WO1991015608A1

WO1991015608A1 - Iron-copper alloy plate with alloy structure excellent in homogeneity

Info

Publication number: WO1991015608A1
Application number: PCT/JP1991/000463
Authority: WO
Inventors: Yoshiyuki Ueshima; Toshiaki Mizoguchi; Kenichi Miyazawa; Satoshi Nishimura
Original assignee: Nippon Steel Corporation
Priority date: 1990-04-09
Filing date: 1991-04-08
Publication date: 1991-10-17
Also published as: CA2058437A1; CA2058437C; EP0477383B1; KR920701496A; DE69116965D1; EP0477383A4; KR940008939B1; EP0477383A1; DE69116965T2

Abstract

An iron-copper alloy plate with an alloy structure excellent in homogeneity, produced by the continuous thin plate casting process, and usable as the material of electronic and magnetic components, said alloy comprising 20 to 90 % of Cu, 1 to 10 % of Cr, 0 to 10 % of Mo, and at least one element selected from the group consisting of Al, Sc, Y, La, Si, Ti, Zr and Hf in an amount ranging from the value calculated according to formula (I) up to 10 %, the balance being substantially Fe wherein $g(a) = 1, and $g(b) = 51 - [% Cu] when Cu = 20 - 50 %, or $g(b) = -19 + 0.4 [% Cu] when Cu = 50 - 90 %. Also boron and/or carbon can exhibit a similar effect to that of the abovementioned aluminum and the like.

Description

Description Title of invention

Fe-Cu alloy sheet with alloy structure excellent in homogeneity

The present invention relates to a Fe—Cu-based alloy plate having excellent uniformity and used as a material for electronic and magnetic parts.

Background art

Conventionally, Kovar (Fe-29Ni-16Co), 42 alloy (Fe-42% Ni), and other specialty materials for electronic and magnetic parts such as semiconductor devices have been used. The stainless steels disclosed in Japanese Unexamined Patent Publication No. 63-2929343 have been used, but these alloys are expensive and have problems in that they are inferior in conductivity and heat dissipation. . Therefore, copper (Cu) -based alloys have recently been used to improve these properties.

The Cu-based alloy has a Cu concentration of 90% or more and low strength. Therefore, in order to further improve the corrosion resistance by adding Fe as a strengthening element, it has been disclosed in, for example, Japanese Patent Application Laid-Open No. 49-91025 (alloys for sliding contacts of electric equipment). It is effective to add Cr as described above. In addition, as disclosed in the Iron and Steel Handbook, 3rd edition, volume 1, p. 211 to 212 (edited by the Iron and Steel Institute of Japan), the corrosion resistance is improved by adding Mo. It is known to improve. However, the addition of these alloying elements has a problem in that the homogenization of the alloy is impaired.

It should be noted that, although the alloy is disclosed in Japanese Patent Application Laid-Open No. 49-91025, the disclosed alloy is not for use in electronic and magnetic parts materials. The stainless steel for electronic materials disclosed in Japanese Patent Application Laid-Open No. 63-293431 is clearly different in components even though the application is the same. In the method for manufacturing an alloy strip disclosed in Japanese Patent Application Publication No. 0-152526, the range of components, the limitation of other elements to be added, and the effective concentration range are unclear. In addition, none of these prior arts has provided any information on the production of the Fe—Cυ alloy with excellent homogeneity aimed at by the present invention, and it may be possible to produce the alloy. No power.

In a Fe-Cu-based alloy, for example, an alloy containing 50% Cu, a homogeneous liquid phase can be obtained if Cr is not included. And a melt separated into a liquid phase rich in Fe and a liquid phase rich in Cu. Even if the production is carried out in such a state that the liquid phase rich in Fe and the liquid phase rich in Cu are separated, a homogeneous product cannot be obtained. That is, after the Fe-rich liquid phase particles and the Cu-rich liquid phase particles that have grown in size during melting have solidified, cracks occur during cold working at the interface between both phases, Problems such as poor bending characteristics occur. Disclosure of the invention

Thus, an object of the present invention is to provide an Fe—Cu—Cr alloy or a Fe—Cu—Cr—Mo alloy with the above-mentioned Fe-enriched liquid phase particles and C In order to eliminate the inhomogeneity of the alloy structure caused by the phenomenon that the liquid-phase particles rich in u grow coarsely, a special element is further added to the alloy, and fine and homogeneous steel is produced by a continuous thin-plate manufacturing method. The purpose is to provide an alloy sheet having a structure.

