技术领域technical field
本发明属于超硬材料工具制作领域，尤其涉及烧结金刚石节块的制造。The invention belongs to the field of superhard material tool production, in particular to the production of sintered diamond nodules.
背景技术Background technique
金刚石磨料具有硬度高、耐磨性好、导热性好的优异性能，因此金刚石工具在加工硬脆材料方面具有寿命长、效率高的优点，工具的制作方法有电镀法、烧结法、钎焊法等，其中电镀金刚石砂轮在加工过程中磨粒易从工具表面脱落，造成加工效率和工具寿命的降低，采用钎焊方法制作的单层金刚石工具，能够在金刚石与钎料之间形成化学冶金结合，因此具有磨粒结合强度高、磨料出露高、工具寿命长等优异特性，并且利于环境保护，有着广泛的应用。但单层钎焊金刚石工具只有一层磨粒使其寿命受到了限制。如果在烧结工具通过添加适量的活性元素，与金刚石磨粒发生适量的界面反应，不仅提高磨粒的把持力，而且多层金刚石磨粒能够有效提高工具的寿命。Diamond abrasives have excellent properties of high hardness, good wear resistance, and good thermal conductivity. Therefore, diamond tools have the advantages of long life and high efficiency in processing hard and brittle materials. The production methods of tools include electroplating, sintering, and brazing. Among them, the abrasive grains of the electroplated diamond grinding wheel are easy to fall off from the surface of the tool during processing, resulting in a reduction in processing efficiency and tool life. The single-layer diamond tool made by brazing can form a chemical metallurgical bond between the diamond and the solder. , so it has excellent characteristics such as high abrasive grain bonding strength, high abrasive exposure, long tool life, etc., and is beneficial to environmental protection, and has a wide range of applications. However, single-layer brazed diamond tools have only one layer of abrasive grains, which limits their life. If an appropriate amount of active elements are added to the sintered tool, an appropriate amount of interfacial reaction with the diamond abrasive grains will not only improve the holding force of the abrasive grains, but also the multi-layer diamond abrasive grains can effectively increase the life of the tool.
高熵合金通常由五种以上的元素组元按照等原子比或接近于等原子比合金化后形成的合金，其混合熵高于合金的熔化熵，一般形成高熵固溶体相，具有良好的综合力学性能。但通常的高熵合金是采用单质金属粉，其熔点较高，而采用合金化的多种共晶合金，经球磨机械合金化后形成高熵合金，其中含有适量的Cr元素适合于烧结金刚石，可作为结合剂用于制造金属基烧结金刚石砂轮。High-entropy alloys are usually alloys formed by alloying more than five elements in an equiatomic ratio or close to an equiatomic ratio. The mixing entropy is higher than the melting entropy of the alloy, and generally forms a high-entropy solid solution phase, which has good comprehensive mechanical properties. However, the usual high-entropy alloy is made of simple metal powder, which has a high melting point, and a variety of alloyed eutectic alloys are used to form a high-entropy alloy after mechanical alloying by ball milling, which contains an appropriate amount of Cr element suitable for sintering diamond. It can be used as a bonding agent for the manufacture of metal-based sintered diamond grinding wheels.
发明内容Contents of the invention
本发明的目的是进一步提高烧结工具中金刚石磨料的结合强度，不仅在金属基中形成高熵合金，而且采用合金化的Cu-Sn、Ni-Cr-B-Si、Fe-Cr-B-Si等多种粉末进行混合，使得最后形成含有Cu、Fe、Ni、Cr、Sn的高熵合金，具有强度、韧性高的优点，Cr在Cu中的溶解度极低，使含有一定的Cr在烧结过程中促使Cr向金刚石界面扩散，进一步促进Cr与金刚石进行界面反应，实现化学冶金结合，提高磨粒的把持强度。由于高熵合金具有扩散速度慢，最后形成金刚石与高熵合金界面处为碳化物，金属基中为含有一定化合物的高熵合金。为提高容屑空间，添加适量的NaHCO3，该化合物在烧结过程中由于加热而发生分解，产生CO2气体，该气体在砂轮内部无法逸出，最后形成气孔，可容纳磨削过程中产生的碎屑，从而提高磨削效率。The purpose of the present invention is to further improve the bonding strength of diamond abrasives in sintered tools, not only to form high-entropy alloys in the metal matrix, but also to use alloyed Cu-Sn, Ni-Cr-B-Si, Fe-Cr-B-Si and other powders are mixed to form a high-entropy alloy containing Cu, Fe, Ni, Cr, and Sn, which has the advantages of high strength and toughness. The solubility of Cr in Cu is extremely low, so that a certain amount of Cr can It promotes the diffusion of Cr to the diamond interface, further promotes the interface reaction between Cr and diamond, realizes chemical metallurgical combination, and improves the holding strength of abrasive grains. Due to the slow diffusion rate of high-entropy alloys, carbides are formed at the interface between diamond and high-entropy alloys, and high-entropy alloys containing certain compounds are formed in the metal matrix. In order to improve the chip space, add an appropriate amount of NaHCO3 , the compound decomposes due to heating during the sintering process, and produces CO2 gas, which cannot escape inside the grinding wheel, and finally forms pores that can accommodate the dust generated during the grinding process. debris, thereby improving grinding efficiency.
