Bond energy prediction of Curie temperature of lithium niobate crystals

A general expression of the Curie temperature (Tc) and spontaneous polarization (Ps) of lithium niobate (LN) crystals is energetically proposed by employing the viewpoint of the bond energy of constituent chemical bonds within the LN crystallographic frame. The calculated Tc values of various pure and doped LN crystals are in a good agreement with those reported data. Ps values of these LN crystals can also be quantitatively estimated in this work. It is found that the Li site is a sensitive lattice position to dominate the ferroelectricity of LN crystals. This novel method provides us a good understanding of ferroelectric behaviors of LN crystals, which may be applicable to the estimation of ferroelectric behaviors of LN-type solids.     

Counter-flow liquid injection plasma synthesis of spinel powders

A novel counter-flow liquid injection plasma synthesis (CF-LIPS) reactor has been developed to produce ceramic powders. By using a counter-flow plasma configuration, entrainment of reactant particles into the plasma is improved compared to conventional injection methods. The counter-flow process also creates large recirculation zones which increase the residence time to more than 100 ms as predicted by modeling results [1]. The long residence time ensures complete evaporation and decomposition of precursor particles and complete reactions to the desirable products. Also, the process employs liquid precursors rather than solids, resulting in less contamination of products from unevaporated reactants. Results show that CF LIPS is an excellent method for producing single-phase and spherical spinel powders with a narrow particle size distribution. Particle size increases with increasing precursor concentration based on the synthesis of magnesium aluminate powders. Characterization techniques include X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), X-ray mapping, centrifugal sedimentation particle size distribution analysis, and vibrating sample magnetometer (VSM) measurements. In addition, crystallographic studies are conducted to determine the bond lengths, bond angles, and stoichiometries of the as-produced spinels.     

Novel ultra-cryo milling and co-grinding technique in liquid nitrogen to produce dissolution-enhanced nanoparticles for poorly water-soluble drugs

A novel ultra-cryo milling micronization technique for pharmaceutical powders using liquid nitrogen (LN2 milling) was used to grind phenytoin, a poorly water-soluble drug, to improve its dissolution rate. LN2 milling produced particles that were much finer and more uniform in size and shape than particles produced by jet milling. However, the dissolution rate of LN2-milled phenytoin was the same as that of unground phenytoin due to agglomeration of the submicron particles. To overcome this, phenytoin was co-ground with polyvinylpyrrolidone (PVP). The dissolution rate of co-ground phenytoin was much higher than that of original phenytoin, single-ground phenytoin, a physical mixture of phenytoin and PVP, or jet-milled phenytoin. X-Ray diffraction showed that the crystalline state of mixtures co-ground by LN2 milling remained unchanged. The equivalent improvement in dissolution, whether phenytoin was co-ground or separately ground and then mixed with PVP, suggested that even when co-ground, the grinding of PVP and phenytoin occurs essentially independently. Mixing original PVP with ground phenytoin provided a slight improvement in dissolution, indicating that the particle size of PVP is important for improving dissolution. When mixed with ground phenytoin, PVP ground by LN2 milling aided the wettability and dispersion of phenytoin, enhancing utilization of the large surface area of ground phenytoin. Co-grinding phenytoin with other excipients such as Eudragit L100, hypromellose, hypromellose acetate-succinate, microcrystalline cellulose, hydroxypropylcellulose and carboxymethyl cellulose also improved the dissolution profile, indicating an ultra-cryo milling and co-grinding technique in liquid nitrogen has a broad applicability of the dissolution enhancement of phenytoin.     

On the thermal decomposition of K2PtCl4 in a hydrogen atmosphere

The reaction of single crystals and powders of K₂PtCl₄ with hydrogen is studied by means of thermogravimetry (TG) at temperatures between 175 and 225°C and by optical microscopy. Two different mechanisms are observed. The rate of decomposition of single crystals is determined by the displacement of the reaction interface, which is similar in every crystallographic direction.The rate of decomposition of the powders is limited by the rate of nucleation in the powder particles. For both mechanisms the kinetic parameters are calculated. The activation energy for the displacement of the interface is much higher than the one necessary for nucleation.     

