CN101748345A - two-way shape-recovery alloy - Google Patents
two-way shape-recovery alloy Download PDFInfo
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- CN101748345A CN101748345A CN200910252029A CN200910252029A CN101748345A CN 101748345 A CN101748345 A CN 101748345A CN 200910252029 A CN200910252029 A CN 200910252029A CN 200910252029 A CN200910252029 A CN 200910252029A CN 101748345 A CN101748345 A CN 101748345A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C21D2201/00—Treatment for obtaining particular effects
- C21D2201/01—Shape memory effect
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Abstract
The present invention provides a two-way shape-recovery alloy, which contains less than 0.20 mass % of C, 13.00 to 30.00 mass % of Mn, 0.10 to 6.00 mass % of Si, 0.05 to 12.00 mass % of Cr, 0.01 to 3.00 mass % of Ni, and less than 0.100 mass % of N, with the remainder being Fe and unavoidable impurities, in which the contents of Mn, Si, Cr and Ni satisfy the following expression (1): 600!<=33Mn+11Si+28Cr+17Ni!<=1050 (1).
Description
Technical field
The present invention relates to a kind of round trip (two-way) shape-recovery alloy.More specifically,
The present invention relates to such two-way shape-recovery alloy: its utilization is accompanied by the expansion and the contraction of phase transformation, and does not utilize viscous deformation in fact, but can reversibly present low temperature phase shape and high temperature shape mutually.
Background technology
When certain material being carried out at low temperatures viscous deformation and being heated to high temperature subsequently, this material returns to the shape that it had before the viscous deformation takes place, and this phenomenon is called shape memory effect.The alloy of display shape memory effect is called shape memory alloy.
People's expectation is used for following purposes with shape memory alloy:
(1) be used for according to the spiral that temperature the changes piston ring tension spring (seeing also international open WO 2004/090318) that expands,
(2) be used for controlling system's (seeing also Japanese documentation JP-A-11-264425) of oily flow according to temperature, and
(3) have the actuator and the various switch block of temperature sensor functionality concurrently.
Known traditionally multiple material is a shape memory alloy.Wherein, the Ti-Ni alloy is the known class shape memory alloy type of behaving most.The Ti-Ni alloy of handling through the shape memory under the high temperature is used to multiple use.The shape memory effect of Ti-Ni alloy is owing to following characteristic: when the low temperature phase (martensitic phase) that produces by the distortion of the twin under the external force effect reverses when becoming high temperature phase (austenite phase), this system can return to the shape that forms by the shape memory processing.
Yet the Ti-Ni alloy exists because of the high problem that is difficult to carry out widespread use of material cost.In addition, also there is such problem:, can not use it for therefore that to need shape recovery temperature be in the purposes more than 100 ℃ because the transition temperature of this alloy is approximately room temperature.
Different with the Ti-Ni alloy is, is that the iron-base marmem of representative has characteristics cheap and that shape recovery temperature is higher with the Fe-Mn-Si alloy.The shape memory effect of ferrous alloy is attributable to following characteristic: when by the ε martensitic transformation under stress induced (promptly by more than or equal to M
sPoint is to being less than or equal to M
dUnder the temperature of some system is carried out viscous deformation, thus bring out by γ (FCC) mutually to the transformation of (HCP) phase) and the ε contrary of generation changes the γ phase time into, this system can return to the shape that is subjected to the first being processed system.
But iron-base marmem exists following problem and some other problems:
(1) shape memory effect of ferrous alloy is not as the Ti-Ni shape memory alloy;
(2) because ferrous alloy contains iron, so its erosion resistance and oxidation-resistance are poor; And
(3) when under as-annealed condition ferrous alloy being carried out viscous deformation, it occurs the crack easily.
In order to overcome these problems, people have proposed multiple motion so far.
For example, Japanese documentation JP-T-2000-501778 (term as used herein " JP-T " is meant the Japanese Translator communique of PCT patent application) discloses the nitrogenous iron-base marmem that the N that contains 28.80% Mn, 5.24% Si, 0.20% Cr and 0.11% and surplus are Fe.
With regard to effect such statement is arranged in this document: by the alloying of nitrogen, the shape memory characteristic of Fe-Mn alloy is improved, and comprises that the mechanical characteristics of damping characteristic also improves.
Japanese documentation JP-A-10-36943 discloses the method for making the Fe-Mn-Si shape memory alloy.In the method, the Fe-Mn-Si alloy that will have given composition forms, and is being higher than 1,000 ℃ and be lower than under 1,200 ℃ the temperature and keep them more than 15 minutes then.
With regard to effect such statement is arranged in this document: the crack when this method can effectively suppress stress deformation forms, and wherein fissured formation is caused by the intergranular precipitation of the tiny intermetallic compound that is rich in manganese and silicon.
Japanese documentation JP-A-2-221321 discloses the method for making iron-base marmem.In the method, more than or equal to M
d' point (add man-hour under this temperature, can not bring out forming ε martensite and α ' martensite) and being less than or equal under 700 ℃ the temperature is processed the Fe-Mn-Si alloy with given composition, then more than or equal to (M
d' point+200 ℃) anneal under the temperature.
Following statement is arranged in this document:
(1) owing to is being not less than M
d' temperature under alloy is processed, therefore can suppress the generation of ε martensite and α ' martensite (ε martensite and α ' martensite can cause adverse influence to processibility), thereby greatly improve manufacturing limit, and
(2) owing to be not less than (M
d' point+200 ℃) anneal under the temperature, therefore can eliminate the γ that produces by processing in mutually strain or can make γ phase recrystallize, thereby shape memory characteristic is improved.
In addition, Japanese documentation JP-A-7-292448 discloses a kind of Fe-Mn-Si shape memory alloy, and it is that the above α of 10 μ m makes mutually by the Fe-Mn-Si alloy with given composition is heat-treated thereby form thickness in its surface.
Following statement is arranged in this document:
(1) by under suitable atmosphere the Fe-Mn-Si alloy being heat-treated, thereby formed the α phase with body-centered (body-centered) cubic structure from the teeth outwards, wherein the manganese concentration of α phase is lower than the manganese concentration of parent phase (γ phase), and
(2) since α have mutually than γ mutually higher erosion resistance and α have the consistence mutually good mutually with γ, even therefore when parent phase deforms, also be not easy to occur peeling off or the crack, can obtain sufficient erosion resistance thus.
Usually, when shape memory alloy is carried out viscous deformation below transition temperature, and when being heated to transition temperature or higher temperature subsequently, its shape can return to the alloy state before the viscous deformation.Yet even this alloy is cooled to transition temperature or lower temperature once more, this alloy can not return to the shape that forms by cold plasticity usually yet.People are called " one way shape-memory effect " with this phenomenon of only remembering high temperature phase shape especially.
