CA1164687A - Improved high-nickel, iron-nickel alloy - Google Patents
Improved high-nickel, iron-nickel alloyInfo
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- CA1164687A CA1164687A CA000344159A CA344159A CA1164687A CA 1164687 A CA1164687 A CA 1164687A CA 000344159 A CA000344159 A CA 000344159A CA 344159 A CA344159 A CA 344159A CA 1164687 A CA1164687 A CA 1164687A
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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
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Abstract
ABSTRACT OF THE DISCLOSURE
An improved high-Ni, Fe-Ni alloy is disclosed comprising:
with the balance comprising substantially Fe and additional inevitable impurities, provided that:
(a) when Al is greater than 0.005 percent by weight, S is not greater than 0.005 percent by weight and Mn is 0.005 percent by weight or greater; and (b) when S is greater than 0.005 percent by weight, Al is not greater than 0.005 percent by weight and Mn is 0.005 percent by weight or greater.
The improved alloy is non-sensitive to stress corrosion cracking and high temperature cracking, is structurally very stable and maintains low thermal expansion coefficient in the temperature range from room temperature to the temperature of liquefied natural gas.
An improved high-Ni, Fe-Ni alloy is disclosed comprising:
with the balance comprising substantially Fe and additional inevitable impurities, provided that:
(a) when Al is greater than 0.005 percent by weight, S is not greater than 0.005 percent by weight and Mn is 0.005 percent by weight or greater; and (b) when S is greater than 0.005 percent by weight, Al is not greater than 0.005 percent by weight and Mn is 0.005 percent by weight or greater.
The improved alloy is non-sensitive to stress corrosion cracking and high temperature cracking, is structurally very stable and maintains low thermal expansion coefficient in the temperature range from room temperature to the temperature of liquefied natural gas.
Description
1 sackground o~ the ~nvent:ion This invention relates to an improvement in low thermal expansion coefficient high-nickel, iron-nickel alloys, commonly known as "Invar" alloys.
Invar alloy, a typical low thermal expansion co-e~icient alloy~ according to the ASTM, comprises 35 ~ 37% Ni and the balance Fe, and may contain up to 0.5~ of Mn, up to 0.5% of Co, up to 0.5% of Cr, up to 0.5~ of Mo, up to 0.1% of C, up to 0.3~ of Si, up to 0.025% of S and up to 0.025% of P
as allowable additive elements and/or impurities. And a small amount of Al, which is used for deoY.idation, may exist as the residue.
Generally speaking, in the Fe-Ni alloys containing high-Ni activities of C, N and 0 are remarkably high because of the high Ni conkent, and in the course of solidification CO bubbles formed from C and O, and ~2 bubbles originated from dissolved N are generated, which result in formation of blisters in the formed ingots. These formed.blisters make the hot working of the alloy impossible, and therefore, vacuum melting is usually employed in ~he production of Invar alloys.
As the high-Ni Fe-Ni alloys solidify in the form of the homogeneous austenite phase, impurities are liable to segregate. Such segregatea impurities are not homogenized by heat.ing in a soaking pit, and therefore they cause cracking in the course of slabbing (intergranular fracture), which constitutes another cause of difficulty in the hot working.
It was already reported that the intergranular fracture could be substantially prevented by limiting the S content 30. -2-*Trade Mark to O.O~o~ or less, the Al conten-t to 0.020~ or less and -the O content to 0~0~5~r or less (Japanese Laying-Open Paten^t Publication No. 52922/76~.
In the meanwhile, demand for the liquefied natural gas (hereinafter called LNG) has been remarkably expanded, and thus need for tankers, storage tanks, -tank trailers, etc.
and related large scale constructions for transporta-tion and storage thereof as wcll as the equipments therefor (hereinafter referred to as "the containers and equipments") is increasing.
Characteris-tic prop~rties required for the material for constructing these containers and equipments are, (a) That the metalographic structure of the material is s-table over the temperature range down to -162C, to which the material is exposed, and thus does not lose its toughness at this low -temperature. (b) That dimensional change in the temperature range from room temperature to -162C, to which the contain-ers and equipments are exposed, is minimum, namely, the thermal expansion coefficient is sufficiently small in this temperature range. (c) That the welding work, which is in-dispensable for constructing the containers and equipments, can be easily carried out, and welding defect, -that is, high temperature cracking, which will result in gas leak or break-down of the containers and equipments, does not develop. (d) That the containers and equipments built of the material are not susceptible to delayed cracking such as stress corrosion cracking, etc.
There is no material -that satis:~actorily mee-ts all these requirements. Among the materials which mee-t some of -these requirements, there are 9~o-Ni steel, aluminum alloys, aus-tenite ~ 1 6~B~7 stainless steels, 36~-Ni Invar alloy, e-tc., whlch are now used as the materials for the containers and equipmen-ts for LNG ~
The 3~o-Ni Invar allo~ satisfies (a) and (b) among -the above-mentioned requirements, That is, this alloy main-tains -the metal structure of face~centered cubic lattice down to -196~', which is the -temperature of lique:~ied nitrogen and thus easily effected in a laboratory, and maintains its toughness without exhibi-ting the ductility-brittleness tran-sition phenomenon, and thus retains sufficient toughness at this temperature. Also this alloy is characterized in that it retains low thermal expansion coefficient over a wide range from room temperature to -196C.
In this alloy, if the ~acuum meling is employed, the above-mentioned problem of residual bubbles can be solved, and hot work cracking caused by intergranular fracture can be prevented in accordance with the teaching of Japanese 1aying-Open Patent Publication No. 52922/76. Although these difficulties are solved, the alloy has defects that it easily develop high -temperature cracking when welded, and its corro-sion resistance is rather poor and it cannot be used when stress corrosion cracking must be considered, because its nickel content is high and the nickel forms low melting com-pounds with sulfur, which is inevi-tably incidental to the raw materials. That is to say, the alloy does not satisfy -the conditions (c) and (d).
We have for many years studied prevention of high tem-: perature cracking in welding and s-tress corrosion crackingof the Fe-Ni alloys, and we have now invented a new Invar alloy whi.ch is provided with the abcve-mentioned characteristic properties (c) and (d) wi.-thout sacrificing -the properties (a) and (b).
~hat is to say, there is provided a new improved Invar alloy, of which the stress corrosion cracking sensi-tivity is remarkably reduced by res-tricting the Co content -to 0.05%
or less by means of careful selection of Ni source; the sen-sitivity to the high temperature cracking in welding is re-duced by modifying the content of Mn and that controlling the Mn conten-t depending upon the content level of S and hl;
and the low thermal expansion coefficient and s-tability in the structure are well maintained by defining the Ni content as 34.5 - 37.~% in relation with the amount of the Mn con-tained.
