Optimization of thermal insulation performance of porous geopolymers under the guidance of thermal conductivity calculation

Porous geopolymers are energy saving, environment-friendly and simple in preparation. However, the thermal conductivity (TC) of present porous geopolymers as well as other inorganic thermal insulation materials can be hardly below 0.050 W m^-1 K^-1 in the markets. In order to further decrease the TC of porous geopolymers, it is vital to understand the heat transfer mechanism of this type of materials. In this work, we made a comparison among the main heat transfer models for porous two-component system reported so far including series model, parallel model, geometric mean model, Maxwell-Eucken equation, Hashin spherical structure model and novel effective medium theory (NEMT) based on the data reported in references and obtained by our group for porous geopolymers, and found that NEMT could describe the heat transfer mechanism of porous geopolymers better. Then we systematically studied the relationship among the effective TC (k_e), porosity (ε), TC of solid skeleton (k_s) and TC of the uniform medium reflecting the heat conduction of the solid skeleton to air (k_m) based on the calculations with NEMT. It was found that it is essential to increase ε and decrease k_s and k_m for reducing the TC of porous geopolymers. Under the guidance of above calculations, we successfully designed and obtained some porous geopolymers with TC as low as 0.040 W m^-1 K^-1. This paper offers not only several porous geopolymers with low TC, but also an idea to design novel thermal insulation materials.     

High thermal conductive shape-stabilized phase change materials based on water-borne polyurethane/boron nitride aerogel

Phase change materials (PCMs) applied in energy storage and temperature control system are important for energy conservation and environmental protection. In this work, structure-adjustable water-borne polyurethane (WPU)/boron nitride (BN) aerogels were synthesized via directional freeze-drying method, and used as supporting scaffolds to confine paraffin wax (PW) and obtain composite phase change materials. The three-dimensional (3D) porous thermal conductivity network of BN was derived by the in-situ ice crystal mound in aerogel, which endows the PW/WPU/BN composite PCM-2.5 with high thermal conductivity (0.96 W m^?1 K^?1) and high energy storage density (140.04 J/g). Shape-stabilized PCMs with high thermal conductivity and excellent electrical insulation prepared by the simple method have great potential for the thermal management of electronic products.     

High-thermal conductivities of epoxy composites via p-phenylenediamine interfacial modification and process intensification

High loadings of fillers are usually needed to achieve high-thermal conductivity (TC) of polymer-based composites, which inevitably sacrifices processability and meanwhile causes high-cost. Therefore, it is of great significance to achieve high-TC composites under low-filler loading. Here, a novel p-phenylenediamine (PPD) modified expanded graphite (EG-PPD)/epoxy (EP) composite with high TC and low-filler content was successfully prepared via pre-dispersion and vacuum assisted mixing strategy. With the improved interfacial compatibility between EG and EP by PPD, the prepared EG-PPD/EP composite exhibited excellent thermal management performance, resulting in the TC of which reached 4.00 W·m⁻¹·K⁻¹ with only 10 wt% (5.59 vol%) of EG-PPD, which is approximately 19 times higher than that of pure EP. Meantime, the interface thermal resistance of EG-PPD/EP composite between EG-PPD and EP is reduced by 33% compared with EG/EP composite. This composite with excellent TC property is expected to be used in thermal management field.     

In situ sintered silver decorated 3D structure of cellulose scaffold for highly thermoconductive electromagnetic interference shielding epoxy nanocomposites

This study presents a 3-dimensional (3D) network structure of cellulose scaffold (CS), which was in situ decorated with silver nanoparticles (AgNPs). The scaffold was then infiltrated with epoxy matrix and cured at elevated temperature to sinter the AgNPs; finally, highly thermoconductive epoxy composites (Ag@CS/epoxy) was obtained. The resultant Ag@CS20/epoxy composite reached a thermal conductivity of 2.52 W·m⁻¹·K⁻¹ at 2.2 vol% of filler loading, which shows an enhancement of over 11-folds in the thermal conductivity compared to the neat epoxy. The superb electrical conductivity value of over 53,691 S·m⁻¹ of the Ag@CS20/epoxy was achieved, which led to exceptional EMI SE values of 69.1 dB. Furthermore, surface temperatures during heating and cooling were also investigated to demonstrate the superior heat dissipating capacity of the Ag@CS/epoxy composite, which can be potentially put an application as thermal dissipating material in the next generation of electronics.     

