JPS60145392A - Production of amorphous alloy - Google Patents

Abstract

PURPOSE:To electrodeposit an Fe-P amorphous alloy on the surface of a steel sheet as a cathode by subjecting the steel sheet to electroplating by using a bivalent Fe ion source of ferrous sulfate or iron sulfamate, etc. and a plating liquid contg. hypophosphorous acid or hypophoshite. CONSTITUTION:Ferrous sulfate, iron sulfamate or a mixture composed thereof is used as a bivalent Fe ion source which is the essential component for a plating liquid. Such an amt. at which the bivalent Fe ion corresponding to 100-500g/l when calculated in terms of FeSO4.7H2O is used. in this case. The plating soln. contg. the hypophosphorous acid or hypophosphite corresponding to 8-30g/l when calculated in terms of NaH2PO2.H2O as a P source and having 1.4-2.2pH is used. A steel sheet is electroplated by the above-mentioned plating liquid at 30-50 deg.C liquid temp. and 5-20A/dm<2> current density, by which the amorphous Fe-P alloy contg. 60-88atom% Fe and 12-30atom% P is deposited on the cathode.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing an amorphous alloy.

In recent years, amorphous alloys have been developed to improve their structure and physical properties (especially thermal,
It is beginning to attract attention for its electrical and magnetic properties, as well as its mechanical properties. That is, the following can be considered as general features of amorphous alloys.

(1) The mechanical strength is higher than that of practical metal materials, and is intermediate between that of practical metal materials and whiskers.

(2) The rigidity is 20 to 40% lower than that of crystalline metals.

(3) Almost no work hardening.

(4) Electrical resistance is generally high.

(5) Corrosion resistance is significantly improved by conversion of Cr, etc.

(6) It is possible to manufacture products with high magnetic permeability.

Conventionally, known methods for producing this type of amorphous alloy include sputtering, rapid cooling of a melt (e.g. gun method, piston anvil method, rolling method, centrifugal method), etc. The law is more commonly practiced. According to this method, Fe-based metal and amorphous elements (such as P and C
, B, Si) (7) Once the two or more species are dissolved,
This is cooled, pulverized, melted again, and quenched by spraying or the like to make it amorphous.

As a result, although it is possible to form an amorphous alloy film,
Since Fe has a high melting point, it is necessary to contain at least two types of amorphous elements in order to lower the eutectic temperature and facilitate manufacturing. Therefore, it is impossible to produce an alloy consisting of two elements, for example Fe--P, and the rapid cooling process is very complicated. Furthermore, it is difficult to control the thickness of the alloy coating or to vary the shape of the alloy coating.

The present invention is intended to correct the above-mentioned defects.
~500g/j! Ferrous sulfate and/or iron sulfamate in an amount that supplies divalent Fe ions corresponding to Na1
Calculated as lzPOz ・tlzo 8-30g/l
Using a plating bath mainly containing hypophosphorous acid and/or hypophosphite corresponding to pH 1.4 to 2.2,
A method for producing an amorphous alloy, in which an amorphous alloy mainly composed of Fe-P is produced by electroplating at a temperature of 30 to 50°C and a current density of 5 to 20 A/dm2. It is. By this method, it is possible to manufacture an amorphous alloy using one type of amorphous element very easily, and the amount of the amorphous element can be reduced, and the film thickness and shape of the alloy can be Control is also very easy.

Note that the Fe-P-based amorphous alloy produced by the method of the present invention contains 60 to 88 at% Fe and 12 to 30 at% P.
% is preferred. The reason for setting Re to 60 to 88 at% (ratio of the number of atoms) is that if Fe is less than 60 at%, plating will not adhere well and the P concentration will increase, resulting in a decrease in magnetic flux density B.
This is because m decreases, and if Fe exceeds 88 at %, the P concentration decreases and an amorphous alloy cannot be formed. Also, P was set to 12 to 3 Qat% because
Because of the exact opposite relationship to the Fe ratio mentioned above, if P is less than 12 at%, it is difficult to obtain an amorphous alloy, and if P exceeds 30 at%, the electrical resistance becomes too high, resulting in poor plating adhesion and magnetic flux. This is because the density Bm will decrease.

FIG. 1 shows the relationship between the concentration of P in the plating bath and the concentration of P in the plating film when plating is performed while satisfying the plating conditions described below. According to this, it can be seen that if the concentration of P in the precipitate (that is, the alloy) is less than 12 at%, it is difficult to become amorphous. Figure 2 also shows how the concentration of P in the plating film changes when the p++ of the plating bath is changed using a sulfamic acid bath, which will be described later, and satisfying the plating conditions described below. However, this shows that unless the concentration of P in the precipitate (that is, the alloy) is 128 t% or more, it is difficult to become amorphous.

