, meanwhile, the ethyl ether belongs to a solvent with a lower boiling point, and the boiling point of the ethyl ether can be far higher than that of the ethyl ether under the environmental condition of 60 ℃, so that most of the ethanol can be removed by filtration in reduced pressure distillation treatment, the ethyl ether can be quickly converted into ethyl ether steam to be removed, the excellent treatment effect is achieved, the residual ethyl ether can be removed based on the temperature far higher than the boiling point temperature, the purification of the mixed powder is realized, and the ethyl ether and the ethyl alcohol cannot be remained; more attention needs to be paid to the replacement effect of diethyl ether and ethanol, so that the temperature requirement for removing gas impurities can be reduced, the steam removal can be realized, and other impurities are prevented from entering.
Step 2, placing the mixed powder into a mould for compression molding to obtain a prefabricated synthetic column, wherein the compression pressure is 10-20MPa, the compression atmosphere is nitrogen atmosphere, and the temperature is 30-40 ℃; at the temperature, the mixed powder is pressed to form a prefabricated synthetic column through high pressure, catalyst powder is uniformly distributed on the periphery of graphite based on the mixing mode, the catalyst powder can form primary package on the graphite, gaps of the catalyst powder can be filled with sodium chloride in ethanol in a particle colloid mode, densification and stabilization are realized, meanwhile, the catalyst powder and the sodium chloride on the synthetic column can form a stable blocking agent to separate the graphite, and conditions are provided for preparing small-particle diamond;
step 3, placing the prefabricated synthetic column into a composite block, drying at constant temperature to obtain the synthetic column, and then synthesizing the synthetic column at high temperature and high pressure to obtain synthetic diamond, wherein the constant temperature for drying is 100-110 ℃, the prefabricated synthetic column is placed in the middle of the composite block, the high temperature and high pressure synthesis is 1400-1500 ℃, the pressure is 5-6GPa, and the time is 20-30min, and the high temperature and high pressure synthesis is completed in a hexahedral top press; the composite block adopts a double-layer composite block structure and comprises an inner-layer stone block and an outer-layer stone block, wherein the inner-layer stone block is a composite stone block of dolomite and sodium chloride, the outer-layer stone block is a composite stone block of dolomite and pyrophyllite, and the pressure transmission property, the sealing property, the heat preservation property and the supporting property of the composite block are guaranteed through the inner-outer double-layer composite stone block, so that an excellent high-temperature high-pressure synthesis environment is provided inside. The composite block takes dolomite as main materials of the inner-layer stone block and the outer-layer stone block, can have good pressure transmission performance and stability, meets the integral pressure transmission requirement, ensures that sodium chloride is arranged in the inner-layer stone block, improves the fluidity of the inner-layer stone block, solves the fluidity problem of the dolomite, but ensures that the heat preservation performance of the sodium chloride is poor, and the inner-layer stone block of the sodium chloride and the dolomite is poor in fluidity, but still has sealing heat preservation performance, so that the problem is solved, the outer-layer stone block formed by pyrophyllite and the dolomite is formed on the outer surface of the inner-layer stone block, and the outer-layer stone block has good heat preservation performance, fluidity and sealing performance by utilizing the pyrophyllite, so that the peripheral protection effect is formed. Meanwhile, it should be noted that sodium chloride has the problem of large crystal grain, and is self-based on sodium chlorideThe dolomite is dispersed and compartmentalized, so that the stable connection characteristic is difficult to process, and a large grain structure is formed, thereby solving the use defect of sodium chloride. Further, the preparation method of the composite block comprises the following steps: b1, adding sodium chloride into ethanol, stirring uniformly, adding dolomite particles, stirring and ball milling for 20-30min to obtain fine powder slurry, wherein the mass ratio of the sodium chloride to the ethanol is 1:4-5, the stirring speed is 1000-2000r/min, the mass ratio of the dolomite to the sodium chloride is 2-3:1, the ball milling temperature is 20-30 ℃, and the ball milling pressure is 1-2MPa, and the steps utilize the sodium chloride as ball milling particles to finely crush the dolomite particles, and meanwhile, the sodium chloride is in the form of small particle colloid in the ethanol and can be used as a fine ball milling material, so that excellent ball milling and crushing effects are realized; adding ethanol into the fine powder slurry, diluting and carrying out ultrasonic treatment for 20-30min, then placing the fine powder slurry into a mould, pressing at a constant temperature for 20-30min, and drying for 2-4h to form an inner stone block, wherein the mass ratio of the fine powder slurry to the ethanol is 1:2-3, the ultrasonic frequency of ultrasonic treatment is 40-50kHz, the temperature is 20-30 ℃, the constant temperature pressing temperature is 80-90 ℃, the pressing pressure is 2-4MPa, and the drying temperature is 100-120 ℃; according to the method, ethanol is used as a diluent, and sodium chloride in the slurry is dispersed in a mode of ultrasonic treatment to form excellent uniform diffusion, and can be uniformly doped into dolomite fine powder, and meanwhile, ethanol is completely removed by means of constant-temperature pressing and drying, so that uniform doping of sodium chloride in dolomite is realized; b3, adding dolomite and pyrophyllite into distilled water, stirring uniformly, performing ball milling treatment to form fine powder slurry, then uniformly coating the slurry on the surface of an inner stone block, standing for 20-30min, pressing at constant temperature for 30-50min, performing constant pressure drying treatment for 2-4h to obtain a composite block, wherein the mass ratio of the dolomite to the pyrophyllite is 3:1-2, the mass ratio of the pyrophyllite to the distilled water is 3-4:1, the ball milling treatment temperature is 30-50 ℃, the ball milling pressure is 2-4MPa, and the coating amount is 20-25g/cm 2 Standing at 10-20deg.C; the constant temperature pressing temperature is 100-110 ℃, the pressure is 3-5MPa, the constant temperature drying temperature is 150-200 ℃ and the pressure is 4-7MPa; the ball milling treatment in this step allows for thorough mixing of the pyrophyllite and dolomite and formation of a homogenized fine particlePowder slurry, and in the in-process of evenly coating, deposit dolomite and the mixed fine powder of pyrophyllite at inlayer stone surface, the hydrone in the slurry can dissolve sodium chloride simultaneously, form the infiltration, and the hole of sodium chloride can be filled by pyrophyllite and dolomite, form the infiltration structure, consequently, in the suppression in-process, outer stone and inlayer stone can reach stable connected system based on the infiltration system, the cooperation dolomite is homoplasmy granule, the tie gap of inlayer stone and outer stone has greatly reduced, the connection support stability of this structure has been realized. The composite block prepared by the process has the characteristics of good heat preservation, support, sealing performance, stability, pressure transmission performance and the like, can form performance complementation among materials, and improves the stability of high temperature and high pressure inside.
