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Relaxor ferroelectric (RFE) polymers hold great promise for artificial muscles due to their high actuation strain, high loading stress, and fast response. However, the structural origin underlying their large electrostrictive deformation remains elusive. In this study, we investigate poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)]-based RFE terpolymers, incorporating 1,1-chlorofluoroethylene (CFE) or chlorotrifluoroethylene (CTFE) (the terpolymers are denoted as terP-CFE and terP-CTFE, respectively) as termonomers. Although both terpolymers show similar semicrystalline morphology, drastically different electrostrictive properties are observed. Specifically, the terP-CFE annealed at 100 °C achieves a record-high transverse strain of ~10.6%, whereas 100 °C-annealed terP-CTFE only shows a much lower actuation strain of ~4.2% at the same poling field of 190 MV/m. To elucidate the origin of this difference, time-resolved wide-angle X-ray diffraction, small-angle X-ray scattering, and Fourier transform infrared experiments are performed during in-situ electric poling. An RFE-to-ferroelectric (FE) crystal phase transition is observed for terP-CFE, but is absent for terP-CTFE. Beyond the contribution of the crystalline phase, the oriented amorphous fraction and crystalline defects (e.g., taut-tie molecules) also play significant roles in enhancing electrostriction. This mechanistic insight provides a valuable foundation for the rational design of next-generation RFE polymers with tunable properties through defect-engineering of their semicrystalline structures. 

Within the linear regime of mechanical and electrical responses, it is commonly accepted that direct and converse piezoelectric coefficients should be the same. However, we observed a consistently higher converse d31 (∼54 pm/V) than the direct d31 (∼42 pC/N) for a quenched, stretched, annealed, and electrically poled poly(vinylidene fluoride-co-trifluorethylene) [P(VDF-TrFE)] 52/48 mol.% sample (abbreviated as coP-52/48QSAP). On the contrary, the direct and converse d31 values were the same for coP-65/35QSAP and coP-55/45QSAP. Small-angle X-ray scattering results showed that coP-52/48QSAP had a higher amount of relaxor-like secondary crystals (SCs) in the oriented amorphous fraction (OAF) (SCOAF) than coP-55/45QSAP and coP-65/35QSAP. To explain the experimental observation, we performed molecular dynamics (MD) simulation of the pure PVDF (without TrFE) to estimate direct and converse piezoelectricity for the PVDF OAF. Based on the MD simulation, the direct d31 had a plateau value around 350 pC/N for the transverse (i.e., along the chain direction) strain up to 1 %, whereas the simulated converse d31 could be lower (for electric field E < 0.8 MV/m), equal (for E = 0.8 MV/m), or higher (for E > 0.8 MV/m) than the direct d31, depending on the poling electric field. From the MD simulation, both mechano-electrostriction and electrostatic interaction were identified in the OAF as the driving force for enhanced piezoelectricity in ferroelectric PVDF. When ferroelectric domains were formed in the OAF by electric poling, the simulated converse d31 became higher than the direct d31. Combining both experimental and MD simulation results, the higher converse d31 than direct d31 for coP-52/48QSAP was understood qualitatively. 

Abstract BackgroundLongitudinal skeletal growth takes place in the cartilaginous growth plates. While growth plates are found at either end of conventional long bones, they occur at a variety of locations in the mammalian skeleton. For example, the metacarpals and metatarsals (MT) in the hands and feet form only a single growth plate at one end, and the pisiform in the wrist is the only carpal bone to contain a growth plate. We take advantage of this natural anatomical variation to test which components of the PTHrP/Ihh feedback loop, a fundamental regulator of chondrocyte differentiation, are specific to growth plate function. ResultsParathyroid hormone‐like hormone(Pthlh), the gene that transcribes parathyroid hormone‐related peptide (PTHrP), is expressed in the reserve zone of the growth plate‐forming end of the MT. At the opposite end, the absence of a PTHrP+ reserve zone results in premature chondrocyte differentiation andIndian hedgehog(Ihh) expression.Pthlhis expressed in the reserve zone of the developing pisiform, confirming the existence of a true growth plate. ConclusionA pool of PTHrP+ reserve zone chondrocytes is a defining characteristic of growth plates, and its patterning may be key to evolved differences in growth plate location in the mammalian skeleton. 

