Phase behaviour of poly(benzophenoneimide)s having n-alkyloxymethyl side chains

A series of poly(benzophenoneimide)s (C_m-BP-PIs) having n-alkyloxymethyl side chains (−CH₂O-n-CmH_2m+1, m = 4, 6, 8) have been examined by X-ray diffraction, differential scanning calorimetry (DSC) and polarizing optical microscopy. The samples showed basically two phase transitions and both transition temperatures decreased with increasing side chain length. The first transitions were ascribed to glass transitions and the second ones were assigned to liquid crystal-to-isotropic transitions. Eicosane (n-C₂₀H₄₂) which is chemically very similar to the side chain was miscible with the side chains of C₈-BP-PI, which induced depression of the glass transition temperature. Received: 17 February 1997/Revised: 1 April 1997/Accepted: 4 April 1997     

Synthesis,thermal, and photo alignment behavior of polyethylene imines having nitro substituent azobenzene side chain group

Polyethylene imines having nitro substituent azobenzene side chain group with different methylene spacer groups (PEImN) were successfully synthesized and characterized by differential scanning calorimetry, polarized optical microscopic, and X‐ray diffraction analysis. All synthesized polyethylene imines showed liquid crystalline properties and the glass transition temperature (Tg) of PEImN decreased as the number of methylene spacers increased. Melting temperatures (Tm) of synthesized PEImN showed an odd‐even effect. Photochemical, thermo‐optical, as well as photo alignment behavior of PEImN were investigated and out‐of‐plane orientational behavior of polymeric films was dependent on number of methylene spacers and polyethylene imines having higher number of methylene spacers (six or more) showed high order parameter values that revealed the well pronounced tendency for the development of out‐of‐plane order from random state on annealing. And the molecular orientation of PEImN between random and out‐of‐plane structures has been achieved by the combination of thermal and photochemical processes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Transformation of C70 peapods into double walled carbon nanotubes

X-ray diffraction studies comparing the transformation of C₆₀ and C₇₀ peapods into double walled carbon nanotubes are presented. The structures of the as-formed DWCNTs are strikingly similar, showing that they are not dependent on the nature of the fullerene precursor. High temperature X-ray diffraction measurements of C₇₀ peapods below the coalescence temperature show that confined C₇₀ molecules in large tubes undergo an orientational transition to free rotations. Fast re-orientations of C₇₀ molecules allow cyclo-addition between adjacent fullerenes to form, in good agreement with the mechanism of coalescence proposed in the literature for C₆₀ molecules.     

Synthesis of pure Cu2O thin layers controlled by in-situ conductivity measurements

An easy synthesis route for cuprous oxide (Cu₂O) nanoparticles is reported via thermal annealing improved and controlled by in-situ conductivity measurements. The crystalline structure, phase transition, surface morphology and particle size/shape, were investigated through X-ray diffraction, a conductivity setup and scanning electron microscopy, respectively. X-ray diffraction patterns revealed that initial metallic Cu nanoparticles were transformed to Cu₂O nanoparticles with high purity, under specific conditions critically dependent on the temperature and annealing duration. This transformation was also dependent on the film thickness and atmospheric composition in the test chamber during the annealing process.     

Aliphatic acid esters of (2-hydroxypropyl) cellulose—Effect of side chain length on properties of cholesteric liquid crystals

A series of aliphatic acid esters of (2-hydroxypropyl) cellulose (C_nPC) were synthesized via the esterification of aliphatic acid chloride and (2-hydroxypropyl) cellulose (HPC). The liquid crystalline (LC) phases and transitions were investigated using differential scanning calorimetry, wide-angle X-ray diffraction (WAXD), and polarized light microscope (PLM) techniques. This series of C_nPC polymers exhibited characteristic features of cholesteric LC phases between their glass transition and isotropization temperatures. The cholesteric LC characteristics were studied utilizing an ultraviolet/visible/near infrared spectrometer in a reflection mode. It was confirmed that, with an increase in the number of methylene units in the side chains of this series of C_nPC polymers, there was an increase, on the scale of nanometers, in the layer spacing values for the cholesteric LC phases measured by WAXD. This periodic layer spacing represents the thickness of the neighboring twisted layers in a helical structure. Based on a unique significant red shift of the maximum reflection peak for the LC phases in this series of C_nPCs, it is evident that the pitch distance in the helical structure also increases with an increase in the length of methylene units in the side chains.     

