CN114702033A - Method for removing metal from polycrystalline diamond by electrolysis combined with acid treatment - Google Patents
Method for removing metal from polycrystalline diamond by electrolysis combined with acid treatment Download PDFInfo
- Publication number
- CN114702033A CN114702033A CN202210401807.0A CN202210401807A CN114702033A CN 114702033 A CN114702033 A CN 114702033A CN 202210401807 A CN202210401807 A CN 202210401807A CN 114702033 A CN114702033 A CN 114702033A
- Authority
- CN
- China
- Prior art keywords
- polycrystalline diamond
- treatment
- metal removal
- solution
- acid
- 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.)
- Pending
Links
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 93
- 239000010432 diamond Substances 0.000 title claims abstract description 93
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 72
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 13
- 238000010306 acid treatment Methods 0.000 title claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 7
- 150000002739 metals Chemical class 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 4
- 230000008646 thermal stress Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 description 11
- 238000004506 ultrasonic cleaning Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/28—After-treatment, e.g. purification, irradiation, separation or recovery
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for removing metals in polycrystalline diamond through electrolysis and acid treatment, and belongs to the field of superhard material abrasive tools. The main process comprises three parts of polycrystalline diamond surface purification, polycrystalline diamond alkaline electrolyte electrolysis treatment and polycrystalline diamond acidolysis metal removal treatment. The method has the advantages of simple operation, high metal removal efficiency, safety, environmental protection and the like, greatly improves the metal removal depth, reduces the residual thermal stress of the polycrystalline diamond in the use process, and enhances the thermal stability and the wear resistance of the polycrystalline diamond. Compared with the traditional acid method for removing metal, the method disclosed by the invention is carried out at room temperature, so that the condition of volatilization of a strong acid solution at high temperature is avoided, and the method has higher practical value and application prospect.
Description
Technical Field
The invention relates to the field of superhard material abrasive tools, in particular to a method for removing metals in polycrystalline diamond by electrolysis combined with acid treatment.
Background
Polycrystalline diamond (PCD) is formed by sintering diamond micropowder and a metal catalyst at high temperature and high pressure, has the high hardness and high wear resistance of diamond, and is widely applied to various industries such as petroleum drill bits, cutters and the like due to good performance of the PCD. With the progress and development of science and technology, new requirements, especially thermal stability, are put forward for ultra-hard materials at home and abroad. PCD is an important part of superhard materials, and the problem to be solved by the inventor at present is to improve the thermal stability of PCD so that the product can better meet the use requirement.
At present, the most effective method for improving the thermal stability of PCD is to remove metallic phase cobalt, aluminum and other elements in a diamond polycrystalline layer. In the sintering process of PCD, the metallic cobalt is used as a sintering aid to play a role of a catalyst, and the combination of diamond particles is promoted to generate D-D bonds. The existence of metal cobalt can reduce the stability of polycrystalline diamond, and has two main reasons, firstly, the difference of the thermal expansion coefficient of the used sintering aid metal cobalt and diamond is large, and because the working condition of the polycrystalline diamond is mostly high-temperature condition, the diamond crystal grains are easy to fall off in the working process so as to reduce the performance of the diamond compact, and secondly, when the temperature is higher than 700 ℃, the diamond can be converted into graphite under the catalysis of cobalt element so as to cause the failure of PCD, and the thermal stability of the PCD is reduced. Meanwhile, the existence of the metal cobalt can destroy D-D bonds formed in the PCD, so that the PCD is subjected to large-scale thermal damage such as abrasion, cracking, layering and the like under a high-temperature condition, and the service life of the tool is shortened. The presence of metals such as aluminum also causes thermal stress in PCD due to the difference in thermal expansion coefficient, causing problems such as internal cracking and a decrease in strength and hardness, thereby reducing its usability.
In order to improve the service performance of PCD products, metal elements such as cobalt and aluminum are required to be removed. At present, a plurality of scholars at home and abroad research the metal removal of PCD, and the common method is the metal removal by an acid method. The acid metal removing technology uses various types of acids, including hydrochloric acid, nitric acid, hydrofluoric acid, phosphoric acid, sulfuric acid and perchloric acid, most of which adopt corrosive strong acid or mix several kinds of strong acid as a metal removing reagent, and the removing effect is achieved by utilizing the strong oxidizing property of the strong acid reagent. The traditional acid method has two disadvantages, on one hand, strong acid volatilizes at high temperature to cause harm to the environment, and on the other hand, the removal depth and the removal effect are not ideal enough. Therefore, the research of a safe, environment-friendly and efficient metal removal method is particularly critical.
