JPS5910998B2 - Manufacturing method of amorphous alloy - Google Patents

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 are considered to be the general features of amorphous alloys: (1) 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. 15(3) Almost no work hardening.

(4) Electrical resistance is generally high.

(5) Corrosion resistance is significantly improved by adding Cr or the like.

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

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 method is more commonly practiced25.

According to this method, an Fe-based metal and two or more types of amorphous elements (for example, P, C, B, and Si) are once dissolved, cooled, crushed, and melted again. It is then quenched by spraying or other means to make it amorphous. As a result, it is possible to form an amorphous alloy film, but since the melting point of Fe is high, it is necessary to include at least two types of amorphous elements in order to lower the eutectic temperature and facilitate manufacturing. . Therefore, it is impossible to manufacture an alloy consisting of two elements, for example Fe--P, and the rapid cooling process is extremely troublesome. Furthermore, it is difficult to control the thickness of the alloy coating or to vary the shape of the alloy coating.
The present invention was invented to correct the above-mentioned defects, and the first invention consists of divalent Fe ions corresponding to 100 to 5009/t calculated as FesO4.7H20, and NaH2pO2. Calculated as H2O 8-3
Using a plating bath mainly containing hypophosphorous acid and/or hypophosphite corresponding to PHL. O~
2.2, temperature 30~50℃, current density 5~20A/Di
The present invention relates to a method for producing an amorphous alloy mainly composed of Fe-P, which is electroplated under the conditions of 2.

The second invention of the present invention has divalent Fe ions equivalent to 100 to 500 g/t calculated as FeSO4.7H20 and 8 to 309 g/t calculated as NaH2PO2.H2O.
/t of hypophosphorous acid and/or hypophosphite;
Ni ions and/or 109/t or less calculated as nickel sulfamate and/or cobalt sulfamate
Or, using a plating bath mainly containing CO ions, PHL. O~2.2, temperature 30~50℃, current density 5
~20A/d! ? By electroplating under the conditions of 60 to 88 at% Fe and a
% or less of Ni and/or CO and 12 to 30 at% of P
The present invention relates to a method for producing an amorphous alloy comprising:

By these methods, 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 alloy film can be manufactured very easily. The thickness and shape can also be controlled very easily. Next, to explain the reason why the proportions of the components of the amorphous alloy produced by the method of the present invention are limited to the above range, first, Fe is
The reason for the 88 at% (ratio of the number of atoms) is that Fe is 60a
If it is less than t%, the plating will be poor b, the P concentration will increase and the magnetic flux density Bm will decrease, and Fe will be 88
This is because if it exceeds at%, the P concentration will decrease and an amorphous alloy will not be formed.

In addition, the P content was set at 12 to 30 at% because of the exact opposite relationship to the above-mentioned negative effects of Fe, so it is difficult to obtain an amorphous alloy when the P content is 12 at%, and when the P content exceeds 30 at%, the electrical resistance This is because D becomes too high, resulting in poor plating and also a decrease in magnetic flux density Bm. In Figure 1,
The relationship between the concentration of P in the plating bath and the concentration of P in the plating film is shown when plating is performed while satisfying the plating conditions described below.

According to this, the concentration of P in the precipitate (i.e. alloy) is 12a
It can be seen that if it is less than t%, it is difficult to become amorphous. Furthermore, Fig. 2 shows how the concentration of P in the plating film changes when the pH 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 also results in the formation of precipitates (i.e. alloys).
It can be seen that unless the concentration of P in the material is 12 at% or more, it is difficult to form an amorphous state. Note that the amorphous alloy produced by the method of the present invention contains, in addition to the above-mentioned Fe and P, for example, Ni, C
O etc. at O-10at (Fe-Ni-P system containing F6,
It may be an amorphous alloy such as Fe-CO-P system or Fe-Ni-CO-P system.

