Morphology,Crystallization, and Melting of Single Crystals and Thin Films of Star‐branched Polyesters with Poly(ϵ‐caprolactone) Arms as Revealed by Atomic Force Microscopy

The morphology and thermal stability of different sectors in solution‐ and melt‐grown crystals of star‐branched polyesters with poly(?‐caprolactone) (PCL) arms, and of a reference linear PCL, have been studied by tapping‐mode atomic‐force microscopy (AFM). Real‐time monitoring of melt‐crystallization in thin films of star‐branched and linear PCL has been performed using hot‐stage AFM. A striated fold surface was observed in both solution‐ and melt‐grown crystals of both star‐branched and linear PCL. The presence of striations in the melt‐grown crystals proved that this structure was genuine and not due to the collapse of tent‐shaped crystals. The crystals of the star‐branched polymers had smoother fold surfaces, which can be explained by the presence of dendritic cores close to the fold surfaces. The single crystals of linear PCL grown from solution showed earlier melting in the {100} sectors than in the {110} sectors, whereas no such sectorial dependence of the melting was found in the solution‐grown crystals of the star‐branched polymers. The proximity of the dendritic cores to the fold surface yields at least one amorphous PCL repeating unit next to the dendritic core and more nonadjacent and less sharp chain folding than in linear PCL single crystals; this evidently erased the difference in thermal stability between the {110} and {100} sectors. Melt‐crystallization in thin polymer films at 53–55°C showed 4 times faster crystal growth along b than along a, and more irregular crystals with niches on the lateral faces in star‐branched PCL than in linear PCL. Crystal growth rate was strictly constant with time. Multilayer crystals with central screw dislocation (growing with or without reorientation of the b–axis) and twisting were observed in both classes of polymers.     

The pH effects on the growth rate of KDP (KH2PO4) crystal by investigating Raman active lattice modes

We report on the dependence of the pH value on the growth rates of KDP single crystals. Extensive experimental work has been carried out in order to find the optimum pH ranges for growing KDP single crystals with suitable sizes and high optical quality. Different techniques including micro‐Raman back‐scattering spectroscopy, UV/vis/IR transmission spectroscopy and X‐ray diffraction have been employed for this investigation. Deuterated substituted single crystals of KDP and DKDP also have been grown for the investigation of growth rates and Raman active mode identification purposes. The molecular vibration modes of the grown crystals, including internal modes of PO₄ tetrahedrons molecular vibrations, external modes of optical phonons and hydrogen bonding modes have been determined exactly by micro‐Raman back‐scattering spectroscopy. The best pH values of the solution for the KDP crystal growth with reasonably higher growth rates from aqueous solutions that have been supersaturated ata temperature range of 30–50 °C have been found to be in the pH range of 3.2–5.4. Copyright © 2007 John Wiley & Sons, Ltd.     

Nucleation studies and characterization of potassium thiocyanate added KDP crystals grown by seed rotation technique

The effect of the addition of potassium thiocyanate on potassium dihydrogen phosphate (KDP) crystals, grown from aqueous solution by the temperature lowering method using a microcontroller based seed rotation technique has been studied. As part of nucleation studies, metastable zone width, induction period and crystal growth rate of additive added KDP are determined and analyzed with the pure system. Dielectric measurements were carried out on pure and doped crystals at various temperatures ranging from 313 to 423 K and compared. The crystalline perfection of the grown crystal was studied by the high resolution X-ray diffraction analysis. The crystal grown from additive added solution was subjected to structural, optical transmission, second harmonic generation and hardness studies and the effect of additive on pure system is investigated.     

Nucleation kinetics,solubility, growth and characterization of novel semiorganic crystal—Bisthiourea zinc formate

Single crystals of bisthiourea zinc formate were grown by the low temperature solution growth technique. The nucleation parameters such as solubility, induction period, interfacial energy and metastable zone width, radius of critical nucleus, critical free energy barrier, number of molecules in the critical nucleus and energy per unit volume have been evaluated. Metastable and induction period values were determined experimentally in order to optimize the growth parameters. Transparent good quality single crystals are characterized by single crystal XRD, powder XRD and FTIR analysis. Optical and photoluminescence studies have been carried out for the grown crystal. The results have been discussed in detail.     

