Thermal characterization of phase change materials based on linear low-density polyethylene,paraffin wax and expanded graphite

Thermal characterization of Phase Change Materials (PCMs) based on linear low-density polyethylene (LLDPE), paraffin wax (W) and expanded graphite (EG) is reported in this paper. Investigated PCMs showed high potential for application in energy storage systems.The latent heat, L_m, sensible heat Q_sens, and the ability of the prepared PCMs to store and release thermal energy were investigated using specific home-made equipment based on the transient guarded hot plane method (TGHPT). The sensible heat of PCM containing 40 wt.% of paraffin wax was investigated in the temperature range 25–35 °C, they exhibited a drop in Q_sens from 31 to 24 J/g depending on the concentration of EG. A similar decrease in sensible heat with increased loading of EG was observed for PCMs containing 50 wt.% of EG.The storage and release of thermal energy during phase change which is associated with the latent heat of the materials were investigated within the temperature range 20–50 °C. PCMs containing 40 wt.% of paraffin wax exhibited latent heat of 36 J/g, whereas the latent heat of PCMs containing 50 wt.% of paraffin wax was 49 J/g. The addition of EG decreased the time needed to melt and solidify PCMs due to increase in thermal conductivity of PCMs with increase in EG content. This behavior was confirmed by the thermal conductivity measurements, where thermal conductivity increased from 0.252 for sample without EG to 1.329 W/m × °C for PCM containing 15 wt.% of EG.The reproducibility of storage and release of thermal energy by PCMs was demonstrated by subjecting them to repeated heating and cooling cycles (over 150 cycles).     

MOF-5 composites exhibiting improved thermal conductivity

The low thermal conductivity of the prototype hydrogen storage adsorbent, metal-organic framework 5 (MOF-5), can limit performance in applications requiring rapid gas uptake and release, such as in hydrogen storage for fuel cell vehicles. As a means to improve thermal conductivity, we have synthesized MOF-5-based composites containing 1–10 wt.% of expanded natural graphite (ENG) and evaluated their properties. Cylindrical pellets of neat MOF-5 and MOF-5/ENG composites with densities of 0.3, 0.5, and 0.7 g/cm³ are prepared and assessed with regard to thermal conductivity, specific heat capacity, surface area, and crystallinity. For pellets of density ∼0.5 g/cm³, we find that ENG additions of 10 wt.% result in a factor of five improvement in thermal conductivity relative to neat MOF-5, increasing from 0.10 to 0.56 W/mK at room temperature. Based on the relatively higher densities, surface areas, and enhanced crystallinity exhibited by the composites, ENG additions appear to partially protect MOF-5 crystallites from plastic deformation and/or amorphization during mechanical compaction; this suggests that thermal conductivity can be improved while maintaining the favorable hydrogen storage properties of this material.     

KNO3/NaNO3 – Graphite materials for thermal energy storage at high temperature: Part I. – Elaboration methods and thermal properties

Composites graphite/salt for thermal energy storage at high temperature (～200 °C) have been developed and tested. As at low temperature in the past, graphite has been used to enhance the thermal conductivity of the eutectic system KNO₃/NaNO₃. A new elaboration method has been proposed as an alternative to graphite foams infiltration. It consists of cold-compression of a physical mixing of expanded natural graphite particles and salt powder. Two different compression routes have been investigated: uni-axial compression and isostatic compression. The first part of the paper has been devoted to the analysis of the thermal properties of these new graphite/salt composites. It is proven that cold-compression is a simple and efficient technique for improving the salt thermal conductivity. For instance, graphite amounts between 15 and 20%wt lead to apparent thermal conductivities close to 20 W/m/K (20 times greater than the thermal conductivity of the salt). Furthermore, some advantages in terms of cost and safety are expected because materials elaboration is carried out at room temperature. The second part of the paper is focused on the analyses of the phase transition properties of these graphite/salt composites materials.     

