CN104290199B - Diamond cutting tool with composite structure plating and preparation method thereof - Google Patents
Diamond cutting tool with composite structure plating and preparation method thereof Download PDFInfo
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- CN104290199B CN104290199B CN201410497254.9A CN201410497254A CN104290199B CN 104290199 B CN104290199 B CN 104290199B CN 201410497254 A CN201410497254 A CN 201410497254A CN 104290199 B CN104290199 B CN 104290199B
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- superhard
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28D—WORKING STONE OR STONE-LIKE MATERIALS
- B28D1/00—Working stone or stone-like materials, e.g. brick, concrete or glass, not provided for elsewhere; Machines, devices, tools therefor
- B28D1/02—Working stone or stone-like materials, e.g. brick, concrete or glass, not provided for elsewhere; Machines, devices, tools therefor by sawing
- B28D1/12—Saw-blades or saw-discs specially adapted for working stone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28D—WORKING STONE OR STONE-LIKE MATERIALS
- B28D5/00—Fine working of gems, jewels, crystals, e.g. of semiconductor material; apparatus or devices therefor
- B28D5/04—Fine working of gems, jewels, crystals, e.g. of semiconductor material; apparatus or devices therefor by tools other than rotary type, e.g. reciprocating tools
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
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- Mechanical Engineering (AREA)
- Mining & Mineral Resources (AREA)
- Polishing Bodies And Polishing Tools (AREA)
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Abstract
The invention discloses a kind of diamond cutting tool with composite structure plating, including matrix and blade layer, the blade layer includes being connected with the composite structure plating of superhard coarse grain, the composite structure plating includes the electrodeposit metals layer of lower floor and the high antifriction layer on upper strata, and superhard particulate is connected with the high antifriction layer;Its preparation method is the compound high-wear layer on the basis of plating diamond tool based on plating diamond tool, diamond tool coating of the composition with composite construction.Blade layer of the invention is under the protection of high antifriction layer; diamond tool will not be caused to be quickly invalidated because of coming off for the superhard coarse grain in part in use; the effective service life for extending diamond tool; it is especially prominent to flexible diamond tool effect; the reinforcement means that can be used for simultaneously after diamond tool failure, the effectively service life of extension diamond tool.
Description
(1) technical field:
The present invention relates to cutting element, specifically a kind of diamond cutting tool and its making with composite structure plating
Method.
(2) background technology:
Diamond tool is mainly used in processing hard brittle material (such as:Sapphire, special cermacis, monocrystalline silicon, gem and jade etc.).Its
Middle service life is to weigh the important indicator of diamond tool, the main abrasion with diamond knife edge layer of failure of diamond tool
Come off failure, based on the inadequate fracture failure of matrix strength.According to investigation and test result indicate that, diamond tool failure mode
Often since most weak spot, when there are diamond particles and comes off in certain point in diamond knife edge layer, whole coating quickly
Will near the particle detachment point continuously come off, and ultimately result in whole tool failures.Factual survey finds, when most weak spot
When starting shedding off, often the overwhelming majority of coating also stands intact, and diamond particles are intact, sharp.If the weakness can be strengthened
Point, the service life of whole diamond tool will extend significantly, and the utilization rate of valuable diamond particles will also be greatly improved.
The material that diamond tool is processed, essentially hard brittle material, and diamond tool is generally electro-plating method preparation.
The tiny superhard particles produced in process, its hardness is far above coated metal hardness, now, when diamond particles come off
Afterwards, the superhard particles that cutting process is produced reversely grind coated metal, and coated metal is worn away totally quickly, cause Buddha's warrior attendant nearby
Stone particle hold not enough, further comes off, and spreads from a point quickly, during high-speed cutting superhard material, expands
Exhibition speed faster, can cause whole diamond tool to fail due to the failure of a point quickly, when serious, or even can may wear to base
Body, causes diamond tool matrix insufficient strength to cause fracture.Meanwhile, continuously distributed diamond tool occurs in cutting process
Diamond drop-off can influence the surface quality of cutting material, the crystalline material higher for processing request, can therefore cause waste product
Appearance, cause huge loss.
