Surface Effect of Two Different Calcium Fluoride Fillers on the Non-Isothermal Crystallization Behavior of Poly(ethylene Terephthalate)

Two different types of calcium fluoride (CaF₂) particles were incorporated into a poly(ethylene terephthalate) (PET) matrix, fine particles (～350 nm), and nanoparticles (～70 nm). Both of them were synthesized by a chemical precipitation method using triethanolamine (TEA) as stabilizer. To obtain the nanoparticles, a greater amount of TEA was added during the synthesis in order to limit their growth. Therefore, unlike the fine particles, nanoparticles contained a greater amount of the stabilizer. Once CaF₂ particles were obtained, the composite materials were prepared by melt-blending PET and particles at different filler loadings. The influence of both kinds of particles on the non-isothermal crystallization behavior of PET was investigated by using differential scanning calorimetry and field emission scanning electron microscopy. The Jeziorny-modified Avrami equation was applied to describe the kinetics of the non-isothermal crystallization, and several parameters were analyzed (half-crystallization time, Avrami exponent, and rate constant). According to the results, it is clear that CaF₂ particles act as nucleating agents, accelerating the crystallization rate of PET. However, the effect on the crystallization rate was more noticeable with the addition of the fine particles where the surface plays an important role for epitaxial crystallization, while the addition of the nanoparticles with an organic surface coating resulted in a crystallization behavior similar to the observed for PET.     

Effect of Ag doping on the crystallization and phase transition of TiO2 nanoparticles

TiO₂ nanoparticles doped with different Ag contents were prepared by a modified sol–gel method, using titanium tetraisopropoxide and silver nitrate as precursors and 2-propanol as solvent. Silver was incorporated into the TiO₂ matrix via decomposition of AgNO₃ during thermal treatment in different atmospheres. Effects of Ag doping on the crystallization and phase transition of the TiO₂ nanoparticles were studied using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and Raman spectroscopy techniques. While air annealing incorporates silver into TiO₂ matrix in silver oxide form, annealing in nitrogen incorporates metallic silver into TiO₂. Formation of silver oxide increases the thermal stability of the TiO₂ particles. Silver oxide affects the crystallization process of TiO₂ particles and the temperature of transition form anatase to rutile. On the other hand, presence of metallic silver in the samples annealed in nitrogen atmosphere decreases the temperature of phase transition of TiO₂ nanoparticles.     

Dispersion of Nano TiO2 in Ethylene Glycol and Poly(ethylene terephthalate)

Nano TiO₂ was dispersed in ethylene glycol (EG) by the replacement of dispersion medium from water sol. EG/TiO₂ suspension was well stabilized by the electrostatic repulsive force when pH value of suspension was less than 4.3. In situ polymerization starting from bis(2-hydroxyethyl) terephthalate (BHET) and EG/TiO₂ suspension was carried out to prepare a series of poly(ethylene terephthalate) (PET)/TiO₂ nanocomposites. Under highly acidic conditions, 97% particles dispersed in PET matrix had the size less than 100 nm. With the increase of pH value, aggregation occurred and larger size particles appeared. A tensile test showed that Young's modulus of PET was increased by the addition of nano TiO₂     

Effect of WO3 on the glass transition and crystallization kinetics of borotellurite glasses

Tellurite glasses of the system xWO₃–75TeO₂–(25 ? x)B₂O₃ (0 ≤ x ≤ 25 mol. %) were prepared and studied by differential thermal analysis to explore the effect of WO₃ on their glass transition and crystallization kinetics. The crystallization kinetics was studied under non-isothermal conditions using the formal theory of transformations for heterogeneous nucleation. The crystallization results were analyzed and both the activation energy of the crystallization process and the crystallization mechanism characterized. The phases into which the glass crystallizes were identified by X-ray diffraction. Diffractograms of the transformed material indicate the presence of microcrystallites of α-tellurite, Te_0.95W_0.05O_2.05, Te₂W and B₂O₃ in the amorphous matrix.     