It is also possible to improve the corrosion resistance of the alloy by further containing 1 to 2 at% of Cr, but in this case Cr is Cr3
Fe2+ is Fe if it is not present in the bath as +.
In addition, in the method for producing an amorphous alloy according to the present invention, divalent Fe ions, which are the main component of the plating bath, are preferably oxidized to ferrous sulfate (FeSO4).
, iron sulfamate (Fe(NH2SO.3)2), etc.
Alternatively, it can be obtained from sources that supply Fe2+, such as mixtures thereof.

The other main component of the plating bath is a source of P, and hypophosphorous acid (H3PO2), hypophosphite, or a mixture thereof is used. Sodium acid (NaH2PO2) and potassium hypophosphite (KH2PO2) are often mentioned.Next, to outline the principle of Metsuki, for example, FesO4 is a combination of Fe2+ and S
Fe2+ dissociates into O42- and moves to the cathode side, where it is reduced and electrodeposited as Fe. Also, hypophosphite, for example, NaH2pO2, once becomes Na+ (H2PO2)
- dissociates into NaOH and H3P by H2O
However, since the pH of the plating bath is low, NaOH changes to Na2SO4.

Therefore, most of the hypophosphite becomes H3PO2, and it is thought that P is supplied from this. Naka NaH2
The Na in PO2 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.

In this case, L-ascorbic acid acts as a stabilizer for Fe2+. In addition to the above basic composition, an appropriate amount of nickel sulfate (NiSO4.7H2) is used as a source of Ni.
0), an appropriate amount of cobalt sulfate (COS) as a source of CO
O4.7H20) may be added. Also, boric acid (H3
BO3) or ammonium chloride (NH4Ct)? ? You may add As a plating condition, the PH is out of the above range,
If it is less than 1.0, the P concentration increases and plating becomes difficult, and if it exceeds 2.2, plating will occur but it will be difficult to form an amorphous plating.

Further, if the current density deviates from the above-mentioned range and becomes less than 5 A/Dm2, plating becomes difficult, and if it exceeds 20 A/Di, 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 pH of the plating bath. The relationship between the redox potential Eh of the 5Fe system is also shown (according to this, Fe and Fe2+
The redox potential between is -0.47mV and PH=
It is constant between 0 and 6.

Figure 4 shows the PH of the plating bath and the redox potential Eh of the P system.
However, F due to the eutectic of Fe and P
In order to plate an e-P eutectic alloy, the redox potential (-0.47 mV) for Fe and the redox potential for P must be close to each other. However, according to Figure 4, if PH becomes 2 or more, P and H3PO2
It can be seen that the oxidation-reduction potential between Fe and H2POi tends to be extremely low, and therefore, at the above-mentioned oxidation-reduction potential of Fe, it is difficult to co-fract P and it is difficult to obtain an amorphous material. Therefore, as shown in Figure 4, in order to flow an amorphous alloy in a state close to the redox potential of P, it is necessary to set the pH to 2.2 or less, preferably 1.5 to 2.0. be. Furthermore, the plating bath according to the present invention may have a modified basic composition, and instead of FeSO4.7H20, ★～→mol of iron sulfamate may be used. O~130g/t for glossiness
20-6, which adjusts the pH and has a buffering effect on urea.
0 g/t of ammonium sulfamate and a small amount of brightener may be added respectively. Furthermore, by adding an appropriate amount of nickel sulfamate or cobalt sulfamate, it is possible to form an Fe--Ni or CO--P based amorphous alloy. When producing an amorphous alloy using the above-mentioned plating bath according to the present invention, for example, Cu
The test piece to be plated was first degreased and cleaned using Triclean vapor, then cathodically cleaned using, for example, 30 g/t Metalex W Special (trade name, manufactured by MacDermid Co., Ltd.), and then rinsed with water before entering the actual plating.

Other pretreatments include cleaning the At specimen with trichlene vapor, followed by Cu strike (i.e., applying a thin Cu film) from a copper cyanide bath using the Zn or Sn substitution method, and then Cu strike (i.e., applying a thin Cu film) from a copper pyrophosphate bath. After finishing the mitsuki, I started the hon-metsuki. The main plating was carried out using plating baths according to the following examples of the present invention.

