Crystalline structures of intercalate molecular complexes of syndiotactic polystyrene with two fluorescent guests: 1,3,5-Trimethyl-benzene and 1,4-dimethyl-naphthalene

The crystal structures of two molecular complex phases of syndiotactic polystyrene (s-PS) with 1,3,5-trimethyl-benzene (TMB) and 1,4-dimethyl-naphthalene (DMN) have been described. These structures present a monoclinic unit cell in which the s(2/1)2 polymer helices and guest molecules are packed according the space group P2₁/a and unit cell constants: a=17.3 Å, b=15.4 Å, c=7.8 Å and γ=95.7° for s-PS/TMB and a=17.4 Å, b=17.2 Å, c=7.8 Å and γ=116.4° for s-PS/DMN. Both structures can be described as intercalates, since they present ac layers of polymer helices alternated to layers of contiguous guest molecules and a guest/monomeric-unit molar ratio of 1/2, as recently observed only for s-PS/norbornadiene molecular complex. On the basis of a comparison between crystalline structures and X-ray diffraction data of several s-PS molecular complexes, a simple criterion to anticipate their clathrate or intercalate nature has been suggested.     

Preparation of physical gel consisting of syndiotactic polystyrene and poly(ethylene glycol)

Syndiotactic polystyrene (s-PS) was blended with poly(ethylene glycol) (PEG) in 1,2-dichloroethane (DCE) solvent. The mixture became a homogeneous solution at 155 °C depending on the composition ratio of PEG to DCE. When the solution was cooled at the rate of 5 °C/min to room temperature, a thermoreversible gelation was occurred. Wide angle X-ray diffraction (WAXD) measurements revealed that the polymer chain of s-PS in the obtained gel was crystallized with a helical conformation, while that in the non-gelated sample was done with an all-trans planar zigzag conformation.After drying gelated samples at 70 °C for 24 h, a novel polymer blend type of the physical gel consisting of s-PS and PEG was obtained. Dynamic mechanical analysis (DMA) revealed that the physical gel had a high modulus and a long elastic plateau in the temperature range of −80-270 °C.     

Polymorphism and β-form structure of poly(octamethylene 2,6-naphthalate)

It was revealed that poly(octamethylene 2,6-naphthalate) (PON) existed in two different crystal structures, α- and β-form, depending on crystallization process: The α-form crystal was dominantly developed from the cold-crystallization, whereas the β-form was from the melt-crystallization. The apparent melting temperatures of α- and β-form crystals were characterized to be 175 and 183 °C, respectively. On the basis of X-ray diffraction and molecular modeling studies, the crystal structure of β-form, developed dominantly from the melt-crystallization, was identified to be triclinic with dimensions of a = 0.601 nm, b = 1.069 nm, c = 2.068 nm, α = 155.68°, β = 123.25°, γ = 52.85°, and with the space group of . The calculated crystal density was 1.243 g/cm³, supporting that one repeating unit of PON exists in a unit cell. The octamethylene units in the PON backbone take largely all-trans conformation in the β-form unit cell.     

Macromolecular effect on crystal pattern formation in ultra-thin films: Molecular segregation in a binary blend of PEO fractions

In this work we report our investigation on the crystal patterns of a 50/50 blend of two polyethylene oxide (PEO) fractions with different molecular weights in ultra-thin films. Using AFM with a hot stage the samples on the surface of silicon wafer were isothermally crystallized at 20.0 ≤ T_c ≤ 60.0 °C. The crystal patterns are different from those of the two pure fractions. Co-crystallization, partial segregation and full segregation have been observed. Especially, within 47.0 ≤ T_c ≤ 54.0 °C dual thickness crystals formed. The thickness of the middle part of the crystal corresponds to the lamella thickness of 35k-PEO fraction with multiple folds, while the thickness of the edge part is nearly equal to an extended-chain lamella thickness of 5k-PEO fraction. We suppose that the appearance of the dual thickness crystals is due to molecular partial segregation. Utilizing in-situ AFM, the growth of the crystal with dual thicknesses as a function of time was monitored at T_c = 54.0 °C. Two growth processes were observed and a pattern formation mechanism was suggested on the basis of specified molecular motion and chain-fold crystallization of polymers.     

