CN113831736A - Multistable rigidity-variable intelligent material and preparation method and application thereof - Google Patents
Multistable rigidity-variable intelligent material and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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Abstract
The invention discloses a multistable rigidity-variable intelligent material and a preparation method and application thereof. The multistable variable-rigidity intelligent material comprises a dispersed phase and a dispersion medium, wherein the dispersed phase is uniformly dispersed in the dispersion medium, the dispersed phase comprises low-melting-point alloy particles with different melting points, and the dispersion medium comprises an elastomer. The multistable rigidity-variable intelligent material provided by the invention has the phenomena of shear thinning and visco-elastic inversion in a slurry state, and can be used in a 3D printing technology; after curing, the stiffness can be changed to a corresponding extent by applying different temperature stimuli. The intelligent material disclosed by the invention is sensitive in reaction, good in stability under each stable state, excellent in heat conductivity, simple and feasible in preparation method, low in cost and capable of being used as a material for 3D printing.
Description
Technical Field
The invention relates to an intelligent material, in particular to a multistable variable-rigidity low-melting-point alloy/elastomer composite intelligent material, a preparation method and application thereof, and belongs to the field of intelligent composite materials.
Background
As a fourth generation material following natural materials, synthetic polymer materials, and artificially designed materials, an intelligent material (also referred to as a responsive material) is designed to have one or more characteristics, and can sense external stimuli, gradually eliminate the limit of a functional material counting structural material in the conventional sense, and realize structural functionalization and functional diversification. In general, a smart material has seven major functions, that is, a sensing function, a feedback function, an information recognition and accumulation function, a response function, a self-diagnosis capability, a self-repair capability, and an adaptive capability.
Smart materials need to have the following characteristics:
(1) sensing function, detecting and recognizing external or internal stimulation intensity, such as electricity, light, heat, stress, strain, chemistry, etc.;
(2) the driving function is changed according to the outside;
(3) the response may be selected and controlled in a designed manner;
(4) the reaction is sensitive, timely and accurate;
(5) after the external part is eliminated, the original state can be quickly restored.
The low-melting point alloy consists of lead, cadmium, tin, antimony, tin, indium, bismuth and other low-melting point metal elements, the melting point temperature of the low-melting point alloy is generally lower than 200 ℃, and the low-melting point alloy is very sensitive to temperature change. When foreign atoms enter the crystal, metal bonds are destroyed, a state of disordered arrangement appears inside the metal, and the internal energy of the metal is increased, so that the melting point is reduced. Upon application of the thermal field, the interaction between the low melting point alloy molecules decreases, macroscopically appearing to melt from the solid state to the liquid state in a short time; after the thermal field is removed, the liquid low-melting-point alloy can be converted back to the solid state in a short time. The low-melting-point alloy is an intelligent material with great development potential, has simple manufacturing process, low manufacturing cost and sensitive reaction speed, and has wide application background in the aspects of flexible robots, soft brakes and the like.
Patent CN105349866A discloses a low-melting-point alloy with a melting point of 40-60 ℃ and a preparation method thereof, wherein the alloy comprises indium, bismuth, tin, gallium and a small amount of lead or cadmium. The low-melting-point alloy has simple preparation process, can be applied to low-temperature occasions in a phase change mode, can be synthesized in the atmospheric environment, has low manufacturing cost, and enlarges the range of liquid metal thermal interface materials. Meanwhile, the material is in a solid state at a lower temperature, and gradually becomes a liquid state along with the temperature rise process, so that the material cannot be molded.
Patent CN110218329A discloses a polysiloxane controlled by temperature sensitivity and related applications, the mechanical properties of the modified material can be changed significantly within a certain temperature range from a low temperature state to a high temperature state. The invention is particularly used for preparing temperature-sensitive quick setting materials, surgical medical fixing materials, correcting materials and the like.
Patent CN110746940A discloses a flexible multi-stage phase change energy storage material and a preparation method thereof, wherein the material has multi-stage phase transition temperature. The phase-change material that this patent adopted is the organic matter, and the substrate is thermoplastic elastomer and thermoplastic resin, is not suitable for in 3D prints the vibration material disk.
