CN1357056A - Iron-nickle alloy with creep resistance and low thermal expansion - Google Patents

Iron-nickle alloy with creep resistance and low thermal expansion Download PDF

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Publication number
CN1357056A
CN1357056A CN00809300A CN00809300A CN1357056A CN 1357056 A CN1357056 A CN 1357056A CN 00809300 A CN00809300 A CN 00809300A CN 00809300 A CN00809300 A CN 00809300A CN 1357056 A CN1357056 A CN 1357056A
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iron
nickel alloy
alloy
content
maximum
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CN00809300A
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CN1140644C (en
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B·格尔曼
B·厄潘贝克
U·布里尔
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Krupp VDM GmbH
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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
    • C22C38/12—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
    • C22C38/08—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
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • 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

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

Abstract

The invention relates to iron-nickel alloys with creep resistance and low thermal expansion, which contain ( % by mass) no more than about 0.2 % C, no more than 0.3 % Mn, no more than 0,3 % Si, from 0.05 to 3.0 % Al, 0.1 to 3.0 % Ti, no more than 1.0 % Nb, from 39.0 to 45.0 % Ni, wherein the rest is composed of iron and impurities that can be generated during the fabrication process. The inventive alloys have a thermal expansion coefficient <6.0 x 10<-6>/K in a temperature range between 20 and 100 DEG C.

