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  • 1995-1999  (350)
  • 1980-1984  (615)
  • 1998  (350)
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  • Physics  (816)
  • Gas chromatography
  • Nuclear reactions
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of biomedical science 5 (1998), S. 415-420 
    ISSN: 1423-0127
    Keywords: Isoprostanes ; Oxidative stress ; Lipid peroxidation ; Gas chromatography ; Mass spectrometry ; Human disease
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The development of a specific, reliable and noninvasive method for measuring oxidative stress in humans is essential for establishing the role of free radicals in human diseases. Currently, accurate techniques to assess oxidant injury in vivo are extremely limited although a number of approaches are being investigated. Of these, the measurement of specific products of nonenzymatic lipid peroxidation, the F2-isoprostanes (F2-IsoPs), appears to be a more accurate marker of oxidative stress in vivo in humans than other available methods. The purpose of this brief review is to acquaint the reader with the IsoPs from a biochemical perspective and to provide information regarding the utility of quantifying these compounds as indicators of oxidant stress.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Zeitschrift für Lebensmittel-Untersuchung und -Forschung 206 (1998), S. 48-51 
    ISSN: 1431-4630
    Keywords: Key words Carbohydrates ; Myo-inositol ; Orange juice quality ; Gas chromatography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract  A gas chromatographic method using a capillary column is described for the quantitative analysis of fructose, glucose, sucrose and myo-inositol in orange juice. The method is evaluated for precision and recovery using phenyl-β-glucoside as an internal standard. The results support the suitability of the method. Carbohydrates (fructose, glucose, sucrose and myo-inositol) were determined in different kinds of orange juice. The determination of carbohydrate composition and ratios of the carbohydrate constituents provide a method to assess orange juice quality, especially the myo-inositol content and myo-inositol/fructose ratio. These new indices, which were found to be lower in samples made from concentrates, provide information on the quality and genuineness of orange juice.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Zeitschrift für Lebensmittel-Untersuchung und -Forschung 206 (1998), S. 77-82 
    ISSN: 1431-4630
    Keywords: Key words Anticarcinogen ; CLA ; Conjugated linoleic acid ; Daily intake ; Foods ; Gas chromatography ; Lipids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract  The quantities of the biologically active isomer of conjugated linoleic acid (CLA) – C18:2 c9t11 – in 139 German foods were analysed by capillary gas chromatography (results are given as a % of all identified fatty acid methyl esters). The CLA content ranged from 0.40% (Gouda) to 1.70% (Jurassic cheese, Old Emmentaler) in dairy products, from 0.11% (rabbit) to 1.20% (lamb) in meat, and from 0.01% (pike-perch) to 0.09% (carp) in fish. CLA could be detected in neither vegetable fats or oils nor in margarines (CLA 〈0.01%). Crisps, chocolates, cakes and pastries, and other foods have only a negligible CLA content. The average estimated CLA intake in Germany was calculated to be 0.35g CLA/day for women and 0.43g CLA/day for men.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Zeitschrift für Lebensmittel-Untersuchung und -Forschung 206 (1998), S. 213-216 
    ISSN: 1431-4630
    Keywords: Key words Milk fat ; Mixed fat ; Milk fat content ; Butyric acid ; Gas chromatography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract  The analysis of butyric acid (C4) is of importance for the determination of the proportion of milk fat in mixed fats. Three gas chromatographic methods were compared with regard to their precision for the measurement of C4, i.e. analysis of butyric acid methyl ester after trans-esterification of fat by sodium methylate (method A) or trimethyl sulphonium hydroxide (method B), as well as analysis of free butyric acid (method C), using an internal standard with each method. The examination of 30 milk fats which varied greatly in terms of their C4 content, using methods A, B and C, resulted in mean values of C4 of 3.42 g/100 g fat, 3.71 g/100 g fat and 3.06 g/100 g fat, respectively. The value determined using method B seemed too high, and this may have been due to the presence of co-eluting artefacts, whereas the value determined using method C was clearly too low, and can probably be attributed to losses during sample preparation. The standard deviation (SD) of 0.015 obtained from repeated analyses using method A was quite good. Results obtained using methods B and C had SDs of 0.029 and 0.074, respectively. Different levels of free fatty acids did not affect the results obtained using method A. When method A was checked by analysis of the reference fat, CRM 164, the C4 level determined was found to deviate from the certified C4 content of 3.49 (± 0.06) g/100 g fat by only 0.05 g C4/fat 100 g. Thus method A proved the most suitable for the determination of the proportion of milk fat in mixed fats by analysis of butyric acid.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Zeitschrift für Lebensmittel-Untersuchung und -Forschung 207 (1998), S. 180-181 
    ISSN: 1431-4630
    Keywords: Key words UHT milk ; Storage ; Monosaccharides ; Gas chromatography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract  Changes in the free monosaccharide fraction and non-casein nitrogen during the 3-month storage of five batches of commercial UHT milk were studied. Batches with high residual proteolytic activity showed a considerable increase in galactose, N–acetyl glucosamine and N–acetyl galactosamine levels during the storage period, whereas their glucose and myo-inositol contents remained unaltered. In batches with slight or negligible proteolytic activity no changes in the free monosaccharide fraction were observed.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Intensive care medicine 24 (1998), S. 415-421 
    ISSN: 1432-1238
    Keywords: Key words Acetone ; Gas chromatography ; Isoprene ; Lipid peroxidation ; Microwave desorption ; N-pentane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Objective: Application of a new method for analysis of exhaled gas in critically ill patients. Design: Open study. Setting: Surgical intensive care unit of an university hospital. Patients: Thirty-seven consecutive, critically ill, mechanically ventilated patients. Interventions: None. Measurements and results: Chemical analysis of the patient's exhaled gas was based upon substance adsorption and concentration onto activated charcoal, microwave desorption and gas chromatographic separation. Patients with acute respiratory distress syndrome (ARDS) exhaled less isoprene than those without ARDS [9.8 (8.2–21.6) vs 21.8 (13.9–41.4) nmol/m2 per min [median (95 % confidence interval)], p = 0.04]. In patients who developed pulmonary infection, pentane elimination increased from 0.4 (0.0–5.4) to 2.7 (0.6–6.1, p = 0.05) nmol/m2 per min and isoprene elimination decreased from 5.2 (0–33) to 5.0 (0–17, p = 0.05) nmol/m2 per min, resulting in a significant increase in pentane/isoprene ratio from 0.1 (0–0.3) to 0.4 (0–15, p = 0.007) when compared to patients without pulmonary infection. Conclusions: The new method allows quantitative analysis of human gas samples with low substance concentrations and is well suited for clinical studies which involve the investigation of metabolic processes in the lung and the body.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    European radiology 8 (1998), S. 849-857 
    ISSN: 1432-1084
    Keywords: Key words: Ultrasound ; Physics ; Vascular studies ; Vascular pathologies ; Ultrasonic contrast agents ; Clinical applications
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract. The choice of the optimal ultrasonic frequency for vascular studies is determined by the required resolution and penetration. Anatomical real-time two-dimensional imaging and blood flow studies provide complementary information. Intravascular scanning allows high-frequency ultrasound to be used, with correspondingly good spatial resolution. Contrast resolution is degraded by beam side lobes and the limited dynamic range of the ultrasonic pulse. The physics of ultrasonic scattering by blood, pulsed Doppler and duplex scanning and colour flow imaging performances determines the limits of clinical applications. Contrast agents enhance the echogenicity of blood, improving sensitivity and, through second harmonic detection, suppressing solid tissue echoes. Three-dimensional display, with segmentation by the presence of the flow signal, facilitates spatial perception. Clinical applications in vascular pathologies are summarised.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Space science reviews 84 (1998), S. 199-206 
    ISSN: 1572-9672
    Keywords: Nuclear reactions ; Nucleosynthesis ; Abundances ; Stars:Evolution ; Interior ; Rotation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We first recall the observational and theoretical facts that constitute the so-called 3He problem. We then review the chemical anomalies that could be related to the destruction of 3He in red giants stars. We show how a simple consistent mechanism can lead to the destruction of 3He in low mass stars and simultaneously account for the low 12C/13C ratios and low lithium abundances observed in giant stars of different populations. This process should both naturally account for the recent measurements of 3He/H in galactic HII regions and allow for high values of 3He observed in some planetary nebulae. We propose a simple statistical estimation of the fraction of stars that may be affected by this process.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Programmed-temperature vaporization (PTV) ; Large-volume injection ; Direct water injection ; Triazines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The potential of large-volume PTV injection was studied for the analysis of triazine herbicides in water samples. Direct water injection and in-vial extraction were described and compared. Detection limits were between 0.01–0.02 μg L−1 and relative standard deviations were 〈9%. Both methods are suitable for the analysis of triazines at ppt-level, although in-vial extraction is favourable for water samples with relatively large amounts of matrix components.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Cholesterol oxides ; Cholesterol oxidation products (COPs) ; Meat products
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method of extraction, purification and gas chromatographic analysis of five cholesterol oxidation products (COPs) (7β-hydroxycholesterol, 5α, 6α-epoxycholesterol, 25-hydroxycholesterol, 7-ketocholesterol and cholestane-3β, 5α, 6β-triol) has been developed. The method is aimed at the determination of COPs in meat and meat products, in particular dry sausages, where large differences in the content of cholesterol and its oxidation derivatives may occur. Linearity of response of trimethylsilyl ethers was defined. The minimum concentration tested was 2.5 μg g−1 in the injected solution. The main feature of the present work is the addition of a purification step of unsaponifiables by SPE on silica cartridges. Extraction recoveries of COP standard mixtures, performed with or without the SPE step, are evaluated. The introduction of the clean-up step results in high purity samples without further losses in the entire process.
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  • 11
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Solid-phase extraction ; Graphitized carbon black ; Volatile organic compounds ; Workplace air
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A fast, simple, and reliable method is presented for the determination of atmospheric semi-volatile organic pollutants at μg m−3 levels. The method has been used to monitor potentially carcinogenic toxic compounds to which workers are exposed in workplaces, and to measure the same compounds in outdoor air.
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 47 (1998), S. 63-71 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Liquid foods ; Food packaging materials ; Vinylchloride
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The interaction of vinylchloride (VC) with liquid foods, such as water, olive oil and honey, was studied using the relatively new technique of Reversed-Flow Gas Chromatography (RFGC). The RFGC method permits the calculation of the VC diffusion coefficient in the liquid phase (water, oil and honey) and the determination of the partition coefficient of VC between the liquid and the carrier gas, as well as the determination of the Henry's constant of VC in the liquid food. From the variation of the above parameters with temperature, thermodynamic parameters (free and excess free energies, enthalpies, entropies and activity coefficients) were calculated for the adsorption of VC by liquid foods. These are discussed in comparison with the same parameters calculated from empirical equations or determined experimentally by other techniques.
