An environmentally friendly and efficient method for etching diamond particles

Abstract

The present invention provides an environmentally friendly and efficient method for etching diamond particles, and relates to the field of diamond etching technology. The method for etching diamond particles is to use water as a solvent to perform a preliminary etching treatment on the diamond particles through an ozone combined with an ultrasonic process, and then perform a rapid heat treatment to fully etch. The present invention overcomes the shortcomings of the existing vapor phase diamond etching technology, significantly improves the surface etching effect of air on diamond particles, and the technology does not produce waste liquid and other pollutants, which is relatively environmentally friendly. The preparation process is fast and efficient, and the etching can be effectively regulated by adjusting parameters such as ozone treatment and temperature, significantly improving the etching effect and efficiency.

Description

Technical Field

[0001] The invention relates to the technical field of diamond etching, and in particular to an environmentally friendly and efficient method for etching diamond particles. Background Art

[0002] Diamond has a wide range of applications in many fields due to its excellent properties such as extremely high hardness, wear resistance, thermal conductivity and chemical stability. The surface properties of diamond will greatly affect its performance in practical applications. Therefore, how to effectively and accurately change the surface morphology and properties of diamond particles has become one of the important research directions in the field of diamond. The surface etching technology of diamond particles has been one of the research hotspots in the field of surface research in recent years. In the processing field, the surface of diamond particles is etched to obtain pits, which can effectively improve the interface bonding with the binder. In the optoelectronic field, etching technology is used to form a specific shape array on the surface of diamond to ensure that the device has excellent performance.

[0003] At present, in the field of processing and manufacturing of superhard materials, the focus is on etching diamonds with iron group metals (iron, cobalt, nickel) or metals or metal oxide materials such as iron oxide and manganese oxide under high temperature heating treatment, in order to improve the bonding between diamond and binder. This etching technology can effectively improve the interfacial bonding force between diamond and binder materials, and has been applied and promoted in the industry. However, this process still has some outstanding disadvantages. First, a large amount of etchant needs to be consumed, among which cobalt powder is expensive and the etching cost is high. Secondly, after high temperature treatment, it is necessary to use strong acid to treat the etchants such as iron, cobalt and nickel, which not only wastes these raw materials, but also pollutes the environment to a considerable extent. In addition, this solid phase etching often causes serious damage to the internal structure of diamond particles, thereby deteriorating their performance.

[0004] In addition to the common solid phase etching techniques mentioned above, gas etching is also a commonly used method, that is, using gas (including air, oxygen or water vapor, etc.) to etch diamond particles. Compared with the above solid phase etching techniques, gas etching technology has the advantages of lower etchant cost, less impact on the surface mechanical properties of diamond particles, and no environmental pollution. However, the inherent disadvantages of gas phase etching technology have inhibited its promotion and application in industrialization. This is due to the inherent limitations of gas flow rate, which causes its etching rate to be much slower than metal solid phase etching. If the same effect of the above metal etching is achieved, it will inevitably consume a lot of energy. Therefore, this method is currently mainly used to study the physical properties of diamond films. Therefore, based on the above shortcomings, it is difficult to promote and apply gas phase etching technology. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention provides an environmentally friendly and efficient method for etching diamond particles. Under the condition of water as a solution, ozone is used to treat diamond particles, so that ozone reacts with carbon on the surface of diamond to play an etching role, and ultrasonic treatment is combined in this process. The high temperature and high pressure generated by ultrasonic cavitation play a role in significantly enhancing the etching efficiency of ozone. After ozone and ultrasonic treatment, the surface of the diamond particles is slightly etched; the ozone-treated diamond particles are further heated to a certain temperature and kept warm for a period of time, so that the etching pits on the surface of the diamond particles are fully grown; finally, diamond particles with an appropriate number and depth of etching pits on the surface are obtained.

[0006] To achieve the above objectives, the technical solution of the present invention is implemented through the following technical solutions:

[0007] An environmentally friendly and efficient method for etching diamond particles, the method comprising the following steps:

[0008] S1, performing surface cleaning treatment on diamond particles to obtain pre-treated diamond particles for standby use;

[0009] S2, ozone combined with ultrasonic process: adding the above pre-treated diamond particles into deionized water, and introducing ozone into the deionized water, and etching the diamond particles in combination with ultrasonic treatment, and then taking out the diamond particles and drying them to obtain pre-etched diamond particles for standby use;

[0010] S3, rapidly heating the pre-etched diamond particles to 600-900° C. and heat treating for 0.5-2 hours to fully etch the diamond particles.

[0011] Preferably, the specific method of the surface cleaning treatment in step S1 is to clean the diamond particles with deionized water and anhydrous ethanol in sequence, and then blow dry.

[0012] Preferably, the particle size of the diamond particles in step S1 is 10-500 μm.