In addition to Fe and P mentioned above, the amorphous alloy produced by the method of the present invention can also contain 1 to 2 at% of Cr, etc. to improve the corrosion resistance of the alloy, but in this case, Cr If it is not present as Cr'' in the plating bath, it is undesirable because Pe2+ will be oxidized to Fe3+.

In addition, in the method for manufacturing an amorphous alloy according to the present invention, divalent Fe ions, which are the main component of the plating bath, are ferrous sulfate (
FeSO4), iron sulfamate (Fe(Nl12SO
3) 2) or a mixture thereof.

In addition, ferrous chloride (ferrous chloride (
Although FeCβ2) also exists, it tends to generate Fe3+, so the Fe component that is not plated and precipitates increases,
Undesirable. The other main component of the plating bath is a source of P, and hypophosphorous acid (113PO2), hypophosphite, or a mixture thereof is used. Thorium oxide (Nat12PO2
) Potassium hypophosphite (Kl12PO2) and the like.

Next, to roughly describe the principle of plating, for example, FeSO
4 dissociates into Fe2+ and S04'-, and p e2+ moves to the cathode side, where it is reduced and electrodeposited as Fe.

In addition, hypophosphite, such as Na1lzPOz, is once converted to Na1lzPOz.
+ and (II2PO2)-2 dissociate, and these become Na0II and Il, pH 6, due to IhO2, but among these, N
a OH is 1Ja2sO4 due to the low pH of the plating bath.
It changes to. Therefore, hypophosphite is mostly H3
P0□, and it is considered that P is supplied from these. Note that Na in Nat12PO2 acts to stabilize this reagent.

The plating bath according to the present invention has the following basic composition and is preferably electroplated under the following conditions.

FeSO4'71120100~500g/AT7-ascorbic acid 2~10g#'Na1lzPOz -1
1208~30 g/7! When the pH is 1.0 to 2.2, the current density is 5 to 208 dm2, and the bath temperature is 30 to 50°, -ascorbic acid acts as a stabilizer for pe2+. In addition to the components of the above basic composition, poric acid (H3BO:+) and ammonium chloride (N11.C7) may be added.

As a plating condition, pll is outside the range specified in "-", 1.
If it is less than 4, the P concentration will increase, so the adhesion of the plating will be poor, and the proportion of Pe will decrease, resulting in a decrease in the magnetic flux density Bm.If it exceeds 2.2, the plating will not be good, but will be amorphous plating. It becomes difficult to do so. Furthermore, if the current density falls outside the range specified in 1. and is less than 5 Δ/dm2, plating becomes difficult, and if it exceeds 20 8/dm2, the electrode will be burnt, which is not preferable. Furthermore, if the bath temperature is too high, the components of the plating bath will precipitate.

Figure 3 shows the relationship between the pll of the plating bath and the Fe-based oxidation-reduction potential Eh.
! :Fe'' is -0.47 mV and is constant at pH=o~6. Figure 4 shows the relationship between the pH of the plating bath and the redox potential Eh of the P system. However, in order to plate a Fe-P-based eutectic alloy made of eutectic Fe and P, the above-mentioned oxidation-reduction potential (
-0.47 mV) and the redox potential with respect to P must be close. However, according to Figure 4, pl
If l becomes 2 or more, P and Il, PO□ or H2PO□
- The redox potential between
Therefore, at the redox potential of Fe, P is eutectoid and <
It turns out that it is difficult to obtain an amorphous material. Therefore, in FIG. 4, in order to obtain an amorphous alloy in a state close to the oxidation-reduction potential of P, pll is 2.2 or less, preferably 1.5-1.
It is necessary to set it to 2.0.

Furthermore, the plating bath according to the present invention may have the above basic composition modified, with FeSO4.1 instead of 711°0.
73 to 573 moles of iron sulfamate may be used and for this modified basic composition, 0 to 130 g #! for low activity and gloss imparting! 20 to 60 g/β of ammonium sulfamate, which adjusts PLL and acts as a buffer, and a small amount of brightener may be added. Furthermore, by adding an appropriate amount of nickel sulfamate or cobalt sulfamate, a Pe-Ni or Co-P based amorphous alloy can be formed.