Current research on ferroelectric polymers centers predominantly on poly(vinylidene fluoride) (PVDF)–based fluoropolymers because of their superior performance. However, they are considered “forever chemicals” with environmental concerns. We describe a family of rationally designed fluorine-free ferroelectric polymers, featuring a polyoxypropylene main chain and disulfonyl alkyl side chains with a C3 spacer: −SO₂CH₂CHRCH₂SO₂− (R = −H or −CH₃). Both experimental and simulation results demonstrate that strong dipole-dipole interactions between neighboring disulfonyl groups induce ferroelectric ordering in the condensed state, which can be tailored by changing the R group: ferroelectric for R = −H or relaxor ferroelectric for R = −CH₃. At low electric fields, the relaxor polymer exhibits electroactuation and electrocaloric performance comparable with those of state-of-the-art PVDF-based tetrapolymers. 

Polymer piezoelectrics hold great potential for energy harvesting and wearable electronics. Efforts have been dedicated to enhancing piezoelectric coefficients and thermostability for several decades, but most of these have not been successful. In this report, we demonstrate a straightforward way to achieve high piezoelectric coefficients and output voltages while maintaining high thermostability at temperatures over 110 °C. Poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)] 80/20 mol.% nanofiber mats (made by electrospinning) with extremely high crystallinity and Curie temperatures were obtained via a two-step annealing process, from which large ferroelectric domains were formed in extended-chain crystals. After corona poling using water, which is a high dielectric constant medium, giant piezoelectricity (apparent d33 = 1045 ± 20 pC/N) and high output voltages (29.9 ± 0.5 V) were achieved. It is found that the dimensional effect induced significant polarization changes, which is the key requirement for piezoelectricity. Our finding in this work paves a way to further improve high-performance polymer piezoelectrics. 

Abstract Despite extensive research on piezoelectric polymers since the discovery of piezoelectric poly(vinylidene fluoride) (PVDF) in 1969, the fundamental physics of polymer piezoelectricity has remained elusive. Based on the classic principle of piezoelectricity, polymer piezoelectricity should originate from the polar crystalline phase. Surprisingly, the crystal contribution to the piezoelectric strain coefficientd₃₁is determined to be less than 10%, primarily owing to the difficulty in changing the molecular bond lengths and bond angles. Instead, >85% contribution is from Poisson's ratio, which is closely related to the oriented amorphous fraction (OAF) in uniaxially stretched films of semicrystalline ferroelectric (FE) polymers. In this perspective, the semicrystalline structure–piezoelectric property relationship is revealed using PVDF‐based FE polymers as a model system. In melt‐processed FE polymers, the OAF is often present and links the crystalline lamellae to the isotropic amorphous fraction. Molecular dynamics simulations demonstrate that the electrostrictive conformation transformation of the OAF chains induces a polarization change upon the application of either a stress (the direct piezoelectric effect) or an electric field (the converse piezoelectric effect). Meanwhile, relaxor‐like secondary crystals in OAF (SC_OAF), which are favored to grow in the extended‐chain crystal (ECC) structure, can further enhance the piezoelectricity. However, the ECC structure is difficult to achieve in PVDF homopolymers without high‐pressure crystallization. We have discovered that high‐power ultrasonication can effectively induce SC_OAFin PVDF homopolymers to improve its piezoelectric performance. Finally, we envision that the electrostrictive OAF mechanism should also be applicable for other FE polymers such as odd‐numbered nylons and piezoelectric biopolymers. 

Evidence-accumulation models (EAMs) are powerful tools for making sense of human and animal decision-making behavior. EAMs have generated significant theoretical advances in psychology, behavioral economics, and cognitive neuroscience and are increasingly used as a measurement tool in clinical research and other applied settings. Obtaining valid and reliable inferences from EAMs depends on knowing how to establish a close match between model assumptions and features of the task/data to which the model is applied. However, this knowledge is rarely articulated in the EAM literature, leaving beginners to rely on the private advice of mentors and colleagues and inefficient trial-and-error learning. In this article, we provide practical guidance for designing tasks appropriate for EAMs, relating experimental manipulations to EAM parameters, planning appropriate sample sizes, and preparing data and conducting an EAM analysis. Our advice is based on prior methodological studies and the our substantial collective experience with EAMs. By encouraging good task-design practices and warning of potential pitfalls, we hope to improve the quality and trustworthiness of future EAM research and applications. 

