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  • Electronic Resource  (6,538)
  • 1990-1994  (3,529)
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  • Electronic Resource  (6,538)
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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. 22-28 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Chiral separation ; Capillary column ; 2,6-Di-O-pentyl-3-O-propionyl-γ-cyclodextrin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary 2,6-Di-O-pentyl-3-O-propionyl-γ-cyclodextrin has been synthesized and used for enantiomer separation in capillary gas chromatography. Experimental results showed that the stationary phase has good enantiomer selectivity toward amino acids, amines, alcohols, diols, epoxides, and lactones,etc. 2,6-Di-O-pentyl-3-O-propionyl-γ-cyclodextrin has good thermal stability: the highest recommended temperature isca 170°C.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Pentachlorophenol residues ; Off-flavours ; Wines and corks ; Electrolytic conductivity detector/mass spectrometry ; detectors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A gas chromatographic methodology with selective detection is presented for the analysis in wines and corks of pentachlorophenol residues, which are suspected to be the most likely precursors of some off-flavours described in several wine samples. After derivatisation, pentachlorophenol acetate residues were monitored by electrolytic conductivity detection and/or mass spectrometric detection in the selective ion mode at m/z 264 and 266. Recoveries varied from 80 to 96% for wine samples fortified with 5 to 100 μg l−1 and from 83 to 91% for corks (fortified at 25 to 100 μg kg−1). The proposed methodology allowed for a determination limit of μg l−1 for wine and 10 μg kg−1 for corks.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 38 (1994), S. 475-478 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Phenolic acids ; Olive and elm tree tissues ; Soil phenolics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method for the separation of phenolic acids along with shikimic and quinic acids by means of capillary gas chromatography is described and discussed. The method involves the previous derivatization of the acids to trimethylsilyl derivatives and it has been applied to the separation of acids extracted from olive leaves and roots, elm leaves and a soil A horizon. Quite good results were achieved both from qualitative and quantitative points of view. Qualitative differences have been pointed out in the phenolic acid composition of two olive cultivars and between leaves and roots of the same cultivar; also two elm species can be discriminated on the basis of the phenolic acid content.
    Type of Medium: Electronic Resource
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  • 5
    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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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 38 (1994), S. 595-598 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Chiral / enantiomeric separation ; Amphetamine ; Methamphetamine ; Cyclodextrin-derivatized phases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Enantiomeric separation of amphetamine and methamphetamine as achiral derivatives on 2,6-di-O-pentyl-3-O-trifluoroacetyl-β-cyclodextrin, 2,6-di-O-pentyl-3-O-trifluoroacetyl-γ-cyclodextrin and 2,6-di-O-pentyl-3-O-propionyl-γ-cyclodextrin stationary phase in capillary gas chromatography is described. Trifluoroacetic anhydride and acetic anhydride were used as derivatizing reagents. Excellent precision was obtained for concentrations down to 0.1% / e.e. On 2,6-di-O-pentyl-3-O-propionyl-γ-cyclodextrin the elution order of R,S-amphetamine was reversed when the derivatizing reagent was changed but could not be reversed on any of the other phase types.
    Type of Medium: Electronic Resource
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  • 7
    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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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Chromatographia 39 (1994), S. 71-73 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Spectinomycin ; Silylation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A gas chromatographic assay for spectinomycin hydrochloride is described. The method is based on that prescribed by the United States Pharmacopeia (USP XXII). The method involves silylation of spectinomycin hydrochloride; phenazone is used as an internal standard. Spectinomycin and phenazone have adequate stability under the prescribed conditions. The stationary phase is 3% OV-17 on Gaschrom Q 100–120 mesh. The selectivity of the proposed method is better than that of the GLC method described in the USP XXII.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Enantiomer separation ; Permethylated cyclodextrin stationary phases ; Side-chain fluorinated alkylbenzenes ; Thermodynamic data
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The separation of racemic side-chain fluorinated alkylbenzenes and bromofluorinated analogues by capillary gas chromatography using permethylated α, β and γ-cyclodextrins dissolved in polysiloxanes of different polarity as stationary phases is described. The influence of the achiral polysiloxane matrices on the separation of enantiomers is discussed in the light of the results obtained with the different phases. For a part of the tested compounds thermodynamic data are determined which describe the interaction of enantiomers with the stationary phase. The mechanism of separation is discussed on this basis and by comparison with data for structurally similar compounds.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Method validation ; Reggedness test ; Residual solvents
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Ruggedness testing is performed on a gas chromatographic method for the quantitative determination of residual solvents in steroids. Eight experimental variables or factors which were expected to influence the quantitative results were selected. These factors were divided into two independent groups, i.e. four factors related to the injection process and four factors related to separation and detection. In order to determine interaction between factors and quadratic effects, a central composite design was selected for the set-up of the experiments. Because in the method an internal standard is used, relative peak area was used as response. A deviation of up to 2.5% per factor for the quantitative results was regarded as acceptable. Other responses studied are related to the system suitability. Observed main, quadratic and interaction effects were translated into rugged intervals of the experimental variables by graphical presentation. It was found that besides main effects significant interaction effects were present, for example between the temperature of the injector and the split-flow. Interaction effects can easily result in the reduction of the rugged intervals by a factor of 2. The calculated rugged intervals were compared with the precision of the instrument or factor settings in order to estimate the ruggedness of the factors. Eventually, the maximum effect of the variation in the instrument settings on the quantitative results regarding the precision of the factor settings was found to be only 2.2%. Overall, the method proved to be rugged for most factors, except for the split-flow of the injector for which the method was only rugged to a limited extent.
    Type of Medium: Electronic Resource
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  • 11
    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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  • 12
    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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  • 13
    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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  • 14
    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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  • 15
    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.
    Type of Medium: Electronic Resource
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  • 16
    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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  • 17
    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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  • 18
    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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  • 19
    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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  • 20
    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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  • 21
    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.