For the above purpose, the following alloy plate is provided.

(1) An alloy sheet manufactured by a continuous thin-plate manufacturing method, in which, by weight%, Cu: 20 to 90%, Cr: 1 to 10%, Mo: 0 to 1 0%, one or two or more elements selected from the group consisting of A, Sc, Y, La, Si, Ti, Zr and Hf, and their amounts or total The quantity is:

[% Cr] +2 benzene o 1 3 I [% Cu] -50

I β

3 300

Where α = 1,

/ 3 = 5 1-{% C u) (for C u = 20-50%),

β = -I 9 +0.4 [% Cu] (C υ = 50 to 90%) Also, it is the absolute value of I [% Cu]-50 l¾ and [% Cu]-50.

Fe—Cu-based alloy plate containing one or more elements that is not less than the calculated value and not more than 10%, and the balance is substantially Fe, and the alloy structure is excellent in homogeneity. .

(2) An alloy sheet manufactured by a continuous thin-plate manufacturing method, in which, by weight%, Cu: 20 to 90%, Cr: 1 to 10% Mo: 0 to 10% , Boron (B) and carbon (C), one or two of which are represented by the following formula:

Where = 0.01,

/ 3 = 51-[% Cu] (when Cu = 20-50%),

β =-I 9 + 0.4 ί% Cu (C υ = 50 to 90%)

Is the lower limit, and the upper limit is 1% for Β alone, 2% for B and C, and 3% for C alone. Fe-Cu-based alloy sheet having an alloy structure with excellent homogeneity, containing the following elements and the balance being Fe in effect. (3) An alloy plate manufactured by a continuous thin-plate manufacturing method, which is expressed in terms of% by weight.

C u: 20 to 90%,

Cr: 1 to 10%,

M 0: 0 to 10%,

A single element or two or more elements selected from the group consisting of A £, S c, Y, La, S i, T i, Z r, and H f, wherein the amount or the total amount is One or two or more of the above elements calculated from the following formula and not more than 10%, one or two of B and C, and the amount or the total amount thereof is It is equal to or more than the calculated value of the formula, and the upper limit is 1% for B alone and 2% for B and C, 3% for C alone. A Fe-Cu-based alloy sheet containing an element and having an alloy structure with excellent homogeneity with the balance being Fe in effect.

Formula: t96Cr + 2 麵 o] 1 3 I [% Cu] 1 50 1 1 β

3 300

However, α = 1 (when calculating the amount of elements belonging to groups such as Α ^),

= 0.01 (when calculating the amounts of B and C), β = 1-ί% C (for Cu = 20-50%),

β =-I 9 + 0.4% Cu (for Cu = 50 to 90%)

The alloy plate of the present invention is used as a material for electronic and magnetic components, and is formed of an alloy containing Fe and Cu as basic alloy components and containing Cu in the range of 20% to 90%. This alloy requires at least 20% or more Cu to increase electrical conductivity. Fe is added to improve the strength of the alloy. The addition range is determined based on the balance between electrical conductivity and strength according to the application, and is determined based on the balance with other addition elements.However, if the addition amount is too large, corrosion resistance may be impaired. . Cr is added in the range of 1 to 10% in order to improve corrosion resistance.However, Cr in the molten metal strengthens repulsion between atoms that are alloy components, so that a liquid phase rich in Fe, Cu Causes a two-phase separation of the rich liquid phase. Mo is added as needed, but the same phenomenon as Cr occurs. As described above, when a metal that has been separated into two phases in the molten state is produced as it is, the piece has a phase rich in Fe and a phase rich in Cu in the form of coarse crystal grains. And As a result, it becomes difficult to process them into electronic equipment materials and the like, and there is a defect in the properties of the products.

In the present invention, one or more selected from the group consisting of A, Sc, Y (yttrium), La, Si, Ti, Zr, and Hf are used as the basic components. Is added, This has the effect of preventing the base alloy from becoming coarse and two-phase. That is, when each of these elements is added to the molten metal, the attraction of each element is increased at the time of melting, and the liquid phase acts so as not to separate into two phases. Therefore, the following equation:

Where = 1,

= 51-[% Cu] (when Cu = 20-50%),

β =-I 9 +0.4 [% Cu] (Cu = 50 to 90%)

It is necessary to add one or more elements selected from the above group, which are equal to or greater than the calculated value of. When the value of the above expression is negative, the lower limit of the amount of addition is set to zero. The above formula is at least one selected from the group consisting of A £, Sc, Y, La, Si, Ti, Zr, and Hf (hereinafter, these are referred to as X! Elements). Addition of X: element to Cr and Mo content that promotes two-phase separation and Cu content (the more away from 50%, the more difficult it is to separate into two phases) The relationship between the lower limits is quantified by experiments of the present inventors. Also, when a large amount of X or element is added, it forms a solid solution in the Cu-rich phase and inhibits conductivity. So one kind of It is necessary that the added amount or the total added amount of two or more types does not exceed 10%.

