Confined Crystallization Polyether-Based Flexible Phase Change Film for Thermal Management.

Phase change materials (PCMs) possess the potential to regulate temperature by utilizing their thermal properties to absorb and release heat. Nevertheless, the application of PCMs in thermal management is constrained by issues such as liquid leakage and limited flexibility. In this study, we propose a novel approach to address these challenges by incorporating a pore structure within nanofibers to confine the crystallization of phase change molecules, thereby enhancing the flexibility of the composite material. Additionally, inspired by the adaptive mechanisms observed in plants, we have developed a form stable PCM based on polyether, which effectively mitigates the issue of liquid leakage at higher temperatures. Despite being a solid-liquid PCM at its core, this material exhibits molecular-scale flow and macroscopic shape stability as a result of intermolecular forces. The composite film material possesses remarkable flexibility, efficient thermal management capabilities, adjustable phase transition temperature, and the ability to undergo repeated processing and utilization. Consequently, it holds promising potential for applications in personal thermal energy management.

The Effect of Expanded Graphite Content on the Thermal Properties of Fatty Acid Composite Materials for Thermal Energy Storage.

The mass content of expanded graphite (EG) in fatty acid/expanded graphite composite phase-change materials (CPCMs) affects their thermal properties. In this study, a series of capric-myristic acid/expanded graphite CPCMs with different EG mass content (1%, 3%, 5%, 8%, 12%, 16%, and 20%) were prepared. The adsorption performance effect of EG on the PCMs was observed and analyzed. The structure and thermal properties of the prepared CPCMs were characterized via scanning electron microscopy, differential scanning calorimetry, thermal conductivity measurements, and heat energy storage/release experiments. The results show that the minimum mass content of EG in the CPCMs is 7.6%. The phase-change temperature of the CPCMs is close to that of the PCMs, at around 19 °C. The latent heat of phase change is equivalent to that of the PCM at the corresponding mass content, and that of phase change with an EG mass content of 8% is 138.0 J/g. The CPCMs exhibit a large increase in thermal conductivity and a significant decrease in storage/release time as the expanded graphite mass content increases. The thermal conductivity of the CPCM with a mass content of 20% is 418.5% higher than that with a mass content of 5%. With an increase in the EG mass content in CPCMs, the heat transfer mainly transitions from phase-change heat transfer to thermal conductivity.

Reversible Laser Imprinting of Phase Change Photonic Structures in Integrated Waveguides.

Formation of laser-induced periodic surface structures (LIPSS) is known as a fast and robust method of functionalization of material surfaces. Of particular interest are LIPSS that manifest as periodic modulation of phase state of the material, as it implies reversibility of phase modification that constitute rewritable LIPSS, and recently was demonstrated for chalcogenide phase change materials (PCMs). Due to remarkable properties of chalcogenide PCMs─nonvolatality, prominent optical contrast and ns switching speed─such novel phase change LIPSS hold potential for exciting applications in all-optical tunable photonics. In this work we explore phase change LIPSS formation in thin films of Ge2Sb2Te5 (GST) integrated with planar and rib waveguides. We demonstrate that by fine-tuning laser radiation, the morphology of phase change LIPSS can be controlled, including their period and fill factor, and investigate the limitations of multicycle rewriting of the structures. We also demonstrate the formation of phase change LIPSS on a 1D waveguide, which has potential for use as tunable Bragg filters or structures for on-demand light decoupling into the far-field. The presented concept of applying phase change LIPSS offers a promising approach to enable fast and simple tuning in integrated photonic devices.

3D Confinement Stabilizes the Metastable Amorphous State of Antimony Nanoparticles - A New Material for Miniaturized Phase Change Memories?