Summary of the Invention According to this invention, in -the Invar alloy which comprises 36% Ni and the balance Fe and may contain C up to 0.1%, Si up to 1%, Mn up to 0.5%, P up to 0.025%, S up to 0.025%, Co up to 0.5%, Cr up to 0.5%, Mo up to 0.5%, and Al up to 0.02% as allowable additives and/or impurities; an improved alloy, whereof the Ni content is 34.5 _ 37,5%, the Co content is not more than 0.05%, and the Mn content is up to 1,2% when both the S content and the Al content are not more than 0.005~0, and the Mn content is at least 0.5% and up to 1.2% when either of the S content or the Al con-tent is not more -than 0.005~0, is provided.
In the alloy of this invention, the Ni content range is a little more expanded than that specified in the ASTM, This is based on the finding tha-t, in -this alloy, in order to maintain the structural stability in the low tempera-ture down to _162Oc~ at least about 34.5% of Ni is required, and there 1 J B~687 1 is no increase in the thermal expans:ion coefficient in the a~orementioned temperature ranye with the Fe-Ni alloys containiny high Ni content up to 37.5% in the relation with the amount o~ Mn which is added to the alloy in accordance with this invention.
Carbon may be contained in this alloy up to 0.1~ as specified in the ASTM when the corrosion resistance of the alloy is not a critical problem. However, its content should pre-ferably be as low as possible for the above-mentioned reason --generation of CO gas. The preferred con~ent is less than 0.01%.
Silicon has undesirable effect in the high Ni Fa-Ni alloys leading to the high temperature cracking in welding. In this invention, however, the problem of the high temperature cracking has been sol~ed by the increase in the Mn content within the Si content range according to the ASTM. The Si content is preferably less than 0.25~.
Manganese is added in the alloy of this invention in excess of the content specified in the ASTM in order to over-come the deleterious effect of S and Al. However, the upper limit of the Mn content is restricted to 1.26 because of the adverse effect of Mn on the low thermal expansion co-efficient of the all~y.
Phosphorus has little influence upon the properties required in the alloy o~ this invention. Therefore, P is allowed to be contained up to 0.025% as specified in ASTM. The preferred P content is less than 0.01%.
Cobalt has been revealed to conduce to stress cor-rosion cracking. Therefore the content thereo~ is limited to not more than 0.05%. The preferable Co content is less than 0.03%.
Chromium is an impurit~ more or less coming ~rom the raw -~t~
~ .
~46~7 materials. Eut this elemen-t has li-t-tle influence upon the properties required in the alloy of this invention, and therefore, it is allowed to be contained up to 0.5%. How-ever, the preferable alloy of this inven-tion con-tains sub-stantially no chromium.
In -the alloy of this invention, little or no Mo will be contained, if it is not posi-tively added. And it iæ no-t a necessary element and thus is not added. However, i-t has no deleterious effect if it is contained up to 0.~ as specified in the ASTM.
Aluminum has adverse effect on the low thermal expansion coefficient and the intergranular fracture. However, this element is effective for deoxidation and denitrid;ng and a small amount of the Al used in the melting step remains. The prior art publication, e.g., the above-mentioned Japanese Laying-Open Patent Publication ~2922/76, teaches that this element should be restricted to 0,02% or less. A1 has also undesirable influence on the high -temperature cracking in welding. However, in this invention, the deleterious effect thereof is overcome by addition of -the specified amount of Mn.
A slight amount of O and N is inevitably involved. In consideration of the intergranular fracture, the O content should preferably be not more than 0. 025~o, Nitrogen is usu-ally contained in the alloys of this kind to the exten-t of
Invar alloy, a typical low thermal expansion co-e~icient alloy~ according to the ASTM, comprises 35 ~ 37% Ni and the balance Fe, and may contain up to 0.5~ of Mn, up to 0.5% of Co, up to 0.5% of Cr, up to 0.5~ of Mo, up to 0.1% of C, up to 0.3~ of Si, up to 0.025% of S and up to 0.025% of P
as allowable additive elements and/or impurities. And a small amount of Al, which is used for deoY.idation, may exist as the residue.
Generally speaking, in the Fe-Ni alloys containing high-Ni activities of C, N and 0 are remarkably high because of the high Ni conkent, and in the course of solidification CO bubbles formed from C and O, and ~2 bubbles originated from dissolved N are generated, which result in formation of blisters in the formed ingots. These formed.blisters make the hot working of the alloy impossible, and therefore, vacuum melting is usually employed in ~he production of Invar alloys.
As the high-Ni Fe-Ni alloys solidify in the form of the homogeneous austenite phase, impurities are liable to segregate. Such segregatea impurities are not homogenized by heat.ing in a soaking pit, and therefore they cause cracking in the course of slabbing (intergranular fracture), which constitutes another cause of difficulty in the hot working.
It was already reported that the intergranular fracture could be substantially prevented by limiting the S content 30. -2-*Trade Mark to O.O~o~ or less, the Al conten-t to 0.020~ or less and -the O content to 0~0~5~r or less (Japanese Laying-Open Paten^t Publication No. 52922/76~.
In the meanwhile, demand for the liquefied natural gas (hereinafter called LNG) has been remarkably expanded, and thus need for tankers, storage tanks, -tank trailers, etc.
and related large scale constructions for transporta-tion and storage thereof as wcll as the equipments therefor (hereinafter referred to as "the containers and equipments") is increasing.
Characteris-tic prop~rties required for the material for constructing these containers and equipments are, (a) That the metalographic structure of the material is s-table over the temperature range down to -162C, to which the material is exposed, and thus does not lose its toughness at this low -temperature. (b) That dimensional change in the temperature range from room temperature to -162C, to which the contain-ers and equipments are exposed, is minimum, namely, the thermal expansion coefficient is sufficiently small in this temperature range. (c) That the welding work, which is in-dispensable for constructing the containers and equipments, can be easily carried out, and welding defect, -that is, high temperature cracking, which will result in gas leak or break-down of the containers and equipments, does not develop. (d) That the containers and equipments built of the material are not susceptible to delayed cracking such as stress corrosion cracking, etc.
There is no material -that satis:~actorily mee-ts all these requirements. Among the materials which mee-t some of -these requirements, there are 9~o-Ni steel, aluminum alloys, aus-tenite ~ 1 6~B~7 stainless steels, 36~-Ni Invar alloy, e-tc., whlch are now used as the materials for the containers and equipmen-ts for LNG ~
The 3~o-Ni Invar allo~ satisfies (a) and (b) among -the above-mentioned requirements, That is, this alloy main-tains -the metal structure of face~centered cubic lattice down to -196~', which is the -temperature of lique:~ied nitrogen and thus easily effected in a laboratory, and maintains its toughness without exhibi-ting the ductility-brittleness tran-sition phenomenon, and thus retains sufficient toughness at this temperature. Also this alloy is characterized in that it retains low thermal expansion coefficient over a wide range from room temperature to -196C.