Disclosure of Invention
The invention aims to: the method for removing metal from polycrystalline diamond by electrolysis combined with acid treatment is provided, wherein the surface of polycrystalline diamond is pretreated in alkaline electrolyte to remove part of surface metal, so that acid solution can smoothly enter gaps among diamond particles to remove metal in the subsequent acid treatment process. The method has the advantages of reliable principle, simple operation, safety and environmental protection, greatly improves the removal depth, reduces the residual thermal stress of the polycrystalline diamond in the use process, and enhances the thermal stability and the wear resistance of the polycrystalline diamond. Compared with the traditional acid method for removing metals, the method is carried out at room temperature, avoids the condition of volatilization of strong acid solution at high temperature, and has higher practical value and application prospect.
Technical scheme
In order to realize the purpose of the invention, the following technical scheme is adopted for realizing the purpose:
a. the surface purification treatment of the polycrystalline diamond comprises the following specific processes: dissolving an organic solvent on the surface of the polycrystalline diamond by using an acetone solution, cleaning the residual acetone solution by using an ethanol solution, and finally drying the cleaned polycrystalline diamond for later use;
b. the electrolytic treatment of polycrystalline diamond alkaline electrolyte comprises the following specific processes: putting the processed polycrystalline diamond into a customized electrolytic cell for electrolytic treatment, wherein the electrolyte is Na2CO3、KOH、H2Mixed solution of O, Na2CO3The ratio of the solution to the KOH solution was 1:1 to 1:3 (Na)2CO3KOH) and H2The ratio of O is 1: 20 to 1: 50, taking the polycrystalline diamond as an anode and the metal copper sheet as a cathode, determining the voltage to be between 0.5v and 1.5v, and determining the electrolysis time to be between 24h and 48 h;
c. the acidolysis metal removal treatment of the polycrystalline diamond comprises the following specific processes: putting the polycrystalline diamond subjected to electrolytic treatment into prepared acidic metal removal liquid for metal removal treatment, wherein the acidic metal removal liquid is a mixed liquid consisting of sulfuric acid (98 wt%) and hydrogen peroxide (30 wt%), and the volume ratio of the acidic metal removal liquid to the hydrogen peroxide is 1: 5-1: 10, putting the prepared metal removal liquid and the polycrystalline diamond into an unsealed polytetrafluoroethylene container for reaction, wherein the metal removal time is between 24h and 48 h.
The preferable process of the polycrystalline diamond surface purification treatment in the step a in the invention is as follows: putting a polycrystalline diamond sample (containing 5-10% of cobalt) into a beaker filled with an acetone solution, cleaning the surface of the sample in an ultrasonic cleaning machine for 10-20 min, putting the polycrystalline diamond treated by the acetone solution into the beaker filled with an alcohol solution, cleaning in the ultrasonic cleaning machine for 10-20 min, drying the cleaned polycrystalline diamond sample in an oven for standby, and setting the temperature to be 60-80 ℃ and the time to be 5-10 h.
The optimal preparation process of the acid metal removal liquid in the step c comprises the following steps: sulfuric acid (98 wt%) is slowly poured into a beaker filled with hydrogen peroxide (30 wt%) along the wall of the beaker or a glass rod, the concentrated sulfuric acid has high density, if the concentrated sulfuric acid is added, water forms a layer of water on the surface of the concentrated sulfuric acid, and the surface water is in danger of boiling rapidly.
The invention has the beneficial effects that:
1. the acetone solution can be used for effectively removing the organic solvent on the surface of the polycrystalline diamond, so that the subsequent electrolyte and the acidic metal removal liquid can enter gaps of diamond particles to a greater extent;
2. the metal on the surface of the polycrystalline diamond can be completely removed through the alkaline electrolyte metal removal pretreatment, the electrolytic metal removal speed is high, the efficiency is high, and better conditions are provided for the next step that the acidic metal removal liquid enters the gaps among diamond particles for further metal removal;
3. through the repeated treatment of electrolysis combined with acid, not only can the metal on the surface of the polycrystalline diamond be removed, but also the residual metal among diamond particles in the polycrystalline diamond can be effectively removed, and the thermal stability and the mechanical property of the polycrystalline diamond are greatly enhanced.
