CN101823240A - The manufacture method of diamond fretsaw and diamond fretsaw - Google Patents
The manufacture method of diamond fretsaw and diamond fretsaw Download PDFInfo
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- CN101823240A CN101823240A CN201010124913A CN201010124913A CN101823240A CN 101823240 A CN101823240 A CN 101823240A CN 201010124913 A CN201010124913 A CN 201010124913A CN 201010124913 A CN201010124913 A CN 201010124913A CN 101823240 A CN101823240 A CN 101823240A
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Abstract
The invention provides the manufacture method of diamond fretsaw and this diamond fretsaw, in the described diamond fretsaw, cover the whole outer surface that dispersion maintains the metal coremaking line of diamond abrasive grain by coating, the nickel alloy that contains tungsten by employing has sufficient hardness as coating, sharpness is good when therefore using, and is difficult for broken string.In addition, the invention provides the manufacture method of diamond fretsaw and this diamond fretsaw, in the described diamond fretsaw, cover the whole outer surface of the diamond fretsaw that comprises coating and diamond abrasive grain by metallic film, thereby make the retentivity height that on the outer surface of metal coremaking line, disperses the diamond abrasive grain of maintenance, and do not damage the sharpness when using.
Description
Technical field
The present invention relates to the manufacture method of diamond fretsaw and this diamond fretsaw.
Background technology
When making various semiconductor devices, raw material ingot cutting processing silicon, crystal etc., for example column that will comprise monocrystalline, polycrystalline or amorphous by slice processing is the thin plate (wafer) of predetermined thickness dimension.As being used for high accuracy and low price, attempting using with the abrasive particle for example online peripheral surface of super abrasive particle set of diamond etc. and the bonded-abrasive molded lines saw that forms to the processing method that so high fragile material cuts.
As such technology, following patent documentation 1～4 is arranged.
Following patent documentation 1 relates to the invention of scroll saw and manufacture method thereof, thus wherein disclose super abrasive particle be affixed to securely on the line and do not come off, the constant scroll saw that can access high cutting accuracy of thickness.
In addition, following patent documentation 2 relates to the manufacture method of scroll saw and the invention of manufacturing installation, wherein discloses to have the electro-deposition scroll saw that the low-density abrasive particle distributes.
In addition, following patent documentation 3 relates to the invention of scroll saw and manufacture method thereof, wherein discloses working (machining) efficiency high and difficult broken string and the high scroll saw of manufacturing efficient.
In addition, following patent documentation 4 relates to the invention of electro-deposition the Line tool and manufacture method thereof, wherein discloses the good electro-deposition the Line tool of sharpness.
But, the scroll saw described in the above-mentioned patent documentation 1～4 and electro-deposition the Line tool, the metal of plating is Ni, Cu etc. on the line, does not therefore have sufficient hardness, has sharpness problem poor, that break easily when using.
In addition, the scroll saw described in the above-mentioned patent documentation 1 will surpass the formation that abrasive particle is fixed on the surface owing to have by coating, and therefore super abrasive particle is only physically imbedded in the coating, has the low problem of retentivity.
In addition, the scroll saw described in the above-mentioned patent documentation 2,3 owing to use the covering abrasive particle that metal is arranged in the abrasive particle surface coverage, therefore has by coating and not only physically keeps abrasive particle but also chemically keep the advantage of abrasive particle.But, though the retentivity of abrasive particle improves, cover the also equal thickening of metal layer thickness of abrasive particle, there is the impaired problem of sharpness when using.
Patent documentation 1: Japanese kokai publication hei 9-150314 communique
Patent documentation 2: No. 4157724 communique of Japan Patent
Patent documentation 3: TOHKEMY 2004-50301 communique
Patent documentation 4: TOHKEMY 2006-181701 communique
Summary of the invention
Therefore, the objective of the invention is to solve above-mentioned existing issue, good and the diamond fretsaw of difficult broken string and the manufacture method of this diamond fretsaw of sharpness in use is provided by having sufficient hardness.In addition, the object of the present invention is to provide the high metallic film of retentivity of the diamond abrasive grain that disperses maintenance by on the whole outer surface of metal coremaking line, covering and do not damage the manufacture method of diamond fretsaw and this scroll saw of sharpness in use.
According to first feature of the invention described above, coating has the formation of the nickel alloy that contains tungsten, therefore has sufficient hardness as diamond fretsaw.Therefore, the good and difficult diamond fretsaw that breaks of the sharpness in the time of can obtaining using.
In addition, diamond fretsaw of the present invention except first feature with the invention described above, also has second feature, that is: nickel alloy contains the tungsten of 1 weight %～60 weight %.
According to second feature of the invention described above, except the action effect of first feature of the invention described above,, therefore, can make the coating that constitutes diamond fretsaw become good overlay film owing to have the formation that nickel alloy contains the tungsten of 1 weight %～60 weight %.
In the diamond fretsaw of the present invention, the outer surface of metal coremaking line cover by coating and this coating in disperse to maintain diamond abrasive grain, it the 3rd is characterized as: the whole outer surface that comprises the diamond fretsaw of described coating and described diamond abrasive grain is covered by metallic film.
The 3rd feature according to the invention described above, the outer surface of metal coremaking line is by disperseing to maintain diamond abrasive grain in coating covering and this coating, the whole outer surface that comprises the diamond fretsaw of described coating and described diamond abrasive grain is covered by metallic film, owing to have such formation, therefore diamond abrasive grain is not only kept by coating, and, can obtain the high diamond fretsaw of retentivity of diamond abrasive grain thus by the metallic film maintenance.
In addition, diamond fretsaw of the present invention except the 3rd feature with the invention described above, also has the 4th feature, that is: the thickness of metallic film is 0.001 μ m～1 μ m.
The 4th feature according to the invention described above, except the action effect of the 3rd feature with the invention described above, because having the thickness of metallic film is the formation of 0.001 μ m～1 μ m, therefore, can obtain having the retentivity of diamond abrasive grain and do not damage the diamond fretsaw of sharpness when using.
In addition, diamond fretsaw of the present invention, except the 3rd or the 4th feature with the invention described above, also have the 5th feature, that is: metallic film is to comprise the metal that is selected from a kind of element among Al, Mo, Nb, Si, Ti, V, W, Y and the Zr or comprise the alloy that is selected from the two or more elements among Al, Mo, Nb, Si, Ti, V, W, Y and the Zr.