The Shear‐Dependent Phase Separation Behavior of the Ternary Blend Polystyrene/Polyvinyl Methyl Ether/Styrene–Acrylonitrile Copolymer

The phase behavior and phase separation dynamics of a PS/PVME/SAN ternary blend using light scattering under a shear rate range of 0.1～40 s^?1 were investigated. The cloud point temperature first increases and then decreases with the increase of shear rates. At higher shear rates, the cloud point temperature again increases. The phase separation behavior in the early and later stages under shear field can be explained by the Cahn–Hilliard theory and the exponential growth law, respectively. The delay time τ _d ?, the apparent diffusion coefficient D _app, the growth rate R(q), and the exponent term show strong dependence on the difference between the experimental temperature and the cloud point temperature (ΔT), and on the shear rates. Compared with PS/PVME binary blends at lower shear rates, τ _d for a PS/PVME/SAN ternary blend is smaller, while at higher shear rates τ _d is larger. At higher shear rates, the introduction of the third component SAN to a PS/PVME binary blends slows the phase separation process.     

Colloidal Crystals of NaYF4 Upconversion Nanocrystals Studied by Small‐Angle X‐Ray Scattering (SAXS)

Spherical NaYF₄ upconversion nanocrystals with mean radii of about 5 and 11 nm are observed to form colloidal crystals, i.e., 3D assemblies of the particles with long‐range order. The colloidal crystals of the larger particles form directly in solution when dispersions of the particles in toluene are stored at room temperature for several weeks. Crystallization of the smaller particles takes place when their dispersions in hexane are slowly dried at elevated temperatures. The formation and the structure of the colloidal crystals are studied by small‐angle X‐ray scattering (SAXS). SAXS measurements show that the smaller as well as the larger particles assemble into a face‐centered cubic lattice with unit cell dimensions of a = 18.7 nm and a = 35.5 nm, respectively. The SAXS data also show that the particles in the colloidal crystals still bear a layer of oleic acid on their surfaces. The thickness of this layer is 1.5–1.8 nm, as determined by comparing the unit cell dimensions of the colloidal crystals with the mean particle sizes. The latter could be very precisely determined from the distinct oscillations observed in the SAXS data of dilute colloidal dispersions of the nanocrystals.     

Process intensification of synthesis of metal organic framework particles assisted by ultrasound irradiation

This study synthesized UiO-66, a typical Zr-Metal Organic Framework (MOF), by using an ultrasound-assisted synthesis method to reduce the synthesis time. This method was short-time ultrasound irradiation at the initial stage of the reaction. As compared with average particle size of conventional solvothermal method (=192 nm), averaged particle size by the ultrasound-assisted synthesis method showed particle sizes that were smaller on average, ranging from 56 to 155 nm. In order to compare the relative reaction rates of the solvothermal method and the ultrasound-assisted synthesis method, the cloudiness of the reaction solution in the reactor was observed with a video camera, and the luminance was calculated from the images obtained by the video camera. It was found that the ultrasound-assisted synthesis method showed a faster increase in luminance and shorter induction time than the solvothermal method. The slope of the luminance increase during the transient period was also found to become increase with the addition of ultrasound, which also affects the growth of particles. Observation of the aliquoted reaction solution confirmed that particle growth was faster in the ultrasound-assisted synthesis method than in the solvothermal method. Numerical simulations were also performed using MATLAB ver. 5.5 to analyze the unique reaction field generated by ultrasound. Bubble radius and temperature inside a cavitation bubble was obtained using the Keller-Miksis equation, which reproduces the motion of a single bubble. The bubble radius expanded and contracted repeatedly according to the ultrasound sound pressure, and eventually collapsed. The temperature at the time of collapse was extremely high, exceeding 17,000 K. It was confirmed that the high-temperature reaction field generated by ultrasound irradiation promoted nucleation, leading to a reduction in particle size and induction time.     

Non-steady state solidification of the Nd-123 superconducting oxides

Crystal growth of the melt-textured bulk Nd_1+xBa_2−xCu₃O_6+d (Nd123) superconducting oxides was investigated by employing isothermal undercooling solidification with hot-seeding in air. From the relationship between growth length and holding time, the Nd123 crystal was found to have almost stopped growing after a certain growth period, while the growth length increased proportionally to the holding time at an early stage of the crystal growth. As a result of quantitative analysis for the Nd123 crystal of which solidification was terminated, the distribution of the Nd/Ba substitution was observed to decrease in the Nd123 single crystal matrix from the seed crystal to the edge of the Nd123 crystals. Also, the substitution content at the edge of the Nd123 crystal, which corresponds to that at the final stage of the crystal growth, was found to be in good agreement with the minimum substitution of the Nd123 solid solution phase in the equilibrium phase diagram at this process temperature. These compositional changes could be explained using the equilibrium phase diagram as associated with the solid solution formation, which is responsible for the non-steady state solidification of the Nd123 crystals even for the isothermal undercooling processing.     

