CN105603428A - Method for removing cobalt from polycrystalline diamond clad sheet - Google Patents

Method for removing cobalt from polycrystalline diamond clad sheet Download PDF

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Publication number
CN105603428A
CN105603428A CN201610049615.2A CN201610049615A CN105603428A CN 105603428 A CN105603428 A CN 105603428A CN 201610049615 A CN201610049615 A CN 201610049615A CN 105603428 A CN105603428 A CN 105603428A
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CN
China
Prior art keywords
cobalt
polycrystalline diamond
acid solution
acid
diamond
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Pending
Application number
CN201610049615.2A
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Chinese (zh)
Inventor
周明
段志明
匡怡新
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Changsha Diat New Material Sci& Tech Co Ltd
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Changsha Diat New Material Sci& Tech Co Ltd
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Priority to CN201610049615.2A priority Critical patent/CN105603428A/en
Publication of CN105603428A publication Critical patent/CN105603428A/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/10Etching compositions
    • C23F1/14Aqueous compositions
    • C23F1/16Acidic compositions
    • C23F1/28Acidic compositions for etching iron group metals

Abstract

The invention provides a method for removing cobalt from a polycrystalline diamond clad sheet. The method comprises the steps that acid liquor is provided and includes phosphoric acid and hydrogen peroxide; a polycrystalline diamond layer of the polycrystalline diamond clad sheet is soaked in the acid liquor to obtain a clad sheet without cobalt. According to the method, phosphoric acid is used for removing the cobalt phase in polycrystalline diamond, phosphate anions and cobalt ions can form stable soluble coordination ions, and therefore cobalt is promoted to continuously enter the solution to be removed from the clad sheet; moreover, hydrogen peroxide is added, so that the removal rate of cobalt is further increased. As a result, through the method for removing cobalt from the polycrystalline diamond clad sheet, the amount of volatilized irritant gas is small, corrosion to a seal of equipment and the clad sheet is small, damage to a base body seal is small, and harm to the working environment is small; meanwhile, a high cobalt removal rate is achieved, cost is lowered, and large-scale application is easy to realize.

