Pyrolysis of petroleum asphaltenes from different geological origins and use of methylnaphthalenes and methylphenanthrenes as maturity indicators for asphaltenes

Asphaltenes separated from two different crude oils from upper Assam, India, having different geological origins, viz. DK (Eocene) and JN (Oligocene-Miocene) were pyrolysed at 600°C and the products were analysed by gas chromatography-mass spectrometry (GC/MS) especially for the generated alkylnaphthalenes and alkylphenanthrenes. Both the asphaltenes produced aliphatic as well as aromatic compound classes. Alkylnaphthalenes and alkylphenanthrenes were identified by using reference chromatograms and literature data and the distributions were used to assess thermal maturity of the asphaltenes. The ratios of β-substituted to α-substituted isomers of both alkylnaphthalenes and alkylphenanthrenes revealed higher maturity of the JN asphaltenes than the DK asphaltenes. For both the asphaltenes the abundance of 1-methylphenanthrene dominated over that of 9-methylphenanthrene showing the terrestrial nature of the organic matter.     

Charge-transfer interaction between C60 fullerene and alkylnaphthalenes

A series of alkylnaphthalenes, namely 1,4-dimethylnaphthalene, 2,6-diethylnaphthalene, 2-ethylnaphthalene and pure naphthalene are not able to form Diels-Alder adducts with C₆₀ fullerene but produce a series of 1:1 charge-transfer complexes (CTC) where the aromatic compounds act as donor and C₆₀ as acceptor. The spectrophotometric analysis of these CTC has permitted to determine the equilibrium constants of the CTC formation at four different temperatures and the relative enthalpies and entropies of formation. The C₆₀-alkylnaphthalenes and C₆₀-naphthalene were identified as weakly bound CTC. Using the Mulliken theory of the CTC also the degree of charge transfer α was determined, confirming the results already suggested by the equilibrium constants, i.e., the weakly interaction between the donor and the acceptor considered.     

Studies on the Properties of Manganese Substituted Nickel Ferrite Nanoparticles

Mn²⁺-substituted Ni ferrite nanoparticles were synthesized by sol-gel auto combustion method. The synthesized samples were annealed at 800 ^°C and characterization studies were carried out by XRD, VSM, electron paramagnetic resonance (EPR), field emission scanning electron microscopy (FE-SEM) and FT-IR spectroscopy. The XRD patterns revealed that Mn ²⁺-substituted Ni ferrite crystallizes in cubic spinel phase and addition of α-Fe ₂ O ₃ phase was also observed. The average crystallite sizes were found to be from 42 to 56 nm using a Scherer equation. The coercivity and remanent magnetization decreases when Mn ²⁺ ion concentration is increased. The EPR spectrum shows the phase homogeneity of the samples. The FE-SEM images revealed that particles are both spherical in shape and particle sizes varied from 22 to 41 nm. The FT-IR spectrum confirmed the two main metal ion vibrations of nickel ferrite near 550 to 560 cm ^?1 (A site) and 441 to 460 cm ^?1 (B site).     

Effect of asphaltenes on the hydraulic drag in pipelines with crude oil

The feasibility has been established of using asphaltenes and tars for reducing the hydraulic drag in pipelines with a turbulent flow of crude oil.Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 25, No. 6, pp. 1023–1026, December, 1973.     

Novel heterocyclic based blue and green emissive materials for opto-electronics

Two different novel heterocyclic compounds namely 2,5-bis(1,3-diphenyl-4,5-dihydro-1H-pyrazol-5-yl)thiophene (Material I) and 2,5-bis(3-(naphthalen-1-yl)-1-phenyl-4,5-dihydro-1H-pyrazol-5-yl)thiophene (Material II) were designed, synthesized and characterized by spectral methods. The synthesized materials were confirmed by standard techniques such as FT-IR, ¹H NMR and elemental analysis. Physical properties include thermal, surface morphology of the materials were explained from TGA, DSC and SEM analysis. Optical properties such as absorption, emission, solvent effect have been investigated by UV–Visible and fluorescence spectrophotometers. The blue and green emission of the materials was confirmed by using UV light as well as fluorescence spectrophotometers. Bandgap energies of these materials were obtained by both experimental and theoretical calculation from of cyclic voltammetry, UV–Visible spectrophotometer and DFT calculation. I–V characteristic analysis used to determine the threshold voltage (V_on) of the two materials. The obtained results of the materials have promising to be applicable for opto-electronic applications.     

