Mechanism of Pressure-Sensitive Adhesion in Nematic Elastomers.

Nematic liquid crystal elastomers (LCEs) have anomalously high vibration damping, and it has been assumed that this is the cause of their anomalously high-pressure-sensitive adhesion (PSA). Here, we investigate the mechanism behind this enhanced PSA by first preparing thin adhesive tapes with LCE of varying cross-linking densities, characterizing their material and surface properties, and then studying the adhesion characteristics with a standard set of 90° peel, lap shear, and probe tack tests. The study confirms that the enhanced PSA is only present in (and due to) the nematic phase of the elastomer, and the strength of bonding takes over 24 h to fully reach its maximum value. Such a long saturation time is caused by the slow relaxation of local stress and director orientation in the nematic domains after pressing against the surface. We confirm this mechanism by showing that freshly pressed and annealed tape reaches the same maximum bonding strength on cooling, when the returning nematic order is forming in its optimal configuration in the pressed film.

Momentum transfer on impact damping by liquid crystalline elastomers.

The effect of elastomeric damping pads, softening the collision of hard objects, is investigated comparing the reference silicone elastomer and the polydomain nematic liquid crystalline elastomer, which has a far superior internal dissipation mechanism. We specifically focus not just on the energy dissipation, but also on the momentum conservation and transfer during the collision, because the latter determines the force exerted on the target and/or the impactor-and it is the force that does the damage during the short time of an impact, while the energy might be dissipated on a much longer time scale. To better assess the momentum transfer, we compare the collision with a very heavy object and the collision with a comparable mass, when some of the impact momentum is retained in the target receding away from the collision. We also propose a method to estimate the optimal thickness of an elastomer damping pad for minimising the energy in impactor rebound. It has been found that thicker pads introduce a large elastic rebound and the optimal thickness is therefore the thinnest possible pad that does not suffer from mechanical failure. We find good agreement between our estimate of the minimal thickness of the elastomer before the puncture through occurs and the experimental observations.

Rheology of vitrimers.

We describe the full rheology profile of vitrimers, from small deformation (linear) to large deformation (non-linear) viscoelastic behaviour, providing concise analytical expressions to assist the experimental data analysis, and also clarify the emerging insights and rheological concepts in the subject. We identify the elastic-plastic transition at a time scale comparable to the life-time of the exchangeable bonds in the vitrimer network, and propose a new method to deduce material parameters using the Master Curves. At large plastic creep, we describe the strain thinning when the material is subjected to a constant stress or force, and suggest another method to characterize the material parameters from the creep curves. We also investigate partial vitrimers including a permanent sub-network and an exchangeable sub-network where the bond exchange occurs. In creep, such materials can exhibit either strain thinning or strain thickening, depending on applied load, and present the phase diagram of this response.

Programmable Shape Change in Semicrystalline Liquid Crystal Elastomers.

Liquid crystal elastomers (LCEs) are stimuli-responsive materials capable of reversible and programmable shape change in response to an environmental stimulus. Despite the highly responsive nature of these materials, the modest elastic modulus and blocking stress exhibited by these actuating materials can be limiting in some engineering applications. Here, we engineer a semicrystalline LCE, where the incorporation of semicrystallinity in a lightly cross-linked liquid crystalline network yields tough and highly responsive materials. Directed self-assembly can be employed to program director profiles through the thickness of the semicrystalline LCE. In short, we use the alignment of a liquid crystal monomer phase to pattern the anisotropy of a semicrystalline polymer network. Both the semicrystalline-liquid crystalline and liquid crystalline-isotropic phase transition temperatures provide controllable shape transformations. A planarly aligned sample's normalized dimension parallel to the nematic director decreases from 1 at room temperature to 0.42 at 250 °C. The introduction of the semicrystalline nature also enhances the mechanical properties exhibited by the semicrystalline LCE. Semicrystalline LCEs have a storage modulus of 390 MPa at room temperature, and monodomain samples are capable of generating a contractile stress of 2.7 MPa on heating from 25 to 50 °C, far below the nematic to isotropic transition temperature. The robust mechanical properties of this material combined with the high actuation strain can be leveraged for applications such as soft robotics and actuators capable of doing significant work.