Description

A kind of method of removing cobalt from composite polycrystal-diamond
Technical field
The present invention relates to composite polycrystal-diamond technical field, relate in particular to a kind of multiple from polycrystalline diamondClose the method for removing cobalt in sheet.
Background technology
Composite polycrystal-diamond (Polycrystallinediamondcompact is called for short PDC) is extensively usedIn oil and geological drilling and metal cutting, in general, it is that hard alloy substrate and diamond are micro-The functional composite crystal material that powder forms at the lower sintering of HTHP (as 1400 DEG C, 4.5GPa~7GPa),Comprise hard alloy substrate and be compounded in the polycrystalline diamond layer (also claiming glomerocryst layer) on matrix. ProducingIn process, conventionally in diadust, can mix the cobalt powder of 5~10% mass ratioes, to promote diadustForm polycrystalline diamond. But cobalt is harmful in the time that composite sheet is used in glomerocryst layer, cobalt at high temperatureCan accelerate adamantine graphitization, produce serious fire damage. Thereby composite sheet generally will be gone before useRemove or partly remove cobalt, to improve the heat endurance of composite sheet.
Existing method generally adopts hydrochloric acid, nitric acid, hydrofluoric acid or mixed acid, goes by immersion or heating bathExcept the cobalt phase of the 100 μ m~500 μ m degree of depth. As the application number Chinese patent literature public affairs that are 201410816291.1A kind of opened de-cobalt Compound-acid based on man-made polycrystalline diamond composite sheet de-cobalt method, the method is by oneOrganic acid, inorganic acid 1 and the inorganic acid 2 of determining mass concentration mix joins to obtain Compound-acid, by man-made polycrystalline Buddha's warrior attendantStone composite sheet immerses in the composite solution preparing, and adjusting dipping temperature is 25~90 DEG C, dipping 48~72h,; Wherein, organic acid is a kind of in tartaric acid, citric acid, malic acid, lactic acid and oxalic acid or itsComposition, inorganic acid 1 is a kind of or its composition in hydrochloric acid, perchloric acid, sulfuric acid, hypochlorous acid and chromic acid,Inorganic acid 2 is a kind of or its composition in boric acid, hydrofluoric acid, hydrobromic acid and nitric acid.
It is remarkable that said method is removed the effect of cobalt to composite polycrystal-diamond, but hydrochloric acid, nitric acid, hydrogenVolatility and the corrosivity of the strong acid such as fluoric acid are excessive, large to operative employee's excitant, work under bad environment;Some also needs acid heating, and volatility is larger like this, higher to the seal request of composite sheet matrix part,Be unfavorable for application.
Summary of the invention
In view of this, the application provides a kind of method of removing cobalt from composite polycrystal-diamond, thisThe corrosion of the sealing frock of the method for the bright removal cobalt providing to equipment and composite sheet matrix is little, to environment friendGood, and the eliminating efficiency of cobalt is high.
The invention provides a kind of method of removing cobalt from composite polycrystal-diamond, comprise the following steps:
Acid solution is provided, and described acid solution comprises phosphoric acid and hydrogen peroxide;
The polycrystalline diamond layer of composite polycrystal-diamond is soaked in above-mentioned acid solution, obtain answering of de-cobaltClose sheet.
Preferably, described acid solution makes in accordance with the following methods: in the phosphoric acid solution of 1mol/L, add qualityConcentration is 30% hydrogen peroxide solution, obtains acid solution.
Preferably, the volume ratio of described phosphoric acid solution and hydrogen peroxide solution is 10:0.5~10:5.
Preferably, the volume ratio of described phosphoric acid solution and hydrogen peroxide solution is 10:1~10:3.
Preferably, the temperature of described immersion is 10 DEG C~40 DEG C.
Preferably, the time of described immersion is 24h~72h.
Preferably, before de-cobalt, the cobalt amount that contains in the polycrystalline diamond layer of described composite polycrystal-diamond is7wt%~10wt%。
Preferably, the cobalt amount that contains in the polycrystalline diamond layer of the composite sheet of de-cobalt is lower than 2wt%.
Compared with prior art, the present invention adopts the de-cobalt acid solution that contains phosphoric acid and hydrogen peroxide, soaks glomerocrystThe polycrystalline diamond layer of diamond compact, removes the cobalt in composite sheet. It is poly-that the present invention uses phosphoric acid to removeCobalt phase in diamond, phosphate anion and cobalt ions can form stable solubility coordination ion, fromAnd impel cobalt constantly to enter solution and remove from composite sheet; And the present invention adds hydrogen peroxide, can enter oneStep improves the removal efficiency of cobalt. Therefore the method that, the present invention removes cobalt from composite polycrystal-diamond can notHave a lot of irritative gas volatilizations, the corrosivity of the sealing to equipment and composite sheet is little, and matrix is sealedDestructiveness is little, little to working environment infringement, has the eliminating efficiency of higher cobalt simultaneously, has reduced cost,Easily realize scale application.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of composite sheet before the de-cobalt of embodiment 1;