Detailed Description
The invention is further described below with reference to specific examples:
example 1:
a. the surface purification treatment of the polycrystalline diamond comprises the following specific processes: putting a polycrystalline diamond sample (containing 5% of cobalt) into a beaker filled with an acetone solution, cleaning the surface of the sample in an ultrasonic cleaning machine for 10 min, then putting the polycrystalline diamond treated by the acetone solution into the beaker filled with an alcohol solution, cleaning the polycrystalline diamond sample in the ultrasonic cleaning machine for 10 min, and drying the cleaned polycrystalline diamond sample in an oven for standby at the set temperature of 60 ℃ for 5 h;
b. the electrolytic treatment of polycrystalline diamond alkaline electrolyte comprises the following specific processes: putting the processed polycrystalline diamond into a customized electrolytic cell for electrolytic treatment, wherein the electrolyte is Na2CO3、KOH、H2Mixed solution of O, Na2CO3The ratio of the solution to the KOH solution is 1:1, (Na)2CO3KOH) and H2The proportion of O is 1: 20, determining the voltage to be 0.5v and the electrolysis time to be 24h by taking the polycrystalline diamond as an anode and the metal copper sheet as a cathode;
c. the acidolysis metal removal treatment of the polycrystalline diamond comprises the following specific processes: putting the polycrystalline diamond subjected to electrolytic treatment into a prepared acidic metal removal liquid for metal removal treatment, wherein the acidic metal removal liquid is a mixed liquid composed of 98 wt% of sulfuric acid and 30 wt% of hydrogen peroxide, the volume ratio is 1:5, putting the prepared metal removal liquid and the polycrystalline diamond into an unsealed polytetrafluoroethylene container for reaction, and the metal removal time is 24 hours;
example 2:
a. the surface purification treatment of the polycrystalline diamond comprises the following specific processes: putting a polycrystalline diamond sample (containing 7% of aluminum) into a beaker filled with an acetone solution, cleaning the surface of the sample in an ultrasonic cleaning machine for 15min, putting the polycrystalline diamond treated by the acetone solution into the beaker filled with an alcohol solution, cleaning the polycrystalline diamond in the ultrasonic cleaning machine for 15min, and drying the cleaned polycrystalline diamond sample in an oven for later use at the set temperature of 70 ℃ for 7 h;
b. the electrolytic treatment of polycrystalline diamond alkaline electrolyte comprises the following specific processes: putting the processed polycrystalline diamond into a customized electrolytic cell for electrolytic treatment, wherein the electrolyte is Na2CO3、KOH、H2Mixed solution of O, Na2CO3The ratio of the solution to the KOH solution is 1:2, (Na)2CO3KOH) and H2The ratio of O is1: 30, determining the voltage to be 1.0 v and the electrolysis time to be 36 h by taking the polycrystalline diamond as an anode and the metal copper sheet as a cathode;
c. the acidolysis metal removal treatment of the polycrystalline diamond comprises the following specific processes: putting the electrolytically treated polycrystalline diamond into a prepared acidic metal removal liquid for metal removal treatment, wherein the acidic metal removal liquid is a mixed liquid composed of sulfuric acid (98 wt%) and hydrogen peroxide (30 wt%), the volume ratio is 1:7, putting the prepared metal removal liquid and the polycrystalline diamond into an unsealed polytetrafluoroethylene container for reaction, and the metal removal time is 36 hours;
example 3:
a. the surface purification treatment of the polycrystalline diamond comprises the following specific processes: putting a polycrystalline diamond sample (containing 10% of cobalt) into a beaker filled with an acetone solution, cleaning the surface of the sample in an ultrasonic cleaning machine for 20 min, putting the polycrystalline diamond treated by the acetone solution into the beaker filled with an alcohol solution, cleaning the polycrystalline diamond sample in the ultrasonic cleaning machine for 20 min, and drying the cleaned polycrystalline diamond sample in an oven for later use, wherein the set temperature is 80 ℃ and the time is 10 hours;
b. the electrolytic treatment of the polycrystalline diamond by the alkaline electrolyte comprises the following specific processes: putting the processed polycrystalline diamond into a customized electrolytic cell for electrolytic treatment, wherein the electrolyte is Na2CO3、KOH、H2Mixed solution of O, Na2CO3The ratio of the solution to the KOH solution is 1:3, (Na)2CO3KOH) and H2The ratio of O is 1: 50, determining the voltage to be 1.5v and the electrolysis time to be 48h by taking the polycrystalline diamond as an anode and the metal copper sheet as a cathode;
c. the acidolysis metal removal treatment of the polycrystalline diamond comprises the following specific processes: putting the electrolyzed polycrystalline diamond into a prepared acidic metal removal liquid for metal removal treatment, wherein the acidic metal removal liquid is a mixed liquid consisting of sulfuric acid (98 wt%) and hydrogen peroxide (30 wt%), the volume ratio is 1:10, and putting the prepared metal removal liquid and the polycrystalline diamond into an unsealed polytetrafluoroethylene container for reaction, and the metal removal time is 48 hours.
