Formation of β-iPP in Isotactic Polypropylene/Acrylonitrile–Butadiene–Styrene Blends: Effect of Resin Type,Phase Composition,and Thermal Condition

The formation of β-iPP (β-modification of isotactic polypropylene) in the iPP/ABS (acrylonitrile–butadiene–styrene), iPP/styrene–butadiene (K resin), and iPP/styrene–acrylonitrile (SAN) blends were studied using differential scanning calorimery (DSC), wide angle X-ray diffraction (WAXD), and scanning electron microscopy (SEM). It was found that α-iPP (α-modification of isotactic polypropylene) and β-iPP can simultaneously form in the iPP/ABS blend, whereas only α-iPP exists in the iPP/K resin and iPP/SAN blend samples. The effects of phase composition and thermal conditions on the β-iPP formation in the iPP/ABS blends were also investigated. The results showed that when the ABS content was low, the ABS dispersed phase distributed in the iPP continuous phase, facilitating the growth of β-iPP, and the maximum amount of β-iPP occurred when the composition of iPP/ABS blend approached 80:20 by weight. Furthermore, it was found that the iPP/ABS blend showed an upper critical temperature T _c * at 130°C for the formation of β-iPP. When the crystallization temperature was higher than the T _c *, the β-iPP did not form. Interestingly, the iPP/ABS blend did not demonstrate the lower critical temperature T _c ** previously reported for pure iPP and its blends. Even if the crystallization temperature decreased to 90°C, there was still β-iPP generation, indicating that ABS has a strong ability to induce the β-iPP. However, the annealing experiments results revealed that annealing in the melt state could eliminate the susceptibility to β-crystallization of iPP.     

Investigation on (EC/DMC)(70−x)wt% to LiBETI(x)wt% impact on PVdF-co-HFP/octadecylamine-MMT(montmorillonite) nano clay composite electrolytes

The composition dependence of plasticizer (ethylenecarbonate(EC)/dimethyl carbonate(DMC))_(70?x)wt% to Lithium bis(perfluoroethanesulfonyl)imide(LIBETI)_(x)wt% salt (where x?=?1.5, 3.0, 4.5, 6.0 wt%) on PVdF-co-HFP (25 wt%)/surface modified octadecylamine containing montmorrillonite (ODA-MMT) nano clay (5 wt%) matrix has been investigated by AC impedance, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and dielectric and cyclic voltammetry studies. The enhanced conductivity 2.1?×?10^?5 Scm^?1 is noted in salt rich phase (EC/DMC)_(70–6)wt% /LiBETI_(x=6)wt% (VK4). In XRD, 2θ at 20.9° confirms β-phase. In FTIR studies, vibrational bands 838, 522 and 611 cm^?1 confirm β-phase of PVdF due to clay intercalation. In DSC studies, the melting of α-phase crystallites is noted between 140–150 °C. In SEM studies, one of the membranes presents fern leaf texture confirming swelling of clay. The increase in dielectric constant and dielectric loss with decrease in frequency is attributed to high contribution of charge accumulation at the electrode–electrolyte interface. In cyclic voltammetry studies, salt-rich phase membrane (VK4) shows good cyclability than other membranes.     

Influence of K<Subscript>2</Subscript>Ti<Subscript>6</Subscript>O<Subscript>13</Subscript> on dielectric and barrier properties of polymer

Polymer composite comprising polyvinylidene fluoride (PVDF) and potassium hexatitante (K₂Ti₆O₁₃) was synthesized by solution casting. The effect of K₂Ti₆O₁₃ on surface, thermal, and electrical properties of polymer composite were investigated. The addition of K₂Ti₆O₁₃ with polymer leads to thermal degradation and transition of polymer composite from semi-crystalline to amorphous phase. The optimum results of contact angle for different loading wt% of K₂Ti₆O₁₃ were directly correlated with the surface morphology. Our experimental results confirmed the incorporation of K₂Ti₆O₁₃ in polymer by SEM micrographs. The evaluated dielectric properties (ε' = 424; tan δ = 2.14 at 130 °C and 100 Hz frequency for 20 wt% loading of K₂Ti₆O₁₃) for polymer composite are higher in compared to pure polymer. The enhancement in dielectric constant and changing the surface properties of polymer composite can be used for the development of electrochemical storage device applications.     