[0013] Preferably, in step S2, the mass ratio of diamond particles to deionized water is 1-1.5:20-25.

[0014] Preferably, in step S2, the ozone dosage for treating the diamond particles by combining ozone with ultrasound is 1000-2000 mg / h, and the ultrasound power is 100W-200W.

[0015] Preferably, in step S2, the time for treating the diamond particles with ozone combined with ultrasound is 0.5-2 hours.

[0016] Preferably, in step S3, the rate at which the pre-etched diamond particles are heated to 600-900° C. is 5-10° C. / min.

[0017] Preferably, the atmosphere for the heat treatment in step S3 is air.

[0018] The present invention provides an environmentally friendly and efficient method for etching diamond particles, which has the following advantages over the prior art:

[0019] The present invention realizes efficient etching of the surface of diamond particles through ozone coordinated ultrasonic etching and subsequent heat treatment, significantly improves the surface roughness of diamond particles, and is beneficial to increasing the adhesion between diamond particles and other materials; through the method of ultrasound combined with ozone and subsequent heat treatment, the surface etching effect of diamond particles is effectively improved, and the technology does not generate waste liquid and pollutants, and is environmentally friendly and safe; the etching process is fast and efficient, and etching control can be achieved by adjusting parameters such as ozone flow or temperature, effectively improving the etching effect and efficiency, and significantly reducing energy consumption. The overall etching process and technology are simple, environmentally friendly, easy to control, and can be mass-produced. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 2 is a schematic diagram of the microscopic morphology of the diamond sample after ozone and ultrasound combined treatment in Example 1 of the present invention, magnified 250 times;

[0021] Figure 2 This is a schematic diagram of the microscopic morphology of a sample of diamond after ozone and ultrasound combined treatment in Example 1 of the present invention, magnified 3000 times;

[0022] Figure 3 This is a schematic diagram of the microscopic morphology of the sample magnified 250 times after the diamond in Example 1 of the present invention was subjected to ozone and ultrasonic combined treatment and then heated to 800° C. and kept warm for 2 hours;

[0023] Figure 4 This is a schematic diagram of the microscopic morphology of the sample magnified 3000 times after the diamond in Example 1 of the present invention was subjected to ozone and ultrasonic combined treatment and then heated to 800° C. and kept warm for 2 hours;

[0024] Figure 5 This is a schematic diagram of the microscopic morphology of a sample of diamond after ozone and ultrasound combined treatment in Example 2 of the present invention, magnified 250 times;

[0025] Figure 6 This is a schematic diagram of the microscopic morphology of a sample of diamond after ozone and ultrasound combined treatment in Example 2 of the present invention, magnified 3000 times;

[0026] Figure 7 This is a schematic diagram of the microscopic morphology of the sample magnified 250 times after the diamond in Example 2 of the present invention was subjected to ozone and ultrasonic combined treatment and then heated to 900° C. and kept warm for 0.5 hours;

[0027] Figure 8 This is a schematic diagram of the microscopic morphology of the sample magnified 3000 times after the diamond in Example 2 of the present invention was subjected to ozone and ultrasonic combined treatment and then heated to 900° C. and kept warm for 0.5 hours;

[0028] Fig. 9 This is a schematic diagram of the microscopic morphology of a sample of diamond after ozone and ultrasound combined treatment in Example 3 of the present invention, magnified 700 times;

[0029] Fig.10 This is a schematic diagram of the microscopic morphology of a sample of diamond after ozone and ultrasound combined treatment in Example 3 of the present invention, magnified 3000 times;

[0030] Fig.11 This is a schematic diagram of the microscopic morphology of the sample magnified 650 times after the diamond in Example 3 of the present invention was subjected to ozone and ultrasonic combined treatment and then heated to 800° C. and kept warm for 1 hour;

[0031] Fig.12 This is a schematic diagram of the microscopic morphology of the sample magnified 3000 times after the diamond in Example 3 of the present invention was subjected to ozone and ultrasonic combined treatment and then heated to 800° C. and kept warm for 1 hour;

[0032] Fig.13 This is a schematic diagram of the microscopic morphology of a sample of diamond after ozone and ultrasound combined treatment in Example 4 of the present invention, magnified 2000 times;

[0033] Fig.14 This is a schematic diagram of the microscopic morphology of a sample obtained by heating the diamond to 700° C. and keeping the temperature for 1 hour after ozone and ultrasonic combined treatment in Example 4 of the present invention, magnified 2000 times;

[0034] Fig.15 This is a schematic diagram of the microscopic morphology of a sample of diamond after ozone and ultrasound combined treatment in Example 5 of the present invention, magnified 6000 times;

[0035] Fig.16 This is a schematic diagram of the microscopic morphology of a sample obtained by subjecting the diamond in Example 5 of the present invention to ozone and ultrasound combined treatment and then heating to 700° C. and keeping the temperature for 1.5 hours, magnified 6000 times;

[0036] Fig.17 This is a schematic diagram of the microscopic morphology of a diamond sample after ozone and ultrasound combined treatment in Example 6 of the present invention, magnified 12,000 times;

[0037] Fig.18 This is a schematic diagram of the microscopic morphology of a sample obtained by heating the diamond to 600° C. and keeping it for 2 hours after ozone and ultrasonic combined treatment in Example 6 of the present invention, magnified 15,000 times. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] The diamond particles of different sizes used below were cleaned with deionized water and anhydrous ethanol before use to remove oil and impurities on the surface, and then blown dry for use as samples.