And 4, separating the synthetic blocks, removing the composite blocks to obtain a prefabricated synthetic column with complete reaction, sequentially placing the prefabricated synthetic column into a nitric acid solution and a sulfuric acid solution, and stirring at constant temperature for 1-2 hours to obtain the artificial diamond, wherein the pH value of the nitric acid solution is 3-4, the pH value of the sulfuric acid solution is 2-3, the temperature of constant temperature stirring is 40-50 ℃, and the stirring speed is 200-600r/min.
Furthermore, when the graphite adopts nitrogen modified graphite to prepare nitrogen modified diamond, the conventional process uses materials such as magnesium nitride and the like as nitrogen sources and is combined with catalyst powder, and in the high-temperature and high-pressure treatment process, nitrogen element is permeated from outside to inside to achieve excellent nitriding modification, but in the nitrogen doping process, new metal element is needed to be added to form metal doping problem, so that the ingested impurities are increased. The preparation method of the nitrogen modified graphite comprises the following steps: adding graphite into ethanol, stirring, performing constant-temperature ball milling for 2-4 hours to obtain graphite fine powder slurry, wherein the mass ratio of the graphite to the ethanol is 3:1-2, the stirring speed is 500-1000r/min, the constant-temperature ball milling temperature is 40-50 ℃, the ball milling pressure is 0.5-0.8MPa, and the steps utilize a ball milling treatment mode to match with a wet ball milling treatment environment to refine graphite particles and uniformly disperse the refined particles in the ethanol; c2, adding diethyl ether into the graphite fine powder slurry, and uniformly stirring to form a homogeneous slurry, wherein the volume of the diethyl ether is stone100-150% of ink fine powder slurry, wherein diethyl ether is used as a compatibilizer to homogenize graphite fine powder and reduce stress among graphite particles; adding sodium chloride, ammonium carbonate and ammonium chloride into the homogeneous slurry, fully stirring, drying at a low temperature to obtain a viscous slurry, granulating at a low temperature, and airing to obtain prefabricated particles, wherein the mass ratio of the sodium chloride to the ammonium carbonate is 1:5-6:2, the addition amount of the ammonium carbonate is 20-30% of the mass of graphite, the stirring speed of the ammonium chloride and the ammonium carbonate is 1000-2000r/min, the temperature of the low temperature drying is 40 ℃, the temperature of the low temperature granulation and airing is 5-10 ℃, the particle size is 5-10mm, the granulating pressure is 0.7-0.9MPa, the step utilizes a low temperature stirring mode to uniformly disperse the ammonium chloride, the ammonium chloride and the ammonium carbonate to the periphery of graphite fine powder to form a stable particle structure, particularly a small particle colloid structure formed by sodium chloride in ethanol, when the low temperature drying is carried out, the diethyl ether is removed to form a stable ethanol solution, the solution viscosity of the colloid structure is continuously increased, and the particle structure is formed in the granulation, the particle structure is ensured to be stable, the particle structure is tightly matched with the granulating mode for the low temperature drying, and the granulating effect is achieved, and the effect of tightly drying is achieved by adopting the low granulating mode, and the granulating effect is achieved; c4, adding ethyl cellulose into diethyl ether, uniformly stirring, spraying to the surface of the particles, and standing to obtain coated particles; the concentration of the ethyl cellulose in the diethyl ether is 300-600g/L, the stirring speed is 300-700r/min, and the spraying amount is 5-10mL/cm 2 Standing at 40-45deg.C; the method comprises the steps of forming a viscous solution by utilizing the solubility of ethyl cellulose and diethyl ether, coating the viscous solution on the surfaces of particles, and removing diethyl ether by matching with the standing temperature, so that an excellent wrapping effect is achieved, and a particle system with a shell-core structure is realized; c4, placing the coated particles into a mold, filling gaps with sodium chloride, standing at a constant temperature for 1-2h, washing with distilled water, and filtering to obtain reacted coated particles, wherein the temperature of the constant temperature standing is 200-220 ℃ and the external pressure is 0.3-0.6MPa, and the steps utilize the blending of the prefabricated particles and the sodium chloride, and the ammonium carbonate and the chloride in the prefabricated particles are matched with the temperature and the external pressureThe ammonia is decomposed and converted into ammonia gas to form internal pressure, so as to ensure the stability of the ethyl cellulose protective layer, prevent the protective layer from being broken, form stable external pressure and reduce pressure difference, meanwhile, the water vapor formed by decomposition can form acid corrosion on graphite by being matched with hydrogen chloride, and the permeation treatment of the ammonia gas can effectively improve the nitrogen permeation effect of graphite materials, namely, under the action of an acid system, pressure and temperature, the ammonia gas can form stable permeation and doping in the graphite based on the concentration and the gas state characteristics of the ammonia gas, so that excellent nitrogen doped graphite is achieved, and the sodium chloride has the effects of pressure transmission and support in the process, and meanwhile, the colloid dispersion improves the dispersibility of the graphite; c5, placing the reacted coated particles into an ethanol water solution, ultrasonically cleaning for 20-40min, filtering and drying to obtain nitrogen-doped graphite, wherein the ethanol volume ratio of the ethanol water solution is 40-50%, the ultrasonic cleaning temperature is 20-30 ℃, the ultrasonic frequency is 40-70kHz, the drying is performed in a nitrogen atmosphere, and the temperature is 140-160 ℃; the method utilizes the solubility of