Liquid Single Crystal Elastomers Research Articles

Programming Positive Mechanofluorescence in Liquid Crystalline Elastomers

Programming Positive Mechanofluorescence in Liquid Crystalline Elastomers

Amine-Acrylate Liquid Single Crystal Elastomers Reinforced by Hydrogen Bonding.

Liquid crystalline elastomers (LCEs) have been considered one of the most promising material concepts for artificial muscles. However, accomplishing actuation of LCEs requires macroscopic alignment of the liquid-crystalline orientation in the rubbery network, which imposes challenges in the materials chemistry and processing. A two-stage curing strategy has been the dominating approach during last three decades. Despite its many successes, the method is difficult in practice and requires delicate experiential skills, dealing with intrinsic fragility of intermediate gels after the first crosslinking stage. Here, a robust fabrication method for monodomain LCE based on the amine-acrylate aza-Michael addition is developed, involving two readily commercially available components with no catalyst. The method is based on the large kinetic difference of hydrogen addition in primary amines to acrylates, which offers a sufficient gap separating two stages of curing and enabling versatile mechanical alignment techniques for manufacturing monodomain LCE in both liquid and gel states. Importantly, the mechanically robust network, helping processability at a partial-crosslinking stage, is facilitated by the chemically generated hydrogen bonding all through the process, as a by-product of hydrogen addition. Such a facile two-component kit-like fabrication should aid researchers from various fields in the search for a practical and reliable process of making soft actuators.

Structural Features Guiding the Design of Liquid-Crystalline Elastomeric Fluorescent Force Sensors

Liquid single crystal elastomers (LSCEs) containing carbazole fluorogenic components alter their luminescence when they are stretched along the director direction. The differential luminescent behavior arises from the distinct interaction between the carbazole fluorophores and their local environment before and after the application of the mechanical input. Indeed, the uniaxial deformation of the material, along its anisotropic direction, forces a closer mesogen–fluorophore interaction, which leads to the quenching of the carbazole luminescence. Importantly, this intermolecular interaction is intimately related to the intrinsic order present in the LSCE. As a result, the amount of light emitted by the material in the form of fluorescence diminishes upon deformation. Thus, the application of mechanical stimuli to liquid-crystalline elastomers furnishes to two interconvertible states for the system with distinct optical properties (with either different emission color or fluorescence intensity). The initial state of the material is completely restored once the applied force is removed. In this way, this kind of macromolecular system can transduce mechanical events into detectable and processable optical signals, thus, having great potential as optical force sensors. In this context, the realization of the distinct structural factors that govern the interactions established between the mesogenic and fluorogenic units at the supramolecular level upon deformation is essential for the development of efficient LSCE-based force sensors. In fact, not only the density of carbazole units and their connection to the main polymer backbone, but also the presence of long range molecular order in the system and the type of mesophase exhibited by the LSCE are key factors for the conception of efficient force sensors based on these self-organized polymer networks. In this review, we present a comprehensive and systematic description of the different features that control the mechanoluminescent behavior of fluorescent liquid-crystalline elastomers and will guide the future design of LSCE-based force sensors with improved performances.

Highly Efficient Elastomeric Fluorescence Sensors for Force Detection

Carbazole-containing nematic liquid single crystal elastomers (LSCEs) alter their luminescence upon the application of an external mechanical force. Therefore, they are valuable flexible materials ...

Smectic‐B Liquid Single Crystal Elastomers as Efficient Optical Mechanotransducers

AbstractCarbazole‐based liquid single‐crystal elastomers (LSCEs) are valuable materials to convert mechanical forces into optical signals, i.e., optical mechanotransduction. The identification and rationalization of the different structural factors governing the mechanotransduction process are essential to guide the future design of these smart sensing materials. Herein, how the type of mesophase displayed by the elastomer impacts its transducing capabilities is explored. Remarkably, smectic‐B LSCEs are significantly more efficient mechanotransducers than their nematic analogs, independent of the length of the flexible spacer that connects the fluorogenic monomers to the main polymeric backbone. In this instance, the fluorogenic moieties are located within the smectic lamellae formed by the mesogenic units, thereby forcing a stronger interaction between both the platforms and resulting in a much more effective fluorescence quenching upon deformation.