Thiol-acrylate side-chain liquid crystal elastomers.

The Michael addition 'click' chemistry was used to graft acrylate-terminated mesogenic groups onto the polysiloxane backbone polymer chain with thiol functional groups, with a constant 15% fraction of diacrylate reacting monomers as crosslinkers. Three different types of mesogens were used, and also their 50 : 50 mixtures, and in all cases we have obtained the smectic-A phase of the resulting liquid crystalline elastomer. Using X-ray diffraction, calorimetry and dynamic mechanical analysis, we investigated the relationship between the molecular structure of mesogenic side groups and the structure and properties of the elastomers. The shape-memory of smectic elastomers was verified. The unusual features were the semi-crystalline nature of elastomers with non-polar mesogens and the clear role of side-by-side rod dimerization of polar mesogens leading to a higher smectic layer spacing. We investigated the evolution of the smectic alignment on uniaxial stretching along the layer normal and identified two distinct ways in which the elastomer responds: the coarsened Helfrich-Hurault zig-zag layer texture and the large-scale stripe domains of uniform layer rotation in the systems with lower order parameter and the associated layer constraints.

Exchangeable Liquid Crystalline Elastomers and Their Applications.

This Review presents and discusses the current state of the art in "exchangeable liquid crystalline elastomers", that is, LCE materials utilizing dynamically cross-linked networks capable of reprocessing, reprogramming, and recycling. The focus here is on the chemistry and the specific reaction mechanisms that enable the dynamic bond exchange, of which there is a variety. We compare and contrast these different chemical mechanisms and the key properties of their resulting elastomers. In the conclusion, we discuss the most promising applications that are enabled by dynamic cross-linking and present a summary table: a library of currently available materials and their main characteristics.

Impact damping and vibration attenuation in nematic liquid crystal elastomers.

Nematic liquid crystal elastomers (LCE) exhibit unique mechanical properties, placing them in a category distinct from other viscoelastic systems. One of their most celebrated properties is the 'soft elasticity', leading to a wide plateau of low, nearly-constant stress upon stretching, a characteristically slow stress relaxation, enhanced surface adhesion, and other remarkable effects. The dynamic soft response of LCE to shear deformations leads to the extremely large loss behaviour with the loss factor tanδ approaching unity over a wide temperature and frequency ranges, with clear implications for damping applications. Here we investigate this effect of anomalous damping, optimising the impact and vibration geometries to reach the greatest benefits in vibration isolation and impact damping by accessing internal shear deformation modes. We compare impact energy dissipation in shaped samples and projectiles, with elastic wave transmission and resonance, finding a good correlation between the results of such diverse tests. By comparing with ordinary elastomers used for industrial damping, we demonstrate that the nematic LCE is an exceptional damping material and propose directions that should be explored for further improvements in practical damping applications.

Dynamic Semicrystalline Networks of Polypropylene with Thiol-Anhydride Exchangeable Crosslinks.

Thermoplastic polyolefins (TPOs) crosslinked by dynamic covalent bonds (xTPOs) have the potential to be the most utilized class of polymer in the world, with applications ranging from household and automotive to biomedical devices and additive manufacturing. xTPO combines the benefits of thermoplastics and thermosets in a "single material" and potentially avoids their shortcomings. Here, we describe a new two-stage reaction extrusion strategy of TPOs with a backbone consisting of inert C-C bonds (polypropylene, PP), and thiol-anhydride, to dynamically crosslink PP through thiol-thioester bond exchange. The degree of PP crosslinking determines the rubber plateau modulus above the melting point of the plastic: the modulus at 200 °C increases from zero in the melt to 23 kPa at 6% crosslinking, to 60 kPa at 20%, to 105 kPa at 40%. The overall mechanical strength of the solid xTPO plastic is 25% higher compared to the original PP, and the gel fraction of xTPO reaches 55%. Finally, we demonstrate that the crosslinked xTPO material is readily reprocessable (recycled, remolded, rewelded, and 3D printed).

