Enhanced out-of-plane thermal conductivity of polyimide composite films by adding hollow cube-like boron nitride

Boron nitride nanosheet (BNNS) is widely used in electronic thermal management due to its excellent planar thermal conductivity and insulating properties. However, it is challenging to improve the out-of-plane thermal conductivity of BNNS-doped composites due to the anisotropy of the thermal conductivity of BNNS. Therefore, the BNNS in the matrix must be oriented to obtain composites with high out-of-plane thermal conductivity. In this study, BNNS powders with directional structures were synthesized directly using sodium chloride templates. The as-obtained BNNS powders have a unique hollow cube-like structure with an ultra-low density of 2.67 × 10⁻² g/cm³ and nearly 8 times the volume of the same mass of two-dimensional (2D) BNNS, making it easy to form the out-of-plane thermal conductivity paths in the polymer matrix. In addition, the high out-of-plane thermal conductivity of 4.93 W m⁻¹ K⁻¹ at 23.3 wt% loadings was obtained by doping it into a polyimide (PI) matrix. This value is 9.7 times higher than that of 2D BNNS-doped PI at the same loadings, 17.6 times higher than pure PI, and 6.1 times higher than the thermally conductive PI film sold by DuPont. Therefore, the prepared composite film has great potential for application in electronic thermal management.     

Processing of polymer-derived,aerogel-filled,SiC foams for high-temperature insulation

Porous polymer-derived ceramics (PDCs) are outperforming materials when low-density and thermal inertia are required. In this frame, thermal insulating foams such as silicon carbide (SiC) ones possess intriguing requisites for aerospace applications, but their thermal conductivity is affected by gas phase heat transfer and, in the high temperature region, by radiative mechanisms. Owing to the versatility of the PDC route, we present a synthesis pathway to embed PDC SiC aerogels within the open cells of a SiC foam, thus sensibly decreasing the thermal conductivity at 1000°C from 0.371 W·m⁻¹K⁻¹ to 0.243 W·m⁻¹K⁻¹. In this way, it was possible to couple the mechanical properties of the foam with the insulating ability of the aerogels. The presented synthesis was optimized by selecting, among acetone, n-hexane, and cyclohexane, the proper solvent for the gelation step of the aerogel formation to obtain a proper mesoporous colloidal structure that, after ceramization at 1000°C, presents a specific surface area of 193 m²·g⁻¹. The so-obtained ceramic composites present a lowest density of 0.18 g·cm⁻³, a porosity of 90% and a compressive strength of 0.76 MPa.     

Low thermal conductivity of atomic layer deposition yttria-stabilized zirconia (YSZ) thin films for thermal insulation applications

Thermal insulation applications have long required materials with low thermal conductivity, and one example is yttria (Y₂O₃)-stabilized zirconia (ZrO₂) (YSZ) as thermal barrier coatings used in gas turbine engines. Although porosity has been a route to the low thermal conductivity of YSZ coatings, nonporous and conformal coating of YSZ thin films with low thermal conductivity may find a great impact on various thermal insulation applications in nanostructured materials and nanoscale devices. Here, we report on measurements of the thermal conductivity of atomic layer deposition-grown, nonporous YSZ thin films of thickness down to 35 nm using time-domain thermoreflectance. We find that the measured thermal conductivities are 1.35–1.5 W m⁻¹ K⁻¹ and do not strongly vary with film thickness. Without any reduction in thermal conductivity associated with porosity, the conductivities we report approach the minimum, amorphous limit, 1.25 W m⁻¹ K⁻¹, predicted by the minimum thermal conductivity model.     

