CN105316576A - FeNi invar alloy with good welding property - Google Patents
FeNi invar alloy with good welding property Download PDFInfo
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Abstract
The invention relates to a FeNi invar alloy with a good welding property. The FeNi alloy is composed of, by mass, 0.04%-0.15% of C, 0.1%-0.5% of Si, 0.10%-0.5% of Mn, 0%-0.008% of P, 0%-0.005% of S, 0.001%-0.015% of Ca, 31.0%-38.0% of Ni, 0%-4.0% of Co, and the balance Fe and unavoidable impurities. Meanwhile, the alloy components are controlled to be within a certain range when the components are designed, so that the alloy is ensured to have a good low-expansion property. According to the FeNi invar alloy with the good welding property, the requirement for the using environment of fields such as large-scale high-precision disc-carving machines, carbon fiber structural molds and low-temperature containers can be met. The FeNi invar alloy is good particularly in properties of the welding hot crack resistant aspect.
Description
Technical field
The invention belongs to low expansion alloy field, relate generally to the invar alloy that a kind of welding property is excellent, specifically, relate to a kind of low bulk invar alloy of novel anti-HOT CRACK FOR WELDING P.
Background technology
Invar alloy is invented in 1893 by Frenchman Guillaume, its main component to be Ni content be 36% Fe-Ni alloy/C, the coefficient of expansion of this alloy is very low, its 20 ~ 100 DEG C of coefficients of expansion are≤1.5 × 10-6/ DEG C, because alloy has the extremely low coefficient of expansion, this alloy is named as INVAR alloy.Because invar alloy has low-expansion feature, first this alloy is used widely in electronics, instrument field.In recent years, invar alloy has had new application demand in fields such as large-scale high-precision CD writer, carbon fiber structural part mould, low-temperature (low temperature) vessels, compared with applying with electronics, instrument field, these Application Areass large assemblies often, need welding, but, there is hot cracking tendency in the invar alloy of classics welding poor-performing.
Table 1 is correlated with the chemical composition (wt%) of typical steel grade
Table 2 is correlated with the performance of typical steel grade
From table 1 and table 2, typical invar alloy of the prior art has excellent low bulk performance, but welding property is not all claimed, in actual use, typical composition invar alloy easily produces HOT CRACK FOR WELDING P and second-heating thermal crack when welding large assemblies, and welding crack occurs in welding welded bonds district and heat affected zone, especially, when second welds, thermal stresses will cause heat affected zone that tiny crack occurs.T.Ogawas ([J] .Weld, 1986,65 (8): 213S ~ 226S.) to this has been further investigation, improved by weldprocedure and adopt thermal crack resistant welding wire, the hot cracking tendency of alloy can be improved, but when requiring high production efficiency, high calorie welding process must be used, and at this moment the hot cracking tendency of alloy is difficult to avoid.Therefore, the welding property inherently improving alloy is very necessary.Publication number is the Japanese Patent that JP11061341A is called " the iron nickel invar alloy of welding property excellence ", its composition characteristics is: Ni30 ~ 45%, S≤0.0030%, P≤0.0070%, O≤0.0040%, Al0.006 ~ 0.030%, N≤0.0030%, B0.0002 ~ 0.0005%, at least containing a kind of Ca≤0.010% in following compositions, Mg≤0.010%, Ti≤0.10, Zr≤0.20%, matrix is Fe, (S+1/50+1/2P)≤0.0045 and (Ca+2Mg+1.5Ti+0.8Zr)/(S+20) >=1and≤0.025%, preferably≤0.019%.The technical thought of this patent is mainly and reduces the precipitation of objectionable impurities at crystal boundary, and by Addition ofelements, prevents low melting point from separating out at crystal boundary, thus reach the object improving alloy welding property.This invention under certain condition, is effective to the welding property improving alloy, but this technology has certain limitation, and the undue foreign matter contents such as low S, P that control also can increase manufacturing cost.Ni Jiaming etc. are at " the thermal crack susceptibility of invar thin plate high-rate laser welding " (Chinese laser, April, 2011, Vol.38, No.4) draw to draw a conclusion in a literary composition: research is in the past thought, solidify final stage alloy impurity S, P segregation and the liquid film forming low melting point will cause thermal crack under tensile stress, but, butt weld center is dentrite, and do not find low melting point eutectic tissue, the major cause of hot tearing is that dentrite solidifies the end of a period stage, liquid film remains, and welding residual stress will make liquid film ftracture.According to solidification theory, the final set bridge joint of liquid film needs certain condensate depression usually, if condensate depression does not reach, liquid film will exist.As previously mentioned, invar alloy single phase austenite weld seam presents obvious medullary ray, under the effect of welding residual-tensile stress, easily causes liquid film to ftracture, forms thermal crack.The alloy of JP11061341A invention mainly reduces crystal boundary low melting point to the method improving welding property, but control overflow is not done on the elemental carbon affecting alloying constituent degree, the constitutional supercooling degree aspect of alloy is not improved, this shows, this invention has effect to improvement welding hot tearing, but can not fundamentally deal with problems.