On the other hand, boron (B) and carbon (C) also have the same effect as the element group of X, so that at least one of them (hereinafter, these are referred to as element X ₂ ) in the above formula is Add the value obtained as 0 1 as the lower limit. However, if it is contained in a large amount, coarse precipitates (for example, Fe ₂ B, Fe 3 C) are formed, which embrittles the structure. Therefore, the content of boron alone or the simultaneous addition of two types of boron and carbon should not exceed 1%, and the addition of carbon alone should not exceed 3%. The X, element, and X 2 elements may be added to each group or both groups together.

Other features of the present invention will be made clear by the following description with reference to the tables and the accompanying drawings. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic view of a twin-roll continuous forming apparatus for carrying out the present invention.

FIGS. 2a and 2b are graphs showing the relationship between the amount of the additive component of the present invention and the size of the structure.

In the present invention, the Fe—Cu-based alloy containing each of the above-described elements is manufactured by a continuous thin-plate manufacturing method. In particular, it is preferable to use a thin piece having a plate thickness of 10 or less and adopt a twin-roll method as the manufacturing method. That is, as schematically shown in FIG. 1, a single-side pressure reduction device 3 is installed on the cooling twin rolls 1 and 2, The molten metal from the molten metal pool 4 formed by the rolls 1 and 2 and the side dam 5 is cooled by the twin rolls 1 and 2 to form a solidified shell 6.鐯 It is pulled out as a piece 7. The pieces manufactured in this manner are cooled rapidly, and can be obtained with a thickness of 5 m or less. In addition to containing the elements X, X2, the pieces are extremely fine. A homogeneous structure. However, the present invention is not limited to the twin-roll manufacturing method, and other methods (for example, the single-roll method, Needless to say, the belt cast method, the caster billet cast method, etc.) may be used.

The thin strip can be directly cold-rolled without hot rolling to obtain a desired product thickness or an intermediate material. When the alloy of the present invention is hot-rolled, for example, heating to 100 ° C. or more may cause embrittlement, which may make rolling difficult. Therefore, in the present invention, the size of the piece is 10 or less, which can be directly cold-rolled. In the case of the twin roll method, a piece of 5 mm or less is obtained as described above, which is convenient for cold rolling. After cold rolling, annealing or the like, or applying plating or punching as necessary, the desired product, for example, thin material such as electromagnetic materials and lead frames, and various uses such as wire and foil Can be used for Example 1 The basic alloy materials (Fe-Cu-based alloys) 1 to 5 shown in Table 1 have various types of X! , X 2 elements were added in different amounts, and 1 kg was melted in a magnesia crucible at 1510, then contacted with a Cu cooling piece and quenched to obtain multiple samples. . The cross section of each quenched sample (4 thigh thickness) obtained was observed with an optical microscope, and the tissue size was measured to examine the tissue uniformity.

A. 1 Ϊ Λ. 2 兀: ¾ fe にゝ

Tables 2 to 6 show the tissue sizes according to the addition ratios defined in (1). Here, the term “structure size” refers to the maximum coarse particle size.

Table 1

Two

Gumi ^ (

0.1 U.O Ό.1 1 Ό 10 n

A £ 1500 1400 480 70 50 40 30

X. S c 1500 1420 520 80 60 40 30

Y 1600 1450 530 100 70 50 40

La 1450 1380 520 90 80 60 40

S i 1480 1410 510 100 70 50 40

Min T i 1520 1390 480 80 60 40 30

Zr 1510 1420 520 90 80 50 40

Hf 1460 1390 500 90 70 50 40

* i £ 3 1480 1400 490 80 60 40 40

B 1520 1300 550 70 50 30 30

C 1480 1400 650 90 70 40 40

* Note 4 1500 1380 530 70 50 40 30

* 1470 1390 500 70 50 30 30

* ¾1: An alloy obtained by adding Xfi¾3 ~ to this {alloy material 1 (50¾) Cu-6% Cr-F e) ^ ^ c ife result ^ ".

* .: The conversion is [% x]

You. However, for Xi = 1, α = 0.01 for X ₂ fi 29 ^ ¾m, and / 3-1.

