CN102480014A - Shape memory metamaterial and preparation method thereof - Google Patents

Shape memory metamaterial and preparation method thereof Download PDF

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Publication number
CN102480014A
CN102480014A CN201110120974XA CN201110120974A CN102480014A CN 102480014 A CN102480014 A CN 102480014A CN 201110120974X A CN201110120974X A CN 201110120974XA CN 201110120974 A CN201110120974 A CN 201110120974A CN 102480014 A CN102480014 A CN 102480014A
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shape
ultra
shape memory
memory
base material
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CN102480014B (en
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刘若鹏
赵治亚
法布里齐亚
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Kuang Chi Institute of Advanced Technology
Kuang Chi Innovative Technology Ltd
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Kuang Chi Institute of Advanced Technology
Kuang Chi Innovative Technology Ltd
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Priority to PCT/CN2011/084575 priority patent/WO2012152021A1/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C61/00Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/06Making preforms having internal stresses, e.g. plastic memory
    • B29C61/0608Making preforms having internal stresses, e.g. plastic memory characterised by the configuration or structure of the preforms
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01QANTENNAS, i.e. RADIO AERIALS
    • H01Q15/00Devices for reflection, refraction, diffraction or polarisation of waves radiated from an antenna, e.g. quasi-optical devices
    • H01Q15/0006Devices acting selectively as reflecting surface, as diffracting or as refracting device, e.g. frequency filtering or angular spatial filtering devices
    • H01Q15/0086Devices acting selectively as reflecting surface, as diffracting or as refracting device, e.g. frequency filtering or angular spatial filtering devices said selective devices having materials with a synthesized negative refractive index, e.g. metamaterials or left-handed materials

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  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

The invention relates to a preparation method of a shape memory metamaterial, which comprises the following steps of: (S1) fabricating a shape memory material into a substrate with an original shape; (S2) attaching an artificial microstructure on the substrate to obtain a metamaterial layer; and (S3) deforming the metamaterial to obtain the shape memory metamaterial, wherein the deformed shape memory metamaterial is recovered into the original shape when meeting shape recovery conditions. The invention also relates to the shape memory metamaterial prepared by the preparation method of the invention. As the shape memory material is used as the substrate, the shape memory metamaterial of the invention has both shape memory and special electromagnetic response functions, thereby widening the application fields of the metamaterial.

Description

Ultra material of shape memory and preparation method thereof
Technical field
The present invention relates to ultra field of materials, more particularly, relate to ultra material of a kind of shape memory and preparation method thereof.
Background technology
Ultra material is a kind of new material, is the base material processed by nonmetallic materials and attached on the substrate surface or be embedded in the inner a plurality of artificial micro-structural of base material and constitute.Base material can be divided into a plurality of square substrates unit that rectangular array is arranged virtually; Thereby be attached with an artificial micro-structural on each base material unit and form a ultra material cell; Whole ultra material promptly by hundreds thousand of, 1,000,000 in addition more than one hundred million so ultra material cell form, just as crystal is to be made up of according to certain arranging countless lattices.Artificial micro-structural on each ultra material cell is identical or incomplete same.Artificial micro-structural is to form certain geometric cylindrical or flat wire, composition be shaped as annular, " worker " shape etc.
Because the existence of artificial micro-structural, each ultra material cell has effective dielectric constant and the equivalent permeability that is different from base material itself, so the ultra material that all ultra material cell constitute demonstrates specific response characteristic to electric field and magnetic field; Simultaneously, concrete structure and the shape different to artificial microstructure design can change the effective dielectric constant and the equivalent permeability of its unit, and then change the response characteristic of whole ultra material.
In the prior art; The base material of ultra material is selected polytetrafluoroethylene or ceramic material usually for use, and its dielectric constant and magnetic permeability all approach air, and is therefore less to the influence of electromagnetic field; Have good intensity simultaneously, applicable at various communication fields such as antenna, radars.But; Polytetrafluoroethylene and pottery are crisp frangible; For making the ultra material of producing, its shape is fixed, and needs the occasion of shape fine setting or distortion at some; For example under the room temperature for spirality, be higher than that room temperature 20 degree is above need to be adjusted under the plate shaped situation, the ultra material that has the base material material now can not satisfy such demand.
