JPS5873787A - Manufacture of electrolytic iron foil of high strength - Google Patents

Abstract

PURPOSE:To manufacture tough electrolytic iron foil of high strength even at high current density by adding Ni and/or Co ions to a ferrous chloride soln. with high concn., using the resulting soln. as an electrolytic soln., and electrodepositing an alloy. CONSTITUTION:A soln. prepared by adding 1-50g/l Ni and/or Co ions to an iron chloride soln. contg. 150-400g/l ferrous ions is used as an electrolytic soln. Electrodeposition is carried out on a substrate for electroforming at 95-120 deg.C in the presence of a soluble or insoluble anode, and by stripping the electrodeposited layer, electrolytic iron foil contg. Ni and/or Co is continuously manufactured.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing electrolytic iron and foil having high strength and toughness.

Electrolytic iron foil is obtained by electrodepositing iron on a peelable electroforming substrate such as titanium, stainless steel, or niobium using an electrolytic bath containing ferrous ions, and then peeling it off from the electroforming substrate. It will be done. Electrolytic iron foil is thinner, wider, and has better shape than steel sheets or foils produced by conventional rolling methods, and it also has higher strength, magnetism, and heat resistance than aluminum foil or copper foil. Because it can be used as a composite material with paper or plastic, or as an electrical material, it has many uses. Among these applications, composite materials require strength even if they are thinner, as well as toughness that can withstand light bending and drawing.
For electrical materials, electrolytic iron foil with even higher strength is desired. For example, building materials, packaging container materials, etc.
It is used by laminating it with plastic, but laminating requires improved strength of the electrolytic iron foil. In addition, as one of the uses of electrical materials, when electrolytic iron foil is perforated and used as a perforated shielding plate for color televisions, it is often used under high tension to prevent thermal distortion caused by electron beam irradiation. , or because the strength of the electrolytic iron foil allows it to maintain a specific shape, an electrolytic iron foil that has the strength to withstand these is required.

In order to make electrolytic iron foil tougher, there is a strengthening method using alloys. Conventional iron alloy electrodeposition is, for example, disclosed in Japanese Patent Publication No. 44-258.
33', Japanese Patent Publication No. 54-12090, the purpose is to improve magnetism, corrosion resistance, and decorativeness, and electrodeposition is not intended. In other words, no consideration is given to manufacturing electrolytic foil by peeling off the plating layer.
-21227 describes a method for manufacturing iron base gold foil, but the alloying element content is as high as 40 to 50%, so it cannot be called electrolytic iron foil, and furthermore, there is no improvement in the mechanical properties of the resulting electrolytic foil. is not mentioned at all.

An object of the present invention is to provide a method for producing an improved electrolytic iron foil that has high strength and can withstand a certain degree of processing even at high current densities.

In order to achieve the above objective, we conducted various studies and found that Ni and Co ions were added to a highly concentrated ferrous chloride solution.
Using a solution containing one or two species as an electrolytic solution, electrodeposit an alloy mainly composed of iron on a substrate for electroforming at a temperature of 95°C or higher to form an electrodeposited layer 1 from the substrate for electroforming. One or two types of Ni or CO obtained by peeling...□t! [MMti#(1, Insect.-It turned out to be Eo66.

Figure 1 shows Ni and C in an electrolytic iron foil with a thickness of 30 μm.
o content and tensile strength, Erichsen* (log rope)
showed the relationship between When the Ni and Co-containing bar is 0.596 or more, the strength and Erichsen value are improved, and the effect of toughening the electrolytic iron foil can be achieved.

In order to produce the above electrolytic iron foil, the concentration of ferrous ions in the electrolytic solution must be 150 to 4 CIOt/l.
If it is less than /l, the stress of the electrodeposited layer will be high and it will become brittle, and the electrolytic iron foil cannot be peeled off from the electroforming substrate. If it exceeds 400,971, the electrolytic voltage becomes extremely high, which unnecessarily increases power consumption, and crystals form as iron chloride, which is undesirable. The violet of N1 and Co ions in the electrolyte is 1 to 509
71 is preferable; if it is less than 12/l, the amount of Ni and Co eutectoid in the electrolytic iron foil is small and there is no toughening effect, and if it is more than 50 t/l, the amount of Ni and Co is too large. Eutectoid, increase electrodeposition stress, and use as electrolytic iron foil:
:X・1. ：、、：、I can't be brave. Co content contained in the electrolytic iron foil is 0.5 to 20%, preferably 0.5 to 10961'#IJ, 20
A strip electrolytic iron foil containing 4 or more Ni and 0,000 or more suffers from significant distortion due to electrodeposition stress and cannot withstand use. Also N
Since i and Co have similar properties, they have the same effect on strengthening electrolytic iron foil, and when Ni and CO are used together, the sum of the amounts of each added is equal to the amount added when added alone. corresponds to To make Ni or Co ions coexist in the electrolyte, there are two methods: adding metal salts such as Ni or CO chlorides and sulfates, using these metals or alloys as part of the anode, or using an insoluble anode. There is a method of chemically dissolving these metals or alloys in a separate tank.

Further, the electrolysis temperature is preferably 95°C or higher; if it is lower than 95°C, the stress of electrodeposition is high, and even if electrodeposition is possible, it cannot be taken out as a foil. In addition, when the temperature exceeds 120℃,
This is not preferable because the electrolytic solution boils and entrains foreign matter into the electrolytic iron foil, resulting in poor surface conditions.

