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61.
We address the problem of correlating the observed FID and T components in wideline 1H relaxation measurements of motionally heterogeneous polymers, and show that different methods of data treatment can highlight different aspects of the correlations present. For a sample of polypropylene we find that the T1ρ relaxation behaviour is driven by relaxation associated with the intermediate FID component, which strongly suggests a motionally inhomogeneous amorphous region in the sample.  相似文献   
62.
The lithium ion conducting solid polymer electrolytes (SPE) based on PVAc-LiClO4 of various compositions were prepared by solution casting technique. Structure and surface morphology characterization were studied by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) measurements, respectively. Thermal and conductivity behavior of polymer-salt complexes were studied by employing differential scanning calorimetry (DSC) and ac impedance measurements, respectively. XRD and SEM analyses indicate the amorphous nature of the polymer-salt complexes. DSC measurements show decrease in Tg with the increase in LiClO4 concentrations. The bulk conductivity of the PVAc:LiClO4 polymer electrolytes was found to vary between 7.6×10−7 and 6.2×10−5 S cm−1 at 303 K with the increase in salt concentration. The temperature dependence of the polymer electrolyte complexes appear to obey Arrhenius law.  相似文献   
63.
The Maxwell-Wagner-Sillars (MWS) relaxation is studied for semi-crystalline polymers poly (ether ether ketone) (PEEK), in the range 20 Hz-1 MHz and temperature varying from 80 to 330 °C. The parameter is the crystallization condition in the case of PEEK, which is a semi-crystalline polymer considered as a particulate composite. The relaxation found in the semi-crystalline polymers above the α relaxation of the PEEK is ascribed to the trapping of conductive carriers at the interface between crystalline lamellae and the amorphous matrix. The study of PEEK microstructure is based on differential calorimetry and X-rays diffraction. Two lamellae populations have been detected, that depends on the crystallization temperature and its duration. The crystallinity rate is increasing with crystallization temperature and duration. In dielectric studies, the use of the electric modulus instead of permittivity allows us to minimize the ionic conduction and then leads to the appearance of the interfacial relaxation. According to our measurements, the crystallinity rate is not the main factor of the interfacial relaxation intensity, which also depends on the nature and degree of perfection of the lamellae.  相似文献   
64.
The performance of many contemporary detergent products critically depends on polymers. Water-soluble polycarboxylates represent an important class of detergent polymers, and their quantitative assessment in detergent matrices stands as a considerable challenge. The presence of high levels of surfactants is a major complication, due to the strong tendency of surfactants to form micelles and to interact with the polymers. First, we addressed critical steps in the subsequent combined use of liquid extraction and off-line size exclusion chromatography-nuclear magnetic resonance (SEC-NMR) for identification and quantification of polycarboxylates in detergent products. Next, the different steps in the off-line SEC-NMR procedure were optimized with respect to precision and accuracy. This resulted in recoveries of more than 80% for maleic acid/acrylic acid copolymers; in detergent products a proportional bias of 30% is achieved. The method showed good precision with a relative standard deviation of within-laboratory reproducibility between 5% and 14%.  相似文献   
65.
Novel family of highly soluble polymers containing 3.3′-bicarbazolyl moieties is reported. Utilizing simple and efficient chemical oxidation of carbazole and its derivatives by iron trichloride exclusively and quantitatively yields the bicarbazolyl dimmers with reactive oxirane groups. The polymers were prepared in polyaddition reaction of bicarbazolyl-containing diepoxydes with 4,4′-thiobisbenzenethiol, 2,5-dimercapto-1,3,4-thiadiazole, or 1,3-benzenedithiol in the presence of catalyst triethylamine. Obtained compounds were characterized using GPC, DSC, IR, UV, fluorescence and 1H NMR spectroscopy. The hole drift mobility reaches 10−4 cm2/Vs at high electric fields. Such processable polymers with conjugated-nonconjugated repeating units in the main chain and good charge carrier mobility are quite promising for fabrication of optoelectronic devices.  相似文献   
66.
