Synthesis of shape-stabilized paraffin/silicon dioxide composites as phase change material for thermal energy storage

The shape-stabilized paraffin/silicon dioxide (SiO₂) composite phase change materials (PCM) were prepared by using sol–gel methods. Paraffin was used as the PCM, and silicon dioxide was acted as the supporting material. Fourier transformation infrared spectroscope (FT-IR) and scanning electronic microscope were used to determine the FT-IR spectra and microstructure of shape-stabilized paraffin/silicon dioxide composite PCM, respectively. The thermal properties and thermal stability were investigated by a differential scanning calorimeter and a thermogravimetric analysis, respectively. The SEM analysis showed that the paraffin was well dispersed into the porous network of silicon dioxide. DSC analysis indicated that the mass content of paraffin in silicon dioxide was up to 92.1%, and paraffin/silicon dioxide composites had solidifying temperature of 57.07 °C, solidifying latent heat of 59.66 kJ/kg, melting temperature of 58.10 °C, and melting latent heat of 139.59 kJ/kg.     

Size and temperature consideration in the liquid layer growth from nanovoids and the melting model construction

A new model for the solid melting point T_m(D) from nanovoids is proposed through considering the liquid layer growth behavior. This model, which does not have any adjustable parameter, introduces the classical thermodynamic treatment, i.e., the liquid nucleation and growth theory, for nanoparticle melting. With increased void diameter D, T_m(D) approaches to T_m0. Moreover, T_m(D) > T_m0 for a small void (T_m0 is the bulk melting point). In other words, the solid can be significantly superheated especially when D decreases, even if the difference of interface energy is larger than zero. This finding can be expected from the negatively curved surface of the void. The model predictions are consistent with the molecular dynamic (MD) simulation results for argon solids. Moreover, the growth of liquid layer from void surface relies on both size and temperature, which directly determine liquid layer thickness, and only when liquid layer thickness reaches to a critical value, can void become instable.     

Grazing incidence X-ray study of Ge-nanoparticle formation in (Ge:SiO2)/SiO2 multilayers

We present the study of formation of Ge-nanoparticles (Ge-NP) in germanosilicate (Ge:SiO₂) multilayer (ML) films under thermal treatment. In anticipation of controllable formation of Ge-NP, ML films were prepared by magnetron deposition at room temperature as 20 bi-layer stacks, each bi-layer comprised of a 7 nm thick layer of (Ge + SiO₂) (molar ratio: 60:40) succeeded by a 7 nm thick layer of pure SiO₂, and then annealed for 1 h, up to T_a = 900 °C. Formation and morphology of Ge-NP were analyzed by combining the information obtained from the grazing incidence small angle X-ray scattering and X-ray diffraction. It was found that precipitation of Ge-NP starts at T_a = 600 °C, while high degree of in-plane confinement and lateral ordering of rather uniform precipitated particles is achieved at T_a =  700-800 °C range. At still higher annealing temperature T_a > 800 °C, volume fraction of precipitated Ge-NP in SiO₂ matrix diminishes due to the out-diffusion of Ge atoms from the film, while Ge-NP are no more well confined to (Ge + SiO₂) layers.     

Growth and characterization of CuInSe2 thin films prepared by successive ionic layer adsorption and reaction method with different deposition temperatures

CuInSe₂ films were prepared at different deposition temperatures (T_D) by successive ionic layer adsorption and reaction method with chelating solutions. Influence of T_D on film growth, morphology, crystal structure, and band gap energy was investigated. Results showed that elevation of T_D mainly enhanced reaction kinetics and ionic diffusion velocity, resulting in fast growth rate of CuInSe₂ films, and maximum 20-30 nm/cycle depended upon T_D were acquired. Films with 60 dip-cycles could grow from 180 nm to 1000 nm by elevating T_D from 30 °C to 90 °C. Surface roughness of CuInSe₂ films was closely related to dip-cycle times and T_D. Accelerated growth rate by T_D could reduce the dip-cycle times for a required film thickness, which improved quality of film morphology.     

