JPH02194154A - Manufacture of water-resistant high permeability alloy - Google Patents

Abstract

PURPOSE:To obtain the magnetic alloy easy to forge and having excellent effective permeability, saturation magnetic flux density and wear resistance by subjecting an alloy having specific compsn. essentially consisting of Ni, Nb, P and Fe to hot working, cold working and heat treatment under specific conditions. CONSTITUTION:An alloy essentially consisting of, by weight, 60 to 90% Ni, 0.5 to 14% Nb, 0.001 to 1% P and the balance Fe and furthermore contg., as auxiliary components, specific amounts of one or more kinds among Cr, Mo, Ge, Au, Co, V, W, Cu, Ta, Mn, Al, Ti, Zr, Hf, Sn, Sb, Ga, In, Tl, rare earth elements, platinum group elements, Be, Ag, Sr, Ba and B is subjected to hot working at 900 to 1000 deg.C and is thereafter cooled. The alloy is successively subjected to cold working at >50% working rate, is thereafter heated to the range of 900 deg.C to the melting temp. and is cooled from the order-disorder lattice transformation point or above at 100 deg.C/sec to 1 deg.C/hr cooling speed in accordance with the compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has Ni, Nb, P, and re as main components, and Cr, Mo+Ge, Au, and Co as subcomponents.
, V, H, Cu.

Ta, Mn, Air Si, Ti, Zr, H
f+ Sn, Sb, Ga, In.

TIl, rare earth elements, platinum group elements, Be+ Ag, S
r, Ba.

This relates to a method for manufacturing a wear-resistant high magnetic permeability alloy containing one or more types of B, and its purpose is to:
The objective is to obtain a magnetic alloy that is easy to forge, has a large effective magnetic permeability, has a saturation magnetic flux density of 40,000 or more, has a recrystallized texture of (110}<112>, and has good wear resistance.

Since magnetic recording/reproducing heads such as tape recorders operate in alternating magnetic fields, the magnetic alloys used therein must have high effective magnetic permeability in high-frequency magnetic fields, and magnetic tapes must slide in contact with each other. Therefore, it is desired that the wear resistance be good. Currently, as magnetic alloys for magnetic heads with excellent wear resistance, sendust (Fe-5i-An alloy) and ferrite (Mn
O-ZnO-FezOs), but these are extremely hard and brittle and cannot be forged or rolled. Grinding and polishing methods are used to manufacture the head core, and the finished product is therefore expensive. Sendust has a high saturation magnetic flux density, but cannot be made into a thin plate, so its effective permeability in a high-frequency magnetic field is relatively low. Further, although ferrite has a high effective magnetic permeability, its drawback is that its saturation magnetic flux density is low at approximately 4000 G. On the other hand, permalloy (Ni-Fe alloy) has a high saturation magnetic flux density but a low effective magnetic permeability (and is easy to forge, roll, and punch and has excellent mass productivity;
A major drawback is that it is easily abraded, and there is a strong desire to improve this.

The present inventors have previously discovered that Ni-Fe-Nb alloys are suitable as magnetic alloys for magnetic recording/reproducing heads because they are easy to forge and have excellent high magnetic permeability, and have patented this alloy. Applied (Special Publication No. 47-29690)
. Subsequently, the present inventors discovered that the wear phenomenon generally differs depending on the orientation of the alloy crystal, and it is known that crystal anisotropy exists. As a result of research on the relationship, Ni-Fe
- In Nb-based alloys, we discovered that the (100) <001> recrystallized texture is easy to wear, while the (110) <112> recrystallized texture has excellent wear resistance, and we have filed a patent application for this (patent application). Publication No. 58-57499, Japanese Unexamined Patent Publication No. 53
-26994).