Structural Relaxation of Polystyrene Glasses with Dis‐interpenetrated Chains Studied by Differential Scanning Calorimetry

The polystyrene (PS) samples were prepared by freeze‐drying solutions with different concentrations. The structural relaxation behaviors and the chain conformation were studied by differential scanning calorimetry and nonradiative energy transfer, respectively. The results showed that PS prepared by freeze‐drying from very dilute solution was in a disinterpenetrated state, and the structural relaxation was faster than that for interpenetrated coils and the cross‐linked samples.     

Recrystallization of pure and strontium-doped KCl crystals

The kinetics of microstructure transformations are studied during annealing of deformed single crystals of KCl and KCl:0.05wt %Sr²⁺ at temperatures of (0.35–0.55)T _m (where T _m is the melting temperature) and during storage at room temperature. The effect of deformation rates ranging from 0.01 mm/min to 0.1 mm/min at a deformation temperature T _d=0.5T _m on the crystal structure and on the recrystallization kinetics is noted. It is found experimentally that the incubation period for static recrystallization in single-crystal KCl:0.05wt%Sr²⁺ is shortened and recrystallization takes place at room temperature after deformation in this temperature range. Here, during the new recrystallization grains have a twinned orientation with respect to the initial single crystal during the first stage and to the subgrains of the deformed crystal. As the annealing temperature is raised, the stage in which twins grow in KCl:0.05wt%Sr²⁺ crystals is shortened and it is displaced by recrystallization through migration of high-angle grain boundaries of the common type. Deformation conditions which ensure prolonged (at least three months) stability of the post-deformation hardening of single crystals are found experimentally for Sr²⁺-doped deformed single crystals. Fiz. Tverd. Tela (St. Petersburg) 41, 259–264 (February 1999)     

Growth and properties of Li,Ta modified (K,Na)NbO3 lead‐free piezoelectric single crystals

Li, Ta modified (K,Na)NbO₃ single crystals with the size of 18 mm × 18 mm × 10 mm were successfully grown by top‐seeded solution growth method, with orthorhombic–tetra‐gonal phase transition temperature ～79 °C and Curie temperature ～276 °C. The electromechanical coupling factors k₃₃ and k_t were found to be ～88% and ～65%, respectively. The piezoelectric coefficient d₃₃ for the [001]_c poled crystals reached 255 pC/N. In addition, the electromechanical coupling factor exhibited high stability over the temperature range of –50 °C to 70 °C, making these lead free crystals good candidates for electromechanical applications. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dispersity and growth kinetics of K<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals in drops of an evaporating solution

Growth of K₂SO₄ crystals is studied in solution drops that have different initial heights and evaporate in different times. The dependences of the crystal size on the crystal growth time are obtained. The following three crystal growth modes are detected: rapid crystal growth in a supersaturated solution, a stop in the growth as a result of complete removal of supersaturation, and slow growth at a quasi-equilibrium solution concentration. The dispersities of the crystals that are retained at the bottom of the drop after complete evaporation of the solvent are calculated. A linear relation between the crystal dispersity and the reciprocal crystal growth time is revealed. The dispersity of K₂SO₄ crystals and the dispersity of the solid-solution dendrites in aluminum alloys are found to exhibit the same character of their dependences on the reciprocal crystal growth time.     

Morphology of Fractured Polymer‐Polymer Interfaces Bonded at Ambient Temperature as Studied by Atomic Force Microscopy

The amorphous polymer surfaces of polystyrene (PS, M _n=200 kg/mol, M _w/M _n=1.05) and poly(methyl methacrylate) (PMMA, M _n=51.9 kg/mol, M _w/M _n≤1.07) were brought into contact at 21°C to form PS‐PS (for 54 days) and PMMA‐PMMA auto‐adhesive joints (for 11 days). After contact at that temperature corresponding to T _g‐bulk ?81°C for PS and to T _g‐bulk–88°C for PMMA, where T _g‐bulk is the calorimetric glass transition temperature of the bulk sample, the bonded interfaces were fractured and their surfaces were analyzed by atomic force microscopy (AFM). The surface roughness, R _q, of the fractured interfaces was larger by a factor of 3–4 than was that of the free PS and PMMA surfaces aged for the same period of time. A similar increase in R _q was found by comparison of the free PS surface aged at T _g‐bulk+15°C for 1 h and of the surface of the PS‐PS interface fractured after healing at T _g‐bulk+15°C for 1 h. These observations, indicative of the deformation of the fractured interfaces, suggest the occurrence of some mass transfer across the interface even below T _g‐bulk ?80°C.     