Effect of different post-annealing durations on electromagnetic properties of La0.67Ca0.33MnO3:Ag0.2 thin films prepared by pulsed laser deposition

La_0.67Ca_0.33MnO₃:Ag_0.2 thin films were obtained by pulsed laser deposition followed by post-annealing at 1200 °C for varied durations. Surface morphologies, structures, and electrical and magnetic properties of films prepared with different annealing durations were significantly different. X-ray diffraction results showed that annealed films exhibited stronger diffraction peaks and C-axis preferred growth. Regarding their electrical properties, metal-insulator transition temperature (T_MI) and temperature coefficient of resistance (TCR) increased first and then decreased with the increase in annealing duration. In terms of their magnetic properties, thin films displayed ferromagnetic-paramagnetic transition. With the increase in annealing duration, Curie temperature increased first and then decreased. Specifically, the film annealed for 3 h showed excellent electromagnetic properties, with relatively high TCR of 20.3%·K^-1 and near room temperature T_MI of 285.7 °C. Owing to these excellent properties, as-prepared thin films have application potential in infrared detectors.     

Biaxial orientation of poly(vinyl chloride) compounds Part 2 –Structure–property relationships and their time dependency

Abstract

X-ray diffraction and thermomechanical analysis have been used, respectively, to examine structural order and shrinkage behaviour for oriented samples of rigid and flexible poly(vinyl chloride) (PVC). Results were compared with previously measured tensile properties and structure–property relationships explored. X-ray diffraction showed that drawing produces planar crystallite orientation in PVC sheets. If drawing and subsequent annealing conditions are held constant, but draw ratio is varied, there is good correlation between structural order measured by X-ray diffraction and tensile strength. Increased annealing time and temperature improve crystallite order and dimensional stability, while tensile strength is unchanged. The greatest enhancement in tensile strength is achieved by stretching PVC towards its maximum draw ratio at 90°C, but optimum thermal stability of the oriented structure is achieved when higher annealing temperatures are used. Room temperature recovery is observed for flexible PVC when the material has a glass transition temperature below ambient. This can be delayed by increased annealing time and temperature, and by increased draw ratio.     

Polymorphism and transformation energetics of saturated monoacid triglycerides from differential scanning calorimetry and theoretical modeling

Differential scanning calorimetry studies on saturated monoacid triglycerides were extended to include most odd and even chain lengths from tricaprylin (C₈) through tritriacontanoin (C₃₀). Two β’-forms were common with triglycerides C₁₅ through C₂₄: shorter odd chain length triglycerides (C₉-C₁₃) exhibited only one β’-form; short even chain length triglycerides (C₈-C₁₄) exhibited three. Odd chain length C₂₁ and C₂₃ triglycerides showed two β-forms. Triglycerides of even chain lengths greater than C₂₁ produced two α-forms. Apparent energies of phase excitation for α-form transformations (determined from scans at different heating rates) showed odd-even alternation for short chain lengths, but increased linearly with chain length above C₁₄, evidencing the importance of extended chain conformation and interactions as determinants of polymorph properties. Changes in melting point patterns, particularly for β’ and β-forms, at C₁₄ correlated with the change in apparent phase excitation energy. Comparisons of X-ray data with dimensions from space-filling models and agreement between observed entropies of fusion and values calculated for probabilistic models also emphasize the importance of extended chain conformation and suggest configurational differences, and possibly different polymorph conversion pathways for odd versus even chain length triglycerides.     

Polymorphism and intersolubility of some palmitic,stearic and oleic triglycerides: PPP,PSP and POP

The polymorphism and intersolubility of a series of palmitic, stearic and oleic triglycerides have been investigated in order to understand the thermal properties of fractions of natural fats. Results are shown for tripalmitin (PPP), 2-stearo-dipalmitin, (PSP) and 2-oleo-dipalmitin (POP); these molecules differ essentially in the number of carbons (P→S) and the degree of unsaturation of chains (S→O). The different polymorphic forms have been verified by variable temperature X-ray powder diffraction. The organization of the fatty acid carbon chains in the most stable polymorphic form(β′ or β) has been studied by variable temperature NMR spectroscopy by means of the protons relaxation times T₁, T₂ and T_1?. The construction of binary phase diagrams (PPP-PSP and PPP-POP), from the data obtained by differential scanning calorimetry and X-ray powder diffraction, shows the formation of solid solutions or monotectic interactions, according to the nature and the polymorphic form of the triglycerides. The kinetic of the very importantβ′→β transition has been analyzed by variable temperature powder X-ray diffraction for PPP, and [PPP-PSP] or [PPP-POP] blends. The molecular interactions occurring between the mixed crystals have been explained, by applying the model of Avrami and by an empirical isolation method.     

