CN1276986C - Fe-Ni series alloy thin band for pressure shaped shadow mask board - Google Patents
Fe-Ni series alloy thin band for pressure shaped shadow mask board Download PDFInfo
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- CN1276986C CN1276986C CNB2004100386075A CN200410038607A CN1276986C CN 1276986 C CN1276986 C CN 1276986C CN B2004100386075 A CNB2004100386075 A CN B2004100386075A CN 200410038607 A CN200410038607 A CN 200410038607A CN 1276986 C CN1276986 C CN 1276986C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02B—PREPARING GRAIN FOR MILLING; REFINING GRANULAR FRUIT TO COMMERCIAL PRODUCTS BY WORKING THE SURFACE
- B02B3/00—Hulling; Husking; Decorticating; Polishing; Removing the awns; Degerming
- B02B3/04—Hulling; Husking; Decorticating; Polishing; Removing the awns; Degerming by means of rollers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02B—PREPARING GRAIN FOR MILLING; REFINING GRANULAR FRUIT TO COMMERCIAL PRODUCTS BY WORKING THE SURFACE
- B02B3/00—Hulling; Husking; Decorticating; Polishing; Removing the awns; Degerming
- B02B3/06—Hulling; Husking; Decorticating; Polishing; Removing the awns; Degerming by means of screws or worms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02B—PREPARING GRAIN FOR MILLING; REFINING GRANULAR FRUIT TO COMMERCIAL PRODUCTS BY WORKING THE SURFACE
- B02B7/00—Auxiliary devices
- B02B7/02—Feeding or discharging devices
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Abstract
PURPOSE: To provide a press forming type Fe-Ni based alloy strip for shadow mask, which is capable of reducing deviation of side etching amount and contributing to shape uniformization and fine pitching of permeation hole even in a Fe-Ni based alloy containing Si or Va group elements. In a Fe-Ni based alloy strip having thickness of 0.05 to 0.3 mm comprising 34 to 38 mass% of Ni, 0.01 to 0.5 mass% of Mn, 0.03 to 0.10 mass% of Si, and the balance of Fe and inevitable impurities, the inevitable impurities comprising 0.01 mass% or less of C, 0.005 mass% or less of S, 0.005 mass% or less of N, and 0.005 mass% or less of O, the press forming type Fe-Ni based alloy strip for shadow mask is characterized in that the maximum Si concentration value is 7% or less in a surface layer region that is 0.1 [mu]m deep from the surface.
Description
Technical field
It is alloy thin band with Fe-Ni that the present invention relates to the pressure shaped shadow mask board, and particularly relating to the pressure shaped shadow mask board that contains Si and Va elements is alloy thin band with Fe-Ni.
Background technology
In the past, can aim at both allocations of the face of distinguishing by unit of cells, and use to be provided with a plurality of shadow mask boards that see through the hole for the electron beam that makes colour picture tube.Be used for the material of shadow mask board, as height become more meticulous and use the few Fe-Ni of thermal expansion is arranged is alloy and added the Fe-Ni-Co alloy (it being generically and collectively referred to as Fe-Ni in the present invention is alloy) of cobalt again.In recent years, more meticulousr in order to make display image than in the past, require narrow and smallization (little spacing) through pitch of holes.With this little spacingization is corresponding two motions are arranged.One of them method is to make the face shield thin-walled property.Owing to by thin-walled property, the erosion of thickness of slab direction is become easily, the lateral erosion amount reduces, so can realize pitchization.
Yet general shadow mask board is that the surface shape with Braun tube matches the ground pressure formed metal plate and makes, and sees through face by the electronics line that makes face shield and bends to spherical this shape that keeps.But, when making, needing to generate smooth electronics line and see through face with the universal recently corresponding shadow mask board of plane Braun tube, face shield can not be a curved shape always, keeps the shape of face shield also to become difficult.This problem is more remarkable under the thin-walled property situation.Therefore, the motion that improves material self intensity has been arranged again, on this point, it is likely having more high-intensity Fe-Ni-Co alloy than Fe-Ni alloy.
On the other hand, as the method beyond the thin-walled property, accuracy factors is corroded in influence when also having adjustment to form through the hole by the resist erosion, the attenuating of lateral erosion amount deviation, the fine pitch technology of raising erosion precision thus in the attenuating of realization lateral erosion amount and each hole.Report about this technology has: reduce face shield with the carbon concentration on the top layer of thin plate, improve the technology (for example referring to Patent Document 1 and 2) of resist closing force, or, for whole the processing of being carried out before evenly corroding, and the technology (for example referring to Patent Document 3) of the boron concentration on the top layer of regulation thin plate.
Patent documentation 1: the spy opens the 2001-316770 communique
Patent documentation 2: the spy opens the 2002-121650 communique
Patent documentation 3: the spy opens the 2001-73089 communique
Yet, under the situation of above-mentioned conventional art, when high silicon content alloy that will be formed by silicon deoxidation dissolving and the alloy that is added with Va elements such as vanadium as the high strength element, niobium were used for shadow mask board, the deviation that has the lateral erosion amount increased, through the uneven problem of hole shape.
Summary of the invention
The present invention proposes in order to address the above problem, its purpose is, even providing at the Fe-Ni that contains Si and Va elements is in the alloy, also can reduce the lateral erosion amount deviation, make through hole shape evenly, can realize that the pressure shaped shadow mask board of fine pitchization is an alloy thin band with Fe-Ni.