A Copolymer-in-Oil Tissue-Mimicking Material With Tuneable Acoustic and Optical Characteristics for Photoacoustic Imaging Phantoms.

Photoacoustic imaging (PAI) standardisation demands a stable, highly reproducible physical phantom to enable routine quality control and robust performance evaluation. To address this need, we have optimised a low-cost copolymer-in-oil tissue-mimickingmaterial formulation. The base material consists of mineral oil, copolymer and stabiliser with defined Chemical Abstract Service numbers. Speed of sound c(f) and acoustic attenuation coefficient α (f) were characterised over 2-10 MHz; optical absorption µa ( λ ) and reduced scattering µs '( λ ) coefficients over 450-900 nm. Acoustic properties were optimised by modifying base component ratios and optical properties were adjusted using additives. The temporal, thermomechanical and photo-stabilitywere studied, alongwith intra-laboratory fabrication and field-testing. c(f) could be tuned up to (1516±0.6) [Formula: see text] and α (f) to (17.4±0.3)dB · cm -1 at 5 MHz. The base material exhibited negligible µa ( λ ) and µs '( λ ), which could be independently tuned by addition of Nigrosin or TiO2 respectively. These properties were stable over almost a year and were minimally affected by recasting. The material showed high intra-laboratory reproducibility (coefficient of variation <4% for c ( f ), α ( f ), optical transmittance and reflectance), and good photo- and mechanical-stability in the relevant working range (20-40°C). The optimised copolymer-in-oil material represents an excellent candidate for widespread application in PAI phantoms, with properties suitable for broader use in biophotonics and ultrasound imaging standardisation efforts.

Continuous spinning aligned liquid crystal elastomer fibers with a 3D printer setup.

Fibrous liquid crystalline elastomers (LCE) are an attractive variant of LCE-based actuators due to their small thickness, leading to faster response times to stimuli, as well as the increased mechanical strength. Fabrication of LCE fibers has been attempted by various research groups using electro-spinning or micro-fluidic techniques, without much success. Here we propose an alternative way to achieve single-step continuous spinning LCE fibers in a more scalable and robust way, based on a liquid-ink 3D printer. We demonstrate this technique in our home-made device by dynamically extruding/stretching liquid crystalline oligomer mixed with photo-reactive cross-linker, to fix the aligned network under UV light after extrusion. The report also describes a protocol for material synthesis and identifies optimal conditions for the stable fiber spinning process. Microns-thick LCE fibers with two different compositions have been successfully spun, and demonstrated enhanced mechanical properties with the inherited thermal-actuation capability. This technique also demonstrates the potential to fine-tune the mechanical properties of fibers to enable further development in fiber-based LCE applications.

Internal constraints and arrested relaxation in main-chain nematic elastomers.

Nematic liquid crystal elastomers (N-LCE) exhibit intriguing mechanical properties, such as reversible actuation and soft elasticity, which manifests as a wide plateau of low nearly-constant stress upon stretching. N-LCE also have a characteristically slow stress relaxation, which sometimes prevents their shape recovery. To understand how the inherent nematic order retards and arrests the equilibration, here we examine hysteretic stress-strain characteristics in a series of specifically designed main-chain N-LCE, investigating both macroscopic mechanical properties and the microscopic nematic director distribution under applied strains. The hysteretic features are attributed to the dynamics of thermodynamically unfavoured hairpins, the sharp folds on anisotropic polymer strands, the creation and transition of which are restricted by the nematic order. These findings provide a new avenue for tuning the hysteretic nature of N-LCE at both macro- and microscopic levels via different designs of polymer networks, toward materials with highly nonlinear mechanical properties and shape-memory applications.