ethanol aqueous solution to sodium chloride and ethylcellulose to form a stable dissolution system, completely dissolves materials in a coating system, exposes insoluble particles of graphite, and obtains graphite particles through filtration and drying. The process utilizes an inner wrapping system to form an ammonia nitrogen source, endogenous pressure and an acidic environment from ammonium carbonate and ammonium chloride, and the inner wrapping structure of ethyl cellulose is matched to realize a miniaturized nitrogen doping reactor, so that rapid and homogeneous nitriding treatment is realized, meanwhile, the nitrogen source is a gaseous nitrogen source, high-quality permeability can be formed in graphite, and the inner and outer uniformity and stability of graphite nitriding are realized by matching with the acidic gaseous system. According to the technical scheme, the graphite nitride with balanced inside and outside is adopted, so that the nitrogen elements are uniformly distributed in the graphite, stable and built-in nitrogen elements are provided for the formation of subsequent artificial diamond, and the built-in nitrogen elements can ensure that the nitrogen sources are uniformly distributed in the diamond.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the defects of the existing artificial diamond, and utilizes sodium chloride and catalyst powder to form a stable coating barrier system, so as to achieve excellent temperature and pressure balance and ensure the internal balance of a high-temperature high-pressure system.
2. According to the invention, graphite nitride is used as a graphite raw material, and nitrogen elements are uniformly distributed in advance, so that the problem of impurity intake of the existing metal nitride serving as a nitrogen source is effectively solved, and the cleanliness of the artificial diamond is reduced.
Detailed Description
The invention is described in detail with reference to examples, but without any limitation to the claims of the invention.
Example 1
A synthesis process of high-grade artificial diamond, comprising the following steps:
step 1, adding sodium chloride into ethanol, uniformly stirring to form slurry, then adding graphite and catalyst powder, performing ultrasonic treatment to form suspension slurry, and drying to obtain mixed powder; the concentration of the sodium chloride in the ethanol is 200g/L, the mass ratio of the sodium chloride to the graphite to the catalyst powder is 1:3:5, the ultrasonic frequency of the ultrasonic wave is 50kHz, and the temperature is 10 ℃; the drying is carried out under the nitrogen atmosphere; the graphite and the catalyst powder adopt micron-sized particles with the particle size of 50 mu m, the catalyst powder consists of micron-sized iron powder, micron-sized nickel powder and micron-sized cobalt powder, the mass ratio of the iron powder to the nickel powder to the cobalt powder is 5:10:1, the drying comprises the following steps of a1, carrying out reduced pressure distillation on suspension slurry in a nitrogen environment for 40min to obtain semi-dry materials, wherein the pressure of reduced pressure distillation is 80% of atmospheric pressure, the temperature is 55 ℃, a2, adding diethyl ether into the semi-dry materials, stirring uniformly, carrying out ultrasonic treatment for 30min to obtain diethyl ether slurry, then carrying out reduced pressure distillation to dry after filtration, repeating for 2 times to obtain dry mixed powder, wherein the concentration of the semi-dry materials in diethyl ether is 600g/L, the ultrasonic treatment temperature is 10 ℃, the ultrasonic frequency is 50kHz, the reduced pressure distillation temperature is 60 ℃, the pressure is 80% of atmospheric pressure, and the reduced pressure distillation atmosphere is nitrogen atmosphere. The graphite adopts nitrogen modified graphite, and the preparation method of the nitrogen modified graphite comprises the following steps: c1, adding graphite into ethanol, stirring, performing constant-temperature ball milling for 2 hours to obtain graphite fine powder slurry, wherein the mass ratio of the graphite to the ethanol is 3:1, and stirringThe speed is 500r/min, the constant-temperature ball milling temperature is 40 ℃, and the ball milling pressure is 0.5MPa; c2, adding diethyl ether into the graphite fine powder slurry, and uniformly stirring to form a homogeneous slurry, wherein the volume of the diethyl ether is 100% of that of the graphite fine powder slurry; adding sodium chloride, ammonium carbonate and ammonium chloride into the homogeneous slurry, fully stirring, drying at a low temperature to obtain a viscous slurry, granulating at a low temperature, and airing to obtain prefabricated particles, wherein the mass ratio of the sodium chloride to the ammonium carbonate to the ammonium chloride is 1:5:2, the addition amount of the ammonium carbonate is 20% of the mass of graphite, the stirring speed of the ammonium chloride and the ammonium carbonate is 1000r/min, the temperature of the low-temperature drying is 40 ℃, the temperature of the low-temperature granulating and airing is 5 ℃, the particle size is 5mm, and the granulating pressure is 0.7MPa; c4, adding ethyl cellulose into diethyl ether, uniformly stirring, spraying to the surface of the particles, and standing to obtain coated particles; the concentration of the ethyl cellulose in the diethyl ether is 300g/L, the stirring speed is 300r/min, and the spraying amount is 5mL/cm 2 The standing temperature is 40 ℃; c4, placing the coated particles into a die, filling gaps with sodium chloride, standing at a constant temperature for 1h, washing and filtering by distilled water to obtain reacted coated particles, wherein the temperature of the constant temperature standing is 200 ℃, and the external pressure is 0.3MPa; and c5, placing the reacted coated particles into an ethanol water solution, ultrasonically cleaning for 20min, filtering, and drying to obtain the nitrogen-doped graphite, wherein the ethanol volume ratio of the ethanol water solution is 40%, the ultrasonic cleaning temperature is 20 ℃, the ultrasonic frequency is 40kHz, and the drying is performed in a nitrogen atmosphere and the temperature is 140 ℃.
