![]() | This article may be too technical for most readers to understand.(May 2017) |
Liquid crystal elastomers (LCEs) are slightly crosslinked liquid crystalline polymer networks. These materials combine the entropy elasticity of an elastomer with the self-organization of the liquid crystalline phase. In liquid crystalline elastomers, the mesogens can either be part of the polymer chain (main-chain liquid crystalline elastomers) or are attached via an alkyl spacer (side-chain liquid crystalline elastomers). [1]
Due to their actuation properties, liquid crystalline elastomers are attractive candidates for the use as artificial muscles or microrobots.
LCE were predicted by Pierre-Gilles de Gennes in 1975 and first synthesized by Heino Finkelmann. [2]
In the temperature range of the liquid crystalline phase, the mesogen's orientation forces the polymer chains into a stretched conformation. Heating the sample above the clearing temperature destroys this orientation and the polymer backbone can relax into (the more favored) random coil conformation. That can lead to a macroscopic, reversible deformation. Good actuation requires a good alignment of the domains' directors before cross-linking. This can be achieved by: stretching of the prepolymerized sample, [3] photo-alignment layers, [4] magnetic or electric fields and microfluidics. [5] [6]
Because of their anisotropy, the mechanical response of aligned nematic LCEs varies depending upon the direction of applied stress. When stress is applied along the direction of alignment (parallel to the director, ), the strain responds in a linear fashion, with a slope dictated by the material’s Young’s modulus. This linear stress-strain behavior continues until the material reaches its yield stress, at which point it may neck or strain harden before eventually failing. The shape of the stress-strain curve for LCEs stretched parallel to their aligned direction matches that of most classical rubbers and can be described using treatments such as rubber elasticity.
In contrast, when stress is applied perpendicular to the direction of alignment, the strain behavior exhibits a drastically different response. For an unconstrained LCE, after an initial region where the stress-strain response matches that of classical rubbers, the material exhibits a large plateau where near-constant stress leads to ever-increasing strain. The term “soft elasticity” describes this large plateau region. [7] After a critical strain is reached in this region, the stress-strain response returns to that of LCEs stretched in a direction parallel to their director.
The theory used to describe soft elasticity first arose to explain experimental observations of the phenomena in unconstrained LCEs that reoriented in the presence of an external electric field. [8] The theory of soft elasticity states that when an LCE is stretched in a direction perpendicular to its alignment direction, its chains rotate and reorient to align in the direction of applied stress. Assuming that the LCE chains are allowed to freely move in all three dimensions, this reorientation occurs without a change in the elastic free energy of the system. This implies that there is no energy barrier to the rotation of the LCE chains, meaning that zero-stress would be required to fully reorient them.
Experimentally, a small but non-zero stress is required to induce soft elasticity and achieve this chain rotation. This deviation from the theoretical prediction arises due to the fact that real LCEs are not truly free in all three dimensions, and are instead geometrically restricted by neighboring chains. As a result, some small, finite stress is necessary in experimental systems to induce chain reorientation. Once the chain has fully rotated and is aligned parallel to the direction of applied stress, the subsequent stress-strain response is again described by that of rubber elasticity.
Soft elasticity has also been exploited to develop materials with unique and useful properties. By controlling the local liquid crystal alignment in an LCE, films with spatially varying mechanical anisotropy can be fabricated. [9] When strained, different regions of these chemically homogeneous films stretch to different extents as a result of the relative orientation of the director to the applied stress. This has the effect of localizing deformation to predetermined regions. This predictable deformation is useful because it allows for the design of soft electronic devices that are globally compliant but locally stiff, ensuring important components do not break when the film is deformed.