Deuteron NMR resolved mesogen vs. crosslinker molecular order and reorientational exchange in liquid single crystal elastomers.

Differences in the temperature behaviour of orientational ordering of structurally equivalent side-chain liquid single crystal elastomers (LSCEs) with (2)H-labelled crosslinker and mesogen have been studied by deuteron quadrupole-perturbed NMR. The impact of nematic director reorientations on the deuteron NMR spectral shapes was analyzed in terms of a discrete reorientational exchange model. This provided for the determination of the degree of nematic director alignment and for the quantification of the influence of the reorientational exchange on the (2)H NMR spectra in terms of two parameters, the nematic director orientational dispersion parameter σθ and the motional effectiveness parameter α. A comparative analysis of model simulations and experimental spectra reveals that mesogenic molecules in LSCEs exhibit faster reorientational dynamics as compared to crosslinker molecules and that mesogens and crosslinkers exhibit a similar and rather substantial static director orientational disorder.

On the Non Linear Behaviour of Nematic Liquid Single Crystal Elastomers (NLSCE) Under Biaxial Mechanic and Electrical Force Fields

A continuum theory has been developed to give account of the three characteristic zones appearing in the “semisoft” behaviour of nematic single crystal elastomers under the effect of biaxial mechanic and electrical force fields considering higher order coupling terms. The analysis is based on a model which takes into account two coexistent coupled components showing a preferred direction. Two cases are analysed according to the type of input: stress and displacement. Bifurcation phenomena are predicted in the first case. Sress-strain curves show the characteristic features experimentally observed. The case where shear terms in the strain are considered is approximately analysed.

Optical mechanotransduction with carbazole-based luminescent liquid single-crystal elastomers.

Carbazole-based liquid single-crystal elastomers (LSCEs) are valuable fluorescent flexible materials to perform optical mechanotransduction under ambient conditions. Indeed, the covalent incorporation of carbazole derivatives into nematic LSCEs allows to tune their luminescence on demand under mechanical control in a quick and reversible fashion. Specifically, the fluorescence intensity for these materials can be switched back and forth in less than a second. Moreover, such a process can be performed several times without detecting any sign of fatigue in the system. In addition, these materials show excellent resistance to aging; 2 years after their preparation they exhibit the very same mechanofluorescent behavior as when freshly prepared. In fact, the here reported fluorescent systems are highly sensitive; the application of a force of 70 mN decreases the fluorescence in the elastomeric material by 7%. Thus, mechanical forces are attractive external stimuli to modulate the fluorescence of nematic elastomers rapidly and reversibly enabling thereby mechanotransduction.

Electromechanical behaviour of biaxially stretched nematic liquid single crystal elastomers

A slab of nematic-side-chain-liquid-single-crystal elastomer (NSCLSCE), with the director initially oriented in the z direction, is subjected to a pair of equal mechanical stretches and electrical force fields in x and y directions. These electric fields tend to make the rotation of the director easier after the application of the mechanical force field. A non-linear expression for the free energy density is used to obtain the interval of stretching for which the system becomes unstable. Also the value of the electric field for which the rotation of the director starts without stretching is obtained. A comparison is made with uniaxial stretched samples and with previous biaxial experimental findings.

Effect of co-monomers' relative concentration on self-assembling behaviour of side-chain liquid crystalline elastomers

A new series of liquid single crystal elastomers having a nematic–SmA and a direct isotropic–SmA phase transition.

Liquid single crystal elastomer/conducting polymer bilayer composite actuator: modelling and experiments