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 47 (1998), S. 570-574 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Compressibility correction factor ; Specific retention volume
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The exact definition of the compressibility correction factor,j, has been extensively discussed in recent literature. In this work, it is shown that this compressibility correction factor has several different interpretations; however, the simplest and most useful meaning involves a correction from the experimentally accessible pressure at the outlet of a column to the average pressure in the column. Also, an unconventional definition of the retention volume of a solute in terms of the sample size and the equilibrium concentration of the solute in the mobile phase is presented. This retention volume definition is presented as an alternative to the common definition ofV R as the volume of carrier gas which passes through the column in a period of time called the retention time. In this discussion, it is emphasized that the temeprature dependence of the specific retention volume is determined by the thermodynamics of the phase distribution process for the solute and not by an equation-of-state for the carrier gas. Finally, the conventional correction of the specific retention volume by a factor of 273/T c can be used to correct a volume of carrier gas to a pseudo-standard state of 273 K and the average pressure in the column; however, this corrected specific retention volume has no relation to the specific retention volume that would be experimentally obtained at this standard state temperature and pressure. compressibility correction factor, and specific retention volume, were examined with regard to the physical interpretation, exact definition and appropriate standard states to be applied to these commonly reported chromatographic parameters. Such arcane discussions are beneficial to the health of science but may lead to confusion among potential and practicing chromatographers. In order to prevent or at least help ameliorate this problem, the following discussion presents a somewhat unorthodox interpretation of the questioned terms along with a pseudo-physical explanation of the so-called retention volume which is ubiquitous throughout the chromatographic literature.
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  • 14
    ISSN: 1612-1112
    Keywords: Gas chromatography ; SPME ; Soil and groundwater samples ; Chlorobenzenes ; Thermal desorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A complex method was developed for the determination of chlorobenzenes in soil and groundwater samples. Samples were taken at two sites in Baranya county, where a mixture of chlorobenzene waste was deposited, causing severe contamination in the environment. Clean-up of these sites demands modern and reliable analytical methods. Several sample preparation techniques were used, such as solid phase microextraction (SPME), supercritical fluid extraction (SFE), and a recently developed thermal desorption method. The applicability of various sample preparation methods was compared by measuring recovery percentages, relative standard deviations and by investigating the matrix dependency of these values. Gas chromatography was used for quantitative determination of chlorobenzenes, using MS, IR, FID and ECD detection techniques. Detection levels were as low as 1 ppt in water, and 10 ppt in soil samples. Chlorobenzene concentration was in the range 1 ppt-1 ppm in water and 100 ppb-100 ppm in soil samples. Identification and calibration of these compounds were performed by quantitative standards. This complex analytical method can be used for rapid and precise quantitative and qualitative determination of chlorobenzenes.
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 47 (1998), S. 305-308 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Silicone phases ; Film thickness ; Large-bore capillary columns
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A technique is described for determination of the amount of bonded phase in commercial columns. It is adapted to the determination of the real nature and the thickness of a siloxane bonded film. Ten-centimeter samples of column are used. The method is tested for large-bore capillary columns. Applications to kinetic studies are suggested.
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 47 (1998), S. 313-345 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Sample pretreatment ; Coupling on-line to capillary GC ; Robotization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Sample pretreatment is often the bottleneck of a tracelevel analytical procedure. In order to increase performance, increasing attention is therefore being devoted to combining sample pretreatment on-line with the separation technique that has to be used. In the present review, a variety of procedures in use today for sample treatment coupled on-line to capillary gas chromatography (GC) is briefly discussed. Special attention is devoted to coupled-column techniques such as SPE-GC and LC-GC (SPE, solid-phase extraction; LC, column liquid chromatography) which are topics of much current interest, also because of their frequent use in so-called hyphenated systems.
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  • 17
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 48 (1998), S. 163-165 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Solid-phase extraction ; Urinary steroids ; Terbutaline treatment ; Asthmatic children
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Steroid metabolites have been measured by capillary gas chromatography in the urine of 38 children aged 3–6 years. The children comprised three groups: those with asthma being treated with Terbutaline (13), children with asthma but not undergoing treatment (17), and control children in hospital but free from endocrine diseases (8). There were significant (P〈0.05) differences between the amounts of steroids excreted by the different groups of children. Terbutaline therapy led to elevated levels of tetrahydrocortisone, androstenediol, 11-ketopregnanetriol and a reduced ratio of androgen to cortisol metabolites compared with those for untreated asthmatic children. We assume that Terbutaline does not have a steroid-like mechanism of action but acts by modification of the activity of several adrenocortical enzymes. We suggest a hypothesis whereby the antiasthmatic effect of Terbutaline could not only be a connected with its well-known mechanism of action, but it might be explained as a result of the modification of the production of certain glucocorticoids and androgen hormones.
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  • 18
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Calix[4]arene-tetramethyldisiloxane stationary phases ; Geometric and positional isomer separations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Poly(p-tert-butyldimethoxydipropyloxycalix[4]arene-tetramethyldisiloxane) (TBCX-TMDS) and poly(dimethoxydipropyloxycalix[4]arene-tetramethyl-disiloxane) (CX-TMDS), have been prepared and used as stationary phases for isothermal capillary gas chromatographic separations of positional isomers. Retention factors and separation factors for the isomers were measured. The isomers investigated were well-resolved on the two phases. Retention of all the solutes investigated is greater on TBCX-TMDS than on CX-TMDS, probably because of extra dispersive interactions of the solutes with thetert-butyl groups of the phase. Separation factors for closely-eluting isomer pairs are similar on the two phases. This seems to indicate either that the solutes are retained by non-inclusion processes or that if the isomer molecules do enter the cavity of the calixarene, i.e. the solute is retained by inclusion, thetert-butyl groups do not play a role in discriminating between the isomers.
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  • 19
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 48 (1998), S. 443-449 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Gas chromatography-mass spectrometry ; Triethanolamine in air
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Low amounts of triethanolamine, collected in ORBO 53 tubes during air sampling, required the development of a very sensitive method for determination. After desorption and silylation reaction with trimethylsilyl imidazole/trimethyl chlorosilane, the derivative was analyzed by gas chromatography-mass spectrometry on an Ultra 2 silica capillary column in single ion monitoring mode (retention time: about 6 min). The method has a detection limit of 1–2 pg with a desorption efficiency of about 81%. Linearity of response was ascertained in the ranges 10–100 ng and 100–1000 ng. Short-term method validation was carried out by intra- and inter-day assays on three amounts for each reference calibration curve. All results satisfied the pre-defined acceptance criteria. In general, the whole procedure was easily performed and was appropriate for our needs. Breakthrough volume was appropriate for our needs. Breakthrough volume was determined on authentic samples and was about 40–60 L, using a flow rate of 1 L·min−1. The amounts of triethanolamine found in the samples ranged from 150 to 250 ng (about 2.5–4.2 μg·m−3).
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  • 20
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Chiral separation ; Alcohols ; Diols ; Trimethylsilylation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Gas chromatographic chiral separation of several chiral 2-and 3-alkanols and diols was studied both in their free hydroxyl and in their trimethylsilyl ether forms. First, the derivatization procedure was verified through the identification of the trimethylsilyl ethers formed on the basis of their mass spectra and optimized to obtain quantitative reaction. The optimized procedure was applied to the trimethylsilylation of racemic mixtures of various hydroxyl compounds. The silylation was found to be highly effective in the improvement of the separation of the individual enantiomers. The major advantages of the derivatization process can be summarized as: (i) excellent baseline separation of the enantiomers of the silyl ethers was achieved in contrast to the parent OH-containing compounds, (ii) the sensitivity of detection highly increased, (iii) the separations do not show any significant concentration dependence and finally (iv) the analysis time needed decreased significantly.
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  • 21
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Atomic emission and MS detection ; Solid-phase extraction ; Aqueous samples
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A procedure is described for the (non-target) screening of hetero-atom-containing compounds in tap and waste water by correlating data obtained by gas chromatography (GC) using atomic emission (AED) and mass selective (MS) detection. Solid-phase extraction (SPE) was coupled on-line to both GC systems to enable the determination of microcontaminants at the 0.02–1 μg L−1 level in 7–50 mL of aqueous sample. The screening was limited to compounds present in at least one heteroatom-selective GC-AED trace above a predetermined concentration level. These compounds were identified by their partial formulae (AED) and the corresponding mass spectra, which were obtained from the GC-MS chromatogram via the retention index concept. The potential of the approach was demonstrated by the identification of target compounds as well as all unknowns present in tap and waste water above the predetermined threshold of 0.05 μg L−1 (tap water) or 0.5 μg L−1 (waste water).
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  • 22
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 48 (1998), S. 817-822 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Crown ether capped cyclodextrin ; Chiral separations ; Isomer separations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The solution of a new synthesized compound, mono-6-(1'-benzo-aza-15-crown-5)-2, 3, 6- permethyl-β-cyclodextrin, in the moderately polar polysiloxane OV-1701 was coated onto fused silica capillary column. The chromatographic characteristics including column efficiency, polarity and selectivity were studied. Excellent selectivity for the separation of enantiomers and positional isomers was obtained. The results show that the combined effect between the special caves of β-cyclodextrin and crown ether plays a significant role in the separation.
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  • 23
    ISSN: 1612-1112
    Keywords: Gas chromatography ; UV-Vis detection ; Gas phase absorption spectrometry ; Alcohols
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary This article describes a theoretical/practical study of the parameters which affect the chromatograms obtained when using a molecular diode-array spectrometer as the detector in gas chromatography. The objective is to offer some rules which permit the identification of the optimum signal/noise relation. To achieve this, we study the effect of the different parameters which affect the noise and how to reduce their impact, as well as alternatives for increasing the signal. All the options tested can be applied by correctly programming the spectrometer with BASIC programs, within reach of any use who has even a small understanding of programming. Finally, we consider the effect that the selection of the acquisition conditions may have on the chromatographic resolution. All the studies are carried out using a mixture of alcohols and phenols.
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  • 24
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Liquid crystal stationary phase ; Packed columns
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The separation ofm-, p-, o- xylenes andm-, p- ethyltoluenes was studied on a packed column with 2,5% of 4-[(4-chlorobenzyl)oxy]-4′-cyanoazobenzene (CBOCA) on Chromosorb W HP 100–120 mesh. The synthesis and study of the mesomorphic behaviour of CBOCA are presented. Temperature range for the separation ofm-, p-, o- xylenes (in this order of elution) is 125–85°C, at cooling. The best separation was achieved at about 90°C. The separation temperature domain ofm-ethyltoluene fromp- ethyltoluene is 160–85°C.
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  • 25
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Water analysis ; Derivatization with bromine ; Aromatic amines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary For improved determination of aromatic amines by gas chromatography and detection with an electron capture detector (GC-ECD) a derivatization method based on the bromination of the aromatic ring in an acetic acid medium was developed. In general, all free ortho and para-positions relative to the amino group undergo electrophilic substitution. Separation of at least 30 compounds in a single chromatographic run in 30 min is possible. With this method, 56 aromatic amines were studied and only in 6 cases were no derivatives obtained. Quantitation limits determined from calibration data are 1.2–40 μg L−1 for a 100 mL sample and an injection volume of 1 μL. Previous experiments suggest that both sample and injection volume may be increased to lower the quantitation limit.
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  • 26
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Soil samples ; Microwave-assisted solvent extraction ; Nitrogen detection ; Triazine herbicides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Recent work demonstrated that the combination of microwave assisted solvent extraction (MASE) and capillary gas chromatography with selective nitrogen detection (GC-NPD) is a viable approach for the efficient determination of triazine herbicides in soils. However, for soils with a high organic matter content or the injection of more concentrated extracts to obtain lower LOD's the performance of gas chromatographic analysis of uncleaned extracts is hampered. This results in both a decrease of the chromatographic response of analytes and a decrease in the life time of the column due to coextracted matrix substances. The effect of various types of soils on the chromatographic analysis of triazine herbicides was studied. It appeared that for the investigated samples with an organic matter content below 5% processing of uncleaned extracts is possible. Samples with a higher organic matter content required a cleanup step. A rapid procedure on 100 mg silica cartridges has been developed using solvents compatible with the MASE extracts and the instrumental analysis. Beside the testing with different standard soils, about 120 samples of an ongoing monitoring program involving three different types of soil (organic matter content: 3–37%) were analysed. The selected compounds atrazine, desethylatrazine, desisopropyl-atrazine and simazine could be assayed in the various soil types to a level of at least 2 μg kg−1. For soil samples with a high organic matter content (〉5%), the rapid cleanup procedure allowed the trace analysis of the triazines and considerably increased the life time of the capillary column. Recoveries at levels from 2 to 50 μg kg−1 ranged from 70 to 100% with RSDs ranging from 5.1 to 9.5%. Confirmation of positive samples was carried out by gas chromatography mass spectrometry.