High interfacial thermal resistance induced low thermal conductivity in porous SiC-SiO2 composites with hierarchical porosity

The incorporation of a thermally insulating secondary phase can significantly increase the interfacial thermal resistance attributed to its low intrinsic thermal conductivity and the creation of multiple phonon scattering interfaces between adjacent SiC particles. The newly developed porous SiC-33 wt% SiO₂ composites with SiO₂ as a thermally insulating secondary phase exhibited a very low thermal conductivity (0.047 Wm⁻¹ K⁻¹, 72.4 % porous), which is an order of magnitude lower than the previously reported lowest thermal conductivity (0.14 Wm⁻¹ K⁻¹, 76.3 % porous) for powder processed porous SiC ceramics and is even lower than the thermal conductivity (0.060 Wm⁻¹ K⁻¹, 87.9% porous) of SiO₂ aerogel. The porous SiC-(16–73 wt%) SiO₂ composites processed from nano β-SiC and a 40 wt% carbon template exhibited a hierarchical (meso-/macro-porous) pore structure that transformed to a trimodal (micro-/meso-/macro-porous) porous structure when polysiloxane was added and sintering was performed at 600–1000 °C in air.     

A flame retarded chitosan binder for insulating miscanthus/recycled textile fibers reinforced biocomposites

The main objective of this study is devoted to the development of new insulating and ignifuged miscanthus fibers (Mf)/recycled textile fibers (RTf) reinforced biocomposites (BCs) using chitosan as polysaccharide-based binder and aluminum trihydroxide (ATH) fillers while focusing on the fire behavior. To achieve this goal, a preliminary study was carried out on flame retarded chitosan-based films with various ATH-filler ratios (20, 33, 50, and 60 wt %). ATG and pyrolysis-combustion flow calorimeter analysis showed significant improvement of chitosan thermal behavior with the addition of 33 wt % and above of ATH. Mechanical properties of films were, however, degraded. Thereafter, different ratios of miscanthus/RTf reinforced BCs (fibers content up to 89.5–90 wt %) were elaborated through thermocompression process using neat chitosan and chitosan/ATH (67/33 wt %) as a binder. Mechanical, thermal, and fire behavior were evaluated. Higher mechanical properties were found for hybrid materials containing the association of both RTf and Mf in comparison to those containing only RTf or Mf. Fireproof BCs (E rating: according to the NF EN ISO 11925-2), with thermal conductivity values between 0.07 and 0.09 W m⁻¹ K⁻¹ and density range between 270 and 299 kg m⁻³ were successfully elaborated. The results of this study show a promising use of the chitosan/ATH system as flame retardant for biobased insulating building materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47306.     

High temperature thermal conductivity of free-standing diamond films prepared by DC arc plasma jet CVD

Free-standing diamond films with 1.68 mm in polished thickness have been prepared by DC arc plasma jet CVD. By means of simply changing the placing orientation of diamond films along the laser transmission direction while testing, the through-thickness thermal conductivity (κ_⊥) together with the in-plane (κ_//) thermal conductivity of free-standing diamond films were measured by laser flash technique over a wide temperature range. Results show that the thermal conductivity κ_⊥ and κ_// of free-standing diamond films are up to 1916 and 1739 Wm^− 1 K^− 1 at room temperature, respectively, showing small anisotropy (9%), and following the relationship κ ~ T^− n as temperature rises. The conductivity exhibits similar value compared to that of high-quality single crystal diamond above 500 K for both through-thickness and in-plane directions of CVD diamond films. The effects of impurities and grain boundaries on thermal conductivity of diamond films with increasing temperature were discussed.     

Functionalized few-layered graphene nanoplatelets for superior thermal management in heat transfer nanofluids

The superior thermal conductivity and lightweight of graphene flakes make them materials of choice for advanced heat transfer applications, especially for transport of electricity from sustainable power stations such as concentrating solar power plants. In view of the excellent thermal conductivity of graphene or graphene-like nanomaterials (3000–5000 W m⁻¹ K⁻¹), their dispersion into conventional host fluids such as water (0.613 W m⁻¹ K⁻¹) or ethylene glycol (0.25 W m⁻¹ K⁻¹) can significantly improve fluid heat transfer characteristics. The two-dimensional structure and high surface area as well as the cost-efficient carbon-based material make graphene nanoplatelets (GNPs) suitable for large-scale applications in colloidal thermal conductive fluids. For an efficient dispersion of GNPs in base fluids, intrinsically hydrophobic GNPs were acid treated to obtain highly concentrated (4 wt.%) graphene-based nanofluids. Investigations on various GNP sizes and reaction parameters showed significant influences on the resulting thermal conductivity values of the nanofluid. After 14 h measurements in a dormant system, the most efficient nanofluid reached a thermal conductivity of 0.586 W m⁻¹ K⁻¹ (the base fluid of 0.391 W m⁻¹ K⁻¹) and a low viscosity of 6.39 cP resulting in an overall efficiency improvement of 77%, when compared to the base fluid without particles.     

