WO2003085148A1 - Feuille mince d'alliage a faible dilatation thermique et son procede de fabrication - Google Patents

Feuille mince d'alliage a faible dilatation thermique et son procede de fabrication Download PDF

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Publication number
WO2003085148A1
WO2003085148A1 PCT/JP2003/003045 JP0303045W WO03085148A1 WO 2003085148 A1 WO2003085148 A1 WO 2003085148A1 JP 0303045 W JP0303045 W JP 0303045W WO 03085148 A1 WO03085148 A1 WO 03085148A1
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thermal expansion
mass
cold rolling
annealing
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PCT/JP2003/003045
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English (en)
Japanese (ja)
Inventor
Akio Kobayashi
Koichiro Fujita
Katsuhisa Yamauchi
Kunikazu Tomita
Saiichi Murata
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Jfe Steel Corporation
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Publication of WO2003085148A1 publication Critical patent/WO2003085148A1/fr

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    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C21D1/32—Soft annealing, e.g. spheroidising
    • 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
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
    • H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
    • H01J29/06—Screens for shielding; Masks interposed in the electron stream
    • H01J29/07—Shadow masks for colour television tubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2229/00—Details of cathode ray tubes or electron beam tubes
    • H01J2229/07—Shadow masks
    • H01J2229/0727—Aperture plate
    • H01J2229/0733—Aperture plate characterised by the material