The 5th feature according to the invention described above, except the action effect of the 3rd or the 4th feature with the invention described above, because having metallic film is the formation that comprises the metal that is selected from a kind of element among Al, Mo, Nb, Si, Ti, V, W, Y and the Zr or comprise the alloy of two or more elements, therefore, can obtain having the metallic film of high rigidity, not damage the diamond fretsaw of sharpness in the time of can obtaining using.
In addition, diamond fretsaw of the present invention each feature, also has the 6th feature in having the 3rd of the invention described above～5th, that is: the average grain diameter of diamond abrasive grain is 1 μ m～60 μ m.
The 6th feature according to the invention described above, in having the 3rd of the invention described above～5th action effect of each feature, because having the average grain diameter of diamond abrasive grain is the formation of 1 μ m～60 μ m, therefore, the abrasive particle diameter can be fully reduced, the diamond fretsaw of abrasive particle difficult drop-off can be obtained.
In addition, diamond fretsaw of the present invention, except having each feature among the 3rd of the invention described above～6th, also have the 7th feature, that is: the coverage rate of the diamond abrasive grain on the outer surface of metal coremaking line be metal coremaking line the whole outer surface area 1%～35%.
The 7th feature according to the invention described above, in having the 3rd of the invention described above～6th action effect of each feature, owing to have the coverage rate of the diamond abrasive grain on the outer surface of metal coremaking line and be 1%～35% formation of the whole outer surface area of metal coremaking line, therefore, the coverage rate of diamond abrasive grain is rested in the small range, can obtain the diamond fretsaw that particularly the sth. made by twisting Qu Buyi in using is broken.
In addition, the manufacture method of diamond fretsaw of the present invention, be used to be manufactured on the diamond fretsaw that disperses to maintain diamond abrasive grain on the outer surface of metal coremaking line, it has the 8th feature, promptly comprises: use the nickel-tungsten that disperses diamond abrasive grain and obtain in the solution that is dissolved with nickel and tungsten to bathe the diamond abrasive grain electro-deposition operation that described metal coremaking line is electroplated.
The 8th feature according to the invention described above, described manufacture method is used to be manufactured on the diamond fretsaw that disperses to maintain diamond abrasive grain on the outer surface of metal coremaking line, and comprise: use the nickel-tungsten that in the solution that is dissolved with nickel and tungsten, disperses diamond abrasive grain and obtain to bathe the diamond abrasive grain electro-deposition operation that described metal coremaking line is electroplated, owing to have such formation, therefore, by diamond abrasive grain electro-deposition operation, can on the outer surface of metal coremaking line, constitute the coating that comprises the nickel alloy that contains tungsten, and can make diamond abrasive grain disperse reliably to remain on the outer surface of metal coremaking line by this coating.Therefore, the good and difficult diamond fretsaw that breaks of the sharpness in the time of can making use.
In addition, the manufacture method of diamond fretsaw of the present invention except the 8th feature with the invention described above, also has the 9th feature, that is: the ratio of nickel and tungsten was 1: 9～9: 1 with molar ratio computing during nickel-tungsten was bathed.
The 9th feature according to the invention described above, except the action effect of the 8th feature with the invention described above, since have nickel-tungsten bathe in the ratio of nickel and tungsten be 1: 9～9: 1 formation with molar ratio computing, therefore, the nickel-tungsten plated film of accomplished abundant hardness stably.
In addition, the manufacture method of diamond fretsaw of the present invention except the 8th or the 9th feature with the invention described above, also has the tenth feature, that is: diamond abrasive grain electro-deposition operation is carried out under 50 ℃～75 ℃ bath temperature.
The tenth feature according to the invention described above, except the action effect of the 8th or the 9th feature with the invention described above, owing to have the formation that diamond abrasive grain electro-deposition operation is carried out under 50 ℃～75 ℃ bath temperature, therefore, can reduce the internal stress in the plated film effectively, can prevent to separate out unusually.Therefore, can obtain making the manufacture method of the diamond fretsaw of excellent in efficiency.
In addition, the manufacture method of diamond fretsaw of the present invention, except have the invention described above the 8th to the tenth in each feature, also have the 11 feature, that is: the solution during nickel-tungsten is bathed is the aqueous solution that is dissolved with diammonium hydrogen citrate, sodium formate, nickelous sulfate and sodium tungstate.
The 11 feature according to the invention described above, except have the invention described above the 8th to the tenth in the action effect of each feature, because the solution that has in nickel-tungsten bath is the formation that is dissolved with the aqueous solution of diammonium hydrogen citrate, sodium formate, nickelous sulfate and sodium tungstate, therefore, the stability of plating bath is high, the life-span is long, therefore can obtain the manufacture method of the good diamond fretsaw of productivity ratio.
In addition, the manufacture method of diamond fretsaw of the present invention is used to be manufactured on the diamond fretsaw that disperses to maintain diamond abrasive grain on the outer surface of metal coremaking line, and it has the 12 feature, that is, comprise:
Diamond abrasive grain electro-deposition operation is wherein used the nickel that disperses diamond abrasive grain and obtain in being dissolved with the solution of nickel to bathe described metal coremaking line is electroplated;
The metallic film covering process wherein further covers by described diamond abrasive grain electro-deposition operation in the whole outer surface that is dispersed with the metal coremaking line after electroplating under the state of diamond abrasive grain with metallic film; With
Heat treatment step is wherein heat-treated under the state that the whole outer surface that makes the metal coremaking line after electroplating under the state that is being dispersed with diamond abrasive grain by described metallic film covering process is covered by metallic film.
According to the 12 feature of the invention described above, described manufacture method is used to be manufactured on the outer surface of metal coremaking line and disperses to maintain the diamond fretsaw of diamond abrasive grain, and comprises:
Diamond abrasive grain electro-deposition operation is wherein used the nickel that disperses diamond abrasive grain and obtain in being dissolved with the solution of nickel to bathe described metal coremaking line is electroplated;
The metallic film covering process wherein further covers by described diamond abrasive grain electro-deposition operation in the whole outer surface that is dispersed with the metal coremaking line after electroplating under the state of diamond abrasive grain with metallic film; With
Heat treatment step is wherein heat-treated under the state that the whole outer surface that makes the metal coremaking line after electroplating under the state that is being dispersed with diamond abrasive grain by described metallic film covering process is covered by metallic film,
Owing to have such formation, therefore,, can make diamond abrasive grain disperse reliably to remain on the outer surface of metal coremaking line by diamond abrasive grain electro-deposition operation.In addition, by metallic film lining operation, can be on the whole outer surface of the metal coremaking line behind the plating under the state that diamond abrasive grain is disperseed coated metal film reliably.In addition, by heat treatment step, can make between metallic film, diamond abrasive grain and the coating and form chemical bond.Therefore, can obtain the high diamond fretsaw of retentivity of diamond abrasive grain.