A poly(ethylene glycol)-based smart phase change material

A shape memory thermoplastic polyurethane (PU) as a phase change material (PCM) was synthesized by employing poly(ethylene glycol) (PEG) as the soft segment via bulk polymerization. Its phase separation structure, crystalline morphology, phase change behaviors, dynamic mechanical properties and melt-processing ability were investigated using polarizing optical microscopy, atomic force microscopy, differential scanning calorimetry, dynamic mechanical analysis, thermogravimetry and melt flow index. A well-formed phase separation structure in the PEG-based polyurethane (PEGPU) was found which accounts for most of the material phase change properties and shape memory effect. The PEG soft segment phase transition between crystalline and amorphous states resulted in heat storage and release of the PEGPU. Due to the hydrogen bonded hard segment phase serving as “physical cross-linking” restricted the free movement of the soft segments, at temperature above the PEG phase melting transition, the PEGPU was still solid. The differential scanning calorimetry results indicated that the PEGPU had high latent heat storage capacity of more than 100 J/g. The dynamic mechanical analysis results showed that it had a plateau elastic modulus about 40 MPa in the region above the PEG phase melting transition while below 150 °C. The thermogravimetry results suggested that the PEGPU had a much broader applicable temperature range compared with pure PEG. The melt flow index results indicated that the material had a good melt-processing ability. The material shape fixity ratio was more than 84% and shape recovery ratio up to 93.7% obtained from thermomechanical cyclic tensile testing.     

Synthesis and thermal properties of poly(styrene-co-ally alcohol)-graft-stearic acid copolymers as novel solid–solid PCMs for thermal energy storage

A series of poly(styrene-co-allyalcohol)-graft-stearic acid copolymers were synthesized as novel polymeric solid–solid phase change materials (SSPCMs). The graft copolymerization reactions between poly(styrene-co-allyalcohol) and stearoyl chloride were verified by Fourier transform infrared (FT-IR) and Proton Nuclear Magnetic Resonance (¹H NMR) spectroscopy techniques. The crystal morphology of the SSPCMs was investigated using polarized optical microscopy (POM) technique. Thermal energy storage properties of the synthesized SSPCMs were measured using differential scanning calorimetry (DSC) analysis. The POM results showed that the crystalline phase of the copolymers transformed to amorphous phase above their phase transition temperatures. Thermal energy storage properties of the synthesized SSPCMs were investigated by differential scanning calorimetry (DSC) and found that they had typical solid–solid phase transition temperatures in the range of 27–30 °C and high latent heat enthalpy between 34 and 74 J/g. Especially, the copolymer with the mole ratio of 1/1 (poly(styrene-co-allyalcohol)/stearoyl chloride) is the most attractive one due to the highest latent heat storage capacity among them. The results of DSC and FT-IR analysis indicated that the synthesized SSPCMs had good thermal reliability and chemical stability after 5000 thermal cycles. Thermogravimetric (TG) analysis results suggested that the synthesized SSPCMs had high thermal resistance. In addition, thermal conductivity measurements signified that the synthesized PCMs had higher thermal conductivity compared to that of poly(styrene-co-allyalcohol). The synthesized copolymers as novel SSPCMs have considerable potential for thermal energy storage applications such as solar space heating and cooling in buildings and greenhouses.     

Laboratory investigation on the use of thermally enhanced phase change material to improve the performance of borehole heat exchangers for ground source heat pumps