Disclosure of Invention
The invention mainly aims to provide a multistable rigidity-variable intelligent material, and a preparation method and application thereof, so that the defects in the prior art are overcome.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides a multistable variable-rigidity intelligent material which comprises a dispersed phase and a dispersion medium, wherein the dispersed phase is uniformly dispersed in the dispersion medium, the dispersed phase comprises low-melting-point alloy particles, and the dispersion medium comprises an elastomer.
Further, the dispersed phase includes low melting point alloy particles of different melting points.
Further, the melting point of the low-melting-point alloy particles in the intelligent material is lower than 200 ℃, and preferably 30-70 ℃.
Further, the multistable variable-rigidity intelligent material has the phenomena of shear thinning and visco-elastic inversion in a slurry state.
Further, after the multistable variable-rigidity intelligent material is cured, rigidity change can be achieved under different temperature stimuli.
The embodiment of the invention also provides a preparation method of the multistable variable-rigidity intelligent material, which comprises the following steps: and uniformly mixing the low-melting-point alloy particles and the elastomer prepolymer to prepare intelligent material slurry, and then curing to obtain the multistable variable-rigidity intelligent material.
In some embodiments, the preparation method specifically comprises:
providing a first mixing system comprising low melting point alloy particles and a first prepolymer component;
and adding a second prepolymer component into the first mixed system, uniformly stirring and mixing to form a second mixed system to obtain intelligent material slurry capable of being printed in a 3D mode, and then curing to obtain the multistable rigidity-variable intelligent material elastomer.
The embodiment of the invention also provides application of the multistable variable-rigidity intelligent material in the field of 3D printing.
Compared with the prior art, the invention has the beneficial effects that:
the multistable rigidity-variable intelligent material provided by the invention adopts a mixture of multiple low-melting-point alloy particles as a dispersion phase, and multiple low-melting-point alloys have multiple stable states, so that the controllability is high, the possibility is wide, and the response speed is high; the method for mixing the elastomer prepolymer with the low-melting-point alloy particles is also adopted, and the obtained intelligent material slurry has the phenomena of shear thinning and visco-elastic inversion and can be used as a material for 3D printing, so that the multistable variable-rigidity intelligent material can be kept in a stable state under various states, is good in stability and excellent in heat conductivity, has a simple and easy preparation method and low cost, and can be applied to the field of additive manufacturing.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph of particle size analysis of micron-sized particles of a low melting point alloy at 47 ℃ in example 1 of the present invention;
FIG. 2 is a structural morphology of micron-sized particles of a low melting point alloy at 47 ℃ in example 1 of the present invention;
FIG. 3 is a schematic diagram showing the variation of the melting point of the intelligent elastomer mixed with the PDMS SE1700 and the micron-sized particles of the low-melting-point alloy at 47 ℃ in example 1 of the present invention;
fig. 4 is a physical diagram of a 3D printing sample prepared in embodiment 1 of the present invention;
FIG. 5 is a graph of shear stress versus shear rate for an intelligent slurry of 47 ℃ low melting point alloy mixed with PDMS SE1700 in example 1 of the present invention;
FIG. 6 is a graph of the elastic and viscous moduli versus shear stress for a smart slurry of 47 deg.C low melting point alloy mixed with PDMS SE1700 in example 1 of the present invention;
FIG. 7 is a graph of the change in elastic modulus with temperature for a smart elastomer of example 1 of the present invention in which a 47 ℃ low melting point alloy was mixed with PDMS SE 1700;
FIG. 8 is a graph of particle size analysis of 30 ℃ micron-sized particles of a low melting point alloy in example 2 of the present invention;
FIG. 9 is a structural morphology of 30 ℃ micron-sized particles of a low melting point alloy in example 2 of the present invention;