On the other hand, when some shape memory alloys are being forced the worker or are being out of shape under martensitic state, and retrain when heating subsequently under the martensitic state, the low temperature phase shape that these alloys can memory section so.Especially with this remember high temperature phase shape and low temperature mutually the phenomenon of shape be called " double process shape-memory effect ".For example, the known portions Ti-Ni alloy that is formed with texture has demonstrated double process shape-memory effect.
In above-mentioned various uses (for example, spiral expand spring, oily flow control system and actuator), usually need shape memory alloy to have the round trip performance characteristics.Therefore, for the shape memory alloy that will have one way shape-memory effect need to be applied in the device of round trip performance characteristics, this shape memory alloy and other parts must to be made up, thereby give the gained device with the round trip performance characteristics.The known round trip method for working properties of giving comprises: one-way shape memory alloy and spring, sliding weight of steelyard etc. are combined, thereby give round trip method for working properties (offsetting (bias method)), and the method (differential method) of using two or more shape memory parts.
Yet, this with the combination of one-way shape memory alloy and other parts to give the miniaturization that the round trip method for working properties has limited device.Therefore, the Application Areas of these methods is limited to.
On the other hand, at present known all two-way shape memory alloys cost an arm and a leg and reproducibility poor.Therefore, have only this alloy of minority to be dropped in the practical application.Conventional iron-base marmem demonstrates such characteristic: it becomes (ε → γ), returned to the shape (that is one way shape-memory effect) that is had before the plastic working by the shape that forms through plastic working by reversing.Yet this iron-base marmem does not demonstrate double process shape-memory effect.
In addition, for shape memory alloy is used for multiple use, this alloy must have high shape and recover precision and can stand the intensity that shape is repeatedly recovered.
Yet, people do not propose as yet about cheap, have the round trip performance characteristics, have the shape recovery temperature higher than Ti-Ni alloy (particularly, being 90 ℃-100 ℃ or higher), have a motion that high shape is recovered precision and can be stood the alloy of the intensity that shape repeatedly recovers.
Summary of the invention
The purpose of this invention is to provide a kind of like this two-way shape-recovery alloy, the intensity that it is cheap, as to have the round trip performance characteristics, have the shape recovery temperature higher than Ti-Ni alloy, have high shape recovery precision and can stand shape recovery repeatedly.
That is, the present invention relates to following the 1st to 4.
1. two-way shape-recovery alloy, it comprises:
Be lower than the C of 0.20 quality %,
13.00 quality % is to the Mn of 30.00 quality %,
0.10 quality % is to the Si of 6.00 quality %,
0.05 quality % is to the Cr of 12.00 quality %,
0.01 quality % is to the Ni of 3.00 quality %, and
Be lower than the N of 0.100 quality %,
Surplus is Fe and unavoidable impurities,
The content of wherein said Mn, Si, Cr and Ni satisfies following formula (1):
600≤33Mn+11Si+28Cr+17Ni≤1050(1)。
2. according to the 1st described two-way shape-recovery alloy,
Transformation end temp (A when wherein heating
fPoint) and the transformation in when cooling begin temperature (M
sPoint) poor (A
f-M
s) be 150 ℃ or littler, and
The transformation of wherein said alloy when heating begins temperature (A
sPoint) is 100 ℃ or higher.
3. according to the 1st or 2 described two-way shape-recovery alloy, it also comprises at least a in the following element:
0.10 quality % is to the Mo of 2.00 quality %,
0.10 quality % is to the W of 2.00 quality %,
0.05 quality % is to the V of 1.00 quality %, and
0.10 quality % is to the Co of 5.00 quality %.
4. according to any described two-way shape-recovery alloy in the 1st to 3, it also comprises Cu+Al, its total content be 0.10 quality % to 1.00 quality %,
The content of wherein said Ni and the total content of Cu+Al satisfy following relation:
Ni≥(Cu+Al)。
In the Fe-Mn-Si alloy,, make martensitic transformation when cooling (γ → ε) in the process volumetric shrinkage takes place, and the reverse when heating becomes (ε → γ) in the process volumetric expansion takes place by optimizing the content of component.The change of shape that is accompanied by expansion is a reversible, and the amount of this change of shape is bigger.In addition, its shape recovery temperature (particularly, being 90 ℃-100 ℃ or higher) is higher than the shape recovery temperature of Ti-Ni alloy, and its shape is recovered the precision height.
In addition, it is cheap and have the intensity that the shape that can stand is repeatedly recovered to have a Fe-Mn-Si alloy of given composition.Particularly, by adding precipitation strength elements such as displaced type solution strengthening element such as Mo or Cu, its intensity is further enhanced.
Therefore, two-way shape-recovery alloy of the present invention can be used for need having in the various functional components of round trip performance characteristics.
Two-way shape-recovery alloy of the present invention can be used as the power switch or the actuator of working based on temperature variation, the pushing out ring that is used for piston ring and as the temperature-sensitive member of the oil supply mechanism of viscosity fluid-flywheel clutch etc.
Description of drawings
Fig. 1 is the figure that eutectoid steel (C of the 0.77 quality %) length variations along with temperature variation and phase transformation is shown.
Fig. 2 is the figure of heating-cooling transformation curve that the alloy of embodiment 7 is shown.
Fig. 3 is the A that illustrates in the alloy of embodiment and comparative example
f-M
sWith A
sBetween the figure of relation.
Fig. 4 shows the result of the thermal fatigue test of the alloy that is obtained among the embodiment 2.
Optimum implementation of the present invention
Below, will be described in detail one embodiment of the invention.
1. two-way shape-recovery alloy
Two-way shape-recovery alloy of the present invention contains element as follows, and surplus is iron and unavoidable impurities, and has the component balanced of satisfied given requirement.The qualification reason of kind, its content range and the content of interpolation element is as described below.In this article, in this manual, all are all identical with the per-cent that limits with weight with the per-cent that quality limits.
In the present invention, term " two-way shape-recovery " is meant such phenomenon: alloy mainly utilizes the expansion that is accompanied by phase transformation and contraction and does not utilize viscous deformation in fact, but can reversibly present low temperature phase shape and high temperature shape mutually.
1.1. main component
(1) C＜0.20 quality %
Carbon exists as interstitial element in iron, and it is stronger austenite former.In ordinary steel, carbon forms (BCT) phase of α ' through quench hardening, and the intensity of steel is improved.Yet it is a kind of transformation that is accompanied by volumetric expansion that FCC-BCT changes.In addition, because this transformation highly depends on the speed of cooling of material, the variation of speed of cooling can cause forming bainite structure or ferritic structure, therefore can not obtain stable volumetric expansion.In addition, this transformation can not produce the two-way shape-recovery effect.