本发明提供了一种高熵合金烧结金刚石节块的制作方法，包括以下步骤：The invention provides a method for manufacturing a high-entropy alloy sintered diamond block, comprising the following steps:
（1）将预合金粉Cu-Sn、Ni-Cr-B-Si、Fe-Cr-B-Si、NaHCO3按一定质量比30~35%：30~35%：30~35%：1~3%的质量比例混合后球磨为高熵合金粉末，每千克高熵合金粉末添加4~5mL含10%重量聚乙烯醇的水溶液；其中所述的各预合金粉的原始粉末粒度目数范围分别为：Cu-Sn：220～180μm，Ni-Cr-B-Si：200～150μm，Fe-Cr-B-Si：300～250μm，NaHCO3：200～150μm。其中Cu-Sn合金中Sn含量的质量百分比为40-50。其中Ni-Cr-B-Si中各种元素质量百分比为：Cr为12-18，B为2.5-4.5，Si为2.5-4.5，C为0.7-1，其余为Ni。其中Fe-Cr-B-Si中各种元素质量百分比为：Cr为13-17，B为2.5-4.5，Si为2.5-4.5，C为0.7-1，其余为Fe。采用钢制球磨罐进行球磨混合，其中的磨球与金属粉质量比为3∶1，密封后打开真空阀抽真空20~30分钟，将球磨罐放入行星式球磨机，转速为300~350r/min，倒向频率30~45Hz，进行球磨混料时间为30~40分钟。(1) The pre-alloyed powder Cu-Sn, Ni-Cr-B-Si, Fe-Cr-B-Si, NaHCO3 according to a certain mass ratio 30~35%: 30~35%: 30~35%: 1~ 3% mass ratio is mixed and ball-milled into high-entropy alloy powder, and 4-5mL aqueous solution containing 10% by weight polyvinyl alcohol is added to each kilogram of high-entropy alloy powder; They are: Cu-Sn: 220-180 μm, Ni-Cr-B-Si: 200-150 μm, Fe-Cr-B-Si: 300-250 μm, NaHCO3 : 200-150 μm. Wherein the mass percent of Sn in the Cu-Sn alloy is 40-50. Among them, the mass percentages of various elements in Ni-Cr-B-Si are: Cr is 12-18, B is 2.5-4.5, Si is 2.5-4.5, C is 0.7-1, and the rest is Ni. Among them, the mass percentages of various elements in Fe-Cr-B-Si are: Cr is 13-17, B is 2.5-4.5, Si is 2.5-4.5, C is 0.7-1, and the rest is Fe. Use steel ball mill jars for ball milling and mixing, in which the mass ratio of balls to metal powder is 3:1. After sealing, open the vacuum valve to evacuate for 20-30 minutes, put the ball mill jars into the planetary ball mill, and the speed is 300~350r/ min, the inverted frequency is 30~45Hz, and the time for ball milling and mixing is 30~40 minutes.
（2）然后将高熵合金粉末与金刚石磨料进行二次混合称为成型料，二次混合按每立方厘米高熵合金粉末加入1.2~1.5克拉金刚石的标准加入，并于常温下混合均匀，为成型料。(2) Then, the secondary mixing of high-entropy alloy powder and diamond abrasive is called molding material. The secondary mixing is added according to the standard of 1.2~1.5 carats of diamond per cubic centimeter of high-entropy alloy powder, and mixed evenly at room temperature. Molding material.