Spontaneously resolved chiral arylsulfonamides

Our recent studies have shown that cocrystallization of 1:1 solutions of (R)-X and (S)-X′ (where X and X′ represent two sterically similar molecules) often form quasiracemic crystals, in which approximately centrosymmetric molecular pairs cocrystallize in an arrangement that resembles a “true” racemic structure. As part of an ongoing study of the influence of molecular shape on crystal packing, the present work centers on the design, synthesis and X-ray structure determination of four homologous N-(α-methylbenzyl)-4-substituted benzenesulfonamides. Crystallization of a solution of these (±)-arylsulfonamides unexpectedly yields enantiomerically pure crystals via a Pasteurian-type resolution process. This mode of crystallization presumably also deters the cocrystallization of different, but structurally similar, arylsulfonamides to form quasiracemates. The X-ray crystal structures of the four sulfonamides reveal the dominance of N–H⋅⋅⋅O–S hydrogen bonds that form infinite helical C(4) molecular chains. For three of the structures this pattern is extended by short inter- and intramolecular π⋅⋅⋅π interactions to form two-dimensional molecular architectures.     

Synthesis and structure characterization of low dielectric constant MSQ films by using octamethyl cyclotetrasiloxane (D4) as a porosity promotion agent

Low dielectric methylsilsesquioxane (MSQ) film can be synthesized by spin-coating on P–Si (100) wafer. Octamethyl cyclotetrasiloxane (D4) was used as a porosity promotion agent to MSQ film. Seven samples with different treatment were prepared. The dielectric constants of these MSQ films significantly lowered from 3.0 to 2.1. Fourier transform infrared spectroscopy was used to identify the Si–O–Si network structure, Si–O–Si cage structure and other bonds. The change of structure resulted in significant lowering of the dielectric constant (k). The capacitance–voltage (C–V) characteristic by HP4294A was used to determine the dielectric constant. Current–voltage (I–V) measurement by Keithley6517A was used to determine the breakdown electric field.     

Influence of interfacial carbide layer characteristics on thermal properties of copper–diamond composites

Copper–diamond composites are increasingly being considered for thermal management applications because of their attractive combination of properties, such as high thermal conductivity (λ) and low coefficient of thermal expansion (CTE). In this research, thermal properties of Cu–diamond composites with two different types of interfacial carbides (Cr₃C₂ and SiC) were studied. The interface thermal conductance (h _c) was calculated with Maxwell mean-field and differential effective medium schemes, wherein experimentally measured λ was entered as an input parameter. The λ and h _c of both the Cu–Cr₃C₂–diamond and Cu–SiC–diamond composites are higher than those reported in previous studies for Cu–diamond composites with no interfacial carbides. The value of h _c is intimately related to the morphology and thickness of the interface carbide layer, with the highest h _c being associated with a thin and continuous interface carbide layer. A lower h _c resulting from a thicker Cr₃C₂ layer can provide an alternate explanation for a previously reported trend in λ of Cu–Cr₃C₂–diamond composites with different Cr-contents. The experimentally measured CTE was compared with the Turner and Kerner model predictions. The CTE of both the Cu–Cr₃C₂–diamond and Cu–SiC–diamond composites is lower and better matches the model predictions than the previously reported CTE of Cu–diamond composite with no interfacial carbides. The CTE of Cu–Cr₃C₂–diamond composites agrees better with the Kerner model than the Turner model, which suggests that deformation during temperature excursions involves shear.     

Preparation and characterization of chitosan/cashew gum beads loaded with Lippia sidoides essential oil

Beads based on chitosan (CH) and cashew gum (CG), were prepared and loaded with an essential oil with larvicide activity (Lippia sidoides – Ls). CH and CH–CG beads were characterized by scanning electron microscopy (SEM), infrared and UV–VIS spectroscopy, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), as well as, regarding their larvicide loading, swelling, in vitro and in vivo release kinetics. The oil encapsulation was evidenced by FTIR analysis and LS loading ranges from 2.4% to 4.4%. CH beads duly showed swelling degree (Q) values from 4.0 to 6.7, reaching equilibrium after 30 min, whereas crosslinked CH–CG beads showed lower swelling values, from 0.4 to 3.8, exhibiting a longer equilibrium time. Liquid transport parameters have revealed diffusion coefficient for CH–CG beads, as low as 2 × 10^? 15 m²/s. TGA and DSC revealed that CH:CG crosslinked beads are more thermally stable than CH beads. In vitro release follows a non-Fickian diffusion profile for both bead types, however, and a prolonged release being achieved only after beads crosslinking. In vivo release showed that both CH and CH–CG presented a prolonged larvicide effect. These aforesaid results, indicate that CH–CG beads loaded with LS are efficient for A. aegypti larval control.     