Description

Creep resistance iron-nickel alloy with low-thermal-expansion
The present invention relates to the iron-nickel alloy of creep resistance and low bulk, especially for producing screen shadow mask frame parts.
The known ferrous alloy that comprises about 36% nickel has the low coefficient of expansion in 20 ℃～100 ℃ temperature range.Therefore, these alloys are in for example application of precision instrument, wrist-watch, the existing many decades of bimetal of the occasion that requires constant length no matter how temperature changes.Have even the development of the computer monitor of the high resolving power under unfavorable optical condition, color fidelity and contrast gradient and colour television set and particularly cause increasing as the use of the iron nickel material of shadow mask towards the development of more and more gentle bigger screen.In 20 ℃～100 ℃ temperature range, because this is a modal temperature in the picture tube, the softening annealing state contains the thermal expansivity of iron-nickel alloy of industry of about 36% nickel 1.2～1.8 * 10 -6Between/the K even higher, as what set forth at " Stahl-Eisen-Werkstoffblatt " (ferrous materials paper) (SEW-385 is published in 1991).For shadow mask, use the advanced material that contains about 36% nickel especially, it can obtain in 20 ℃～100 ℃ temperature range 0.6～1.2 * 10 -6Low thermal coefficient of expansion between the/K.
For be added with prestressed shadow mask at middle frame, need have with the alloy phase that uses so far than the low-expansion material that has improved creep resistance.The frame parts of shadow mask and shadow mask bears the annealing of so-called melanism being up under about 580 ℃ temperature.Produce a black oxide ferroelectric layer here, the eye impressions quality that obtains by it.
So far the ferrous alloy that contains about 36% nickel of Shi Yonging obtains about 2.6% creep resistance A under following test conditions 80: 580 ℃, 1 hour, load 138MPa.
Virgin stress in the mask vertical direction produces by upright frame member.Because used the iron-nickel alloy that contains about 41% nickel so far, so these alloys are as known as the material of metallic glass sealing or lead frame.Technical characterictic is as follows: with promptly 580 ℃ of the same conditions of the aforementioned alloy that contains 36% nickel, 1 hour, load 138MPa measured down, creep resistance A 80About 0.5%.According in 20 ℃～100 ℃ temperature range about 4.8 * 10 -6The thermal expansivity of/K, it is bigger to use this alloy upright frame member of making and the shadow mask of being made by the iron-nickel alloy that contains about 36% nickel to compare expansion.
Horizontal frame member should have identical expansion characteristics with shadow mask, so that horizontal frame member is used the identical iron-nickel alloy that contains 36% nickel with shadow mask.
Resemble for shadow mask, also for frame parts, need with the alloy phase that uses so far than having to being up to the material of better creep resistance under 580 ℃ the temperature.The temperature of the coefficient of expansion and size dependence should be about the same in the material that uses so far.
Know further that also the suitable additive of adding can cause precipitated phase to produce in iron-nickel alloy.For example Ti and Al cooperatively interact and add as such additive.γ (Ni 3Ti/Ni 3Al) formation of phase has improved apparent yield-point and intensity.
Yet Ti and the too high meeting of Al element total amount make thermal expansivity too high.
By DE-C 29 40 532, known a kind ofly have linear expansivity less than 5 * 10 in 20 ℃～300 ℃ temperature range -6/ ℃ and 20 ℃ the time apparent yield-point at 350N/mm 2Above age hardening ferronickel casting alloy, the nickel that it contains 35-45 weight % is less than the free Ti of 4 weight %, the Nb of 0-1 weight %, the Co of 1.5-2.5 weight %, all the other are for iron and depend on the impurity of thaw process.This alloy is fit to do machinery and heavily stressed mechanical part heat, for example rotor of Pneumatic pressure ripple machinery.
Optimizing creep resistance and low bulk iron-nickel alloy in the following manner is purpose of the present invention: no longer exist described prior art shortcoming, can low-cost make and can be used as especially the shadow mask frame parts and use.
This purpose can obtain by creep resistance and low bulk iron-nickel alloy, it contains (in weight %) C except maximum 0.2%, maximum 0.3% Mn, outside maximum 0.3% the Si, Al content is between 0.05～3.0%, and Ti content is between 0.1%～3.0%, ≤ 1.0%Nb, also have Ni content between 39.0～45.0%, remaining is the impurity that iron and production process are introduced, and has thermal expansivity＜6.0 * 10 in 20 ℃～100 ℃ temperature range -6/ K.
Favourable form according to this alloy of the present invention is disclosed in the relevant attached claim.
Be surprised to find, when Al that only adds set amount in described iron-nickel alloy respectively and Ti, iron-nickel alloy is at 580 ℃ under Cold Rolled Strip, and load 138MPa obtains the improvement of required creep resistance down.
Use can obtain particularly to do as materials used the desired technical characterictic of upright frame member of shadow mask according to iron-nickel alloy of the present invention, and this alloy contains Ni between 39.0～45.0 weight percents.
Preferably form except that nickel and iron, mainly be Al be 1.0～2.5 weight percents and the C that (by weight percentage) maximum 0.02% arranged again and, in case maximum 0.1%Mn, maximum 0.1% Si and very a spot of impurity relevant with production process are arranged.In manufacturing processed, show good processibility and without any need for additional processing step according to alloy of the present invention.Its further show for the permanent stability of the corresponding thermal property of described requirement.
