The invention relates generally to polymer composites. More specifically, the invention relates to a composite having liquid metal inclusions dispersed within an elastic polymer, where the composite has electrical conductivity, permittivity, and thermal conductivity properties that differ from other elastomeric materials.
High compliance (low E) and elasticity (high ∈f) represent key challenges in the development of mechanically robust electronics that are compatible with natural human tissue for wearable computing, implantable devices, and physical human-machine interaction. Presently, soft and stretchable functionality can be introduced through so-called “deterministic” architectures in which thin flexible circuits are bonded to an elastomer substrate and buckled or patterned into wavy/serpentine planar geometries. Alternatively, solid metal wiring can be replaced with metal alloys that are liquid at room temperature. Liquid-phase gallium-indium alloys are popular for this “microfluidics” approach to stretchable electronics since they are non-toxic and form an oxide layer that aids in microcontact printing, electrode alignment, and 3D printing. Lastly, a common approach to stretchable electronics is to embed thin films of elastomer with a percolating network of conductive particulates, such as structured carbon black or silver nanoparticles, for example. However, their volumetric conductivity is poor compared to bulk conductors and improving conductivity by increasing the weight % of conductive filler increases the mechanical stiffness and brittleness of the material.
Soft electronic systems capable of dielectric behavior are also needed for new technologies such as wearable devices. Traditionally, the electronic properties of rubbery polymers like silicones, polyurethanes, or copolymers such as styrene ethylene butylene styrene are tailored by adding 10-30% by volume of inorganic fillers such as Ag powder, Ag-coated Ni microspheres, structured carbon black (CB), exfoliated graphite, carbon nanotubes, BaTiO3, TiO2, or other metallic, carbon-based, or ceramic micro/nanoparticles. Although rigid particles have been incorporated into silicones, urethanes, and acrylate-based elastomers to increase their dielectric constant, the loadings required to achieve significant electric property enhancement can degrade the mechanical properties of these soft and stretchable material systems. The inherently rigid nature of the inorganic filler particles creates a dramatic compliance mismatch with the soft, stretchable elastomer matrix that leads to internal stress concentrations, delamination, and friction that increase bulk rigidity, reduces extensibility, and results in inelastic stress-strain responses that can limit long term durability at the mesoscale. Other approaches have used fluid fillers to modify mechanical properties, but the electrical properties were not enhanced.
Similarly, efficient thermal transport is critical for applications involving soft electronics. However, heat transport within soft materials is limited by the dynamics of phonon transport, which results in a trade-off between thermal conductivity and compliance. For example, materials with high thermal conductivity are typically rigid and elastically incompatible with soft and mechanically deformable systems. In the general case of non-metallic and electrically insulating solids, this limitation arises from kinetic theory and the Newton-Laplace equation, which imply that thermal conductivity (k) will increase with a material's elastic modulus (E). For polymers like polyethylene, thermal conductivity can be enhanced through macromolecular chain alignment (from k˜0.3 to 100 W/m·K), but this also leads to a dramatic increase in elastic modulus from approximately 1 to 200 GPa. Likewise, glassy polymer blends have been engineered to increase thermal conductivity through interchain hydrogen bonding and relatively higher thermal conductivity has been observed in amorphous polythiophene (k˜4.4 W/m·K), but the high elastic modulus (E˜3 GPa) and low strain at failure (<5% strain) of films make them unsuitable for soft functional materials.
To overcome this fundamental tradeoff with thermal transport in soft materials, attempts have been made to engineer composites with various fillers, including metals, ceramics, carbon fibers, and nanomaterials such as carbon nanotubes and graphene. Although these composites exhibit increased thermal conductivity, they typically utilize rigid fillers that result in mechanically stiff materials that cannot support stretchable functionality and in the case of carbon based fillers, become electrically conductive even at low volume loadings, which can interfere with functionality. To date, the combination of low elastic modulus on the order of biological tissue, large mechanical deformability, and high thermal conductivity remains elusive.
It would therefore be advantageous to develop an elastomeric material with enhanced electrical and thermal properties, yet remains flexible.