The effect of alignment on the rate-dependent behavior of a main-chain liquid crystal elastomer.

This study investigated the effect of alignment on the rate-dependent behavior of a main-chain liquid crystal elastomer (LCE). Polydomain nematic LCE networks were synthesized from a thiol-acrylate Michael addition reaction in the isotropic state. The polydomain networks were stretched to different strain levels to induce alignment then crosslinked in a second stage photopolymerization process. The LCE networks were subjected to dynamic mechanical tests to measure the temperature-dependent storage modulus and uniaxial tension load-unload tests to measure the rate-dependence of the Young's modulus, mechanical dissipation, and characteristics of the soft stress response. Three-dimensional (3D) digital image correlation (DIC) was used to characterize the effect of domain/mesogen relaxation on the strain fields. All LCE networks exhibited a highly rate-dependent stress response with significant inelastic strains after unloading. The Young's modulus of the loading curve and hysteresis of the load-unload curves showed a power-law dependence on the strain rate. The Young's modulus increased with alignment and larger anisotropy and a smaller power-law exponent was measured for the Young's modulus and hysteresis for the highly aligned monodomains. The polydomain and pre-stretched networks loaded perpendicular to the alignment direction exhibited a soft stress response that featured a rate-dependent peak stress, strain-softening, and strain-stiffening. The 3D-DIC strain fields for the polydomain network and programmed networks stretched in the perpendicular direction were highly heterogeneous, showing regions of alternating higher and lower strains. The strain variations increased initially with loading, peaked during the strain softening part of the stress response, then decreased during the strain stiffening part of the stress response. Greater variability was measured for lower strain rates. These observations suggest that local domain/mesogen relaxation led to the development of the heterogeneous strain patterns and strain softening in stress response. These findings improved understanding of the kinetics of mesogen relaxation and its contributions to the rate-dependent stress response and mechanical dissipation.

Light-Driven Dynamic Adhesion on Photosensitized Nematic Liquid Crystalline Elastomers.

In liquid crystal elastomers (LCEs), the internal mechanical loss increases around the nematic-isotropic phase transition and remains high all through the nematic phase, originating from the internal orientational relaxation related to the so-called "soft elasticity". Because the viscoelastic dissipation of the materials affects their adhesion properties, the nematic-isotropic phase transition can cause dramatic changes in the adhesion strength. Although the phase transitions can generally be induced by heat, here, we demonstrate the light-driven transition in dynamic adhesion in dye-doped nematic LCE. The special dye is chosen to efficiently generate local heat on light absorption. The adhesion strength is lowered with fine tunability depending on the light power, which governs the effective local temperature and through that the viscoelastic damping of the system. We demonstrate the light-assisted dynamic control of adhesion in a 90°-peel test and in pick-and-release of objects, which may lead to the development of stimuli-responsive adhesive systems with fine spatio-temporal controls.

Rates of transesterification in epoxy-thiol vitrimers.

Vitrimers, an important subset of dynamically crosslinked polymer networks, have many technological applications for their excellent properties, and the ability to be re-processed through plastic flow above the so-called vitrification temperature. We report a simple and efficient method of generating such adaptive crosslinked networks relying on transesterification for their bond exchange by utilising the 'click' chemistry of epoxy and thiols, which also has the advantage of a low glass transition temperature. We vary the chemical structure of thiol spacers to probe the effects of concentration and the local environment of ester groups on the macroscopic elastic-plastic transition. The thermal activation energy of transesterification bond exchange is determined for each chemical structure, and for a varying concentration of catalyst, establishing the conditions for the optimal, and for the suppressed bond exchange. However, we also discover that the temperature of elastic-plastic transition is strongly affected by the stiffness (dynamic rubber modulus) of the network, with softer networks having a much lower vitrification temperature even when their bond-exchange activation energy is higher. This combination of chemical and physical control factors should help optimise the processability of vitrimer plastics.