Effects of α/β Compound Nucleating Agents on Mechanical Properties and Crystallization Behaviors of Isotactic Polypropylene

Sodium 2,2’-methylene-bis (4,6-di-tert-butylphenyl) phosphate (commercial name: Irgastab NA-11) and N,N’-dicyclohexylnaphthalene-2,6-dicarboxamide (commercial name: NU-100) are highly effective nucleating agents for α-isotactic polypropylene (iPP) and β-isotactic polypropylene (iPP) respectively. Effects of a total concentration of 0.2 wt% NA-11/NU-100 compound nucleating agents with different ratios of NU-100 on mechanical properties and crystallization behaviors of iPP were studied in this paper. The results showed that good balance between decreased stiffness and increased toughness of iPP was realized when the ratio of NU-100 was 50 wt%. Compared with those of virgin iPP, tensile strength, tensile modulus, flexural strength, and flexural modulus of iPP nucleated by the compound nucleating agent with 50 wt% NU-100 decreased by only 2.9%, 4.8%, 3.8% and 6.1% respectively, while the notched Izod impact strength of the nucleated iPP was increased by 212.8%. In addition, differential scanning calorimetry analysis results showed that addition of the NA-11/NU-100 compound nucleating agent increased the peak crystallization temperature of iPP significantly, but the crystallization rate of the nucleated iPP decreased with increasing ratio of NU-100 in compound nucleating agents.     

Preparation and Flammability of a Flame-Retardant Poly(Butyl Acrylate-Vinyl Acetate) System Based on Gemin-Surfactant Modified Montmorillonite and Ammonium Polyphosphate

Gemin-surfactant modified montmorillonite (G-MMT) was successfully prepared by an ion exchange reaction and characterized via Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The P(BA-VAc)/G-MMT emulsion was prepared via an in-situ polymerization method using potassium persulfate (K₂S₂O₈, KPS) as an initiator. Ammonium polyphosphate (APP) was introduced for obtaining P(BA-VAc)/APP/G-MMT flame-retardant latex with a constant total content of 15 wt% of APP and G-MMT in P(BA-VAc). The flame retardancy and thermal behavior of the latex films were investigated by limiting oxygen index (LOI), vertical burning test (UL-94) and thermal gravimetric analysis (TG/DTA). Compared with the P(BA-VAc)/APP composite, the LOI value of P(BA-VAc)/APP/G-MMT containing 0.5 wt% G-MMT at the same total additive loading increased to 29.1 from 20.0 and its UL-94 increased from no rating to V-0. Thermal gravimetric (TG) data showed that the amount of residues increased significantly with the loading of G-MMT. In addition, the LOI values increased with the increase in char residues. The morphology and microstructure of the residues generated during LOI testing were investigated by scanning electron microscopy (SEM). The outer surfaces of P(BA-VAc)/APP/G-MMT charred layers were more continuous and compact than those of P(BA-VAc)/APP.     

Dielectric,thermal, and electrochemical properties of PVC/PEMA blended polymer electrolytes complexed with zinc triflate salt

A new solid polymer electrolyte system based on poly (vinyl chloride) (PVC) and poly (ethyl methacrylate) (PEMA) containing zinc triflate [Zn(CF₃SO₃)₂] salt obtained in the form of thin film specimens using solution casting technique has been examined by means of complex impedance analysis, thermogravimetry (TG) and differential scanning calorimetric (DSC) studies, linear sweep voltammetry (LSV) and cyclic voltammetric (CV) measurements. The relevant mechanism of zinc ion transport involved in the case of the present polymer blend electrolyte viz., [PVC (30 wt%)/PEMA (70 wt%)] : x wt% [Zn(CF₃SO₃)₂] (where x = 10, 15, 20, 25, 30, and 35, respectively) has been evaluated in terms of AC impedance method, dielectric and electrical modulus formalisms. The optimized composition of the chosen blended polymer electrolyte system having 30 wt% loading of zinc triflate salt exhibited a single glass transition temperature (T _g) and possessed appreciable levels of thermal and electrochemical stability for possible utilization in zinc batteries.     

