CN1059933C - Fe-Ni-Co alloy and use for manufacture of shadow mask - Google Patents

Fe-Ni-Co alloy and use for manufacture of shadow mask Download PDF

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Publication number
CN1059933C
CN1059933C CN96104495A CN96104495A CN1059933C CN 1059933 C CN1059933 C CN 1059933C CN 96104495 A CN96104495 A CN 96104495A CN 96104495 A CN96104495 A CN 96104495A CN 1059933 C CN1059933 C CN 1059933C
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CN
China
Prior art keywords
alloy
less
content
equal
baffle
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Legal status (The legal status 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 status listed.)
Expired - Fee Related
Application number
CN96104495A
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Chinese (zh)
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CN1138634A (en
Inventor
R·科扎
M-P·索利纳克
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Imphy SA
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Imphy SA
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Publication of CN1138634A publication Critical patent/CN1138634A/en
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Publication of CN1059933C publication Critical patent/CN1059933C/en
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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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • 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
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt

Abstract

Fe-Ni-Co alloy whose chemical composition contains, by weight: 32%<=Ni<=34%, 3.5%<=Co<=6.5%, 0%<=Mn<=0.1%, 0%<=Si<=0.1%, 0%<=Cr<=0.1%, 0.005%=C<=0.02%, S<=0.001%, 0.0001%<=Ca<=0.002%, 0.0001%<=Mg<=0.002%, the substantial remainder preferably being iron and impurities resulting from smelting; the chemical composition of the alloy furthermore satisfying the relationships: Co+Ni<=38.5%, Co+0.5xNi>=20%, Co+5xNi>=165.5% and S<=0.02xMn+0.8xCa+0.6xMg. Use of the alloy for the manufacture of a shadow mask for a display cathode ray tube.