Long terminal linear alkyl group as internal crystallization accelerating moiety of poly(l-lactide)

Poly(l-lactide) (PLLA) polymers having terminal n-alkyl groups with a wide variety of lengths (C₀–C₂₂) were synthesized by ring-opening polymerization of l-lactide in the presence of coinitiators of l-lactic acid (C₀), 1-hexanol (C₆), 1-dodecanol (C₁₂), and 1-docosanol (C₂₂) and their segmental mobility and non-isothermal and isothermal crystallization behavior were investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffractometry (WAXD). Glass transition and cold crystallization temperatures of melt-quenched samples during heating decreased with an increase in the length of terminal n-alkyl groups. The enhanced PLLA segmental mobility and hydrophobic interaction-based accelerated PLLA nucleation by the presence of terminal long n-alkyl groups should have caused the accelerated non-isothermal and isothermal crystallization of PLLA segments traced by cold crystallization temperature during heating and by radial growth rate of spherulites, respectively. The crystallization accelerating effect became higher with the length of terminal n-alkyl groups. The effects of the length of terminal n-alkyl group on the crystalline growth mechanism of PLLA at the lowest crystallizable temperature was insignificant, whereas the effects of the length of terminal n-alkyl group on the nucleation mechanism of PLLA chains were significant and insignificant for PLLA having M_n of 6–7 × 10³ of 2 × 10⁴ g mol⁻¹, respectively. WAXD measurements revealed that the transition crystallization temperature at which crystalline modification changes from δ-form to α-form was affected by the length of terminal n-alkyl group for PLLA having M_n of 6–7 × 10³ g mol⁻¹, but was not altered by the length of terminal n-alkyl group for PLLA having M_n of 2 × 10⁴ g mol⁻¹.     

Phase formation and microstructure evolution of plasma sprayed Cr2AlC MAX phase coatings under post annealing

In this study, thick Cr₂AlC coatings were first synthesized via plasma spraying of Cr₃C₂–Al–Cr agglomerated powders and post annealing. The microstructure evolution and mechanical properties of the Cr₂AlC coatings annealed at 500–1000 °C were investigated. The as-sprayed coatings exhibited a lamellar structure, primarily consisting of Cr₂AlC, Cr₇C₃, Cr₂₃C₆, and (Cr, Al)C_x solid solutions. The short residence time during spraying led to incomplete reactions in the Cr₃C₂@Al–Cr agglomerates, resulting in the formation of (Cr, Al)C_x. Post annealing provided sufficient energy for the transition of (Cr, Al)C_x → Cr₂AlC. With an increase in the annealing temperature (<900 °C), gradual transition of the (Cr, Al)C_x phase led to a slight increase in the Cr₂AlC content, and thus, the as-annealed coatings maintained high hardness (>1000 HV_0.2) with improved fracture toughness. Higher annealing temperatures (>900 °C) promoted clear enhancement of the Cr₂AlC content, thus reducing the coating hardness. The transition phase (Cr, Al)C_x and high temperature annealing were the primary factors to promoting the formation of the Cr₂AlC phase in sprayed coatings. This study indicates that the Cr₃C₂@Al–Cr agglomerates can be effective alternatives to expensive MAX phase powders as feedstock for plasma spraying of Cr₂AlC coatings.     

Structural change in the Brill transition of Nylon m/n (1) Nylon 10/10 and its model compounds

Structural changes in the Brill transitions of Nylon 10/10 and its model compounds have been investigated by carrying out the temperature-dependent measurements of X-ray diffraction and infrared spectra along with the DSC measurement. The crystal structure at room temperature was found to be the so-called α form with the all-trans zigzag methylene segments. When the samples were heated, the infrared progression bands of the methylene segments, which are sensitive to the length of all-trans segmental parts, were found to change their spectral patterns in the transition temperature region: the progression bands decreased in intensity and disappeared above the transition region. At the same time several new bands were observed to appear, which were found to correspond to the progression bands of (CH₂)₇-(CH₂)₅trans-zigzag segments. These spectral changes indicate that the methylene segments were conformationally disordered by an invasion of some gauche bonds and as a result the effective length of trans-zigzag segments became shorter. This conformational disordering was found to occur more remarkably in the methylene segment of NH-(CH₂)₁₀-NH part than the CO-(CH₂)₈-CO part. At the same time the infrared bands of amide groups, in particular the bands sensitive to the twisting angles about the CH₂-amide bonds were found to show the remarkable change, indicating the local conformational change from planar-zigzag to twisted form in the CH₂-amide moiety. The frequency shift of amide A band (NH stretching mode) indicated a weakening of intermolecular hydrogen bonds, which however, did not disappear up to the melting region. From these data combined with the X-ray diffraction data, the structural disordering in the Brill transition phenomena was deduced concretely.     

