Enhancing the thermal conductivity of n-eicosane/silica phase change materials by reduced graphene oxide

Reduced graphene oxide (rGO) sheets prepared by different methods are incorporated to boost the thermal conductivity of organic phase change materials (n-eicosane) in silica microcapsules. Low concentration (1 wt%) of graphene dosing already results in notable increase of the thermal conductivity. The preparation methods of rGO significantly affect the thermal properties of the composite. With 1 wt% dosing, sodium borohydride (NaBH₄) reduced rGO increases the thermal conductivity by 83% and decrease the phase change enthalpy by 6%. On the other hand, the thermal reduced rGO increases the thermal conductivity by 193% but leads to a 15% loss of the phase enthalpy. The difference is attributed to the different surface morphology and functional groups of the rGO sheets.     

Synthesis and thermal properties of polystyrene-graft-PEG copolymers as new kinds of solid–solid phase change materials for thermal energy storage

A series of polystyrene-graft-PEG₆₀₀₀ copolymers were synthesized as new kinds of polymeric solid–solid phase change materials (SSPCMs). The synthesized SSPCMs storage latent heat as the soft segments PEG₆₀₀₀ of the copolymers transform from crystalline phase to amorphous phase and therefore they can keep its solid state during the phase transition processing. The graft copolymerization reaction between polystyrene and PEG was verified by Fourier transform infrared (FT-IR) and ¹H NMR spectroscopy techniques. The morphology of the synthesized SSPCMs was characterized by polarization optical microscopy (POM). Thermal energy storage properties, thermal reliability and thermal stability of the synthesized SSPCMs were investigated by differential scanning calorimetry (DSC) and thermogravimetric (TG) analysis methods. The DSC results showed that the synthesized SSPCMs had typical solid–solid phase transition temperatures in the range of 55–58 °C and high latent heat enthalpy in the range of 116–174 J g⁻¹. The TG analysis findings showed that the synthesized SSPCMs had high thermal durability above their working temperatures. Also, thermal conductivity measurements indicated that the synthesized PCMs had higher thermal conductivity compared to that of polystyrene. The synthesized polystyrene-graft-PEG₆₀₀₀ copolymers as new kinds of SSPCMs could be used for thermal energy storage.     

Structure and properties of mixtures based on long chain polyacrylate and 1-alcohol composites

A series of phase change materials (PCMs) based on long chain polyacrylate and 1-alcohol, i.e., poly (stearyl methacrylate) and 1-tetradecanol (PSMA/C14OH) were prepared through the solution-mixing method. Thermal energy storage capacity, thermal stability and morphology of PSMA/C14OH PCMs were characterized by Fourier transform infrared spectroscopy (FTIR), polarized optical microscopy (POM), field emission scanning electron microscopy (FE-SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). DSC results demonstrated that the heat of fusion of PSMA/C14OH PCMs increased from 85.9 to 172.3 J g⁻¹ with the weight fraction of C14OH increasing from 20 to 80 wt%. And, the thermal stability also enhanced with PSMA weight. The spherulite (ca. 250 μm) in PSMA/C14OH composites containing 60 wt% C14OH proved the compatibility between PSMA and C14OH, indicating the cocrystallization behavior of alkyl side groups appeared. The cocrystallization behavior contributes the enhanced thermal stability of PSMA/C14OH PCMs, and it is suitable as the thermal energy storage materials in the future.     

Acrylonitrile-capped poly(propyleneimine) dendrimer curing agent for epoxy resins: Model-free isoconversional curing kinetics,thermal decomposition and mechanical properties