Effect of side chains and solvents on the film surface of linear fluorosilicone pentablock copolymers

The linear fluorosilicone pentablock copolymers PDMS-b-(PMMA-b-PFMA)₂ are synthesized via two-step ATRP approaches by dimethylsiloxane (DMS), methyl methacrylate (MMA) and fluorinated methacrylate (FMA). Trifluoroethyl methacrylate (3FMA), hexafluorobutyl methacrylate (6FMA), octafluoropentyl methacrylate (8FMA) and dodecafluoroheptyl methacrylate (12FMA) are used as FMA. The effect of different fluorinated side chains on the surface properties of PDMS-b-(PMMA-b-PFMA)₂ films indicates that 3FMA, 6FMA and 8FMA behave the similar surface properties as lower water contact angles (θ(H₂O) = 105–106°) and higher surface free energy (26.83–27.55 mN/m) than P12FMA (θ(H₂O) = 116°, 19.52 mN/m) due to the competing migration between the PFMA and PDMS chains. Therefore, the effect of chloroform (CHCl₃), tetrahydrofuran (THF), trifluorotoluene (TFT) and CHCl₃–TFT solvents on the self-assembly and surface properties of PDMS-b-(PMMA-b-P12FMA)₂ film is investigated by DLS, TEM, SCA, XPS, SEM, AFM and QCM-D. A typical bimodal distribution with high content of micelles (310 nm, 93%) in CHCl₃ solution and high content of unimers (17 nm, 70%) in CHCl₃–TFT solution are formed, but a special unimodal distribution of unimers (15 nm) in THF solution and micelles (75 nm) in TFT solution are found. The micelles are confirmed by TEM as P12FMA core–PDMS/PMMA shell in CHCl₃ solution, but PDMS core–PMMA/P12FMA shell in TFT and CHCl₃–TFT solutions. The results reveal that the higher content of unimers contributes much to the fluorine-rich surface, higher cetane contact angle, lower surface energy and lower viscoelasticity for the film, but the higher content of micelles promote forming the roughness surface. Therefore, the most hydrophobic surfaces are the films casting from THF and CHCl₃–TFT solution.     

Synthesis and self-assembly of comb-like amphiphilic Doxifluridine-poly(?-caprolactone)-graft-poly(γ-glutamic acid) copolymer

Advances in amphiphilic copolymers can potentially be exploited in drug or gene delivery. This study develops novel comb-like amphiphilic copolymers that comprise poly(γ-glutamic acid) (γ-PGA) as a hydrophilic backbone and Doxifluridine-poly-(?-caprolactone) (5′-deoxy-5-fluorouridine-poly(?-caprolactone), 5′DFUR-PCL) as a hydrophobic side chain. A novel 5′DFUR-PCL polymer was synthesized with antitumor agent Doxifluridine (5′DFUR) as the initiator via the ring-opening polymerization of ?-caprolactone (?-CL) using tin(II) 2-ethylhexanoate (Sn(Oct)₂) as the catalyst. The 5′DFUR-PCL polymer was then grafted on γ-PGA to yield a 5′DFUR-PCL-γ-PGA comb-like copolymer with the help of 1-ethyl-3-(3-dimethyl-aminopropyl) carbodiimide (EDC). The characteristics of these copolymers were examined by ¹H NMR, FT-IR, GPC, contact angle measurement and thermal properties. Grafting 5′DFUR-PCL would significantly increase the contact angle and decrease the melting temperature (T_m) of the copolymers. The micelles self-assembled from these amphiphilic copolymers were formed in an aqueous phase and were examined via fluorescence approaches, dynamic light scattering (DLS) and transmission electron microscopy (TEM). The average sizes of the micelles were in the range from 130 to 230 nm and their zeta potentials were negative and less than −16.7 mV. The critical micelle concentration (CMC) was from 1.49 mg/L to 4.63 mg/L at 25 °C. TEM images demonstrated that the micelles were spherical and clearly had a core-shell structure.     