All results of study that the present inventor carried out show, are in the alloy at the Fe-Ni that contains Si, and the concentration of Si on the surface corrodes and can easily carry out when increasing, and can be stoped the deviation of lateral erosion amount by this concentration difference.And find that the silicon concentration by the control top layer can address the above problem.And, found that also the concentration of the Va elements on top layer and Cr is also influential to the deviation of erosion amount, stipulated its concentration.
In other words, in order to achieve the above object, pressure shaped shadow mask board of the present invention is that alloy thin band is characterised in that with Fe-Ni: by the nickel (Ni) of mass percent 34～38%, 0.01～0.5% manganese (Mn), 0.03～0.10% silicon (Si), all the other are constituted by iron (Fe) and unavoidable impurities, carbon in the described unavoidable impurities (C) is below 0.01%, sulphur (S) is below 0.005%, nitrogen (N) is below 0.005%, oxygen (O) is below 0.005%, described Fe-Ni is that alloy thin band thickness is 0.05～0.3mm, and the maximum value of Si concentration is below 7% the zone, top layer dark to 0.1 μ m from the surface.And then in mass percent, contain and add up to 0.05～0.5% selected more than one Va elements from V, Nb, Ta, to add up to the maximum value of concentration be 0.3～5% to Va elements in zone, described top layer.
Also have, pressure shaped shadow mask board of the present invention is that alloy thin band is characterised in that with Fe-Ni:
By the nickel (Ni) of mass percent 30～35%, 2～6% cobalt (Co), 0.01～0.5% manganese (Mn), 0.03～0.10% silicon (Si), all the other are constituted by iron (Fe) and unavoidable impurities (impurity), carbon in the described impurity (C) is below 0.01%, sulphur (S) is below 0.005%, nitrogen (N) is below 0.005%, oxygen (O) is below 0.005%, described Fe-Ni is that alloy thin band thickness is 0.05～0.3mm, and the maximum value of Si concentration is below 7% the zone, top layer dark to 0.1 μ m from the surface.And then in mass percent, contain and add up to 0.05～0.5% selected more than one Va elements from V, Nb, Ta, to add up to the maximum value of concentration be 0.3～5% to Va elements in zone, described top layer.
Is in the alloy thin band at pressure shaped shadow mask board of the present invention with Fe-Ni, preferred and then contain the chromium (Cr) of mass percent 0.03～0.20%, and the maximum value of chromium is 0.5～5% in zone, described top layer.
Embodiment
Be that the embodiment of alloy thin band is illustrated to pressure shaped shadow mask board among the present invention with Fe-Ni below.
The invention is characterized in, be in the alloy at the Fe-Ni that contains Si, and the top layer concentration of arranging the Si of resist adaptation by control is below the prescribed value, suppresses the deviation of lateral erosion amount.
Here, Fe-Ni of the present invention is an alloy thin band, comprises that more particularly Fe-Ni is that alloy thin band and Fe-Ni-Co are alloy thin band, is applicable to any pressure shaped shadow mask board.The pressure shaped shadow mask board is to be the shape of shadow mask board by pressure forming, owing to do not have tension load through on the face at the electronics line of face shield, so be also referred to as smooth tension force face shield.Particularly, the present invention can be used for plane Braun tube etc., is very suitable for the electronics line and sees through the almost smooth pressure shaped shadow mask board of face.
Then, the reason of stipulating each composition constituent content among the present invention is illustrated.Here, so-called each composition constituent content is the amount of composition element in the expression matrix, is different from the constituent concentration in zone, top layer described later.Also have, the so-called % among the present invention is not having to be meant mass percent under the situation of specified otherwise.
Nickel (Ni) is in order to make the necessary element of stabilization of austenite in the alloy thin band, to also have, in order to lower the thermal expansivity of alloy, being set at 34～38% under the situation of Fe-Ni alloy.This is owing to less than 34% and above 38% o'clock, thermal expansivity is increased.Also have, under the situation of Fe-Ni-Co alloy,, thermal expansivity is increased, so be set at 30～35% less than 30% and above 35% o'clock.
Cobalt (Co) is the element that reduces thermal expansivity by a part of nickel of displacement Fe-Ni alloy in the Fe-Ni-Co alloy, is set at 2～6%.This is because less than 2% o'clock, and the replacement amount of nickel is few and do not lower the effect of thermal expansivity, has reached capacity and surpass the effect that lowered thermal expansivity at 6% o'clock, and cost is improved.
Manganese (Mn) is set at 0.01～0.5% from the viewpoint of hot workability and thermal expansivity.This is because less than 0.01% o'clock, the sulfide of sulphur and nickel worsened hot workability at grain boundary segregation.Also have, owing to surpass thermal expansivity is increased at 0.5% o'clock, simultaneously, a plurality of MnS that separate out make selective erosion take place when erosion forms shadow mask board, make the concavo-convex increase of corroding treated side.But, surpassing under 0.002% the situation at the content of sulphur, the content of preferred manganese is 0.2～0.5%.
Silicon (Si) during from magnetic property and refining the viewpoint of deoxidation effect be set at 0.03～0.10%.This is because when refining under the situation by the silicon deoxidation, the content of silicon can not reduce the concentration of oxygen in the melt after a little while, if the content of silicon, just can not be seen the effect of magnetic property raising and the effect of deoxidation less than 0.03%.On the other hand, though be that the content of silicon increases and can improve magnetic property, the content of silicon surpasses at 0.10% o'clock, owing to a large amount of meals takes place when forming shadow mask board corroding, causes the obstruction of corroding nozzle and strainer easily, so be set at below 0.10%.
Then, unavoidable impurities is illustrated.
Carbon (C) is because formation carbide and carbonitride make the concavo-convex increase of above-mentioned erosion treated side, so be set at below 0.01%.
