JP2003301243A - Fe-Ni ALLOY SHEET SHOWING EXCELLENT CORROSION RESISTANCE AND ELECTROCHEMICAL PROCESSABILITY - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an Fe-Ni alloy sheet showing both corrosion resistance and electrochemical processability. <P>SOLUTION: The Fe-Ni alloy sheet comprises, by mass, 29-55% Ni, 0.001-0.1% Si, 0.001-0.5% Mn, ≤0.01% C, ≤0.01% O and the balance being Fe and unavoidable impurities. A photoelectron spectrometry of its outermost surface detects substantially ≤4% Si+Mn atoms and a metal peak accounting for 0.5-6% of the total area of an FeO peak, an Fe<SB>2</SB>O<SB>3</SB>peak and the metal peak. Here, Ni may be partially replaced by ≤10 mass% Co, and the alloy sheet may comprise, by mass, ≤0.005% B, ≤0.01% N and at least one chosen from ≤0.1% Nb, ≤0.1% Zr and ≤0.1% Hf. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to Fe-Ni which is excellent in corrosion resistance and electrochemical treatment characteristics used for a shadow mask used in a picture tube of a color television or a computer display or a lead material of various electronic parts.
The present invention relates to a thin alloy sheet.

[0002]

2. Description of the Related Art Fe-Ni alloys are produced by pressing a steel ingot or subjecting it to hot rolling, or by continuously casting a hoop produced by continuous casting to a predetermined sheet thickness by repeating cold rolling and annealing. It Fe produced in this way
In the Ni-based alloy thin plate, defective rust often occurred during storage or during transportation. For such a problem that requires corrosion resistance, for example, JP-A-6-7345
2, JP-A-7-252600, JP-A-7-252601, JP-A-8-3
No. 33654 proposes to improve rust resistance by forming a thin oxide on the surface of an alloy thin plate for a shadow mask.

[0003]

The method described above is an excellent method from the viewpoint of corrosion resistance. However, Fe-N
It has been considered that the presence of the above-described oxide film deteriorates these characteristics in various electrochemical treatments performed on the i-based alloy, such as etching and plating. Therefore, it is usually pure hydrogen or ammonia decomposition gas (A
X gas, 75 Vol% hydrogen, 25 Vol% nitrogen) is used, and control is performed so that an oxide film is not formed by the treatment in a highly reducing atmosphere. That is, at present, no material has been proposed that has both the corrosion resistance and the basic characteristics required for Fe-Ni. In view of the above problems, the present invention is to provide an Fe-Ni alloy thin plate having both corrosion resistance and electrochemical treatment characteristics.

[0004]

[Means for Solving the Problems] The inventors of the present invention proceeded with research on the surface state of a Fe-Ni-based alloy in order to achieve both corrosion resistance while maintaining the basic characteristics of electrochemical treatment such as etching. Found that it is effective to prioritize the oxidation of Fe, which is a matrix, over the oxidation of Si, Mn, etc., and to adjust the surface state to detect Fe in the metal state in a specific range. That is, in the present invention, N in mass%
i: 29-55%, Si: 0.001-0.1%, Mn: 0.001-0.5%, C: 0.01%
Hereinafter, O: 0.01% or less, the balance is Fe and Ni-based alloy thin plate consisting of inevitable impurities, when the outermost surface is measured by a photoelectron spectroscopy analyzer, the atomic% of Si + Mn detected is substantially In the peak of Fe 2p3 / 2, which is detected at 700 to 740 eV at a binding energy of 4% or less, a linear background is defined, and the detected peak is detected by curve fitting with a Gauss / Lorentz product function. Is separated into FeO peak, Fe ₂ O ₃ peak and metal peak, and the separated metal peak is FeO peak, Fe ₂ O ₃
Is a Fe-Ni alloy thin plate excellent in corrosion resistance and electrochemical treatment characteristics, characterized in that the area ratio is 0.5% or more and 6% or less in the total sum of the peaks and the metal peaks.