Summary of the invention
The object of the present invention is to provide a kind of low bulk iron nickel invar alloy, this alloy has complete austenite structure, is namely stable austenite structure from initial solidification to-196 DEG C.This alloy has good welding property, low expansion character and good mechanical property.The field environments for use such as large-scale high-precision CD writer, carbon fiber structural part mould, low-temperature (low temperature) vessel can be met.This alloy is excellent performance in anti-HOT CRACK FOR WELDING P especially.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of FeNi invar alloy with superior weldability energy, the composition of described alloy forms by with following elements, in mass percentage: C0.04 ~ 0.15%, Si0.1 ~ 0.5%, Mn0.10 ~ 0.5%, Ca0.001 ~ 0.015%, Ni31.0 ~ 38.0%, P≤0.008%, S≤0.005%, Co≤4.0%, surplus is Fe and inevitable impurity.
Below the design of alloying constituent of the present invention is described:
Ni: the matrix element in iron nickel invar alloy, iron nickel invar alloy is in nickel content about 36% scope, and the coefficient of expansion is minimum, depart from certain limit, the coefficient of expansion of alloy rises with very precipitous slope, controls in certain limit, can guarantee that alloy has low expansion character by the nickel content of alloy.Nickel also has good phase stability effect, when nickel content is on the low side, may form martensitic phase under very low temperature, once there is martensitic transformation, the coefficient of expansion of invar alloy there will be and sharply raises, and mechanical property also can occur sharply to change.Ni still improves the principal element of alloy cryogenic mechanics performance.
Controlled by Ni to be necessary between 31.0 ~ 38.0% to reach technique effect of the present invention, exceed this scope, the coefficient of expansion of alloy can not meet the demands.
C: usually exist with the form of interstitial atom in iron nickel invar alloy, when there is carbide forming element in alloy, also can exist with carbide form, control the residual of carbide forming element due to strict in alloy, alloy C of the present invention mainly exists with the form of interstitial atom.C can increase the solid, liquid phase temperature head of iron nickel invar alloy, namely, increase C content, solid, liquid phase line stretching degree increases, and solute balance partition ratio K0 reduces, and the constitutional supercooling degree of alloy increases, the final set bridge joint of welding end of a period stage liquid film needs certain condensate depression, the increase of alloying constituent condensate depression, is conducive to the rapid solidification welding end of a period stage liquid film, thus avoids the generation of thermal crack.Such as, in alloy, C is increased to 0.08% from 0.02%, and solid, liquid liquidus temperature difference is increased to 25 DEG C from 9 DEG C, the increase of constitutional supercooling degree when being conducive to alloy graining.
Carbon also has certain strengthening effect, but too high carbon content can make the coefficient of expansion of material raise.
Controlled by C to be necessary between 0.04 ~ 0.15% to reach technique effect of the present invention, exceed this scope, the welding property of alloy and the coefficient of expansion have at least one can not meet the demands.
P: be harmful impurity element, the liquid film district segregation that the compound of low melting point P in the end solidifies in welding process, can cause cracking under the effect of thermal stresses, forms thermal crack.In addition, P, at Grain Boundary Segregation, can cause crystal boundary fragility to increase, and under thermal stresses effect, forms crystal boundary tiny crack.It is more low better that P controls, but the low P content of undue control will increase manufacturing cost, be controlled by P≤0.008, effectively can control the generation of above-mentioned situation.