Crystal structure and magnetic properties of the compound FeDy6Sb2

The crystal structure of a compound FeDy₆Sb₂ was determined by X-ray powder diffraction using the Rietveld method. The compound crystallizes in the hexagonal, space group P6¯2m (No. 189) with the Fe₂P structure type and lattice parameters a = 0.81449(5) nm, c = 0.41641(3) nm, z = 1 and D_calc = 8.842 g/cm³. The maximum magnetic entropy change ΔS_M for the compound is 3.41 J kg^− 1 K^− 1 near its Curie temperature (143.4 K) on the magnetic field changes of 0-2.0 T.     

Thermal Conductivity of High-Temperature Multicomponent Materials with Phase Change

This work focuses on the investigation of the effective thermal conductivity (λ_eff) of heterogeneous materials consisting of a phase change material (PCM) and expanded graphite (EG). These composites may be employed in latent heat storage systems, where a PCM stores energy by being heated to a temperature higher than its melting point (T _m), and releases it during solidification. For the determination of λ_eff, the steady-state comparative method was used and modified to measure composite samples at temperatures above T _m. Results were compared with the thermal conductivity of the pure PCMs, and a significant increase could be observed. The dependence of λ_eff on temperature, as well as the influence of the material microstructure on the enhancement of λ_eff, were examined. Paper presented at the Seventeenth European Conference on Thermophysical Properties, September 5–8, 2005, Bratislava, Slovak Republic.     

Photovoltaic performance of dye-sensitized solar cells fabricated with polyvinylidene fluoride–polyacrylonitrile–silicondioxide hybrid composite membrane

Electrospun fibrous membranes of hybrid composites of polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN) and silicon dioxide (SiO₂) (PVdF–PAN–SiO₂) are prepared with different proportions of SiO₂ (3, 5 and 7% w/w). The field emission scanning electron microscopy (FE-SEM) reveals that these membranes have three-dimensional, fully interconnected network structures, which are combined with micropores of fine SiO₂ distribution. The surface roughness of the membranes increases with increasing the SiO₂ content. It is found that 7 wt% SiO₂/PVdF–PAN electrolyte membrane has the highest ionic conductivity (6.96 × 10⁻² S cm⁻¹) due to the large liquid electrolyte uptake (about 570%). As the concentration of SiO₂ nanoparticles increase, the contact angle value also increases, ranging from 135.70° to 140.60° which indicates that the membrane has higher hydrophobicity. The dye sensitized solar cells (DSSCs) are fabricated using the hybrid composite membrane with PVdF–PAN with 7 wt % SiO₂. Its photovoltaic performance exhibits an open circuit voltage (V_oc) of 0.79 V and a short circuit current 11.6 mA cm⁻² at an incident light intensity of 100 mW cm⁻², producing an efficiency of 5.61%. DSSC, using the hybrid composite electrospun membrane which shows more stable photovoltaic performance than other assembled DSSCs.     

Core/shell structured sSiO2/mSiO2 composite particles: The effect of the core size on oxide chemical mechanical polishing

In a typical chemical mechanical polishing (CMP) process, the type, morphology, structure, mechanical, and surface characteristics of abrasive particles play an important role in influencing the material removal process. The novel abrasive particles with special mechanical and/or tribochemical properties have been introduced into CMP processes for the improvement of surface quality and finishing efficiency. In this work, the composite particles containing solid silica (sSiO₂) cores and mesoporous silica (mSiO₂) shells were prepared via a developed Stöber method using cetyltrimethylammonium bromide as a structure-templating surfactant. The as-synthesized core/shell structured sSiO₂/mSiO₂ composite particles were characterized by powder X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, and nitrogen sorption–desorption measurements. The effect of the sSiO₂ core size of the composite particles on oxide CMP performance was evaluated in terms of surface roughness and material removal rate (MRR). The root-mean-square surface roughness (0.15–0.31 nm) of the polished substrates slightly increased with increasing of the sSiO₂ core size (168–353 nm) of the composites with a comparable mSiO₂ shell thickness (16–18 nm). The sSiO₂/mSiO₂ composite particles with a relatively smaller or larger core presented a relatively high MRR for silicon oxide films. These oxide CMP results could be rationalized according to the contact area mechanism and indentation-based mechanism, incorporating the total contact area and chemical reactivity between particles and wafers, and the indentation depth of an abrasive particle onto the substrate surface.     