Multicomponent transport studies of crude oils and asphaltenes in DSC program

Crude oils have matured during ages in reservoirs under obvious non-equilibrium conditions. The resulting stratification and phases present can be predicted only with non-equilibrium thermodynamics tools. Possibly, convection is present and enforced by the Soret effect. These parameters are the focus of the MAP DSC (Diffusion and Soret Coefficients) multicomponent studies. Theoretical and ground based studies are completed by measurements performed in the SCCO experiments (Soret Coefficients of Crude Oils), of the DSC experiment on SODI facility (Beginning 2008). The problem is presented here in a simplified manner using Maxwell-Stéfan formalism, and is applied to some situations occurring in reservoirs and in the GATE experiment proposed for the study of growth conditions of asphaltenes.     

Surfactant assisted solvothermal synthesis of ZnO nanoparticles and study of their antimicrobial and antioxidant properties

This study demonstrated a solvothermal method of growth of three different morphologies of zinc oxide nanoparticles(ZnO NPs): i) flower-like nanorod and nanoflakes, ii) assembled hierarchical structure,and iii) nano granule. Oleic acid(C_(18)H_(34)O_2), gluconic acid(C_6H_(12)O_7) and tween 80(C_(64)H_(124)O_(26)) were used as surfactant/capping/reducing agent for the formation of different morphologies of nanoparticles.The as-synthesized ZnO NPs were characterized by different physicochemical techniques such as UV–vis(UV–vis) spectroscopy, X-ray diffraction(XRD), fourier transform infrared spectroscopy(FTIR), field emission scanning electron microscopy(FE-SEM), energy dispersive X-ray(EDX) analysis and dynamic light scattering(DLS) studies. Further, the antioxidant and antimicrobial activity of these nanostructures was evaluated. The antioxidant activity of these nanostructures was assessed via 2,2-diphenyl,1-1 picrylhydrazyl(DPPH), 2,2-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid)(ABTS) and H_2O_2 free radical scavenging activity. The in vitro antimicrobial activity of the obtained nanostructures was demonstrated against both gram negative(Escherichia coli) and gram positive(Staphylococcus aureus) bacterial genera.This study revealed antioxidant and antimicrobial properties of different structures of ZnO NPs suggesting their biomedical and industrial applications.     

A comparative study regarding effects of interfacial ferroelectric Bi4Ti3O12 (BTO) layer on electrical characteristics of Au/n-Si structures

Present study focuses on the effects of interfacial ferroelectric BTO layer on the electrical characteristics of Au/n-Si structures, hence Au/n-Si (MS) and Au/BTO/n–Si (MFS) structures were fabricated and admittance measurements (capacitance–voltage: C–V and conductance–voltage: G/ω–V) of both structures were conducted between 10 kHz and 1 MHz at room temperature. Results showed that C–V and G/ω–V characteristics were affected not only by frequency but also through deposition of BTO layer. Some effects can be listed as sharper peaks in C–V plots, higher capacitance and conductance values. Structure’s series resistance (R _s) also decreased due to BTO layer. Interface states (N _ss) profiles of the structures were obtained using Hill–Coleman and high-low frequency capacitance (C _HF–C _LF). Some of the main electrical parameters were extracted from C ^?2–V plots using depletion capacitance approach. Furthermore, current–voltage characteristics of MS and MFS structures were presented.     