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  • 27
    ISSN: 1612-1112
    Keywords: Gas chromatography ; On-line SPE-GC-MS ; Beverage carton packages ; Contaminant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An unknown migration contaminant was found in a number of mineral water samples contained in beverage carton packages. This compound was isolated by a fully automatic solid phase extraction system and identified by means of GC-MS as 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) [126-86-3], which is used as a surfactant in water-based printing inks and migrates during the production of the beverage carton material into the inner polyethylene film and subsequently into the product. The determined concentrations of TMDD ranged up to more than 50 μg L−1.
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  • 28
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Column liquid chromatography ; Solid-phase microextraction ; Local anaesthetic lidocaine ; Optimisation of extraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Solid-phase microextraction (SPME) has been combined with gas chromatography (GC) and liquid chromatography (LC) for the determination of lidocaine in human urine. A polydimethylsiloxane (PDMS) coated fibre was directly immersed into buffered urine. Extraction conditions such as time, pH, ionic strength, temperature, and agitation were optimised. The extracted lidocaine was thermally desorbed in a split/splitless injector for analysis with a GC-FID system or desorbed with liquid in a specially designed SPME-LC interface for analysis with an LC-UV system. After optimisation the method developed was evaluated and validated. Extraction yields of 22% were obtained in about 45 min. The reproducibility of the method is 〈5% (relative standard deviation). For five-times diluted urine, linear ranges were found from 5–1000 and 25–1000 ng·mL−1 for SPME-GC and SPME-LC, with detection limits of 5 ng·mL−1 for SPME-GC and 25 ng·mL−1 for SPME-LC. SPME can be used as a simple sample pretreatment method for the determination of lidocaine in urine by GC and LC.
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  • 29
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Stationary phases ; β-Cyclodextrin derivatives
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Five β-cyclodextrin derivatives, heptakis[2,6-di-O-pentyl-3-O-(4-nitrobenzyl)-β-CD (CD-I), heptakis [2,6-di-O-pentyl-3-O-(5-hexenyl)]-β-CD (CD-II), heptakis-(2, 6-di-O-cinnamyl-3-O-methyl)-β-CD (CD-III), heptakis-(2, 6-di-O-cinnamyl-3-O-acetyl)-β-CD (CD-IV) and heptakis(2, 6-di-O-cinnamyl-3-O-trifluoroacetyl)-β-CD (CD-V), were synthesized and coated on fused-silica capillary coluns. Their chromatographic characteristics were tested and compared with heptakis (2,3,6-tri-O-pentyl)-β-CD (CD-VI) and heptakis (2,6-di-O-pentyl-3-O-trifluoroacetyl)-β-CD (CD-VII). It was found that the size, polarity, and aromatic property of the substituted group at the 3-position of heptakis (2,6-di-O-pentyl)-β-cyclodextrins greatly influenced their chromatographic properties and separation ability. The introduction of aromatic group or a group containing a double-bond may bring π-π interactions between the host and guest molecules, and therefore increased the separation ability of the β-CDs for substituted benzene isomers. Introduction of cinnamyl groups in to the 2,6-3-position of β-CD has a significant effect on the chromatographic properties of the stationary phases(CD-III-CD-V).
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  • 30
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Heats of vaporization ; Gibbs free energies ; Kováts retention indices ; Alkylbenzenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary In our paper we propose a new method for the determination of heats of vaporization (ΔH vap(i)) and the Gibbs free energies of vaporization (Δμp(i)) for individually selected alkylbenzenes, chromatographed on stationary phases of low and medium polarity. The method is based on a new thermodynamic description of the Kováts retention index (I (i)) making use of Trouton's rule. In fact, we attribute physical significance to two empirical relationships, well known from the literature. We can describe thermodynamically the magnitude ofI (i) using two relations, each of them potentially useful for further determination of δH vap(i) and Δμp(i). A comparison was made of the results obtained with the use of our new approach and of those already existing in the literature attained in a completely different way. The comparison suggests that the calculated δH vap(i) and Δμp(i) values are thermodynamically acceptable and hence correct, and the data suit into the series of similar values determined on stationary phases of different polarity.
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  • 31
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Solid phase extraction ; Polychlorobiphenyls ; Clorinated pesticides ; Organochlorine separation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Gas chromatography of polychlorinated biphenyls and chlorinated pesticides in water samples is carried out after adsorption from a 25–500 mL sample, on a cartridge containing 100 mg aminopropyl-bonded porous silica. The clean-up step in which the PCBs and chlorinated pesticides are separated in different eluates is achieved by passing 25 mL of 40% aqueous methanol through the NH2 Sep-Pak cartridge. The PCBs are desorbed with 500 μL ethylacetate, which is concentrated and analysis by GC-ECD. The average recovery, at 1 ppb is 〉97% with a standard deviation 〈2. The limits of detection are 0.1 ng μL−1 and 5 pg μL−1 respectively for Cl3-PCB and Cl8-PCB congeners. In the separation of PCBs from the chlorinated pesticides tested in this work, only the Aldrin is adsorbed for 60% with the PCBs by the NH2 Sep-Pak cartridge. The method described is rapid, simple and reproducible.
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  • 32
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    Chromatographia 48 (1998), S. 728-738 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Stationary phases ; Prototypical phases ; Retention model ; Retention value ; Dipolarity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Stationary phases are characterised in a multilinear retention model by retention data of a set of selected prototypical substances. Prototypical stationary phases confirm the application of prototypical substances in the retention model. For comparison, 27 stationary phases are characterized with solute descriptors of the solvation model. New adjusted substance factors are calculated for 33 selected compounds for a new characterization of GC stationary phases in the extended retention model with retention values, calculated from retention indices and b-values of the n-alkane equation. Substance dipolarityD N-factors are separated from πN, the adjusted dipolarity-polarisability. New substance factors give satisfying correlation results and new explanatory factors as phase descriptors for 27 stationary phases.
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  • 33
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    Chromatographia 48 (1998), S. 758-762 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Butyric acid ; Milk fat content ; Mixed fats
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Quantitation of the milk fat content in mixed fats is of interest in food analysis. It can be achieved by calculation from the butyric acid (C4) content in the mixed fat and a mean C4 content for pure milk fats. Alternatively, instead of applying a C4 mean value, the C4 content in the actual milk fat can be used if this reference sample is available. A recently improved analytical method based on gas chromatography of butyric acid methyl ester using an internal standard has been applied to determine the milk fat content in mixtures with beef tallow, lard, soybean oil, olive oil, sunflower oil, palm kernel oil and palm oil ranging from 1 to 90% milk fat content. Within the whole range of mixtures, mean absolute deviations between the determined and the actual milk fat content were below 0.5% and the maximum absolute deviation was not more than 1.0% when using the reference sample. The overall mean absolute deviation was 0.04% for milk fat contents of 1 to 10% and 0.28% for milk fat contents of 10 to 90%.
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  • 34
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Solid phase extraction ; Brazilian sugar cane spirit ; Lower fatty acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A gas chromatographic method for the analysis of seventeen acids in a water/ethanol matrix is described. The diluted samples were first concentrated by solid phase extraction. Nonanoic acid was the internal standard. A good separation profile was obtained for all compounds, including the isomers: n and iso-butyric acids, n and isovaleric acids and n and iso-caproic acids. The method is fast, sensitive (20–30 μg L−1) and has a good reproducibility (4–7 %). The recovery was in the range of 94%–116% for the medium chain acids (C7-C16). This method allowed the identification of fourteen acids in caninhas and other spirits. The total acid content and the profile of the exportation type caninhas are similar to the ones obtained for several international beverages.
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  • 35
    ISSN: 1612-1112
    Keywords: Gas chromatography ; UV-Vis detection ; Gas phase absorption spectrometry ; Derivatization ; Alcohols and phenols
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method is proposed for the determination of alcohols and phenols based on their derivatization to benzoates and gas chromatography-gas phase molecular absorption spectrometry. All parameters affecting the derivatization reaction, such as the solvent, basic medium, benzoyl chloride and stirring time, were optimized. Chromatographic and instrumental conditions were also studied. Finally, a calibration study was performed and the results were compared to that obtained by the direct determination of the compounds.
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  • 36
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    Chromatographia 48 (1998), S. 156-157 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Gel permeation chromatography ; Organophosphorous pesticides ; Plant samples
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The work presents a GC method for the determination of six organophosphorous pesticide residues in cabbage. Chopped cabbage was blended with acetone, then extracted with the mixture of n-hexane:methylene chloride (1:1). The extract was purified on a GPC column packed with BioBeads SX-3 gel. The pesticides were eluted with the mixture of methylene chloride:cyclohexane (1:1) at the flow rate of 0.5 mL min−1. After concentrating the extract was analysed by GC. Nearly 100 samples of cabbage were analysed; trace residues of dimethoate (about 0.05 ppm) were found in 10 samples. The average recoveries of the pesticides were above 80% with a relative standard deviation mostly less than 10%.
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  • 37
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Solid-phase extraction ; Rapeseed oil ; Sterols
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A capillary gas chromatographic method is described for the determination of major plant sterols and cholesterol in edible oils and fats. In the sample preparation procedure reversed-phase, solid-phase extraction with C18 adsorbent was used to extract the unsaponifiable matter and for sample cleanup after saponification. Sterols were quantitated as their trimethylsilylether derivatives using an internal standard method (betulin). The method was validated by recovery tests and analysis of two reference materials representing vegetable oil mixture and milk fat matrices. Average recoveries of spiked cholesterol and cholesterol acetate in rapeseed oil were 103±4% (n=12) and 101±3% (n=10), respectively. The sterol values determined in the reference materials were found to be in a good agreement with their given certified or indicative values. Applied to edible oils and fats, plant sterols and cholesterol at levels〉20 mg kg−1 could be accuratively quantitated.
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  • 38
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    Chromatographia 48 (1998), S. 299-304 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Headspace sampling ; Ethoxylated alcohols ; Ethoxylated alkylamines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Headspace-gas chromatography was used to determine the contents of toxic 1,4-dioxane, ethylene oxide and ethylene glycol in ethoxylated alcohols and alkylamines, and in commercial cosmetics and washing products. A Permaphase PEG capillary column was used for the determination of 1,4-dioxane and ethylene oxide and a DB-17 column for ethylene glycol determination. Dimethylformamide was used as the solvent in the determination of 1,4-dioxane and ethylene oxide, and undecanol in the case of ethylene glycol. The detection limits for ethylene oxide, 1,4-dioxane and ethylene glycol are 1,2 and 10 μg·g−1, respectively.