    Type of Medium: Electronic Resource
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  • 22
    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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  • 23
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 6-11 
    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 class of materials based on a spirodilactam structure has been recently synthesized as part of research into new polymeric materials. Not only is the spirodilactam structure novel, but it was not even the intended product in the synthesis as originally designed. The polymerization process discovered by the reaction of 4-ketopimelic acid or its corresponding spirodilactone with primary amines opened a new field of polysprodilactam chemistry. This paper describes the chemistry leading to the discovery of spirodilactam-based polymers and initial applications in the area of thermoplastics and thermosets. Most recent developments to be covered include aromatic spirodilactams and isomeric spirodilactams.
    Additional Material: 1 Tab.
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  • 24
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 12-16 
    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: Spirodilactam bisallylether is a new high temperature performance monomer. It melts at 154°C, and is thermally inactive in forming a homopolymer. However, it reacts readily with a bismaleimide via “ene” reaction. Therefore, it could be used as a comonomer and an effective toughening modifier for bismaleimide. The properties of the blends of spirodilactam bisallylether and 4,4'-bismaleimidodiphenyl-methane were studied. The cocured resins have high glass transition temperature, 〉 300°C. By adding 30 to 40 mole % of the bisallylether, the compact tension toughness of the bismaleimide was improved to 0.7 MPa-m1/2. Therefore, the resins have a combination of high glass transition temperature and toughness. They also showed good flexural properties. Despite the high water absorption, 5 to 7%, the resins retained high hot/wet flexural properties because of the high glass transition.
    Additional Material: 3 Ill.
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  • 25
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 59-68 
    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: Four immiscible blend systems, styrene-maleic anhydride/styrene-acrylonitrile (SMA/SAN). styrene-maleic anhydride/acrylonitrile-butadiene-styrene (SMA/ABS), poly(vinylidene fluoride)/SAN (PVF2/SAN), and PVF2/ABS, were investigated. The effect of adding up to about 10 wt% of a third polymer that is miscible with each blend component, poly(methylmethacrylate) (PMMA), was determined. In every case, the addition of PMMA led to the improvement of properties such as tensile strength, tensile elongation, and notched impact strength. Furthermore, the addition of PMMA resulted in finer, more uniform dispersions of the primary blend components. The experimental results are interpreted in terms of interfacial activity of the common phase component, PMMA.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 26
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 81-85 
    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: Differential scanning calorimetry (DSC) was used to investigate the solid-state cure process of poly(phenylene sulfide)(PPS) resin. Virgin PPS resin in an open sample pan was cured in DSC cell. Either air or oxygen was used as a curing atmosphere. Cure temperatures were in the range of 200 and 250 °C, which are below the melting point of PPS resin. Cure temperature as well as atmospheric condition influenced the cure behavior of PPS in the solid state. Both the rate and the amount of cure increased with increasing cure temperature. On the other hand, the time to reach the maximum cure rate was independent of cure temperature. Changing the atmosphere from air to oxygen increased both the cure rate and the amount of cure. The size effect of PPS particles on the cure reaction was also discussed.
    Additional Material: 9 Ill.
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  • 27
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 109-115 
    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: Slow crack growth was measured in the perpendicular and parallel directions relative to the extrusion direction of the pipe. For five pipes from different manufacturers, the anisotropy factor, the lifetime to fracture in the perpendicular direction divided by lifetime in the parallel direction, varied from 1.2 to 4.7 for complete fracture and 1.4 to 4.0 for crack initiation. The degree of molecular orientation was determined by measuring the shrinkage that occured when a pipe specimen was heated near its melting point. The amount of shrinkage correlated with the anisotropy factor for slow crack growth. The shape change after shrinkage was related to the flow pattern of the resin during extrusion and the cooling rate after extrusion.
    Additional Material: 9 Ill.
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  • 28
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 135-140 
    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 complex Young's modulus, E*(ω), and the complex strain-optical coefficient, O*(ω), of poly(ether sulfone) (PES), polysulfone (PSF), and polyethermide (PEI), were measured over the frequency range 1 to 130 Hz. The data were analyzed with a modified stress-optical rule: The Young's modulus was decomposed into two complex functions, EG*(ω) and ER*(ω); the modified stress-optical coefficient, CR and CG, associated with the rubber (R) and glass (G) components, respectively, were determined. The results for six polymers, including polystyrene, poly(α-methyl styrene), and bisphenol A polycarbonate were compared with each other. One of the coefficients, CR, equivalent to the stress-optical coefficient in melts, mainly depended on the way in which phenyl groups were connected to the chain. The other, CG, was in the range of 20 to 40 Brewsters, and did not strongly depend on the details of polymer structure. The component function, EG*(ω), which was located in the glassy region and originated from the high glassy modulus, was almost the same in shape when plotted against ω with double logarithmic scales. The R component, ER*(ω), located at the long time end of the glass-to-rubber transition zone, was slightly sensitive to the molecular structure of polymers.
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  • 29
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 159-165 
    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: While there is abundant evidence that the molecular weight distribution (MWD) of a linear polymer has an influence on the shape of the viscosity function, the ability to convert the viscosity function to an MWD has been questioned. Using strictly numerical techniques, we have shown that the viscosity function can be transformed to the MWD, but always with some distortion. However, distinct bimodality can be qualitatively preserved through both the MWD-viscosity and viscocity-MWD transforms.
    Additional Material: 10 Ill.
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  • 30
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 169-173 
    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 microcellular plastics, an unfoamed skin that is integral with the foamed core can be created by allowing the nucleating gas to diffuse from the surfaces of a gas saturated specimen prior to foaming. In this paper, a semi-empirical model is proposed that predicts the skin thickness variation in microcellular foams as a function of gas desorption time. The model shows good agreement with experimental results on the polycarbonate-carbon dioxide system.
    Additional Material: 7 Ill.