Step 2, placing the mixed powder into a mould for compression molding to obtain a prefabricated synthetic column, wherein the compression pressure is 10MPa, the compression atmosphere is nitrogen atmosphere, and the temperature is 30 ℃;
step 3, placing the prefabricated synthetic column into a composite block, drying at constant temperature to obtain the synthetic column, and then synthesizing the synthetic column at high temperature and high pressure to obtain synthetic diamond, wherein the constant temperature for drying is 100 ℃, the prefabricated synthetic column is placed in the middle of the composite block, the high temperature and high pressure synthesis is 1400 ℃, the pressure is 5GPa, and the time is 20min, and the high temperature and high pressure synthesis is completed in a hexahedral top press; the saidThe composite block adopts a double-layer composite block structure and comprises an inner-layer stone block and an outer-layer stone block, wherein the inner-layer stone block is a composite stone block of dolomite and sodium chloride, the outer-layer stone block is a composite stone block of dolomite and pyrophyllite, and the preparation method of the composite block comprises the following steps: b1, adding sodium chloride into ethanol, stirring uniformly, then adding dolomite particles, stirring and ball milling for 20min to obtain fine powder slurry, wherein the mass ratio of the sodium chloride to the ethanol is 1:4, the stirring speed is 1000r/min, the mass ratio of the dolomite to the sodium chloride is 2:1, the ball milling temperature is 20 ℃, and the ball milling pressure is 1MPa; adding ethanol into the fine powder slurry, diluting and carrying out ultrasonic treatment for 20min, then placing the fine powder slurry into a mould, carrying out constant-temperature pressing for 20min, and drying for 2h to form an inner stone, wherein the mass ratio of the fine powder slurry to the ethanol is 1:2, the ultrasonic frequency of ultrasonic treatment is 40kHz, the temperature is 20 ℃, the constant-temperature pressing temperature is 80 ℃, the pressing pressure is 2MPa, and the drying temperature is 100 ℃; b3, adding dolomite and pyrophyllite into distilled water, stirring uniformly, performing ball milling treatment to form fine powder slurry, then uniformly coating the slurry on the surface of an inner stone block, standing for 20min, pressing at constant temperature for 30min, performing constant-pressure drying treatment for 2h to obtain a composite block, wherein the mass ratio of the dolomite to the pyrophyllite is 3:1, the mass ratio of the pyrophyllite to the distilled water is 3:1, the temperature of the ball milling treatment is 30-50 ℃, the ball milling pressure is 2MPa, and the coating amount is 20g/cm 2 The standing temperature is 10 ℃; the constant temperature pressing temperature is 100 ℃, the pressure is 3MPa, the constant temperature drying temperature is 150 ℃ and the pressure is 4MPa.
And 4, separating the synthetic blocks, removing the composite blocks to obtain a prefabricated synthetic column with complete reaction, sequentially placing the prefabricated synthetic column into a nitric acid solution and a sulfuric acid solution, and stirring at constant temperature for 1h to obtain the artificial diamond, wherein the pH value of the nitric acid solution is 3, the pH value of the sulfuric acid solution is 2, the constant temperature stirring temperature is 40 ℃, and the stirring speed is 200r/min.
The artificial diamond prepared by the preparation method has the advantages of brilliant color, good transparency and complete structure, the particle size of the particles is mainly 40-50 mu m, the total mass of the particles accounts for 96%, and nitrogen element detection shows that the content is 2030ppm.
