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Living systems are intrinsically nonequilibrium: They use metabolically derived chemical energy to power their emergent dynamics and self-organization. A crucial driver of these dynamics is the cellular cytoskeleton, a defining example of an active material where the energy injected by molecular motors cascades across length scales, allowing the material to break the constraints of thermodynamic equilibrium and display emergent nonequilibrium dynamics only possible due to the constant influx of energy. Notwithstanding recent experimental advances in the use of local probes to quantify entropy production and the breaking of detailed balance, little is known about the energetics of active materials or how energy propagates from the molecular to emergent length scales. Here, we use a recently developed picowatt calorimeter to experimentally measure the energetics of an active microtubule gel that displays emergent large-scale flows. We find that only approximately one-billionth of the system’s total energy consumption contributes to these emergent flows. We develop a chemical kinetics model that quantitatively captures how the system’s total thermal dissipation varies with ATP and microtubule concentrations but that breaks down at high motor concentration, signaling an interference between motors. Finally, we estimate how energy losses accumulate across scales. Taken together, these results highlight energetic efficiency as a key consideration for the engineering of active materials and are a powerful step toward developing a nonequilibrium thermodynamics of living systems.

Ion beam plays a pivotal role in ion implantations and the fabrication of nanostructures. However, there lacks a quantitative model to describe the residual stresses associated with the ion-beam radiation. Radiation-induced residual stress/transformation strain have been mostly recognized in the hydrostatic sub strain space. Here, we use molecular dynamics (MD) simulations to show that the response of a material to irradiation is generally anisotropic that depends on the ion-beam direction, and should be described using tensorial quantities. We demonstrate that accelerator-based ion beam irradiation, combined with the intrinsic lattice anisotropy and externally induced anisotropy (such as anisotropic mechanical loadings), causes radiation-actuated shear transformation strains in addition to hydrostatic expansion. We map out these complex correlations for several materials. Radiation-induced defects are shown to be responsible for residual shear stresses in the manner of Eshelby inclusion transformation. We propose such tensorial response model should be considered for accurate nanoscale fabrication using ion-beam irradiation., 33 pages, 5 figures

The development of hydrogels for cartilage replacement and soft robotics has highlighted a challenge: load-bearing hydrogels need to be both stiff and tough. Several approaches have been reported to improve the toughness of hydrogels, but simultaneously achieving high stiffness and toughness remains difficult. Here we report that alginate-polyacrylamide hydrogels can simultaneously achieve high stiffness and toughness. We combine short- and long-chain alginates to reduce the viscosity of pregel solutions and synthesize homogeneous hydrogels of high ionic cross-link density. The resulting hydrogels can have elastic moduli of ∼1 MPa and fracture energies of ∼4 kJ m–2. Furthermore, this approach breaks the inverse relation between stiffness and toughness: while maintaining constant elastic moduli, these hydrogels can achieve fracture energies up to ∼16 kJ m–2. These stiff and tough hydrogels hold promise for further development as load-bearing materials.

Tunable-impedance mechanisms can improve the adaptivity, robustness, and efficiency of a vast array of engineering systems and soft robots. In this study, we introduce a tunable-stiffness mechanism called a "sandwich jamming structure," which fuses the exceptional stiffness range of state-of-the-art laminar jamming structures (also known as layer jamming structures) with the high stiffness-to-mass ratios of classical sandwich composites. We experimentally develop sandwich jamming structures with performance-to-mass ratios that are far greater than laminar jamming structures (e.g., a 550-fold increase in stiffness-to-mass ratio), while simultaneously achieving tunable behavior that standard sandwich composites inherently cannot achieve (e.g., a rapid and reversible 1800-fold increase in stiffness). Through theoretical and computational models, we then show that these ratios can be augmented by several orders of magnitude further, and we provide an optimization routine that allows designers to build the best possible sandwich jamming structures given arbitrary mass, volume, and material constraints. Finally, we demonstrate the utility of sandwich jamming structures by integrating them into a wearable soft robot (i.e., a tunable-stiffness wrist orthosis) that has negligible impact on the user in the off state, but can reduce muscle activation by an average of 41% in the on state. Through these theoretical and experimental investigations, we show that sandwich jamming structures are a lightweight highly tunable mechanism that can markedly extend the performance limits of existing structures and devices.