Therefore, in order to make alloy performance two-way shape-recovery effect, should avoid alloy to generate α ' phase through quench hardening.Therefore, the carbon content of alloy must be lower than 0.20 quality %.Its carbon content more preferably is lower than 0.10 quality %.
(2) 13.00 quality %≤Mn≤30.00 quality %
Manganese is that a kind of round trip that stably obtains between γ and the ε changes necessary interpolation element.At high temperature, manganese plays the effect of austenite former.Manganese content is high more, the easy more ε martensite that generates at low temperatures.Consider that from generating the martensitic angle of ε manganese content is necessary for 13.00 quality % or higher.Manganese content is 15.00 quality % or higher more preferably.
On the other hand, when the manganese too high levels, the transition temperature in the time of can making cooling significantly reduces, thus, even austenite also might become stable phase mutually under-50 ℃.Therefore, manganese content should be 30.00 quality % or lower.This manganese content more preferably is lower than 25.00 quality %.(3) 0.10 quality %≤Si≤6.00 quality %
Silicon is that a kind of meeting reduces stacking fault energy, thus the element that promotion is changed to ε mutually mutually by γ.Consider that from this angle silicone content should be 0.10 quality % or higher.Silicone content is 0.30 quality % or higher more preferably.
On the other hand, if silicone content is too high, then solid solution strengthening effect is remarkable, reduces material ductility thus.Therefore, silicone content is necessary for 6.00 quality % or lower.Silicone content is 4.00 quality % or lower more preferably.
(4) 0.05 quality %≤Cr≤12.00 quality %
Chromium is to having controlled function to the occurrence temperature that ε changes mutually mutually by γ, and has the function of the erosion resistance that improves material.Consider that from the angle that obtains such effect chromium content is necessary for 0.05 quality % or higher.
On the other hand, chromium at high temperature plays the effect of α phase stable element.Therefore, too high chromium content often makes and is subjected to heat treated structural transformation and becomes α ' martensitic stucture.Therefore, chromium content is necessary for 12.00 quality % or lower.
(5) 0.01 quality %≤Ni≤3.00 quality %
Nickel has to be regulated transition temperature and can not cause the function that tissue changes when thermal treatment.Consider that from the angle that obtains such effect nickel content should be 0.01 quality % or higher.
On the other hand, nickel is stronger austenite former.For this reason, too high nickel content can cause the change organized.Therefore, nickel content is necessary for 3.00 quality % or lower.
(6) N＜0.100 quality %
Nitrogen combines with aluminium and other element and forms nitrogen compound, thus hot workability or cold-workability is caused adverse influence.In addition, nitrogen plays the effect of interstitial element, thereby forms sosoloid in iron, and it is also as stronger austenite former.Identical with the situation of carbon, too high nitrogen content can change the transformation behavior, and causes (BCT) formation of phase of α ' when quench hardening,
Therefore, in order to bring into play the two-way shape-recovery effect, should avoid alloy to generate α ' phase through quench hardening.Consider that from this angle nitrogen content must be lower than 0.100 quality %.Nitrogen content more preferably is lower than 0.050 quality %.
1.2. unavoidable impurities
Unavoidable impurities specifically comprises following element.
(1) P＜0.050 quality %
Phosphorus can be sneaked in the alloy by raw material inevitably.Phosphoric is in the segregation of crystal boundary place, thus the hot workability of reduction material.Therefore, preferably phosphorus content is brought down below 0.050 quality %.Phosphorus content more preferably is lower than 0.010 quality %.
(2) S＜0.100 quality %
Sulphur can be sneaked in the alloy by raw material inevitably.Sulphur is in the segregation of crystal boundary place, thus the infringement hot workability.In the present invention, because the manganese content of alloy is higher, therefore the sulphur of sneaking in the alloy can form MnS, so sulphur is limited to the influence of hot workability.But sulphur content is low more, and alloy mass is good more.Therefore, preferably sulphur content is brought down below 0.100 quality %.Sulphur content more preferably is lower than 0.050 quality %.
(3) O＜0.050 quality %
Oxygen can be sneaked in the steel inevitably.Oxygen combines with aluminium and silicon and forms oxide compound, thereby hot workability or cold-workability are caused adverse influence.Therefore, preferably oxygen level is brought down below 0.050 quality %.Oxygen level more preferably is lower than 0.020 quality %.
(4) Mo＜0.10 quality %
(5) W＜0.10 quality %
(6) V＜0.05 quality %
(7) Co＜0.10 quality %
Molybdenum, tungsten, vanadium and cobalt all may be sneaked in the steel inevitably.Although these elements can not produce bigger influence to transition temperature or tissue morphology, preferably its content is brought down below in the scope of above-mentioned value.
Incidentally, these elements all play the effect of displaced type solution strengthening element.In this case, the addition of this element can be more than or equal to above-mentioned value.About this respect, will be explained hereinafter.
(8) Cu＜0.10 quality %
Copper is a kind ofly to sneak into element in the alloy by raw material inevitably.Too high copper content makes alloy demonstrate red brittleness, and significantly damages its processibility.Consider from the angle of keeping processibility, preferably copper content is brought down below 0.10 quality %.Copper content more preferably is lower than 0.05 quality %.
Incidentally, under the prerequisite of the nickel that should add institute's specified rate, can add copper energetically, thereby separate out based on the secondary of copper and carry out precipitation strength.In this case, allow copper content to be up to 1.00 quality %.About this respect, will be explained hereinafter.
(9) Al＜0.10 quality %
Identical with the situation of silicon, because aluminium is used as reductor, so it is sneaked in the alloy inevitably.Aluminium combines with oxygen and forms oxide compound, thus hot workability or cold-workability is caused adverse influence.For this reason, preferably aluminium content is brought down below 1.00 quality %.
Incidentally, under the condition of the nickel that should add institute's specified rate, can add aluminium energetically, thereby separate out and make the intensity raising based on the secondary of Al-Ni intermetallic compound.In this case, allow aluminium content to be up to 1.00 quality %.About this respect, will be explained hereinafter.
1.3. it is component balanced
The component element content of two-way shape-recovery alloy of the present invention not only needs also must satisfy following formula (1) in above-mentioned each scope.