Sulphur (S), owing to generate thermal crack, and combine generation MnS with manganese, make the concavo-convex increase of above-mentioned erosion treated side, so be set at below 0.005%, be preferably below 0.002%.
Nitrogen (N) is because formation nitride and carbonitride make the concavo-convex increase of above-mentioned erosion treated side, so be set at below 0.005%.
Oxygen (O) owing to form most thick oxide compounds, makes the concavo-convex increase of above-mentioned erosion treated side, so be set at below 0.005%.
Then, the interpolation element that adds as required is illustrated.
Va elements is vanadium (V), niobium (Nb), tantalum (Ta), is the element that improves the strength of materials.In the present invention, vanadium (V), niobium (Nb), tantalum (Ta) can contain separately, also can contain two or more.And, above-mentioned element is contained sometimes amount separately, or the total amount that contains when two or more is 0.05～0.5%.This is because the amount of Va elements is insufficient less than the raising of 0.05% o'clock strength of materials, increase and surpass 0.5% o'clock thermal expansivity, and a large amount of meals takes place when corroding the formation shadow mask board, cause the obstruction of corroding nozzle and strainer easily, when simultaneously, meal attaches to erosive new life face erosive speed is descended.
Chromium (Cr) is the element that suppresses lateral erosion amount deviation, and content is 0.03～0.20%.This be since the content of chromium, to suppress the effect of lateral erosion amount deviation less than 0.03% o'clock insufficient.On the other hand, though many more these effects that can make of chromium content are remarkable, owing to surpass thermal expansivity is increased at 0.20% o'clock, so be set at below 0.20%.Also have, chromium content is above-mentioned scope in the matrix by making, and the chromium concn in zone, top layer can also be adjusted into following scope, suppresses lateral erosion amount deviation.
Then, the reason in Si in the top layer zone dark to 0.1 μ m, top layer, Va elements and Cr concentration regulation is illustrated.These elements since other of alloy manufacturing processed is former thus denseization in the top layer.Here so-called denseization is meant that the composition in the matrix is concentrated near surface, and the result makes the constituent concentration in the top layer be higher than basic intravital constituent concentration.The present invention for so set element in denseization on top layer and the influence that the deviation of side erosion amount is brought has given attention.
At first, making the maximum value of the silicon concentration in zone, top layer is below 7%.This is because when the maximum value of silicon concentration surpassed 7%, the deviation of lateral erosion amount increased, and its reason is considered to descend because corrode the connectivity of employed resist and alloy surface.Also have, the maximum value of the so-called concentration among the present invention is meant the concentration of having represented the maximum in any degree of depth in the zone, above-mentioned top layer.Also have, the lower limit of silicon concentration is more than the silicone content in the matrix in the zone, top layer.
Also have, under the situation of adding Va elements, the total maximum value of Va elements concentration is 0.3～5% in the preferred zone, top layer.Maximum value had the irreducible situation of deviation of lateral erosion amount less than 0.3% o'clock.On the other hand, though the big more deviation that can suppress the lateral erosion amount more of maximum value, because concentration surpasses at 5% o'clock, the deterioration of the melanism of the shadow mask board property handled is so be set at below 5%.
Under the situation of adding chromium (Cr), the maximum value that preferably makes Cr concentration in the zone, top layer is 0.5～5%.The qualification reason of the upper limit of chromium concn and lower limit is identical with the situation of adding Va elements.
Though for Si in the zone, top layer, Va elements, and the measuring method of Cr concentration have no particular limits, from the viewpoint of the speed of the precision measured and mensuration, preferably use GDS (GlowDischarge Spectroscopy: the glow discharge luminescent spectrum).As the condition of measuring.For example analyzed area is set at the bowlder of the about 4mm of diameter, the electronics line that can become for shadow mask board sees through fully wide zone, hole.
Then, the method that each element in the zone, top layer is controlled to be above-mentioned scope is carried out the example explanation.
As with silicon (Si) though the method that concentration is reduced to below 7% has no particular limits, make alloy thin band to be processed as final thickness (method that the dew point of 0.05～0.3mm) continuous annealing of being carried out only may be low is the most effective.In this case, in continuous annealing, be not only heating region, and be below one 35 ℃ at the also preferred dew point of cooled region.Also have, continuous annealing is normally carried out in reducing atmospheres such as hydrogen or decomposed ammonia body.And, by strengthening the draft in final when calendering, and use the big roll of surfaceness to roll, the thickness of denseization of surface silicon layer is reduced, but the surface of alloy thin band excessively can reduce the erosion precision during alligatoring, so preferred such processing is not excessively carried out.Can also carry out cleanup acid treatment and basic treatment to the strip after the annealing, reduce the concentration of silicon.
About the total maximum value of control Va elements concentration is 0.3～5% method, can example go out following method.At first, under dense situation about turning to more than 5%, be to be effective below 5% with the same cleanup acid treatment of silicon.Also have, concentration less than 0.3% situation under since adopt surface treatment improve Va elements concentration industrial be difficult, make its concentration be not less than 0.3% so must in annealing atmosphere, modulate.
Be controlled to be 0.5～5% method about maximum value, can example go out following method chromium concn.At first, surpassing under 5% the situation in maximum value, is below 5% in order to make concentration, and it is effective carrying out cleanup acid treatment.On the other hand, maximum value less than 0.5% situation under, for concentration is brought up to more than 0.5%, can after alloy thin band is processed as final thickness, this strip be flooded in 0.2～5% chromic acid.
