CN105369043B - The high high martensitic traoformation limit stress marmem of super-elasticity and preparation method - Google Patents
The high high martensitic traoformation limit stress marmem of super-elasticity and preparation method Download PDFInfo
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Abstract
The present invention relates to the preparation method of the high martensitic traoformation limit stress marmem of high super-elasticity, the preparation method of the marmem：Being prepared first using directional freeze method has high hyperelastic columanar structure Cu Al Mn alloy blanks, the martensitic traoformation limit stress of the alloy blank is lifted by being heat-treated again, so as to obtain the Cu Al Mn marmems with high super-elasticity and high martensitic traoformation limit stress.Cu Al Mn marmems prepared by the present invention have columanar structure, phase composition includes β austenites and bainite at room temperature, the super-elasticity of the marmem is up to 5% 10%, martensitic traoformation limit stress is up to 440MPa 700MPa, tensile strength is up to 550MPa~800MPa, modulus of elasticity is up to 34GPa~55GPa, and Vickers hardness is 290Hv~370Hv.
Description
Technical field
The invention belongs to field of metal preparation, it is related to a kind of high martensitic traoformation limit stress Cu-Al- of high super-elasticity
The preparation method of Mn marmems.
Background technology
Marmem be it is a kind of integrate perceive and the intellectual material that drives, can be made sensor, detector,
Damping device, energy converter and intelligent micro device etc., are widely used in electronic communication, health care, machine-building, boat
The various fields such as empty space flight, derived energy chemical and daily life.Cu-Al-Mn marmems are a kind of important Cu base shapes
Shape memory alloys, because its cheap (equivalent to 1/10 of NiTi marmems), shape-memory properties are good, and lead
Thermal conducting excellent performance, it has also become most New Shape Memory Alloys of application potential.
As material is intelligent and intelligence system is continued to develop, the combination property of marmem is proposed higher
Requirement, wherein high super-elasticity and high martensitic traoformation limit stress are topmost property development trend.However, routine casting
The super-elasticity of common polycrystalline tissue cu-Al-Mn marmems prepared by method is only 3% or so, and martensitic traoformation is critical
Stress is generally less than 400MPa；Although and monocrystalline Cu-Al-Mn super elastic shape memory alloys are up to more than 10%, its geneva
It is only 100MPa or so that body phase, which becomes limit stress, causes the driving force that can be provided during Alloyapplication and fatigue strength all very low,
It significantly limit the application of alloy.
In general, lifting Strength of Metallic Materials main method have addition alloying element, refined crystalline strengthening, working hardening and
Heat treatment reinforcement etc..But for marmem, addition alloying element can have a strong impact on the phase transition temperature of alloy, super-elasticity and
The important performance such as shape-memory properties, the alloying element such as adding Zn, Fe, Co, Ni, Ti can be closed improving to a certain degree
The intensity of gold, but the low-alloyed super-elasticity of drop and shape-memory properties that can be serious.Prepare fine grain or ultrafine-grained's shape
Memorial alloy, the intensity and toughness of alloy can get a promotion, but because a large amount of of crystal boundary increase, the obstruction to martensitic traoformation is made
With significantly increasing, the super-elasticity and shape-memory properties degradation of alloy can be caused.The effect and refined crystalline strengthening of working hardening
It is similar, due to a large amount of generations of the defects such as dislocation, also result in the deterioration of alloy performance.Heat treatment reinforcement is a kind of feasible
Marmem intensifying method.Cu-Al-Mn marmems are heat-treated in certain temperature range, alloy
It can separate out with high rigidity, the bayesian body phase of high intensity, so as to be lifted, the hardness of marmem, martensitic traoformation are critical to answer
Power and fatigue strength etc. (precipitation strength), and alloy super-elasticity with the rise (extension) of heat treatment temperature and time it is slow under
Drop.After heat treatment although its intensity result in lifting to monocrystalline Cu-Al-Mn marmems, but due in monocrystal not
The martensitic traoformation limit stress that there is alloy after crystal boundary, heat treatment is no more than 400MPa.At present, prepare has high superlastic simultaneously
The Cu-Al-Mn marmems of property and high martensitic traoformation limit stress still face great challenge.
