CN104532016A - Cobalt leaching method of cobalt-leached composite acid based on synthetic polycrystalline diamond composite sheet - Google Patents
Cobalt leaching method of cobalt-leached composite acid based on synthetic polycrystalline diamond composite sheet Download PDFInfo
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- 239000010432 diamond Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 60
- 239000002253 acid Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 title abstract description 24
- 239000010941 cobalt Substances 0.000 title abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract description 24
- 238000002386 leaching Methods 0.000 title description 6
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
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- 238000007598 dipping method Methods 0.000 claims abstract description 4
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Chemical class O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 7
- 229910001429 cobalt ion Inorganic materials 0.000 description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
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- 238000005516 engineering process Methods 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- REGASCSYIKCEDA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid hydrochloride hydrofluoride Chemical compound C(CC(O)(C(=O)O)CC(=O)O)(=O)O.F.Cl REGASCSYIKCEDA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000000739 chaotic effect Effects 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 239000011435 rock Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000036346 tooth eruption Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- 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
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Abstract
本发明公开了一种基于人造聚晶金刚石复合片的脱钴复合酸的脱钴方法，包括：将有机酸溶于蒸馏水中；将无机酸1与有机酸所得溶液混合；再将无机酸2与步骤2)所得溶液混合配得复合酸；将人造聚晶金刚石复合片浸入所配好的复合酸中；调整浸渍温度为25～90℃，浸渍48～72h。完成后即得脱钴的聚晶金刚石复合片，经过测试其耐磨性提高了10倍左右。利用复合酸的脱钴方法，使聚金刚石复合片中的金属钴得到高效、安全、无污染的去除，具有脱钴深度大、成本低的优势，经济效益明显。The invention discloses a cobalt removal method based on a cobalt-free composite acid based on an artificial polycrystalline diamond composite sheet, comprising: dissolving an organic acid in distilled water; mixing an inorganic acid 1 with a solution obtained from the organic acid; Step 2) The obtained solution is mixed to prepare a compound acid; the artificial polycrystalline diamond composite sheet is immersed in the prepared compound acid; the dipping temperature is adjusted to 25-90° C., and the dipping time is 48-72 hours. After the completion, the cobalt-free polycrystalline diamond composite sheet is obtained, and its wear resistance has been improved by about 10 times after testing. Using the method of decobalt removal with compound acid, the metal cobalt in the polydiamond composite sheet can be removed efficiently, safely and without pollution, which has the advantages of large decobalt depth, low cost, and obvious economic benefits.
Description
技术领域technical field
本发明属于石油勘探钻头用材料，特别是涉及一种基于人造聚晶金刚石复合片的脱钴复合酸的脱钴方法。The invention belongs to materials for oil exploration drill bits, in particular to a decobalt removal method based on a decobalt composite acid of an artificial polycrystalline diamond composite sheet.
背景技术Background technique
PDC钻头已广泛应用于国内外石油勘探，为极软至中硬地层的钻井提速发挥了重要作用，特别是能为我国的石油勘探事业提高钻井速度、缩短钻井周期、降低钻井成本提供强有力的支撑。随着深井的增多，提高钻头使用效率的有效办法之一就是提高切削齿的综合性能。PDC drill bits have been widely used in oil exploration at home and abroad, and have played an important role in increasing the drilling speed of extremely soft to medium-hard formations. In particular, they can provide a powerful tool for my country's oil exploration industry to increase drilling speed, shorten drilling cycle, and reduce drilling costs. support. With the increase of deep wells, one of the effective ways to improve the efficiency of the drill bit is to improve the overall performance of the cutting teeth.
PDC刀具热稳定性下降的主要因素并不是在受热过程中金刚石发生了氧化/石墨化反应，而是粘结剂Co热胀冷缩和氧化所产生的热龟裂裂纹导致了PDC刀具机械性能的下降。提高PDC热稳定性的方法之一就是尽量减少粘结剂Co的含量。The main reason for the decline in the thermal stability of PDC tools is not the oxidation/graphitization reaction of the diamond during the heating process, but the thermal cracks and cracks generated by the thermal expansion and contraction of the binder Co and oxidation, which lead to the deterioration of the mechanical properties of the PDC tools. decline. One of the methods to improve the thermal stability of PDC is to minimize the content of Co in the binder.