Synergistic effect of alkyl lactate functional groups on properties of methacrylate polymers

In this work, four novel different alkyl lactate methacrylate monomers were synthesized through azeotropic esterification method by reacting methyl, ethyl, propyl and butyl lactates with methacrylic acid. The prepared monomers were polymerized through solution polymerization technique and both monomers and polymers were analyzed by FTIR, ¹H NMR and ¹³C NMR spectroscopy techniques to elucidate the structure and to confirm their formation. Increasing the number of methylene units in alkyl lactate side chain decreases the glass transition temperature (T_g) of the polymers. Average molecular interchain spacing (〈R〉) of polymers was obtained from the wide-angle X-ray diffraction measurement and the values ranged from 6.26 to 7.18 Å based on the length of alkyl lactate group. The prepared polymers showed hygroscopic property and their moisture absorption was in the range of 10–24% (w/w) depending upon the length of alkyl lactate moiety, relative humidity and time. These polymers have the potential for hydrogel applications owing to their increased moisture absorption capacity. Both polymethyl and propyl lactate methacrylate showed two distinct and prominent thermal degradations whereas polyethyl and butyl lactate methacrylates showed only a single distinct and prominent thermal degradation step. An interesting result of as-synthesized polymers showed odd–even chain length effect in the properties of 〈R〉, moisture uptake and thermal stability.

     

The polymorphism of odd and even saturated single acid triglycerides,C8–C22

The polymorphism of single fatty acid odd triglycerides, C₁₁ through C₁₇ has been reinvestigated, with extension of the study to C₉, C₁₉ and C₂₁. With study of the even glycerides C₈, C₂₀ and C₂₂ it has been possible to review the whole series (odd and even) C₈ through C₂₂. The odd glycerides resemble the even in showing three distinct melting levels. Lowest melting forms are α. Stable forms are β except for C₉ and C₁₁ which show a different structure type. Intermediate melting β′ forms of odd glycerides are substantially more stable than their even counterparts as well illustrated by differential thermal analysis. There are no vitreous forms. Alternation in mp (between odd and even) is confirmed for stable phases and nonalternation for α and (within experimental error) for β′. Both β′ and β long spacings show alternation but not α. Alternation is evident in the short spacings of β′ and β forms. While short spacings of β′ forms of even triglycerides are much alike especially for C₁₄ through C₂₂, those of odd glycerides show a fortuitous 4-carbon cycle. This appears to involve no significant structural variation as chain length increases but simply an approximate 4-carbon cycle of variation in diffraction details derived from the presumed unvarying 0 ⊥ type subcell structure.     

The structure of a cyanobiphenyl side chain liquid crystalline poly(silylenemethylene)

The structure of a side chain liquid crystalline poly(silylenemethylene) (-(SiCH₃R-CH₂)-: R=O(CH₂)₁₁O-Ph-Ph-CN, Ph=phenyl) (CN-11) has been studied by X-ray diffraction and differential scanning calorimetry (DSC). The DSC results showed that CN-11 has transitions at ∼92 °C (T₂) and ∼147 °C (T₁) during both cooling and immediate heating. A third transition occurred at ∼50 °C (T₃) during heating after annealing at room temperature. The X-ray fiber pattern of the CN-11 annealed at room temperature showed several wide and small angle reflections which were indexed by a monoclinic unit cell with parameters a=16.8 Å, b=7.42 Å, c=43.6 Å and β=102.1° (b: fiber direction), representing a crystal structure with layer thickness of ∼43 Å. Upon heating at T₃, the crystal structure became less ordered (but somewhat more ordered than smectic A (S_A) and smectic C (S_C)). This was followed by S_A (or S_C) phase at T₂, and ultimately an isotropic state (I) at T₁. The observed layer thickness (∼43 Å) is about ∼1.5 times the most extended side chain length, indicating a double-layer structure with tilted or interdigitated side chains. The X-ray fiber pattern had a four-point pattern at d=4.52 Å, suggesting that the side chains in the crystal are likely to be tilted by 56° from the polymer fiber axis.     