600≤33Mn+11Si+28Cr+17Ni≤1050(1)
The value of being determined by formula (1) is relevant with the transition temperature of alloy, and it is an empirical value.By optimizing component balanced between manganese, silicon, chromium and the nickel, can under high temperature (300 ℃ or higher), stably guarantee to obtain the γ phase respectively, and can under low temperature (50 ℃ or lower), stably guarantee to obtain the ε phase.
As mentioned above, manganese mainly plays the effect of austenite former, and plays the effect that forms the element of ε phase when cooling.Silicon promotes by γ at low temperatures mutually to the transformation of ε phase, but at high temperature plays the effect of α phase stable element.Though chromium at high temperature plays the effect of α phase stable element, it is a kind ofly can effectively control the element that γ arrives the transition temperature of ε phase mutually.Nickel is effectively to control the element that γ arrives the transition temperature of ε phase mutually.
The value of formula (1) is more little, the transformation end temp (A during heating
fPoint) high more.If A
fPoint is too high, and then (ε → γ) in the process creep may take place recovers precision thereby reduce shape reversing change.Recover precision, A in order to obtain high shape
fPoint should be 400 ℃ or lower.Consider that from the angle that obtains this effect the value of formula (1) should be 600 or bigger.The value of formula (1) more preferably 700 or bigger.
On the other hand, the value of formula (1) is big more, and the transformation during heating begins temperature (A
sPoint) low more.Under the situation that the value of formula (1) becomes too big, A
sPoint becomes room temperature or lower, thereby is difficult to make under the temperature of the shape recovery temperature that is higher than the Ti-Ni alloy alloy generation shape to be recovered.The A that is higher than the shape recovery temperature of Ti-Ni alloy from acquisition
sPoint, and and then make alloy of the present invention can under 90 ℃-100 ℃ or higher temperature, carry out the angle that shape recovers to consider that the value of formula (1) should be 1,050 or littler.The value of formula (1) more preferably 900 or littler.
1.4. transition temperature
(transformation of γ → when ε) starting from cooling off begins temperature (M in martensitic transformation
sTransformation end temp (M when point), ending to cool off
fThe point).On the other hand, reverse to become that (transformation of ε → when γ) starting from heating begins temperature (A
sTransformation end temp (A when point), ending to heat
fThe point).
As mentioned above, by the value of optimization formula (1), A
sPoint can be increased to 90 ℃ or higher or 100 ℃ or higher.
The two-way shape-recovery effects applications is had in the situation of device of round trip performance characteristics in needs, and the situation that people wish is that the reversible change of shape should take place in narrower temperature range.That is the transformation end temp (A during heating,
f) begin temperature (M with the transformation in when cooling
s) poor (A
f-M
s) more little, then alloy is good more.As a rule, the A of low alloy steel
f-M
sValue is 200 ℃-300 ℃ or bigger.Different with it is, in two-way shape-recovery alloy of the present invention, and by optimizing the content that influences the component element of transition temperature such as Mn and Si etc., can be with A
f-M
sValue is reduced to 200 ℃-300 ℃ or littler.Consider A from the angle of the size that reduces to be accompanied by heating/refrigerative magnetic hysteresis loop
f-M
sValue is preferably 150 ℃ or littler.A
f-M
sMore preferably 100 ℃ or littler of values.
Incidentally, can come to determine transition temperature in the following way: before the zone that the slope of expansion-shrinkage curve changes, draw tangent line on afterwards the each point, with the pairing temperature of the intersection point of these tangent lines as transition temperature.
1.5. less important component
Except above-mentioned element, two-way shape-recovery alloy of the present invention also can comprise one or more column elements down.
1.5.1. displaced type solution strengthening element
(1) 0.10 quality %≤Mo≤2.00 quality %
(2) 0.10 quality %≤W≤2.00 quality %
(3) 0.05 quality %≤V≤1.00 quality %
(4) 0.10 quality %≤Co≤5.00 quality %
Improve at needs under the situation of intensity of two-way shape-recovery alloy of the present invention, only otherwise the transformation behavior that alloy is shown during influence heating/cooling just can be added displaced type solution strengthening element.The example of displaced type solution strengthening element comprises molybdenum, tungsten, vanadium and cobalt.Any in these elements can be added or wherein two or more can be added.
Consider that from the angle that obtains solid solution strengthening effect preferably, the content of molybdenum, tungsten, vanadium and cobalt all should not be lower than above-mentioned each lower value.
On the other hand, when the too high levels of these elements, not only can not continue to strengthen solid solution strengthening effect and cost is increased, and such high-content influences the transformation behavior sometimes.The content that it is therefore preferable that these elements all should not be higher than above-mentioned each higher limit.
1.5.2. precipitation strength element
The quality % of (5) 0.10 quality %≤(Cu+Al)≤1.00
(6)Ni≥(Cu+Al)
If only add copper, thereby then copper can be separated out at the crystal boundary place hot workability is reduced.Yet when the nickel that adds specified rate when adding copper, nickel can suppress copper separating out at the crystal boundary place.As a result, copper carries out secondary in crystal grain separates out, thereby intensity is improved.
Consider that from the angle that obtains this effect preferably, control copper content is 0.10 quality % or higher.On the other hand, too high copper content can cause the reduction of hot workability.Therefore, preferably, control copper content is 1.00 quality % or lower.
Do not reduce the angle of hot workability from obtaining precipitating reinforcing effect and consider that preferably, the amount of the nickel that is added is equal to or higher than the amount of copper.More preferably, nickel content is at least the twice of copper content.
Equally,, then a large amount of oxide compounds be can produce, thereby hot workability or cold-workability reduced if only add aluminium.Yet when the nickel that adds specified rate when adding aluminium, the secondary that the Ni-Al intermetallic compound can take place is separated out, thereby intensity is improved.
Consider that from the angle that obtains this effect preferably, control aluminium content is 0.10 quality % or higher.On the other hand, too high aluminium content can cause the reduction of hot workability or cold-workability.Therefore, preferably, control aluminium content is 1.00 quality % or lower.
Can not reduce the angle of hot workability or cold-workability from obtaining precipitating reinforcing effect and consider that preferably, the addition of nickel is equal to or higher than the amount of aluminium.More preferably, nickel content is at least the twice of aluminium content.
In addition, can add copper and aluminium simultaneously, prerequisite is to add the nickel of specified rate, thereby obtains these two precipitating reinforcing effect of copper and aluminium.Consider that from the angle that obtains this effect preferably, the total content of control copper and aluminium is 0.1 quality % or higher.
On the other hand, consider that from this angle of reduction that suppresses hot workability or cold-workability preferably, the total content of control copper and aluminium is 1.00 quality % or lower.
And, add at the same time under the situation of copper and aluminium, preferably the amount of the nickel that is added is equal to or higher than the total amount of copper and aluminium.More preferably, nickel content is at least the twice of the total content of copper and aluminium.