Definitions

  • the present invention relates to an Fe-Ni-based low thermal expansion alloy thin plate used for a shadow mask of a cathode ray tube and a method for manufacturing the same.
  • Kyogyo Technology CRT shadow masks are manufactured by etching a thin alloy plate of a material to form holes that allow the passage of electron beams, and performing soft annealing before pressing to make it easier to form, and press forming according to the shape of the CRT. After that, it is assembled into a cathode ray tube.
  • an Fe-Ni alloy thin plate has been 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 heated by the doping, that is, irradiation of the electron beam, and the thermal expansion causes the deformation of the shadow mask, and the electron beam passing through the holes of the shadow mask emits fluorescent light. The phenomenon that color misregistration occurs because it does not hit a predetermined position on the surface is unlikely to occur. In fact, the present inventors have found that the average thermal expansion coefficient of Fe—Ni-based alloy thin plates at 20 to: L00 ° C. is 1.2 ⁇ 10—. If C or less, doming hardly occurs, if further 0. 9 X 10- 6 Pa C or less, it was confirmed that no happening command and Ho is doming.
  • the Fe-Ni alloy thin plate has a color due to dents in the shadow mask surface caused by shocks such as vibration when transporting the cathode ray tube, and deviations of the electron beam caused by insufficient magnetic shielding.
  • shocks such as vibration when transporting the cathode ray tube
  • deviations of the electron beam caused by insufficient magnetic shielding.
  • misalignment There is a problem of misalignment, and there is a strong demand for improvement of impact resistance after soft annealing before press and improvement of magnetic properties.
  • the present inventor has studied impact resistance and magnetic properties after soft annealing before press beforehand. However, if the 0.2% proof stress after softening and annealing before pressing is 270 MPa or more, the incidence of dents in the impact test after shadow mask forming is significantly reduced, and if the 0.2 proof stress exceeds 320 MPa, the shadow mask It was found that press forming itself became difficult. In addition, when the maximum magnetic permeability was 8000 or more, it was found that in the magnetic shield test after the etching process, the penetrating magnetic flux was significantly reduced.
  • Japanese Patent No. 3150831 proposes a low thermal expansion alloy sheet in which Nb is added to an Fe-Ni alloy to improve Young's modulus.
  • C 0.003-0.02, N: 0.01% or less, Si: 0.01-2.0, Mn: 0.01-3.0, Ni: 25-453 ⁇ 4, Cr: 1.0% or less, Nt>: 0.01-; Fe-Ni alloy sheet containing L.0%, B: 0.01 or less, S: 0.01 or less, balance of Fe and unavoidable impurities, and (C + N) ⁇ -0.008Nt> +0.023 It is.
  • Japanese Patent Application Laid-Open No. Hei 10-199719 proposes a Fe-Ni-based alloy sheet in which N is reduced and B is added.
  • the details are as follows: N is set to 50 ppm or less, and B is added within the range of 5 to 50 ppm so that B [at.ru] / N [at.ru] becomes 0.8 or more.
  • This is a thin alloy sheet.
  • excellent magnetic properties can be obtained by setting A1 to 400 ppm or less and 0 to 50 ppm or less, and it is stated that the addition of Cr, Mo, Cu, Si, etc. is effective in improving the magnetic properties. .
  • Nb-added Fe-Ni alloys as described in Japanese Patent No. 3150831 are difficult to progress in recrystallization and subsequent crystal grain growth.Therefore, when a thin plate using this kind of alloy is applied to a shadow mask, However, pre-press annealing at a temperature of 850 ° C or higher is required. However, from the viewpoint of manufacturing cost, a material that can be softened even in a temperature range of less than 850 ° C is desired.
  • the present invention provides a Fe having a sufficiently low coefficient of thermal expansion, and having excellent impact resistance and magnetic properties after shading by shading annealed before pressing at a temperature of less than 850 ° C. It is an object of the present invention to provide a -Ni-based low thermal expansion alloy sheet and a method for producing the same.
  • Ni 35 to 37, C: 0.02% or less, Si: 0.3 or less, Mn: 0.6% or less, P: 0.01% or less, S: 0.005 or less, N: 0.013 ⁇ 4 or less, A1: 0.1 or less, ⁇ : 0.08 or less, Nb: 0.05 to l, V: 0.01 to: L, and pull l? Fe force, and (Nb + V) ⁇ l .0 can be achieved with a low thermal expansion alloy sheet.
  • low-thermal-expansion alloy sheets are subjected to a step of repeating cold rolling and recrystallization annealing at least once or more on a hot-rolled sheet having the above components, and after the final recrystallization annealing, a final cold-rolling rate of 15 or more.
  • the present invention can be realized by a method of manufacturing a low thermal expansion alloy sheet having a step of performing cold rolling and a step of performing strain relief annealing at 800 ° C or lower after final cold rolling.
  • BRIEF DESCRIPTION OF THE DRAWINGS-FIG. 1 is a diagram showing the relationship between 0.2% strength (0.2% PS) and maximum magnetic permeability (max) after soft annealing before press.
  • Figure 2 is a diagram showing the relationship between the press before anneal temperature and 0.2 ⁇ Ka (0.2 PS).
