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  • 1990-1994  (5,145)
  • 1980-1984  (4,309)
  • Chemical Engineering  (5,890)
  • Atomic, Molecular and Optical Physics  (2,918)
  • Gas chromatography
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Year
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Amino acids 6 (1994), S. 205-211 
    ISSN: 1438-2199
    Keywords: Amino acids ; Amino acid enantiomers ; Chiral analysis ; Chirasil-L-Val ; Gas chromatography ; Mass spectrometry ; Selected ion monitoring ; D-Serine ; D-Alanine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The relative amounts of free D-amino acids (D-AA) in the urine of seven healthy volunteers (age 27 to 49 years) were determined using chiral phase (Chirasil-L-Val) capillary gas chromatography in conjunction with selected ion monitoring mass spectrometry. The absolute amounts of free D-AA were determined by pre-column derivatization of the amino acids witho-phthaldialdehyde andN-isobutyryl-L-cysteine followed by high-performance liquid chromatographic separation and fluorescence detection of the isoindol derivatives formed. The following most abundant D-AA were found (highest and lowest absolute and relative amounts): D-Ser (379.8 — 30.1µMol/L; 56.5 — 19.0%), D-Ala (53.8 — 7.6µMol/L; 19.6 — 5.7%), D-Thr (5.8 — 0.25µMol/L; 3.4 — 1.0%), D-Val (3.7 — 0µMol/L; 4.2 — 0%), and D-Phe (3.5 — 0.35µMol/L; 4.8 — 1.4%).
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 38 (1994), S. 689-693 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Enantioselectivity ; GC-MS ; GC-GC-MS ; Pinus peuce ; Monoterpenes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Needles of the Macedonian Pine,Pinus peuce Griseb., a conifer growing in the Balkan mountains, were extracted by a Likens-Nickerson simultaneous distillation-solvent extraction device. The components of this essential oil were identified by the retention times obtained on two columns differing in polarity and by GC-MS. Because of the complex nature of such plant extracts, a multidimensional GC method for enantiomer analysis, using a non-chiral pre-column and a chiral main column has been developed. The enantiomeric ratios of five monoterpene hydrocarbons were estimated by GC-GC and GC-GC-MS.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Gas chromatography ; Particle beam MS detection ; Polycyclic aromatic metabolites ; Biodegradation in water
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Two liquid chromatography-particle beam mass spectrometry (LC-PBMS) systems have been used for analysis of polycyclic aromatic hydrocarbon metabolites in water samples from a biological decomposition model experiment. The results were compared with those obtained by classical gas chromatography-mass spectrometry. Evaluation of spectral data indicated the presence of six main metabolites; 1H,3H-naphtho [1,8-cd]pyran-1,3-dione, 1-(hydroxymethyl)naphthalene, and 1,2-acenaphthenedione were identified by use of standard substances and spiking experiments. Enrichment of the investigated water samples with online pre-column (C18) concentration, freeze-drying, and solvent extraction led to similar results with only slight differences. The application of microbore separation columns proved to be a promising tool in particle beam LC-MS measurements.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Porous polymer stationary phase ; Selectivity studies
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The behaviour of GC columns packed with the copolymer of methacrylic ester of p,p'-dihydroxydiphenylpropane diglicydyl ether and divinylbenzene was studied. Selectivity studies were made for three polymer samples of different molar ratio of monomers. To determine the selectivities of these copolymers retention indices for seven test compounds in comparison to those obtained on Porapak Q are calculated. Additionally, the efficiency of porous polymer purification was studied by a SFE-GC-MS technique.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 39 (1994), S. 265-270 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Triglycerides ; Packed vs. capillary columns ; Milk fat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Quantitative gas chromatography of triglycerides in conjunction with established triglyceride formulae can be used to determine various milk fat parameters. Since the evaluation of, for example, iodine number or content of non-milk fats (foreign fats) in milk fat requires only the separation of triglycerides by carbon number and since repeatabilities, especially of the highboiling triglycerides, have been less acceptable with capillary columns in the past, packed columns have been used exclusively. There is, however, an increasing demand for the use of capillary instead of packed columns and to that end the present investigation has been carried out. To achieve a suitable resolution, with this particularly exacting high-temperature application, a short 5 m capillary column of extreme temperature stability has been used. As well as modification of various analytical conditions different injection techniques have been investigated. On-column, PTV and split injection were compared with regard to repeatability. The cold-on-column injection technique was found to produce the best results, being comparable to the excellent precision of a packed column. Thus, a method is now available by means of which the determination of milk fat parameters by the triglyceride formulae, such as the amount of foreign fats in milk fat, can now be carried out with a standardized capillary column.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Liquid modified adsorption capillary columns ; Polar compound analysis ; Aqueous solution analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The preparation of graphite layer open tubular (GLOT) columns is described together with their application to the analysis of priority pollutants and polar compounds such as alcohols, free carboxylic acids, aliphatic amines and phenols at the sub-nanogram level. A specific application of GLOT columns is for the direct analysis of aqueous solutions avoiding solvent extraction procedures. Several chromatograms of critical separations are reported together with calibration curves. A study of the reproducibility of column preparation is reported in terms of the standard deviation of the capacity ratio and of the minimum HETP obtained.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 38 (1994), S. 679-688 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Stationary phases ; Phase constants ; Explanatory coefficients
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Explanatory phase coefficients according to Abraham et al. are calculated from McReynolds index differences and the phase constant B. The retention expression (log Vg)−A=BI/100 connects specific retention volumes and retention indices. McReynolds phase constants and Abrahams explanatory coefficients can be used with similar accuracy for the prediction of relative retention data and for the characterization of stationary phases in gas chromatography. The application of polarity constants for the characterization of stationary phases is discussed.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 38 (1994), S. 304-312 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Electron capture detector ; Theoretical model of ECD
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary This paper reports a theoretical model of the ECD detector. The model presented here can be used to examine the influence of pulse parameters on the current and signal characteristics of the detector. On the basis of this model it was found that a space charge is created in the detector when it is supplied with pulse voltage. Due to the electric potential generated by the space charge, in the time between the pulses the electrons and negative ions move towards the detector electrodes. The ionization current of the detector is the sum of the electron current flowing to the anode under the influence of the supplied pulse voltage and the current flowing under the space charge potential in the time between the pulses. It was also found that the detector signal is the sum of the differences between those two currents caused by introducing the sample molecules to the detector. The model was tested for a detector with different electrode configurations which worked at temperature of 300 K or 573 K and which was supplied with nitrogen or Ar+10% CH4 as the carrier gas.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Curie-point pyrolysis ; Multivariate analysis ; Sodium dodecylbenzene sulfonate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Multivariate analysis was used to develop a viable method for determination of sodium dodecylbenzene sulfonate (DBS) by Curie-point pyrolysis gas chromatography. The pyrograms obtained were normalized against a maximum peak area and peak height. Normalized values were used for Quantification IV, which is one of the multivariate analysis methods, to select useful values initially. Then cluster analysis was carried out using both the selected values and their deviations. This method corresponds to qualitative analysis and indicates which data-base is similar to the sample. On the basis of this data-base, calibration data-bases are chosen. Principal component analysis (PCA) was performed using the calibration data-base and a set of sample data simultaneously. The principal component scores and contribution coefficients obtained were used to construct a calibration curve from which the DBS content of the sample was calculated. The results are in fair agreement with theoretical values.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Nitrogen phosphorus detection ; Atrazine and simazine ; Freeze-dried water analysis ; ELISA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The determination of atrazine in freeze-dried water samples containing simazine, 0.6% glycine as stabilizer and other pesticides has been compared using three different techniques: (i) direct rapid-magnetic particlebased ELISA, (ii) dichloromethane liquid-liquid extraction (LLE) and Florisil column clean-up prior to ELISA determination and (iii) LLE, Florisil column clean-up and gas chroamtography with nitrogen phosphorus detection (GC-NPD). The methodology developed in this paper has shown the advantages of the introduction of a clean-up step prior to ELISA determination and its correlation with GC-NPD determinations. Atrazine could be determined at levels between 0.1 to 5 μg l−1 in water smaples using the different methods described in this paper. The crossreactivity problems found in the ELISA test associated with the presence of simazine are also discussed.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 39 (1994), S. 210-215 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Correlation chromatography ; Concentration methods ; Polymer dynamic head-space sampling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Gas chromatography has been used to study the kinetics of evolution of volatiles from polypropylene samples (at 70°C). Correlation chromatography (CC) and the trapping of volatiles on Tenax sorbents and activated charcoal were employed to improve the detector signal. As a reference, the kinetics of gas evolution was studied by making a series of direct single injections of polymer head-space gas on a GC column. The results of trapping differed from those obtained by single injection. However, the data from single injections and CC were in good agreement. The CC method was found to offer far more operator convenience for dynamic head-space analysis than sample trapping, being less subject to operator errors.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 39 (1994), S. 294-298 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Preconcentration ; Thermal modulator ; Cross-correlation ; Trace analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The inside wall of an uncoated polyethylene capillary traps organic substances from a water sample pumped through it by a nitrogen gas stream. Heating the capillary in a chromatographic oven slowly releases the trapped organic substances from the wall. Nitrogen carrier gas transports sample substances released through a thermal desorption modulator and onto a chromatographic column. Pulsing the temperature of the modulator modulates the concentrations of sample components as they enter the column. Computing the cross correlation of the detector output signal against the applied modulation signal generates the chromatogram. Detection limits below 1 ppb are possible using a flame ionization detector. No sample pretreatment or cold trap is required.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 39 (1994), S. 363-365 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Light hydrocarbons ; Stabilized crude oil ; Capillary guard column
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary This paper reports a quick, and simple method for quantitative determination of C2 to C6 hydrocarbons in stabilized crude oil without using a back flush system. A mixture of crude oil and internal standard is injected into a GC equipped with a 6 meter length of fused silica capillary as a guard column. The light hydrocarbons are separated individually up to the last peak of the hexane group with the heavier components trapped in the guard column. The total analysis time for each sample is 15 minutes. The base line is table for up to 15 consecutive analyses. The guard column and the injector port are then reconditioned by simply heating them for one hour at 300 °C.