Siloxane crosslinks with dynamic bond exchange enable shape programming in liquid-crystalline elastomers.

Liquid crystalline elastomers (LCE) undergo reversible shape changes in response to stimuli, which enables a wide range of smart applications, in soft robotics, adhesive systems or biomedical medical devices. In this study, we introduce a new dynamic covalent chemistry based on siloxane equilibrium exchange into the LCE to enable processing (director alignment, remolding, and welding). Unlike the traditional siloxane based LCE, which were produced by reaction schemes with irreversible bonds (e.g. hydrosilylation), here we use a much more robust reaction (thiol-acrylate/thiol-ene 'double-click' chemistry) to obtain highly uniform dynamically crosslinked networks. Combining the siloxane crosslinker with click chemistry produces exchangeable LCE (xLCE) with tunable properties, low glass transition (-30 °C), controllable nematic to isotropic transition (33 to 70 °C), and a very high vitrification temperature (up to 250 °C). Accordingly, this class of dynamically crosslinked xLCE shows unprecedented thermal stability within the working temperature range (-50 to 140 °C), over many thermal actuation cycles without any creep. Finally, multiple xLCE sharing the same siloxane exchangeable bonds can be welded into single continuous structures to allow for composite materials that sequentially and reversibly undergo multiple phase transformations in different sections of the sample.

Catalytic Control of Plastic Flow in Siloxane-Based Liquid Crystalline Elastomer Networks.

Liquid crystalline elastomer networks cross-linked by dynamic covalent bonds (xLCE) have the ability to be (re)processed during the plastic flow. However, the current bond-exchange strategies that are used to induce plastic flow in xLCE lack the efficient method to control the elastic-plastic transition. Here we describe a straightforward method to manipulate the transition to plastic flow via the choice of catalyst in xLCE cross-linked by siloxane. The nature and the amount of catalyst have a profound effect on the elastic-plastic transition temperature, and the stress relaxation behavior of the network. The temperature of fast plastic flow and the associated bond-exchange activation energy varied from 120 °C and 83 kJ/mol in the "fastest" exchange promoted by triazobicyclodecene (TBD) to 240 °C and 164 kJ/mol in the "slowest" exchange with triphenylphosphine (PPH), with a range of catalysts in between. We have identified the optimum conditions for programming an aligned monodomain xLCE, high programming temperature (230 °C) and low nematic to isotropic transition (60 °C), to achieve thermally and mechanically stable actuators.

Enhanced Dynamic Adhesion in Nematic Liquid Crystal Elastomers.

Smart adhesives that undergo reversible detachment in response to external stimuli enable a wide range of applications in household products, medical devices, or manufacturing. Here, a new model system for the design of smart soft adhesives that dynamically respond to their environment is presented. By exploiting the effect of dynamic soft elasticity in nematic liquid crystal elastomers (LCE), the temperature-dependent control of adhesion to a solid glass surface is demonstrated. The adhesion strength of LCE is more than double in the nematic phase, in comparison to the isotropic phase, further increasing at higher detachment rates. The static work of adhesion, related to the interfacial energy of adhesive contact, is shown to change very little within the explored temperature range. Accordingly, the observed enhanced adhesion in the nematic phase is primarily attributable to the increased internal energy dissipation during the detachment process. This adhesion effect is correlated with the inherent bulk dynamic-mechanical response in the nematic LCE. The reported enhanced dynamic adhesion can lead to the development of a new class of stimuli-responsive adhesives.

Responsive, 3D Electronics Enabled by Liquid Crystal Elastomer Substrates.

