JPS6277491A - Production of high resistance amorphous nip foil strip of large width - Google Patents

Abstract

PURPOSE:To produce high resistance amorphous NiP foil of a large width by pulse electrolysis by depositing an NiP alloy on a substrate at a specified current density with a specified period of pulsation in a bath prepd. by mixing a Watts bath with an oxy-acid of phosphorus or a salt thereof and by stripping the resulting NiP alloy film. CONSTITUTION:A bath prepd. by mixing a Watts bath with an oxy-acid of phosphorus or a salt thereof such as phosphorous acid, hypophosphorous acid or sodium hypophosphite is used. A pulsating current ip having 0.01-100msec on-time and off-time is supplied at a current density represented by the formula to deposit an NiP alloy on a substrate of an easily passivatable and electrically conductive material. The resulting NiP alloy film is stripped from the substrate. Thus, high resistance amorphous NiP foil of large width is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for manufacturing an amorphous NIP high resistance foil strip,
More specifically, pulse electrolysis produces a wide amorphous NIP.
The present invention relates to a method of manufacturing high resistance foil.

(Conventional technology) Conventionally, methods for producing metal foil by electrolytic method include iron foil,
A manufacturing method for copper foil printed circuit boards, etc. was published in Japanese Patent Application Laid-Open No. 58-737.
No. 86, No. 58-73787, No. 53-37549, No. 57-82488, etc.

On the other hand, a known method for producing NIP amorphous alloys is the rapid solidification method.In addition, Ni containing a large amount of phosphorus is produced by electrolytic methods (plating, electroless plating).
Attempts to form a p-precipitated film and utilize its high resistance to stabilize and protect circuits such as power transistors include, for example, rPlating and 5surface.
Finishing.

It was proposed in 9.72 (1982) J.

(Problems to be solved by the invention) However, the method of producing metal foil by electroforming is
However, the scope of its application was limited to metals with a crystalline structure, and the characteristics of the inner foil were limited, so the range of use was also limited.

In addition, the method of manufacturing an amorphous NIP alloy using the rapid solidification method has the problem that it is only possible to manufacture an amorphous alloy of about 50 mm at most, and it is not suitable for manufacturing wide materials. Therefore, the nfC metal foil produced by this method is only used as a foil after brazing, taking advantage of its low melting point.

Furthermore, the above-mentioned method of producing NIP alloy by electrolytic method or electroless plating method is limited to the technique of depositing NIP alloy on a substrate, and does not involve isolating the deposited film to produce metal foil. .

Therefore, an object of the present invention is to provide a method for producing an amorphous NIP foil having a desired planar shape such as a flat plate or unevenness, an arbitrary area and an arbitrary thickness, and having high resistance, high corrosion resistance, and low melting point. There is a particular thing.

(Means for Solving the Problems) In order to solve the above problems, the present invention uses a bath composition in which a phosphorus oxyacid or oxyacid salt is mixed as a phosphorus eutectoid in a Watts bath, Pulsed current ip with on-time and off-time lengths of ~100 m sec <10
A current density of i p < 30 OA/d is applied to deposit the Nip alloy on a substrate made of a material that is easily passivable and conductive, and then the Nip alloy film is peeled off from the substrate. That is.

Watt bath (nickel sulfate 2401/11. dichloride chloride 451/1. phosphorous re3og/1). Examples include sodium acid, phosphoric acid, and the like.

In the present invention, the pulse period is o, ol~100771
sec because the recovery effect of the concentration boundary layer is incomplete at a pulse period exceeding 10OTrLsec, so phosphorus does not precipitate into the film and becomes similar to normal crystalline Ni metal. Also, the pulse period is 0.01 @ Be
e If the liquid is not purified, it becomes virtually impossible to apply an appropriate pulse waveform due to the capacitance effect between the electric double layer and the electrodes. 1p(sA/d
Phosphorus easily enters in the molten metal, but high-speed deposition cannot be performed.When applying zero pulse current, the duty cycle T o
Although it depends on n/(T, on+T6ff) (Fig. 2), phosphorus precipitates in the current density range of lO < ip < 30 OA/d and an amorphous structure is obtained. The substrate to be used is selected from conductive materials that are easily passivated, such as stainless steel or titanium. It is possible to obtain an N19 alloy foil having a surface shape such as the following. The film thickness of the alloy foil can be freely controlled by selecting the electroforming time and the like. In addition, according to the present invention, there is no particular limitation on the surface area of the foil that can be produced, and it can be made to any area. In the method of the present invention, under the above-mentioned specific conditions, the foil surface area that can be manufactured is as shown in FIG. An amorphous NIP alloy was deposited on a substrate by a conventional electrolytic method using the apparatus shown in Figure 1, where l indicates an electrolytic cell;
The inside is filled with a bath 2 having a composition of a Watts bath mixed with a phosphorus oxyacid or oxyacid salt, as described above. In the bath 2, an anode 3 and a cathode of a substrate 4 are immersed. 05 is a pulse generator, and 6 is an oscilloscope for viewing the current waveform applied to the electrodes.