In this alloy, if the ~acuum meling is employed, the above-mentioned problem of residual bubbles can be solved, and hot work cracking caused by intergranular fracture can be prevented in accordance with the teaching of Japanese 1aying-Open Patent Publication No. 52922/76. Although these difficulties are solved, the alloy has defects that it easily develop high -temperature cracking when welded, and its corro-sion resistance is rather poor and it cannot be used when stress corrosion cracking must be considered, because its nickel content is high and the nickel forms low melting com-pounds with sulfur, which is inevi-tably incidental to the raw materials. That is to say, the alloy does not satisfy -the conditions (c) and (d).
We have for many years studied prevention of high tem-: perature cracking in welding and s-tress corrosion crackingof the Fe-Ni alloys, and we have now invented a new Invar alloy whi.ch is provided with the abcve-mentioned characteristic properties (c) and (d) wi.-thout sacrificing -the properties (a) and (b).
~hat is to say, there is provided a new improved Invar alloy, of which the stress corrosion cracking sensi-tivity is remarkably reduced by res-tricting the Co content -to 0.05%
or less by means of careful selection of Ni source; the sen-sitivity to the high temperature cracking in welding is re-duced by modifying the content of Mn and that controlling the Mn conten-t depending upon the content level of S and hl;
and the low thermal expansion coefficient and s-tability in the structure are well maintained by defining the Ni content as 34.5 - 37.~% in relation with the amount of the Mn con-tained.
Summary of the Invention According to this invention, in -the Invar alloy which comprises 36% Ni and the balance Fe and may contain C up to 0.1%, Si up to 1%, Mn up to 0.5%, P up to 0.025%, S up to 0.025%, Co up to 0.5%, Cr up to 0.5%, Mo up to 0.5%, and Al up to 0.02% as allowable additives and/or impurities; an improved alloy, whereof the Ni content is 34.5 _ 37,5%, the Co content is not more than 0.05%, and the Mn content is up to 1,2% when both the S content and the Al content are not more than 0.005~0, and the Mn content is at least 0.5% and up to 1.2% when either of the S content or the Al con-tent is not more -than 0.005~0, is provided.
In the alloy of this invention, the Ni content range is a little more expanded than that specified in the ASTM, This is based on the finding tha-t, in -this alloy, in order to maintain the structural stability in the low tempera-ture down to _162Oc~ at least about 34.5% of Ni is required, and there 1 J B~687 1 is no increase in the thermal expans:ion coefficient in the a~orementioned temperature ranye with the Fe-Ni alloys containiny high Ni content up to 37.5% in the relation with the amount o~ Mn which is added to the alloy in accordance with this invention.
Carbon may be contained in this alloy up to 0.1~ as specified in the ASTM when the corrosion resistance of the alloy is not a critical problem. However, its content should pre-ferably be as low as possible for the above-mentioned reason --generation of CO gas. The preferred con~ent is less than 0.01%.
Silicon has undesirable effect in the high Ni Fa-Ni alloys leading to the high temperature cracking in welding. In this invention, however, the problem of the high temperature cracking has been sol~ed by the increase in the Mn content within the Si content range according to the ASTM. The Si content is preferably less than 0.25~.
Manganese is added in the alloy of this invention in excess of the content specified in the ASTM in order to over-come the deleterious effect of S and Al. However, the upper limit of the Mn content is restricted to 1.26 because of the adverse effect of Mn on the low thermal expansion co-efficient of the all~y.
Phosphorus has little influence upon the properties required in the alloy o~ this invention. Therefore, P is allowed to be contained up to 0.025% as specified in ASTM. The preferred P content is less than 0.01%.
Cobalt has been revealed to conduce to stress cor-rosion cracking. Therefore the content thereo~ is limited to not more than 0.05%. The preferable Co content is less than 0.03%.
Chromium is an impurit~ more or less coming ~rom the raw -~t~
~ .
~46~7 materials. Eut this elemen-t has li-t-tle influence upon the properties required in the alloy of this invention, and therefore, it is allowed to be contained up to 0.5%. How-ever, the preferable alloy of this inven-tion con-tains sub-stantially no chromium.
In -the alloy of this invention, little or no Mo will be contained, if it is not posi-tively added. And it iæ no-t a necessary element and thus is not added. However, i-t has no deleterious effect if it is contained up to 0.~ as specified in the ASTM.
Aluminum has adverse effect on the low thermal expansion coefficient and the intergranular fracture. However, this element is effective for deoxidation and denitrid;ng and a small amount of the Al used in the melting step remains. The prior art publication, e.g., the above-mentioned Japanese Laying-Open Patent Publication ~2922/76, teaches that this element should be restricted to 0,02% or less. A1 has also undesirable influence on the high -temperature cracking in welding. However, in this invention, the deleterious effect thereof is overcome by addition of -the specified amount of Mn.
A slight amount of O and N is inevitably involved. In consideration of the intergranular fracture, the O content should preferably be not more than 0. 025~o, Nitrogen is usu-ally contained in the alloys of this kind to the exten-t of
2~ 0.04% or so. But the N content should be as low as possible, since it is a cause of blistering. The preferred N content is less than 0.01~.
The alloy of this invention is usually prepared by vacuum melting.
The alloy of this invention is usually prepared by vacuum melting.
3 The correlation of -the contents of S, A1 and Mn will be made clear in, the following descrip-tion of specific embodi,-ments of the inven-tion.
Now the invention is illustrated by way of the working examples with reference to the a-ttached drawings.
Brief Explanation of the Attached Drawings Fig. 1 is a schematic presentation of the appara~tus used for the stress corrosion cracking tex-t in this inven-tion.
Fig. 2 is a diagram showing the results of the stress corrosiGn cracking.
Fig, 3 is a graph showing the relation between the Mn conten-t and the average thermal expansion coefficient of the Invar alloys at lower temperatures.
Detailed Description of_the Invention The chemical anal~vses of the samples used in -these examples are listed in Table 1. Samples 1 - 13 are of alloys of this invention, while samples A - N are comparative alloys.
1 1 6 ~ 7 Table 1 Chemical Analyses o:E Sample A]loys -, . . . _ Sam- _ _ ~
ple C N 0 P Si Ni Co Mn S A l No .