S: be to welding property and harmful element thereof, S forms low melting point MnS with Mn in crystallisation process, the liquid film district of in the end solidifying in welding process and Grain Boundary Segregation, the liquid film setting rate of final set is caused to reduce, the liquid film long period keeps, when there is larger tensile stress, produce thermal crack.MnS, when crystal boundary is separated out, causes embrittlement of grain boundaries, produces along grain-boundary crack under thermal stresses effect.It is more low better that S controls, but the low S content of undue control will increase manufacturing cost, be controlled by S≤0.005, effectively can control the generation of above-mentioned situation.
Ca:Ca is a kind of strong reductor in smelting process, effectively can reduce the oxygen in metallurgical melt.Ca and S combines and forms CaS, has de-S effect in smelting process, and in process of setting, first Ca and S combines and form CaS, prevents the formation of low melting point MnS, can effectively put forward heavy alloyed welding property.When in alloy during Ca < 0.001%, the formation of low melting point MnS can not be stoped, when in alloy during Ca > 0.015%, alloy thermoplasticity will be reduced, be unfavorable for that Alloy Forming is processed, therefore, Ca controls at 0.001-0.015% by invention alloy.
Si: be effective reductor, but Si can increase the coefficient of expansion, preferably more low better, often have residual in this element smelting process, therefore, suitably select its content very important.Si is controlled in 0.1 ~ 0.5% scope.
Mn: favourable to the raising of hot workability, but unfavorable to the coefficient of expansion, should be more low better, often have residual in this element smelting process, be defined as 0.1 ~ 0.5%.
Co: have similar action with Ni, adds in right amount and is conducive to reducing the alloy coefficient of expansion.But the price of Co is higher, Co composition range is controlled≤4.0.
Prepare a method for FeNi invar alloy of the present invention, comprise the steps: smelting, forging, hot rolling, cold rolling, thermal treatment.
Preferably, the mode of described smelting is the mode refining that vacuum induction furnace smelting or electric arc furnace add external refining, and the temperature of described smelting or refining is 1560 ~ 1620 DEG C.
Preferably, the temperature of described forging is 1100 ~ 1250 DEG C.
Preferably, the temperature of described hot rolling is 1050 ~ 1200 DEG C.
Preferably, described cold rolling processing parameter is: draft 40 ~ 95%.
Preferably, described heat treated temperature is 800 ~ 1200 DEG C.
The main thought of the present invention on Composition Design carries heavy alloyed constitutional supercooling degree, and reduce impurity S, P segregation and form low melting point, make the existing opposing of material because of impurity S like this, P segregation and the liquid film forming low melting point cause the ability of thermal crack under tensile stress, again because material has high constitutional supercooling degree, make welding liquid film in latter stage rapid solidification, thus put forward heavy alloyed anti-welding hot tearing ability.Meanwhile, when Composition Design, also to alloying constituent be controlled in certain limit, guarantee that alloy has excellent low bulk performance.
The iron nickel invar alloy of the present invention's design, have the coefficient of expansion little, the features, particularly alloy such as cryogenic mechanics performance is excellent have the feature of anti-HOT CRACK FOR WELDING P.Be applicable to manufacture the component needing welding processing, be specially adapted to make low temperature low bulk parts
Compared with relevant typical steel grade, principal feature of the present invention adds carbon, to increase the opening degree of alloy solid-liquid phase line, increase the constitutional supercooling degree in crystallisation process, make alloy at welding solidification end liquid film rapid solidification, liquid film is thinning rapidly, until disappear, thus avoid the liquid film cracking phenomena of answering tension stress to cause to occur, stop the generation of HOT CRACK FOR WELDING P.
With existing alloy phase ratio, the present invention has following beneficial effect:
In order to improve the welding property of alloy, composition adjustment has been carried out on Fe-Ni36 alloy basis, by increasing carbon content, solid-liquid phase line temperature range is increased, add constitutional supercooling degree, be conducive to alloy welding to solidify final stage liquid film and solidify, thus the hot tearing avoiding welding stress to cause produces.On the other hand, by controlling sulphur, phosphorus content, and calcium trace adds, and decreases welding and solidifies in final stage liquid film and crystal boundary low-melting impurities, avoid the generation of welding hot tearing.Invention alloy improves the welding property of alloy, is applicable to make large-scale welding assembly.