Fe-Ni of the present invention is an alloy thin band, for example can be by following method manufacturing.At first, making the Fe-Ni with above-mentioned composition is alloy pig, after carrying out suitable thermal treatment, reaches desirable thickness through hot calender with colding pressing to prolong.And then carry out several continuous annealing (Bright Annealing) and cold pressing prolonging, making plate thickness is the alloy thin band of 0.05～0.3mm.And, above-mentioned alloy thin band is cut starting material as shadow mask board aptly, to its carry out degreasing, resist coating, print and development, erosion is handled, afterwards, cut off respectively and obtain the starting material unit of shadow mask board.Then, annealed in non-oxidizing atmospheres such as reducing atmosphere in shadow mask board starting material unit, after the smoothing processing, pressure forming is shadow mask board.At last, this shadow mask board is carried out degreasing, afterwards, at atmosphere or CO/CO
2Carry out melanism in the gas atmosphere and handle, generate the oxide film of black on the surface.
Then, the present invention will be described in more detail to enumerate embodiment.But the present invention is not limited to these embodiment.
Embodiment
1. the manufacturing of sample
By the alloy of composition shown in vacuum induction calciner melting table 1, the table 2, implement to forge and hot calender, obtain the thick material of 3mm.And then, repeat Bright Annealing and cold pressing to prolong, obtain about 0.12mm thick colding pressing prolonging material.Afterwards, this material is cut into the wide shadow mask board starting material of set plate in reducing atmosphere, anneals (900 ℃, 30min in the hydrogen), give its pressure forming, be cut into set size and be made for sample.
Also have, alloy shown in the table 1 is the Fe-Ni alloy that does not add cobalt, is the Fe-Ni-Co alloy that has added cobalt shown in the table 2.
Table 1
| Alloy No. | Ni | Co | Mn | Si | Va elements | Cr | C | S | N | O | |
| Example of the present invention | 1 | 34.8 | ＜0.05 | 0.08 | 0.03 | - | ＜0.01 | 0.003 | 0.0018 | 0.0022 | 0.0028 |
| 2 | 35.6 | ＜0.05 | 0.23 | 0.04 | - | 0.01 | 0.003 | 0.0023 | 0.0032 | 0.0031 | |
| 3 | 36.1 | ＜0.05 | 0.23 | 0.04 | - | 0.01 | 0.004 | 0.0017 | 0.0035 | 0.0034 | |
| 4 | 36.4 | ＜0.05 | 0.31 | 0.09 | - | 0.03 | 0.005 | 0.0021 | 0.0043 | 0.0023 | |
| 5 | 37.2 | ＜0.05 | 0.23 | 0.04 | - | 0.02 | 0.003 | 0.0032 | 0.0019 | 0.0019 | |
| 6 | 36.3 | ＜0.05 | 0.28 | 0.04 | 0.25Nb | 0.01 | 0.005 | 0.0021 | 0.0028 | 0.0026 | |
| 7 | 35.9 | ＜0.05 | 0.26 | 0.04 | 0.08Nb | 0.02 | 0.005 | 0.0015 | 0.0028 | 0.0031 | |
| 8 | 35.8 | ＜0.05 | 0.27 | 0.03 | 0.22Nb+0.11Ta | 0.02 | 0.004 | 0.0024 | 0.0026 | 0.0028 | |
| 9 | 35.8 | ＜0.05 | 0.42 | 0.05 | - | 0.13 | 0.004 | 0.0038 | 0.0025 | 0.0041 | |
| 10 | 35.9 | ＜0.05 | 0.26 | 0.04 | 0.46Nb | 0.01 | 0.005 | 0.0019 | 0.0035 | 0.0031 | |
| 11 | 36.1 | ＜0.05 | 0.27 | 0.05 | 0.45Nb | 0.08 | 0.004 | 0.0018 | 0.0019 | 0.0037 | |
| 12 | 35.9 | ＜0.05 | 0.22 | 0.05 | - | 0.08 | 0.004 | 0.0021 | 0.0029 | 0.0033 | |
| Comparative example | 13 | 33.5 | ＜0.05 | 0.22 | 0.05 | - | 0.01 | 0.004 | 0.0016 | 0.0021 | 0.0041 |
| 14 | 38.7 | ＜0.05 | 0.25 | 0.04 | - | 0.01 | 0.004 | 0.0021 | 0.0024 | 0.0037 | |
| 15 | 36.1 | ＜0.05 | 0.23 | 0.04 | - | 0.01 | 0.004 | 0.0017 | 0.0035 | 0.0034 | |
| 16 | 36.3 | ＜0.05 | 0.28 | 0.04 | 0.25Nb | 0.01 | 0.005 | 0.0021 | 0.0028 | 0.0026 | |
| 17 | 35.8 | ＜0.05 | 0.005 | 0.05 | - | 0.01 | 0.004 | 0.0025 | 0.0026 | 0.0037 | |
| 18 | 35.9 | ＜0.05 | 0.57 | 0.04 | - | 0.01 | 0.006 | 0.0024 | 0.0031 | 0.0033 | |
| 19 | 36.1 | ＜0.05 | 0.27 | 0.02 | - | 0.02 | 0.005 | 0.0021 | 0.0023 | 0.0048 | |
| 20 | 36.1 | ＜0.05 | 0.27 | 0.12 | - | 0.01 | 0.004 | 0.001 | 0.0033 | 0.0041 | |
| 21 | 35.9 | ＜0.05 | 0.25 | 0.05 | - | 0.02 | 0.013 | 0.0019 | 0.0029 | 0.0035 | |
| 22 | 35.8 | ＜0.05 | 0.24 | 0.04 | - | 0.01 | 0.005 | 0.0057 | 0.0032 | 0.0034 | |
| 23 | 36.1 | ＜0.05 | 0.22 | 0.04 | - | 0.01 | 0.004 | 0.0021 | 0.0053 | 0.0031 | |
| 24 | 35.9 | ＜0.05 | 0.24 | 0.05 | - | 0.02 | 0.005 | 0.0023 | 0.0036 | 0.0057 |
Table 2
| Alloy No. | Ni | Co | Mn | Si | Va elements | Cr | C | S | N | O | |