* m: When all X, are equal to ^^ π.

* Note 4: J ^ fra equal to all χ ₂ ^

*: All X,, χ ₂ ^^ etc. * ¾¾ι 卩 * &.

3 Table

Group age (m)

* m: An alloy obtained by adding X ^^ to 2fe ^^ 2 (50¾Cu-3% Cr-0.3% Mo-Fe)

*: Nada [ _{% X} a ([]].] -3 — []

3 300 ^5QI . However, in the case of the Xi component ^ flB, α = 1, in the case of the Χ _two- component translation, = 0.01, and / 3 = 1.

the 4th

Tissue size (m)

t m: This alloy is obtained by adding Χβ ^ to this sickle 3 (70% Cu-3% Cr-Fe).

* ¾2: w itl, ί6Χ + a \ β Τ I ^! Is

3 300 Where Xi 劂 B has = 1, X ₂ has α = 0.01, and; 3 = 9

No.

Group ¾ t "(m)

0.1 0.5 0.7 1 2 5 10

A £ 1620 1550 490 70 50 40 40

Xl Sc 1510 1520 510 100 70 30 40

Y 1630 1610 500 80 60 40 30

La 1600 1550 420 75 60 50 40

Si 1580 1530 390 80 50 40 30

Min Ti 1390 1410 350 70 50 40 30

Zr 1400 1510 400 90 70 50 40

Hf 1450 1490 520 70 70 30 40

B 1510 1470 530 80 70 40 30

C 1480 1450 430 90 80 50 40

* m: This is ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^

[% Cr] +2 [cage o] 1 3 Cu] —50

* ^ 2: 满 Hfti (MX) ÷ a _p ”[%

τ¾¾

3 300

It is. However, X! Has α = 1, ₂ »¾ ^ has £ ϊ = 0.01, and = 31.

Table 6

Size (m)

0.1 0.5 0.7 1 2 5 10

AS 1620 1600 500 80 50 40 30

Xl Sc 1630 1650 610 90 50 30 30

Y 1550 1500 410 100 80 40 40 La 1620 1610 520 90 70 40 40

S i 1610 1520 390 100 60 50 30 min Ti 1610 1530 410 70 80 40 40

Zr 1540 1540 420 80 70 40 30

Hf 1380 1410 380 70 50 30 40

B 1430 1380 370 90 70 50 30

C 1440 1410 430 80 70 40 30

*: This is obtained by adding Xfi¾ ^ to this ¾ {合 ^ 15 (90% Cu-9% Cr-0.05% Mo-Fe) and a and a, ^ CrJ ₊ 2 ( _¾ Mo) -3 ! - Five. I,

3 300

You. However, Mel in i ^ 3 ^ & in Β of the Do _{= 1, Χ 2 5¾ ^ 1} = 0 Do the ¾ ^ of卩. 01, and = 17.

Each of the above basic alloy materials (samples) is also X! When the addition amount of each element of X and X ₂ becomes 1 respectively, the fine structure rapidly becomes, and the two phase (Fe-rich phase and Cu-rich phase) coarse structure disappears. Are shown. Example 2

As shown in Table 7, A £ and T i were added in six levels, each in the range of 0.1 to 5%, and the 50% Cu-6% Cr-Fe alloy was melted. A piece was manufactured by the twin-roll method shown in FIG. As the twin cooling rolls 1 and 2 in the twin-roll method continuous forming apparatus, copper rolls each having a diameter of 3 O mm and a width of 10 mm were used. Fabrication was performed at a fabrication temperature of 1510 ° C and a roll rotation speed of 20 rpm to obtain pieces having a thickness of 2.2.铸 Observation of the cross section of the piece with an optical microscope and measurement of the tissue size are shown in Figs. 2a and 2b (marked with A ^ added, with Kunimark Ti added).

As is evident from Figs. 2a and 2b, when the addition ratio of element X1 is less than 1, a two-phase coarsely separated structure is obtained, whereas when the addition ratio is 1 or more, the microstructure sharply decreases. .

In addition, the measurement results (shaded area) of X and the components of Example 1 are also shown in FIGS. 2a and 2b. Here, as can be seen from FIG. 2a, the basic alloy materials 1 to 3 of Example 1 showed the same tendency as that of Example 2. However, for the basic alloy materials 4 and 5 of Example 1, a shift was observed in the horizontal axis direction. The correction factor S was introduced into the denominator of, and integration was performed as shown in Fig. 2b.