（3）再将成型料置于石墨模具进行烘干，烘干参数为在金属烘干炉中80~100℃进行烘干3-8 min。(3) The molding material is then placed in a graphite mold for drying. The drying parameters are 3-8 minutes at 80-100°C in a metal drying furnace.
（4）然后将烘干后的成型料放入模具中进行预压，预压压力为100~250MPa，称为坯体；(4) Then put the dried molding material into the mold for pre-pressing, the pre-pressing pressure is 100~250MPa, which is called green body;
（5）将坯体放入金属模具中，再将模具放在烧结炉内，采用氩气保护气氛中进行加压烧结，烧结后为节块。加压烧结的具体工艺为：在氩气保护下加压烧结炉中加压60~220MPa，烧结温度范围为820-870℃，保温2~8分钟。(5) Put the green body into the metal mold, then put the mold in the sintering furnace, and carry out pressure sintering in the protective atmosphere of argon gas, and the sintered blocks will be formed. The specific process of pressure sintering is: pressurize 60~220MPa in a pressure sintering furnace under the protection of argon, the sintering temperature range is 820-870°C, and keep warm for 2~8 minutes.
具体实施方式Detailed ways
实施例1Example 1
1.一种高熵合金烧结金刚石节块的制作方法，包括下述工艺步骤：1. A method for making a high-entropy alloy sintered diamond block, comprising the following process steps:
（1）将预合金粉Cu-Sn、Ni-Cr-B-Si、Fe-Cr-B-Si、NaHCO3按一定质量比30%：32%：35%：3%的质量比例混合后球磨为高熵合金粉末，每千克高熵合金粉末添加4.5mL含10%重量聚乙烯醇的水溶液；其中所述的各预合金粉的原始粉末粒度目数范围分别为：Cu-Sn：220～180μm，Ni-Cr-B-Si：200～150μm，Fe-Cr-B-Si：300～250μm，NaHCO3：200～150μm。其中Cu-Sn合金中Sn含量的质量百分比为40。其中Ni-Cr-B-Si中各种元素质量百分比为：Cr为12-18，B为2.5-4.5，Si为2.5-4.5，C为0.7-1，其余为Ni。其中Fe-Cr-B-Si中各种元素质量百分比为：Cr为13-17，B为2.5-4.5，Si为2.5-4.5，C为0.7-1，其余为Fe。采用钢制球磨罐进行球磨混合，其中的磨球与金属粉质量比为3∶1，密封后打开真空阀抽真空20分钟，将球磨罐放入行星式球磨机，转速为300r/min，倒向频率45Hz，进行球磨混料时间为40分钟。(1) Mix the pre-alloyed powder Cu-Sn, Ni-Cr-B-Si, Fe-Cr-B-Si, NaHCO3 according to a certain mass ratio of 30%: 32%: 35%: 3% and then ball mill For high-entropy alloy powder, add 4.5mL aqueous solution containing 10% by weight polyvinyl alcohol per kilogram of high-entropy alloy powder; the ranges of the original powder particle size and mesh number of each pre-alloyed powder are: Cu-Sn: 220～180μm , Ni-Cr-B-Si: 200-150 μm, Fe-Cr-B-Si: 300-250 μm, NaHCO3 : 200-150 μm. The Sn content in the Cu-Sn alloy is 40% by mass. Among them, the mass percentages of various elements in Ni-Cr-B-Si are: Cr is 12-18, B is 2.5-4.5, Si is 2.5-4.5, C is 0.7-1, and the rest is Ni. Among them, the mass percentages of various elements in Fe-Cr-B-Si are: Cr is 13-17, B is 2.5-4.5, Si is 2.5-4.5, C is 0.7-1, and the rest is Fe. Steel ball milling jars are used for ball milling and mixing. The mass ratio of balls and metal powder is 3:1. After sealing, open the vacuum valve to evacuate for 20 minutes. The frequency is 45Hz, and the time for ball milling and mixing is 40 minutes.
（2）然后将高熵合金粉末与金刚石磨料进行二次混合称为成型料，二次混合按每立方厘米高熵合金粉末加入1.2克拉金刚石的标准加入，并于常温下混合均匀，为成型料。(2) Then, the secondary mixing of high-entropy alloy powder and diamond abrasive is called forming material, and the secondary mixing is added according to the standard of 1.2 carats of diamond per cubic centimeter of high-entropy alloy powder, and mixed evenly at room temperature, forming a forming material .