Example 2
A synthesis process of high-grade artificial diamond, comprising the following steps:
step 1, adding sodium chloride into ethanol, uniformly stirring to form slurry, then adding graphite and catalyst powder, performing ultrasonic treatment to form suspension slurry, and drying to obtain mixed powder; the concentration of the sodium chloride in the ethanol is 500g/L, the mass ratio of the sodium chloride to the graphite to the catalyst powder is 1:3:7, the ultrasonic frequency of the ultrasonic wave is 70kHz, and the temperature is 20 ℃; the drying is carried out under the nitrogen atmosphere; the graphite and the catalyst powder adopt micron-sized particles with the particle size of 500 mu m, the catalyst powder consists of micron-sized iron powder, micron-sized nickel powder and micron-sized cobalt powder, the mass ratio of the iron powder to the nickel powder to the cobalt powder is 8:14:1, the drying comprises the following steps of a1, carrying out reduced pressure distillation on suspension slurry in a nitrogen environment for 60min to obtain semi-dry materials, wherein the pressure of reduced pressure distillation is 90% of atmospheric pressure, the temperature is 65 ℃, a2, adding diethyl ether into the semi-dry materials, stirring uniformly, carrying out ultrasonic treatment for 40min to obtain diethyl ether slurry, then carrying out reduced pressure distillation to dry after filtration, repeating for 3 times to obtain dry mixed powder, wherein the concentration of the semi-dry materials in diethyl ether is 900g/L, the ultrasonic treatment temperature is 20 ℃, the ultrasonic frequency is 70kHz, the reduced pressure distillation temperature is 70 ℃, the pressure is 90% of atmospheric pressure, and the reduced pressure distillation atmosphere is nitrogen atmosphere. The graphite adopts nitrogen modified graphite, and the preparation method of the nitrogen modified graphite comprises the following steps: c1, adding graphite into ethanol, stirring, and performing constant-temperature ball milling treatment for 4 hours to obtain graphite fine powder slurry, wherein the mass ratio of the graphite to the ethanol is 3:2, the stirring speed is 1000r/min, the constant-temperature ball milling temperature is 50 ℃, and the ball milling pressure is 0.8MPa; c2, adding diethyl ether into the graphite fine powder slurry, and uniformly stirring to form a homogeneous slurry, wherein the volume of the diethyl ether is 150% of that of the graphite fine powder slurry; adding sodium chloride, ammonium carbonate and ammonium chloride into the homogeneous slurry, fully stirring, drying at a low temperature to obtain a viscous slurry, granulating at a low temperature, and airing to obtain prefabricated particles, wherein the mass ratio of the sodium chloride to the ammonium carbonate to the ammonium chloride is 1:6:2, the adding amount of the ammonium carbonate is 30% of the mass of graphite, and the stirring speed of the ammonium chloride and the ammonium carbonate is 2000r for micro-nano particlesThe temperature of the low-temperature drying is 40 ℃, the temperature of the low-temperature granulation and air drying is 10 ℃, the particle size is 10mm, and the granulation pressure is 0.9MPa; c4, adding ethyl cellulose into diethyl ether, uniformly stirring, spraying to the surface of the particles, and standing to obtain coated particles; the concentration of the ethyl cellulose in the diethyl ether is 600g/L, the stirring speed is 700r/min, and the spraying amount is 10mL/cm 2 The standing temperature is 45 ℃; c4, placing the coated particles into a die, filling gaps with sodium chloride, standing at a constant temperature for 2 hours, washing and filtering by distilled water to obtain reacted coated particles, wherein the temperature of the constant temperature standing is 220 ℃, and the external pressure is 0.6MPa; and c5, placing the reacted coated particles into an ethanol water solution, ultrasonically cleaning for 40min, filtering, and drying to obtain the nitrogen-doped graphite, wherein the ethanol volume ratio of the ethanol water solution is 50%, the ultrasonic cleaning temperature is 30 ℃, the ultrasonic frequency is 70kHz, and the drying is performed in a nitrogen atmosphere and the temperature is 160 ℃.
Step 2, placing the mixed powder into a mould for compression molding to obtain a prefabricated synthetic column, wherein the compression pressure is 20MPa, the compression atmosphere is nitrogen atmosphere, and the temperature is 40 ℃;
step 3, placing the prefabricated synthetic column into a composite block, drying at constant temperature to obtain the synthetic column, and then synthesizing the synthetic column at high temperature and high pressure to obtain synthetic diamond, wherein the constant temperature for drying is 110 ℃, the prefabricated synthetic column is placed in the middle of the composite block, the high temperature and high pressure synthesis is 1500 ℃, the pressure is 6GPa, and the time is 30min, and the high temperature and high pressure synthesis is completed in a hexahedral top press; the composite block adopts a double-layer composite block structure and comprises an inner-layer stone block and an outer-layer stone block, wherein the inner-layer stone block is a composite stone block of dolomite and sodium chloride, the outer-layer stone block is a composite stone block of dolomite and pyrophyllite, and the preparation method of the composite block comprises the following steps: b1, adding sodium chloride into ethanol, uniformly stirring, adding dolomite particles, stirring, and ball milling for 30min to obtain fine powder slurry, wherein the mass ratio of the sodium chloride to the ethanol is 1:5, the stirring speed is 2000r/min, the mass ratio of the dolomite to the sodium chloride is 3:1, the ball milling temperature is 30 ℃, and the ball milling pressure is 2MPa; b2, finely mixing the powderAdding ethanol into the slurry for dilution and ultrasonic treatment for 30min, then placing the slurry into a mould for constant-temperature pressing for 30min, and drying the slurry for 4h to form an inner stone block, wherein the mass ratio of the fine powder slurry to the ethanol is 1:3, the ultrasonic frequency of ultrasonic treatment is 50kHz, the temperature is 30 ℃, the constant-temperature pressing temperature is 90 ℃, the pressing pressure is 4MPa, and the drying temperature is 120 ℃; b3, adding dolomite and pyrophyllite into distilled water, stirring uniformly, performing ball milling treatment to form fine powder slurry, then uniformly coating the slurry on the surface of an inner stone block, standing for 30min, pressing at constant temperature for 50min, performing constant-pressure drying treatment for 4h to obtain a composite block, wherein the mass ratio of the dolomite to the pyrophyllite is 3:2, the mass ratio of the pyrophyllite to the distilled water is 4:1, the temperature of the ball milling treatment is 50 ℃, the ball milling pressure is 4MPa, and the coating amount is 25g/cm 2 The standing temperature is 20 ℃; the constant temperature pressing temperature is 110 ℃, the pressure is 5MPa, the constant temperature drying temperature is 200 ℃, and the pressure is 7MPa.