_ . _ _ 1 <0 . 010 <0 . C10 ~0 . o25 o ~ oo7 o .23 35 ~ 85 o ~ OlC 0 . 22 o ~ oo3 o ~ oo3 2 ~l l~ .l co~ 005 o ~ 17 35~ 96 0 ~ o37 0 ~ 29 0 ~ oo4 0 ~ oo4 - ---- - -3 ~l ll llo ~ oo6 o ~ 21 33 ~ 7g o ~ oo7 o ~ 47 o ~ oo3 o ~ oo4 - - -
Now the invention is illustrated by way of the working examples with reference to the a-ttached drawings.
Brief Explanation of the Attached Drawings Fig. 1 is a schematic presentation of the appara~tus used for the stress corrosion cracking tex-t in this inven-tion.
Fig. 2 is a diagram showing the results of the stress corrosiGn cracking.
Fig, 3 is a graph showing the relation between the Mn conten-t and the average thermal expansion coefficient of the Invar alloys at lower temperatures.
Detailed Description of_the Invention The chemical anal~vses of the samples used in -these examples are listed in Table 1. Samples 1 - 13 are of alloys of this invention, while samples A - N are comparative alloys.
1 1 6 ~ 7 Table 1 Chemical Analyses o:E Sample A]loys -, . . . _ Sam- _ _ ~
ple C N 0 P Si Ni Co Mn S A l No .
_ . _ _ 1 <0 . 010 <0 . C10 ~0 . o25 o ~ oo7 o .23 35 ~ 85 o ~ OlC 0 . 22 o ~ oo3 o ~ oo3 2 ~l l~ .l co~ 005 o ~ 17 35~ 96 0 ~ o37 0 ~ 29 0 ~ oo4 0 ~ oo4 - ---- - -3 ~l ll llo ~ oo6 o ~ 21 33 ~ 7g o ~ oo7 o ~ 47 o ~ oo3 o ~ oo4 - - -
4 ll --wll -- ll<o~ oo5 o~ 28 35.80 o ~ oo9 o ~ 55 o ~ oo3 0.013 ll l~ llll o ~ 16 36 ~ Ol o ~ OlO o ~ 65 o ~ Oll o ~ oo3 ~ - ~ - - ~ - ~
d 6 .l n l~.l 0,14 35.82 O,Oll 0-72 o,ol3 o,oo4 - ~ --~ ----7 ~l ll llo,oo6 0,20 35.90 O,Oll o,98 o,oo4 0,002 ~1 _ ~ _ 8 ll ll l~~o ~ oo5 o ~ 23 35 ~ 64 o ~ 02s l ~ 02 ll o ~ 019 ~ - ~ -9 ll ll l~ ll 0,17 35.71 O,OlO 1,17 0,014 o,oo4 H .... _ . ~ _ ,21 37.34 O,Oll 0,27 0,002 o,oo5 37 ~ 40 o ~ OlO o ~ 61 o ~ oo9 o ~ oo4 - - ~-- - -12 ll ll .- ~0.005 O,l9 37.21 0,012 l,lO O,Oll o,oo4 ~ - ~ - - ~- -13 ~ ll l~ ~ 0,21 34,72 O,Oll o,24 o,oo4 o,oo5 - - ~ - -- ~--A .. .. .. .. 0,15 36,02 O,OlO 0,2L~ o,oo4 o,oo9 _ _ _ . _ A _ _ _ _ . --B . __ 0,22 35.56 o ~ 2 a 0,27 O, Ol O 0,008 C -- ~ o, oo6 o ~ 1 9 35 ~ 94 o ~ 012 o ~ 28 o, ol 5 0 ~ o o3 D ll ll ll0 . oo7 o ~ 23 35 ~ 61 o ~ 65 o ~ 30 o ~ oo9 o ~ 002 - - - - - -E _ o, oo c o . 1 8 36 ~ 02 0 . o74 o ~ 32 o ~ 012 o ~ 032 F .l .l .. .. 0 . 18 35 ~ 9l 0 ~ Ol O 0 ~ 41 0 ~ 002 0.016 ¢
G _ _ _ .- 0, 21 35.6 a 0 ~ o o9 o ~ 47 0 ~ o o5 o ~ 01 0 H __ 0 . 16 35 ~ 70 ~ Ol l l ~ 32 o . oo4 0 ~ oo3 I .. .. .. .. 0 . 20 36 ~ 94 o,4g 0 ~ 84 o - - ~ - ~ -J ll " ._ " 0 . 00 ~ 0, 19 37 ~ 21 o ~ Ol O l ~ 29 o ~ 01 K _=_ ~0.00~ 0,27 3a,L~6 o,oo9 o,L~7 0,012 o,oo4 L ll ll ............... " o~2L~ 38,30 o~oo9 o,96 ~ 0,012 _ . _ _ ~ ~_ ~ __ ~ _ . .
Mll ll ll ll o . 18 34 ~ 36 ll o ~ 20 llo ~ o34 ~ --- - - - - - -~l - - ~
. N L_ __ _ _ o ~ 1 4 34 ~ 01 o, o l 5 1 ~ o4 .l o ~ 008 - ~
~ 3 6~7 Each sample was mel-ted in a vacuum high frequency e]ec--tric furnace of lOkg capacity, and cast. The cast specimen was forged at about 1150C, and by repeti-tion of thermal treatment and cold working, i-t was formed into plates o~
predetermined thickness (2.Omm and l.Omm). Thereafter the specimen was finally subjected to a thermal trea-tment at 80ooc for 10 minutes.
The control of the Co content was effected by combined use of ferronickel and electroly-tic nickel. Manganese was added in the form of me-talic manganese. In order to prepare low S level specimens the desulfuration was carried ou-t by using lime and fluorspar.
Using -these specimens and the apparatus schematlcally shown in ~ig. 1, a stress corrosion cracking test was carried out and the results are shown in Fig. 2, The tes-t solution was a 20% aqueoussolution of NaCl containing o.46N Cr6~.
The te~pera-ture was 450C and the applied stress was 30kg/mm2.
The test resul-ts show that the s-tress corrosion cracking has nothing to do wi-th N1 and Mn but 1argely depends on the amount of Co contained. Therefore, the Co content should pref-erably be as low as possible. Although the Co conten-t can be lowered by strict selection of the Ni source, there is a limit as a matter of course and the allowable upper limit is 0.05%.
Cobalt has the same effect as Ni for the structural s-ta-bility and ferronickel is far more inexpensive than electroly-tic nickel. Thus economically i-t is advantageous to set the allow-able limit of the Co con-ten-t high. Bu-t ;-t is essen-tlal -to re-strict the Co content in order to con-trol -the s-tress corrosion cracking sensitivity of the alloy.