New insight on nanostructure assembling of high-performance electrode materials: synthesis of surface-modified hexagonal β-Ni(OH)<Subscript>2</Subscript> nanosheets as an example

Hexagonal β-Ni(OH)₂ nanosheets with thickness of ～12 nm were synthesized by a hydrothermal method at 150 °C using nickel chloride as nickel source and morpholine as alkaline. Electrodes for application in pseudocapacitor were assembled through a traditional technique: pressing a mixture of β-Ni(OH)₂ nanosheets and acetylene black onto nickel foam. Due to the hexagonal shape of rigid β-Ni(OH)₂ nanosheet and the mediation of surface-modified glycerol during electrochemical charge–discharge cycles, a nanostructure of electrode material with facile interior pathway for the transfer of electrolyte was formed. As a result, the as-formed electrodes presented high specific capacitance of 1,917 F g^?1 at current density of 1.6 A g^?1 in 3 mol L^?1 KOH solution. At high charge and discharge current density of 31.3 A g^?1, the electrodes still remained a high specific capacitance of 1,289 F g^?1. The interesting results obtained from this investigation may provide a new insight for the synthesis of electrode materials with high electrochemical performance.     

Solid‐phase cadmium speciation in soil using L3‐edge XANES spectroscopy with partial least‐squares regression

Cadmium (Cd) has a high toxicity and resolving its speciation in soil is challenging but essential for estimating the environmental risk. In this study partial least‐square (PLS) regression was tested for its capability to deconvolute Cd L₃‐edge X‐ray absorption near‐edge structure (XANES) spectra of multi‐compound mixtures. For this, a library of Cd reference compound spectra and a spectrum of a soil sample were acquired. A good coefficient of determination (R²) of Cd compounds in mixtures was obtained for the PLS model using binary and ternary mixtures of various Cd reference compounds proving the validity of this approach. In order to describe complex systems like soil, multi‐compound mixtures of a variety of Cd compounds must be included in the PLS model. The obtained PLS regression model was then applied to a highly Cd‐contaminated soil revealing Cd₃(PO₄)₂ (36.1%), Cd(NO₃)₂·4H₂O (24.5%), Cd(OH)₂ (21.7%), CdCO₃ (17.1%) and CdCl₂ (0.4%). These preliminary results proved that PLS regression is a promising approach for a direct determination of Cd speciation in the solid phase of a soil sample.     

Effect of β-Nucleating Agent on the Crystallization,Mechanical Properties,and Heat Resistance of Injection-Molded Isotactic Polypropylene

Injection-molded β-isotactic polypropylene (β-iPP) was prepared with a commercial β-nucleating agent (NT-A). The effect of NT-A on the crystallization, mechanical properties, and heat resistance of β-iPP was investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), polarized light microscopy (PLM), and mechanical and heat deflection tests. DSC and WAXD analysis showed that the content of β-crystals in the nucleated iPP was higher than that of pure iPP, and the content of β-crystals of the core was higher than that of the skin. PLM observations showed that injection-molded iPP had an obvious skin-core structure. NT-A induced abundant β-crystals and resulted in small spherulites which improved the Izod notched impact strength. When the content of NT-A was 0.075wt%, the Izod notched impact strength reached a maximum, 2.6 times more than that of pure iPP. The heat distortion temperature was also improved by NT-A.     

Room temperature synthesis and characterization of ultralong Cd(OH)2 nanowires: a simple and template-free chemical route

Ultralong Cd(OH)₂ nanowires were fabricated in high yield by a convenient chemical method using alkali medium at room temperature without using any templates. The preparation conditions induce a unilateral growth of nanowires, despite the absence of any template. The length of the nanowires reached several hundreds of micrometers, giving an aspect ratio of a few thousands. The X-ray diffraction shows that the Cd(OH)₂ nanostructures crystallized in the wurtzite structure without any special orientation. The photoluminescence spectrum of Cd(OH)₂ nanostructures appears as two emission bands: one related to green emission at 475–510 nm, and the other related to deep level emission at 510–540 nm. Also the formation mechanisms of the nanowires are presented. The growth mechanism involves the irreversible and specifically oriented self-assembly of primary nanocrystals and results in the formation of the nanowires.     