[0040] Embodiment 1:

[0041] Surface etching of diamond particles:

[0042] (1) Take 10 grams of diamond particles with an average particle size of 500 microns and put them into a beaker. Pour 200 ml of water into it and put it into an ultrasonic device. Adjust the power to 100 W. Then put the probe of the ozone generator into the bottom of the beaker and introduce ozone gas (the ozone output is 2000 mg / h).

[0043] (2) Start the ultrasonic instrument and ozone generator, and treat with ultrasound and ozone for 1 hour. Then take out the diamond particles and dry them at 80℃ for half an hour. The surface morphology of the diamond particles is as follows: Figure 1 and Figure 2 As shown, there are some traces of etching, but they are not obvious overall;

[0044] (3) Then put the dried diamond particles into a corundum crucible, and then put it into a heating furnace, and heat it to 800°C at a heating rate of 5 degrees / minute, and keep it warm for 2 hours. Finally, the treated diamond particles are naturally cooled to room temperature to obtain diamond particles with a large number of etched pits with a certain depth on the surface, such as Figure 3 and Figure 4 As shown, Figure 4 It can be clearly observed that a large number of triangular etching pits appear on the surface of diamond particles, indicating that effective etching has been completed.

[0045] Embodiment 2:

[0046] Surface etching of diamond particles:

[0047] (1) Take 10 grams of diamond particles with an average particle size of 400 microns and put them into a beaker. Pour 200 ml of water into it and put it into an ultrasonic device. Adjust the power to 200 W. Then put the probe of the ozone generator into the bottom of the beaker and introduce ozone gas (the ozone output is 1000 mg / h).

[0048] (2) Start the ultrasonic instrument and ozone generator, and treat with ultrasound and ozone for 2 hours. Then take out the diamond particles and dry them at 80℃ for half an hour. The surface morphology of the diamond particles is as follows: Figure 5 , Figure 6 As shown, there are slight etching marks, but they are not noticeable overall;

[0049] (3) Then, the dried diamond particles are placed in a corundum crucible, and then placed in a heating furnace, and the temperature is increased at a rate of 10 degrees per minute to 900°C, and the temperature is kept for 0.5 hours. Finally, the treated diamond particles are naturally cooled to room temperature to obtain diamond particles with a certain number of etching pits with different depths on the surface, such as Figure 7 , Figure 8 As shown, Figure 8 It can be clearly observed that triangular etching pits of different sizes and depths appear on the surface of diamond particles, indicating that effective etching has been completed.

[0050] Embodiment 3:

[0051] Surface etching of diamond particles:

[0052] (1) Take 15 grams of diamond particles with an average particle size of 150 microns and put them into a beaker. Pour 250 ml of water into it and put it into the ultrasonic instrument. Adjust the power to 200 W. Then put the probe of the ozone generator into the bottom of the beaker and pass ozone gas (the ozone output is 2000 mg / h).

[0053] (2) Start the ultrasonic instrument and ozone generator, and treat with ultrasound and ozone for 2 hours. Then take out the diamond particles and dry them at 80℃ for half an hour. The surface morphology of the diamond particles is as follows: Fig. 9 , Fig.10 As shown, there are slight etching marks, but they are not noticeable overall;

[0054] (3) Then, the dried diamond particles are placed in a corundum crucible, and then placed in a heating furnace, and the temperature is increased at a rate of 10 degrees / minute to 800°C, and the temperature is kept for 1 hour. Finally, the treated diamond particles are naturally cooled to room temperature to obtain diamond particles with a large number of etched pits of different depths on the surface, such as Fig.11 , Fig.12 As shown, Fig.12 It can be clearly observed that multiple continuous triangular etching pits of different sizes appear on the surface of the diamond particles, indicating that effective etching has been completed.

[0055] Embodiment 4:

[0056] Surface etching of diamond particles:

[0057] (1) Take 10 grams of diamond particles with an average particle size of 50 microns and put them into a beaker. Pour 200 ml of water into it and put it into an ultrasonic device. Adjust the power to 200 W. Then put the probe of the ozone generator into the bottom of the beaker and introduce ozone gas (the ozone output is 2000 mg / h).

