CN110144618A - A kind of method of metallic cobalt in removal composite polycrystal-diamond - Google Patents

A kind of method of metallic cobalt in removal composite polycrystal-diamond Download PDF

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Publication number
CN110144618A
CN110144618A CN201910478653.3A CN201910478653A CN110144618A CN 110144618 A CN110144618 A CN 110144618A CN 201910478653 A CN201910478653 A CN 201910478653A CN 110144618 A CN110144618 A CN 110144618A
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China
Prior art keywords
diamond
composite polycrystal
electrolyte
electrolysis
metallic cobalt
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CN201910478653.3A
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Chinese (zh)
Inventor
魏昊
王彩利
刘慧苹
方海江
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HENAN SIFANG SUPER HARD MATERIAL CO Ltd
Henan SF Diamond Co Ltd
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HENAN SIFANG SUPER HARD MATERIAL CO Ltd
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Priority to CN201910478653.3A priority Critical patent/CN110144618A/en
Publication of CN110144618A publication Critical patent/CN110144618A/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25FPROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00Electrolytic etching or polishing
    • C25F3/02Etching

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention belongs to superhard material preparation fields, a kind of more particularly to method for removing metallic cobalt in composite polycrystal-diamond, including as cathode and being electrically connected electrolysis power using the portion PCD of composite polycrystal-diamond as anode, stainless steel plate, the portion PCD and stainless steel plate are immersed in electrolyte and are electrolysed, the pH of the electrolyte is 7, and decomposition voltage is 1.5-3V.Present invention utilizes the principle of electrolysis, simple process and low cost and non-corrosive can effectively solve the problem that and current be electrolysed de- cobalt electrolyte and have corrosivity, the high requirements on the equipment and environment series problem easy to pollute.