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  • 39
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Stationary phases ; Calix[4]arene derivatives
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Two new kinds of calix[4]arene derivatives, 5,11,17,23-tetra-tert-butyl-25,27-bis(isopropylcarbamoyl-methoxy)-26,28-diundecenyloxy calix[4]arene (C[4]A) and 25,27-dibutoxy-5,11,17,23-tetra-tert-butyl-26,28-diundecenyloxy calix[4]arene (C[4]B), have been synthesized for use as stationary phases in capillary gas chromatography with OV1701. These stationary phases demonstrate high column efficiencies, wide operating temperature ranges, good thermal stability and excellent selectivity for aromatic isomers, especially phenol compounds. Their inclusion properties are also discussed.
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  • 40
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Correlation equation ; Alkylbenzenes ; Naphthalenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A detailed statistical analysis is presented for comparing the validity of selected literature-recommended equations with the unified retention index concept for calculating the retention indexes of alkylbenzenes on UCON LB 550X and naphthalenes on polydimethylsiloxane. Comparison with literature sources shows that the unified retention index provides the smallest residual error for a set of aromatic hydrocarbons.
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  • 41
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Pyrolysis GC ; Residual polystyrene ; Streptomycin ; Vitamin B1
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Residual synthetic adsorbent, cross-linked polystyrene, used in drug purification has been analyzed quantitatively by Curie-point pyrolysis gas chromatography. The peaks of intact polystyrene adsorbent in the pyrogram were used as key peaks for quantitative measurement of residues of the adsorbent in vitamin B1 and streptomycin sulfate. It was shown that them-ethylstyrene orp-ethylstyrene peaks in the pyrolyzates were suitable for determination of polystyrene adsorbent content. The levels of residual adsorbent in the drugs were found to be 〈0.1 %, the value stipulated by the International Conference on Harmonization (ICH). In quantitative evaluation of an adsorbent content of 0.1 % the precision was 3.6 % and 2.7 % for vitamin B1 and streptomycin sulfate, respectively.
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  • 42
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Alkenes ; Epoxides ; Retention index
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Retention indices or five 1-alkenes, seven branched alkenes and five cycloalkenes and the corresponding epoxides were determined at two temperatures on a fused-silica capillary column coated with cyanopropyl methyl siloxane to interpret their chromatographic behaviour. The standard deviation was 0.2 index units.
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  • 43
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    Chromatographia 47 (1998), S. 685-688 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Headspace sampling ; Safrole ; Asarum species
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The development of a headspace GC method (HS-GC) to determine the safrole content in differentAsarum species from China and Europe, using eugenol as internal standard, is presented in this paper. The best results could be achieved by thermostating the samples at 100°C for 30.0 min, adding 10 μL of water to each sample. Optimum pressurisation and injection time showed to be 3.0 min and 12 s, respectively. GC separation was performed on an SE-54 column. The HS-GC results for safrole were in good agreement with those obtained by direct GC analysis of the dichloromethane (DCM) plant extracts. The investigated Asarum samples showed great deviations concerning the safrole content even within the sameAsarum species, e.g.Asarum himalaicum from Sichuan contained 0.0051% of this compound, the same species from the province of Hebei 0.53%.
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  • 44
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    Chromatographia 47 (1998), S. 724-726 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Phthalate esters ; PVC ; Plastic toys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method for the analysis of 10 phthalate esters in plastic toys is described. The samples are soxhlet extracted in dichloromethane and phthalate esters in the extract are analysed by GC. Detection limits of dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis(2-ethylhexyl) phthalate, di-n-octyl phathalate, di-n-nonyl phthalate, benzyl butyl phthalate and benzyl octyl phthalate were approximately 5 ppm. The detection limits of diisononyl phthalate and diisodecyl phthalate, which are mixtures of several isomers, were approximately 200ppm. Analysis of 17 plastic toys revealed that only PVC-toys contained phthalate esters. Bis(2-ethylhexyl) phthalate, diisononyl phthalate and diisodecyl phthalate in concentrations up to 40% were present in the PVC-toys.
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  • 45
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Solid-phase microextraction ; Headspace sampling ; Cyanide in blood
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Cyanide can be extracted from whole blood samples by headspace solid-phase microextraction (SPME) with a Carbowax/divinylbenzene-coated fiber. During heating a vial of a whole blood sample containing cyanide and acetonitrile as internal standard (IS) at 50°C in the presence of Na2SO4, a Carbowax/divinylbenzene-coated SPME fiber was exposed in the headspace of the vial for 45 min to allow adsorption of cyanide and IS. The fiber needle was then injected into a capillary gas chromatography (GC) instrument equipped with nitrogen-phosphorus detection. The headspace SPME-GC with a Supel-Q PLOT fused silica capillary column gave large peaks for cyanide and IS; almost no interfering peaks appeared. Recoveries of cyanide dnd IS from human whole blood were 3.02–4.06% and 0.21%, respectively. The calibration curve for cyanide added to human blood showed excellent linearity in the range of 0.04–4.0 μg mL−1; the detection limit was about 0.02 μg mL−1. The coefficients of intra-day and inter-day variation were not greater than 7.1 and 9.2%. Good correlation (r 2=0.999) was found between the present SPME-GC method and the conventional microdiffusion colorimetric method. Data on determination of cyanide in rat blood after intraperitoneal administration are also presented.
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  • 46
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Mixed stationary phases ; Dibenzo-18-crown-6 ether ; MPBHpB ; Synergistic effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The synergistic effect is investigated in mixed gas chromatographic stationary phases containing dibenzo-18-crown-6 +MPBHpB [o-methyl-p-phenylene-bis-(p-heptoxy benzoate)], [o-methyl-p-phenylene-bis-(p-heptoxy benzoate)], with benzene/cyclohexane, cyclokexanes, phenols, alcohols and aniline derivatives as sample compounds pairs. Some of the separations reveal positive or negative synergistic effect. This effect depends on the temperature, the mixing ratio and the linear velocity of the carrier gas.
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  • 47
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Organochlorine and organophosphorus pesticides ; Herbal medicine ; Essential oils ; Sulfuric acid treatment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A rapid and new clean-up method utilizing sulfuric acid treatment is demonstrated to identify and quantify the level of organochlorine (OC) and organophosphorus (OP) pesticide residue concentrations in herbal essential oils by gas chromatography (GC). Essential oils fortified with pesticides, that are extracted from herbs by steam distillation are partitioned with 65% acetonitrile/water(v/v) and treated with sulfuric acid at different reaction times and sulfuric acid concentrations. Optimal conditions, to avoid interference from essential oils in gas chromatographic analysis, is 17% (v/v) of a mixed phase ratio of sulfuric acid to organic solvent (hexane/ethyl ether=9∶1, v/v) and a reaction time of 30s. The response of the flame ionization detector (FID) is linear for all pesticides determined. Recovery of pesticides from fortified herbs studied are in the range of 75% to 111% (RSD, 4% to 11%) for OC, and 72% to 116% (RSD, 2% to 11%) for OP. Although sulfuric acid treatment destroys carbamate and some organophosphorus pesticides, this method has efficiently reduced matrix interference and provides a rapid, economical clean-up method with excellent linear data having low coefficients of variation for the GC analyses of BHC isomers, DDD, DDE, DDT, chlorothalonil, chloropyrifos, tetradifon, fenitrothion, malathion, and parathion in matrices of herbal essential oils.
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  • 48
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Gas chromatography ; Enantiomeric separation ; Chiral derivatization ; Unusual secondary aromatic amino acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary High-performance liquid chromatographic and gas chromatographic methods were developed for the separation of unusual secondary aromatic amino acids. Amino acids containing 1,2,3,4-tetrahydroisoquinoline, 1,2,3,4-tetrahydronorharmane-1-carboxylic acid and 1,2,3,4-tetrahydro-3-carboxy-2-carboline moieties were synthetized in racemic or chiral forms. The high-performance liquid chromatography was carried out either on a teicoplanin-containing chiral stationary phase or on an achiral C18 column. In the latter case the diastereomers of the amino acids formed by precolumn derivatization with the chiral reagents 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl isothiocyanate or 1-fluoro-2,4-dinitrophenyl-5-L-alanine amide were separated. The gas chromatographic analyses were based on separation on a Chirasil-L-Val column.
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  • 49
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    Chromatographia 48 (1998), S. 86-88 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Solid phase extraction ; Methoxime-silyl derivate ; Urinary steroids ; Women with effluvium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Urinary steroid metabolites were measured by capillary gas chromatography in 25 women (aged 33.3±12.0 years) with effluvium and 16 control healthy laboratory workers women (aged 34.6±8.4 years). There was significant elevation in the level of a number of steroids and steroid metabolites. The elevation of most steroid metabolites refers to the increased steroid secretion of the adrenal and the high cortisol metabolites levels may be do to stress in some of the patients with effluvium.
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  • 50
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Chiral stationary phases ; Enantioseparation ; Toxaphene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The separation of the enantiomers of the compounds of technical toxaphene (CTTs) on heptakis(6-O-tert-butyldimethylsilyl-2,3-di-O-methyl)-β-cyclodextrin (β-TBDM) has been studied by gas chromatography with electron-capture detection (GC-ECD). Enantiomers of eight of the nine CTTs under investigation were separated on this chiral stationary phase. Separations of the enantioners of CTTs have hitherto been achieved ontert-butyldimethylsilylated β-cyclodextrin (β-BSCD). The chiral resolution values and separation factors of the CTTs on β-TBDM have been compared with those obtained on β-BSCD. Although several components coeluted, enantioselective determination of three CTTs was possible in an extract of seal blubber. For each CTT the first-eluting enantiomer was enantioenriched. Enantioselective accumulation of2-endo, 3-exo,5-endo,6-exo,-8,8,9,10-octachlorobornane (B8-1412) in biota has been established for the first time.
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  • 51
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    Chromatographia 47 (1998), S. 579-586 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Column liquid chromatography ; Ewe's cheese ; Triacylglycerols
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Triacylglycerols from Idiazabal cheese fat were analysed by high-performance liquid chromatography (LC) with a non-linear gradient of acetone in acetonitrile and a light-scattering detector. Molecular species of triacylglycerols were predicted by a simple and a multiple linear regression analysis of logk of the LC peaks and molecular variables such as equivalent carbon number of the possible triacylglycerol, chain length and number of double bonds of each fatty acid of the triacylglycerol. Predicted results were confirmed by gas chromatographic analysis of the fatty acids in the LC peaks. The main triacylglycerols of Idiazabal cheese fat contained butyric acid, butyroyl-dipalmitin, butyroyl-myristoyl-palmitin and butyroyl-palmitoyl-olein. The most abundant triacylglycerols were those with even partition numbers of 36, 34 and 38.