Upon transitioning from a liquid crystalline phase to an isotropic (orientationally disordered) phase, or vice versa, an LCE sample will spontaneously deform into a different shape. For example, if a nematic LCE transitions to its isotropic state, it will undergo contraction parallel to its director and expansion in the perpendicular plane. Any stimulus that drives the ordered ⇔ disordered phase transition can induce such actuation (or 'activation'). A patterned director field thus allows an LCE sample to morph into a radically different shape upon stimulation, returning to its original shape when the stimulus is removed. Due to its reversibility, large strain, and the potential to prescribe extremely complex shape changes, this shape morphing effect has attracted much interest as a potential tool for creating soft machines such as actuators or robots. As a simple example, consider a thin disk-shaped LCE sheet with a 'concentric-circles' (everywhere azimuthal) in-plane director pattern. Upon heating to the isotropic state, the disk will rise into a cone, which can be used to lift a weight thousands of times the weight of the LCE itself. [10]
Beside the thermal deformation of a sample, a light-responsive actuation can be obtained for samples by incorporating azobenzenes in the liquid crystalline phase. [11] The phase transition temperature of an azo-liquid crystalline elastomer can be reduced due to the trans-cis isomerization of the azobenzenes during UV-irradiation and thus the liquid crystalline phase can be destroyed isothermally. For liquid crystalline elastomers with a high azo-concentration, a light-responsive change of the sample's length of up to 40% could be observed. [12] [13]
LCE have been examined for use as a light-weight energy absorption material. Tilted slabs of LCE were attached to stiff materials, approximating a honeycomb lattice. Arranged in multiple layers, allowed the material to buckle at different rates on impact, efficiently dissipating energy across the structure. Increasing the number of layers increased absorption capacity. [14] [15]
Young's modulus is a mechanical property of solid materials that measures the tensile or compressive stiffness when the force is applied lengthwise. It is the modulus of elasticity for tension or axial compression. Young's modulus is defined as the ratio of the stress applied to the object and the resulting axial strain in the linear elastic region of the material.
In engineering, deformation refers to the change in size or shape of an object. Displacements are the absolute change in position of a point on the object. Deflection is the relative change in external displacements on an object. Strain is the relative internal change in shape of an infinitesimal cube of material and can be expressed as a non-dimensional change in length or angle of distortion of the cube. Strains are related to the forces acting on the cube, which are known as stress, by a stress-strain curve. The relationship between stress and strain is generally linear and reversible up until the yield point and the deformation is elastic. The linear relationship for a material is known as Young's modulus. Above the yield point, some degree of permanent distortion remains after unloading and is termed plastic deformation. The determination of the stress and strain throughout a solid object is given by the field of strength of materials and for a structure by structural analysis.
In physics and materials science, elasticity is the ability of a body to resist a distorting influence and to return to its original size and shape when that influence or force is removed. Solid objects will deform when adequate loads are applied to them; if the material is elastic, the object will return to its initial shape and size after removal. This is in contrast to plasticity, in which the object fails to do so and instead remains in its deformed state.
Soft matter or soft condensed matter is a subfield of condensed matter comprising a variety of physical systems that are deformed or structurally altered by thermal or mechanical stress of the magnitude of thermal fluctuations. These materials share an important common feature in that predominant physical behaviors occur at an energy scale comparable with room temperature thermal energy, and that entropy is considered the dominant factor. At these temperatures, quantum aspects are generally unimportant. Soft materials include liquids, colloids, polymers, foams, gels, granular materials, liquid crystals, flesh, and a number of biomaterials. When soft materials interact favorably with surfaces, they become squashed without an external compressive force. Pierre-Gilles de Gennes, who has been called the "founding father of soft matter," received the Nobel Prize in Physics in 1991 for discovering that methods developed for studying order phenomena in simple systems can be generalized to the more complex cases found in soft matter, in particular, to the behaviors of liquid crystals and polymers.
In materials science and continuum mechanics, viscoelasticity is the property of materials that exhibit both viscous and elastic characteristics when undergoing deformation. Viscous materials, like water, resist shear flow and strain linearly with time when a stress is applied. Elastic materials strain when stretched and immediately return to their original state once the stress is removed.
An elastomer is a polymer with viscoelasticity and with weak intermolecular forces, generally low Young's modulus (E) and high failure strain compared with other materials. The term, a portmanteau of elastic polymer, is often used interchangeably with rubber, although the latter is preferred when referring to vulcanisates. Each of the monomers which link to form the polymer is usually a compound of several elements among carbon, hydrogen, oxygen and silicon. Elastomers are amorphous polymers maintained above their glass transition temperature, so that considerable molecular reconformation is feasible without breaking of covalent bonds. At ambient temperatures, such rubbers are thus relatively compliant and deformable. Their primary uses are for seals, adhesives and molded flexible parts.
Smart materials, also called intelligent or responsive materials, are designed materials that have one or more properties that can be significantly changed in a controlled fashion by external stimuli, such as stress, moisture, electric or magnetic fields, light, temperature, pH, or chemical compounds. Smart materials are the basis of many applications, including sensors and actuators, or artificial muscles, particularly as electroactive polymers (EAPs).