Description

A kind of method of metallic cobalt in removal composite polycrystal-diamond
Technical field
The invention belongs to metallic cobalts in superhard material preparation field more particularly to a kind of removal composite polycrystal-diamond Method.
Background technique
Superhard material is primarily referred to as diamond and cubic boron nitride, and superhard material is suitable for being used to manufacturing processing other materials Tool has unrivaled superiority, occupies irreplaceable critical role especially in terms of processing hard material.It is poly- Diamond (PCD) composite sheet is in high temperature and pressure by many fine-particle diamonds and cemented carbide substrate joint sintering Made of bulk agglomerate.It has high intensity, high rigidity, high-wearing feature and high toughness.As machining tool, PCD is mainly used for petroleum, metallurgy, geological drill bit, reamer etc., and rate of penetration and timeliness are many of natural diamond Times, while aperture can also be effectively kept in drilling process.
In the production process of composite polycrystal-diamond, a certain amount of Co powder can be added, to promote diadust shape At polycrystalline diamond.However due to friction in the use process of composite polycrystal-diamond, impact can generate high temperature, a side The thermal expansion coefficient of face, Co phase and diamond has larger difference, can generate biggish internal stress under high temperature, will cause diamond Crystal grain falls off and the case where disintegrating tablet;On the other hand, in the case of a high temperature, Co, which meets, promotes diamond graphitization, to reduce The wearability and service life of product.Therefore in composite sheet before use, needing to remove the cobalt of a part.
Commonly de- cobalt method has chemical method and two kinds of electrolysis method both at home and abroad at present, and the selection of the solution of both methods is logical Acid or alkalinity condition is often needed, either acid or alkali is all harmful for environment, due to the corrosivity of soda acid, is held The safety of staff easily is threatened, and hard alloy can be corroded, and the de- cobalt rate of existing de- cobalt method is lower, cost Height can no longer meet current production needs.
Summary of the invention
The object of the present invention is to provide it is a kind of removal composite polycrystal-diamond in metallic cobalt method, present invention utilizes The principle of electrolysis, simple process and low cost and non-corrosive can effectively solve the problem that and current be electrolysed de- cobalt electrolyte and have corruption Corrosion, the high requirements on the equipment and environment series problem easy to pollute.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of method of metallic cobalt in removal composite polycrystal-diamond, including using the portion PCD of composite polycrystal-diamond as Anode, stainless steel plate as cathode and are electrically connected electrolysis power, and the portion PCD and stainless steel plate are immersed in electrolyte and are electrolysed, described The pH of electrolyte is 7, and decomposition voltage is 1.5-3V.
Specifically, the electrolyte is made of the electrolyte that quality proportioning is 1-8:90-110 and water.
Preferably, the electrolyte is one of NaCl, KCl or mixing.
Preferably, the electrolyte has quality proportioning to be mixed for NaCl, KCl and water of 1-3:3-5:90-110.
Preferably, the electrolyte has quality proportioning to be mixed for NaCl, KCl and water of 2:4:100.
Preferably, the electrolyte has quality proportioning to be mixed for NaCl, KCl and water of 3:5:100.
Preferably, it also needs to carry out package processing to the hard alloy portion of composite polycrystal-diamond before the electrolysis.
Preferably, the package processing is as follows, is passing through magnet for the hard alloy of conducting wire and composite polycrystal-diamond After portion's electrical connection, it is set to be isolated from the outside hard alloy portion surface package using polytetrafluoroethylene (PTFE).
Specifically, the method for removing metallic cobalt in composite polycrystal-diamond, steps are as follows:
1) prepare electrolysis power, electrolytic cell, and will connect the positive and negative conducting wire of electrolysis power respectively with composite polycrystal-diamond Hard alloy portion and stainless steel plate electrical connection;
2) preparation electrolyte is taken by the mass ratio, the portion PCD of composite polycrystal-diamond and stainless steel plate is placed in electrolyte In, electrolysis power is powered and voltage is that 1.5 ~ 3V carries out electrolysis 20-30 hours.