Contrary to most or all other materials, crystallization of chiral but racemic polymers such as isotactic polypropylene is accompanied by a conformational rearrangement which leads to helical geometries: the building units of the crystal are helical stems, -20nm long, which can be either right-handed or left-handed. Helical hand cannot be reversed within the crystal structure: it is therefore a permanent marker and an indicator of molecular processes (in particular segregation/selection of helical hands) which take place during crystal growth, and more precisely during the crucial step of “efficient” helical stem deposition. The issue of proper helical hand selection during polymer crystal growth is mainly illustrated with isotactic polypropylene. Its various crystalline polymorphs (, , and smectic) display virtually all possible combinations of helical hands, azimuthal settings and even non-parallel orientation of helix axes in space. Furthermore, a specific homoepitaxy which generates a lamellar branching in the phase “quadrites” and composite structures makes it possible a) to determine the helical hand and associated azimuthal setting of every stem in the crystalline entities and b) to determine the impact on the crystal structure and morphology of “mistakes” in helical hand of the depositing stem. Analysis of these morphologies demonstrates that the crystallization of isotactic polypropylene (and by implication of other achiral, helical polymers) is a highly sequential and “substrate-determined” process, i.e. that the depositing stem probes the topography of the growth face prior to attachment. These observations appear difficult to reconcile with crystallization schemes in which molecules (helical segments) are prearranged in a kind of pseudo-crystalline bundle (and as such, are not subjected to the high constraints of crystal symmetry) before deposition as a preassembled entity on the substrate. Received: 5 May 2000  相似文献   
67.
Ultra thin films of glassy polymers such as polystyrene (PS) can show a) anomalously large thickness changes, b) unexpected dewetting properties, c) large shifts in the glass temperature Tg. The present discussion focusses mainly on point a). A certain cascade of metastable states is presented together with (tentative) explanations. Received 1 March 2001 and Received in final form 10 May 2001  相似文献   
68.
Reaction of iron(II) thiocyanate with 4,4‐bipyridine (bipy) in methanol leads to the formation of three new solvates of different composition depending on the reaction conditions: At room temperature two new ligand‐rich 1:2 (1:2 = ratio between metal and N‐donor ligand) polymorphic forms [Fe(NCS)2(bipy)2 · 2MeOH]n ( 1I ) and [Fe(NCS)2(bipy)(MeOH)2 · (bipy)]n ( 1II ) are obtained, whereas solvothermal conditions leads to the formation of the new ligand‐deficient 1:1 compound [{Fe(NCS)2(bipy)(MeOH)}2]n ( 2 ). All crystal structures were determined by X‐ray single crystal structure analysis. In the crystal structure of modification 1I the metal atoms are coordinated by four bridging bipy ligands, which connect them into layers. The methanol molecules occupy voids in the structure. Compared to 1I in modification 1II the crystal structure contains of linear Fe–bipy–Fe chains, which are further connected by hydrogen bonds between coordinating MeOH and noncoordinated bipy ligands into layers. The ligand‐deficient 1:1 compound 2 shows a completely different coordination topology with linear Fe–bipy–Fe chains, which are connected by coordinating methanol molecules into double‐chains. In all compounds the thiocyanato anions are terminal N‐bonded to the metal atoms. Investigation of the thermal behavior of compound 1I shows a two‐step decomposition, in which ligand‐deficient intermediates are formed. Magnetic measurements on 1I reveal Curie–Weiss paramagnetism with increasing antiferromagnetic interactions on cooling.  相似文献   
69.
A mixed‐polymeric electrokinetic chromatography system has been developed for the simultaneous determination of a contaminant like oversulfated condroitin sulfate (OSCS) and impurities expressed as dermatan (Der) in heparin (Hep) samples. The EKC system consisted of 0.5% w/v polymeric β‐CD, 0.4% w/v tetronic® 1107 and 400 mM tris‐phosphate buffer at pH 3.5. The optimized electrophoretic conditions included the use of an uncoated‐silica capillary of 50 cm of total length and 75 μm id, an applied voltage of ?7 kV, a temperature of 30°C and 200 nm UV‐detection. The highly sensitive method developed showed low values of LOD, 0.07% w/w (0.07 μg/mL) (OSCS) and 0.1% w/w (0.1 μg/mL) (Der), and values of LOQ 0.2% w/w (0.2 μg/mL) (OSCS) and 0.3% w/w (0.3 μg/mL) (Der) with a concentration level of Hep sample as low as 0.1 mg/mL. Additional parameters of validation such as specificity, linearity, accuracy, and robustness were evaluated according to international guidelines. Owing to its simplicity, high sensitivity, and reliability, the proposed method can be an advantageous alternative to the traditional methodologies for the analysis of Hep in raw material and specially in finished products because of the low amounts of Hep sample required.  相似文献   
70.
We fabricated microstructures and micro craters in thin films and bulk of PS. To the best of our knowledge, this is the first report of the emission from fs laser modified regions of PS when excited at 337, 400, 458, 488 and 514 nm wavelengths with different emission peaks. We systematically studied the emission in context of formation of optical centers and analyzed the spectra of irradiated PS. Change in the excitation wavelength leads to a shift in the emission peak, whereby, we infer that the emission should be due to a myriad of optical centers. Interestingly these optical centers have a similar excitation spectrum. Diphenylbutadiene (DPBD) is probably the main optical center among other optical centers thus formed in the process of fs laser irradiation of PS.  相似文献   
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