Fig. 2 is the stereoscan photograph of composite sheet after the de-cobalt of embodiment 1;
Fig. 3 is the stereoscan photograph of composite sheet after the de-cobalt of embodiment 1;
Fig. 4 is the stereoscan photograph in composite sheet Spectrum acquisition district after the de-cobalt of embodiment 1;
Fig. 5 is the power spectrum peak of composite sheet after the de-cobalt of embodiment 1.
Detailed description of the invention
Below the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, institute retouchesThe embodiment stating is only the present invention's part embodiment, instead of whole embodiment. Based on the present inventionIn embodiment, those of ordinary skill in the art are not making the institute obtaining under creative work prerequisiteThere are other embodiment, all belong to the scope of protection of the invention.
The invention provides a kind of method of removing cobalt from composite polycrystal-diamond, comprise the following steps:
Acid solution is provided, and described acid solution comprises phosphoric acid and hydrogen peroxide;
The polycrystalline diamond layer of composite polycrystal-diamond is soaked in above-mentioned acid solution, obtain answering of de-cobaltClose sheet.
Method provided by the invention can be removed the cobalt phase in polycrystalline diamond better, reduces equipment simultaneouslyWith the corrosion of the sealing frock of composite sheet matrix, environmentally friendly, cost is low.
The embodiment of the present invention can be prepared the acid solution for removing cobalt, and described acid solution also claims de-cobalt liquid, de-cobalt acidLiquid, comprises phosphoric acid and hydrogen peroxide. In the present invention, described acid solution comprises phosphoric acid; The present invention uses phosphoric acidRemove the cobalt phase in polycrystalline diamond, phosphoric acid volatility is little, and has strong complexing, phosphate radical fromSon can form stable solubility coordination ion with cobalt ions, thereby impels cobalt constantly to enter solution and from multipleClose in sheet and remove. Meanwhile, described acid solution comprises hydrogen peroxide, can further improve the removal efficiency of cobalt.
When the acid solution that comprises phosphoric acid and hydrogen peroxide is provided, the present invention does not have the addition sequence of phosphoric acid and hydrogen peroxideThere is particular restriction, can adopt phosphoric acid solution and hydrogen peroxide solution preparation to obtain. Wherein, described phosphoric acid is moltenThe concentration of liquid can be 1mol/L~2mol/L; Described hydrogen peroxide solution adopts commercially available prod, as dense in qualityDegree is 30% hydrogen peroxide product.
In preferred embodiments more of the present invention, described acid solution makes in accordance with the following methods: at 1mol/LPhosphoric acid solution in to add mass concentration be 30% hydrogen peroxide solution, obtain acid solution. The embodiment of the present inventionCan adopt the phosphoric acid solution of conventional method preparation 1mol/L, then preferably according to described phosphoric acid solution and dioxygenThe volume ratio of the aqueous solution is 10:0.5~10:5, and adding concentration is 30% hydrogen peroxide solution; Wherein, described inThe volume ratio of phosphoric acid solution and hydrogen peroxide solution is preferably 10:1~10:3, as 10:1, and 10:2 etc.
The polycrystalline diamond layer that the embodiment of the present invention adopts above-mentioned acid soak composite polycrystal-diamond, soaksAfter bubble certain hour, obtain the composite sheet of de-cobalt.
The present invention, using composite polycrystal-diamond as de-cobalt object, adopts commercially available polycrystalline diamond compoundSheet. Diameter, height and the diamond grits etc. of the present invention to composite sheet are not particularly limited, as multipleThe thickness that closes the polycrystalline diamond layer of sheet is generally 2mm~4mm; Before de-cobalt, described polycrystalline diamond is compoundIn the polycrystalline diamond layer of sheet is 7wt%~10wt% containing cobalt amount. The embodiment of the present invention can adopt 1913 ruleThe composite polycrystal-diamond of lattice is de-cobalt object; In an embodiment of the present invention, before de-cobalt, described poly-In the polycrystalline diamond layer of diamond composite sheet is 8wt% containing cobalt amount. In addition, the embodiment of the present invention canThe body portion of composite sheet is carried out to anti-corrosion protection, and conventional anti-corrosion protection comprises coating anti-corrosion materialOr with frock sealing etc.