The wet-chemical synthesis of 3D confined antimony nanoparticles (Sb-NP) at low and high temperatures is described. Using reaction conditions that are mild in temperature and strong in reducing power allows the synthesis of amorphous Sb-NP stabilized with organic ligands. Exchanging the organic ligand 1-octanethiol by iodide enabled to investigate the unusual strong stability of this metastable material through simultaneous thermal analysis combining differential scanning calorimetry and thermogravimetric analysis. Additionally, in situ high temperature powder x-ray diffraction (p-XRD) shows a significant increase in stabilization of the amorphous phase in comparison to thin layered, 1D confined Sb or bulk material. Further, it is shown with scattering-type scanning near-field optical microscopy (s-SNOM) experiments that the optical response of the different phases in Sb-NP make the distinctness of each phase possible. It is proposed that the Sb-NP introduced here can serve as a 3D-confined optically addressable nanomaterial of miniaturized phase change memory devices.

Multi-wavelength and broadband plasmonic switching with V-shaped plasmonic nanostructures on a VO2coated plasmonic substrate.

In this paper, periodic arrays of identicalV-shaped gold nanostructures and variableV-shaped gold nanostructures are designed on top of a gold-coated silicon dioxide (SiO2) substrate with a thin spacer layer of vanadium dioxide (VO2) to realize multi-wavelength and broadband plasmonic switches, respectively. The periodic array of identicalV-shaped nanostructures (IVNSs) with small inter-particle separation leads to coupled interactions of the elementary plasmons of aV-shaped nanostructure (VNS), resulting in a hybridized plasmon response with two longitudinal plasmonic modes in the reflectance spectra of the proposed switches when the incident light is polarized in thex-direction. Thex-direction is oriented along the axis that joins theV-junctions of all VNSs in one unit cell of the periodic array. On exposure to temperature, electric field, or optical stimulus, the VO2layer transforms from its monoclinic semiconducting state to its rutile metallic state, leading to an overall change in the reflectance spectra obtained from the proposed nanostructures and resulting in an efficient multi-wavelength switching action. Finite difference time domain modelling is employed to demonstrate that an extinction ratio (ER) >12 dB at two wavelengths can be achieved by employing the proposed switches based on periodic arrays of IVNSs. Further, plasmonic switches based on variableV-shaped nanostructures-i.e. multiple VNSs with variable arm lengths in one unit cell of a periodic array-are proposed for broadband switching. In the broadband operation mode, we report an ER >5 dB over an operational wavelength range >1400 nm in the near-IR spectral range spanning over all optical communication bands, i.e. theO, E, S, C, LandUbands. Further, it is also demonstrated that the wavelength of operation for these switches can be tuned by varying the geometrical parameters of the proposed switches. These switches have the potential to be employed in communication networks where ultrasmall and ultrafast switches with multi-wavelength operation or switching over a wide operational bandwidth are inevitably required.

Multi-Scale Study of a Phase Change Material on a Tropical Island for Evaluating Its Impact on Human Comfort in the Building Sector.

Our study explores the utilization of a phase change material (PCM) to optimize energy efficiency and thermal comfort in buildings in tropical climates. Employing a comprehensive multi-scale approach, this research encompasses both microscopic and macroscopic analyses to rigorously evaluate the PCM's performance under various environmental conditions. It evaluates the effect of PCMs on ambient conditions in the face of temperature variations and high humidity, utilizing experimental methods at different scales (microscopic and macroscopic). Microscopic analyses reveal the composite structure of the PCM, consisting of microencapsulated paraffin within a cellulose fiber matrix. At a macroscopic scale, experiments using two real-scale test cells evaluated thermal performance and its influence on thermal comfort. Temperature and humidity data were meticulously collected over an extended period to assess the PCM's impact on indoor regulation. We employed type T thermocouples and flux meters to monitor thermal dynamics and energy flux across the building walls. This setup facilitated a detailed comparison of temperature variations and thermal comfort metrics between the PCM-equipped test cell and a control cell. The results indicate a seasonal duality of the PCM: beneficial in winter for thermal regulation but problematic in summer due to excessive heat retention. The conclusions highlight the importance of carefully selecting and adapting PCMs for tropical climates, thus providing valuable insights for designing sustainable buildings in regions facing similar climatic challenges.

Mechanical Properties and Durability of Composite Cement Pastes Containing Phase-Change Materials and Nanosilica.