Summary of the invention
The technical problem that the present invention will solve is, to the above-mentioned defective of prior art, a kind of ultra preparation methods of shape memory that under given conditions can deformation is provided.
The technical solution adopted for the present invention to solve the technical problems is: provide a kind of shape memory ultra preparation methods.
The ultra preparation methods of a kind of shape memory of the present invention comprises the steps:
S1, process base material with shape-memory material with original shape;
S2, on said base material, adhere to artificial micro-structural, obtain ultra material layer;
S3, give distortion for said ultra material layer, obtain the ultra material of shape memory, the ultra material of said strained shape memory will revert back to original shape when reaching its recovery of shape condition.
In the ultra preparation methods of shape memory of the present invention, the original shape of said base material is plate shaped.
In the ultra preparation methods of shape memory of the present invention, said step S3 has carried out twice, and figuration is semi-cylindrical shaped or cylindrical shape for the first time, is spirality with semi-cylindrical shaped or the ultra material figuration of cylindrical shape memory for the second time.
In the ultra preparation methods of shape memory of the present invention, said shape-memory material is a thermic induction type shape-memory material, but has immobile phase and anti-phase.
In the ultra preparation methods of shape memory of the present invention, said thermic induction type shape-memory material is a SB, its immobile phase transition temperature T fBe 120 ℃, reversible phase transition temperature T rIt is 60 ℃.
In the ultra preparation methods of shape memory of the present invention, said step S1 adopts injection molding process.
In the ultra preparation methods of shape memory of the present invention, said step S2 adopts photochemical etching technology that artificial micro-structural is printed on the said base material.
In the ultra preparation methods of shape memory of the present invention, said artificial micro-structural has the metal wire of geometrical pattern for the one-tenth of being arranged by the metallic particles fusing.
In the ultra preparation methods of shape memory of the present invention, said step S3 to ultra material layer give the distortion comprise the steps:
S31, said ultra material layer is warming up to temperature is higher than its reversible phase transition temperature and is lower than its immobile phase transition temperature;
S32, said ultra material layer is out of shape through artificial or machinery;
S33, said ultra material layer is cooled rapidly, said ultra material layer is solidified and keep distortion after shape.
The present invention also provides a kind of shape memory ultra material, comprises the base material processed by shape-memory material and attached to the artificial micro-structural on the said base material, and the shape of said base material has been endowed distortion with respect to the original shape when creating.
Ultra material of shape memory of embodiment of the present invention and preparation method thereof; Has following beneficial effect: owing to adopt shape-memory material as base material; Make the ultra material of shape memory of the present invention have the function that shape memory and special electromagnetic respond two aspects simultaneously concurrently, for ultra material has been widened new application.
Description of drawings
To combine accompanying drawing and embodiment that the present invention is described further below, in the accompanying drawing:
Fig. 1 is the FB(flow block) of the ultra preparation methods of shape memory of the present invention;
Fig. 2 is the detailed step figure of step S3 in the flow process shown in Figure 1;
Fig. 3 is ultra material layer that step S2 the makes end view when being plate shaped;
Fig. 4 is the front view of ultra material layer shown in Figure 3;
Fig. 5 is the end view of ultra material layer shown in Figure 4 when being deformed into semi-cylindrical shaped;
Fig. 6 is a ultra material layer shown in Figure 4 end view when being deformed into cylindrical shape;
Fig. 7 is the end view when Fig. 3 or ultra material layer shown in Figure 4 further are deformed into spirality.
Embodiment
The shape memory function that the present invention will surpass distinctive electromagnetic response function of material and shape-memory material combines, and designs the ultra material of a kind of shape memory, and its preparation method is provided.