At this on the one hand, for each contained in the alloy of the present invention element, according to an embodiment, the minimum content of each element is an employed smallest non-zero quantity in the example of the alloy of being developed listed in table 1 and the table 2 in the alloy.According to another embodiment, the high-content of each element is an employed maximum amount in the example of the alloy of being developed listed in table 1 and the table 2 in the alloy.
2. use the functional component of two-way shape-recovery alloy
Two-way shape-recovery alloy of the present invention has such function: it is based on the expansion that is accompanied by the transformation between γ and the ε, and does not utilize viscous deformation in fact, but can reversibly present low-temperature condition mutually with the condition of high temperature mutually.
Therefore, the two-way shape-recovery alloy with this effect can be applied to such as in following these functional components:
(1) utilize the condition of high temperature mutually and the power switch or the actuator of the variation of low-temperature condition between mutually,
(2) have the actuator of such mechanism, in this mechanism, amplify the shape amount of recovery (shape recoverydeflection) that is accompanied by temperature variation according to the principle of spring or lever,
(3) need have the power switch or the actuator of 100 ℃ or higher shape recovery temperature,
(4) be used for the pushing out ring (for example, seeing also international open WO2004/090318) of piston ring, and
(5) be used for the temperature-sensitive member (for example, seeing also Japanese documentation JP-A-11-264425) of the oil supply mechanism of viscosity fluid-flywheel clutch.
Though can directly use two-way shape-recovery alloy of the present invention, can carry out any various surface treatment to its surface, then used.The example of surface treatment method comprises nitrogenize, PVD and CVD.By this surface treatment, can give oxidation-resistance and wear resistance.
The two-way shape-recovery alloy of giving wear resistance by surface treatment can be applied to the contacted state of mating material under the mechanical part (for example, whisker, piston ring etc.) that uses.
3. make the step of two-way shape-recovery alloy
To then melt be cast according to given mixed raw materials melt together, thereby make two-way shape-recovery alloy of the present invention.Preferably, after foundry goods is forged into given shape, the alloy after forging is carried out solution heat treatment (ST processing) then carry out air cooling, forge the influence that is brought to eliminate.Solution heat treatment temperature is preferably 700 ℃-1,200 ℃.
Under the situation of having added the precipitation strength element, preferably after carrying out solution heat treatment and air cooling subsequently, carry out ageing treatment.Preferably, ageing treatment is carried out 0.5 hour to 5 hours time of less than under 400 ℃ to 600 ℃ temperature.
4. the function of two-way shape-recovery alloy
Fig. 1 shows the variation along with the eutectoid steel of temperature variation and phase transformation (carbon of 0.77 quality %) length.
Under the temperature about room temperature (some A), eutectoid steel has ferrite (α) phase constitution.When this eutectoid steel being heated to austenite (γ) region, its along A → B → C → D curve as shown in Figure 1 expand → shrink → expand.And, when with this eutectoid steel when the γ region is cooled to room temperature gradually, its along D → E → F → A curve shrink → expand → shrink, and return to the shape that steel had before the heating.The reason that eutectoid steel shrinks along B → C curve in heat-processed is α → γ to have taken place change.To carry out the expansible reason along E → F curve be γ → α to have taken place change to eutectoid steel in process of cooling.
On the other hand, when eutectoid steel was cooled off rapidly by the γ region, this steel was along as shown in Figure 1 dashed curve (curve D-H) shrink → expand, and finally its shape is different from the shape of the steel before the heating.When will be when rapid refrigerative eutectoid steel heats once more, this eutectoid steel expands repeatedly and shrinks last point of arrival D along H → J → K → L → M → N → O curve.
The length of the steel that rapid cooling back is measured (some H) is not to be higher than M by eutectoid steel is cooled to rapidly by the γ region than the long reason of length (some A) of steel measured before heating
sThe temperature of point has caused being accompanied by the generation of the martensitic transformation (γ (FCC) → α ' (BCT) changes) of volumetric expansion.In addition, greater than by the length variations that thermal expansion caused, this is because along with the rising of temperature, the decomposition of the formation of εTan Huawu, remaining γ phase and the formation of θ carbide have taken place in the expansion that is taken place below 400 ℃ or shrinkage degree.
The martensitic transformation and the reverse change that take place by this thermal treatment are used for common employed ferrous alloy energetically, to carry out organizational controls.
Yet the γ → α ' transformation that is taken place during owing to cooling is accompanied by volumetric expansion, and therefore common ferrous alloy can not be used as the shape-recovery alloy that need shrink when cooling off.
γ → α ' changes the speed of cooling that highly depends on material.Therefore, the variation of speed of cooling can cause the formation of bainite structure or ferritic structure, thereby can not obtain stable volumetric expansion (for example, shape is recovered reproducibility).
In addition, the α during heating → γ changes end temp (A
fPoint) up to 700 ℃ or more than.In addition, A
fγ → α ' when putting with cooling changes beginning temperature (M
sPoint) difference is up to 200 ℃-300 ℃ or bigger.That is it is bigger, to be accompanied by heating/refrigerative magnetic hysteresis loop.
Different with it is that two-way shape-recovery alloy of the present invention comprises the Fe-Mn-Si alloy as substrate, and has optimized component content wherein.Therefore, when with this alloy when high temperature (300 ℃ or higher) is cooled to low temperature (50 ℃ or lower), take place by γ (FCC) also can not generate (BCT) phase of α ' and neither can generate α (BCC) phase mutually to the transformation of ε (HCP) phase.Because γ → ε transformation can cause volumetric shrinkage, therefore the shrinkage degree of being brought by cooling is greater than the change of shape that is accompanied by thermal contraction.
On the other hand, when adding thermalloy, ε → γ takes place change.Therefore, by the degrees of expansion brought of heating greater than the change of shape that is accompanied by thermal expansion.In addition, the change of shape that is accompanied by expansion is a reversible.Therefore, need not carry out viscous deformation for the recovery of shape.
In addition, two-way shape-recovery alloy of the present invention demonstrates bigger change of shape amount.Particularly, by optimizing component element, tensile strain rate (the Δ L/L when making heating
0* 100) be 0.3% or higher, be preferably 0.5% or higher, more preferably 0.7% or higher.By optimizing the shape (for example, alloy being shaped to the shape of spring) of two-way shape-recovery alloy, can further improve the change of shape amount.
Tensile strain rate when on the other hand, the tensile strain rate during cooling is with heating is identical.Particularly, the tensile strain rate of each heating is 0.1% or lower, and shape recovery ratio is very high.Even repeat the heating hundreds of, As time goes on shape recovery ratio also can reduce hardly.
