WO2003069007A1 - Feuille mince en alliage a faible expansion thermique et procede permettant de produire cette feuille - Google Patents

Feuille mince en alliage a faible expansion thermique et procede permettant de produire cette feuille Download PDF

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Publication number
WO2003069007A1
WO2003069007A1 PCT/JP2003/001529 JP0301529W WO03069007A1 WO 2003069007 A1 WO2003069007 A1 WO 2003069007A1 JP 0301529 W JP0301529 W JP 0301529W WO 03069007 A1 WO03069007 A1 WO 03069007A1
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WO
WIPO (PCT)
Prior art keywords
less
thermal expansion
cold rolling
etching
low thermal
Prior art date
Application number
PCT/JP2003/001529
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English (en)
Japanese (ja)
Inventor
Akio Kobayashi
Koichiro Fujita
Katsuhisa Yamauchi
Takashi Samukawa
Kunikazu Tomita
Makoto Chujo
Original Assignee
Jfe Steel Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jfe Steel Corporation filed Critical Jfe Steel Corporation
Publication of WO2003069007A1 publication Critical patent/WO2003069007A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C21D9/48—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals deep-drawing sheets
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni

Definitions

  • the present invention relates to a Fe-Ni-Co-based low-thermal-expansion alloy thin plate used for a shadow mask of a cathode ray tube and a method for manufacturing the same.
  • BACKGROUND ART CRT shadow masks are manufactured by etching a thin metal plate made of a material by etching it to make holes for passing electron beams, annealing it to make it easier to mold, and press-forming it to the shape of the CRT. After that, it is incorporated into a cathode ray tube.
  • Fe-Ni alloy thin plates such as Fe-36Ni alloy have been conventionally known as a material for a shadow mask of a cathode ray tube. Since this alloy has a lower coefficient of thermal expansion than mild steel, it is less likely to be deformed by shadowing, which is caused by thermal expansion due to heating, ie, electron beam irradiation. As a result, a color shift that occurs because the electron beam passing through the hole of the shadow mask does not hit a predetermined position on the phosphor screen is unlikely to occur.
  • an Fe-Ni-Co alloy thin plate represented by an Fe-32% Ni-5Co alloy has been developed.
  • This alloy has a lower coefficient of thermal expansion and higher mechanical strength than Fe-Ni alloys, but has poor etching characteristics (speed and dimensional accuracy). Therefore, various attempts have been made to improve the etching characteristics of Fe-Ni-Co alloy thin plates. example For example, Japanese Patent No. 2723718 or Japanese Patent No. 3022573 proposes a technique for controlling the crystal orientation.
  • Japanese Patent No. 2723718 includes 28-34Ni, 2-7% Co, 0.1-1.0Mn, 0.10 or less Si, and 0.01 or less C, and has an average crystal grain size of 30m or less, 60-95 of the grains are accumulated on the ⁇ 100 ⁇ plane, and the crystal orientation of the ⁇ 100 ⁇ plane is accumulated at ⁇ 5 to 45 °, preferably ⁇ 10 to 30 ° with respect to ⁇ 100 ⁇ [001] Alloy sheets have been proposed.
  • the etching rate etching depth / lateral etching amount
  • the crystal orientation of the ⁇ 100 ⁇ plane is improved.
  • the roundness of the etched holes is improved by accumulating some of them from the ⁇ 100 ⁇ [001] to some extent. It is stated that such control of the crystal orientation can be performed by performing cold working after recrystallization annealing, and that dispersion of an arbitrary crystal orientation can be obtained by controlling the rate of cold working.
  • Japanese Patent No. 3022573 includes 30 to 60% Ni, 5 to 20Co, 0.25% or less Si, 0.50% or less Mn, 0.002 and less C, 0.005 or less P, 0.005 or less S, Alloy sheets have been proposed in which the total content of other impurity elements is 0.10 or less and the (200) (same as ⁇ 100 ⁇ ) plane strength is 50 or more.
  • the etching rate is increased by increasing the integration of the ⁇ 100 ⁇ plane and reducing the C content to 0.002 or less. Therefore, after hot rolling or cold rolling, decarburization annealing is performed in an atmosphere having a dew point of ⁇ 10 to 40 ° C.
  • Another method is to change the direction during rolling before annealing, for example, but this is possible in the laboratory, but the rolling direction of the coiled sheet is changed at the factory. It is very difficult.
  • An object of the present invention is to provide a Fe-Ni-Co-based low thermal expansion alloy sheet having excellent etching characteristics, particularly excellent dimensional accuracy of etching.
  • the above object is to provide a low thermal expansion alloy sheet having a mass of Ni: 30 to 34%, Co: 2 to 6%, the balance being substantially Fe, and a (200) plane having a degree of integration of less than 50. It is solved by.
  • Such a low-thermal-expansion alloy sheet can be obtained by subjecting a hot-rolled sheet having the above components to cold rolling and recrystallization annealing at least once. A step of repeating the above-mentioned steps, and a step of further performing cold rolling after the final recrystallization annealing.