Ground source heat pumps have high efficiency and high capital cost primarily due to borehole drillings. This research investigates the inclusion of high‐conductivity phase change material (PCM) in the borehole heat exchanger of a ground source heat pump to reduce the borehole length required and improve its coefficient of performance (COP). In the laboratory model, the borehole heat exchanger was represented by a cylindrical electrical heater having a total power of 9.216 W, operating for 1 hour while resting for 3 hours. Surrounding the heater in the annular region, either soil, PCM, or high‐conductivity PCM was used as grouting material. The annular region was surrounded by a large amount of soil enclosed in a large bin as a representation of ground soil. The high‐conductivity graphite was impregnated with the commercial PCM “PureTemp29.” Results from the experiments revealed that the PCM is able to decrease the temperature fluctuations in the annular and soil regions, while graphite increases the thermal conductivity of the annular region and hence increases the rate of heat dissipation from the heater to the soil surrounding it. The maximum COP values of a ground source heat pump calculated assuming ideal reversed Carnot cycle for cooling mode showed an increase of approximately 81% with PCM and by 112% with graphite‐enhanced PCM.     

Thermal conductivity and latent heat thermal energy storage characteristics of paraffin/expanded graphite composite as phase change material

This study aimed determination of proper amount of paraffin (n-docosane) absorbed into expanded graphite (EG) to obtain form-stable composite as phase change material (PCM), examination of the influence of EG addition on the thermal conductivity using transient hot-wire method and investigation of latent heat thermal energy storage (LHTES) characteristics of paraffin such as melting time, melting temperature and latent heat capacity using differential scanning calorimetry (DSC) technique. The paraffin/EG composites with the mass fraction of 2%, 4%, 7%, and 10% EG were prepared by absorbing liquid paraffin into the EG. The composite PCM with mass fraction of 10% EG was considered as form-stable allowing no leakage of melted paraffin during the solid–liquid phase change due to capillary and surface tension forces of EG. Thermal conductivity of the pure paraffin and the composite PCMs including 2, 4, 7 and 10 wt% EG were measured as 0.22, 0.40, 0.52, 0.68 and 0.82 W/m K, respectively. Melting time test showed that the increasing thermal conductivity of paraffin noticeably decreased its melting time. Furthermore, DSC analysis indicated that changes in the melting temperatures of the composite PCMs were not considerable, and their latent heat capacities were approximately equivalent to the values calculated based on the mass ratios of the paraffin in the composites. It was concluded that the composite PCM with the mass fraction of 10% EG was the most promising one for LHTES applications due to its form-stable property, direct usability without a need of extra storage container, high thermal conductivity, good melting temperature and satisfying latent heat storage capacity.     

Polyethylene glycol (PEG)/diatomite composite as a novel form-stable phase change material for thermal energy storage

This paper deals with the preparation, characterization, and determination of thermal energy storage properties of polyethylene glycol (PEG)/diatomite composite as a novel form-stable composite phase change material (PCM). The composite PCM was prepared by incorporating PEG in the pores of diatomite. The PEG could be retained by 50 wt% into pores of the diatomite without the leakage of melted PEG from the composite. The composite PCM was characterized by using SEM and FT-IR analysis technique. Thermal properties of the composite PCM were determined by DSC analysis. DSC results showed that the melting temperature and latent heat of the composite PCM are 27.70 °C and 87.09 J/g, respectively. Thermal cycling test was conducted to determine the thermal reliability of the composite PCM and the results showed that the composite PCM had good thermal reliability and chemical stability. TG analysis showed that the impregnated PEG into the diatomite had good thermal stability. Thermal conductivity of the composite PCM was improved by adding expanded graphite in different mass fractions. Thermal energy storage performance of the composite PCM was also tested.     

Role of the glass transition temperature of Nafion 117 membrane in the preparation of the membrane electrode assembly in a direct methanol fuel cell (DMFC)