人造聚晶金刚石复合片脱钴技术是一种能够提高复合片工作热稳定性从而实现提高使用性能的有效手段。国外应用该项技术较早，国内还处于探索阶段。The cobalt removal technology of synthetic polycrystalline diamond compact is an effective means to improve the thermal stability of the composite and thus improve the performance of the composite. This technology was applied earlier in foreign countries, and it is still in the exploratory stage in China.
复合片脱钴技术就是去除金刚石层内的钴元素。钴元素是烧结复合片时加入的结合剂，在金刚石内呈现宏观均匀分布状态。去除比较困难。通常采取酸融或者电解。之所以要去除钴元素就是考虑到钻头在工作时，复合片与岩石摩擦生热。自身温度会不断提高。但是碳元素(人造金刚石)与钴元素的热膨胀系数不同，在工作时会伴随温度升高而体积变大，从而引起内应力的增加，造成复合片的破环。The cobalt removal technology of the composite sheet is to remove the cobalt element in the diamond layer. Cobalt element is a binder added when sintering the composite sheet, and it is in a state of macroscopically uniform distribution in the diamond. Removal is more difficult. Usually acid melting or electrolysis is used. The reason for removing cobalt element is to consider that when the drill bit is working, the friction between the composite sheet and the rock generates heat. Its own temperature will continue to increase. However, the thermal expansion coefficient of carbon (artificial diamond) and cobalt is different, and the volume will increase with the increase of temperature during work, which will cause an increase in internal stress and cause damage to the composite sheet.
因此，提供一种能够去除金刚石层内的钴元素的人造聚晶金刚石复合片的脱钴复合酸的脱钴方法，成为本领域目前亟待解决的技术问题。Therefore, it is a technical problem to be solved urgently in this field to provide a method for decobalt removal of cobalt compound acid of artificial polycrystalline diamond compact that can remove the cobalt element in the diamond layer.
发明内容Contents of the invention
本发明的目的是提供一种基于人造聚晶金刚石复合片的脱钴复合酸的脱钴方法，该方法利用脱钴复合酸能够减少粘结剂Co的含量并使其与金刚石微粒充分均匀混合，甚至做到无粘结剂Co，从而使金刚石以D-D键结合，减少金刚石晶粒间Co叶脉状分布的可能。该复合酸的配制简单，脱钴效果显著，并且属于环境友好材料。The object of the present invention is to provide a kind of decobalt method based on the decobalt complex acid of artificial polycrystalline diamond compact, the method utilizes decobalt complex acid to reduce the content of binder Co and make it fully and uniformly mixed with diamond particles, There is even no binder Co, so that diamonds are bonded by D-D bonds, reducing the possibility of Co vein-like distribution among diamond grains. The compound acid has simple preparation, remarkable cobalt removal effect, and belongs to environment-friendly material.
本发明的目的是通过下述技术方案来实现的。The purpose of the present invention is achieved through the following technical solutions.
一种基于人造聚晶金刚石复合片的脱钴复合酸的脱钴方法，该方法包括下述步骤：A kind of decobalt method based on the decobalt complex acid of artificial polycrystalline diamond compact, the method comprises the following steps:
1)配置质量浓度为15g/L～200g/L的有机酸溶液；1) Prepare an organic acid solution with a mass concentration of 15g/L-200g/L;
2)将质量浓度为1g/L～20g/L的无机酸1溶液与步骤1)所得溶液混合；2) mixing the inorganic acid 1 solution with a mass concentration of 1 g/L to 20 g/L with the solution obtained in step 1);
3)再将质量浓度为1g/L～30g/L的无机酸2溶液与步骤2)所得溶液混合配得复合酸溶液；3) Then mix the inorganic acid 2 solution with a mass concentration of 1g/L-30g/L and the solution obtained in step 2) to prepare a composite acid solution;
4)将人造聚晶金刚石复合片浸入所配好的复合酸溶液中；4) Immersing the synthetic polycrystalline diamond composite sheet in the prepared composite acid solution;
5)调整浸渍温度为25～90℃，浸渍48～72h，即可。5) Adjust the dipping temperature to 25-90°C and dip for 48-72 hours.