Photoelectric fields in lithium niobate crystals

Photovoltaic and diffusion fields in nominally pure single crystals of stoichiometric composition (R = Li/Nb = 1) grown in the presence of 6 wt% K₂O flux (LiNbO₃ stoich. K₂O) in nominally pure single crystals of complementary composition (LiNbO₃), complementary single crystals doped with Zn²⁺, Er³⁺ at wavelength of 476, 514.5, 530 nm are defined according to parameters of photo induced light scattering indicatrix. Photo induced changes of crystals’ refractive index are defined.     

Spectrophotometric and 27‐Al NMR Characterization of Aluminum(III) Complexes with l‐Histidine

Abstract

The complex formation between l‐histidine (HHis) and aluminum(III) ion in water solutions was studied by UV spectrophotometric and 27‐Al NMR measurements at 298 K. UV spectra were measured on solutions in which the total concentration of histidine was from 15.0 to 50.0 mmol/dm³ and the concentration ratio of histidine to aluminum was varied from 3∶1 to 10∶1 in the pH range between 4.2 and 6.0. The spectra were taken in the wavelength interval 240–340 nm. Nonlinear least‐squares treatment of the spectrophotometric data indicates the formation of the complexes Al(HHis)³⁺, Al(His)²⁺, Al(HHis)His²⁺, and Al₂(OH)His⁴⁺ with the overall formation constants β_p,q,r: log β_1,1,1=11.90±0.04, log β_1,1,0=7.25±0.08, log β_1,2,1=20.1±0.1, and log β_2,1,1=5.92±0.12 (p, q, r are stoichiometric indices for metal, ligand, and proton, respectively). ²⁷Al‐NMR spectra were taken on solutions with the concentration of aluminum 50 mmol/dm³ and that of histidine 250 mmol/dm³. In the pH interval 5.0–6.1, two resonances at 9.5 ppm and 12.0 ppm were assigned to Al(HHis)²⁺ and Al(HHis)(His)²⁺ (or Al(OH)(HHis)₂ ²⁺), respectively.     

Solvothermal synthesis of Cd(OH)2 and CdO nanocrystals and application as a new electrochemical sensor for simultaneous determination of norfloxacin and lomefloxacin

Cadmium hydroxide (Cd(OH)₂) microcrystals were synthesized in ethanol–water medium by using cadmium chloride as cadmium source and 1,10-phenanthroline as complexation agent under solvothermal condition. The sample was characterized by FT-IR, X-ray diffraction (XRD), scanning electron microscopy (SEM) and TEM. The as-prepared Cd(OH)₂ product were transformed to hexagonal CdO nanocubes by thermal treatment in air at 500 °C. The possible growth mechanism for the formation of different morphologies at basic medium has been proposed. DPV experiments were carried out for the simultaneous determination of norfloxacin and lomefloxacin in the acetate buffer solution with pH 4.5.     

Effect of alkali ions on the strength development of cement paste by Mössbauer spectrometry

Two clinker raw mixtures (83 wt% limestone +12 wt% clay +5 wt% α-Fe₂O₃) were fired at 1150°C for three hours in open furnace, each with 100 wt%-in addition-of an alkali carbonate (Na₂CO₃ and K₂CO₃) respectively. Each produced cliker was mixed with 5 wt% natural gypsum to produce portland cement, then with 25 wt% tap water. Compressive strength, ultrasonic pulse test, X-ray diffraction and Mossbauer effect measurements were carried out each at different times of hydration (21, 28 and 45 days). The effect of alkali ions on the strength development of cement pastes is discussed, the accuracy of Mössbauer, spectrometer in determining the cement strength is demonstrated.     