In addition, because two-way shape-recovery alloy of the present invention comprises the Fe-Mn-Si alloy as matrix, so its shape recovery temperature (A
sPoint) is higher than the shape recovery temperature of conventional Ti-Ni alloy.Owing to carried out the optimization of component element, therefore be accompanied by heating/refrigerative magnetic hysteresis loop (A
f-M
s) less than the magnetic hysteresis loop of common ferrous alloy.
Particularly, when optimizing component element when having satisfied formula (1), A
sPoint is 90 ℃ or higher, is preferably 100 ℃ or higher.Similarly, when optimizing component element when having satisfied formula (1), A
f-M
sValue is 200 ℃ or littler, is preferably 150 ℃ or littler, more preferably 100 ℃ or littler.
In addition, because two-way shape-recovery alloy of the present invention comprises the Fe-Mn-Si alloy as matrix, so its shape cheap and that its intensity can stand is repeatedly recovered.Particularly, by adding precipitation strength elements such as displaced type solution strengthening element such as Mo or Cu, further improved its intensity.
Therefore, two-way shape-recovery alloy of the present invention can be used for need having in the various functional components of round trip performance characteristics.
Embodiment
(embodiment 1 to 28 and comparative example 1 to 10)
1. the manufacturing of sample
In the ratio-frequency heating smelting furnace, the material (being 50kg) that will have the various chemical constitutions shown in table 1 and the table 2 carries out fusion, casts subsequently.With each foundry goods of obtain 1,200 ℃ of following soaking 24 hours, under 800 ℃ or higher temperature, forge subsequently to diameter of phi be 30mm, then it is cooled off gradually.In order to eliminate the influence that is brought by forging condition etc., resulting each alloy after forging is carried out solution heat treatment 30 minutes under 800 ℃, carry out air cooling then.
In addition, about embodiment 10 to 13 (wherein being added with 0.1 quality % or above copper) and embodiment 14 to 18 (wherein being added with 0.1 quality % or above aluminium), after solution heat treatment and air cooling, carry out ageing treatment.This ageing treatment was carried out under 500 ℃ 1.5 hours.
2. test method
2.1. transition temperature and tensile strain rate
Use the transition temperature (A of differential dilatometer when determining heating/cooling
s, A
f, M
sAnd M
f) and the tensile strain rate (coefficient of expansion) that when adding heat deflection, takes place.Each test block is of a size of Φ 5mm * 20mm, and heating rate is 10 ℃/minute, and rate of cooling is 10 ℃/minute.
2.2. tissue
The sample that remains under-50 ℃ is carried out the x ray diffraction, to carry out the identification of phase.Use the K of cobalt
αLine is with as X ray.
2.3. thermal fatigue test
To having length is that the test block of the parallel portion of 40mm carries out thermal fatigue test.Strain-gauging part (it is the zone of 15mm for length) in the parallel portion of heating test block, and when reaching top temperature, the two ends of fixing test spare.The test block that will be in this state repeats cooling circulation 300 times, with the relation between the stress that is produced in research temperature variation and the test block.Top temperature and minimum temperature are set at 300 ℃ and 50 ℃ respectively.250 ℃/minute of heating rate average out to, 83 ℃/minute of rate of cooling average out to.
2.4. tension test
Use JIS 14A (M18) sample to carry out tension test.The condition of this tension test is abideed by the regulation among the JIS Z2241.
3. result
3.1. transition temperature, tensile strain rate and tissue
Tensile strain rate (Δ L/L when table 3 shows heating
0* 100), A
f-M
s, A
s, formula (1) value and at-50 ℃ of following viewed tissues.
Table 3
| ??ΔL/L 0??(％) | ??A f-M s??(℃) | ??A s??(℃) | Formula (1) | Tissue (50 ℃) | |
| Embodiment 1 | ??0.88 | ??168 | ??234 | ??685 | ??ε |
| Embodiment 2 | ??0.55 | ??145 | ??154 | ??918 | ??ε |
| Embodiment 3 | ??0.79 | ??180 | ??234 | ??751 | ??ε |
| Embodiment 4 | ??0.80 | ??132 | ??233 | ??742 | ??ε |
| Embodiment 5 | ??0.47 | ??103 | ??121 | ??979 | ??ε+γ |
| Embodiment 6 | ??0.75 | ??189 | ??198 | ??781 | ??ε |
| Embodiment 7 | ??0.70 | ??195 | ??207 | ??815 | ??ε |
| Embodiment 8 | ??0.52 | ??134 | ??145 | ??943 | ??ε+γ |
| Embodiment 9 | ??0.91 | ??230 | ??251 | ??666 | ??ε |
| ??ΔL/L 0??(％) | ??A f-M s??(℃) | ??A s??(℃) | Formula (1) | Tissue (50 ℃) | |
| Embodiment 10 | ??0.70 | ??141 | ??195 | ??818 | ??ε |
| Embodiment 11 | ??0.50 | ??127 | ??138 | ??956 | ??ε+γ |
| Embodiment 12 | ??0.57 | ??152 | ??161 | ??906 | ??ε+γ |
| Embodiment 13 | ??0.70 | ??149 | ??193 | ??815 | ??ε |
| Embodiment 14 | ??0.44 | ??92 | ??98 | ??1000 | ??ε+γ |
| Embodiment 15 | ??0.81 | ??189 | ??232 | ??734 | ??ε |
| Embodiment 16 | ??0.66 | ??166 | ??185 | ??865 | ??ε |
| Embodiment 17 | ??0.42 | ??98 | ??104 | ??1028 | ??ε+γ |
| Embodiment 18 | ??0.79 | ??202 | ??223 | ??751 | ??ε |
| Embodiment 19 | ??0.85 | ??211 | ??233 | ??708 | ??ε |
| Embodiment 20 | ??0.81 | ??207 | ??243 | ??738 | ??ε |
| Embodiment 21 | ??0.74 | ??189 | ??201 | ??789 | ??ε |
| Embodiment 22 | ??0.58 | ??149 | ??155 | ??901 | ??ε+γ |
| Embodiment 23 | ??0.80 | ??214 | ??234 | ??739 | ??ε |
| Embodiment 24 | ??0.42 | ??103 | ??119 | ??1011 | ??ε+γ |
| Embodiment 25 | ??0.80 | ??203 | ??221 | ??743 | ??ε |
Table 3 (connecting table)
| ??ΔL/L 0??(％) | ??A f-M s??(℃) | ??A s??(℃) | Formula (1) | Tissue (50 ℃) | |
| Embodiment 26 | ??0.40 | ??89 | ??108 | ??1026 | ??ε+γ |
| Embodiment 27 | ??0.79 | ??211 | ??231 | ??750 | ??ε |
| Embodiment 28 | ??0.90 | ??246 | ??257 | ??669 | ??ε |
| ??ΔL/L 0??(％) | ??A f-M s??(℃) | ??A s??(℃) | Formula (1) | Tissue (50 ℃) | |
| Comparative example 1 | ??0.34 | ??183 | ??56 | ??1072 | ??γ+ε |
| Comparative example 2 | ??0.25 | ??135 | ??45 | ??1138 | ??γ+ε |
| Comparative example 3 | ??0.28 | ??699 | ??674 | ??1118 | ??α+ε |
| Comparative example 4 | ??0.87 | ??690 | ??γ | ||
| Comparative example 5 | ??1.28 | ??320 | ??665 | ??398 | ??α |
| Comparative example 6 | ??1.28 | ??469 | ??654 | ??403 | ??α |
| Comparative example 7 | ??1.13 | ??354 | ??333 | ??507 | ??ε+α |
| Comparative example 8 | ??0.11 | ??228 | ??32 | ??1236 | ??ε |
| Comparative example 9 | ??0.28 | ??397 | ??632 | ??1115 | α ' martensite |
| Comparative example 10 | ??0.43 | ??1007 | ??γ |
Because the value of the formula (1) in comparative example 1 (JST) and the comparative example 2 (NSC) surpasses 1,050, so its A
sLower.Because the chromium too high levels in the comparative example 3 (JST-2) and the value of formula (1) surpass 1,050, so its A
f-M
sValue have α to produce mutually when surpassing 600 ℃ and cooling.