The embodiment of the present invention is placed on the polycrystalline diamond of described composite polycrystal-diamond in de-cobalt liquid and soaksBubble certain hour, removes cobalt phase wherein. Described immersion can be carried out at normal temperatures, and the temperature of immersion is preferredBe 10~40 DEG C, more preferably 20~30 DEG C; When soaking de-cobalt, the present invention without heating, matrix is sealedDestructive little. The time of described immersion is preferably 24h~72h, and the present invention adopts phosphoric acid that volatility is little and twoThe mix reagent of oxygen water, 24h~72h deviates from cobalt fast at normal temperatures, and the de-cobalt degree of depth can reach 300 μM~500 μ m, eliminating efficiency is higher. In an embodiment of the present invention, the glomerocryst Buddha's warrior attendant of the composite sheet of de-cobaltThe cobalt amount that contains in stone layer is lower than 2wt%.
In sum, the method that the present invention removes cobalt from composite polycrystal-diamond does not have a lot of stimulationsProperty gaseous volatilization, reduced the corrosivity of the sealing to equipment and composite sheet, destructiveness to matrix sealingWith the extent of damage to working environment, there is the eliminating efficiency of higher cobalt simultaneously, reduce cost, easilyRealize scale application.
In order further to understand the application, below in conjunction with embodiment, the application is provided from polycrystalline diamondIn composite sheet, removing the method for cobalt describes particularly.
Embodiment 1
The phosphoric acid solution of preparation 1mol/L, adding 10mL concentration by every 100mL is that 30% dioxygen is water-solubleLiquid, preparation obtains de-cobalt acid solution.
Adopt the composite polycrystal-diamond (Chang Shadai strangles new material Science and Technology Co., Ltd.) of 1913 specificationsAs de-cobalt object, the cobalt content (mass percent, as follows) before de-cobalt in composite sheet glomerocryst layer is8%. First composite sheet matrix part is sealed by frock, carry out anti-corrosion protection, then by above-mentioned composite sheetPolycrystalline diamond be placed in de-cobalt liquid, 25 DEG C are soaked 48 hours.
Adopt ESEM to carry out morphology observation to the composite sheet before and after de-cobalt, and measure the de-cobalt degree of depth. KnotFruit is referring to Fig. 1, Fig. 2 and Fig. 3, and Fig. 1 is the stereoscan photograph of composite sheet before the de-cobalt of embodiment 1, figure2 be the stereoscan photograph of composite sheet after the de-cobalt of embodiment 1, and Fig. 3 is composite sheet after the de-cobalt of embodiment 1Stereoscan photograph. In Fig. 1, what canescence was the distribution of vein shape is cobalt phase, and black is polycrystalline diamond,And cobalt is wrapped in diamond particles mutually, between diamond crystals, even dispersion distributes. In Fig. 2,Upper strata approximately has the thickness of 305 μ m substantially to can't see cobalt phase. In Fig. 3, can obviously observe cobalt and remove mutuallyAfter the hole that stays.
Utilize energy disperse spectroscopy to detect the cobalt content of composite sheet after de-cobalt, Fig. 4 is composite sheet after the de-cobalt of embodiment 1The stereoscan photograph in Spectrum acquisition district, utilizes energy disperse spectroscopy to carry out composition face to black box region in Fig. 4Scan, obtain the EDAX results of Fig. 5 and table 1, Fig. 5 is the energy of composite sheet after the de-cobalt of embodiment 1Spectrum peak, table 1 is the composition result of composite sheet after the de-cobalt of embodiment 1. Energy disperse spectroscopy testing result shows, surplusRemaining cobalt content deficiency 2wt%. Continue to be dipped into 72 hours, the de-cobalt degree of depth can reach 500 μ m.
The composition result of composite sheet after the de-cobalt of table 1 embodiment 1
Composition (Element) Wt% At%
CK 97.42 99.60
WM 1.21 0.10
CoK 1.37 0.30
Matrix (Matrix) Correction ZAF
Embodiment 2
The phosphoric acid solution of preparation 1mol/L, adding 20mL concentration by every 100mL is that 30% dioxygen is water-solubleLiquid, preparation obtains de-cobalt acid solution.
Adopt the de-cobalt object identical with embodiment 1, polycrystalline diamond is placed in de-cobalt liquid to 25 DEG CSoak 48 hours.
According to the identical detection method of embodiment 1, measuring the de-cobalt degree of depth is 350 μ m. Continue to soakBy 72 hours, the de-cobalt degree of depth was 600 μ m, and residue cobalt content is less than 2wt%.
Comparative example
The phosphoric acid solution of preparation 1mol/L is as de-cobalt acid solution.
Adopt the de-cobalt object identical with embodiment 1, polycrystalline diamond is placed in de-cobalt liquid to 25 DEG CSoak 48 hours.
According to the identical detection method of embodiment 1, measuring the de-cobalt degree of depth is 200 μ m. Continue to soakBy 72 hours, the de-cobalt degree of depth was 350 μ m, and residue cobalt content is 2wt%.
As seen from the above embodiment, the present invention uses phosphoric acid can remove the cobalt phase in polycrystalline diamond, andThe hydrogen peroxide adding can further improve the removal efficiency of cobalt. The present invention removes from composite polycrystal-diamondThe method of cobalt does not have a lot of irritative gas volatilizations, and the corrosivity of the sealing to equipment and composite sheet is little,Destructiveness to matrix sealing is little, little to working environment infringement, has the eliminating efficiency of higher cobalt simultaneously,Reduce cost, easily realized scale application.