Claims (4)
1. A method for removing metals in polycrystalline diamond by electrolysis combined with acid treatment is characterized by comprising the following steps:
a. the surface purification treatment of the polycrystalline diamond comprises the following specific processes: dissolving an organic solvent on the surface of the polycrystalline diamond by using an acetone solution, cleaning the residual acetone solution by using an ethanol solution, and finally drying the cleaned polycrystalline diamond for later use;
b. the electrolytic treatment of polycrystalline diamond alkaline electrolyte comprises the following specific processes: putting the processed polycrystalline diamond into a customized electrolytic cell for electrolytic treatment, wherein the electrolyte is Na2CO3、KOH、H2Mixed solution of O, Na2CO3The ratio of the solution to the KOH solution was 1:1 to 1:3 (Na)2CO3KOH) and H2The ratio of O is 1: 20 to 1: 50, taking the polycrystalline diamond as an anode and the metal copper sheet as a cathode, determining the voltage to be between 0.5v and 1.5v, and determining the electrolysis time to be between 24h and 48 h;
c. the acidolysis metal removal treatment of the polycrystalline diamond comprises the following specific processes: putting the polycrystalline diamond subjected to electrolytic treatment into a prepared acid metal removal liquid for treatment, wherein the acid metal removal liquid is a mixed liquid consisting of sulfuric acid (98 wt%) and hydrogen peroxide (30 wt%), and the volume ratio of the acid metal removal liquid to the hydrogen peroxide is 1: 5-1: 10, putting the prepared metal removal liquid and the polycrystalline diamond into an unsealed polytetrafluoroethylene container for reaction, wherein the cobalt removal time is between 24 hours and 48 hours.
2. The decobalting process of claim 1, wherein: firstly, polycrystalline diamond is pretreated by removing metals in alkaline electrolyte.
3. The polycrystalline diamond alkaline electrolyte electrolytic process of claim 1, wherein: the electrolyte is composed of Na2CO3、KOH、H2Mixed solution of O, Na2CO3The ratio of the solution to the KOH solution was 1:1 to 1:3 (Na)2CO3KOH) and H2The ratio of O is1: 20 to 1: and between 50, taking the polycrystalline diamond as an anode and the metal copper sheet as a cathode, and determining the voltage to be between 0.5v and 1.5 v.