Study on Dispersion of TiO2 Particles During Polymerization of PET

An important factor influencing the stability of colloidal suspension is zeta potential (ζ-potential) on the surface of particles. In this work, ζ-potential of TiO₂ particles in ethylene glycol (EG) with various additives for poly(ethyleneterephthalate) (PET) polymerization, such as metallic salts, phosphoric acid and alkyl phosphates, were investigated by electrophoretic mobility method. The dispersion stability of TiO₂/EG suspension was influenced by decrease in the absolute value of the ζ-potential by the addition of metal acetates as well as phosphates. The addition of triethylamine (TEA) in the TiO₂/EG suspension restrained the change of ζ-potential from negative to positive, which resulted from phosphoric acid. The molar ratio of phosphoric acid to an acetate was found to have an influence on the dispersion ability of TEA in TiO₂/EG suspension. Effect of metallic salts, phosphoric acid and TEA on the stability of TiO₂/EG suspension was studied in the actual polymerization of PET. It was proved that the addition of TEA is highly effective for the dispersion of TiO₂ particles in PET, even in the presence of metallic salts, phosphoric acid and its alkyl phosphates.     

ZnO nanoparticles favours heterogeneous nucleation in PET–ZnO nanocomposites

The structural and chemical properties with non-isothermal crystallization kinetics of PET–ZnO nanocomposites have been reported in this article. ZnO nanoparticles have been synthesized via chemical route with average diameter 19 nm which made confirm by transmission electron microscopy and X-ray diffractometer (XRD) techniques. PET–ZnO nanocomposites have been prepared by solution casting method. The structural and chemical changes occurred in poly (ethylene terephthalate) after inclusion of ZnO nanoparticles have been studied with the help of XRD and Fourier transform infrared spectroscopy, respectively. It was observed from differential scanning calorimeter that ZnO nanoparticles work as nucleating agent for heterogeneous nucleation in PET matrix under non-isothermal crystallization process. The combined Avrami and Ozawa models have been proved adequate to explain non-isothermal crystallization kinetics of PET–ZnO nanocomposites, and also, ZnO nanoparticles have been caused to reduce crystallization activation energy in pristine PET as per the applied Kissinger model.     

Preparation and Characterization of Nano‐TiO2 Doped Polystyrene Materials by Melt Blending for Inertial Confinement Fusion

Abstract

Nano‐TiO₂ doped polystyrene (PS) materials (TiO₂‐d‐PS) used for inertial confinement fusion (ICF) targets were prepared by means of melt blending. The effect of the pretreatment process, including coupling agents and ultrasonic dispersion on nano‐TiO₂, was studied. Tensile tests were conducted to evaluate the mechanical properties of the TiO₂‐d‐PS materials. Scanning electron microscopy (SEM) combined with energy dispersive spectroscopy (EDS) was used to characterize the degree of dispersion of nano‐TiO₂ in the PS matrix. Transmission electron microscopy (TEM) and dynamic contact angle (DCA) measurements were introduced to demonstrate the surface state of untreated and pretreated nano‐TiO₂. The results showed that coupling agents improved the interfacial adhesion between the PS matrix and dopants; ultrasonic dispersion contributed to the increase in the tensile properties of the TiO₂‐d‐PS materials. The dispersion stability of nano‐TiO₂ powder and the stability of the TiO₂‐d‐PS materials were significantly enhanced through pretreatment, which was supported by the increase in the DCA when the nano‐TiO₂ was pretreated by the coupling agent. The results of SEM and EDS indicated that the nano‐TiO₂ dispersed homogeneously in the PS matrix. The pretreatment process is an effective way to break the aggregation of nano‐TiO₂, which was confirmed by TEM results. Melt blending is a feasible method to prepare PS doped high Z element ICF target materials.     

Elaboration and characterization of TiO2 nanoparticles incorporated in SiO2 host matrix

Nanometer-scale TiO₂ particles have been synthesized by sol-gel method. It was incorporated in a glass-based silica aerogel. The composite was characterized by various techniques such as particle size analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD), infrared spectroscopy (IR) and photoluminescence (PL). The bulk glass presents a strong luminescence at wavelengths ranging from 750 to 950 nm. This PL was attributed to various non-bridging oxygen hole centers (NBOHCs) defects resulting from thermal treatment and crystallization of TiO₂ at the interface between titania nanoparticles and silica host matrix.     