  • FIG. 1 is a diagram showing the relationship between the degree of integration of the (200) plane and the standard deviation ⁇ of the etching factor. MODES FOR CARRYING OUT THE INVENTION The present inventors have studied the variation in etching hole diameter that occurs when an Fe—Ni—Co alloy thin plate is etched for a shadow mask. As a result, it was found that randomizing the crystallographic orientation is more advantageous in reducing the variation in the hole diameter than increasing the degree of integration of the (200) plane in order to improve the etching rate. The details are described below.
  • Ni is an essential element for obtaining low thermal expansion characteristics. When Co is added, the lowest low thermal expansion coefficient can be obtained when the amount of Ni is around 32. If the Ni content is less than 30% or more than 34, the coefficient of thermal expansion will not be sufficiently low. Therefore, the amount of Ni is assumed to be 30 to 34.
  • Co is an element essential for obtaining low thermal expansion characteristics together with Ni. If the Co content is less than 2 or more than 6, the coefficient of thermal expansion will not be sufficiently low. Therefore, the amount of Co is assumed to be 2 to 6.
  • the balance may be substantially Fe, but the following elements that are usually included as impurities: Mn: 0.6 or less, Al: 0.1 or less, C: 0.02 or less, Si: 0.3 or less, P: 0.01% or less, S: 0.005, N: if 0.01 Ru or less, 0.7X10- 6 excellent etching characteristics and average thermal expansion coefficient in the path C below. 20 to 100 ° C is obtained.
  • Mn When n exceeds 0.6%, the coefficient of thermal expansion increases. To obtain a lower coefficient of thermal expansion, the content is preferably 0.1% or less, but from the viewpoint of deoxidation and improvement of hot workability.
  • Al If A1 exceeds 0.1, it increases the coefficient of thermal expansion and precipitates as nitrides, deteriorating hot workability. In order to obtain a lower coefficient of thermal expansion, the content is preferably set to 0.04 or less, but is preferably set to 0.005 or more from the viewpoint of reducing inclusions in the steel during smelting.
  • C If C exceeds 0.02%, the coefficient of thermal expansion increases and the etching characteristics deteriorate. In order to obtain a lower coefficient of thermal expansion and better etching characteristics, the content is preferably 0.005 or less.
  • Si When Si exceeds 0.3%, the coefficient of thermal expansion increases and the blackness of the shadow mask deteriorates. In order to obtain a lower coefficient of thermal expansion, the content is preferably set to 0.09 or less.
  • S If S exceeds 0.005, it precipitates as sulfide and deteriorates hot workability.
  • N When N coexists with elements such as A1, N precipitates as nitrides, deteriorating hot workability and deteriorating etching characteristics. In particular, when the value exceeds 0.01, such tendency becomes remarkable.
  • ⁇ reduces the corrosion rate between the grain boundaries and the grains, that is, the difference between the etching rates by reducing the corrosion rate at the grain boundaries by biasing toward the grain boundaries, thereby reducing the variation in the etching hole diameter.
  • ⁇ ⁇ ⁇ suppresses clustering of crystal grains in a specific orientation due to the sizing action, thereby reducing variations in the etching rate due to the etching holes and improving the etching dimensional accuracy.
  • ⁇ exceeds 0.0030, the adhesion of the black capita film in the blackening treatment is reduced.
  • the present inventors can evaluate the variation of the etching hole diameter based on the standard deviation ⁇ of the etching factor described above, and if ⁇ .25, the etching dimension is such that the brightness variation of the display screen cannot be recognized practically. It has been found that accuracy can be obtained.
  • the degree of integration of the (200) plane was determined by X-ray diffraction using ⁇ -ray, and the austenitic seven planes (111), (200), (220), (311), (331), (420), and (422) ) was measured, and the strength of each surface was divided by the theoretical integrated strength of the sample in the random orientation.
  • I (hkl) The theoretical integrated intensity of the (hkl) plane in a sample with random orientation
  • the standard deviation ⁇ of the etching factor is obtained by applying a resist film to a thin plate sample, exposing, removing a part of the resist film, etching with a FeCl 3 solution to form 10 hemispherical holes, and forming the resist film. After removal, the hole diameter in the rolling direction was measured, and the etching factor, that is, the etching depth / lateral etching amount was calculated. At this time, the average value is calculated at the same time.
  • the degree of integration of the (200) plane is less than 50, then ⁇ 0.25, and excellent etching dimensional accuracy can be obtained. Further, when ⁇ is added, more excellent etching dimensional accuracy can be obtained.