The glass transition temperature (T_g) of the Nafion 117 membrane was traced by DSC step by step during the preparation of the membrane electrode assembly (MEA). Wide-angle x-ray diffraction and frequency response analysis were used for the determination of the crystallinity and proton conductivity of the membrane. As-received Nafion 117 membrane showed two glass transition temperatures in the DSC thermogram. The first T_g, caused by the mobility of the main chain in the polymer matrix, was 125 °C; the second T_g, derived from the side chain due to the strong interaction between the sulfonic acid functional groups, was 195 °C. During the pretreatment of the membrane, the T_g of the Nafion 117 membrane drastically decreased because of the plasticizer effect of water. In the hot-pressing process, the T_g of the Nafion 117 membrane gradually increased due to the loss of water. When the Nafion 117 was completely dried, the T_g of the membrane finally reached 132 °C. Thermal heat treatment was then applied to the MEA to obtain high interfacial stability; however, the membrane developed a crystalline morphology that led to reduced water uptake and proton conductivity. Therefore, the thermal heat treatment of the MEA should be carefully controlled in the region of the glass transition temperature (120–140 °C) of the Nafion 117 membrane to ensure the high performance of the MEA.     

Hydrophilic expanded graphite–magnesium nitrate hexahydrate composite phase change materials: Understanding the effect of hydrophilic modification on thermophysical properties

Expanded graphite (EG) has shown excellent performances in compression resilience, thermal conductivity, and adsorption ability. EG can adsorb liquid phase change materials (PCMs) mainly because of capillary action; however, EG is hydrophobic, which makes it less compatible with hydrated salts. Herein, hydrophilic EG (HEG) was prepared with Triton X‐100 (TX‐100) as surface modifier. The HEG–magnesium nitrate hexahydrate (HEG‐MNH) composite as a PCM was investigated for thermal energy storage (TES) to understand the effect of hydrophilic modification on thermophysical properties. The powder‐state HEG is added into MNH to prepare HEG‐MNH composite PCM, which contains 1.71 wt% of TX‐100, 7.29 wt% of EG, and 91.00 wt% of MNH by control variable method. The melting point and latent heat of HEG‐MNH composite PCM were 89.05°C and 137.28 J/g, respectively. The endothermic enthalpy change of HEG‐MNH composite PCM only decreased by 0.90%, along with the exothermic values of HEG‐MNH composite that increased by 3.80% after 100 cycles. The thermal conductivity is higher 5.17 times than that of the pure MNH. Our work suggests that the HEG‐MNH composite PCM has a great potential to be used as a PCM for TES.     

Mechanical and thermal properties of cement composite graphite for solar thermal storage materials

The comprehensive survey on an attractive thermal storage material consisted of aluminate cement and graphite is obtained in this paper. The effect of different water/cement (w/c) ratio and graphite content on compressive strength and thermal properties including thermal conductivity, volume heat capacity and thermal expansion coefficient of hardened aluminate cement pastes were investigated to pursue the optimum material design for solar parabolic trough power plant. It is observed that thermal conductivity and volume heat capacity were improved with the decrease of w/c and the increase of graphite content. The results show that w/c is a key factor affecting thermal properties of pastes and graphite even has some influence on the hydration process. After heat treatment at 350 °C for 6 h, compressive strength and thermal properties descended in a certain extent. XRD and FTIR were used to characterize the evolution of hydration products together. Furthermore, the properties obtained from the paper will lay the foundation for thermal storage materials of solar thermal power plants in the future.     

KNO3/NaNO3 – Graphite materials for thermal energy storage at high temperature: Part II. – Phase transition properties

Composites graphite/salt for thermal energy storage at high temperature (～200 °C) have been developed and tested. As at low temperature in the past, graphite has been used to enhance the thermal conductivity of the eutectic system KNO₃/NaNO₃. A new elaboration method has been proposed as an alternative to graphite-foams infiltration. It consists of compression at room temperature of a physical mixing of expanded natural graphite particles and salt powder. Two different compression routes have been investigated: uni-axial compression and isostatic compression. The first part of the paper shows that both uni-axial and isostatic cold-compression are simple and equally efficient techniques for improving the salt thermal conductivity. The second part of the paper is focused on the analysis of their phase transition properties. It is shown that graphite does not degrade the salt within the composites; that is, no changes are observed neither in the salts transition temperatures nor in its latent heat. On the contrary, some negative effects as pores over pressurization and salt leakage can appear if no void space enough is available within the composite for salt volume expansion when melting. Such negative effects are only observed in the composites obtained by isostatic cold-compression.     