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

Using this plating bath, plating was performed under the following conditions.

As a result, as shown in Fig. 5, an At
On the Cu film 2 having a thickness of about lμ on the test piece 1, an Fe-P based amorphous alloy plating film 3 was deposited to a thickness of 30 to 100μ (for example, about 50μ).

In order to remove only the plating film 3, the At test piece 1 should first be removed by etching with NaOH or KOH, and then the Cu film 2 should be removed by electrolytic etching with NH4OH+NH4Ct. 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, pH, current density, etc.

Furthermore, if a plating resist 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 plating resist layer does not exist, so depending on the shape of the plating resist layer. Plating films with various patterns 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 if the temperature exceeds 300°C and it is crystalline, then the dotted line shows It can be seen that although the magnetization decreases to zero (single point), in the case of the amorphous alloy according to this example, the magnetization does not become zero and increases as the temperature rises. . This increase in magnetization is caused by the crystallization of amorphous material, and it is therefore clear that the plating film produced in this example is amorphous. Also the 8th
The figure shows the results of differential thermal analysis of the plating film, which shows that at the temperature at which the above-mentioned increase in magnetization (Figure 7) occurs, differential heat is generated due to crystallization of the amorphous material. It is clear that an exothermic reaction is occurring. The Fe-P amorphous alloy obtained in this example is, for example, Fe85.
．． b from lpl4.9, magnetic flux density Bm=13200g
It was auss.

In addition, by adding metal ions such as Ni or CO to the above plating bath, Fe-Ni-P system or Fe-C
It was also possible to manufacture O-P type amorphous alloys. As explained above, electroplating is carried out using an acidic plating bath whose main components are FesO4, which is a source of Fe, and NaH2PO2, which is a source of P. It has now become possible to produce an amorphous alloy consisting of two elements, P.

Since it is based on the plating method, 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 properties of conventional amorphous alloys. That is,
It has high mechanical strength, almost no work hardening, relatively low rigidity, high electrical resistance, and high magnetic permeability, making it suitable for small parts that require strength, including magnetic materials. Very useful for composite materials, plates, wires, etc. Example 2 In this example, an acidic solution having the following composition was used.

Prepare a lucky bath Then, using this metal bath, I did this.

Although the content of NaH2PO2.H2O in the above plating bath was lower than that in Example 1, an Fe--P amorphous alloy similar to that described in Example 1 could be produced under the following conditions.

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

The amorphous alloy produced from this plating bath is Fe85Ni
2. lPl was 2.9. 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, plating was carried out under the same conditions as in Example 2 using an acidic plating bath having the following composition.

The amorphous alloy produced from this plating bath is Fe-CO-
P group, its composition is Fe84. lCO2.8Pl3
．． It was l. Example 5 In this example, an acid plating bath having the following composition was prepared.

Using this plating bath, plating was performed under the following conditions.

Regarding the Fe-P alloy precipitated from the above plating bath
When line diffraction was performed, a broad spectrum was obtained as shown in spectrum a shown in FIG. This indicates that it is amorphous.

Moreover, as a result of analysis, the alloy according to this example has Fe87.2
The material had a composition of Pl 2.8, and the measurement result of the magnetic quantity using a magnetic balance was that the magnetic flux density Bm was 14,200 gauss, and its temperature characteristics were as shown in FIG. That is, the amount of magnetization decreases as the temperature rises, 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 Figure 11, which shows the results of differential 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 substance. . For comparison, the pH of the plating bath was set to 2.
When plated as No. 27, a (110) peak of α-iron appears as shown in spectrum b in FIG. 9, indicating that this alloy plating is not amorphous.

Example 6 In this example, in addition to the plating bath described in Example 5, NaH2PO2.H2O was increased to 42 g/t and 20 g of H3BO3 was added.