CuZr-based alloys are being considered as potential shape memory alloys for use in high-temperature applications. We have conducted a study on the effects of several alloying elements on the shape memory properties of these alloys using polycrystalline thin-film samples. Here we report on the explosive formation of martensite in supercooled CuZr, CuZrNi and CuZrCo samples. This explosive transformation behavior is characterized by the following observations: 1) The high-temperature austenitic phase can be supercooled below the martensite finish temperature Mf. At a critical temperature below Mf, austenite transforms to martensite across the entire sample in less than a microsecond. 2) The critical temperature has a narrow distribution and decreases slightly with higher cooling rate. 3) Observation of supercooling and explosive transformation behavior depends on the temperature history above the austenite finish temperature Af. If a sample is quenched immediately after heating above Af, martensite forms gradually on cooling below Ms; if a sample is allowed to dwell a few seconds above Af, the martensite forms explosively. We suggest that the gradual transformation proceeds by martensite growth on defects that accumulate during successive transformation cycles. If the sample is allowed to dwell at a temperature above Af, however, these defects are annihilated and the transformation is nucleation-limited. Nucleation of martensite then requires significant supercooling. The defect annihilation process is highly sensitive to temperature and has an apparent activation energy of 326 kJ/mol, which is too large for a simple diffusion-limited process. Transmission electron microscopy of CuZrCo samples suggests that the defects may be related to the presence of residual martensite.

We introduce a class of ultra-light and ultra-stiff sandwich panels designed for use in photophoretic levitation applications and investigate their mechanical behavior using both computational analyses and micro-mechanical testing. The sandwich panels consist of two face sheets connected with a core that consists of hollow cylindrical ligaments arranged in a honeycomb-based hexagonal pattern. Computational modeling shows that the panels have superior bending stiffness and buckling resistance compared to similar panels with a basketweave core, and that their behavior is well described by Uflyand-Mindlin plate theory. By optimizing the ratio of the face sheet thickness to the ligament wall thickness, panels maybe obtained that have a bending stiffness that is more than five orders of magnitude larger than that of a solid plate with the same area density. Using a scalable microfabrication process, we demonstrate that panels as large as 3x3 cm^2 with a density of 20 kg/m^3 can be made in a few hours. Micro-mechanical testing of the panels is performed by deflecting microfabricated cantilevered panels using a nanoindenter. The experimentally measured bending stiffness of the cantilevered panels is in very good agreement with the computational results, demonstrating exquisite control over the dimensions, form, and properties of the microfabricated panels., Comment: Main: 26 pages, 10 figures. Supporting information: 5 pages, 4 figures

We present a computational-experimental study on the ternary alloying effect of CuZr-based shape memory alloy. The transformation behavior, including crystallization, martensite-austenite transformation temperature and hysteresis of Cu-Zr-X (X = Ni, Co, Hf) thin-film samples were investigated by nanocalorimetry. We used ab initio simulations to determine the B2-Cm transformation pathway, evaluate the lattice parameters, the relative phase stability, and the twin boundary energy as a function of composition. Experimental results show that alloying with Ni or Co reduces the hysteresis of the martensitic transformation, while Hf increases it. These observations are in agreement with the trend of the middle eigenvalue of the martensitic transformation matrix. The energy difference between the pure phases obtained from simulations suggests that both Co and Ni stabilize martensite against austenite. However, experiments show that Co decreases transformation temperature, while Ni increases it. We attribute this observation to the larger twin boundary energy and strain energy in the Co-containing alloy. Our results indicate that ab initio simulations are a helpful tool in the development of new shape memory alloys, provided the energy terms associated with the fine twin structure of the martensite are taken into account.

Elastic modulus and residual stress in freestanding ultrathin films (

The past two decades have witnessed the rapid development of nanocalorimetry, a novel materials characterization technique that employs micromachined calorimetric sensors. The key advances of this technique are the ultrahigh scanning rate, which can be as high as 106 K/s, and the ultrahigh heat capacity sensitivity, with a resolution typically better than 1 nJ/K. Nanocalorimetry has attracted extensive attention in the field of materials science, where it is applied to perform quantitative analysis of rapid phase transitions. This paper reviews the development of nanocalorimetry over the last three decades and summarizes its applications to various materials ranging from polymers to metals. The glass transition and crystallization of non-crystalline materials, melting and solidification of metallic droplets, and solid-state phase transitions of thin films are introduced as typical examples. Furthermore, nanocalorimetry coupled with structural characterization techniques, such as transmission electron microscopy and synchrotron X-ray diffraction, is presented. Finally, current challenges and future outlooks for the technique are discussed. Given the unique attributes of the technique, we expect nanocalorimetry to attract increasing attention, especially with regard to characterization of fast phase transitions and evaluation of size effects.