  • the reason why excellent etching dimensional accuracy can be obtained by adjusting the degree of integration of the (200) plane to less than 50 is considered as follows. Collection of (200) faces When the moment is high, the crystal grains of the (200) plane are clustered due to their close orientation, even if they are originally generated from different recrystallization nuclei. Behave like. However, the etching rate becomes slow as compared to (2 00) since the 100 Lud no integration of surface, (2 00) crystal grains in the portion other than the face is class Yuka (200) plane grain portion of Therefore, when the alloy sheet is drilled from both surfaces by etching, the pore diameter of the portion of the crystal grains other than the (200) plane becomes smaller.
  • the low-thermal-expansion alloy sheet of the present invention is obtained by repeating cold rolling and recrystallization annealing at least once on a hot-rolled sheet having the above-described components of the present invention, and further performing cold rolling after final recrystallization annealing.
  • it can be manufactured by setting the cold rolling rate of the cold rolling immediately before the final recrystallization annealing to 65 or less and the final recrystallization annealing temperature to 1100 ° C or less, preferably 1000 or less.
  • a cooling pressure ratio of 10 or more is preferable.
  • the standard deviation of the etching factor becomes smaller. In order to make the standard deviation of the etching factor 0.25 or less, it is preferable to set the recovery annealing temperature to 780 ° C or less.
  • the standard deviation of the etching factor is 0.25 or less if at least one of the conditions is satisfied. The same effect can be obtained even if both are satisfied.
  • the flow of the method for producing a low thermal expansion alloy sheet according to the present invention is as follows: “hot rolled sheet ⁇ (cold rolling + recrystallization annealing) X n (n ⁇ l) ⁇ cold rolling— hand) Recovery annealing ".
  • the hot-rolled sheet of the present invention is produced by smelting the alloy of the above components, forming a slab by an ingot-making method or a continuous forming method, and then heating the steel to 900 ° C. or more and hot rolling.
  • the ingot making method ⁇ After the ingot is subjected to homogenizing heat treatment at 1000 ° C or more, if necessary, it is slab rolled into slabs.
  • the slab manufactured by the continuous manufacturing method is subjected to a homogenizing heat treatment at 1000 ° C. or higher, if necessary, and then hot-rolled.
  • the hot rolling is performed, for example, at a finishing temperature of 850 to 950 ° C and a winding temperature of 650 to 800 ° C.
  • the hot-rolled sheet is subjected to pickling or grinding to remove the scale of the surface, cold rolling and recrystallization annealing are repeated at least once as described above, and then cold-rolled to a thickness of 0.05 to It is a thin plate of about 0.5 mm.
  • Steels A to E having the components shown in Table 1 were melted in an electric furnace.
  • Steels A to E are all 32% Ni-5Co type steels, and B is added to steels D and E.
  • the steel after ingot was soaked at 1150 ° C or higher and slab rolled.
  • the entire surface of the slab is ground by a grinder, heated, and then hot-rolled at a finishing temperature of 850 to 950 ° C and a winding temperature of 650 to 800 ° C to form a coil with a thickness of 2 to 4 mm.
  • Hot rolled sheet hot rolled coil).
  • the hot-rolled coil was pickled to remove the surface scale, and cold-rolled and annealed as described in 1) to 3) below to produce a 0.12 mm-thick thin coil.
  • the average value and standard deviation of the degree of integration of the (200) plane and the etching factor were measured by the method described above.
  • a test piece for measuring the thermal expansion coefficient is taken from the center in the width direction of the thin-plate coil, and heat treatment is performed before press forming into a shadow mask, that is, 850 ° C for 15 minutes in an Ar atmosphere. After post-gas cooling, the average thermal expansion coefficient at 20 to 100 ° C was measured by an optical interference type thermal expansion measurement device.
  • the degree of integration of the (200) plane is less than 50
  • the standard deviation of the etching factor is 0.25 or less. Small and excellent in etching dimensional accuracy.
  • Thermal expansion coefficient is less than all 0.7X10- 6 / ° C.
  • steels C and E with reduced amounts of Si, n and A1 have a thermal expansion coefficient of 0.5X10-6 / ° C or less.
  • the sample with B added has a smaller standard deviation of the etching factor than the sample without B added.
  • the degree of integration of the (200) plane decreases and the etching factor decreases, that is, the etching rate decreases.
  • sheet A5 in which the cold rolling rate in the final cold rolling was 10%
  • sheet A6 in which the recovery annealing temperature was 780, were larger than sheet A2, which had the same degree of integration of the etching factor. It is equal to or higher than the highly integrated thin plates A3 and A4, and the etching speed is improved.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Electrodes For Cathode-Ray Tubes (AREA)

