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1.
Starch belongs to the polyglucan group. This type of polysaccharide shows a broad β-relaxation process in dielectric spectra at low temperatures, which has its molecular origin in orientational motions of sugar rings via glucosidic linkages. This chain dynamic was investigated for α(1,4)-linked starch oligomers with well-defined chain lengths of 2, 3, 4, 6, and 7 anhydroglucose units (AGUs) and for α(1,4)-polyglucans with average degrees of polymerization of 5, 10, 56, 70, and so forth (up to 3000; calculated from the mean molecular weight). The activation energy (Ea) of the segmental chain motion was lowest for dimeric maltose (Ea = 49.4 ± 1.3 kJ/mol), and this was followed by passage through a maximum at a degree of polymerization of 6 (Ea = 60.8 ± 1.8 kJ/mol). Subsequently, Ea leveled off at a value of about 52 ± 1.5 kJ/mol for chains containing more than 100 repeating units. The results were compared with the values of cellulose-like oligomers and polymers bearing a β(1,4)-linkage. Interestingly, the shape of the Ea dependency on the chain length of the molecules was qualitatively the same for both systems, whereas quantitatively the starch-like substances generally showed higher Ea values. Additionally, and for comparison, three cyclodextrins were measured by dielectric relaxation spectroscopy. The ringlike molecules, with 6, 7, and 8 α(1,4)-linked AGUs, showed moderately different types of dielectric spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 188–197, 2004 相似文献
2.
3.
Der‐Jang Liaw Ching‐Cheng Huang En‐Tang Kang 《Journal of polymer science. Part A, Polymer chemistry》2006,44(9):2901-2911
Diblock copolymers of 5‐(methylphthalimide)bicyclo[2.2.1]hept‐2‐ene (NBMPI) and 1,5‐cyclooctadiene were synthesized by living ring‐opening metathesis polymerization with a well‐defined catalyst {RuCl2(CHPh)[P(C6H11)3]2}. Unhydrogenated diblock copolymers showed two glass transitions due to poly(NBMPI) and polybutadiene segments, such as two glass‐transition temperatures at ?86.5 and 115.3 °C for poly 1a and ?87.2 and 115.3 °C for poly 1b . However, only one melting temperature could be observed for hydrogenated copolymers, such as 119.8 °C for poly 2a and 121.7 °C for poly 2b . The unhydrogenated diblock copolymer with the longer poly(NBMPI) chain (poly 1a ; temperature at 10% mass loss = 400 °C) exhibited better thermal stability than the one with the shorter poly(NBMPI) chain (poly 1b ; temperature at 10% mass loss = 385 °C). Two kinds of hydrogenated diblock copolymers, poly 2a and poly 2b , exhibited relatively poor solubility but better thermal stability than unhydrogenated diblock copolymers because of the polyethylene segments. Poly[(hydrochloride quaternized 2‐norbornene‐5‐methyleneamine)‐b‐butadiene]‐1 (poly 3a ) was obtained after the hydrolysis and quaternization of poly 1a . Dynamic light scattering measurements indicated that the hydrodynamic diameters of the cationic copolymer (poly 3a ) in water (hydrodynamic diameter = 1580 nm without salt), methanol/water (4/96 v/v; hydrodynamic diameter = 1500 nm without salt), and tetrahydrofuran/water (4/96 v/v; hydrodynamic diameter = 1200 nm without salt) decreased with increasing salt (NaCl) concentration. The effect of temperature on the hydrodynamic diameter of hydrophobically modified poly 3a was also studied. The inflection point of the hydrodynamic diameter of poly 3a was observed at various polymer concentrations around 30 °C. The critical micelle concentration of hydrophobically modified poly 3a was observed at 0.018 g dL?1. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2901–2911, 2006 相似文献
4.
Optogalvanic spectra of some 30 transitions of calcium originating from the ground state as well as from several excited states (4s4p 1,3P, 4s3d 1,3D, 4s5p 3P, 3d4p 3D, 3F) have been investigated using laser-irradiation of a low-current glow discharge in a thermionic diode. The influence of various experimental parameters such as bias field, oven temperature and buffer gas pressure on the spectra are reported. Seven previously unreported transitions are recorded including four forbidden transitions which violate the J selection rules. An interesting anomaly observed in the non-statistical population of the 4s3d 3D3,2,1 multiplet is discussed where the populations of 3D3:3D2:3D1 are in the ratio of 94:5:1. A possible explanation is based on avoided crossing between potential energy curves of the Ca-Ar molecule. 相似文献
5.
