Nature and philosophy of thermal processes in minerals and inorganic materials

Solid-state thermal processes have their own specificity, distinguishing them from the processes in gases and liquids. This specificity includes, among others, their limited reversibility and the limited or modified role of chemical affinity as the main driving force indicating the direction of real solid-state processes. The consequency is the formation of metastable compounds or phases during heating, as intermediate steps towards the state of thermodynamic equilibrium. They are a results of the particular properties of the rigid internal structure of minerals and materials as the thermal reaction medium. The peculiarities of thermal reactions of solids are presented on the example of those of oxides (silicates and borates) with polymeric structures. The significance of crystal-chemical factors for the prediction or explanation of the course of high-temperature processes, as complementing the thermodynamic factors, is discussed.Dedicated to Dr. Robert Mackenzie on the occasion of his 75th birthdayThis work was supported by grant P040703406 from the National Committee of Scientific Research of Poland.     

Phase transformations and phase diagram at equilibrium in the Cu-Ni-Sn system

The Cu-Ni-Sn ternary phase diagram in the Cu rich side has not been experimentally determined or calculated at low temperatures. Two Cu9NixSn alloys with x=2 and 6 mass% Sn were studied. The precipitation sequence during the ageing and phases responsible for the strengthening were determined.     

Internal thermal reactions in minerals and materials

Rebuilding reactions of the internal structure of minerals and their artificial analogues are considered. Solid products of these reactions are formed within the structure of the parent substance. This factor determines the course of the reactions and product formation. The mechanism of internal thermal dissociation and rebuilding reactions of internal structure connected with segregation of chemical components and their redistribution (crystallization of multicomponent amorphous solids) is discussed. The internal pressure of gaseous decomposition products and rate of diffusion of chemical components are critical factors influencing kinetics of these processes. Diffusional mass transfer during internal structure rebuilding reactions is directed by acid-base interaction of the parent-structure components; this determines the stages of the reaction pathway.     

Kinetic phenomena in non-crystalline materials studied by thermal analysis

The structural relaxation and viscosity behavior of Ge₃₈S₆₂ glass has been studied by thermomechanical analysis. The relaxation response to any thermal history is well described by the Tool-Naraynaswamy-Moynihan model. The apparent activation energy of structural relaxation is very close to the activation energy of viscous flow (Eη=478±12 kJ mol^-1). However, the activation energy of crystal growth obtained by optical microscopy is about one half of this value. Similar result has been obtained from isothermal DSC measurement (Ea=220±20 kJ mol^-1). The kinetic analysis of these data reveals interface controlled crystal growth with zero nucleation rate. This revised version was published online in July 2006 with corrections to the Cover Date.     

Relationship between transport properties and phase transformations in mixed-conducting oxides

To elucidate the relationship between transport properties and phase transformations in mixed-conducting oxides, Sr_0.9Ca_0.1Co_0.89Fe_0.11O_3−δ (SCCFO) and SrCoO_3−δ (SCO) were chosen as the model materials and have been investigated in detail. Oxygen permeation measurements verified that both oxides are well permeable to oxygen at elevated temperatures, e.g., at 900 °C during a cooling procedure, oxygen permeation rates as large as 1.5 and 2.0 mL/min/cm² could be obtained with disk-shaped SCCFO and SCO membranes of thickness 1.5 mm, respectively. But when cooled to critical temperatures, the oxygen permeability of these kinds of oxides diminished sharply, which could be recovered by increasing the temperature again to certain values. Abrupt changes on electrical conductivity were also observed for both oxides around the same region of temperature as that of oxygen permeability. As indicated by high-temperature X-ray diffraction and thermal analysis, the SCCFO and SCO systems undergo phase transformation between a low-temperature orthorhombic brownmillerite structure (B) or a hexagonal 2H-type structure (H) and a high-temperature cubic perovskite structure (C), respectively. The present results suggest the observed abrupt changes in transport properties versus temperature are attributed to such phase transformation, which may be directly associated with the order-disorder transition of oxygen vacancies. Moreover, compared to the B/C transformation that mainly involves an order-disorder transition on the oxygen sublattice, the H/C one necessarily also involves the cooperative long-range reorganization on the cation sublattice. Therefore it occurs at a higher temperature and absorbs more heat quantity than those of B/C transformation.     