有机-无机复合相变材料的研究进展

有机相变材料具有过冷度小、无相分离、蓄热强等优势,在相变储热领域一直受到广泛的关注。然而,较低的热导率、液相泄漏和较差的热稳定性成为限制其应用的瓶颈缺陷。近几年,有机-无机复合相变材料的研究成为新的热点,极大地促进了有机相变材料的应用和发展。本文综述了常见的提高有机相变材料导热性能的高导热性纳米材料,以及制备有机-无机定形复合相变材料常选用的多孔支撑材料,并从制备方法、作用方式和热物性等方面介绍了有机-无机复合相变材料,复合相变材料相比于单一纯相变材料具有诸多优越的性能。预测有关结构优化、封装工艺并与高效储能系统结合的研究会成为有机-无机复合相变材料未来的发展趋势。     

Geopolymer with Hierarchically Meso‐/Macroporous Structures from Reactive Emulsion Templating

We present a simple synthetic route to hierarchically porous geopolymers using triglyceride oil for a reactive emulsion template. In the new synthetic method, highly alkaline geopolymer resin was first mixed with canola oil to form a homogeneous viscous emulsion which was then cured at 60°C to give a hard monolithic material. During the process, the oil in the alkaline emulsion undergoes a saponification reaction to be decomposed to water‐soluble soap and glycerol molecules which were then extracted with hot water to finally yield porous geopolymers. Nitrogen adsorption studies indicated the presence of mesopores, whereas the SEM studies revealed that the mesoporous geopolymer matrix are dotted with spherical macropores (10–50 μm) which are due to oil droplet template in the emulsion. Various synthetic parameters including the precursor compositions were examined to control the porosity. BET surface area and BJH pore volume of the materials were up to 124 m²/g and 0.7 cm³/g, respectively, and the total pore volumes up to 2.1 cm³/g from pycnometry.     

Electronic structure and thermal conductivity of zirconium carbide with hafnium additions

The lattice thermal conductivity of ZrC with different Hf contents was investigated theoretically. The density of states and electron density differences were calculated for ZrC and (Zr,Hf)C containing 3.125 or 6.25 at% Hf. It was found that the electronic structure did not change significantly with the Hf additions. Lattice thermal conductivities were calculated for all of the compositions by combining first-principles calculations with the Debye–Callaway model. The theoretical lattice thermal conductivity of ZrC was 68 W·m⁻¹·K⁻¹ at room temperature. When adding 3.125 and 6.25 at% Hf into ZrC, the lattice thermal conductivities decreased to 18 and 15 W·m⁻¹·K⁻¹, respectively. The mechanism for the decreased conductivity is that with the addition of Hf impurities, the frequency of the acoustic phonons decreased, which resulted in decreases in the Debye temperature and lattice thermal conductivity.     

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.     

Expanded Vermiculite/Paraffin Composite as a Solar Thermal Energy Storage Material

A solar thermal energy storage material was prepared from expanded vermiculite (EVM) and paraffin by vacuum impregnation. Samples were characterized by thermogravimetric and differential scanning calorimetry (TG‐DSC), X‐ray diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), scanning electron microscopy (SEM), petrographic analysis, and thermal conductivity measurements. The results indicated that EVM existed as a phlogopite structure in the EVM/paraffin composite. The composite latent heat was 137.6 J/g at the freezing temperature of 52.5°C and 135.5 J/g at the melting temperature of 48.0°C, when the paraffin content was 67%. The phlogopite structure of EVM benefited paraffin heat transfer because the composite exhibited a thermal conductivity of 0.545 W·(m·K)^?1 higher than that of paraffin. Morphology and structural changes of EVM during composite preparation were investigated. The composite exhibited excellent thermal stability and has potential application in solar thermal energy storage and solar heating.     

