JP2011084774A - Method of manufacturing nickel alloy electroformed blade - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a high hardness nickel alloy electroformed blade without damaging it. <P>SOLUTION: A plating bath contains nickel sulfonate, citric acid and an alloy material supply source, wherein the concentration of nickel sulfonate is 250-600 g/L, the concentration of citric acid is 84-147 g/L and the concentration of the alloy material supply source is 0.5-8.5 g/L and further contains abrasive grain. The method of manufacturing the nickel alloy electroformed blade, in which one surface 24a of an electrode 24 of one in two electrodes 23, 24 is arranged to face another electrode 23, voltage is applied between two electrodes 23, 24 to form a nickel alloy electroformed film 2 in which the abrasive grain 3 is dispersed on one surface 24a side of one electrode 24, is used to form the high hardness nickel alloy electroformed blade without damaging it. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a nickel alloy electroformed blade.

  An electroformed film formed by using an electroforming technique (plating technique), in which diamond abrasive grains and hard ceramic particles are dispersed, is known as a film having excellent wear resistance. Therefore, the electroformed film is used for a blade of a grinding apparatus for grinding and cutting ceramics, cemented carbide, and various electronics-related materials.

  For example, Patent Documents 1 to 3 disclose electroformed blades used for ultra-precise cutting of semiconductor elements and electronic components. This electroformed blade is a disc-shaped blade in which diamond abrasive grains are held by an extremely thin nickel plating film. A base metal is placed in a nickel plating solution in which diamond abrasive grains are dispersed, and diamond abrasive grains are taken in. On the other hand, an abrasive layer is formed by depositing a nickel plating film on the base metal by electrolytic plating, and when it reaches a predetermined thickness, it is peeled off from the base metal and the abrasive grains are sharpened.

  Further, in Patent Document 4, when polishing the surface of a semiconductor wafer or the like with a pad of a CMP apparatus, as a CMP conditioner for conditioning the polishing pad, diamond abrasive grains are also deposited on the surface of the conditioner body. There has been proposed one in which an abrasive layer fixed by the above is formed. In addition to processing such electronics-related materials, such grinding tools can be used for precision processing such as ferrite processing and lens centering processing, or groove processing of cemented carbide rolls. Also do.

  The higher the hardness of the electroformed film, the better the wear resistance of the blade and the better the grinding and cutting ability of the blade. Therefore, in recent years, the demand for high-hardness electroformed films has increased.

The electroformed film is usually formed by energizing between two electrodes immersed in a plating bath (plating solution) to deposit the metal component in the plating bath on the surface of one electrode. As the plating bath, a nickel plating bath (Watt bath) mainly composed of nickel sulfate, nickel chloride and boric acid is known, and a nickel electroformed film can be produced by this method. An electroformed film using nickel (Ni) as a constituent material can be a high hardness film.
However, a high-hardness electroformed film tends to be a high-stress film, and when peeled off from the electrode, the electroformed film may be cracked or shattered.

Patent Document 5 relates to a nickel belt and a manufacturing method thereof, a photoreceptor, and an image forming apparatus, and Patent Document 6 relates to a manufacturing method of an optical disc stamper. Patent Documents 5 and 6 disclose that the stress of the Ni electroformed film can be reduced by using a nickel sulfamate bath.
However, the nickel sulfamate baths described in Patent Document 5 and Patent Document 6 contain boric acid as a buffer component. The plating bath containing boric acid has a problem that wastewater treatment is difficult.

Patent Document 7 relates to an electro nickel plating bath, which includes nickel sulfate: 200 to 360 g / L, nickel chloride: 30 to 90 g / L, nickel citrate: 24 to 42 g / L, and pH: 3 to 5. An electrolytic nickel plating bath is disclosed. The electric nickel plating bath described in Patent Document 7 is a plating bath not containing boric acid, and does not have the problem of the waste water treatment.
However, the electroformed film made of pure Ni disclosed in Patent Document 7 has insufficient hardness.

When a P source and a B source are added to a conventional plating bath to produce an electroformed film made of a nickel alloy such as phosphorus (P) or boron (B), the hardness is higher than when pure nickel is used. It can be a membrane.
However, when this method is applied to the method disclosed in Patent Document 7, the stress of the electroformed film cannot be reduced, and the electroformed film is cracked during plating or peeled off from the electrode after plating. There was a problem of cracking or shattering.

JP 2002-187071 A JP 2003-225867 A JP 2005-288614 A JP 2004-66409 A JP 2007-1000015 A JP-A-9-35337 Japanese Patent No. 3261676

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for manufacturing a high-hardness nickel alloy electroformed blade without breakage.

In order to achieve the above object, the present invention employs the following configuration. That is,
The method for producing a nickel alloy electroformed blade of the present invention includes nickel sulfamate, citric acid, and an alloy material supply source, wherein the concentration of the nickel sulfamate is 250 to 600 g / L, and the concentration of the citric acid Are 84 to 147 g / L, the concentration of the alloy material supply source is 0.5 to 8.5 g / L, and further, two electrodes immersed in the plating bath using a plating bath containing abrasive grains A nickel alloy electroformed film in which the abrasive grains are dispersed on one surface side of the one electrode by energizing between the two electrodes after arranging one surface of the electrode facing the other electrode. It is characterized by forming.