Thermal behavior,microstructure, phase transformation,and crystal growth kinetics of nano-scale Fe3+-doped TiO2 xerogel powders

Titania based ceramics are promising materials for environmental sensors, high efficiency photocatalyst. Ion doping is an effective method to improve the properties by modifying their microstructure and phase composition. In this study, TiO₂ particles doped with Fe³⁺ were prepared by sol-gel method using Ferric nitrate and tetrabutyl titanate as precursors. Fe³⁺ was incorporated in the TiO₂ matrix during thermal treatment in different temperatures. Thermal analysis, TEM and X-ray diffraction were used to characterize the TiO₂ powder. Microstructure, phase content, and cell parameters were calculated according to Rietveld refinement software GSAS. The interaction mechanism of Fe³⁺ in crystal lattice of titanium dioxide and the crystal growth kinetics of Fe³⁺-doped TiO₂ are discussed.     

Super-hydrophilic properties of TiO2-DLC nanocomposite films fabricated by the simple electrochemical process

Anatase TiO₂ nanoparticles incorporated DLC films were successfully deposited on single crystalline silicon substrates by the electrolysis of TiO₂-methanol solution under ambient atmospheric pressure and low temperature. Anatase TiO₂ nanoparticles were embedded into amorphous carbon matrix, forming the typical nanocrystalline/amorphous nanocomposite films, confirmed by transmission electron microscopy (TEM). TiO₂ incorporation effectively increased the sp³-hybridized carbon concentration in the composite film, and further regulated the microstructure and surface morphology. Furthermore, the static contact testing completely displayed, TiO₂ incorporation got the composite films super-hydrophilic, which fundamentally improved the wetting ability of DLC film.     

Isothermal and non-isothermal crystallization kinetics of PVA + ionic liquid [BDMIM][BF4]-based polymeric films

The effect of ionic liquid (IL), 1-butyl-2,3-dimethylimidazolium tetrafluoroborate [BDMIM][BF₄], on crystallization behavior of poly(vinyl alcohol) (PVA) has been studied by isothermal and non-isothermal differential scanning calorimetry techniques. The PVA + IL based polymer electrolyte films have been prepared using solution casting technique. To describe the isothermal and non-isothermal crystallization kinetics, several kinetic equations have been employed on PVA + IL based films. There is strong dependence of the peak crystallization temperature (T_c), relative degree of crystallity (X_t), half-time of crystallization (t_1/2), crystallization rate constants (Avrami K_t and Tobin A_T), and Avrami (n) and Tobin (n_T) exponents on the cooling rate and IL loading.     

Combined ultrasonic and gamma-irradiation to prepare TiO2@PET-g-PAAc fabric composite for self-cleaning application

The grafting of polyacrylic acid (PAAc) onto the fabric of Poly(ethyleneterephthalate) (PET) was loaded with TiO₂ by a mixture sonication of TiO₂ dispersed in AAc dissolved in acetone solvent. Ultrasonic irradiation was utilized as a tool for a good dispersion of TiO₂ onto the PET fabric. The grafted PET fabrics with acrylic acid AAc monomer were successfully obtained using gamma-ray induced graft polymerization, the degree of grafting PET-g-PAAc fiber was 105%. The chemical compositions and crystal structure of grafted TiO₂@PET-g-PAAc fabrics were characterized by ATR-FTIR and XRD. It was found that loading of PET fiber with in TiO₂ particles showing the formation of anatase and rutile as performed by XRD. The thermal property of TiO₂@PET-g-PAAc was investigated by differential thermal analysis (DTA). The obtained result indicated the thermal property of the grafted TiO₂@PET-g-PAAc was increased. Image of scanning electron microscope (SEM) indicated the good adherent and good distribution of PAAc and TiO₂ with PET fabric. The self-cleaning property of TiO₂@PET-g-PAAc has been evaluated by using three kinds of dyes as models.     