FIG. 10 is a schematic diagram showing the change of melting points of the smart elastomer in which the low melting point alloy of 30 ℃ and the low melting point alloy of 47 ℃ are mixed with DMS SE1700 in example 2 of the present invention;
fig. 11 is a physical diagram of a 3D printing sample prepared in embodiment 2 of the present invention;
FIG. 12 is a graph of shear stress versus shear rate for an intelligent slurry of 30 ℃ low melting point alloy and 47 ℃ low melting point alloy mixed with PDMS SE1700 in example 2 of the present invention;
FIG. 13 is a graph of the elastic modulus and viscous modulus versus shear stress for the smart pastes of example 2 of the invention in which 30 ℃ low melting point alloy and 47 ℃ low melting point alloy were mixed with PDMS SE 1700;
FIG. 14 is a graph of the change in elastic modulus with temperature for the smart elastomers of example 2 of the present invention in which 30 ℃ low melting point alloy and 47 ℃ low melting point alloy were mixed with PDMS SE 1700;
FIG. 15 is a graph of particle size analysis of micron-sized particles of a low melting point alloy at 70 ℃ in example 3 of the present invention;
FIG. 16 is a structural morphology of 70 ℃ low melting point alloy micro-scale particles in example 3 of the present invention;
FIG. 17 is a schematic diagram showing the change of melting point of the smart elastomer in which the low melting point alloy of 30 deg.C, the low melting point alloy of 47 deg.C and the low melting point alloy of 70 deg.C are mixed with DMS SE1700 in example 3 of the present invention;
fig. 18 is a physical diagram of a 3D printed sample prepared in example 3 of the present invention;
FIG. 19 is a graph of shear stress versus shear rate for an intelligent slurry of 30 deg.C low-melting alloy, 47 deg.C low-melting alloy, and 70 deg.C low-melting alloy mixed with PDMS SE1700 in example 3 of the present invention;
FIG. 20 is a graph of elastic modulus and viscous modulus versus shear stress for a smart paste of 30 deg.C low melting point alloy, 47 deg.C low melting point alloy, and 70 deg.C low melting point alloy mixed with PDMS SE1700 in example 3 of the present invention;
FIG. 21 is a graph of the change in elastic modulus with temperature for a smart elastomer in which 30 deg.C low-melting alloy, 47 deg.C low-melting alloy, and 70 deg.C low-melting alloy were mixed with PDMS SE1700 in example 3 of the present invention;
fig. 22 is a physical diagram of a 3D printed sample prepared in example 4 of the present invention;
fig. 23 is a physical diagram of a 3D printed sample prepared in example 5 of the present invention;
fig. 24 is a real object diagram of a 3D printing sample prepared in embodiment 6 of the present invention.
Detailed Description
Multiphase stable materials are composite structures having a variety of different stable states. The material has a certain load bearing capacity in each stable state, and the transition between the stable states of the material can occur after the external stimulus is given. The elastic modulus of the cured material reflects the rigidity of the intelligent material, and the change of the rigidity shows that the intelligent material can be converted among various stable states. In addition, shear thinning, also known as pseudoplasticity, is the most common phenomenon of non-newtonian fluids, reflecting that the viscosity of the smart material decreases with increasing shear strain rate. For polymer systems, shear thinning is caused by entanglement of the polymer chains during flow; at rest, the high molecular weight polymers are entangled and randomly oriented; when shear is imparted at a sufficiently high rate, the highly anisotropic polymer chains begin to unravel, which results in fewer particle or molecular interactions and a large amount of free space for movement, thereby reducing viscosity. The phenomenon of visco-elastic inversion is an important parameter for judging that the intelligent material can be subjected to 3D printing, and the change of the elastic modulus and the viscous modulus is crossed at a certain point along with the increase of the provided dynamic shear stress; meanwhile, the crossing point may reflect a pressure value that needs to be given when 3D direct write printing is performed.
In view of the above, and the deficiencies in the prior art, the inventors of the present invention have long studied and practiced in great numbers to provide the technical solutions of the present invention, which will be further explained below.