    Type of Medium: Electronic Resource
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  • 14
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Retention/structure and retention/temperature ; relationships ; Experimental design ; Enthalpy-entropy compensation ; para-Hydroxy benzoic esters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An experimental design has been used to study the effect of column temperature on the gas chromatographic retention of eightpara-hydroxy benzoic esters. A rapid procedure has been developed to reduce the number of experiments compared with traditional methods. Capacity factors were determined and the enthalpy and entropy of transfer from the mobile phase to the stationary phase, ΔHo and ΔSo, respectively, were calculated using the linear Van't Hoff equation (dependence of ln k′ on 1/T). A retention prediction system (RPS) for these compounds in GC was investigated. The molecular connectivity index was used to describe the quantitative structure relationships. Enthalpy — entropy compensation revealed that the mechanism was similar for all the compounds studied.
    Type of Medium: Electronic Resource
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  • 15
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Priority pollutants ; EPA methods ; Unleaded gasoline ; Volatile organochlorine compounds
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The complete separation of the sixty volatile organochlorine (VOC) priority pollutants has been achieved by coupling two different liquid-modified adsorption chromatography columns. Two temperature programs were used to obtain the complete separation in a relatively short analysis time. Detection was by FID alone
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 38 (1994), S. 93-97 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Retention index ; Adsorption effects ; Terpene alcohols ; Fused-silica capillary columns
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Retention indices of 6 selected hydroxy compounds (aliphatic and bicyclic alcohols, phenols) were determined on 2 HP-5 fused-silica, capillary columns with different film thicknesses (0.11 μm and 0.33 μm) at 8 different oven temperatures between 80 and 150°C. For some substances the I-T plot was found to show a minimum which cannot be explained by the common retention-index temperature-dependence in gas-liquid chromatography. This result is discussed in terms of adsorption at the liquid-solid interface of the capillary column.
    Type of Medium: Electronic Resource
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  • 17
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Stationary Phase and solute polarity ; Molecular structural coefficients ; Retention index ; Takács equation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Molecular structural coefficients, Sc, for one hundred solutes have been calculated by means of the Takács equation using retention data obtained with over fifty stationary phases, SP. Employing data of seven SP's (characterized in our laboratories) it was found that the variation of Sc with column temperature was linear for most solutes. With data of n-decane and the ten McReynolds probes on up to fifty SP's of polarity less than RP=72, at 120°C, it was found that the Sc of n-decane and cis-hydrindane decreased slightly with increasing SP polarity, while the Sc of non-alkanes remained constant or increased very little as the SP polarity increased. The points for n-decane fit well to a second order polynomial. Again using a temperature of 120°C, the increments of Sc for solutes belonging to an homologous series were correlated with the polarity of SP's. Reasonably straight lines were obtained for all the chemical functions studied, Sc increasing with increasing SP polarity.
    Type of Medium: Electronic Resource
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  • 18
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Stationary phase characterization ; Principal component analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary In this study, several new stationary phases were characterized by principal component analysis. Fourteen new stationary phases, including substituted phenyl and oligoethyleneoxide functionalities on polysiloxane polymers, were tested and compared to three well known stationary phases. The main features of these phases were studied using a series of test solutes of varying chemical characteristics representing the data set for principal component analysis. Two principal compounds were found to account for 99.20% of the variance (the first accounted for 94.96% and the second for 4.24%). The data were represented as a two-dimensional map for visual representation of the characteristics of these stationary phases. The first principal component represented a selectivity based on polarity (r2=0.998), while the second showed Lewis acid-base characteristics of the phases. Polarizable and amphoteric characteristics of these phases also became evident using this evaluation method.
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  • 19
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Liquid-liquid extraction ; Supercritical fluid extraction ; Pesticides ; Freeze-dried water
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The stability of freeze-dried water samples spiked with eight agrochemicals (atrazine, simazine, linuron, carbaryl, propanil, fenitrothion, parathion and fenamiphos) were examined to evaluate their suitability as candidate reference materials for their determination in water samples. In addition, two different extraction procedures, liquid-liquid and supercritical fluid extraction, were compared for the isolation and trace enrichment of target analytes from freeze-dried water samples. Final analytical determinations were by gas chromatography-nitrogen phosphorus detection and electronic impact mass spectrometry, and by liquid chromatography-diode array detection. The whole methodology developed in this paper permitted the determination of pesticides spiked in water at levels varying from 0.03 to 6.9 μg L−1.
    Type of Medium: Electronic Resource
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  • 20
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 38 (1994), S. 624-628 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Ion-trap detection ; Nitriles ; Cerelas ; Perfluoroacylation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Bromoxynil and ioxynil have been determined inplants and soil by gas chromatography. These herbicides are extracted from soil samples with methylene chloride at acidic pH. Plant samples are extracted with a basic acqueous solution and extracts purified by solvent partitioning. Herbicide residues are submitted to perfluoroacylation prior to GC separation. These compoiunds are determined by ion-trap detection with single ion monitoring; N-(3-chloro-4 methyl-phenyl_ perfluoropropyl amide is used as internal standard. The detection limit of the method is near 0.001 μg g−1 for the samples studied. The proposed methods are sensitive and reproducible enough to allow determination of these herbicides at residue levels in plants and soil.
    Type of Medium: Electronic Resource
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  • 21
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 39 (1994), S. 11-14 
    ISSN: 1612-1112
    Keywords: Supercritical fluid extraction (SFE) ; Gas chromatography ; Pesticide residues ; Oxadixyl
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary This work describes the study of a degradation curve of Oxadixyl in field-treated potato and tomato samples. The residues were extracted using classical and supercritical fluid (SFE) extraction methods and analyzed by HRGC/ECD. The extraction techniques were compared and the results indicate the advantages of using SFE as an alternative method for pesticide analyses in these samples.
    Type of Medium: Electronic Resource
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  • 22
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 39 (1994), S. 706-712 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Short chain fatty acids ; Intestinal fluids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The quantification of short chain fatty acids in their free form, by gas chromatography, is the method of choice provided that the underivatized acids elute with good peak shape and reproducibility. In biological samples not only the highly polar acids themselves but also deposits of nonvolatile sample components may interact with the column or the packing material. As a result, the peak symmetry of the fatty acids and their reproducibility can become increasingly poor. Reduction of the nonvolatile matrix components by filtration of the sample has been examined in order to achieve direct analysis of the short chain fatty acids in intestinal samples by packed column GC. Membrane filter units (0.8 μm) allow a quick and simple filtration of the samples. This pretreatment reduces the peak tailing and the broadening of the peaks. The method, when applied to different intestinal samples, allowed the quantification of short chain fatty acids in hundreds of samples without derivatization. Good results are obtained at sample concentrations higher than 0.2 mmol l−1 for each acid.
    Type of Medium: Electronic Resource
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  • 23
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 39 (1994), S. 224-227 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; C1−C4 alkyl tert-butyl ethers ; Retention index
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The separation of C1−C4 alkyl tert-butyl ethers with the general formula (CH3)3C−O−R (R-alkyl substituent) on fused-silica capillary columns coated with dimethylsilicone and cyanopropylmethylsilicone stationary phases was investigated. Retention indices were determined at two temperatures in order to understand their chromatographic behaviour. The respective standard deviations were 0.3 and 0.5 i.u.
    Type of Medium: Electronic Resource
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  • 24
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Organonitrogen pesticides ; Organophosphorus pesticides ; Apples ; Solvent extraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A gas chromatographic method employing a capillary column and a selective nitrogen/phosphorus detector (NPD) has been developed for the determination of organophosphorus (OP) and organonitrogen (NP) pesticides in horticultural samples (apples). The separation of sixteen pesticides and the internal standard was performed in thirteen minutes. The analytical characteristics of the method, including linear response ranges, detection limits, and reproducibility, have been studied using a 1∶1 mixture of ethyl acetate and xylene as extraction solvent. The possibility of mutual interference between pesticides has also been studied. A procedure for the quantitative extraction of the sixteen pesticides from apple samples has also been developed; for fifteen of the pesticides recoveries 〉85% were obtained after 90 minutes extraction. The effect of different solvents both on recovery and on the sensitivity of the subsequent chromatography were also investigated. It was found that the sensitivity required must be considered when the solvent for sample treatment is selected.
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  • 25
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 39 (1994), S. 419-426 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Gas chromatography ; Chirasil-Val ; Amino acid enantiomers ; N-Isobutyryl-cysteine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Free D-amino acids (D-AA) were detected as native constituents in juices of vegetables (cultivars of cabbage, tomato, carrot, garlic) and fruits (organes, clementine, grapefruit, lemon, apples, pear, grapes) using gas chromatography (GC) or high-performance liquid chromatography (LC). For investigation by GC, AA enantiomers were converted into theirN(O)-pentafluoropropionyl 2-propyl esters and resolved on a Chirasil-L-Val capillary column. For determination by LC, precolumn derivatization of AA enantiomers usingo-phthaldialdehyde together with the chiral thiolsN-isobutyryl-L-cysteine orN-isobutyryl-D-cysteine and fluorescence detection of the diastereomeric isoindole derivatives, resolvable on an octadecylsilyl stationary phase, were used. D-Ala (0.6–3.8%) was detected in all freshly pressed plant juices usually in the highest relative amounts. Other D-AA detected were D-Asx (0.1–1.9%), D-Glx (0–1.3%), D-Ser (0–1.7%), D-Arg (0.4–1.2%, in grapes, orange, grapefruit, and clementine) and D-Leu and D-Val (1% in cabbage). Absolute amounts of native D-AA were totally 28–57 μmol L−1 in fruit juices, 14.5 μmol L−1 in a tomato juice and 8.5 μmol L−1 in a carrot juice.