High thermal conductivity of liquid crystalline monomer-poly (vinyl alcohol) dispersion films containing microscopic-ordered structure

The thermal conductivity of bulk polymers is usually very low, which is due to the amorphous domains where chains are randomly entangled, improving the degree of the chain alignment and forming a continuous thermal conduction network are expected to enhance the thermal conductivity. A series of liquid crystalline monomer-poly (vinyl alcohol) dispersion (MDLC) films with high thermal conductivity containing microscopic-ordered structure were prepared by introducing a highly ordered liquid crystalline monomer (LCM) exhibiting Smectic phase. The thermal conductivity of MDLC films was strongly related to the amount of LCM, which firstly increased and then decreased with the increase of LCM content. The thermal conductivity of MDLC film reached up to 1.20 W m⁻¹ K⁻¹ when the content of LCM was 15 wt% and rapidly decreased to 0.85 W m⁻¹ K⁻¹ as the content of LCM further increased to 25 wt%. LCM with low content (1–15 wt%) showed good fluidity, dispersity and interfacial compatibility in PVA molecular chains, which further increases the regularity of molecular chains alignment.     

Strategies for Preparing Continuous Ultraflexible and Ultrastrong Poly(Vinyl Alcohol) Aerogel Fibers with Excellent Thermal Insulation

Aerogel fibers are thermally insulating and can be woven, so they are expected to form a new generation of smart textiles that can efficiently reduce heat consumption. However, producing continuous aerogel fibers that have the necessary strength and toughness to be woven remains a great challenge. Herein, with the aid of freeze-thaw treatment of poly(vinyl alcohol) (PVA) solution and freeze-spinning technology, continuous PVA aerogel fibers with an aligned porous morphology are prepared in a large-scale. Freeze–thaw treatment greatly contributes to improving the spinnability of the spinning dope of aerogel fibers, which leads to the formation of the continuous fibers. Remarkably, through this process the aerogel fibers achieve ultraflexible and ultrastrong features, which results in excellent weaving ability, as well as attractive mechanical properties that benefit from the cross-linking of PVA molecular chains with the aligned porous structure. More importantly, a textile woven with the special porous structure aerogel fibers shows extraordinary thermal insulation (thermal conductivity as low as 0.026 W m⁻¹ K⁻¹) and infrared stealth. This study illustrates a promising direction for the design of next generation, wearable, intelligent materials that have great potential for personal thermal management applications.     

Influence of the dopant on the polypyrrole moisture content: Effects on conductivity and thermal stability

Having in mind to produce electrically conductive carbon–epoxy composite materials, we have filled an insulating epoxy resin with an electronic conducting polymer, polypyrrole (PPy). To select the PPy that best suits this process, various PPys were chemically synthesized. The syntheses were performed in water via a dispersion polymerization route using, initially, either FeCl₃ (PPy–Cl⁻) or (NH₄)₂S₂O₈ (PPy–HSO₄⁻) as oxidizing agents. Then, using (NH₄)₂S₂O₈ as the oxidant, two other PPy doped with aromatic species were obtained due to the dissolution of paratoluenesulfonic acid (PPy–TS⁻) or naphtalenesulfonic acid (PPy–NS⁻) in the reaction media. The characterization of the PPy samples by conductivity measurements, together with elemental and thermal analysis, showed that PPy–TS⁻ exhibits the highest conductivity and thermal stability, with the conductivity remaining steady over 14 days. In addition, a stabilizing effect of the aromatic anions was observed. The experiments have shown that moisture in the PPy cannot be entirely removed and that, with increasing moisture content, the conductivity also increases, indicating an ionic conductivity superimposed on the electronic conductivity usually observed in PPy. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1567–1577, 1998     