By peeling the amorphous 812 alloy film deposited on the substrate 4 from the substrate 4, a metal foil having a desired surface shape, desired O film thickness and area can be obtained. is located near the eutectic structure in the N1-P phase diagram and has amorphous properties, that is, high resistance, high corrosion resistance, and low melting point.

The separation from the substrate 4 is carried out by using a different passivating material such as stainless steel or titanium, and passivating the material with an oxidizing acid.

In order to facilitate separation from the substrate 4, a release layer may be provided on the substrate 4.

(Function) Using a Watts bath mixed with phosphorous oxyacid or oxyacid, 0.01 <'r On , T off < 10
07Fl sec and IO<ip<300A/
Figure 3 and Table 1 show the relationship between the eutectoid amount of phosphorus and the electrodeposition conditions when electroforming is performed under the electrodeposition conditions of It becomes large in low IP area. Phosphorus has a eutectic composition (19A
t%), it becomes amorphous.

Table 1 Under the experimental conditions shown in Table 1, phosphorus enters above the eutectic point and the amorphous electrodeposited NIP film is deposited on stainless steel (for example, SUS 304BA finish), which is easy to passivate.The physical properties of the isolated metal foil are as follows. The resistance of the metal foil was measured using the four-point probe method using the 0(1) resistance physical property shown in FIG. Resistance measurement is digital mΩ
The resistance value of the foil increases depending on the amount of OP eutectoid using a meter (resolution 0.01 mΩ), and when it reaches near the eutectic point, the resistance value is comparable to that of 1NiP amorphous foil produced by the rapid cooling method. . Figure 4 shows the relationship between the internal resistance and the resistance value.〇(2) Pure nickel foil manufactured as corrosion-resistant electrodeposited foil and NiP amorphous foil with phosphorus eutectoid up to the eutectic composition. ．．
Polarization curves in 8N sulfuric acid solution were measured. The cathodic polarization Terfel gradient is flO, 13v/, 0.06v/, respectively, and the exchange current density for hydrogen generation is smaller for the eutectoid.

In addition, the dissolution current of anodic polarization also decreases due to the eutectoid of phosphorus,
It can be seen that it has excellent corrosion resistance. FIG. 5 shows O polarization curves for pure nickel foil and NiP eutectoid.

(Example) Next, the effects of the present invention will be explained by examples.0 (Example 1) NiP alloy foil with a width of 1 to 6 m was manufactured according to the method of the present invention using the apparatus shown in Fig. 6. This device was similar to that used for manufacturing electroformed steel foil, and the drum 5 made of stainless steel and titanium was used as the cathode material. 8
9 is a water washing spray for cleaning the electrolytic solution adhering to the NiP alloy foil peeled off from the drum 5 and pulled out, 9 is a water washing tank, and 1O is a dryer. Obtained: AfcNi
Table 2 shows the P alloy wheels and resistance values in the P alloy foil.

(Example 2) Using a single plate cathode 5 having an uneven shape as shown in FIG.
A P alloy foil was manufactured. The P content and resistance value of the obtained alloy foil f' are also shown in Table 2.

Table 2 ○: Good wide material with no split n on the end face △: Slight split n on the end face ×: Split n on the end face + center part As shown in Table 2, both Example 1 and Example 2: It was possible to produce a good wide material and obtain sufficient performance.

[Brief explanation of drawings]

Figure 1 is a conceptual diagram of the electrolyzer used in the method of the present invention, Figure 2
The figure shows the pulse period and current density, Figure 3 shows the relationship between ip and the amount of P eutectoid, Figure 4 shows the relationship between in-vehicle P% and resistance value, and Figure 5 6 and 7 are diagrams showing the electroforming equipment used in the examples.01... Electrolytic cell 2... Electrolyte solution 3... Anode 4
...Cathode (substrate) 5..Pulse generator 6-.Oscilloscope P (%) P content (At%) Electricity (fl (V, S, 5CE) Fig. 6 Fig. 7

Claims (1)

[Claims] (1) Using a Watts bath with a composition of phosphorus oxyacid or oxyacid salt, pulse current ip with on-time and off-time of 0.01 to 100 msec is applied to 10<i
Applying a current density of p<300 A/dm^3, Ni
A method for producing an amorphous NIP wide high resistance foil strip, which comprises depositing a P alloy and then peeling off a NIP alloy film from a substrate.