Further, in the present invention, a part of Ni is used as a mass.
% Can replace 10% or less of Co. Further, in the shadow mask alloy thin plate of the present invention, in order to improve the hot workability, it may contain 0.005% or less of B, in addition, in order to improve the strength N: 0.01% One or more of the following may be included, Nb: 0.1% or less, Zr: 0.1% or less, and Hf: 0.1% or less.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION One of the important features of the present invention is that Mn
This is because the oxidation of Fe, which is the matrix, is prioritized over the oxidation of Fe. Mn and Si are semi-metal elements that are added or remain for refining and workability, etc., and are elements that are more likely to combine with oxygen than Fe and Ni forming the matrix. According to the study by the present inventor, when a strong reducing atmosphere mainly containing hydrogen is applied to all annealing steps,
Although the detailed cause is unknown, it was found that highly active Mn and Si are preferentially oxidized to form a surface state in which these elements are concentrated. These oxides are stable and deteriorate the characteristics in electrochemical treatment such as etching. On the other hand, when an inert gas atmosphere, for example, is used instead of the strong reducing atmosphere and the treatment is performed at a specific temperature, the formation of an oxide film of Mn or Si is suppressed, and the surface is dominated by the oxide of the matrix instead. Oxides of Fe are more likely to react electrochemically than oxides of Mn and the like, and are preferable as materials for applying various surface treatments such as etching and plating treatments.

In the present invention, the atomic% of Mn + Si detected when the outermost surface is measured by a photoelectron spectroscopic analyzer is an index indicating the form in which the formation of an oxide layer of Mn, Si is suppressed.
It is desirable to reduce the amount of stable Mn oxide by 4% or less, and preferably, the Mn atom% detected when the outermost surface is measured by a photoelectron spectrometer is substantially 1% or less.

Further, in the present invention, the oxidation state of the surface is not limited to that if the matrix is oxidized more than Mn or the like, and it is important to set the oxidation state within a specific range. That is, it is necessary to adjust the surface state to detect Fe in the metal state in a specific range on the outermost surface in order to achieve both corrosion resistance and electrochemical characteristics such as etching and plating properties. Specifically, Fe 2p detected at a binding energy of 700 to 740 eV when the outermost surface is measured by a photoelectron spectroscopy analyzer (ESCA)
At the peak of 3/2, a linear background is defined, and the detected peak is separated into the FeO peak, the Fe ₂ O ₃ peak and the metal peak by curve fitting with the Gauss / Lorentz product function. Then
The ratio of the metal peak after separation to the sum of the FeO peak, the Fe ₂ O ₃ peak and the metal peak is 0.5% in area ratio.
Adjust to 6% or less.

If the metal peak exceeds 6%, the surface is overactivated and there is a risk of rusting. If the metal peak ratio is less than 0.5%, the oxide layer becomes thick and the electrochemical characteristics deteriorate. More preferably, the percentage of the metal peak is 3 to 5%.

ESCA irradiates a sample with X-rays,
Electrons in specific electron orbits of the atoms that make up the sample are excited,
This is a device that measures the number distribution of kinetic energies of projected photoelectrons and analyzes the polar surface. In actual measurement, first, a qualitative analysis of the outermost surface of the test material is performed to confirm the detected elements. Next, for each detected element, the corresponding binding energy range is measured. For example, binding energy is 275-285 eV for C, 520-540 eV for O, and 700-740 for Fe.
eV, Ni 845-885eV, Co 770-810eV, B 180-200eV
V and N are 400 to 410 eV, S is 155 to 175 eV, Si is 95 to 115 eV, Mn
Is 43 to 63 eV, and Al is 65 to 85 eV. The measurement results were quantified by integrating the peak areas of the respective elements so that all the detected elements would be 100 atom% using the relative sensitivity coefficient peculiar to the apparatus.

The method of measuring the metal peak will be described in detail. When measuring the peak of Fe 2p3 / 2, the shift amount of the binding energy when the compound is formed is taken into consideration in the range of 700 to 740 eV. FIG. 1 shows an example in which the peaks of Fe 2p3 / 2 of the product of the present invention and the comparative example were measured. NIST (The US National Institut
(e of Standards and Technology) and ULVAC-PHI Co., Ltd. handbooks and other databases, the Fe 2p3 / 2 peaks are determined.
There are multiple peaks such as the peak of Fe 3+ corresponding to Fe ₂ O ₃ near 1 eV.