Acrylonitrile-modified aliphatic amine adducts are often used as curing agents for room-temperature epoxy formulations (coatings, adhesives, sealants, castings, etc.), yet the curing reaction and properties of resultant epoxy systems still remain less fundamentally understood. Herein we systematically investigate our newly-developed acrylonitrile-modified multifunctional polyamine curing agent for bisphenol A epoxy resin (DGEBA): an acrylonitrile-capped poly(propyleneimine) dendrimer (PAN4). The impact of the molecular structure of PAN4 and a controlled poly(propyleneimine) dendrimer (1.0GPPI) on the curing reactivity, reaction mechanisms, thermal stability, viscoelastic response and mechanical properties of the epoxy systems are highlighted. Differential scanning calorimetry (DSC) confirms DGEBA/PAN4 shows markedly lower reactivity and reaction exotherm than DGEBA/1.0GPPI, and the model-free isoconversional kinetic analysis reveals that DGEBA/PAN4 has the generally lower reaction activation energy. To be quantitative, the progress of the isothermal cure is predicted from the dynamic cure by using the Vyazovkin equation. The isothermal kinetic prediction shows that DGEBA/PAN4 requires about 10 times longer time to achieve the same conversion than DGEBA/1.0GPPI, which agrees with the experimentally observed much longer gel time of DGEBA/PAN4. Subsequently, dynamic mechanical analysis shows that PAN4 results in the cured epoxy network with the lower β- and glass-relaxation temperatures, crosslink density, relaxation activation energy, enthalpy, entropy, but the higher damping near room temperature than 1.0GPPI. Finally, thermogravimetric analysis (TGA) demonstrates cured DGEBA/PAN4 is thermally stable up to 200 °C, and mechanical property tests substantiate that PAN4 endows the cured epoxy with much higher impact and adhesion strengths than 1.0GPPI. Our data can provide a deeper insight into acrylonitrile-modified aliphatic amine curing agents from the two good model compounds (PAN4 and 1.0GPPI).     

Coupling of conductivity to the relaxation process in polymer electrolytes

Conductivity relaxation using modulus formalism has been used to explore the coupling of ionic conductivity to dielectric relaxation in polymer electrolyte based on polyethylene oxide complexed with various content of LiAsF₆. The temperature dependence of conductivity followed the VTF behavior suggesting close correlation between conductivity and the segmental relaxation process in polymer electrolytes. The coupling of conductivity to the segmental process has been discussed in terms of coupling index. For all compositions studied, the coupling index was within the range of 1–11 in the temperature range of investigation, which was in agreement with the coupled systems.     

Synthesis,characterization, thermal and dielectric properties of pure and cadmium doped calcium hydrogen phosphate

The synthesis of pure and cadmium doped calcium hydrogen phosphate as single crystal has been accomplished by a room temperature solution growth technique viz., silica gel technique. Silica gel obtained from sodium metasilicate with a strongly acidic cation exchanger in the H-form, was used for crystal growth experiments. The nature of the grown material was established by powder X-ray diffraction (PXRD) studies, whereas from single crystal X-ray diffraction (SXRD) the crystal system comes out to be monoclinic. The stoichiometry of the grown composition was established by energy dispersive X-ray analysis (EDAX). Fourier transform infrared spectroscopic (FTIR) studies signifies the presence of phosphate (PO₄)²⁻ group and water of crystallization. Thermo gravimetrical analysis and investigations of dielectric properties were undertaken to study the thermal stability, dielectric constant and transition temperature of the grown material. Dielectric studies suggest that there is a shift in the value of transition temperature (T_c) thereby indicating relaxor behaviour of the material.     

Porous graphene gels: Preparation and its electrochemical properties

Ultra-light porous 3D network graphene oxide (GO) gels were prepared using a simple process of aqueous gel precursor freezing, solvent exchange, and ethanol drying rather than supercritical drying technology. The GO sheets were consolidated by cross-linked sodium alginate (SA) and the obtained GO–SA gel was reduced by glucose to prepare graphene nanosheet–SA (GN–SA) gel. The gels were characterized by FTIR, XRD, SEM, and nitrogen adsorption–desorption measurements. SA was proven to attach to GO or GN surfaces to form gels composed of macropores and mesopores. GO–SA gel exhibited a bulk density of 16.79 mg cm⁻³, and adsorbed water 17.4 times, ethanol 20.5 times, and soybean oil 22.4 times the weight of GO–SA gel, while GN–SA gel exhibited a lower bulk density of 12.93 mg cm⁻³, and adsorbed water 12.2 times, ethanol 16.9 times and soybean oil 32.3 times the weight of GN–SA gel. The electrochemical performance of the GN–SA gel was analyzed using cyclic voltammetry, electrochemical impedance spectrometry, and chronopotentiometry. The results revealed that GN–SA gel displayed superior capacitive performance with large capacitance (114.12 F g⁻¹) and excellent cyclic performance.     