Synthesis of nanocrystalline lithium niobate powders via a fast chemical route

Lithnium niobate (LiNbO₃) can be obtained by mixing lithium nitrate (LiNO₃), ammonium niobate oxalate hydrate (C₄H₄NNbO₉) and glycine and then calcining at 600 °C for 1 h. The thermal analysis, structure, and morphology of the as-prepared LiNbO₃ were characterized by thermogravimetric and differential thermal analyses (TG/DTA), powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The crystallization temperature of LiNbO₃ precursor is 580 °C based on the TG/DTA results. After being calcined at 600 °C, the structure of the LiNbO₃ synthesized using various ratios of glycine to metal nitrates (Ψ-value) was formed with a particle size of about 29-38 nm, as found by XRD analysis. The crystal size has the lowest value at Ψ = 2, and the highest level of crystallization is at Ψ = 3.     

Hydrophilicity transition of the clean rutile TiO2 (1 1 0) surface

We present contact angle measurements of water on single-crystal rutile TiO₂ (1 1 0) surfaces, exposed to ambient air, or protected in dry air. Our measurements indicate that the surfaces exposed to ambient air are hydrophobic, with a contact angle of θ = 61(5)°. However, the well-protected dry surface also exhibits some hydrophobic tendency, with θ = 32(5)°. It is known that UV irradiation transforms both surfaces superhydrophilic, with θ = 0° [R. Wang, K. Hashimoto, A. Fujishima, M. Chikuni, E. Kojima, A. Kitamura, M. Shimohigoshi, T. Watanabe, Nature 388 (1997) 431-432]. We also present preliminary X-ray crystal truncation rod measurements on the hydrophobic TiO₂ (1 1 0) surface, and of the effect of UV illumination on the surface.     

Pure color and stable blue-light emission-alternating copolymer based on fluorene and dialkoxynaphthalene

A new blue-light emitting polymer that alternates between fluorene and alkoxynaphthalene structure has been developed. The fluorene and naphthalene units were highly distorted with an angle of 76.22° according to theoretical calculations. The obtained polymer has a weight average molecular weight of 273,800 with a polydispersity index of 2.35, good solubility and high thermal stability with a T_g of 176 °C. The film photoluminescence (PL) spectrum (405 nm) is consistent with that of solution and the PL spectra of the polymer did not show any peak in the long wavelength region even after annealing for 24 h at 100 °C. The double-layered device with an ITO/PEDOT/polymer/LiF/Al structure has a turn-on voltage of about 5.4 V, maximum brightness of 110 cd/m² and an electroluminescent efficiency of 0.09 cd/A. The OLED generates pure blue EL emission (λ_max = 405 nm) with excellent CIE coordinates (x = 0.15, y = 0.10) as well as stable blue EL emission that is not altered by voltage increase.     

Thermal, spectroscopy, and morphological studies on polymorphic crystals in poly(heptamethylene terephthalate)

Polymorphism and its influential factors in poly(heptamethylene terephthalate) (PHepT) were probed using differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and wide angle X-ray diffraction (WAXD). PHepT exhibits two crystal types (α and β) upon crystallization at various isothermal melt-crystallization temperatures (T_cs) by quenching from different T_maxs (maximum temperature above T_m for melting the original crystals). Melt-crystallized PHepT with either initial α- or β-crystal by quenching from T_max lower than 110 °C leads to higher fractions of α-crystal, but crystallization from T_max higher than 140 °C leads to higher fractions of β-crystal. In addition to T_max, polymorphism in PHepT is also influenced by crystallization temperature (T_c = 25-75 °C). When PHepT is melt-crystallized from a high T_max = 150 °C (completely isotropic melt), it shows solely β crystal for higher T_c, and solely the α-crystal for T_c < 25 °C; in-between T_c = 25 and 35 °C, mixed fractions of both α- and β-crystals. However, by contrast, when PHepT is melt-crystallized from a lower T_max = 110 °C, it shows α-crystal only at all T_cs, high or low.     