Anisotropic films photopolymerized from aligned cross-linkable gemini ammonium liquid crystals for ion conduction

Cross-linkable gemini ionic liquid crystals are prepared by jacketing the diammonium moiety between two biphenyl benzoate mesogens. Anisotropic films are obtained by photopolymerization of the macroscopically aligned gemini ionic liquid crystals for ion conduction. Small angle X-ray scattering (SAXS) measurements indicate that the monolayer nanostructure is formed in the films and scanning electron microscope (SEM) observations reveal that the smectic layers are perpendicular to the film surface. Electrochemical impedance spectroscopy (EIS) characterization shows that the films exhibit strong anisotropy in ion conduction. The ion conduction across the film is enhanced while that within the plane of the film is impeded. The ionic conductivity in vertical direction of the film reaches up to 10⁻³ cm S⁻¹ at 180 °C and the measured anisotropy (ratio of the measured conductivities in vertical direction of the film versus in parallel to the film) is 100–350. The photopolymerization of the cross-linkable gemini ammonium liquid crystals offers excellent potential for the development of solid electrolytes for electrochemical devices. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47349.     

Highly flexible and thermal conductive films of graphene/poly(naphthylamine) and applications in thermal management of LED devices

In 5G era, integration and miniaturization of electronic components lead to increasing challenges in thermal management. Materials with high thermal conductivity and flexibility are strongly desired for dissipating heat locally generated in such devices. Due to its extraordinary thermal conducting performance, graphene has been exhibiting great potential in thermal management. In this work, composite films based on graphene oxide and poly-naphthylamine (gGO/PNA) with enhanced thermal conducting performance have been achieved by employing poly (naphthylamine) (PNA) as repairing additives to restore topological defects of graphene oxide (GO). Specifically, gGO/PNA films are prepared with a facile operation of vacuum filtration followed by an elevated temperature treatment. The optimal thermal conductivity (κ) of gGO/PNA reaches to 1016.03 W m⁻¹ K⁻¹, 31.3% enhancement over that of the pristine graphene one. The thermal conducting performance test demonstrates the film an efficient heat-dissipation ability from a heat-generating LED bulb. Furthermore, the film exhibits excellent flexibility, making it survival from a 1000-cycle bending test. This finding may promote the development of heat-spreading materials and their applications in thermal management of highly integrated electronics.     

Crystal structure,mechanical and thermal properties of Yb4Al2O9: A combination of experimental and theoretical investigations

The key requirements for a successful thermal and environmental barrier coating (T/EBC) material include stability in high temperature water vapor, low Young's modulus, close thermal expansion coefficient (TEC) with mullite, low thermal conductivity and weak mechanical anisotropy. The current prime candidates for top coat are ytterbium silicates (Yb₂SiO₅ and Yb₂Si₂O₇). A major weakness of these two silicates is the severe anisotropy in mechanical properties and thermal expansion that would lead to cracking of the coating. Thus, searching for new materials with weak mechanical and thermal anisotropy is of signification. In this work, the crystal structure, mechanical and thermal properties of a promising T/EBC candidate, Yb₄Al₂O₉, are investigated theoretically and experimentally. Good ductility, low shear deformation resistance, low Young's modulus (151 GPa) and low thermal conductivity (0.78 W m⁻¹ K⁻¹) is underpinned by heterogeneous bonding characteristic and distortion of the structure. Close TEC (6.27 × 10⁻⁶ K⁻¹) with mullite and weak mechanical anisotropy highlight the suitability of Yb₄Al₂O₉ as a prospective T/EBC.     