| Example of the present invention | 25 | 32.1 | 4.9 | 0.25 | 0.04 | - | 0.01 | 0.004 | 0.0018 | 0.0024 | 0.0024 |
| 26 | 33.1 | 4.1 | 0.23 | 0.04 | - | 0.01 | 0.003 | 0.0022 | 0.0024 | 0.0028 | |
| 27 | 30.7 | 5.6 | 0.08 | 0.05 | - | 0.01 | 0.004 | 0.0019 | 0.0026 | 0.0028 | |
| 28 | 34.3 | 3.2 | 0.12 | 0.08 | - | 0.02 | 0.005 | 0.0025 | 0.0038 | 0.0033 | |
| 29 | 31.9 | 5.1 | 0.23 | 0.05 | - | 0.02 | 0.004 | 0.0022 | 0.0032 | 0.0026 | |
| 30 | 31.8 | 4.8 | 0.28 | 0.06 | 0.23Nb | 0.01 | 0.005 | 0.0021 | 0.0028 | 0.0026 | |
| 31 | 32.5 | 4.5 | 0.26 | 0.05 | 0.08Nb | 0.02 | 0.004 | 0.0019 | 0.0031 | 0.0034 | |
| 32 | 32.2 | 5.1 | 0.27 | 0.05 | 0.46Nb | 0.01 | 0.005 | 0.0022 | 0.0035 | 0.0029 | |
| 33 | 32.1 | 4.8 | 0.23 | 0.05 | - | 0.08 | 0.004 | 0.0019 | 0.0032 | 0.0027 | |
| Comparative example | 34 | 32.5 | 1.6 | 0.24 | 0.05 | - | 0.01 | 0.006 | 0.0024 | 0.0026 | 0.0036 |
| 35 | 32.5 | 4.9 | 0.23 | 0.05 | - | ＜0.01 | 0.004 | 0.0021 | 0.0029 | 0.0320 | |
| 36 | 31.8 | 4.9 | 0.25 | 0.04 | 0.25Nb | 0.01 | 0.005 | 0.0018 | 0.0033 | 0.0025 | |
| 37 | 29.2 | 5.1 | 0.22 | 0.05 | - | 0.01 | 0.005 | 0.0022 | 0.0028 | 0.0039 | |
| 38 | 35.5 | 5.4 | 0.25 | 0.05 | - | 0.01 | 0.004 | 0.0019 | 0.0024 | 0.0029 | |
| 39 | 32.1 | 6.7 | 0.22 | 0.04 | - | ＜0.01 | 0.005 | 0.0019 | 0.0031 | 0.0033 |
2. the mensuration of top layer regional concentration
By GDS (Glow Discharge Spectroscopy: glow discharge luminescent spectrum device) measured from said sample the most surperficial to the dark zone, top layer of 0.1 μ m, the concentration of silicon, Va elements, chromium.The mensuration area of sample is the circle of diameter 4mm, and condition determination is 700V, 40mA, and the pressure of Ar is 755Pa.Also have, the 0.2 μ m degree of depth of sample has been measured in flash of light (flashing) 20 seconds.
3. the mensuration of lateral erosion amount standard deviation
By common photolithography, on sample, form the resist opening of diameter 100 μ m, at 50 ℃, sprayed 1 minute to sample with the spraying pressure of 0.3MPa ferric chloride in aqueous solution with 50 Baumes.For 100 resist peristomes, calculate resist opening diameter of equivalent circle poor of the actual aperture diameter after diameter of equivalent circle and the above-mentioned injection of expression when each opening diameter is considered as 100 μ m, obtain respectively that this is on duty with 1/2 value, with the standard deviation of 100 values obtaining standard deviation as the lateral erosion amount.Since when the deviation of the standard deviation of lateral erosion amount lateral erosion amount during less than 1.5 μ m little, so will be less than 1.5 μ m as permissible value.
4. the mensuration of mean thermal expansion coefficients and 0.2% yield strength
For said sample, measured 25～150 ℃ mean thermal expansion coefficients by method commonly used.Also have, carried out tension test, measured 0.2% yield strength.The permissible value of mean thermal expansion coefficients is about 2.6 * 10 under the situation of the Fe-Ni of table 1 alloy
-6/ ℃ below, but under thickness of slab is situation more than the 0.2mm, because thermal capacity increases, with 3.5 * 10
-6/ ℃ below as permissible value.And, under the situation of the Fe-Ni-Co of table 2 alloy, be about 1.5 * 10
-6/ ℃ below, but under thickness of slab is situation more than the 0.2mm, because thermal capacity increases, with 2.0 * 10
-6/ ℃ below as permissible value.Also have, the permissible value of 0.2% yield strength, in 8% hydrogen-92% nitrogen atmosphere behind 800 ℃, 15min annealing, at room temperature the value of Ce Dinging is more than the 250MPa with sample.
5. the evaluation of melanism film uniformity
After the said sample degreasing, in air atmosphere, carry out melanism and handle, form black oxide film on the surface, its state has been carried out range estimation judged.The melanism film evenly forms is evaluated as " zero ", intersection (for example, resemble edge (skirt) part of shadow mask board, estimation contacts inadequate part during with the overlapping annealing of each sample with atmosphere gas, in fact with the part of the overlapping processing of each sample) can find out be evaluated as " △ " of tonal difference, uneven be evaluated as " * " of tone.