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  • 26
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Atomic emission detection (AED) ; Programmed temperature vaporization (PTV) ; Nitro musks ; Human adipose tissue ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Atomic emission detection (AED) has been successfully applied to the determination of nitro musks in the fat of human adipose tissue by gas chromatography at trace concentration levels. Element specific detection with the AED combined with a clean-up procedure for nonpolar substances makes target screening analysis for lipophilic nitro aromatic compounds possible for the first time. The lack of sensitivity, especially in the AED nitrogen and oxygen trace, was compensated by higher concentration of the extracts and injection of larger sample volumes performed by cold programmed temperature vaporization (PTV) in the solvent split mode. The combination of the superior quantification properties of the atomic emission detector with large sample volume introduction makes the quantification of nitro musks down to the ppb level possible. All five nitro musks investigated exhibit linear dynamic ranges going down close to instrumental limits of detection. Moreover, organochlorine compounds could be sensitively detected in the same sample extract by the AED chlorine trace without any interferences from coeluting matrix compounds.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 27
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 17 (1994), S. 457-462 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Flame photometric detector ; Pyrolyzer ; Sulfur boiling point distribution ; Light cycle oils ; Exponential dilution flask ; Low sulfur diesel ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method has been developed to determine the boiling point distribution of sulfur compounds in light cycle oils (LCO'S). The method chosen for this analysis was GC with a flame photometric detector (FPD) and pyrolyzer. Tests were carried out to evaluate the recovery efficiency, repeatability, and accuracy of the method. Repeatabilities within 2% were obtained. The recovery of benzothiophenes and dibenzothiophenes was close to 100%; this was important because these are the major sulfur components in LCO's. No hydrocarbon or solvent interferences were observed with the use of the pyrolyzer, even for a 95% solvent level. Comparison with results from other techniques showed that the method accurately determined the levels of sulfur compounds in the LCO boiling point range.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 28
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 221-228 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A study of the influence of a compatibilizing agent on phase morphology development in a 75/25 polyethylene/polyamide-6 blend in a modular co-rotating twin screw extruder is presented. The development of phase morphology along the axis of the modular screw was observed by cooling the extruder and removing the polymer from the screw channels. Changes in phase morphology due to the addition of a compatibilizer have been investigated using scanning electron microscopy. Sufficient quantities of compatibilizing agent produce significant increases in the rate of mixing and also reduce the scale of the phase morphology. Much larger quantities (5%) than actually required for interface coverage are needed for rapid mixing. This seems to be due to the high viscosity of the matrix.
    Additional Material: 10 Ill.
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  • 29
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyalkylene-imides (i.e., aliphatic-aromatic polyimides) were prepared smoothly in N-methyl pyrollidone from straight chain aliphatic diamines and pyrromellitic dianhydride. Melting points of the polymers ranged from about 300 to 450°C, depending of the length of the alkylene chains. An odd/even effect related to the alkylene chain was noted for melting points and glass transition temperatures (Tg) of the polymers. The Tgs were relatively high, especially when compared to similarly structured polyalkylene-heterocycles, e.g., polyakylenebenzoxazoles.
    Additional Material: 2 Ill.
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  • 30
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 308-317 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The true crystallite modulus of polyoxymethylene (POM) was evaluated experimentally and thoeretically as a function of temperature. The mechanical deformation mechanism of POM was lattice-dynamically predicted and confirmed by measuring the stress-induced vibrational frequency shifts of the infrared and Raman spectra, which were interpreted on the basis of anharmonic potential field.
    Additional Material: 11 Ill.
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  • 31
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 318-329 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Transmission electron microscopy and optical studies of thin films of isotactic polystyrene (iPS) and polyoxymethylene (POM) provide evidence for a distinction between crazing mechanisms in semicrystalline polymers above and below Tg. In the latter temperature regime, deformation in iPS and POM crystallized at high supercooling has been discussed in terms of existing models for crazing in amorphous glassy polymers, based on entanglement ideas. Above Tg, where the difference in mechanical behavior of the amorphous and crystalline regions becomes marked, the fibrillar nature of local deformation appears to be a consequence of the inhomogeneity of the undeformed polymer.
    Additional Material: 11 Ill.
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  • 32
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 352-360 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Simplifying assumptions are used to reduce micromechanical treatments to compact expressions which directly reveal the role of the inclusion shape and aspect ratio in establishing the elastic behavior of heterogeneous materials. Attention is directed to the comparison of aligned ellipsoidal and cylindrical inclusions that exhibit transversely isotropic behavior characterized by five independent elastic constants. These comparisons show that the effective transverse in-plane moduli (ET*, k* and GTT*) are essentially independent of inclusion shape for aspect ratio greater than ∼ 20; ellipsoidal inclusions provide higher longitudinal reinforcement than cylindrical inclusions of equivalent aspect ratio. Comparison of predictions with measured elastic moduli shows that both the cylindrical and ellipsoidal shape models for isolated inclusions overpredict longitudinal elastic constants for systems which exhibit evidence of inclusion agglomeration. The notion of an effective aspect ratio based on clusters of filaments responding as a coherent unit appears to provide a means for reconciling a wide range of experimental observations.
    Additional Material: 1 Tab.
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  • 33
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 341-351 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Imide formation from -CONH and -COOH functional groups of 2-carboxyphenylmethacrylamide (2-CPM), 4-carboxyphenylmethacrylamide (4-CPM), 4-carboxyphenyl methacrylamide/methylmethacrylate (4-CPM/MMA) and 4-carboxyphenylmethacrylamide/N-phenylmalemide (4-CPM/NPMI) electropolymerized matrices was investigated. It was found that 2-CPM polymers undergo intramolecular imidization and anhydride formation, which result in a small amount of crosslinked network. On the other hand, the thermally cured 4-CPM polymer demonstrates a significant increase in gel fraction. Tg and dynamic storage modulus, owing to crosslinked network formation. Tgs of 4-CPM/MMA and 4-CPM/NPMI composites measured by thermomechanical analysis after thermal heating were increased and were correlated very well with the preheating time. The 4-CPM/MMA composites with a particle crosslinking (Tg increased to 245°C) maintained a higher Izod impact strength than a typical epoxy composite (200 kJ/m2 vs. 100 kJ/m2). Upon heating to promote crosslinking, a lower shear strength (65 MPa) of a 4-CPM/MMA composite increased to a strength of 78 MPa, close to the 80 MPa of an epoxy composite at 67% fiber volume fraction. A lower water absorption of around 1% was associated with the increased crosslinking. The mechanical properties of the 4-CPM/NPMI composites showed a similar trend upon preheating.
    Additional Material: 17 Ill.
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  • 34
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 330-340 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The diffusion equation of low molecular weight substances (penetrant) into a coaxial cylinder of multiple components (m) was formulated in general and solved rigorously. As the simplest but a practical case of m = 2, which corresponds to the diffusion of penetrant into fibrous material with skin and core structure, the diffusion of penetrant was analyzed in detail. That is, changes in the penetrant concentration distribution within the coaxial dual cylinder of skin and core components and the total amount of penetrant sorbed within the cylinder both with time after exposing the cylinder to atmosphere of fixed penetrant concentration of Cout were calculated with variation of the diffusion coefficient ratio (D1/D2) and the radius ratio (R2/R1), where D1 and D2 are the diffusion coefficients of penetrant in the core and the skin, and R2 and R1 are the radii of the fibrous material and the core, respectively. Keeping (R2/R1) at a constant value of 1.2 but varying (D1/D2) from 104 to 10-2, the penetrant concentration distribution was calculated and found to be much different particularly within the core between (D1/D2) 〉 1 and (D1/D2) 〈 1. The sorption curves were also found to deviate in their respective ways from that of Fickian curve of a homogeneous cylinder with (D1/D2) = 1 except at initial stage of sorption. Further, by keeping (D1/D2) constant but varying (R2/R1) from 1.1 to 1.5, the effects of relative skin thickness upon the sorption curve were studied.
    Additional Material: 11 Ill.
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  • 35
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 361-370 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A general formulation is presented for the orientation averaging of the properties of representative volume elements of heterogeneous materials. Approximations are introduced that result in the identification of four independent orientation parameters that are required to specify a general state of three-dimensional orientation. The general relationships are reduced further for the special case of “planar” and “axial” distribution and applied to an aggregate averaging scheme for short-fiber composites.
    Additional Material: 2 Ill.
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  • 36
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 377-378 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 37
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 371-376 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper deals with a new approach to nonlinear and nonequilibrium thermodynamics. The new concept, developed by P. H. Lindenmeyer, states that in a heat-setting process, with the same average processing temperature, the addition of a sinusoidal fluctuation (approximately) can produce two opposite changes depending upon the frequency and amplitude of the temperature fluctuation. Preliminary experimental results obtained on nylon 6 monofilaments using a flexible thermomechanical analyzer have clearly shown that the physical properties (in this case torque-twist modulus) depend not only upon the average temperature but also upon its time rate of change.
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  • 38
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 39
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 266-268 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Additional Material: 1 Ill.
