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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 735-742 
    ISSN: 0887-6266
    Keywords: poly(3-alkylthiophene) ; whiskers ; crystallization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is shown that poly(3-alkylthiophene)s may readily crystallize from poor solvents in the form of whiskers. The experimental conditions required for the formation of whiskers were found to depend upon the alkyl side-chain length, solvent quality, and temperature. In all cases studied for alkyl side-chain lengths of 3-12 carbon atoms, the widths of the whiskers were of the order of 15nm, while their lengths often exceeded tens of microns. The thickness of the whiskers formed under the experimental conditions employed was found to scale with side-chain length, and was approximately 2 or 3 times the a/2 lattice dimension of the polymer unit cell. Packing of the macromolecules within the whiskers was such that the polymer backbones were normal to the whisker length; that is, the b-axis was oriented parallel to the long axis of the whiskers. These results are thought to be relevant to known thermochromism phenomena associated with poly(3-alkylthiophene)s. © 1993 John Wiley & Sons, Inc.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 1383-1393 
    ISSN: 0887-6266
    Keywords: self-nucleation ; crystallization ; melting ; isotactic polypropylene ; thermal analysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization behavior after partial or complete melting of the α phase of iPP is examined by combined differential scanning calorimetry (DSC) and optical microscopy: calorimetric results are directly correlated with corresponding morphologies of microtome sections of DSC samples. On partial melting at various temperatures (hereafter referred to as Ts) located in a narrow range (4°C) below and near Tm, the number of nuclei increases (as in classical self-nucleation experiments), by several orders of magnitude; on subsequent cooling, the crystallization peak is shifted by up to 25°C. After partial melting in the lower part of the Ts range and recrystallization, the polymers display a prominent morphology “memory effect” whereby a phantom pattern of the initial spherulite morphology is maintained.After partial melting in the upper part of the Ts range the initial morphology is erased and self-nucleation affects only the total number of nuclei. The present experimental procedures make it possible to define, under “standard” conditions, the crystallization range of the polymer and in particular, the maximum crystallization temperature achievable when “ideally” nucleated. © John Wiley & Sons, Inc.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 32 (1994), S. 573-577 
    ISSN: 0887-6266
    Keywords: crystallization ; nucleation ; spherulites ; liquid-liquid phase separation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization of poly(butylene terephthalate) (PBT) from moderately dilute solutions of PBT in a diglycidyl ether of bisphenol-A epoxy has been investigated. PBT dissolves in this epoxy approximately 35°C below its usual melting temperature of 227°C to form a one-phase solution. Cooling this solution below 165°C leads to rapid crystallization of the PBT. The resulting mixture of liquid epoxy and crystalline PBT has a low viscosity and contains highly birefringent, individual PBT spherulites. The PBT spherulites have a narrow size distribution and a high surface-to-volume ratio. These particles are suggested to arise from a rapid crystallization that follows liquid-liquid phase separation. © 1994 John Wiley & Sons, Inc.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 265-271 
    ISSN: 0887-6266
    Keywords: Nylon-12 ; dielectric properties ; crystallization ; calorimetry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric properties of 30% crystalline dry Nylon-12 have been measured over the frequency range 10-105 Hz and temperature range 300-450 K, and the effect of its annealing at 423 K investigated both by dielectric measurement and differential scanning calorimetry. Annealing causes its crystallization to α phase, which increase the dc conductivity and decreases the contribution to orientation polarization, but does not alter the shape of the relaxation spectrum. The orientation polarization in Nylon-12 involves two processes, each of which occurs above the glass-transition temperature of Nylon-12, but only the spectra of the lowest temperature process could be clearly resolved. © 1993 John Wiley & Sons, Inc.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 1957-1967 
    ISSN: 0887-6266
    Keywords: liquid crystals ; polyesters ; smectic mesophase ; crystallization ; optical textures ; DSC ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This work reports the phase behavior of the polyesters made from the condensation of isophthalic acid (IA) and terephthalic acid (TA) with the mesogenic diol 4,4′-bis (6-hydroxy hexoxy) biphenyl (BHHBP). The latter monomer forms a smectic mesophase in the interval 98-179°C. Fischer et al., who investigated the room temperature x-ray patterns of the oriented polyesters of BHHBP and IA, as well as BHHBP and TA, claimed that both polymers also showed smectic mesophases. However, they showed no other evidence to support their interpretation. In the present work, examination of these polyesters under the optical microscope revealed focal conic textures for the IA polyester, but spherulitic textures for the TA polyester. DSC studies revealed thermograms with two peaks in the cooling scan for the IA polyester, at different cooling rates, which supported the view that there were two phase transitions. The heating scans of the TA polyester showed multiple peaks that depended on heating rate whereas on cooling, only a single exothermic peak was observed at all cooling rates. Thus, the current results definitely support the case for a smectic A mesophase in the IA polyester but, contrary to Fischer et al.'s opinion, do not suggest any mesophase formation in the TA polyester. © 1995 John Wiley & Sons, Inc.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 1995-2001 
    ISSN: 0887-6266
    Keywords: tussah silk fibroin ; methanol treatment ; molecular conformation ; crystallization ; Raman spectroscopy analysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Structural changes of tussah (Antheraea pernyi) silk fibroin films treated with different water-methanol solutions at 20°C were studied as a function of methanol concentration and immersion time. X-ray diffraction measurements showed that the α-helix structure, typical of untreated tussah films, did not change for short immersion times (2 min), regardless of methanol concentration. However, crystallization to β-sheet structure was observed following immersion of tussah films for 30 min in methanol solutions ranging from 20 to 60% (v/v). IR spectra of tussah films untreated and methanol treated for 2 min exhibited strong absorption bands at 1265, 892, and 622 cm-1, typical of the α-helix conformation. The intensity of the bands assigned to the β-sheet conformation (1245, 965, and 698 cm-1) increased for the sample treated with 40% methanol for 30 min. Raman spectra of tussah films with α-helix molecular conformation exhibited strong bands at 1657 (amide I), 1263 (amide III), 1106, 908, 530, and 376 cm-1. Following α → β conformational transition, amide I and III bands shifted to 1668, and to 1241, 1230 cm-1, respectively. The band at 1106 cm-1 disappeared and new bands appeared at 1095 and 1073 cm-1, whereas the intensity of the bands at 530 and 376 cm-1 decreased significantly. ©1995 John Wiley & Sons, Inc.