Coating comes off for flexible diamond tool (such as:Diamond fretsaw, annular diamond fretsaw, annular diamond belt
Saw etc.) it is the most notable in the influence of high-speed cutting hard brittle material, by taking annular diamond fretsaw as an example, a diameter of 0.5mm annulars gold
When diamond wire saw cuts 6 inches sapphire crystal with the linear velocity of 20m/s, after there is particle detachment in certain point in scroll saw, one
As within half an hour scroll saw wear and rupture, linear velocity faster when, rupture time is shorter.
Above mentioned problem, be due to diamond tool in manufacturing process existing defects, the defect often turn into Buddha's warrior attendant lapicide
The most weak place of tool, is also the control point of diamond tool service life.
(3) content of the invention:
In view of the shortcomings of the prior art, the technical problems to be solved by the invention are to provide a kind of simple structure, making side
Just, can efficient hardening weak spot, improve diamond cutting tool with composite structure plating and its making of service life
Method.
The diamond cutting tool with composite structure plating of above-mentioned technical problem is can solve the problem that, its technical scheme includes
Matrix and blade layer, the blade layer include being connected with the electrodeposit metals layer of superhard coarse grain, unlike the prior art institute
State to be applied on electrodeposit metals layer and be coated with high antifriction layer, superhard particulate is inlaid with the high antifriction layer;Electrodeposit metals layer and height
Wearing layer forms the composite structure plating of blade layer.
In said structure, the high antifriction layer mainly plays a part of to protect and holds superhard coarse grain, prevents process from producing
Raw superhard particles are reversely ground electrodeposit metals layer.
To reach preferably cutting and wear-resistant efficiency, the superhard coarse grain of selection Li Jing≤200 μm selects Li Jing≤50 μm
Superhard particulate.
To reach the requirement that plates to superhard coarse grain, the thickness of the high antifriction layer can be selected between 30 μm~40 μm.
The superhard coarse grain and superhard particulate can select diamond or from polycrystalline cubic boron nitride (PCBN) or selection
Other superhard particles, or be used in mixed way.
The superhard coarse grain and the preferred diamond of superhard particulate.
Can be continuously distributed or for Disjunct distribution or be irregular distribution according to cutting condition selection blade layer.
The electrodeposit metals layer preferably nickel or nickel cobalt (alloy).
The diamond cutting tool preparation method with composite structure plating of above-mentioned technical problem is can solve the problem that, is taken
Following processing step:
1st, the surface preparation of superhard coarse grain and superhard particulate.
Required superhard coarse grain and superhard particulate are placed in after removing surface grease in alkaline solution, are washed with clear water, then
It is 3 to be placed in volume ratio:In 1 concentrated hydrochloric acid and concentrated nitric acid, after removing the metal oxide on superhard coarse grain and superhard particulate surface, use
Clear water is washed.
2nd, superhard coarse grain and superhard particulate surface cationic.
By the 1st step treatment after superhard coarse grain and superhard particulate be placed in cationic surface active agent solution, to sun from
Subtype surfactant solution applies the positive potential of 0.1~0.2V, the work of the cation of cationic surface active agent in electrophoresis
Under, one layer of film with positive charge is formed in superhard coarse grain and superhard particulate surface.
3rd, electrodeposit metals layer is electroplated on matrix using burying micromicrofarad, and the superhard coarse grain of surface cationic is uniformly solid
Knot is in electrodeposit metals layer.
4th, continuously stirring plating solution makes superhard particulate be in suspended state, the electroplating deposition high antifriction layer on electrodeposit metals layer,
And be uniformly embedded in high antifriction layer the superhard particulate of surface cationic;So far, electrodeposit metals layer and high antifriction layer are total to
With the composite structure plating for forming blade layer.
The electrodeposit metals layer electroplating technique parameter is selected:Current density is in 0.8A/dm2~1.0A/dm2Between,
Temperature is 45 ± 5 DEG C;The high antifriction layer electroplating technique parameter is:Current density is in 0.5A/dm2~0.6A/dm2Between, temperature
Spend is 45 ± 5 DEG C.
