Thermal Conductivity Of Polymers Research Articles

Enhanced Thermal Conductivity in Thermoplastic Polyether Ester Elastomer Vitrimer Composite Foams via Cell Growth-Induced Orientation and Lap of Hybrid Fillers

Lightweight thermal conductive polymer foams own a great potential application in some weight sensitive fields such as aerospace and encapsulation. Herein, the enhancement of thermal conductivity of thermoplastic polyether ester elastomer (TPEE) vitrimer composites foams caused by cell growth inducing fillers orientation and lap was investigated with hybrid fillers of fixed 15 vol.% h-BN and various SiC nanowires. First, the hybrid fillers orientation in TPEE vitrimer composites (TVC) characterized by SEM and XRD patterns showed that the hybrid fillers were induced to be through-plane orientation and no interfacial defects were observed owing to the increasing contact area among fillers caused by large specific area and length of SiC nanowires. Based on that, cells were generated into TVC through scCO2 foaming. The effect of through-plane orientation and lap of hybrid fillers caused by cell growth of different cell structures on the thermal conductivity of TVC foams was investigated using extended Hashin-Shtrikman model and Maxwell-Eucken I model. The results showed that the thermal conductivity of TVC foams could greatly be enhanced to be higher than that of TVC by cell growth of continuous cell structures as it contributed to the through-plane orientation and lap of hybrid fillers to increase the contact and lap ratio among fillers. Thereby, the thermal conductive networks favorable to heat transfer were constructed in TVC foams to enhance the thermal conductivity as well as merit of lightweight.

An Effective Approach for the Preparation of High Performance Thermal Conductive Polymer Composites Containing Liquid Metal

An Effective Approach for the Preparation of High Performance Thermal Conductive Polymer Composites Containing Liquid Metal

Modulating thermal and electrical conductivities in polymers: An approach toward extracting molecular design rules through atomistic simulations

Polymers are extensively employed in diverse industries, including electrical equipment and electronic devices. Recent technological advancements have intensified the demand for dielectric polymers with both high insulation resistance and high thermal conductivity. We employed molecular dynamics simulations to clarify the intricate relationship between molecular structures, thermal conductivity, and ionic mobility from an atomistic point of view. Examined polymers include polyethylene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyoxymethylene, and polyethylene oxide. Based on the elucidated correlations among force field parameters, we found that the parameters can be clustered into four groups: group 1 (atomic and bond parameters and force constant of the bond angle), group 2 (equilibrium angle and force constant of dihedral angle), and group 3 (side chain atom charges). Thermal conductivity showed relationships with parameters in group 1, with correlation coefficients mostly exceeding 0.7 in the absolute value. Considering the correlations between the parameters, we systematically altered the parameters within each group and computed thermal conductivity and ionic mobility. When altering the force field parameters of groups 1 and group 2, a trade-off relationship between thermal conductivity and ionic mobility becomes evident. Conversely, altering the force field parameters in group 3 increased thermal conductivity while decreasing ionic mobility, breaking the trade-off relationship. The proposed clustered-parameter variation method can predict the changes in the electrical and thermal conductivity of polymers through molecular structure modifications. The method, being a general and first-principles approach, is likely to have significant advantages in the molecular design across a diverse range of polymers.

Core-sheath smart polymer fiber composites with high elasticity and thermal conductivity

Thermal conductive polymer fibers have broad development prospects because of its excellent thermal and mechanical properties. However, currently reported polymer fibers cannot simultaneously possess high thermal conductivity and high resilience, which greatly limits the application of thermal conductive polymer fibers. Therefore, preparing fibers with high thermal conductivity and high resilience is extremely challenging. The thermoplastic polyurethane/boron nitride liquid metal (TPU/BN-LMs) fiber with core sheath structure is prepared by coaxial wet spinning technology, the boron nitride (BN) doped in thermoplastic polyurethane elastomer (TPU) as sheath and the liquid metal (LMs) as core. The maximum tensile strength of the fiber is 3.9 MPa, and the elongation can reach 400 %. After multiple cycles of stretching, it can return to its original state. In addition, the thermal conductivity of the fiber in the horizontal direction and the vertical direction are 10.0 W m−1 K−1 and 4.6 W m−1 K−1, respectively. This work solves the current problem of high thermal conductivity and high resilience of thermally conductive polymer fibers that are difficult to be compatible. And it provides a new research idea for the design and preparation of new high thermal conductivity and high resilience polymer fiber materials.