Based on this knowledge, the present inventors went further and discovered that Cu is one of the elements that is said to have the effect of suppressing the formation of (100) <001> recrystallization texture in face-centered cubic metals. P was added to the same face-centered cubic Ni-Fe-Nb alloy, and the formation of recrystallization texture was studied. In other words, when the Ni-Fe binary alloy is cold-rolled (11
0) <112> + (112) <111> is produced, but when this is heated at high temperature, (100
) It is known that a <001> recrystallization texture develops. However, when Nb is added to this, the stacking fault energy decreases and a (110) <112> recrystallization texture is generated, but this can be changed by adding a small amount of P to the (100} <00b recrystallization texture. The growth of the recrystallized texture is suppressed, the growth of the (110}<112> recrystallized texture is preferentially promoted, and the (110) d12> recrystallized texture is formed, resulting in significantly improved wear resistance. It's about finding ways to improve.

Also, when P is added to Ni-Fe-Nb alloy, N1-P
.

Fe-P and Nb-P-based hard phosphides are precipitated in the matrix, increasing hardness and contributing to improved wear resistance, and the dispersed precipitation of these weakly ferromagnetic and non-ferromagnetic fine phosphides It was also found that the eddy current loss in an alternating magnetic field is reduced by dividing the magnetic domain, thereby increasing the effective magnetic permeability. In short, due to the synergistic effect of Nb and P, the (110) d12> recrystallization texture develops and the effective magnetic permeability increases, resulting in a high permeability alloy with excellent wear resistance.

To make the alloy of the present invention, 60-90% Ni, Nb0
．． 5-14%, P 0.001-1% and the balance Fe were melted in air, preferably in a non-oxidizing atmosphere (hydrogen, argon, nitrogen, etc.) or in vacuum using a suitable melting furnace. After that, a small amount of deoxidizing and desulfurizing agents such as manganese, silicon, aluminum, titanium, calcium alloy, magnesium alloy, beryllium alloy, etc. is added to remove as much impurity as possible.

In the present invention, Cr and Mo are added to the above alloy as subcomponents.

Ge, 7% or less of U, Co, 10% or less of V, 15% or less of W, Cu, Ta, 25% or less of Mn, Al
I St+ Tt, Zr+Ill Sn, Sb,
5 of Ga, In, Ti, rare earth elements, and platinum group elements
% or less, Be, Ag, Sr, Ba 3% or less, 8
1% or less of one or more types o, oi ~ 30
A predetermined amount of % is further added. The mixture thus obtained is thoroughly stirred to produce a compositionally uniform molten alloy.

Next, this is poured into a mold of an appropriate shape and size to obtain a sound ingot, which is further heated to over 900°C and 1000'C.
It is forged or hot-worked into a suitable shape, such as a bar or plate, at a high temperature below, and annealed at a temperature of 600° C. or higher, if necessary.

Next, this is subjected to a processing rate of 50% by methods such as cold rolling.
The above cold working is performed to produce a thin plate of the desired shape, for example, a thickness of 0.1m.
Punch out an annular plate with a diameter of 5 m and an inner diameter of 33 m, heat it in hydrogen or other suitable non-oxidizing atmosphere (hydrogen, argon, nitrogen, etc.) or in vacuum at a temperature of 900°C or higher and lower than the melting point for a suitable period of time, Then, from a temperature above the ordered-disordered lattice transformation point (approximately 600°C), it is cooled at an appropriate rate corresponding to the composition of 100°C/sec to 1°C/hour, or this is further cooled down to the ordered-disordered lattice transformation point (approximately 600°C). It is reheated for an appropriate time at a temperature of about 600"C or less, and then cooled. In this way, it has an effective magnetic permeability of 3,000 or more, a saturation magnetic flux density of 40,000 or more, and a recrystallized set of (110) <112>. A wear-resistant, high permeability alloy with a microstructure is obtained.

The invention will now be explained with reference to the drawings.