Electrodeposit metals layer is preferably with nickel or nickel cobalt (alloy) that nickel sulfamic acid is main salt.
Particle diameter Xuan Ze≤200 μm of the superhard coarse grain, particle diameter Xuan Ze≤50 μm of the superhard particulate.
To reach the requirement that plates to superhard coarse grain, the thickness of the high antifriction layer is selected between 30 μm~40 μm.
Beneficial effects of the present invention:
1st, the present invention is to be divided to two independent composite plating processes to make diamond tool, deposited metal with electric plating method
(generally nickel or nickel cobalt (alloy)) two processes independently of one another, are independent of each other, with modularization feature.
2nd, the present invention with the addition of high antifriction layer outside the electroplated metal layer of script, be effectively protected holding diamond particles
Coating be subject to cutting particle reverse grinding, effectively extend the service life of diamond tool.
3rd, the present invention can carry out overall reinforcing to coating, it is also possible to the independent reinforcing of weak spot, and reinforcing works well, effectively
The diamond tool that solves the problems, such as prepare the uneven short slab for bringing, protect weak link, improve diamond tool blade layer
Utilization rate, extension uses service life, reduces cutting cost.
4th, the present invention is that subsequent step is added on the basis of script electroplated diamond technique, simple to operate, convenient, not right
Former technique produces influence.
5th, the present invention can flexibly change according to the processing characteristic of diamond tool, can be needed to choose different according to different cuttings
The grain matches of granularity, choose different coating methods, it might even be possible to mix superhard aggregate using coating and prepare high antifriction layer.
6th, the superhard characteristic of superhard particles material and super abrasive characteristic are combined together in the present invention, is given full play to
The characteristic of superhard material.
7th, the present invention is directed the common problem of diamond tool, technology can do appropriate change and apply to portion big absolutely at present
Parting diamond tool is prepared in link, helps to improve the technology of preparing of diamond tool.
8th, present invention is particularly suitable for high-speed cutting flexible diamond tool (diamond fretsaw, annular diamond fretsaw,
Band-saw diamond etc.), with process is simple, the characteristics of effect is significant.
9th, in the present invention, will be greatly increased by the service life of the diamond fretsaw after Combined Processing, generally use the longevity
Life can extend 2~3 times.
10th, the composite construction for being prepared by the present invention just reinforcement defect, strengthens weakest link, effectively prevent
The puzzlement that " Bucket Principle " brings, extends the service life of diamond tool, improves the utilization rate of diamond tool, it is ensured that
Machining accuracy.
(4) illustrate:
Fig. 1 is the structural representation of one embodiment of the present invention.
Fig. 2 is enlarged drawing at the A in Fig. 1 implementation methods.
Figure number is identified:1st, matrix;2nd, blade layer;3rd, superhard coarse grain;4th, electrodeposit metals layer;5th, high antifriction layer;6th, it is superhard
Particulate.
(5) specific embodiment:
Illustrated embodiment is described further to technical scheme below in conjunction with the accompanying drawings.
The technical scheme of diamond cutting tool of the present invention with composite structure plating, including matrix 1 and conduct cutting
Partial blade layer 2, the blade layer 2 includes being connected with the electrodeposit metals layer 4 of superhard coarse grain 3, the electrodeposit metals layer 4
It is attached on matrix 1 by first time plating mode, high antifriction layer 5 is attached to by electrodeposit metals layer by second time electroplating mode
On 4, the electrodeposit metals layer 4 is, with nickel or nickel cobalt (alloy) that nickel sulfamic acid is main salt, to be inlaid with the high antifriction layer 5
Superhard particulate 6, in conventional design, the superhard coarse grain 3 exposes high antifriction layer 5, and high antifriction layer 5 and electrodeposit metals layer 4 are constituted
The composite structure plating of blade layer 2, as shown in Figure 1 and Figure 2.
The superhard coarse grain 3 and superhard particulate 6 can select diamond or from polycrystalline cubic boron nitride (PCBN) or
From other superabrasive particles, or both, any mix and match selection between three.