Effect of synthesis duration on the morphological and structural modification of the sea urchin-nanostructured γ-MnO2 and study of its electrochemical reactivity in alkaline medium

Single-crystalline nanorods and sea urchin-like morphology of the γ-MnO₂ nanostructures were successfully synthesized by hydrothermal method at different synthesis durations. The as-synthesized products were characterized by the techniques X-ray powder diffraction (XRD), field emission gun-scanning electron microscope (FEG-SEM) coupled with energy-dispersive X-ray elemental analysis (EDX), transmission electron microscope (TEM), isotherms of N₂ adsorption/desorption and BET-BJH models. The effect of synthesis duration on the morphology, porous structure, and crystallographic form of MnO₂ powders was studied. The electrochemical reactivity of as-prepared powders was investigated in 1 mol L^?1 KOH by both cyclic voltammetry and impedance spectroscopy by using a micro-cavity electrode. The results show that the best electrochemical reactivity of the MnO₂ powder was obtained with synthesis duration of 24 h.     

Influence of chain architecture on phase behaviour of styrene-(styrene/butadiene)-styrene triblock copolymers and their binary blends

The phase behaviour of symmetric (LN4) and asymmetric (LN3) triblock copolymers based on styrene-b-(styrene-co-butadiene)-b-styrene (S-SB-S) and their blends have been studied using transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and were correlated with rheological properties. A direct control over the final morphology and segregation strength for the block copolymer blends was achieved by blending of LN3 and LN4. The interaction parameter (χ) for LN4 is extracted by fitting the SAXS patterns at temperatures well above the ODT in consistency with Leibler mean-field structure-function for ABA triblock copolymers. A weak temperature dependency of χ has been observed which revealed that the phase behaviour in LN4 is mainly controlled by the entropic term. In the low frequency regime a non-terminal flow behaviour was observed in LN3 revealing the persistence of ordered structure within the experimental temperature range whereas a terminal flow behaviour with composition fluctuation was observed in LN4. G′ vs. G″ plots indicated a solid-like elastic melt behaviour for LN3 whereas presence of ODT over a broad temperature range was observed for LN4. ODT is observed to increase non-linearly with increase in LN3 content in the blends. ODT behaviour of the blends further reveals that the blends shift from weak-segregation to intermediate-segregation strength with the increase in LN3 content. The improvement in the state of ordering along with the change in morphology with the increase of LN3 content is attributed to co-surfactant effect between the PS end-blocks of LN3 and LN4 inside PS-rich phase.     

环烷酸铅和烷基水杨酸铅的微波原位合成及其摩擦学性能

在液体石蜡中采用微波技术原位合成了油溶性环烷酸铅(LN)和十二烷基水杨酸铅(LAS).在高速低负荷(r=1500±10 rpm、 P=196～392 N)和低速高负荷(r=300±10 rpm、 P=800 N)两种条件下,用四球摩擦磨损试验对LN、 LAS和对应的羧酸进行了摩擦学性能评价,用往复式摩擦试验机考察了LN和LAS抗磨减摩性能.结果表明: LN具有良好的抗磨减摩性能和中等的极压性能,且各项摩擦学性能指标均好于LAS.为弄清其作用机理,从分子结构分析了产生摩擦学性能差异的原因,并用SEM及XPS研究了磨斑表面.结果发现: 摩擦过程中, LN和LAS都能在摩擦副表面形成吸附膜且部分吸附膜发生摩擦化学反应产生了铅氧化物转化膜,但所形成的吸附膜和转化膜厚度不同.     

Dynamic mechanical and rheological properties of binary S–(S/B)–S triblock copolymer blends

The rheology and dynamic mechanical properties of binary block copolymer blends consisting of a symmetrical triblock copolymer with thermoplastic elastomeric behavior (LN4) and an asymmetrical thermoplastic triblock copolymer (LN3) were investigated. TEM images of the blends show a systematic variation in the morphologies from worms (～20–0 wt % LN3) to cylinders (～60–30 wt % LN3) to lamellae (100–70 wt % LN3) as a function of LN3 content. DMA analysis has revealed that the increase in LN3 content leads to a decrease in miscibility between the PS end blocks and the S/B middle block. The frequency and temperature dependence of the storage modulus (G′), loss modulus (G″), and complex viscosity (|η*|) has been studied for LN4 (weakly segregated) and LN3 (strongly segregated) from their master curves. By comparing the rheological properties of these blend compositions at low‐frequency regime, it is observed that with the increase in LN3 content the shear modulus and complex viscosity increase. Blend compositions with 70–100 wt % of LN3 show nonterminal behavior at reduced frequencies due to the presence of highly ordered microdomains when compared to blends with ～0–20 wt % of LN3 content. van Gurp–Palmen plots were constructed to observe the transition from liquid‐ to solid‐like behavior in the vicinity of order‐to‐disorder transition (ODT) temperature. ODT temperature increases as the thermoplastic LN3 content increases which are also confirmed by the Han plots. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 329–343, 2008     

Laser fragmentation in liquid medium: a new way for the synthesis of PbTe nanoparticles

Synthesis of PbTe nanoparticles has been performed by pulsed laser fragmentation of PbTe micron-sized powders in distilled water with a Nd:YAG laser. The influence of various experimental parameters (wavelength, treatment duration, and output energy) on the yield of fragmentation, the size and the crystallographic structure of the nanoparticles produced has been investigated. Characterization of the nanopowders was performed by X-ray diffraction analyses and transmission electron microscopy observations. Thanks to a careful control of the synthesis parameters, PbTe nanoparticles with an average diameter close to 6 nm and exhibiting a sharp distribution in size have been produced.     