In order to integrate electroconductive properties in a Liquid Single Crystal Elastomer (LSCE) and to test direct actuation of the LSCE by Joule heating, we present a new bi-layered all-organic composite actuator based on the coupling of a nematic LSCE with a conductive polymer. The bending actuator is fabricated by depositing a thin conductive polymer layer of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) over the surface of a polysiloxane-based monodomain nematic LSCE film. Mechanical properties of PEDOT:PSS, better matched with LSCE ones compared with metals or inorganic nanoparticles used in other approaches, allowed us to develop an all-organic reliable millimetre-scale actuating composite. The thermally induced elongation/compression of the LSCE over 30% is exploited for the fabrication of bending actuators with curvature up to κ = 0.64 mm−1. The LSCE and the composite material are characterized as regards their thermo-mechanical and electrical properties. A model is introduced to describe bending of the composite as a function of the thermo-mechanical properties of the LSCE, and the model is assessed by comparing the model results with the experimental findings. Bending actuation via direct Joule heating of the composite is also assessed by supplying the necessary current (50 mA at 1.3 V) through wires connected to the composite. These results open new possibilities for the application of LCEs in the micro and soft robotics fields, as well as in the biomedical field.

Polar Liquid Crystal Elastomers Cross Linked Far from Thermodynamic Phase Transitions: Dislocation Loops in Smectic Clusters

Nematic networks with three different concentrations of polar and nonpolar mesogens and the same concentration of a novel cross-linking agent give rise to unusual liquid single crystal elastomers (LSCEs) that are transparent monodomain nematic networks with smectic clusters. The largest spontaneous length change is observed in the sample with 70 mol% of the polar mesogen which also has the highest glass transition temperature and smectic clusters with a slowly increasing but nearly constant layer spacing on cooling from 90°C to 25°C. X-ray scattering intensity from smectic clusters with layer spacings that monotonically increase on cooling first increases to a maximum atT*~60∘C corresponding to clusters of about 30 layers. BelowT∗, the scattering intensity decreases as the number of layers in a cluster decreases. To account for this surprising nonlinear behavior that correlates with nonlinear features of the networks’ macroscopic spontaneous shape change and birefringence, a model is proposed where dislocations form in the layers atT∗. BelowT∗, more dislocations form to break down the layer structure. The possibility of dislocation formation atT∗independent of mesogenic concentrations is attributed to a conformational change in the crosslinker which is present at the same concentration in the three LSCEs.

First liquid single crystal elastomer containing lactic acid derivative as chiral co-monomer: Synthesis and properties

For the first time new type of liquid single crystal elastomers forming the chiral smectic A* (SmA*) phase has been prepared using chiral lactic acid derivative as a co-monomer. The synthesis and the basic characterization of the ferroelectric liquid crystalline co-monomer based on differential scanning calorimetry and small/wide-angle X-ray scattering are reported and discussed. The monomer possesses the paraelectric SmA* and the ferroelectric SmC* phases over a broad temperature range. The preparation of new smectic liquid crystalline elastomers together with characterization of their mesomorphic and structural properties is also reported. New elastomers possess the orthogonal paraelectric SmA* phase over 50 K broad temperature range.

Azophenol-Based Liquid−crystalline Elastomers for Light-Driven Actuators

Para-substituted azophenols exhibit a fast thermal cis-to-trans isomerization rate in ethanol, which can be transferred to the solid state by obtaining liquid-crystalline elastomeric systems. The absence of protic solvent is compensated by the establishment of hydrogen bonding between azophenol monomers that are close to each other. Opto-mechanical experiments reveal that azophenol-containing liquid single-crystal elastomers are valuable materials for light-controlled actuators exhibiting relaxation times of 1 s at room temperature.

New composite films based on MoO3−x nanowires aligned in a liquid single crystal elastomer matrix

In this study, we report the preparation, structure characterization, and application of new MoO3−x nanowires, promising candidates for lithium intercalation, hydrogen sensing, and smart windows due to their photochromic property. These nanowires are a mixture of MoO3 and conductive Mo5O14 phase and have been used to prepare composite films based on liquid single crystal elastomers (LSCE). The structure, morphology, and thermomechanic behavior of these films are discussed. In particular, we show that the particular combination of molybdenum-based nanowires and LSCEs allows for doping of liquid single crystal elastomers, preserving the pristine mechanical and optical properties of the host matrix.