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  • 52
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Metal complexes ; Chemically bonded phases ; Thermodynamic parameters ; Specific interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Results are presented of studies of packings containing copper (II) acetylacetonate (acac), hexafluoroacetylacetonate (hfac), and chloride, chemically bonded via β-dik-etonate groups. The retention parameters retention factor (k) specific retention volume (V g), and molecular retention index (M e) were measured and used to calculate the thermodynamic parameters free energy of adsorption (ΔG a) heat of adsorption (−ΔH a), and entropy of adsorption (ΔS a). These parameters enable, characterization of specific interactions between aromatic and cyclic hydrocarbons, ethers and thioethers and metal complexes chemically bonded, to a silica surface.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1025-1035 
    ISSN: 0887-6266
    Keywords: polymer thin films ; thermosets ; microelectronics ; moisture ; physical aging ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In polymers for microelectronics applications, moisture is known to have a deleterious effect upon device reliability. In this paper, the moisture transport behaviors of a newly developed family of all-aromatic and aromatic/aliphatic copolyester thermosetting films were described. The moisture uptake as a function of temperature, relative humidity, sample thickness, and processing conditions were presented via conjugate moisture sorption tests.1 It was found that the post curing near but below Tg resulted in an increase in both total moisture uptake and diffusion coefficient due to the effect of physical aging and the generation of sample defect volume. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1025-1035, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1061-1080 
    ISSN: 0887-6266
    Keywords: polymer blends ; dilatometry ; free volume ; specific volume ; excess volume ; compressibility ; thermal expansivity ; equation of state ; scaling parameters ; crystallinity ; glass transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Melt-miscible polymer blends of poly(ethylene oxide)/atactic poly(methyl methacrylate (PEO/a-PMMA)) were prepared by melt-mixing and characterized by pressure-volume-temperature (PVT) dilatometry in the pressure and temperature range of 0 to 200 MPa and 20 to 200°C, respectively. The PVT data were analyzed in terms of two equations of state (EOS). The empirical Tait EOS was applied in the glassy, semicrystalline, and equilibrium melt state, and the Simha-Somcynsky EOS theory was applied in the equilibrium melt and glassy state. The Simha-Somcynsky EOS theory contains a free volume function. The temperature, pressure, and composition dependence of the free volume fraction h calculated from the Simha-Somcynsky EOS theory was studied. As a function of blend composition we observe that the free volume fraction, thermal expansivity, and compressibility all deviate mainly positively from linearity while the specific volume deviates mainly negatively from linearity. These findings are reconciled with composition-dependent free volume parameters, the free volume and cell volume as well as with self- and cross-interaction parameters derived from the Simha-Somcynsky EOS theory as applied to polymer mixtures. Moreover, the pressure dependence of glass and melting transitions as well as crystallization kinetics have been investigated. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1061-1080, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1201-1209 
    ISSN: 0887-6266
    Keywords: polymer electrolytes ; NMR ; conductivity ; glasses ; Arrhenius and VTF dependences ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have studied the temperature variation of conductivity and 1H NMR linewidth of (PEG)xNH4ClO4 (x = 20, 30, 46, 100, 200, & 1000) polymer electrolyte systems. The temperature dependence of the conductivity shows two distinct behaviors, the low temperature VTF dependence crossing over to Arrhenius dependence at higher temperatures. The departure from the VTF behavior is found to be composition dependent. NMR spectra indicate the presence of large fractions of crystalline regions that start to melt around the crossover temperature. We understand the deviation from the VTF behavior as a consequence of this crystalline to elastomer transition. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1201-1209, 1998
    Additional Material: 9 Ill.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1227-1233 
    ISSN: 0887-6266
    Keywords: FTIR spectroscopy ; isotactic polystyrene ; crystallization process ; induction period ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melt crystallization process of isotactic polystyrene (i-PS) was studied by means of in situ Fourier transform infrared (FTIR) spectroscopy, with a focus on the conformational changes during the induction period. The spectra obtained during the induction period suggested the occurrence of some ordered structure that is characterized by higher regularity and packing of the helical moieties than observed in the melt. This ordered structure was clearly different from the amorphous structure, and close to the crystal structure. The Avrami analysis indicated that the formation process of the ordered structure at the late stage of the induction period is similar to the growth process of the crystallites after the induction period. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1227-1233, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 237-251 
    ISSN: 0887-6266
    Keywords: segmented ; polyurethanes ; crosslinked ; mechanical ; dielectric properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical and dielectric properties of two series of segmented polyurethanes having soft segment concentration of 50 and 70% and a varying degree of crosslinking through the hard segment were studied. The degree of crosslinking in each series was varied by varying the butane diol/trimethylol propane ratio in the chain extender mixture. Tensile strength, elongation at break decrease, but elastic recovery increases monotonically with increasing crosslinking. The plateau modulus in the dynamic mechanical test decreases and then increases with increasing TMP content. Crosslinking causes broadening of the soft segment glass transition as seen by permittivity and loss factor measurements. It also affects high temperature behavior (above the glass transition of the hard segment); it lowers permittivity, loss factor, and ionic conductivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 237-251, 1998
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  • 58
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2379-2391 
    ISSN: 0887-6266
    Keywords: block copolymer ; thermoplastic elastomer ; physical gel ; polymer micelle ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoplastic elastomer gels (TPEGs) composed of a poly[styrene-b-(ethylene-co-butylene)-b-styrene] triblock copolymer and a low-volatility, midblock-compatible mineral oil have been investigated at different oil concentrations to ascertain the effect of composition on TPEG morphology and mechanical properties. The impact of thermal processing is also examined by comparing gels thermally quenched to 0°C or slowly cooled to ambient temperature. Transmission electron micrographs reveal that gels with 70 to 90 wt % oil exhibit styrenic micelles measuring ca. 24 nm in diameter. Variation in composition or cooling rate does not have any perceivable effect on micelle size or shape, whereas the rate at which the gels are cooled influences the extent of microstructural order and the time to rupture (tR) at constant strain. Dynamic rheological testing confirms the presence of a physically crosslinked network at TPEG compositions ranging from 70 to 90 wt % oil, independent of cooling rate. Results presented here suggest that the dynamic elastic shear modulus (G′) scales as tαR where α varies from 0.41 to 0.59, depending on cooling rate. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2379-2391, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2423-2433 
    ISSN: 0887-6266
    Keywords: gelation theory ; nonlinear polymerization ; nonrandom crosslinking ; molecular weight distribution ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On the basis of the first-order Markovian statistics, we propose a general matrix formula for the weight-average molecular weight of crosslinked polymer systems, explicitly given by M̄w = M̄w,0 + WX0 (I - X)-1 Sf. This equation is valid for both step and chain-growth polymerizations, including those in a nonequilibrium state irrespective of the reactor types used. In the context of the present theory, the onset of gelation is simply stated as a point at which the largest eigenvalue of the matrix X reaches unity (i.e., det(I - X) = 0). The present theory provides a unified point of view for various types of gelling systems. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2423-2433, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 555-565 
    ISSN: 0887-6266
    Keywords: polyester ; annealing ; birefringence ; mechanical loss factor ; orientation ; density ; crystalline ; profile ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyester (Egyptian) fibers were annealed at constant temperature (190°C) with different annealing times. Density, crystallinity, mean square density fluctuation, mechanical loss factor, and molecular orientation were calculated. Densities and mechanical loss factor were determined using an acoustic method. Changes in the molecular orientation were evaluated from the resulting optical data using the polarizing Pluta interference microscope. Correlation of data obtained by one method with another leads to relational changes in optothermal properties and in the molecular orientation. Changes of refractive index profiles of annealed PET fibers are provided. Illustrations using graphs and microinterferograms are shown. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 555-565, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 595-606 
    ISSN: 0887-6266
    Keywords: IR ; perfluoro(sulfonate/carboxylate) bilayer ; sol-gel reactions ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: [Perfluoro-organic]/[silicon oxide] hybrids were formed by conducting sol-gel reactions of tetraethylorthosilicate within a perfluoro(carboxylate/sulfonate) bilayer membrane in the Co+2 form. FTIR and 29Si solid-state NMR spectroscopies were used to probe general aspects of molecular structure within the silicon oxide phase as a function of its relative content. The internal gel structure is considerably unconnected in terms of the population of Si—O—Si groups in cyclic vs. linear substructures and degree of Si atom coordination about bonded SiO4 units. In situ (HO)xSiO2[1-1/4x] intrastructure become increasingly less connected and more strained with regard to bonding geometry with increasing percent silicon oxide. Structural differences are seen between the silicon oxide component incorporated in carboxylate and sulfonate layers. These inorganically modified perfluorinated ionomers have potential as fast-proton conducting membranes for fuel cells and as permselective membranes in liquid pervaporation cells. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 595-606, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 607-615 
    ISSN: 0887-6266
    Keywords: ternary phase diagram ; binodal curve ; Flory-Huggins theory ; interaction parameter ; membrane formation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this work, the ternary phase diagrams in three nonsolvent/solvent/PMMA systems (n-hexane/n-butyl acetate/PMMA, water/acetone/PMMA, and n-hexane/acetone/PMMA) were constructed by theoretical calculation and experimental measurement. Binodal curves were calculated by using the Flory-Huggins theory for three-component systems and measured by titrating the PMMA solution with nonsolvent until the onset of turbidity. By using concentration-dependent nonsolvent/solvent and solvent/PMMA interaction parameters and constant nonsolvent/PMMA interaction parameters, good agreement has been obtained between the calculation and the measurement. The values of nonsolvent/solvent interaction parameters were taken from the literature sources, and the values of solvent/PMMA and nonsolvent/PMMA interaction parameters were measured by vapor sorption and swelling equilibrium, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 607-615, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 143-154 
    ISSN: 0887-6266
    Keywords: polymer simulation ; stress relaxation ; molecular dynamics ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We have been developing a physical picture on the atomic level of stress relaxation in polymer melts by means of computer simulation of the process in model systems. In this article we treat a melt of freely jointed chains, each with N = 200 bonds and with excluded-volume interactions between all nonbonded atoms, that has been subjected to an initial constant-volume uniaxial extension. We consider both the stress relaxation history σ(t) based on atomic interactions, and the stress history σe(t; NR) based on subdividing the chain into segments with NR bonds each, with each segment regarded as an entropic spring. It is found that at early times σ(t) 〉 σe(t; NR) for all NR, and that, for the remainder of the simulation, there is no value of NR for which σ(t) = σe(t; NR) for an extended period; by the end of the simulation σ(t) has fallen just below the value σe(t; 50). The decay of segment orientation, 〈P2(t; NR)〉, and of bond orientation 〈P2(t; 1)〉, is computed during the simulation. It is found that the decay of the atom-based stress σ(t) is closely related to that of 〈P2(t; 1)〉. This result may be understood through the concept of steric shielding. The change in local structure of the polymer melt during relaxation is also studied. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 143-154, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 181-190 
    ISSN: 0887-6266
    Keywords: dynamics ; rigid-rod ; semidilute ; birefringence ; rotational diffusivity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamics of rigid-rod-like molecules are studied using rheo-optical techniques. Measurements of flow birefringence as a function of shear rate are utilized to understand the scaling behavior of rotational diffusivity with respect to concentration and temperature. The concentration scaling exponent increases with increasing concentration and the scaling laws are valid in narrow concentration windows. The Doi-Edwards (DE) scaling law Dr ∼ c-2, holds at very high concentrations (cL3 〉 150). The concentration scaling exponent decreases dramatically with increasing temperature at concentrations, cL2d 〉 1. Scaling of rotational diffusivity, with respect to temperature and solvent viscosity in the semidilute regime, does not follow the predictions of DE theory (and related caging ideas). On the contrary, a model proposed by Fixman was found to explain both the temperature and concentration dependence of the rotational diffusivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 181-190, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 221-235 