To obtain preferably cutting and anti-wear effect, Xuan Ze≤200 μm of the particle diameter of superhard coarse grain 3 are described superhard thin
Xuan Ze≤50 μm of 6 particle diameters of grain;The ratio between further selection, superhard coarse grain 3 and particle diameter of superhard particulate 6 more than 2 times, generally
In the case of, when particle diameter is bigger, multiple is smaller, and when particle diameter is got over hour, multiple is bigger.
By taking diamond as an example, the particle diameter of superhard coarse grain 3 is preferably 120 μm (140#~170#), the preferred grain of superhard particulate 6
Preferably 40 μm of footpath (w40).
To reach the requirement that plates to superhard coarse grain 3, the electroplating thickness of the high antifriction layer 5 is selected between 30 μm~40 μm
Select.
The preparation method of the diamond cutting tool with composite structure plating, can take following processing step:
1st, the superhard coarse grain 3 and superhard particulate 6 of particle size matching, superhard coarse grain 3 and the preferred diamond of superhard particulate 6 are chosen
Grain.
2nd, diamond particle surfaces pretreatment.Diamond particles are placed in alkaline solution (NaOH), in 70 DEG C of alkalescence
30 minutes are incubated in solution, after removal surface grease, are washed with clear water;It is 3 that the diamond particles of washes clean are placed in volume ratio:
1 concentrated hydrochloric acid (HCl) and concentrated nitric acid (HNO3) in, soak 24 hours, after removing the metal oxide of diamond particle surfaces, use
Clear water is washed.
3rd, the diamond particles after abovementioned steps are processed are placed in cationic surfactant solution, to cationic
Surfactant solution apply 0.1~0.2V positive potential, the cation of cationic surface active agent in the presence of electrophoresis,
One layer of film with positive charge is formed in diamond particle surfaces.
4th, it is 0.8A/dm in current density using micromicrofarad is buried2~1.0A/dm2(preferably 1.0A/dm2), temperature is 45 ± 5
Electrodeposit metals 4 (being attached on matrix 1) of layer are prepared under the process conditions of DEG C (preferably 45 DEG C), superhard coarse grain 3 is uniform affixed
After in electrodeposit metals layer 4, washed with clear water.
5th, it is 0.5A/dm in current density using plating or brush technique2~0.6A/dm2(preferably 0.5A/dm2), temperature
Under spending for 45 ± 5 DEG C of process conditions of (preferably 45 DEG C), (kept outstanding when superhard particulate 6 is sufficiently stirred for dispersion in the electrolytic solution
Floating state) plating afterwards, in high antifriction layer 5 is prepared on electrodeposit metals layer 4, superhard particulate 6 is uniformly embedded in high antifriction layer 5.
So far, the electrodeposit metals layer 4 of affixed superhard coarse grain 3 is collectively forming gold with the high antifriction layer 5 for inlaying superhard particulate 6
The composite structure plating of the blade layer 2 of hard rock cutting tool, can select blade layer 2 to be continuously distributed or be according to cutting condition
Disjunct distribution is irregular distribution.
6th, after the completion of plating, decorated, quality inspection.
A kind of embodiment of specific diamond cutting tool (annular diamond double-cutting band saw):It is 3800mm to use specification
The stainless steel band of × 8mm × 0.2mm, the two ends of stainless steel band are welded into annular;The steel band positive and negative (inner peripheral surface,
Outer circumference surface) both sides (width) edge and edge be coated with symmetrical diamond coating, diamond coating is along steel band
Length direction (circumferencial direction) it is continuously distributed;Band saw prepares one-shot forming, and because girth is more long, CURRENT DISTRIBUTION is uneven, meeting
There is diamond particles phenomenon pockety, wherein from conductiving point more away from, plate weaker, diamond more easily comes off, can
Weak spot is strengthened in second plating.
1st, the stainless steel band of 3800mm × 8mm × 0.2mm is chosen, by seamless welding technology by the initial and end of stainless steel band
End welding is circularized, and pre-treatment step according to plating diamond tool matrix is processed.