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2771-2773 
    ISSN: 0887-6266
    Keywords: chondroitin sulfate ; fiber period ; x-ray diffraction ; annealing ; crystallization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Without elongational treatments, the fiber period of chondroitin-4-sulfate (0.87 nm) is shorter than in the elongated case (0.96 nm). The fiber period may change corresponding to its mechanical history. © 1996 John Wiley & Sons, Inc.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1843-1854 
    ISSN: 0887-6266
    Keywords: crystallization ; DNA ; fractionation ; gel-electrophoresis ; morphology ; phase transition ; SALLS ; sonication ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polydisperse DNA of reasonable molecular weights was prepared from a mammalian source via sonication and fractionation. A method for characterizing the molecular weight using gel electrophoresis is described. Quiescent crystallization was studied in thin films of one of the fractions induced by rapidly changing the hydration state isothermally. We report the occurrence of the semicrystalline nature of DNA. The crystal growth occurring via aggregates is best described as sheaves and spherulites from DNA gels in the relative humidity range (RH) corresponding to A-DNA. These habits exhibit primary nucleation and secondary growth, which closely resemble those of melt-crystallized, synthetic macromolecules and, in a follow-up report, will be shown to be lamellar in nature. Small, needle-like crystals are observed for B-DNA hydration levels, and are unstable at lower hydration levels. A transformation from needle to lamellar crystals can occur, even when the primary nucleation of lamellar forms is otherwise absent at that hydration level, through a cylindrical phase exhibiting selective reflection of colored bands. The hydration level plays, in part, the role of the supercooling in this system and the long-known hysteresis in the formation and dissolution of the A-DNA (crystals) can now be viewed in light of those factors known to operate in semicrystalline systems. A morphological phase diagram is developed and is in accord with the known physical evidence. Because this preparation and these morphological observations are without precedence, substantial detail into methodology is included for this first article in the series. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1843-1854, 1997
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2077-2084 
    ISSN: 0887-6266
    Keywords: liquid crystals ; polyesters ; nematic-smectic biphase ; monotropic ; crystallization ; optical textures ; DSC ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polyesters made from the condensation of isophthalic acid (IA) or terephthalic acid (TA) with the mesogenic diol 4,4′-bis (6-hydroxy hexoxy)biphenyl (BHHBP) are both reported to show a smectic mesophase. However, in our previous work, we found evidence for a mesophase in the polyester containing BHHBP and IA, but not in the one with BHHBP and TA. For the BHHBP-IA polyester, we thought the phase sequence on cooling was I → SA → K, while on heating the situation was unresolved; there was some indication that on heating, a K → I transition occurs without any intervening mesophase. In other words, it was suspected that the mesophase in the IA polyester was monotropic. In this work, we have now obtained firm evidence that the mesophase behavior of the BHHBP-IA polyester is indeed monotropic. Further, an additional complexity has been found: on cooling, there is in fact a nematic phase, besides a smectic A, and a crystal phase. However, the mesophase appears to be complex. As the nematic and smectic textures occurred simultaneously, it seems that the mesophase is a nematic-smectic biphase. © 1996 John Wiley & Sons, Inc.