Influence of third monomer on the crystal phase transition behavior of ethylene-tetrafluoroethylene copolymer

Crystal phase transition between the low- and high-temperature phases has been investigated for ethylene (E)-tetrafluoroethylene (TFE) alternating copolymer (ETFE) containing the third monomeric species by the temperature dependent measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) and differential scanning calorimetry. Nonafluoro-1-hexene (NFH) and hexafluoropropylene (HFP) were chosen as the third monomers, where they are different in the side-branch length, -(CF₂)₃CF₃ and -CF₃, respectively. In the case of E/TFE/NFH copolymer (ET-C4F9), the crystal phase transition temperature of the original ETFE two-components copolymer was not very much affected by the existence of NFH in the range of NFH content from 0.7 to 3 mol%. Contrarily, the crystal phase transition temperature of E/TFE/HFP copolymer (ET-CF3) was found to decrease drastically with increasing HFP content. The melting temperature and the higher-order structure were also affected sensitively depending on the HFP content. This difference in phase transition behavior between ET-C4F9 and ET-CF3 copolymers is reasonably interpreted as follows: the short side groups (-CF₃) of HFP monomeric unit are included in the crystal lattice of E/TFE chains and the unit cell is expanded gradually with an increment of the HFP content, resulting in the decrease in phase transition point because of easier thermal motion of the chains. On the other hand, the long side groups [-(CF₂)₃CF₃] of NFH monomeric units are excluded out of the crystal lattice and located on the lamellar surfaces or in the amorphous region and do not affect very much the phase transition temperature even when the NFH content is increased. In association with such a change in crystal structure, the long period of stacked lamellar structure was found to decrease remarkably in the case of NFH, whereas it does not change very much for HFP, consistent with the interpretation of the above-mentioned WAXD data.     

Nematic-like mesophase photoconductive polymer for photorefractive applications

A new nematic-like mesophase photoconductive polymer PPT-TPA consisting of wholly aromatic rigid backbone of poly(p-phenyleneterephthalate), PPT and pendent hole-transporting triphenylamine (TPA) groups attached to the ends of oxydecyl spacers has been synthesized. The photorefractive composite contains the photoconductor PPT-TPA, the chromophore diethylaminodicyanostyrene (DDCST), and the photosensitizer C₆₀. Although no plasticizer was added, the glass transition temperature T_g of the composite is 15 °C, which characterizes it as a low-T_g photorefractive material. We investigate the correlation between the mesophase structure and its optical/physical properties by X-ray diffraction, photoconductive and photorefractive experiments. The new composite and its properties are compared to PPT-CZ composites with only a different charge transporting agent (carbazole, CZ) but a much more ordered mesophase structure, which were studied previously and have shown very good photorefractive properties. Despite of a lower photoconductivity of the new photorefractive composite PPT-TPA (n=10):DDCST:C₆₀ this material shows a higher photorefractive sensitivity S_n2 of 2±0.2 cm²/kJ at E=50 V/μm than the previously synthesized composite PPT-CZ (n=10):DDCST:C₆₀.     

Microstructure,optical, electrical properties,and leakage current transport mechanism of sol–gel-processed high-k HfO2 gate dielectrics

Deposition of high-k HfO₂ gate dielectric films on n-type Si and quartz substrates by sol–gel spin-on coating technique has been performed and the structural, optical and electrical characteristics as a function of annealing temperature have been investigated. The structural and optical properties of HfO₂ thin films related to annealing temperature are investigated by X-ray diffraction (XRD), ultraviolet–visible spectroscopy (UV–vis), and spectroscopic ellipsometry (SE). Results indicate that the monoclinic form of HfO₂ appears when temperature rises through and above 500 °C. The reduction in band gap is observed with the increase of annealing temperature. Moreover, the increase of refractive index (n) and density and the decrease of the extinction coefficient with the increase of annealing temperature are obtained by SE measurements. Additionally, the electrical properties based on Al/Si/HfO₂/Al capacitor are analyzed by means of the high frequency capacitance–voltage (C–V) and the leakage current density–voltage (J–V) characteristics. And the leakage current conduction mechanisms as functions of annealing temperatures are also discussed.     

Sperm whale oil analysis by gas chromatography and mass spectrometry

Gas liquid chromatography of winterized sperm oil showed that its wax esters with even carbon numbers range from C₂₄ to C₄₂ and are present in quantities resembling a normal distribution curve with C₃₄ as the mean. Between these even-numbered wax esters, ones with odd chain lengths were eluted. Triglycerides, similarly present in a normal distribution pattern, ranged from C₄₂ to C₅₈ and also included traces of odd chain species. The component acids and alcohols were analyzed by gas chromatography-mass spectrometry, and double bond positions in the monoenoid components were established. Branched chain and odd chain constituents, both saturated and unsaturated, were detected among both alcohols and acids. These moieties, when combined with those having even chains, are responsible for the wax esters and triglycerides with odd carbon numbers. ARS, USDA.