According to the manufacture method of diamond fretsaw of the present invention and this diamond fretsaw, can obtain having sufficient hardness, the sharpness when using is good and is difficult for the diamond fretsaw of broken string and the manufacture method of this diamond fretsaw.In addition, can obtain on the outer surface of metal coremaking line disperseing the retentivity height of the diamond abrasive grain that keeps and do not damage the manufacture method of diamond fretsaw and this diamond fretsaw of sharpness when using.
Description of drawings
Fig. 1 is the stereogram of a part of the diamond fretsaw of expression first embodiment of the present invention.
Fig. 2 is the profile of the diamond fretsaw of first embodiment of the present invention, (a) is the meet at right angles whole profile of direction of axle with diamond fretsaw, (b) is the meet at right angles part amplification profile of direction of axle with diamond fretsaw.
Fig. 3 is the stereogram of a part of the diamond fretsaw of expression second embodiment of the present invention.
Fig. 4 is the profile of the diamond fretsaw of second embodiment of the present invention, (a) is the meet at right angles whole profile of direction of axle with diamond fretsaw, (b) is the meet at right angles part amplification profile of direction of axle with diamond fretsaw.
Fig. 5 is the figure of manufacturing process of the diamond fretsaw of simple expression first embodiment of the present invention.
Fig. 6 is the figure of the diamond abrasive grain electro-deposition operation in the manufacturing process of diamond fretsaw of simple expression first embodiment of the present invention.
Fig. 7 is the figure that the sclerosis of nickel-tungsten coating under heat treatment of the tungsten 40 weight % of expression first embodiment of the present invention changes.
Fig. 8 is the figure of manufacturing process of the diamond fretsaw of simple expression second embodiment of the present invention.
Symbol description
1 diamond fretsaw
10 metal coremaking lines
11 outer surfaces
20 coating
21 outer surfaces
30 diamond abrasive grains
31 outer surfaces
32 coating
40 metallic films
50 rollers
51 pulleys
52 rollers
60 degreasing baths
70 descaling baths
80 rinsing bowls
90 coating baths
91 anode chambers
The 91a insoluble anode
91b solution
The 91c cation-exchange membrane
Plating chambers 92
The 92a nickel anode
92b tungsten anode
The 92c plating liquor
100 rinsing bowls
200 power supplys
300 metal foil membrane formation devices
400 annealing devices
The specific embodiment
With reference to following accompanying drawing the diamond fretsaw of first and second embodiments of the present invention and the manufacture method of this diamond fretsaw are described, so that understand the present invention.But the following description is embodiments of the present invention, the content that the scope of patent request is not limited to put down in writing.
In addition, in the description of the drawings, identical key element is used identical symbol, and omits repeat specification.In addition, the dimensional ratios of accompanying drawing and explanation may not be consistent.
(first embodiment)
At first, with reference to figure 1, Fig. 2, the diamond fretsaw of first embodiment of the present invention is described.
The diamond fretsaw 1 of first embodiment of the present invention as shown in Figure 1 and Figure 2, is to disperse to keep diamond abrasive grain 30 and the diamond fretsaw that obtains in the coating 20 of the whole outer surface that covers metal coremaking line 10.
Described metal coremaking line 10 so long as can electroplate and have the metal system line of certain intensity to outer surface 11, then can be a metal system line arbitrarily.For example, can use steel wire, tungsten line, molybdenum wires etc. such as piano wire.
The diameter of metal coremaking line 10 can be according to appropriate changes such as the material that is cut material, shapes, preferred 0.05mm～0.30mm.
Described coating 20 is used to cover the outer surface 11 of metal coremaking line 10 as shown in Figure 1 and Figure 2, and makes diamond abrasive grain 30 disperse to remain on the metal coremaking line 10.
This coating 20 is made of the nickel alloy of tungstenic.By having such formation, only compare with coating 20 by the situation that nickel constitutes, the hardness of diamond fretsaw 1 can be improved, and corrosion resistance can be improved.Therefore, the good and difficult diamond fretsaw 1 that breaks of the sharpness in the time of can obtaining using.
The concentration that contains of tungsten is preferably 1 weight %～60 weight % in the nickel alloy.This be because, if be lower than 1 weight % then can not obtain the solid solution effect, if surpass 60 weight % then can not get good tunicle.
In addition, more preferably 10 weight %～40 weight %.
The thickness of coating 20 is preferably 20%～90% with respect to the diameter dimension of the diamond abrasive grain 30 on the diametric(al) of metal coremaking line 10.
In addition, more preferably 25%～80%, further preferred 30%～70%.
Described diamond abrasive grain 30 is the covering abrasive particle that outer surface 31 is covered by coating 32 as shown in Figure 2, in the coating 20 that is embedded to the outer surface that covers metal coremaking line 10, is disperseed to keep by coating 20.
Described coating 32 is made of nickel.By having such formation,, therefore, not only can physically remain on the metal coremaking line 10, and chemically remain on the metal coremaking line 10 by coating 20 because metal coremaking lines 10 such as nickel and piano wire have chemical affinity.Therefore, diamond abrasive grain 30 is firmly held on the outer surface of metal coremaking line 10.Therefore, diamond abrasive grain 30 comes off in the time of can preventing to use.In addition, a spot of coating 20 just can disperse diamond abrasive grain 30 to remain on the metal coremaking line 10, thereby can obtain making the good diamond fretsaw of efficient 1.
The average grain diameter of diamond abrasive grain 30 is preferably 1 μ m～60 μ m.By having such formation, can fully reduce the abrasive particle diameter, therefore, diamond abrasive grain 30 is difficult for coming off from metal coremaking line 10, can obtain the good diamond fretsaw of working (machining) efficiency 1.
In addition, average grain diameter is during less than 1 μ m, because abrasive particle is too small so working (machining) efficiency descends, and abrasive particle comes off easily when surpassing 60 μ m.
In addition, more preferably be limited to down more than above, the further preferred 3 μ m of 2 μ m, preferred upper limit is below the 50 μ m.