（3）再将成型料置于石墨模具进行烘干，烘干参数为在金属烘干炉中100℃进行烘干3 min。(3) The molding material is then placed in a graphite mold for drying, and the drying parameter is 100°C in a metal drying furnace for 3 minutes.
（4）然后将烘干后的成型料放入模具中进行预压，预压压力为125MPa，称为坯体；(4) Then put the dried molding material into the mold for pre-pressing, the pre-pressing pressure is 125MPa, called green body;
（5）将坯体放入金属模具中，再将模具放在烧结炉内，采用氩气保护气氛中进行加压烧结，烧结后为节块。加压烧结的具体工艺为：在氩气保护下加压烧结炉中加压220 MPa，烧结温度范围为820℃，保温5分钟。(5) Put the green body into the metal mold, then put the mold in the sintering furnace, and carry out pressure sintering in the protective atmosphere of argon gas, and the sintered blocks will be formed. The specific process of pressure sintering is: pressurize 220 MPa in a pressure sintering furnace under the protection of argon, the sintering temperature range is 820°C, and keep warm for 5 minutes.
实施例2Example 2
1.一种高熵合金烧结金刚石节块的制作方法，包括下述工艺步骤：1. A method for making a high-entropy alloy sintered diamond block, comprising the following process steps:
（1）将预合金粉Cu-Sn、Ni-Cr-B-Si、Fe-Cr-B-Si、NaHCO3按一定质量比32%：35%：30%：3%的质量比例混合后球磨为高熵合金粉末，每千克高熵合金粉末添加5mL含10%重量聚乙烯醇的水溶液；其中所述的各预合金粉的原始粉末粒度目数范围分别为：Cu-Sn：220～180μm，Ni-Cr-B-Si：200～150μm，Fe-Cr-B-Si：300～250μm，NaHCO3：200～150μm。其中Cu-Sn合金中Sn含量的质量百分比为45。其中Ni-Cr-B-Si中各种元素质量百分比为：Cr为12-18，B为2.5-4.5，Si为2.5-4.5，C为0.7-1，其余为Ni。其中Fe-Cr-B-Si中各种元素质量百分比为：Cr为13-17，B为2.5-4.5，Si为2.5-4.5，C为0.7-1，其余为Fe。采用钢制球磨罐进行球磨混合，其中的磨球与金属粉质量比为3∶1，密封后打开真空阀抽真空30分钟，将球磨罐放入行星式球磨机，转速为328 r/min，倒向频率30Hz，进行球磨混料时间为40分钟。(1) Mix the pre-alloyed powder Cu-Sn, Ni-Cr-B-Si, Fe-Cr-B-Si, NaHCO3 according to a certain mass ratio of 32%: 35%: 30%: 3% and then ball mill For high-entropy alloy powder, add 5mL aqueous solution containing 10% by weight polyvinyl alcohol per kilogram of high-entropy alloy powder; wherein the original powder particle size ranges of each pre-alloyed powder are: Cu-Sn: 220 ~ 180μm, Ni-Cr-B-Si: 200-150 μm, Fe-Cr-B-Si: 300-250 μm, NaHCO3 : 200-150 μm. Wherein the mass percentage of Sn content in the Cu-Sn alloy is 45%. Among them, the mass percentages of various elements in Ni-Cr-B-Si are: Cr is 12-18, B is 2.5-4.5, Si is 2.5-4.5, C is 0.7-1, and the rest is Ni. Among them, the mass percentages of various elements in Fe-Cr-B-Si are: Cr is 13-17, B is 2.5-4.5, Si is 2.5-4.5, C is 0.7-1, and the rest is Fe. A steel ball mill was used for ball milling and mixing, in which the mass ratio of balls to metal powder was 3:1. After sealing, the vacuum valve was opened to evacuate for 30 minutes, and the ball mill was put into a planetary ball mill at a speed of 328 r/min. To the frequency of 30Hz, the mixing time of ball milling is 40 minutes.