Nonisothermal crystallization behavior and mechanical properties of PEEK/SCF/nano-SiO2 composites

Nonisothermal crystallization of hybrid PEEK composites reinforced with short carbon fibers (SCF) and nano-SiO₂ (1, 1.5 and 2 wt%) was investigated using DSC. Composites were fabricated by melt-mixing process at 400 °C. The Size of the nanoparticles was 13 nm. Samples were cooled from 410 °C to 25 °C with cooling rates of 10, 30, 50 and 70 °C min⁻¹. The onset, peak and end crystallization temperatures were investigated as well as absolute crystallization percentage and crystallization time. Avrami, Ozawa and Ozawa–Avrami equations were fitted to the data in order to investigate the crystallization kinetics. Mechanical behaviors of the composites were examined using nanoindentation and nanoscratching. DSC results revealed that absolute crystallization percentage increases in PEEK/SCF/1%SiO₂ and PEEK/SCF/1.5%SiO₂ samples compared to PEEK/SCF, however it decreases by adding more nano-SiO₂. Ozawa–Avrami is proved to be the best model for describing crystallization behavior of the composites while Avrami equation was suitable for describing a part of the crystallization process. The Avrami and Ozawa–Avrami constants were calculated. Besides, adding SCFs and nano-SiO₂ into PEEK results in a significant decrease in plasticity index, while increases the resistance to plastic deformation of the composite.     

Organic/inorganic flame retardants containing phosphorus,nitrogen and silicon: Preparation and their performance on the flame retardancy of epoxy resins as a novel intumescent flame retardant system

This paper presents the preparation of novel organic/inorganic flame retardants containing phosphorus, nitrogen and silicon (organic/inorganic FRs). The organic/inorganic FRs were highly water resistant, as suggested by the water contact angle and water solubility tests. The organic/inorganic FRs were then incorporated into epoxy resins (EP) at different phosphorus/nitrogen ratios and the flame retardancy of EP/FRs composites was characterized. The results showed that synergistic effects on the flame retardancy of EP composites existed between the DOPO-VTS and TGIC-KH. The char residues for EP/FRs composites were increased, and the highest char residues were obtained in air atmosphere (3.8 wt.%) when the DOPO-VTS/TGIC-KH is 4/1. The MCC results also showed that the THR of epoxy resins were also decreased when the DOPO-VTS/TGIC-KH is 4/1, which was in accordance with the highest LOI and UL-94 results. The SEM, FTIR, XPS and TG-FTIR results of pyrolysis products in both condensed and gases phases indicated that the strategy of organic/inorganic FRs combined condensed phase and gases phase flame retardant strategies such as the phosphorus–nitrogen synergism systems, the silicon reinforced effects in the condensed phase and DOPO flame retardant systems in the gases phase, resulting in significant improvements in the flame retardancy of epoxy resins.     

Capacitive behavior studies on electrical double layer capacitor using poly (vinyl alcohol)–lithium perchlorate based polymer electrolyte incorporated with TiO2