In the method for manufacturing a nickel alloy electroformed blade of the present invention, a substrate made of a metal or an alloy is disposed on one surface of the one electrode, and the one surface of the substrate faces the other electrode. The nickel alloy electroformed film in which the abrasive grains are dispersed is formed on one surface of the substrate, and the other surface of the substrate is disposed on the one surface of the one electrode with the other electrode facing the other electrode. Then, a current is passed between the two electrodes to form a nickel alloy electroformed film in which the abrasive grains are dispersed on the other surface of the substrate.
The method for producing a nickel alloy electroformed blade of the present invention is characterized in that, together with the abrasive grains, fillers made of ceramic particles or fluorine resin are dispersed in the plating bath.
The nickel alloy electroformed blade manufacturing method of the present invention is characterized in that the nickel alloy electroformed film is formed in a state where the one electrode is rotated around the central axis of the one electrode.

The method for producing a nickel alloy electroformed blade of the present invention uses a plating bath in which the alloy material supply source is phosphorous acid and the phosphorous acid concentration is 3.5 to 8.5 g / L. And
The method for producing a nickel alloy electroformed blade of the present invention is characterized in that the alloy material supply source is trimethylamine borane, and a plating bath in which the concentration of trimethylamine borane is 0.5 to 3.5 g / L is used. .
The nickel alloy electroformed blade manufacturing method of the present invention is characterized in that the plating bath contains a brightener and / or a surfactant.

The nickel alloy electroformed blade manufacturing method of the present invention is characterized in that the plating bath has a pH of 3 to 5.
The method for producing a nickel alloy electroformed blade of the present invention is characterized in that the nickel alloy electroformed film in which the abrasive grains are dispersed is heat-treated at 200 to 400 ° C. for 30 minutes or more in an inert atmosphere. To do.

  According to said structure, the method of manufacturing a high-hardness nickel alloy electroformed blade can be provided, without damaging.

  The method for producing a nickel alloy electroformed blade of the present invention includes nickel sulfamate, citric acid, and an alloy material supply source, wherein the concentration of the nickel sulfamate is 250 to 600 g / L, and the concentration of the citric acid Are 84 to 147 g / L, the concentration of the alloy material supply source is 0.5 to 8.5 g / L, and further, two electrodes immersed in the plating bath using a plating bath containing abrasive grains A nickel alloy electroformed film in which the abrasive grains are dispersed on one surface side of the one electrode by energizing between the two electrodes after arranging one surface of the electrode facing the other electrode. Since it is a structure to be formed, a nickel alloy electroformed blade with low stress and high hardness can be manufactured, it is not damaged in the manufacturing process, and the rigidity after manufacturing can be kept high.

  In the method for manufacturing a nickel alloy electroformed blade of the present invention, a substrate made of a metal or an alloy is disposed on one surface of the one electrode, and the one surface of the substrate faces the other electrode. The nickel alloy electroformed film in which the abrasive grains are dispersed is formed on one surface of the substrate, and the other surface of the substrate is disposed on the one surface of the one electrode with the other electrode facing the other electrode. Then, since the nickel alloy electroformed film in which the abrasive grains are dispersed is formed on the other surface of the substrate by energizing between the two electrodes, the nickel alloy electrode having low stress and high hardness is formed. Cast blades can be manufactured.

  The method for producing a nickel alloy electroformed blade of the present invention is a structure in which a filler made of ceramic particles or a fluororesin is dispersed in the plating bath together with the abrasive grains, so that the nickel alloy electroformed with low stress and high hardness. Blades can be manufactured.

  Since the nickel alloy electroformed blade manufacturing method of the present invention is configured to form a nickel alloy electroformed film in a state where the one electrode is rotated about the central axis of the one electrode, the film thickness is uniform. Thus, the concentration distribution of the abrasive grains and / or fillers can be made uniform, the hardness variation of the nickel alloy electroformed film 10 can be reduced, and a nickel alloy electroformed blade having low stress and high hardness can be manufactured. .

  Since the manufacturing method of the nickel alloy electroformed blade of the present invention is configured to use a plating bath in which the alloy material supply source is phosphorous acid and the concentration of phosphorous acid is 3.5 to 8.5 g / L, A NiP alloy electroformed blade having low stress and high hardness can be produced.

  The method for producing a nickel alloy electroformed blade of the present invention uses a plating bath in which the alloy material supply source is trimethylamine borane and the concentration of the trimethylamine borane is 0.5 to 3.5 g / L. In addition, a highly hard NiB alloy electroformed blade can be manufactured.