Polydimethylsiloxane (PDMS), also known as dimethylpolysiloxane or dimethicone, is a silicone polymer with a wide variety of uses, from cosmetics to industrial lubrication.
An electroactive polymer (EAP) is a polymer that exhibits a change in size or shape when stimulated by an electric field. The most common applications of this type of material are in actuators and sensors. A typical characteristic property of an EAP is that they will undergo a large amount of deformation while sustaining large forces.
A rheometer is a laboratory device used to measure the way in which a viscous fluid flows in response to applied forces. It is used for those fluids which cannot be defined by a single value of viscosity and therefore require more parameters to be set and measured than is the case for a viscometer. It measures the rheology of the fluid.
Liquid crystal polymers (LCPs) are polymers with the property of liquid crystal, usually containing aromatic rings as mesogens. Despite uncrosslinked LCPs, polymeric materials like liquid crystal elastomers (LCEs) and liquid crystal networks (LCNs) can exhibit liquid crystallinity as well. They are both crosslinked LCPs but have different cross link density. They are widely used in the digital display market. In addition, LCPs have unique properties like thermal actuation, anisotropic swelling, and soft elasticity. Therefore, they can be good actuators and sensors. One of the most famous and classical applications for LCPs is Kevlar, a strong but light fiber with wide applications, notably bulletproof vests.
Strain crystallization is a phenomenon in which an initially amorphous solid material undergoes a phase transformation due to the application of strain. Strain crystallization occurs in natural rubber, as well as other elastomers and polymers. The phenomenon has important effects on strength and fatigue properties.
Rubber elasticity refers to a property of crosslinked rubber: it can be stretched by up to a factor of 10 from its original length and, when released, returns very nearly to its original length. This can be repeated many times with no apparent degradation to the rubber. Rubber is a member of a larger class of materials called elastomers and it is difficult to overestimate their economic and technological importance. Elastomers have played a key role in the development of new technologies in the 20th century and make a substantial contribution to the global economy. Rubber elasticity is produced by several complex molecular processes and its explanation requires a knowledge of advanced mathematics, chemistry and statistical physics, particularly the concept of entropy. Entropy may be thought of as a measure of the thermal energy that is stored in a molecule. Common rubbers, such as polybutadiene and polyisoprene, are produced by a process called polymerization. Very long molecules (polymers) are built up sequentially by adding short molecular backbone units through chemical reactions. A rubber polymer follows a random, zigzag path in three dimensions, intermingling with many other rubber molecules. An elastomer is created by the addition of a few percent of a cross linking molecule such as sulfur. When heated, the crosslinking molecule causes a reaction that chemically joins (bonds) two of the rubber molecules together at some point. Because the rubber molecules are so long, each one participates in many crosslinks with many other rubber molecules forming a continuous molecular network. As a rubber band is stretched, some of the network chains are forced to become straight and this causes a decrease in their entropy. It is this decrease in entropy that gives rise to the elastic force in the network chains.
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Polymer characterization is the analytical branch of polymer science.
Ferroelectric polymers are a group of crystalline polar polymers that are also ferroelectric, meaning that they maintain a permanent electric polarization that can be reversed, or switched, in an external electric field.
Crystallization of polymers is a process associated with partial alignment of their molecular chains. These chains fold together and form ordered regions called lamellae, which compose larger spheroidal structures named spherulites. Polymers can crystallize upon cooling from melting, mechanical stretching or solvent evaporation. Crystallization affects optical, mechanical, thermal and chemical properties of the polymer. The degree of crystallinity is estimated by different analytical methods and it typically ranges between 10 and 80%, with crystallized polymers often called "semi-crystalline". The properties of semi-crystalline polymers are determined not only by the degree of crystallinity, but also by the size and orientation of the molecular chains.
Rheological weldability (RW) of thermoplastics considers the materials flow characteristics in determining the weldability of the given material. The process of welding thermal plastics requires three general steps, first is surface preparation. The second step is the application of heat and pressure to create intimate contact between the components being joined and initiate inter-molecular diffusion across the joint and the third step is cooling. RW can be used to determine the effectiveness of the second step of the process for given materials.
Soft robotics is a subfield of robotics that concerns the design, control, and fabrication of robots composed of compliant materials, instead of rigid links. In contrast to rigid-bodied robots built from metals, ceramics and hard plastics, the compliance of soft robots can improve their safety when working in close contact with humans.