Among all ferroelectric polymers, poly(vinylidene fluoride) (PVDF)-based polymers exhibit the best piezoelectric properties and thus are promising for sensors, actuators, and energy harvesters in flexible/wearable electronics and soft robotics. Despite decades of research effort, the structure-property relationship is still unclear for ferroelectric polymers, and their piezoelectric performance is often limited to ~30 pC/N. In this study, we report the effects of chemical defects [i.e., the head-to-head and tail-to-tail (HHTT) sequence] and high-power ultrasonication on the piezoelectric performance of PVDF. Two PVDF homopolymers with different HHTT contents were studied. The PVDF with a lower HHTT content (4.3%) exhibited a higher melting temperature (Tm, denoted as HMT), whereas that with a higher HHTT content (5.9%) exhibited a lower Tm (denoted as LMT). In addition to the primary crystals (PCs) and the isotropic amorphous fraction, wide-angle X-ray diffraction also suggested the presence of the oriented amorphous fraction (OAF) and secondary crystals (SCs), which are important in enhancing the piezoelectricity for PVDF. Intriguingly, the LMT PVDF exhibited higher piezoelectric performance than the HMT PVDF, because it had a higher OAF/SC content. In addition, high-power ultrasonication was shown to effectively break relaxor-like SCs off from the PCs, further enhancing the piezoelectric performance. That is, the inverse piezoelectric coefficient d31 reached as high as 76.2 pm/V at 65 °C for the ultrasonicated LMT PVDF. The insight from this study will enable us to design better piezoelectric PVDF polymers for practical electromechanical applications. 

Cartilage histomorphometry is often performed on decalcified, paraffin-embedded bone sections, which provide versatility in staining applications from basic morphology to immunohistochemistry. Safranin O is a cationic dye that binds to proteoglycans in cartilage and is routinely used to assess growth plate dynamics and/or fracture repair at bone–cartilage interfaces. When used with a counterstain such as fast green, safranin O can offer exquisite differentiation of cartilage from surrounding bone. However, various decalcification and processing methods can deplete proteoglycans, rendering inconsistent, weak, or absent safranin O staining with indiscriminate bone–cartilage boundaries. We sought to develop an alternative staining methodology that preserves the contrast of bone and cartilage in cases of proteoglycan depletion that can be applied when other cartilage stains are unsuccessful. Here, we describe and validate a modified periodic acid-Schiff (PAS) protocol that we developed using Weigert's iron hematoxylin and light green stains as an alternative to safranin O for discriminating bone–cartilage interfaces of skeletal tissues. This method provides a practical solution for differentiating bone and cartilage when safranin O staining is not detected after decalcification and paraffin processing. The modified PAS protocol can be useful for studies in which identification of the bone–cartilage interface is essential but may not be preserved with standard staining approaches. © 2023 The Authors. JBMR Plus published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research. 

The Carbon monOxide Mapping Array Project (COMAP) Pathfinder survey continues to demonstrate the feasibility of line-intensity mapping using high-redshift carbon monoxide (CO) line emission traced at cosmological scales. The latest COMAP Pathfinder power spectrum analysis is based on observations through the end of Season 2, covering the first three years of Pathfinder operations. We use our latest constraints on the CO(1–0) line-intensity power spectrum atz~ 3 to update corresponding constraints on the cosmological clustering of CO line emission and thus the cosmic molecular gas content at a key epoch of galaxy assembly. We first mirror the COMAP Early Science interpretation, considering how Season 2 results translate to limits on the shot noise power of CO fluctuations and the bias of CO emission as a tracer of the underlying dark matter distribution. The COMAP Season 2 results place the most stringent limits on the CO tracer bias to date, at ⟨T b⟩ < 4.8 μK, which translates to a molecular gas density upper limit ofρ_H2< 1.6 × 10⁸M_⊙Mpc⁻³atz~ 3 given additional model assumptions. These limits narrow the model space significantly compared to previous CO line-intensity mapping results while maintaining consistency with small-volume interferometric surveys of resolved line candidates. The results also express a weak preference for CO emission models used to guide fiducial forecasts from COMAP Early Science, including our data-driven priors. We also consider directly constraining a model of the halo–CO connection, and show qualitative hints of capturing the total contribution of faint CO emitters through the improved sensitivity of COMAP data. With continued observations and matching improvements in analysis, the COMAP Pathfinder remains on track for a detection of cosmological clustering of CO emission.