Claims (8)

1. a method of removing cobalt from composite polycrystal-diamond, comprises the following steps:
Acid solution is provided, and described acid solution comprises phosphoric acid and hydrogen peroxide;
The polycrystalline diamond layer of composite polycrystal-diamond is soaked in above-mentioned acid solution, obtain answering of de-cobaltClose sheet.
2. method according to claim 1, is characterized in that, described acid solution is made in accordance with the following methods: in the phosphoric acid solution of 1mol/L, adding mass concentration is 30% hydrogen peroxide solution, obtains acid solution.
3. method according to claim 2, is characterized in that, described phosphoric acid solution and dioxygen are water-solubleThe volume ratio of liquid is 10:0.5~10:5.
4. method according to claim 3, is characterized in that, described phosphoric acid solution and dioxygen are water-solubleThe volume ratio of liquid is 10:1~10:3.
5. method according to claim 1, is characterized in that, the temperature of described immersion is 10 DEG C~40℃。
6. method according to claim 5, is characterized in that, the time of described immersion is 24h~72h.
7. according to the method described in claim 1~6 any one, it is characterized in that, before de-cobalt, described poly-In the polycrystalline diamond layer of diamond composite sheet is 7wt%~10wt% containing cobalt amount.
8. method according to claim 7, is characterized in that, the glomerocryst Buddha's warrior attendant of the composite sheet of de-cobaltThe cobalt amount that contains in stone layer is lower than 2wt%.
CN201610049615.2A 2016-01-25 2016-01-25 Method for removing cobalt from polycrystalline diamond clad sheet Pending CN105603428A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107085002A (en) * 2017-04-24 2017-08-22 河南四方达超硬材料股份有限公司 A kind of high temperature resistant wire drawing die takes off the lossless detection method of cobalt depth
CN107803507A (en) * 2017-09-28 2018-03-16 河南亚龙金刚石制品股份有限公司 A kind of quick method for removing residual cobalt in diamond compact glomerocryst layer
CN108265297A (en) * 2018-03-12 2018-07-10 河南工业大学 A kind of de- cobalt method of man-made polycrystalline diamond composite sheet supercritical fluid
CN109731935A (en) * 2018-12-06 2019-05-10 宜昌给立金刚石工业有限公司 The method of Glomerocryst adamas legging mould insert blank and its de- cobalt

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CN102597324A (en) * 2009-08-25 2012-07-18 Tdy工业公司 Coated cutting tools having a platinum group metal concentration gradient and related processes
CN104551154A (en) * 2014-11-14 2015-04-29 深圳市迈高机械工具有限公司 PCD cutter with high performance
CN105803419A (en) * 2016-04-27 2016-07-27 富耐克超硬材料股份有限公司 Cobalt leaching solution system, hard alloy cobalt leaching method and blade with diamond coating

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US6242348B1 (en) * 1999-10-04 2001-06-05 National Semiconductor Corp. Method for the formation of a boron-doped silicon gate layer underlying a cobalt silicide layer
GB2477459A (en) * 2006-05-03 2011-08-03 Omg Electronic Chemicals Inc Method and composition for selectively stripping nickel from a substrate
CN102597324A (en) * 2009-08-25 2012-07-18 Tdy工业公司 Coated cutting tools having a platinum group metal concentration gradient and related processes
CN104551154A (en) * 2014-11-14 2015-04-29 深圳市迈高机械工具有限公司 PCD cutter with high performance
CN105803419A (en) * 2016-04-27 2016-07-27 富耐克超硬材料股份有限公司 Cobalt leaching solution system, hard alloy cobalt leaching method and blade with diamond coating

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107085002A (en) * 2017-04-24 2017-08-22 河南四方达超硬材料股份有限公司 A kind of high temperature resistant wire drawing die takes off the lossless detection method of cobalt depth
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CN107803507A (en) * 2017-09-28 2018-03-16 河南亚龙金刚石制品股份有限公司 A kind of quick method for removing residual cobalt in diamond compact glomerocryst layer
CN107803507B (en) * 2017-09-28 2019-04-30 河南亚龙金刚石制品股份有限公司 The method of cobalt is remained in a kind of quick removal diamond compact plycrystalline diamond layer
CN108265297A (en) * 2018-03-12 2018-07-10 河南工业大学 A kind of de- cobalt method of man-made polycrystalline diamond composite sheet supercritical fluid
CN109731935A (en) * 2018-12-06 2019-05-10 宜昌给立金刚石工业有限公司 The method of Glomerocryst adamas legging mould insert blank and its de- cobalt

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Application publication date: 20160525