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  • 40
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 269-278 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The crack growth behavior of polypropylene biaxially oriented by cross-rolling was studied at low temperature. Single edge notch testing produced a stable tearing type of crack growth in both 50% and 80% biaxially oriented polypropylene at -40°C, in contrast to the brittle fracture of unoriented polypropylene. The crack growth in the two oriented materials began slowly and accelerated to a constant rate that was higher in the 80% oriented material than in the 50% oriented material. The main difference between the crack growth behavior of the two was the longer period of initial slow growth in the case of 80% orientation. This period of slow growth corresponded to crack growth through the notch tip damage zone. Residual strength diagrams were used to present the crack growth data obtained when the stress state was intermediate between plane stress and plane strain. Fractography revealed large differences among the fracture surfaces of the three materials with the unoriented polypropylene showing a grainy appearance from the brittle fracture. The two oriented materials showed considerable ductility. The 50% oriented material showed many voids in the fracture surface, indicating that voiding during the fracture process contributed significantly to the toughness improvement. The 80% oriented polypropylene showed delamination crazing on the fracture surface with layered material and fibrils bridging the crazes.
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  • 41
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 279-284 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The reactions of N-phenylphthalimide films with ozone have been studied under a variety of conditions: dry ozone, moist ozone, ozone plus ultraviolet light, as well as ozone plus water vapor plus ultraviolet light. This compound is a conveniently available model for imide polymers. These reaction conditions represent simulation of certain aspects of the space environment. For each set of reaction conditions the reaction products were determined by combined gas chromatography/mass spectrometry. Semiempirical molecular orbital computations were made of the relative energetics of possible reaction pathways consistent with the generation of the observed products. The reaction products found indicate fragmentation of the imidic moiety for which the energetics are favorable.
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  • 42
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 414-419 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A model to predict the temperature-induced added loss in dual-coated optical fibers is presented. Longitudinal and lateral temperature-induced forces, originating from fiber irregularities and from the mismatch among the expansion coefficients of the glass fiber and of the coatings, are consistently included in the model. Both the bendings of the glass fiber and of the coating are considered. Transmission losses are explicity computed according to Petermann's theory on the microbending of single-mode fibers.
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  • 43
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 405-413 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The curing of epoxy-amine polymer has been modeled by the reaction of functional groups, and the mole balance of these is governed by a set of six nonlinear differential equations. In this work, we have first developed a complete analytical solution for isothermal curing. For nonisothermal curing, we have divided the domain of hydroxyl group concentration β into small increments Δβ and adopted our analytical results for this domain. In addition, we solved the energy balance equation analytically and obtained the temperature rise for Δβ. We have compared our results with those obtained from the Runge Kutta numerical solutions. We have shown that our semianalytical technique is about a thousand times more efficient and faster.
    Additional Material: 4 Ill.
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  • 44
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 613-624 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: At 75/25 concentration ratio, bisphenol a polycarbonate (PC)/styreneacry-lonitrile copolymer (SAN) blend has poor impact resistance compared to PC/ABS. A rubber phase methacrylate-butadiene-styrene (MBS) of core/shell type was dispersed in PC/SAN blend. The morphology of the unmodified and modified blend was investigated. The influence of the acrylonitrile ratio in the SAN on the microstructure was studied. It clearly shows that core/shell resides at the interface between PC and SAN. It seems that core/shell particles enhance the adhesion between the different phases. Their presence influences the interface mobility; i.e., the coalescence of the dispersed phase observed in pure PC/SAN is considerably reduced when the MBS particles are added. The impact resistance of the samples was correlated with the morphology.
    Additional Material: 14 Ill.
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  • 45
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 598-612 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper presents the development of a model for free radical initiated polypropylene degradation during reactive extrusion that combines a kinetic model of the polypropylene degradation reaction with a simplified model of the melting mechanism in the extruder. The free radical initiated degradation of polypropylene is characterized by a narrowing of the molecular weight distribution (MWD) and a decrease in the molecular weight averages. A high temperature SEC is used to determine MWD's for three different commercially available polypropylenes degraded at various initiator concentrations in a 1.5 inch single screw extruder (L/D = 24:1). The predictions of the kinetic model alone and the combined kinetic-melting model are compared with the experimentally determined MWD's and molecular weight averages for the degraded polypropylenes. The predictions of a modified kinetic model that includes the possibility of termination by combination are also examined. The kinetic-melting model is found to provide significantly improved predictions of the experimentally determined MWD's and molecular weight averages in comparison to the original kinetic model. A viscosity-molecular weight relationship is also developed, which is then used to determine the gain of the degradation process as a function of the initiator concentration from the molecular weight averages predicted by the kinetic-melting model. Earlier work has shown such prior knowledge of the process gain can be used to significantly improve the performance of process control schemes for the degradation process.
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  • 46
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 625-631 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The curing and vitrification effect during the reaction of ATBN modified epoxy resin was studied through the dynamic differential scanning calorimetry method and a new reaction kinetic equation containing generalized WLF equation was developed to describe the reaction rate at both glassy and rubbery state. An autocatalytic mechanism was found to describe adequately the cure kinetics of the rubber modified epoxy resin and the overall order of reaction was assumed to be 2. The kinetic parameters were determined from the DSC data through the Marquardt's multivariable nonlinear regression method and Runge-Kutta integration technique. The presence of rubber indicated minor effect on the cure kinetics of epoxy resin. The Arrhenius type viscosity function was employed to establish a relationship between viscosity data measured by RMS and chemical conversion calculated from the reaction kinetic equation.
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  • 47
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 642-649 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyurethane foam formation involves both polymerization and expansion processes. The dynamics of the water and R-11 blown foams depend on the rates of chemical and physical blowing processes, along with the rate of viscosity increase of the reacting mixture. Experiments were carried out to study the dynamics of free rising, water and R-11 blown rigid polyurethane foams. The density and temperature change during the foam formation were monitored. A theoretical model was developed to predict the density and temperature variation with time. In the model, the physical blowing agent (R-11) evaporation process is assumed to be heat generation-controlled and the carbon dioxide generation process to be controlled by the rate of the water-isocyanate reaction. The kinetic parameters of the reactions of isocyanate with polyol and water were obtained separately and were asssumed to be independent of each other. The water-isocyanate reaction appears to follow first-order kinetics with respect to concentration of water. The theoretical predictions of the model show good agreement with the experimental data for density variation with time. The model predictions for temperature rise also match experimental data, except at the later stages of foaming when it is found to be slower than the experimental measurements. However, this deviation does not affect the dynamics of density change since it occurs after the completion of the expansion process.
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  • 48
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    Polymer Engineering and Science 34 (1994), S. 707-715 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper describes the application of a molecular sensor for in-situ monitoring of epoxy-diamine cure via remote sensing fiberoptic probes. A custom-built, fiberoptic fluorimeter allows on-line recording of fluorescence spectra directly from the cure environment. Cure reactions in epoxy-diamine network, such as diglycidyl ether of bisphenol A-diaminodiphenyl sulfone (DGEBA-DDS) or diglycidyl ether of butanediol-diaminodiphenyl sulfone (DGEB-DDS), have been monitored by a reactive molecular sensor, diamino azobenzene (DAA). DAA exhibits sensitive changes in UV-visible and fluorescence spectra due to the conversion of its primary amine groups to secondary and tertiary amine groups. Fluorescence intensities are correlated with extent of reaction in epoxy network and processing parameters, such as cure temperatures and time. The use of an internal reference dye for normalization of fluorescence intensities is necessary for the quantitative correlation of spectral signals with the network structure. Variables affecting the fluorescence intensity such as excitation volume, probe location, excitation intensity fluctuation, temperature, and background intensities from optical fiber can be calibrated by normalizing the signal intensities against the internal reference. Sulforhodamine 101 was found to be a satisfactory reference dye which provides stable, readable signals over temperatures up to 200°C.
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  • 49
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    Polymer Engineering and Science 34 (1994), S. 742-749 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A new graphical estimation technique is proposed for the determination of the kinetic parameters describing an autocatalytic reaction. A differential scanning calorimeter was used to monitor the reaction kinetics of an epoxy-based vinyl ester resin. The method utilizes information from a zero initial reaction rate, conversation at vitrification, the ratio of reaction rate constants under different isothermal conditions, and characteristics of the phenomenological kinetic model with assumptions being made about the overall reaction order. By fitting data to the integrated reaction rate equation with adjustments for the isothermal conditions, the kinetic parameters are estimated without using a linear or nonlinear regression method. Different kinetic parameters can be estimated from data before and after the gel point which was obtained from the relationship between the glass transition temperature and the degree of cure.
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  • 50
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    Polymer Engineering and Science 34 (1994), S. 734-741 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Diethylene gycol bis(allyl carbonate) is widely used for the production of optical plastic for lenses, safety glasses and guards, watch crystal, and instrument windows. The monomer polymerizes via a free radical mechanism using benzoyl peroxide as an initiator to form a thermosetting polycarbonate. This polymerization process involves a long cure cycle at temperature below 100°C. Differential scanning calorimetry (DSC) and rheometric dynamic testing are used to characterize the thermal and kinetic properties. These properties include the heat of reaction, activation energy, rate constants of polymerization, and time and extent of cure at gelation.