And 4, separating the synthetic blocks, removing the composite blocks to obtain a prefabricated synthetic column with complete reaction, sequentially placing the prefabricated synthetic column into a nitric acid solution and a sulfuric acid solution, and stirring at constant temperature for 2 hours to obtain the artificial diamond, wherein the pH value of the nitric acid solution is 4, the pH value of the sulfuric acid solution is 3, the constant temperature stirring temperature is 50 ℃, and the stirring speed is 600r/min.
The artificial diamond prepared by the preparation method has the advantages of brilliant color, good transparency and complete structure, the particle size of the particles is mainly 450-500 mu m, the total mass of the particles accounts for 93%, and nitrogen element detection shows that the content is 2210ppm.
Example 3
A synthesis process of high-grade artificial diamond, comprising the following steps:
step 1, adding sodium chloride into ethanol, uniformly stirring to form slurry, then adding graphite and catalyst powder, performing ultrasonic treatment to form suspension slurry, and drying to obtain mixed powder; the concentration of the sodium chloride in the ethanol is 300g/L, the mass ratio of the sodium chloride to the graphite to the catalyst powder is 1:3:6, the ultrasonic frequency of the ultrasonic wave is 60kHz, and the temperature is 15 ℃; the drying is carried out under the nitrogen atmosphere; the graphite and the catalyst powder adopt micron-sized particles with the particle size of300 mu m, wherein the catalyst powder consists of micron-sized iron powder, micron-sized nickel powder and micron-sized cobalt powder, the mass ratio of the iron powder to the nickel to the cobalt powder is 7:12:1, the drying comprises the following steps of a 1), carrying out reduced pressure distillation on suspension slurry for 50min under a nitrogen environment to obtain semi-dry materials, wherein the reduced pressure distillation pressure is 85% of atmospheric pressure, the temperature is 60 ℃, a2, adding diethyl ether into the semi-dry materials, uniformly stirring, carrying out ultrasonic treatment for 35min to obtain diethyl ether slurry, then carrying out filtration, carrying out reduced pressure distillation to dry, and repeating for 3 times to obtain dry mixed powder, wherein the concentration of the semi-dry materials in diethyl ether is 800g/L, the ultrasonic treatment temperature is 15 ℃, the ultrasonic frequency is 60kHz, the reduced pressure distillation temperature is 65%, the pressure is 85% of the atmospheric pressure, and the reduced pressure distillation atmosphere is nitrogen. The graphite adopts nitrogen modified graphite, and the preparation method of the nitrogen modified graphite comprises the following steps: c1, adding graphite into ethanol, stirring, and performing constant-temperature ball milling for 3 hours to obtain graphite fine powder slurry, wherein the mass ratio of the graphite to the ethanol is 3:1, the stirring speed is 800r/min, the constant-temperature ball milling temperature is 45 ℃, and the ball milling pressure is 0.7MPa; c2, adding diethyl ether into the graphite fine powder slurry, and uniformly stirring to form a homogeneous slurry, wherein the volume of the diethyl ether is 130% of that of the graphite fine powder slurry; adding sodium chloride, ammonium carbonate and ammonium chloride into the homogeneous slurry, fully stirring, drying at a low temperature to obtain a viscous slurry, granulating at a low temperature, and airing to obtain prefabricated particles, wherein the mass ratio of the sodium chloride to the ammonium carbonate to the ammonium chloride is 1:6:2, the addition amount of the ammonium carbonate is 25% of the mass of graphite, the stirring speed of the ammonium chloride and the ammonium carbonate is 1500r/min, the temperature of the low-temperature drying is 40 ℃, the temperature of the low-temperature granulating and airing is 8 ℃, the particle size is 8mm, and the granulating pressure is 0.8MPa; c4, adding ethyl cellulose into diethyl ether, uniformly stirring, spraying to the surface of the particles, and standing to obtain coated particles; the concentration of the ethyl cellulose in the diethyl ether is 500g/L, the stirring speed is 500r/min, and the spraying amount is 8mL/cm 2 The standing temperature is 43 ℃; c4, placing the coated particles into a die, filling gaps with sodium chloride, standing at a constant temperature for 2 hours, washing and filtering with distilled water to obtain reacted coated particles, wherein the constant temperature is the same as that of the dieThe standing temperature is 210 ℃, and the external pressure is 0.5MPa; and c5, placing the reacted coated particles into an ethanol water solution, ultrasonically cleaning for 30min, filtering, and drying to obtain the nitrogen-doped graphite, wherein the ethanol volume ratio of the ethanol water solution is 45%, the ultrasonic cleaning temperature is 25 ℃, the ultrasonic frequency is 50kHz, and the drying is performed in a nitrogen atmosphere and the temperature is 150 ℃.