Fabrication and electrochemical performance of La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> impregnated porous YSZ cathode

La_0.5Sr_0.5CoO₃-yttria-stabilized zirconia (LSCO-YSZ) composite cathode for solid oxide fuel cell (SOFC) has been fabricated by wet impregnation method. Nitrate precursors of La, Sr, and Co have been impregnated into the pre-sintered porous YSZ matrix, which is converted into LSCO phase after calcination at 850 °C in the presence of glycine as confirmed from X-ray diffraction. LSCO of 5, 7, and 10 wt% impregnated porous YSZ have been electrochemically characterized using 2-probe AC conductivity method. Maximum ionic conductivity of 0.27 S/cm at 800 °C and activation energy of 0.15 eV between 600 and 800 °C have been observed for 10 wt% LSCO-YSZ cathode. Area-specific resistance of 1.01 Ω cm² at 800 °C is estimated for the electrolyte-supported half-cell (10 wt% LSCO-YSZ/YSZ). After testing the LSCO-YSZ cathode matrix, the electrolyte-supported full cell (10 wt% LSCO-YSZ/YSZ/NiO-YSZ) has been tested and produced maximum power density 51.12 mW/cm² (109.38 mA/cm²) at 800 °C. The electrolyte-supported full cell exhibited 6 Ω cm² electrode polarization at 800 °C in H₂, which is in higher side leading to low performance. LSCO-YSZ/YSZ/NiO-YSZ SOFC found to give stable performance up to 2 h and scanning electron microscopy analysis has been carried out before and after cell testing to assess the morphological changes.     

Conductivity studies of poly(ethylene oxide)(PEO)/poly(vinyl alcohol) (PVA) blend gel polymer electrolytes for dye-sensitized solar cells

Poly(ethylene oxide)(PEO)–poly(vinyl alcohol) (PVA) blend-based gel polymer electrolytes (GPEs) have been prepared by blending equal weights of PEO and PVA in ethylene carbonate (EC), dimethyl sulfoxide (DMSO), tetrabutylammonium iodide (TBAI), and iodine crystals (I₂). The conductivity, diffusion coefficient, number density, and ion mobility of the electrolytes have been calculated from the impedance data obtained from electrochemical impedance spectroscopy (EIS) measurements. The GPE with the composition of 7.02 wt%, PVA, 7.02 wt% PEO, 30.11 wt% ethylene carbonate (EC), 30.11 wt% DMSO, 24.08 wt% TBAI and 1.66 wt% I₂ exhibits the highest conductivity of 5.5 mS cm^?1 at room temperature. Dye-sensitized solar cells (DSSCs) with configuration fluorine tin oxide (FTO)/titanium dioxide/N3-dye/GPE/platinum/FTO have been fabricated and tested under the white light of intensity 100 mW cm^?2. The DSSC containing the highest conducting GPE exhibits the highest power conversion efficiency, η of 5.36 %.     

Synthesis and characterization of cadmium hydroxide nano-nest by chemical route

A facile chemical route based on room temperature chemical bath deposition (CBD) was developed to deposit the Cd(OH)₂ nano-nest. The growth mechanism follows two-stage crystallization with initial growth of nucleation centers, followed by subsequent anisotropic growth. The nano-nest morphological evolution of Cd(OH)₂ on different substrates has been carried out. These films have been characterized by the techniques; such as X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), optical absorption, contact angle measurement and thermoelectric power (TEP) measurements. The X-ray diffraction study revealed that the as deposited film consists of cadmium hydroxide (Cd(OH)₂) phase. The nano-nest consisted of wires with nearly uniform in dimensions, with diameter around 30 nm and length of few microns. As-deposited Cd(OH)₂ film used in this study showed water contact angle of 66°. The optical bandgap was found to be 3.2 eV, with n-type electrical conductivity as confirmed from thermo-emf measurements.     