It is a cross-sectional schematic diagram of the plating bath used with the manufacturing method of the nickel alloy electroforming blade of this invention. It is a figure which shows an example of the nickel alloy electroforming blade manufactured by the manufacturing method of the nickel alloy electroforming blade of this invention, Comprising: Fig.2 (a) is a perspective view, FIG.2 (b) is an expanded sectional view. is there. It is an expanded sectional view which shows another example of the nickel alloy electroforming blade manufactured by the manufacturing method of the nickel alloy electroforming blade of this invention. 4A is an optical micrograph of a nickel alloy electroformed blade, FIG. 4A is an optical micrograph of the nickel alloy electroformed blade of Example 1, and FIG. 4B is a nickel alloy electroformed blade of Comparative Example 5. FIG. It is an optical microscope photograph of.

Hereinafter, modes for carrying out the present invention will be described.
(Embodiment 1)
A method for producing a nickel alloy electroformed blade according to an embodiment of the present invention includes nickel sulfamate, citric acid, and an alloy material supply source, wherein the concentration of the nickel sulfamate is 250 to 600 g / L, The concentration of citric acid is 84 to 147 g / L, the concentration of the alloy material supply source is 0.5 to 8.5 g / L, and further immersed in the plating bath using a plating bath containing abrasive grains. A nickel alloy electroformed film comprising one of the two electrodes facing the other electrode and then energized between the two electrodes and containing abrasive grains on one surface of the one electrode A method for forming a nickel alloy electroformed blade comprising:

  First, the nickel sulfamate, citric acid, and an alloy material supply source, the nickel sulfamate concentration is 250-600 g / L, the citric acid concentration is 84-147 g / L, and the alloy An abrasive grain is disperse | distributed to the plating bath whose density | concentration of a material supply source is 0.5-8.5 g / L, and the plating bath containing an abrasive grain is adjusted.

<Nickel sulfamate>
Nickel sulfamate is the main source of nickel ions in the plating bath.
The concentration of nickel sulfamate in the plating bath is preferably 250 to 600 g / L. When the concentration of nickel sulfamate is less than 250 g / L, sufficient nickel ions cannot be supplied to the surface of the cathode. In addition, decomposition of sulfamate ions tends to occur, and there is a problem in the stability of the plating bath. When the concentration of nickel sulfamate exceeds 600 g / L, the viscosity of the plating bath increases and defects such as pits are likely to occur. In addition, precipitation tends to occur in the plating bath, and there is a problem in the stability of the plating bath. For example, nickel sulfamate is 450 g / L.

<Citric acid>
Citric acid is used as a pH buffer for the plating bath, and the pH of the plating bath can be adjusted to a desired range.
The concentration of citric acid is preferably 84 to 147 g / L. By setting it as this range, the stress of the nickel alloy electroformed film 2 can be reduced, and a nickel alloy electroformed film having a high hardness can be produced without being damaged when peeled from the electrode. When citric acid is less than 84 g / L, the fluctuation of the pH near the surface of the cathode cannot be suppressed to a desired range. In some cases, the stress of the film cannot be reduced and the film is turned up. In addition, when citric acid exceeds 147 g / L, precipitation of nickel hydroxide or the like may occur, and there is a problem in the stability of the plating bath.

<Alloy material source>
The alloy material supply source supplies a material combined with nickel as a nickel alloy. For example, in order to produce a nickel alloy electroformed film (NiP alloy electroformed film) containing phosphorus (P), phosphorous acid, which is a material containing P (P source), is used as the alloy material supply source. Can do. In order to produce a nickel alloy electroformed film containing boron (B) (NiB alloy electroformed film), trimethylamine borane (TMAB), which is a material containing B as the alloy material supply source (B source), is used. ) Etc. can be used.

The concentration of the alloy material supply source is preferably 0.5 to 8.5 g / L. By setting the concentration of the alloy material supply source within this range, there is no film cracking due to stress when the plating is thickened, and there is no risk of breakage when peeled from the electrode. Membranes can be manufactured.
The concentration of phosphorous acid is preferably 3.5 to 8.5 g / L, and more preferably 4 to 8 g / L. When phosphorous acid is less than 3.5 g / L, a sufficient amount of phosphorus for increasing the hardness cannot be co-deposited in the electroformed film. Moreover, when phosphorous acid is more than 8.5 g / L, precipitation is likely to occur in the plating bath, which causes a problem in the stability of the plating bath. By setting the concentration of phosphorous acid to 4 to 8 g / L, a highly hard film can be stably deposited.
The concentration of TMAB is preferably 0.5 to 3.5 g / L, more preferably 1 to 3 g / L. When TMAB is less than 0.5 g / L, a sufficient amount of boron for increasing the hardness cannot be co-deposited in the electroformed film. Moreover, when TMAB is more than 3.5 g / L, precipitation tends to occur in the plating bath, which causes a problem in the stability of the plating bath. By setting the concentration of TMAB to 1 to 3 g / L, a highly hard film can be stably deposited.

<Abrasive>
The concentration of the abrasive grains is preferably 1 to 20 g / L. By making the concentration of the abrasive grains in the above range, when the nickel alloy electroformed blade is manufactured, the concentration of the abrasive grains can be in the range of 5 to 40 vol% with respect to the nickel alloy electroformed film. .
The grain size (average grain size) of the abrasive grains is preferably in the range of 0.3 μm to 50 μm.
By dispersing the abrasive grains in the plating bath, a nickel alloy electroformed blade in which the abrasive grains are dispersed can be formed, and the grinding ability of the blade can be improved.
For example, diamond is used as the abrasive.