A novel approach towards high-performance composite photocatalyst of TiO2 deposited on activated carbon

TiO₂ photocatalysts deposited on activated carbon (TiO₂/AC) were prepared by dip-hydrothermal method at 180 °C using peroxotitanate as a precursor, then calcinated at 300-800 °C. The samples were characterized by X-ray diffraction, scanning electron microscopy, Raman spectroscopy and the nitrogen absorption. Their photocatalytic activity was evaluated by degradation of methyl orange (MO). The results showed that TiO₂ particles of anatase type were well deposited on the activated carbon surface. TiO₂/AC calcinated at 600 °C exhibited the best photocatalytic performance. For the comparison, the same photocatalysis experiment was carried out for two mixtures of commercial TiO₂ (Degussa P25) with AC and synthetic TiO₂ with AC. It was found that the composite catalyst TiO₂/AC was better than the two mixtures. Besides, different from fine powdered TiO₂, the granular TiO₂/AC photocatalysts could be easily separated from the bulk solution and reused; indeed, its photocatalytic ability was hardly decreased after a five-cycle for MO degradation. The kinetics of the MO degradation fitted well the Langmuir-Hinshelwood model.     

Effect of TiO2 nanoparticle size on the performance of PVDF membrane

The comparison of the performance and morphology was carried out between neat PVDF membrane and PVDF composite membranes with nanosized TiO₂ particles of different size. The results of permeability and instrumental analysis illustrated that nanometer size obviously affected the performance and structure of the PVDF membranes. The smaller nanoparticles could improve the antifouling property of the PVDF membrane more remarkably. The surface and cross-section of the membranes were observed with an atomic force microscopy (AFM), a scanning electron microscope (SEM). The TiO₂/PVDF membrane with smaller nanoparticles had smaller mean pore size on its surface and more apertures inside the membrane. X-ray diffraction (XRD) experiments also suggested that smaller TiO₂ nanoparticles had stronger effect on the crystallization of PVDF molecules.     

Microemulsion synthesis, characterization of bismuth oxyiodine/titanium dioxide hybrid nanoparticles with outstanding photocatalytic performance under visible light irradiation

Reverse microemulsions, consisting of n-hexanol, Triton X-100, Cyclohexane and aqueous salt solutions, were used to synthesize BiOI, TiO₂ and BiOI/TiO₂ hybrid nanoparticles at room temperature. The particles had been characterized by X-ray powder diffraction, FT-IR spectra, TG-DSC analysis, nitrogen sorption, electron microscopy, and UV-vis diffuse reflectance spectroscopy. The photocatalytic properties of those particles were evaluated by degradation of methyl orange under visible light irradiation. The BiOI/TiO₂ composites showed about 5 times higher photocatalytic performances than BiOI when the mole ratio of BiOI to TiO₂ was 75%. The remarkable enhancement in the visible light photocatalytic activities of the BiOI/TiO₂ heterostructures could be first attributed to the effective electron-hole separations at the interfaces of the two semiconductors, which facilitated the transfer of the photoinduced carriers. Meanwhile, the heterojunction formed between BiOI and TiO₂ would further retard the recombination of photoinduced carriers. In addition, high degree of crystallization, bimodal porous structure, relative large specific surface area, and appropriate energy band gap have great contribution to the enhancement of photocatalytic performance.     

Crystallization kinetics of the TeO2–BaO glass system

Tellurite glasses of the system (100–x)TeO₂–xBaO, with x = 05, 10, 15 and 20 wt%, have been prepared and studied by differential scanning calorimetry (DSC). The crystallization kinetics of the glasses were investigated under non-isothermal conditions, applying the formal theory of transformations for heterogeneous nucleation to the experimental data obtained by DSC, using continuous-heating techniques. In addition, from the dependence of the glass-transition temperature (T _g) on heating rate, the activation energy for the glass transition was derived. Similarly, the activation energy of the crystallization process was determined and the crystallization mechanism characterized. The thermal stability of these glasses are considered in terms of the characteristic temperatures, T _g and T _in (the onset temperature of crystallization), via ΔT = T _in?T _g and a kinetic parameter K(T _g). The results confirm that thermal stability decreases with increasing BaO content. The phases into which the glass crystallizes have been identified by X-ray diffraction. Diffractograms of the transformed material indicate the presence of microcrystallites of α-TeO₂, γ-TeO₂ and BaTeO₃ in the remaining amorphous matrix.     