Shown in Fig. 5 to 7, the ultra material 4 of shape memory of the present invention comprises base material 1 and attached to the artificial micro-structural 2 on the base material 1.Traditional base material 1 is selected materials such as polytetrafluoroethylene, pottery usually for use, and what the present invention was different with it is to adopt the material of shape-memory material as base material 1.
Shape-memory material; As its name suggests; The material that promptly has shape memory function; According to shape memory principle difference can be divided into the thermic induction type, electricity causes several types of induction type, photic induction type, chemical co-ordination type, mangneto induction types etc., the basic principle that back different materials all is based on the thermotropic shape-memory material designs.The shape-memory material of nonmetal or alloy no matter belongs to which kind, so long as all can be used in the ultra material of the present invention as base material 1.
Thermic induction type shape-memory material; Be meant this material under a specified temp, to receive the external force effect and be out of shape; Thereby the cooling cooling of distortion back is with fixed in shape; And this material will automatically revert to the preceding shape of distortion when temperature is elevated to above-mentioned specified temp, and such material just belongs to thermic induction type shape-memory material.Usually, the specified temp here, and the absolute difference between the room temperature is bigger, at least more than 10 degrees centigrade, to satisfy the application of shape-memory material under the specific occasion.
Thermic induction type shape-memory material commonly used has:
1) TPO shape-memory materials such as PETG, polynorbornene, using trans-polyisoprene, SB, polyethylene, ethylene-vinyl acetate copolymer, polytetrafluoroethylene and polyvinyl chloride;
2) 4; 4 '-'-diphenylmethane diisocyanate/polycaprolactone/1; 4 butanediols, 4; 4 '-'-diphenylmethane diisocyanate/PolyTHF/1,4 butanediol, 4,4 '-'-diphenylmethane diisocyanate/polyurethanes block shape-memory materials such as poly adipate succinic acid ester dihydroxylic alcohols/trimethylolpropane;
3) polyesters shape-memory materials such as PETG H, polycaprolactone and PLA.
The base material 1 that shape-memory material is processed can be any required shape under its operating state; For example be spirality, as shown in Figure 6, and before being endowed distortion; Produced original shape is plate shaped, as shown in Figure 3 under the very little free state of internal stress free or internal stress.When temperature reaches the recovery of shape temperature and is the specified temp in the preceding text, spiral base material 1 will expand into plate shaped again, thereby realize certain function.
Solar panel for example; Be transported to expand into when absorbing solar energy in the space and plate shapedly absorb sunlight as much as possible to increase surface area; In being transported to the process of space, then need be wound into spirality in order to reduce transportation volume; Such solar panel is that the ultra material 4 of available shape memory of the present invention is realized; Automatically launch when on the one hand realizing reaching uniform temperature through the base material 1 of shape-memory material, on the other hand, the electromagnetic response that the artificial micro-structural 2 on the base material 1 and base material 1 send the sun jointly and absorb heat energy.
Artificial micro-structural 2 is attached on the substrate before base material 1 distortion.Artificial micro-structural 2 is generally the wire of forming certain geometrical pattern, for example " worker " font, snowflake shape, " ten " font, split ring resonator even other arbitrary shapes.Existence wiry; Make and when electromagnetic wave passes, can produce electric field and/or magnetic responsiveness electromagnetic wave; Thereby make whole ultra material bodies reveal distinctive electromagnetic response characteristic, realize the specific function that nature material did not have, for example inhale ripple, converge or divergent electromagnetic ripple etc.
Attached on the base material 1, every plate substrate 1 and lip-deep artificial micro-structural 2 thereof constitute a ultra material layer 3 to artificial micro-structural 2 through modes such as etching, ion quarter, plating, printings, and the ultra material 4 of each shape memory comprises one or more ultra material layers 3 like this.
The preparation method of the ultra material 4 of shape memory of the present invention, as shown in Figure 1, comprise following step:
S1, process base material 1 with shape-memory material with original shape;
In this step, available shape-memory material has had detailed description in preamble, and above-mentioned nonmetal, unalloyed thermic induction type shape-memory material is all available in the present invention as base material 1.In practical operation, shape-memory material commonly used is selected a kind of among the prepolymer of SB, methyl diphenylene diisocyanate and butanediol, the polynorbornene, optimization styrene-butadiene copolymer for use.