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  • 31
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 174-189 
    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 present paper proposes “Deformation Characteristics” (DC) as a new deformation measure of screw extrusion processes, based on the Green deformation tensor. In contrast to previous strain measures heuristically proposed by Mohr, et al., Mckelvey, and Pinto and Tadmor, the new DC can naturally incorporate the demixing phenomena and systematically take into account the three-dimensional circulatory flow with the screw flight effect. Therefore, DC can be regarded as an improved strain measure. “Weighted Average Deformation characteristics” (WADC) is also proposed to indicate the overall deformation characteristics as a quantitative measure to the “goodness of mixing” of the extrusion process. The present paper includes discussion on delicate differences between DC and several other strain measures in case of the two-dimensional velocity approximation, and on the application of DC into a general three-dimensional velocity field obtained by a quasi-three-dimensional finite element analysis of extrusion processes. In determining WADC in the three-dimensional application, the residence time distribution function, including the three-dimensional circulatory flow effect, is used.
    Additional Material: 15 Ill.
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  • 32
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 229-237 
    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-isothermal flow is simulated in the screw and kneading disc elements in a modular co-rotating twin screw extruder. Methods of calculating mean temperature rises for individual elements are discussed and results are presented. The implications of non-isothermal operation for scale-up is discussed. A method is then described for making calculations in a modular co-rotating machine, that contains many different elements. Example calculations are given showing the tendency of larger machines to buildup greater temperatures when viscous heating is included.
    Additional Material: 5 Ill.
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  • 33
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    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.
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  • 34
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 251-251 
    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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  • 35
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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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  • 36
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 260-265 
    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: Penrose states that quantum effects can occur even in relatively large systems when energy differences remain small. This is just the situation with polymer materials. A quantum description by Penrose of the formation of quasi-crystals can be rewritten to apply to polymer crystallization. The implications of the need to take account of quantum effects are discussed. Another approach based on the quantization of energy levels in clusters of atoms offers a possible explanation of heat setting in nylon and polyester fibers. Finally some problems of the interpretation of quantum theory are discussed.
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  • 37
    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 novel approach to a truly dynamic thermodynamics is proposed in which equilibrium is defined in terms of explicit time, distance, and acceptable error scales. This approach involves reformulating the second law of thermodynamics in terms of an excess energy that vanishes at equilibrium instead of an entropy that assumes some unknown maximum value. Excess energy is defined mathematically as the total Legendre transform of energy with respect to an independent set of extensive variables. Excess energy is effectively the free energy functional of a nonequilibrium system and is a function of the time, distance, and acceptable error scales. Elimination of entropy from thermodynamics requires recognizing temperature as a thermal stress, proportional to the antimetric component of the stress tensor that is neglected when one assumes the validity of Cauchy's second law of motion. The inclusion of temperature as part of the stress-strain couple completes the science of thermomechanics and opens the way for a practical unification of chemistry and physics in strictly mechanical terms.The last sentence of the abstract shows how high the goals that Lindem meyer set for himself were. I personally do not agree with the idea that mechanics is the queen of all sciences, and that given deep enough probing one could achieve “a practical unification of chemistxy and physics in strictly mechanical terms”; for instance, electromagnetism has full citizenship's rights in physics, and it is hard to conceive that it could be reduced to mechanics.
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  • 38
    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 interfacial strength of two paper-polypropylene-paper laminates used for electrical power transmission cable insulation has been measured using a peel test after a variety of conditionings that simulate the service thermal stress conditions. Immersion in dielectric oil at 23°C causes little decrease in peel strength, but heating in the oil at 90°C causes a rapid initial loss followed by a slow loss of strength. Cyclic and static heating show that cyclic fatigue is not a factor as the initial loss of strength occurs in a time comparable to the first two test cycles and further heating causes much less loss of strength. Tensile and compressive stresses resulting from cable winding have no effect on the loss of bond strength during heating in oil. Vacuum drying of the laminate and oil (as in cable manufacture) before heating results in less decrease in peel strength than heating without prior drying. Optical and electron microscopy show minimal wetting of the paper fibrils by the polypropylene with only a few having been either normal to or at a steep angle to the polypropylene surface. That is, the fibrils appear to be parallel to the interface and only partially immersed in the polypropylene. Micrographs show little, if any, differences between the interfaces on the two sides as well as little paper on the polypropylene after delamination and vice versa. It is suggested that the bonding mechanism is a combination of weak mechanical interlocking and secondary bonds. It is also suggested that swelling of the polypropylene relative to the paper by the dielectric oil at 90°C weakens the interfacial bond.
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  • 39
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 290-300 
    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: Variations of stress with temperature for stretched networks of trans-polyisoprene networks in the crystallization region are reported. Such profiles are characteristically U-shaped with the stress at lower temperatures often climbing to high levels. Valley widths of the profiles narrow as annealing temperature increases to about 50°C, then widen at yet higher temperatures. The degree of crystallization at 22°C is 37% and independent of deformation and annealing temperature. The β crystal form is overwhelmingly present with traces of other crystal forms appearing only at high deformations. The theory of stress-induced crystallization provides a good description of experimental results provided the nucleation parameter σ is dependent upon deformation. Therefore, the data provide good qualitative support for the theory in its current form.
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  • 40
    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: Polyalkylenebenzoxazoles of high molecular weight (inherent viscosity values from 0.76 to 2.95) were prepared from 4,6-diaminoresorcinol dihydrochloride and aliphatic diacids in polyphosphoric acid by heating at 180 to 200°C for 3-5 h. Melting points of the polymers ranged from 148 to 423°C, depending on the length of the alkylene chain. Glass transition temperatures were relatively low, ranging from 50 to 100°C and did not show the pronounced odd/even effect noted for melting points. In all cases, rapid weight loss occurred above 400°C. No evidence for the formation of a molecular composite was observed in an attempt to prepare in situ a rod-like polybenzoxazole in a polyalkylenebenzoxazole.