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.     

High-entropy (Ho0.2Y0.2Dy0.2Gd0.2Eu0.2)2Ti2O7/TiO2 composites with excellent mechanical and thermal properties

High-performance ceramics with low thermal conductivity, high mechanical properties, and idea thermal expansion coefficients have important applications in fields such as turbine blades and automotive engines. Currently, the thermal conductivity of ceramics has been significantly reduced by local doping/substitution or further high-entropy reconfiguration of the composition, but the mechanical properties, especially the fracture toughness, are insufficient and still need to be improved. In this work, based on the high-entropy titanate pyrochlore, TiO₂ was introduced for composite toughening and the high-entropy (Ho_0.2Y_0.2Dy_0.2Gd_0.2Eu_0.2)₂Ti₂O₇-xTiO₂ (x = 0, 0.2, 0.4, 1.0 and 2.0) composites with high hardness (16.17 GPa), Young's modulus (289.3 GPa) and fracture toughness (3.612 MPa·m^0.5), low thermal conductivity (1.22 W·m⁻¹·K⁻¹), and thermal expansion coefficients close to the substrate material (9.5 ×10⁻⁶/K) were successfully prepared by the solidification method. The fracture toughness of the composite toughened sample is 2.25 times higher than that before toughening, which exceeds most of the current low-thermal conductivity ceramics.     

On the hydrogen production of geopolymer wasteforms under irradiation

The hydrogen gas (H₂) production of wasteforms is a major safety concern for encapsulating nuclear wastes. For geopolymers, the H₂ produced by radiolytic processes is a key factor because of the large amount of water present in their porous structure. Herein, the hydrogen production was measured under ⁶⁰Co gamma irradiation. The effect of water saturation and sample size were studied for pure geopolymers, or using zeolites as an example waste. To interpret results, a simple model was used, considering only hydrogen production, a potential recombination and its diffusion in the geopolymer matrix. When geopolymer monolithic samples were large and saturated by water, the hydrogen released was measured up to two orders of magnitude lower with a 40-cm long cylinder samples (1.9 × 10⁻¹⁰ mol/J) than a sample in powder form (2.2 × 10⁻⁸ mol/J). Knowing the diffusion constant of the matrix, the model was able to reproduce the evolution of the hydrogen release as a function of the water saturation level and predict accurately the evolution when sample size is increased up to 40 cm.     

Multi-component strategy for remarkable suppression of thermal conductivity in strontium diyttrium oxide: The case of high-entropy Sr(Y0.2Sm0.2Gd0.2Dy0.2Yb0.2)2O4 ceramic

Anti-spinel oxide SrY₂O₄ has attracted extensive attention as a promising host lattice due to its outstanding high-temperature structural stability and large thermal expansion coefficient (TEC). However, the overhigh thermal conductivity limits its application in the field of thermal barrier coatings. To address this issue, a novel high-entropy Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ ceramic was designed and synthesized for the first time via the solid-state method. It is found that the thermal conductivity of Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ is reduced to 1.61 W·m⁻¹·K⁻¹, 53 % lower than that of SrY₂O₄ (3.44 W·m⁻¹·K⁻¹) at 1500 °C. Furthermore, reasonable TEC (11.53 ×10⁻⁶ K⁻¹, 25 °C ∼ 1500 °C), excellent phase stability, and improved fracture toughness (1.92 ± 0.04 MPa·m^1/2) remained for the high-entropy Sr(Y_0.2Sm_0.2Gd_0.2Dy_0.2Yb_0.2)₂O₄ ceramic, making it a promising material for next-generation thermal barrier coatings.     