In addition, the coverage rate of the diamond abrasive grain 30 on the outer surface 11 of metal coremaking line 10 is preferably 1%～35%.By having such formation, coverage rate is rested in the fully little scope, can suppress to improve and the rigidity increase owing to the elastic modelling quantity of the diamond fretsaw 1 that disperses maintenance diamond abrasive grain 30 to cause.
In addition, guaranteed that the dissipation space of cutting powder is enough big, therefore,, further improved working (machining) efficiency even under the situation of glass or the quartzy material that is easy to generate obstruction like this, also can suppress to stop up.
In addition, coverage rate more preferably 1%～25%, further preferred 5%～25%.
In addition, in this first embodiment, adopt the formation that forms one deck coating 20, but be not limited to such formation, also can adopt the formation that forms multilayer coating 20.
For example, can have the la m that forms by nickel and the outside layer that forms with the nickel alloy of tungstenic this is two-layer.By having such formation, can obtain having the high diamond fretsaw of retentivity of sufficient hardness and diamond abrasive grain 30.
Below, with reference to figure 5～Fig. 7, the manufacture method of the diamond fretsaw of first embodiment of the present invention is described.
The diamond fretsaw 1 of first embodiment of the present invention, following as shown in Figure 5 manufacturing: make by the metal coremaking line of supplying with as the roller 50 of the supply source of metal coremaking line 10 10 by degreasing bath 60, descaling bath 70, rinsing bowl 80, coating bath 90 and rinsing bowl 100 by pulley 51, and batch by roller 52.
Described pulley 51 is used to change the direct of travel of metal coremaking line 10, as shown in Figure 5, and above degreasing bath 60, descaling bath 70, rinsing bowl 80, coating bath 90, rinsing bowl 100 and be provided with a plurality of in the groove.
Described degreasing bath 60 is to store for example groove of NaOH (NaOH) aqueous solution, by having the degreasing process of this degreasing bath 60, the soil release such as oil content of adhering on the surface with metal coremaking line 10.
In addition, the aqueous solution that stores in the degreasing bath 60 is so long as to be generally used for the aqueous solution of degreasing bath then can be the aqueous solution arbitrarily.
Described descaling bath 70 is to store for example groove of hydrochloric acid (HCl) aqueous solution, and by having the pickling process of this descaling bath 70, the oxide skin(coating) (rust) that adheres on the surface with metal coremaking line 10 is removed.
In addition, the aqueous solution that stores in the descaling bath 70 then can be the aqueous solution arbitrarily so long as be generally used for the aqueous solution of descaling bath.
Described rinsing bowl 80 is the grooves that store running water, well water, pure water, by having the washing step of this rinsing bowl 80, can dilute the chemicals that adheres on the surface of metal coremaking line 10, thereby can prevent that chemicals from sneaking into subsequent processing is in the coating in the diamond abrasive grain electro-deposition operation.
Described coating bath 90 is grooves of bearing diamond abrasive grain electro-deposition operation, in the described diamond abrasive grain electro-deposition operation, uses the nickel-tungsten that disperses diamond abrasive grain 30 and obtain in the solution that is dissolved with tungsten and nickel to bathe, and metal coremaking line 10 is electroplated.
Below, with reference to figure 6, diamond abrasive grain electro-deposition operation is elaborated.
Diamond abrasive grain electro-deposition operation uses the coating bath 90 that is divided into the dual-slot structure of anode chamber 91 and plating chamber 92 by cation-exchange membrane 91c described later to carry out as shown in Figure 6.
Described anode chamber 91, insoluble anode 91a, the solution 91b and the cation-exchange membrane 91c that are connected by the anode with power supply 200 constitute.
Described insoluble anode 91a is so long as the insoluble anode that stainless steel, platinum etc. usually use as insoluble anode then can be an insoluble anode arbitrarily.
Described solution 91b can use nickel salt beyond demineralizing acid, nitric acid and the salt thereof, sulfuric acid etc.Hydrochloric acid, nitric acid and salt thereof produce harmful chlorine, nitrogen oxide gas on insoluble anode, therefore can not use.
Described cation-exchange membrane 91c is to be used for preventing that insoluble anode 91a from directly contacting with plating liquor 92c described later and the selective membrane of the oxidation Decomposition of the citric acid that prevents to exist as anion at plating liquor 92c etc.
By using like this coating bath 90 that is divided into the dual-slot structure of anode chamber 91 and plating chamber 92 by cation-exchange membrane 91c to carry out diamond abrasive grain electro-deposition operation, can improve the stability of plating liquor 92c, for a long time continuous electroplating.
In addition, it is cation that insoluble anode 91a goes up the hydrogen ion that produces, and therefore sees through cation-exchange membrane 91c according to the magnitude of current that passes through, and is transported to plating chamber 92.
Described plating chamber 92, nickel anode 92a, the tungsten anode 92b and the plating liquor 92c that are connected by the anode with power supply 200 constitute.
Described nickel anode 92a for tabular, is used for replenishing nickel ion to plating liquor 92c as shown in Figure 6.As nickel anode 92a, can use the known plates that can be used in nickel plating such as electrolytic nickel, S-nickel.
In addition, in this first embodiment, nickel anode 92a adopts tabular formation, still, is not necessarily limited to such formation, also can adopt the formation of using the strip nickel anode.When using the strip nickel anode, the basket of putting into titanium system uses.
In addition, because the dissolved state of nickel anode 92a is a cation, therefore, nickel anode 92a also can adopt and not be configured among the plating chamber 92a and be configured in formation in the anode chamber 91.
Described tungsten anode 92b for tabular, is used for replenishing the tungsten composition to plating liquor 92c as shown in Figure 6.As tungsten anode 92b, can use tungsten.
In addition, in this first embodiment, tungsten anode 92b adopts and is tabular formation, still, is not necessarily limited to such formation, also can adopt the formation of using strip tungsten anode.When using strip tungsten anode, the basket of putting into titanium system uses.
Described plating liquor 92c is to make nickel and tungsten be dissolved in the aqueous solution of nickelous sulfate etc. and be dispersed with not shown diamond abrasive grain 30 and the nickel tungsten that obtains is bathed.More specifically, constitute by diammonium hydrogen citrate, sodium formate, nickelous sulfate and sodium tungstate.
By having such formation, the stability of plating bath is high, the life-span is long, therefore, can obtain the manufacture method of the good diamond fretsaw of productivity ratio.