Electrolysis method of the invention takes off cobalt principle: using the portion PCD of composite polycrystal-diamond as anode, stainless steel plate is made For cathode, preferably the mixed solution of NaCl, KCl or NaCl and KCl are as electrolyte, by the PCD of composite polycrystal-diamond Portion is soaked in the electrolytic solution, and hard alloy portion and air and electrolyte completely cut off, and under the action of decomposition voltage, the Co atom of anode is lost De-electromation is oxidized to Co2+(the later period Co of cell reaction2+It is oxidized to Co again3+), the H of cathode2O obtains electronics and is reduced At H2And OH-, under the action of electric field, Co ion and OH-It is detached from anode and cathode respectively, enters and forms Co(OH in solution)2 Precipitating, so that the cobalt in the portion PCD be removed.
Since composite polycrystal-diamond is by polycrystalline diamond portion, that is, portion PCD and hard alloy portion (WC-Co) two parts group At polycrystalline diamond portion is for being ground and being crushed, and hard alloy one end is used to fix polycrystalline diamond portion, and the other end is then used to weld Connect bit matrix.Due to also containing cobalt in hard alloy portion, reaction also will do it in electrolysis, therefore the present invention is to hard alloy Portion has carried out the processing of surface package, for completely cutting off air and electrolyte.
Compared with the prior art, the invention has the following advantages: present invention employs neutral electrolyte, with polycrystalline diamond Portion is anode, and stainless steel plate is cathode, by the effect of decomposition voltage, has carried out de- cobalt to polycrystalline diamond portion and has handled, thus The service life and wear-resisting property of composite polycrystal-diamond are increased, preparation process of the present invention is simple, without any corrosive goods Matter, it is low in cost, and the cobalt in polycrystalline diamond portion can be effectively removed, can effectively solve the problem that existing de- cobalt method it is existing at The serial problem such as this higher, complex process, environmental pollution.Using the method for the present invention for being electrolysed de- cobalt, it is bright to take off cobalt effect It is aobvious, 500 ~ 800 microns of de- cobalt depth can be reached.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
Embodiment 1
A kind of method of metallic cobalt in removal composite polycrystal-diamond, steps are as follows:
1) prepare electrolysis power, electrolytic cell, and will connect the positive and negative conducting wire of electrolysis power respectively with composite polycrystal-diamond Hard alloy portion and stainless steel plate electrical connection;
2) it takes NaCl, KCl and water to prepare electrolyte by the mass ratio of 2:4:100, then electrolyte is poured into electrolytic cell, then will In the portion PCD of composite polycrystal-diamond and stainless steel plate merging electrolyte, electrolysis power is powered, initial voltage 0.73V, so After be slowly increased to 1.5V, the cobalt at this time it can be observed that cathode has bubble generation, with the progress of reaction, in polycrystalline diamond It is gradually removed, taking off the cobalt time is that for 24 hours, taking off cobalt depth is 500 microns.
Embodiment 2
A kind of method of metallic cobalt in removal composite polycrystal-diamond, steps are as follows:
1) prepare electrolysis power, electrolytic cell, and will connect the positive and negative conducting wire of electrolysis power respectively with composite polycrystal-diamond Hard alloy portion and stainless steel plate electrical connection;
2) it takes NaCl, KCl and water to prepare electrolyte by the mass ratio of 3:5:100, then electrolyte is poured into electrolytic cell, then will In the portion PCD of composite polycrystal-diamond and stainless steel plate merging electrolyte, electrolysis power is powered, initial voltage 0.73V, so After be slowly increased to 1.5V, the cobalt at this time it can be observed that cathode has bubble generation, with the progress of reaction, in polycrystalline diamond It is gradually removed, taking off the cobalt time is that for 24 hours, taking off cobalt depth is 550 microns.
Embodiment 3
A kind of method of metallic cobalt in removal composite polycrystal-diamond, steps are as follows:
1) prepare electrolysis power, electrolytic cell, and will connect the positive and negative conducting wire of electrolysis power respectively with composite polycrystal-diamond Hard alloy portion and stainless steel plate electrical connection;
2) it takes NaCl, KCl and water to prepare electrolyte by the mass ratio of 3:5:100, then electrolyte is poured into electrolytic cell, then will In the portion PCD of composite polycrystal-diamond and stainless steel plate merging electrolyte, electrolysis power is powered, initial voltage 0.73V, so After be slowly increased to 2.0V, the cobalt at this time it can be observed that cathode has bubble generation, with the progress of reaction, in polycrystalline diamond It is gradually removed, taking off the cobalt time is that for 24 hours, taking off cobalt depth is 800 microns.