The current density is preferably IOA/ds or more, and is 10 A.
/d or less, a large amount of Ni or CO will precipitate,
Electrodeposition stress becomes high, cracks occur significantly, and the foil cannot be peeled off from the electroforming substrate. Furthermore, is it preferable to adjust the pH of the electrolyte to below O? , If the pH is 0 or more, the ductility of the electrolytic iron foil will be impaired.

the above? By electrodepositing under these conditions, 0.5 to 20% of Ni or CO, preferably 0.5%, is added to the electrolytic iron foil.
-1096 can be contained, and a strong electrolytic iron foil with less distortion due to electrodeposition stress etc. can be obtained.

The present invention can also be applied to a method of manufacturing electrolytic iron foil using a soluble anode or an electrolytic iron foil using an insoluble anode. In addition, in the use of the electrolytic iron foil of the present application, the thickness of the electrolytic iron foil with remarkable effects is 5 to 70 μm,
It is preferably 10 to 50 μm, but depending on the use,
There are cases where it deviates from this range, so the thickness is not particularly limited.1.1.

As a substrate for electroforming, a metal plate such as titanium, stainless steel, or 1,000 ohms is processed into a drum shape or an endless belt shape, and iron is electrodeposited while rotating or transferring in an electrolytic solution.
By peeling off the electrodeposited layer, if the Ni
Electrolytic iron foil containing one or two species can be produced continuously.

The electrolytic iron foil according to the present invention has higher strength and toughness than those containing neither Ni nor CO, and has sufficient strength even when laminated with plastic, and can be subjected to light drawing. It can also be used in perforated shielding plates for color televisions, and can withstand use under tension.

- Next, the present invention will be specifically explained using examples.

Example Using a carbon plate as an anode and a titanium plate as a substrate for electroforming, iron was electrodeposited to a thickness of 30 μm under the conditions shown in Table 1 and peeled off from the titanium plate to obtain electrolytic iron foil. Ta. In addition, since ferric ions are formed at the anode, the electrolytic solution is taken out from the electrolytic tank to a separate tank, reduced to ferrous ions by iron scrap, and returned to the electrolytic tank.
The pH of the electrolytic solution was maintained at 0 or less by adjusting the amount of iron scrap or by using hydrochloric acid, and nickel chloride and cobalt chloride were added to adjust the concentration as shown in Table 1.

Analysis of Nj and Co amount of the obtained electrolytic iron foil,
Tensile test, Erichsen tension test, (10 ■ steel balls)
The results are shown in Table 3.

Comparative Example Iron electrodeposition was carried out in the same manner as in the example, under the conditions shown in Table 2, and on those that could be peeled off from the titanium plate, tests were conducted in the same manner as in the examples, and the results are shown in Table 3. Indicated. Third
Like me, 1゛ shown in the example.

Although the electrolytic iron foil (corrosion 1-/%15) has a current density of 50 A/d; IL6, it has a lower strength and Erichsen value than the comparative electrolytic iron foil (416) that does not contain N1 and CO. All of them are high (and the toughness has been significantly improved.

Comparative Examples Nos. 17 and 18 have low N1 and Co contents, and the strength and toughness have not been improved much, and Nos. 19 and 20 have too low ferrous ion concentration, resulting in high electrodeposition stress and poor performance of the foil. 1
′− is not achieved. Also /1621-23 is N
Examples where there were too many i and CO groups to remove the foil as a foil, %24-25 are examples where the electrolytic temperature was too low and the electrodeposition stress was high, so the foil could not be peeled off from the titanium plate. “・: RU, KIT・ ′i:,.

[Brief explanation of drawings]

Figure 1 shows the relationship between the Ni and Co contents of electrolytic iron foil and its strength, and Figure 2 shows the relationship between the Ni and Co contents in electrolytic iron foil. Table 3 of manufacturing conditions for electrolytic iron foil shows the relationship between test results and Erichsen values. 1, Ill; Mt. N; OJ and Ca4 quantity (X) Nib, rv (,! Amount (%) Procedural amendment (method) % formula % 1. Indication of the case 1982 Patent Application No. 17Q724 2. Invention Name: Manufacturing method for high-strength electrolytic iron foil 3, relationship with the amended case Patent applicant address: 4-3 Kasumigaseki-chome, Chiyoda-ku, Tokyo Name: Toyo Kohan Co., Ltd. Representative: Kozo Yoshizaki 4, Agent Person: 100 Address: 4-3 Kasumigaseki-chome, Chiyoda-ku, Tokyo February 23, 1982 (shipped) Specifications and drawings: 12, θ, \0, -;
7. Contents of the amendment (1) Lines 3 to 1 from the bottom of page 8 of the specification will be deleted; (2) Page 12 of the specification will be amended as shown in the attached sheet. (3) Amend the drawing as shown in the attached sheet. FIG. 1 shows the relationship between the N1 and co contents of the electrolytic iron foil and its strength, and FIG. 2 shows the relationship between the N1 and co contents in the electrolytic iron foil and the Erichsen value. Patent applicant: Toyo Kohan Co., Ltd.

Claims (1)

[Claims] ・An electrolytic solution is a solution in which 1 to 509/l of one or two types of Ni ions, especially Co, and 4 ions are added to a ferrous chloride solution containing 150 to 400 t/l of ferrous ions. A method for producing high-strength electrolytic iron foil, which is electrodeposited on a substrate for electroforming at a temperature of ss-' 120°C and peeled off from the substrate for electroforming.