Large‐Scale Fluctuation Behavior Prior to the Crystallization of Poly(ethylene terephthalate) Glass: A Small‐Angle Light Scattering Study

The crystallization processes of amorphous, glassy‐state poly(ethylene terephthalate) (PET) at two temperatures, a low temperature near T _g where PET has a slow crystallization speed and a middle temperature (about 55°C above T _g ) where PET crystallization is rapid, were monitored in situ by a time‐resolved small‐angle light scattering (SALS) device. It was found that large‐scale fluctuations happened prior to the crystallization at both temperatures, but the kind of fluctuation had a temperature dependence: at the middle temperature, pure density fluctuation took place during the induction period, whereas at low temperature, both density fluctuation and orientation fluctuation occurred, but the latter was the dominant factor. Analyses of the kinetics of these two kinds of fluctuation processes demonstrated that the spinodal decomposition (SD) type of phase‐separation character was undistinguishable in the SALS scale, while the nucleation‐growth (NG) type of phase behavior could describe the scattering results as well.     

Direct Observation of Crystallization of Polybutene-1 Under Low Shear Rate Flow

The isothermal crystallization process of polybutene-1 melt under shear flow was investigated with an optical microscope and a device (shear flow direct observation system, SF-DOS) newly developed by our group. The nucleation rate and growth rate of polybutene-1 were studied under slow shear rates (0–0.1 s^?1) at high crystallization temperature (102–108°C) with the SF-DOS. The nucleation remains heterogeneous. The number of nuclei after long times increased and induction time decreased by increasing the shear rate. Anisotropic and distorted spherulites were observed under shear flow, while the spherulites in the static condition were isotropic. It was clearly observed that the spherulites were rotating under shear. The average growth rates were enhanced by increasing shear rates, which acts as the main factor affecting the overall crystallization kinetics. Finally, the crystallization kinetics were analyzed on the basis of the secondary nucleation theory of Hoffman and Lauritzen. Even under very low shear rates, the product of lateral‐surface free energy σ _s and fold-surface free energy σ _e was found to be reduced as shear rate increased.     

Reaction‐Induced Phase‐Separation in Polyoxyethylene/Polystyrene Blends. II. Structure Development

Abstract

The morphology development in model polymer blends was investigated in relation to the processing pathway. Reaction‐induced phase separation was used to make polyoxyethylene (POE) and polystyrene (PS) blends from a solution of POE/styrene. As the styrene underwent polymerization by photo‐initiation with ultraviolet light, phase separation, and phase inversion were induced, whereby the POE became the matrix phase. Optical microscopy showed that liquid–liquid (L–L) phase separation occurred soon after the styrene polymerization was initiated. Nucleation and growth was identified as the mechanism of L–L phase separation. Polystyrene/styrene‐rich domains formed in a POE/styrene‐rich matrix. The domain size developed until arrested by the POE liquid–solid phase separating and crystallizing, since the experiments were conducted below the melt temperature of POE. The POE crystal growth process also followed a nucleation and growth mechanism. The time to the onset of crystallization was observed to decrease as the POE content increased, until the POE formed a saturated solution in styrene. As the crystallization onset time decreased, the PS‐rich domain size also decreased. The phase diagram previously established can now be used to describe (and predict) the number density and size of the PS‐rich domains in the POE matrix of the blends.     

Surface morphology and growth kinetics of zinc single crystals as influenced by vapour diffusion

The effect of diffusion in the vapour phase on both the surface morphology and growth kinetics of zinc single crystals growing in the presence of argon has been investigated. The shift of the basal face in the normal direction and the growth of the edge of that face as a function of time have been determined at constant temperature and supersaturation and at argon pressures within the range 5–250 Torr as well as in high vacuum of 1 × 10⁻⁶ Torr. It has been found that the crystal size R and the edge length a change with time t following a linear law in the kinetic and a parabolic law in the diffusion regime respectively. The results obtained by kinetic investigations and morphological observations of the basal face are compared.     

