JPS6187889A - Production of thin alloy strip - Google Patents

Abstract

PURPOSE:To produce an extra thin or ultra-extra thin strip in a wide component compsn. range including a hardly workable material by forming multi-layered coating layers consisting of >=2 kinds of pure metals or alloys on a conductive substrate then stripping said layers from the substrate and subjecting the same to a solution heat treatment. CONSTITUTION:The substrate 1 which is a stainless steel strip is made into an endless belt shape and conductive carbon black is coated thereon to permit easy stripping. The substrate 1 is operated and is subjected to Ni plating in the 1st plating cell 6. The strip is washed in a washing tank 8 is subjected to Fe plating in the 2nd plating cell 7. The plated strip is washed in a washing tank 9. Such operation is repeated to form the multi-layered coating layers and thereafter the multi-layered coating layers are stripped by a stripping roll 11 and are taken up on a winder 12. The thin strip of the multi-layered coating layers is then subjected to the soln. heat treatment.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for manufacturing alloy ribbons, and in particular to a method for manufacturing an alloy ribbon, and in particular, for manufacturing electromagnetic alloys such as Fe-Ni alloys, which are soft magnetic materials with high magnetic permeability. Permalloy), hard magnetic materials Fe-Qr-QO system, Cu-)ii-F
It is particularly advantageous when applied to the production of extremely thin or ultra-thin ribbons made of e-based alloys, other stainless steel alloys, etc., and having a thickness of approximately several μm to 100 pm.

(Prior Art) With the progress in the field of electronics, the use of magnetic alloy ribbons has been increasing, especially as iron cores for computer power supplies and motors used in high frequency ranges, and even as circuit components for communication devices. In such applications, especially as the frequency of use increases, ultra-thin magnetic alloy ribbons with lower iron loss are required. It is expected that ultra-thin Fe-Ni alloys will come into use.In general, when manufacturing alloy ribbons, including the magnetic alloy ribbons mentioned above, it is necessary to prepare the alloy to a predetermined alloy composition. Generally, after casting molten metal into an ingot or slab, it is subjected to multiple stages of cold rolling including hot rolling and intermediate arm annealing to achieve the desired thickness, followed by a final heat treatment. Met.

(Problems to be Solved by the Invention) However, in this conventional method, even if the alloy is relatively easy to roll, it requires multiple cold rolling and intermediate arm annealing in order to finish it into a thin strip. necessary, especially 10
When trying to obtain an ultra-thin ribbon with a thickness of 0 μm or less, rolling becomes difficult as the sheet thickness decreases, and even if rolling is carried out slowly and carefully, the ribbon may sometimes break, making rolling difficult. A significant drop in efficiency and yield is unavoidable, which has the drawback of significantly increasing manufacturing costs.

Moreover, generally speaking, alloy materials undergo significant work hardening due to rolling, so it is often difficult to produce ultra-thin ribbons by cold or warm rolling, and depending on the alloy components, rolling itself may be problematic. There are also materials that can be punched, and for this reason, it has hitherto been extremely difficult to economically produce desired alloy ribbons on an industrial scale.

The present invention advantageously solves the above problems, and provides an alloy ribbon that can advantageously obtain an alloy ribbon of any composition and thickness without the need for thickness reduction processing. ! The purpose is to propose a method of construction.

(Means for Solving the Problem) That is, in the present invention, a multi-N coating layer made of two or more types of pure metals and/or alloys is formed on a conductive substrate, and then the coated layer is coated on the substrate. This is a method for producing an alloy ribbon, which is characterized in that the obtained multilayer coated R ribbon is then subjected to a solution treatment that causes mutual diffusion of constituent components of each layer.

Moreover, this invention provides rolling and/or! prior to or after the solution treatment. ! In this invention, the multilayer coating layer forming means includes electroplating, chemical plating, hot-dip plating, thermal spraying, vacuum The present invention will be described in detail below.

In the first vff, an example of the manufacturing process according to the present invention is shown in a flowchart.