3 We studied the high tempera-ture cracking in welding by 1 3 64B~37 way of the arc strike -tes-t, and -the resul-ts are summarized in Table 2. The text condi-tions were as follows. Curren-t:
llOA, arc length: 2rnm and arcking time: 4 seconds.
1 3 ~8~7 -~-rc~
..1 , , ., C~3 1 O ~ O
. . ... ~.. ..,.... .
. . O
. C~l O O ~0 C~
.. .... . ,..~..., ~0, C~ O ~ O C) .. .. ~ O .. .
. O O ~ O C)_ O ~. O ~
E~ _ _ _ _ -- ----_ _ _ . . .. _ _ ~
~ O ~ O ~C
c~ ~ . , .,. ..
~ C~ ¢ O C~l O ~ .
h o o o td ¢ _ __ _ _. _ _ _ _ _ _ _. _ _ _ C) 4 1 O ~\1 O r h .; O ~ O ~1 O ~) ~
,- ~1 . -t ..
CD CO O O O O
. ~. . ~ G
. o_ .
: . . ., O
o~ ~ ~oO G ~, . o o ..
o ~o o ~ (^J
_ . __ _~
Z ~ ~ ~ *
~1 U~ ~ ¢ ~ *
~ _ ,. _ ~
From this table, -the following -three fac-ts are learned.
(1~ When the S content is 0.~05% or less and the content of the residual Al is also 0.005% or less, high -temperature cracking does not occur regardless of the Mn content.
(2) When the S content is 0.005% or less and -the Mn conten-t is not less than 0.5%, high temperature cracking does not occur even if the amount of the residual A1 is large.
(3) When the S content is more than 0.005% bu-t the residual Al content is not more than 0,00~%, high temperature cracking is prevented, if the Mn content is not less than 0.5%.
Therefore it is concluded that the high temperature cracking which frequently occur in the high-Ni Fe-Ni alloy can be controlled by regula-ting the Mn content depending on the S level and the content of the residual Al. From this viewpoint, the higher the Mn content, the better. ~ut it is restricted from the aspect of thermal expansion coefficient as explained below.
Fig. 3 shows the change of the average thermal expansion coefficient over the temperature range 0C - -180C of the Fe~Ni alloys respec-tively containing 3~.8(~0.10)% and 37.3 (~0,10)% Ni when Mn content is varied. Also average therrnal expansion coefficient of 38.4~ Ni level alloys is shown.
From Fig. 3, it is learned that average thermal expansion coefficient is largely influenced by the contents of Ni and Mn and it becomes remarkably large when Ni content exceeds 37.~%
and Mn content exceeds 1.2%, We also studied the structural stabili-ty of the alloy a-t low temperature (-162C). Specimens were kept at -162C for 10 hours and thereafter formation of rnartensi-te was checked.
The results are shown in Table 3. The amout of mar-tensi-te was 1~6~7 measured by point counting under an op-tical microscope.
'rable 3 Amount of martensite aftcr kept at -162C for 10 hours - Sample No. 1 13 M N
Amount of martensite 0 0 5.2% ~.9%
From Table 3, it is learned that both Mn and Ni have in-fluence on the formation of martensite, and at least 3L~,5% Ni is required in consideration of the case where the Mn con-tent is low, in order to obtain Fe-Ni alloy with good s-tructural stability that does not form martensite at -162C.
As has been described in the above examples, the Fe-Ni alloy used for the containers and equipments for LNG is largely restricted in composition. That is, in order to maintain the - structural stability at low temperature (-162C), it must con-tain at least 34.5% Ni. Cobalt which is incidental to Ni must be restricted to 0.05% or less for the prevention of stress - corrosion cracking.
For the purpose of keeping the thermal expansion coeffi-cient low, the Ni content cannot exceeds 37.5%. Manganese is ; 20 effective for the prevention of high temperature cracking in welding. But the content thereof must be not more than 1.2%.
The high temperature cracking in welding largely depends on the S level and the amountof the residual Al, but i-t is com-pletely preven-ted by addition of Mn in an amount determined by the content of S and Al.
~ 14 -
d 6 .l n l~.l 0,14 35.82 O,Oll 0-72 o,ol3 o,oo4 - ~ --~ ----7 ~l ll llo,oo6 0,20 35.90 O,Oll o,98 o,oo4 0,002 ~1 _ ~ _ 8 ll ll l~~o ~ oo5 o ~ 23 35 ~ 64 o ~ 02s l ~ 02 ll o ~ 019 ~ - ~ -9 ll ll l~ ll 0,17 35.71 O,OlO 1,17 0,014 o,oo4 H .... _ . ~ _ ,21 37.34 O,Oll 0,27 0,002 o,oo5 37 ~ 40 o ~ OlO o ~ 61 o ~ oo9 o ~ oo4 - - ~-- - -12 ll ll .- ~0.005 O,l9 37.21 0,012 l,lO O,Oll o,oo4 ~ - ~ - - ~- -13 ~ ll l~ ~ 0,21 34,72 O,Oll o,24 o,oo4 o,oo5 - - ~ - -- ~--A .. .. .. .. 0,15 36,02 O,OlO 0,2L~ o,oo4 o,oo9 _ _ _ . _ A _ _ _ _ . --B . __ 0,22 35.56 o ~ 2 a 0,27 O, Ol O 0,008 C -- ~ o, oo6 o ~ 1 9 35 ~ 94 o ~ 012 o ~ 28 o, ol 5 0 ~ o o3 D ll ll ll0 . oo7 o ~ 23 35 ~ 61 o ~ 65 o ~ 30 o ~ oo9 o ~ 002 - - - - - -E _ o, oo c o . 1 8 36 ~ 02 0 . o74 o ~ 32 o ~ 012 o ~ 032 F .l .l .. .. 0 . 18 35 ~ 9l 0 ~ Ol O 0 ~ 41 0 ~ 002 0.016 ¢
G _ _ _ .- 0, 21 35.6 a 0 ~ o o9 o ~ 47 0 ~ o o5 o ~ 01 0 H __ 0 . 16 35 ~ 70 ~ Ol l l ~ 32 o . oo4 0 ~ oo3 I .. .. .. .. 0 . 20 36 ~ 94 o,4g 0 ~ 84 o - - ~ - ~ -J ll " ._ " 0 . 00 ~ 0, 19 37 ~ 21 o ~ Ol O l ~ 29 o ~ 01 K _=_ ~0.00~ 0,27 3a,L~6 o,oo9 o,L~7 0,012 o,oo4 L ll ll ............... " o~2L~ 38,30 o~oo9 o,96 ~ 0,012 _ . _ _ ~ ~_ ~ __ ~ _ . .