The content of the invention
The present invention based on columanar structure's marmem there is high super-elasticity and bainite to separate out and can be substantially improved
The characteristics of Cu-Al-Mn marmem martensitic traoformation limit stresses, by using the preparation side of directional solidification+heat treatment
Method, is accurately controlled alloy structure and phase composition, so as to obtain while having high super-elasticity and high martensitic traoformation critical
The Cu-Al-Mn marmems of stress.
It is an object of the invention to provide a kind of Cu-Al-Mn with high super-elasticity and high martensitic traoformation limit stress
Marmem and preparation method thereof, solves the high high martensitic traoformation limit stress Cu base marmems of super-elasticity at present
The problem of preparing difficult.
The present invention is achieved by the following technical solutions：
The preparation method of the high high martensitic traoformation limit stress marmem of super-elasticity, the marmem
Preparation method is specifically：Being prepared first using directional freeze method has high hyperelastic columanar structure Cu-Al-Mn alloy preforms
Material, then by being heat-treated the martensitic traoformation limit stress of the raising alloy blank, so as to obtain with high super-elasticity and height
The Cu-Al-Mn marmems of martensitic traoformation limit stress.
Further, the preparation method specifically includes following steps：
(1) preparation of material and proportioning：99.9% oxygen-free copper, electrolytic aluminium and electrolytic manganese are above as raw material using purity；
During proportioning, in terms of atomicity percentage composition, the content of the aluminium of selection, copper and manganese is respectively：Aluminium：16at%~24at%, manganese：
9at%~13at%, copper：63at%~75at%；
(2) alloy blank is prepared：The raw material of proportioning in step (1) is subjected to melting, smelting temperature is 1100 DEG C~1200
℃；Then solidification is oriented, the directional solidification process is circumferentially heated using graphite casting mould, and the graphite casting mould temperature is
1000 DEG C~1100 DEG C, the graphite casting mould is placed on copper mold base, and the type of cooling of the copper mold base is water cooling, by melting
The molten metal injection graphite casting mould of acquisition, then stops circumferentially heating the graphite casting mould, the molten metal is fixed from bottom to top
To solidification, Cu-Al-Mn alloy blanks are prepared；
(3) martensite start temperature MsMeasurement：The horse of Cu-Al-Mn alloy blanks prepared by measuring process (2)
Family name's body starting temperature of transformation Ms, the martensite start temperature MsMeasuring method be differential thermal analysis or resistance method of temperature measurement；
(4) Cu-Al-Mn marmems are prepared：The Cu-Al-Mn alloy blanks prepared in step (2) are carried out
Heat treatment, heat treatment condition：Heat treatment temperature is higher than martensite start temperature Ms200℃-500℃；Heat treatment time is
1min-100h, carries out air cooling or water quenching after heat treatment, obtain the Cu-Al-Mn marmems.
Further, during step (2) prepares alloy blank, the Cu-Al-Mn alloy blanks prepared are post
Shape crystalline substance tissue, the Cu-Al-Mn alloy blanks are made up of β austenite one phases.
Further, heat treatment temperature and the heat treatment time are according to alloy after heat treatment described in step (4)
What performance was determined, the performance of alloy meets public with the heat treatment temperature and the relation of the heat treatment time after the heat treatment
Formula [1]：
Y (T, t)=y∞+(y0-y∞)/{1+[a·exp(-b·T)·t]n} [1]
In formula [1]：(T t) represents that in heat treatment temperature be alloy after T, heat treatment time are to be heat-treated under conditions of t to y
Performance, after the heat treatment performance of alloy include martensitic traoformation limit stress, tensile strength, hardness, modulus of elasticity and
Whole or any of which combination in super-elasticity；y0Represent the performance number of alloy before heat treatment, t=0 before heat treatment；y∞Represent
The performance number of alloy during hot place's time endless, hot place's time endless refers to t >=100h；A, b and n are in formula [1]
Material constant.