进一步地，所述有机酸为酒石酸、柠檬酸、苹果酸、乳酸、草酸中的一种或其组合物。Further, the organic acid is one of tartaric acid, citric acid, malic acid, lactic acid, oxalic acid or a combination thereof.
进一步地，所述无机酸1为盐酸、高氯酸、硫酸、次氯酸、铬酸中的一种或其组合物。Further, the inorganic acid 1 is one of hydrochloric acid, perchloric acid, sulfuric acid, hypochlorous acid, chromic acid or a combination thereof.
进一步地，所述无机酸2为硼酸、氢氟酸、氢溴酸、硝酸中的一种或组合物。Further, the inorganic acid 2 is one or a combination of boric acid, hydrofluoric acid, hydrobromic acid, and nitric acid.
本发明的有益效果在于：The beneficial effects of the present invention are:
通过采用不能有强氧化性酸，不能产生沉淀的无机酸1，并且无机酸1与无机酸2的混合酸与金刚石晶体里面的钴及钴的化合物反应形成钴离子。并利用有机酸具有较强的酸性，能溶解金刚石晶体的特性，以及具有较强鳌合能力，能够将金刚石晶格中的Co2+游离出来溶解到溶液中。By adopting inorganic acid 1 that cannot have strong oxidizing acid and cannot produce precipitation, and the mixed acid of inorganic acid 1 and inorganic acid 2 reacts with cobalt and cobalt compounds in the diamond crystal to form cobalt ions. And the use of organic acid has strong acidity, can dissolve the characteristics of diamond crystals, and has strong chelating ability, and can dissociate Co 2+ in the diamond lattice and dissolve it into the solution.
通过控制各个酸的浓度、浸出温度、浸出时间等条件，使得脱钴的聚晶金刚石复合片的耐磨性提高了10倍左右，金刚石层的电阻率得到了大幅度地提高。By controlling the concentration of each acid, leaching temperature, leaching time and other conditions, the wear resistance of the decobaltized polycrystalline diamond composite sheet is increased by about 10 times, and the resistivity of the diamond layer is greatly improved.
附图说明Description of drawings
图1是脱钴复合片与原片的磨耗比对比。Figure 1 is a comparison of the wear ratio between the decobalt composite sheet and the original sheet.
图2(a)是脱钴后的聚晶金刚石复合片。Figure 2(a) is the polycrystalline diamond composite sheet after cobalt removal.
图2(b)是未脱钴的聚晶金刚石复合片。Figure 2(b) is a polycrystalline diamond compact without cobalt removal.
图3是脱钴复合片电阻率测试结果图。Fig. 3 is a graph showing the resistivity test results of the cobalt-removed composite sheet.
具体实施方式Detailed ways
下面通过具体实施例对本发明实施方式作详细说明。The implementation of the present invention will be described in detail below through specific examples.
实施例1Example 1
本发明利用复合酸对人造聚晶金刚石复合片的高效脱钴方法，包括下述步骤：The present invention utilizes compound acid to the efficient decobalt method of artificial polycrystalline diamond composite sheet, comprises the following steps:
1)配置质量浓度为40g/L的草酸溶液100ml；1) Configure 100ml of oxalic acid solution with a mass concentration of 40g/L;
2)将质量浓度为15g/L的盐酸溶液100ml与步骤1)所得溶液混合；2) 100ml of hydrochloric acid solution with a mass concentration of 15g/L is mixed with the solution obtained in step 1);
3)将质量浓度为20g/L的氢氟酸溶液100ml与步骤2)所得溶液混合配得复合酸溶液；3) 100ml of hydrofluoric acid solution with a mass concentration of 20g/L is mixed with the solution obtained in step 2) to obtain a composite acid solution;
4)将人造聚晶金刚石复合片浸入所配好的复合酸溶液中；4) Immersing the synthetic polycrystalline diamond composite sheet in the prepared composite acid solution;
5)按上述方法将复合酸溶液配好后，将人造聚晶金刚石复合片浸入所配好的复合酸溶液中，保持温度70℃浸渍72h。5) After preparing the composite acid solution according to the above method, immerse the synthetic polycrystalline diamond composite sheet in the prepared composite acid solution, and keep the temperature at 70° C. for 72 hours.