Mll ll ll ll o . 18 34 ~ 36 ll o ~ 20 llo ~ o34 ~ --- - - - - - -~l - - ~
. N L_ __ _ _ o ~ 1 4 34 ~ 01 o, o l 5 1 ~ o4 .l o ~ 008 - ~
~ 3 6~7 Each sample was mel-ted in a vacuum high frequency e]ec--tric furnace of lOkg capacity, and cast. The cast specimen was forged at about 1150C, and by repeti-tion of thermal treatment and cold working, i-t was formed into plates o~
predetermined thickness (2.Omm and l.Omm). Thereafter the specimen was finally subjected to a thermal trea-tment at 80ooc for 10 minutes.
The control of the Co content was effected by combined use of ferronickel and electroly-tic nickel. Manganese was added in the form of me-talic manganese. In order to prepare low S level specimens the desulfuration was carried ou-t by using lime and fluorspar.
Using -these specimens and the apparatus schematlcally shown in ~ig. 1, a stress corrosion cracking test was carried out and the results are shown in Fig. 2, The tes-t solution was a 20% aqueoussolution of NaCl containing o.46N Cr6~.
The te~pera-ture was 450C and the applied stress was 30kg/mm2.
The test resul-ts show that the s-tress corrosion cracking has nothing to do wi-th N1 and Mn but 1argely depends on the amount of Co contained. Therefore, the Co content should pref-erably be as low as possible. Although the Co conten-t can be lowered by strict selection of the Ni source, there is a limit as a matter of course and the allowable upper limit is 0.05%.
Cobalt has the same effect as Ni for the structural s-ta-bility and ferronickel is far more inexpensive than electroly-tic nickel. Thus economically i-t is advantageous to set the allow-able limit of the Co con-ten-t high. Bu-t ;-t is essen-tlal -to re-strict the Co content in order to con-trol -the s-tress corrosion cracking sensitivity of the alloy.
3 We studied the high tempera-ture cracking in welding by 1 3 64B~37 way of the arc strike -tes-t, and -the resul-ts are summarized in Table 2. The text condi-tions were as follows. Curren-t:
llOA, arc length: 2rnm and arcking time: 4 seconds.
1 3 ~8~7 -~-rc~
..1 , , ., C~3 1 O ~ O
. . ... ~.. ..,.... .
. . O
. C~l O O ~0 C~
.. .... . ,..~..., ~0, C~ O ~ O C) .. .. ~ O .. .
. O O ~ O C)_ O ~. O ~
E~ _ _ _ _ -- ----_ _ _ . . .. _ _ ~
~ O ~ O ~C
c~ ~ . , .,. ..
~ C~ ¢ O C~l O ~ .
h o o o td ¢ _ __ _ _. _ _ _ _ _ _ _. _ _ _ C) 4 1 O ~\1 O r h .; O ~ O ~1 O ~) ~
,- ~1 . -t ..
CD CO O O O O
. ~. . ~ G
. o_ .
: . . ., O
o~ ~ ~oO G ~, . o o ..
o ~o o ~ (^J
_ . __ _~
Z ~ ~ ~ *
~1 U~ ~ ¢ ~ *
~ _ ,. _ ~
From this table, -the following -three fac-ts are learned.
(1~ When the S content is 0.~05% or less and the content of the residual Al is also 0.005% or less, high -temperature cracking does not occur regardless of the Mn content.
(2) When the S content is 0.005% or less and -the Mn conten-t is not less than 0.5%, high temperature cracking does not occur even if the amount of the residual A1 is large.
(3) When the S content is more than 0.005% bu-t the residual Al content is not more than 0,00~%, high temperature cracking is prevented, if the Mn content is not less than 0.5%.
Therefore it is concluded that the high temperature cracking which frequently occur in the high-Ni Fe-Ni alloy can be controlled by regula-ting the Mn content depending on the S level and the content of the residual Al. From this viewpoint, the higher the Mn content, the better. ~ut it is restricted from the aspect of thermal expansion coefficient as explained below.
Fig. 3 shows the change of the average thermal expansion coefficient over the temperature range 0C - -180C of the Fe~Ni alloys respec-tively containing 3~.8(~0.10)% and 37.3 (~0,10)% Ni when Mn content is varied. Also average therrnal expansion coefficient of 38.4~ Ni level alloys is shown.
From Fig. 3, it is learned that average thermal expansion coefficient is largely influenced by the contents of Ni and Mn and it becomes remarkably large when Ni content exceeds 37.~%
and Mn content exceeds 1.2%, We also studied the structural stabili-ty of the alloy a-t low temperature (-162C). Specimens were kept at -162C for 10 hours and thereafter formation of rnartensi-te was checked.
The results are shown in Table 3. The amout of mar-tensi-te was 1~6~7 measured by point counting under an op-tical microscope.
'rable 3 Amount of martensite aftcr kept at -162C for 10 hours - Sample No. 1 13 M N
Amount of martensite 0 0 5.2% ~.9%
From Table 3, it is learned that both Mn and Ni have in-fluence on the formation of martensite, and at least 3L~,5% Ni is required in consideration of the case where the Mn con-tent is low, in order to obtain Fe-Ni alloy with good s-tructural stability that does not form martensite at -162C.
As has been described in the above examples, the Fe-Ni alloy used for the containers and equipments for LNG is largely restricted in composition. That is, in order to maintain the - structural stability at low temperature (-162C), it must con-tain at least 34.5% Ni. Cobalt which is incidental to Ni must be restricted to 0.05% or less for the prevention of stress - corrosion cracking.
For the purpose of keeping the thermal expansion coeffi-cient low, the Ni content cannot exceeds 37.5%. Manganese is ; 20 effective for the prevention of high temperature cracking in welding. But the content thereof must be not more than 1.2%.
The high temperature cracking in welding largely depends on the S level and the amountof the residual Al, but i-t is com-pletely preven-ted by addition of Mn in an amount determined by the content of S and Al.
~ 14 -
Claims (10)
1. A high-nickel, iron-nickel alloy comprising:
with the balance comprising substantially Fe and additional inevitable impurities, provided that:
(a) when Al is greater than 0.005 percent by weight, S is not greater than 0.005 percent by weight and Mn is 0.005 percent by weight or greater; and (b) when S is greater than 0.005 percent by weight, Al is not greater than 0.005 percent by weight and Mn is 0.005 percent by weight or greater.
with the balance comprising substantially Fe and additional inevitable impurities, provided that:
(a) when Al is greater than 0.005 percent by weight, S is not greater than 0.005 percent by weight and Mn is 0.005 percent by weight or greater; and (b) when S is greater than 0.005 percent by weight, Al is not greater than 0.005 percent by weight and Mn is 0.005 percent by weight or greater.