<Filler>
A filler made of ceramic particles or a fluorine-based resin may be added to the plating bath.
As the ceramic particles, for example, hard particles such as Al ₂ O ₃ , SiO ₂ , ZrO _2, or Si ₃ N ₄ can be used.
Examples of the fluororesin include perfluoroethylene propene copolymer (FEP), perfluoroalkoxyalkane (PFA), tetrafluoroethylene-perfluorodioxole copolymer (TFE / PDD), and ethylene / tetrafluoroethylene polymer (ETFE). ), Polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF), and polytetrafluoroethylene (PTFE). In particular, polytetrafluoroethylene is preferable because it has excellent heat resistance and chemical resistance in addition to lubricity and is relatively inexpensive.

The concentration of the filler is preferably 0.5 to 40 g / L. By setting it as this range, when manufacturing a nickel alloy electroformed blade, the density | concentration of a filler can be in the range of 5-40 vol% with respect to a nickel alloy electroformed film | membrane.
Moreover, it is preferable that the particle size (average particle size) of a filler shall be the range of 0.1 micrometer-70 micrometers.
By forming a nickel alloy electroformed blade in which filler is dispersed together with abrasive grains, the grinding ability of the blade can be further improved.

<Brightener, surfactant>
A brightener and / or a surfactant may be added to the plating bath.
By adding a brightening agent and / or a surfactant, the surface of the formed metal film can be made smooth and glossy. In addition, the film quality can be made dense, and defects such as protrusions (pits) and recesses (pinholes) can be reduced.
As the brightener, alkynediol or the like can be used. Examples of the alkyne diol include 2-butyne-1,4-diol which is also a hardness increasing agent.

Further, saccharin can be used as a brightener. Saccharin is also a stress reducing agent, and examples thereof include saccharin sodium. Further, sodium allyl sulfonate, which is a stress reducing agent, can be used as the brightener. Examples of the surfactant include sodium lauryl sulfate which is also a pit inhibitor.
Moreover, the said plating bath may contain the other trace amount inevitable component.
A predetermined amount of each of the above materials is mixed to adjust the plating bath (plating solution).

  Next, after arranging one surface of the two electrodes immersed in the plating bath in which the abrasive grains are dispersed toward the other electrode, the current is passed between the two electrodes. A nickel alloy electroformed film in which abrasive grains are dispersed is formed on one surface side of the electrode.

FIG. 1 is a schematic cross-sectional view showing an example of a plating bath used in a method for producing a nickel alloy electroformed blade according to an embodiment of the present invention.
As shown in FIG. 1, the plating tank 21 is filled with the plating bath 22 adjusted in the previous step. In the plating bath 22, abrasive grains 3 and fillers 4 are dispersed.
A disk-shaped base 27 is immersed on the bottom side of the plating tank 21. The base portion 27 is attached to one end side of a rod-shaped rotating shaft 26 immersed in the plating bath 22. The central axis n of the base portion 27 is coaxial with the central axis m of the rotating shaft 26.
A cathode (hereinafter referred to as a cathode plate) 24 made of an annular plate material serving as a base metal is disposed on one surface 27 a of the base portion 27. An anode (hereinafter referred to as an anode plate) 23 made of an annular plate material as a counter electrode is arranged so as to be separated from the cathode plate 24 and the other surface 23b faces the one surface 24a of the cathode plate 24. The shape and size of the anode plate 23 are substantially the same as those of the cathode plate 24.

Both the anode plate 23 and the cathode plate 24 are immersed in the plating bath 22.
The anode plate 23 and the cathode plate 24 are each connected to a power source, and can be energized between the anode plate 23 and the cathode plate 24.
In addition, the cathode plate 24 disposed on one surface of the pedestal 27 can be rotated by rotating the rotating shaft 26 and rotating the pedestal 27.
For example, a nickel plate is used as the anode plate 23 and a SUS plate is used as the cathode plate 24.

When the power source is operated and the anode plate 23 and the cathode plate 24 are energized, the metal ions dissolved in the plating bath 22 are deposited and deposited on the one surface 24a of the plating bath cathode plate 24 as a metal. An alloy electroformed film 2 is formed. At this time, the abrasive grains 3 and the filler 4 dispersed in the plating bath 22 settle on the one surface 24 a of the cathode plate 24 disposed on the bottom surface side of the plating tank 21 and are taken into the nickel alloy electroformed film 2.
The current value and current application time of the plating bath 22 are appropriately set according to the thickness of the nickel alloy electroformed film 2 to be formed.

  The pH of the plating bath 22 is preferably 3-5. When the pH of the plating bath 22 is less than 3, sulfamic acid ions are decomposed. On the other hand, when the pH of the plating bath 22 exceeds 5, precipitation tends to occur in the plating bath 22, which causes a problem in the stability of the plating bath 22.