Enhanced photocatalytic degradation of Safranin-O by heterogeneous nanoparticles for environmental applications

Nanostructure titanium dioxide (TiO₂) has been synthesized by hydrolysis of titanium tetrachloride in aqueous solution and Ag-TiO₂ nanoparticles were synthesized by photoreduction method. The resulting materials were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier-transform infrared (FT-IR) and UV-vis absorption spectroscopy. The experimental results showed that the sizes of the synthesized TiO₂ and Ag-TiO₂ particles are in the range of 1.9-3.2 nm and 2-10 nm, respectively. Moreover, Ag-TiO₂ nanoparticles exhibit enhanced photocatalytic activity on photodegradation of Safranin-O (SO) dye as compared to pure TiO₂. The positive effect of silver on the photocatalytic activity of TiO₂ may be explained by its ability to trap electrons. This process reduces the recombination of light generated electron-hole pairs at TiO₂ surface and therefore enhances the photocatalytic activity of the synthesized TiO₂ nanoparticles. The effects of initial dye and nanoparticle concentrations on the photocatalytic activity have been studied and the results demonstrate that the dye photodegradation follows pseudo-first-order kinetics. The observed maximum degradation efficiency of SO is about 60% for TiO₂ and 96% for Ag-TiO₂.     

Highly Active TiO2/Polyelectrolytes Hybrid Multilayered Hollow Nanofibrous Photocatalyst Prepared from Electrouspun Fibers Using Electrostatic Layer-by-Layer Technique

Compared to conventional film photocatalysts, fiber photocatalyst has a greater surface-to-volume ratio and a 3-D open structure that allows its surface active sites to be accessible for reactants more easily and effectively. However, TiO ₂ powder (Degussa P25), by itself, cannot be prepared in the form of fibers, but with the help of a polymer nanofiber, TiO ₂ particles can be immobilized in a fibrous network of polyelectrolyte. Here, hybrid multilayered hollow nanofibers (HMHNFs) composed of TiO ₂ /polyelectrolyte (PE) have been prepared by a combination of a electrospinning method and layer-by-layer (LBL) technology. The results show that both the average diameter and the wall thickness of the HMHNFs can be well controlled by the template, as well as the number of coating layers. The dried morphology of the obtained HMHNFs is dependent on the inner deposited numbers of the polyelectrolyte layers. When compared with other nanostructured TiO ₂ materials, such as commercial TiO ₂ nanoparticles (P25, Degussa) and TiO ₂ films, the hollow TiO ₂ /PE hybrid nanofibers exhibited higher photocatalytic activities.     

Thermal features and physical properties of sulfur modified barium vanadate glasses

Differential scanning calorimetry (DSC) and XRD were used to investigate the role of sulfur in the network of V₂O₅–Fe₂O₃–BaO glasses. The crystallization kinetics of the glasses were investigated under non-isothermal conditions applying the formal theory of transformations for heterogeneous nucleation to the experimental data obtained by DSC. The activation energy for the glass transition (E _g) was derived from dependence of the glass-transition temperature (T _g) on the heating rate. Similarly the activation energy of the crystallization (E _c) and the frequency factor (K ₀) were determined. The results reveal the increase of the activation energy for glass transition was attributed to the increase in the rigidity and the cross-link density of these composites. The evaluated thermal stability decreases with increasing sulfur content. The phases of BaFe₂O₄, V₂O₅ and FeVO₄ micro-crystallites in the remaining amorphous matrix have been identified by X-ray diffraction.     

Deposition of Au/TiO2 film by pulsed laser

Au nanoparticles, which were photoreduced by a Nd:YAG laser in HAuCl₄ solution containing TiO₂ colloid and accompanied by the TiO₂ particles, were deposited on the substrate surface. The film consisting of Au/TiO₂ particles was characterized by the absorption spectra, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The adhesion between the film and substrate was evaluated by using adhesive tape test. It was found that the presence of TiO₂ dramatically enhanced the adhesion strength between the film and the substrate, as well as the deposition rate of film. The mechanism for the deposition of Au/TiO₂ film was also discussed.