Specifically, as one aspect of the technical solution of the present invention, the present invention relates to a multistable variable stiffness smart material, which includes a dispersed phase and a dispersion medium, wherein the dispersed phase is uniformly dispersed in the dispersion medium, the dispersed phase includes low melting point alloy particles with different melting points, and the dispersion medium includes an elastomer.
In some preferred embodiments, the melting point of the low-melting-point alloy particles in the multistable variable-stiffness smart material is lower than 200 ℃, and preferably 30-70 ℃.
In some preferred embodiments, the content of the low-melting-point alloy particles in the multistable variable-stiffness smart material is 20-60 vol%, and preferably 40-60 vol%.
Further, the low-melting-point alloy particles are low-melting-point alloy micro-particles, and specifically contain elements such as indium, bismuth, tin, lead, cadmium and the like.
Further, the particle size of the low-melting-point alloy particles is 1-100 mu m.
Further, the elastomer includes any one or a combination of two or more of PDMS SE1700, PDMS184, Ecoflex 00-30, Ecoflex 00-50, and the like, but is not limited thereto.
In some embodiments, the low-melting-point alloy particles in the multistable variable-rigidity intelligent material have multiple stable states, the controllability is high in possibility and multiple ranges, and the response speed is high; the dispersion medium elastomer prepolymer has the phenomena of shear thinning and visco-elastic inversion, and can be used as a material for 3D printing.
Wherein, the manufacturing of the low-melting-point alloy micron particles in the intelligent material adopts a uniform dispersion cooling method.
Further, the preparation of the low-melting-point alloy micro-particles can mix the low-melting-point alloy particles with different melting points together without any chemical reaction, and different stable states can be generated at different temperatures respectively.
Furthermore, the multistable variable-rigidity intelligent material has the phenomena of shear thinning and visco-elastic inversion in a slurry state, and can be used in a 3D printing technology.
Further, after the multistable variable-rigidity intelligent material is cured, the rigidity of the multistable variable-rigidity intelligent material can be changed to a corresponding degree by giving different temperature stimuli.
The action mechanism of the invention may be that: applying a thermal field to vibrate atoms of low-melting-point alloy particles in the intelligent material; at different thermal field strengths, the corresponding low melting point alloy melts, thereby changing the elastic modulus of the elastomer.
As another aspect of the technical solution of the present invention, a method for preparing a multistable variable stiffness smart material, includes: and uniformly mixing the low-melting-point alloy particles and the elastomer prepolymer to prepare intelligent material slurry, and then curing to obtain the multistable variable-rigidity intelligent material.
In some embodiments, the preparation method of the multistable variable-stiffness smart material specifically comprises the following steps:
providing a first mixed system (also referred to as "mixed system 1") comprising low melting point alloy particles and a first prepolymer component (also referred to as "prepolymer component a");
adding a second prepolymer component (also called as a prepolymer component B) into the first mixed system, uniformly stirring and mixing to form a second mixed system (also called as a mixed system 2) to obtain the intelligent material slurry capable of being 3D printed, and then curing to obtain the multistable variable-rigidity intelligent material elastomer.
In another specific embodiment, the preparation method of the multistable variable-stiffness smart material may further include the following steps:
providing a first mixing system comprising low melting point alloy particles and a first prepolymer component;
providing a second mixing system comprising low melting point alloy particles and a second prepolymer component;
and uniformly stirring and mixing the first mixed system and the second mixed system to obtain intelligent material slurry capable of being printed in a 3D mode, and then curing to obtain the multistable rigidity-variable intelligent material elastomer.
In some embodiments, the preparation method specifically comprises: and uniformly mixing the low-melting-point alloy particles and the elastomer prepolymer A by stirring, and uniformly mixing the low-melting-point alloy particles and the elastomer prepolymer B by stirring.
Furthermore, the stirring treatment is not strictly limited in time, and is preferably 20-30 min.
Further, the curing time is 8-12 h.
Further, in order to uniformly mix the two, an organic solvent, preferably hexane, may be added to the first mixed system or the second mixed system, but is not limited thereto.