Stability and phase transformations of the mesomorphic form of isotactic polypropylene in stereodefective polypropylene

A study of the thermodynamic stability and the related polymorphic transformations induced by thermal treatments of the mesomorphic form that crystallizes in stereodefective metallocene isotactic polypropylene (iPP) is presented. We show that the mesomorphic form of the more isotactic samples is stable at room temperature, whereas the mesomorphic form crystallizing in the more stereoirregular sample is unstable and crystallizes at room temperature in the crystalline α form. In any case, the mesomorphic form transforms during heating or by annealing at temperatures higher than 60–80 °C always in the α form, regardless of the stereoregularity, even in the case of stereoirregular samples generally crystallizing from the melt in the γ form. These data confirm the proposed model of structure of the mesomorphic form as small aggregates of chains in three-fold helical conformation packed with lateral correlations similar to the α form of iPP.     

Thermal and Chemical Properties of a Glass in the SiO2-CaO-F System for Dental Applications

The crystallization behaviour of a glass in the SiO₂-CaO-F system was analyzed using differential scanning calorimetry (DSC), X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Three crystalline phases were detected according to ICDD patterns. The first phase formed at 583°C was identified as CaF₂. The morphology was spherulitic with a diameter of approximately 100 nm. The second phase was formed at 664°C. It was identified as calcium fluoride silicate ‘Ca₂SiO₂F₂’ (ICDD 35-0002). SEM investigation showed that the crystals were spherulitic with a diameter smaller than 100 nm. The crystals were precipitated in the volume of the glass and homogeneously distributed. As a third phase, cristobalite crystallized at 895°C. The simultaneous release of calcium and fluorine ions from the vitreous glass in lactate buffer solution at pH 4.0, simulating an acidic oral environment, was investigated using X-ray photoelectron spectroscopy (XPS). The release of calcium and fluorine ions is of special interest for dental applications. The atomic ratios of the components Si, Ca and F at the glass surface after different leaching periods were determined. In order to investigate the leaching process, concentration profiles were measured using ion beam sputtering with Ar⁺ -ions. The dependence of the atomic ratios of Si, Ca and F on the sputter time was determined in order to measure the depth of the leaching layers. Most probably, the release of calcium and fluoride was controlled by a surface layer rich in calcium and flourine ions which dissolved with increasing leaching time. After 2 min leaching, a fluoride-rich surface layer measuring approximately 10 nm was detected. The atomic ratios of Si, Ca and F were different from the bulk composition ratios in a surface reaction layer of 800 nm thickness. After 30 min leaching time, a calcium- and fluoride-rich surface layer approximately 50 nm thick was formed. The bulk composition was reached at a depth of approximately 500 nm. The main component in the surface layer, after 12 days leaching in acidic environment, was silicon. This revised version was published online in August 2006 with corrections to the Cover Date.     

High-temperature XRD studies of the phase transformations in a MnOx/Al2O3 catalyst for deep oxidation of hydrocarbons

Omsk Branch of Boreskov Institute of Catalysis     

Acetone transport in poly(ethylene terephthalate) and related phenomena

The acetone transport in poly(ethylene terephthalate) (PET) and related phenomena was investigated. Based on Harmon's model for Case I, Case II, and the anomalous transport, we analyzed the data of mass uptake. The diffusivity for Case I and the velocity for Case II satisfied the Arrhenius plot. It was found that the solvent moves from outer surfaces to the center according to Case I kinetics, and there is movement in the opposite direction according to Case II kinetics during the mass uptake. This result indicated that pure Case II behavior did not appear in the PET–acetone system. The saturated amount of acetone in PET satisfied the van't Hoff plot. X-ray diffraction pattern and DSC curve showed solvent-induced crystallites and thermal crystallites. The results of density measurement explained the difference of the sorption kinetics between the acetone-treated PET crystallites and thermally treated PET. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 163–169, 1998     

Diffusion and phase transformations in spark plasma synthesized and sintered Cu-V2O5 couples

Fast diffusion of Cu into V₂O₅ at 520 °C is studied in Cu-V₂O₅ diffusion couples sintered by spark plasma sintering. The impact, on the diffusion profiles, of phase transformations and of variations of the diffusion coefficient with Cu concentration is discussed. From the pure Cu source, two phases are observed to spread, leading to a “two-step-like” shape of the diffusion profiles. In the more concentrated phase (phase ε), the diffusion coefficient D of Cu is ≈3×10⁻⁸ m²/s. This is a remarkably high value, of the same order of magnitude as self-diffusion in liquid metals. In the less concentrated phase (phase β′), D is lower than in ε. This is due to the differences in the diffusion mechanisms of Cu in these two phases: two dimensional in ε and one dimensional in β′. In β′, D strongly depends on Cu concentration. This is in good agreement with computer simulations reported in the literature.     