6. the evaluation of magnetic shielding
The sample stamping-out is become internal diameter 6mm, the ring-type of external diameter 10mm, in 8% hydrogen-92% nitrogen atmosphere behind 800 ℃, 15min annealing, the a plurality of samples of lamination, making thickness is 2mm, then, roll with this multilayer body is the coil of magnetic core, this coil coiling body is measured its DC magnetization curve with maximum field 790A/m, and the coercive force of this moment is that 50A/m is evaluated as " zero " when following, is evaluated as during above 50A/m " * ".
7. the evaluation of tafoni shape
Identical with the sample of made during the standard deviation of above-mentioned lateral erosion amount is measured, forming diameter on sample is the resist opening of 100 μ m, 20 openings (tafoni) have been observed with the about 500 times magnification of scanning electronic microscope, average good being evaluated as of tafoni shape " O ", corrode to handle concavo-convex be evaluated as " △ " that generation is arranged slightly in cross section (wall), corrode be evaluated as " * " of the concavo-convex remarkable generation of handling cross section (wall).
8. the evaluation of processibility
In the hot calender when the manufacturing of said sample, do not take place that the limit is split, squamous is folding surface imperfection such as peels off and then in the time-delay of colding pressing be evaluated as " zero " by the caused defective of internal soundness, be evaluated as " * " that surface imperfection significantly takes place are not taken place on the surface in any operation.
The evaluation result of using the sample of Fe-Ni alloy shown in the described table 1 is shown in table 3.
Table 3
| No. | The peak concentration in zone, top layer (%) | The standard deviation of lateral erosion amount (μ m) | 25 ℃～150 ℃ mean thermal expansion coefficients (* 10 -6/℃) | 0.2% yield strength (MPa) | The melanism film uniformity | Magnetic shielding | The etch-hole shape | Processibility | |||
| Si | Va family | Cr | |||||||||
| Example of the present invention | 1 | 1.8 | ＜0.1 | ＜0.1 | 0.4 | 2.0 | 268 | ○ | ○ | ○ | ○ |
| 2 | 2.4 | ＜0.1 | ＜0.1 | 0.5 | 2.2 | 272 | ○ | ○ | ○ | ○ | |
| 3 | 2.9 | ＜0.1 | ＜0.1 | 0.8 | 2.2 | 265 | ○ | ○ | ○ | ○ | |
| 4 | 3.1 | ＜0.1 | 0.5 | 0.6 | 2.3 | 273 | ○ | ○ | ○ | ○ | |
| 5 | 6.3 | ＜0.1 | 0.2 | 0.9 | 2.1 | 261 | ○ | ○ | ○ | ○ | |
| 6 | 1.6 | 2.8 | ＜0.1 | 0.3 | 2.4 | 295 | ○ | ○ | ○ | ○ | |
| 7 | 2.2 | 0.4 | 0.2 | 0.6 | 2.4 | 292 | ○ | ○ | ○ | ○ | |
| 8 | 3.8 | 1.3 | 0.3 | 0.5 | 2.4 | 297 | ○ | ○ | ○ | ○ | |
| 9 | 3.3 | ＜0.1 | 4.3 | 0.4 | 2.6 | 257 | ○ | ○ | ○ | ○ | |
| 10 | 5.2 | 5.8 | 0.1 | 0.6 | 2.8 | 305 | △ | ○ | △ | ○ | |
| 11 | 3.5 | 4.3 | 5.2 | 0.3 | 2.6 | 301 | △ | ○ | ○ | ○ | |
| 12 | 4.9 | ＜0.1 | 5.7 | 0.5 | 2.5 | 261 | × | ○ | ○ | ○ | |
| Comparative example | 13 | 3.3 | ＜0.1 | ＜0.1 | 0.5 . | 3.2 | 258 | ○ | ○ | ○ | ○ |
| 14 | 3.5 | ＜0.1 | ＜0.1 | 0.6 | 3.5 | 280 | ○ | ○ | ○ | ○ | |
| 15 | 7.8 | ＜0.1 | ＜0.1 | 1.5 | 2.2 | 266 | ○ | ○ | ○ | ○ | |
| 16 | 9.2 | 4.2 | 0.1 | 2.1 | 2.4 | 295 | △ | ○ | ○ | ○ | |
| 17 | 2.8 | ＜0.1 | 0.1 | 0.5 | 2.2 | 268 | ○ | ○ | ○ | × | |
| 18 | 3.7 | ＜0.1 | 0.1 | 0.6 | 2.8 | 272 | ○ | × | × | ○ | |
| 19 | 3.2 | ＜0.1 | ＜0.1 | 0.3 | 2.2 | 266 | ○ | × | △ | ○ | |
| 20 | 6.3 | ＜0.1 | 0.1 | 0.8 | 2.4 | 265 | ○ | ○ | × | ○ | |
| 21 | 4.2 | ＜0.1 | ＜0.1 | 0.5 | 2.3 | 271 | ○ | ○ | × | ○ | |
| 22 | 3.7 | ＜0.1 | ＜0.1 | 0.4 | 2.2 | 268 | ○ | × | × | × | |
| 23 | 4.1 | ＜0.1 | 0.3 | 0.6 | 2.3 | 273 | ○ | × | × | ○ | |
| 24 | 2.8 | ＜0.1 | 0.1 | 0.4 | 2.1 | 268 | ○ | ○ | × | ○ | |
As known from Table 3, example of the present invention (alloy numbering) 1～9, all below permissible value, the deviation of lateral erosion amount significantly reduces the standard deviation of lateral erosion.Also have, any one index of the mean thermal expansion coefficients of above-mentioned each sample, 0.2% yield strength, melanism film uniformity, magnetic shielding, tafoni shape, processibility is all excellent.Example of the present invention (alloy numbering) 10～12, though only the evaluation of melanism film uniformity is bad, other estimates good, and is no problem in practicality, and then the standard deviation of lateral erosion is also below permissible value.