AI-assisted inverse design of sequence-ordered high intrinsic thermal conductivity polymers

Artificial intelligence (AI) promotes the polymer design paradigm from a traditional trial-and-error approach to a data-driven style. Achieving high thermal conductivity (TC) for intrinsic polymers is urgent because of their importance in the thermal management of many industrial applications such as microelectronic devices and integrated circuits. In this work, we have proposed a robust AI-assisted workflow for the inverse design of high TC polymers. By using 1144 polymers with known computational TCs, we construct a surrogate deep neural network model for TC prediction and extract a polymer-unit library with 32 sequences. Two state-of-the-art multi-objective optimization algorithms of unified non-dominated sorting genetic algorithm III (U-NSGA-III) and q-noisy expected hypervolume improvement (qNEHVI) are employed for sequence-ordered polymer design with both high TC and synthetic possibility. For triblock polymer design, the result indicates that qNHEVI is capable of exploring a diversity of optimal polymers at the Pareto front, but the uncertainty in Quasi-Monte Carlo sampling makes the trials costly. The performance of U-NSGA-III is affected by the initial random structures and usually falls into a locally optimal solution, but it takes fewer attempts with lower costs. 20 parallel U-NSGA-III runs are conducted to design the pentablock polymers with high TC, and half of the candidates among 1921 generated polymers achieve the targets (TC > 0.4 W m−1K−1 and SA < 3.0). Ultimately, we check the TC of 50 promising polymers through molecular dynamics simulations and reveal the intrinsic connections between microstructures and TCs. Our developed AI-assisted inverse design approach for polymers is flexible and universal, and can be extended to the design of polymers with other target properties.

Thermal performance of polymer gyroid heat exchangers combined with phase change materials as a latent heat thermal energy storage system: An experimental investigation

Latent heat thermal energy storage (LHTES) systems utilizing phase-change materials (PCMs) in conjunction with heat exchangers (HXs) have been widely investigated for efficient thermal energy utilization. This study experimentally evaluated the heat transfer performance and pressure loss of a PCM-based gyroid HX fabricated using a polymer 3D printer. Initially, the study compared the phase change time, heat storage and release characteristics, and pressure drop of the gyroid HX with those of a conventional shell-and-tube HX (S&T HX). The results demonstrate that the gyroid HX achieved up to 20 % shorter thermal charge and discharge times than the S&T HX, which is attributed to a higher heat transfer rate. Additionally, the measured pressure drop of the gyroid HX was up to 44 % lower than that of the S&T HX. Consequently, considering both the heat transfer rate and pressure drop, the gyroid HX showed an average improvement of 57 % and 31 % in the overall enhancement factor during charging and discharging, respectively, compared to the S&T HX. Further, metal gyroid HXs fabricated from steel and aluminum using metal 3D printing were experimentally compared with the polymer gyroid HX. Despite the polymer thermal conductivity being only 1/90 and 1/790 that of steel and aluminum, respectively, the heat transfer rate per unit mass of the polymer gyroid HX was 1.7 times that of the steel gyroid HX and approximately half that of the aluminum gyroid HX. This finding suggests that the polymer gyroid HX is suitable for LHTES applications where lightweight characteristics are crucial.