Step 2, placing the mixed powder into a mould for compression molding to obtain a prefabricated synthetic column, wherein the compression pressure is 15MPa, the compression atmosphere is nitrogen atmosphere, and the temperature is 35 ℃;
step 3, placing the prefabricated synthetic column into a composite block, drying at constant temperature to obtain the synthetic column, and then synthesizing the synthetic column at high temperature and high pressure to obtain synthetic diamond, wherein the constant temperature for drying is 105 ℃, the prefabricated synthetic column is placed in the middle of the composite block, the high temperature and high pressure synthesis is 1450 ℃, the pressure is 6GPa, and the time is 25min, and the high temperature and high pressure synthesis is completed in a hexahedral press; the composite block adopts a double-layer composite block structure and comprises an inner-layer stone block and an outer-layer stone block, wherein the inner-layer stone block is a composite stone block of dolomite and sodium chloride, the outer-layer stone block is a composite stone block of dolomite and pyrophyllite, and the preparation method of the composite block comprises the following steps: b1, adding sodium chloride into ethanol, stirring uniformly, then adding dolomite particles, stirring and ball milling for 25min to obtain fine powder slurry, wherein the mass ratio of the sodium chloride to the ethanol is 1:5, the stirring speed is 1500r/min, the mass ratio of the dolomite to the sodium chloride is 3:1, the ball milling temperature is 25 ℃, and the ball milling pressure is 2MPa; adding ethanol into the fine powder slurry, diluting and carrying out ultrasonic treatment for 25min, then placing the fine powder slurry into a mould, carrying out constant-temperature pressing for 25min, and drying for 3h to form an inner stone, wherein the mass ratio of the fine powder slurry to the ethanol is 1:3, the ultrasonic frequency of ultrasonic treatment is 45kHz, the temperature is 25 ℃, the constant-temperature pressing temperature is 85 ℃, the pressing pressure is 3MPa, and the drying temperature is 110 ℃; b3, adding dolomite and pyrophyllite into distilled water, stirring uniformly, ball milling to form fine powder slurry, then uniformly coating the slurry on the surface of an inner stone block, standing for 25min, pressing at constant temperature for 40min, and drying at constant pressure for 3h to obtain a composite block, wherein the composite block is prepared byThe mass ratio of dolomite to pyrophyllite is 3:2, the mass ratio of pyrophyllite to distilled water is 3:1, the temperature of ball milling treatment is 40 ℃, the ball milling pressure is 3MPa, and the coating amount is 24g/cm 2 The standing temperature is 15 ℃; the constant temperature pressing temperature is 105 ℃, the pressure is 4MPa, the constant temperature drying temperature is 180 ℃ and the pressure is 6MPa.
And 4, separating the synthetic blocks, removing the composite blocks to obtain a prefabricated synthetic column with complete reaction, sequentially placing the prefabricated synthetic column into a nitric acid solution and a sulfuric acid solution, and stirring at a constant temperature for 2 hours to obtain the artificial diamond, wherein the pH value of the nitric acid solution is 3, the pH value of the sulfuric acid solution is 3, the constant temperature stirring temperature is 45 ℃, and the stirring speed is 400r/min.
The artificial diamond prepared by the preparation method has the advantages of brilliant color, good transparency and complete structure, the particle size of particles is mainly 260-310 mu m, the total mass of the particles accounts for 95%, and nitrogen element detection shows that the content is 2170ppm.
It is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those of ordinary skill in the art that the present invention may be modified or substituted for elements thereof to achieve the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.
Claims (8)
1. A synthetic process of artificial diamond is characterized in that: the method comprises the following steps:
step 1, adding sodium chloride into ethanol, uniformly stirring to form slurry, then adding graphite and catalyst powder, performing ultrasonic treatment to form suspension slurry, and drying to obtain mixed powder;
step 2, placing the mixed powder into a mould for pressing and forming to obtain a prefabricated synthetic column;
step 3, placing the prefabricated synthetic column into a composite block, drying at constant temperature to obtain a synthetic column, then synthesizing the synthetic column at high temperature and high pressure to obtain synthetic diamond,
step 4, separating the synthetic blocks, removing the composite blocks to obtain a prefabricated synthetic column with complete reaction, and then sequentially placing the prefabricated synthetic column into a nitric acid solution and a sulfuric acid solution and stirring at constant temperature for 1-2 hours to obtain the artificial diamond;
the concentration of sodium chloride in the step 1 in ethanol is 200-500g/L, the mass ratio of the sodium chloride to graphite to the catalyst powder is 1:3:5-7, the ultrasonic frequency of ultrasonic waves is 50-70kHz, and the temperature is 10-20 ℃; the graphite adopts nitrogen modified graphite;
the drying method comprises the steps of a1, carrying out reduced pressure distillation on suspension slurry for 40-60min under a nitrogen environment to obtain semi-dry materials, wherein the pressure of reduced pressure distillation is 80-90% of atmospheric pressure, the temperature is 55-65 ℃, a2, adding diethyl ether into semi-dry materials, stirring uniformly, carrying out ultrasonic treatment for 30-40min to obtain diethyl ether slurry, then carrying out reduced pressure distillation to dry after filtering, and repeating for 2-3 times to obtain dry mixed powder, the concentration of the semi-dry materials in diethyl ether is 600-900g/L, the ultrasonic treatment temperature is 10-20 ℃, and the ultrasonic frequency is 50-70kHz; the temperature of the reduced pressure distillation is 60-70 ℃, the pressure is 80-90% of the atmospheric pressure, and the reduced pressure distillation atmosphere is nitrogen atmosphere.
2. A synthetic process according to claim 1, wherein: the graphite and the catalyst powder adopt micron-sized particles with the particle size of 50-500 mu m, the catalyst powder consists of micron-sized iron powder, micron-sized nickel powder and micron-sized cobalt powder, and the mass ratio of the iron powder to the nickel powder to the cobalt powder is 5-8:10-14:1.
3. A synthetic process according to claim 1, wherein: the drying in the step 1 is carried out under nitrogen atmosphere.
4. A synthetic process according to claim 1, wherein: the pressing pressure in the step 2 is 10-20MPa, the pressing atmosphere is nitrogen atmosphere, and the temperature is 30-40 ℃.
5. A synthetic process according to claim 1, wherein: the constant temperature drying temperature in the step 3 is 100-110 ℃, and the prefabricated synthetic column is placed in the middle of the composite block.
6. A synthetic process according to claim 5, wherein: the composite block adopts a double-layer composite block structure and comprises an inner layer stone block and an outer layer stone block.