Electric double layer capacitors (EDLCs) based on activated carbon electrodes and poly (vinyl alcohol)–lithium perchlorate (PVA–LiClO₄)-nanosized titania (TiO₂) doped polymer electrolyte have been fabricated. Incorporation of TiO₂ into PVA–LiClO₄ system increases the ionic conductivity. The highest ionic conductivity of 1.3 × 10⁻⁴ S cm⁻¹ is achieved at ambient temperature upon inclusion of 8 wt.% of TiO₂. Differential scanning calorimetry (DSC) analyses reveal that addition of TiO₂ into polymer system increases the flexibility of polymer chain and favors the ion migration. Scanning electron microscopy (SEM) analyses display the surface morphology of the nanocomposite polymer electrolytes. The electrochemical stability window of composite polymer electrolyte is in the range of −2.3 V to 2.3 V as shown in cyclic voltammetry (CV) studies. The performance of EDLC is evaluated by electrochemical impedance spectroscopy (EIS), CV and galvanostatic charge–discharge technique. CV test discloses a nearly rectangular shape, which signifies the capacitive behavior of an ELDC. The EDLC containing composite polymer electrolyte gives higher specific capacitance value of 12.5 F g⁻¹ compared to non-composite polymer electrolyte with capacitance value of 3.0 F g⁻¹ in charge–discharge technique. The obtained specific capacitance of EDLC is in good agreement with each method used in this present work. Inclusion of filler into the polymer electrolyte enhances the electrochemical stability of EDLC.     

Intermetallic compounds dynamic formation during annealing of stacked elemental layers and its influences on the crystallization of Cu2ZnSnSe4 films

A combined in-situ investigation using X-ray diffraction and differential scanning calorimetry during annealing was carried out to investigate the formation of intermetallic compounds in the stacked elemental layers and to reveal its influences on the crystallization of kesterite Cu₂ZnSnSe₄. The Mo/Cu/Zn, Mo/Cu/Sn/Zn, Mo/Cu/Zn/Se and Mo/Cu/Sn/Zn/Se stacked films were prepared with a composition resembling a typical kesterite Cu-poor and Zn-rich metallic composition. In-situ experiments during annealing of pure metallic stacked films reveal a dynamic intermetallic compounds formation of Cu₅Zn₈ → CuZn → Cu₂Zn → Cu₃Zn and Cu₆Sn₅ → Cu₄₁Sn₁₁. The CuZn and Cu₅Zn₈ layer formed at the interface of metals/Se may prevent the stacked metallic layers from selenization below 320 °C. On the other side, the dynamic formation of Cu–Zn phases in the stacked films is found to be an origin of a ZnSe gradual formation starting from 320 °C. Phase analysis suggests that the ternary Cu₂SnSe₃ phase forms almost immediately after the formation of Cu₂Se and SnSe. The formation of Cu₂SnSe₃ is indicated by the consumption of SnSe by the Cu₂Se which occurs at 530–540 °C. Crystallization of kesterite takes place above 540 °C. On a phenomenological basis of present results, consequences for the thin film kesterite fabrication for solar cell application are discussed.     

DSC Study on the Polyacrylonitrile Precursors for Carbon Fibers

Different polyacrylonitrile (PAN) precursor fibers that displayed various thermal properties were studied by using differential scanning calorimetry (DSC). Results showed that some commercial PAN precursor fibers displayed double separated peaks and these fibers were of high quality because of their process stability during their conversion to carbon fibers of high performance. Some fabrication processes, such as spinning, drawing, could not apparently change the DSC features of a PAN precursor fiber. It was concluded that the thermal properties of a PAN precursor fiber was mainly determined from its comonomer content type and compositions.     

Preparation and characterisation of polyamide 11/montmorillonite (MMT) nanocomposites for use in angioplasty balloon applications

With increased demands on catheter balloon functionality, there is an emphasis to blend new materials which can improve mechanical performance. Polymer nanocomposites were prepared by melt blending polyamide 11 (PA 11) with organically modified montmorillonite nanoclay. The effects of incorporating the nanoclay on the short-term mechanical properties of PA 11 were assessed using a design of experiments (DoEs) approach. X-ray diffraction (XRD), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis techniques (DMA) were used to characterise the morphology of the nanocomposites. Design of experiments studies revealed that the optimum nanocomposites properties can be achieved by carefully controlling the melt compounding parameters. XRD and TEM data proved that exfoliated clay morphologies existed within the matrix at low clay loading (2%). Whereas the interaction between the polymer matrix and nanoclay was quantified in the DMA spectra, showed a significant increase in storage modulus (up to 80%). The reinforcing effect of nanoclay within the PA 11 was further investigated using mechanical testing, where significant increases in the ultimate tensile strength and strain at break of reinforced tri-layer balloon tubing were observed.     

