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61.
Melting points in mixtures of a crystallizable polymer
with a low-molar-mass diluent depend on both, the diluent
fraction and the crystal thickness. A differentiation of the two
factors can be achieved by temperature-dependent SAXS
experiments. A corresponding study, complemented by DSC,
dilatometry, microscopy and AFM-imaging, was carried out for
mixtures of a poly(ethylene-co-octene) with
n-C16H34,
c-C16H32
and methyl-anthracene, respectively. All diluents lead for a
constant crystal thickness to melting point depressions in
agreement with Raoult's law. On the other hand, the effect of
the diluents on the thickness of the crystals formed at a fixed
crystallization temperature varies. While in the presence of the
two alkanes thicker crystals form, no effect arises for the
methyl-anthracene—as was previously found for the
octene-co-units. We consider these observations as a further
support for our view that polymer crystallization follows a
multi-stage route which includes a passage through an
intermediate mesomorphic phase. Under such conditions crystal
thicknesses would only be affected if the diluent is still
present in the mesomorphic phase and stay invariant if the
diluent molecules are already rejected when this intermediate
phase forms. 相似文献
62.
O.V. Borisov F. Hakem T.A. Vilgis J.-F. Joanny A. Johner 《The European physical journal. E, Soft matter》2001,6(1):37-47
We present a scaling theory for the adsorption of a weakly charged polyelectrolyte chain in a poor solvent onto an oppositely
charged surface. Depending on the fraction of charged monomers and on the solvent quality for uncharged monomers, the globule
in the bulk of the solution has either a spherical conformation or a necklace structure. At sufficiently high surface charge
density, a chain in the globular conformation adsorbs in a flat pancake conformation due to the Coulombic attraction to the
oppositely charged surface. Different adsorption regimes are predicted depending on two screening lengths (the Debye screening
length monitored by the salt concentration and the Gouy-Chapman length monitored by the surface charge density), on the degree
of ionization of the polymer and on the solvent strength. At low bulk ionic strength, an increase in the surface charge density
may induce a transition from an adsorbed necklace structure to a uniform pancake due to the enhanced screening of the intra-chain
Coulombic repulsion by the counterions localized near the surface.
Received 12 April 2001 相似文献
63.
We address the problem of correlating the observed FID and T1ρ 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
64.
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
65.
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
66.
Ilona Visser Monique Klinkenberg Peter Hoos Hans-Gerd Janssen John van Duynhoven 《Analytica chimica acta》2009,654(1):40-44
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
67.
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
68.
B. Lotz 《The European physical journal. E, Soft matter》2000,3(2):185-194
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
69.
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
70.
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