CN113831736A - A kind of multi-stable variable stiffness smart material and its preparation method and application - Google Patents

A kind of multi-stable variable stiffness smart material and its preparation method and application Download PDF

Info

Publication number
CN113831736A
CN113831736A CN202111134383.8A CN202111134383A CN113831736A CN 113831736 A CN113831736 A CN 113831736A CN 202111134383 A CN202111134383 A CN 202111134383A CN 113831736 A CN113831736 A CN 113831736A
Authority
CN
China
Prior art keywords
low
smart material
point alloy
melting
melting point
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111134383.8A
Other languages
Chinese (zh)
Inventor
龙菲
程昱川
方明权
邵迎春
赵自辉
马思维
郭建军
孙爱华
许高杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Institute of Material Technology and Engineering of CAS
Original Assignee
Ningbo Institute of Material Technology and Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Institute of Material Technology and Engineering of CAS filed Critical Ningbo Institute of Material Technology and Engineering of CAS
Priority to CN202111134383.8A priority Critical patent/CN113831736A/en
Publication of CN113831736A publication Critical patent/CN113831736A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

本发明公开了一种多稳态可变刚度的智能材料及其制备方法与应用。所述多稳态可变刚度的智能材料包括分散相和分散介质，所述分散相均匀分散于分散介质中，所述分散相包括不同熔点的低熔点合金颗粒，所述分散介质包括弹性体。本发明提供的多稳态可变刚度的智能材料在浆料状态时存在剪切稀变和黏弹逆变的现象，可用于3D打印技术中；固化后，给予不同温度刺激其刚度可发生相应程度的改变。本发明的智能材料反应灵敏，在各个稳态下稳定性好，导热性优异，并且制备方法简单易行，成本低廉，还可作为3D打印的材料。

Figure 202111134383

The invention discloses a multi-stable and variable-stiffness intelligent material and a preparation method and application thereof. The multistable variable stiffness smart material includes a dispersed phase and a dispersion medium, 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. The multi-stable variable stiffness smart material provided by the present invention has shear thinning and viscoelastic inversion phenomena in the slurry state, and can be used in 3D printing technology; after curing, the stiffness can be correspondingly stimulated by different temperatures degree of change. The smart material of the invention has sensitive response, good stability in various steady states, excellent thermal conductivity, simple and easy preparation method, low cost, and can also be used as a material for 3D printing.

Figure 202111134383

Description

Multistable rigidity-variable intelligent material and preparation method and application thereof
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)