Liquid foam as a template for the synthesis of iron oxyhydroxide nanoparticles

Liquid foams have been used as a template to prepare iron oxyhydroxide nanoparticles. This is achieved by a process of electrostatic entrapment of Fe2+/Fe3+ ions in the foam stabilized by the surfactant sodium dodecyl sulfate followed by the in situ hydrolysis of the metal ions. Infrared and selected area electron diffraction measurements suggest the formation of a mixture of beta-FeO(OH) and gamma-FeO(OH) crystallographic phases after the in situ hydrolysis of the metal ions in the foam template. Transmission electron microscopy analysis of the powders obtained from the foam indicates that the particles are fairly monodisperse with an average size of around 50 nm. Scanning electron microscopy pictures reveal that the particles form loosely bound aggregates of around 300 nm. After the powders obtained in the foam are annealed at 400 degrees C, X-ray diffraction measurements show that the FeO(OH) particles are converted to alpha-Fe2O3. The mechanistic aspects of metal ion hydrolysis in a foam are discussed, and some of the advantages of this method vis-à-vis the normal solution-based methods are outlined.     

Morphology and surface heterogeneities in synthetic goethites

In the framework on a study of the acido-basic and sorption properties of iron oxides, a thorough characterization of two types of goethite powders was performed in several laboratories joined in a common project. Chemical analysis by ICPAES; high-resolution SEM, TEM, and AFM observations; XRD with line width analysis; and argon and nitrogen sorption isotherms were used for that purpose. The main crystallographic faces of goethite particles could be identified as {001}, {101}, and {121}, and their abundance correlated with the distribution of low-pressure argon adsorption local isotherms. These results will be very useful for further studies on the relationship between surface reactivity in aqueous solution and orientation of solid surfaces.     

Analysis of intact erythropoietin and novel erythropoiesis-stimulating protein by capillary electrophoresis-electrospray-ion trap mass spectrometry

Recombinant human erythropoietin (rHuEPO) and novel erythropoiesis-stimulating protein (NESP) were analyzed by CE-ESI-MS using an IT as analyzer. The IT parameters were optimized by direct infusion of solutions of different intact proteins (myoglobin, transferrin, alpha1-acid glycoprotein and fetuin) with different degrees of glycosylation (from 0 to 35% w/w). Two physically adsorbed capillary coatings from UltraTol Pre-Coats (low normal (LN) and high reverse (HR)) were evaluated for the separation of rHuEPO and NESP glycoforms by CE-ESI-IT-MS. The results obtained with the neutral LN coating suggest that an IT mass spectrometer enables identification of the main glycoforms of a complex glycoprotein such as rHuEPO. Although LN provided acceptable glycoform resolution for rHuEPO, the separation obtained for NESP was less significant due to the higher microheterogeneity of this glycoprotein. Reproducibility studies confirmed the lack of stability and bleeding of the LN coating, which caused problems with MS detection, such as a dramatic loss of sensitivity and the presence of peaks in the mass spectra corresponding to molecular ions in the coating. In contrast, the cationic HR coating gave faster but poorer glycoform separations due to the presence of an anodal EOF. However, the positive charge of the coating provided enhanced hydrolytic stability, making it more suitable than the LN coating for the on-line MS coupling.     

Holographic Storage Properties of In：Fe：Mn：LiNbO3 Crystals

In:Fe:Mn:LiNbO3(LN) crystals were grown in air atmosphere by Czochralski method with different concentration of In (0,1,2,3 mol%) in the melts,while the contents of Fe2O3 and MnO were 0.1 and 0.5 mol%,respectively. The location of doping ions was analyzed by Ultraviolet-visible absorption spectra and differential thermal analysis. The diffraction efficiency (η),writing time (τw) and erasure time (τe) of the crystals were measured by two-beam coupling experiment. The dynamic range and photorefractive sensitivity have also been calculated. The results showed that with the increase of In ions in the melt,the absorption edge of In:Fe:Mn:LN crystal shifts to the violet firstly and then makes the Einstein shift,the Curie temperature of crystal increases firstly and then decreases,the storage ratio speeds up,diffraction efficiency decreases,and dynamic range and photorefractive sensitivity increase. The mechanism of holographic storage properties of In:Fe: Mn:LN crystal with different doping concentration of In3+ was investigated,suggesting the In: Fe:Mn:LN crystals are excellent holographic storage materiel with better synthetical properties than Fe:Mn:LN crystals.     