Because therefore the nickel too high levels of comparative example 4 (being equivalent to SUS304) even also only contain the γ phase under-50 ℃.Because the alloy of comparative example 5 (SUS420), comparative example 6 and comparative example 7 does not all have suitable component balanced, so its generation has the α phase.
Because the value of comparative example 8 Chinese styles (1) surpasses 1,050, so its A
sLower.Because chromium too high levels in the comparative example 9, so it has generated α ' phase.In addition, because the nitrogen content of comparative example 10 is too high, even therefore under-50 ℃, also only comprise the γ phase.
Different with above-mentioned situation is, because the component of embodiment 1 to 28 is optimized, therefore under-50 ℃, they all comprise the ε phase, and neither comprises α and also do not comprise α ' phase mutually.In each embodiment, the tensile strain rate during heating is 0.3% or higher.In each embodiment, A
f-M
sValue is 300 ℃ or littler, and the A among each embodiment
sIt is 90 ℃ or higher.
Fig. 2 shows the heating-cooling transformation curve of the alloy of embodiment 7.As can be seen from Figure 2, γ and the ε transformation between mutually takes place during cooling, and caused the reversible change of shape thus.
Fig. 3 shows the A in the alloy of embodiment and comparative example
f-M
sWith A
sBetween relation.Be organized as ε mutually or in the alloy of each embodiment of being constituted mutually with γ mutually by ε of tissue, A
sBe positioned at relative low temperature side, and A
f-M
sBe worth less relatively.Different with it is that the alloy that comprises the comparative example of α phase or α ' phase often has 600 ℃ or higher A
s, and A
f-M
sBe worth bigger.
3.2. thermal fatigue test
Fig. 4 shows the relation between the stress that the alloy that obtained among the embodiment 2 produced in the temperature variation of circulation for the first time, the 100 circulation and the 300 circulation time and test block.
As can be seen from Figure 4:
(1) in whole thermal fatigue test, the transition temperature (A during heating
sAnd A
f) and the transition temperature (M in when cooling
s) almost constant, and
(2) no matter repeat how many times, it is constant that the stress that is produced all almost keeps.
Found that from above when alloy of the present invention was used as two-way shape-recovery alloy, it demonstrated stable properties.
3.3. tension test
Table 4 has shown the result of this tension test.Listed as table 4, the therefrom following as can be seen fact:
(1) intensity of some alloys in the comparative example is low, and all alloys among the embodiment 1-28 all have the intensity that is higher than 800MPa.
(2) also adding a certain amount of A1 and/or Cu in addition and subsequently alloy has been carried out under the situation of ageing treatment except main component, tensile strength is further improved.
(3) as a certain amount of Mo of interpolation, W, V, and/or under the situation of Co, tensile strength is further improved.
Table 4
| Tensile strength (MPa) | |
| Embodiment 1 | ??820 |
| Embodiment 2 | ??873 |
| Embodiment 3 | ??855 |
| Embodiment 4 | ??863 |
| Embodiment 5 | ??903 |
| Embodiment 6 | ??835 |
| Embodiment 7 | ??842 |
| Embodiment 8 | ??863 |
| Embodiment 9 | ??837 |
| Embodiment 10 | ??867 |
| Embodiment 11 | ??887 |
| Embodiment 12 | ??989 |
| Tensile strength (MPa) | |
| Embodiment 13 | ??997 |
| Embodiment 14 | ??1065 |
| Embodiment 15 | ??1013 |
| Embodiment 16 | ??899 |
| Embodiment 17 | ??964 |
| Embodiment 18 | ??997 |
| Embodiment 19 | ??1124 |
| Embodiment 20 | ??946 |
| Embodiment 21 | ??955 |
| Embodiment 22 | ??997 |
| Embodiment 23 | ??948 |
| Embodiment 24 | ??1015 |
| Embodiment 25 | ??976 |
| Embodiment 26 | ??996 |
| Embodiment 27 | ??1004 |
| Embodiment 28 | ??896 |
| Comparative example 1 | ??834 |
| Comparative example 2 | ??842 |
| Comparative example 3 | ??863 |
| Comparative example 4 | ??630 |
| Comparative example 5 | ??753 |
| Comparative example 6 | ??793 |
| Tensile strength (MPa) | |
| Comparative example 7 | ??673 |
| Comparative example 8 | ??621 |
| Comparative example 9 | ??1134 |
| Comparative example 10 | ??593 |
Although the present invention is had been described in detail, never be interpreted as the present invention and be confined to above-mentioned embodiment with reference to embodiments of the present invention.Can in the scope that does not break away from purport of the present invention, carry out various changes.
The application is based on the Japanese patent application No.2008-309262 that submitted on December 4th, 2008 with in the Japanese patent application No.2009-266700 of submission on November 24th, 2009, and its content is incorporated this paper by reference into.