We have developed sensor arrays using a simple and inexpensive fabrication process to measure the electrical resistance of thin-film materials as a function of temperature and composition. The sensors are capable of characterizing materials from liquid‑nitrogen temperature to approximately 900 K and are not limited by low sample conductivity. We demonstrate the sensitivity and accuracy of the technique by analyzing the phase evolution in Ti-Ni-Cu shape memory alloys and PdSi-based metallic glasses. For the latter, we find that the change in resistance on crystallization correlates with glass-forming ability. This observation may be useful in identifying good glass formers using high-throughput techniques.

In this work, we use nanocalorimetry to characterize the diffusion kinetics of Cu-Zr and Ni-Zr glass-forming alloys in both the solid state and the super-cooled liquid state, covering a temperature range from 0.67Tg to 1.49Tg. We find that diffusion in the solid state follows Arrhenius behavior, while the kinetics in the super-cooled liquid state is well described by a fragility-based model that takes into account breakdown of the Stokes-Einstein relationship between the diffusivity and viscosity. The current work uses a single experimental technique to map out the kinetics of diffusion over a broad temperature range in both states.

Discovering new metallic glasses, non-crystalline alloys with unique combinations of mechanical and chemical properties, is a challenging endeavor because it requires exploration of a vast composition space. High-throughput experiments have greatly enhanced the efficiency with which composition-dependent properties of potential glass-forming alloys can be measured, but phase identification remains a bottleneck because slow or expensive techniques such as table-top or synchrotron-based X-ray diffraction measurements are required. In this study, we developed machine learning (ML) models that can classify amorphous and crystalline phases of alloys using electrical resistivity as a primary descriptor. Artificial neural networks were constructed to correlate the electrical resistivities and the X-ray diffractograms of a broad range of combinatorially synthesized alloys. The ML models are found to classify amorphous/crystalline phases in both thin-film libraries and bulk alloys with high accuracy.

We have investigated the phase transformations in sputtered CuZr shape memory thin films using a differential nanocalorimetry technique that is capable of making calorimetric measurement on thin-film samples with a sensitivity as small as 12 pJ/K. We first present a general procedure to accurately measure the heat capacity and enthalpies of transformation of a sample, even if there is a significant difference in the heat capacities of sample and reference. We then demonstrate the technique by analyzing the phase evolution of equiatomic CuZr thin films and explore the conditions for the formation of the martensitic phase responsible for the shape memory properties of this alloy. We show that fast, low-temperature cycling through the martensitic transformation increases the hysteresis, which we attribute to the accumulation of defects during the martensitic transformation. If the austenitic phase is given sufficient time at elevated temperature to annihilate these defects, the transformation is stable under thermal cycling conditions.

Functional devices that use hydrogels as ionic conductors and elastomers as dielectrics have the advantage of being soft, stretchable, transparent, and biocompatible, making them ideal for biomedical applications. These devices are typically fabricated by manual assembly. Techniques for the manufacturing of soft materials have generally not looked at integrating multiple dissimilar materials. Silane coupling agents have recently shown promise for creating strong bonds between hydrogels and elastomers but have yet to be used in the extrusion printing of complex devices that integrate both hydrogels and elastomers. Here, we demonstrate the viability of silane coupling agents in a system with the rheology and functional composition necessary for three-dimensional (3D) extrusion printing of hydrogel-elastomer materials, specifically polyacrylamide (PAAm) hydrogel and poly(dimethylsiloxane) (PDMS) hydrophobic elastomer. By introducing a charge-neutral surfactant in the PDMS and adjusting silane concentrations in the PAAm, cast material samples demonstrate strong adhesion. We were also able to achieve an interfacial toughness of up to Γ = 193 ± 6.3 J/m2 for a fully extrusion printed PAAm hydrogel-on-PDMS bilayer. This result demonstrates that an integration strategy based on silane coupling agents makes it possible for extrusion printing of a wide variety of hydrogel and silicone elastomers.