Further, material constant a, b and n and needed for preparing the Cu-Al-Mn marmems in formula [1]
Heat treatment process temperature T and heat treatment process time t computational methods comprise the following steps：
(1) it is heat-treated preliminary experiment：Higher than martensite start temperature MsSelected within the temperature range of 200 DEG C~500 DEG C
Take no less than 4 heat treatment temperature T values, and no less than 4 heat treatment time t values of selection in 1min~100h time range
Heat treatment preliminary experiment is carried out, heat treatment temperature T and heat treatment time t selection described in the heat treatment preliminary experiment should try one's best point
Dissipate, and ensure to have the heat treatment time t in one group of preliminary experiment to be 100h；
(2) alloy performance test：The alloy sample that step (1) is heat-treated before preliminary experiment and after heat treatment preliminary experiment enters
Row alloy performance test, the alloy property includes martensitic traoformation limit stress, tensile strength, hardness, modulus of elasticity and surpassed
Elasticity, measures the performance number y of alloy before the heat treatment0, hot place's time endless when alloy performance number y∞It is worth and a series of
(then T, t) value are fitted, obtain a, b and n value the y of different heat treatment temperature and time according to formula [1] logarithm value；
(3) calculating of the heat treatment temperature T and heat treatment time t needed for the Cu-Al-Mn marmems are prepared：
The alloy property y of the Cu-Al-Mn marmems to be prepared is determined first, then by measuring in step (2)
The alloy property y of material constant a, b and n value and the Cu-Al-Mn marmems is substituted into formula (1), you can calculated
Go out to prepare the heat treatment temperature T and heat treatment time t needed for the Cu-Al-Mn marmems.
Further, heat treatment time is 1min~100h described in step (1) heat treatment preliminary experiment, and has one group of pre- reality
The heat treatment time tested is 100h.
Cu-Al-Mn marmems with high super-elasticity and high martensitic traoformation limit stress, according to described height
The preparation method of the high martensitic traoformation limit stress marmem of super-elasticity is prepared, in terms of atomicity percentage composition,
The main component of the Cu-Al-Mn marmems is：Aluminium：16at%~24at%, manganese：9at%~13at%, copper：
63at%~75at%, the Cu-Al-Mn marmems are columanar structure, at room temperature the Cu-Al-Mn shapes note
Recalling the phase composition of alloy includes β austenites and bainite, and bayesian phase content is in the Cu-Al-Mn marmems
33%~77%, super-elasticity is that 5%~10%, martensitic traoformation limit stress is 440MPa~700Mpa.
Further, the tensile strength of the Cu-Al-Mn marmems is 550Mpa~800Mpa, modulus of elasticity
It is 290Hv~370Hv for 34GPa~55Gpa and Vickers hardness.
Brief description of the drawings
Fig. 1：Columanar structure Cu prepared by directional solidification70.9Al17.9Mn11.2The metallograph of alloy blank；
Columanar structure Cu prepared by Fig. 2 directional solidifications70.9Al17.9Mn11.2The super-elasticity stress-strain of alloy blank is bent
Line；
Columanar structure Cus of the Fig. 3 after 350 DEG C of heat treatment 60min70.9Al17.9Mn11.2The metallographic of marmem shines
Piece, wherein grey gill shape for bainite precipitated phase, matrix is austenite phase；
Columanar structure Cus of the Fig. 4 after 350 DEG C of heat treatment 30min70.9Al17.9Mn11.2The super-elasticity of marmem
Load-deformation curve；
Fig. 5 columanar structures Cu70Al20Mn10Super elastic shape memory alloy and martensitic traoformation limit stress are with heat treatment
Temperature and the contour of heat treatment time change, wherein dash area corresponds to super-elasticity more than 5% and martensitic traoformation is critical
Stress is more than the 440MPa high martensitic traoformation critical stress area of high super-elasticity.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.
On the contrary, the present invention covers any replacement done in the spirit and scope of the present invention being defined by the claims, repaiied
Change, equivalent method and scheme.Further, in order that the public has a better understanding to the present invention, below to the thin of the present invention
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
Description can also understand the present invention completely.