According to embodiments of the present invention is a composite comprised of an elastomer having inclusions of a liquid metal. As a conductive filler, the liquid-phase metal alloy represents an alternative to rigid particulates and does not increase the stiffness and brittleness of the elastomeric composite. The composition of the composite eliminates the internal compliance mismatch of rigid fillers and thus preserves the mechanics of the host material, offering a unique combination of low mechanical rigidity and desirable electrical and thermal properties. These liquid-metal embedded elastomer composites can be tailored to match the elastic and rheological properties of soft synthetic materials and biological tissue to enable signal transduction, rigidity tuning, and a rich set of other functionalities for bio-compatible machines and electronics.
According to one embodiment of the present invention is a composite 101 comprising an elastomer 102 embedded with a plurality of liquid metal inclusions 103. The elastomer 102 can include materials such as polysiloxane (e.g. ‘silicone’, polydimethylsiloxane, RTV silicones), polyurethane, polyacrylate, natural (latex) rubber, block copolymer elastomers (e.g. styrene ethylene butylene styrene), thermoplastic elastomers (e.g. propylene-ethylene co-polymer), and other similar materials. The liquid metal 103 can include materials such as eutectic gallium indium (EGaIn), gallium-indium-tin (Galinstan), Indalloy, NewMerc, mercury, and other metals that are liquid at lower temperatures than other metals.
In one example embodiment, the composite 101 comprises a thin sheet of poly(dimethylsiloxane) (PDMS) embedded with microscopic inclusions of liquid-phase gallium-indium-tin (“Galinstan”; electrical conductivity, o=3.46×106 S*m−1, melting point=−19° C.) droplets 103. (See to
In another example embodiment, the liquid metal embedded elastomer composite 101 comprises a Pt-catalyzed silicone elastomer 102 embedded with a randomly distributed, polydisperse suspension of non-toxic, liquid-phase eutectic gallium-indium (EGaIn) microdroplets 103. In this embodiment of the composite 101, strain creates thermally conductive pathways through the in-situ elongation of the deformable liquid metal inclusions 103, which significantly enhances thermal conductivity in the stretching direction. For permanent (stress-free) and strain-controlled elongation of the liquid metal inclusions 103, this enhanced k is nearly 25-50× greater than the unfilled elastomer (0.20±0.01 W/m·K) and approaches the limit for the parallel rule of mixtures of an EGaIn-silicone composition without the aid of percolating networks. Referring to
Fabrication of the elastomer composite 101 comprises mixing the elastomer 102 and liquid metal 103 to ensure an even distribution of the liquid metal 103 within the elastomer 102. During mixing, the liquid metal 103 can form droplets suspended in the elastomer 102. Depending on the intended application, the components can be mixed until the metal droplets 103 are reduced to a desired size.
In one example embodiment, a composite 101 is fabricated by mixing Galinstan (Ga 68.5%, In 21.5%, Sn 10% by weight) with uncured PDMS (Sylgard® 184) using mixing techniques known in the art, such as with a mortar and pestle or through sonication. In this example embodiment, the ratio of the two materials is 1:1 by volume (6.6:1 Galinstan to PDMS by weight) and they are mixed until the Galinstan droplets are 2-30 μm in size, as shown in
To mix via sonication, in an alternative embodiment, the elastomer 102 (PDMS) and liquid metal 103 (Galistan) are combined at a weight ratio of 0.9 g to 6.6 g in a sealable polypropylene jar. Hexane (anhydrous, 95%) is the added, using 8 mL for a mixture of 1.8 g elastomer 102 and 13.2 g Galinstan. To distribute the polymer 102 and metal 103, the jar is sealed and shaken vigorously, before being placed in a bath sonicator (i.e. Branson B1510) for several hours. The mixture is checked periodically to ensure that the metal droplets 103 are not settling out. The mixture can be stirred or agitated to redistribute the components, if necessary. After several hours, the lid is removed, sonication continuing until the hexane evaporates. Once solvent free, the elastomer 102 curing agent is added (0.1 g per 0.9 g base) via stirring. This stirring will also disperse any large droplets 103 that have settled to the bottom of the jar. The PDMS-Galinstan composite 101 can then be formed to a desired shape.