But thermic induction type shape-memory material generally includes immobile phase and anti-phase.But anti-phase is generally the transformation of unbodied rubbery state and glassy state, the fusion and the recrystallization of crystallization as the part of dynamic equilibrium realization shape memory.Immobile phase can be to be in its fusing point T mOr glass transition temperature T gFollowing molecule twines interpenetrating networks; PCL (PLC) and polynorbornene like HMW; This base polymer forms the immobile phase with physical crosslinking point; Can also be amorphous regions,, form the immobile phase of chemical crosslinking like the shape memory high molecule crosslinked polyethylene of finding the earliest with cross-linked structure.
For example for above-mentioned preferred SB, its immobile phase is the polystyrene crystalline portion, but anti-phase is the butadiene part, and immobile phase is by the solid-state transition temperature T that is molten into liquid state fBe about 120 ℃, but the transition temperature T of anti-phase rBe about 60 ℃.Will shape-memory material be processed base material 1, in order to make base material 1 internal stress little, adopt injection mo(u)lding or moulding by casting usually, in the die cavity with the shape-memory material injection molding machine of liquid state, this moment, the temperature of liquid material should be apparently higher than T f, between 125~135 ℃, it is little to guarantee that material can flow freely internal stress usually, makes it to solidify through natural cooling or water-cooled behind the injection die cavity, obtains having the base material 1 of original shape.Base material 1 thin words can be processed slab through cast or injection mo(u)lding earlier, and calendering formation obtains thin plate then.
Original shape can be plate shaped, and perhaps other arbitrary shapes are decided according to the actual requirements, as long as the difform die cavity of design.
Step S1 accomplishes, make base material 1 with original shape after, carry out step:
S2, on said base material 1, adhere to artificial micro-structural 2, obtain ultra material layer 3, like Fig. 3, shown in Figure 4;
Step S2 can adopt etching or electroplate and realize.The etch process here typically refers to photochemical etching (photochemical etching), is similar to the making of PCB; Promptly earlier at substrate surface deposition layer of metal paper tinsel layer, after exposure plate-making, developing, diaphragm that will etching area is removed; Metal Contact chemical solution that should the zone when etching; Dissolved corrosion, remaining is the metal wire with certain geometrical shape pattern, is artificial micro-structural 2.
If the employing etch process should avoid being used for etched chemical solvent and base material 1 reaction, in order to avoid destroy the surface flatness of base material 1 even the overall structure and the shape of destruction base material 1.
Step S2 also can adopt typography to be printed on the base material 1.Be similar to traditional printer; The metal powder granulates of certain particle size scope is positioned in the printing machine; The zone of artificial micro-structural 2 is set at needs; Metallic particles being shifted onto on this zone of base material 1 and heating and melting, is that metallic particles is melted into an integrally formed strip metal silk thread, forms the effect of " printing " artificial micro-structural 2.
If the employing typography it should be noted, the immobile phase conversion temperature that the temperature that metallic particles heating is made it to melt should be lower than shape-memory material is the fusing point of immobile phase, to avoid the material melts distortion; Perhaps, metallic particles heating and the speed of solidifying be exceedingly fast, and before heat does not conduct to base material 1, accomplish the action of " printing " artificial micro-structural 2.
Adopt typography to make the concrete technology of artificial micro-structural 2; All right referenced patent " Fabrication of electronic components in plastic " (application number EP20060752653; Inventor David Victor Thiel and Neeli Madhusudanrao), it adopts embossing machine (embossing machine) on plastic basis material 1, to print the artificial micro-structural 2 of conduction with certain geometrical pattern.This patent of invention explains that step S2 of the present invention is feasible.
Make each artificial micro-structural 2 successively, then substrate and on artificial micro-structural 2 constitute a ultra material layer 3 jointly.