2nd, the diamond abrasive material particles of the suitable two kinds of different-grain diameters (140#~170# and W40) of size are chosen, and
Carry out step-by-step processing:
The first step, diamond particle surfaces pretreatment.Required diamond abrasive material particles are placed in alkaline solution (NaOH),
70 DEG C of insulation 30min are maintained at, after removal surface grease, are washed with clear water.
Second step, it is 3 that the diamond abrasive material particles of washes clean are placed in volume ratio:1 concentrated hydrochloric acid (HCl) and concentrated nitric acid
(HNO3) in, soak 24 hours, after removing the metal oxide of diamond particle surfaces, washed with clear water.
3rd step, diamond particle surfaces cationization.Diamond abrasive material particles after second step is processed be placed in sun from
In subtype surfactant solution, the positive potential of 0.1V~0.2V, cationic are applied to cationic surface active agent solution
The cation of surfactant forms one layer of film with positive charge in the presence of electrophoresis in diamond particle surfaces.
3rd, by diamond particles (the superhard coarse grain 3) isotropic consolidation of surface cationic in electrodeposit metals layer 4, in steel
The blade layer 2 of single coating is formed in belt edge, and takes out clear water and rinsed well.Wherein, the plating mode is electroplated with watt type
Liquid is electrolyte, and main salt is nickel sulfamic acid, and anode is nickel wire and nickel ball, and stainless steel band is negative electrode, is 1A/ in current density
dm2, temperature is under conditions of 45 DEG C, the diamond particles of leaching surface cationic are prepared using micromicrofarad is buried.
4th, after the completion of prepared by single coating blade layer 2, clean up, as early as possible into the preparation of high antifriction layer 5.
5th, by diamond particles (superhard particulate 6) another groove plating solution of addition of surface cationic, after ultrasonic disperse, hold
Continuous stirring plating solution, it is ensured that particle suspension.
6th, the circular band saw of third step moistened surface is put into aqueduct, after immersion 10min, is switched on power.
7th, it is 0.5A/dm in current density2~0.6A/dm2, temperature under 45 ± 5 DEG C of process conditions, electrodeposit metals
Plating prepares high antifriction layer 5 on layer 4, so as to form the blade layer 2 with composite deposite.
8th, decorated and quality inspection after the completion of preparing.
Claims (2)
1. the diamond cutting tool with composite structure plating, including flexible substrate (1) and blade layer (2), the blade layer
(2) including be connected with superhard coarse grain (3) electrodeposit metals layer (4), it is characterised in that:Electrodeposit metals layer (4) be with
Nickel sulfamic acid is the nickel or nickel cobalt (alloy) of main salt, is applied on electrodeposit metals layer (4) and is coated with high antifriction layer (5), the height
Superhard particulate (6) is inlaid with wearing layer (5), electrodeposit metals layer (4) and high antifriction layer (5) form the compound of blade layer (2)
Structure coating;Li Jing≤200 μm of the superhard coarse grain (3), Li Jing≤50 μm of the superhard particulate (6);To reach to super
Hard coarse grain (3) plates requirements, and the thickness of the high antifriction layer (5) is 30 μm~40 μm, the superhard coarse grain (3) and it is superhard carefully
Grain (6) is diamond or is polycrystalline cubic boron nitride.