Abstract

L'invention concerne une feuille mince composée d'un alliage présentant une faible expansion thermique, contenant de 30 à 34 % en masse de Ni, de 2 à 6 % en masse de Co, le reste étant constituée principalement de Fe, et présentant un degré d'accumulation par face (200) inférieur à 50 %. Cette feuille mince en alliage à faible expansion thermique est produite au moyen d'un procédé dont la première étape consiste à répéter à une ou plusieurs reprise les opérations de laminage à froid et de recuit de recristallisation d'une feuille laminée à chaud contenant les composants mentionnés ci-dessus, et la seconde étape consiste à effectuer un laminage à froid après le dernier recuit de recristallisation. Le taux de réduction du laminage à froid effectué immédiatement avant le dernier recuit de recristallisation est égal ou inférieur à 65 %, et la température du dernier recuit de recristallisation est égale ou inférieure à 1100 °C. La feuille d'alliage à faible expansion thermique ainsi produite présente d'excellentes caractéristiques de gravure, en particulier en ce qui concerne la précision dimensionnelle de la gravure, et peut par conséquent remplacer avantageusement le masque perforé d'un tube cathodique.
PCT/JP2003/001529 2002-02-15 2003-02-14 Feuille mince en alliage a faible expansion thermique et procede permettant de produire cette feuille WO2003069007A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002037975A JP2003239042A (ja) 2002-02-15 2002-02-15 エッチング精度に優れた低熱膨張合金薄板およびその製造方法
JP2002/37975 2002-02-15

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WO2003069007A1 true WO2003069007A1 (fr) 2003-08-21

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TW (1) TW200305653A (fr)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117867245A (zh) * 2024-03-11 2024-04-12 成都先进金属材料产业技术研究院股份有限公司 一种高温合金板材及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6452024A (en) * 1987-08-24 1989-02-28 Kobe Steel Ltd Production of shadow mask material for cathode ray tube
JPH04221039A (ja) * 1990-12-19 1992-08-11 Nikko Kyodo Co Ltd リードフレーム用合金材及びその製造方法
JPH05311357A (ja) * 1991-12-26 1993-11-22 Nikko Kinzoku Kk シャドウマスク材
US5522953A (en) * 1992-02-28 1996-06-04 Nkk Corporation Method of manufacturing an alloy sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6452024A (en) * 1987-08-24 1989-02-28 Kobe Steel Ltd Production of shadow mask material for cathode ray tube
JPH04221039A (ja) * 1990-12-19 1992-08-11 Nikko Kyodo Co Ltd リードフレーム用合金材及びその製造方法
JPH05311357A (ja) * 1991-12-26 1993-11-22 Nikko Kinzoku Kk シャドウマスク材
US5522953A (en) * 1992-02-28 1996-06-04 Nkk Corporation Method of manufacturing an alloy sheet

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TW200305653A (en) 2003-11-01

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