Grafted Alkene Chains: Triggers for Defeating Contact Thermal Resistance in Composite Elastomers.

The pursuit of enhancing the heat transfer performance of composite elastomers as the thermal interface materials (TIMs) is a compelling and timely endeavor, given the formidable challenges posed by interfacial thermal transport in the domains of energy science, electronic technology, etc. Despite the efficacy of phase change materials (PCMs) in enhancing composite elastomers' interfacial compatibility, thereby reducing contact thermal resistance for heat transfer improvement, their leakage post-transition has impeded the widespread adoption of this approach. Herein, a strategy is proposed for developing a solid-solid phase change composite elastomer by grafting alkene chains onto the crosslink network to eliminate the possibility of leakage. A series characterization suggest that the resulting material possesses a self-adjusting interfacial compatibility feature to help reduce contact thermal resistance for heat transfer facilitating. The investigations on adhesion strength and surface energy reveal that the presence of amorphous grafted alkane chains at the interface facilitates easier absorption onto the contacting solid surface, enhancing intermolecular interactions at the interface to promote across-boundary heat transfer. By integrating these findings with the thermal performance evaluation of composite elastomers using a real test vehicle, valuable insights are gained for the design of composite elastomers, establishing their suitability as TIMs in relevant fields.

Intrinsically Flexible Phase Change Fibers for Intelligent Thermal Regulation.

Owing to the significant latent heat generated at constant temperatures, phase change fibers (PCFs) have recently received much attention in the field of wearable thermal management. However, the phase change materials involved in the existing PCFs still experience a solid-liquid transition process, severely restricting their practicality as wearable thermal management materials. Herein, we, for the first time, developed intrinsically flexible PCFs (polyethylene glycol/4,4'-methylenebis(cyclohexyl isocyanate) fibers, PMFs) through polycondensation and wet-spinning process, exhibiting an inherent solid-solid phase transition property, adjustable phase transition behaviors, and outstanding knittability. The PMFs also present superior mechanical strength (28 MPa), washability (>100 cycles), thermal cycling stability (>2000 cycles), facile dyeability, and heat-induced recoverability, all of which are highly significant for practical wearable applications. Additionally, the PMFs can be easily recycled by directly dissolving them in solvents for reprocessing, revealing promising applications as sustainable materials for thermal management. Most importantly, the applicability of the PMFs was demonstrated by knitting them into permeable fabrics, which exhibit considerably improved thermal management performance compared with the cotton fabric. The PMFs offer great potential for intelligent thermal regulation in smart textiles and wearable electronics.

Recyclable Solid-Solid Phase Change Materials with Superior Latent Heat via Reversible Anhydride-Alcohol Crosslinking for Efficient Thermal Storage.

Solid-solid phase change materials (SSPCMs) with crosslinked polymer structures have received sustained interest due to their remarkable shape stability, enabling their application independently without the need for encapsulation or supporting materials. However, the crosslinking structure also compromises their latent heat and poses challenges to their recyclability. Herein, a novel strategy harnessing the internal-catalyzed reversible anhydride-alcohol crosslinking reaction to fabricate SSPCMs with superior latent heat and exceptional dual recyclability is presented. Easily accessible anhydride copolymers (e.g., propylene-maleic anhydride alternating copolymers), provide abundant reactive anhydride sites within the polymer matrix; polyethylene glycol serves as both the grafted phase change component and the crosslinker. The resulting SSPCMs attain a peak latent heat value of 156.8 J g-1 which surpasses all other reported recyclable crosslinked SSPCMs. The materials also exhibit certain flexibility and a tunable tensile strength ranging from 6.6 to 11.0 MPa. Beyond that, leveraging the reversible anhydride-alcohol crosslinks, the SSPCMs demonstrate dual recyclability through bond-exchange remolding and reversible-dissociation-enabled dissolving-recrosslinking without any reactive chemicals. Furthermore, by integrating solar-thermal conversion fillers like polydopamine nanoparticles, the potential of the system in efficient conversion, storage, and release of solar energy is highlighted.

Ionenes as Potential Phase Change Materials with Self-Healing Behavior.

Ionenes are poly(ionic liquids) (PILs) comprising a polymer backbone with ionic groups along the structure. Ionenes as solid-solid phase change materials are a recent research field, and some studies have demonstrated their potential in thermal dissipation into electronic devices. Eight ionenes obtained through Menshutkin reactions were synthesized and characterized. The analysis of the thermal tests allowed understanding of how the thermal properties of the polymers depend on the aliphatic nature of the dihalogenated monomer and the carbon chain length. The TGA studies concluded that the ionenes were thermally stable with T10% above 420 °C. The DSC tests showed that the prepared ionenes presented solid-solid transitions, and no melting temperature was appreciated, which rules out the possibility of solid-liquid transitions. All ionenes were soluble in common polar aprotic solvents. The hydrophilicity of the synthesized ionenes was studied by the contact angle method, and their total surface energy was calculated. Self-healing behavior was preliminarily explored using a selected sample. Our studies show that the prepared ionenes exhibit properties that make them potential candidates for applications as solid-solid phase change materials.