Embodiment 1
A kind of preparation method of the high martensitic traoformation limit stress marmem of high super-elasticity, the shape memory is closed
The preparation method of gold specifically includes following steps：
(1) preparation of material and proportioning：It is raw material to choose oxygen-free copper, electrolytic aluminium and electrolytic manganese that purity is 99.95%, with
Atomicity percentage composition meter, aluminium, copper and the corresponding content of manganese of selection are respectively：Aluminium：17.9at%, manganese：11.2at%, copper：
70.9at%；
(2) alloy blank is prepared：The raw material of proportioning in step (1) is subjected to melting, smelting temperature is 1200 DEG C；Then enter
Row directional solidification, the directional solidification process is circumferentially heated using graphite casting mould, and the graphite casting mould temperature is 1100 DEG C, described
Graphite casting mould is placed on copper mold base, and the type of cooling of the copper mold base is water cooling, and the molten metal that melting is obtained injects stone
Black casting mold, then stops circumferentially heating the graphite casting mould, molten metal directional solidification from bottom to top prepares size
For 150mm × 80mm × 50mm Cu70.9Al17.9Mn11.2Alloy blank；The Cu70.9Al17.9Mn11.2Alloy blank is column
Crystalline substance tissue, its metallographic structure β austenite one phases as shown in figure 1, be made up of, and its super-elasticity load-deformation curve such as Fig. 2 institutes
Show；
(3) martensite start temperature MsMeasurement：The horse of Cu-Al-Mn alloy blanks prepared by measuring process (2)
Family name's body starting temperature of transformation Ms, the martensite start temperature MsMeasuring method be differential thermal analysis (DSC), measure institute
State the martensite start temperature M of Cu-Al-Mn alloy blankssFor -50 DEG C；And it is 14.8%, horse to measure super-elasticity at room temperature
Family name's body phase becomes limit stress into 210MPa；
(4) the high martensitic traoformation limit stress Cu-Al-Mn marmems of high super-elasticity are prepared：To being made in step (2)
The standby Cu-Al-Mn alloy blanks are heat-treated, heat treatment condition：Heat treatment temperature starts temperature higher than martensitic traoformation
Spend Ms350 DEG C, be 300 DEG C；Heat treatment time is 5min-725min, and air cooling or water quenching are carried out after heat treatment, after heat treatment its
Hardness, limit stress, modulus of elasticity and super-elasticity are as shown in table 1.The horse of alloy before and after heat treatment is measured using differential thermal analysis
Family name's body starting temperature of transformation, as a result shows martensite start temperature M after heat treatmentsChange is less than 30 DEG C.In heat treatment
In the range of 120min-300min, super-elasticity 5%-8.3%, martensitic traoformation limit stress can be obtained for 453MPa-674MPa
The high martensitic traoformation limit stress Cu-Al-Mn marmems of high super-elasticity.
Heat treatment temperature can also be chosen higher than martensite start temperature M in the present embodiments400 DEG C, that is, it is heat-treated
Temperature be 350 DEG C, and when heat treatment time be 60min, choose the heat treatment condition processing after carry out air cooling sample, Fig. 3 and
Fig. 4 is the metallograph and super-elasticity load-deformation curve of the air cooling sample respectively.As shown in Figure 3, after heat treatment, occur
The bainite precipitated phase of gill shape, bainite and the column crystal crystal boundary of precipitation have interaction, alloy is obtained significantly
Better than the reinforcing effect of single crystal organization.
The columanar structure Cu of table 170.9Al17.9Mn11.2Performance number after 300 DEG C of heat treatment different times of alloy
Embodiment 2
A kind of preparation method of the high martensitic traoformation limit stress marmem of high super-elasticity, the shape memory is closed
The preparation method of gold specifically includes following steps：
(1) preparation of material and proportioning：It is raw material to choose oxygen-free copper, electrolytic aluminium and electrolytic manganese that purity is 99.95%, with
Atomicity percentage composition meter, aluminium, copper and the corresponding content of manganese of selection are respectively：Aluminium：19.9at%, manganese：9.8at%, copper：
70.3at%；
(2) alloy blank is prepared：The raw material of proportioning in step (1) is subjected to melting, smelting temperature is 1150 DEG C；Then enter
Row directional solidification, the directional solidification process is circumferentially heated using graphite casting mould, and the graphite casting mould temperature is 1050 DEG C, described