Multifunctional Shape-Stabilized Phase Change Materials with Enhanced Thermal Conductivity and Electromagnetic Interference Shielding Effectiveness for Electronic Devices

A paraffin-based shape-stabilized composite phase change material (CPCM) is fabricated with dramatically enhanced thermal conductivity and excellent electromagnetic interference (EMI) shielding capacity. The as-prepared CPCMs are supported by graphene-based frameworks with many bubble-like micropores that are prepared by the addition of polystyrene microspheres into graphene oxide hydrogel as hard templates. These bubble-like micropores can encapsulate paraffin wax (PW) due to the strong capillary force between the graphene-based framework and PW and leading to enhanced shape stability of the as-prepared CPCMs. Moreover, the continuous thermally and electrically conductive network formed by graphene nanoplatelets endows the as-prepared CPCMs with a high thermal conductivity and an excellent EMI shielding effectiveness. When the ratio of graphene-based framework is 23.0 wt%, the thermal conductivity and latent heat of CPCM reaches 28.7 W m⁻¹ k⁻¹ and 175.8 J g⁻¹, respectively, and the EMI shielding effectiveness is higher than 45 dB in the frequency of 8.2–12.4 GHz. Their outstanding thermal and EMI shielding performance makes the as-prepared CPCMs promising candidates for use in thermal management and EMI shielding of electronic devices.     

Preparation and performance study of cordierite/mullite composite ceramics for solar thermal energy storage

The employment of solar energy in recent years has reached a remarkable edge. It has become even more popular as the cost of fossil fuel continues to rise. Energy storage system improves an adjustability and marketability of solar thermal and allowing it to produce electricity in demand. This study attempted to prepare cordierite/mullite composite ceramics used as solar thermal storage material from calcined bauxite, talcum, soda feldspar, potassium feldspar, quartz, and mullite. The thermal physical performances were evaluated and characterized by XRD, SEM, EPMA, and EDS. It was found that the optimum sintering temperature was 1280°C for preparing, and the corresponding water adsorption was 11.25%, apparent porosity was 23.59%, bulk density was 2.10 mg·cm^?3, bending strength was 88.52 MPa. The residual bending strength of specimen sintered at 1280°C after thermal shock of 30 times decreased to be 57 MPa that was 36% lower than that before. The thermal conductivity of samples sintered at 1280°C was tested to be 2.20 W·(m·K)^?1 (26°C), and after wrapped a PCM (phase change materials) of K₂SO₄, the thermal storage density was 933 kJ·kg^?1 with the temperature difference (ΔT) ranged in 0‐800°C. The prepared cordierite/mullite composite ceramic was proved to be a promising material for solar thermal energy storage.     

Isolating the effects of thixotropy in geopolymer pastes

The rheological properties of potassium-based geopolymers were investigated through a series of experiments intended to isolate the influence of shear rate, recovery time, and shear ramping on thixotropy for a greater understanding of geopolymer thixotropic properties within the context of the geopolymer setting reaction. It is shown that for thixotropic disruption to occur a critical shear rate of 100 s⁻¹ must be reached or surpassed, full thixotropic restructuring occurs at around 90–100 min of total undisturbed rest time, and that reaching a state of full thixotropic disturbance heavily depends on subjected processing parameters. In addition, a consistent crossover between the storage and loss modulus within 1–3 min of oscillation during cyclical oscillatory measurements greatly indicates the repeatability and reversibility of thixotropy in geopolymers and the potential for tailorable viscosity. Overall, it is found that geopolymer pastes exhibit strong evidence of thixotropy, which is favorable for additive manufacturing, and that allotted rest time before shear and shear rate greatly influence the overall rheological properties.     

Large-Scale Fabrication of Flexible EVA/EG@PW Phase Change Composites with High Thermal Conductivity for Thermal Management

The working electronic devices and batteries generate a lot of heat, if this heats not release quickly, it will not only have a great impact on the performance of the devices, but also cause certain safety hazards. The passive thermal management based on organic phase change materials (PCMs) stands out due to its excellent temperature regulation capability as well as the buffer protection capability for device overload. In view of these, a series of flexible EVA/EG@PW (EE@P) phase change composites (PCCs) with high thermal conductivity are prepared by efficiently constructing porous skeletons and thermal conductive pathways through sacrificial template method, and introducing paraffin wax (PW) by simple vacuum impregnation technique. The PCC exhibits high thermal conductivity (2.6 W m⁻¹ K⁻¹), high enthalpy (153.5 J g⁻¹), and good flexibility. In addition, the PCC possesses excellent cycling stability and thermal stability. In practical application, the PCC shows good temperature control ability for LED and shows great potential application in the field of thermal management.     