Bonding at Compatible and Incompatible Amorphous Interfaces of Polystyrene and Poly(Methyl Methacrylate) Below the Glass Transition Temperature

Abstract

Films of high‐molecular‐weight amorphous polystyrene (PS, M _w = 225 kg/mol, M _w/M _n = 3, T _g‐bulk = 97°C, where T _g‐bulk is the glass transition temperature of the bulk sample) and poly(methyl methacrylate) (PMMA, M _w = 87 kg/mol, M _w/M _n = 2, T _g‐bulk = 109°C) were brought into contact in a lap‐shear joint geometry at a constant healing temperature T _h, between 44°C and 114°C, for 1 or 24 hr and submitted to tensile loading on an Instron tester at ambient temperature. The development of the lap‐shear strength σ at an incompatible PS–PMMA interface has been followed in regard to those at compatible PS–PS and PMMA–PMMA interfaces. The values of strength for the incompatible PS–PMMA and compatible PMMA–PMMA interfaces were found to be close, both being smaller by a factor of 2 to 3 than the values of σ for the PS–PS interface developed after healing at the same conditions. This observation suggests that the development of the interfacial structure at the PS–PMMA interface is controlled by the slow component, i.e., PMMA. Bonding at the three interfaces investigated was mechanically detected after healing for 24 hr at T _h = 44°C, i.e., well below T _g‐bulks of PS and PMMA, with the observation of very close values of the lap‐shear strength for the three interfaces considered, 0.11–0.13 MPa. This result indicates that the incompatibility between the chain segments of PS and PMMA plays a negligible negative role in the interfacial bonding well below T _g‐bulk.     

Direct NMR measurement of rotation rates: solvent effects on rotation barriers

2,2,4,4‐Tetramethyl‐3‐{2‐[3,4‐dialkoxy‐5‐(3‐pyridyl)]thienyl}pentan‐3‐ols self‐associate both in the solid state and in solution. The IR spectra of the solids display a broad OH absorption at 3320 cm^?1, corresponding to an intermolecularly hydrogen‐bonded syn rotamer, probably a dimer, as well as absorptions around 3500 cm^?1 of the intramolecularly hydrogen‐bonded anti form. Well‐crystallized samples of these derivatives go into solution in the syn form but undergo rotation to the anti rotamer at a rate which can be measured directly by proton Nuclear Magnetic Resonance (NMR) spectroscopy. The diethoxy derivative was studied in a wide variety of solvents. The activation energy for syn→anti rotation is practically solvent‐independent, whereas that of the reverse reaction falls in hydrogen‐bonding solvents, by more than 2 kcal mol^?1 on going from chloroform or benzene to dimethylsulfoxide (DMSO). By combining direct measurements at low temperature and Dynamic Nuclear Magnetic Resonance (DNMR) results at high temperature, rotation rates were evaluated over a range of more than 100 K, and significantly large negative activation entropies determined. Copyright © 2007 John Wiley & Sons, Ltd.     

A Study on Compatibility and Properties of POE/PS/SEBS Ternary Blends

Ethylene‐α‐olefin copolymer (POE)/polystyrene (PS)/poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS) blends were prepared via melt blending in a co‐rotating twin‐screw extruder. The effects of SEBS copolymer on the morphology and rheological and mechanical properties of the blends were studied. Scanning electron microscopy (SEM) photos showed that the addition of SEBS copolymer resulted in finer dispersion of PS particles in the POE matrix and better interfacial adhesion between POE and PS compared with POE/PS blends, which exhibited a very coarse morphology due to the immiscibility between them. Interestingly, the tensile strength increased from 12.5 MPa for neat POE to 23.5 MPa for the POE/PS/SEBS (60/10/30) blend, whereas the tensile strengths of POE/PS (85.7/14.3) blend and POE/SEBS (66.7/33.3) blend were only 10.5 and 16.5 MPa, respectively. This indicates that both SEBS copolymer and PS have a synergistic reinforcing effect on POE. Dynamic mechanical thermal analysis (DMTA) and dynamic rheological property measurement also revealed that there existed some interactions between POE and SEBS as well as between SEBS and PS. DMTA results also showed that the storage modulus of POE increased when PS and SEBS were incorporated, especially at high temperature, which means that the service temperature of POE was improved.