  • MODES FOR CARRYING OUT THE INVENTION The present inventors studied the impact resistance and magnetic properties of Fe-Ni alloy thin sheets after soft annealing before press, and also examined soft soft properties during soft annealing before press. did. As a result, And magnetic properties can be improved by adding Nb and V in combination, and the magnetic properties can be further improved by adding B and Sb. It was clarified that it greatly depends on the 0.2 proof stress after soft annealing before press. The details are described below.
  • Ni is an essential element for obtaining low thermal expansion. If it is less than 35 or more than 37, the coefficient of thermal expansion does not become sufficiently low, so Ni is assumed to be 35 to 37.
  • C Since C deteriorates the etching property and the low thermal expansion property, it is set to 0.02 or less, preferably 0.005% or less, more preferably less than 0.003. -
  • Si has a low thermal expansion property, so that the black mask processing property of the shadow mask is inferior, so that the content is set to 0.3 or less, preferably 0.09 or less.
  • n Mil should be set to 0.6 or less, preferably 0.1 or less, in order to deteriorate the low thermal expansion property. Further, since Mn is an element effective for deoxidation and hot workability of the alloy, it is preferably 0.01 or more.
  • P is set to 0.01 or less in order to degrade the etching property.
  • S Since S precipitates as sulfide and deteriorates the hot workability of the alloy, S is set to 0.005 or less.
  • N If N is included together with elements such as Al, Nb, and V, it will precipitate as nitrides, deteriorating the etchability, and also degrade the hot workability of the alloy.
  • A1 precipitates as precipitates such as nitrides and oxides, deteriorating the magnetic properties and low thermal expansion, and also deteriorating the hot workability of the alloy. Therefore, the content of A1 is set to 0.1 or less, preferably 0.04 or less. . A1 also has the effect of reducing inclusions in the alloy during smelting, and is therefore preferably 0.005 or more.
  • Cr Cr is deposited at 0.08% or less because it precipitates as carbides, nitrides, and the like, thereby deteriorating magnetic properties. Since Cr also deteriorates the low thermal expansion property, it is desirable to reduce it as much as possible.
  • Nb is the most important element in the present invention. Improve impact resistance and magnetic properties after pre-softening annealing. For this purpose, Nb is required to be 0.05 or more. However, a large amount of Nb degrades low thermal expansion, so it should be 1 or less, preferably 0.6 or less.
  • V As described above, when V is added in combination with Nb, the impact resistance and magnetic properties after soft annealing before press are improved. For this purpose, V needs to be 0.01, but a large amount of addition degrades the low thermal expansion property, so it should be 1 or less, preferably 0.6 or less.
  • the balance is substantially Fe. That is, other elements may be contained as long as the effects of the present invention are not impaired.
  • Ni 35-37, C: 0.02 or less, Si: 0.3% or less, Mn: 0.6% or less, P: 0.01 or less, S: 0.005 or less, N: 0.01 or less, ⁇ 1 : 0.13 ⁇ 4 ⁇ 3 ⁇ 4, Cr: 0.08% or less, Nb: 0.05 ⁇ l3 ⁇ 4, V: 0.01 ⁇ l, and residual Fe force, and by setting (Nb + V) ⁇ 1.0, doming is reduced. A thermal expansion coefficient of 1.2X10-6 Pa C or less, which is unlikely to occur, is obtained.
  • B and Sb which have the function of homogenizing crystal grains, are added to the above components, the content of B is 0.0005 or more, and the content of Sb is 0.0015 or more. Later a higher maximum permeability is obtained. At this time, B must be 0.003 or less, Sb must be 0.010 or less, and (2B + Sb) must be 0.001 to 0.010% so as not to deteriorate the blackening processability of the shadow mask.
  • the low-thermal-expansion alloy thin sheet of the present invention includes a step of repeating cold rolling and recrystallization annealing at least once or more on a hot-rolled sheet having the above-mentioned components; Final cold rolling process, and after final cold rolling, strain relief at 800 ° C or less And a step of performing annealing.
  • the final cold rolling rate of cold rolling of 15 or more and the strain relief annealing temperature of 800 ° C or less are used for Nb-added Fe-Ni-based alloys, where recrystallization and grain growth are difficult to proceed, before softening before pressing. This is for softening without annealing at a temperature of 850 ° C or higher.
  • 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) Xn (n ⁇ l) ⁇ final cold rolling ⁇ strain relief annealing It becomes.
  • the hot rolled sheet is manufactured by melting the alloy of the above components, forming a slab by ingot making method or continuous forming method, and then heating to 900 ° C. or higher and hot rolling.
  • the ingot making method the ⁇ ⁇ ingot is subjected to homogenization heat treatment at 1000 ° C or more as necessary, and then slab-rolled into a slab.
  • the slab manufactured by the continuous production method is subjected to a homogenizing heat treatment at 1000 ° C or more, if necessary, and then hot-rolled.
  • the hot rolling is performed, for example, at a finishing temperature of 850 950 ° C. and a winding temperature of 650 800 t.