Facile self-assembly approach to construct a novel MXene-decorated nano-sized phase change material emulsion for thermal energy storage

In recent years, phase change material emulsions (PCMEs) with enhanced energy storage capacities and good flow characteristics have drawn significant attention. However, due to the thermodynamically unstable nature and tiny particle confinement, the nanomaterial modification strategies at PCM/water interface to improve stabilities and reduce supercooling of nano-sized PCMEs (NPCMEs) are very limited and challenging. Herein, we report a facile strategy for constructing MXene-decorated NPCME with good stability, little supercooling, and high thermal conductivity by self-assembly of MXene nanosheets at PCM/water interface. The concentrations of MXene have great influences on the average droplet diameters, stabilities, and thermophysical properties of the NPCMEs. The results show that the PCMs have been well dispersed into the water in the form of quasi-spherical droplets, with average droplet diameters of 242–805 nm. The thermal conductivity of 10 wt% n-tetradecane/water NPCME containing 9 mg ml^-1 MXene is 0.693 W m^-1·K^-1, achieving an enhancement by 15.5%, as compared to that of water. Besides, the MXene-decorated paraffin/water NPCMEs exhibit little supercooling and enhanced heat storage capacities. More importantly, this facile self-assembly strategy opens a new platform for preparing high-performance NPCMEs, which can be used as novel heat transfer fluids for thermal energy storage systems.     

High lumen density of Al2O3-LuAG: Ce composite ceramic for high-brightness display

Thermally robust and highly efficient green-emitting luminescent ceramics are gradually attracting great attention as promising phosphors using in high-brightness laser phosphor display to reduce serious speckle noise as well as high cost. However, lumen density is still seriously restricting their potential applications especially under high-power density laser due to insufficient absorption of blue laser and significant thermal quenching. Here, we report an Al₂O₃-LuAG: Ce composite ceramic phosphor (CCP) for high-brightness laser phosphor display. Owing to good optical properties and high thermal conductivity of Al₂O₃, the Al₂O₃-LuAG: Ce CCP shows high photoluminescence quantum yield (79.6%), low thermal quenching (only 3.2% loss in luminescence at 200°C), and high thermal conductivity (18.9 W·m⁻¹·K⁻¹). Moreover, the Al₂O₃, as scattering centers, enhances the Rayleigh–Mie scattering of the blue laser, and hence the absorption of the Al₂O₃-LuAG: Ce CCP exhibits a remarkable improvement (~2.3 times) at 450 nm. Finally, with optimized thickness (0.3 mm) of Al₂O₃-LuAG: Ce CCP, an excellent luminous efficiency (216 lm·W⁻¹) and outstanding lumen density (6129 lm·mm⁻²) of the green-emitting light source was obtained by driving under a high-power density (28.33 W·mm⁻²) blue laser. All of those validate the suitability of the Al₂O₃-LuAG: Ce CCP for high-brightness display.     

Influence of sintering atmosphere and BN additives on microstructure and properties of porous SiC ceramics

The effects of the boron nitride (BN) content on the electrical, thermal, and mechanical properties of porous SiC ceramics were investigated in N₂ and Ar atmospheres. The electrical resistivity was predominantly controlled by the sintering atmosphere and secondarily by the BN concentration, whereas the thermal conductivity and flexural strength were more susceptible to changes in the porosity and necking area between the SiC grains. The electrical resistivities of argon-sintered porous SiC ceramics (6.3 × 10⁵ – 1.6 × 10⁶ Ω·cm) were seven orders of magnitude higher than those of nitrogen-sintered porous SiC ceramics (1.5 × 10⁻¹ – 6.0 × 10⁻¹ Ω·cm). The thermal conductivity and flexural strength of the argon-sintered porous SiC ceramics increased from 8.4–11.6 W·m⁻¹ K⁻¹ and from 9.3–28.2 MPa, respectively, with an increase in the BN content from 0 to 1.5 vol%, which was attributed to the increase in necking area and the decrease in porosity.