Influence of the photo-active azo cross-linker spacer on the opto-mechanics of polysiloxane elastomer actuators

Nematic liquid single crystal elastomers (LSCEs) that contain azobenzenes as cross-linkers have a clear application in the field of light-controlled actuators. They are able to modify their macroscopic dimensions upon irradiation with UV light and furthermore relax back thermally or by irradiation with visible light. Many efforts have been put forward to improve the photo-mechanical effect. However, there are no previous studies about the role of the length of the photo-active cross-linker spacer on the opto-mechanics of light-controlled actuators. In this way, we have prepared several photo-active side-chain nematic polysiloxane LSCEs that contain 4,4′-dialkoxyazobenzenes as cross-linkers, which bear spacers of different lengths. The opto-mechanical behaviour of the different LSCEs prepared has been analyzed. The use of photo-active cross-linkers with long spacers yields actuators with higher mechanical responses under irradiation with UV light. Neither the irradiation nor the thermal relaxation time of the actuator depends on the spacer length.

The role of NMR in the study of partially ordered materials: Perspectives and challenges

The development of NMR techniques applied in the last 10 years to partially oriented systems, and in particular to liquid crystals (LCs), is the object of this brief perspective. The evolution of NMR methods (i.e., new NMR pulse sequences) and the improvement of both theoretical models and mathematic tools for the analysis of NMR data (specifically, for partially ordered systems) allowed scientists to extend their research to increasingly complex materials, such as dendrimers, polymers, and membranes, and to investigate unique phenomena, such as field-induced alignment and confining effects. Furthermore, the fast development of nanoscience and biomedicine is offering a rich variety of new “physical chemical” problems related to partially ordered materials. Starting from a brief perspective of recent works on thermotropic and lyotropic LCs based on different NMR methods, new challenges in this field will be drawn. Moreover, recent selected research works will be discussed in detail with particular emphasis on: (i) the effect of high magnetic fields on the supramolecular structure of chiral liquid-crystalline phases, such as the SmC*, TGBA*, and “de Vries”-type SmA* phases, by means of solid-state 2H NMR; (ii) the slow dynamics in the isotropic phase of bent-core LCs (BLCs) and of liquid single-crystal elastomers evidenced by 2H NMR relaxation studies; and (iii) the influence of the LC environment on the conformational properties of rod-like mesogens studied by high-resolution solid-state 13C NMR methods. This work aims to offer an occasion of reflection on this field of physical chemistry with a glance at future trends and challenges in view of the celebration of the International Year of Chemistry, 2011.

Response of prestretched nematic elastomers to external fields

We investigate the response of prestretched nematic side-chain liquid single-crystal elastomers to superimposed external shear, electric, and magnetic fields of small amplitude. The prestretching direction is oriented perpendicular to the initial nematic director orientation, which enforces director reorientation. Furthermore, the shear plane contains the direction of prestretch. In this case, we obtain a strongly decreased effective shear modulus in the vicinity of the onset and the completion of the enforced director rotation. For the same regions, we find that it becomes comparatively easy to reorient the director by external electric and magnetic fields. These results were derived using conventional elasticity theory and its coupling to relative director-network rotations.

Interplay between nematic ordering and thermomechanical response in a side-chain liquid single crystal elastomer containing pendant azomesogen units

Photoactive materials based on azobenzene derivatives exhibit interesting properties related to the reversible photo-isomerisation between the trans and cis isomers of the azo-compound. In this work we report the preparation and physical–chemical characterization of Liquid Single Crystal Elastomers (LSCEs) containing azobenzene derivative side-chain mesogens as co-monomer. The interplay between the orientational ordering and mechanical response in the nematic phase is investigated by thermomechanical measurements as well as by deuteron NMR spectroscopy. We demonstrate that local nematic order can be reliably probed in azo-LSCEs using low molar mass deuterated cyanobiphenyl nematogen in low concentrations. No phase separation of the dopant is observed. The nematoelastic coupling e av ( T ) ∝ S av ( T ) between the effective sample deformation and average nematic order parameter is present over a wide temperature range even in the systems with relatively large heterogeneity of the nematic order and misaligned nematic domains.

Controlling the Critical Behavior of Paranematic to Nematic Transition in Main-Chain Liquid Single-Crystal Elastomers

We investigated the paranematic-to-nematic phase transition of nematic main-chain liquid single-crystal elastomers by means of high-resolution ac calorimetry and deuteron quadrupole-perturbed nucle...