To carry out following steps after making ultra material layer 3:
S3, give distortion, obtain the ultra material 4 of shape memory for said ultra material layer 3.
Give distortion, be called for short figuration, order about ultra material layer 3 with external force exactly and be deformed into another shape that is different from original shape, for example spirality.The distinctive SME of thermic induction type shape-memory material derives from its special construction, its immobile phase transition temperature T f(the T of immobile phase gOr T m) be higher than reversible phase transition temperature T rBut (the T of anti-phase gOr T m), but and the T of requirement anti-phase gOr T mOn room temperature, but following anti-phase of room temperature condition and immobile phase all are in glassy state or crystalline state, and sub-chain motion is restricted.
When temperature is higher than T rAnd be lower than T fThe time, but the strand of anti-phase has enough energy to make conformation change, sub-chain motion aggravation, and macro manifestations is the transformation to elastomeric state of fusion or the glassy state of crystalline phase.At this moment; Material can produce deformation under external force or other factor effects, and immobile phase still is in crystalline state or glassy state this moment, and molecule is fixed by its mutual physical action; Stop strand to produce slippage; Opposing deformation, but the effect between anti-phase and the immobile phase, the plasticity that has suppressed chain are moved and are produced back-shaped shape memory effect.The processing of lowering the temperature of the material of figuration, but the deformation of anti-phase be fixed, sub-chain motion is limited, but then anti-phase comes back to glassy state or crystalline state, and material exists with this dimensionally stable.
Shape-memory material behind outer bound pair figuration is given incentive condition, and this material will produce the process of recovery of shape.That is, after heating up once more, strand is because entropic elasticity effect and hai roll is bent, and the resilience force of immobile phase obtains release, and deformation recovery promptly returns to the original shape among the step S1.
Ultra material layer 3 of the present invention belongs to the scope of ultra material, owing to be attached with the artificial micro-structural 2 of metal on the base material 1, can produce response to electromagnetic wave, makes material internal give birth to heat, recovery of shape will take place up to original shape after reaching uniform temperature.The preferred low material of thermal conductivity in the shape-memory material makes heat be not easy diffusion, gives birth to hot temperature height, and recovery of shape is very fast.
Therefore, carrying out step S3, is in order to make ultra material in being applied to actual environment, in case when environmental condition reaches its recovery of shape condition, will revert to original shape.For thermic induction type shape-memory material, its recovery of shape condition is the recovery of shape temperature.
The recovery of shape temperature also is the temperature during for ultra material layer 3 figurations, and its value is not less than reversible phase transition temperature T rAnd be not higher than immobile phase transition temperature T f, the reversible glassy state that is in mutually of this moment.Therefore, as shown in Figure 2, step S3 can the branch following steps carry out:
S31, the ultra material layer 3 that step S2 is obtained are warming up to the recovery of shape temperature;
S32, said ultra material layer 3 is out of shape through artificial or machinery;
S33, said ultra material layer 3 is cooled rapidly, said ultra material layer 3 is solidified and keep distortion after shape.
Like Fig. 5, shown in Figure 6, the mode through punching press among the step S32 can be deformed into semi-cylindrical shaped or cylindrical shape with plate shaped ultra material layer 3.
If ultra material layer 3 once is out of shape the shape for example during the spirality of solar panel that can not reach required, can realize through repeatedly being out of shape.For example, carry out step S31, S32, a S33 earlier and will surpass material layer 3 punching presses and be deformed into cylindrical shape or semi-cylindrical shaped, and then carry out step S31, S32, S33 and be deformed into spirality with the ultra material of cylindrical shape or semi-cylindrical shaped 4 is manual, as shown in Figure 7.
Need to prove; Shape-memory material of the present invention is not limited in thermic induction type material mentioned above; Also can utilize other shape-memory materials for example mangneto induction type, photic induction type shape-memory material; After they are used and make ultra material layer 3 with step S1, the identical method of S2, when carrying out step S3, no longer be temperature but magnetic field, illumination by the environmental condition of figuration or recovery of shape condition.For example when shape-memory material was photic induction type material, step S3 should the branch following steps carry out:
S31, the ultra material layer 3 that step S2 is obtained carry out illumination;
S32, said ultra material layer 3 is out of shape through artificial or machinery;
S33, said ultra material layer 3 is stopped illumination, said ultra material layer 3 is solidified and keep distortion after shape.