Preparation of high thermal conductivity vat photopolymerization used UV-curable resin synergistically enhanced by silicon nitride and boron nitride

Additive manufacturing (3D printing) technologies, especially vat photopolymerization (VPP), provide a cost-effective and efficient approach for the fabrication of heat dissipation devices with complex geometric designs. The incorporation of inorganic thermal conductive fillers into resin matrix is widely recognized as an effective way to enhance thermal conductivity. Notably, the synergistic effect of hybrid fillers can further enhance thermal conductivity. However, the consequent drastic increase in viscosity of the UV-curable resin may decrease the success rate and accuracy of printing on commercial VPP 3D printers. In this work, hexagonal boron nitride (h-BN) platelets and spherical h-BN together with β-Si3N4 are introduced into the UV-curable resin system. Corresponding results proved that h-BN together with β-Si3N4 provide a synergistic effect on the thermal conductivity enhancement compared to the filler in single morphology only. Moreover, owing to the spherical structure, low-viscosity UV-curable resin with high solid content can be prepared. In specific, a thermal conductive polymer composite material with a solid content of 60 wt% is prepared, which exhibits high thermal conductivity (1.42 W/mK), representing an enhancement of up to 610 % compared to neat resin. In subsequent application demonstrations, 3D printed heat dissipation devices with as-prepared resin composite material have been shown to effectively enhance the heat dissipation rate for the heating device.

A review: From the whole process of making thermal conductive polymer, the effective method of improving thermal conductivity

AbstractWith the development of high power‐density electronic devices on smaller scales and emerging new energy vehicles, high thermal conductive materials have attracted more attention for better thermal management to adapt to various applications. By combining both the advantages of polymer materials and thermally conductive fillers, thermal conductive polymer composite materials are widely used in packaging and the protection of electronic devices for their mechanical robustness, high thermal conductivity, excellent insulation properties, heat resistance, and chemical resistance. In this review, first, the basic theory of heat conduction of polymer composites is discussed. Second, according to the classification of the composition of the thermal conductive polymer, the filled thermal conductive material is emphatically introduced. In this paper, the construction process of a thermal conductive network of polymer and composites is discussed from the perspective of processing. The simple construction of a thermal conductive network includes core‐shell structure, external force orientation, electrostatic spinning, electrostatic spraying, induced orientation, and vacuum‐assisted filtration. The three‐dimensional thermal conductivity network can be constructed using self‐assembly and template methods. From the above processing methods, this paper analyzes how to effectively improve thermal conductivity and achieve the goal of high thermal conductivity and excellent mechanical properties under low filling. After that, the contribution of filler and polymer modification to thermal conductivity is explained in detail. Finally, the future research direction of functionalization is prospected.

Flexible phase change materials based on hexagonal boron nitride (hBN) surface modification and styrene-butadiene-styrene (SBS)/low-density polyethylene (LDPE) crosslinking for battery thermal management applications

In battery thermal management (BTM), flexible phase change materials (FPCMs) emerge as highly promising substances, owing to their simple installment and low contact thermal resistance. However, FPCMs based on high thermal conductivity fillers and polymers always suffer from the enduring challenges of poor high-temperature resistance and poor filler-matrix compatibility. To solve these problems, a novel strategy is reported in this work, wherein FPCMs with excellent filler-matrix compatibility and satisfactory high-temperature resistance are synthesized by two steps: functionalizing the hexagonal boron nitride (hBN) surface and inducing the inter crosslinking between Styrene-Butadiene-Styrene(SBS) and Low-density polyethylene(LDPE). Vinyltrimethoxysilane (VTMS) molecules were introduced on the surface of raw hBN by hydroxylation and silanization surface modification to improve the compatibility of hBN with the matrix. Concluding from the results, the addition of 6.7 wt% LDPE doubled the high-temperature resistance of FPCMs, enabling them to maintain their structural integrity even at 200 °C for 1 h. The prepared FPCMs also exhibited higher thermal conductivity (increased by 20.5 %), low leakage rate (<0.6 wt% after 70 heating–cooling cycles), high enthalpy (122 J g−1), and strong adhesion (>0.1 MPa), etc. In terms of BTM performance, the FPCMs-based passive cooling BTM presents remarkable temperature control capabilities (maximum temperature reduction by 16.3 ℃) and uniform temperature performance (maximum temperature difference < 2.5 ℃). Collectively, this work will provide a promising approach for the fabrication of high-performance FPCMs in BTM and other thermal management applications for electronic devices.