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  • 10
    Electronic Resource
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 447-453 
    ISSN: 0887-6266
    Keywords: polyethylene terephthalate ; low density polyethylene ; isocyanate functional group ; compatibility ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: To evaluate the compatibilizing effects of isocyanate (NCO) functional group on the polyethylene terephthalate/low density polyethylene (PET/LDPE) blends, LDPE grafted with 2-hydroxyethyl methacrylate-isophorone diisocyanate (LDPE-g-HI) was prepared and blended with PET. The chemical reaction occurred during the melt blending in the PET/LDPE-g-HI blends was confirmed by the result of IR spectra. In the light of the blend morphology, the dispersions of the PET/LDPE-g-HI blends were very fine over the PET/LDPE blends. DSC thermograms indicated that PET microdispersions produced by the slow cooling of the PET/LDPE-g-HI blends were largely amorphous, with low crystallinity, due to the chemical bonding. The tensile strengths of the PET/LDPE-g-HI blends were higher than those of the PET/LDPE blends having a poor adhesion. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 447-453, 1998
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  • 11
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 901-915 
    ISSN: 0887-6266
    Keywords: poly(aryl ether ketones) ; poly(ether imide) ; crystallization ; melting ; glass transition ; morphology ; small-angle x-ray scattering ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The relationships among glass transition, crystallization, melting, and crystal morphology of poly(aryl ether ketone) (PAEK)/poly(other imide) (PEI) blends was studied by thermal, optical and small-angle x-ray scattering (SAXS) methods. Two types of PAEK were chosen for this work: poly(aryl ether ether ketone), PEEK, and poly(aryl ether ketone ketone), PEKK, which have distinctly different crystallization rates. Both PAEKs show complete miscibility with PEI in the amorphous phase. As PAEK crystallizes, the noncrystallizable PEI component is rejected from the crystalline region, resulting in a broad amorphous population, which was indicated by the broadening and the increase of Tg over that of the purely amorphous mixture. The presence of the PEI component significantly decreases the bulk crystallization and crystal growth rate of PAEK, but the equilibrium melting temperature and crystal surface free energies are not affected. The morphology of the PEI segregation was investigated by SAXS measurements. The results indicated that the inter(lamellar-bundle) PEI trapping morphology was dominant in the PEEK/PEI blends under rapid crystallization conditions, whereas the interspherulitic morphology was dominant in the slow crystallizing PEKK/PEI blends. These morphologies were qualitatively explained by the expression δ=D/G, where G was the crystal growth rate and D was the mutual diffusion coefficient. © 1993 John Wiley & Sons, Inc.
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  • 12
    ISSN: 0887-6266
    Keywords: crystallization ; nucleation ; nucleating additives ; isotactic polypropylene ; DSC ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple, convenient and reliable calorimetric efficiency scale is proposed for the evaluation of nucleating additives for polymers. The scale is based on conventional differential scanning calorimetry cooling runs and makes use of a crystallization range determined in self-nucleation experiments. It can be correlated with spherulite sizes, and indicates the potential range of improvement of nucleating additives. Typical nucleating agents for isotactic polypropylene are evaluated; at best they rate at 60 to ca. 70% on this efficiency scale. © 1993 John Wiley & Sons, Inc.
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  • 13
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 1407-1424 
    ISSN: 0887-6266
    Keywords: isotactic polypropylene ; β phase ; α nucleation ; melting ; crystallization ; growth transitions ; thermal analysis ; morphology ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanisms which, in isotactic polypropylene, create α phase nuclei on partial melting of β phase spherulites are investigated by thermal analysis and optical and electron microscopy. Nuclei concentrations are determined from recrystallization characteristics. α phase nuclei are formed within β spherulites via two different mechanisms: (1) a low temperature formation of latent α phase nuclei (αβ* nuclei) linked with a hitherto unsuspected β to α growth transition at T = T* ∼ 105°C, and (2) a high temperature α phase nucleation process (αβ nuclei), also linked with a similar β to α growth transition at 140°C first reported by Varga et al. The low temperature nucleation mechanism is the more efficient one: it significantly affects the melting of β phase, and results in samples with over 1013 α nuclei · cm-3. © 1993 John Wiley & Sons, Inc.
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  • 14
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 1627-1639 
    ISSN: 0887-6266
    Keywords: semi-IPN ; crystallization ; phase separation ; compatability ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Differential scanning calorimetry together with dynamic mechanical analysis were employed to investigate the crystallinity and the miscibility in poly(ethylene oxide)/crosslinked poly(methyl methacrylate) semi-IPN (interpenetrating polymer networks). The crystallinity of poly(ethylene oxide) in the semi-IPN is found to depend on the crosslink density of PMMA as well as the overall content of PEO. Of special interest is that an increase in the crosslink density tends to increase the crystallinity contrary to our expectation, indicating crystallization and phase separation may proceed simultaneously during IPN formation. The investigation of glass transition behaviors with dynamic mechanical analysis suggests phase separation (i.e., there exist two amorphous phases: one PEO-rich phase, the other a PMMA-rich phase). © 1993 John Wiley & Sons, Inc.
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  • 15
    Electronic Resource
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 32 (1994), S. 1183-1190 
    ISSN: 0887-6266
    Keywords: polyamide ; aliphatic ; crystallization ; binodal ; ternary ; phase diagram ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Concentration-dependent ternary interaction parameters are experimentally determined for the polyamide homopolymers, Nylon-6, -66, -610, and for the Nylon-66/610/6 terpolymer in formic acid-water systems. The binodal envelope, the tie lines, and the crystallization isotherms at 25°C are given for each of the ternary systems. © 1994 John Wiley & Sons, Inc.