Graphite casting mould is placed on copper mold base, and the type of cooling of the copper mold base is water cooling, and the molten metal that melting is obtained injects stone
Black casting mold, then stops circumferentially heating the graphite casting mould, molten metal directional solidification from bottom to top prepares size
For 150mm × Φ 50mm Cu70.3Al19.9Mn9.8Alloy blank；The Cu70.3Al19.9Mn9.8Alloy blank is column crystal group
Knit；
(3) martensite start temperature MsMeasurement：The horse of Cu-Al-Mn alloy blanks prepared by measuring process (2)
Family name's body starting temperature of transformation Ms, the martensite start temperature MsMeasuring method be differential thermal analysis (DSC), measure institute
State the martensite start temperature M of Cu-Al-Mn alloy blankssFor -61 DEG C；And it is 14.5%, horse to measure super-elasticity at room temperature
Family name's body phase becomes limit stress into 262MPa；
(4) the high martensitic traoformation limit stress Cu-Al-Mn marmems of high super-elasticity are prepared：To being made in step (2)
The standby Cu-Al-Mn alloy blanks are heat-treated, heat treatment condition：Heat treatment temperature starts temperature higher than martensitic traoformation
Spend Ms411 DEG C, be 350 DEG C；Heat treatment time is 5min-600min；Air cooling or water quenching are carried out after heat treatment.Using differential thermal point
The martensite start temperature of alloy, as a result shows martensite start temperature after heat treatment before and after the measurement heat treatment of analysis method
MsChange is less than 30 DEG C, and its hardness, limit stress, modulus of elasticity and super-elasticity as shown in table 2, are being heat-treated after heat treatment
In the range of 30min-90min, it is 480MPa-700MPa's that can obtain super-elasticity 5%-9.8%, martensitic traoformation limit stress
The high high martensitic traoformation limit stress Cu-Al-Mn marmems of super-elasticity.
The columanar structure Cu of table 270.3Al19.9Mn9.8Performance number after 350 DEG C of heat treatment different times of alloy
Embodiment 3
A kind of preparation method of the high martensitic traoformation limit stress marmem of high super-elasticity, the shape memory is closed
The preparation method of gold specifically includes following steps：
(1) preparation of material and proportioning：It is raw material to choose oxygen-free copper, electrolytic aluminium and electrolytic manganese that purity is 99.95%, with
Atomicity percentage composition meter, aluminium, copper and the corresponding content of manganese of selection are respectively：Aluminium：16.4at%, manganese：11.3at%, copper：
72.3at%；
(2) alloy blank is prepared：The raw material of proportioning in step (1) is subjected to melting, smelting temperature is 1200 DEG C；Then enter
Row directional solidification, the directional solidification process is circumferentially heated using graphite casting mould, and the graphite casting mould temperature is 1100 DEG C, described
Graphite casting mould is placed on copper mold base, and the type of cooling of the copper mold base is water cooling, and the molten metal that melting is obtained injects stone
Black casting mold, then stops circumferentially heating the graphite casting mould, molten metal directional solidification from bottom to top prepares size
For 150mm × Φ 50mm Cu70.3Al19.9Mn9.8Alloy blank；The Cu70.3Al19.9Mn9.8Alloy blank is column crystal group
Knit；
(3) martensite start temperature MsMeasurement：The horse of Cu-Al-Mn alloy blanks prepared by measuring process (2)
Family name's body starting temperature of transformation Ms, the martensite start temperature MsMeasuring method be differential thermal analysis (DSC), measure institute
State the martensite start temperature M of Cu-Al-Mn alloy blankssFor -24.1 DEG C；And it is 16.0% to measure super-elasticity at room temperature,
Martensitic traoformation limit stress is 180MPa；
(4) it is heat-treated preliminary experiment：Heat is carried out under 200 DEG C, 250 DEG C, 300 DEG C, 350 DEG C and 400 DEG C five groups of temperature conditionss
Handle, five heat treatment times of 10min, 30min, 1h, 10h and 100h are respectively provided with a temperature of every group；
(5) determination of alloy performance test and alloy table material constant：To before step (4) heat treatment preliminary experiment and hot
Handle preliminary experiment after alloy sample carry out alloy property value test, the alloy property include martensitic traoformation it is critical should
Power, hardness, modulus of elasticity and super-elasticity, wherein：The performance number y of alloy before heat treatment0Closed when expression, hot place's time endless
The performance number y of gold∞Represent and heat treatment temperature is that the performance number that T, heat treatment time are alloy after being heat-treated under the conditions of t is used
(T t) is represented y.