As a conductive substrate for forming a multilayer coating, for example, a composite multi-stage plating layer, it is necessary to have suitable adhesion of the plating layer and surface characteristics that allow for easy peeling. It is preferable to apply a very thin coating of carbon black or graphite powder mixed with fine metal powder such as copper or silver. In addition, such a substrate includes:
When considering characteristics such as durability against plating baths, hydrogen embrittlement resistance, and non-magnetism, austenitic stainless steel thin copper sheets are especially suitable for G-1, and as for the plating surface, the smooth surface quality of alloy thin strips In order to obtain good releasability, it is desirable to perform smoothing treatment such as mirror polishing in advance.

Furthermore, the plating metal for forming the composite multi-stage plating layer may be any metal that can be electroplated; Select the metal, and at the same time, in order to control the desired mixed concentration, deposit the predetermined plating thickness for each metal layer in one or multiple stages, so that the total thickness of each plating layer is equal to the required ribbon thickness. It would be better to control it.

When targeting magnetic alloy ribbons as metals that can be electroplated, F8, Ni, ○O# Or
Examples include #Ou and punishment. When plating such metals, any known electroplating method may be used, but it is preferable to select a plating method that has fewer impurities in the plating layer and fewer lattice defects and pinholes. That is essential. The plating layer thickness is
Since it is proportional to the product of "electricity", "plating time" and "cathode efficiency", it is easy to set the "electricity JXr plating time" appropriately according to the cathode efficiency determined for each plating method and condition. and can be controlled accurately.

The reason why the electroplating method is basically used in this invention is that the above-mentioned plating layer thickness can be easily and accurately controlled, that is, the concentration of each alloy component can be controlled with little variation to the desired set value. This is because. Therefore, as long as the control and management of the plating layer thickness is easy and accurate, there is no problem in using plating techniques other than electroplating, such as chemical plating, hot-dip plating, or thermal spraying.

In this regard, when the desired alloy component cannot be electroplated or is difficult to electroplat, especially when the component element is a secondary additive element and the alloy concentration is below a numerical coefficient, As described above, in the intermediate step of forming electroplated layers in multiple stages, it is necessary to perform composite lamination using a surface coating method other than electroplating. For example, AI
, Si, V.

In cases where alloying elements such as Nb, Mo, and W are desired, in such cases, the above metals are compositely laminated to a predetermined thickness by vacuum layer deposition, ion blasting, sputtering, etc. The desired alloy concentration can be adjusted.

(Function) Next, the case where composite multi-stage plating is performed according to the method of the present invention will be specifically explained in the order of steps.

FIGS. 2 to 4 illustrate the procedure for forming the multilayer coating layer ribbon, respectively.

FIG. 2 shows the case of manufacturing a rectangular alloy ribbon, in which number 1 is a conductive substrate, 2 to 4 are plating baths,
Composite multi-stage plating is performed by sequentially immersing the substrate 1 into a plating bath.

FIG. 8 shows a case where a long alloy ribbon is manufactured using an endless belt-shaped substrate, and in the figure, number 5 is a substrate made of an endless belt, 6.7 is a plating tank, 8.9 is a cleaning tank, and 10 is a surface coating device, and the plating WJa*
't or the multilayer coating layer formed on the substrate 5 by the surface coating device 10 is cleaned after leaving the '19
1 and then wound into a coil by a ribbon winder 12.

Further, FIG. 4 shows a case where a multilayer coating layer ribbon 18 is produced by a continuous plating method, and the procedure for forming the plating layer and other surface coating layers on the substrate 14 is the same as that shown in FIG. 8. It's the same.

The thus obtained multilayer coating is subjected to solution treatment to cause interdiffusion of the alloy components, thereby producing an alloy ribbon that is homogeneous in the thickness direction as well.

When such solution treatment is performed by short-time soaking treatment using a continuous annealing method, it is desirable to reduce the thickness of each coating layer and increase the number of layers so that the mutual diffusion distance between alloy components is shortened. On the other hand, in the case of long-time soaking treatment by patch annealing, the thickness of each coating layer can be increased to reduce the number of laminated layers. In addition, such solution treatment is generally preferably performed at a high temperature, or needs to be performed in a temperature range in which gold 8, which has the lowest melting point among the metals constituting the coating layer, does not melt. Furthermore, if there is a strong possibility that a eutectic with a low melting point will be formed between adjacent metals, the adjacent metals are diffused at a temperature below the eutectic point to form an alloy with a higher melting point, and It is important to use a method that raises the temperature to a certain level. Note that the atmosphere during the solution treatment is preferably neutral or reducing.