Figure 1 shows the recrystallization texture and various properties of an 80% Ni-Fe-5χNb-P alloy that was cold rolled at a processing rate of 85%, heated at 1050°C, and then cooled at a rate of 1000°C/hour. It shows the relationship between the characteristics and the amount of P.
When Ni-Fe-Nb alloy is cold rolled (110
) <112>+(112) <111> is produced, but when this is heated at high temperature, (110) <1
12>+ (100) A recrystallized texture of <001> is generated.

However, when P is added to this, (100) <Ool>
The formation of recrystallized texture is suppressed, and (110) <11
2> recrystallization texture develops, and the amount of wear decreases accordingly. Moreover, the effective magnetic permeability increases by adding P. Figure 2 shows 80%Ni-Fe-5%Nb-0.05%P
The graph shows the relationship between the recrystallized texture and various properties and cold working rate when the alloy is heated at 1050°C, and the increase in cold working rate is due to the recrystallized texture of (110) Provides development, improves wear resistance, and increases effective permeability. Figure 3 shows 80%Ni-Fe-5%Nb
This figure shows the relationship between the heating temperature, recrystallization texture, and various properties after rolling a -0.05% P alloy at a cold working rate of 85%. As the heating temperature increases, (112) < 11
1> component decreases, (110) <112> develops,
Wear resistance is improved and effective permeability is increased. Figure 4 shows alloy number 8 (80%Ni-Fe-5%Nb-0,05
%P alloy), alloy number 41 (79,5%Ni-Fe-
8%Nb-0,035%P-2%Mo alloy), alloy number 89 (82%Ni-Pe-2%Nb-0,085%P
Optimum cooling corresponding to the composition of the 0 alloy, which shows the relationship between effective magnetic permeability and cooling rate and the effective magnetic permeability (x mark) when this is further reheated for (-3% Si alloy) It can be seen that there is a speed, optimum heating temperature and reheating time.

Figure 5 is a characteristic diagram of the wear resistance of a magnetic head when Cr, Mo, Ge, Au, or Co is added to an 80% Ni-Fe-5% Nb-0.05% P alloy.
When No, Ge, Au, or Co is added, the effective permeability increases and the amount of wear decreases, but when Cr,
If Mo, Ge or Au exceeds 7%, the saturation magnetic flux density will be less than 4000 G, which is undesirable.
If it is more than 10%, the effective magnetic permeability will be less than 3000, which is not preferable.

Figure 6 shows the same 80%Ni-Fe-5%Nb-0.05
This is a characteristic diagram of the wear amount and effective magnetic permeability of the magnetic head when V, W, Cu, Ta or Mn is added to the %P alloy. increases and the amount of wear decreases, but if 10% or more of ■, 15% or more of W, and 25% or more of Cu, Ta, or Mn are added, the saturation magnetic flux density increases to
00 G or less, which is not preferable.

Figure 7 shows the same 80%Ni-Fe-5%Nb-0,05
%P alloy to AIr Sll Tll Zr+ Hft
Characteristic diagram when Sn, sb or Ga is added,
Affi, Si, Tit Zr+elbow, Sn, S
When 5% or more of b or Ga is added, the effective magnetic permeability increases and the amount of wear decreases, but Sll Tit
When Zr, Hf or Ga is 5% or more, the saturation magnetic flux density is 4000 G or less, and A1. If Sn or sb is 5% or more, forging becomes difficult, which is not preferable.

Figure 8 shows the same 80%Ni-Fe-5%Nb-0,05
%P alloy with In+ Ti, La, Ru, Be+
This is a characteristic diagram when Ag, Sr, Ba or B is added.In, Tit La.

When Ru, Be, ^L sr, Ha, or B is added, the effective magnetic permeability increases and the amount of wear decreases, but In, tj! , La+Ru at 5% or more, Be
If 3% or more of , Sr, or Ba is added, the saturation magnetic flux density becomes 4000 G or less, and if 3% or more of Ag or 1% or more of B is added, forging becomes difficult, which is not preferable.