Electric-field-aligned liquid crystal polymer for doubling anisotropic thermal conductivity

High thermal conductive polymers have become more important because equipment requires high performance, high-energy density, and high integration. There are different strategies to make high thermal conductive polymers, among which is the synthesis of polymers in the liquid crystal phase. However, the thermal conductivity of such material is rarely beyond 1 W m−1 K−1 because of the disordered molecular directionality. The disordered directionality between crystal zones limits the thermal conductivity in a specific direction. Here, we show a method for unifying the direction of crystal zones by applying an external electric field on the liquid crystal monomers. Meanwhile, by exposing the transparent equipment and specially designed photopolymerisable monomer in UV light, the liquid crystal monomer is in situ polymerised into a liquid crystal polymer with a high intrinsic thermal conductivity of 1.02 W m−1 K−1. The molecular alignment was characterised and resulted in the resultant high conductivity.

Thermal Conductivity of Bottle-Brush Polymers.

Using molecular dynamics (MD) simulations of a generic model, we investigated heat propagation in bottle-brush polymers (BBP). An architecture is referred to as a BBP when a linear (backbone) polymer is grafted with the side chains of different length Ns and grafting density ρg, which control the bending stiffness of a backbone. Investigating κ-behavior in BBP is of particular interest due to two competing mechanics: increased backbone stiffness, via Ns and ρg, increases the thermal transport coefficient κ, while the presence of side chains provides additional pathways for heat leakage. We show how a delicate competition between these two effects controls κ. These results reveal that going from a weakly grafting (ρg < 1) to a highly grafting (ρg ≥ 1) regime, κ changes non-monotonically that is independent of Ns. The effect of side chain mass on κ and heat flow in the BBP melts is also discussed.

Enhanced thermal conductivity in boron nitride incorporated polyethylene/polymethyl methacrylate composites via double percolation structure

AbstractDue to the miniaturization, integration and multi‐functional development of contemporary electronic devices, there is a growing need for efficient thermal conductive composite materials. This study focuses on enhancing the dispersion of modified boron nitride (mBN) within a linear low‐density polyethylene (LLDPE) phase by incorporating LLDPE‐graft‐Aminomethylpyridine (LLDPE‐g‐Py) to non‐covalently modify BN. Additionally, polymethyl methacrylate (PMMA) and LLDPE polymers were introduced to create modified BN/LLDPE/PMMA (mBN/LLDPE/PMMA) composites with a double percolation structure. The co‐continuous structure of the polymer composites was observed by using scanning electron microscopy (SEM). By selectively locating the BN modified by LLDPE‐g‐Py within the LLDPE phase, the co‐continuous structure of the LLDPE/PMMA blend was upgraded to a double percolation structure. This double percolation structure establishes a dense and optimal heat transfer network within the polymer matrix. The thermal conductivity of the mBN/LLDPE/PMMA composite with BN loading of 40 wt% was significantly increased to 1.12 Wm−1 K−1, which was 350% higher than that of pure LLDPE, 38% higher than that of the BN/LLDPE composite, and 17% higher than that of the BN/LLDPE/PMMA composite. This study offers valuable insights into non‐covalent modification techniques for BN and the design of double percolation structures in thermal conductive polymer composites.Highlights The double percolation structure was successfully constructed by simple melt blending method with LLDPE and PMMA as matrix and BN as thermal conductive filler. The double percolation structure can significantly promote the efficiency of heat transfer inside the thermal conductive composites. A novel non‐covalent modifier LLDPE‐g‐Py was prepared to modify the surface of BN, and the selective localization of modified BN (mBN) in the LLDPE phase was realized.

Intrinsically thermally conductive polymers.