Because the composite 101 is a thermoset with a long working time (≧30 min), multiple fabrication techniques can be used to pattern liquid metal materials, including 3D printing, soft lithography, laser ablation, or stencil lithography techniques. Thin films can also be prepared and, as an example, a stencil patterned EGaIn-silicone composite 101 is presented in
In a bulk virgin state, the closed-cell geometry of the composite 101 prevents conductivity between adjacent liquid metal inclusions 103. However, applying concentrated mechanical load, most notably through localized compression, causes the elastomer composite 101 to exhibit volumetric conductivity. Applying pressure to the composite 101 causes tearing or rupturing of the cell walls and the formation of a continuous network of Galinstan droplets (see
In one embodiment, the final composite 101 can be prepared using stencil lithography (mask depositon). Laser tape and backing is patterned using a laser cutter and placed tape side down onto a metal substrate prepared with mold release. An applicator is used to distribute the uncured composite 101 over the laser tape mask. Afterwards, the mask is removed and the metal substrate is placed on a hot plate set to 150° C. to cure for at least 1 hour. The cured composite 101 can then be removed with tweezers. An example of a comb capacitor with 1 mm wide fingers and gaps made through the mask deposition process is shown in
In an alternative embodiment, the composite 101 was fabricated with a 100 μm layer of elastomer 102 on the top and bottom surface, this layer deposited before and after the composite 101 using the thin film applicator. To induce conductivity, the composite 101 is placed between two 0.05 mm sheets of copper and a 9.5 mm steel rod is rolled along the surface. Similarly, the tip of a ball-point pen can be used directly on the surface to target select regions for conduction activation. With a conductive layer of composite 101 disposed between two non-conductive layers of elastomer 102, a flexible capacitor is created.
In yet another embodiment, the composite 101 is prepared by mixing the liquid metal 103 (eutectic Ga—In (EGaIn) alloy (75% Ga-25% In, by wt.) with uncured liquid silicone elastomer 102 (Ecoflex® 00-30, Smooth-On) or polyurethane (Vytaflex® 30, Smooth-On) at volume loadings (φ) of liquid metal 103 from 0 to 50%. In this embodiment, EGaIn is selected as the liquid metal 103 due to its low melting point (MP=15° C.), high electrical conductivity (σ=3.4×106 S/m), low viscosity (η=2 mPa·s), and low toxicity (compared to Hg). Additionally, EGaIn oxidizes in air to form a ˜1-3 nm thick Ga2O3 skin that allows the liquid droplets 103 to be broken apart and dispersed in solution without the need for emulsifying agents.
Optical microscopy and 3d X-ray imaging have shown a disordered but statistically uniform dispersion of liquid metal droplets 103 and the absence of percolating networks that could result in electrical conductivity or shorting. (See
The electrical polarizability of the LMEE composites 101 is crucial for their use as soft, stretchable electronic components.
For applications where thermal conductivity is required, the composite 101 according to one embodiment can exhibit a combination of high thermal conductivity (4.7±0.2 W/m·K under stress-free conditions; 9.8±0.8 W/m·K at 400% strain) with a low modulus (89±2 kPa after 200% pre-strain) and high strain limit (>600%). This approach overcomes the Newton-Laplace scaling since the inclusions have a thermal conductivity that is dominated by electrons, rather than phonons, and can deform with the surrounding matrix to support strain and thermal-mechanical coupling. Previously, it was shown that LM-embedded elastomer composites 101 can be engineered to exhibit dramatic enhancements in electrical permittivity and conductivity without sacrificing the elastic properties of the matrix elastomer. Others have designed materials that suffer from increased stiffness or lower thermal conductivity. Comparing previous results with the performance of the composite 101 (see
To assess the performance of the composite 101, thermal conductivity is measured using the transient hotwire (THW) method in which an embedded wire simultaneously acts as a resistive heat source and thermometer that measures the change in temperature (ΔT) as a function of time (t), which are related to thermal conductivity through the cylindrical heat diffusion equation. Experimental measurements are presented in
This configuration enables examination of the thermal-mechanical coupling between thermal conductivity and deformation. Upon stretching the unfilled (φ=0%) homogenous elastomer, the thermal conductivity in the direction of stretch (ky˜0.20 W/m·K) remains largely unchanged (
Furthermore, the composite 101 can be “programmed” to achieve permanently elongated liquid metal 103 inclusions in a stress-free state by stretching a virgin sample of composite 101 to 600% strain and then unloading to zero stress. An unrecoverable plastic strain of 210% is induced, enabling elongated inclusions 103 in an un-loaded (stress-free) state. As shown in
Such an unprecedented enhancement in k arises from the discovery of a unique thermal-mechanical coupling in which the deformable liquid metal inclusions 103 elongate into needle-like microstructures along the pre-strained or mechanically loaded direction to create enhanced thermally conductive pathways. When composites 101 with φ=30% and 50% liquid metal 103 (by vol.) are subjected to strains ranging from 0% to 400% in increments of 100%, the thermal conductivity in the y (stretching) direction increases by greater than a factor of five beyond 300% strain.