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  • 16
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 32 (1994), S. 1991-1998 
    ISSN: 0887-6266
    Keywords: polypropylene (PP) ; blend ; compatibilization ; crystallization ; fractionated crystallization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The compatibilization of incompatible polypropylene (PP)/poly(ethylene oxide) (PEO) blends was studied. The experimental results showed that the graft copolymer [(PP-MA)-g-PEO] of maleated PP(PP-MA) and mono-hydroxyl PEO (PEO-OH) was a good compatibilizer for the PP/PEO blends in which PP-MA also had some compatibilization. The crystallization of the blends was affected by the compatibility between PP and PEO. The interfacial behavior of the compatibilizers had an important effect on crystallization behavior of the PP/PEO blends. PEO showed fractionated crystallization in the PP/PEO blends. This behavior was studied from the view point of the theory of fractionated crystallization. © 1994 John Wiley & Sons, Inc.
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  • 17
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 32 (1994), S. 2585-2594 
    ISSN: 0887-6266
    Keywords: PEKK ; copolymer ; terephthalate/isophthalate ; structure ; crystallization ; melting ; x-ray diffraction ; thermal analysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In a previous study, we have investigated the structure, crystallization, and morphology of poly(aryl ether ketone ketone), PEKK, copolymers prepared from diphenyl ether (DPE), terephthalic acid (T), and isophthalic acid (I) with T/I ratios from 100/0 to 50/50. These materials were considered as having -DPE-T-DPE-T- (TT) and/or -DPE-T-DPE-I- (TI) “phthalate diads.” In this work, we continue the study of this copolymer series with six different T/I ratios (40/60, 30/70, 20/80, 15/85, 10/90, and 0/100), which are viewed as having TI and/or -DPE-I-DPE-I- (II) “diads.” The I moieties (1,3-linked isomers) were always found to be incorporated in the crystals and acted as “entropy or symmetry” defects that effectively decreased the equilibrium melting temperature Tmo and the rate of crystallization. However, the retardation of crystallization in PEKK 0/100 (the homopolymer with pure II diads) was significantly less than expected, which was attributed to the segregation of I moieties between the chains leading to a reduction of total entropy in the unit cells. The evidence of segmental segregation in PEKK 0/100 was seen in x-ray diffraction patterns, where several extra reflections were seen that could only be indexed by the published unit cell modified with a larger c-axis dimension (3.048 nm, corresponding to the length of six phenyl residues or 1.524 nm, the length of three phenyl residues). The composition of 15/85 was found to have the lowest value of Tmo and the slowest crystallization rate. Upon heating, the “II” crystals (T/I from 30/70 to 0/100) exhibited the conventional double-melting behavior rather than the triple-melting behavior as in the “TI” crystals (50/50 to 40/60). No indication of the second polymorph form 2 was found in “II” crystals. © 1994 John Wiley & Sons, Inc.
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  • 18
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 32 (1994), S. 201-204 
    ISSN: 0887-6266
    Keywords: poly[styrene-b-(ethylene-co-butylene)-b-styrene] ; poly (vinylidene fluoride) ; miscibility ; crystallization ; melting ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abstract
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  • 19
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 173-180 
    ISSN: 0887-6266
    Keywords: AFM ; tapping mode AFM ; thin films ; polycarbonate ; solvent ; crystallization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thin films of bisphenol-A polycarbonate (PC) were progressively crystallized in a controllable manner under the action of an appropriate plasticizing agent. No conducting layer was applied to the polymer surface, so that imaging with the atomic force microscope (AFM) left the sample exposed for additional plasticizer treatment. The PC sample was observed many times throughout the crystallization process using the AFM in both the contact and tapping modes. Data regarding the growth process for spherulites in addition to high-resolution morphology studies were achieved. © 1996 John Wiley & Sons, Inc.
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  • 20
    ISSN: 0887-6266
    Keywords: polymer blends ; crystallization ; diffusion ; composition inhomogeneities ; computer simulation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is well known that crystallization of one component in a polymer blend causes composition profiles around the growing spherulites. Amplitude and width of these profiles, respectively, depend on the ratio between the rates of diffusion and of spherulite growth. They can be determined by suitable experimental means. In the present article, the profiles are modeled, starting from Frank's solution of the diffusion equation in spherical coordinates under the boundary condition of moving walls that simultaneously are sources of the diffusing material. Modeled and experimentally determined profiles in PVDF/PEA and PCL/PS blends agree well. The analysis yields estimates for the diffusion coefficient D in polymeric melts as D ≅ (50··· 500) μm2/h. Finally, the interference of the composition profiles around several adjacent spherulites can be demonstrated. © 1996 John Wiley & Sons, Inc.