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  • 41
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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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  • 42
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 93-101 
    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: Low levels of oligomer molecules are generally desirable in polymeric materials. It is known that several reactor variables can affect the oligomer distribution, and therefore it is useful to have predictive models for molecular weight distribution. The normal approach of a differential equation-based model is very complex to set up if it is applied rigorously to include all the non-Flory aspects of the step growth polycondensation and in particular the interfacial polycarbonate polymerization. In this paper, simple methods based on the Monte Carlo method and Stockmayer distribution are applied to simulate the effects of mass-transfer, unequal reactivity, and the starting stoichiometry of the polycondensing functional groups on the oligomer distribution. It is shown that these parameters can have a significant effect on the oligomer weight distribution and polydispersity of the final polymer.
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  • 43
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    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.
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  • 44
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    Polymer Engineering and Science 34 (1994), S. 141-152 
    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 ultra-high strength/modulus, extended chain polyethylene fiber (Spectra® fiber) composite has shown great potential as a lightweight armor material with its extraordinary capability of absorbing the kinetic energy of projectiles. But the relatively low melting point of this fiber (∼ 145°C) has caused concerns regarding the effect of temperature rise during the impact/penetration process on the performance as armor material. In this article, an analysis of temperature rise in projectile and the fiber composite during the impact/penetration process is described. Combining the simulation of impact deformation by finite element analysis and the simulation of temperature rise by a finite difference approximation of the related dynamic equations, the temperature rise caused by the projectile/composite interaction was estimated. Results show that there is a significant temperature rise at the projectile/composite interface due to the friction but that the short length of time involved in the process and the low thermal conductivity of Spectra fiber composite keep the temperature rise in a very small region (in the order of 0.001 cm) around the interface during the impact/penetration process. Consequently, the volume that is affected by the temperature rise is very small, in the order of total 0.001 cm3 around the projectile, and this is too small to generate any detectable effect on the armor performance. After the projectile is stopped, however, substantial heating of fiber composite can occur under specific conditions as the result of heat flow from the hot projectile embedded in the composite. This heating of fibers, however, is a postmortem effect and hence inconsequential to the ballistic performance of the composite armor.
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  • 45
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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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  • 46
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 190-200 
    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 mathematical model of a polycondensation reactor that can be used in the final stage for poly(ethylene terephthalate) (PET) is established and compared with experimental data obtained from a laboratory scale reactor with film renewal. Detailed side reactions are considered along with the diffusional removal of the small molecules through thin film. Among several kinetic constants, the polycondensation reaction rate constant k1(= k8) and diester group degradation reaction rate constant k7 have an influence over the degree of polymerization. The values of k1(= k8) and k7 for 0.05 wt% Sb2O3 were obtained as curve-fit values: (1) k1(= k8) = 3.4 × 106 exp(- 18.500/RT′) (L/mol-min); (2) k7 = 1.3 × 1011 exp(- 37,800/RT′) (min-1). Effects of the film exposure time, reduced pressure of vacuum, temperature, the initial terephthalic acid (TPA)/ethylene glycol (EG) mole ratio, the initial degree of polymerization, and catalysts were well explained by the model.
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  • 47
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    Polymer Engineering and Science 34 (1994), S. 209-212 
    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: Entrance pressure losses for the creeping flow of a power-law fluid are calculated for an abrupt contraction of ratio 2, 4, 8 and ∞ for both the axisymmetric and planar cases using P2P1 and P+2P1 finite elements. Contrary to some earlier findings in the literature, the entrance pressure loss obtained by using the two different types of finite elements, both of which satisfy the Babus̆ka-Brezzi condition, are found to converge to the same results. The present results also confirm that the variational method of Duda and Vrentas gives excellent upper bounds for both the axisymmetric and planar cases with infinite contraction ratio.
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  • 48
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    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.
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  • 49
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    Polymer Engineering and Science 34 (1994), S. 513-518 
    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 shear test is proposed as a complement to the tensile test in order to characterize the short time mechanical behavior of thermoplastic polymers. The proposed test geometry makes the test easy to perform and to evaluate and gives relevant information about anisotropy, plastic deformation, crack initiation, and propagation properties. Three different materials have been tested and the results are discussed.
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  • 50
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    Polymer Engineering and Science 34 (1994), S. 500-506 
    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: Material property models for poly(etheretherketone) (PEEK) have been combined with a residual stress model to provide a means for investigating the effect of crystallization process on the residual stress development in semicrystalline materials. The analysis shows that crystallization causes an increase in the residual stress levels. This increase is affected through an increase in the resin modulus values and through the resin modulus build-up at higher temperatures. The shrinkage due to crystallization was found to have no effect on the residual stress development in neat PEEK.
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  • 51
    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: Temperature sweeps of dynamic viscoelastic properties have shown that phydroxybenzoic acid (PHB)-based liquid crystalline polyesters, specifically in this case those copolymerized with poly(ethylene terephthalate) (PET), can be subjected to considerable supercooling if initial heating curves are compared to subsequent cooling curves, indicating that this type of material can be in quite different states even at the same temperature, depending on thermal history. Utilizing this supercooling behavior, viscoelastic properties of a 60 mol% PHB/40 mol% PET material produced by Unitika were monitored before and, particularly, after large-scale shear deformation to determine how potential structure changes induced by the shear are reflected in viscoelastic properties immediately, and with time. According to dynamic viscoelastic temperature sweep data four quite different initial states were employed including conditions with, as well as largely free of, crystallites. However, in all cases, post-shear monitoring showed decreased G′ and G″ values with almost no evidence of return towards initial values within approximately 25 min. These results, in addition to furthering somewhat the fundamental understanding of the flow and relaxation properties of liquid crystalline polymers, may be useful in polymer processing, where large-scale shear deformations employed in forming processes appear to be capable of changing considerably the subsequent behavior of such materials.