4. The acid-decomposable metal removal treatment for polycrystalline diamond according to claim 1, wherein: the acid metal removal liquid is a mixed liquid consisting of sulfuric acid (98 wt%) and hydrogen peroxide (30 wt%), and the volume ratio is 1:5 to 1:10, respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210401807.0A CN114702033A (en) | 2022-04-18 | 2022-04-18 | Method for removing metal from polycrystalline diamond by electrolysis combined with acid treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210401807.0A CN114702033A (en) | 2022-04-18 | 2022-04-18 | Method for removing metal from polycrystalline diamond by electrolysis combined with acid treatment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114702033A true CN114702033A (en) | 2022-07-05 |
Family
ID=82174113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210401807.0A Pending CN114702033A (en) | 2022-04-18 | 2022-04-18 | Method for removing metal from polycrystalline diamond by electrolysis combined with acid treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114702033A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5650059A (en) * | 1995-08-11 | 1997-07-22 | Credo Tool Company | Method of making cemented carbide substrate |
| JPH09295224A (en) * | 1996-04-26 | 1997-11-18 | Korea Advanced Inst Of Sci Technol | Method for coating super hard tool with diamond film |
| US20100095602A1 (en) * | 2008-10-20 | 2010-04-22 | Smith International, Inc. | Techniques and materials for the accelerated removal of catalyst material from diamond bodies |
| CN104046785A (en) * | 2014-04-09 | 2014-09-17 | 中南大学 | Method for processing waste copper/iron-based diamond tool bit |
| CN104389012A (en) * | 2014-10-21 | 2015-03-04 | 西南石油大学 | Preparation method of cobalt-removed PDC (polycrystalline diamond) composite sheet |
-
2022
- 2022-04-18 CN CN202210401807.0A patent/CN114702033A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5650059A (en) * | 1995-08-11 | 1997-07-22 | Credo Tool Company | Method of making cemented carbide substrate |
| JPH09295224A (en) * | 1996-04-26 | 1997-11-18 | Korea Advanced Inst Of Sci Technol | Method for coating super hard tool with diamond film |
| US20100095602A1 (en) * | 2008-10-20 | 2010-04-22 | Smith International, Inc. | Techniques and materials for the accelerated removal of catalyst material from diamond bodies |
| CN104046785A (en) * | 2014-04-09 | 2014-09-17 | 中南大学 | Method for processing waste copper/iron-based diamond tool bit |
| CN104389012A (en) * | 2014-10-21 | 2015-03-04 | 西南石油大学 | Preparation method of cobalt-removed PDC (polycrystalline diamond) composite sheet |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101973552B (en) | Method for separating silicon from impurities | |
| CN104973662B (en) | Oxide anode for treatment of ship domestic sewage and preparation method thereof | |
| CN1900384A (en) | Process for removing part surface oxidized skin using supersonic wave and electrolytic combination | |
| CN110157916A (en) | A kind of method using neodymium iron boron oil base slice greasy filth preparation high-performance anisotropy NdFeB magnetic powder of low cost | |
| US20190039888A1 (en) | Device and method for hydrogen production with waste aluminum, and method for hydrogen production with aluminum | |
| CN102634805A (en) | Method for preparing magnesium alloy with super-hydrophobic layer on surface | |
| CN110655151A (en) | Preparation method of titanium-based titanium suboxide porous electrode | |
| CN112538651A (en) | Method for polishing titanium alloy by ultrasonic-assisted electrolytic plasma | |
| CN101575257B (en) | Catalytic hydrogenation method by taking toluene as hydrogen storing agent | |
| CN105603453A (en) | In-situ regeneration method of solid polymer electrolyte water electrolyzer | |
| CN108557814A (en) | Charcoal and fluoride extend the method for service life of equipment simultaneously in a kind of purification ＆ isolation aluminum cell waste carbonaceous material | |
| CN114702033A (en) | Method for removing metal from polycrystalline diamond by electrolysis combined with acid treatment | |
| CN110144618A (en) | Method for removing metallic cobalt in polycrystalline diamond compact | |
| CN105648494B (en) | A kind of wear resistant corrosion resistant processing method of aluminium base valve type piece surface | |
| CN113562729A (en) | Citric acid bacteria residue co-production active carbon | |
| CN113061955B (en) | Preparation method of conductive polyaniline modified electrode | |
| CN111763979A (en) | Preparation method of long-life anode material | |
| CN101463196B (en) | Purification processing method for superhard grinding medium | |
| CN118835248A (en) | Method for removing metallic cobalt in polycrystalline diamond compact | |
| CN109576495A (en) | A kind of solar battery sheet recovery and treatment method | |
| CN113818070B (en) | Aluminum alloy surface treatment method | |
| CN116425160B (en) | Nb (Nb) alloy4C3TxMXene material and rapid preparation method thereof | |
| CN215048706U (en) | Waste lithium ion battery lithium recycling system | |
| CN103590081B (en) | A kind of preprocess method of low argentalium alloy surface | |
| CN108295885A (en) | A kind of preparation method for the photocatalysis block being used to prepare grapheme material |
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 |