1.一种多稳态可变刚度的智能材料，其特征在于包括分散相和分散介质，所述分散相均匀分散于所述分散介质中，所述分散相包括低熔点合金颗粒，所述分散介质包括弹性体。1. A multi-stable variable stiffness smart material, characterized in that it comprises a dispersed phase and a dispersion medium, the dispersed phase is uniformly dispersed in the dispersion medium, the dispersed phase comprises low melting point alloy particles, and the dispersed phase is dispersed. The medium includes an elastomer. 2.根据权利要求1所述的多稳态可变刚度的智能材料，其特征在于：所述分散相包括不同熔点的低熔点合金颗粒，优选的，所述智能材料中低熔点合金颗粒的熔点低于200℃，优选为30～70℃。2. The multi-stable 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 smart material It is lower than 200 degreeC, Preferably it is 30-70 degreeC. 3.根据权利要求1所述的多稳态可变刚度的智能材料，其特征在于：所述多稳态可变刚度的智能材料中低熔点合金颗粒的含量为20～60vol％，优选为40～60vol％。3 . The multi-stable variable stiffness smart material according to claim 1 , wherein the content of the low-melting alloy particles in the multi-stable variable stiffness smart material is 20-60 vol %, preferably 40 vol %. 4 . ~60vol%. 4.根据权利要求1所述的多稳态可变刚度的智能材料，其特征在于：所述低熔点合金颗粒为低熔点合金微米颗粒，包含铟、铋、锡、铅和镉元素，所述低熔点合金颗粒的粒径为1～100μm。4 . The multi-stable variable stiffness smart material according to claim 1 , wherein the low-melting alloy particles are low-melting alloy micro-particles, including indium, bismuth, tin, lead and cadmium, and the The particle size of the low melting point alloy particles is 1 to 100 μm. 5.根据权利要求1所述的多稳态可变刚度的智能材料，其特征在于：所述弹性体包括PDMS SE1700、PDMS 184、Ecoflex 00-30、Ecoflex 00-50中的任意一种或两种以上的组合。5 . The multi-stable variable stiffness smart material according to claim 1 , wherein the elastomer comprises any one or both of PDMS SE1700, PDMS 184, Ecoflex 00-30, and Ecoflex 00-50. 6 . more than one combination. 6.根据权利要求1所述的多稳态可变刚度的智能材料，其特征在于：所述多稳态可变刚度的智能材料在浆料状态时存在剪切稀变和黏弹逆变的现象；和/或，所述多稳态可变刚度的智能材料在固化后，能够在不同温度刺激下实现刚度的改变。6 . The multi-stable variable stiffness smart material according to claim 1 , wherein the multi-stable variable stiffness smart material has shear thinning and viscoelastic inversion in a slurry state. 7 . and/or, after curing, the multi-stable variable stiffness smart material can realize stiffness changes under different temperature stimuli. 7.如权利要求1-6中任一项所述多稳态可变刚度的智能材料的制备方法，其特征在于包括：将低熔点合金颗粒和弹性体预聚体混合均匀，制得智能材料浆料，之后固化，得到多稳态可变刚度的智能材料。7. The method for preparing a multi-stable and variable-stiffness smart material according to any one of claims 1 to 6, characterized in that it comprises: uniformly mixing low-melting alloy particles and an elastomer prepolymer to prepare the smart material The slurry, which is then cured, yields a multistable variable stiffness smart material. 8.根据权利要求7所述的制备方法，其特征在于包括：8. preparation method according to claim 7 is characterized in that comprising: 提供包含低熔点合金颗粒与第一预聚物组分的第一混合体系；providing a first mixing system comprising low melting point alloy particles and a first prepolymer component; 向所述第一混合体系中加入第二预聚物组分，通过搅拌混合均匀形成第二混合体系，得到可3D打印的智能材料浆料，之后进行固化，得到多稳态可变刚度的智能材料弹性体。A second prepolymer component is added to the first mixing system, and a second mixing system is formed by stirring and mixing uniformly to obtain a 3D-printable smart material slurry, which is then cured to obtain a multi-stable and variable-stiffness smart material. Material Elastomer. 9.根据权利要求8所述的制备方法，其特征在于：所述搅拌的时间为20～30min，优选的，所述固化的时间为8h～12h；和/或，所述制备方法还包括：向所述第一混合体系中加入有机溶剂，所述有机溶剂包括己烷。9. The preparation method according to claim 8, characterized in that: the stirring time is 20-30min, preferably, the curing time is 8h-12h; and/or the preparation method further comprises: An organic solvent is added to the first mixed system, the organic solvent including hexane. 10.权利要求1-6中任一项所述多稳态可变刚度的智能材料于3D打印领域中的应用。10. The application of the multi-stable variable stiffness smart material according to any one of claims 1 to 6 in the field of 3D printing.
CN202111134383.8A 2021-09-27 2021-09-27 A kind of multi-stable variable stiffness smart material and its preparation method and application Pending CN113831736A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111134383.8A CN113831736A (en) 2021-09-27 2021-09-27 A kind of multi-stable variable stiffness smart material and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111134383.8A CN113831736A (en) 2021-09-27 2021-09-27 A kind of multi-stable variable stiffness smart material and its preparation method and application

Publications (1)

Publication Number Publication Date
CN113831736A true CN113831736A (en) 2021-12-24

Family

ID=78970545

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111134383.8A Pending CN113831736A (en) 2021-09-27 2021-09-27 A kind of multi-stable variable stiffness smart material and its preparation method and application

Country Status (1)