Thermal conductivity enhancement of form-stable phase-change composites by milling of expanded graphite,micro-capsules and polyethylene

Structured form-stable phase change composites were prepared by wet milling and hot-compaction of microencapsulated phase change material (MPCM), expanded graphite (EG) and high density polyethylene (HDPE). In the composites, MPCM serves as a latent heat storage material, EG as a heat transfer promoting agent and HDPE as a matrix. Scanning electron microscope (SEM) characterization reveals that MPCM particles kept undamaged with a uniform dispersion in the composites. Thermal conductivity of the composites with 20 wt% EG loaded could be enhanced by 22 times compared to HDPE/MPCM composites without EG. And thermal conductivity of the composite could be increased by 10 times at a loading of 10 wt% EG.     

Study of thermal conductivity,permeability, and adsorption performance of consolidated composite activated carbon adsorbent for refrigeration

Composite adsorbents, comprising activated carbon and expanded natural graphite, have been developed, and their thermal conductivity, permeability and adsorption performance were tested. The thermal conductivity varied with the ratio of activated carbon to expanded natural graphite. Thermal conductivity increased as the ratio of expanded graphite increased. Considering that the density of activated carbon for the composite adsorbent should not be lower than 200 kg/m³, otherwise the volumetric cooling capacity would be unacceptably low, the highest thermal conductivity obtained from experiments was 2.47 W m^?1 K^?1. The permeability was also measured, and the best result obtained was 4.378 × 10^?12 m². In order to evaluate the influence of heat and mass transfer on adsorption performance, the adsorption rate was tested using a Rubotherm magnetic suspension balance, and results showed that for the freezing conditions lower than ?10 °C the performance of granular activated carbon was better than that of solidified adsorbent because of the reduced mass transfer of ammonia at low saturated pressure. The adsorption performance of consolidated adsorbents increased rapidly when the evaporating temperature was higher than ?10 °C. When the evaporating temperature was 8 °C, the adsorption rate of consolidated adsorbent was improved by 29% if compared with that of granular adsorbent.     

石蜡/膨胀石墨复合相变储热材料的研究

以膨胀石墨为基体,石蜡为相变储热介质,利用膨胀石墨对石蜡良好的吸附性能,制备出了石蜡／膨胀 石墨复合相变储热材料。由于毛细作用力和表面张力的作用,石蜡在固-液相变时,很难从膨胀石墨的微孔中渗 透出来。实验结果表明,石蜡/膨胀石墨复合相变储热材料没有改变膨胀石墨的结构和石蜡的固-液相变温度, 且其结合了石墨高的导热系数和石蜡大的相变潜热,因而储热密度较高,导热性能好。其相变潜热与对应质量 分率下的石蜡相当,储/放热时间比石蜡明显减少。     

A temperature-regulating fiber made of PEG-based smart copolymer

A poly(ethylene glycol) (PEG)-based thermoplastic shape memory polyurethane was synthesized via bulk polymerization. The corresponding fiber, as a temperature-regulating fiber, was fabricated via melt spinning. The prepared 100-dtex fiber had a tenacity of 0.7 cN/dtex and breaking elongation of about 488%. The fiber's phase change behaviors, crystalline morphology, dynamic mechanical properties, and temperature-resistant performance were investigated using polarizing optical microscopy, differential scanning calorimetry, dynamic mechanical analysis, and thermogravimetry. The PEG soft segment phase transfer between crystalline and amorphous states resulted in heat storage and release. The hydrogen-bonded hard segment phase, serving as ‘physical cross-links,’ restricted the free movement of soft segments, hence at temperatures above the PEG phase melting transition, the fiber still possessed certain mechanical strength. The differential scanning calorimetry results indicated that the fiber had large latent heat-storage capacity of about 100 J/g with a crystallizing temperature of 20.9 °C and a melting temperature of 44.7 °C. The dynamic mechanical analysis results showed that the fiber has a plateau elastic modulus in the region above the PEG phase melting transition and below 160 °C. The thermogravimetry results suggested that the fiber had a much broader applicable temperature range compared to pure PEG. The thermo-mechanical cyclic tensile testing results showed that the fiber had good shape memory effect with the shape fixity ratio more than 85.8% and the recovery ratio above 95.4%.     