  • the hot-rolled sheet manufactured in this manner is subjected to pickling or grinding to remove the scale on the surface, and then cold-rolled and recrystallized and annealed at least once as described above to obtain a sheet thickness of 0. It is a thin plate of about 050.5.
  • Steel Ar having the components shown in Table 1 was melted in an electric furnace, ingot-formed, subjected to soaking at 1200 ° C or higher, and subjected to slab rolling to form a slab.
  • Steel AG is an example of the present invention, and is a steel in which components such as Nt V B Sb are appropriately adjusted.
  • steels AC and E are Nb-V-added steel
  • steel D is Nb-V-Bb-added steel
  • steel F is Nb-V-Sb-added steel
  • steel G is Nb-V-B-Sb-added steel.
  • the slab is heated to 1000 ° C or more, and hot-rolled at a finishing temperature of 850 950 ° (: winding temperature 650 800 ° C to form a hot-rolled coil.
  • cold rolling at a cold rolling rate of 2080 and 750
  • final cold rolling is performed at a cold rolling rate of 20 to 25
  • strain relief annealing is performed at 700 to 800 ° C, and a thin plate with a thickness of 0.12 thighs was prepared.
  • a JIS No. 5 tensile test specimen, a ring test specimen for evaluating magnetic properties, and a test specimen for measuring thermal expansion coefficient were collected from the center of the thin-sheet coil in the width direction, and were subjected to a heat treatment equivalent to softening annealing before pressing in an Ar atmosphere. Heat treatment was performed at 800-900 ° C for 15 minutes to evaluate the impact resistance, magnetic properties, and coefficient of thermal expansion of the shadow mask.
  • the tensile test was performed according to the tensile test method of JIS Z 2241, and 0.2 resistance was obtained.
  • the magnetic properties were evaluated based on JIS C 2531, and the maximum magnetic permeability at an applied magnetic field of 100 e was obtained.
  • the coefficient of thermal expansion was measured using an optical interference type thermal expansion measuring device, and the average coefficient of thermal expansion at 20 to 100 ° C was determined.
  • Fig. 1 shows the relationship between 0.2 proof stress after soft annealing and pre-pressing and the maximum magnetic permeability.
  • three results are shown for the same steel, which correspond to the results of softening annealing temperatures before press of 900, 850, and 800 ° C in order from the left.
  • annealing at 900 ° C is relatively high in the temperature range normally used for softening annealing before pressing, and causes a significant increase in manufacturing costs.
  • a thin plate having a thickness of 0.12 was produced in the same manner as in Example 1 using the structural ingots of steels A and p shown in Table 1. At this time, as shown in Table 3, the cold rolling ratio and the strain relief annealing temperature in the final cold rolling were changed in five ways for steel A and three ways for steel p. Then, the same test as in Example 1 was performed on this thin plate. The softening annealing before pressing was performed in an Ar atmosphere at 750 to 900 ° C for 15 minutes. Table 3 shows the results.
  • Fig. 2 shows the relationship between the pre-press softening annealing temperature and the 0.2 proof stress.
  • Steels ⁇ -1 to ⁇ -3 are manufactured by setting the temperature for strain relief annealing to 750 ° C and changing the cold rolling rate in the final cold rolling.
  • the 0.2 proof stress is greatly reduced to 320 MPa or less with the rise of the softening annealing temperature before pressing.
  • the annealing temperature at which the 0.2% proof stress becomes 32 OMPa or less is 800 ° C. for steel A-3 of the present invention, whereas 850: for steel A-2 of the comparative example and 850: for steel A-1. 900 ° C.
  • pre-press softening annealing is performed at around 800 ° C, so steel A-3 is better than steels A-1 and A-2, which have a cold rolling reduction of less than 15% in the final cold rolling. Softening characteristics.
  • Steels A-3 to A-5 are manufactured with a final cold-rolling rate of 25% and a different strain relief annealing temperature.
  • the softening annealing temperature before pressing at which the proof stress is 320 MPa or less is 800 ° C for steels A-3 and A-4 of the present invention, whereas it is 850 ° C for steel A-5 of the comparative example. is there. Therefore, steels A-3 and A-4 have better softening properties than steel A-5. From the above, when Nb is added, the cold rolling rate of final cold rolling and the temperature of strain relief annealing should be controlled to specific ranges in order to secure softening characteristics in softening annealing before pressing. You can see that.
  • the resistance to 0.2 at a strain relief annealing temperature of 800 ° C or higher was less than 270 MPa, which is a preferable range of 270 to 320 MPa. More out of place.
  • the 0.2% proof stress at a softening annealing temperature before press of 750 ° C was 278 MPa, but when the magnetic properties were evaluated by performing the same tests as in Example 1, the maximum permeability was Magnetic susceptibility was less than 8000.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical 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)
  • Heat Treatment Of Steel (AREA)