Accompanying drawing explanation
Fig. 1 is that the HOT CRACK FOR WELDING P of the alloy that the present invention obtains evaluates metallograph.
Embodiment
Below embodiment is described:
Embodiment 1
One, prepare burden according to the constituent content of table 3, with vacuum induction furnace smelting, refining temperature is 1560 ~ 1620 DEG C, be cast into steel ingot, be specially C:0.041%, Si:0.18%, Mn:0.39%, P :≤0.004%, S :≤0.001%, Ca:0.001%, Ni:35.83%, Co:0.02%, surplus is iron and inevitable impurity;
Two, after being forged at 1100 ~ 1250 DEG C by steel ingot, at 1050 ~ 1200 DEG C, carry out hot rolling, then carry out cold rolling, and to control cold rolling draft be 40 ~ 95%, finally anneal at 800 ~ 1200 DEG C, obtain alloy product.
The properties of the alloy product that the present embodiment obtains is in table 4, and property indices is all very excellent.
The weld seam thermal crack evaluation of the alloy product that the present embodiment obtains is carried out as follows:
Specimen size: 1.5 × 50 × 200 cold rolled sheets, first at middle portion laterally weldering one weld seam of sample, weld width is 5mm, welding current: 60A, welding speed: 100mm/min, arc length: approximately 1.5-1.6mm.Then sample is loaded along its length, load: 120MPa stress, the experiment of Article 2 weld seam is carried out after sample pulling force loads, Article 2 position while welding: mid-way, specimen width direction is along loading direction, welding bead length 200mm, vertical leap Article 1 weld seam, the welding current of Article 2 weld seam, welding speed, arc length are identical with Article 1 weld seam.
Then carry out HOT CRACK FOR WELDING P inspection, adopt metallographic examination mode to evaluate, its metallographic examination photo is shown in accompanying drawing 1, figure to exist without any crackle, illustrates that embodiment 1 alloy does not find HOT CRACK FOR WELDING P.
Embodiment 2
One, prepare burden according to the constituent content of table 3, with vacuum induction furnace smelting, refining temperature is 1560 ~ 1620 DEG C, be cast into steel ingot, be specially C:0.050%, Si:0.17%, Mn:0.39%, P :≤0.004%, S :≤0.001%, Ca:0.005%, Ni:35.81%, Co:0.03%, surplus is iron and inevitable impurity;
Two, after being forged at 1100 ~ 1250 DEG C by steel ingot, at 1050 ~ 1200 DEG C, carry out hot rolling, then carry out cold rolling, and to control cold rolling draft be 40 ~ 95%, finally anneal at 800 ~ 1200 DEG C, obtain alloy product.
Embodiment 3
One, prepare burden according to the constituent content of table 3, with vacuum induction furnace smelting, refining temperature is 1560 ~ 1620 DEG C, be cast into steel ingot, be specially C:0.050%, Si:0.17%, Mn:0.37%, P :≤0.004%, S :≤0.001%, Ca:0.002%, Ni:36.42%, Co:0.01%, surplus is iron and inevitable impurity;
Two, after being forged at 1100 ~ 1250 DEG C by steel ingot, at 1050 ~ 1200 DEG C, carry out hot rolling, then carry out cold rolling, and to control cold rolling draft be 40 ~ 95%, finally anneal at 800 ~ 1200 DEG C, obtain alloy product.
The properties of the alloy product that the present embodiment obtains is in table 4, and property indices is all very excellent.
Embodiment 4
One, prepare burden according to the constituent content of table 3, with vacuum induction furnace smelting, refining temperature is 1560 ~ 1620 DEG C, be cast into into steel ingot, be specially C:0.100%, Si:0.10%, Mn:0.35%, P :≤0.002%, S :≤0.005%, Ca:0.004%, Ni:37.20%, Co:0.01%, surplus is iron and inevitable impurity;
Two, after being forged at 1100 ~ 1250 DEG C by steel ingot, at 1050 ~ 1200 DEG C, carry out hot rolling, then carry out cold rolling, and to control cold rolling draft be 40 ~ 95%, finally anneal at 800 ~ 1200 DEG C, obtain alloy product.