During the energization, the cathode plate 24 is preferably rotated about the central axis m of the cathode plate 24. By rotating the cathode plate 24, the nickel alloy electroformed film 10 can be formed on the one surface 24a of the cathode plate 24 with a uniform film thickness. Further, by rotating the cathode plate 24, the abrasive grains 3 and the filler 4 can be uniformly dispersed and settled in the plating bath 22, and the concentration distribution of the abrasive grains 3 and the filler 4 can be made uniform. Variations in hardness of the alloy electroformed film 2 can be reduced.
The rotation is not limited to the condition of rotating at a constant speed for a certain period of time. For example, the rotation may be stopped once and then rotated again.

  After the nickel alloy electroformed film 2 having a predetermined thickness was formed on the cathode plate 24, the energization was stopped and the nickel alloy electroformed film 2 was peeled off from the cathode plate 24, whereby the abrasive grains 3 and the filler 4 were dispersed. An annular nickel alloy electroformed blade 11 made of the nickel alloy electroformed film 2 can be manufactured.

  Note that the nickel alloy electroformed blade 11 manufactured in the above process may be heat-treated (annealed) for 30 minutes or more in a temperature range of 200 ° C. to 400 ° C. in an inert atmosphere. Thereby, the hardness of the nickel alloy electroformed blade 11 can be further increased.

2 is a view showing an example of a nickel alloy electroformed blade manufactured by a method for manufacturing a nickel alloy electroformed blade according to an embodiment of the present invention, and FIG. 2 (a) is a perspective view. (B) is an expanded sectional view of the A section of Fig.2 (a).
As shown in FIG. 2A, the nickel alloy electroformed blade 11 is a blade made of an annular plate having an outer diameter of 30 to 150 mm with the axis m ′ as the center. The inner diameter portion is attached to the main shaft of the cutting device and rotated around the axis m ′ while being sent out in a direction perpendicular to the axis m ′. And to-be-processed parts can be cut precisely.
2B, the nickel alloy electroformed blade 11 has a thickness T of 0.01 to 0.5 mm and is dispersed in the nickel alloy electroformed film 2 and the nickel alloy electroformed film 2. It is comprised from the abrasive grain 3 and the filler 4 which were made.
The concentration of the abrasive grains 3 is preferably in the range of 5 to 40 vol% with respect to the nickel alloy electroformed film 2. Moreover, it is preferable that the density | concentration of the filler 4 shall be in the range of 5-40 vol% with respect to the nickel alloy electroforming film | membrane 2. FIG. The filler 4 has a lump shape, a block shape, or a shape having irregularities on the surface.

Since the nickel alloy electroforming blade 11 is made of a nickel alloy containing phosphorus or boron, the hardness of the film can be set to 680 Hv or more.
The nickel alloy electroformed blade 11 can be formed as a low-stress film because of the buffering effect of citric acid. Therefore, even if the thickness is formed as thick as about 100 μm, no cracking occurs during plating. Further, it can be easily peeled off from the cathode plate 24 after plating, and the nickel alloy electroformed film 10 is not cracked or shattered.

FIG. 3 is an enlarged cross-sectional view showing another example of a nickel alloy electroformed blade manufactured by a method for manufacturing a nickel alloy electroformed blade according to an embodiment of the present invention.
As shown in FIG. 3, the nickel alloy electroforming blade 12 includes a substrate 8 made of a metal or an alloy, nickel alloy electroformed films 2 and 2 'formed on one surface 8a and the other surface 8b of the substrate 8, and nickel. It consists of abrasive grains 3, 3 'and fillers 4, 4' dispersed in the alloy electroformed films 2, 2 ', respectively.

The nickel alloy electroformed blade 12 is manufactured as follows, for example.
First, a substrate made of an annular metal or alloy is disposed on one surface of one of two electrodes immersed in a plating bath in which abrasive grains are dispersed, and the one surface of the substrate faces the other electrode. To do. Next, a current is passed between the two electrodes to form a nickel alloy electroformed film in which abrasive grains are dispersed on one surface of the substrate disposed on one surface side of the one electrode. Next, after the substrate on which the nickel alloy electroformed film in which the abrasive grains are dispersed is formed is taken out of the plating bath, the other surface of the substrate is disposed on one surface of the one electrode with the other electrode facing the other electrode. Then, a current is passed between the two electrodes to form a nickel alloy electroformed film in which the abrasive grains are dispersed on the other surface of the substrate disposed on one surface of the one electrode.

The method for forming nickel alloy electroformed blades 11 and 12 according to an embodiment of the present invention includes nickel sulfamate, citric acid, and an alloy material supply source, and the concentration of the nickel sulfamate is 250 to 600 g / L. The concentration of the citric acid is 84 to 147 g / L, the concentration of the alloy material supply source is 0.5 to 8.5 g / L, and the plating bath 22 containing the abrasive grains 3 is used. One surface 24a of one electrode 24 out of the two electrodes 23 and 24 immersed in 22 is disposed toward the other electrode 23 and then energized between the two electrodes 23 and 24. The nickel alloy electroformed film 2 in which the abrasive grains 3 are dispersed in 24a is provided, so that a nickel alloy electroformed blade made of a nickel alloy electroformed film having dispersed abrasive grains, low stress and high hardness is provided. To do It can be. Since it is a low stress film, it does not cause cracking or shattering in the nickel alloy electroformed film during plating. Also, a nickel alloy electroformed blade with high hardness can be produced without being damaged when peeled off from the electrode.
Further, when the alloy material supply source does not contain boron, it is not necessary to perform the removal treatment of boric acid and boron in the drainage of the plating bath, so that the manufacturing process can be facilitated.