RGO-Coated Polyurethane Foam/Segmented Polyurethane Composites as Solid-Solid Phase Change Thermal Interface Material.

Thermal interface material (TIM) is crucial for heat transfer from a heat source to a heat sink. A high-performance thermal interface material with solid-solid phase change properties was prepared to improve both thermal conductivity and interfacial wettability by using reduced graphene oxide (rGO)-coated polyurethane (PU) foam as a filler, and segmented polyurethane (SPU) as a matrix. The rGO-coated foam (rGOF) was fabricated by a self-assembling method and the SPU was synthesized by an in situ polymerization method. The pure SPU and rGOF/SPU composite exhibited obvious solid-solid phase change properties with proper phase change temperature, high latent heat, good wettability, and no leakage. It was found that the SPU had better heat transfer performance than the PU without phase change properties in a practical application as a TIM, while the thermal conductivity of the rGOF/SPU composite was 63% higher than that of the pure SPU at an ultra-low rGO content of 0.8 wt.%, showing great potential for thermal management.

Carboxylated nanocellulose/poly(ethylene oxide) composite films as solid-solid phase-change materials for thermal energy storage.

Composite films of poly(ethylene oxide) (PEO) and 0%-20% surface-carboxylated cellulose nanofibrils (CNFs) were prepared by mixing the aqueous CNF dispersion and aqueous PEO solution at various weight ratios followed by casting and drying. The 20% CNF/PEO composite film was transparent, whereas the 100% PEO film was translucent. The addition of CNFs to the PEO matrix resulted in decreases of the crystallinity and crystal size of spherical PEO. The Young's modulus and tensile strength of the 100% PEO film were 0.2 GPa and 6.1 MPa, respectively, and remarkably increased to 2.4 GPa and 86 MPa, respectively, with the addition of 20% CNF. The CNF/PEO composite films had clear melting and crystallization temperatures in the heating and cooling processes, respectively. Nevertheless, the coefficients of thermal expansion at temperatures above the melting point of PEO significantly decreased with the CNF addition. The CNF/PEO composite films are therefore promising solid-solid phase-change materials for energy storage with high film dimensional stability.

Homogeneous synthesis of cellulose acrylate-g-poly (n-alkyl acrylate) solid-solid phase change materials via free radical polymerization.

A novel solid-solid phase change materials, namely, cellulose acrylate-g-poly (n-alkyl acrylate) (CA-g-PAn) (n = 14, 16 and 18) were successfully synthesized by free radical polymerization in N, N-dimethylacetamide (DMAc). The successful grafting was confirmed by fourier transform infrared spectra (FT-IR) and nuclear magnetic resonance (NMR). The properties of the CA-g-PAn copolymers were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The phase change temperatures and the melting enthalpies of CA-g-PAn copolymers are in the range of 10.1-53.2 °C and 15-95 J/g, respectively. It can be adjusted by the contents of poly (n-alkyl acrylate) and the length of alkyl side-chain. The thermal resistant temperatures of CA-g-PA14, 16 and 18 copolymers are 308 °C, 292 °C and 273 °C, respectively. It show that all of grafting materials exhibit good thermal stability and shape stability. Therefore, it is expected to be applied in the cellulose-based thermos-regulating field.

Effects of Fatty Acid Anhydride on the Structure and Thermal Properties of Cellulose-g-Polyoxyethylene (2) Hexadecyl Ether.

Cellulose was premodified by short-chain fatty acid anhydrides, such as acetic anhydride (CA), propionic anhydride (CP), and butyric anhydride (CB), followed by grafting of polyoxyethylene (2) hexadecyl ether (E2C16) using toluene-2,4-diisocyanate as a coupling agent. The feeding molar ratio of E2C16 and the anhydroglucose unit (AGU) was fixed at 4:1, and then a series of CA-g-E2C16, CP-g-E2C16, and CB-g-E2C16 copolymers were successfully prepared. The structures and properties of the copolymers were characterized using FTIR (fourier transform infrared spectra), ¹H-NMR (Proton nuclear magnetic resonance), DSC (Differential scanning calorimeter), POM (polarized light microscopy), TGA (thermogravimetric analysis) and WAXD (wide-angle X-ray diffraction). It was shown that with the anhydride/AGU ratio increasing, the degree of substitution (DS) value of E2C16 showed a trend of up first and then down. With the carbon chain length increasing, the DS value of E2C16 continuously increases. The phase transition temperature and thermal enthalpy of the copolymers increased with an increasing DS value of E2C16. When the ratio of CB/AGU was 1.5:1, the DS of E2C16 was up to the maximum value of 1.02, and the corresponding melting enthalpy and crystallization enthalpy were 32 J/g and 30 J/g, respectively. The copolymers showed solid⁻solid phase change behavior. The heat resistant temperature of cellulose-based solid⁻solid phase change materials was always higher than 270 °C. After the grafting reaction, the crystallinity of E2C16 decreased, while the crystal type was still hexagonal.