Planar limit-assisted structural interpretation of saturates/aromatics/resins/asphaltenes fractionated crude oil compounds observed by Fourier transform ion cyclotron resonance mass spectrometry

Planar limits, defined as lines generated by connecting maximum double-bond equivalence (DBE) values at given carbon numbers, are proposed as a means of predicting and understanding the molecular structure of compounds in crude oil. The slopes and y-intercepts of the lines are determined by the DBE/carbon number ratios of functional groups defining the planar limits. For example, the planar limit generated by a serial addition of saturated cyclic rings has a slope of 0.25. The planar limit formed by the linear and nonlinear addition of benzene rings yields lines with slopes of 0.75 and 1, respectively. The y-intercepts of these lines were determined by additional functional groups added within a series of molecules. Plots of DBE versus carbon number for S(1) class compounds observed by Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) showed that saturates/aromatics/resins/asphaltenes (SARA) fractions exhibited unique slopes and y-intercepts. The slope of the planar limit observed from a saturates fraction matched well with the slope of a planar limit generated by the serial addition of saturated cyclic rings. The slopes of planar limits of aromatics and resins fractions were very similar to that obtained from the linear addition of benzene rings. Finally, the slope of the asphaltenes fraction was almost identical to the slope obtained from the nonlinear addition of benzene rings. Simulated and experimental data show that SARA fractions exhibit different molecular structure characteristics. On the basis of the slope and y-intercept of the planar limit, the structures of molecules in SARA fractions were predicted and suggested. The use of planar limits for structural interpretation is not limited to crude oil compounds but can also be used to study other organic mixtures such as humic substances or metabolites.     

Measurements of the microhardness,electrical and thermal properties of the Al–Ni eutectic alloy

Al–5.7 wt% Ni eutectic alloy was directionally solidified upward with different temperature gradients (0.83–4.02 K/mm) at a constant growth rate (0.008 mm/s) and with different growth rates (0.008–0.483 mm/s) at a constant temperature gradient (4.02 K/mm). Microhardness (HV) and electrical resistivity (ρ) of directionally solidified samples were measured using microhardness test device and a standard d.c. four-point probe technique, respectively. Dependency of the microhardness and electrical resistivity on the solidification processing parameters (temperature gradient, G and growth rate, (V) were analyzed. According to these results, it has been found that the values of HV and ρ increase with the increasing values of G and V. Variations of electrical resistivity and electrical conductivity (σ) for casting Al–Ni eutectic alloy were also measured at the temperature in range 300–720 K. The enthalpy of fusion (ΔH) for the Al–Ni eutectic alloy was determined by differential scanning calorimeter (DSC) from heating trace during the transformation from solid to liquid.     

Thermodynamic and structural studies of mixed monolayers: Mutual mixing of DPPC and DPPG with DoTAP at the air–water interface

Phospholipid monomolecular films at the air–water interface are useful model membranes to understand miscibility among various components. Surface pressure (π)–area (A) isotherms of pure and mixed monolayers of dioleoyltrimethylammonium propane (DoTAP)–dipalmitoylphosphatidylcholine (DPPC) and DoTAP–dipalmitoyphosphatidylglycerol (DPPG) were constructed using a surface balance. DPPC and DPPG produced isotherms as expected and reported earlier. DoTAP, an unsaturated lipid, demonstrated a continuous π–A isotherm. Associative interactions were identified in DPPC–DoTAP mixtures compared to the pure components, while DPPG–DoTAP mixtures showed repulsive interaction up to an equimolar ratio. Compression moduli of the monolayers revealed that DPPC–DoTAP mixtures had increasing stability with increasing surface pressure, but addition of DoTAP to DPPG showed instability at low and intermediate concentrations. In both cases increased stability was returned at higher X_DoTAP values and surface pressures. Lipid monolayer film thickness values, determined on a gold coated glass substrate by surface plasmon resonance spectroscopy (SPR), indicated a systematic change in height profile for DPPC–DoTAP mixtures with increasing X_DoTAP. However, DPPG–DoTAP mixed monolayer systems demonstrated a biphasic response. The SPR data were in excellent agreement with our interpretation of the structure of solid supported lipid monolayers.     

Mechanical Properties of BSCCO Superconductor by Oliver–Pharr Method and Work of Indentation Approach

Polycrystalline superconducting Bi–Pb–Gd–Sr–Ca–Cu–O bulk samples with nominal composition Bi_1.7Pb_0.3?x Gd _x Sr₂Ca₃Cu₄O_12+y (x=0.00,0.01,0.05) were produced by the melt quenching method. The mechanical properties of the samples were characterized by depth sensing indentation technique under different peak loads ranging from 200 to 1800 mN. The experimental data were comparatively analyzed by the Oliver–Pharr method and a work of indentation approach. It was found that the work of indentation approach gave more reliable results because of the reducing pile-up effect. The results implied that both microhardness and reduced elastic modulus increased with increasing Gd substitution.     