We describe a sensor for measuring the electrical resistance of a conducting thin-film material as a function of temperature and composition. The sensor has excellent sensitivity and can be used at temperatures as high as the melting temperature of the material of interest. The sensor is fabricated by applying a simple lift-off process to a thin film. By combining combinatorial sputtering to fabricate composition spreads with arrays of sensors, the phase transformation behavior of complex alloys can be mapped. We demonstrate this capabilities by using the sensor to determine the glass transition and crystallization temperatures of several PdSiCu-based metallic glasses. We found that in two glass-forming systems, PdCuSi and NiZr, the ratio of the resistance of the crystallized to as-deposited material is correlated with the glass-forming ability. The ability to readily determine glass forming ability, suggests that the sensor is a powerful tool for measuring the glass-forming ability in a high-throughput manner over large compositional spaces.

Soft machines are a promising design paradigm for human-centric devices1,2 and systems required to interact gently with their environment3,4. To enable soft machines to respond intelligently to their surroundings, compliant sensory feedback mechanisms are needed. Specifically, soft alternatives to strain gauges—with high resolution at low strain (less than 5 per cent)—could unlock promising new capabilities in soft systems. However, currently available sensing mechanisms typically possess either high strain sensitivity or high mechanical resilience, but not both. The scarcity of resilient and compliant ultra-sensitive sensing mechanisms has confined their operation to laboratory settings, inhibiting their widespread deployment. Here we present a versatile and compliant transduction mechanism for high-sensitivity strain detection with high mechanical resilience, based on strain-mediated contact in anisotropically resistive structures (SCARS). The mechanism relies upon changes in Ohmic contact between stiff, micro-structured, anisotropically conductive meanders encapsulated by stretchable films. The mechanism achieves high sensitivity, with gauge factors greater than 85,000, while being adaptable for use with high-strength conductors, thus producing sensors resilient to adverse loading conditions. The sensing mechanism also exhibits high linearity, as well as insensitivity to bending and twisting deformations—features that are important for soft device applications. To demonstrate the potential impact of our technology, we construct a sensor-integrated, lightweight, textile-based arm sleeve that can recognize gestures without encumbering the hand. We demonstrate predictive tracking and classification of discrete gestures and continuous hand motions via detection of small muscle movements in the arm. The sleeve demonstration shows the potential of the SCARS technology for the development of unobtrusive, wearable biomechanical feedback systems and human–computer interfaces. Strain gauges with both high sensitivity and high mechanical resilience, based on strain-mediated contact in anisotropically resistive structures, are demonstrated within a sensor-integrated, textile-based sleeve that can recognize human hand motions via muscle deformations.

Researchers have developed variable-impedance mechanisms to control the dynamic response of robotic systems and improve their adaptivity, robustness, and efficiency. However, these mechanisms have limitations in size, cost, and convenience, particularly for variable damping. We demonstrate that laminar jamming structures can transform the dynamic response of robotic structures and systems while overcoming these limitations. In laminar jamming, an external pressure gradient is applied to a laminate of compliant material, changing its stiffness and damping. In this latter, we combine analysis, simulation, and characterization to formulate a lumped-parameter model that captures the nonlinear mechanical behavior of jamming structures and can be used to rapidly simulate their dynamic response. We illustrate that by adjusting the vacuum pressure, the fundamental features of the dynamic response (i.e., frequency, amplitude, decay rate, and steady-state value) can be tuned on command. Finally, we demonstrate that jamming structures can be integrated into soft structures and traditional rigid robots to considerably alter their response to impacts. With the models and demonstrations provided here, researchers may move further toward building versatile and transformative robots.

We propose a 3D-printable soft, stretchable, and transparent hydrogel-elastomer device that is able to detect simulated ‘nerve’ signals. The signal is passed to a conductive hydrogel electrode through a non-contact method of capacitive coupling through polydimethylsiloxane (PDMS). We demonstrate that the device is able to detect sinusoidal waveforms passed through a simulated ‘nerve’ made from conductive hydrogel over a range of frequencies (1 kHz – 1 MHz). Analysis of signal detection showed a correlation to the electrode contact area and a Vin/Vout of larger than 10%. This provides the framework for the future development of a soft, 3D-printable, capacitive coupling device that can be used as a cuff electrode for detecting peripheral nerve signals.