Oxygen exchange study in phase transformations of superconducting bismuth cuprates (Pb2212 and Pb2223)

The oxygen exchange between the condensed phase(s) and the gas phase was studied as a function of temperature for superconducting phases of the system (Bi,Pb)-Sr-Ca-Cu-O.An oxygen probe apparatus allowed confirmation that the variation in oxygen composition in the Pb2212 and Pb2223 superconducting phases is a reversible phenomenon on heating and cooling. It was demonstrated that the mass loss of both phases, for the 905 and 980°C isotherms, was due to the oxygen composition variation and to PbO loss (this latter phenomenon begin irreversible).     

Capillary electrophoresis study on phase of mixed micelles and its role in transport phenomena of particles

In the present work comprehensive studies on electrophoretic effects induced by a phase of mixed micelles, that migrates surrounded with background electrolyte (BGE) and is denoted as the BGE/segment of mixed micelles/BGE system, were undertaken using capillary electrophoresis coupled with contactless conductivity or UV–vis detector. It was established that mixed micelles under electrophoresis are subject of evolution in terms of mobility, peak area and presence of sub-zones enforced by the composition of micellar phase, segment length and applied voltage. Established features allowed us to explain the electrophoretic behavior of nanoparticles in the system BGE/sample containing nanocrystals/segment of mixed micelles/BGE and it was postulated that a pseudomicellar state of nanoparticles can be useful term in analyzing the migration phenomena of nanoparticles within micellar environment. In contrast to the previous works, where transport of nanocrystals (NCs) within micellar segment or between two micellar segments was analyzed, the present work is focused on the transport of NCs from sample of NCs dispersed in BGE to phase of mixed micelles, i.e., to rear boundary between micellar zone and BGE. Based on these results, systematic studies on transport efficiency for nanoparticles in the system BGE/sample containing nanocrystals/segment of mixed micelles/BGE show that the system assures efficient transport of nanoparticles from BGE based sample to micellar phase and their efficient preconcentration at the micellar segment/BGE rear boundary.     

Intermolecular interactions and phase equilibria in nitrocellulose - s-diethyldiphenylurea system

Values of the Flory-Huggins interaction parameters c were predicted on the base of mixing enthalpy H ^M for nitrocellulose-s-diethyldiphenylurea system. The phase diagram of the system and the glass transition temperature of mixtures T _g12 were estimated using calculated c parameters. The predicted glass transition temperatures were in accordance with values determined experimentally. This revised version was published online in July 2006 with corrections to the Cover Date.     

Recent advances in intermixed phase of organic solar cells: Characterization,regulating strategies and device applications

Organic solar cells (OSCs) have unique advantages of low-cost solution processing, light weight, flexibility, and semitransparency, which is a promising photovoltaic technology. The intermixed phase plays a key role in determining the power conversion efficiencies (PCE) of OSCs. The intermixed phase is an amorphous region, where the donor and acceptor mix at the molecular level. Great efforts have been devoted to optimize the content and the composition of the intermixed phase. This perspective focuses on the functions of intermixed phase and elaborates the relationship between intermixed phase behavior and photophysical process, in particular, the exciton dissociation and charge transport. Then the characterization methods, including quantitative and qualitative characterizations, for the content and composition of intermixed phases are introduced. Meanwhile, this review also introduces the strategies to control the intermixed phase behavior, such as adjusting the miscibility between donor and acceptor, changing the ratio of donor to acceptor, regulating the crystallinity and so on. Moreover, representative examples are given and discussed to understand the key parameters on tuning the intermixed phase behavior. Finally, a future controlling and development of intermixed phase behavior is briefly outlooked, which may help to achieve high PCE of OSCs.     

Isothermal phase behavior of Nylon-6, -66, and -610 polyamides in formic acid–water systems

Concentration-dependent ternary interaction parameters are experimentally determined for the polyamide homopolymers, Nylon-6, -66, -610, and for the Nylon-66/610/6 terpolymer in formic acid-water systems. The binodal envelope, the tie lines, and the crystallization isotherms at 25°C are given for each of the ternary systems. © 1994 John Wiley & Sons, Inc.     