Claims (8)
1. two-way shape-recovery alloy, it comprises:
Be lower than the C of 0.20 quality %,
13.00 quality % is to the Mn of 30.00 quality %,
0.10 quality % is to the Si of 6.00 quality %,
0.05 quality % is to the Cr of 12.00 quality %,
0.01 quality % is to the Ni of 3.00 quality %, and
Be lower than the N of 0.100 quality %,
Surplus is Fe and unavoidable impurities,
The content of wherein said Mn, Si, Cr and Ni satisfies following formula (1):
600≤33Mn+11Si+28Cr+17Ni≤1050??(1)。
2. two-way shape-recovery alloy according to claim 1,
Transformation end temp (A when wherein heating
fTransformation during point) with cooling begins temperature (M
sPoint) poor (A
f-M
s) be 150 ℃ or littler, and
The transformation of wherein said alloy when heating begins temperature (A
sPoint) is 100 ℃ or higher.
3. two-way shape-recovery alloy according to claim 1, it also comprises at least a in the following element:
0.10 quality % is to the Mo of 2.00 quality %,
0.10 quality % is to the W of 2.00 quality %,
0.05 quality % is to the V of 1.00 quality %, and
0.10 quality % is to the Co of 5.00 quality %.
4. two-way shape-recovery alloy according to claim 2, it also comprises at least a in the following element:
0.10 quality % is to the Mo of 2.00 quality %,
0.10 quality % is to the W of 2.00 quality %,
0.05 quality % is to the V of 1.00 quality %, and
0.10 quality % is to the Co of 5.00 quality %.
5. two-way shape-recovery alloy according to claim 1, it also comprises Cu+Al, its total content be 0.10 quality % to 1.00 quality %,
Relation: Ni below the content of wherein said Ni and the total content of described Cu+Al satisfy 〉=(Cu+Al).
6. two-way shape-recovery alloy according to claim 2, it also comprises Cu+Al, its total content be 0.10 quality % to 1.00 quality %,
Relation: Ni below the content of wherein said Ni and the total content of described Cu+Al satisfy 〉=(Cu+Al).
7. two-way shape-recovery alloy according to claim 3, it also comprises Cu+Al, its total content be 0.10 quality % to 1.00 quality %,
Relation: Ni below the content of wherein said Ni and the total content of described Cu+Al satisfy 〉=(Cu+Al).
8. two-way shape-recovery alloy according to claim 4, it also comprises Cu+Al, its total content be 0.10 quality % to 1.00 quality %,
Relation: Ni below the content of wherein said Ni and the total content of described Cu+Al satisfy 〉=(Cu+Al).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008309262 | 2008-12-04 | ||
| JP2008-309262 | 2008-12-04 | ||
| JP2009-266700 | 2009-11-24 | ||
| JP2009266700A JP2010156041A (en) | 2008-12-04 | 2009-11-24 | Two-way shape-recovery alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101748345A true CN101748345A (en) | 2010-06-23 |
Family
ID=42045204
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910252029A Pending CN101748345A (en) | 2008-12-04 | 2009-12-04 | two-way shape-recovery alloy |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20100139813A1 (en) |
| EP (1) | EP2194154A1 (en) |
| JP (1) | JP2010156041A (en) |
| CN (1) | CN101748345A (en) |
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| CN104388829A (en) * | 2014-12-05 | 2015-03-04 | 哈尔滨理工大学 | Oriented iron-based shape memory alloy and preparation method thereof |
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| DE102012113053A1 (en) * | 2012-12-21 | 2014-06-26 | Thyssenkrupp Steel Europe Ag | Lanyard with shape memory |
| JP6182725B2 (en) * | 2012-12-28 | 2017-08-23 | 国立研究開発法人物質・材料研究機構 | Damping alloy |
| DE102013102353A1 (en) * | 2013-03-08 | 2014-09-11 | Thyssenkrupp Steel Europe Ag | Temperature-controlled deflection |
| WO2014146733A1 (en) | 2013-03-22 | 2014-09-25 | Thyssenkrupp Steel Europe Ag | Iron-based shape memory alloy |
| CN105377472B (en) | 2013-07-10 | 2018-01-02 | 蒂森克虏伯钢铁欧洲股份公司 | By the method for iron-base marmem manufacture flat steel product |
| KR101665803B1 (en) * | 2014-12-23 | 2016-10-13 | 주식회사 포스코 | Non-release bolt, wire rod for non-release bolt, and method for manufacturing thereof |
| CN109477175B (en) * | 2016-09-06 | 2021-02-12 | 国立大学法人东北大学 | Fe-based shape memory alloy material and method for producing same |
| WO2020108754A1 (en) * | 2018-11-29 | 2020-06-04 | Thyssenkrupp Steel Europe Ag | Flat product consisting of an iron-based shape memory material |
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| GB2173816B (en) * | 1985-03-28 | 1989-06-21 | Sumitomo Metal Ind | Superplastic ferrous duplex-phase alloy and a hot working method therefor |
| JPH0382741A (en) * | 1989-08-25 | 1991-04-08 | Nisshin Steel Co Ltd | Shape memory staiinless steel excellent in stress corrosion cracking resistance and shape memory method therefor |
| FR2654748B1 (en) * | 1989-11-22 | 1992-03-20 | Ugine Aciers | STAINLESS STEEL ALLOY WITH SHAPE MEMORY AND METHOD FOR PRODUCING SUCH AN ALLOY. |
| JPH0672285B2 (en) * | 1991-09-07 | 1994-09-14 | 新日本製鐵株式会社 | Shape memory alloy |
| JP2000501778A (en) * | 1995-07-11 | 2000-02-15 | ウラコ，カリ，マーティ | Nitrogen-containing iron-based shape memory and vibration damping alloy |
| JPH1036943A (en) * | 1996-07-24 | 1998-02-10 | Taiheiyo Kinzoku Kk | Manufacture of iron-manganese-silicon shape memory alloy |
| US20060113730A1 (en) * | 2003-04-07 | 2006-06-01 | Takao Suzuki | Combination oil ring |
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2009
- 2009-11-24 JP JP2009266700A patent/JP2010156041A/en active Pending
- 2009-12-03 US US12/630,128 patent/US20100139813A1/en not_active Abandoned
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|---|---|---|---|---|
| CN104388829A (en) * | 2014-12-05 | 2015-03-04 | 哈尔滨理工大学 | Oriented iron-based shape memory alloy and preparation method thereof |
| CN104388829B (en) * | 2014-12-05 | 2016-05-25 | 哈尔滨理工大学 | A kind of preparation method who is orientated iron-base marmem |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2194154A1 (en) | 2010-06-09 |
| JP2010156041A (en) | 2010-07-15 |
| US20100139813A1 (en) | 2010-06-10 |
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