Origin of photoluminescence peaks in Ge–SiO2 thin films

Ge–SiO₂ thin films were prepared by the RF magnetron sputtering technique on p-Si substrates from a Ge–SiO₂ composite target. The as-deposited films were annealed in the temperature range of 300–1000 °C under nitrogen ambience. The structure of films was evaluated by X-ray diffraction, X-ray photoemission spectroscopy and Fourier transform infrared absorption spectroscopy. Results show that the content of Ge and its oxides in the films change with increasing annealing temperature (T_a), the photoluminescence (PL) characteristics are closely dependent on the contents of Ge and its oxides in SiO₂ matrix. The dependence observed strongly suggests that the PL peak at 394 nm is related to the existence of GeO and 580 nm to that of Ge nanocrystal (nc-Ge) in the films.     

High-speed deposition of dense,dendritic and porous SiO2 films by Nd: YAG laser chemical vapor deposition

Dense, dendritic and porous SiO₂ films were prepared by laser chemical vapor deposition (LCVD) using a high-power continuous-wave mode Nd: YAG laser (206 W) and a TEOS (tetraethyl orthosilicate) precursor. The effects of laser power (P_L) and total chamber pressure (P_tot) on the microstructure and deposition rate (R_dep) were investigated. Amorphous SiO₂ films were obtained independent of P_L and P_tot. Flame formation was observed between the nozzle and the substrate at P_L > 160 W and P_tot > 15 kPa. At P_L = 206 W, dense, dendritic and porous SiO₂ films were obtained at P_tot < 20 kPa, P_tot = 23 kPa and P_tot > 25 kPa, respectively. The R_dep increased thousands of times under flame formation conditions, the highest R_dep being reached at 1200 μm h^?1, 22,000 μm h^?1 and 28,000 μm h^?1 for the dense, dendritic and porous SiO₂ films, respectively.     

Fabrication and characterization of three dimensional woven carbon fiber/silica ceramic matrix composites

Carbon fiber reinforced fused silica composites exhibit the advantages of excellent mechanical properties, high heat resistance, low thermal expansion and low density, but low impact resistance or toughness. A novel modified slurry impregnation and hot pressing (SIHP) method was adopted to fabricate a new type of three dimensional orthogonal woven structure carbon fiber reinforced silica ceramic matrix composites (3D Cf/SiO₂ CMCs) with higher density and lower porosity. Physical characterization, flexural behavior, impact performance and toughening mechanism of the composites were investigated by three-point bending tests, impact tests, and scanning electron microscopy analysis. The 3D Cf/SiO₂ CMC showed a higher flexural strength in both warp (201.6%) and weft (263.6%) directions than those of pure SiO₂ and failed at a non-brittle mode due to the fiber debonding and pullout, and a delaminated failure of the 3D preform. The maximum impact energy absorption of the 3D Cf/SiO₂ CMC was 96.9 kJ/m², almost 4 times as much as those for typical other carbon fiber reinforced CMCs.     

Phase separation and crystallization in LiNbO3/SiO2 glasses

Various samples with the compositions (100 ? x)LiNbO₃·xSiO₂ (with x = 10, 20, 25, 30, 35, 40, 50 and 60) were prepared by conventional melting technique. Samples with 20 ≤ x ≤ 35 were transparent, while products with x = 10 or x ≥40 were at least partly opaque under the conditions supplied. TEM-micrographs of replicas gave evidence on phase separation in these glasses. At SiO₂-concentrations >30 mol%, the formed structures consist of SiO₂-rich droplets in a LiNbO₃-rich matrix phase. The size of the structures increases with increasing SiO₂-concentration. At an SiO₂-concentration of 50 mol%, the droplets are as large as 450 nm. During thermal treatment, the LiNbO₃-rich matrix phase crystallizes and forms lithium niobate.     

Compaction and sintering behaviour of glass–alumina composites

The effects of Al₂O₃ additions on the compaction and sintering behaviour of a leadborosilicate glass (LG) have been investigated. LG powder was prepared by melting, fritting and milling a glass of the composition: 77PbO, 10B₂O₃, 10SiO₂, 2Al₂O₃ and 1P₂O₅ (wt.%). The mean particle sizes of the powders were: LG, 6.5 μm and Al₂O₃, 3.3 μm. The compaction behaviour of LG–Al₂O₃ powder mixtures can be represented by a new compaction equation: [(D_g−D₀)/(1−D₀)]=(P/P_f)ⁿ, where D_g is the relative green density, D₀ the relative tap density and n and P_f are material constants. The exponent n decreases from 0.192 to 0.065 as the Al₂O₃ content is increased from 0 to 100 vol.%. The Frenkel equation for isothermal shrinkage has been found to be valid. It is shown that in the glass matrix composites the minimum sintering temperature can be determined by measuring the dilatometric deformation temperature. The presence of Al₂O₃ in excess of 15 vol.% has been found to strongly retard the sintering kinetics. An addition of 45 vol.% Al₂O₃ increases the activation energy for sintering from 67 to 112 kcal mol⁻¹. The presence of Al₂O₃ particles also induced a partial crystallisation in LG matrix.     