At this, the ratio of nickel and tungsten was 1: 9 to 9: 1 with molar ratio computing during nickel tungsten was bathed.By having such formation, the nickel of accomplished abundant hardness-tungsten plated film stably.
Use such plating liquor 92c, as shown in Figure 6, metal coremaking line 10 is impregnated among the plating liquor 92c, the negative pole of power supply 200 is connected with metal coremaking line 10, and the anode of power supply 200 is connected with tungsten anode 92b with insoluble anode 91a, nickel anode 92a, suitably select current density and electroplating time to electroplate, on the outer surface 11 of metal coremaking line 10, form coating 20 thus, and make diamond abrasive grain 30 disperse to remain on the outer surface 11.
Described rinsing bowl 100 is the grooves that store running water, well water, pure water, by having the washing step of this rinsing bowl 100, after washing at the metal coremaking line 10 that disperses to maintain diamond abrasive grain 30 on the outer surface 11, heat-treat by not shown heat treatment step, thereby make diamond fretsaw 1.
In addition, diamond abrasive grain electro-deposition operation is not limited to the electro-deposition operation of this first embodiment.
For example, can adopt following formation: between rinsing bowl 80 and coating bath 90, be provided with that use disperses diamond abrasive grain 30 in being dissolved with the solution of nickel and the nickel that obtains is bathed the groove of electroplating.In addition, at this moment, do not disperse diamond abrasive grain 30 among the plating liquor 92c of coating bath 90.
By having such formation, and electroplate, diamond abrasive grain 30 is temporarily fixed on the outer surface of metal coremaking line 10 by using nickel to bathe.Afterwards, electroplate, diamond abrasive grain 30 is fixedly attached on the outer surface of metal coremaking line 10 by using nickel tungsten to bathe.
Because the electroplating current efficient of using nickel tungsten to bathe is low, in addition, the upper limit of the current density of using is also low, therefore compare with the plating of using nickel to bathe, form same thickness and need spend more time, by using nickel to bathe diamond abrasive grain 30 is temporarily fixed on the outer surface of metal coremaking line 10, can shortens electroplating time.Therefore, can make the good diamond fretsaw of efficient.
Below, enumerate embodiment, illustrate in greater detail the present invention, still, the invention is not restricted to these embodiment.
By Fig. 5, operation shown in Figure 6, make diamond fretsaw 1.
After dipping carried out ungrease treatment in degreasing bath 60, descaling bath 70 and rinsing bowl 80 continuously with 10m/ minute transporting velocity with the long piano wire of diameter 0.14mm, carry out the diamond abrasive grain electro-deposition operation of in the coating bath 90 of the dual-slot structure that is divided into anode chamber 91 and plating chamber 92 by cation-exchange membrane 91c, electroplating.
At this, the prescription of plating bath is in the coating bath 90: diammonium hydrogen citrate 0.4mol, sodium formate 0.2mol, nickelous sulfate 0.2mol, sodium tungstate 0.2mol.
In addition, plating condition is: bathe temperature 65 ℃, current density 10A/dm
2, 7.5 minutes time, pH6.0, normalized current efficient 55%.
In addition, be dispersed in the diamond abrasive grain 30 in the plating bath, the nickel plating diamond abrasive grain that uses outer surface to cover by nickel.Nickel plating amount is 30 weight % with respect to diamond abrasive grain, and the average grain diameter of diamond abrasive grain 30 is 13.4 μ m.In plating chamber 92, drop into this diamond abrasive grain 30 of 0.25g/L.
After carrying out diamond abrasive grain electro-deposition operation, the metal coremaking line 10 after the electro-deposition end is washed in rinsing bowl 100, under 600 ℃, heat-treated again, obtain the diamond fretsaw of hardness 1000HV (Vickers hardness).The tungsten ratio on the surface of this diamond fretsaw is 40 weight %.
As the reference data, the sclerosis of the nickel-tungsten alloy plating of tungsten 40 weight % under heat treatment changes as shown in Figure 7.
By Fig. 5, operation shown in Figure 6, make diamond fretsaw.
After dipping carried out ungrease treatment in degreasing bath 60, descaling bath 70 and rinsing bowl 80 continuously with 10m/ minute transporting velocity with the long piano wire of diameter 0.14mm, in not shown coating bath, use the nickel that in being dissolved with the solution of nickel, disperses diamond abrasive grain 30 and obtain to bathe and electroplate.
At this, the prescription that nickel is bathed is: nickel sulfate hexahydrate compound 240g/L, nickel chloride hexahydrate 45g/L, boric acid 30g/L.
In addition, plating condition is: bathe temperature 50 ℃, current density 20A/dm
2, 1 minute time, pH4.0.
In addition, be dispersed in the diamond abrasive grain 30 in the nickel bath, the nickel plating diamond abrasive grain that uses outer surface to cover by nickel.Nickel plating amount is 30 weight % with respect to diamond abrasive grain, and the average grain diameter of diamond abrasive grain 30 is 13.4 μ m.In being dissolved with the solution of nickel, drop into this diamond abrasive grain 30 of 0.25g/L.
The identical nickel coating of thickness when as a result, formation is carried out electroplating in 3.5 minutes with the bath of use nickel tungsten.
Afterwards, in the coating bath 90 of the dual-slot structure that is divided into anode chamber 91 and plating chamber 92 by cation-exchange membrane 91c, use nickel tungsten to bathe and electroplate.
At this, the prescription of plating bath is in the coating bath 90: diammonium hydrogen citrate 0.4mol, sodium formate 0.2mol, nickelous sulfate 0.2mol, sodium tungstate 0.2mol.
In addition, plating condition is: bathe temperature 65 ℃, current density 10A/dm
2, 3.75 minutes time, pH6.0, normalized current efficient 55%.
Afterwards, metal coremaking line 10 is washed in rinsing bowl 100, under 600 ℃, heat-treated again.
As a result, obtain having diamond fretsaw with the hardness 950HV of the diamond fretsaw same degree shown in the embodiment 1.
The tungsten ratio on the surface of this diamond fretsaw is 38 weight %.
(second embodiment)
At first, with reference to figure 4, the diamond fretsaw of second embodiment of the present invention is described.
The diamond fretsaw 1 of second embodiment of the present invention, as shown in Figure 3, Figure 4, the outer surface 11 that is metal coremaking line 10 is by disperseing to maintain diamond abrasive grain 30 in coating 20 coverings and this coating 20, in addition, comprise the diamond fretsaw that the whole outer surface of the diamond fretsaw of coating 20 and diamond abrasive grain 30 is covered by metallic film 40.