7. A synthetic process according to claim 1, wherein: the high-temperature high-pressure synthesis in the step 3 is performed in a hexahedral press at 1400-1500 ℃ and 5-6GPa for 20-30 min.
8. A synthetic process according to claim 1, wherein: the pH value of the nitric acid solution in the step 4 is 3-4, the pH value of the sulfuric acid solution is 2-3, the constant temperature stirring temperature is 40-50 ℃, and the stirring speed is 200-600r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211130313.XA CN115634622B (en) | 2022-09-15 | 2022-09-15 | Synthesis process of high-grade artificial diamond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211130313.XA CN115634622B (en) | 2022-09-15 | 2022-09-15 | Synthesis process of high-grade artificial diamond |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115634622A CN115634622A (en) | 2023-01-24 |
| CN115634622B true CN115634622B (en) | 2024-02-06 |
Family
ID=84942845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211130313.XA Active CN115634622B (en) | 2022-09-15 | 2022-09-15 | Synthesis process of high-grade artificial diamond |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115634622B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0332353A2 (en) * | 1988-03-08 | 1989-09-13 | Sumitomo Electric Industries, Ltd. | A method of synthesizing diamond |
| CN105921076A (en) * | 2016-06-03 | 2016-09-07 | 湖北鄂信钻石科技股份有限公司 | Preparation method for green artificial diamond |
| CN106975421A (en) * | 2017-05-07 | 2017-07-25 | 河南黄河旋风股份有限公司 | A kind of manufacture method of high self-sharpening diamond |
| CN108164253A (en) * | 2018-01-17 | 2018-06-15 | 吴亚良 | A kind of preparation method of aluminium oxide-aluminium titanates porous ceramics |
-
2022
- 2022-09-15 CN CN202211130313.XA patent/CN115634622B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0332353A2 (en) * | 1988-03-08 | 1989-09-13 | Sumitomo Electric Industries, Ltd. | A method of synthesizing diamond |
| CN105921076A (en) * | 2016-06-03 | 2016-09-07 | 湖北鄂信钻石科技股份有限公司 | Preparation method for green artificial diamond |
| CN106975421A (en) * | 2017-05-07 | 2017-07-25 | 河南黄河旋风股份有限公司 | A kind of manufacture method of high self-sharpening diamond |
| CN108164253A (en) * | 2018-01-17 | 2018-06-15 | 吴亚良 | A kind of preparation method of aluminium oxide-aluminium titanates porous ceramics |
Non-Patent Citations (1)
| Title |
|---|
| 《一种高自锐性人造金刚石的制造方法》;李振宇等;《科技成果工程科技Ⅰ辑》;第1-2页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115634622A (en) | 2023-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105175682B (en) | Process for preparing polyurethane foam by using novel lignin liquefaction method | |
| CN115634622B (en) | Synthesis process of high-grade artificial diamond | |
| CN103420850A (en) | Continuous production method of paranitroaniline | |
| CN107163969A (en) | A kind of method that medium temperature coal pitch prepares mesophase pitch | |
| CN101633627A (en) | A kind of method of producing 3-(N, N-diallyl) amino-4-methoxyacetanilide | |
| CN114538483A (en) | Hydrogenation system and method for producing battery-grade lithium carbonate from crude lithium carbonate | |
| CN115400691A (en) | Preparation method of artificial diamond | |
| CN112675839B (en) | High-performance palladium-carbon catalyst and preparation method thereof | |
| CN115845881B (en) | Hydrogenation catalyst and preparation method thereof, and preparation method of N, N-dimethylbenzylamine | |
| CN115215782B (en) | Preparation method of 4-bromoindole | |
| CN102295620A (en) | Co-production synthesizing technology of rubber vulcanization promoter NS | |
| CN116395721A (en) | A kind of method of lithium carbonate carbonization | |
| CN108424761A (en) | A kind of preparation method of high mating type film-coated ceramisite proppant material | |
| CN115872727B (en) | Method for isostatic pressing of ceramic material | |
| CN113620287A (en) | Nitrogen-doped capacitance carbon using lignin as precursor of carbon and adopting 'inner leaching-outer wrapping' technology and preparation method thereof | |
| CN104130545B (en) | A kind of preparation method of Graphene modified furan resin | |
| CN112592411A (en) | Method and device for preparing modified cellulose | |
| CN112320771A (en) | Thin-layer porous g-C prepared by supercritical water3N4Method (2) | |
| CN118579781B (en) | Lignite-based honeycomb activated carbon and preparation method thereof | |
| CN111002450A (en) | Curing method of cement product | |
| CN118063279B (en) | A clean production method for co-producing phosphorous acid with ethyl chloride | |
| CN117384334B (en) | Easily-collapsible phenolic resin for precoated sand and preparation method thereof | |
| CN119219399A (en) | Alumina ceramic granulated powder and preparation method thereof | |
| CN111961140B (en) | Aminated starch and preparation method and application thereof | |
| CN115784671B (en) | Method for preparing baking-free bricks from tailings in machine-made sand production process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 027099 East of Donghuan South Road, Baochang Town, Taipusi Banner, Xilingol League, Inner Mongolia Autonomous Region Patentee after: Tanghe Technology (Inner Mongolia) Co.,Ltd. Country or region after: China Address before: 027099 East of Donghuan South Road, Baochang Town, Taipusi Banner, Xilingol League, Inner Mongolia Autonomous Region Patentee before: Inner Mongolia Tanghe Technology Co.,Ltd. Country or region before: China |
|
| CP03 | Change of name, title or address |