Figure 9 shows an 80%Ni-Pe-5%Nb-0.05%P alloy manufactured in the same manner as in the example, forged at about 1000"C to a thickness of 7", and then heated at various heating temperatures. Thickness 0.67a
The thin plate was hot-rolled to 0.1 mm (cold-rolling rate: 85%) at room temperature, then heated in hydrogen at 1050°C for 2 hours, and then rolled at 1000°C/
FIG. 3 is a characteristic diagram showing the relationship between hot working temperature, recrystallized texture, and wear amount when cooling to room temperature at a rate of hr.

When the hot rolling temperature is below 900°C, (112) <
ltl> remains and the amount of wear is large, but from 900℃ to 10
At a temperature of 00°C, (110) <112> develops and the amount of wear becomes particularly small.

In the method for producing the alloy of the present invention, the temperature at 900°C to 1000°C
The recrystallized texture of (110}<112> develops significantly due to the correlation between the processes of repeating hot rolling at a temperature between 50°C, cold working at a working rate of 50% or higher, and heat treatment at a temperature of 900°C or higher. N1 with excellent wear resistance
-Fe-Nb-P alloy is obtained.

In the present invention, cold working is (110) <112>+
It is necessary to form the (112) <111> texture and develop the (110) <112> recrystallization texture based on this, and as seen in Figures 1 and 2, po , above ooi%, especially when the processing rate is 50%
When subjected to the above cold working, (110) <112>
The development of the recrystallized texture is remarkable, the wear resistance is significantly improved, and the effective magnetic permeability is also high. In addition, the heating performed after the cold working described above not only homogenizes the structure and removes processing distortion, but also develops a (110) <112> recrystallized texture, resulting in high effective magnetic permeability and excellent wear resistance. However, as shown in Figure 3, the temperature is particularly high at 900°C.
The effective magnetic permeability and wear resistance are significantly improved by the above heating.

It should be noted that repeating the above cold working and the subsequent heating above 900°C below the melting point is (110) <
112> is effective for increasing the degree of accumulation of recrystallized assembled fibers and improving wear resistance. In this case, the (110}<112> recrystallized texture can be obtained even if the working rate of the final cold working is 50% or less, but this is included in the technical idea of the present invention.

When cooling from a temperature above 900°C below the melting point to a temperature above the ordered-irregular lattice transformation point (approximately 600°C), there is no significant difference in the magnetism obtained whether cooling is rapid or gradual. , as seen in Figure 4, the cooling rate below this transformation point has a great effect on magnetism, that is, the cooling rate below this transformation point is 100''C/sec>1℃/hour. By cooling the earth to room temperature, the degree of regularity of the earth can be adjusted appropriately and excellent magnetism can be obtained.Then, when cooling at a rate close to 100"C/sec of the above cooling rates, the degree of regularity is small. (So, if it is cooled any faster than this, regularization will not progress, the degree of order will further decrease, and the magnetism will deteriorate.

However, if the alloy with low order is 2 below its transformation point,
100°C for 1 minute or more depending on the composition at 00°C to 600°C.
If the material is reheated for a period of time or less and then cooled, ordering progresses and the degree of order becomes appropriate, improving magnetism.

On the other hand, if it is slowly cooled from a temperature above the above-mentioned transformation point at a rate of, for example, 1° C./hour or less, ordering will proceed too much and the magnetism will decrease.

Note that it is preferable to perform the above heat treatment in an atmosphere where hydrogen is present, since this is particularly effective in increasing the effective magnetic permeability.

Next, the invention will be explained with reference to examples.

Then, it is cold rolled at room temperature with various processing rates to obtain 0.
．． A thin plate of one size was made, and an annular plate with an outer diameter of 451III11 and an inner diameter of 33 m was punched out.