Escalating global surface temperatures are highlighting the urgent need for energy-saving solutions. Phase-change materials (PCMs) have emerged as a promising avenue for enhancing thermal comfort in the construction sector. This study assessed the impact of incorporating PCMs ranging from 1% to 10% by mass into composite Portland cement partially replaced by fly ash (FA) and nanosilica particles (NS). Mechanical and electrochemical techniques were utilized to evaluate composite cements. The results indicate that the presence of PCMs delayed cement hydration, acting as a filler without chemically interacting within the composite. The combination of FA and PCMs reduced compressive strength at early ages, while thermal conductivity decreased after 90 days due to the melting point and the latent heat of PCMs. Samples with FA and NS showed a significant reduction in the CO2 penetration, attributed to their pozzolanic and microfiller effects, as well as reduced water absorption due to the non-absorptive nature of PCMs. Nitrogen physisorption confirmed structural changes in the cement matrix. Additionally, electrical resistivity and thermal behavior assessments revealed that PCM-containing samples could reduce temperatures by an average of 4 °C. This suggested that PCMs could be a viable alternative for materials with thermal insulation capacity, thereby contributing to energy efficiency in the construction sector.

Chaotropic Ions Mediated Polymer Gelation for Thermal Management.

Energy and environmental issues have increasingly garnered significant attention for sustainable development. Flexible and shape-stable phase change materials display great potential in regulation of environmental temperature for energy saving and human comfort. Here, inspired by the water absorption behavior of salt-tolerant animals and plants in salinity environment and the Hofmeister theory, highly stable phase change salogels (PCSGs) are fabricated through in situ polymerization of hydrophilic monomers in molten salt hydrates, which can serve multiple functions including thermal management patches, smart windows, and ice blocking coatings. The gelation principles of the polymer in high ion concentration solution are explored through the density functional theory simulation and verified the feasibility of four types of salt hydrates. The high concentration chaotropic ions strongly interacted with polymer chains and promoted the gelation at low polymer concentrations which derive highly-stable and ultra-moisturizing PCSGs with high latent heat (> 200 J g-1). The synergistic adhesion and transparency switching abilities accompanied with phase transition enable their smart thermal management. The study resolves the melting leakage and thermal cycling stability of salt hydrates, and open an avenue to fabricate flexible PCM of low cost, high latent heat, and long-term durability for energy-saving, ice-blocking, and thermal management.

Functional and financial analysis of an inclined step solar desalination using phase change nanomaterials.

Recent decades have seen a shortage of water, which has led scientists to concentrate on solar desalination technologies. The present study examines the solar water desalination system with inclined steps, while considering various phase change materials (PCMs). The findings suggest that the incorporation of PCM generally enhances the productivity of the solar desalination system. Additionally, the combination of nanoparticles has been used to PCM, which is a popular technique utilized nowadays to improve the efficiency of these systems. The current investigation involves the transient modeling of a solar water desalination system, utilizing energy conservation equations. The equations were solved using the Runge-Kutta technique of the ODE23s order. The temperatures of the salt water, the absorbent plate of the glass cover, and the PCM were calculated at each time. Without a phase changer, the rate at which fresh water is produced is around 5.15 kg/m2·h. The corresponding mass flow rates of paraffin, n-PCM I, n-PCM III, n-PCM II, and stearic acid are 22.9, 28.9, 5.9, 11.9, and 73 kg/m2·h. PCMs, with the exception of stearic acid, exhibit similar energy efficiency up to an ambient temperature of around 29°. However, at temperatures over 29°, n-PCM II outperforms other PCM.

The Effect of Sputtering Sequence Engineering in Superlattice-like Sb-Rich-Based Phase Change Materials.