When producing an amorphous alloy using the above-mentioned plating bath according to the present invention, as a pretreatment for plating, the object to be plated, for example, consisting of a Cu test piece, is first degreased and cleaned in trichlene vapor, and then, for example, 30 g/j2 After cathodic cleaning with Metalex W Special (trade name, manufactured by MacDermid), and subsequent washing with water, the main plating was carried out. In addition, as another pretreatment,
The β test piece was cleaned with trichlene vapor, then Cu struck (i.e., applying a thin Cu film) from a copper cyanide bath using the Zn or Sn substitution method, and then Cu plated from a copper pyrophosphate bath before main plating. Has entered.

This plating was carried out using plating baths according to the following examples of the present invention.

Example 1 An acidic plating bath having the following composition was prepared.

Fe5Ot ・7!120 300 g/ A'113
B03 30 g/e L-ascorbic acid 5 g/β Na1lzPOz 21 g/l1 NI1. Cβ 20g/Il Using this plating bath, plating was performed under the following conditions.

pll 2.2 Current density 10 A/dm2 Bath 'Pi, 40°C As a result, as shown in Fig. 5, the Cu film 2 with a thickness of about 1°C on the An specimen 1 with a thickness of about 0.2 mm , Fe-
The P-based amorphous alloy plating film 3 has a thickness of 30 to 100 mm!
(for example, about 50μ). To remove only this plating film 3, first remove the Aff test piece 1 by etching with Na0Il or KO)I, and then remove the Cu film 2 with NI+4
．． OH+NI+4. It is sufficient to remove it by electrolytic etching with CR.

According to this embodiment, the thickness of the plating film 3 can be freely changed by controlling the concentration of the components of the plating bath, pl+, current density, etc. In addition, if a mesochyresist layer (not shown) with a predetermined pattern is deposited on the surface of the Cu film 2, the plating film 3 can be applied to areas where this mesochyresist layer does not exist, so various patterns can be formed depending on the shape of the mesochyresist layer. A plating film can be easily formed.

Next, when X-ray diffraction was performed on the Fe--P alloy produced in the above manner, it showed a broad spectrum as shown in FIG. 6, and no peaks characteristic of crystallinity appeared. Figure 7 shows the change in magnetization with temperature using a magnetic balance, and it shows that as the temperature rises, the magnetization decreases, and when the temperature exceeds 300°C, it becomes crystalline as shown by the dotted line. It can be seen that although the amount of magnetization decreases to zero (one Curie point), in the case of the amorphous alloy according to this example, the amount of magnetization does not become zero and increases as the temperature rises1. This increase in magnetization is caused by crystallization of amorphous material, and it is therefore clear that the plated film produced according to this example is amorphous. Furthermore, Fig. 8 shows the results of differential thermal analysis of the plating film, which shows that amorphous crystallization occurs at the temperature at which the amount of magnetization increases (Fig. 7). It is clear that an exothermic reaction with differential heat is occurring.

Note that the Re-P-based amorphous alloy obtained in this example is, for example, FeBs, IP + 4. q, and the magnetic flux density was Bm-13200 gauss.

As explained above, since electroplating is performed using an acidic plating bath whose main components are Fe5On, which is a Fe supply source, and NaHzPO□, which is a P supply source,
It has now become possible to manufacture an amorphous alloy consisting of two elements, Fe-P, which was previously impossible.

Since the plating method is used, the operation is extremely simple compared to conventional methods, and the amount of P, which is an amorphous element, is relatively small. The amorphous alloy according to this example has various characteristics possessed by conventional amorphous alloys. In other words, it has high mechanical strength, almost no work hardening, relatively low rigidity, high electrical resistance, and high magnetic permeability. Very useful for composite materials, plates, wires, etc.

Example 2 In this example, an acidic plating bath having the following composition was prepared.

Fe5Ot ・71120 300 g/n113B
03 30 g/ll l7-ascorbic acid 5g/n NaHzPOz ・t120 8.5g/EN84C
620 g/β Using this plating bath, plating was performed under the following conditions.

pH 1,8 Current density 108 dm2 Bath temperature 40°C In the above plating bath, NaH and PO□・H2O are lower than in Example 1, but Fe-P similar to 3 mentioned in Example 1 is used. We were able to produce a non-crystalline alloy.

Example 3 In this example, plating was carried out under the same conditions as in Example 2 using an acidic plating bath having the following composition.