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  • 51
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    Polymer Engineering and Science 34 (1994), S. 1065-1069 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Poly(tetrafluoroethylene) (PTFE) is a versatile engineering plastic with excellent chemical and electrical resistance, a wide working temperature range, and a low coefficient of friction. PTFE is processed by the powder processing technique because of its high melt viscosity. The powder processing of polymers involves cold compaction of the polymeric powders, followed by sintering of the preforms at elevated temperatures. Sintering is a critical operation since the mechanical properties of the products are determined by the interparticle coalescence and diffusion of polymer chains across the interface. The results of the studies of the strength development during sintering of PTFE are reported here. The strength was measured in terms of the tensile strength at break, and the dependence of the tensile strength on compaction pressure, particle size, and processing time is discussed. The time dependence of strength development could be described by a diffusion controlled process in which the strength is proportional to the 1/4th power of the processing time.
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  • 52
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1161-1172 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Multiobjective dynamic optimization has been carried out on a nonvaporizing nylon 6 batch reactor. Three objective functions have been identified, viz., minimization of the concentration of unreacted monomer in the product, minimization of the dimer concentration, and minimization of the reaction time, for producing polymer having a specified value, μn, d, of the number average chain length. Two problems have been studied in this paper, each consisting of two objective functions taken from the above set. Pareto solutions have been generated using an algorithm based on Pontryagin's minimum principle and the method of Lagrangian multipliers. The effects of various physical and computational parameters have been studied, and methods have been developed to overcome the numerical difficulties that arise during the solution. The Pareto sets so generated can be coupled with the surrogate worth trade-off (SWT) method, which facilitates interaction with a decision maker (DM). The optimal temperature histories obtained for the two problems studied are quite different and suggest that one must solve the three-dimensional problem in which the vector objective function incorporates all three objective functions. Results from the present study could be used as starting guesses to converge rapidly on the solution of the three-dimensional problem.
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  • 53
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    Polymer Engineering and Science 34 (1994), S. 1187-1195 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The entrance pressure drop during extrusion cooking of corn grits was measured using a cylindrical die viscometer attached to a single screw extruder and compared with results obtained using low-density polyethylene (LDPE). The cylindrical die viscometer had a length to diameter ratio of 40 with half-entry angles of 30, 37.5, 45 and 90° with the horizontal. The entrance pressure drop at the die was measured as a function of extrusion temperature, product moisture content and the die entry angle. Results indicate that the flow behavior of corn grits and the entrance pressure drop were affected by product moisture content, process temperature and the shear history in the extruder. Entrance pressure drop also increased with wall shear stress for plastic melt, but for food biopolymer, the increase was observed provided shear history effects were minimized. Entrance correction increased with apparent shear rate for LDPE, but the reverse was true for corn meal. Using Cogswell's analysis, corn grits exhibit severe extension thinning behavior in entry flow.
    Additional Material: 13 Ill.
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  • 54
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1173-1186 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Guidelines are developed for molding large composite parts via structural reaction injection molding using glass preforms and polyisocyanurate resins. These are based on numerical simulations of the simultaneous heat transfer and reaction kinetics of a commercial system during and after mold filling. Premised requirements are that resin does not gel before the mold is filled, yet, reactions are sufficiently vigorous to approach completion. An existing mechanistic kinetic model is used and material parameters found from a chemical kinetics study employing an insulated cup. It is found desirable to use a high mold temperature and a low preform temperature in molding. Nondimensionalization of the governing equations reveals the existence of a Nusselt number (Nu), which describes the relative importance of heat transfer between resin and glass relative to thermal diffusion to the mold wall. With a Nusselt number of about 50 or higher it is possible to use the cooling capacity of the preform to extend gel time. The magnitude of Nu is influenced by part thickness, glass fraction, strand diameter, and flow velocity. Thus, the effect of the preform on extending resin gel time is within control of the molder.
    Additional Material: 14 Ill.
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  • 55
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    Polymer Engineering and Science 34 (1994), S. 1196-1201 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A detailed study of the effect of several extrusion variables was made on the rheological and thermal properties of Delrin II acetal homopolymer and Zytel 42 polyamide 66 materials. A 63.5 mm Davis Standard extruder was used to measure the effect of screw design, screw rpm, die and head pressure, and melt temperature on the rheology of acetal and nylon 66 resins. A single stage metering screw was used to determine the effect of screw geometry and viscous heating on the melt viscosity breakdown and the rate of degradation of each polymer. The melt temperature was measured in the melt stream in the channel and correlations are shown between ideal melt temperature predicted from the rheology data and the actual loss of properties of each polymer due to viscous heating. The paper also discusses how to measure the melt temperature accurately in extrusion, and to use it as a key indicator to optimize the extrusion process, and to control the rheology, thermal stability, and the molecular weight of a polymer during processing.
    Additional Material: 10 Ill.
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  • 56
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1202-1210 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In this article, we investigate the effect of weld lines on the tensile mechanical properties of unmodified and copolymer modified high density polyethylene (HDPE) and polystyrene (PS) blends. The homopolymers were melt blended in the proportion of 20 wt% HDPE and 80 wt% PS using a twin screw extruder at a temperature of 200°C. The results show that the mechanical properties are generally lower when weld lines are present. The decrease of the mechanical properties is much more pronounced for the blends. The addition of small amounts of a commercial styrene/butadiene copolymer significantly improves the strength and the elongation at break of this blend. An optimum copolymer concentration was observed at 3 wt%. This value coincides with the interphase saturation concentration of the copolymer obtained from the analysis of the DMTA (dynamic mechanical and thermal) properties of the blends. The copolymer was also found to induce important changes in the morphology of the blend. The interdiffusion of the polymer fronts in the weld region was also improved by the presence of the copolymer. It is believed that these two aspects contribute to the enhanced properties obtained with copolymer modified blends in presence of weld lines. An important effect of the injection temperature on the tensile strength and the elongation at break of welded samples with copolymer modified blends was observed. The effect of mold temperature on these properties was less important mainly at low injection temperatures. Only a slight effect of these two parameters was observed for the tensile modulus in the range of mold and injection temperatures considered in this study.
    Additional Material: 11 Ill.
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  • 57
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    Polymer Engineering and Science 34 (1994), S. 1211-1218 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In injection molding of substrates for optical discs, precise transcription of pits and grooves is very important. For high-density optical discs, molding transcription for minute grooves with widths on the sub-micron level is required. In this paper, in order to clarify the relationship between molding conditions and transcription quantitatively, transcription of minute rectangular grooves (width 0.55 μm, depth 70 nm) in injection molding of polycarbonate resin was studied. The relationship between molding conditions and the transcription heights was verified. And, by introducing the equivalent thickness of the vitrified layer concept, a transcription model related to the minute groove width is proposed. This equivalent thickness of the vitrified layer is estimated to be 100 to 150 nm at the point of filling completion under a certain molding condition. Also, using the above description of the equivalent thickness of the vitrified layer, it is possible to estimate the extent of transcription under the various molding conditions.
    Additional Material: 18 Ill.
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  • 58
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 59
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    Polymer Engineering and Science 34 (1994), S. 929-936 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Moldability diagrams for the filling and curing stages of a dicyclopentadiene (DCPD) based reaction injection molding (RIM) system were established based on a simplified engineering approach. Initial monomer temperature and filling time are the critical parameters for the filling stage whereas in the curing stage, mold wall temperature and demold time proved to be the main processing variables. The physical and thermal properties of the molded samples were examined and the results indicate that such simplified moldability diagrams are sufficiently accurate to establish the processing conditions for the system under investigation.
    Additional Material: 13 Ill.
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  • 60
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    Polymer Engineering and Science 34 (1994), S. 913-920 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Anisotropy and molecular orientation are well known phenomena in the field of thermoplastics, but only a few studies have described anisotropy in rubber materials. It has been shown that injection molding gives rise to a higher degree of anisotropy than compression molding. The anisotropy in the rubber material was strengthened by carbon black and is presumably due to molecular orientation. This paper describes the anisotropy of injection-molded ethylene-propylene-diene rubbers. The two polymers had different molecular weight distributions and thus different rheological properties. The compounds were injected into center-gated 4mm thick disks. The disks were subsequently split into three layers using a water-jet cutting technique. Measurement of mechanical and swelling properties in the different layers and directions showed that the anisotropy varied through the thickness of the disk. By X-ray scattering it was shown that rubber molecules had a preferred direction and thus, that the anisotropy was probably predominantly due to molecular orientation created during the mold filling.
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  • 61
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    Polymer Engineering and Science 34 (1994), S. 937-945 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Only recently has increasing use been made of computer simulation in the field of extruder engineering. This simulation is based on physico-mathematical process models. In order to achieve a closed, process engineering-based extruder layout and operating behavior simulation it is necessary to have models describing the throughput behavior, the melting process, the temperature development, the pressure profile over the screw length, the residence time distribution, the mixing and dispersion processes, and also the torque and power requirements. In the Plastics Technology Section of the University of Paderborn (KTP) a program for the computer-aided design of extruders (REX), financed by 17 companies, was developed which will permit rapid application of the models developed there and will fulfill the requirements set out above. Since no computation-intensive numerical methods like Finite Element or Finite Difference Methods (FEM, FDM) are required, the algorithms are very rapid, which means that short computing times are achieved (just a few seconds on an IBM AT).
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  • 62
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 63
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    Polymer Engineering and Science 34 (1994), S. 949-957 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Linear thermotropic liquid crystalline polymers based on two bisphenol monomers and terephthaloyldichloride were prepared via melt polymerization. Fibers from liquid crystalline polymers were spun above the mesophase transition temperature. In this work, the mechanical and morphological properties of fibers based on such polymers were studied. High values of tensile strength and tensile modulus were obtained, and we tried to prove these high mechanical properties quantitavely by using rheological properties of these polymers and morphology of their fibers. These values were varied by the take-up speed.