Incidentally, the alloy obtained as described above has sufficiently satisfactory properties as it is, but in this invention, it is necessary to further improve the vA performance, for example, to improve the magnetic permeability and magnetic anisotropy. Furthermore, in order to square the hysteresis curve, the alloy ribbon can be subjected to various heat treatments such as regular lattice annealing and magnetic field annealing.

Furthermore, if necessary, the alloy ribbon after solution treatment can be rolled and then heat treated in order to improve the crystal texture. To!Q5 It is necessary to limit the rolling to only one time.If the obtained alloy is difficult to process and it is preferable to carry out rolling, the multi-layered coating layer ribbon stage before solution treatment. It is also possible to apply rolling and then perform heat treatment that serves as both recrystallization and alloying.

In this way, ultra-thin or ultra-thin ribbons with thicknesses of several μm to 100 μm, which were difficult or impossible to produce on an industrial scale using conventional techniques, can now be produced inexpensively and efficiently on an industrial scale. I started getting it.

(Example) Example 1 An austenitic stainless steel strip with a thickness of 0.6 mm, a width of 500 mm, and a length of 10 m was made into an endless belt, and then
A substrate was prepared by applying conductive carbon black to the surface to improve peelability. Next, using the apparatus shown in Fig. 8, Ni plating is carried out using a nickel sulfamate bath in the first plating tank, and Fe plating is carried out using a mixed bath of ferrous sulfate and ferrous chloride in the second plating tank. Ni plating and Fe plating were alternately and repeatedly applied to the endless belt-shaped substrate described above to form a Ni-Fe composite multi-stage plating layer. The thickness of each plating layer was 1.0 μm, and composite lamination was performed by repeating each layer alternately 5 times, for a total of 10 layers, 1
The plated layer was 0.2 m thick.

After that, the thin strip consisting of this composite multi-stage plating layer is peeled off from the substrate, and then subjected to solution treatment in a continuous annealing furnace at 1150"C for 10 minutes in an atmosphere consisting of 2% H and the remainder 1R gas, and then rapidly cooled. and thickness 10 μm 1 width 5
Alloy NW with a composition of 514Ni -49%Fe with a length of 101n and a length of 101n! And so.

The variation in composition of the obtained alloy ribbon was within ±1%, and the variation in thickness was within 3%.

Example 3 As a conductive substrate, a plate thickness of 1. Using an austenitic stainless steel Z plate with a smooth surface Qw, width 80c+a, and length 1m with a thin coating of carbon black, a multilayer coating layer was formed as follows using the equipment shown in Figure 2. did.

That is, Ni plating with a thickness of 2.0 μm as the first coating layer,
After applying 0.4 μm thick ye plating as the second layer,
MO was laminated to a thickness of 0.152 m using a vacuum evaporation method, and then a 0.4 μm thick layer of ye plating was applied as the fourth layer and a fifth layer was layered.
By applying 2.0 μm thick N1 plating as a layer,
The multilayer coating had a total thickness of approximately 5 μm. Note that the same plating baths as in Example 1 were used for Ni plating and F13 plating.

Thereafter, 20 thin strips obtained by peeling off this multilayer coating layer from the substrate were stacked between annealed side plates and subjected to solution treatment. During this lamination, alumina flour was used as an annealing separator. The solution treatment was performed using a batch furnace and annealing at 1250''C for 1 hour in an Ar gas atmosphere containing ＠ amount of N3. 'The analysis result of W7 band is 15
%Fe-80%N1-5%MO,
It had the same composition as a high permeability soft magnetic material called Supermalloy.