Abstract

L'invention concerne une feuille mince d'alliage à faible dilatation thermique comprenant sensiblement entre 35 et 37 % en masse de Ni, 0,02 % en masse ou moins de C, 0,3 % en masse ou moins de Si, 0,6 % en masse ou moins de Mn, 0,01 % en masse ou moins de P, 0,005 % en masse ou moins de S, 0,01 % en masse ou moins de N, 0,1 % en masse ou moins d'Al, 0,08 % en masse ou moins de Cr, entre 0,05 % et 1 % en masse de Nb, entre 0,01 et 1 % en masse de V, le reste se composant de Fe, et (Nb+V) ≤ 1,0 % en masse. Cette feuille présente un coefficient de dilatation thermique suffisamment faible, une résistance aux chocs élevée et d'excellentes caractéristiques magnétiques après sa formation en un masque perforé par ramollissement de la feuille à une température inférieure à 850 °C avant le pressage. Par conséquent, ladite feuille est préférable à un masque perforé d'un tube cathodique.
PCT/JP2003/003045 2002-04-05 2003-03-14 Feuille mince d'alliage a faible dilatation thermique et son procede de fabrication WO2003085148A1 (fr)

Applications Claiming Priority (2)

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JP2002-103533 2002-04-05
JP2002103533A JP2003293091A (ja) 2002-04-05 2002-04-05 強度および磁気特性に優れた高強度低熱膨張合金薄板およびその製造方法

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WO2003085148A1 true WO2003085148A1 (fr) 2003-10-16

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CN110760764B (zh) * 2019-11-05 2021-09-28 重庆材料研究院有限公司 一种铁镍基含Al高强度定膨胀合金

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07188860A (ja) * 1993-12-27 1995-07-25 Nkk Corp 加工性に優れたカラー受像管用Ｆｅ−Ｎｉ系合金薄板およびＦｅ−Ｎｉ−Ｃｏ系合金薄板
JPH1017997A (ja) * 1996-06-28 1998-01-20 Sumitomo Metal Ind Ltd 熱間加工性に優れた高強度インバ−合金
JPH1060528A (ja) * 1996-08-14 1998-03-03 Sumitomo Metal Ind Ltd 高強度インバ−合金板の製造方法
JP2001049395A (ja) * 1999-08-11 2001-02-20 Hitachi Metals Ltd エッチング性および低熱膨張特性に優れたＦｅ−Ｎｉ−Ｃｏ系合金およびエッチング孔内郭形状の円滑性に優れたシャドウマスク

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07188860A (ja) * 1993-12-27 1995-07-25 Nkk Corp 加工性に優れたカラー受像管用Ｆｅ−Ｎｉ系合金薄板およびＦｅ−Ｎｉ−Ｃｏ系合金薄板
JPH1017997A (ja) * 1996-06-28 1998-01-20 Sumitomo Metal Ind Ltd 熱間加工性に優れた高強度インバ−合金
JPH1060528A (ja) * 1996-08-14 1998-03-03 Sumitomo Metal Ind Ltd 高強度インバ−合金板の製造方法
JP2001049395A (ja) * 1999-08-11 2001-02-20 Hitachi Metals Ltd エッチング性および低熱膨張特性に優れたＦｅ−Ｎｉ−Ｃｏ系合金およびエッチング孔内郭形状の円滑性に優れたシャドウマスク

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TW200304953A (en) 2003-10-16
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