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  • 64
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    Polymer Engineering and Science 34 (1994), S. 965-974 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effects of processing conditions on the morphology of molecular composite films are examined by optical and electron microscopy. During coagulation processing from solutions in methanesulfonic acid (MSA), rigid-rod polymer, such as poly(p-phenylenebenzobisoxazole) (PBO), phase separates into undesirable aggregates. The coagulant and the method of its introduction have been found to exert a strong impact on the final film morphology. A quench of a PBO solution in MSA into a water bath results in a three dimensional interconnected network of PBO, while a slower introduction of water results in a more amorphous material. A computer simulation program of the coagulation process has been developed to better understand the different structures emerging from coagulation processing of molecular composites. The simulation results are in qualitative agreement with the experimental observations.
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  • 65
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    Polymer Engineering and Science 34 (1994), S. 958-964 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Measurements are reported for air drag on fine filaments whose axes are oriented at oblique and normal angles to the air velocity. In terms of the drag coefficient CDN the data are fit well by the following relation: CDN = 6.96(ReDN)-0.440(d/d0)0.404, where ReDN is the Reynolds number based on flow normal to the fiber axis, and d/d0 is a dimensionless fiber diameter. A wide range of conditions were tested: filament diameters ranged from 13 to 390 microns, gas velocities ranged from 22 to 83 m/s, and fiber Reynolds numbers ranged from 29 to 2120.
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  • 66
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    Polymer Engineering and Science 34 (1994), S. 981-985 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Compounds based on poly(vinyl chloride) (PVC), and containing CaCO3 filler and trifunctional acrylic crosslinking agent have been crosslinked by exposure to γ-rays at dosages to 70 kGy. The crosslinking agent was found to be essential for crosslinking to proceed, only minor sensitivity to the irradiation having been found in compounds omitting the chemical. The presence of filler somewhat inhibits crosslink effectiveness, as measured by solvent uptake data. Elastic moduli and elongations at rupture respond to crosslinking processes, the latter being particularly sensitive to the effects of irradiation. The presence of filler was found to raise modulus, while ductilities of compounds were greater than expected, owing to adhesion at polymer/filler interfaces. Favorable acid/base interaction forces appear responsible for the effect. The reduced sensitivity of filled PVC compounds to γ-ray exposure is attributed to polymer immobilization, the consequence of strong interfacial bonding with the filler.
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  • 67
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    Polymer Engineering and Science 34 (1994), S. 975-980 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The relationship between spinnability and composition of poly(vinyl alcohol)/polyacrylonitrile block copolymer emulsions prepared by an ultrasonic technique is presented. Theoretical analysis and experimental investigation by multiple techniques show that the micellar structure characteristics of the block copolymer emulsions and the behavior of emulsion in shear flowing and coagulating in spinning process are the key factors affecting the spinnability. The mechanical properties of the final fibers are related to the composition, molecular weight, spinnability of the copolymers, and the processability of the as-spun fibers.
    Additional Material: 7 Ill.
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  • 68
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    Polymer Engineering and Science 34 (1994), S. 986-994 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The flow analysis network (FAN) method was modified to analyze the flow of poly(methyl methacrylate) (PMMA) in a model counter-rotating nonintermeshing screw extruder. The numerical prediction of the pressure profiles was compared with the experimental results. Flow patterns in the screw elements of the model counter-rotating nonintermeshing twin screw extruder were also predicted. A new flow path method was developed to calculate the residence time distribution. This result will be applied to analyze the flow during the reaction in the model twin screw extruder.
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  • 69
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    Polymer Engineering and Science 34 (1994), S. 1016-1024 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The mechanical properties of isotactic polypropylene can be enhanced in one direction by a combination of rolling and drawing in a rolling mill. The longitudinal strength and modulus of the oriented polypropylene (OPP) increases with an increase in draw ratio; however, the transverse properties remain relatively unchanged. In this study, multidirectional OPP laminates [with (0)2, (0/90)s and (0/±45)s lay-ups] were made to obtain sheet materials with improved properties in more than one direction in the plane. A hot-plate welding technique was used to produce these translucent and recyclable laminates. The in-plane properties of the laminates were successfully predicted with classical laminate theory (CLT), which is commonly used to predict the properties of fiber reinforced materials. These laminates can be quasi-isotropic and were found to have improved modulus [up to 6 GPa for (0/90)s laminates] and strength [up to 150 MPa for (0/90)s laminates] as well as exceptionally good impact toughness.
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  • 70
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    Polymer Engineering and Science 34 (1994), S. 1011-1015 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The transesterification reaction catalyzed by dibutyltin oxide has been used to crosslink miscible blends (at about 200°C) of ethylene vinyl acetate (EVA) and ethylene methyl acrylate (EMA) copolymers. Then, microwave heating at 2.45 GHz with the fundamental TE01 mode was used for activation of this crosslinking reaction. The microwave treatment was carried out in a continuous process through a resonant cavity on line with a twin screw extruder equipped with a strip die or a circular die, which imposed the shape of the samples in the waveguide. Therefore, a shape factor due to the geometry of the samples and their orientation with respect to the electromagnetic field was defined. Last, this technique was applied to the microwave crosslinking of an EVA/EMA blend dispersed in a polypropylene matrix and consequently offers a new route to control the morphology of the polymer blends.
    Additional Material: 6 Ill.
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  • 71
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    Polymer Engineering and Science 34 (1994), S. 1025-1032 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The cure reactions of epoxy-diamine and its composites are monitored in-situ using the intrinsic fluorescence of the aromatic diamine, diaminodiphenyl sulfone (DDS). With a fiberoptic fluorimeter, in-situ cure monitoring was performed via a single fiber, distal-end probe, in neat epoxy as well as in commercial grade prepregs containing graphite fibers and DDS curing agent. The prepregs were investigated during multiply lamination in an oven. The fluorescence excitation spectra were obtained by emitting at 420 nm with a scan range of 320 to 400 nm, and the DDS peak position was determined as a function of cure time and temperature. The DDS spectra show a progressive red shift up to 24 nm when the primary amine is reacted with epoxide to become the secondary and the tertiary amines. The spectral shift of the DDS is also correlated with the extent of epoxide reaction determined by the Fourier transform infrared (FTIR) spectroscopy. Both data exhibit a linear relation, consistent with the behavior of the DDS peak shift, which increases linearly with the amine reaction. The excitation spectra also show a temperature dependency such that the amount of red shift increases with the measurement temperature in a manner that can be described by an exponential function. The temperature effects also depend on the state of cure in the sample. The temperature correction can be made by the application of an empirically developed equation. Thus, a direct comparison can be made among the on-line data obtained under varying conditions of cure, by reducing the spectral data to any reference temperature. This intrinsic fluorescence technique is much simpler than the previously reported extrinsic fluorophore technique, which requires the addition of an extrinsic fluorophore and an internal dye, and can be applied to any commercial prepregs containing DDS, thus making it a very powerful and widely applicable monitoring tool for composite processing.
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  • 72
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    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 73
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    Polymer Engineering and Science 34 (1994), S. 1327-1335 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The molecular orientation and disclination defects in injection molded bulk samples of liquid crystal polymers have been revealed by transmission electron microscopy (TEM). Using a recently optimized lamellar decoration and etch technique for use with poly(benzoate-co-naphthoate), we have studied in detail the skin-core morphology produced by realistic injection molding processing. In the skin, the director is observed to be highly aligned along the flow direction, and the defect density is very low (10 cm-2). In the core, however, the defect density is six orders of magnitude greater, and the director lies predominantly in the plane defined by the flow and neutral directions. The flow during processing is turbulent, giving rise to distinct morphological features and disclination clusters. When the material is filled at 20% volume fraction with long glass fibers, the molecular and filler orientations are nearly parallel. Dimensional precision also correlates with the morphology and improves with increasing core fraction.
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  • 74
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    Polymer Engineering and Science 34 (1994), S. 1047-1055 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A screening design is used to establish the contribution of various parameters to the roughness of cylindrical extrudates. A dimensionless response variable is proposed to characterize the extrudate roughness, and the effects of ten parameters on this roughness response were examined. Two polyethylenes (one high density and one linear low density) were investigated using a 45 mm single screw extruder. The results show that the main parameters affecting the extrudate roughness are, in order of importance, apparent shear stress at the die wall, die diameter, ratio of die length to diameter, and type of polymer. The other six parameters (the use of an additive, recycling, type of entrance adapter, die material, die temperature, melt temperature) were found to have a non-significant contribution to roughness.
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  • 75
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Molecular dynamics has been used to study possible dynamic mechanisms that may contribute to the property degradation known to exist for polybenzimidazole (PBI) upon hydration. During this study, chaotic movements of a chain pair were observed. Changes in onset and duration of this movement were also observed, which depended upon both hydration state and stress direction involved. Such trends suggested that specific mechanistic pathways may exist that could directly lead to property (such as modulus) loss.
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  • 76
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    Polymer Engineering and Science 34 (1994), S. 1056-1064 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Dynamic viscoelastic properties of blends of alkali metal salts of sulfonated polystyrene ionomers with polyamide 6 were investigated in the melt. The blends of lithium-sulfonated polystyrene (10 mol% sulfonation) with polyamide 6 (LiSPS/PA-6) behaved as a homogeneous viscoelastic fluid over most of the blend composition range, since blending with PA-6 disrupted the ionic network of the LiSPS. Specific interactions between the lithium sulfonate group and the amide group are believed to be responsible for the behavior. By contrast, blends of sodium-sulfonated polystyrene with PA-6 (NaSPS/PA-6) showed typical behavior of immiscible systems in that they exhibited large positive deviations from the log-additivity rule for complex viscosity. This implied that sodium sulfonate groups did not interact strongly with amide groups, in contrast to the behavior of lithium sulfonates. Oldroyd's emulsion model was applied to the results of dynamic viscoelasticity studies of both the immiscible ionomer/PA-6 blends and the polystyrene/PA-6 blends. For the latter, the fit was much better than for the former. This difference in behavior might be due to partial miscibility or to the presence of an indistinct phase boundary in the “immiscible” ionomer-based systems.