  In the method of forming the nickel alloy electroformed blade 12 according to the embodiment of the present invention, the substrate 8 made of metal or alloy is placed on one surface 24 a of one electrode 24, and the one surface 8 a of the substrate 8 is directed to the other electrode 23. After being disposed, electricity is passed between the two electrodes 23 and 24 to form the nickel alloy electroformed film 2 in which the abrasive grains 3 are dispersed on one surface 8 a of the substrate 8, and then on one surface 24 a of one electrode 24. The nickel alloy electroforming in which the other surface 8b of the substrate 8 is disposed toward the other electrode 23 and then energized between the two electrodes 23 and 24, and the abrasive grains 3 are dispersed on the other surface 8b of the substrate 8. Since the film 2 is formed, a nickel alloy electroformed blade with low stress and high hardness can be provided.

  The formation method of the nickel alloy electroformed blades 11 and 12 according to the embodiment of the present invention is a structure in which the filler 4 made of ceramic particles or fluorine-based resin is dispersed in the plating bath 22 together with the abrasive grains 3. A high-hardness nickel alloy electroformed blade can be produced.

  In the method of forming the nickel alloy electroformed blades 11 and 12 according to the embodiment of the present invention, the nickel alloy electroformed film 2 is formed with the one electrode 24 rotated around the central axis m of the one electrode 24. Since the structure is formed, the film thickness of the nickel alloy electroformed film 2 can be made uniform, and the concentration distribution of the abrasive grains 3 and the filler 4 can be made uniform to reduce the variation in hardness of the nickel alloy electroformed film 2. A nickel alloy electroformed blade having a low stress and a high hardness can be produced.

  In the method of forming nickel alloy electroformed blades 11 and 12 according to an embodiment of the present invention, the alloy material supply source is phosphorous acid, and the concentration of phosphorous acid is 3.5 to 8.5 g / L. Since the plating bath 22 is used, a NiP alloy blade with low stress and high hardness can be manufactured.

  In the method of forming nickel alloy electroformed blades 11 and 12 according to an embodiment of the present invention, the alloy material supply source is trimethylamine borane, and the concentration of the trimethylamine borane is 0.5 to 3.5 g / L. Therefore, a NiB alloy blade with low stress and high hardness can be manufactured.

  The formation method of the nickel alloy electroforming blades 11 and 12 according to the embodiment of the present invention is a structure in which the brightening agent and / or the surfactant is contained in the plating bath 22, so that nickel having low stress and high hardness is obtained. An alloy electroformed blade can be manufactured.

  The formation method of the nickel alloy electroformed blades 11 and 12 according to the embodiment of the present invention is a configuration in which the pH of the plating bath 22 is 3 to 5, so that a nickel alloy electroformed blade having low stress and high hardness is manufactured. can do.

  In the method of forming the nickel alloy electroformed blades 11 and 12 according to the embodiment of the present invention, the nickel alloy electroformed film in which the abrasive grains 3 are dispersed is subjected to a temperature range of 200 ° C. to 400 ° C. for 30 minutes in an inert atmosphere. Since the heat treatment is performed as described above, a nickel alloy electroformed blade with low stress and higher hardness can be manufactured.

Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited only to these examples.
Example 1
<Preparation of plating bath>
First, nickel sulfamate tetrahydrate (Ni sulfamate) 450 g / L, citric acid monohydrate (citric acid) 105 g / L as buffer, phosphorous acid 4 g / L as P source, dissolved in water did. Further, a predetermined concentration of an additive for nickel plating (manufactured by Atotech) was added as an additive to prepare a plating bath. Nickel carbonate and amidosulfuric acid were used for pH adjustment.
Next, 10 g / L of diamond abrasive grains having a particle size of 6 to 12 μm was dispersed in the plating bath.

<Plating process>
Next, after putting the plating bath into the plating tank, a SUS cathode plate (test plate) and a nickel anode plate were inserted.
The plating bath conditions were an initial pH of 4, a plating bath temperature of 50 ° C., and a current density of 5 A / dm ² . Under this condition, the test plate and the nickel anode plate were energized for 20 minutes, and plating was performed while rotating the test plate at 100 rpm, whereby a nickel alloy electroformed film having a thickness of about 20 μm was formed on the test plate. Got.
Next, the nickel alloy electroformed film was peeled from the test plate, and this was used as a nickel alloy electroformed blade (Example 1).