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  • 21
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    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 1751-1759 
    ISSN: 0887-6266
    Keywords: tetrafluoroethylene-perfluoroalkylvinylether copolymers ; melting ; crystallization ; annealing ; crystal-crystal transitions ; differential scanning calorimetry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By differential scanning calorimetry (DSC), the effect of thermal treatments on the melting of tetrafluoroethylene-perfluoroalkylvinylether copolymers (PFA) with different contents of perfluoromethylvinylether as a comonomer has been investigated. Two melting peaks can be identified for all copolymers, whose presence, value, and extent depend upon the thermal treatments. The higher temperature one, scarcely influenced by the crystallization conditions (i.e., cooling rate and annealing), can be attributed to more perfect crystals present in the original samples. The lower temperature one is produced only by annealing (annealing peak) and can be interpreted as resulting from much poorer crystals grown among the larger ones. For the copolymer with the lowest content of comonomer, the effect of thermal treatments on the low-temperature (crystal-crystal) transitions has also been studied. The rejection of the counits from the crystals, at least in equilibrium conditions, is confirmed. © 1996 John Wiley & Sons, Inc.
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    ISSN: 0887-6266
    Keywords: polylactide ; membrane formation ; morphology ; crystallization ; liquid-liquid demixing ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of liquid-liquid demixing, solid-liquid demixing, and vitrification on the membrane morphologies obtained from several polylactide-solvent-nonsolvent systems has been investigated. The polymers investigated were the semicrystalline poly-L-lactide (PLLA) and the amorphous poly-DL-lactide (PDLLA). The solvent-nonsolvent systems used were dioxane-water, N-methyl pyrrolidone-water and dioxane-methanol. For each of these systems it was attempted to relate the membrane morphology to the ternary phase diagram at 25°C. It was demonstrated that for the amorphous poly-DL-lactide the intersection of a glass transition and a liquid-liquid miscibility gap in the phase diagram was a prerequisite for the formation of stable membrane structures. For the semicrystalline PLLA a wide variety of morphologies could be obtained ranging from cellular to spherulitical structures. For membrane-forming combinations that show delayed demixing, trends expected on the basis of phase diagrams were in reasonable agreement with the observed membrane morphologies. Only for the rapidly precipitating system PLLA-N-methyl pyrrolidone-water were structures due to liquid-liquid demixing obtained when structures due to solid-liquid demixing were expected. Probably, rapid precipitation conditions promote solid-liquid demixing over liquid-liquid demixing, because the activation energy necessary for liquid-liquid demixing is lower than that for crystallization. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1175-1183 
    ISSN: 0887-6266
    Keywords: crystallization ; morphology ; chain folding ; lamella ; hydrogen bonding ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Morphologies of solution-grown crystals in systems containing strong and specific intralattice hydrogen bonding (nylons) are compared with systems displaying only van der Waals intracrystal attractions. The latter are shown to produce crystals that clearly mirror the underlying crystallographic symmetry; in the former systems the morphologies are much more complex and disorganized. This difference is discussed in terms of intralattice forces affecting growth rates and chain rearrangement during crystallization. Arguments deriving from differences in lamellar thickening behavior are also used to demonstrate this point. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1175-1183, 1997
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 495-517 
    ISSN: 0887-6266
    Keywords: crystallization ; DSC ; multiple melting ; nascent morphology ; polyethylene ; synchrotron ; UHMW PE ; WAXS ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The nascent morphology of UHMW PE exhibits high melting point, high crystallinity, and increased WAXS line breadth relative to samples formed by melt crystallization. Different empirical relationships between crystal size and melting point are observed for nascent and molded samples. This differentiation is removed following nitric acid treatment of the nascent flake. Solid-state annealing behavior is differentiated by several regimes. Regime I is characterized by increasing crystallite dimensions and crystallinity at low annealing temperatures. Regime II[a] and II[b] is identified by double melting in DSC scans of moldings and nascent flake, respectively. The double melting is due to partial melting with incomplete recrystallization. Regime II[a] of moldings is differentiated from Regime II[b] of flake by an increase in melting point of the higher melting endotherm. Within Regime II[b], the partial melting of the nascent structure is sensitive to the distribution of morphological stability. Regime III is initiated at annealing temperatures approaching the zero heating rate melting point, and shows melting kinetics by DSC or time-resolved WAXS using synchrotron x-ray radiation. The superheat, partially associated with Regime III behavior, is sensitive to morphological heterogeneity and annealing history. Morphological models are discussed which highlight the role of noncrystalline regions and melting kinetics on the melting behavior of nascent form crystallinity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 495-517, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2849-2863 
    ISSN: 0887-6266