This paper presents a comprehensive investigation into the thermal stability of superlattice-like (SLL) thin films fabricated by varying the sputtering sequences of the SLL [Ge8Sb92(25nm)/GeTe(25nm)]1 and SLL [GeTe(25nm)/Ge8Sb92(25nm)]1 configurations. Our results reveal significantly enhanced ten-year data retention (Tten) for both thin films measured at 124.3 °C and 151.9 °C, respectively. These values surpass the Tten of Ge2Sb2Te5 (85 °C), clearly demonstrating the superior thermal stability of the studied SLL configurations. Interestingly, we also observe a distinct difference in the thermal stability between the two SLL configurations. The superior thermal stability of SLL [GeTe(25nm)/Ge8Sb92(25nm)]1 is attributed to the diffusion of the Sb precipitated phase from Ge8Sb92 to GeTe. This diffusion process effectively reduces the impact of the Sb phase on the thermal stability of the thin film. In contrast, in the case of SLL [Ge8Sb92(25nm)/GeTe(25nm)]1, the presence of the Sb precipitated phase in Ge8Sb92 facilitates the crystallization of GeTe, leading to reduced thermal stability. These findings underscore the significant influence of the sputtering sequence on the atomic behavior and thermal properties of superlattice-like phase change materials. Such insights provide a robust foundation for the design and exploration of novel phase change materials with improved thermal performance.

Electron-Deficient Multicenter Bonding in Phase Change Materials: A Chance for Reconciliation.

In the last few years, a controversy has been raised regarding the nature of the chemical bonding present in phase change materials (PCMs), many of which are minerals such as galena (PbS), clausthalite (PbSe), and altaite (PbTe). Two opposite bonding models have claimed to be able to explain the extraordinary properties of PCMs in the last decade: the hypervalent (electron-rich multicenter) bonding model and the metavalent (electron-deficient) bonding model. In this context, a third bonding model, the electron-deficient multicenter bonding model, has been recently added. In this work, we comment on the pros and cons of the hypervalent and metavalent bonding models and briefly review the three approaches. We suggest that both hypervalent and metavalent bonding models can be reconciled with the third way, which considers that PCMs are governed by electron-deficient multicenter bonds. To help supporters of the metavalent and hypervalent bonding model to change their minds, we have commented on the chemical bonding in GeSe and SnSe under pressure and in several polyiodides with different sizes and geometries.

The cores regulation of paraffin-chitosan phase change microcapsules for constant temperature building.

Phase change materials (PCMs) can store and release latent heat under the designed phased change temperature and have received substantial interest for energy conservation and thermal control purposes. The use of PCMs in the construction of constant temperature buildings can improve the comfortable environment and save more energy. However, the leakage of PCMs during phase change process limits the application of PCMs. In this paper, a series of PCMs microcapsules with controllable core numbers is synthesized with paraffin (37 ℃) as the core and cross-linked chitosan as the wall. The single-core phase-change microcapsules (S-PCM) and multicore phase-change microcapsules (M-PCM) were prepared by adjusting the preparation condition. The latent heat of S-PCM and M-PCM are 61.4 mJ mg-1 and 50.1 mJ mg-1, respectively. The S-PCM and M-PCM display good stability without paraffin leakage. In addition, the composite blocks of gypsum and S-PCM (GSCM) and M-PCM (GMCM) were prepared and the thermoregulatory effection was investigated, where the surface temperature of GSCM was 5-10 ℃ lower than that of pure gypsum block. PCMs may also have broad application space in electronics, cold chain, and other industries.

Rewritable Photonic Integrated Circuit Canvas Based on Low-Loss Phase Change Material and Nanosecond Pulsed Lasers.

Programmable photonic integrated circuits (PICs) are an increasingly important platform in optical science and engineering. However, current programmable PICs are mostly formed through subtractive fabrication techniques, which limits the reconfigurability of the device and makes prototyping costly and time-consuming. A rewritable PIC architecture can circumvent these drawbacks, where PICs are repeatedly written and erased on a single PIC canvas. We demonstrate such a rewritable PIC platform by selective laser writing a layer of wide-band-gap phase change material (PCM) Sb2S3 with a low-cost benchtop setup. We show arbitrary patterning with resolution up to 300 nm and write dielectric assisted waveguides with a low optical loss of 0.0172 dB/µm. We envision that using this inexpensive benchtop platform thousands of PIC designs can be written, tested, and erased on the same chip without the need for lithography/etching tools or a nanofabrication facility, thus reducing manufacturing cost and increasing accessibility.