    ISSN: 0887-6266
    Keywords: segmented ; polyurethanes ; crosslinked ; properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two series of segmented polyurethanes, one containing 50% soft segments and the other with 70% soft segments were synthesized. Chemical crosslinks were introduced through the hard segment in a controlled way. Chemical polyurethane networks were characterized by swelling. The effect of the degree of crosslinking on properties was examined. It was found that chemical crosslinks in the hard segment reduce the mobility of the soft phase and destroy the crystallinity of the hard phase, but they improve heat stability of the hard domains. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 221-235, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 281-288 
    ISSN: 0887-6266
    Keywords: side-chain liquid-crystalline polymer membrane ; pervaporation ; benzene/cyclohexane mixture ; state-transformation ; benzene permselectivity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When a benzene/cyclohexane mixture of 10 wt % benzene was permeated through side-chain liquid-crystalline polymer (LCP) membranes by pervaporation at various temperatures, the permeation rate increased with increasing permeation temperature. The LCP membranes also exhibited a benzene permselectivity. The permselectivity for the benzene/cyclohexane mixture through the LCP membrane was different in the glassy, liquid-crystalline, and isotropic states. The LCP membrane had different apparent activation energies for permeation at each state. LCP membrane in the liquid-crystalline state had the highest apparent activation energy of the three states. Results suggest that the benzene permselectivity was influenced by changes in the LCP membrane structure, i.e., a state-transformation. It was found that a balance of the orientation of mesogenic groups and the flexibility of the siloxane chains was very important for benzene permselectivity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 281-288, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 325-335 
    ISSN: 0887-6266
    Keywords: dispersion polymerization ; styrene ; water-ethanol mixtures ; partitioning behavior ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simulation model has been developed to predict the partitioning behavior of styrene in dispersion polymerization in ethanol-water mixtures. The composition of both the continuous phase and the dispersed phase are quantitatively estimated throughout the polymerization process. The presence of water in the system causes a considerable increase of the styrene partitioning in favor of the particles. Thus, at 70°C and for an initial composition of ethanol/water/styrene = 63.3/26.9/9.8, the concentration of styrene in the particles is about 4.8 times higher than that in the serum instead of about one in pure ethanol. The higher the polymerization temperature, the lower the styrene concentration in the particles; the higher the initial styrene concentration, the higher the styrene concentration in the particles, whereas the partition coefficient is not largely effected. In contrast, neither the interfacial tension nor the final particle size do significantly alter the simulation results. The predicted data from this model have been successfully applied to clarify the mechanisms involved in dispersion polymerization, in terms of stabilization and of kinetic events. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 325-335, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 357-371 
    ISSN: 0887-6266
    Keywords: gelation theory ; nonlinear polymerization ; molecular weight distribution ; branched polymers ; polymer modification ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A Markovian model is proposed for nonrandom branching reactions, by using free-radical polymerization that involves chain transfer to polymer as an example. Free-radical polymerizations are kinetically controlled; therefore, each primary polymer molecule experiences different history of branched structure formation. By assuming that the primary chains with the identical birth time conform to the same chain connection probabilities, the nonlinear structural development can be viewed as a system in which the primary chains formed at different birth times are combined into nonlinear polymers in accordance with the first-order Markov chain statistics. An explicit formula for the weight-average chain length is derived in a matrix form. The onset of gelation is simply stated as a point at which the largest eigenvalue of the transition matrix X reaches unity, i.e., det(X - I) = 0. This criterion for the onset of gelation can be considered as an extension of the Flory/Stockmayer theory to a nonequilibrium reaction system. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 357-371, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2811-2819 
    ISSN: 0887-6266
    Keywords: PTFE/hexafluoropropylene copolymers ; crystal ; disorder ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of new copolymers of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) containing up to 50 mol % of the hexafluoropropylene comonomer have been investigated with respect to chain conformation and crystal structure using wide-angle X-ray diffraction (WAXD). Increasing HFP content leads to significant departures from the highly ordered crystalline structure of the homopolymer PTFE; the helical conformation of the chain relaxes and untwists to accommodate the larger —CF3 pendant group in the HFP unit. Simultaneously the lateral hexagonal packing of the helices becomes less ordered and the a-dimension of the hexagonal cell increases. The above effects are progressive with increasing HFP content. At 50 mol % HFP incorporation the structure is a disordered crystalline phase. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2811-2819, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2865-2868 
    ISSN: 0887-6266
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2877-2886 
    ISSN: 0887-6266
    Keywords: ionomers ; NIR ; chemometrics ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Near Infrared (NIR) spectroscopy coupled with chemometrics techniques were utilized to study the composition and properties of styrene-sodium methacrylate ionomers. Predictive models were obtained for mol % ionic content, as well as for the ionic cluster glass transition temperature, storage modulus, and tan δ peak parameters. The results illustrate the feasibility of using NIR and chemometrics algorithms as a property predictive tool, as well as the potential for the development of full calibration models. The chemometric parameters are discussed based on correlations with ionomer NIR spectral features and the role water molecules play as a probe for the associated structure of the ionomer. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2877-2886, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2905-2910 
    ISSN: 0887-6266
    Keywords: polyalkylthiophenes ; heterojunction ; BF3-diethyl ether ; electropolymerization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new kind of all-organic heterojunction consisting of polythiophene and its derivatives was prepared by the electrochemical method in the presence of boron trifluoride diethyl ether as supporting electrolyte on indium-tin oxide glass electrode. It was observed that sequential-different oxidation potential among layers of polythiophenes is a prerequisite for the heterojunction to show rectification effect. The carrier-flow of the three semiconductors for PBrT/PT/PMT heterojunction was discussed in detail. Its rectification ratio, barrier height, and ideality factor were 392 (±2 V), 0.89 eV, and 8.1, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2905-2910, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2931-2939 
    ISSN: 0887-6266
    Keywords: associations ; random copolymers ; self-diffusion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The self-diffusion of four styrene-methylmethacrylate random copolymers dissolved in acetone, a thermodynamically bad solvent for the styrene sequences in the copolymer, were investigated by pulsed-field gradient NMR. The echo attenuations Sinc(q,t) are dominated by diffusion of clusters. At higher concentrations, physical gelation sets in (formation of a transient network), which is manifested in an anomalous, restricted diffusion at short observation times. The measured fluctuations of the positions of the chain segments in the transient network have an amplitude of about 100 nm. The free long-range diffusion attained at long observation times shows a much stronger concentration dependence than in the nonassociating solvent benzene. The results are in accord with light-scattering investigations. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2931-2939, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 95-104 
    ISSN: 0887-6266
    Keywords: blends ; melting behavior ; miscibility ; FTIR ; hydrogen bond interactions ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The miscibility of poly(4-hydroxystyrene-co-methoxystyrene) (HSMS) and poly(ε-caprolactone) (PCL) was investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy (FTIR). HSMS/PCL blends were found to be miscible in the whole composition range by detecting only a glass transition temperature (Tg), for each composition, which could be closely described by the Fox rule. The crystallinity of PCL in the blends was dependent on the Tg of the amorphous phase. The greater the HSMS content in the blends, the lower the crystallinity. The polymer-polymer interaction parameter, χ32, was calculated from melting point depression of PCL using the Nishi-Wang equation. The negative value of χ32 obtained for HSMS/PCL blends has been compared with the value of χ32 for poly(4-hydroxystyrene) (P4HS)/PCL blends. The specific nature, quantitative analysis, and average strength of the intermolecular interactions in HSMS/PCL and P4HS/PCL blends have been determined at room temperature and in the molten state by means of Fourier transform infrared spectroscopy (FTIR) measurements. The FTIR results have been in good correlation with the thermal behavior of the blends. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 95-104, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 133-141 
    ISSN: 0887-6266
    Keywords: recrystallization rate ; equilibrium melting temperature ; differential scanning calorimetry (DSC) ; poly(butylene terephthalate) (PBT) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is described for measuring the heat and rate of recrystallization following partial melting. The method uses a specific sequence of temperatures with a differential scanning calorimeter, and the melting and recrystallization processes were confirmed by optical observations. The method was applied to poly(butylene terephthalate). The rate of recrystallization was found to be roughly two orders of magnitude faster than isothermal crystallization from the melt. The melting temperatures obtained from recrystallization were used in the Hoffman-Weeks equation to deduce 236°C as the equilibrium melting temperature for poly(butylene terephthalate). © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 133-141, 1998
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  • 76
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3115-3125 
    ISSN: 0887-6266
    Keywords: interfacial thickness ; PPO ; SAN ; SMA ; neutron reflectivity NR ; binary interaction energies ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Estimates for the thickness of the interface between poly (2,6-dimethyl-1,4-phenylene oxide) (PPO) and copolymers of styrene-acrylonitrile (SAN) and styrene-maleic anhydride (SMA) based on the theory of Helfand and Tagami are compared to neutron reflectivity (NR) measurements. Good agreement is found between the NR measurements and theoretical predictions that make use of a mean field binary interaction model and previously reported binary interaction energies. The techniques outlined in this work may be used to understand relationships between the mechanical properties of multiphase polymer blends and the fundamental thermodynamics of polymer interactions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3115-3125, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 447-453 
    ISSN: 0887-6266
    Keywords: polyethylene terephthalate ; low density polyethylene ; isocyanate functional group ; compatibility ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To evaluate the compatibilizing effects of isocyanate (NCO) functional group on the polyethylene terephthalate/low density polyethylene (PET/LDPE) blends, LDPE grafted with 2-hydroxyethyl methacrylate-isophorone diisocyanate (LDPE-g-HI) was prepared and blended with PET. The chemical reaction occurred during the melt blending in the PET/LDPE-g-HI blends was confirmed by the result of IR spectra. In the light of the blend morphology, the dispersions of the PET/LDPE-g-HI blends were very fine over the PET/LDPE blends. DSC thermograms indicated that PET microdispersions produced by the slow cooling of the PET/LDPE-g-HI blends were largely amorphous, with low crystallinity, due to the chemical bonding. The tensile strengths of the PET/LDPE-g-HI blends were higher than those of the PET/LDPE blends having a poor adhesion. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 447-453, 1998
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  • 78
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1401-1417 
    ISSN: 0887-6266
    Keywords: polyelectrolytes ; Brownian dynamics ; shear flow ; extensional flow ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformational and rheological dynamics of dilute solutions of polyelectrolyte macromolecules undergoing shear and extensional flow are modeled using Nonequilibrium Brownian Dynamics (NEBD) and Configuration-Biased Monte Carlo (CBMC) simulations. The mathematical model utilizes a bead-spring chain with charged beads that interact through a screened Debye-Hückel potential, and that also interact through stretching and bending forces. The diffusion (or Fokker-Planck) equation for the probability density of the positions of the beads of the chain is converted to a Stochastic Differential Equation (SDE), from which the simulation algorithm for the NEBD is obtained. The CBMC is used in the initial chain generation and in determining steady-state properties in elongational flows. Various conformational and rheological quantities, such as the stress and birefringence, are monitored, under both steady-state and transient conditions, with the primary independent variable being the salt concentration (parametrized through the Debye length) and the strength of interaction q, related to the degree of ionization of the chain. It is found that this model is able to describe qualitatively many of the experimentally observed features in such systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1401-1417, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 543-553 
    ISSN: 0887-6266