Effect of Spherical Nanoparticles on the Motion of Macromolecular Chains and Segments of Isotactic Polypropylene. I. Dynamic Mechanical and Thermal Properties

The role of spherical nano-CaCO₃ particles treated with 2 wt% and 6 wt% stearic acid (SA), respectively, on the motion of macromolecular chains and segments of isotactic polypropylene (iPP) was studied through the dynamic mechanical analysis and nonisothermal crystallization. Higher nucleation activity of the particles and more nucleating sites were achieved in the 6 wt% SA treated particle nanocomposites with respect to the 2 wt% SA counterpart. The increased nucleation efficiency caused high inhomogeneity and thus large mobility of the amorphous phase of iPP, which favored a low glass transition temperature (T_g ) in the nanocomposites. However, the spherical nanoparicles also spatially restrained the motion of macromolecular chains and segments, and the better the nanoparticles dispersed, the stronger the restriction was. Thus the glass transition temperature (T_g ) of the nanocomposites decreased with increasing filler loading but recovered at a certain particle concentration. At this filler content, the maximal α-transition temperature (T_α ) and the main melting peak temperature (T_m1 ) as well as the lowest degree of crystallinity (X_PP ) also occurred. This critical filler loading appeared at lower value (20 wt%) in 6 wt% SA treated nano-CaCO₃ composites with respect to 2 wt% SA counterpart (25%) due to the better dispersion of particles in the former. It was concluded that the mobility of the macromolecular chains and segments of iPP was dominated by the competition of the spatial confinement and nucleation effect of nano-CaCO₃ particles in the matrix.     

Laser Light and X-Ray Diffraction Studies of Oriented Isotactic Polypropylene (iPP) Prepared by Temperature Slope Crystallization

Isotactic polypropylene (iPP) film was melt-crystallized in a temperature gradient. The iPP film showed well oriented α- and β-crystalline textures along the gradient. The crystalline structure, phase transition boundary and lamellar twisting were examined by X-ray diffraction and laser light diffraction (LLD). On the α-β boundary, LLD shows a sharp streak perpendicular to the boundary, where the a-axis of the β-crystal is oriented perpendicular to the temperature gradient. Apart from the boundary, the a-axis of the β-crystal becomes parallel to the gradient. The β-crystal shows lamellar twisting with a pitch of 200 μm at room temperature. When heated the β-crystal, the lamellar distance of 295Å at room temperature decreases to 285Å at 80–100°C and then increases to more than 300Å above 120°C. During the heating, the value of the twist period increases from 200 to 210 μm at 90–100°C, and then to above 224 μm at 140°C. The increase of the twist period is related to the increasing crystalline thickness of the β-lamellae.     

Electrochemical and structural properties of a polymer electrolyte system based on the effect of CeO<Subscript>2</Subscript> nanofiller with PVDF-co-HFP for energy storage devices

In the present work, a series of five different nanocomposite polymer electrolytes (NCPEs) have been reported with varying contents of ceria, CeO₂ nanofiller suitably incorporated within an optimized composition having 75:25 wt% ratio of poly(vinylidenefluoride-co-hexafluoropropylene) [(PVDF-co-HFP)] and zinc trifluoromethanesulfonate (ZnTf) in the form of films obtained by mean of solution casting technique with a general formula [75 wt% PVDF-co-HFP:25 wt% ZnTf]-x wt% CeO₂ where x = 1, 3, 5, 7, and 10, respectively. The chosen NCPE system is found to exhibit the maximum electrical conductivity of 3 × 10^?4 S cm^?1 for 5 wt% loading of CeO₂ nanofiller at ambient temperature. The observed conductivity enhancement has been attributed to the occurrence of an increase in the amorphous content as confirmed by X-ray diffraction (XRD) analysis. Detailed Fourier transform infrared (FTIR) spectral analysis has indicated the feasibility of complexation of the host polymer matrix with ZnTf salt and CeO₂ nanofiller. The incorporation of CeO₂ nanofiller has further increased the decomposition voltage of the polymer electrolyte from 2.4 to 2.7 V as revealed from the voltammetric studies performed on such NCPEs, thereby suggesting the suitability of these NCPE films with an enhanced electrical conductivity as new electrolytes in order to design and fabricate eco-friendly zinc rechargeable batteries and other electrochemical devices.