Fe5On・711zO278g/ ItN:SO4・
711□0 8 g/j! +1JO3a o g/
p L-ascorbic acid 5 g/7! Na1lzPOz ・H2O10.6g/7! N11
tC130g/ρ The amorphous alloy produced from this plating bath is pegsNi
It consisted of z, +P+□,,. When this alloy was subjected to X-ray diffraction, a broad spectrum similar to that shown in FIG. 6 was obtained, and other characteristics were also similar to those obtained in Example 1.

Example 4 In this example, an acidic plating bath having the following composition was prepared.

Iron sulfamate (as iron) 56g#! 4 L-ascorbic acid 5g/4 Urea 120g/A Ammonium sulfamate 40g/ρNa1l. P
Plating was carried out using a small amount of O□・1120 10.68/ff brightener and this plating bath under the following conditions.

pl+ 1.83 Current density 108 dm2 Bath temperature 30°C Regarding the Fe-P alloy deposited from the above plating bath
When line diffraction was carried out, a broad spectrum was obtained as shown in spectrum a shown in Figure 9, but compared to spectrum b of α-iron, which shows a sharp peak, the alloy according to this example was amorphous. It shows that it is of high quality. Further, as a result of analysis, the alloy according to this example has Pe8□,
2P1□1. It has a composition of
s, and its temperature characteristics were as shown in FIG. That is, the amount of magnetization decreases as the temperature increases 5, but unlike the crystalline material shown by the dotted line, the amount of magnetization increases when the temperature is further increased. This is due to crystallization and shows that the alloy according to this example is clearly amorphous. Furthermore, according to FIG. 11 showing the results of suggestive thermal analysis, as the temperature rises, the endothermic reaction turns into an exothermic reaction, which indicates that this is due to crystallization of the amorphous state.

For comparison, when plating was carried out with the pH of the above plating bath set to 2.27, a (110) peak of α-iron appeared as shown in spectrum b in Figure 9, indicating that this alloy plating was amorphous. It turns out that it is not.

Example 5 In this example, in the plating bath described in Example 4, NaHzPO□・thO was increased to 42 g/ff,
And If, 20g of BO3 was added. Then, plating was performed using this plating bath under the following conditions.

pH 1,68 Current density 7 A/dm2 Bath temperature 40°C It shows. Further, as a result of analysis, the alloy according to this example has a composition of Few+, a P ze, z, and a magnetic flux density Bm = 12000 gau.
It was ss.

Since the present invention has the above-described configuration, it is possible to manufacture an amorphous alloy having a large magnetic flux density Bm and having characteristics peculiar to Fe-P-based amorphous alloys.

In addition, since this amorphous alloy is manufactured by electroplating, it is possible to manufacture an amorphous alloy using one kind of amorphous element P very easily, and the film thickness and shape can also be controlled very easily. Easy to use.

[Brief explanation of the drawing]

The drawings are for explaining the amorphous alloy according to the present invention, and FIG. 1 shows the PGM degree in the plating bath and the P? of the plating precipitate. Curve diagram showing the relationship with a degree and the amorphous region, 2nd
The figure is a curve diagram showing the relationship between the pn of the plating bath and the P concentration of the plating precipitates and the amorphous region.
A diagram showing the relationship between the oxidation-reduction potential Eh7 ■b of the e system, and Figure 4 shows the pH of the plating bath.
Fig. 5 is a cross-sectional view of an An specimen on which a Fe-P-based amorphous alloy plating film has been deposited, and Fig. 6 is a diagram showing the relationship between P-based oxidation-reduction potential Eh and An X-ray diffraction spectrum diagram of the alloy, Figure 7 is a curve diagram showing the temperature characteristics of its magnetization, Figure 8 is a curve diagram showing the results of its differential thermal analysis, and Figure 9 is another Fe-P amorphous one. FIG. 10 is a curve diagram showing the temperature characteristics of magnetization of the amorphous alloy, and FIG. 11 is a curve diagram showing the results of differential thermal analysis. Agent Ueya Katsutsunekae Yoshio 8 F -Yo=0--Hat) -Kikki:! A Zero Semi V Horror

Claims (1)

[Claims] Calculated as Fe5Ot' 7+120, 100~5
Ferrous sulfate and/or iron sulfamate in an amount that supplies divalent Fe ions corresponding to 00g/12, and NaHzP
Using a plating bath mainly containing hypophosphorous acid and/or hypophosphite corresponding to 8 to 30 g/It calculated as O2.1120, p I+ 1, 4 to 2.2
, iWt degree 30~50℃, current density 5~20A/dm
A method for producing an amorphous alloy, in which an amorphous alloy mainly composed of Fe-P is produced by electroplating under the conditions of 2.