Rapid hydrogen hydrate growth from non-stoichiometric tuning mixtures during liquid nitrogen quenching

In this study the rapid growth of sII H(2) hydrate within 20 min of post formation quenching towards liquid nitrogen (LN(2)) temperature is presented. Initially at 72 MPa and 258 K, hydrate samples would cool to the conditions of ~60 MPa and ~90 K after quenching. Although within the stability region for H(2) hydrate, new hydrate growth only occurred under LN(2) quenching of the samples when preformed hydrate "seeds" of THF + H(2) were in the presence of unconverted ice. The characterization of hydrate seeds and the post-quenched samples was performed with confocal Raman spectroscopy. These results suggest that quenching to LN(2) temperature, a common preservation technique for ex situ hydrate analysis, can lead to rapid unintended hydrate growth. Specifically, guest such as H(2) that may otherwise need sufficiently long induction periods to nucleate, may still experience rapid growth through an increased kinetic effect from a preformed hydrate template.     

Copper(I) and copper(II) complexes possessing cross-linked imidazole-phenol ligands: structures and dioxygen reactivity

Catalytic reduction of O2 to H2O, and coupling to membrane proton translocation, occurs at the heterobinuclear heme a3-CuB active site of cytochrome c oxidase. One of the CuB ligated histidines is cross-linked to a neighboring tyrosine (C-N bond; tyrosine C6 and histidine epsilon-nitrogen), and the protic residue of this cross-linked His-Tyr moiety is proposed to participate as both an electron and a proton donor in the catalytic dioxygen reduction event. To provide insight into the chemistry of such a moiety, we have synthesized and characterized tetra- and tridentate pyridylalkylamine chelate ligands {LN4OR and LN3OR (R = H or Me)}, which include an imidazole-phenol (or anisole) cross-link and their copper(I/II) complexes. [CuI(LN4OH)]B(C6F5)4 (1) reacts with dioxygen at -80 degrees C in THF, forming an unstable trans-mu-1,2-peroxodicopper(II)complex, which subsequently converts to a dimeric copper(II)-phenolate complex [{Cu(LN4O-)}2](B(C6F5)4)2 (5a). The close analogue [CuI(LN4OMe)]B(C6F5)4 (3) binds dioxygen reversibly at -80 degrees C in tetrahydrofuran. Stopped-flow kinetics of the reaction [CuI(LN3OH)]ClO4 (2) with O2 in CH2Cl2 indicate a steady formation of the purple dimeric product [{Cu(LN3O-)}2](ClO4)2 (5b), which has been analyzed in the temperature range from -40 to +20 degrees C, DeltaH = -9.6 (6) kJ mol-1, DeltaS = -168 (2) J mol-1 K-1 (k(-40 degrees C) = 1.05(4) x 106 and k(+20 degrees C) = 4.6(2) x 105 M-2 s-1). The X-ray crystal structures of 1, [CuII(LN3OH)(MeOH)(OClO3-)](ClO4) (4), 5a, and 5b are reported.     

Spectroscopic investigations of nanohydroxyapatite powders synthesized by conventional and ultrasonic coupled sol-gel routes

In the present work, the synthesis and characterization of nano-HAP powders by a novel ultrasonic coupled sol-gel synthesis is reported. The obtained powders were sintered by conventional means at different temperatures. In addition to this, HAP powders prepared through the sol-gel method without the aid of the ultrasonic waves is also studied. The obtained nano-HAP powders were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscopic (SEM) techniques. The results have proved that the nano-HAP powders synthesized by ultrasonic coupled sol-gel synthesis showed remarkable reduction in the particle size when compared with the conventional sol-gel method and hence these powders could be used as a coating material in biomedical applications.     