High-Safety Lithium-Ion Battery Separator with Adjustable Temperature Function Inspired by the Sugar Gourd Structure.

As the power core of an electric vehicle, the performance of lithium-ion batteries (LIBs) is directly related to the vehicle quality and driving range. However, the charge-discharge performance and cycling performance are affected by the temperature. Excessive temperature can cause internal short circuits and even lead to safety issues, such as thermal runaway. The separator plays a crucial role in protecting the battery from regular operation, preventing direct touch between the cathode and the anode while allowing the transport of lithium ions. In this study, we have designed a thermoregulating separator in the shape of calabash, which uses melamine-encapsulated paraffin phase change material (PCM) with a wide enthalpy (0-168.52 J g-1) to dissipate the heat generated inside the battery promptly. Under extra-long-use conditions, the heat emitted by the battery is absorbed by the PCM without causing a significant temperature rise that triggers thermal runaway. The PCM separator can effectively suppress the temperature increase caused by battery penetration. Due to the unique structure of the PCM, the battery is short-circuited; it can significantly delay the internal temperature rise of the battery and quickly dissipate the heat, which is consistent with the characteristics of natural calabash in nutrient absorption and water diffusion, improving the melting and heat storage efficiency of the PCM. The design of the phase change separator provides an effective reference for overheat protection and improved safety in lithium-ion batteries.

Physical-Entanglements-Supported Polymeric Form Stable Phase Change Materials with Ultrahigh Melting Enthalpy.

With the rapid development of new energy and the upgrading of electronic devices, structurally stable phase change materials (PCMs) have attracted widespread attentions from both academia and industries. Traditional cross-linking, composites, or microencapsulation methods for preparation of form stable PCMs usually sacrifice part of the phase change enthalpy and recyclability. Based on the basic polymer viscoelasticity and crystallization theories, here, a kind of novel recyclable polymeric PCM is developed by simple solution mixing ultrahigh molecular weight of polyethylene oxide (UHMWPEO) with its chemical identical oligomer polyethylene glycol (PEG). Rheological and leakage-proof experiments confirm that, even containing 90% of phase change fraction PEG oligomers, long-term of structure stability of PCMs can be achieved when the molecular weight of UHMWPEO is higher than 7000 kg mol-1 due to their ultralong terminal relaxation time and large number of entanglements per chain. Furthermore, because of the reduced overall entanglement concentration, phase change enthalpy of PCMs can be greatly promoted, even reaching to ≈185 J g-1, which is larger than any PEG-based form stable PCMs in literatures. This work provides a new strategy and mechanism for designing physical-entanglements-supported form stable PCMs with ultrahigh phase change enthalpies.

Measuring Electrical Resistivity at the Nanoscale in Phase-Change Materials.

Electrical resistivity is the key parameter in the active regions of many current nanoscale devices, from memristors to resistive random-access memory and phase-change memories. The local resistivity of the materials is engineered on the nanoscale to fit the performance requirements. Phase-change memories, for example, rely on materials whose electrical resistance increases dramatically with a change from a crystalline to an amorphous phase. Electrical characterization methods have been developed to measure the response of individual devices, but they cannot map the local resistance across the active area. Here, we propose a method based on operando electron holography to determine the local resistance within working devices. Upon switching the device, we show that electrical resistance is inhomogeneous on the scale of only a few nanometers.

Electrically Reconfigurable Phase-Change Transmissive Metasurface.