实施例2Example 2
本发明利用复合酸对人造聚晶金刚石复合片的高效脱钴方法，包括下述步骤：The present invention utilizes compound acid to the efficient decobalt method of artificial polycrystalline diamond composite sheet, comprises the following steps:
1)将质量浓度为50g/L的草酸溶液100ml；1) 100ml of oxalic acid solution with a mass concentration of 50g/L;
2)将质量浓度为18g/L的硫酸溶液100ml与步骤1)所得溶液混合；2) 100ml of sulfuric acid solution with a mass concentration of 18g/L is mixed with the solution obtained in step 1);
3)将质量浓度为22g/L的硼酸溶液100ml与步骤2)所得溶液混合配得复合酸溶液；3) 100ml of boric acid solution with a mass concentration of 22g/L is mixed with the solution obtained in step 2) to obtain a compound acid solution;
4)将人造聚晶金刚石复合片浸入所配好的复合酸溶液中；4) Immersing the synthetic polycrystalline diamond composite sheet in the prepared composite acid solution;
5)将人造聚晶金刚石复合片浸入上述表格所配好的复合酸溶液中，保持温度80℃浸渍48h。5) Immerse the synthetic polycrystalline diamond composite sheet in the compound acid solution prepared in the above table, and keep the temperature at 80°C for 48 hours.
实施例3Example 3
本发明利用复合酸对人造聚晶金刚石复合片的高效脱钴方法，包括下述步骤：The present invention utilizes compound acid to the efficient decobalt method of artificial polycrystalline diamond composite sheet, comprises the following steps:
1)配制质量浓度为50g/L的柠檬酸溶液100ml；1) preparation mass concentration is 100ml of citric acid solution of 50g/L;
2)将质量浓度为1g/L的盐酸溶液100ml与步骤1)所得溶液混合；2) 100ml of hydrochloric acid solution with a mass concentration of 1g/L is mixed with the solution obtained in step 1);
3)将质量浓度为15g/L的氢氟酸溶液100ml与步骤2)所得溶液混合配得复合酸溶液；3) 100ml of hydrofluoric acid solution with a mass concentration of 15g/L is mixed with the solution obtained in step 2) to obtain a composite acid solution;
4)将人造聚晶金刚石复合片浸入所配好的复合酸溶液中；4) Immersing the synthetic polycrystalline diamond composite sheet in the prepared composite acid solution;
5)按上述方法将复合酸溶液配好后，将人造聚晶金刚石复合片浸入所配好的复合酸溶液中，保持温度75℃浸渍48h。5) After preparing the composite acid solution according to the above method, immerse the artificial polycrystalline diamond composite sheet in the prepared composite acid solution, and keep the temperature at 75° C. for 48 hours.