Table 7 shows the results of investigations on the processing characteristics of the obtained alloy (judgment of the cold-rolled sheet) and the material properties as a lead frame material (limit number of breaks and shochu resistance). . That is, first, the 2.2 mm-thick pieces of Sample Nos. 1 to 12 were subjected to softening annealing at 800 ° C. for one hour, and then heated to 50 ° C. The iron phase was selectively etched by passing through a 1.5 m tank containing a 0% by volume nitric acid aqueous solution at a speed of 1 mZmin. After that, the primary cold rolling of the obtained sample was performed at 85%, and the cold rolled sheet cracking was judged. Next, the sample after cracking judgment was annealed at a temperature of 550 ° C for 3 hours, and during the subsequent cooling process, aging was performed at a temperature of 480 ° C for 3 hours, and then to a temperature of 100 ° C. After cooling at 50 ° C, secondary cold rolling was performed 8% to obtain a 0.3 mm thick product plate.

The product plate obtained in this manner was subjected to a repeated bending test in the following manner, and the maximum number of fractures was obtained. In other words, the center of the product plate with a width of 10 m and a length of 50 thighs is sandwiched by a vice, and repeatedly bent to an angle of 90 ° with an arc of 0.25 thighs, leading to fracture. The number of breaks was measured, and this was defined as the breaking limit.

In addition, the corrosion resistance was evaluated to be higher than the Fe-42Ni level by the salt spray test for 48 hours. No.

* m and use T50% Cu-6% Cr-Fe? ^

*: The quality of the mask was indicated as a case and X failed.

* m: In this case, the translation Blifc is equal to the translation amount [% x].

From the results in Table 7, it can be seen from the results in Tables 1 and 2 that the addition of 1% or more of A and Ti results in good cold rolled sheet cracking judgment, the maximum number of fractures, and corrosion resistance (range of the present invention). 1 to 3 and 7 to 9 all failed. Industrial applicability

The alloy material obtained by the present invention has excellent cold working properties and material properties, does not cause two-phase separation upon melting, has an extremely fine structure, and can be used as an electronic or magnetic material. It is preferably used.

Claims

The scope of the claims

1. An alloy sheet manufactured by a continuous thin-plate manufacturing method, in which, by weight, Cu: 20 to 90%, Cr: 1 to 10% Mo: 0 to 10%, A single element or two or more elements selected from the group consisting of A ^, Sc, Y, La, Si, TiZr, and Hf, wherein the amount or the total amount is The following formula:

Where = 0.01,

β = 1-C% C u) (for C u = 20-50%),

β =-I 9 + 0.4 ί% C) (Cu = 50 to 90%)

Fe-Cu alloy plate containing the one or more elements that is not less than the calculated value and not more than 10%, and the balance is substantially Fe, and the alloy structure is excellent in homogeneity. .

2. An alloy sheet manufactured by a continuous thin-plate manufacturing method, in which, by weight%, Cu: 20 to 90%, Cr: 1 to 10%,

M 0: 0 to 10%, one or two of B and C, whose amount or total amount is represented by the following formula:

Where hi = 0.01,

S = 5 1 — [% Cu] (when Cu = 20 to 50%),

1 9 + 0.4 C% C u) (when C u = 50 to 90%)

Is the lower limit, and the upper limit is 1% when B is added alone, 1% when B and C are added 2 types, and 3% when C is added alone. Fe-Cu-based alloy sheet having an alloy structure with excellent homogeneity, containing the following elements and the balance being Fe in effect.

3. An alloy plate manufactured by a continuous thin-plate manufacturing method,

C u: 20 to 90%,

Cr: 10%,

M 0: 0 to 10%,

A single element or two or more elements selected from the group consisting of A £, S c, Y, La, S i, T i, Z r, and H f, wherein the amount or the total amount is One or more of the one or two or more of B and C elements which are not less than the calculated value of the following formula and not more than 10%, The amount or total amount is equal to or greater than the calculated value of the following formula, and the upper limit is 1% for B alone and 2% for B and C, and 3% for C alone. An Fe—Cu-based alloy sheet containing one or two kinds of said elements, and having an alloy structure excellent in homogeneity with the balance being Fe in fact. Expression:

/ [Cr] Ten 2 [o] one 3 I [% Cu] one 50 of _β

3 300 /

α = 0.01 (when calculating the amount of Β and C),

/ 5 = 5 1 — [% Cu] (if Cu = 20-50%),

β =-\ 9 + 0.4 [% Cu] (When Cu = 50 to 90%)