The ultra material that obtains so also belongs to the ultra material 4 of shape memory of the present invention.
Adopt the ultra material 4 of shape memory of the present invention; Utilize the design of its artificial micro-structural 2; Can realize electromagnetic specific response, for example can be used as microwave regime such as lens, wave beam compressor reducer (beam compressor), beam (beam shifter), antenna, absorbing material; And among the present invention shape-memory material as base material 1, with range of application that further expands ultra material and applied environment, the described solar panel of preamble for example.Another example and for example; Ultra material can be used as the switch of anti-electromagnetic radiation; The base material 1 of ultra material is a mangneto induction type shape-memory material, and base material 1 contact-making switch contact into a bent shape and not when not having electromagenetic wave radiation or radiation intensity low breaks off switch; And when receiving stronger electromagnetic wave, magnetic field excitation makes the living heat of shape-memory material and is out of shape, and the distortion back contacts with the switch contact, switch conduction, and then people can judge has stronger electromagenetic wave radiation.
Other application examples of the present invention also have a lot, and this paper enumerates no longer one by one.Every method and the ultra material of shape memory that adopts method of the present invention to make that meets step of the present invention all belongs within the protection range of the present invention.

Claims (10)

1. the ultra preparation methods of shape memory is characterized in that, comprises the steps:
S1, process base material with shape-memory material with original shape;
S2, on said base material, adhere to artificial micro-structural, obtain ultra material layer;
S3, give distortion for said ultra material layer, obtain the ultra material of shape memory, the ultra material of said strained shape memory will revert back to original shape when reaching its recovery of shape condition.
2. the ultra preparation methods of shape memory according to claim 1 is characterized in that the original shape of said base material is plate shaped.
3. the ultra preparation methods of shape memory according to claim 2 is characterized in that said step S3 has carried out twice, and figuration is semi-cylindrical shaped or cylindrical shape for the first time, is spirality with semi-cylindrical shaped or the ultra material figuration of cylindrical shape memory for the second time.
4. the ultra preparation methods of shape memory according to claim 1 is characterized in that said shape-memory material is a thermic induction type shape-memory material, but has immobile phase and anti-phase.
5. the ultra preparation methods of shape memory according to claim 4 is characterized in that, said thermic induction type shape-memory material is a SB, its immobile phase transition temperature T fBe 120 ℃, reversible phase transition temperature T rIt is 60 ℃.
6. the ultra preparation methods of shape memory according to claim 4 is characterized in that, said step S1 adopts injection molding process.
7. the ultra preparation methods of shape memory according to claim 4 is characterized in that, said step S2 adopts the photochemistry etching technics that artificial micro-structural is printed on the said base material.
8. the ultra preparation methods of shape memory according to claim 7 is characterized in that, said artificial micro-structural has the metal wire of geometrical pattern for the one-tenth of being arranged by the metallic particles fusing.
9. the ultra preparation methods of shape memory according to claim 4 is characterized in that, said step S3 to ultra material layer give the distortion comprise the steps:
S31, said ultra material layer is warming up to temperature is higher than its reversible phase transition temperature and is lower than its immobile phase transition temperature, the reversible glassy state that is in mutually in this moment shape-memory material;
S32, said ultra material layer is out of shape through artificial or machinery;
S33, said ultra material layer is cooled rapidly, said ultra material layer is solidified and keep distortion after shape.
10. the ultra material of shape memory is characterized in that, comprises the base material processed by shape-memory material and attached to the artificial micro-structural on the said base material, and the shape of said base material has been endowed distortion with respect to the original shape when creating.
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CN105461946B (en) * 2015-12-14 2017-11-17 哈尔滨工业大学 Deformation controllable composite material of shape memory and its deformation method
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