According to the present invention, alloy E1 because its Al content and can age hardening, under the load of 580 ℃ test temperatures, 138MPa 1 hour, compares with the conventional T2 iron-nickel alloy that generally contains 41%Ni according to prior art, obtains A 80The tangible improvement of=0.17% creep resistance.
Purpose of the present invention preferably can be used for following goods :-thermostat is with the frame parts-electron beam gun of the assembly-lead frame-metallic glass sealing-screen of bimetallic passive block-laser technology and the watch-dog shadow mask assembly of structure unit-manufacturing, storage and the transport liquefied gases of television tube particularly
According to E1 alloy of the present invention and with the corresponding T1 of prior art and T2 alloy 580 ℃ test temperature, apply or table 1 is listed in the mechanical features do not determined in the hot tensile test of applied load and the characteristic contrast of magnetic coercive field strength and thermal expansivity.T2580 ℃ of hot tensile test residual set of alloy E1 E2 T1 yielding stress R P0.005(N/mm 2) 369 261 189R P0.2(N/mm 2) 574 206 322 312 yield strength R m(N/mm 2) 613 566 381 411 tension sets
4.3 18 6.4 7.5A 80(%) creep resistance (138N/mm 2Load) A 80(580 ℃ 1 hour) are 0.17 0.06 2.61 0.54 coercive field strength H (%) C(580 ℃/15 minutes) are 433 424 405H (A/m) C(580 ℃/1 hour) (A/m) 327 154 170 thermal expansivity (from 20 ℃ to test temperature T, with 10 -6/ K meter)
T(℃)
50 4.78 4.11 0.63 4.98
100 4.81 3.99 1.26 4.88
150 4.83 3.95 1.76 4.62
200 4.95 4.04 2.45 4.49
250 5.09 4.28 3.69 4.42
300 5.74 5.15 5.47 4.52
350 6.94 6.38 7.01 5.18
400 8.01 7.49 8.28 6.31
450 8.92 9.43 9.34 7.28
500 9.60 9.22 10.23 8.14
550 10.30 9.89 10.98 8.91
600 11.09 10.47 11.61 9.69
Table 1: according to alloy E1 contrast of the present invention and corresponding T1 of prior art and T2, mechanical features of determining by hot tensile test such as residual set yielding stress, yield strength, 580 ℃ tension set, and creep resistance, coercive field strength and thermal expansivity under 580 ℃ of 138MPa loads 1 hour.Sample is prepared by the 1.4mm cold rolling strap.
With regard to the E2 alloy, sample was (load is 200MPa during the creep resistance test) of softening annealing and age hardening before test.
According to alloy E1 of the present invention together with the coercive field strength H of corresponding alloy T1 of prior art and T2 CAfter 580 ℃ of thermal treatment in 15 minutes much at one.After 580 ℃ of thermal treatments in 1 hour, according to alloy E1 coercive field strength H of the present invention CFor the material as the shadow mask frame parts is enough low.
With regard to regard to alloy E1 of the present invention, be approximately 4.8 * 10 at the thermal expansivity of 20 ℃～100 ℃ of temperature ranges -6Therefore/K can satisfy the requirement as the upright frame member material.Temperature dependency according to the coefficient of expansion of the temperature dependency of the coefficient of expansion of alloy E1 of the present invention and the alloy T2 relevant with prior art is similar.Be shown in Fig. 1, the coefficient of expansion of taking this alloy E1 and T2 as can be seen intersects with the coefficient of expansion of alloy T1 between 270 ℃～320 ℃, to such an extent as to the thermal expansivity of low nickel content alloy below crossover temperature less than the thermal expansivity of high nickel content alloys.More than crossover temperature, situation is opposite.The inflection temperature of thermal expansivity roughly is equivalent to the Curie-point temperature T of respective alloy C
Fig. 1: according to alloy E1 of the present invention and E2 and with the temperature dependency of the coefficient of expansion of corresponding alloy T1 of prior art and T2
Example chemical ingredients contrast according to alloy E1 of the present invention and E2 is listed in table 2 with the chemical ingredients of corresponding alloy T1 of prior art and T2.Element
E1 E2 T1 T2 (% by weight) C 0.002 0.020 0.003 0.007S 0.0014 0.0006 0.0002 0.0030N 0.001 0.001 0.0025 0.002Cr 0.01 0.06 0.03 0.03Ni 42.95 42.2 36.15 40.80Mn 0.01 0.12 0.24 0.55 Si 0.01 0.16 0.06 0.17Mo 0.05 0.01Ti＜0.01 1.85＜0.01 0.005Nb, 0.52 0.01＜0.01Cu, 0.02 0.05 0.04Fe is remaining Yus 63.3 58.30P, 0.002 0.009 0.002 0.003Al, 1.88 0.13 0.007 0.002Mg 0.0002 0.002＜0.001Pb＜0.001 0.001 0.001Ca 0.0007zr＜0.01＜0.01Co, 0.01 0.02 0.04 0.04O 0.001 0.002 0.002 0.002
Table 2: according to the example chemical ingredients contrast of alloy E1 of the present invention and E2 and the example chemical ingredients of corresponding alloy T1 of prior art and T2
Limiting the quantity of according to alloy E1 chemical ingredients of the present invention described in following table.Element
E1 (% by weight) minimax C 0.2S 0.005Cr 0.2Ni 39.0 45.0Mn 0.3Si 0.3Mo 0.1Ti 0.1Nb 0.01Cu 0.1Fe R100.0P 0.005Al 0.1 3.0Mg 0.005Zr 0.10Co 0.3O 0.001
Table 3: according to limiting the quantity of of alloy E1 chemical ingredients of the present invention.
Another embodiment according to alloy of the present invention is modification E2.According to table 4, preferred composition comprises except that the Ni of 39.0-45.0%, also contains the Al and 0.2-1.0%Nb and balance iron and the impurity relevant with production process of Ti, the 0.05-0.3% of 1.5-2.5%.
Limiting the quantity of according to alloy E2 chemical ingredients of the present invention described in following table.Element
E2 (% by weight) minimax C 0.2S 0.005Cr 0.2Ni 39.0 45.0Mn 0.3Si 0.3Mo 0.3Al 0.05 0.3Nb 0.2 1.0Cu 0.3Fe R100.0P 0.01Ti 0.5 2.5Mg 0.005Zr 0.10Co 0.5O 0.003
Table 4: according to limiting the quantity of of alloy E2 chemical ingredients of the present invention.
At first alloy E2 changes system into frame parts under the softening annealing state.Under the age hardening state (promptly 750 ℃ 30 minutes) then, it is increased under 200MPa, 1 hour the situation at 580 ℃, load satisfies A in the creep resistance test 80＜0.1% high request.Machinery, magnetic and thermal expansion character value are listed in table 1.According to the typical composition of alloy E1 of the present invention as shown in Table 2.