Monitoring of the shrinkage during the photopolymerization of acrylates using hyphenated photorheometry/near‐infrared spectroscopy
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This article describes a new method for the quantitative determination and time‐resolved monitoring of the polymerization shrinkage during ultraviolet (UV) photopolymerization. It is based on rheometry using a modified oscillating rheometer. Shrinkage is determined from the decrease of the gap between the rheometer plates. Moreover, near‐infrared (NIR) spectra can be recorded directly in the rheometer, which allows continuous determination of the conversion at any time of a shrinkage measurement. As both shrinkage and conversion data come from the same experiment, shrinkage can be analyzed in dependence on the current conversion achieved during UV irradiation, which enables direct investigation of correlations between both parameters. Hyphenated photorheometry/FT‐NIR spectroscopy was used for the determination of the polymerization shrinkage of pure acrylate monomers and oligomers as well as acrylate‐based formulations. Quantitative shrinkage values were found to be in excellent correlation with data that were determined by an independent method (via buoyancy measurements) and data from literature. Furthermore, the effect of ambient and irradiation conditions or the content of nanoparticles on the degree of shrinkage was studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 729–739 相似文献
6.
Sergey V. Nikitin Dmitriy A. Parkhomenko Mariya V. Edeleva Elena G. Bagryanskaya 《Journal of polymer science. Part A, Polymer chemistry》2015,53(21):2546-2556
Simulation on the kinetic scheme of enhanced spin capturing polymerizations (ESCP) were performed to reveal the influence of different parameters, e.g., initiation rate, spin capturing and side reactions on the properties (the monomer conversion, degree of polymerization, polydispersity index, and the fraction of “living” chains) of polymer obtained. The kinetic scheme of ESCP was solved numerically as well as the method of statistical moments of molecular weight distribution was applied to get some numerical expressions for analysis. The simulations showed that fast initiation rate can lead to decrease of living fraction and broadening of molecular weight distribution. Whereas high rate of spin capturing makes the polymer chains shorter but increases living character. And side reactions always decrease livingness of the polymer obtained. Finally in the case of absence of side reaction we were able to formulate criteria for formation of polymer with target molecular weight and quota of living chains via ESCP process. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2546–2556 相似文献
7.
The ohmic contact characteristics of Au/Pt/Ti on degenerated doped n-GaAs were evaluated. Structural and electrical properties
were studied by means of X-ray diffraction (XRD), Auger Energy Spectrum (AES) and a HP4145B parameter analyzer. The structural
analysis revealed a TiAs phase in the interface between metal multilayer and GaAs at higher annealing temperatures. Electrical
measurement showed a minimum ohmic contact resistance of 3×10-4 Ω cm2. The dominant current mechanism was found to be thermionic emission with a barrier height of Φb, of 0.09 V by comparing the experimental data with different theoretical models.
Received: 14 December 2001 / Accepted: 4 April 2002 / Published online: 22 November 2002
RID="*"
ID="*"Corresponding author. Fax: +86-21/6226-4397, E-mail: zhoujian999@163.net 相似文献
8.
N. I. Boiko V. P. Shibaev M. Kozlovsky 《Journal of Polymer Science.Polymer Physics》2005,43(17):2352-2360
Narrow fractions of a side‐chain acrylate oligomer/polymer with phenyl benzoate side chains are separated in a broad range of the degree of polymerization (7 ≤ Pw ≤ 149). An examination of the phase behavior of the obtained fractions has shown that only the longer macromolecules can form the two‐dimensional K (TDK) mesophase, whereas oligomers of a shorter main chain form the conventional nematic phase only. A critical Pw value has been observed to be necessary for the TDK mesophase formation. The temperatures and enthalpies of liquid‐crystalline phase transitions have been studied as a function of the molar mass, and the phase‐growth kinetics for the TDK phase have been studied with an Avrami treatment. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2352–2360, 2005 相似文献
9.
Kamil Kaminski Marian Paluch R. Wrzalik Jerzy Ziolo Radoslav Bogoslovov C. Michael Roland 《Journal of polymer science. Part A, Polymer chemistry》2008,46(11):3795-3801
The polymerization and crosslinking of tetraethylene glycol dimethacrylate were induced by high pressure. The product was analyzed by both swelling experiments and broadband dielectric spectroscopy to determine the structure, with IR measurements used to follow the extent of reaction and its temperature dependence. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3795–3801, 2008 相似文献
10.