Recrystallization and grain growth of nanocomposite Ti–B–N coatings

Nanocomposite Ti–B–N coatings with different chemical composition were prepared by non-reactive co-sputtering of a segmented TiN–TiB₂ target. The coatings investigated are primarily composed of nanocrystalline TiN and TiB₂ phases. Increasing boron content results in a decreasing grain size from approximately 6 to 2 nm. During a thermal treatment of such coatings solely recovery and recrystallization with subsequent grain growth would appear, since the two phases are in thermodynamic equilibrium. Differential scanning calorimetry (DSC) and X-ray diffraction analysis were used to investigate the recrystallization behavior and subsequent grain growth of the nanocomposite Ti–B–N coatings. On heating the coating samples, which were removed chemically from their low alloyed steel substrates, an exothermal peak appeared during the DSC measurements indicating grain growth. From the onset temperature of this peak the recrystallization temperature was found which increases with increasing boron content from 1032 to 1070 °C. Activation energies for grain growth are obtained from Kissinger plots and yield values decreasing from 7.9 to 4.4 eV with increasing boron content. After heat treatment up to 1400 °C during the DSC measurements the coatings showed grain sizes within the range of 15–30 nm. It was found that the highest recrystallization temperature does not imply the highest activation energy for grain growth.     

Modeling and simulation of curing kinetics for the cardanol-based vinyl ester resin by means of non-isothermal DSC measurements

The cure kinetics of vinyl ester-styrene system was studied by non-isothermal differential scanning calorimetric (DSC) technique at four different heating rates. The kinetic parameters of the curing process were determined by isoconversional method for the kinetic analysis of the data obtained by the thermal treatment. Activation energy (E_a = 56.63 kJ mol⁻¹) was evaluated for the cure process and a two-parameter (m, n) autocatalytic model was found to be the most adequate to describe the cure kinetics of the studied cardanol-based vinyl ester resin. Non-isothermal DSC curves, as obtained by using the experimental data, show good agreement with the DSC curves obtained by theoretically calculated data.     

Properties of (0.5−x)Zn-xFe2O3-0.5P2O5 glasses

Experimental determination of the properties of less studied zinc-iron-phosphate glasses was investigated. Glasses of the general composition (50−x)ZnO-xFe₂O₃-50P₂O₅, mol%, with x=0, 10, 20, 30 and 40, was chosen for these investigations. These studies included, glass forming, glass density, thermal expansion coefficient, dilatometric softening temperature, an initial test of chemical durability and vibrational properties. It is shown that an Fe/P ratio of the compositions at about 0.6 and 0.8 and the O/P ratio at 3.4 and 3.8 could be considered as chemically durable phosphate candidates.     

Effect of maleic anhydride modified MWCNTs on the morphology and dynamic mechanical properties of its PMMA composites

This study successfully grafted multiwalled carbon nanotubes (MWCNTs) with maleic anhydride (Mah-g-MWCNTs) via Friedel–Crafts acylation with the aluminum chloride catalyst (AlCl₃), investigated by Raman and TGA analysis. The covalent bonds and carboxylic groups of maleic anhydride provided additional active species, improving adhesion between the MWCNTs and poly(methyl methacrylate) (PMMA). This investigation also studied the morphology and dynamic mechanical properties of pristine MWCNTs (P-MWCNTs) and modified MWCNTs (Mah-g-MWCNTs) reinforced with PMMA. Findings show a homogeneous distribution of MWCNTs throughout the matrix for Mah-g-MWCNTs/PMMA composites, as revealed by transmission electron microscope (TEM). The addition of both MWCNTs influenced the molecular arrangement of the PMMA matrix and also increased the dynamic mechanical properties of MWCNTs/PMMA composites. Glass transition temperature (Tg) and storage moduli (E′) of the Mah-g-MWCNTs/PMMA composites increased significantly comparing with P-MWCNTs/PMMA composites, attributed to improved interfacial adhesion between the reinforcement and the matrix. DMA studies revealed that adding 4.76 wt% Mah-g-MWCNTs into PMMA generates a 184% enhancement in the storage modulus and a 19 °C increase in Tg. However, adding 4.76 wt% P-MWCNTs into PMMA only generates 108% enhancement in the storage modulus and a 14 °C increase in Tg.     