Embodiment 5
One, prepare burden according to the constituent content of table 3, with vacuum induction furnace smelting, refining temperature is 1560 ~ 1620 DEG C, be cast into steel ingot, be specially C:0.042%, Si:0.15%, Mn:0.50%, P :≤0.008%, S :≤0.001%, Ca:0.015%, Ni:31.00%, Co:4.0%, surplus is iron and inevitable impurity;
Two, after being forged at 1100 ~ 1250 DEG C by steel ingot, at 1050 ~ 1200 DEG C, carry out hot rolling, then carry out cold rolling, and to control cold rolling draft be 40 ~ 95%, finally anneal at 800 ~ 1200 DEG C, obtain alloy product.
Embodiment 6
One, prepare burden according to the constituent content of table 3, with vacuum induction furnace smelting, refining temperature is 1560 ~ 1620 DEG C, be cast into steel ingot, be specially C:0.045%, Si:0.50%, Mn:0.13%, P :≤0.007%, S :≤0.0018%, Ca:0.005%, Ni:35.53%, Co:0.01%, surplus is iron and inevitable impurity;
Two, after being forged at 1100 ~ 1250 DEG C by steel ingot, at 1050 ~ 1200 DEG C, carry out hot rolling, then carry out cold rolling, and to control cold rolling draft be 40 ~ 95%, finally anneal at 800 ~ 1200 DEG C, obtain alloy product.
Embodiment 7
One, prepare burden according to the constituent content of table 3, with vacuum induction furnace smelting, refining temperature is 1560 ~ 1620 DEG C, be cast into steel ingot, be specially C:0.052%, Si:0.15%, Mn:0.45%, P :≤0.003%, S :≤0.002%, Ca:0.005%, Ni:36.25%, Co:0.01%, surplus is iron and inevitable impurity;
Two, after being forged at 1100 ~ 1250 DEG C by steel ingot, at 1050 ~ 1200 DEG C, carry out hot rolling, then carry out cold rolling, and to control cold rolling draft be 40 ~ 95%, finally anneal at 800 ~ 1200 DEG C, obtain alloy product.
Embodiment 8
One, prepare burden according to the constituent content of table 3, with vacuum induction furnace smelting, refining temperature is 1560 ~ 1620 DEG C, be cast into steel ingot, be specially C:0.150%, Si:0.10%, Mn:0.12%, P :≤0.006%, S :≤0.001%, Ca:0.007%, Ni:38.00%, Co:0.04%, surplus is iron and inevitable impurity;
Two, after being forged at 1100 ~ 1250 DEG C by steel ingot, at 1050 ~ 1200 DEG C, carry out hot rolling, then carry out cold rolling, and to control cold rolling draft be 40 ~ 95%, finally anneal at 800 ~ 1200 DEG C, obtain alloy product.
Comparative example 1
Prepare burden according to the constituent content of table 3, be specially C:0.003%, Si:0.012%, Mn:0.60%, P :≤0.003%, S :≤0.001%, Ni:35.89%, Co:0.01%, surplus is iron and inevitable impurity; The manufacture method of alloy is with embodiment 1 ~ 8.
Comparative example 2
Prepare burden according to the constituent content of table 3, be specially C:0.010%, Si:0.18%, Mn:0.32%, P :≤0.003%, S :≤0.004%, Ni:36.20%, Co:0.02%, surplus is iron and inevitable impurity; The manufacture method of alloy is with embodiment 1 ~ 8.
Comparative example 3
Prepare burden according to the constituent content of table 3, be specially C:0.037%, Si:0.015%, Mn:0.40%, P :≤0.003%, S :≤0.004%, Ni:36.78%, Co:0.01%, surplus is iron and inevitable impurity; The manufacture method of alloy is with embodiment 1 ~ 8.