As described above, in the photoelectron spectroscopy,
When the Fe peak is measured, the average Fe binding state from the surface to a depth of tens of nm can be analyzed in detail.
Also, when focusing on such Fe state, a linear background is set for the Fe 2p peak detected at 700 to 740 eV, and the detected peak is Fe 2p 3/2 peak by the Gauss / Lorentz product function. FeO peak, Fe ₂ O ₃ peak,
By separating into metal peaks and determining the peak area,
The abundance ratio of Fe in each state is known. Regarding the spectral separation, the peak of FeO, the peak of Fe ₂ O _{3 and} the peak of the metal were determined by approximating the peak by the Gauss / Lorentz product function and curve fitting by the nonlinear least squares method. The background removal described here and the peak separation by curve fitting were performed with the analysis software attached to ESCA5300 manufactured by ULVAC-PHI.

FIG. 2 shows an example of the present invention for a situation where peaks are actually separated by such a procedure. A metal peak is shown near 706 eV, a Fe 2+ peak corresponding to FeO is shown near 708 eV, and a Fe 3+ peak corresponding to Fe ₂ O ₃ is shown near 711 eV. Regarding the measurement area of ESCA, in order to obtain highly accurate information with little error, it is good to take in a large amount of signal,
Therefore, the larger the measurement area, the better. Therefore, in the photoelectron spectrometer, it is appropriate to secure the measurement area in a wide range of about 10 mm x 2 mm and perform the measurement.

In the present invention, in the Fe-Ni alloy thin plate, when the plate has a large strain, a shape defect such as warpage occurs. As the strain measuring method, the half-value width measuring method by X-ray diffractometry, which enables the combined evaluation of the grain size and the strain, can be used for the evaluation. When the half width is large, it means that the crystal grains of the material are small and the lattice strain is large. The sample surface, which was electropolished 10 μm from the surface, was Co Kα of an X-ray diffractometer
When the half-value width of the diffraction peak of the (311) plane is more than 0.85 when measured by 1-line, unevenness occurs due to electrochemical treatment such as etching, and when it becomes 0.30, the variation in grain size due to recrystallization of the surface becomes large, Promote unevenness. Therefore, in the present invention, the full width at half maximum is preferably 0.30 or more and 0.85 or less.

Each chemical composition specified in the present invention will be described in detail below. Ni: Ni is an alloy composition having excellent adjustability of thermal expansion characteristics due to interaction with Fe, and the Ni content is in the range of 29 to 55% by mass. For example, about 36%, which has the lowest thermal expansion, is used for the shadow mask, and about 42% is used for the lead frame.
Si: Used for improving the hot workability of Si or as a deoxidizing element. If the Si content exceeds 0.1% by mass, a thick oxide film is likely to be formed and the electrochemical characteristics are deteriorated. Therefore, in the present invention, it is specified to be 0.1% or less. Also, 0.001%
Since it is practically difficult to make it less than 0.001%, it was set to 0.001% or more.

Mn: Mn has an effect of improving hot workability, but Mn has a problem that an oxide film is easily formed like Si. Therefore, in the present invention, it is specified to be 0.3 mass% or less. Also, it is practically difficult to make it less than 0.001%, so 0.
001% or more. C: C forms carbides and deteriorates electrochemical properties such as etching. Therefore, it is desirable to reduce the content as much as possible, and in the present invention, it is defined as 0.01% or less by mass%. O: O combines with elements such as Al, Si, and Mn to become oxide-based inclusions and deteriorates electrochemical properties, so it is desirable to reduce as much as possible. Therefore, in the present invention, the mass% is set to 0.01% or less.

Further, in the present invention, it is effective to replace a part of Ni with Co in order to obtain further low thermal expansion. Co is expensive, and the preferable addition amount in the present invention is 10% or less. Further, in the present invention, B may be added to improve hot workability. However, if the addition amount is large, an oxide film is likely to be formed. Therefore, when the addition amount is 0.003 mass% or less is preferable. Furthermore, the combined addition of N and Nb, Zr, Hf has the effect of forming fine nitrides and obtaining high strength.

If a large amount of N is added, the nitride will be coarsened and the electrochemical characteristics will be deteriorated. Therefore, it is desirable that the amount be 0.01% by mass or less. In addition, Nb, Zr, Hf, since it forms a coarse nitride when added excessively, if added, contains one or less of 0.1% by mass% or two or more such that the total is 0.1% or less. Preferably. Of these, the element that promotes the highest strength is Nb, and it is desirable to add Nb: 0.1% or less.