Study of crystallization kinetics and structural relaxation behavior in phase separated Ag33Ge17Se50 glassy alloys

We report on the crystallization processes and structure (crystal phases) of Ag₃₃Ge₁₇Se₅₀ glassy alloy using differential scanning calorimetry and x-ray diffraction techniques, respectively. The devitrification that gives rise to the first exothermic peak results in the crystallization of Ag₂Se and Ag₈GeSe₆ phases, while the growth of GeSe₂ accompanied by the transformation of Ag₈GeSe₆ to Ag₂Se phase occurs during the second crystallization process. Different theoretical models are used to elucidate various kinetic parameters for the crystallization transformation process in this phase separated system. With annealing below the glass transition temperature, an inverse behavior between the variation of the optical gap and the band tailing parameter is observed for the thermally evaporated films. These results are explained as the mixing of different clusters/species in the amorphous state and/or changes caused by structural relaxation of the glassy network for the thermally evaporated films.     

Thermo-mechanical,Wear and Fracture Behavior of High-density Polyethylene/Hydroxyapatite Nano Composite for Biomedical Applications:Effect of Accelerated Ageing

The objective of this work is to demonstrate how the viscoelastic,thermal,rheological,hardness,wear resistance and fracture behavior of bioinert high-density polyethylene（HDPE） can be changed by the addition of hydroxyapatite（HAP） nano particles.Also the effects of accelerated thermal ageing on the composite properties have been investigated.Different weight fractions of HAP nano particles up to 30 wt%have been incorporated in HDPE matrix by using melt blending in co-rotating intermeshing twin screw extruder.The fracture toughness results showed a remarkable decrease in proportion to the HAP content.The differential scanning calorimetry results indicated that the melting temperature and crystallinity were affected by the addition of HAP nano particles into the matrix.The complex viscosity increased as the percentage of HAP increased due to the restriction of the molecular mobility.The dynamic mechanical analysis results revealed that higher storage modulus(8.3 10¹¹ Pa) could be obtained in the developed HDPE/HAP in 30 wt% compared to neat HDPE(5.1 10¹¹ Pa).Finally,the hardness and wear resistance of HDPE were improved significantly due to the addition of HAP nano particles.The changes in the HDPE and its nano composite properties due to ageing showed that the HDPE and its nano composites crystallinity increased while the fracture toughness,hardness,wear resistance,storage and loss modulus decreased.     

Hydration dynamics of collagen/PVA composites: Thermoporometric and impedance analysis

Porous scaffolds like collagen/PVA (polyvinyl alcohol) composites have potential applications in the field of biomedical engineering. The pore properties and electrical behavior of collagen/PVA composite system were investigated by thermoporometry technique and electrochemical impedance analysis. The porous composites were crosslinked by less cytotoxic genipin due to the versatility in the crosslinking reactivity between the amino groups. Different physicochemical properties like rheological behavior, thermal stability of the protein and morphological changes of the composites were investigated as a function of PVA concentration by viscosity profile, temperature dependant circular dichroic spectroscopic studies, scanning electron microscopy. Bound water constrained within the pores of collagen/PVA composites seems to provide signatures for changes induced by amount of additives on the pore diameter and distribution in composite molecules. Impedance measurements of the composites in the frequency range of 10⁻² to 10⁵ Hz reveal that concentration of the additive and crosslinking significantly influence the permittivity of the composites. The tunable physicochemical properties help to gain insight for regulating cellular events for tissue and organ regeneration.