2. The alloy as claimed in claim 1 comprising not greater than 0.005 percent by weight Al.
3. The alloy as claimed in claim 1 comprising not greater than 0.005 percent by weight S.
4. The alloy as claimed in claim 1 comprising not greater than 0.005 percent by weight Al, and not greater than 0.005 percent by weight S.
5. The alloy as claimed in claim 1 or 4 comprising less than 0.01 percent by weight C.
6. The alloy as claimed in claim 1 or 4 comprising less than 0.25 percent by weight Si.
7. The alloy as claimed in claim 1 or 4 comprising less than 0.03 percent by weight Co.
8. The alloy as claimed in claim 1 or 4 comprising substantially no Cr or Mo.
9. The alloy as claimed in claim 1 comprising less than 0.01 percent by weight C, less than 0.25 percent by weight Si, less than 0.03 percent by weight Co, and substantially no Cr or Mo.
10. The alloy as claimed in claim 1, 4 or 9 wherein said additional inevitable impurities comprise elements selected from the group consisting of P, N and O provided that:
P is present as from 0 to 0.02 percent by weight;
N is present as from 0 to 0.01 percent by weight; and O is present as from 0 to 0.025 percent by weight.
P is present as from 0 to 0.02 percent by weight;
N is present as from 0 to 0.01 percent by weight; and O is present as from 0 to 0.025 percent by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP007041/79 | 1979-01-26 | ||
| JP704179A JPS55100959A (en) | 1979-01-26 | 1979-01-26 | Invar alloy with excellent welding high temperature crack resistance and strain corrosion crack resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1164687A true CA1164687A (en) | 1984-04-03 |
Family
ID=11654955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000344159A Expired CA1164687A (en) | 1979-01-26 | 1980-01-22 | Improved high-nickel, iron-nickel alloy |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS55100959A (en) |
| CA (1) | CA1164687A (en) |
| DE (1) | DE3002743C2 (en) |
| FR (1) | FR2447406A1 (en) |
| GB (1) | GB2041405B (en) |
Families Citing this family (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5934225B2 (en) * | 1981-06-15 | 1984-08-21 | 川崎製鉄株式会社 | Fe-Ni low thermal expansion amber type alloy with excellent welding hot cracking resistance |
| DE3202223A1 (en) * | 1982-01-25 | 1983-08-11 | Nisshin Steel Co., Ltd., Tokyo | Improved 36% Ni iron-nickel alloy |
| GB2117399B (en) * | 1982-01-25 | 1986-07-09 | Nisshin Steel Co Ltd | Low thermal expansion alloys |
| JPS60177164A (en) * | 1984-02-24 | 1985-09-11 | Nisshin Steel Co Ltd | Low-expansion fe-ni alloy having superior resistance to weld hot cracking |
| JPS60144180U (en) * | 1984-03-01 | 1985-09-25 | 東芝機器株式会社 | Serpentine product storage mechanism |
| JPS60251253A (en) * | 1984-05-28 | 1985-12-11 | Toshiba Corp | Color picture tube |
| US5391241A (en) * | 1990-03-22 | 1995-02-21 | Nkk Corporation | Fe-Ni alloy cold-rolled sheet excellent in cleanliness and etching pierceability |
| US5127965A (en) * | 1990-07-17 | 1992-07-07 | Nkk Corporation | Fe-ni alloy sheet for shadow mask and method for manufacturing same |
| JP2596210B2 (en) * | 1990-10-31 | 1997-04-02 | 日本鋼管株式会社 | Method of preventing adhesion seizure during annealing, Fe-Ni alloy for shadow mask excellent in gas emission, and method for producing the same |
| DE4402684C2 (en) * | 1993-05-27 | 2001-06-21 | Krupp Vdm Gmbh | Use of a low-expansion iron-nickel alloy |
| JPH1036948A (en) * | 1996-07-25 | 1998-02-10 | Nkk Corp | Iron-nickel base invar alloy excellent in weld high temperature cracking resistance |
| US6379378B1 (en) | 2000-03-03 | 2002-04-30 | Innercool Therapies, Inc. | Lumen design for catheter |
| US6261312B1 (en) | 1998-06-23 | 2001-07-17 | Innercool Therapies, Inc. | Inflatable catheter for selective organ heating and cooling and method of using the same |
| US6096068A (en) | 1998-01-23 | 2000-08-01 | Innercool Therapies, Inc. | Selective organ cooling catheter and method of using the same |
| US6051019A (en) | 1998-01-23 | 2000-04-18 | Del Mar Medical Technologies, Inc. | Selective organ hypothermia method and apparatus |
| US6585752B2 (en) | 1998-06-23 | 2003-07-01 | Innercool Therapies, Inc. | Fever regulation method and apparatus |
| US6464716B1 (en) | 1998-01-23 | 2002-10-15 | Innercool Therapies, Inc. | Selective organ cooling apparatus and method |
| US6491716B2 (en) | 1998-03-24 | 2002-12-10 | Innercool Therapies, Inc. | Method and device for applications of selective organ cooling |
| US6471717B1 (en) | 1998-03-24 | 2002-10-29 | Innercool Therapies, Inc. | Selective organ cooling apparatus and method |
| US6238428B1 (en) | 1998-01-23 | 2001-05-29 | Innercool Therapies, Inc. | Selective organ cooling apparatus and method employing turbulence-inducing element with curved terminations |
| US6231595B1 (en) | 1998-03-31 | 2001-05-15 | Innercool Therapies, Inc. | Circulating fluid hypothermia method and apparatus |
| US6325818B1 (en) | 1999-10-07 | 2001-12-04 | Innercool Therapies, Inc. | Inflatable cooling apparatus for selective organ hypothermia |
| US6383210B1 (en) | 2000-06-02 | 2002-05-07 | Innercool Therapies, Inc. | Method for determining the effective thermal mass of a body or organ using cooling catheter |
| US6245095B1 (en) | 1998-03-24 | 2001-06-12 | Innercool Therapies, Inc. | Method and apparatus for location and temperature specific drug action such as thrombolysis |
| US6251130B1 (en) | 1998-03-24 | 2001-06-26 | Innercool Therapies, Inc. | Device for applications of selective organ cooling |
| US6719779B2 (en) | 2000-11-07 | 2004-04-13 | Innercool Therapies, Inc. | Circulation set for temperature-controlled catheter and method of using the same |