Nanostructural features of a spider dragline silk as revealed by electron and X-ray diffraction studies

Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were used to examine the nanostructure of a natural polymer—a spider dragline silk—that has potential applications as an engineering material. The silk studied was collected from the cob-web weaving spider Latrodectus hesperus. Single crystal and polycrystalline electron diffraction patterns indicate the presence of crystals with a bimodal size distribution, in the range of 2 nm and 40-120 nm. The chain axis of the smaller crystals is more strictly aligned with the fiber axis than that of the larger crystals. Lattice parameters for the orthogonal unit cell are: a=9.4 Å (interchain), b=7.0 Å (dipeptide, fiber axis) and c=10.8 Å (intersheet). A fine structure in single crystal electron diffraction patterns indicates possible composition-dependent lattice strains. Results of tensile tests of the spider dragline silk are reported, and a simple model is presented linking the observed nanostructural features to the force-elongation response of this material.     

Transparent polycrystalline MgAl2O4 ceramic fabricated by spark plasma sintering: Microwave dielectric and optical properties

The optical properties and microwave dielectric properties of transparent polycrystalline MgAl₂O₄ ceramics sintered by spark plasma sintering (SPS) through homemade nanosized MgAl₂O₄ powders at temperatures between 1250 °C and 1375 °C are discussed. The results indicate that, with increasing sintering temperatures, grain growth and densification occurred up to 1275 °C, and above 1350 °C, rapid grain and pore growth occurred. The in-line light transmission increases with the densification and decreases with the grain/pore growth, which can be as high as 70% at the wavelength of 550 nm and 82% at the wavelength of 2000 nm, respectively. As the sintering temperature increases, Q×f and dielectric constant ε_r values increase to maximum and then decrease respectively, while τ_f value is almost independent of the sintering temperatures and remains between −77 and −71 ppm/°C. The optimal microwave dielectric properties (ε_r=8.38, Q×f=54,000 GHz and τ_f=−74 ppm/°C) are achieved for transparent MgAl₂O₄ ceramics produced by spark plasma sintering at 1325 °C for 20 min.     

Microstructure and mechanical properties of silicon carbide processed by Spark Plasma Sintering (SPS)

The unique combination of SiC properties opens the ways for a wide range of SiC-based industrial applications. Dense silicon carbide bodies (3.18±0.01 g/cm³) were obtained by an SPS treatment at 2050 °C for 10 min using a heating rate of 400 °C/min, under an applied pressure of 69 MPa. The microstructure consists of fine, equiaxed grains with an average grain size of 1.29±0.65 μm. TEM analysis showed the presence of nano-size particles at the grain boundaries and at the triple-junctions, formed mainly from the impurities present in the starting silicon carbide powder. The HRTEM examination revealed high angle and clean grain boundaries. The measured static mechanical properties (H_V=32 GPa, E=440 GPa, σ_b=490 MPa and K_C 6.8 MPa m^0.5) and the Hugoniot Elastic Limit (HEL=18 GPa) are higher than those of hot-pressed silicon carbide samples.     