Claims (12)

1. creep resistance and low bulk iron-nickel alloy, it contains, in weight %, and the C except maximum 0.2%, maximum 0.3% Mn, outside maximum 0.3% the Si, Al content is between 0.05～3.0%, and Ti content is between 0.1%～3.0%, ≤ 1.0%Nb, also have Ni content between 39.0～45.0%, remaining is iron and the impurity relevant with production process, and has thermal expansivity＜6.0 * 10 in 20 ℃～100 ℃ temperature range -6/ K.
2. according to the iron-nickel alloy of claim 1, it is characterized in that, in weight %, C content be set to maximum 0.02% and Al content between 1.5～2.5%.
3. according to the iron-nickel alloy of claim 1, it is characterized in that, in weight %, C content be limited in maximum 0.02% and Ti content between 1.5～2.5%.
4. according to each iron-nickel alloy in the claim 1 to 3, it is characterized in that in weight %, Mn content is limited in maximum 0.05% and Si maximum 0.05%.
5. according to each iron-nickel alloy in the claim 1 to 4, it is characterized in that,, add Co≤0.5% in weight %.
According to each iron-nickel alloy of claim 1 to 5 as the bimetallic passive block of thermostat.
According to each iron-nickel alloy of claim 1 to 5 as the assembly of manufacturing, storage and transport liquefied gases.
According to each iron-nickel alloy of claim 1 to 5 as the assembly of laser technology.
According to each iron-nickel alloy of claim 1 to 5 as lead frame.
According to each iron-nickel alloy of claim 1 to 5 as metallic glass sealing.
11. according to each iron-nickel alloy of claim 1 to 5 as the frame parts of screen or watch-dog shadow mask.
12. according to each iron-nickel alloy of claim 1 to 5 as the electron beam gun structure unit of television tube particularly.
CNB008093008A 1999-07-22 2000-02-16 Iron-nickle alloy with creep resistance and low thermal expansion Expired - Fee Related CN1140644C (en)

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DE19934401.9 1999-07-22
DE19934401A DE19934401A1 (en) 1999-07-22 1999-07-22 Creep-resistant, low-expansion iron-nickel alloy