Each performance number of the alloy measured is substituted into respectively numerical fitting is carried out in formula [1]：
Y (T, t)=y∞+(y0-y∞)/{1+[a·exp(-b·T)·t]n} [1]
Respectively obtain each performance of the alloy corresponding material constant a, b and n value；
(6) each performance is obtained with heat treatment temperature T (units：Kelvin) and heat treatment time t (units：Second) function close
System is as follows：
Martensitic traoformation limit stress (MPa)：
σMs(T, t)=900-720/ { 1+ [2285exp (- 10047/T) t]1.1}；
Hardness (Hv)：HV (T, t)=400-122/ { 1+ [2285exp (- 10047/T) t]1.4}；
Modulus of elasticity (GPa)：
E (T, t)=70-50/ { 1+ [2285exp (- 10047/T) t]1.3}；
Super-elasticity (%)：SE (T, t)=16/ { 1+ [2285exp (- 10047/T) t]0.9}。
According to above-mentioned performance equation, alloy martensite phase can be made by controlling heat treatment temperature T and heat treatment time t
Become limit stress, hardness, modulus of elasticity and super-elasticity in 180MPa-900MPa, 278Hv-400Hv, 20GPa-70GPa and
Adjusted in the range of 16%-0%.
Embodiment 4
A kind of preparation method of the high martensitic traoformation limit stress marmem of high super-elasticity, the shape memory is closed
The preparation method of gold specifically includes following steps：
(1) preparation of material and proportioning：It is raw material to choose oxygen-free copper, electrolytic aluminium and electrolytic manganese that purity is 99.95%, with
Atomicity percentage composition meter, aluminium, copper and the corresponding content of manganese of selection are respectively：Aluminium：20at%, manganese：10at%, copper：
70at%；
(2) alloy blank is prepared：The raw material of proportioning in step (1) is subjected to melting, smelting temperature is 1100 DEG C；Then enter
Row directional solidification, the directional solidification process is circumferentially heated using graphite casting mould, and the graphite casting mould temperature is 1000 DEG C, described
Graphite casting mould is placed on copper mold base, and the type of cooling of the copper mold base is water cooling, and the molten metal that melting is obtained injects stone
Black casting mold, then stops circumferentially heating the graphite casting mould, molten metal directional solidification from bottom to top prepares size
For 150mm × Φ 50mm Cu70Al20Mn10Alloy blank；The Cu70Al20Mn10Alloy blank is columanar structure；
(3) martensite start temperature MsMeasurement：The horse of Cu-Al-Mn alloy blanks prepared by measuring process (2)
Family name's body starting temperature of transformation Ms, the martensite start temperature MsMeasuring method be differential thermal analysis (DSC), measure institute
State the martensite start temperature M of Cu-Al-Mn alloy blankssFor -61.2 DEG C；And it is 15.5% to measure super-elasticity at room temperature,
Martensitic traoformation limit stress is 262MPa；
(4) it is heat-treated preliminary experiment：It is heat-treated under 250 DEG C, 300 DEG C, 350 DEG C and 400 DEG C four groups of temperature conditionss, often
Five heat treatment times of 2h, 10h, 50h and 100h are respectively provided with a temperature of group；In preliminary experiment, in order to obtain a performance with heat
The curve of processing time change is, it is necessary at least 4 groups heat treatment time data, it is necessary to obtain the unlimited prolonged performance of heat treatment
Value, generally accepted heat treatment time >=100h in general experiment approximately think that to be equal to heat treatment unlimited for a long time, it is considered to
To time cost during actual experiment, typically take 100h as the time upper limit of heat treatment, therefore, pre- reality is required in this patent
Test in middle heat treatment time 1min-100h time range and choose, and ensure to have the heat treatment time in one group of preliminary experiment be
100h, that is, guarantee to obtain " the unlimited prolonged performance number of heat treatment ".
(5) determination of alloy performance test and alloy table material constant：To before step (4) heat treatment preliminary experiment and hot
Handle preliminary experiment after alloy sample carry out alloy property value test, the alloy property include martensitic traoformation it is critical should
Power, hardness, modulus of elasticity and super-elasticity, wherein：The performance number y of alloy before heat treatment0Closed when expression, hot place's time endless
The performance number y of gold∞Represent and heat treatment temperature is that the performance number that T, heat treatment time are alloy after being heat-treated under the conditions of t is used
(T t) is represented y.