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  • 52
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    Polymer Engineering and Science 34 (1994), S. 507-512 
    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 thermodynamic model was proposed to correlate the phase behavior of a swelling polymeric gel (vinyl alcohol-sodium acrylate copolymer) and the volume phase transition in alcohol (methanol, ethanol or propanol)-water solutions. The model is based on the Flory-Huggins formula for polymer solution coupled with the osmotic pressure by rubber elasticity proposed by Flory. The volume change behavior and the equilibrium concentrations inside and outside the gel were successfully correlated using the present model.
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  • 53
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    Polymer Engineering and Science 34 (1994), S. 528-531 
    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: Terpolymerization was investigated by dilatometry for zincacrylate (ZnA2), acrylonitrile (AN), and styrene (St), radically initiated by a As2S3-styrene complex (I) in dimethyl sulphoxide (DMSO), at 90 ± 0.1°C for 1 h under inert atmosphere. The system follows non-ideal kinetics, due to primary radical termination as well as a degradative chain transfer reaction. The kinetic expression for the system is Rpα(I)0.27 (St)0.31 (AN) 0.22[ZnA2]0.12. The value for the activation energy and kp2/kt are 55 kJ mol-1 and 1.87 × 10-7 1 mol-1 s-1 respectively. The terpolymer has been characterized by IR and NMR spectroscopy. The thermal stability and solubility of the terpolymer have also been studied.
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  • 54
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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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  • 55
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    Polymer Engineering and Science 34 (1994), S. 551-558 
    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 intermeshing counterrotating twin screw extruder is widely used for compounding, devolatilization, blending, and reactive extrusion. A fluid dynamics analysis package-FIDAP, using the finite element method, was implemented to simulate the 3-D flow patterns in the region of conveying elements and shearing discs of a Leistritz LSM30.34 twin screw extruder. The rheological behavior of the fluid was described by a power law model. The flow fields were characterized in terms of velocity profiles, pressure distributions, shear stresses generated, and a parameter λ quantifying the elongational flow components. The influence of screw rotational speed and axial pressure difference on the flow characteristics was also analyzed. A comparison between the flow characteristics in the shearing discs operated in a corotating or counterrotating mode was also presented.
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  • 56
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    Polymer Engineering and Science 34 (1994), S. 532-540 
    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 for the phase distribution and evolution of the heterogeneous (suspension) polymerization of vinyl chloride is presented. Experimental information on pressure, temperature, and conversion has been obtained from a 34 liter bench reactor reproducing reaction conditions and product properties typical of industrial operation. A calculation procedure based on simple plant data is proposed for the description of the phase compositions and their evolution over the entire process. Results based on classical Flory-Huggins theory of solutions are presented and compared with existing data.
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  • 57
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    Polymer Engineering and Science 34 (1994), S. 559-569 
    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 mathematical model is presented for the computer simulation of multilayer flow of polymer melts in coexitrusion. The proposed model can handle an arbitrary number of layers. The viscosity of each layer is shear-rate and temperature dependent. Given the material properties, die dimensions, and process conditions, the model determines the flow field throughout the die gap. Computer simulations and experimental data are presented for a three-layer polyester/EVA/polyester film coextrusion, with emphasis on the interfacial instability and its effects on optical properties of the film. The rsults are discussed in the context of the critical interfacial shear stress criterion that has been proposed by Schrenk, et al. (1) for the onset of interfacial instability. It appears that elasticity differences between layers contribute to the interfacial instability. It is conjectured that minimizing interfacial shear stress and matching elasticities of adjacent layers is an appropriate criterion in coextrusion analysis.
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  • 58
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    Polymer Engineering and Science 34 (1994), S. 541-550 
    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 simple unified lubrication approach has been proposed to design a coat-hanger die that can deliver wide and uniform liquid sheets. This approach requires that the wall stress in the manifold be constant. With this constraint, any inelastic non-Newtonian fluid model can be used to describe the liquid motion inside the die. Fluid models that can represent the pseudoplastic or viscoplastic behavior of polymeric liquids have been selected for illustration. A general equation that can be solved to determine the effect of production variations on flow uniformity inside the die has also been derived.
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  • 59
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    Polymer Engineering and Science 34 (1994), S. 570-579 
    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 paper we address the aspects associated with shear modification of low density polyethylene by extrusion. By successive passes of the polymer through an extruder it can be shown that both the melt viscosity and melt elasticity are reduced by shear modification. These reversible variations are not accompanied by significant changes in molecular weight distribution. The major effects of extrusion are to decrease the amount of elastically effecitve material. Study of proton relaxation times at 150°C shows that the melt comprises regions of relatively ordered, entangled, and unentangled polymer. Shearing reduces the proportion of more ordered material. The elastically effective anchors that are reduced by shearing are regions with restricted segmental mobility rather than conventional entanglements or intermolecular knots. Successive extrusions produce a relatively small decrease in the number of such constraints to molecular motion. Repeated shearing has a diminishing effect on the proportion of more ordered material in the polyethlene melt. This parallels observations of the effects of repeated shear modification on the properties of polyethylene films and other extrudates.
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  • 60
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    Polymer Engineering and Science 34 (1994), S. 585-597 
    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 design and analysis of a process control strategy for a reactive extrusion polypropylene degradation process. The primary control objective is to continuously produce polypropylene with desired properties (viscosity) despite variations in the properties of the feed material. The viscosity of the polypropylene, measured using an In-line Wedge Rheometer, is controlled by manipulating the feed concentration of the peroxide which acts as the initiator for the degradation reaction. An empirical model of the reactive degradation process is developed which describes the process dynamics and the characteristic process disturbances. Minimum variance (MV), constrained minimum variance (CMV), and pole placement (PP) controllers are first evaluated and compared in simulation. Then, a pole placement controller is implemented on the actual reactive extrusion process, with results being presented for the response of the controlled process to load disturbances due to feed material changes.