The observed anisotropic thermal-mechanical response is controlled by the directional change in aspect ratio of the liquid metal inclusions 103. Lastly, for all volume fractions, the composite 101 materials have an elastic modulus less than 90 kPa and can support uniaxial strains above 600%, properties that are similar to that of the homogeneous elastomer. The modest increase in elastic modulus (<20%) for the composites 101 can be attributed to surface tension at the liquid-solid interface.
As previously described, electrical conductivity can be induced in the composite 101 through compression, which causes the liquid metal inclusions 103 to coalesce within the elastomer 102. To assess the pressure-controlled transition from the non-conductive virgin state to a permanently conductive state, the composite 101 is compressed using a 3.2 mm diameter cylindrical probe. The resistance through the axis of loading is then measured. On average, conductivity is initiated with a surface pressure of 1.7 MPa (n=5 samples). Increasing the compressive stress causes the conductivity to monotonically increase due to further degradation of the closed-cell matrix structure. In addition to concentrated loading, conductivity can also be permanently induced by pressing and rolling a rigid cylinder into the sample, altering the electrical properties of the entire composite 101. In both cases, compression causes the material to darken and trace amounts of liquid metal 103 are sometimes observed to appear on the surface of the composite 101. Coating the material in a thin layer of elastomer 102 prevents this outflow of the liquid metal 103. Tension can also induce conductivity, but this occurs at very large strains that are close to the failure limit of of the material. Once compressed, the conductivity of the composite 101 is 1.05×104 S*m−1 and exhibits unique electromechanical coupling.
When loaded in tension, the electrical resistance R through the length of the composite 101 undergoes only modest increase, which implies that the volumetric conductivity σ=L/RA increases significantly with load (
Tensile tests were performed on the composite 101 and reveal highly nonlinear elastic deformation. As before, the assumption of incompressibility is used to calculate cross-sectional area and true stress. Large strains (100%) of a virgin specimen show strain hardening while loading, with a dramatic decrease in mechanical resistance during unloading (
These LMEE composites 101 are also able to undergo significant deformations. The LMEEs composites 101 are able to stretch to strains on the order of 600%, similar to that of the unfilled elastomer. The composite also exhibits very little hysteresis when comparing the loading and unloading curves. This suggests negligible internal friction and losses due to viscoelasticity.
The electrical response to mechanical deformation is a significant parameter for stretchable dielectrics.
It is observed that as the composite 101 is loaded in tension the capacitance increases by a factor of over 4.5 while the dielectric constant decreases from 18 to 9 when stretched from 0% to 700% strain. To further study the durability of the composite 101 as a dielectric material cyclic testing experiments were performed to 100% strain under tensile loading over 100 cycles (
In addition to exploring composites 101 with silicone elastomers 102, the composite's 101 behavior was also investigated using polyurethane elastomer 102 matrixes at high volume loadings (φ=50%). Compared to the silicone elastomer 102, the polyurethane-based composite 101 has a higher elastic modulus (E=780 kPa) and a lower average strain to break of 182%. However, the dielectric constant of the polyurethane composite 101 is found to be greater. Therefore, if extreme strains and moduli on the order of 100-200 kPa are not required, the general strategy developed for silicone-based composites 101 can be extended to polyurethane-based composites 101. The dielectric constant across the frequency range from 1-200 kHz for the polyurethane-based composites 101 at φ=50% is above 42. Additionally, the dissipation factor is below 0.1.
Referring again to
While the disclosure has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modification can be made therein without departing from the spirit and scope of the embodiments. Thus, it is intended that the present disclosure cover the modifications and variations of this disclosure provided they come within the scope of the appended claims and their equivalents.
This application claims the benefit under 35 U.S.C. §119 of Provisional Application Ser. No. 62/388,614, filed Feb. 2, 2016, and Provisional Application Ser. No. 62/496,288, filed Oct. 10, 2016, each of which is incorporated herein by reference.
This invention was made with government support under AFOSR No. FA9550-13-1-0123 and NASA No. NNX14A049G. The government has certain rights in this invention.
Number | Date | Country | |
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62388614 | Feb 2016 | US | |
62496288 | Oct 2016 | US |