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  • 77
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    Polymer Engineering and Science 34 (1994), S. 1535-1546 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A slit viscometer to measure the viscosity of polymer melts under processing conditions is described. Along the slit a pressure drop is generated by applying a pressure at both the entrance and the exit. In this way the pressure in the center can be controlled independently of the shear rate. The pressure gradient in the slit is measured by means of three pressure transducers which are mounted in the region of fully developed flow. Results of pressure-dependent viscosity measurements on polystyrene, polyacrylonitrile-butadiene-styrene, and polypropylene are presented in a shear rate range of five decades. The flow curves obtained at different pressures and temperatures can be shifted onto a master curve. The shear thinning behavior of the three materials is adequately described with the generalized Cross-Carreau equation, while the zero shear viscosity is modeled with a generalized Arrhenius-W.L.F. relationship, incorporating a pressure dependency. Alternatively, it is possible to describe the zero shear viscosity in terms of the free volume fraction and the temperature.
    Additional Material: 11 Ill.
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  • 78
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1401-1405 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The objective of this research is to demonstrate the application of a general model of reaction injection molding (RIM) to a complex shaped mold part. Using the fundamental physical and chemical properties of the RIM system, prediction of RIM moldability can be made. The numerical techniques used in this research are presented in a previous paper (1). The rigorous modeling of the transport processes and the dynamics of the filling front for a particular application are described in this work.
    Additional Material: 6 Ill.
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  • 79
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In this research a model to simulate both the filling the curing stages of a reaction injection molding (RIM) process in complex three-dimensional molds is developed. This model can be used to predict not only the temperature and conversion changes with time but also the front position during filling. Using given physical and chemical properties of the RIM system, moldability can be determined in advance. The numerical techniques used in this research include adaptation of the SIMPLE algorithm developed by Patankar for a moving-front, two-phase system with non-negligible inertial effects, and exothermic chemical reaction. The model predictions of temperature and conversion compare favorably with available data on simple two-dimensional molds. The ability of the model to predict the dynamics of filling in more complicated molds was verified by comparison to mold filling experiments with water and a polyurethane foam.
    Additional Material: 12 Ill.
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  • 80
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Non-ionic, hydrophobically associating, water soluble N-isopropylacrylamide-co-acrylamide (IPAM) copolymers have been synthesized and characterized specifically for the study of drag reduction. The drag reduction (DR) performance has been measured with a rotating disk rheometer and a capillary flow apparatus. The DR studies were performed in deionized water, 0.514 M NaCl and 1 M urea. DR efficiency is dependent on copolymer structure, composition, and solvation. Copolymers showing intermediate values of hydrophobic character are found to be the most effective drag reducers. For this copolymer series, IPAM-70 (the copolymer synthesized with 70 mole% N-isopropylacrylamide in the feed) is the most efficient drag reducer. The DR properties of the IPAM copolymers are influenced by hydrophobic associations as well as hydrogen bonding. The effects of salts from the Hofmeister series, cosolvents such as dioxane, and temperature are also examined. Drag reduction performance of the various copolymers is correlated to empirical relationships involving degree of polymerization, second virial coefficient or other solvation parameters, and concentration.
    Additional Material: 18 Ill.
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  • 81
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 82
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1564-1579 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A fundamental study of electrical conductivity of uniaxially and biaxially stretched poly-p-phenylene sulfide (PPS) film was conducted. In this paper, we paid special attention to understand the effect of processing conditions on the electrical conductivity as well as the conduction mechanism of tantalum pentafluoride (TaF5) doped PPS. The electrical conductivity of PPS film was measured by a four-point probe method in the parallel and perpendicular directions to the stretching direction. The infrared spectra of doped and undoped stretched PPS films demonstrate that the TaF5 doping causes distortion (polaron) in PPS chain and conduction. A similar discussion was reported by Tsukamoto, et al. (1, 2). They found the delocalization of π-electrons in doped PPS by X-ray spectoscopy (XPS), infrared spectroscopy (IR), and C13-NMR. The conductivity of doped PPS films increased with increasing stretching ratio. The crystallinity effect on the electrical conductivity was investigated by changing crystallinity of PPS films in terms of annealing and multi-axially stretching. Orientation development was investigated by wide angle X-ray scattering and birefringence techniques. The relationship between conductivity and orientation of stretched PPS films was investigated by introducing electrical anisotropy.
    Additional Material: 13 Ill.
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  • 83
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1598-1604 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: DGEBA (diglycidyl ether of bisphenol A)-ATBN (amine terminated butadiene acrylonitrile copolymer) blends exhibited upper critical solution temperature (UCST) behavior. Triethylene tetramine (TETA) was introduced as an amine curing agent of epoxy. The real-time phase separation behavior of ATBN-added epoxy system during cure was investigated using laser light scattering. SEM (scanning electron microscopy) and optical microscopy were also employed to observe the morphology of the epoxy blends. Since the DGEBA-ATBN blends showed UCST behavior, the degree of phase separation when cured at low temperature was higher than that when cured at high temperature. The domain correlation length increased as the curing temperature was lowered. Dynamic mechanical analysis (DMA) results indicated that the phase inversion occurred above 20 wt% of ATBN composition.
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  • 84
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1605-1612 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Ternary blends of polyarylate (PAR) U-Polymer 100, thermotropic liquid crystalline copolyester (LCP) Vectra A950, and a block copolyesterether Hytrel 7246 were investigated in terms of rheological properties, morphology, and mechanical properties. The PAR/Hytrel blend exhibited melting point depression and gave a unique single Tg over the entire range of blend compositions. Addition of Hytrel to the PAR/LCP blend decreased both dynamic viscosity and storage modulus over the normal processing temperature range. Further, it notably reduced the voids between the LCP domains and the matrix, and improved the mechanical properties. The optimum usage level of Hytrel proved to be 2 phr.
    Additional Material: 13 Ill.
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  • 85
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1581-1588 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An extrusion-grade medium-density polyethylene was fractionated by size exclusion chromatography and selective solvent extraction. The fractions were studied by infrared spectroscopy, differential scanning calorimetry, and transmission electron microscopy. Infrared spectroscopy showed that chain branching was concentrated to the low molar mass material. Transmission electron microscopy showed the presence of roof-shaped crystals in the low molar mass samples and curved S-or C-shaped lamellae in the high molar mass samples. These features could be used for identification of different molar mass species in the unfractionated sample.
    Additional Material: 12 Ill.
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  • 86
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    Polymer Engineering and Science 34 (1994), S. 1589-1597 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A light scattering technique using a normal-incidence polarized light beam for the characterization of skin/core simulated polymer blend samples is described. The patterns of reflected, polarized scattered light from an inhomogeneous blend were captured using a video camera. The blend was illuminated from a focused laser source. The simulated samples were constructed by incorporating glass fibers (skin) and glass microspheres (core) in a polymer matrix. Asymmetrical patterns were obtained. They reflect the anisotropic nature of the near-surface morphology. Moreover, the change of the anisotropy ratio of the iso-intensity curves plotted, as a function of distance from the position of the incident laser beam on the sample, gives information about the skin and the core content as well as the skin thickness.
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  • 87
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    Polymer Engineering and Science 34 (1994), S. 1613-1618 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Physical blends of polycarbonate (PC) with polycarprolactone (PCL), containing 0 to 30% PCL were prepared by melt mixing. The compatible blends were studied using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), mechanical testing, rheological and density measurements. Yield strength, elastic modulus, and density of the blends were found to attain maximum values, depending on PCL content, while Tg continuously decreased. PCL presence resulted in the embrittlement of PC as detected by impact and tensile tests. These combined data lead to propose a mechanism of polymeric antiplasticization in the PC/PCL system; a phenomenon uncommon in polymer-polymer blends. Simultaneously, the PC's β-transition intensity was depressed, as detected by DMA. Activation energy of PC secondary relaxation process was found to be higher for PC/PCL blends than for PC. Thus, local, intermolecularly non-cooperative motions, usually associated with β-relaxation, are restricted in the presence of PCL. The addition of PCL to PC results in increased shear sensitivity and lower high shear rates viscosity, improving processability.
    Additional Material: 7 Ill.
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  • 88
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    Polymer Engineering and Science 34 (1994), S. 1619-1627 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A general, but simple, analytical technique is proposed for the solution of diffusion-controlled reaction problems (as, for example, occur during the photooxidation of polymers). With this technique the stationary concentration and reaction rate profiles can be calculated for arbitrary reaction kinetics and concentration dependent diffusion coefficients. As an example, the photo-oxidation of polyolefins is considered, which involves complex, concentration dependent, reaction kinetics. Excellent agreement between the analytical approximation and the numerical solution is obtained. Further, an analytical expression for the degradation profile (extend of reaction) is derived, which includes the starting-up effect. It is shown that owing to instationary effects, the degradation profiles obtained with artificial weathering tests may differ considerably from those obtained with outdoor weathering experiments. It is therefore suggested that artificial weathering tests be used to measure the reaction rate parameter and calculate the degradation profile rather than measuring the degradation profile directly.
    Additional Material: 7 Ill.
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  • 89
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 90
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1628-1634 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A quantitative model has been developed relating electrical resistance with strain and time for carbon black filled silicone rubber compounds. The model is based on concepts and methods used in the field of viscoelasticity. Relaxation experiments are performed in order to evaluate material parameters. With these, resistance-strain-history relations, under other loading conditions may be predicted.