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  • 61
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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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  • 62
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    Polymer Engineering and Science 34 (1994), S. 580-584 
    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 sliding plate rheometer has been developed to measure the normal thrust of a molten plastic in large amplitude oscillatory shear. The normal thrust of a molten plastic in large amplitude oscillatory shear is a significant nonlinear effect that has previously been unobtainable. Normal thrust measurements may now be used to help understand and characterize nonlinear viscoelastic behavior inherent in most molten plastics. The new rhemoeter incorporates a piezoelectric pressure transducer in a very stiff plate that minimizes compliance. Normal thrust measurements with cone and plate rheometers are made by measuring the total force on the plate (or cone) and are subject to error due to edge effects. The new rheometer measures the local pressure in the sample and is therefore unaffected by sample size or edge effects. Normal thrust measurements in large amplitude oscillatory shear are reported for both molten Phillips TR480 high density polyethylene pipe resin which contains 2% by weight of carbon black filler and IUPAC LDPE X. Crosstalk due to shear stress on the active face of the pressure transducer causes signal error which for oscillatory shear is filtered out using a discrete Fourier transform.
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  • 63
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    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.
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  • 64
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    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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  • 65
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    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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  • 66
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    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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  • 67
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    Polymer Engineering and Science 34 (1994), S. 657-664 
    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 good extrusion die must distribute the polymer melt in the flow channel such that the material exits from the die with a uniform velocity and temperature. Coathanger dies are commonly used for the extrusion of plastic sheets and films. The die is usually provided with a straining bar allowing a regulation of the flowrate in the case of a poor design. But this, in turn, can affect temperature uniformity. Therefore, the design of coathanger die is a complex task which is mainly accomplished by trial and error in industry. Analyses of the flow in coathanger dies have been reported in the literature. Analytical and numerical approaches are used to solve this problem. The first one involves many simplifying assumptions: the most important ones being the unidirectional and isothermal flow of the polymer. Most numerical methods deal with a 2-D geometry, but only a few of them have considered the non-isothermal flow. A new model has been developed using a modified FAN method (Flow Analysis Network introduced by Tadmor) for the calculation of the 2-D flow, coupled with a finite-difference scheme for the calculation of temperature. The overall model can run on a PC with only a few minutes of calculation. Good agreement was obtained between experimental data and simulations.
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  • 68
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    Polymer Engineering and Science 34 (1994), S. 650-656 
    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 finite element model named Corrected Slice Method (CSM) has been developed to cope with three-dimensional vacuum cooling calibrator problems. Such problems appear whenever the cooling channel lay-out comprises transverse channels in the calibrator. The CSM is an extension of the 2D approach (8), which takes into account the axial heat fluxes within the calibrator. The proposed model was validated by comparing the numerical results obtained on a test problem with a rigorous finite element approach. Moreover, a real complex profile-calibrator system was simulated in order to illustrate the full performance of the porposed method.
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  • 69
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    Polymer Engineering and Science 34 (1994), S. 665-670 
    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 use of bend testers for the determination of critical strains in the study of environmental stress cracking has been assessed. Using the combination of polystyrene in ethanol, various factors affecting the measurement of critical strains were investigated, including the strain applied during the bend testing, the time of immersion in the liquid prior to straining, the surface finish, and the extent of physical aging. It was concluded that the best determination of critical strain is the strain at which a sample just shows signs of crazing, rather than the strain at the outer edge of a band of crazes. The measured value of critical strain increases with increased prior immersion time, decreased surface roughness, and decreased physical aging time. Reasons for these variations are discussed. It is concluded that although the use of bend testers is valuable for qualitative testing, careful testing methodologies need to be adopted for it to be a useful quantitative test.
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    Polymer Engineering and Science 34 (1994), S. 632-641 
    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 dynamics of R-11 blown polyurethane foam formation depend on the rates of viscosity increase of the reacting mixture and R-11 evaporation, and both are controlled by the polymerization process. Detailed experiments were carried out to study the dynamics of foaming and the measurements made included the cream and rise times, the density change of the expanding foam with time, and the temperature rise during reaction. Dynamic temperature measurements at different points in the foaming mixture were also made to study the spatial variation of the temperature in the foam. The experimental results showed the rate of foaming, the final density, and the maximum temperature decreased with increasing R-11 concentration. The heat losses from the foam were also found to be significant towards the later stages of foaming when density was low. Theoretical models were developed to predict the temperature and density change with time and spatial variation of temperature in the foam due to heat losses, by considering the foaming dynamics to be either heat generation controlled or heat and mass transfer controlled. In the former, the foam was assumed to be a pseudohomogeneous phase and the approach was similar to that of Rojas, et al. (5). New features accounted for in the model were dilution of the reactant concentration due to the presence of liquid blowing agent and heat loss from the foam due to radiation. While excellent agreement between theoretical predictions and experimental results was obtained for temperature variation with time at different locations in the foam, the model gave a much sharper reduction in density with time as compared to the experimental data. In the second model, the rate of foaming was assumed to be controlled by the rate of heat and mass transfer to a single bubble in the foam. Assuming a film model for heat and mass transfer, the theoretical predictions for both temperature and density were found to be in very good agreement with experimental data.
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    Polymer Engineering and Science 34 (1994), S. 821-826 
    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: When diffusion coefficients are measured with the cup method, the exposed area is often less than the area of the sample. Because of this masking effect the measured diffusion coefficient is overestimated. The present article presents simple formulas based on two-dimensional analytical solutions to correct for this in cylindrical cup samples. Different cases of anisotropical diffusion are dealt with. The error in the analytical solutions is determined by numerical computer simulations.
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  • 72
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    Polymer Engineering and Science 34 (1994), S. 815-820 
    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 comparative study of warpage, global shrinkage, and residual quench stresses developed in rotational molding is made for a series of thermoplastics including various polythylenes, polypropylene, polyamide-6, polycarbonate, and polystyrene. The influence of rate of quench on uniaxial stress strain and impact behavior of rotomolded parts was also studied. Generally, warpage, global shrinkage, and residual stresses increase with increasing quench rate for all the polymers. Further, the levels of warpage and global shrinkage increases with extent of crystallization, i.e., products from glassy polymers exhibit little warpage and those from highly crystalline polymers are highly warped. Increasing rate of quench tends to increase elongation to break and impact strength.