Each performance number of the alloy measured is substituted into respectively numerical fitting is carried out in formula [1]：
Y (T, t)=y∞+(y0-y∞)/{1+[a·exp(-b·T)·t]n} [1]
Respectively obtain each performance of the alloy corresponding material constant a, b and n value；
(6) each performance is obtained with heat treatment temperature T (units：Kelvin) and heat treatment time t (units：Second) function close
System is as follows：
Martensitic traoformation limit stress (MPa)：
σMs(T, t)=900-679/ { 1+ [919exp (- 9291/T) t]1.1}；；
Hardness (Hv)：HV (T, t)=400-140/ { 1+ [919exp (- 9291/T) t]1.4}；
Modulus of elasticity (GPa)：
E (T, t)=70-50/ { 1+ [919exp (- 9291/T) t]1.3}；
Super-elasticity (%)：SE (T, t)=14/ { 1+ [919exp (- 9291/T) t]0.9}。
According to above-mentioned performance equation, alloy martensite phase can be made by controlling heat treatment temperature T and heat treatment time t
Become limit stress, hardness, modulus of elasticity and super-elasticity in 221MPa-900MPa, 260Hv-400Hv, 20GPa-70GPa and
Adjusted in the range of 14%-0%.
And calculate super-elasticity and martensitic traoformation limit stress with heat treatment time and heat treatment temperature change it is contour
Line chart (as shown in Figure 5).Under heat treatment condition shown in shaded region in Fig. 5, super-elasticity can be obtained for 5%-9%, horse
Family name's body phase becomes limit stress and remembered into the Cu-Al-Mn shapes of the high martensitic traoformation limit stress of 443MPa-677MPa high super-elasticity
Recall alloy.
Claims (8)
1. the preparation method of the high high martensitic traoformation limit stress marmem of super-elasticity, it is characterised in that the shape
The preparation method of memorial alloy is specifically：Being prepared first using directional freeze method has high hyperelastic columanar structure Cu-
Al-Mn alloy blanks, then by being heat-treated the martensitic traoformation limit stress of the raising alloy blank, so as to obtain with height
The Cu-Al-Mn marmems of super-elasticity and high martensitic traoformation limit stress；
Occur the bainite precipitated phase of gill shape, heat treatment condition after heat treatment：Heat treatment temperature starts higher than martensitic traoformation
200 DEG C -500 DEG C of temperature Ms；Heat treatment time is 1min-100h；
The phase composition of the Cu-Al-Mn marmems includes β austenites and bainite at room temperature.
2. the preparation method of the high martensitic traoformation limit stress marmem of high super-elasticity according to claim 1, its
It is characterised by, the preparation method specifically includes following steps：
(1) preparation of material and proportioning：99.9% oxygen-free copper, electrolytic aluminium and electrolytic manganese are above as raw material using purity；It is described
The content of aluminium, copper and manganese is respectively in raw material：Aluminium：16at%~24at%, manganese：9at%~13at%, copper：63at%~
75at%；
(2) alloy blank is prepared：The raw material of proportioning in step (1) is subjected to melting, smelting temperature is 1100 DEG C~1200 DEG C；So
After carry out directional solidification, the directional solidification process is circumferentially heated using graphite casting mould, and the graphite casting mould temperature is 1000 DEG C
~1100 DEG C, the graphite casting mould is placed on copper mold base, and the type of cooling of the copper mold base is water cooling, and melting is obtained
Molten metal injects graphite casting mould, then stops circumferentially heating the graphite casting mould, molten metal directional solidification from bottom to top,
Prepare Cu-Al-Mn alloy blanks；
(3) martensite start temperature MsMeasurement：The martensite of Cu-Al-Mn alloy blanks prepared by measuring process (2)
Starting temperature of transformation Ms, the martensite start temperature MsMeasuring method be differential thermal analysis or resistance method of temperature measurement；
(4) Cu-Al-Mn marmems are prepared：Hot place is carried out to the Cu-Al-Mn alloy blanks prepared in step (2)
Reason, carries out air cooling or water quenching after heat treatment, obtain the Cu-Al-Mn marmems.
3. the preparation method of the high martensitic traoformation limit stress marmem of high super-elasticity according to claim 2, its
It is characterised by, step (2) is prepared during alloy blank, the Cu-Al-Mn alloy blanks prepared are column crystal group
Knit, the Cu-Al-Mn alloy blanks are made up of β austenite one phases.