| US7371254B2 (en) | 1998-01-23 | 2008-05-13 | Innercool Therapies, Inc. | Medical procedure |
| US6254626B1 (en) | 1998-03-24 | 2001-07-03 | Innercool Therapies, Inc. | Articulation device for selective organ cooling apparatus |
| US6251129B1 (en) | 1998-03-24 | 2001-06-26 | Innercool Therapies, Inc. | Method for low temperature thrombolysis and low temperature thrombolytic agent with selective organ temperature control |
| US6491039B1 (en) | 1998-01-23 | 2002-12-10 | Innercool Therapies, Inc. | Medical procedure |
| US6312452B1 (en) | 1998-01-23 | 2001-11-06 | Innercool Therapies, Inc. | Selective organ cooling catheter with guidewire apparatus and temperature-monitoring device |
| US6576002B2 (en) | 1998-03-24 | 2003-06-10 | Innercool Therapies, Inc. | Isolated selective organ cooling method and apparatus |
| US6599312B2 (en) | 1998-03-24 | 2003-07-29 | Innercool Therapies, Inc. | Isolated selective organ cooling apparatus |
| US6224624B1 (en) | 1998-03-24 | 2001-05-01 | Innercool Therapies, Inc. | Selective organ cooling apparatus and method |
| US6685732B2 (en) | 1998-03-31 | 2004-02-03 | Innercool Therapies, Inc. | Method and device for performing cooling- or cryo-therapies for, e.g., angioplasty with reduced restenosis or pulmonary vein cell necrosis to inhibit atrial fibrillation employing microporous balloon |
| US6602276B2 (en) | 1998-03-31 | 2003-08-05 | Innercool Therapies, Inc. | Method and device for performing cooling- or cryo-therapies for, e.g., angioplasty with reduced restenosis or pulmonary vein cell necrosis to inhibit atrial fibrillation |
| US6905494B2 (en) | 1998-03-31 | 2005-06-14 | Innercool Therapies, Inc. | Method and device for performing cooling- or cryo-therapies for, e.g., angioplasty with reduced restenosis or pulmonary vein cell necrosis to inhibit atrial fibrillation employing tissue protection |
| US7291144B2 (en) | 1998-03-31 | 2007-11-06 | Innercool Therapies, Inc. | Method and device for performing cooling- or cryo-therapies for, e.g., angioplasty with reduced restenosis or pulmonary vein cell necrosis to inhibit atrial fibrillation |
| US6241722B1 (en) | 1998-06-17 | 2001-06-05 | Cryogen, Inc. | Cryogenic device, system and method of using same |
| US6830581B2 (en) | 1999-02-09 | 2004-12-14 | Innercool Therspies, Inc. | Method and device for patient temperature control employing optimized rewarming |
| DE19944578C2 (en) * | 1999-09-17 | 2001-08-23 | Krupp Vdm Gmbh | Use of a low-expansion iron-nickel alloy with special mechanical properties |
| KR100334253B1 (en) * | 1999-11-22 | 2002-05-02 | 장인순 | Alloy steel having corrosion resistance in molten salt |
| US6726708B2 (en) | 2000-06-14 | 2004-04-27 | Innercool Therapies, Inc. | Therapeutic heating and cooling via temperature management of a colon-inserted balloon |
| US6755822B2 (en) | 2001-06-01 | 2004-06-29 | Cryocor, Inc. | Device and method for the creation of a circumferential cryogenic lesion in a pulmonary vein |
| DE10146301C1 (en) * | 2001-09-19 | 2002-07-18 | Krupp Vdm Gmbh | Production of a strip made from an iron-nickel alloy, used for shadow masks in flat monitors and TV screens, comprises continuous or batch-type annealing a strip made from an iron alloy containing nickel, molybdenum and chromium |
| BR0313376A (en) * | 2002-10-01 | 2005-06-21 | Magotteaux Int | Substantially graphite and nitrogen-free alloy and process for manufacturing it |
| CN110106448B (en) * | 2019-06-17 | 2020-10-02 | 江苏省沙钢钢铁研究院有限公司 | Low-expansion alloy material and preparation method thereof |
| CN110699591B (en) * | 2019-09-29 | 2021-04-02 | 佛山市川东磁电股份有限公司 | Preparation method of hot double-metal component layer Fe-Ni-Mn alloy |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB260039A (en) * | 1925-07-21 | 1926-10-21 | Bell Telephone Labor Inc | Magnetic material |
| DE708808C (en) * | 1935-04-09 | 1941-07-29 | Heraeus Vacuumschmelze Akt Ges | Process to achieve a constant and stable permeability in materials with 35 to 60% nickel and 65 to 40% iron |
| GB501337A (en) * | 1936-07-21 | 1939-02-21 | Bendix Aviat Corp | Improvements in and relating to diaphragm devices |
| FR1309618A (en) * | 1961-12-29 | 1962-11-16 | Gen Comm Company | Low coefficient of expansion alloy |
| GB1080625A (en) * | 1964-06-23 | 1967-08-23 | Henry Johnson | Woven fabric for paper-making machines |
| FR2148954A5 (en) * | 1971-08-11 | 1973-03-23 | Creusot Loire | Cryogenic nickel contg steel - retains austenitic structure after deformation at low temps |
| DE2217280A1 (en) * | 1972-04-11 | 1973-10-31 | Metallgesellschaft Ag | PERFORATED SCREEN IN COLOR TUBES |
| JPS5152922A (en) | 1974-11-06 | 1976-05-11 | Nisshin Steel Co Ltd | Netsukankakoseino sugureta ko niife gokin |
| JPS5292276A (en) * | 1976-01-29 | 1977-08-03 | Dainippon Printing Co Ltd | Method of producing container |
| GB1534944A (en) * | 1976-11-17 | 1978-12-06 | Bicc Ltd | Continuous casting of molten metal |
-
1979
- 1979-01-26 JP JP704179A patent/JPS55100959A/en active Granted
-
1980
- 1980-01-22 CA CA000344159A patent/CA1164687A/en not_active Expired
- 1980-01-25 DE DE19803002743 patent/DE3002743C2/en not_active Expired
- 1980-01-25 GB GB8002550A patent/GB2041405B/en not_active Expired
- 1980-01-25 FR FR8001632A patent/FR2447406A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55100959A (en) | 1980-08-01 |
| FR2447406A1 (en) | 1980-08-22 |
| FR2447406B1 (en) | 1982-11-12 |
| DE3002743C2 (en) | 1987-04-30 |
| JPS5645989B2 (en) | 1981-10-30 |
| GB2041405A (en) | 1980-09-10 |
| GB2041405B (en) | 1983-02-16 |
| DE3002743A1 (en) | 1980-08-21 |
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