On the other hand, nickel content is less than 34% comparative example (alloy numbering) 13, and nickel content surpasses 38% comparative example (alloy numbering) 14, and mean thermal expansion coefficients is all high.Also have, the silicon concentration in zone, top layer surpasses 7% comparative example (alloy numbering) 15,16, and the standard deviation of lateral erosion has surpassed permissible value.Manganese content is less than 0.01% comparative example (alloy numbering) 17, and processibility is bad.Manganese content surpasses 0.5% comparative example (alloy numbering) 18, and the evaluation of magnetic shielding and tafoni shape is bad.Silicone content is less than 0.03% comparative example (alloy numbering) 19, and magnetic shielding is bad.Silicone content surpasses 0.1% comparative example (alloy numbering) 20, and the evaluation of tafoni shape is bad.Carbon content surpasses 0.01% comparative example (alloy numbering) 21, and oxygen level surpasses 0.005% comparative example (alloy numbering) 24, and the evaluation of its tafoni shape is all bad.Sulphur content surpasses 0.005% comparative example (alloy numbering) 22, and the evaluation of magnetic shielding, tafoni shape, processibility is all bad.Also have, nitrogen content surpasses 0.005% comparative example (alloy numbering) 23, and the evaluation of magnetic shielding and tafoni shape is bad.
From as can be known above, the content of nickel, manganese, silicon, carbon, sulphur, nitrogen, oxygen is all in the scope of prescribed value, the maximum value of the silicon concentration in zone, top layer is in the present invention below 7% simultaneously, although contain the silicon and the Va elements that can improve magnetic property and intensity, but still can reduce the deviation of lateral erosion amount.
Also have, the maximum value of the concentration of the Va elements in zone, top layer surpasses 5% example of the present invention (alloy numbering) 10, the maximum value of the chromium concn in zone, top layer surpasses 5% example of the present invention (alloy numbering) 11,12, and only the inhomogeneity evaluation of melanism film is lower than other example of the present invention.Hence one can see that, and in Fe-Ni alloy of the present invention, the Va elements concentration in preferred zone, top layer and the maximum value of chromium concn are below 5%.
Equally, the evaluation result of using the sample of Fe-Ni-Co alloy shown in the described table 2 is shown in table 4.
Table 4
| Alloy No. | The peak concentration in zone, top layer (%) | The standard deviation of lateral erosion amount (μ m) | 25 ℃～150 ℃ mean thermal expansion coefficients (* 10 -6/℃) | 0.2% yield strength (MPa) | The melanism film uniformity | Magnetic shielding | The etch-hole shape | Processibility | |||
| Si | Va family | Cr | |||||||||
| Example of the present invention | 25 | 2.1 | ＜0.1 | ＜0.1 | 05 | 1.0 | 303 | ○ | ○ | ○ | ○ |
| 26 | 2.7 | ＜0.1 | ＜0.1 | 05 | 1.4 | 298 | ○ | ○ | ○ | ○ | |
| 27 | 3.1 | ＜0.1 | ＜0.1 | 0.7 | 1.5 | 312 | ○ | ○ | ○ | ○ | |
| 28 | 4.2 | ＜0.1 | 0.5 | 0.7 | 1.6 | 288 | ○ | ○ | ○ | ○ | |
| 29 | 6.7 | ＜O.1 | 0.3 | 0.9 | 1.1 | 307 | ○ | ○ | ○ | ○ | |
| 30 | 1.8 | 2.8 | ＜0.1 | 0.3 | 1.3 | 332 | ○ | ○ | ○ | ○ | |
| 31 | 2.8 | 0.4 | ＜0.1 | 0.6 | 1.2 | 292 | ○ | ○ | ○ | ○ | |
| 32 | 4.9 | 6.0 | 0.1 | 0.6 | 1.4 | 340 | × | ○ | △ | ○ | |
| 33 | 4.5 | ＜0.1 | 5.7 | 0.4 | 1.6 | 292 | × | ○ | ○ | ○ | |
| Comparative example | 34 | 2.8 | ＜0.1 | 0.1 | 0.5 | 1.9 | 282 | ○ | ○ | ○ | ○ |
| 35 | 7.5 | ＜0.1 | ＜0.1 | 1.7 | 1.1 | 307 | ○ | ○ | ○ | ○ | |
| 36 | 8.3 | 3.2 | 0.1 | 1.9 | 1.3 | 338 | △ | ○ | ○ | ○ | |
| 37 | 3.2 | ＜0.1 | ＜0.1 | 0.5 | 3.6 | 265 | ○ | ○ | ○ | ○ | |
| 38 | 2.9 | ＜0.1 | ＜0.1 | 0.5 | 1.9 | 348 | ○ | ○ | ○ | ○ | |
| 39 | 3.7 | ＜0.1 | ＜0.1 | 0.5 | 1.8 | 352 | ○ | ○ | ○ | ○ | |
As known from Table 4, example of the present invention (alloy numbering) 25～31, all below permissible value, the deviation of lateral erosion amount significantly reduces the standard deviation of lateral erosion amount.Also have, any one index of the mean thermal expansion coefficients of above-mentioned each sample, 0.2% yield strength, melanism film uniformity, magnetic shielding, tafoni shape, processibility is all excellent.Example of the present invention (alloy numbering) 32,33, though only the evaluation of melanism film uniformity is bad, other estimates good, and is no problem in practicality, and then the standard deviation of lateral erosion amount is also below permissible value.