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    Polymer Engineering and Science 34 (1994), S. 799-803 
    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 of melt strength and breaking stretching ratio of several blends of thermoplastic polymers with liquid crystalline polymers are presented. The melt strength behavior depends not only on the viscosity of the blends but also on the temperature dependence of the viscosity. In particular, even if the viscosities of the blends are, at the extrusion temperature, lower than that of the thermoplastic matrices, the melt strength can be larger than that of the pure thermoplastics if its viscosity-temperature curve exceeds that of the matrices far from the solidification temperature. This behavior allows one to spin or film blow these blends despite the low viscosity.
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    Polymer Engineering and Science 34 (1994), S. 804-814 
    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 mathematical model of the high pressure polymerization of ethylene in tubular reactors was tested with experimental data obtained from an industrial size tubular reactor. Series of experiments involving changes in operating conditions were carried out, and process data and polyethylene samples were collected. The collected samples were characterized for their molecular weight distributions and various rheological material functions involving shear and extensional flows. The findings of the model were compared against the generated process data and the molecular weight distributions of the samples. The determined rheological behavior exhibited strong dependence on the primary characteristics of the resins. Overall, this study should introduce a better understanding of the interactions between high pressure reaction conditions and the primary properties of polyethylene, including moments of molecular weight distribution and extent of branching on one hand and the interrelationships between primary properties and the rheological behavior of the high pressure polyethylene product on the other hand.
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  • 75
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    Polymer Engineering and Science 34 (1994), S. 827-834 
    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 Galerkin finite element method has been applied to study the three-dimensional flow field of power-law fluids inside an extrusion die. Two inlet designs, i.e., center-fed and end-fed, have been considered. The effects of inertial force as represented by the Reynolds number Re, inlet geometry, and the power-law index n on lateral flow uniformity and vortex formation in the entrance region have been examined. A flow visualization technique has been carried out to experimentally verify the theoretical prediction of the three-dimensional flow field inside a die. It has been found that increasing Re or decreasing n will deteriorate flow uniformity. Depending on the direction of the inlet jet stream, the inertial force may create a flow peak in the central region of a center-fed die, or the maximum flow rate will appear close to the end of the die for an end-fed die. For highly shear-thinning fluids, lower flow rates are always observed close to the end of the dies. It is concluded that creating a plug flow in the inlet tube of the extrusion die is advantageous for both center-fed and end-fed designs.
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    Polymer Engineering and Science 34 (1994), S. 835-846 
    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 two-phase model is presented for simulating the post-filling stage of injection molding of amorphous and semicrystalline materials. A finite-element scheme with quadratic shape function for the pressure is proposed. The melt is considered in terms of Hele-Shaw flow for a non-Newtonian fluid using a modified-Cross model with either an Arrhenius-type or WLF-type functional form to describe the viscosity under nonisothermal conditions; the compressible behavior of the polymer is assumed to obey either a double-domain Tait or single-domain Spencer Gilmore equation of state. The interfacial energy balance equation including the latent-heat effect for semicrystalline materials is coupled with the transient energy equation for the solid and melt phases in order to predict the solidified layer and temperature profile. Two well-characterized materials, namely a commercial-grade PP and PS, were used in the present work. Good agreement is obtained between the present simulation and experimental pressure traces from this study and from previous investigation in the literature. The effects of compressibility, viscosity model, and thermal properties upon the predicted pressure field are also considered.
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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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    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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    Polymer Engineering and Science 34 (1994), S. 1148-1156 
    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: We have generated microcellular polymeric foam structures using a pressure induced phase separation in concentrated mixtures of supercritical CO2 and poly(methyl methacrylate). The process typically generates a microcellular core structure encased by a nonporous skin, the thickness of which decreases with increasing saturation pressure. This trend can be described by a model for skin formation that is based on the diffusion rate of gas out of the sample. Significant density reductions on the order of 30 to 70% can be achieved by changing the pressure and temperature conditions in the foaming process. There are several ways in which the saturation pressure affects the average cell size, with the net effect that cell size decreases sharply with increasing pressure above 2000 psi, leveling out at higher pressures. Cell size increases with increasing temperature from 40°C to 70°C. A model for cell growth, based on a cell model of Aremanesh and Advani, modified to include the effect of CO2 on model parameters, reproduces these trends.
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  • 80
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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.
    Additional Material: 14 Ill.
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  • 81
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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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  • 82
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    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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  • 83
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    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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  • 84
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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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  • 85
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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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  • 86
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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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  • 87
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    Polymer Engineering and Science 34 (1994), S. 1224-1230 
    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 cavity transfer mixer (CTM) was primarily designed as a distributive mixing device to be used as an add-on unit to existing extruders. In determining the CTM overall mixing efficiency as well as its potential use for various applications, the flow patterns/characteristics within this mixer must be well understood. In this work, a fluid dynamics analysis package, FIDAP, based on the finite element method was employed to simulate the flow patterns in a CTM with 6 rows and 4 cavities per row. A 3D, isothermal flow analysis was carried out and the fluid of choice was a flexible polyvinylchloride whose rheological behavior is described by a power-law model fluid. The flow field was characterized in terms of velocity profiles, pressure distributions, shear rates/shear stresses generated and a parameter λ quantifying the elongational flow components. The results of the flow simulations were compared with experimental data. The CTM potential use for dispersive mixing was discussed.
    Additional Material: 14 Ill.
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  • 88
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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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  • 89
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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.
    Additional Material: 4 Ill.
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  • 90
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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.
    Additional Material: 11 Ill.
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  • 91
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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.
    Additional Material: 6 Ill.
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  • 92
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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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  • 93
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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.
    Additional Material: 21 Ill.