Degradable polymers are under intense development for sustainability and healthcare. Evidence has accumulated that the chemical reaction that decomposes a polymer an also grow a crack. Even under a small load, the crack speed can be orders of magnitude higher than the overall rate of degradation, leading to premature failure. Here, we demonstrate that a crack slows down markedly in a composite of two degradable materials. In a homogeneous degradable material, the stress concentrates at the crack tip, so that a relatively small applied stretch induces a high stress and a high rate of reaction. The fracture behavior of a composite that consists of two degradable materials, a stiff material for the fibers and a compliant material for the matrix, with strong adhesion between both, is different: The soft matrix blunts the crack and distributes the stresses at the crack tip over a long length of the fibers. The same rate of reaction requires a larger applied stretch. This stress de-concentration retards crack growth in the composite. We demonstrate this concept using a composite made of stiff polydimethylsiloxane (PDMS) fibers in a soft PDMS matrix. In the presence of water molecules in the environment, siloxane bonds in the PDMS hydrolyze, causing hydrolytic crack growth. We show that a hydrolytic crack grows much more slowly in a PDMS composite than in homogeneous PDMS, and may even arrest in the composite. It is hoped that this concept will contribute to the development of degradable materials that resist premature failure.

Tough hydrogels of many chemical compositions have been developed in recent years, but their fatigue fracture has not been studied. The lack of study hinders further development of hydrogels for applications that require long lifetimes under cyclic loads. Examples include tissue engineering, soft robots, and stretchable electronics. Here we study the fatigue fracture of a polyacrylamide–alginate tough hydrogel. We find that the stress–stretch curve changes cycle by cycle, and reaches a steady state after thousands of cycles. The threshold for fatigue fracture is about 53 J/m2, much below the fracture energy ( ∼ 10,000 J/m2) measured under monotonic load. Nonetheless, the extension of crack per cycle in the polyacrylamide–alginate tough hydrogel is much smaller than that in a single-network polyacrylamide hydrogel.

The glass forming ability (GFA) of metallic glasses (MGs) is quantified by the critical cooling rate (RC). Despite its key role in MG research, experimental challenges have limited measured RC to a minute fraction of known glass formers. We present a combinatorial approach to directly measure RC for large compositional ranges. This is realized through the use of compositionally-graded alloy libraries, which were photo-thermally heated by scanning laser spike annealing of an absorbing layer, then melted and cooled at various rates. Coupled with X-ray diffraction mapping, GFA is determined from direct RC measurements. We exemplify this technique for the Au-Cu-Si system, where we identify Au56Cu27Si17 as the alloy with the highest GFA. In general, this method enables measurements of RC over large compositional areas, which is powerful for materials discovery and, when correlating with chemistry and other properties, for a deeper understanding of MG formation.

Sticky even when wet Tissue adhesives are used as an alternative to stitches or staples and can be less damaging to the healthy tissues. But they can suffer from low biocompatibility and poor matching of the mechanical properties with the tissues. Li et al. combined an adhesive surface with a flexible matrix to develop an adhesive that has the right level of stick but moves with the surrounding tissues. The adhesive is effective in the presence of blood and thus might work during wound repair. Science , this issue p. 378

Microphysiological systems and organs-on-chips promise to accelerate biomedical and pharmaceutical research by providing accurate in vitro replicas of human tissue. Aside from addressing the physiological accuracy of the model tissues, there is a pressing need for improving the throughput of these platforms. To do so, scalable data acquisition strategies must be introduced. To this end, we here present an instrumented 24-well plate platform for higher-throughput studies of engineered human stem cell-derived cardiac muscle tissues that recapitulate the laminar structure of the native ventricle. In each well of the platform, an embedded flexible strain gauge provides continuous and non-invasive readout of the contractile stress and beat rate of an engineered cardiac tissue. The sensors are based on micro-cracked titanium-gold thin films, which ensure that the sensors are highly compliant and robust. We demonstrate the value of the platform for toxicology and drug-testing purposes by performing 12 complete dose-response studies of cardiac and cardiotoxic drugs. Additionally, we showcase the ability to couple the cardiac tissues with endothelial barriers. In these studies, which mimic the passage of drugs through the blood vessels to the musculature of the heart, we regulate the temporal onset of cardiac drug responses by modulating endothelial barrier permeability in vitro.