It is desirable that P, S, and Al, which are other typical elements contained inevitably, have the following compositions. S is an element that deteriorates hot workability, but if it is 0.002% or less by mass%, it can be produced without reducing the yield in the hot working step, so 0.002% or less is desirable. P
Is an element that enhances solidification cracking susceptibility of alloys and welding cracking susceptibility, but if its content is 0.015% or less by mass%,
Since the decrease in the alloy material production yield due to the above-mentioned adverse effect becomes not significant, it is desirable to limit it to 0.015% or less. Al has the effect of precipitation strengthening, but it is desirable to limit it to 0.05% or less because excessive addition facilitates the formation of non-metallic inclusions.

[0020]

Example (Example 1) A steel ingot having the components shown in Table 1 was produced in a vacuum induction melting furnace. After that, forging and hot rolling were performed to obtain a plate material having a thickness of 3 mm. Further, this plate material was repeatedly subjected to cold rolling and annealing using AX gas to obtain a cold rolled material having a thickness of 0.2 mm.

[0021]

[Table 1]

This cold rolled material was heated to 650 ° C. in a predetermined atmosphere.
A heat treatment of × 2 min was performed to control the surface oxidation state. X of the sample surface that was electropolished 10 μm from the surface of each sample
The full width at half maximum of the diffraction peak of the (311) plane was measured when measured with the Co Kα1 ray of a line diffractometer. By X-ray diffraction (31
1) The half width of the plane was 0.58 to 0.63. For the outermost surface of each sample, use Si and M with a photoelectron spectroscopy analyzer.
The concentration of n is detected and the binding energy is 700 to 7
The peak of Fe 2p3 / 2 detected at 40 eV was confirmed. Then, by the measurement method described above, Fe 2p3 / 2 detected as the peak of FeO, the peak of Fe ₂ O _{3 and} the peak of the metal.
The peaks were separated and each area ratio was calculated. The values are shown in Table 2. Table 3 shows the results of the rust generation test, the wettability as an electrochemical property, and the etching rate as an index of the electrochemical property. Here, the atmosphere used, as pure nitrogen gas, oxygen 0.02Vol%, hydrogen 0.5Vol%,
Residual nitrogen N ₂ gas and hydrogen, which is ammonia decomposition gas
It is AX gas with 75 Vol% and 25 Vol% nitrogen.

In Table 3, the rust generation test was an atmospheric storage test to evaluate the frequency of rust generation. In actual counting of rust, the surface of the material was magnified 50 times using an optical microscope so that fine rust could be detected, and the number of rust was counted when observing a visual field of 200 mm ² in total. From the data at this time, 100 mm ²
Table 3 shows the numerical values converted into the per hit data. For the purpose of reproducing the storage conditions, which are relatively severe as conditions for causing rust, the samples were left in a place where the humidity fluctuates at 70 to 80% and the temperature fluctuates at about 30 to 40 ° C. 96 in Table 2
The results of counting the number of rusts generated on the surface when left for each time are also shown. Regarding wettability, JI
The method specified in S K6768 was performed. In addition, regarding the etching speed, after the surface treatment by nitric acid immersion after alkaline degreasing, applying resist on the surface, baking and developing the mask pattern, the depth of the etching hole when spraying ferric chloride at 45Be, 60 ° C was sprayed. It was measured and determined.

[0024]

[Table 2]

[0025]

[Table 3]

As shown in Table 3, the etching rate of the sample of the present invention is higher than that of the sample No. 4 treated with AX gas which is supposed to be active. Therefore, according to the present invention, it can be seen that a material having excellent electrochemical treatment characteristics such as etching can be provided without deterioration of corrosion resistance, which is a problem due to the use of an active surface. In addition, it can be seen that Sample No. 1 having almost no metal peak has an unfavorably low etching rate because the surface is so altered.

(Example 2) In the same manner as in Example 1, steel ingots having the components shown in Table 4 were produced. After that, forging and hot rolling were performed to obtain a plate material having a thickness of 3 mm. Further, this plate material is repeatedly cold-rolled and annealed using AX gas to obtain a thickness.
A cold rolled material of 0.15 mm was obtained.

[0028]

[Table 4]

This cold rolled material was heated to 650 ° C. in a predetermined atmosphere.
A heat treatment of × 2 min was performed to control the surface oxidation state. X of the sample surface that was electropolished 10 μm from the surface of each sample
The full width at half maximum of the diffraction peak of the (311) plane was measured when measured with the Co Kα1 ray of a line diffractometer. By X-ray diffraction (31
1) The half width of the plane was a value between 0.60 and 0.70.
For the obtained sample, Si and M were prepared in the same manner as in Example 1.
Area ratios of n concentration, FeO peak, Fe ₂ O ₃ peak, and metal peak were obtained, and rust generation test, wettability as an electrochemical property, and etching rate as an index of electrochemical property were investigated. . The results are shown in Tables 5 and 6.