Further, the volume ratio of the first mixed system to the second mixed system is 20: 100-60: 100.
Wherein, the steps are operated at room temperature.
In some more specific embodiments, the method for preparing the low-melting-point alloy microparticles specifically comprises the following steps:
1) dissolving the low-melting-point alloy block in boiling deionized water, and dispersing to obtain a suspension A;
furthermore, the dispersion treatment is not strictly limited in time, and is preferably 20-30 min.
2) Rapidly placing the suspension A in ice water for cooling, and stirring until the temperature is lower than the melting point of the low-melting-point alloy to obtain a suspension B;
further, the stirring treatment is not strictly limited in time, and is preferably 30 to 50 min.
3) And standing the suspension B until the particles settle, extracting clear liquid at the upper part, adding a small amount of volatile organic solvent, centrifuging, and then placing in an oven for drying.
Furthermore, the invention selects and mixes low melting point alloys with different melting points to obtain the alloy which is melted at different temperatures and has different phase change degrees at different temperatures.
Further, standing treatment is not strictly limited in time, and preferably lasts for 7-8 hours; the drying treatment is not strictly limited in time, and is preferably 36-48 h.
Still further, the volatile organic solvent is preferably, but not limited to, absolute ethanol.
Further, the preparation of the low-melting-point alloy micro-particles can mix the low-melting-point alloy particles with different melting points together without any chemical reaction, and different stable states can be generated at different temperatures respectively.
Another aspect of the embodiments of the present invention also provides a multistable variable stiffness smart material prepared by the above method.
In conclusion, the multistable rigidity-variable intelligent material disclosed by the invention is good in stability and excellent in thermal conductivity under each stable state, the preparation method is simple and easy to implement, the cost is low, and the multistable rigidity-variable intelligent material can be used as a material for 3D printing.
The embodiment of the invention also provides application of the multistable variable-rigidity intelligent material in the field of 3D printing.
It is understood that within the scope of the present invention, the above-described technical features of the present invention and the technical features specifically described below (e.g., examples) may be combined with each other to constitute a new or preferred technical solution. For reasons of space, they will not be described in detail.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention. In the following examples, experimental methods without specific conditions noted are generally performed under conventional conditions or conditions recommended by the manufacturer, based on a full understanding of the present invention.
Example 1
(1) 20g of a 47 ℃ low melting point alloy (in the composition indium, bismuth, tin, lead and cadmium) was weighed out and dissolved in 300mL of boiling deionized water until molten.
(2) And dispersing the molten low-melting-point alloy into boiling deionized water to obtain a suspension A.
(3) And (4) putting the suspension A into ice water for cooling, keeping the stirring state until the temperature is reduced to be lower than the melting point of the alloy, and standing until the suspension A is precipitated.
(4) And (4) extracting supernatant, adding a small amount of absolute ethyl alcohol, centrifuging, and drying in an oven to obtain the required low-melting-point alloy micro-particles. As shown in fig. 1-2, is a particle size analysis and a micro-topography of the low melting point alloy micro-particles at 47 ℃.
(5) The 4.58g of the low-melting-point alloy microparticles are stirred and mixed with 0.8475g of PDMS SE 1700A part to prepare composite slurry B with the volume fraction of 40%.
(6) 0.08475g of PDMS SE1700B was added to the composite paste B at a ratio of 10:1 by mass of part A to part B to obtain composite paste C, which was ready for 3D printing.
As shown in fig. 3, the melting point range of the elastomer of the smart material is shown.
Fig. 4 is a real image of a 3D printing sample prepared from the intelligent paste (i.e., the composite paste C).
(7) The obtained mold was placed in an oven for drying.
As shown in FIGS. 5-6, the shear rate of the smart slurry is 1s-1～100s-1The phenomenon of shear thinning and the phenomenon of visco-elastic inversion occur when the shear pressure is 1 Pa-10000 Pa. As shown in fig. 7, the elastic modulus of the smart paste decreased significantly as the temperature increased.