Described metal coremaking line 10 so long as can electroplate and have the metal system line of certain intensity to outer surface 11, then can be a metal system line arbitrarily.For example, can use steel wire, tungsten line, molybdenum wires etc. such as piano wire.
The diameter of metal coremaking line 10 can be according to appropriate changes such as the material that is cut material, shapes, preferred 0.05mm～0.30mm.
Described coating 20 is used to cover the outer surface 11 of metal coremaking line 10 as shown in Figure 4, and makes diamond abrasive grain 30 disperse to remain on the metal coremaking line 10.
This coating 20 is made of nickel alloys such as nickel (Ni) or nickel tungstens.Certainly, be not limited to nickel (Ni), so long as the common material that uses as the metal or alloy of the coating that constitutes diamond fretsaw then can use any materials, as described later, preferably constitute the material of alloys and formation chemical bond through heat treatment steps with metallic film 40.
The thickness of coating 20 is preferably 5%～90% with respect to the diameter dimension of the diamond abrasive grain 30 on the diametric(al) of metal coremaking line 10.
In addition, more preferably 25%～80%, further preferred 30%～70%.
Described diamond abrasive grain 30 in the coating 29 that is embedded to the outer surface 11 that covers metal coremaking line 10, is disperseed to keep by coating 20 as shown in Figure 4.
The average grain diameter of diamond abrasive grain 30 is preferably 1 μ m～60 μ m.By having such formation, can fully reduce the abrasive particle diameter, therefore, diamond abrasive grain 30 is difficult for coming off from metal coremaking line 10, can obtain the good diamond fretsaw of working (machining) efficiency 1.
In addition, average grain diameter is during less than 1 μ m, because abrasive particle is too small so working (machining) efficiency descends, and abrasive particle comes off easily when surpassing 60 μ m.
In addition, more preferably be limited to down more than above, the further preferred 3 μ m of 2 μ m, preferred upper limit is below the 50 μ m.
In addition, the coverage rate of the diamond abrasive grain 30 on the outer surface 11 of metal coremaking line 10 is preferably 1%～35%.By having such formation, coverage rate is rested in the fully little scope, can suppress to improve and the rigidity increase owing to the elastic modelling quantity of the diamond fretsaw 1 that disperses maintenance diamond abrasive grain 30 to cause.
In addition, guaranteed that the dissipation space of cutting powder is enough big, therefore,, further improved working (machining) efficiency even under the situation of glass or the quartzy material that is easy to generate obstruction like this, also can suppress to stop up.
In addition, coverage rate more preferably 1%～25%, further more preferably 5%～25%.
Described metallic film 40 is the metallic films that cover the whole outer surface of the diamond fretsaw 1 that comprises coating 20 and diamond abrasive grain 30.More specifically, as shown in Figure 4, be the metallic film of whole outer surface of diamond fretsaw 1 that covers the outer surface 31 of the outer surface 21 comprise coating 20 and diamond abrasive grain 30.
By having such formation, the diamond abrasive grain that disperses to keep by coating 20 is remained on the outer surface 11 of metal coremaking line 10 more firmly.Therefore, can obtain the high diamond fretsaw 1 of retentivity of diamond abrasive grain 30.
In addition, all pass through heat treatment step by the every kind of metal that makes aluminium (Al), molybdenum (Mo), niobium (Nb), silicon (Si), titanium (Ti), vanadium (V), tungsten (W), yttrium (Y), zirconium (Zr), make they and diamond abrasive grain 30 reaction, form metal carbides as carbon simple substance.Therefore, can obtain having the diamond fretsaw 1 of high rigidity.Therefore, the diamond fretsaw 1 that the sharpness in the time of can obtaining using is good.
In addition, by adopting the constituting of whole outer surface that covers the diamond fretsaw 1 that comprises coating 20 and diamond abrasive grain 30 by metallic film 40, make every kind of metal of the aluminium (Al) that constitutes metallic film 40, molybdenum (Mo), niobium (Nb), silicon (Si), titanium (Ti), vanadium (V), tungsten (W), yttrium (Y), zirconium (Zr) all pass through heat treatment step, between coating 20 that constitutes by nickel (Ni) and diamond abrasive grain 30, form chemical bond thus.Therefore, can obtain the high diamond fretsaw 1 of retentivity of diamond abrasive grain 30.
The thickness of metallic film 40 is preferably 0.001～1 μ m.Because: if less than 0.001 μ m, then the retentivity of diamond abrasive grain 30 is insufficient, if surpass 1 μ m, can not obtain high sharpness when then using.Therefore, the thickness by making metallic film 40 is 0.001～1 thin μ m, can obtain the diamond fretsaw 1 of the sharpness formedness that can realize the high retentivity of diamond abrasive grain 30 simultaneously and use when.
In addition, the thickness of metallic film 40 0.01 μ m～0.1um more preferably.
Below, with reference to figure 8, the manufacture method of the diamond fretsaw of second embodiment of the present invention is described.
The diamond fretsaw 1 of second embodiment of the present invention, as following manufacturing shown in Fig. 8 is concise and to the point: make by the metal coremaking line of supplying with as the roller 50 of the supply source of metal coremaking line 10 10 by degreasing bath 60, descaling bath 70, rinsing bowl 80, coating bath 90, rinsing bowl 100, metal foil membrane formation device 300 and annealing device 400 by pulley 51, and batch by roller 52.
Described pulley 51 is used to change the direct of travel of metal coremaking line 10, as shown in Figure 8, above degreasing bath 60, descaling bath 70, rinsing bowl 80, coating bath 90, rinsing bowl 100, metal foil membrane formation device 300, annealing device 400 and in the groove, be provided with in the device a plurality of.
Described degreasing bath 60 is to store for example groove of NaOH (NaOH) aqueous solution, by having the degreasing process of this degreasing bath 60, the soil release such as oil content of adhering on the surface with metal coremaking line 10.
In addition, the aqueous solution that stores in the degreasing bath 60 is so long as to be generally used for the aqueous solution of degreasing bath then can be the aqueous solution arbitrarily.
Described descaling bath 70 is to store for example groove of hydrochloric acid (HCl) aqueous solution, and by having the pickling process of this descaling bath 70, the oxide skin(coating) (rust) that adheres on the surface with metal coremaking line 10 is removed.