实施例4Example 4
本发明利用复合酸对人造聚晶金刚石复合片的高效脱钴方法，包括下述步骤：The present invention utilizes compound acid to the efficient decobalt method of artificial polycrystalline diamond composite sheet, comprises the following steps:
1)配置质量浓度为100g/L酒石酸溶液100ml+100g/L的苹果酸溶液100ml；1) Configure 100ml of malic acid solution whose mass concentration is 100g/L tartaric acid solution 100ml+100g/L;
2)将质量浓度为5g/L次氯酸溶液100ml+5g/L的高氯酸溶液200ml与步骤1)所得溶液混合；2) 200ml of perchloric acid solution whose mass concentration is 5g/L hypochlorous acid solution 100ml+5g/L is mixed with step 1) gained solution;
3)将质量浓度为1g/L的氢溴酸溶液100ml与步骤2)所得溶液混合配得复合酸溶液；3) the hydrobromic acid solution 100ml of 1g/L is mixed with the solution gained in step 2) to obtain a compound acid solution with a mass concentration;
4)将人造聚晶金刚石复合片浸入所配好的复合酸溶液中；4) Immersing the synthetic polycrystalline diamond composite sheet in the prepared composite acid solution;
5)按上述方法将复合酸溶液配好后，将人造聚晶金刚石复合片浸入所配好的复合酸溶液中，保持温度25℃浸渍60h。5) After preparing the composite acid solution according to the above method, immerse the synthetic polycrystalline diamond composite sheet in the prepared composite acid solution, and keep the temperature at 25°C for 60 hours.
实施例5Example 5
本发明利用复合酸对人造聚晶金刚石复合片的高效脱钴方法，包括下述步骤：The present invention utilizes compound acid to the efficient decobalt method of artificial polycrystalline diamond composite sheet, comprises the following steps:
1)将质量浓度为5g/L乳酸溶液100ml+200g/L的酒石酸溶液100ml；1) 100ml of tartaric acid solution whose mass concentration is 5g/L lactic acid solution 100ml+200g/L;
2)将质量浓度为10g/L铬酸溶液100ml+10g/L的高氯酸溶液100ml与步骤1)所得溶液混合；2) 100ml of perchloric acid solution whose mass concentration is 10g/L chromic acid solution 100ml+10g/L is mixed with step 1) gained solution;
3)将质量浓度为15g/L硼酸溶液100ml+15g/L的硝酸溶液100ml与步骤2)所得溶液混合配得复合酸；3) the nitric acid solution 100ml that mass concentration is 15g/L boric acid solution 100ml+15g/L is mixed with the solution obtained in step 2) to obtain a compound acid;
4)将人造聚晶金刚石复合片浸入所配好的复合酸溶液中；4) Immersing the artificial polycrystalline diamond composite sheet in the prepared composite acid solution;
5)按上述方法将复合酸溶液配好后，将人造聚晶金刚石复合片浸入所配好的复合酸溶液中，保持温度90℃浸渍48h。5) After preparing the composite acid solution according to the above method, immerse the synthetic polycrystalline diamond composite sheet in the prepared composite acid solution, and keep the temperature at 90° C. for 48 hours.
下面给出本发明的机理来进一步说明本发明效果。The mechanism of the present invention is given below to further illustrate the effect of the present invention.
1、材料的选择1. Selection of materials
通过采用不能有强氧化性酸，不能产生沉淀的无机酸2，并考虑在加工金刚石晶体的过程中会出现钙和硅的粉尘，与酸中的离子会产生沉淀，由于反应过程中可能出现酸性不足，因此，加入无机酸降低溶液的pH值，防止二次沉淀。两种无机酸的混合酸与金刚石晶体里面的钴及钴的化合物反应形成钴离子。由于复合酸溶液与金刚石晶体里存在钴的浓度差，钴离子从高浓度的金刚石层游离到低浓度的溶液中，但是分子的热运动是杂乱无章的，所以金刚石晶体中钴离子还有一部分未能脱出来。By using an inorganic acid 2 that cannot have strong oxidizing acids and cannot produce precipitation, and consider that calcium and silicon dust will appear during the processing of diamond crystals, and precipitation will occur with ions in the acid. Due to the possibility of acidity during the reaction process Insufficient, therefore, the addition of mineral acid lowers the pH of the solution and prevents secondary precipitation. The mixed acid of two inorganic acids reacts with cobalt and cobalt compounds in the diamond crystal to form cobalt ions. Due to the concentration difference of cobalt in the compound acid solution and the diamond crystal, the cobalt ions dissociate from the high-concentration diamond layer to the low-concentration solution, but the thermal motion of the molecules is chaotic, so some of the cobalt ions in the diamond crystal cannot come out.