Traditional electronic devices are rigid, planar, and mechanically static. The combination of traditional electronic materials and responsive polymer substrates is of significant interest to provide opportunities to replace conventional electronic devices with stretchable, 3D, and responsive electronics. Liquid crystal elastomers (LCEs) are well suited to function as such dynamic substrates because of their large strain, reversible stimulus response that can be controlled through directed self-assembly of molecular order. Here, we discuss using LCEs as substrates for electronic devices that are flat during processing but then morph into controlled 3D structures. We design and demonstrate processes for a variety of electronic devices on LCEs including deformation-tolerant conducting traces and capacitors and cold temperature-responsive antennas. For example, patterning twisted nematic orientation within the substrate can be used to create helical electronic devices that stretch up to 100% with less than 2% change in resistance or capacitance. Moreover, we discuss self-morphing LCE antennas which can dynamically change the operating frequency from 2.7 GHz (room temperature) to 3.3 GHz (-65 °C). We envision applications for these 3D, responsive devices in wearable or implantable electronics and in cold-chain monitoring radio frequency identification sensors.

Liquid Crystal Elastomer-Based Microelectrode Array for In Vitro Neuronal Recordings.

Polymer-based biomedical electronics provide a tunable platform to interact with nervous tissue both in vitro and in vivo. Ultimately, the ability to control functional properties of neural interfaces may provide important advantages to study the nervous system or to restore function in patients with neurodegenerative disorders. Liquid crystal elastomers (LCEs) are a class of smart materials that reversibly change shape when exposed to a variety of stimuli. Our interest in LCEs is based on leveraging this shape change to deploy electrode sites beyond the tissue regions exhibiting inflammation associated with chronic implantation. As a first step, we demonstrate that LCEs are cellular compatible materials that can be used as substrates for fabricating microelectrode arrays (MEAs) capable of recording single unit activity in vitro. Extracts from LCEs are non-cytotoxic (>70% normalized percent viability), as determined in accordance to ISO protocol 10993-5 using fibroblasts and primary murine cortical neurons. LCEs are also not functionally neurotoxic as determined by exposing cortical neurons cultured on conventional microelectrode arrays to LCE extract for 48 h. Microelectrode arrays fabricated on LCEs are stable, as determined by electrochemical impedance spectroscopy. Examination of the impedance and phase at 1 kHz, a frequency associated with single unit recording, showed results well within range of electrophysiological recordings over 30 days of monitoring in phosphate-buffered saline (PBS). Moreover, the LCE arrays are shown to support viable cortical neuronal cultures over 27 days in vitro and to enable recording of prominent extracellular biopotentials comparable to those achieved with conventional commercially-available microelectrode arrays.

High strain actuation liquid crystal elastomers via modulation of mesophase structure.

Control of the mesophase in liquid crystalline elastomers (LCEs) is a critical aspect in harnessing their unique stimuli-responsive properties. Few studies have compared nematic and smectic main-chain LCEs in a direct way. Traditionally, it is believed that the mesogen core and synthetic route determines the phase behavior. In this study, we hypothesized that tuning the LC phases in main-chain LCE systems can be achieved by varying the spacer length while maintaining the same mesogen (RM257). By increasing the length of dithiol alkyl spacers containing two to eleven carbons along the spacer backbone (C2 to C11), we can modulate the mesophase from nematic to smectic, tailor the nematic to isotropic transition temperature between 90 and 140 °C, and increase the average work capacity from 128 to 262 kJ m-3. Phase nano-segregation resulting in the smectic C phase is achieved at room temperature for the C6, C9, and C11 spacers. In a shape switching system, this manifests in impressive actuation stroke of 700%. Upon heating from room temperature, these samples transition into the nematic and later, the isotropic phase. Furthermore, this segregation occurs along with polymer chain crystallinity, which increases the modulus of the networks by an order of magnitude; however, the crystallization rate is highly time dependent on the spacer length and can vary between 5 minutes for the C11 spacer and 24 hours for shorter spacers. This study presents several possibilities of a thiol-acrylate reaction in modulation of the thermomechanical and liquid-crystalline properties of LCEs and discusses their potential use for biomedical applications.