In addition, the aqueous solution that stores in the descaling bath 70 then can be the aqueous solution arbitrarily so long as be generally used for the aqueous solution of descaling bath.
Described rinsing bowl 80 is the grooves that store running water, well water, pure water, by having the washing step of this rinsing bowl 80, can dilute the chemicals that adheres on the surface of metal coremaking line 10, thereby can prevent that chemicals from sneaking into subsequent processing is in the coating in the diamond abrasive grain electro-deposition operation.
Described coating bath 90 is grooves of bearing the diamond abrasive grain electro-deposition operation that metal coremaking line 10 is electroplated.Diamond abrasive grain electro-deposition operation, shown in Fig. 8 is concise and to the point, by with the negative pole of power supply 200 with pass the metal coremaking line 10 that possesses the coating bath 90 that the nickel that obtains among the solution 92c that diamond abrasive grain 30 is dispersed in be dissolved with nickel bathes and be connected, and the positive pole of power supply 200 be connected with nickel anode 92a in impregnated in coating bath 90 carry out.In addition, though not shown,, constitute as the coating bath and the electrode of first embodiment of the present invention, also can carry out nickel alloy platings such as nickel tungsten.
At this, the diamond abrasive grain 30 that disperses in the coating bath 90 uses the diamond abrasive grain after handling in advance in cationic surfactant solution.By having such formation, can make diamond abrasive grain 30 positively charged.Therefore, on the metal coremaking line 10 that can diamond abrasive grain 30 is adsorbed onto to be connected with negative pole.Therefore,, therefore, can improve the transporting velocity of metal coremaking line 10 in the coating bath 90 before obtaining by the abrasive particle maintenance effect of electroplating generation, make efficient thereby improve even the diamond abrasive grain 30 that adhered on the metal coremaking line 10 is also incrust.
In addition, the transporting velocity of metal coremaking line 10 is preferably 1m/ minute～100m/ minute in the coating bath 90.
In addition, as cationic surfactant, can use monoethanolamine, triethanolamine etc.
By this diamond abrasive grain electro-deposition operation, on the outer surface 11 of metal coremaking line 10, form coating 20, and disperse to keep diamond abrasive grain 30 by this coating 20.
Described rinsing bowl 100 is the grooves that store running water, well water, pure water, by having the washing step of this rinsing bowl 100, the metal coremaking line 10 that disperses to maintain diamond abrasive grain 30 on outer surface 11 is washed.
Described metal foil membrane formation device 300 is devices of bearing the metallic film covering process, in the described metallic film covering process, further with the whole outer surface of metallic film 40 coverings by the metal coremaking line 10 of diamond abrasive grain electro-deposition operation after electroplating under the state that is dispersed with diamond abrasive grain 30.
This metal foil membrane formation device 300, detailed icon not in Fig. 8 is the device that forms metallic film 40 on the whole outer surface that is dispersed with the metal coremaking line 10 after electroplating under the state of diamond abrasive grain by sputtering method.
By such metallic film covering process, further cover by diamond abrasive grain electro-deposition operation in the whole outer surface that is dispersed with the metal coremaking line 10 after electroplating under the state of diamond abrasive grain, can will remain on the outer surface 11 of metal coremaking line 10 by the diamond abrasive grain 30 that coating 20 disperses to keep more firmly thus with metallic film 40.Therefore, can obtain the high diamond fretsaw 1 of retentivity of diamond abrasive grain 30.
Metal as constituting metallic film 40 can use to comprise metal that is selected from a kind of element in aluminium (Al), molybdenum (Mo), niobium (Nb), silicon (Si), titanium (Ti), vanadium (V), tungsten (W), yttrium (Y), the zirconium (Zr) or the alloy that comprises two or more elements.
The thickness of metallic film 40 is preferably 0.001～1 μ m.Because: if less than 0.001 μ m, then the retentivity of diamond abrasive grain 30 is insufficient, if surpass 1 μ m, can not obtain high sharpness when then using.Therefore, the thickness by making metallic film 40 is 0.001～1 thin μ m, can obtain the diamond fretsaw 1 of the sharpness formedness that can realize the high retentivity of diamond abrasive grain 30 simultaneously and use when.
In addition, the thickness of metallic film 40 0.01 μ m～0.1 μ m more preferably.
In addition, in this second embodiment, adopt the formation that forms metallic film 40 by sputtering method, still as the vacuum plating, be not necessarily limited to such formation, also can wait other vacuum plating or chemical plating to form metallic film 40 by PVD (physical vapor deposition), CVD (chemical vapor deposition method).
Described annealing device 400 is devices of bearing heat treatment step, in the described heat treatment step, under the state that the whole outer surface that makes the metal coremaking line 10 after electroplating under the state that is being dispersed with diamond abrasive grain 30 by the metallic film covering process is covered by metallic film 40, heat-treat.
By carrying out this heat treatment step, can obtain following effect.
At first, all pass through heat treatment step by the every kind of metal that makes the aluminium (Al) that constitutes metallic film 40, molybdenum (Mo), niobium (Nb), silicon (Si), titanium (Ti), vanadium (V), tungsten (W), yttrium (Y), zirconium (Zr), make they and the nickel (Ni) that constitutes coating 20 form alloy.
Therefore, can obtain having the diamond fretsaw 1 of high rigidity.Therefore, the broken string in the time of can preventing to use.
In addition, all pass through heat treatment step by the every kind of metal that makes the aluminium (Al) that constitutes metallic film 40, molybdenum (Mo), niobium (Nb), silicon (Si), titanium (Ti), vanadium (V), tungsten (W), yttrium (Y), zirconium (Zr), make they and diamond abrasive grain 30 reaction, form metal carbides as carbon simple substance.
Therefore, can obtain having the diamond fretsaw 1 of high rigidity.Therefore, the diamond fretsaw 1 that the sharpness in the time of can obtaining using is good.
In addition, all pass through heat treatment step by the every kind of metal that makes the aluminium (Al) that constitutes metallic film 40, molybdenum (Mo), niobium (Nb), silicon (Si), titanium (Ti), vanadium (V), tungsten (W), yttrium (Y), zirconium (Zr), between coating 20 that constitutes by nickel (Ni) and diamond abrasive grain 30, form chemical bond.Therefore, can obtain the high diamond fretsaw 1 of retentivity of diamond abrasive grain 30.
In addition, heat-treat conditions such as the temperature of heat treatment step, time can suitably be set according to the material of metal coremaking line 10 and the kind that constitutes the metal or alloy of metallic film 40.