    Keywords: nylon oligoamides ; new crystal structure ; morphology ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three-amide oligomers of nylon 6 and nylon 6 6 have been investigated using electron microscopy (imaging and diffraction), X-ray diffraction, and computational modeling. A new crystal structure has been discovered for the three-amide oligomer of nylon 6. This material crystallizes from chloroform/dodecane solutions into an unfolded crystal form that has progressively sheared hydrogen bonding in two directions between polar (unidirectional) chains. This structure is quite different from the usual room temperature α-phase structure of chain-folded nylon 6 crystals, in which alternatingly sheared hydrogen bonding occurs between chains of opposite polarity in only one direction. The occurrence of this new structure illustrates the extent to which progressively sheared hydrogen bonding is preferred over alternatingly sheared hydrogen bonding. Indeed, the progressive hydrogen bonding scheme occurs in the three-amide nylon 6 material even though it requires a disruption to the lowest potential energy all-trans conformation of the chain backbone, and requires all the chains in each hydrogen-bonded layer to be aligned in the same direction. We believe the presence of chain folding, which necessarily incorporates adjacent chains of opposite polarity into the crystal structure, prevents the formation of this new crystal structure in the nylon 6 polymer. In contrast, the three-amide nylon 6 6 crystal structure is analogous to the polymeric nylon 6 6 α-phase structure, found in both fibers and chain-folded crystals, and consists of progressive hydrogen-bonded sheets which stack with a progressive shear. In both structures, the molecules (≈ 3 nm in length) form smectic C-like layers with well-orchestrated stacking of 2.2 nm to form a three-dimensional crystal. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2849-2863, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2267-2274 
    ISSN: 0887-6266
    Keywords: poly(ether ether kotone) ; polyimide ; miscibility ; crystallization ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Miscibility and crystallization behavior of solution-blended poly(ether ether ketone)/polyimide (PEEK/PI) blends were investigated by using DSC, optical microscopy and SAXS methods. Two kinds of PIs, YS-30 and PEI-E, which consist of the same diamine but different dianhydrides, were used in this work. The experimental results show that blends of PEEK/YS-30 are miscible over the entire composition range, as all the blends of different compositions exhibit a single glass transition temperature. The crystallization of PEEK was hindered by YS-30 in PEEK/YS-30 blends, of which the dominant morphology is interlamellar. On the other hand, blends of PEEK/PEI-E are immiscible, and the effect of PEI-E on the crystallization behavior of PEEK is weak. The crystallinity of PEEK in the isothermally crystallized PEEK/YS-30 blend specimens decreases with the increase in PI content. But the crystallinity of PEEK in the annealed samples almost keeps unchanged and reaches its maximum value, which is more than 50%. The spherulitic texture of the blends depends on both the blend composition and the molecular structure of the PIs used. The more PI added, the more imperfect the crystalline structure of PEEK. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2267-2274, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2895-2904 
    ISSN: 0887-6266
    Keywords: polyamide 11 ; dynamic rheo-optical spectra ; deformation mechanism ; thermal treatment ; hydrogen bonds ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dynamic mechanical analysis, coupled with polarized step-scan FTIR transmission spectroscopy, has been used to monitor the submolecular motional behavior of uniaxially oriented polyamide 11. The dynamic in-phase spectra depend upon the morphology of the samples as well as on the polarization direction of the infrared radiation. The lineshape features of the dynamic in-phase spectra and their relationship to sample deformation are analyzed on the basis of changes of the internal coordinates, the reorientation movement of several functional groups, and the thickness change of the film during the stretching cycle. Dynamic infrared spectra are helpful for deconvolution of overlapping bands on the basis of their different responses to the external perturbation, which sometimes cannot be resolved well by derivative spectroscopy or curve-fitting analysis. The lineshape features have been used to follow microstructural changes after isothermal heat treatment. Near the N—H stretching frequency, two bands at 3270 cm-1 and 3200 cm-1 are resolved and analyzed in terms of Fermi resonance between the N—H stretching fundamental mode and the overtone and combination modes of the amide I and II vibrations. The dynamic response of the N—H stretching mode correlates with the modulation of hydrogen bond strength in uniaxially oriented PA-11. After thermal treatment at the highest temperature (190°C), the dynamic response in this region is mainly caused by the modulation of crystals. In amide I region, three bands at 1680 cm-1, 1648 cm-1, and 1638 cm-1 are separated and assigned to hydrogen bond-free, hydrogen-bonded amorphous, and hydrogen-bonded crystalline regions, respectively. The dynamic responses of the hydrogen-bonded regions are more sensitive to external perturbation. Two components are found in the amide II region, and the band at 3080 cm-1 is assigned to the overtone resonance of the component with perpendicular polarization. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2895-2904, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2961-2970 
    ISSN: 0887-6266
    Keywords: micelle ; blends ; crystallization ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The crystallization, morphology, and crystalline structure of dilute solid solutions of tetrahydrofuran-methyl methacrylate diblock copolymer (PTHF-b-PMMA) in poly(ethylene oxide) (PEO) and PTHF have been studied with differential scanning calorimetry (DSC), X-ray, and optical microscopy. This study provides a new insight into the crystallization behavior of block copolymers. For the dilute PTHF-b-PMMA/PEO system containing only 2 to 7 wt % of PTHF content, crystallization of the PTHF micellar core was detected both on cooling and on heating. Compared the crystallization of the PTHF in the dilute solutions with that in the pure copolymer, it was found that the crystallizability of the PTHF micellar core in the solution is much greater than that of the dispersed PTHF microdomain in the pure copolymer. The stronger crystallizability in the solution was presumably due to a softened PMMA corona formed in the solution of the copolymer with PEO. However, the “soft” micelles formed in the solution (meaning that the glass transition temperatures (Tg) of the micelle is lower than the Tm of the matrix phase) showed almost no effects on the spherulitic morphology of the PEO component, compared with that of the pure PEO sample. In contrast, significant effects of the micelles with a “hard” PMMA core (meaning that the Tg of the core is higher than the Tm of the PTHF homopolymer) on the nucleation, crystalline structure, and spherulitic morphology were observed for the dilute PTHF-b-PMMA/PTHF system. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2961-2970, 1998