Structural features of inclusion complexes of γ-cyclodextrin with various polymers

The crystalline structures of inclusion complexes of γ-cyclodextrin (γ-CD) with poly(ethylene glycol), poly(ethylene adipate), poly(propylene glycol) and poly(isobutylene) were studied by electron microscopy, in combination with X-ray diffraction works and measurements of thermal properties by DSC and TGA. The crystalline structure of as-prepared complexes was tetragonal and its cell dimensions were a = b = 2.380 nm and c = 1.48 nm. When an as-prepared sample was dried in a vacuum at room temperature, the tetragonal modification was transformed into the monoclinic one with the projected cell dimensions of a = 1.75, b = 1.36 nm and γ = 110°. The transformation occurred by progressive ‘shifting’ of rows of polymer necklaces in the [110] direction along the (110) plane in an original tetragonal lamellar crystal. Complexes lost weight by 10-15% in the process of heating up to 140 °C. The tetragonal crystalline modification was transformed into the hexagonal one, and concurrently, the X-ray diffraction profiles of annealed complexes were broadened. When a sample was dried in a vacuum at room temperature or annealed at high temperatures, followed by exposure to water vapor, the original tetragonal crystalline structure was recovered, restoring the original degree of orientation of crystallites in the sample. When water molecules were removed, the lateral stacking order of γ-CD-polymer complexes was destroyed, but the basic necklace structure in which polymer chains threaded through the cavity of γ-CD rings' structure could be retained.     

Structural and electrical properties of LaNiO3 thin films grown on (1 0 0) and (0 0 1) oriented SrLaAlO4 substrates by chemical solution deposition method

LaNiO₃ thin films were deposited on SrLaAlO₄ (1 0 0) and SrLaAlO₄ (0 0 1) single crystal substrates by a chemical solution deposition method and heat-treated in oxygen atmosphere at 700 °C in tube oven. Structural, morphological, and electrical properties of the LaNiO₃ thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), and electrical resistivity as temperature function (Hall measurements). The X-ray diffraction data indicated good crystallinity and a structural preferential orientation. The LaNiO₃ thin films have a very flat surface and no droplet was found on their surfaces. Samples of LaNiO₃ grown onto (1 0 0) and (0 0 1) oriented SrLaAlO₄ single crystal substrates reveled average grain size by AFM approximately 15–30 nm and 20–35 nm, respectively. Transport characteristics observed were clearly dependent upon the substrate orientation which exhibited a metal-to-insulator transition. The underlying mechanism is a result of competition between the mobility edge and the Fermi energy through the occupation of electron states which in turn is controlled by the disorder level induced by different growth surfaces.     

Polymorphism of syndiotactic poly(p-fluoro-styrene)

Syndiotactic poly(p-fluoro-styrene) (s-PPFS) has been prepared with a polymerization procedure which allows reaching high average molecular masses and satisfactory yields. The polymorphic behavior of the polymer has been mainly studied by X-ray diffraction, calorimetric and infrared analyses. The main crystalline phase of s-PPFS, obtained by melt processing or cold-crystallization, exhibits trans-planar chains, is orthorhombic (a = 9.5 Å, b = 28.7 Å, c = 5.1 Å) and melts at nearly 320 °C. The X-ray analysis shows a strict analogy of this orthorhombic phase with the β phase of s-PS, also as for the occurrence of two limit ordered (β″) and disordered (β′) modifications, which differ for the intensity of reflections characterized by h + k = 2n + 1. A metastable crystalline phase, also exhibiting trans-planar chains, has been observed for as-polymerized samples as well as for amorphous samples crystallized by sorption of toluene or 1,4-difluoro-benzene. Mainly on the basis of solvent sorption and desorption experiments, it is suggested that this metastable phase is a co-crystalline phase with the low-molecular-mass guest molecules.     