Claims (9)

1. a kind of method of metallic cobalt in removal composite polycrystal-diamond, including the portion the PCD work with composite polycrystal-diamond As cathode and it is electrically connected electrolysis power for anode, stainless steel plate, the portion PCD and stainless steel plate are immersed in electrolyte and are electrolysed, It is characterized in that, the pH of the electrolyte is 7, and decomposition voltage is 1.5-3V.
2. removing the method for metallic cobalt in composite polycrystal-diamond as described in claim 1, which is characterized in that the electrolysis Liquid is made of the electrolyte that quality proportioning is 1-8:90-110 and water.
3. removing the method for metallic cobalt in composite polycrystal-diamond as claimed in claim 2, which is characterized in that the electrolysis Matter is one of NaCl, KCl or mixing.
4. removing the method for metallic cobalt in composite polycrystal-diamond as claimed in claim 3, which is characterized in that the electrolysis Liquid is mixed by NaCl, KCl that quality proportioning is 1-3:3-5:90-110 and water.
5. removing the method for metallic cobalt in composite polycrystal-diamond as claimed in claim 4, which is characterized in that the electrolysis Liquid is mixed by NaCl, KCl that quality proportioning is 2:4:100 and water.
6. removing the method for metallic cobalt in composite polycrystal-diamond as claimed in claim 4, which is characterized in that the electrolysis Liquid is mixed by NaCl, KCl that quality proportioning is 3:5:100 and water.
7. removing the method for metallic cobalt in composite polycrystal-diamond as described in claim 1, which is characterized in that the electrolysis It is preceding also to need to carry out package processing to the hard alloy portion of composite polycrystal-diamond.
8. removing the method for metallic cobalt in composite polycrystal-diamond as claimed in claim 7, which is characterized in that the package Processing is as follows, after being electrically connected the hard alloy portion of conducting wire and composite polycrystal-diamond by magnet, using polytetrafluoroethyl-ne Hard alloy portion surface package is made it be isolated from the outside by alkene.
9. the method for metallic cobalt in removal composite polycrystal-diamond a method as claimed in any one of claims 1-8, which is characterized in that step It is rapid as follows:
1) prepare electrolysis power, electrolytic cell, and will connect the positive and negative conducting wire of electrolysis power respectively with composite polycrystal-diamond Hard alloy portion and stainless steel plate electrical connection;
2) preparation electrolyte is taken by the mass ratio, the portion PCD of composite polycrystal-diamond and stainless steel plate is placed in electrolyte In, electrolysis power is powered and voltage is that 1.5 ~ 3V carries out electrolysis 20-30 hours.
CN201910478653.3A 2019-06-03 2019-06-03 A kind of method of metallic cobalt in removal composite polycrystal-diamond Pending CN110144618A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113445117A (en) * 2021-06-29 2021-09-28 中国地质大学(武汉) Electrolytic method and device for removing metallic cobalt in polycrystalline diamond compact
CN115125537A (en) * 2022-08-05 2022-09-30 四川轻化工大学 Method for removing cobalt in polycrystalline diamond compact

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0461756A1 (en) * 1990-05-09 1991-12-18 Ykk Corporation Electrolytic machining using pulsed electric current
US6866769B2 (en) * 2001-11-14 2005-03-15 General Electric Company Drive head and ECM method and tool for making same
CN104389012A (en) * 2014-10-21 2015-03-04 西南石油大学 Preparation method of cobalt-removed PDC (polycrystalline diamond) composite sheet
CN104862771A (en) * 2015-05-28 2015-08-26 吉林大学 Method for removing partial metal cobalt in polycrystalline diamond compact by electrolytic method
JP2015231642A (en) * 2014-06-09 2015-12-24 三菱電機株式会社 Electrolytic processing method and electrolytic processing device for hard metal
CN105705283A (en) * 2013-11-05 2016-06-22 三菱电机株式会社 Electrochemical machining method, electrochemical machining device, and electrochemical machining solution

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0461756A1 (en) * 1990-05-09 1991-12-18 Ykk Corporation Electrolytic machining using pulsed electric current
US6866769B2 (en) * 2001-11-14 2005-03-15 General Electric Company Drive head and ECM method and tool for making same
CN105705283A (en) * 2013-11-05 2016-06-22 三菱电机株式会社 Electrochemical machining method, electrochemical machining device, and electrochemical machining solution
JP2015231642A (en) * 2014-06-09 2015-12-24 三菱電機株式会社 Electrolytic processing method and electrolytic processing device for hard metal
CN104389012A (en) * 2014-10-21 2015-03-04 西南石油大学 Preparation method of cobalt-removed PDC (polycrystalline diamond) composite sheet
CN104862771A (en) * 2015-05-28 2015-08-26 吉林大学 Method for removing partial metal cobalt in polycrystalline diamond compact by electrolytic method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113445117A (en) * 2021-06-29 2021-09-28 中国地质大学(武汉) Electrolytic method and device for removing metallic cobalt in polycrystalline diamond compact
CN115125537A (en) * 2022-08-05 2022-09-30 四川轻化工大学 Method for removing cobalt in polycrystalline diamond compact
CN115125537B (en) * 2022-08-05 2023-04-11 四川轻化工大学 Method for removing cobalt in polycrystalline diamond compact

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