Ti/SiO2 composite fabricated by powder metallurgy for orthopedic implant

Titanium/silica (Ti/SiO₂) composites are fabricated using powder metallurgy (P/M). Nanoscale biocompatible SiO₂ particles are selected as reinforcement for the Ti/SiO₂ composite to enhance its biocompatibility and strength, especially when with high porosity. Effects of the SiO₂ particle addition and sintering temperature on mechanical properties of the Ti/SiO₂ composites are investigated. The results indicate that the mechanical property of Ti/SiO₂ composites sintered at 1100 °C are better than those at 900 and 1000 °C. The strength of the Ti/SiO₂ composites is significantly higher than that of pure titanium. The composite with the SiO₂ content of 2 wt% sintered at 1100 °C for 4 h shows an appropriate mechanical property with a relative density of 96.5%, a compressive strength of 1566 MPa and good plasticity (an ultimate strain of 15.96%). In vitro results reveal that the Ti/SiO₂ composite possesses excellent biocompatibility and cell adhesion. Osteoblast-like cells grow and spread well on the surfaces of the Ti/SiO₂ composites. The Ti/SiO₂ composite is a promising material for great potential used as an orthopedic implant material.     

Enhancement of photoluminescence properties of CaAl2Si2O8:Eu2+ by SiO2 addition

SiO₂ added phosphors, CaAl₂Si₂O₈:Eu²⁺ + xSiO₂ (x = 0, 1, 2, 3, 4, 5, 6 and 13 mol) were synthesized by a novel liquid phase precursor (LPP) method. The photoluminescence properties of phosphor added by 5 mol of SiO₂ showed 110% enhancement in the emission intensity compared to the CaAl₂Si₂O₈:Eu²⁺ phosphor. A broad emission and excitation wavelength was observed approximately from 400 nm to 600 nm centered at 430 nm and from 280 nm to 400 nm centered at 365 nm, respectively. Photoluminescence intensity of the phosphors increased continuously by SiO₂ addition up to x = 5 mol and then it decreased with further addition of SiO₂. The observed photoluminescence properties of the phosphors were discussed related to their crystalline structure and morphology.     

Synthesis and electrorheological properties of polyaniline/silicon dioxide composites

This study was to synthesize the inherently conductive polymer polyaniline using an optimized process to prepare polyaniline/silicon dioxide (PANI/SiO₂) composites by in situ polymerization and ex situ solution mixing. PANI and PANI/SiO₂ composite films were prepared by drop-by-drop and spin-coating methods. The morphology of particles and films were examined by a scanning electron microscope (SEM). SEM measurements indicated that the SiO₂ were well-dispersed and isolated in composite films. The electrorheological (ER), characteristics of the PANI/SiO₂ composites were investigated. A volume fraction series (φ = 5–25 %) of the PANI/SiO₂/silicone oil dispersions were prepared and sedimentation stabilities were determined. An ER activity was observed from the samples, when subjected to external electric field strength thus, they were classified as smart materials. Some parameters affecting the ER properties of the dispersions such as volume fraction, shear rate, electric field strength, frequency, and temperature were investigated.     

Effect of TiOx seed layer on the texture and electric properties in La and Ca modified PbTiO3 thin films

Lanthanum-and calcium-modified PbTiO₃ (PLCT) ferroelectric thin films were successfully prepared on Pt(111)/Ti/SiO₂/Si substrates by pulsed laser deposition. Influence of TiO_x seed layer on texture and electric properties of PLCT films was investigated. It is found the PLCT films without seed layer exhibited highly (100)-textured, while using about 9 nm TiO_x as seed layer lead to highly (301)-textured. The PLCT film with TiO_x seed layer possess higher remnant polarization (Pr = 26 µC/cm²), better pyroelectric coefficient and figure of merit at room temperature (p = 370 µC/m²k, F_d = 190 × 10^− 5 Pa^− 1/2) than that of film without seed layer. The mechanism of the enhanced electric properties was also discussed.     