2. there is the diamond cutting tool preparation method of composite structure plating, it is characterised in that take following processing step:
1., the surface preparation of the superhard particulate (6) of the superhard coarse grain (3) of Li Jing≤200 μm and Li Jing≤50 μm, will be required super
Hard coarse grain (3) and superhard particulate (6) are placed in after removing surface grease in alkaline solution, are washed with clear water, are subsequently placed in volume ratio
It is 3:In 1 concentrated hydrochloric acid and concentrated nitric acid, after removing the metal oxide on superhard coarse grain (3) and superhard particulate (6) surface, clear water is used
Washing;
2., superhard coarse grain (3) and superhard particulate (6) surface cationic, superhard coarse grain (3) after the first step is processed and superhard
Particulate (6) is placed in cationic surface active agent solution, and 0.1~0.2V is being applied just to cationic surface active agent solution
Current potential, the cation of cationic surface active agent in the presence of electrophoresis, on superhard coarse grain (3) and superhard particulate (6) surface
Form one layer of film with positive charge;
3. electrodeposit metals layer (4), are prepared on flexible substrate (1) using burying micromicrofarad, electrodeposit metals layer (4) are with ammonia
Base nickel sulphonic acid is the nickel of main salt or with the nickel cobalt (alloy) that nickel sulfamic acid is main salt, and by the superhard coarse grain of surface cationic
(3) in electrodeposit metals layer (4), the technological parameter of electrodeposit metals layer (4) is isotropic consolidation:Current density is
0.8A/dm2~1.0A/dm2, temperature is 45 ± 5 DEG C;
4., continuously stirring plating solution makes superhard particulate (6) in suspended state, the electroplating deposition high abrasion on electrodeposit metals layer (4)
Layer (5), and the superhard particulate (6) of surface cationic is uniformly embedded in high antifriction layer (5), to reach to superhard coarse grain
(3) plate requirement, the thickness of the high antifriction layer (5) is 30 μm~40 μm, electrodeposit metals layer (4) and high antifriction layer (5)
It is collectively forming the composite structure plating of blade layer (2);High antifriction layer (5) the electroplating technique parameter is:Current density is
0.5A/dm2~0.6A/dm2, temperature is 45 ± 5 DEG C.
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CN105196196B (en) * | 2015-09-22 | 2017-12-22 | 郑州磨料磨具磨削研究所有限公司 | A kind of plated diamond grinding wheel of grinding material sequential arrangement |
WO2018084811A1 (en) * | 2016-11-07 | 2018-05-11 | Jcs Group Pte Ltd | A cutting wire and method of manufacture |
CN108747874A (en) * | 2018-05-31 | 2018-11-06 | 芜湖昌菱金刚石工具有限公司 | A kind of scuff-resistant coating diamond composite and preparation method thereof |
CN109183079B (en) * | 2018-08-14 | 2020-09-04 | 华侨大学 | Preparation method of high-self-sharpening metal-based diamond cutting blade |
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CN111593374A (en) * | 2020-07-01 | 2020-08-28 | 信丰崇辉科技有限公司 | Electroplating solution for diamond cutting wire and preparation method thereof |
CN112725856A (en) * | 2020-12-20 | 2021-04-30 | 华中光电技术研究所(中国船舶重工集团公司第七一七研究所) | Diamond drill bit with long service life and preparation method thereof |
CN115213824A (en) * | 2021-04-16 | 2022-10-21 | 王军林 | A high-performance diamond tool containing a wear-resistant matrix layer |
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JPH09150314A (en) * | 1995-11-27 | 1997-06-10 | Asahi Daiyamondo Kogyo Kk | Wire saw and manufacturing method thereof |
JP4083177B2 (en) * | 2005-02-25 | 2008-04-30 | 株式会社ノリタケスーパーアブレーシブ | Wire saw |
CN101602231B (en) * | 2009-06-26 | 2011-08-03 | 江苏锋菱超硬工具有限公司 | Preparation method of electroplating diamond fret saw |
JP5542938B2 (en) * | 2009-08-14 | 2014-07-09 | サンーゴバン アブレイシブズ,インコーポレイティド | Abrasive article comprising abrasive particles bonded to an elongated object |
CN102011168A (en) * | 2010-11-30 | 2011-04-13 | 哈尔滨工程大学 | Electroplated diamond bur and manufacturing method thereof |
CN204109153U (en) * | 2014-09-25 | 2015-01-21 | 中国有色桂林矿产地质研究院有限公司 | There is the diamond cutting tool of composite structure plating |
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Effective date of registration: 20241009 Address after: No. 20 Tieshan Road, Guilin High-tech Zone, Guangxi Zhuang Autonomous Region, 541004 Patentee after: Guilin Tebang New Materials Co.,Ltd. Country or region after: China Address before: 541004 auxiliary Star Road, Guilin City, the Guangxi Zhuang Autonomous Region, No. 9 Patentee before: CHINA NONFERROUS METAL (GUILIN)GEOLOGY AND MINING Co.,Ltd. Country or region before: China |