[0058] (2) Start the ultrasonic instrument and ozone generator, and treat with ultrasound and ozone for 2 hours. Then take out the diamond particles and dry them at 80℃ for half an hour. The surface morphology of the diamond particles is as follows: Fig.13 As shown, there are slight etching marks, but they are not noticeable overall;

[0059] (3) Then put the dried diamond particles into a corundum crucible, and then put it into a heating furnace, heating it to 700°C at a rate of 5 degrees per minute, and keep it warm for 1 hour. Finally, the treated diamond particles are naturally cooled to room temperature to obtain diamond particles with a certain amount of surface etching and different degrees, such as Fig.14 As shown, triangular etching pits can be clearly observed on the surface of the diamond particles, indicating that effective etching has been completed.

[0060] Embodiment 5:

[0061] Surface etching of diamond particles:

[0062] (1) Take 15 grams of diamond particles with an average particle size of 200 microns and put them into a beaker. Pour 200 ml of water into it and put it into an ultrasonic device. Adjust the power to 100 W. Then put the probe of the ozone generator into the bottom of the beaker and introduce ozone gas (the ozone output is 2000 mg / h).

[0063] (2) Start the ultrasonic instrument and ozone generator, and treat with ultrasound and ozone for 0.5 hours. Then take out the diamond particles and dry them at 80℃ for half an hour. The surface morphology of the diamond particles is as follows: Fig.15 As shown, there are slight etching marks, but they are not noticeable overall;

[0064] (3) Then, the dried diamond particles are placed in a corundum crucible, and then placed in a heating furnace, and the temperature is increased at a rate of 10 degrees per minute to 700°C, and the temperature is kept for 1.5 hours. Finally, the treated diamond particles are naturally cooled to room temperature to obtain diamond particles with a large number of tiny etching pits on the surface, such as Fig.16 As shown, effective etching is completed.

[0065] Embodiment 6:

[0066] Surface etching of diamond particles:

[0067] (1) Take 10 grams of diamond particles with an average particle size of 10 microns and put them into a beaker. Pour 250 ml of water into it and put it into an ultrasonic device. Adjust the power to 100 W. Then put the probe of the ozone generator into the bottom of the beaker and pass ozone gas (the ozone output is 2000 mg / h).

[0068] (2) Start the ultrasonic instrument and ozone generator, and treat with ultrasound and ozone for 2 hours. Then take out the diamond particles and dry them at 80℃ for half an hour. The surface morphology of the diamond particles is as follows: Fig.17 As shown, there are slight etching marks, but they are not noticeable overall;

[0069] (3) Then, the dried diamond particles are placed in a corundum crucible, and then placed in a heating furnace, and the temperature is increased at a rate of 10 degrees per minute to 600°C, and the temperature is kept for 2 hours. Finally, the treated diamond particles are naturally cooled to room temperature to obtain diamond particles with a large number of tiny etching pits on the surface, such as Fig.18 As shown, effective etching is completed.

[0070] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An environmentally friendly and efficient method for etching diamond particles, characterized in that: The method comprises the following steps: S1, cleaning the surface of diamond particles to obtain pre-treated diamond particles for standby use; S2, ozone combined with ultrasonic process: adding the above pre-treated diamond particles into deionized water, and introducing ozone into the deionized water, and etching the diamond particles by ultrasonic treatment, then taking out the diamond particles and drying them, to obtain pre-etched diamond particles for standby use, and the ozone introduction amount for treating the diamond particles in the ozone combined with ultrasonic process is 1000-2000 mg / h, and the ultrasonic power is 100W-200W; S3, heat-treating the pre-etched diamond particles, heating to 600-900° C., heat-treating for 0.5-2 hours, and completing sufficient etching of the diamond particles.

2. The environmentally friendly and efficient method for etching diamond particles according to claim 1, characterized in that: The specific method of the surface cleaning treatment in step S1 is to use deionized water and anhydrous ethanol to clean the diamond particles in sequence, and then blow dry.

3. The environmentally friendly and efficient method for etching diamond particles according to claim 1, characterized in that: The particle size of the diamond particles in step S1 is 10-500 μm.

4. The environmentally friendly and efficient method for etching diamond particles according to claim 1, characterized in that: In step S2, the mass ratio of diamond particles to deionized water is 1-1.5:20-25.

5. The environmentally friendly and efficient method for etching diamond particles according to claim 1, characterized in that: The ozone combined with ultrasonic process in step S2 is used to treat the diamond particles for 0.5-2 hours.

6. The environmentally friendly and efficient method for etching diamond particles according to claim 1, characterized in that: In step S3, the rate of heating the pre-etched diamond particles to 600-900° C. is 5-10° C. / min.

7. The environmentally friendly and efficient method for etching diamond particles according to claim 1, characterized in that: The atmosphere for the heat treatment in step S3 is air.

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