Raw materials are 99.8% pure nickel, iron and 99.8%
An iron-phosphorus mother alloy with purity of niobium, molybdenum and phosphorus of 10x was used. To prepare the sample, raw materials were placed in an alumina crucible with a total weight of 800 g, melted in a high-frequency induction electric furnace in a vacuum, and then thoroughly stirred to obtain a homogeneous molten alloy. Next, this was poured into a mold with a hole of 25 mm in diameter and 170 mm in height, and the obtained ingot was forged at about 1000"C to form a plate with a thickness of about 1 tma.
The alloys listed in each of the above examples, Table 2 and the drawings include relatively pure metal Nb,
Crt Mot Poetry, Mn.

v, Ti, A7! , Si and rare earth elements, etc., but economically advantageous commercially available ferroalloys, master alloys, and Mitsushi metals can be used instead of these metals if sufficient deoxidation and desulfurization are performed during melting. Almost the same magnetic properties, wear resistance, and processability as when used alone can be obtained.

As mentioned above, the alloy of the present invention is easy to process, has excellent wear resistance, and has a saturation magnetic flux density of 40,000 or more, high magnetic permeability, and low coercive force. Not only is it suitable as an alloy, but
It is also suitable as a magnetic material for general electromagnetic equipment that requires wear resistance and high magnetic permeability.

Next, in the present invention, the composition of the alloy is Ni 6 as the main component.
0~90χ, Nb 0.5~14χ, P 0.001~
1χ and the balance is Fe, and the elements added as subcomponents are Cr + Mo + Ge, Au is 7z or less, C
o, V to! Below, W is 15% or less, Cu, T
a, Mn 25% or less, A1. St, Tit
Zr, If, Sn+ Sb, Ga
+ In, Tll.

Rare earth elements, platinum group elements less than 5%, Be, ^g, S
r.

The reason why Ba is limited to 3% or less and B is limited to 0.01 to 30χ in total of one or more types of 1% or less is shown in each example, Table 2, and drawings, especially in Figures 5 to 8. As is clear, the effective magnetic permeability in this composition range is 3000 or more, the saturation magnetic flux density is 40000 or more, and (110}<112>
It has a recrystallized texture and has excellent wear resistance, but
This is because if the composition falls outside of this range, the magnetic properties or wear resistance will deteriorate.

That is, Nb 0.5% or less and P 0.001%
Below, the recrystallization texture of (110) and <112> is not sufficiently developed, resulting in poor wear resistance, and when Nb is 14% or more and 211 or more, forging becomes difficult, and the effective magnetic permeability is 3000 or less, and the saturation magnetic flux density is 4000. This is because it becomes less than G.

And Ni 60~90χ, Nb 0.5~14χ, P
Alloys with a composition range of 0.001 to 1χ and the balance Fe have an effective magnetic permeability of 3000 or more, a saturation magnetic flux density of 40000 or more, excellent wear resistance, and good workability.
Generally, in addition to this, Cr+Mo, Ge+Au,
W, V, Cu+Ta, Mn, AI! tZr
+Si, Ti+Hf, Ga, rare earth elements.

Adding Be, Ag, B, etc. has the effect of particularly increasing the effective magnetic permeability, and adding Co has the effect of particularly increasing the saturation magnetic flux density.Ge + Au, vl Ta, w
, Ti, Zr.

Hf, ^1. Si, Sn+ Sb, Ga+
In, Tl + rare earth elements, platinum group elements, Be,
Addition of Ag, Sr, Ba, B, etc. is particularly effective in improving wear resistance, and Au, Mn.

T+, Coo rare earth element + Be+ Sr+ Ba+
Adding B has the effect of improving forging and processing.