    Keywords: polyacrylonitrile ; polyimine ; isotacticity ; dynamic mechanical analysis ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyacrylonitrile (PAN) films have been “grafted” onto copper electrodes by cathodic polarization and analyzed by infrared spectroscopy and dynamic mechanical thermal analysis (DMTA). The dynamic mechanical response shows two or three transitions depending on the film thickness and the potential deposition. The viscoelastic properties of “ungrafted” PAN films, e.g., solvent cast films of commercially available PAN, are deeply different from those of “electrografted” films. The experimental data support that “ungrafted” chains are paracrystalline in contrast to the “grafted” ones which are essentially amorphous. Moreover, the irreversible transformation of the “grafted” PAN chains observed beyond 225°C is confirmed by Fourier transform infrared (FTIR) analysis and ascribed to an intramolecular cyclization of PAN into polyimine. This reaction occurs rapidly and at a comparatively low temperature with respect to “ungrafted” PAN, which suggests that the “grafted” chain configuration might be predominantly isotactic. The isotacticity and the amorphous structure appear to decrease as the thickness of the PAN film is increased. Literature data and the herein reported observations would suggest a dependence of the amorphous structure of PAN on the chain isotacticity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 543-553, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 583-593 
    ISSN: 0887-6266
    Keywords: enthalpy relaxation ; differential scanning calorimetry ; peak-shift method ; polymethyl(α-n-alkyl)acrylates ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this work, we have investigated by DSC the structural relaxation of amorphous polymethyl(α-n-alkyl)acrylates in which it is possible to change the length of the alkyl chain. We have evaluated the Narayanaswamy parameter, x, which controls the relative contribution of temperature and of structure to the relaxation time, the apparent activation energy, Δh*, and the nonexponentiality parameter, β, of the stretched exponential response function. The results suggest that x increases while Δh* decreases and β remains constant as the length of the side chain increases. This allows us to comment on the effect of chemical modification on the relaxation kinetics. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 583-593, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 641-653 
    ISSN: 0887-6266
    Keywords: impedance spectroscopy ; chemical and physical changes ; glass formers ; reactive polymers ; in situ monitoring ; dielectric properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study was conducted aimed at establishing the nature of chemical and physical phenomena in polymeric and nonpolymeric glass formers that can be observed by impedance measurements. Various systems were investigated that undergo a temporal evolution of structure as a result of chemical reactions and physical processes such as crystallization, vitrification, or phase separation. Distinct and systematic changes in impedance during crystallization and vitrification confirmed that these events could be monitored by impedance spectroscopy. Of particular interest was the potential use of impedance measurements in detecting gelation in crosslinking polymers. It was shown that the experimentally observed “knee” in imaginary impedance during reaction shifts with frequency and, hence, cannot be used to measure gelation. But a new insight at the molecular level was obtained by employing a novel experimental approach based on simultaneous dielectric-infrared measurements. Evidence was generated to support the formation of a hydrogen-bonded complex in the vicinity of gel point in polymer networks, which affords a vehicle for the migration of intrinsic charges and provides a contribution to the overall conductivity. This finding should be explored further because it suggests the possibility of correlating dielectric response with gelation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 641-653, 1998
    Additional Material: 11 Ill.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 665-671 
    ISSN: 0887-6266
    Keywords: clustering ; water ; wood ; adsorption ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Clustering behavior of water molecules during adsorption of water in wood was studied using the Zimm-Lundberg theory. The average cluster size of water molecules was determined with the help of wood adsorption isotherms at five temperatures. The effects of both relative humidity and temperature on average cluster size were studied. Average cluster size progressively increased with an increase in humidity. At humidities corresponding to fiber saturation, larger clusters were formed. Cluster size increased sharply with an increase in temperature at humidities close to saturation. Formation of large clusters at high temperature and humidities close to saturation is attributed to increased fraction of weakly bonded water and capillary condensation in such conditions. A description of adsorption of water in wood was provided in terms of average cluster size. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 665-671, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 705-714 
    ISSN: 0887-6266
    Keywords: molecular weight distribution ; comb copolymer ; branching ; grafting ; nonlinear polymerization ; modeling ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Grafting one type polymer onto a different polymer type may yield a comb-branched copolymer. The branching density has a significant effect on its overall molecular weight distribution. A general model is derived to describe the bivariate distribution of molecular weight and branching density for such comb copolymers. The model is applicable for various grafting mechanisms provided the side chains are randomly grafted onto the backbone. The determining parameters are the molecular weight distributions of backbone and side chains, and the branching density. Analytical expressions are obtained for the cases of the side chains having uniform and Schulz-Zimm distributions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 705-714, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 715-725 
    ISSN: 0887-6266
    Keywords: polyethylene ; ion implantation ; surface structure ; wear ; hardness ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyethylene (PE) film was implanted with 1000-keV Ar+ ions to a fluence of 5 × 1014 ions/cm2 under high vacuum conditions (2.5 × 10-6 torr) and the film surface was investigated by means of microhardness and microwear measurements, and FTIR/ATR, Raman, and XPS techniques. Ion implantation significantly increased the subsurface hardness and also significantly improved the microwear resistance of the polymer. The implanted surface region of the film was found to consist of two distinct layers. One was the outermost carbon layer with a thickness of the order of 10 nm. In this layer, ca. 75% of carbon atoms were combined by graphitic sp2 and diamond-like sp3 bonds, and the remaining 25% had chemical links with oxygen atoms. Spectroscopic data suggested that the sp2-bonded carbons segregated in graphite-like clusters containing imbedded oxygen atoms, interconnected by the sp3-bonded carbons. The other was the subsurface layer resulting from PE oxidation after ion-beam treatment. This layer was characterized by high contents of O—H and C=O groups as well as ester and double bonds. The chemical composition of the layer was uniform and did not vary over the layer thickness of about 1.4 μm. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 715-725, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 783-788 
    ISSN: 0887-6266
    Keywords: poly(ethylene terephthalate) ; sub-Tg ; annealing ; conformation ; infrared spectra ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using FTIR spectroscopy we have examined conformational changes in the quenched and slowly cooled amorphous PET films during physical aging process. It was observed that the amount of trans conformers for quenched sample decreased upon sub-Tg annealing. For the slowly cooled sample that corresponds to a state closer to equilibrium, the amount of trans conformers hardly decreased, but increased gradually during sub-Tg annealing process. The conformational populations of these two samples tend to be identical with annealing time. These results demonstrate that sub-Tg annealing will lead to closer interchain packing and result in the formation of new cohesional entanglements along the chains. In situ FTIR studies on the conformational changes of these samples were also carried out during heating up of the sample through the glass transition region. The results showed that incremental changes of the amount of trans conformers in Samples Q and SC were gradual, while an abrupt change of trans conformers occurred in the sub-Tg annealed samples. These results were in agreement with the formation of the interchain cohesional entanglement due to sub-Tg annealing. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 783-788, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 841-850 
    ISSN: 0887-6266
    Keywords: specific volume ; Tait equation ; compressibility ; scaling parameter ; hole theory ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pressure-volume-temperature (PVT) properties of three commercial samples of poly(dimethylsiloxane) are studied experimentally and theoretically in the temperature range 25-150°C and for pressure to ∼ 3 kbar. The Tait equation is employed to represent the data at elevated pressure. Isothermal compressibilities are computed for the three samples. The melt data are analyzed in terms of the Simha-Somcynsky hole theory, and scaling parameters of pressure, volume, and temperature are obtained. Satisfactory agreement between theory and experiment is found over the entire range of experimental pressures. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 841-850, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 851-859 
    ISSN: 0887-6266
    Keywords: poly(aryl ether ketone)s ; dielectric relaxation spectroscopy ; dynamic mechanical analysis ; α-relaxation ; β-relaxation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relaxation behavior of four amorphous poly(aryl ether ketone)s was investigated using dielectric relaxation spectroscopy and dynamic mechanical analysis. The temperature dependence of the relaxation times of the glass transition process and the cooperative nature of this process were unaffected by changes in polymer structure. The temperature location of the loss peaks for all polymers progressed smoothly between the low frequency of the mechanical measurements and the higher frequencies of the dielectric probe. Differences were observed in mechanical activation energy and dielectric relaxation strength for one polymer which contained a significant concentration of meta linkages, compared with the para-linked polymers, while relaxation broadness was generally greater in the dynamic mechanical mode. Changes in chemical structure had little effect on the shape, intensity, and location of the β-relaxation peak, the main observation being that the Arrhenius activation energy measured by dynamic mechanical analysis was significantly higher than that calculated from the dielectric data. The dielectric β-relaxation was sensitive to absorbed moisture. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 851-859, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1731-1738 
    ISSN: 0887-6266
    Keywords: poly(p-phenylene sulfide) fiber ; zone-drawing ; zone-annealing ; mechanical properties ; DSC thermogram ; viscoelastic properties ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A zone-drawing and zone-annealing treatment was applied to poly(p-phenylene sulfide) fibers in order to improve their mechanical properties. The zone-drawing (ZD) was carried out at a drawing temperature of 90°C under an applied tension of 5.5 MPa, and the zone-annealing (ZA) was carried out at an annealing temperature of 220°C under 138.0 MPa. The differential scanning calorimetry (DSC) thermogram of the ZD fiber had a broad exothermic transition (Tc = 110°C) attributed to cold-crystallization and a melting endotherm peaking at 286°C. The Tc of the ZD fiber was lower than that (Tc = 128°C) of the undrawn fiber. In the temperature dependence of storage modulus (E′) for the ZD fiber, the E′ values decreased with increasing temperature, but increased slightly in the temperature range of 90-100°C, and decreased again. The slight increase in E′ was attributable to the additional increase in the crosslink density of the network, which was caused by strain-induced crystallization during measurement. The resulting ZA fiber had a draw ratio of 6.0, a degree of crystallinity of 38%, a tensile modulus of 8 GPa, and a tensile strength of 0.7 GPa. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1731-1738, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 937-958 
    ISSN: 0887-6266
    Keywords: thermodynamics ; heteropolymers ; phase diagram ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On the basis of a variational principle a quantitative theory is developed enabling a thermodynamic description in terms of mean field approximation of heteropolymer mixtures of macromolecules with an arbitrary distribution for both degree of polymerization and composition. Rather simple general equations are derived to calculate compositions and volume fractions of spatially homogeneous macroscopic phases as well as to find the cloud-point curve, spinodal, and critical points. Potentialities of general theory are illustrated for copolymers synthesized by traditional methods. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 937-958, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 983-989 
    ISSN: 0887-6266
    Keywords: positron annihilation ; free-volume ; Nafion ; free-volume size distribution ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report a new result of free-volume hole size distribution in water and ethanol-swollen Nafion-117 polymer. With the increase in water content, free-volume hole size decreases, but overall the volume fraction increases. The hole size distribution in dry polymer is seen to be distinctly different from hydrated membranes. The narrow and symmetric distribution in hydrated membrane as compared to dry membrane is believed to be a consequence of crosslinking due to cluster formation. In alcohol-swollen membranes, on the other hand, not only are the free-volume size and fraction seen to be higher, the hole size distribution is seen to be broader compared to dry or hydrated membranes, indicating the effect of penetration of alcohol into the hydrophobic backbone region. We have also examined our results vis-a-vis reported gas diffusion studies in Nafion in the framework of existing free-volume model. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 983-989, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1013-1024 
    ISSN: 0887-6266