Example 2
(1) 20g of a 47 ℃ low melting point alloy (in the composition indium, bismuth, tin, lead and cadmium) was weighed out and dissolved in 300mL of boiling deionized water until molten.
(2) And dispersing the molten low-melting-point alloy into boiling deionized water to obtain a suspension A.
(3) And (4) putting the suspension A into ice water for cooling, keeping the stirring state until the temperature is reduced to be lower than the melting point of the alloy, and standing until the suspension A is precipitated.
(4) And (4) extracting supernatant, adding a small amount of absolute ethyl alcohol, centrifuging, and drying in an oven to obtain the required low-melting-point alloy micro-particles.
(5) Repeating the four steps to obtain the low melting point alloy micron particles at 30 ℃. As shown in fig. 8-9, the particle size analysis and the micro-topography of the low melting point alloy micro-particles at 30 ℃.
(6) 0.9g of the low-melting-point alloy microparticles with the temperature of 47 ℃ and 0.45g of the low-melting-point alloy microparticles with the temperature of 30 ℃ are taken to be stirred and mixed with 0.1276g of PDMS SE 1700A part to prepare composite slurry B with the volume fraction of 60%.
(7) To the composite paste B, 0.01276g of PDMS SE1700B part was added in a mass ratio of 10:1 of PDMS SE170A part to B part to obtain a composite paste C, which was ready for 3D printing.
As shown in fig. 10, the melting point range of the elastomer of the smart material is shown.
Fig. 11 is a real object diagram of a 3D printing sample prepared from the composite paste C.
(8) The obtained mold was placed in an oven for drying.
As shown in fig. 12-13, the shear rate of the smart slurry was 1s-1～100s-1The phenomenon of shear thinning and the phenomenon of visco-elastic inversion occur when the shear pressure is 1 Pa-10000 Pa. As shown in fig. 14, the elastic modulus of the smart paste decreased two places significantly as the temperature increased.
Example 3
(1) 20g of a 47 ℃ low melting point alloy (in the composition indium, bismuth, tin, lead and cadmium) was weighed out and dissolved in 300mL of boiling deionized water until molten.
(2) And dispersing the molten low-melting-point alloy into boiling deionized water to obtain a suspension A.
(3) And (4) putting the suspension A into ice water for cooling, keeping the stirring state until the temperature is reduced to be lower than the melting point of the alloy, and standing until the suspension A is precipitated.
(4) And (4) extracting supernatant, adding a small amount of absolute ethyl alcohol, centrifuging, and drying in an oven to obtain the required low-melting-point alloy micro-particles.
(5) Repeating the four steps to obtain the low melting point alloy micron particles at 30 ℃.
(6) And (4) repeating the steps (1) to (4) to obtain the low-melting-point alloy micro-particles at 70 ℃. As shown in fig. 15-16, the particle size analysis and the micro-topography of the low melting point alloy micro-particles at 70 ℃.
(7) 0.5g of the low-melting-point alloy microparticles with the temperature of 47 ℃, 0.5g of the low-melting-point alloy microparticles with the temperature of 30 ℃, 0.5g of the low-melting-point alloy microparticles with the temperature of 70 ℃ and 0.1438g of PDMS SE 1700A are stirred and mixed to prepare composite slurry B with the volume fraction of 60%.
(8) The composite paste C was obtained by adding 0.01438g of PDMS SE1700B to the composite paste B at a mass ratio of PDMS SE 1700A to B of 10:1, and 3D printing was performed.
As shown in fig. 17, the melting point range of the elastomer of the smart material is shown.
Fig. 18 is a real object diagram of a 3D printing sample prepared from the composite paste C.
(9) The obtained mold was placed in an oven for drying.
As shown in FIGS. 19-20, the shear rate of the smart slurry was 1s-1～100s-1The phenomenon of shear thinning and the phenomenon of visco-elastic inversion occur when the shear pressure is 1 Pa-10000 Pa. As shown in fig. 21, the elastic modulus of the smart paste decreased two places significantly as the temperature increased.