由于有机酸与钴离子可以发生络合反应形成钴的配合物，把钴转移到溶液中。所选的有机酸具有较强的酸性，它能溶解金刚石晶体，使束缚在里面的钴离子和钴的化合物裸露或游离出来。此外，其具有较强鳌合能力，反应时离解出来的酸根配位体能迅速与从金刚石晶格中游离出来的Co2+反应，生成稳定的钴柠檬酸配合物，使钴转移到溶液中。离子反应式如下：Since organic acid and cobalt ion can undergo complex reaction to form cobalt complex, cobalt is transferred to the solution. The selected organic acid has a strong acidity, which can dissolve the diamond crystal, and make the cobalt ions and cobalt compounds bound inside exposed or freed. In addition, it has a strong chelating ability, and the acid radical ligand dissociated during the reaction can quickly react with the free Co 2+ from the diamond lattice to form a stable cobalt citrate complex, so that the cobalt can be transferred into the solution. The ionic reaction formula is as follows:
2、脱钴条件的选择2. Selection of cobalt removal conditions
采用柠檬酸-氢氟酸-盐酸体系直接浸出聚晶金刚石复合片中钴工艺中，柠檬酸浓度、氢氟酸浓度、盐酸浓度、浸出温度、浸出时间等对前后溶液pH差值的影响直接影响到脱钴的聚晶金刚石复合片的效果。采用了上述工艺条件的限定能够在同样磨削路程下，磨削体积小、耐磨性能好，经检测结果显示脱钴样品耐磨性能明显优于未脱钴样品。经过脱钴的聚晶金刚石复合片耐磨性提高了10倍左右。并且金刚石层的电阻率得到了提高。In the citric acid-hydrofluoric acid-hydrochloric acid system for direct leaching of cobalt in polycrystalline diamond compacts, the influence of citric acid concentration, hydrofluoric acid concentration, hydrochloric acid concentration, leaching temperature, leaching time, etc. on the pH difference before and after the solution directly affects To the effect of cobalt-free polycrystalline diamond compact. The limitation of the above process conditions can achieve small grinding volume and good wear resistance under the same grinding distance. The test results show that the wear resistance of the decobaltized sample is significantly better than that of the non-decobaltized sample. The wear resistance of the polycrystalline diamond composite sheet after cobalt removal is increased by about 10 times. And the resistivity of the diamond layer is improved.
通过CVD金刚石磨耗比测试设备对金刚石复合片进行磨耗比测试结果见图1所示。由图1可以看出，同样磨削路程，磨削体积越小耐磨性能越好，检测结果显示脱钴样品耐磨性能明显优于未脱钴样品。经过脱钴的聚晶金刚石复合片耐磨性提高了10倍左右。The wear ratio test results of the diamond composite sheet by CVD diamond wear ratio test equipment are shown in Figure 1. It can be seen from Figure 1 that for the same grinding distance, the smaller the grinding volume, the better the wear resistance. The test results show that the wear resistance of the decobaltized sample is significantly better than that of the non-decobaltized sample. The wear resistance of the polycrystalline diamond composite sheet after cobalt removal is increased by about 10 times.
图2(a)和图2(b)给出了脱钴前后的聚晶金刚石复合片图示结果。Figure 2(a) and Figure 2(b) show the graphical results of polycrystalline diamond compacts before and after cobalt removal.
由图3可以看出，随着钴的析出，金刚石层的电阻率越来越高，导电性越越差，最终趋于稳定，电阻约为3000Ω。It can be seen from Figure 3 that with the precipitation of cobalt, the resistivity of the diamond layer is getting higher and higher, and the conductivity is getting worse and worse, and finally tends to be stable, with a resistance of about 3000Ω.
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施方式仅限于此，对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单的推演或替换，都应当视为属于本发明由所提交的权利要求书确定专利保护范围。The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments. It cannot be determined that the specific embodiments of the present invention are limited thereto. Under the circumstances, some simple deduction or replacement can also be made, all of which should be regarded as belonging to the scope of patent protection determined by the submitted claims of the present invention.
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