    Additional Material: 9 Ill.
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  • 91
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    Polymer Engineering and Science 34 (1994), S. 1480-1484 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The mechanical properties of carbon fiber, especially tensile modulus, are closely related to the orientation of crystals. Hence, the stretching of carbon fiber during carbonization is of importance. In this study, the tension arm between the carbonization furnaces was used to stretch carbon fiber. The relationships among the stretching tensions of the first stage carbonization (〈 800°C) and the second stage carbonization (〉 1200°C), the aromatization index for oxidized polyacrylonitrile fiber, and the properties of carbon fiber are discussed.
    Additional Material: 8 Ill.
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  • 92
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1492-1496 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The dynamic rheological properties of poly(etherimide)/poly(etheretherketone)/liquid crystalline polymer (LCP) ternary blends were measured in order to correlate these properties with the morphology obtained after extrusion. The viscosity radio, ηd/ηm, where ηd = disperse phase viscosity and ηm = matrix viscosity, had to be redefined. Below 50 wt% LCP, ηd = ηLCP, ηm = ηPEEK+PEI and ηd/ηm 〈 1. Above 50 wt% LCP, ηd = ηPEEK+PEI, ηm = ηLCP and ηd/ηm 〉 1. Fibrillar morphologies were obtained in both cases, except below a concentration of 20 wt% LCP. At low concentrations of LCP the ternary blends had lower viscosities than the component polymers, showing a flow promotion effect of the LCP on the PEI- and PEEK-rich phases.
    Additional Material: 7 Ill.
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  • 93
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 94
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1506-1514 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Molecular orientation imparted during film fabrication is known to have a major effect on mechanical and thermal properties of both glassy and semicrystalline polymers. A three-variable Box-Behnken designed experiment was used to study the effects of die gap, die land length, and blowup ratio (BUR) on key linear low density polyethylene (LLDPE) blown film properties at constant final film thickness. In addition, differences in molecular orientation in the films were studied using optical birefringence and shrinkage methods. Measured key film properties were correlated to processing conditions and to measured molecular orientation. Die land length had no significant effect on film structure and properties. All LLDPE films exhibited about 70 to 80% shrinkage in the machine direction (MD) but expanded in the cross direction (CD). Most films exhibited negative in-plane birefringence. MD Elmendorf tear was found to be inversely related to drawdown ratio and MD shrinkage, suggesting that MD tear is dependent primarily on amorphous chain extension and hence, amorphous segments orientation for LLDPE blown films. Dart impact strength of the films was shown to be related to MD shrinkage and to the induced surface roughness due to varying die gap. In a separate study, blown films of three high pressure LDPEs were fabricated under nearly identical conditions. No correlation was found between birefringence and shrinkage data on the LDPE blown films.
    Additional Material: 12 Ill.
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  • 95
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    Polymer Engineering and Science 34 (1994), S. 1517-1528 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A model is developed to describe the evolution of dielectric behavior during the cure of epoxy resins and of blends containing soluble polymeric additives. Data on cure kinetics are used to predict: (a) changes in viscosity and hence in ion mobility; (b) gelation times; (c) vitrification times; and (d) dipolar relaxation times, for both resin and blends. These predictions are then used in conjunction with the Maxwell-Wagner-Sillars (MWS) theory to calculate dielectric permittivity ∊′ and loss ∊″ as functions of cure time and test frequency in both resin and blends. The predictions are compared with experimental data on dielectric behavior obtained during cure of both neat epoxy resin and of blends containing 15 wt% CTBN (carboxyl-terminated poly(butadiene-co-acrylonitrile)).
    Additional Material: 16 Ill.
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  • 96
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    Polymer Engineering and Science 34 (1994), S. 1497-1505 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This study investigated the interrelationship between strength and flow characteristics of general-purpose polystyrene (GPPS) used in injection molding applications. The ease of flow was chosen as a measure of processability and was evaluated using the melt flow rate and capillary rheometer techniques. Of the different strength tests that were examined, flexural and notched tensile strength tests were most effective in differentiating between commercial grades of high and low molecular weight GPPS. While characterizing strength of injection molded specimens, the degree of molecular orientation was taken into consideration. For unplasticized resins, increasing the weight average molecular weight by about 100,000 enhanced the flexural strength by 10%, but also increased the viscosity at low shear rates (10 to 100 s-1). The increase in molecular weight had virtually no effect on viscosity at the highest shear rates (up to 10,000 s-1). Plasticized resins displayed a 6% loss in flexural strength as well as a significant reduction in viscosity (throughout the shear rate range) as compared with the unplasticized resins. As expected, the improvement in strength achieved by increasing molecular weight leads to a simultaneous increase in the viscosity, i.e., a deterioration of processability. In addition, our study indicates that for samples without preferential molecular orientation, narrowing the molecular weight distribution significantly improves the balance of strength and melt flow rate properties.
    Additional Material: 6 Ill.
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  • 97
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyethylene terephtyalate (PET) and high-density polyethylene (HDPE) constitute a major portion of the thermoplastic materials currently being used in the packaging industry. Blends of HDPE/PET can be compatibilized by utilizing ester groups or terminal carboxyl and hydroxyl groups present in PET. An ethyleneglycidyl methacrylate copolymer (EGMA) was found to be very effective in compatibilizing this blend by forming a compatibilizer in-situ. The in-situ formation of the compatibilizer and its distribution could be affected by different sequences and modes of component addition. To determine the best protocol of component addition for such a reactive compatibilization process, different sequences and modes of component addition were tried out in an intensive batch mixer and in a twin-screw extruder. All these experiments resulted in blends with vastly different dispersion of the minor phase and mechanical properties. In general, sequences where the reactive polymer was grouped with the nonpolar component of the blend initially resulted in the best compatibilization.
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  • 98
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    Polymer Engineering and Science 34 (1994), S. 1758-1766 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The concept of improved product quality and reduced costs has revolutionized analytical techniques in the polymer industry. It has brought in-line analysis to the forefront, with near infrared (NIR) spectroscopy proving to be a very viable technique for such operations. A system for continuous in-line near infrared monitoring of molten polymer blends, copolymers, and polymer reactions is being developed. The ultimate objective is to use this monitoring system to develop feedback control for polymeric processes. Experiments on blends of polystyrene and poly(phenylene oxide) have been performed by using a flow cell, located at the exit port of a single-screw extruder. Qualitative analysis of spectral data has been substantiated by a variety of quantitative (multivariate) techniques. Robust calibration models, suitable for on-line predictions, have been developed. The success of in-line process analysis depends on the performance of fiber-optic probes that are inserted into the process stream. These probes normally succumb to the demands of the rigorous process environment, typical of polymeric processes, i.e., high temperatures, high pressures, and adverse chemical conditions. Design and development of fiber-optic probes that are capable of withstanding such harsh conditions have also been undertaken. Results will be reported on the polymeric systems and optical probes.
    Additional Material: 16 Ill.
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  • 99
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1773-1787 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This is a review on the long-term behavior of polyolefin pipes used in hot-water environments. Included in the review is work done on pipes of crosslinked polyethylene, isotactic poly(butene-1), isotactic polypropylene and medium-density polyethylene, and in particular the extensive work performed at Studsvik, Sweden. A collective view of the changes in antioxidant concentration profiles and molecular/physical structure accompanying hot-water exposure is presented. Failure at high stress levels is preceded by gross deformation (Stage I failure), whereas at lower stresses fracture is brittle either without any signs of thermal oxidation (Stage II) or induced by a strong and spatially concentrated thermal oxidation (Stage III). It is shown that the Stage III lifetime can be divided into three phases, denoted Regimes A, B, and C. They involve internal precipitation of antioxidant from a supersaturated solution (Regime A), diffusion-controlled migration of antioxidant to the surrounding media (Regime B), and degradation of the polymer by thermal oxidation (Regime C). For hitherto reported cases the Regime B life constitutes 80% to 90% of the entire life. A presentation is also made of current lifetime extrapolation methods.
    Additional Material: 21 Ill.
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  • 100
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    Polymer Engineering and Science 34 (1994), S. 1799-1807 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Experimental data on the standard Charpy notched impact strength (CNIS) for a large sampling of particulate-filled and rubber-modified polypropylenes were analyzed. To determine the significance of the CNIS for material selection and design, CNIS data were compared with fracture toughness measurements expressed as the critical strain energy release rate G′c, measured under impact loading. A scale factor representing the state of stress at the crack tip was calculated, assuming small scale yielding, Class I linear elastic fracture mechanics (LEFM). Based on the data, three principal groups of materials were identified. In the smallest of the three, CNIS and G′c measurements showed the same functional dependence on the material variables studied and were characterized by a scale factor independent of the composition. In these cases, one can justify comparisons of toughness of different compositions using single values of the CNIS, since the materials are probably being compared in equivalent states of stress. In a second group, CNIS and G′c also show the same functional dependence on material variables, but exhibit large variations in the scale factor with composition. One should not compare the toughness of different materials from this group based on single values of CNIS, since it is likely that the comparisons would not be made relative to equivalent states of stress. In these cases, only measurements of G′c can separate the effect of specimen geometry from those of the intrinsic properties of the material. The majority of materials studied fell into a third group, in which the CNIS and G′c exhibited substantially different functional dependencies on the material properties, and the scale factors depended also on composition. In these latter cases, a comparison of CNIS values for different compositions is not a reliable indication of the relative toughness and is of little value as a parameter for material selection and design.
    Additional Material: 10 Ill.
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