4. the preparation method of the high martensitic traoformation limit stress marmem of high super-elasticity according to claim 2, its
It is characterised by, heat treatment temperature and the heat treatment time described in step (4) are determined according to the performance of alloy after heat treatment
, the performance of alloy and the relation of the heat treatment temperature and the heat treatment time meet formula [1] after the heat treatment：
Y (T, t)=y∞+(y0-y∞)/{1+[a·exp(-b·T)·t]n} [1]
In formula [1]：(T t) is represented in the property that heat treatment temperature is alloy after T, heat treatment time are to be heat-treated under conditions of t y
Can, the performance of alloy includes martensitic traoformation limit stress, tensile strength, hardness, modulus of elasticity and superlastic after the heat treatment
Property in whole or any of which combination；y0Represent the performance number of alloy before heat treatment, t=0 before heat treatment；y∞Represent at heat
The performance number of alloy during time endless, hot place's time endless refers to t >=100h；A, b and n are material in formula [1]
Constant.
5. the preparation method of the high martensitic traoformation limit stress marmem of high super-elasticity according to claim 4, its
It is characterised by, material constant a, b and n and heat treatment needed for the Cu-Al-Mn marmems is prepared in formula [1]
Treatment temperature T and heat treatment process time t computational methods comprise the following steps：
(1) it is heat-treated preliminary experiment：Higher than being chosen not within the temperature range of 200 DEG C~500 DEG C of martensite start temperature Ms
Less than 4 heat treatment temperature T values, and no less than 4 heat treatment time t values of selection are carried out in 1min~100h time range
Preliminary experiment is heat-treated, heat treatment temperature T and heat treatment time t selection described in the heat treatment preliminary experiment, which should try one's best, to be disperseed,
And ensure to have the heat treatment time t in one group of preliminary experiment to be 100h；
(2) alloy performance test：The alloy sample that step (1) is heat-treated before preliminary experiment and after heat treatment preliminary experiment is closed
Golden performance test, the alloy property includes martensitic traoformation limit stress, tensile strength, hardness, modulus of elasticity and super-elasticity,
Measure the performance number y of alloy before the heat treatment0, hot place's time endless when alloy performance number y ∞ values and a series of differences
(then T, t) value are fitted, obtain a, b and n value the y of heat treatment temperature and time according to formula [1] logarithm value；
(3) calculating of the heat treatment temperature T and heat treatment time t needed for the Cu-Al-Mn marmems are prepared：First
The alloy property y of the Cu-Al-Mn marmems to be prepared is determined, then by the material measured in step (2)
The alloy property y of constant a, b and n value and the Cu-Al-Mn marmems is substituted into formula (1), you can calculate system
Heat treatment temperature T and heat treatment time t needed for the standby Cu-Al-Mn marmems.
6. the preparation method of the high martensitic traoformation limit stress marmem of high super-elasticity according to claim 5, its
It is characterised by, heat treatment time is 1min~100h described in step (1) heat treatment preliminary experiment, and is had at the heat of one group of preliminary experiment
The reason time is 100h.
7. the Cu-Al-Mn marmems with high super-elasticity and high martensitic traoformation limit stress, according to claim
The preparation method of the high martensitic traoformation limit stress marmem of high super-elasticity described in one of 1-6 is prepared, and it is special
Levy and be, in terms of atomicity percentage composition, the main component of the Cu-Al-Mn marmems is：Aluminium：16at%~
24at%, manganese：9at%~13at%, copper：63at%~75at%, the Cu-Al-Mn marmems are column crystal group
Knit, the phase composition of the Cu-Al-Mn marmems at room temperature includes β austenites and bainite, the Cu-Al-Mn shapes
Bayesian phase content is that 33%~77%, super-elasticity is that 5%~10%, martensitic traoformation limit stress is in memorial alloy
440MPa~700MPa.
8. the Cu-Al-Mn shape memories according to claim 7 with high super-elasticity and high martensitic traoformation limit stress are closed
Gold, it is characterised in that the tensile strength of the Cu-Al-Mn marmems is that 550MPa~800MPa, modulus of elasticity are
34GPa~55GPa and Vickers hardness are 290Hv~370Hv.
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