Crystalline morphology and properties of multi-walled carbon nanotube filled isotactic polypropylene nanocomposites: Influence of filler size and loading

Isotactic polypropylene (PP) nanocomposites with multi-walled carbon nanotubes (MWCNTs) of various diameters (10–50 nm) were fabricated by extrusion and compression-molding techniques and characterized by X-ray diffraction measurements, differential scanning calorimetry, scanning electron microscopy, mechanical test and differential thermal analyses. The pure PP exhibits both the a- and b-axes oriented α-crystal, whereas the MWCNTs induce the b-axis orientation of the α-crystal along with the formation of minor γ-phase crystal in nanocomposites. Crystallinity, long period of lamellae, tensile strength, tensile modulus (TM) and microhardness (H) of PP considerably change by different loading and sizes of MWCNTs. The estimated values H/TM = 0.09–0.10 for all samples approach the predicted value of 0.10 for polymers. The increase in crystallinity has been demonstrated by both XRD and DSC studies. Mathematical models have been invoked to explain the changes in mechanical properties. An increase in thermal stability of polymer matrix occurs with increasing MWCNTs size and loading.     

Reactive compatibilization of composites of ethylene–vinyl acetate copolymers with cellulose fibres

Composites based on ethylene–vinyl acetate copolymers (EVA) functionalised with reactive groups (maleic anhydride, glycidyl methacrylate) and cellulose fibres (Cell) of different type were obtained by melt mixing, in the composition range 0–50 wt% Cell. The phase behaviour, the morphology and matrix–fibre interactions of the composites were analysed by DSC, DMTA, TGA, SEM and FT-IR spectroscopy. FT-IR analysis indicated the chemical interactions between the functional groups (MA, GMA) of EVA and the hydroxyl groups of cellulose. Accordingly, SEM microscopy pointed out an improved adhesion between cellulose and matrix in both EVA–MA/Cell and EVA–GMA/Cell composites, as compared to EVA/Cell composites. Glass transition behaviour and filler effectiveness (C_FE) were analysed by DMTA. T_g of EVA and EVA–GMA changed markedly by the incorporation of cellulose. Cellulose was found to be more effective filler for EVA–GMA (C_FE = 0.02) than EVA–MA (C_FE = 0.22). Thermal resistance and tensile properties were significantly improved for GMA functionalised systems.     

Synthesis,crystal growth and characterization of novel semiorganic nonlinear optical crystal: Dichlorobis(l-proline)zinc(II)

Single crystals of the semiorganic material, dichlorobis(l-proline)zinc(II) (DCBPZ), were grown from aqueous solution. The grown crystals were tested by single crystal X-ray diffraction, energy-dispersive spectrometry, FT-IR, UV–vis and TG–DTA. The structural prefection of the grown crystals has been analyzed by high-resolution X-ray diffraction (HRXRD) rocking curve measurements. The dielectric and mechanical behavior of the specimen was also studied. The SHG efficiency of DCBPZ is three times greater than that of KDP. Measuring transmittance of DCBPZ permitted the calculation of the refractive index n, the extinction coefficient K and both the real ?_r and imaginary ?_i components of the dielectric constant as functions of photon energy. The optical band gap of DCBPZ is 4.8 eV.     

Phase transition and piezoelectric properties of (1 − x)K0.5Na0.5NbO3–xLiSbO3 ceramics by hydrothermal powders

KNbO₃, NaNbO₃ and LiSbO₃ powders were synthesized by a hydrothermal route have been used to prepare (1 ? x)K_0.5Na_0.5NbO₃–xLiSbO₃ (KNN–LS; x = 0.00–0.08) ceramics. The effects of LiSbO₃ doping on the structures of KNN–LS ceramics have been systematically investigated by X-ray diffraction (XRD) and Rietveld refined XRD patterns. A gradual phase transition from orthogonal to tetragonal with the increase of LiSbO₃ content is demonstrated. Thereinto, the monoclinic phase is identified for the KNN–LS ceramic with the LiSbO₃ content of x = 0.08. Meanwhile, the XRD pattern reveals that the intensity ratio of (200)/(002) crystal face of the ceramic with x = 0.08 was bigger than one, which is different from the tetragonal phase. The tetragonal phase is revealed in the KNN–LS ceramic in the vicinity of x = 0.07, accompanying with relatively higher piezoelectric and ferroelectric properties. Tetragonal phase is beneficial to improve the piezoelectric properties of the KNN–LS ceramics.