[0030]

[Table 5]

[0031]

[Table 6]

As shown in Table 6, as in Example 1, 42
Even in the% Ni-Fe system, it can be seen that by setting the content within the range of the present invention, it is possible to provide a material excellent in electrochemical treatment characteristics such as etching without deterioration of corrosion resistance.

(Example 3) In the same manner as in Example 1, steel ingots having the components shown in Table 7 were prepared. After that, forging and hot rolling were performed to obtain a plate material having a thickness of 3 mm. Further, this plate material is repeatedly cold-rolled and annealed using AX gas to obtain a thickness.
A 0.20 mm cold rolled material was obtained.

[0034]

[Table 7]

This cold rolled material was heated to 650 ° C. in a predetermined atmosphere.
A heat treatment of × 2 min was performed to control the surface oxidation state. X of the sample surface that was electropolished 10 μm from the surface of each sample
The full width at half maximum of the diffraction peak of the (311) plane was measured when measured with the Co Kα1 ray of a line diffractometer. By X-ray diffraction (31
1) The half width of the plane was a value between 0.57 and 0.63.
For each of the obtained samples, the area ratios of Si and Mn concentrations, FeO peaks, Fe ₂ O ₃ peaks and metal peaks were determined in the same manner as in Examples 1 and 2, and a rust generation test was performed and wetting was performed as an electrochemical property. The etching rate was investigated as an index of the characteristics and electrochemical characteristics. The results are shown in Tables 8 and 9. In addition, in Table 7, No. Nos. In Tables 8 and 9 were obtained by heat-treating C to G. It corresponds to each of 5 to 9.

[0036]

[Table 8]

[0037]

[Table 9]

As shown in Table 9, in the same manner as in Example 1, other Ni-Fe-based materials are also within the scope of the present invention, and electrochemical treatment such as etching is performed without deterioration of corrosion resistance. It can be seen that a material with excellent characteristics can be provided.

[0039]

According to the present invention, it is possible to achieve both the corrosion resistance and the electrochemical processability, which could not be achieved in the past, by setting the Fe-Ni alloy to a specific surface state. Therefore, it is an important technique for further promoting the industrial use of Fe—Ni alloys having useful properties such as low thermal expansion properties and soft magnetic properties.

[Brief description of drawings]

FIG. 1 ESCA of the surface state of the material of the present invention and the comparative material
It is a figure which shows an example of a measurement.

FIG. 2 is an example of peak separation performed from the measurement shown in FIG.

Claims (4)

[Claims] 1. Ni: 29 to 55%, Si: 0.001 to 0.1% in mass%,
Mn: 0.001-0.5%, C: 0.01% or less, O: 0.01% or less, balance is Fe
And in the Fe-Ni alloy thin plate consisting of inevitable impurities, when the outermost surface is measured by a photoelectron spectroscopy analyzer, the atomic% of Mn + Si detected is substantially 4% or less, and the binding energy is 700 to 740 eV. In the detected Fe 2p3 / 2 peak, a linear background is defined, and the detected peak is curve-fitted by the Gauss / Lorentz product function, and the detected peak is FeO peak, Fe ₂ O ₃ peak, metal. Corrosion resistance, which is characterized by the area ratio of 0.5% to 6% of the total of the FeO peak, the Fe ₂ O ₃ peak and the metal peak. And a Fe-Ni alloy thin plate having excellent electrochemical treatment characteristics. 2. A Fe—Ni alloy thin plate excellent in corrosion resistance and electrochemical treatment properties according to claim 1, wherein a part of Ni is replaced by 10% by mass or less of Co. . 3. The Fe—Ni alloy thin plate excellent in corrosion resistance and electrochemical treatment characteristics according to claim 1, wherein B: 0.005% or less is contained. 4. N: 0.01% or less, Nb: 0.1% or less, Z
The Fe-Ni system excellent in corrosion resistance and electrochemical treatment characteristics according to any one of claims 1 to 4, which contains one or more of r: 0.1% or less and Hf: 0.1% or less. Alloy sheet.