（2）然后将高熵合金粉末与金刚石磨料进行二次混合称为成型料，二次混合按每立方厘米高熵合金粉末加入1.3克拉金刚石的标准加入，并于常温下混合均匀，为成型料。(2) Then, the secondary mixing of high-entropy alloy powder and diamond abrasive is called molding material. The secondary mixing is added according to the standard of 1.3 carats of diamond per cubic centimeter of high-entropy alloy powder, and mixed evenly at room temperature to form a molding material. .
（3）再将成型料置于石墨模具进行烘干，烘干参数为在金属烘干炉中80℃进行烘干8 min。(3) The molding material is then placed in a graphite mold for drying. The drying parameter is 80°C in a metal drying furnace for 8 minutes.
（4）然后将烘干后的成型料放入模具中进行预压，预压压力为250MPa，称为坯体；(4) Then put the dried molding material into the mold for pre-compression, the pre-compression pressure is 250MPa, called green body;
（5）将坯体放入金属模具中，再将模具放在烧结炉内，采用氩气保护气氛中进行加压烧结，烧结后为节块。加压烧结的具体工艺为：在氩气保护下加压烧结炉中加压220 MPa，烧结温度范围为870℃，保温2分钟。(5) Put the green body into the metal mold, then put the mold in the sintering furnace, and carry out pressure sintering in the protective atmosphere of argon gas, and the sintered blocks will be formed. The specific process of pressure sintering is as follows: pressurize 220 MPa in a pressure sintering furnace under the protection of argon, the sintering temperature range is 870°C, and hold for 2 minutes.
实施例3Example 3
1.一种高熵合金烧结金刚石节块的制作方法，包括下述工艺步骤：1. A method for making a high-entropy alloy sintered diamond block, comprising the following process steps:
（1）将预合金粉Cu-Sn、Ni-Cr-B-Si、Fe-Cr-B-Si、NaHCO3按一定质量比33%：33%：33%：1%的质量比例混合后球磨为高熵合金粉末，每千克高熵合金粉末添加4.5mL含10%重量聚乙烯醇的水溶液；其中所述的各预合金粉的原始粉末粒度目数范围分别为：Cu-Sn：220～180μm，Ni-Cr-B-Si：200～150μm，Fe-Cr-B-Si：300～250μm，NaHCO3：200～150μm。其中Cu-Sn合金中Sn含量的质量百分比为50。其中Ni-Cr-B-Si中各种元素质量百分比为：Cr为12-18，B为2.5-4.5，Si为2.5-4.5，C为0.7-1，其余为Ni。其中Fe-Cr-B-Si中各种元素质量百分比为：Cr为13-17，B为2.5-4.5，Si为2.5-4.5，C为0.7-1，其余为Fe。采用钢制球磨罐进行球磨混合，其中的磨球与金属粉质量比为3∶1，密封后打开真空阀抽真空25分钟，将球磨罐放入行星式球磨机，转速为350r/min，倒向频率35Hz，进行球磨混料时间为35分钟。(1) Mix the pre-alloyed powder Cu-Sn, Ni-Cr-B-Si, Fe-Cr-B-Si, NaHCO3 according to a certain mass ratio of 33%: 33%: 33%: 1% and then ball mill For high-entropy alloy powder, add 4.5mL aqueous solution containing 10% by weight polyvinyl alcohol per kilogram of high-entropy alloy powder; the ranges of the original powder particle size and mesh number of each pre-alloyed powder are: Cu-Sn: 220～180μm , Ni-Cr-B-Si: 200-150 μm, Fe-Cr-B-Si: 300-250 μm, NaHCO3 : 200-150 μm. Wherein the mass percentage of the Sn content in the Cu-Sn alloy is 50%. Among them, the mass percentages of various elements in Ni-Cr-B-Si are: Cr is 12-18, B is 2.5-4.5, Si is 2.5-4.5, C is 0.7-1, and the rest is Ni. Among them, the mass percentages of various elements in Fe-Cr-B-Si are: Cr is 13-17, B is 2.5-4.5, Si is 2.5-4.5, C is 0.7-1, and the rest is Fe. A steel ball milling jar is used for ball milling and mixing, in which the mass ratio of balls to metal powder is 3:1. After sealing, open the vacuum valve to evacuate for 25 minutes, put the ball mill jar into a planetary ball mill at a speed of 350r/min, pour The frequency is 35Hz, and the time for ball milling and mixing is 35 minutes.