The identical course of processing is adopted with embodiment 1, identical method is adopted to test, carry out seven groups of alloying constituent processing and the Performance Detection of embodiment 2 ~ 8 and comparative example 1 ~ 3, its chemical composition and performance test results are respectively in table 3 and table 4, from the Performance comparision of table 4 embodiment and comparative example, under the prerequisite that mechanical property is suitable with the coefficient of expansion, embodiment steel welding hot tearing susceptibility significantly declines, under equivalent assay conditions, all there is HOT CRACK FOR WELDING P in comparative example, and the equal welding thermal crack of embodiment steel grade, obtain good implementation result.
The chemical composition (wt%) of table 3 embodiment and comparative example
The HOT CRACK FOR WELDING P performance that table 4 is embodiment steel and comparative example steel, mechanical property and expansion character compare.Wherein, Mechanics Performance Testing detects yield strength, tensile strength, unit elongation.Get 3 mean value calculation net results in experiment, HOT CRACK FOR WELDING P evaluation is tested by preceding method.
The performance of table 4 embodiment and comparative example
In sum, be only preferred embodiment of the present invention, not be used for limiting scope of the invention process, all equalizations of doing according to shape, structure, feature and the spirit described in the claims in the present invention scope change and modify, and all should be included in right of the present invention.
Claims (7)
1. one kind has the FeNi invar alloy of superior weldability energy, it is characterized in that, the composition of described alloy forms by with following elements, in mass percentage: C0.04 ~ 0.15%, Si0.1 ~ 0.5%, Mn0.10 ~ 0.5%, Ca0.001 ~ 0.015%, Ni31.0 ~ 38.0%, P≤0.008%, S≤0.005%, Co≤4.0%, surplus is Fe and inevitable impurity.
2. a manufacture method for FeNi invar alloy as claimed in claim 1, is characterized in that, comprises the steps: smelting, forging, hot rolling, cold rolling, thermal treatment.
3. manufacture method as claimed in claim 2, it is characterized in that, the mode of described smelting is the mode refining that vacuum induction furnace smelting or electric arc furnace add external refining, and the temperature of described smelting or refining is 1560 ~ 1620 DEG C.
4. manufacture method as claimed in claim 2, it is characterized in that, the temperature of described forging is 1100 ~ 1250 DEG C.
5. manufacture method as claimed in claim 2, it is characterized in that, the temperature of described hot rolling is 1050 ~ 1200 DEG C.
6. manufacture method as claimed in claim 2, it is characterized in that, described cold rolling processing parameter is: draft 40 ~ 95%.
7. manufacture method as claimed in claim 2, it is characterized in that, described heat treated temperature is 800 ~ 1200 DEG C.
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| CN105861935A (en) * | 2016-04-12 | 2016-08-17 | 太原理工大学 | Fe-36Ni Invar alloy material good in thermoplasticity and preparation method thereof |
| CN107746933A (en) * | 2017-10-16 | 2018-03-02 | 太原钢铁(集团)有限公司 | The method of low bulk Precise Alloy hot continuous rolling |
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| CN110541119A (en) * | 2018-05-28 | 2019-12-06 | 宝钢特钢有限公司 | Low-expansion iron-nickel alloy and manufacturing method thereof |
| CN113774271A (en) * | 2020-06-10 | 2021-12-10 | 宝武特种冶金有限公司 | Ultralow temperature-resistant fixed expansion alloy and preparation method thereof |
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Cited By (7)
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| US10433679B2 (en) | 2017-02-28 | 2019-10-08 | Skip Hop, Inc. | Tub receptacle and bathing sling |
| CN107746933A (en) * | 2017-10-16 | 2018-03-02 | 太原钢铁(集团)有限公司 | The method of low bulk Precise Alloy hot continuous rolling |
| CN110541119A (en) * | 2018-05-28 | 2019-12-06 | 宝钢特钢有限公司 | Low-expansion iron-nickel alloy and manufacturing method thereof |
| CN110541119B (en) * | 2018-05-28 | 2021-07-09 | 宝武特种冶金有限公司 | Low-expansion iron-nickel alloy and manufacturing method thereof |
| CN113774271A (en) * | 2020-06-10 | 2021-12-10 | 宝武特种冶金有限公司 | Ultralow temperature-resistant fixed expansion alloy and preparation method thereof |
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