固相萃取-液相色谱-串联质谱法测定食品包装材料中16种全氟烷基类化合物

建立了使用固相萃取-液相色谱-串联质谱(SPE-LC-MS/MS)同时检测食品包装材料中16种全氟烷基类化合物(PFAS)的方法。分别对样品前处理方法、质谱条件等进行了比较和优化,样品用甲醇超声提取,经Oasis WAX固相萃取小柱净化后,用Atlantis T3 C₁₈色谱柱分离,以乙腈和5 mmol/L乙酸铵溶液为流动相进行梯度洗脱,多反应监测(MRM)负离子模式扫描,同位素内标法和外标法结合定量。16种PFAS在0.5~20.0 μg/L范围内线性关系良好,相关系数(r²)均大于0.99。加标回收率为68.6%~109.2%,RSD为2.5%~18.1%(n=6)。检出限为0.2~0.5 μg/kg,定量限为0.5~1.0 μg/kg。该方法简便、快速、准确,可用于食品包装材料样品中PFAS的检测。     

Controlling morphological and electro-optical properties via the phase separation in polymer/liquid-crystal composite materials

ABSTRACT

The polymer/liquid-crystal composite materials have been extensively studied for their potential applications. Various optical devices based on this composite material have been proposed and realised. The device performance is highly dependent on the phase separation of this composite material. Here, we investigate the photopolymerisation-induced phase separation in this composite material. Depending on the mass ratios between the polymer and the liquid crystal, the phase separation can be well controlled and subsequently affect the morphological and electro-optical properties. At a fixed ratio, we can realise either phase-separated composite films or conventional polymer-dispersed liquid crystal films with completely different optical properties. By carefully controlling the exposure conditions, the morphologies and electro-optical properties have been studied and optimised in details. With in-depth studies and optimisation, the photopolymerisation-induced phase separation technique could be utilised to realise many different optical functions based on the polymer/liquid-crystal composite materials.     

Morphologies and crystalline forms of polyvinylidene fluoride membranes prepared in different diluents by thermally induced phase separation

We have studied the morphologies and crystalline forms of polyvinylidene fluoride (PVDF) membranes separately prepared in four different diluents bearing >C?O groups, namely 1,2‐propylene glycol carbonate (PGC), dimethyl phthalate (DMP), diphenyl ketone (DPK), and dibutyl phthalate (DBP), by the thermally induced phase separation (TIPS) method. The permittivities of the diluents and PVDF were measured to compare the different PVDF–diluent systems. The results showed the permittivity of PGC to be much greater than that of PVDF, and those of DMP and DBP to be lower than that of PVDF. The permittivity difference between DPK and PVDF was not apparent above 120 °C. On cooling mixtures with a PVDF concentration of 10 wt %, PVDF crystallization was observed in the PVDF–DMP, PVDF–DBP, and PVDF–PGC systems, while liquid–liquid phase separation occurred in the PVDF–DPK system. A cross‐section of the PVDF–PGC membrane presented smooth PVDF particles in the β‐phase crystalline form. Those of the PVDF–DMP and PVDF–DBP membranes presented PVDF particles consisting of a fibrillar network in the α‐phase. The PVDF–DPK membrane preferentially adopted an α‐phase bicontinuous channel structure. When the concentration of PVDF was 60 wt %, the cross‐sections of the above four membranes revealed PVDF polyhedra, among which the PVDF–DMP, PVDF–DBP, and PVDF–DPK membranes retained the α‐phase crystalline form, and the diffraction peak of the α‐phase became visible in the X‐ray diffraction (XRD) spectrum of the PVDF–PGC membrane. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Diffusion limited crystallization and phase partitioning in ZrO2-metal oxide binary systems

Chemical routes to synthesize inorganics can start with solutions where multiple elements remain well mixed during liquid evaporation, precursor decomposition and crystallization. Because crystallization generally occurs at temperatures where diffusion is very limited, a single phase can crystallize with a greatly extended solid-solution that does not achieve its equilibrium phase assemblage until much higher temperatures where diffusion is no longer constrained. Partitioning at these higher temperatures can lead to unique microstructures such as the nano-composite illustrated here for a metastable Zr_(1–x)Al _x O_2–x/2 (x0.57) phase that partitions into a composite containing t-ZrO₂ grains and -Al₂O₃ plates.     

离子交换固相萃取高效液相色谱联用法检测河豚鱼中的河豚毒素

优化建立了采用混合模式阳离子交换固相萃取柱代替传统的C18固相萃取柱进行前处理,联用高效液相色谱检测河豚鱼中河豚毒素的方法.样品经合1％乙酸的乙腈甲醇(3:1,V:V)溶液提取,混合模式阳离子交换固相萃取柱(MCX)净化,5％氨水/甲醇溶液洗脱,采用高效液相色谱-二极管阵列检测器(HPLC-PAD)测定,外标法定量.河...