On the other hand, contain the cobalt amount less than 2% comparative example (alloy numbering) 34, and contain the cobalt amount and surpass 6% comparative example (alloy numbering) 39, mean thermal expansion coefficients is all high.Also have, the silicon concentration maximum value in zone, top layer surpasses 7% comparative example (alloy numbering) 35,36, and the standard deviation of lateral erosion amount has surpassed permissible value.Nickel content surpasses 35% comparative example (alloy numbering) 38 less than 30% comparative example (alloy numbering) 37 with nickel content, and mean thermal expansion coefficients is all high.
From as can be known above, the content of nickel, cobalt, manganese, silicon, carbon, sulphur, nitrogen, oxygen is all in the scope of prescribed value, the maximum value of the silicon concentration in zone, top layer is in the present invention below 7% simultaneously, although contain the silicon and the Va elements that can improve magnetic property and intensity, but still can reduce the deviation of lateral erosion amount.
Also have, the maximum value of the concentration of the Va elements in zone, top layer surpasses the maximum value of chromium concn in 5% example of the present invention (alloy numbering) 32, zone, top layer above 5% example of the present invention (alloy numbering) 33, and only the inhomogeneity evaluation of melanism film is lower than other example of the present invention.Hence one can see that, and in Fe-Ni-Co alloy of the present invention, the Va elements concentration in preferred zone, top layer and the maximum value of chromium concn are below 5%.
By above explanation as can be known, pressure shaped shadow mask board according to the present invention is an alloy thin band with Fe-Ni, in containing the alloy of silicon, by the silicon top layer concentration that weathers easily is controlled at low concentration, can reaches the deviation, the raising that suppress the lateral erosion amount and corrode precision, make the shape homogenizing through the hole, the purpose of fine pitchization.
Claims (5)
1. a pressure shaped shadow mask board is an alloy thin band with Fe-Ni, it is characterized in that: by the Ni of mass percent 34～38%, 0.01～0.5% Mn, 0.03～0.10% Si, all the other are constituted by Fe and unavoidable impurities, C is below 0.01% in the described unavoidable impurities, S is below 0.005%, N is below 0.005%, O is below 0.005%, described Fe-Ni is that alloy thin band thickness is 0.05～0.3mm, and the maximum value of Si concentration is below 7% the zone, top layer dark to 0.1 μ m from the surface.
2. pressure shaped shadow mask board according to claim 1 is an alloy thin band with Fe-Ni, it is characterized in that: in mass percent, and then contain and add up to 0.05～0.5% selected more than one Va elements from V, Nb, Ta, to add up to the maximum value of concentration be 0.3～5% to Va elements in zone, described top layer.
3. a pressure shaped shadow mask board is an alloy thin band with Fe-Ni, it is characterized in that: by the Ni of mass percent 30～35%, 2～6% Co, 0.01～0.5% Mn, 0.03～0.10% Si, all the other are constituted by iron Fe and unavoidable impurities, C is below 0.01% in the described unavoidable impurities, S is below 0.005%, N is below 0.005%, O is below 0.005%, described Fe-Ni is that alloy thin band thickness is 0.05～0.3mm, and the maximum value of silicon concentration is below 7% the zone, top layer dark to 0.1 μ m from the surface.
4. pressure shaped shadow mask board according to claim 3 is an alloy thin band with Fe-Ni, it is characterized in that: in mass percent, and then contain and add up to 0.05～0.5% selected more than one Va elements from V, Nb, Ta, to add up to the maximum value of concentration be 0.3～5% to Va elements in zone, described top layer.
5. be alloy thin band according to each described pressure shaped shadow mask board in the claim 1～4 with Fe-Ni, it is characterized in that: and then in mass percent, contain 0.03～0.20% Cr, the maximum value of Cr concentration is 0.5～5% in zone, described top layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003123230 | 2003-04-28 | ||
| JP2003123230A JP2004323949A (en) | 2003-04-28 | 2003-04-28 | Fe-Ni BASED ALLOY THIN STRIP FOR PRESS MOLDING TYPE SHADOW MASK |
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| Publication Number | Publication Date |
|---|---|
| CN1550563A CN1550563A (en) | 2004-12-01 |
| CN1276986C true CN1276986C (en) | 2006-09-27 |
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| CNB2004100386075A Expired - Fee Related CN1276986C (en) | 2003-04-28 | 2004-04-28 | Fe-Ni series alloy thin band for pressure shaped shadow mask board |
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| Country | Link |
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| JP (1) | JP2004323949A (en) |
| KR (1) | KR100606169B1 (en) |
| CN (1) | CN1276986C (en) |
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| CN105803333A (en) * | 2015-01-20 | 2016-07-27 | 日立金属株式会社 | Manufacturing method for Fe-Ni alloy sheet metal |
| KR20240091663A (en) * | 2022-12-14 | 2024-06-21 | 주식회사 포스코 | Low thermal expansion steel with improved low-temperature impact toughness and manufacturing method thereof |
| KR20240098517A (en) * | 2022-12-21 | 2024-06-28 | 주식회사 포스코 | Non-coated austenitic steel sheet with improved corrosion resistance in an alkaline environment and method for manufacturing the same |
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2004
- 2004-04-28 KR KR1020040029330A patent/KR100606169B1/en not_active IP Right Cessation
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| KR20040093439A (en) | 2004-11-05 |
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| JP2004323949A (en) | 2004-11-18 |
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