[Brief explanation of the drawing]

Figure 1 is a characteristic diagram showing the relationship between the characteristics and PI of the 80χNi-Fe-5XNb-P alloy, and Figure 2 is the characteristic diagram of the 80χNi-Fe-5X Nb-0,05χP.
Figure 3 is a characteristic diagram showing the relationship between the strength properties of the 80χNi-Fe-5χNb-0,05χP series alloy and the relationship between the heating temperature. 80% Ni-Fe-5χNb-0,05χp alloy (
Alloy number 8), 79.5χNi-Fe-8χNb-
0,035χP-2XMo alloy (41), and 82χ
A characteristic diagram showing the relationship between the effective magnetic permeability, cooling rate, reheating temperature, and reheating time of Ni-Fe-2χNb-0,085χP-3χSi alloy (89). Figure 5 is for 802Ni.
-Fe-5χNb-0,05X P alloy with Cr and Mo
Figure 6 is a characteristic diagram showing the relationship between the characteristics and the amount of each element added when Ge, Au or CO is added.
V+' to χNi-Fe-5χNb-0,05χP alloy
Figure 7 is a characteristic diagram showing the relationship between the characteristics and the amount of each element added when Cu, Ta or Mn is added.
Af+ in 0χNi-Fe-5χNb-0,05χP alloy
St+ Ti+ Zr, or, Sn+ Characteristic diagram showing the relationship between the initial characteristics and the amount of each element added when Sb or Ga is added. Figure 8 shows In+ Tl+ La, Ru, Be, A.
A characteristic diagram showing the relationship between the properties and the amount of each element added when g+ Sr+ Ba or B is added. FIG. 3 is a characteristic diagram showing the relationship between texture and wear amount. Figure 5 Cr, No, ere, Attor or Co ('1
0) Tough Urinary Award Kiku Figure 7 Figure 8 In, T1. La orRu (%)Be, Al
, Sr, Ba or B (%) Mr. Warm (0C
) Report December 2, 1989,

Claims (1)

[Claims] 1. Ni 60-90%, Nb 0.5-14% by weight
, P0.001-1% and the balance Fe as main components, Cr, Mo, Ge, Au as subcomponents each at 7% or less, Co, V at 10% or less, W at 15% or less, C
u, Ta, Mn each 25% or less, Al, Si, T
i, Zr, Hf, Sn, Sb, Ga, In, Tl, rare earth elements, platinum group elements each at 5% or less, Be, Ag,
An alloy consisting of 3% or less each of Sr and Ba, 1% or less of B, a total of 0.01 to 30% of one or more types, and a small amount of impurities, is heated to a temperature of more than 900°C and less than 1000°C. After processing, it is cooled, and then subjected to cold working at a processing rate of 50% or more, and then heated at a temperature of 900°C or more and below the melting point,
Then, from the temperature above the regular-irregular lattice transformation point to 100°C
By cooling to room temperature at an appropriate rate corresponding to the composition of
00 or more, saturation magnetic flux density 4000G or more, and {11
A method for producing a wear-resistant high magnetic permeability alloy, which is characterized by forming a recrystallized texture of 0}<112>. 2.Ni60-90%, Nb0.5-14% by weight
, P0.001-1% and the balance Fe as main components, Cr, Mo, Ge, Au as subcomponents each at 7% or less, Co, V at 10% or less, W at 15% or less, C
u, Ta, Mn each 25% or less, Al, Si, T
i, Zr, Hf, Sn, Sb, Ga, In, Ti, rare earth elements, platinum group elements each at 5% or less, Be, Ag,
An alloy consisting of 3% or less each of Sr and Ba, 1% or less of B, a total of 0.01 to 30% of one or more types, and a small amount of impurities, is heated to a temperature of more than 900°C and less than 1000°C. After processing, it is cooled, and then subjected to cold working at a processing rate of 50% or more, and then heated at a temperature of 900°C or more and below the melting point,
Then, from the temperature above the regular-irregular lattice transformation point to 100°C
Cool at an appropriate rate corresponding to the composition/second to 1°C/hour,
By further heating this at a temperature below the regular-disorder lattice transformation point for an appropriate time corresponding to the composition for 1 minute to 100 hours and cooling, the effective magnetic permeability at 1 KHz is 30.
00 or more, saturation magnetic flux density 4000G or more, and {11
A method for producing a wear-resistant high magnetic permeability alloy, which is characterized by forming a recrystallized texture of 0}<112>.