Example 4
(1) 20g of a 47 ℃ low melting point alloy (in the composition indium, bismuth, tin, lead and cadmium) was weighed out and dissolved in 300mL of boiling deionized water until molten.
(2) And dispersing the molten low-melting-point alloy into boiling deionized water to obtain a suspension A.
(3) And (4) putting the suspension A into ice water for cooling, keeping the stirring state until the temperature is reduced to be lower than the melting point of the alloy, and standing until the suspension A is precipitated.
(4) And (4) extracting supernatant, adding a small amount of absolute ethyl alcohol, centrifuging, and drying in an oven to obtain the required low-melting-point alloy micro-particles.
(5) Repeating the four steps to obtain the low melting point alloy micron particles at 30 ℃.
(6) And (4) repeating the steps (1) to (4) to obtain the low-melting-point alloy micro-particles at 70 ℃.
(7) 0.5g of the 47 ℃ low-melting-point alloy microparticles, 0.5g of the 30 ℃ low-melting-point alloy microparticles, and 0.5g of the 70 ℃ low-melting-point alloy microparticles are mixed with 0.234g of PDMS184 by stirring to prepare a composite slurry B with the volume fraction of 60%.
(8) The composite paste C was obtained by adding 0.01438g of PDMS184B to the composite paste B at a mass ratio of PDMS 184A to B of 10:1, and was ready for 3D printing.
Fig. 22 is a real object diagram of a 3D printing sample prepared from the composite paste C.
(9) The obtained mold was placed in an oven for drying.
Example 5
(1) 20g of a 47 ℃ low melting point alloy (in the composition indium, bismuth, tin, lead and cadmium) was weighed out and dissolved in 300mL of boiling deionized water until molten.
(2) And dispersing the molten low-melting-point alloy into boiling deionized water to obtain a suspension A.
(3) And (4) putting the suspension A into ice water for cooling, keeping the stirring state until the temperature is reduced to be lower than the melting point of the alloy, and standing until the suspension A is precipitated.
(4) And (4) extracting supernatant, adding a small amount of absolute ethyl alcohol, centrifuging, and drying in an oven to obtain the required low-melting-point alloy micro-particles.
(5) Repeating the four steps to obtain the low melting point alloy micron particles at 30 ℃.
(6) And (4) repeating the steps (1) to (4) to obtain the low-melting-point alloy micro-particles at 70 ℃.
(7) 0.5g of the low-melting-point alloy micro-particles at 47 ℃, 0.5g of the low-melting-point alloy micro-particles at 30 ℃ and 0.5g of the low-melting-point alloy micro-particles at 70 ℃ are taken to be stirred and mixed with 0.269g of Ecoflex 00-30A part to prepare composite slurry B with the volume fraction of 60%.
(8) 0.01438g of Ecoflex 00-30B part was added to composite paste B in a mass ratio of 1:1 of Ecoflex 00-30A part to B part to obtain composite paste C, which was ready for 3D printing.
Fig. 23 is a real object diagram of a 3D printing sample prepared from the composite paste C.
(9) The obtained mold was placed in an oven for drying.
Example 6
(1) 20g of a 47 ℃ low melting point alloy (in the composition indium, bismuth, tin, lead and cadmium) was weighed out and dissolved in 300mL of boiling deionized water until molten.
(2) And dispersing the molten low-melting-point alloy into boiling deionized water to obtain a suspension A.
(3) And (4) putting the suspension A into ice water for cooling, keeping the stirring state until the temperature is reduced to be lower than the melting point of the alloy, and standing until the suspension A is precipitated.
(4) And (4) extracting supernatant, adding a small amount of absolute ethyl alcohol, centrifuging, and drying in an oven to obtain the required low-melting-point alloy micro-particles.
(5) Repeating the four steps to obtain the low melting point alloy micron particles at 30 ℃.
(6) And (4) repeating the steps (1) to (4) to obtain the low-melting-point alloy micro-particles at 70 ℃.