    Keywords: nonlinear optical polymer ; pressure ; chromophore reorientation ; poly(alkyl methacrylates) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Activation volumes for chromophore reorientation were measured for a series of guest-host polymeric materials, indicating a significant coupling between chromophore motion and the glassy α and β relaxation dynamics of the polymer host. The specific systems studied were formed by individually dissolving N,N-dimethyl-p-nitroaniline (DpNA), 4-(dimethylamino)-4′-nitrotolane (DMANT), 4-(diethylamino)-4′-nitrotolane (DEANT), and 1-((4-(dimethylamino)phenyl)ethynyl)-4-((4-nitrophenyl)ethynyl)benzene (DMAPEANT) in poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA), and poly(isobutyl methacrylate) (PiBMA). In each of these systems, the isothermal, sub-Tg decay of the second-order optical susceptibility χ(2) was monitored as a function of pressure using second harmonic generation. In each system, the observed decay of χ(2) was represented by a stretched exponential equation from which the decay time τ0 and decay distribution width βKWW were determined. For each dopant molecule, the decrease in activation volume with the increasing size of the polymer host's alkyl side group and the pressure dependence of βKWW were indicative of partial coupling between chromophore rotation and the glassy β relaxation dynamics of the polymer host. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1013-1024, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1091-1094 
    ISSN: 0887-6266
    Keywords: electrorheological fluids (ERFs) ; poly(dimethyl siloxane) gels ; artificial muscle ; electromechanical actuators ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1115-1128 
    ISSN: 0887-6266
    Keywords: interface structure ; fluorescence energy transfer ; polymer blends ; latex films ; poly(methyl methacrylate) ; poly(butyl methacrylate-co-butyl acrylate) ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Immiscible polymer blend films were formed by air drying aqueous dispersions containing mixtures of a high-Tg latex, poly(methyl methacrylate), and a film-forming low-Tg latex, poly(butyl methacrylate-co-butyl acrylate). Fluorescence energy transfer experiments were used to characterize the interfaces in these films, in which one component was labeled with a donor dye and the other with an acceptor. The quantum efficiency of energy transfer (ΦET) between the donors and acceptors is influenced by the interfacial contact area between the two polymer phases. As the amount of soft component in the blend is increased, ΦET approaches an asymptotic value, consistent with complete coverage of the hard polymer surface with soft polymer. This limiting extent of energy transfer is very sensitive to the total surface area in the film, with correspondingly more energy transfer at constant volume fraction for small hard particles. Some of the details of the energy transfer are revealed through a fluorescence lifetime distribution analysis. The presence of ionic surfactant (sodium dodecyl sulfate) in the dispersion from which the latex blend film is prepared reduces the cross-boundary energy transfer by 30%, which implies that in these films the surfactant decreases the interfacial contact. After annealing the surfactant-free blends above 100°C, we observe an increase in energy transfer, consistent with a broader interface between the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1115-1128, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1153-1165 
    ISSN: 0887-6266
    Keywords: even-odd nylons ; lamellar crystals ; structure ; hydrogen-bonding schemes ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nylon 6 9 has been shown to have structures with interchain hydrogen bonds in both two and in three directions. Chain-folded lamellar crystals were studied using transmission electron microscopy and sedimented crystal mats and uniaxially oriented fibers studied by X-ray diffraction. The principal room-temperature structure shows the two characteristic (interchain) diffraction signals at spacings of 0.43 and 0.38 nm, typical of α-phase nylons; however, nylon 6 9 is unable to form the α-phase hydrogen-bonded sheets without serious distortion of the all-trans polymeric backbone. Our structure has c and c* noncoincident and two directions of hydrogen bonding. Optimum hydrogen bonding can only occur if consecutive pairs of amide units alternate between two crystallographic planes. The salient features of our model offer a possible universal solution for the crystalline state of all odd-even nylons. The nylon 6 9 room-temperature structure has a C-centered monoclinic unit cell (β = 108°) with the hydrogen bonds along the C-face diagonals; this structure bears a similarity to that recently proposed for nylons 6 5 and X3. On heating nylon 6 9 lamellar crystals and fibers, the two characteristic diffraction signals converge and meet at 0.42 nm at the Brill temperature, TB · TB for nylon 6 9 lamellar crystals is slightly below the melting point (Tm), whereas TB for nylon 6 9 fibers is ≅ 100°C below Tm. Above TB, nylon 6 9 has a hexagonal unit cell; the alkane segments exist in a mobile phase and equivalent hydrogen bonds populate the three principal (hexagonal) directions. A structure with perturbed hexagonal symmetry, which bears a resemblance to the reported γ-phase for nylons, can be obtained by quenching from the crystalline growth phase (above TB) to room temperature. We propose that this structure is a “quenched-in” perturbed form of the nylon 6 9 high-temperature hexagonal phase and has interchain hydrogen bonds in all three principal crystallographic directions. In this respect it differs importantly from the γ-phase models. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1153-1165, 1998
    Additional Material: 9 Ill.
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  • 95
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1557-1566 
    ISSN: 0887-6266
    Keywords: polyesters ; PET ; PEN ; PEI ; 13C NMR ; dynamics ; nuclear relaxation times ; gas diffusion ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamics of amorphous aromatic polyesters consisting of poly(ethylene terephthalate) (PET), poly(ethylene isophthalate) (PEI), and poly(ethylene 2,6-naphthalenedicarboxylate) (PEN) has been investigated by means of solid state CPMAS 13C NMR. Proton T2, 13C T1ρ, and proton T1ρ decays have been measured in particular, and the experimental data fitted to suitable model functions to determine best relaxation parameters. The fitting results show for proton T2 and 13C T1ρ measurements the presence of two components with different relaxation times and intensities, arising from different motional domains. The proton T1ρ, on the contrary, shows a single component which limits the dimensions of the two regions to less than 20 Angstroms. The dependence of 13C T1ρ values on two different irradiating field strengths (H1 = 38 KHz, H1 = 60 KHz) allowed the assignment of each component to relatively rigid and mobile regions. By comparing the three polymers we observe that PEN and PEI have a similar relaxation behavior, while a higher fraction of mobile components was found for PET. These differences are believed to arise mainly from local motions of the aromatic rings. The relaxation measurements have been evaluated to suggest a correspondence to O2 and CO2 gas permeabilities in PET, PEI, and PEN. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1557-1566, 1998
    Additional Material: 7 Ill.
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  • 96
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2165-2175 
    ISSN: 0887-6266
    Keywords: temperature-modulated differential scanning calorimetry ; DSC ; heat capacity ; glass transition ; thermal relaxation ; polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass transition can be measured at different experimental conditions. Using spectroscopic methods at relative high frequency the α-relaxation is measured in the thermodynamic equilibrium. In the caloric case we call this phenomenon thermal relaxation transition (TRT). With a conventional differential scanning calorimeter (DSC) the transition of the equilibrium (the melt) into a nonequilibrium (the glassy state) is measured. This effect is called thermal glass transition (TGT). In contrast to the TGT, the TRT can be described using the linear response approach. The temperature-modulated differential scanning calorimetry (TMDSC) technique superimposes a periodical temperature perturbation upon the constant scanning rate of conventional DSC. This technique combines a spectroscopic method with a linear temperature scan. Both the TGT and the TRT are measured simultaneous. Because the frequencies are relatively low in a TMDSC experiment, the temperature ranges of both transitions overlap. In this case, the experimental results show an influence of the TGT on the TRT. The reason of that is the deviation from the nonequilibrium. In this case, the fictive temperature is different from the external temperature. This effect can be described by means of a Tool-Narayanaswamy-Moynihan model for the TGT. Based on this model, a description of the complex heat capacity close to the thermal glass transition is shown. The influence of the beginning freezing-in process on the thermal relaxation is characterized by the fictive temperature. Using the presented description, a quantitative calculation of the nonlinear effects in the thermal relaxation is possible. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2165-2175, 1998
    Additional Material: 7 Ill.
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  • 97
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2177-2189 
    ISSN: 0887-6266
    Keywords: yield ; polyethylene ; stem length ; crystal plasticity ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The yield stress behavior of a range of polyethylene materials which differ with respect to their short chain branch content has been studied. Measurements carried out over a wide range of temperatures have shown that there is a sudden transition in the behavior of the yield stress at a temperature which is dependent on both the grade of material and the applied strain rate. These results are in agreement with previous results found from analysis of the yield strain behavior.Above the transition temperature the materials all behave in a nonlinear viscoelastic manner, and the yield process is considered as being propagation controlled. Below the transition temperature the materials all behave in an elastic-plastic manner, and the yield process is considered as being nucleation controlled. Below the transition temperature the temperature dependence of the yield stress is determined by the thickness of the crystalline lamellae. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2177-2189, 1998
    Additional Material: 16 Ill.
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  • 98
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2225-2235 
    ISSN: 0887-6266
    Keywords: PEEK ; composite ; stability ; nonisothermal ; crystallinity ; melting ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal stability of a short carbon-fiber-reinforced PEEK composite was assessed by thermogravimetry and by a Rheometrics dynamic analyzer. The results indicated that holding for 10 min at 380°C was a suitable melting condition to avoid the thermooxidative degradation under air. After proving that the heating rate of 50°C/min can be used to evaluate the crystallinity, a heating stage was used to prepare nonisothermally crystallized specimens using cooling rates from 1 to 100°C/min after melting at 400°C for 3 or 15 min. The degree of crystallinity and the melting behavior of these specimens were investigated by DSC at a heating rate of 50°C/min. The presence of three or four regions indicated that the upper melting temperature, Tm, changed with the crystallization temperature. The first region with the highest Tm, which corresponded to the cooling rate of 1°C/min, can be associated with the crystallization in regime II. There was a second region where Tm decreased as the amount of crystals formed in regime II decreased with increasing cooling rate from 5 to 20°C/min. The third region, a plateau region, corresponded to regime III condition in which the crystals were imperfect. In the fourth region, the cooling was so fast that crystallization was incomplete during the cooling for the melting condition of 400°C for 15 min. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2225-2235, 1998
    Additional Material: 8 Ill.
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  • 99
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2513-2523 
    ISSN: 0887-6266
    Keywords: block copolymer ; thermoplastic elastomer ; physical gel ; order-disorder transition ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermoplastic elastomer gels (TPEGs) composed of a poly[styrene-b-(ethylene-co-butylene)-b-styrene] triblock copolymer and a low-volatility, midblock-compatible mineral oil have been investigated here to ascertain the effects of composition on TPEG morphology, and temperature on mechanical properties. Cryofracture-replication transmission electron micrographs reveal the existence of spheroidal bumps due to copolymer micelles, as well as a network of irregularly shaped, high-aspect-ratio features. Since the density of this network decreases with increasing oil concentration, these features are attributed to copolymer grain boundaries. Micellar periodicities are discerned from small-angle X-ray scattering as a function of copolymer concentration and compared with previously reported data from related systems. Dynamic rheological tests performed up to 140°C indicate that the linear viscoelastic regime for these TPEGs decreases with both increasing copolymer concentration and temperature. A concentration-dependent thermal transition, signified by an abrupt reduction in the dynamic elastic modulus (G′), has also been identified.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2513-2523, 1998
    Additional Material: 9 Ill.
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  • 100
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2949-2959 
    ISSN: 0887-6266
    Keywords: ultrasound ; crystallization kinetics ; film formation ; polychloroprene ; shear modulus ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We report the application of an ultrasonic shear wave reflection technique for the investigation of film formation and crystallization kinetics of one amorphous and two semicrystalline polychloroprene samples with different gel content. Both isothermal and temperature-dependent measurements of the complex dynamic shear modulus (G* = G′ + iG″) have been performed at a frequency of 5.32 MHz. The process of film formation during the evaporation of water is expressed by a stepwise increase of the shear modulus. For the semicrystalline samples a further increase, which is due to crystallization, can be observed. Film formation and crystallization are delayed for the sample with high gel content and its minor final modulus is explained by a lower degree of crystallinity. The time-dependent increase of the shear modulus due to the growth of spherulites has been analyzed by the Avrami equation combined with the Kerner model for the modulus of a two-phase composite (spherulites in an amorphous matrix). The dynamic shear modulus for the spherulites has been estimated by a model introduced by Halpin and Kardos. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2949-2959, 1998
    Additional Material: 8 Ill.
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