Description

Fernico and uses thereof
The present invention relates to a kind of low-expansion Fe-Ni-Co alloy, and the purposes when manufacturing is used for the baffle of display cathode x ray tube.
It is well-known having low-expansion Fe-Ni-Co alloy, is commonly called SUPERINVAR.These alloys are particularly suitable for making baffle, for example in European patent application EP 05340460, propose, its suggestion uses a kind of Fe-Ni-Co alloy to make baffle, outside this alloy deironing, contain 28-34% nickel, the 2-7% cobalt, 0.1-1% manganese, less than 0.1% silicon, less than 0.01% carbon, all the other impurity for from melting, bringing into.But this alloy also has a shortcoming, be exactly its martensite transformation is put initial temperature Ms near room temperature, therefore, no matter be when forming baffle or storing it at low temperatures, all can cause the tension set of baffle because of martensite transformation takes place.In addition, because the necessary element of hot rolling alloy that manganese is considered to form, above-mentioned manganese content also makes the coefficient of expansion of alloy too high, thereby can not effectively reduce the defective of baffle local crowning.
Purpose of the present invention just provides a kind of Fe-Ni-Co alloy, and its martensite transformation starting point is lower than-50 ℃, and mean thermal expansion coefficients is less than 0.7 * 10 between 20 ℃ and 100 ℃ -6/ ° K, mean thermal expansion coefficients is less than 1 * 10 between 80 ℃ and 130 ℃ -6/ ° K.
Thus, theme of the present invention is a kind of Fe-Ni-Co alloy, and its chemical constitution comprises (by weight):
32％≤Ni≤34％
3.5％≤Co≤6.5％
0％≤Mn≤0.1％
0％≤Si≤0.1％
0％≤Cr≤0.1％
0.005％≤C≤0.02％
S≤0.001％
0.0001％≤Ca≤0.002％
0.0001％≤Mg≤0.002％
All the other are iron and the impurity that produced by melting; The chemical constitution of this alloy further satisfies following relation:
Co+Ni≤38.5％
Co+0.5×Ni≥20％
Co+5×Ni≥165.5％
And S≤0.02 * Mn+0.8 * Ca+0.6 * Mg
Preferably, copper, molybdenum, vanadium and content of niobium every kind all should be less than 0.1%.More preferably, manganese, silicon, chromium, copper, molybdenum, vanadium and content of niobium summation are less than 0.30%.
At last, preferred oxygen content is less than or equal to 0.01%, and nitrogen content is less than or equal to 0.005%, and phosphorus content is less than or equal to 0.005%.
Another theme of the present invention is to use according to alloy of the present invention to make baffle, and the baffle that makes.
To narrate more accurately the present invention below, but the present invention is not limited to following narration.
Although the distortion of all knowing baffle is to be heated to by middle temperature to be lower than 100 ℃ temperature, normally 80 ℃ cause, the present invention supposes that now image deflects is because the local heating baffle extremely can be up to causing under 130 ℃ the temperature.In order to reduce image deflects as far as possible, the mean thermal expansion coefficients of alloy between 20 ℃ to 100 ℃ that not only requires to be used for to make baffle is low as far as possible, and the mean thermal expansion coefficients of this alloy between 80 ℃ and 130 ℃ is also low as far as possible.In addition, this alloy must be under enough low temperature, and that is to say at least has stable microstructure at-50 ℃.
Alloy according to the present invention is a kind of Fe-Ni-Co alloy, regulates its chemical constitution, and it is met the following conditions simultaneously, and the mean thermal expansion coefficients between 20 ℃ and 100 is less than or equal to 0.7 * 10 -6/ ° K, the mean thermal expansion coefficients between 80 ℃ and 130 ℃ is less than or equal to 1 * 10 -7/ ° K, and the Ms of this alloy point temperature is lower than-50 ℃.
The chemical constitution of this alloy comprises, by weight, at least 32%, at the most 34% nickel, and at least 3.5%, at the most 6.5% cobalt, the content of nickel and cobalt satisfies:
Co+Ni≤38.5％
So that the mean thermal expansion coefficients of alloy between 20 ℃ and 100 ℃ is less than 0.7 * 10 -6/ ° K;
Co+0.5×Ni≥20％
So that the mean thermal expansion coefficients of alloy between 80 ℃ and 130 ℃ is less than 1 * 10 -6/ ° K;
Co+5×Ni≥165.5％
So that the Ms point is lower than-50 ℃.
In addition, in order to guarantee that the mean thermal expansion coefficients of alloy between 20 ℃ and 100 ℃ is less than 0.7 * 10 -6/ ° K requires manganese in the alloy, silicon and chromium content to be less than or equal to 0.1%.
For the Ms point that makes alloy remains below-50 ℃, alloy must contain at least 0.005% carbon, but carbon content can not surpass 0.02%, so that be unlikely to influence the drawing plasticity of alloy.
In addition, industrial alloy contains impurity element usually, as copper, molybdenum, vanadium or niobium, for making the alloy thermal expansivity as far as possible little, wishes that every kind of content of these elements all is less than or equal to 0.1%, and, preferably,
Mn+Si+Cr+Mo+V+Nb+Cu≤0.30％
At last, for the high-temperature ductility that obtains, preferably, oxygen level is less than or equal to 0.01%, and nitrogen content is less than or equal to 0.005%, and phosphorus content is less than or equal to 0.005%.
This alloy is particularly suitable for making baffle.For this reason, with alloy melting, cast ingot blank or slab ingot, hot rolling is to form the thick band of about 4mm then; Cold rolling this band is to obtain the thick cold rolling strap of about 0.15mm.The 0.2% yielding stress R of this cold rolling strap in the time of 20 ℃ P0.2About 600MPa, this too high and difficult shaping in addition, after chemical chop processing baffle base, is annealed these blanks between 700 ℃ and 850 ℃, make its 0.2% yielding stress R in the time of 20 ℃ P0.2Drop to about 320MPa.Then, each blank is shaped, for example draws, to obtain baffle.
As embodiment, prepare alloy A of the present invention to D, its chemical constitution is as follows, in weight %: alloy Ni Co Mn Si Cr C S Ca Mg Fe A 32.7 4.5 0.06 0.08 0.04 0.014 0.0006 0.0005 0.0015 surplus B 33.5 4.5 0.05 0.08 0.07 0.014 0.0009 0.0012 0.0009 surplus C 33.5 3.5 0.05 0.08 0.05 0.011 0.0007 0.0008 0.0007 surplus D 33.3 4.2 0.05 0.09 0.06 0.018 0.0008 0.0011 0.0011 surpluses
These alloy properties are as follows:
R p0.2 R p0.2 R p0.2
20 °/100 ° 20 °/80 ° 80 °/130 ° M of α α α MPa MPa MPa alloy s20 ℃ 20 ℃ 200 ℃
10 -6/ ° K 10 -6/ ° K 10 -6/ ° K ℃ of work hardening annealing *Annealing *A 0.31 0.23 0.78-90 615 320 141B 0.65 0.65 0.80＜-186 615 318 137C 0.49 0.45 0.90＜-186 607 304 133D 0.51 0.49 0.77＜-186 629 322 148
*Annealed 15 minutes for 780 ℃
Use these alloys, can make baffle, comprise the paillon foil of boring, and pass through drawing forming.Even be shaped in cold environment and after storing, these baffles still have austenitic structure completely.And its local crowning defective reduces 40% than the local crowning defective of the baffle made from the iron nickel alloy of prior art.