Country Link
CN (1) CN113831736A (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030234074A1 (en) * 2002-06-25 2003-12-25 Bhagwagar Dorab Edul Thermal interface materials and methods for their preparation and use
CN102181170A (en) * 2011-04-25 2011-09-14 东北大学 Resin-based Ni-Co-Mn-In alloy composite material and preparation method thereof
CN107365430A (en) * 2016-05-12 2017-11-21 云南科威液态金属谷研发有限公司 Application and electrically conductive elastic deformation vulcanization rubber of the liquid metal in conductive rubber is prepared
CN110079035A (en) * 2019-04-15 2019-08-02 华南理工大学 Rubber/low-melting alloy/nano carbon composite material with three-dimensional conductive network and preparation method thereof
CN110564157A (en) * 2019-09-05 2019-12-13 西安电子科技大学 Mixed material of liquid metal polymer and preparation method thereof
US20200216630A1 (en) * 2019-01-04 2020-07-09 Syracuse University Polymeric composites with tunable properties
CN113265121A (en) * 2021-05-18 2021-08-17 吉林大学 Variable-stiffness composite material based on temperature change and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030234074A1 (en) * 2002-06-25 2003-12-25 Bhagwagar Dorab Edul Thermal interface materials and methods for their preparation and use
CN102181170A (en) * 2011-04-25 2011-09-14 东北大学 Resin-based Ni-Co-Mn-In alloy composite material and preparation method thereof
CN107365430A (en) * 2016-05-12 2017-11-21 云南科威液态金属谷研发有限公司 Application and electrically conductive elastic deformation vulcanization rubber of the liquid metal in conductive rubber is prepared
US20200216630A1 (en) * 2019-01-04 2020-07-09 Syracuse University Polymeric composites with tunable properties
CN110079035A (en) * 2019-04-15 2019-08-02 华南理工大学 Rubber/low-melting alloy/nano carbon composite material with three-dimensional conductive network and preparation method thereof
CN110564157A (en) * 2019-09-05 2019-12-13 西安电子科技大学 Mixed material of liquid metal polymer and preparation method thereof
CN113265121A (en) * 2021-05-18 2021-08-17 吉林大学 Variable-stiffness composite material based on temperature change and preparation method thereof

Similar Documents

Publication Publication Date Title
Chuang et al. Rheological behavior of polymer blends
JP3251585B2 (en) Non-adhesive elastomeric acrylate microspheres
Roos et al. Effect of the presence of diblock copolymer on the nonlinear elastic and viscoelastic properties of elastomeric triblock copolymers
Colombini et al. Influence of the particle size and particle size ratio on the morphology and viscoelastic properties of bimodal hard/soft latex blends
CN103613706B (en) Monodisperse ternary copolymer microspheres and preparation method thereof
CN110819308B (en) Phase-change energy-storage microcapsule, and preparation method and application thereof
CN102477138B (en) Silica cross-linking shape memory polymer material
CN111763292A (en) A kind of snowman-shaped Janus particle and preparation method thereof
CN104072722A (en) Shear thickening fluid microcapsule, reinforced high molecular material and preparation method and application of shear thickening fluid microcapsule and reinforced high molecular material
CN113831736A (en) A kind of multi-stable variable stiffness smart material and its preparation method and application
Canetta et al. A comparison of tackified, miniemulsion core− shell acrylic latex films with corresponding particle-blend films: structure− property relationships
CN113429746B (en) Low-temperature-resistant slow-bonding agent and preparation method thereof
CN109627499B (en) A kind of preparation method of biomass composite gel with shear thickening effect
Ghasemirad et al. How do soft nanoparticles affect temperature-induced nonlinearity of a UCST copolymer blend?
CN119798997A (en) A smart material and its preparation method and application
CN106334503B (en) A kind of preparation method for reviewing one's lessons by oneself multiplexing epoxy resin micro-capsule
CN103087541A (en) Production method of SBS (Styrene-butadiene-styrene block copolymer) dissolved and rare earth mixed accessory ingredient for pavement modified asphalt
CN113502139B (en) Low-temperature-resistant slow-bonding prestressed tendon
CN109734547A (en) A kind of original position hyper-branched polyester graft modification explosive and its preparation method and application
Cai et al. Model filled rubber. II. Particle composition dependence of suspension rheology
CN104030947B (en) A kind of sulfonate type reactive polymer emulsifier and its preparation method and application
CN111500243B (en) High-performance fiber-reinforced polyurethane conductive pressure-sensitive adhesive and preparation method thereof
Wilson et al. Temperature modulated polymer nanoparticle bonding: a numerical and experimental study
CN110093021A (en) A polylactic acid modified shape memory intelligent deformation material and its preparation method
WO2022070868A1 (en) Thickener for cyanoacrylate adhesive

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20211224

RJ01 Rejection of invention patent application after publication