Iron chelation equilibria, redox, and siderophore activity of a saccharide platform ferrichrome analogue

A complete characterization of the aqueous solution Fe(III) and Fe(II) coordination chemistry of a saccharide-based ferrichrome analogue, 1-O-methyl-2,3,6-tris-O-[4-(N-hydroxy-N-ethylcarbamoyl)-n-butyryl]-alpha-D-glucopyranoside (H3LN236), is reported including relevant thermodynamic parameters and growth promotion activity with respect to both Gram-negative and Gram-positive bacterial strains. The saccharide platform is an attractive backbone for the design and synthesis of ferrichrome analogues because of its improved water solubility and hydrogen-bonding capabilities, which can potentially provide favorable receptor recognition and biological activity. The ligand deprotonation constants (pKa values), iron complex (FeIII(LN236) and FeII(LN236)1-) protonation constants (KFeHxL-236-N), overall Fe(III) and Fe(II) chelation constants (beta110), and aqueous solution speciation were determined by spectrophotometric and potentiometric titrations, EDTA competition equilibria, and cyclic voltammetry. Log betaIII110 = 31.16 and pFe = 26.1 for FeIII(LN236) suggests a high affinity for Fe(III), which is comparable to or greater than ferrichrome and other ferrichrome analogues. The E1/2 for the FeIII(LN236)/FeII(LN236)1- couple was determined to be -454 mV (vs NHE) from quasi-reversible cyclic voltammograms at pH 9. Below pH 6.5, the E1/2 shifts to more positive values and the pH-dependent E1/2 profile was used to determine the FeII(LN236)1- protonation constants and overall stability constant log betaII110 = 11.1. A comparative analysis of similar data for an Fe(III) complex of a structural isomer of this exocyclic saccharide chelator (H3LR234), including strain energy calculations, allows us to analyze the relative effects of the pendant arm position and hydroxamate moiety orientation (normal vs retro) on overall complex stability. A correlation between siderophore activity and iron coordination chemistry of these saccharide-hydroxamate chelators is made.     

Corrosion protection performance of ceria‐copolymer bilayer coating on low nickel stainless steel in 0.5 M H2SO4 medium

In this paper, we have reported the anti‐corrosion performance of ceria / poly (indole‐co‐pyrrole) (Ce/(poly(In‐co‐Py)) bilayer coating on low nickel stainless steel (LN SS). Electrochemical polymerization of (poly (In‐co‐Py)) was achieved on ceria‐coated LN SS (CeO₂/LN SS) in acetonitrile medium containing LiClO₄ (ACN‐LiClO₄) by cyclic voltammetric technique. The coatings were characterized by analytical techniques like Fourier transform infrared spectroscopy, scanning electron microscopy with energy dispersive analysis of X‐ray, respectively. The mechanical behavior of the coatings was studied using peel test, hardness and wear resistance tests. The corrosion defensive performance of this bilayer coating on LN SS was investigated using electrochemical techniques such as potentiodynamic polarization and electrochemical impedance spectroscopy in 0.5 M H₂SO₄. These results show that the bilayer coating on LN SS lowered the permeability of corrosive ions present in the acidic medium and thus acts as a barrier against the attack of corrosive environment. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of surface composition on the flowability of industrial spray-dried dairy powders

The surface composition of four industrial spray-dried dairy powders (skim milk powder, whole milk powder, cream powder and whey protein concentrate) was estimated by electron spectroscopy for chemical analysis (ESCA), and its influence on powder flowability was studied. It was found that skim milk powder flows well compared to the other powders because the surface is made of lactose and protein with a small amount of fat, whereas the high surface fat composition inhibits the flow of whole milk, cream and whey protein powders. However, the poor flowability of the powders with high surface fat coverage was drastically improved by removal of fat present on the surface through a brief wash with petroleum ether. The results obtained indicate that, although there are several parameters including particle size, which influence the flowability of powders, the flowability of powders is strongly influenced by the surface composition of powders, particularly for fat-containing powders.     

Crystallographic Groups Prediction from Chemical Composition via Deep Learning

Crystallographic group is an important character to describe the crystal structure, but it is difficult to identify the crystallographic group of crystal when only chemical composition is given. Here, we present a machine-learning method to predict the crystallographic group of crystal structure from its chemical formula. 34528 stable compounds in 230 crystallographic groups are investigated, of which 72% of data set are used as training set, 8% as validation set, and 20% as test set. Based on the results of machine learning, we present a model which can obtain correct crystallographic group in the top-1, top-5, and top-10 results with the estimated accuracy of 60.8%, 76.5%, and 82.6%, respectively. In particular, the performance of deep-learning model presents high generalization through comparison between validation set and test set. Additionally, 230 crystallographic groups are classified into 19 new labels, denoting 18 heavily represented crystallographic groups with each containing more than 400 compounds and one combination group of remaining compounds in other 212 crystallographic groups. A deep-learning model trained on 19 new labels yields a promising result to identify crystallographic group with the estimated accuracy of 72.2%. Our results provide a promising approach to identify crystallographic group of crystal structures only from their chemical composition.