Using this plating bath, plating was performed under the following conditions. PHL. 68 The X-ray diffraction of the Fe--P alloy deposited from the plating bath is similar to spectrum a shown in FIG. 9, indicating that it is amorphous.

Further, as a result of analysis, the alloy according to this example has Fe7l. 8
It has a composition of P28.2}, and magnetic flux density Bm=120
It was 00gauss. Example 7 In this example, plating was performed by adding 2.0 g/t of nickel sulfamate to the plating bath described in Example 5, and the resulting alloy plating film was Fe87.2N.
iO. It had a composition of 4Pl2.4.

When this alloy was measured with a magnetic balance, the magnetic flux density Bm=
13,700 gauss, and the temperature characteristics of magnetic quantity and the results of differential thermal analysis had almost no difference from those shown in FIGS. 10 and 11. Example 8 In this example, 10 g/t of nickel sulfamate was further added to the plating bath described in Example 5 for plating, and the resulting alloy plating film was Fe85.2Ni.
l. It has a composition of 9Pl2.9 and a magnetic flux density of B
m=13300 gauss.

Example 9 In this example, plating was performed by adding 5 g/t of cobalt sulfamate to the plating bath described in Example 5, and the resulting alloy plating film was made of Fe.
85.2 cOl. 8pl8. It had a composition of O, and the magnetic flux density Bm was 13,500 gauss.

In addition, the temperature characteristics of the magnetization amount and the results of differential thermal analysis are the first
There was almost no change from what was shown in Figures 0 and 11. As described above, in the present invention, since Fe is 60 to 88 at% and P is 12 to 30 at%, an amorphous alloy having various characteristics unique to an amorphous alloy can be manufactured.

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

[Brief explanation of drawings]

The drawings are for explaining the amorphous alloy according to the present invention, and FIG. 1 is a curve diagram showing the relationship between the P concentration in the plating bath and the P concentration in the plating precipitate and the amorphous region. Figure 2 is a curve diagram showing the relationship between the PH of the plating bath and the P concentration of the plating precipitate and the amorphous region, and Figure 3 is a diagram showing the relationship between the PH of the plating bath and the Fe-based redox grains Eh. Fourth
The figure is a diagram showing the relationship between the PH of the plating bath and the redox potential Eh of the P system, Figure 5 is a cross-sectional view of the A1 specimen on which the Fe-P amorphous alloy plating film was deposited, and Figure 6 is the diagram showing the relationship between the PH of the plating bath and the P-based redox potential Eh.
- An X-ray diffraction spectrum diagram of the P-based amorphous 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 a separate diagram. Fig. 10 is a curve diagram showing the temperature characteristics of the magnetization amount of the amorphous alloy;
Figure 1 is a curve diagram showing the results of differential thermal analysis.

Claims (1)

[Claims] 100~calculated as 1 FeSO_4.7H_2O
Divalent Fe ions equivalent to 500g/l and NaH_2
Using a plating bath mainly containing hypophosphorous acid and/or hypophosphite corresponding to 8 to 30 g/l calculated as PO_2.H_2O, pH 1.0 to 2.2, temperature 30 to 50. A method for manufacturing an amorphous alloy, which comprises manufacturing an amorphous alloy mainly composed of Fe--P by electroplating under the conditions of .degree. C. and a current density of 5 to 20 A/dm^2. 2 Calculated as FeSO_4・7H_2O 100~
Divalent Fe ions equivalent to 500g/l and NaH_2
Hypophosphorous acid and/or hypophosphite corresponding to 8 to 30 g/l calculated as PO_2・H_2O, and Ni ions and/or not more than 10 g/l calculated as nickel sulfamate and/or cobalt sulfamate. / or C
Using a plating bath mainly containing o ions, pH
1.0-2.2, temperature 30-50℃, current density 5-20
By electroplating under the condition of A/dm^2, 6
A method for producing an amorphous alloy comprising 0 to 88 at% Fe, greater than 0 and 10 at% Ni and/or Co, and 12 to 30 at% P.