Rapid advances are taking place to develop hydrogels of high stretchability and toughness, but fatigue fracture has not been studied for any hydrogels. This negligence hinders the development of hydrogels and their applications. Here we initiate a study of fatigue fracture of hydrogels. We choose polyacrylamide hydrogel as a model material. To place fatigue fracture in context, we apply monotonic, static, and cyclic load, and observe three types of fracture behavior: fast fracture, delayed fracture, and fatigue fracture. Below the critical load for fast fracture, we find two distinct thresholds, one for delayed fracture, and the other for fatigue fracture. The fracture behavior of hydrogel is sensitive to both the amplitude of load and the concentration of water. We relate the experimental observations to the molecular picture of swollen polymer networks. Fatigue fracture of hydrogels is a topic ready for scientific studies and engineering advances.

We have investigated the crystallization kinetics of Cu50Zr50 metallic glass thin films using nanocalorimetry. The crystallization process is growth-controlled during heating and nucleation-controlled during cooling, resulting in different critical heating and cooling rates to suppress crystallization. Measurements over a wide range of scanning rates (13 K/s to 21,000 K/s) reveal that crystallization does not follow Arrhenius kinetics upon heating. Instead, the behavior on heating is well described by a fragility-based model of growth-controlled kinetics that takes into account breakdown of the Stokes-Einstein relationship. Upon cooling, the quench rate required to suppress crystallization of the melt is much higher than for bulk samples. This reduced asymmetry in critical heating and cooling rates compared to bulk materials suggests that crystallization of the thin-film metallic glass is controlled by heterogeneous nucleation.

Recent innovations highlight the integration of diverse materials with synthetic and biological hydrogels. Examples include brain-machine interfaces, tissue regeneration, and soft ionic devices. Existing methods of strong adhesion mostly focus on the chemistry of bonds and the mechanics of dissipation but largely overlook the molecular topology of connection. Here, we highlight the significance of molecular topology by designing a specific bond-stitch topology. The bond-stitch topology achieves strong adhesion between preformed hydrogels and various materials, where the hydrogels have no functional groups for chemical coupling, and the adhered materials have functional groups on the surface. The adhesion principle requires a species of polymer chains to form a bond with a material through complementary functional groups and form a network in situ that stitches with the polymer network of a hydrogel. We study the physics and chemistry of this topology and describe its potential applications in medicine and engineering.

We present a computational-experimental study on the ternary alloying effect of CuZr-based shape memory alloy. The transformation behavior, including crystallization, martensite-austenite transformation temperature and hysteresis of Cu-Zr-X (X = Ni, Co, Hf) thin-film samples were investigated by nanocalorimetry. We used ab initio simulations to determine the B2-Cm transformation pathway, evaluate the lattice parameters, the relative phase stability, and the twin boundary energy as a function of composition. Experimental results show that alloying with Ni or Co reduces the hysteresis of the martensitic transformation, while Hf increases it. These observations are in agreement with the trend of the middle eigenvalue of the martensitic transformation matrix. The energy difference between the pure phases obtained from simulations suggests that both Co and Ni stabilize martensite against austenite. However, experiments show that Co decreases transformation temperature, while Ni increases it. We attribute this observation to the larger twin boundary energy and strain energy in the Co-containing alloy. Our results indicate that ab initio simulations are a helpful tool in the development of new shape memory alloys, provided the energy terms associated with the fine twin structure of the martensite are taken into account.

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Recent progress in the printing of soft materials has made it possible to fabricate soft stretchable devices for a range of engineering applications. These devices tend to be heterogeneous systems, and their reliability depends to a large extent on the integrity of the interfaces between the various materials in the system. Previous studies on the printing of hydrogels have highlighted the need to investigate the adhesion between extrusion printable dielectric elastomers and hydrogels. Here we consider polydimethylsiloxane (PDMS) and a polyacrylamide hydrogel that contains lithium chloride and a nonionic rheological modifier. We show that the adhesion between oxygen plasma-treated PDMS and the hydrogel increases with time to reach a stable value of 15 J m

Calorimetry has long been used to probe the physical state of a system by measuring the heat exchanged with the environment as a result of chemical reactions or phase transitions. Application of calorimetry to microscale biological samples, however, is hampered by insufficient sensitivity and the difficulty of handling liquid samples at this scale. Here, a micromachined calorimeter sensor that is capable of resolving picowatt levels of power is described. The sensor consists of low‐noise thermopiles on a thin silicon nitride membrane that allow direct differential temperature measurements between a sample and four coplanar references, which significantly reduces thermal drift. The partial pressure of water in the ambient around the sample is maintained at saturation level using a small hydrogel‐lined enclosure. The materials used in the sensor and its geometry are optimized to minimize the noise equivalent power generated by the sensor in response to the temperature field that develops around a typical sample. The experimental response of the sensor is characterized as a function of thermopile dimensions and sample volume, and its capability is demonstrated by measuring the heat dissipated during an enzymatically catalyzed biochemical reaction in a microliter‐sized liquid droplet. The sensor offers particular promise for quantitative measurements on biological systems., A highly sensitive chip calorimetric sensor that is capable of resolving picowatt‐level heat dissipation using low‐noise thermopiles is developed. Four references are used to eliminate any effect of ambient temperature changes; a hydrogel‐lined enclosure minimizes sample evaporation without impact on the thermal mass of the sensor. The sensor is demonstrated for the oscillating Briggs–Rauscher reaction and the enzymatic hydrolysis of ATP.