Claims (5)

1. low-expansion Fe-Ni-Co alloy, its chemical constitution comprise, by weight:
32％≤Ni≤34％
3.5％≤Co≤6.5％
0％≤Mn≤0.1％
0％≤Si≤0.1％
0％≤Cr≤0.1％
0.005％≤C≤0.02％
S≤0.001％
0.0001％≤Ca≤0.002％
0.0001％≤Mg≤0.002％
All the other reach the impurity that is produced by melting for iron, relation below this alloy composition further satisfies:
Co+Ni≤38.5％
Co+0.5×Ni≥20％
Co+5×Ni≥165.5％
And S≤0.02 * Mn+0.8 * Ca+0.6 * Mg
2. according to the alloy of claim 1, it is characterized in that copper, molybdenum, vanadium and content of niobium are separately less than 0.1%.
3. according to the alloy of claim 2, it is characterized in that the summation of manganese, silicon, chromium, copper, molybdenum, vanadium and content of niobium is less than 0.3%.
4. according to each alloy in the claim 1 to 3, it is characterized in that oxygen level is less than or equal to 0.01%, nitrogen content is less than or equal to 0.005%, and phosphorus content is less than or equal to 0.005%.
5. be used to make baffle according to each alloy in the claim 1 to 4.
CN96104495A 1995-05-05 1996-05-03 Fe-Ni-Co alloy and use for manufacture of shadow mask Expired - Fee Related CN1059933C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9505362 1995-05-05
FR9505362A FR2733767B1 (en) 1995-05-05 1995-05-05 FE-CO-NI ALLOY AND USE FOR THE MANUFACTURE OF A SHADOW MASK

Publications (2)

Publication Number Publication Date
CN1138634A CN1138634A (en) 1996-12-25
CN1059933C true CN1059933C (en) 2000-12-27

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Country Status (8)

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EP (1) EP0745697B1 (en)
JP (1) JP3756984B2 (en)
KR (1) KR100416116B1 (en)
CN (1) CN1059933C (en)
DE (1) DE69606737T2 (en)
DK (1) DK0745697T3 (en)
FR (1) FR2733767B1 (en)
PL (1) PL314075A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW442575B (en) * 1998-12-15 2001-06-23 Nippon Mining & Amp Metals Co Fe-Ni based alloy for tension mask, as well as tension mask, for which the same is used, and color brauon-tube
EP1352981B1 (en) 2000-11-21 2011-01-19 Nippon Yakin Kogyo Co., Ltd. Iron-nickel alloy material for shadow mask with excellent suitability for etching
DE10258356B3 (en) * 2002-12-12 2004-05-27 Thyssenkrupp Vdm Gmbh Use of an iron-nickel-cobalt alloy for shadow masks and their frames in flat monitors and TV screens
CN103924153B (en) * 2014-04-22 2016-04-27 钢铁研究总院 A kind of low bulk magnetic shielding Alloy And Preparation Method
CN105316576A (en) * 2014-07-31 2016-02-10 宝钢特钢有限公司 FeNi invar alloy with good welding property
CN108165889B (en) * 2017-12-27 2019-12-20 北京北冶功能材料有限公司 Low-expansion alloy with high maximum magnetic conductivity and preparation method thereof
CN108359915B (en) * 2018-02-13 2020-02-18 鞍钢股份有限公司 Smelting method of Fe-Ni low-expansion alloy
CN109023348A (en) * 2018-08-22 2018-12-18 哈尔滨工程大学 A kind of FeNiCo system alloy cladding coating material based on invarable effect

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0174196A2 (en) * 1984-09-06 1986-03-12 Kabushiki Kaisha Toshiba Material for in-tube components & method of manufacture thereof
EP0534460A1 (en) * 1991-09-27 1993-03-31 Yamaha Metanix Corporation Iron-nickel-cobalt alloy for a shadow mask

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4853298A (en) * 1986-04-08 1989-08-01 Carpenter Technology Corporation Thermally stable super invar and its named article

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0174196A2 (en) * 1984-09-06 1986-03-12 Kabushiki Kaisha Toshiba Material for in-tube components & method of manufacture thereof
EP0534460A1 (en) * 1991-09-27 1993-03-31 Yamaha Metanix Corporation Iron-nickel-cobalt alloy for a shadow mask

Also Published As

Publication number Publication date
CN1138634A (en) 1996-12-25
PL314075A1 (en) 1996-11-12
EP0745697B1 (en) 2000-02-23
FR2733767B1 (en) 1997-06-06
DK0745697T3 (en) 2000-06-19
KR100416116B1 (en) 2004-03-30
JP3756984B2 (en) 2006-03-22
KR960041391A (en) 1996-12-19
DE69606737T2 (en) 2000-08-17
FR2733767A1 (en) 1996-11-08
DE69606737D1 (en) 2000-03-30
EP0745697A1 (en) 1996-12-04
JPH08311622A (en) 1996-11-26

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