The manufacturing and properties of a nano-laminate derived from graphene powder

The work presents a method of consolidation of graphene flakes (platelets) into a bulk material showing high anisotropy of thermal, electrical and mechanical properties. Such materials can be used as directional high-temperature thermal insulators similar to graphite foils, but due to much finer microstructure they may exhibit different, possibly enhanced properties. The graphene flakes were consolidated by a filter pressing of propanol suspension followed by a hot-pressing of produced green bodies at 2200 °C under 25 MPa in a protective atmosphere.The hot-pressing step was necessary to force orientation of the flakes and to densify the material. Microstructural observations, mechanical strength and elastic properties assessment, as well as thermal and electrical properties analysis were performed. Scanning electron microscopy revealed that microstructure of the material consisted of highly-oriented layers of the graphene flakes. It resulted in a distinct anisotropy of thermal conductivity (360 vs. 3 W/mK), coefficient of thermal expansion (25·10⁻⁶ vs. −1·10⁻⁶ 1/K) and electrical resistivity (60·10⁻⁶ vs. 850·10⁻⁶ Ω m) of the material in the in-plane and through plane direction, respectively. The material showed brittle behavior, but it could be machined.     

Patterned Electroconductive Networks in Ag-Polyamide 6 Composites by Laser Ablation

A simple, fast, and cost-effective method to fabricate conductive paths on insulating Ag-containing polyamide 6 (PA6) composites by laser beam treatment is presented in this study. First, Ag-hybrid microparticles (Ag-MP) with a total metal load of up to 19 wt% are synthesized based on a reactive encapsulation strategy utilizing activated anionic polymerization of ε-caprolactam in solution, in the presence of Ag nanoparticles. Then, the Ag-MP are compression molded into plates (Ag-PL) on which a scanning laser treatment is applied to create conductive paths in their selected parts. A comparison between structural, morphological, and thermal properties of the Ag-MP and the molded Ag-PL composites is performed. The electric conductive properties of the Ag-loaded hybrid materials are investigated before and after laser ablation, and it is concluded that the laser treatment results in selected paths with widths in the range of 500 µm with conductivity values in the range of 1.12 to 8.90 S m⁻¹ while the untreated Ag-PA6 surface remains isolating with conductivity values of 1.27 × 10⁻⁰⁸ S m⁻¹. These results prove that applying laser ablation with controlled parameters on initially insulating Ag-PL composites can efficiently produce conductive line patterns in composite plates.     

Highly electrically and thermally conductive silicon carbide-graphene composites with yttria and scandia additives

Dense silicon carbide/graphene nanoplatelets (GNPs) and silicon carbide/graphene oxide (GO) composites with 1 vol.% equimolar Y₂O₃–Sc₂O₃ sintering additives were sintered at 2000 °C in nitrogen atmosphere by rapid hot-pressing technique. The sintered composites were further annealed in gas pressure sintering (GPS) furnace at 1800 °C for 6 h in overpressure of nitrogen (3 MPa). The effects of types and amount of graphene, orientation of graphene sheets, as well as the influence of annealing on microstructure and functional properties of prepared composites were investigated. SiC-graphene composite materials exhibit anisotropic electrical as well as thermal conductivity due to the alignment of graphene platelets as a consequence of applied high uniaxial pressure (50 MPa) during sintering. The electrical conductivity of annealed sample with 10 wt.% of GNPs oriented parallel to the measuring direction increased significantly up to 118 S·cm⁻¹. Similarly, the thermal conductivity of composites was very sensitive to the orientation of GNPs. In direction perpendicular to the GNPs the thermal conductivity decreased with increasing amount of graphene from 180 W·m⁻¹ K⁻¹ to 70 W·m⁻¹ K⁻¹, mainly due to the scattering of phonons on the graphene – SiC interface. In parallel direction to GNPs the thermal conductivity varied from 130 W·m⁻¹ K⁻¹ up to 238 W·m⁻¹ K⁻¹ for composites with 1 wt.% of GO and 5 wt.% of GNPs after annealing. In this case both the microstructure and composition of SiC matrix and the good thermal conductivity of GNPs improved the thermal conductivity of composites.     