Influence of thermal history on primary nucleation and crystal growth rates of isotactic polystyrene

The influence of thermal history on primary nucleation and crystal growth rate of isotactic polystyrene (i-PS) was studied in a wide range of time and temperature. Samples were melted at several temperatures from 230 to 250 °C and then crystallized from those molten states and also crystallized from the glassy state. The primary nucleation rate is strongly influenced by the thermal history but the crystal growth rate is mainly governed by the crystallization temperature. Below a melt temperature of 230 °C, the nucleation density was attributed to the seed nuclei, which result from incomplete melting of the spherulites. Above 250 °C, a limited number of heterogeneous nucleation sites remain, and these sites are activated on the surface of impurities or foreign bodies in the melt. The primary nucleation is controlled heterogeneously both from the molten and the glassy states. The nucleation rate from the glassy state is faster than that from the molten state. A linear relationship between the nucleation rate and the inverse of induction time was found in each experimental condition and their slopes are related to the saturation density of the nuclei. The activation energy for the molecular transport and the primary nucleation energy were smaller than those of the crystal growth. The primary nucleation energy from the glass was lower than that from the melt. These energies are discussed in the present work.     

The porous network in carbon aerogels investigated by small angle neutron scattering

Small angle neutron scattering treated with the Porod approach has been applied to compare the influence of catalysts (C = NaOH, Na₂CO₃ and Ca(OH)₂) on the porous structure of resorcinol-formaldehyde (RF) carbon aerogels. Investigated parameters are the molar ratio (R/C varies from 10 to 800 mol/mol) and the pyrolysis temperature (1050 °C, 1700 °C and 2600 °C).At 1050 °C, carbon aerogels based on NaOH and Na₂CO₃ catalysts provide denser materials than with Ca(OH)₂-based one, due to a three-dimensional network of smaller particles. The density of particles decreases with the amount of catalyst. At 2600 °C the development of an intraparticle microporosity, which is quantified, leads to a slight decrease of the interparticle mesoporosity noticed at 1050 °C. This effect is induced by a stiffness of carbon layers in polyhedral pore walls as illustrated by the feature of the chords length distribution g(r) and TEM micrographs.     

Preparation,structure and properties of comb-branched waterborne polyurethane/OMMT nanocomposites

Comb-branched waterborne polyurethane/organo-montmorillonite (CWPU/OMMT) nanocomposites were prepared by in situ intercalating polymerization process based on the main materials including IPDI, DMPA, polycaprolactone diols, comb-branched polymeric diols and OMMT. The average particle size of emulsion increases and the particle size distribution of emulsion becomes broader with the increase of OMMT content. The results of X-ray diffraction (XRD) and transmission electron microscope (TEM) show that OMMT is homogeneously dispersed into the CWPU matrix with intercalated or exfoliated structure. The properties of CWPU/OMMT nanocomposites are dependent on OMMT content. When the OMMT content is 3 wt%, CWPU/OMMT nanocomposite exhibits excellent overall properties: the particle size of emulsion 63.6 nm, tensile strength 42.0 MPa, E′ 20.3 MPa at 80 °C, water absorption 13% at 24 h and surface contact angle for water over 100°.     

The nucleation and crystallization of MgO-B2O3-SiO2 glass

The nucleation and crystallization of MgO-B₂O₃-SiO₂ (MBS) glass were studied by means of a non-isothermal, thermal analysis technique, X-ray diffraction and scanning electron microscopy. The temperature range of the nucleation and the temperature of the maximum nucleation rate for MBS glass were determined from the dependences of the inverse temperature at the DSC peak (1/T_p) and the maximum intensity of the exothermic DSC crystallization peak ((δT)_p) on the nucleation temperature (T_n). For MBS glass the nucleation occurred at 600-750 °C, with the maximum nucleation rate at 700 °C, whereas the nucleation and crystal growth processes overlapped at 700 °C < T ≤ 750 °C. The analyses of the non-isothermal data for the bulk MBS glass using the most common models (Ozawa, Kissinger, modified Kissinger, Ozawa-Chen, etc.) revealed that the crystallization of Mg₂B₂O₅ was three-dimensional bulk with a diffusion-controlled crystal growth rate, that n = m = 1.5 and that the activation energy for the crystallization was 410-440 kJ/mol.