（2）然后将高熵合金粉末与金刚石磨料进行二次混合称为成型料，二次混合按每立方厘米高熵合金粉末加入1.5克拉金刚石的标准加入，并于常温下混合均匀，为成型料。(2) Then, the secondary mixing of high-entropy alloy powder and diamond abrasive is called molding material. The secondary mixing is added according to the standard of 1.5 carats of diamond per cubic centimeter of high-entropy alloy powder, and mixed evenly at room temperature to form a molding material. .
（3）再将成型料置于石墨模具进行烘干，烘干参数为在金属烘干炉中80℃进行烘干6 min。(3) The molding material is then placed in a graphite mold for drying. The drying parameter is 6 min at 80°C in a metal drying furnace.
（4）然后将烘干后的成型料放入模具中进行预压，预压压力为100MPa，称为坯体；(4) Then put the dried molding material into the mold for pre-compression, the pre-compression pressure is 100MPa, called green body;
（5）将坯体放入金属模具中，再将模具放在烧结炉内，采用氩气保护气氛中进行加压烧结，烧结后为节块。加压烧结的具体工艺为：在氩气保护下加压烧结炉中加压150 MPa，烧结温度范围为820℃，保温7分钟。(5) Put the green body into the metal mold, then put the mold in the sintering furnace, and carry out pressure sintering in the protective atmosphere of argon gas, and the sintered blocks will be formed. The specific process of pressure sintering is: pressurize 150 MPa in a pressure sintering furnace under the protection of argon, the sintering temperature range is 820°C, and hold the temperature for 7 minutes.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710209968.9ACN107012347B (en) | 2017-03-31 | 2017-03-31 | A kind of high-entropy alloy sintered diamond locking nub |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710209968.9ACN107012347B (en) | 2017-03-31 | 2017-03-31 | A kind of high-entropy alloy sintered diamond locking nub |
| Publication Number | Publication Date |
|---|---|
| CN107012347A CN107012347A (en) | 2017-08-04 |
| CN107012347Btrue CN107012347B (en) | 2018-09-21 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710209968.9AActiveCN107012347B (en) | 2017-03-31 | 2017-03-31 | A kind of high-entropy alloy sintered diamond locking nub |
| Country | Link |
|---|---|
| CN (1) | CN107012347B (en) |
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| CN107663607B (en)* | 2017-09-12 | 2019-06-28 | 中南大学 | A kind of high-entropy alloy holds the composite material and preparation method and application of abrasive grain |
| CN108380892B (en)* | 2018-04-03 | 2019-11-26 | 武汉理工大学 | A kind of preparation method of ceramics/high-entropy alloy laminated material |
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| CN109623685A (en)* | 2019-01-09 | 2019-04-16 | 苏州科技大学 | A kind of preparation method of metal-ceramic base cubic boron nitride sintered nodules |
| CN111644629B (en)* | 2020-06-05 | 2022-11-11 | 江苏应用元素科技有限公司 | Preparation method of Ni-Cr-B-Si alloy welding wire |
| CN115255368B (en)* | 2022-07-15 | 2023-08-04 | 广东工业大学 | Diamond tool with soft and hard composite metal binding agent and preparation method thereof |
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| CN102787267A (en)* | 2012-09-04 | 2012-11-21 | 四川大学 | Multiple boride metal ceramic based on high-entropy alloy adhesion agent and preparation method thereof |
| CN104399985A (en)* | 2014-12-18 | 2015-03-11 | 广东新劲刚新材料科技股份有限公司 | Preparation method of diamond segment |
| CN105922146A (en)* | 2016-04-22 | 2016-09-07 | 柳州凯通新材料科技有限公司 | Method for preparing metal bond diamond grinding wheel |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102787267A (en)* | 2012-09-04 | 2012-11-21 | 四川大学 | Multiple boride metal ceramic based on high-entropy alloy adhesion agent and preparation method thereof |
| CN104399985A (en)* | 2014-12-18 | 2015-03-11 | 广东新劲刚新材料科技股份有限公司 | Preparation method of diamond segment |
| CN105922146A (en)* | 2016-04-22 | 2016-09-07 | 柳州凯通新材料科技有限公司 | Method for preparing metal bond diamond grinding wheel |
| Publication number | Publication date |
|---|---|
| CN107012347A (en) | 2017-08-04 |
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