Make diamond fretsaw 1 by above operation.
Below, enumerate embodiment, the present invention will be described in more detail, still, the invention is not restricted to these embodiment.
By operation shown in Figure 8, make diamond fretsaw 1.
After dipping carried out ungrease treatment in degreasing bath 70, descaling bath 80 and rinsing bowl 90 continuously with 10m/ minute transporting velocity with the long piano wire of diameter 0.14mm, carry out the diamond abrasive grain electro-deposition operation of in possessing the coating bath 100 that nickel bathes, carrying out electrolysis.
At this, the prescription of plating bath is in the coating bath 100: nickel sulfate hexahydrate compound 240g/L, nickel chloride hexahydrate 45g/L, boric acid 30g/L.
Concentration with 1g/L in this nickel is bathed is dropped in the diamond abrasive grain after the processing in the cationic surfactant solution.The average grain diameter of diamond abrasive grain 30 is 13.4 μ m, as cationic surfactant, uses the mixture of monoethanolamine and triethanolamine.
In addition, plating condition is: bathe temperature 50 ℃, current density 20A/dm
2, 90 seconds time.
Thus, obtain having the diamond fretsaw of 6 μ m thickness of coating.
Then, on the whole outer surface of this diamond fretsaw, cover the thick titanium (Ti) of 0.05 μ m by sputtering method.
Afterwards, carry out heat treatment in 30 seconds, obtain diamond fretsaw 1 at 500 ℃.
The diamond fretsaw of the present invention of Zhi Zuoing can be used as the Line tool use that is used to cut the contour fragile material of silicon ingot as mentioned above.
Claims (12)
1. a diamond fretsaw wherein covers the whole outer surface that dispersion maintains the metal coremaking line of diamond abrasive grain by coating, it is characterized in that,
Described coating is the nickel alloy that contains tungsten.
2. diamond fretsaw as claimed in claim 1 is characterized in that,
Nickel alloy contains the tungsten of 1 weight %～60 weight %.
3. diamond fretsaw, wherein the outer surface of metal coremaking line cover by coating and this coating in disperse to maintain diamond abrasive grain, it is characterized in that,
The whole outer surface that comprises the diamond fretsaw of described coating and described diamond abrasive grain is covered by metallic film.
4. diamond fretsaw as claimed in claim 3 is characterized in that,
The thickness of metallic film is 0.001 μ m～1 μ m.
5. diamond fretsaw as claimed in claim 3 is characterized in that,
Metallic film is to comprise the metal that is selected from a kind of element among Al, Mo, Nb, Si, Ti, V, W, Y and the Zr or comprise the alloy that is selected from the two or more elements among Al, Mo, Nb, Si, Ti, V, W, Y and the Zr.
6. diamond fretsaw as claimed in claim 3 is characterized in that,
The average grain diameter of diamond abrasive grain is 1 μ m～60 μ m.
7. diamond fretsaw as claimed in claim 3 is characterized in that,
The coverage rate of the diamond abrasive grain on the outer surface of metal coremaking line be metal coremaking line the whole outer surface area 1%～35%.
8. the manufacture method of a diamond fretsaw is used to be manufactured on the diamond fretsaw that disperses to maintain diamond abrasive grain on the outer surface of metal coremaking line, it is characterized in that, comprises:
Use disperses diamond abrasive grain in the solution that is dissolved with nickel and tungsten and the nickel that obtains-tungsten is bathed, the diamond abrasive grain electro-deposition operation that described metal coremaking line is electroplated.
9. the manufacture method of diamond fretsaw as claimed in claim 8 is characterized in that,
The ratio of nickel and tungsten was 1: 9～9: 1 with molar ratio computing during nickel-tungsten was bathed.
10. the manufacture method of diamond fretsaw as claimed in claim 8 is characterized in that,
Diamond abrasive grain electro-deposition operation is carried out under 50 ℃～75 ℃ bath temperature.
11. the manufacture method of diamond fretsaw as claimed in claim 8 is characterized in that,
Solution during nickel-tungsten is bathed is the aqueous solution that is dissolved with diammonium hydrogen citrate, sodium formate, nickelous sulfate and sodium tungstate.
12. the manufacture method of a diamond fretsaw is used to be manufactured on the diamond fretsaw that disperses to maintain diamond abrasive grain on the outer surface of metal coremaking line, it is characterized in that, comprises:
Diamond abrasive grain electro-deposition operation: use the nickel that in being dissolved with the solution of nickel, disperses diamond abrasive grain and obtain to bathe described metal coremaking line is electroplated;
Metallic film covering process: further cover by described diamond abrasive grain electro-deposition operation in the whole outer surface that is dispersed with the metal coremaking line after electroplating under the state of diamond abrasive grain with metallic film; With
Heat treatment step: under the state that the whole outer surface that makes the metal coremaking line after electroplating under the state that is being dispersed with diamond abrasive grain by described metallic film covering process is covered by metallic film, heat-treat.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009048354A JP2010201541A (en) | 2009-03-02 | 2009-03-02 | Diamond wire saw, and method of manufacturing the same |
| JP2009048355A JP5356071B2 (en) | 2009-03-02 | 2009-03-02 | Diamond wire saw, diamond wire saw manufacturing method |
| JP2009-048355 | 2009-03-02 | ||
| JP2009-048354 | 2009-03-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101823240A true CN101823240A (en) | 2010-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010124913A Pending CN101823240A (en) | 2009-03-02 | 2010-03-01 | The manufacture method of diamond fretsaw and diamond fretsaw |
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| Country | Link |
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| CN (1) | CN101823240A (en) |
| TW (1) | TW201111106A (en) |
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| CN111727266A (en) * | 2018-02-14 | 2020-09-29 | 住友电气工业株式会社 | Composite member and method for manufacturing composite member |
| CN112536735A (en) * | 2020-10-30 | 2021-03-23 | 河南富莱格超硬材料有限公司 | Diamond grinding wheel and preparation method thereof |
| CN118322114A (en) * | 2024-06-17 | 2024-07-12 | 浙江微铸科技有限公司 | Bus preparation method, diamond wire, preparation method of diamond wire and silicon wafer cutting application |
| CN118322114B (en) * | 2024-06-17 | 2024-08-23 | 浙江微铸科技有限公司 | Bus preparation method, diamond wire, preparation method of diamond wire and silicon wafer cutting application |
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| TW201111106A (en) | 2011-04-01 |
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