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  • 94
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    Polymer Engineering and Science 34 (1994), S. 1005-1010 
    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: Brittle isotactic polystyrene has been toughened by the presence of emulsified rubber particles. Semicrystalline diblock copolymers of isotactic polystyrene and polybutadiene functioned successfully as emulsifying agents, as revealed by the results of scanning and transmission electron microscopy. Semiquantitative measures of the toughness of the various materials were obtained via a home-built micromechanical testing device. The minimum amount of copolymer required to achieve emulsified morphologies and significant toughness depended on the thermal history of the material being tested.
    Additional Material: 7 Ill.
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  • 95
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    Polymer Engineering and Science 34 (1994), S. 1319-1326 
    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: Stress-relaxation behavior is studied in polypropylene samples subjected to different cyclic preloadings and to simple tension. The relaxation tests are performed under different sets of strain amplitude, number of cycles, and strain rate, using a closed-loop, electrohydraulic, servocontrolled testing machine. The calculated stress-strain curves are determined from a constitutive equation based on an overstress theory in which an equilibrium stress and a viscosity function are treated. The calculated results agree well with the experimental ones. It is concluded that the overstress theory explains the nonlinear viscoelastic-plastic behavior of polypropylene.
    Additional Material: 14 Ill.
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  • 96
    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 work we report the effects of single stage zone drawing on the properties of NEW-TPI thermoplastic polyimide homopolymer, and its blends with Amoco's Xydar liquid crystalline polymer. Zone drawing was performed first on homopolymer NEW-TPI films to determine the effect of load weight, heater speed, and drawing temperature on the attainable draw ratio. Degree of crystallinity and chain orientation increase as the draw ratio increases for NEW-TPI. Blends of NEW-TPI/Xydar compositions 90/10 and 70/30 were studied next. In blends, the Xydar component is not molecularly dispersed, and is initially preferentially oriented along the machine direction during the film processing stage. Xydar acts as a nucleation site and lowers the temperature for crystallization of the NEW-TPI from the rubbery amorphous state. Zone drawing was performed either parallel or perpendicular to Xydar's initial preferred orientation direction. Blends with lower Xydar fraction could be zone-drawn to higher ratios. Zone drawing perpendicular to Xydar's initial orientation direction also resulted in increased draw ratio. Dynamic mechanical properties of the zone drawn materials were studied. In homopolymer NEW-TPI, dynamic modulus increased by a factor of two to 4.0 GPa in zone drawn films, largely as a result of the formation of oriented crystallites. In the blends, the modulus parallel to Xydar's initial orientation direction was greater than that in the transverse direction. Depending upon composition and test direction, zone drawing increased the dynamic moduli of the blends from 1.5 up to 2.7 times, in the temperature range from 150°C to 300°C.
    Additional Material: 9 Ill.
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  • 97
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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.
    Additional Material: 10 Ill.
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  • 98
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    Polymer Engineering and Science 34 (1994), S. 1305-1313 
    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: Comb-shaped graft polymers were synthesized and complexed with a LiCF3SO3 salt to form a new class of polymer electrolytes. The polymers based on an acrylonitrile-butadiene copolymer (NBR) have pendant, short-chain poly(ethylene oxide) (PEO) grafted onto a butadiene unit. The characteristics of these polymer electrolytes were investigated in terms of number of pendant EO groups and grafting degree in the graft copolymer. The maximum conductivity was observed at the optimum side PEO chain length, and the PEO chain length for the maximum conductivity decreased with an increase in the grafting degree. And a solid 7Li NMR relaxation technique was used to study the local environments and dynamics of the ions in the polymer electrolytes. The maximum conductivity value obtained from our study was three orders of magnitude higher than that of classical PEO-based electrolytes at ambient temperature. These improved low temperature conducting polymers with higher relative mechanical strength are expected to be suitable for practical applications, such as in rechargeable lithium batteries or electrochromic devices.
    Additional Material: 9 Ill.
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  • 99
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 34 (1994), S. 1336-1345 
    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: Injection molded samples of binary blends of Vectra (LCP) and the three amorphous polymers polyethersulfone (PES), polycarbonate (PC), and aromatic poly(ester carbonate) (APEC) have been subjected to morphological and rheological characterization, and coefficients of linear thermal expansion and Young's moduli have been determined. The Young's modulus of the PES/LCP blends exhibited a near lower-bound behavior that could be predicted by the one-adjustable-parameter equations of Halpin-Tsai (ζ = 0.18) and Takayanaga (b = 0.23), whereas the coefficients of linear thermal expansion followed the Takayanaga equation with a value of b = 0.50. The chain orientation of the LCP component was essentially constant in all PES/LCP blends with a Herman's orientation parameter of 0.39 ± 0.03. Transesterification reactions led to randomization of the constituents of the PC/LCP and APEC/LCP blends. The effect was more pronounced in the PC/LCP blends. The introduction of the LCP into the PC/LCP blends led to no reduction in melt viscosity and no self-reinforcement. APEC/LCP exhibited self-reinforcement in blends with a content greater than 27 vol% LCP, and especially the blend with 67 vol% LCP. The self-reinforcement was caused by the presence of an oriented LCP phase, confirmed by X-ray diffraction, and by improved interfacial bonding, presumably resulting from the transesterification reactions occurring at the phase boundaries.
    Additional Material: 11 Ill.
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  • 100
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Correlation chromatography ; Simulation model ; Adsorption effects ; Separation improvement
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Experiments and simulations prove that correlation chromatography can greatly reduce the disadvantage of a non-linear response of the chromatographic column. A factor that has been accepted as being an important source of error in correlation or multiplex chromatography, has been shown not to be. Separations affected, improve dramatically when correlation chromatography is used, and a substantial amount of correlation noise only arises when there is a large difference in separation between a conventional chromatogram and a correlogram. A model has been developed for simulating these nonlinearities. It is shown that, especially for correlation chromatography, the simulation results match the practical measurements very well.
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