Programmable and reconfigurable optics hold significant potential for transforming a broad spectrum of applications, spanning space explorations to biomedical imaging, gas sensing, and optical cloaking. The ability to adjust the optical properties of components like filters, lenses, and beam steering devices could result in dramatic reductions in size, weight, and power consumption in future optoelectronic devices. Among the potential candidates for reconfigurable optics, chalcogenide-based phase change materials (PCMs) offer great promise due to their non-volatile and analogue switching characteristics. Although PCM have found widespread use in electronic data storage, these memory devices are deeply sub-micron-sized. To incorporate phase change materials into free-space optical components, it is essential to scale them up to beyond several hundreds of microns while maintaining reliable switching characteristics. This study demonstrated a non-mechanical, non-volatile transmissive filter based on low-loss PCMs with a 200 µm×200 µm switching area. The device/metafilter can be consistently switched between low- and high-transmission states using electrical pulses with a switching contrast ratio of 5.5 dB. The device was reversibly switched for 1250 cycles before accelerated degradation took place. The work represents an important step toward realizing free-space reconfigurable optics based on PCMs. This article is protected by copyright. All rights reserved.

Chemical bonding in phase-change chalcogenides.

Almost all phase-change memory materials (PCM) contain chalcogen atoms, and their chemical bonds have been denoted both as 'electron-deficient' [sometimes referred to as 'metavalent'] and 'electron-rich' ['hypervalent', multicentre]. The latter involve lone-pair electrons. We have performed calculations that can discriminate unambiguously between these two classes of bond and have shown that PCM have electron-rich, 3c-4e ('hypervalent') bonds. Plots of charge transferred between (ET) and shared with (ES) neighbouring atoms cannot on their own distinguish between 'metavalent' and 'hypervalent' bonds, both of which involve single-electron bonds. PCM do not exhibit 'metavalent' bonding and are not electron-deficient; the bonding is electron-rich of the 'hypervalent' or multicentre type.

Highly reproducible and CMOS-compatible VO2-based oscillators for brain-inspired computing.

With remarkable electrical and optical switching properties induced at low power and near room temperature (68 °C), vanadium dioxide (VO2) has sparked rising interest in unconventional computing among the phase-change materials research community. The scalability and the potential to compute beyond the von Neumann model make VO2 especially appealing for implementation in oscillating neural networks for artificial intelligence applications, to solve constraint satisfaction problems, and for pattern recognition. Its integration into large networks of oscillators on a Silicon platform still poses challenges associated with the stabilization in the correct oxidation state and the ability to fabricate a structure with predictable electrical behavior showing very low variability. In this work, the role played by the different annealing parameters applied by three methods (slow thermal annealing, flash annealing, and rapid thermal annealing), following the vanadium oxide atomic layer deposition, on the formation of VO2 grains is studied and an optimal substrate stack configuration that minimizes variability between devices is proposed. Material and electrical characterizations are performed on the different films and a step-by-step recipe to build reproducible VO2-based oscillators is presented, which is argued to be made possible thanks to the introduction of a hafnium oxide (HfO2) layer between the silicon substrate and the vanadium oxide layer. Up to seven nearly identical VO2-based devices are contacted simultaneously to create a network of oscillators, paving the way for large-scale implementation of VO2 oscillating neural networks.

Ab Initio Study of Novel Phase-Change Heterostructures.

Neuromorphic devices constitute a novel approach to computing that takes inspiration from the brain to unify the processing and storage units. Memories based on phase-change materials (PCMs) are potential candidates for such devices due to their non-volatility and excellent scalability, however their use is hindered by their conductance variability and temporal drift in resistance. Recently, it has been shown that the utilization of phase-change heterostructures consisting of nanolayers of the Sb2Te3 PCM interleaved with a transition-metal dichalcogenide, acting as a confinement material, strongly mitigates these problems. In this work, superlattice heterostructures made of TiTe2 and two prototypical PCMs, respectively GeTe and Ge2Sb2Te5 are considered. By performing ab initio molecular dynamics simulations, it is shown that it is possible to switch the PCMs without destroying the superlattice structure and without diffusion of the atoms of the PCM across the TiTe2 nanolayers. In particular, the model containing Ge2Sb2Te5 shows weak coupling between the two materials during the switching process, which, combined with the high stability of the amorphous state of Ge2Sb2Te5, makes it a very promising candidate for neuromorphic computing applications.