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Cited By (8)

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CN102888557A (en) * 2011-07-18 2013-01-23 宝山钢铁股份有限公司 High-strength and low-expansion coefficient alloy wire and manufacturing method thereof
CN102965570A (en) * 2006-02-02 2013-03-13 蒂森克鲁普德国联合金属制造有限公司 Iron-nickel alloy
CN103074523A (en) * 2013-01-31 2013-05-01 安徽工业大学 Mould material for detecting high-temperature fatigue performance and preparation method of mould material
CN103084753A (en) * 2013-01-23 2013-05-08 宝山钢铁股份有限公司 Ferronickel precision alloy welding wire
CN107452690A (en) * 2016-03-31 2017-12-08 Tdk株式会社 Composite magnetic encapsulant
CN108074878A (en) * 2016-11-16 2018-05-25 Tdk株式会社 Composite magnetic sealing material and use its electronic circuit package body
CN108539354A (en) * 2018-03-21 2018-09-14 东莞市冠顺实业有限公司 A kind of resonant rod with long service life and preparation method thereof
US10615089B2 (en) 2016-03-31 2020-04-07 Tdk Corporation Composite magnetic sealing material

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US8808475B2 (en) 2006-02-02 2014-08-19 Outokumpu Vdm Gmbh Iron-nickel alloy
CN102965570A (en) * 2006-02-02 2013-03-13 蒂森克鲁普德国联合金属制造有限公司 Iron-nickel alloy
CN101495663B (en) * 2006-02-02 2013-05-22 蒂森克鲁普德国联合金属制造有限公司 Iron-nickel alloy
CN102888557B (en) * 2011-07-18 2014-10-29 宝钢特钢有限公司 High-strength and low-expansion coefficient alloy wire and manufacturing method thereof
CN102888557A (en) * 2011-07-18 2013-01-23 宝山钢铁股份有限公司 High-strength and low-expansion coefficient alloy wire and manufacturing method thereof
CN103084753A (en) * 2013-01-23 2013-05-08 宝山钢铁股份有限公司 Ferronickel precision alloy welding wire
CN103084753B (en) * 2013-01-23 2016-07-27 宝山钢铁股份有限公司 A kind of ferronickel Precise Alloy welding wire
CN103074523A (en) * 2013-01-31 2013-05-01 安徽工业大学 Mould material for detecting high-temperature fatigue performance and preparation method of mould material
CN107452690A (en) * 2016-03-31 2017-12-08 Tdk株式会社 Composite magnetic encapsulant
US10615089B2 (en) 2016-03-31 2020-04-07 Tdk Corporation Composite magnetic sealing material
CN107452690B (en) * 2016-03-31 2021-03-09 Tdk株式会社 Composite magnetic sealing material
CN108074878A (en) * 2016-11-16 2018-05-25 Tdk株式会社 Composite magnetic sealing material and use its electronic circuit package body
CN108074878B (en) * 2016-11-16 2021-07-27 Tdk株式会社 Composite magnetic sealing material and electronic circuit package using same
CN108539354A (en) * 2018-03-21 2018-09-14 东莞市冠顺实业有限公司 A kind of resonant rod with long service life and preparation method thereof
CN108539354B (en) * 2018-03-21 2019-07-23 东莞市冠顺实业有限公司 A kind of resonant rod with long service life and preparation method thereof

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PL353027A1 (en) 2003-10-06
DE50008438D1 (en) 2004-12-02
DE19934401A1 (en) 2001-03-22
EP1206588B1 (en) 2004-10-27
PL195127B1 (en) 2007-08-31
KR20020016649A (en) 2002-03-04
EP1206588A1 (en) 2002-05-22
JP2003505594A (en) 2003-02-12
HK1047772A1 (en) 2003-03-07
KR100531951B1 (en) 2005-12-02
WO2001007673A1 (en) 2001-02-01
TWI234588B (en) 2005-06-21
HK1047772B (en) 2004-08-20

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