(7) 0.5g of the low-melting-point alloy micro-particles at 47 ℃, 0.5g of the low-melting-point alloy micro-particles at 30 ℃, 0.5g of the low-melting-point alloy micro-particles at 70 ℃ and 0.269g of Ecoflex 00-50A are stirred and mixed to prepare composite slurry B with the volume fraction of 60%.
(8) 0.01438g of Ecoflex 00-50B part was added to composite paste B in a mass ratio of 1:1 of Ecoflex 00-50A part to B part to obtain composite paste C, which was ready for 3D printing.
Fig. 24 is a real object diagram of a 3D printing sample prepared from the composite paste C.
(9) The obtained mold was placed in an oven for drying.
In conclusion, according to the technical scheme, the multistable rigidity-variable intelligent material has the advantages of good stability and excellent thermal conductivity under each stable state, the preparation method is simple and easy to implement, the cost is low, and the multistable rigidity-variable intelligent material can be used as a material for 3D printing.
In addition, the inventor also refers to examples 1-6, tests are carried out by using other raw materials and conditions listed in the specification, and the intelligent material with good stability and excellent heat conductivity and multistable variable rigidity is also successfully prepared.
It should be noted that, in the present context, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in steps, processes, methods or experimental facilities including the element.
It should be understood that the above preferred embodiments are only for illustrating the present invention, and other embodiments of the present invention are also possible, but those skilled in the art will be able to adopt the technical teaching of the present invention and equivalent alternatives or modifications thereof without departing from the scope of the present invention.
Claims (10)
1. A multistable variable stiffness smart material is characterized by comprising a dispersed phase and a dispersion medium, wherein the dispersed phase is uniformly dispersed in the dispersion medium, the dispersed phase comprises low-melting-point alloy particles, and the dispersion medium comprises an elastomer.
2. A multistable variable stiffness smart material according to claim 1 wherein: the dispersed phase comprises low-melting-point alloy particles with different melting points, preferably, the melting point of the low-melting-point alloy particles in the intelligent material is lower than 200 ℃, and preferably 30-70 ℃.
3. A multistable variable stiffness smart material according to claim 1 wherein: the content of the low-melting-point alloy particles in the multistable variable-rigidity intelligent material is 20-60 vol%, and preferably 40-60 vol%.
4. A multistable variable stiffness smart material according to claim 1 wherein: the low-melting-point alloy particles are low-melting-point alloy micron particles and contain indium, bismuth, tin, lead and cadmium elements, and the particle size of the low-melting-point alloy particles is 1-100 mu m.
5. A multistable variable stiffness smart material according to claim 1 wherein: the elastomer comprises any one or the combination of more than two of PDMS SE1700, PDMS184, Ecoflex 00-30 and Ecoflex 00-50.
6. A multistable variable stiffness smart material according to claim 1 wherein: the multistable variable-rigidity intelligent material has the phenomena of shear thinning and visco-elastic inversion in a slurry state; and/or the multistable rigidity-variable intelligent material can realize rigidity change under different temperature stimuli after being cured.
7. A method for preparing a multistable variable stiffness smart material according to any one of claims 1 to 6, comprising: and uniformly mixing the low-melting-point alloy particles and the elastomer prepolymer to prepare intelligent material slurry, and then curing to obtain the multistable variable-rigidity intelligent material.
8. The production method according to claim 7, characterized by comprising:
providing a first mixing system comprising low melting point alloy particles and a first prepolymer component;
and adding a second prepolymer component into the first mixed system, uniformly stirring and mixing to form a second mixed system to obtain intelligent material slurry capable of being printed in a 3D mode, and then curing to obtain the multistable rigidity-variable intelligent material elastomer.
9. The method of claim 8, wherein: the stirring time is 20-30 min, and preferably, the curing time is 8-12 h; and/or, the preparation method further comprises the following steps: adding an organic solvent to the first mixed system, the organic solvent comprising hexane.
10. Use of a multistable variable stiffness smart material according to any one of claims 1 to 6 in the field of 3D printing.
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