<Evaluation>
Next, the hardness (Vickers hardness) of the nickel alloy electroformed blade (Example 1) was evaluated using a hardness meter. The hardness of the nickel alloy electroformed blade (Example 1) was 705 Hv. Further, it was visually evaluated whether or not a crack occurred in the film state.
Next, the amount of warpage was measured by judging whether or not a clearance gauge was inserted.
Next, the dispersibility of the diamond abrasive grains was calculated by counting the number of abrasive grains in the range of 100 μm × 100 μm by observation with an optical microscope.
Next, an optical micrograph of a nickel alloy electroformed blade (Example 1) was taken.

(Example 2)
A nickel alloy electroformed blade having a thickness of about 20 μm (Example 2) except that 3 g / L of trimethylamine borane (TMAB) was added as a B source instead of phosphorous acid in the plating bath. )
Thereafter, the hardness of the nickel alloy electroformed blade (Example 2) was evaluated using a hardness meter. The hardness of the nickel alloy electroformed blade (Example 2) was 830 Hv. Further, the warpage amount and the dispersibility of the diamond abrasive grains were measured.

(Example 3)
The nickel alloy electroformed blade (Example 2) obtained in Example 2 was heat-treated at a heat treatment temperature of 300 ° C. for 1 hour in a nitrogen atmosphere to obtain a nickel alloy electroformed blade (Example 3).
Thereafter, the hardness of the nickel alloy electroformed blade (Example 3) was evaluated using a hardness meter. The hardness of the nickel alloy electroformed blade (Example 3) was 1052 Hv. Further, the warpage amount and the dispersibility of the diamond abrasive grains were measured.

(Examples 4 and 5)
By plating in the same manner as in Example 1 except that the concentration of citric acid in the plating bath was changed to 84 g / L (Example 4) and 147 g / L (Example 5), A nickel alloy electroformed blade (Examples 4 and 5) having a thickness of about 20 μm was obtained.
Further, hardness, warpage amount and dispersibility of diamond abrasive grains were measured.

(Examples 6 to 8)
The same as Example 2 except that the concentration of TMAB in the plating bath was changed to 0.5 g / L (Example 6), 1 g / L (Example 7), and 3.5 g / L (Example 8). By plating, a nickel alloy electroformed blade (Examples 6 to 8) having a film thickness of about 20 μm was obtained on the test plate.
Further, hardness, warpage amount and dispersibility of diamond abrasive grains were measured.

(Examples 9 to 11)
Example 1 except that the concentration of phosphorous acid in the plating bath was changed to 3.5 g / L (Example 9), 4 g / L (Example 10), and 8.5 g / L (Example 11). In the same manner as above, plating was performed to obtain a nickel alloy electroformed blade (Examples 9 to 11) having a film thickness of about 20 μm on the test plate.
Further, hardness, warpage amount and dispersibility of diamond abrasive grains were measured.

(Example 12)
A nickel alloy electroformed blade (Example 12) having a thickness of about 100 μm was obtained on the test plate by performing plating in the same manner as in Example 1 except that electricity was supplied for 100 minutes. The film state was good with no cracks.
Further, hardness, warpage amount and dispersibility of diamond abrasive grains were measured.

(Examples 13 to 16)
Plating is performed in the same manner as in Example 3 except that the heat treatment temperature is 100 ° C. (Example 13), 200 ° C. (Example 14), 400 ° C. (Example 15), and 500 ° C. (Example 16). Thus, a nickel alloy electroformed blade (Examples 13 to 16) having a film thickness of about 100 μm was obtained on the test plate.
While observing the film state, the hardness, the amount of warpage, and the dispersibility of the diamond abrasive grains were measured.

(Comparative Example 1)
A nickel electroformed blade (Comparative Example 1) having a film thickness of about 20 μm was obtained on the test plate by performing plating in the same manner as in Example 1 except that phosphorous acid was not added to the plating bath.
Thereafter, the hardness of the nickel electroformed blade (Comparative Example 1) was evaluated using a hardness meter. The hardness of the nickel electroformed blade (Comparative Example 1) was 540 Hv. Further, the warpage amount and the dispersibility of the diamond abrasive grains were measured.

(Comparative Example 2)
By plating in the same manner as in Comparative Example 1 except that 30 g / L of boric acid (H ₃ BO ₃ ) was added in place of citric acid in the plating bath, nickel having a film thickness of about 20 μm was formed on the test plate. An electroformed blade (Comparative Example 2) was obtained.
Thereafter, the hardness of the nickel electroformed blade (Comparative Example 2) was evaluated using a hardness meter. The hardness of the nickel electroformed blade (Comparative Example 2) was 550 Hv. Further, the warpage amount and the dispersibility of the diamond abrasive grains were measured.

(Comparative Examples 3 to 7)
The concentration of citric acid in the plating bath was 21 g / L (Comparative Example 3), 63 g / L (Comparative Example 4), 168 g / L (Comparative Example 5), 189 g / L (Comparative Example 6), 210 g / L ( A nickel alloy electroformed blade (Comparative Examples 3 to 7) having a film thickness of about 20 μm was obtained on the test plate by performing plating in the same manner as in Example 1 except that it was changed to Comparative Example 7).
Further, hardness, warpage amount and dispersibility of diamond abrasive grains were measured.
Furthermore, an optical micrograph of a nickel alloy electroformed blade (Comparative Example 5) was taken.
Table 1 shows the conditions and states of the plating baths of Examples 1 to 16 and Comparative Examples 1 to 7, and Table 2 shows the film thickness and evaluation results.