We report the results of tensile experiments on 900 nm sputter-deposited films of ZrB 2 , performed at temperatures ranging from ambient to 1016 K. The ZrB 2 samples were tested using micromachined sample frames with integrated micro-heaters. Transmission electron microscopy shows that both as-deposited films and films heated above 1000 K consist of two distinct layers, an amorphous layer and a crystalline layer with a very fine columnar structure. The ZrB 2 films have a room-temperature tensile strength in excess of 1.2 GPa, far exceeding the tensile strength of bulk ZrB 2 , but their stiffness is lower and decreases significantly with increasing temperature. The reduction in stiffness is attributed to the presence of the amorphous phase and the high density of transverse grain boundaries in the crystalline region. The fracture toughness of the ZrB 2 films was measured by introducing pre-cracks in the tensile specimens with a focused ion beam, and was found to be 2.57 ± 0.03 MPa√m, similar to values reported for bulk ZrB 2 .

Contact resonance atomic force microscopy (CR-AFM) is a nondestructive technique based on atomic force microscopy (AFM) that allows one to perform single-point measurements as well as surface mapping of the indentation modulus of a material. In this work, we demonstrate the potential of CR-AFM in applied mineralogy research. As a case study, we report the characterization of natural and thermally treated diaspore. Natural diaspore samples from the Ilbirdagi diasporic metabauxite (diasporite) deposit in the Milas (Mugla) region in Turkey were heat treated in a muffle furnace causing them to transform from diaspore to corundum. After the treatment, the samples had a polycrystalline structure with ordered micrometer-size rectangular grains of uniform crystallographic orientation. Nanomechanical characterization by CR-AFM allowed us to visualize inclusions with different mechanical properties and to determine the average indentation modulus of the surface of the thermally treated diaspore. Quantitative maps of the indentation modulus reveal the variation of the indentation modulus on the surface of single micro-grains with nanometer spatial resolution.

Carbon is known to significantly accelerate the formation reaction of zirconium diboride in reactive nanolaminates, although the detailed mechanism remains unclear. Here we investigate the catalytic effect of both C and N on the synthesis of ZrB2 using a first-principles theoretical approach. We show that the strong interactions of C and N with Zr at the B/Zr interfaces of the nanolaminate enhance the solid-state amorphization of the Zr lattice. Amorphization of the Zr, in turn, accelerates intermixing of the constituent layers of the reactive nanolaminate. On the basis of these results we propose that the addition of elements with strong binding energies to transition metals may facilitate low-temperature synthesis of transition metal diborides using reactive nanolaminates.

We measure stresses that develop in sputter-deposited amorphous Ge thin films during electrochemical lithiation and delithiation. Amorphous LixGe electrodes are found to flow plastically at stresses that are significantly smaller than those of their amorphous LixSi counterparts. The stress measurements allow for quantification of the elastic modulus of amorphous LixGe as a function of lithium concentration, indicating a much-reduced stiffness compared to pure Ge. Additionally, we observe that thinner films of Ge survive a cycle of lithiation and delithiation, whereas thicker films fracture. By monitoring the critical conditions for crack formation, the fracture energy is calculated using an analysis from fracture mechanics. The fracture energies are determined to be Γ = 8.0 J m−2 for a-Li0.3Ge and Γ = 5.6 J m−2 for a-Li1.6Ge. These values are similar to the fracture energy of pure Ge and are typical for brittle fracture. Despite being brittle, the ability of amorphous LixGe to flow at relatively small stresses during lithiation results in an enhanced ability of Ge electrodes to endure electrochemical cycling without fracture.