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    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 1285-1291 
    ISSN: 0887-6266
    Keywords: crystallization ; isotactic polypropylene ; high-density polyethylene ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting behavior of spherulites in thin sections of isotactic polypropylene bulk samples and high-density polyethylene thin films crystallized isothermally at various temperatures has been studied by polarized light microscopy. The regions around cavities and multiple boundary points between spherulites have higher melting temperatures than the other parts of spherulites crystallized in Regime III. The increase in melting temperature is explained as a result of crystallization under negative pressure arising locally in pockets of occluded melt due to density change during spherulitic crystallization. The negative pressure lowers locally the equilibrium melting temperature and therefore decreases the undercooling, which results in an increase in lamellar thickness. Sectioning of bulk samples releases frozen negative pressure and reveals the increase in melting temperature of those parts of spherulites that were crystallized at lower undercooling. © 1993 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 619-627 
    ISSN: 0887-6266
    Keywords: nylon-6I ; crystallization ; x-ray diffraction ; differential scanning calorimetry ; infrared spectroscopy ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ability of various hydrogen bond-forming solvents to induce crystallinity in nylon-6I was studied using DSC, FTIR spectroscopy, and x-ray diffraction. Comparison was made with predictions using the solubility parameter, which is related to possibilities of interaction formation. General predicted tendencies agreed with experimental results, in agreement with proposed influence of solvent-polymer interactions in the solvent-induced crystallization process. FTIR investigation of polymers treated with methanol and methanol-d shows that polymer segments forming hydrogen bonds with solvent molecules crystallize preferentially. It is therefore concluded that hydrogen bond exchanges with the solvent favor chain rearrangements leading to crystallization. © 1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 32 (1994), S. 961-968 
    ISSN: 0887-6266
    Keywords: silk fibroin ; β structure ; crystallization ; molecular conformation ; glass transition ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Structural changes of native and regenerated silk fibroin membranes were induced by immersion in water-methanol solutions and examined as a function of immersion time and methanol concentration. X-ray diffractometry and infrared spectroscopy data showed that transition from random coil to β-sheet structure occurred favorably when both native and regenerated silk fibroin membranes were immersed in water-methanol solutions, regardless of the different immersion time. Only native silk membrane, treated for 2 min with pure methanol, maintained its original amorphous structure, as demonstrated by differential scanning calorimetric (DSC) curves. The degree of displacement, measured by thermomechanical analysis (TMA), was much greater for regenerated than for native silk fibroin membranes. SDS-PAGE pattern showed that native silk fibroin has a molecular weight of 350, while the regenerated sample is formed by a large number of polypeptides in the range of 200-50 KD. The amount of acidic and basic amino acids decreased slightly in regenerated silk fibroin. Physical properties of silk membranes treated with water-methanol solutions are discussed in terms of membrane structure, treatment conditions, and chemical structure of starting material. © 1994 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 32 (1994), S. 1999-2003 
    ISSN: 0887-6266
    Keywords: polytridecanolactone ; specific heat capacity ; melting ; crystallization ; transition enthalpy ; differential scanning calorimetry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An investigation of the thermodynamical properties of polytridecanolactone (PTDL) was made with the aid of a differential scanning calorimeter (DSC). PTDL is a linear polyester and belongs to the polylactones, which have been poorly investigated. In this paper we contribute with specific heat capacity in the range 180-400 K, and melting and glass transition characteristics. Further, we present unique results corresponding to the effect of different cooling rates on crystallization temperatures and crystallization energies. PTDL has a melting temperature of 350 K, and a glass transition at about 237 K. The crystallization results show that PTDL crystallizes easily, with a crystallization degree of about 80%. In addition, the crystallization energy decreases with increasing cooling rate, and levels out at a constant value at higher cooling rates. The crystallization temperature, on the other hand, shows an increasing sensitivity of cooling rate, where the supercooling is increasing more rapidly at higher cooling rates. © 1994 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2715-2721 
    ISSN: 0887-6266
    Keywords: crystallization ; PEO ; PPO ; blends ; compatibility ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isothermal and nonisothermal crystallization kinetics of different poly(ethylene oxide)/poly(propylene oxide) blends were investigated by means of differential scanning calorimetry (DSC). Glass transition temperature of quenched samples have also been reported. Phase morphologies and poly(ethylene oxide) spherulite growth rates were analyzed by polarizing light transmission microscopy. Results show morphological changes along with regime transitions of poly(ethylene oxide) crystal growth. Kinetic analyses of the data suggest that, although the blend behaves as a noncompatible, phase-separated system, there exists a certain degree of interaction between polymer chains. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 657-670 