  In Table 1, those in which no precipitation occurred in the plating bath were regarded as stable plating bath states. In Table 2, the film state is a visual observation of the state of the nickel alloy electroformed film formed on the test plate, and “crack” indicates that a crack has occurred, and “partial crack” Only a part of the film is cracked. “End burn” is a film with a dull black film at the edge of the film. “Part burn” is a black film with a dull film. In this film, “abnormal” indicates that these abnormalities did not occur. Furthermore, in Comparative Example 3 in Table 2, since the film state was “cracked”, the hardness, dispersibility, and warpage amount were not evaluated.

  In Examples 1, 4, and 5, the plating bath state was stable, a low-stress film was formed, and the film state was good. In Comparative Examples 4 and 5, the plating bath state was stable, but the film state was “partially cracked” and “partially burned”. In Comparative Examples 3 and 4, since the concentration of citric acid was low, it was considered that the coating state was “cracked” or “partially cracked”.

4 is an optical micrograph of a nickel alloy electroformed blade, FIG. 4 (a) is an optical micrograph of the nickel alloy electroformed blade of Example 1, and FIG. 4 (b) is a nickel alloy of Comparative Example 5. It is an optical microscope photograph of an electroforming blade.
Compared with the nickel alloy electroformed blade of Example 1, the nickel alloy electroformed blade of Comparative Example 5 had more needle-like crystals. As a result of analysis, these acicular crystals were identical to the crystals constituting the precipitates observed in Comparative Examples 6 and 7. Since many such needle-like crystals were generated, it was speculated that the diamond abrasive grains were not dispersed in the nickel alloy electroformed film and the hardness could not be improved.

  The present invention relates to a method for manufacturing a nickel alloy electroformed blade, and has applicability in industries that manufacture and utilize a high hardness nickel alloy electroformed blade.

2, 2 '... nickel alloy electroformed film, 3, 3' ... abrasive, 4, 4 '... filler, 8 ... substrate, 8a ... one side, 8b ... other side, 11, 12 ... nickel alloy electroformed blade, 21 DESCRIPTION OF SYMBOLS ... Plating tank, 22 ... Plating bath, 23 ... Anode (anode plate), 23b ... Other side, 24 ... Cathode (cathode plate), 24a ... One side, 26 ... Rotating shaft, 27 ... Base part, 27a ... One side, m, m ', n ... central axis.

Claims (9)

Including nickel sulfamate, citric acid, and an alloy material supply source, wherein the nickel sulfamate concentration is 250 to 600 g / L, the citric acid concentration is 84 to 147 g / L, and the alloy material supply Using a plating bath having a source concentration of 0.5 to 8.5 g / L and further containing abrasive grains,
One surface of one of the two electrodes immersed in the plating bath is arranged facing the other electrode, then energized between the two electrodes, and abrasive grains are placed on the surface of the one electrode. A method for producing a nickel alloy electroformed blade, comprising forming a nickel alloy electroformed film. A substrate made of a metal or an alloy is disposed on one surface of the one electrode, and the one surface of the substrate is disposed with the other electrode facing the other electrode. After forming the nickel alloy electroformed film with dispersed grains,
Nickel in which the other surface of the substrate is disposed on one surface of the one electrode with the other electrode facing the other electrode and then energized between the two electrodes, and the abrasive grains are dispersed on the other surface of the substrate. 2. The method for producing a nickel alloy electroformed blade according to claim 1, wherein an alloy electroformed film is formed.   The method for producing a nickel alloy electroformed blade according to claim 1, wherein a filler made of ceramic particles or a fluorine resin is dispersed in the plating bath together with the abrasive grains.   4. The nickel alloy according to claim 1, wherein the nickel alloy electroformed film is formed in a state where the one electrode is rotated around the central axis of the one electrode. 5. A method for manufacturing an electroformed blade.   The alloy material supply source is phosphorous acid, and a plating bath having a concentration of the phosphorous acid of 3.5 to 8.5 g / L is used. The manufacturing method of the nickel alloy electroformed blade of description.   The alloy material supply source is trimethylamine borane, and a plating bath having a concentration of the trimethylamine borane of 0.5 to 3.5 g / L is used. Manufacturing method of nickel alloy electroformed blade.   The method for producing a nickel alloy electroformed blade according to claim 1, wherein the plating bath contains a brightener and / or a surfactant.   The pH of the said plating bath is 3-5, The manufacturing method of the nickel alloy electroforming blade of any one of Claims 1-7 characterized by the above-mentioned.   The nickel alloy electroformed film in which the abrasive grains are dispersed is heat-treated in an inert atmosphere at a temperature range of 200 ° C to 400 ° C for 30 minutes or more. Method for producing a nickel alloy electroformed blade.

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