High latent heat storage and high thermal conductive phase change materials using exfoliated graphite nanoplatelets

Using exfoliated graphite nanoplatelets (xGnP), paraffin/xGnP composite phase change materials (PCMs) were prepared by the stirring of xGnP in liquid paraffin for high electric conductivity, thermal conductivity and latent heat storage. xGnP of 1, 2, 3, 5 and 7 wt% was added to pure paraffin at 75 °C. Scanning electron microscopy (SEM) morphology showed uniform dispersion of xGnP in the paraffin wax. Good dispersion of xGnP in paraffin/xGnP composite PCMs led to high electric conductivity. The percolation threshold of paraffin/xGnP composite PCMs was between 1 and 2 wt% in resistivity measurement. The thermal conductivity of paraffin/xGnP composite PCMs was increased as xGnP loading contents. Also, reproducibility of paraffin/xGnP composite PCMs as continuous PCMs was manifested in results of electric and thermal conductivity. Paraffin/xGnP composite PCMs showed two peaks in the heating curve by differential scanning calorimeter (DSC) measurement. The first phase change peak at around 35 °C is lower and corresponds to the solid-solid phase transition of the paraffin, and the second peak is high at around 55 °C, corresponding to the solid-liquid phase change. The latent heat of paraffin/xGnP composite PCMs did not decrease as loading xGnP contents to paraffin. xGnP can be considered as an effective heat-diffusion promoter to improve thermal conductivity of PCMs without reducing its latent heat storage capacity in paraffin wax.     

Highly filled graphite/graphene/carbon nanotube in polybenzoxazine composites for bipolar plate in PEMFC

This research aims to develop polybenzoxazine (PBA) based composites suitable for bipolar plates in proton exchange membrane fuel cells (PEMFCs). PBA composites filled with carbon derivatives i.e. graphite, graphene, and multiwall carbon nanotubes (CNTs) were prepared. The effects of CNT contents from 0–2 wt% at an expense of graphite with constant content of graphene and benzoxazine on properties of the obtained composites were investigated. It was found that the composite with 2 wt% of CNTs exhibited through-plane thermal conductivity as high as 21.3 W/mK which is 44 times higher than that of the composite without CNTs. Also, this composite showed electrical conductivity of 364 S/cm, Flexural Strength of 41.5 MPa and Modulus 49.7 GPa, respectively. These values meet the requirements suggested by the Department of Energy, USA and confirm that these composites are great candidates as bipolar plates for PEMFCs.     

Effects of compaction pressure and graphite content on hydrogen storage properties of Mg(NH2)2–2LiH hydride

Preparation of hydride–graphite compacts serves as an effective method to improve the volumetric hydrogen storage density and the effective thermal conductivity for light complex hydrides. This paper presents the effects of compaction pressure and expanded natural graphite (ENG) content on the hydrogen storage properties of the Mg(NH₂)₂–2LiH–0.07KOH compacts. The results show that the hydrogen desorption kinetics of the 1st sorption cycle decreases with the increase of the compaction pressure. However, the compacts exhibit the similar hydrogen desorption kinetics and capacities from the 2nd sorption cycles on regardless of the compaction pressure. The ENG addition significantly enhances the desorption kinetics because of the improvement of the heat transfer performance of the hydride. Furthermore, the volumetric hydrogen storage density of the hydride reaches 47 g/L after the compaction at 365 MPa, but it reduces by increasing the ENG content.