Example 8 As a conductive substrate, the thickness is 0.5! , width 800IIJ1
1. Using an austenitic thread stainless steel hoop with a length of 100 m, a suspension of conductive carbon black in alcohol was coated on the surface of the hoop and dried to improve the surface's surface plating and peeling. The plating process uses a continuous plating apparatus as shown in Fig. 4.0 First plating layer: a mixed bath of ferrous sulfate and ferrous salt;
1re plating 6.0 μm thickness 0 2nd plating J9j: Cobalt sulfate bath CO plating 2.
7 μm thickness 0 8th plating layer: Sulfamine nickel-resistant bath Ni plating 1.5 μm thickness 0 4th plating layer: Sulfur! l! i5 steel bath o,a
Each C4 section was made to have a thickness of μm. Moreover, between the second plating tank and the eighth plating tank, an IW layer with a thickness of 2.0 μm is formed using a vacuum evaporation method. A continuous vacuum evaporation device was installed to cover the evaporation process.

The coating process begins with the first plating layer and passes through to the 4th plating tank, and then electroplating and vacuum deposition are performed to the above-mentioned thicknesses, and then from the 4th plating layer to the 1st plating tank. I plated it all at once in reverse order and applied 74 kukyogi.

The structure of the obtained multilayer coating layer was as follows: from the first layer to the seventh layer, Fe
6.074m -002,7pm -A/
2.0.4m -Ni 1.5μm -Ou
O,6pm -N11.5pm -1112,
0pm-O.

It was as follows: 2.7 μm - B'e a, o μm.

After this multilayer coating was peeled off from the substrate, C alumina flour was sprinkled as an annealing thickening agent, and the product was wound into a coil.

Solution treatment for alloying uses a batch furnace with a trace amount of H8
During heating, the temperature was maintained at 640°C below the melting point of A for 10 hours to form a kl-IJi-Co alloy with a higher melting point.
The test was carried out using a heat pattern in which the temperature was removed to 0''C and maintained for 5 hours to make the alloy components uniform in the thickness direction of the plate.

The alloy ribbon thus obtained has a composition of 51%1i'e -24%00 which is almost equal to the permanent magnet component called Alnico 5.
-18%Ni-8%Al-il1%CU.

In order to give this alloy ribbon even more magnetic anisotropy, the cooling process after the solution treatment was conducted at 1200 to 900
Rapid cooling between ℃ and then 1℃/S between 900 and 700"C
We performed magnetic field cooling by applying a magnetic field of 2,000 oe while gradually cooling at a cooling rate of
By holding for 0 hours to promote the growth of α, an ultra-thin thin strip of alnico permanent magnet with excellent magnetic unidirectionality was obtained.

Alnico permanent magnets are difficult-to-process materials and were thought to be impossible to manufacture into thin strips on an industrial scale.

(Effects of the Invention) Thus, according to the present invention, a wide range of compositions can be used, including difficult-to-process alloys that were conventionally considered impossible or difficult to form into R-bands, and the plate thickness is from 100 μm to several μm. Thin or ultra-thin alloy ribbons can be produced inexpensively and efficiently on an industrial scale.

[Brief explanation of the drawing]

FIG. 1 is a flowchart of the Komagome process according to the present invention, and FIGS. 2 to 4 are schematic diagrams of a coating apparatus suitable for use in forming a multilayer coating layer according to the present invention.

Claims (1)

[Claims] 1. After forming a multilayer coating layer made of two or more types of pure metals and/or alloys on a conductor substrate, the coating layer is peeled off from the substrate, and then the obtained multilayer coating A method for manufacturing an alloy ribbon, characterized by subjecting the layered ribbon to solution treatment. 2. After forming a multilayer coating layer made of two or more types of pure metals and/or alloys on a conductive substrate, the coating layer is peeled off from the substrate, and then the obtained multilayer coating layer ribbon is formed by solution treatment. A method for producing an alloy ribbon, which comprises rolling and/or heat treatment before or after the treatment. 3. The method according to claim 1 or 2, wherein the means for forming the multilayer coating layer is electroplating. 4. The method according to claim 1 or 2, wherein the means for forming the multilayer coating layer is a combination of electroplating and other surface coating methods.