Dependence of Seebeck coefficient on a load resistance and energy conversion efficiency in a thermoelectric composite

The thermo-emf ΔV and current ΔI generated by imposing the alternating temperature gradients (ATG) at a period of T and the steady temperature gradient (STG) on a thermoelectric (TE) composite were measured as a function of t, where t is the lapsed time and T was varied from 60 to or ∞ s. The STG and ATG were produced by imposing steadily and alternatively a source voltage V in the range from 1.0 to 4.0 V on two Peltier modules sandwiching a composite. ΔT, ΔV, ΔI and V_P oscillate at a period T and their waveforms vary significantly with a change of T, where ΔV and V_P are the voltage drops in a load resistance R_L and in resistance R_P of two modules. The resultant Seebeck coefficient |α| = |ΔV|/ΔT of a composite under the STG was found to be expressed as |α| = |α₀|(1 − R_comp/R_T), where R_T is the total resistance of a circuit for measuring the output signals and R_comp is the resistance of a composite. The effective generating power ΔW_eff has a local maximum at T = 960 s for the p-type composite and at T = 480 s for the n-type one. The maximum energy conversion efficiency η of the p- and n-type composites under the ATG produced by imposing a voltage of 4.0 V at an optimum period were 0.22 and 0.23% at ΔT_eff = 50 K, respectively, which are 42 and 43% higher than those at ΔT = 42 K under the STG. These maximum η for a TE composite sandwiched between two Peltier modules, were found to be expressed theoretically in terms of R_P, R_T, R_L, α_P and α, where α_P and α are the resultant Seebeck coefficients of Peltier modules and a TE composite.     

Mechanical and magnetic properties of γ-Ni–xFe/Al2O3 composites

Ultra-fine grained γ-Ni–xFe (x = 20, 50, and 64 (nominal)) dispersed Al₂O₃-matrix composites were fabricated by a mechano-chemical process plus hot-pressing, and their mechanical and magnetic properties were explored. The results indicated that all composites incorporated with different γ-Ni–xFe alloys possessed high densities (relative density D ⩾ 98%) and sub-micrometer-sized matrix dispersed with γ-Ni–xFe particles of sizes below ∼500 nm. As compared to other two composite systems, γ-Ni–20Fe/Al₂O₃ had finer microstructures and displayed superior fracture toughness and strength. In high iron-contained γ-Ni–64Fe/Al₂O₃ composite undesired FeAl₂O₄ phase formed on the matrix grain boundaries, which is mainly responsible for its inferior mechanical properties. Although Young’s modulus and hardness of Ni–20Fe/Al₂O₃ composite system decreased, its fracture toughness increased monotonously with increasing the alloy content in the composition range investigated. Moreover, incorporation of ferromagnetic γ-Ni–xFe particles led all the composite systems to display ferromagnetism with their saturation magnetization increasing almost linearly with increasing alloy content. In addition, experiments showed that their ferromagnetism had high thermal stability (T_c = ∼580 °C), no obvious magnetism degradation and magnetic interactions of the alloys with the matrix being observed. The combination of good mechanical properties with excellent magnetic performance would make this material be very valuable in industry.     

Luminescence properties of Sn2P2Se6 crystals

A large family of Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) semiconductor-ferroelectric crystals were obtained by the Bridgman technique. The photoluminescence properties of the Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) family crystals strongly depend on their chemical composition, excitation energy and temperature. The influence of the Pb → Sn and S → Se isovalent substitutions on the luminescence properties of a crystal with the Sn₂P₂Se₆ basic composition was investigated. A broad emission band observed in the Sn₂P₂Se₆ crystal with a maximum roughly at 600 nm (at T = 8.6 K) was assigned to a band-to-band electron-hole recombination, whereas broad emission bands, peaked near 785 nm (at T = 8.6 K) and 1025 nm (at T = 44 K) were assigned to an electron-hole recombination from defect levels localised within the bandgap. Possible types of recombination defect centres and specific mechanisms of luminescence in the Sn₂P₂Se₆ semiconductor-ferroelectric crystals were considered and discussed on the basis of the obtained results and the referenced data.