There is a large demand for fabrics that can survive high-temperature fires for an extended period of time, and protect the skin from burn injuries. Even though fire-resistant polymer fabrics are commercially available, many of these fabrics are expensive, decompose rapidly, and/or become very hot when exposed to high temperatures. We have developed a new class of fire-retarding materials by laminating a hydrogel and a fabric. The hydrogel contains around 90% water, which has a large heat capacity and enthalpy of vaporization. When the laminate is exposed to fire, a large amount of energy is absorbed as water heats up and evaporates. The temperature of the hydrogel cannot exceed 100 °C until it is fully dehydrated. The fabric has a low thermal conductivity and maintains the temperature gradient between the hydrogel and the skin. The laminates are fabricated using a recently developed tough hydrogel to ensure integrity of the laminate during processing and use. A thermal model predicts the performance of the laminates and shows that they have excellent heat resistance in good agreement with experiments, making them viable candidates in life saving applications such as fire-resistant blankets or apparel.

Reactive nanolaminates afford a promising route for the low-temperature synthesis of zirconium diboride, an ultrahigh-temperature ceramic with metallic properties. Although the addition of carbon is known to facilitate sintering of ZrB2, its effect on the kinetics of the formation reaction has not been elucidated. We have employed a combined approach of nanocalorimetry and first-principles theoretical studies to investigate the kinetic role of carbon in the synthesis of ZrB2 using B4C/Zr reactive nanolaminates. Structural characterization of the laminates by XRD and TEM reveal that the reaction proceeds via interdiffusion of the B4C and Zr layers, which produces an amorphous Zr3B4C alloy. This amorphous alloy then crystallizes to form a supersaturated ZrB2(C) compound. A kinetic analysis shows that carbon lowers the energy barriers for both interdiffusion and crystallization by more than 20%. Energetic calculations based on first-principles modeling suggest that the reduction of the diffusion barrier may be attributed to the stronger bonding between Zr and C as compared to the bonding between Zr and B.

We have measured the fracture energy of lithiated silicon thin-film electrodes as a function of lithium concentration using a bending test. First, silicon thin-films on copper substrates were lithiated to various states of charge. Then, bending tests were performed by deforming the substrate to a pre-defined shape, producing a variation of the curvature along the length of the electrode. The bending tests allow determination of the critical strains at which cracks initiate in the lithiated silicon. Using the substrate curvature technique, we also measured the elastic moduli and the stresses that develop in the electrodes during electrochemical lithiation. From these measurements, the fracture energy was calculated as a function of lithium concentration using a finite element simulation of fracture of an elastic film on an elastic–plastic substrate. The fracture energy was determined to be Γ = 12.0 ± 3.0 J m−2 for amorphous silicon and Γ = 10.0 ± 3.6 J m−2 for Li3.28Si, with little variation in the fracture energy for intermediate Li concentrations. These results provide a guideline for the practical design of high-capacity lithium ion batteries to avoid fracture. The experimental technique described in this paper also provides a simple means of measuring the fracture energy of brittle thin-films.

The Poisson's ratio and residual strain of ultra-thin films (

We demonstrate a hydrogel bowl capable of selectively and rapidly collecting spilled oil while floating on water. The bowl has macroscopic openings in its sidewall, and its surface is first coated with octadecyltrichlorosilane (OTS) and then with diffusion pump oil, which imparts exceptional hydrophobic, oleophilic, and high oil wettability properties. The use of a hydrogel makes it possible to obtain surface hydrophobicity and oleophilicity, while also being inexpensive, eco-friendly, and easy to fabricate. Using a prototype of the bowl and a small pump system, we demonstrate that oils with a broad range of viscosities (2.7–2000.0 cSt at 20–40 °C) are more rapidly and efficiently collected from the surface of both pure water and seawater than with any other reported technique. The hydrogel bowl can collect oil for more than one month without losing its efficiency and can be stored in oil for reuse. Therefore, such hydrogel bowls represent a new alternative to conventional oil spill remediation techniques.

Based on atomic force microscopy (AFM), contact resonance AFM (CR-AFM) is a nondestructive technique that allows one to perform single point measurements as well as surface mapping of the indentation modulus of a material. In this work we exploit the possibility to use CR-AFM to study synthetic materials representative of K-basalt from Roman comagmatic Province. Having observed the presence of subsurface voids and inclusions at micrometer and sub-micrometer scale, a preliminary study has been conducted to verify the capability of CR-AFM nanomechanical mapping to nondestructively detect these features.