Here, we describe the design features that lead to intrinsically thermally conductive polymers. Though polymers are conventionally assumed to be thermal insulators (<0.3 W m-1 K-1), significant efforts by the thermal transport community have shown that polymers can be intrinsically thermally conductive (>1.0 W m-1 K-1). However, these findings have not yet driven comprehensive synthetic efforts to expose how different macromolecular features impact thermal conductivity. Preliminary theoretical and experimental investigations have revealed that high k polymers can be realized by enhancing the alignment, crystallinity, and intermolecular interactions. While a holistic mechanistic framework does not yet exist for thermal transport in polymeric materials, contemporary literature suggests that phonon-like heat carriers may be operative in macromolecules that meet the abovementioned criteria. In this review, we offer a perspective on how high thermal conductivity polymers can be systematically engineered from this understanding. Reports for several classes of macromolecules, including linear polymers, network polymers, liquid-crystalline polymers, and two-dimensional polymers substantiate the design principles we propose. Throughout this work, we offer opportunities for continued fundamental and technological development of polymers with high thermal conductivity.

Enhance thermal conductivity via constructing a low heat resistance interface with quaternized graphene

Interfacial thermal resistance of fillers in thermal conductive polymer composites is a barrier restricting heat dissipation function. In-situ graft of quaternary ammonium group on the surface of graphene can form cation-π interaction, providing a medium for heat transfer between graphene layers. Accordingly, we fabricate polyvinyl alcohol (PVA)-based heat conductive composite containing quaternized graphene stacking structure. With the assistance of non-covalent bonding, the in-plane thermal conductivity of the composite formed by self-precipitation method reaches 9.97 W m−1 K−1 at a filling content of 30 vol%. Molecular dynamics (MD) simulation further explores the promoting effect of the interfacial structure constructed between the charged group and graphene on the interfacial heat transfer. The optimized interfacial structure not only alleviates the bottleneck of interface thermal resistance but also enhances the mechanical properties of composite. This strategy provides an ideal solution to preparation of high-performance thermal management materials for electronic equipment.

Recent Progress in Fabrication and Structural Design of Thermal Conductive Polymer Composites

Recent Progress in Fabrication and Structural Design of Thermal Conductive Polymer Composites

Preparation and construction mechanism of thermal conductive epoxy‐based composite via magnetic field induced orientation

AbstractBN was modified with Fe3O4 to confer it with paramagnetic responsivity. The scanning electron microscopy and energy dispersive spectrometer (EDS) results demonstrated that with the assistance of an external magnetic field, the paramagnetic BN particles within an epoxy matrix are effectively aligned along the direction of the magnetic field during the curing process of epoxy resin, hence forming continuous thermal conduction pathways. Therefore, the thermal conductivity of the epoxy‐based composite filled with 30 wt% of BN and externally applied with a 50 mT magnetic flux density was 0.7417 (W/m·K), an improvement of 207.89% relative to the pure epoxy resin. The establishment of continuous thermal pathways facilitates effective phonon conduction, thereby further enhancing the thermal conductivity of the material. Meanwhile, this study investigates the chain formation mechanism of Fe3O4‐modified BN under the influence of a magnetic field. When subjected to an applied magnetic field, the magnetic BN embedded in an epoxy resin matrix undergoes magnetization, rotation, and contact. Subsequently, multiple particles initially form short chains, then aggregate into longer chains aligned with the direction of the magnetic field. The findings indicate that the magnetic field induced particle alignment method holds significant potential in the fabrication of high thermal conductivity polymer composites with low filler loading.

Thermal conductivity and orientation of liquid crystal polymer filled with boron nitride

This work focuses on the study of effect of hexagonal boron nitride (BN) on the self-orientation, rheology and thermal conductivity of thermotropic liquid crystalline polymer (LCP), which possesses a semirigid-rod molecular structure. The LCP/BN composites are prepared by extrusion and injection molding processes. The 2D-WAXD analysis evidences the presence of self-orientation and typical “skin-core” structure of LCP and LCP composites. As a consequence, there are abundant macro fibrils in the matrices. The role of the lateral dimension of BN on the properties of LCP was investigated. It is confirmed that BN with a larger lateral size can more effectively improve the TC and thermal stability of LCP. Being filled with 30% BN with a large lateral size of 50 μm, the thermal conductivity of LCP/BN50-30 composite is increased by 88.11% compared with pure LCP, in contrast, the increment ratio of 38.43% and 43.93% when the LCP is filled with BN with lateral size of 0.5 μm and 5.0 μm at the same loading.