Determining the thermal conductivity of ceramic coatings by relative method

Thermal conductivity is a crucial parameter for evaluating the quality and thermal effects of ceramic coatings, especially for thermal barrier coatings. However, measurement by conventional method involves two problems: (a) it is difficult to peel off a ceramic coating from a substrate; (b) even if the coating can be peeled off, it is still hardly used as standard specimen in test. Therefore, the relative method was proposed to evaluate the thermal conductivity of ceramic coating. An analytical relationship among the thermal conductivities of the coating, the substrate, and the coating/substrate composite was established. Experiments on TA4 coated with YSZ coatings were carried out to demonstrate the feasibility of this novel method and to investigate the impact of temperature on the thermal conductivity of YSZ coatings. The experimental results demonstrated the validity and convenience of the relative method. With the increasing testing temperature, the thermal conductivity value of YSZ coatings displayed nonlinearity feature, that is, decreased from 1.4 to 1.3 (W m⁻¹ K⁻¹) in the temperature range of 32-300°C and then increased up to 1.58 W m⁻¹ K⁻¹ at 1000°C.     

Transient hot-strip (THS) method for measuring thermal conductivity of thermally insulating materials

The fast and precise transient hot-strip (THS) method is well suited for thermal conductivity measurements on solid materials. The THS method may, however, give large experimental errors when applied to thermally insulating materials of low heat capacity per unit volume. Models to deal with those potential error sources and some indications about the precautions to be taken in order to minimize them are described in the present work. Measurements of thermal conductivity of a styrofoam insulating material (thermal conductivity 0.036 W m^?1K^?1, density 25.4 kg m^?3) was performed to verify the models. The result obtained is in good agreement with the standard hot plate method, indicating that the THS method is also well suited for thermal conductivity measurements of thermal insulators.     

Thermal,mechanical and electrical properties of hard B4C,BCN, ZrBC and ZrBCN ceramics

We study the thermal, mechanical and electrical properties of B₄C, BCN, ZrBC and ZrBCN ceramics prepared in the form of thin films by magnetron sputtering. We focus on the effect of Zr_x(B₄C)_1−x sputter target composition, the N₂+Ar discharge gas mixture composition, the deposition temperature and the annealing temperature after the deposition. The thermal properties of interest include thermal conductivity (observed in the range 1.3–7.3 W m⁻¹ K⁻¹), heat capacity (0.37–1.6×10³ J kg⁻¹ K⁻¹ or 1.9–4.1×10⁶ Jm⁻³ K⁻¹), thermal effusivity (1.6–4.5×10³ J m⁻² s^−1/2 K⁻¹) and thermal diffusivity (0.38–2.6×10⁻⁶ m² s⁻¹). We discuss the relationships between materials composition, preparation conditions, structure, thermal properties, temperature dependence of the thermal properties and other (mechanical and electrical) properties. We find that the materials structure (amorphous×crystalline hexagonal ZrB₂-like×nanocrystalline cubic ZrN-like), more than the composition, is the crucial factor determining the thermal conductivity and other properties. The results are particularly important for the design of future ceramic materials combining tailored thermal properties, mechanical properties, electrical conductivity and oxidation resistance.     

Powder injection molding of complex-shaped aluminium nitride ceramic with high thermal conductivity

Aluminum nitride (AlN) is a promising material for heat sinks and microelectronic applications because of the advantages of high theoretical thermal conductivity, high mechanical strength, good electrical insulation, low dielectric constant and low thermal expansion coefficient. However, the difficulties in shaping complex-shaped parts with a high thermal conductivity have retarded the wide applications of AlN ceramic. Herein, we design a new binder system containing resin components and adopt the powder injection molding technology to fabricate complex-shaped AlN parts. After the debinding process, the special binder system would produce residual carbon, which could react with Al₂O₃ and result in decreasing oxygen impurity and forming the yttrium-rich aluminates. The yttrium-rich aluminates can accelerate the densification of AlN ceramic and fasten the oxygen on the triangular grain boundary, leaving the clean grain boundary beneficial for high thermal conductivity. The as-prepared AlN parts with complex shape possess a high thermal conductivity of 248 W m⁻¹ K⁻¹.