One-pot upcycling strategy achieved in Bi-continuous thermal conductive polymer composites

Though upcycling post-consumer polymers into high-value materials is appealing, it faces challenges including complex, costly processes and difficulties to achieve a circular lifecycle. To address these issues, we have developed a novel approach that involves designing a unique bi-continuous phase morphology with selective distribution of the conductive fillers in the semi-crystalline polymer phase. As a result, these composites exhibited excellent thermal conductivity (7.07 W m−1·K−1) and stable environmental longevity (thermal aging and 500 h UV irradiation) and can be upcycled as effective flame retardant (vertical combustion grade V-0) and smoke suppressed materials (smoke density grade 64.1) after their service life as a thermal conductive material has ended. Rather than being discarded or undergo molecular upcycling, they could be straightforwardly repurposed through melt processing and even displayed better processability, suggesting a one-pot but effective upcycle strategy for polymeric materials.

Investigations on thermal contact resistance between filled polymer composites and solids using micro thermography

This article reports the use of a new measurement technique based on micro thermography for determining the thermal contact resistances (TCRs) between filled polymers and solids. The thermal conductivity of polymers can be significantly increased by using thermally conductive fillers. For numerous applications, not only is a high intrinsic thermal conductivity required but also a good thermal transfer between the filled polymer and an adjacent solid surface. The physical principles of thermal transport when considering this type of contact have not yet been investigated in detail, and only a few experimental results are available. The most common measurement techniques determine a macroscopic resistance and project it onto the contacting surface. However, the heterogeneous microstructure of a filled polymer causes the TCR to be a volumetric phenomenon in the overall boundary region. The utilized IR camera system takes thermal images with a spatial resolution of less than per pixel. The new method resolves the TCRs spatially and gives new insights into the microscale effects on the particle level. In addition to the common zero-gap extrapolation for the extraction of TCRs, we propose another evaluation method that considers all microscale effects of the boundary layers and evaluates TCR as a volumetric phenomenon. For the first systematic study, samples consisting of two aluminum substrates and a filled epoxy polymer were prepared and investigated. We studied the effects of filler size, filler material, filler volume fraction, and surface structure, focusing on monomodally filled polymers with filler amounts between and . The obtained results and the uncertainties of the new method are discussed within this paper.

The Effect of Mechanical Elongation on the Thermal Conductivity of Amorphous and Semicrystalline Thermoplastic Polyimides: Atomistic Simulations.

Over the past few decades, the enhancement of polymer thermal conductivity has attracted considerable attention in the scientific community due to its potential for the development of new thermal interface materials (TIM) for both electronic and electrical devices. The mechanical elongation of polymers may be considered as an appropriate tool for the improvement of heat transport through polymers without the necessary addition of nanofillers. Polyimides (PIs) in particular have some of the best thermal, dielectric, and mechanical properties, as well as radiation and chemical resistance. They can therefore be used as polymer binders in TIM without compromising their dielectric properties. In the present study, the effects of uniaxial deformation on the thermal conductivity of thermoplastic PIs were examined for the first time using atomistic computer simulations. We believe that this approach will be important for the development of thermal interface materials based on thermoplastic PIs with improved thermal conductivity properties. Current research has focused on the analysis of three thermoplastic PIs: two semicrystalline, namely BPDA-P3 and R-BAPB; and one amorphous, ULTEMTM. To evaluate the impact of uniaxial deformation on the thermal conductivity, samples of these PIs were deformed up to 200% at a temperature of 600 K, slightly above the melting temperatures of BPDA-P3 and R-BAPB. The thermal conductivity coefficients of these PIs increased in the glassy state and above the glass transition point. Notably, some improvement in the thermal conductivity of the amorphous polyimide ULTEMTM was achieved. Our study demonstrates that the thermal conductivity coefficient is anisotropic in different directions with respect to the deformation axis and shows a significant increase in both semicrystalline and amorphous PIs in the direction parallel to the deformation. Both types of structural ordering (self-ordering of semicrystalline PI and mechanical elongation) led to the same significant increase in thermal conductivity coefficient.