    ISSN: 0887-6266
    Keywords: α-polypropylene ; β-polypropylene ; crystallization ; cylindrite ; isotactic polypropylene ; melting ; nucleation ; quiescent melt ; sheared melt ; supermolecular structure ; thermo-optical study ; transcrystallization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Shear-induced crystallization of isotactic polypropylene (iPP) homo-, block, and random copolymers was studied and compared to that in quiescent melt. It was evidenced by means of the thermo-optical technique that melt-shearing, caused by fiber pulling, is associated with the development of α-row-nuclei. The surface of the in situ formed α-row-nuclei may induce the growth of the β-modification of iPP resulting in a cylindrite of polymorphous composition. The polymorphous composition is controlled by the temperature-dependent relative growth rate of the α- and β-iPP for which a model explanation was given. The β-nucleation ability of the α-row-nuclei is lost by melt-shearing at high temperature or remelting. This was attributed to a coverage of the β-nuclei by the α-phase. The structural memory of the supermolecular structures was studied in repeated melting and crystallization cycles and discussed. It was found that the quality of the fiber did not influence the mechanisms concluded. The shear-induced crystallization of propylene block copolymers was highly analogous to the homopolymers. In case of the random copolymers, however, crystallization in sheared melt resulted in an α-cylindritic structure, because for propylene random copolymers the growth rate of the α-modification is always higher than that of the β. It was also demonstrated that the mechanism of shear-induced crystallization was unaffected when the crystallizing PP melt contained selective β-nucleants. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 3095-3105 
    ISSN: 0887-6266
    Keywords: crystallization ; spherulite ; anomalous growth ; poly(aryl ether ketones) ; optical microscopy ; SALS ; SAXS ; lamellar structure ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Anomalous two-stage spherulite growth has been observed in poly(aryl ether ketones) during isothermal crystallization. The first stage consists of a conventional growth with Maltesecross pattern at a lower growth rate. The morphology shows a smooth interface, dense structure and negative birefringence. The second stage grows in the form of “aggregate” at a higher rate. The morphology shows an open dendrite structure without preferred optical orientation. The second morphology is also termed the “overgrowth.” The occurrence of overgrowth is favored only near the maximum growth rate region and diminishes in the slow growth region. The transition of the two-stage growth is attributed to the change of growth direction of the constituent lamellae. We have confirmed this by microbeam small-angle light-scattering measurements. The lamellar structures in both growth stages were followed by time-resolved small-angle synchrotron x-ray scattering. It was found that the lamellar structures of the crystals formed at both stages are the same. A possible explanation for the two-stage growth is the interface breakdown caused by large perturbations of local composition and/or stress fields. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2523-2533 
    ISSN: 0887-6266
    Keywords: chirality ; morphology ; structure ; crystallization ; defects ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In previous work we have shown that the stable form of syndiotactic polypropylene (sPP) adopts a fully antichiral packing in its crystalline lattice. At the same time, we had also discovered a number of prohibited reflections from crystallographic planes with a c-axis component, indicating distortions or defects along the molecular-chain direction and possible departures from the ideal Ibca unit-cell structure. Three studies that appeared in 1996 have proposed a number of possible minimized structures to explore the energetics of departure from such an ideal Ibca symmetry and to account for the prohibited reflections. Two of the studies were based upon energy minimization of the unit cell using empirical or spectroscopically derived force fields. The third model was based upon Rietveld refinement of the bulk X-ray diffractogram combined with ad hoc choices of space groups selected to reproduce the prohibited reflections, and results in a structure with minimal departures from Ibca. In the present article we examine the structural implications of all these models on various reciprocal-lattice sections of sPP by comparing calculated electron-diffraction patterns for appropriate zones with those we obtained experimentally from single crystals. We find that none of the proposed models fully accounts for the experimental data. One of the energy-minimized models (involving translation along the molecular axis) and the Rietveld-refined structure reproduce some of the observed reflections but are not in agreement with observed intensities and introduce additional unobserved reflections or other artifacts. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2523-2533, 1997
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 763-781 
    ISSN: 0887-6266
    Keywords: random copolyesters ; copolymers ; crystallization ; melting ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting behavior of poly(ethylene terephthalate co-1,4-cyclohexylene dimethylene terephthalate) [PET/CT] random copolyesters has been studied. The basis of this analysis was the triple melting behavior of PET homopolymers, which is commonly observed after a period of isothermal crystallization followed by linear heating in a differential scanning calorimeter. Both ET and CT homopolymers are able to crystallize, and as a consequence, the copolymer morphology depends on the ET/CT ratio. It has been reported that at low CT concentrations, the ET units can crystallize with complete rejection of the CT units and that at high CT concentrations, the CT units can cocrystallize with the ET units. In the present work, low CT concentrations were selected, as they are completely rejected from the ET crystals. The purpose was to further test the hypothesis that in the triple melting behavior of PET homopolymers, the second DSC melting endotherm is related to secondary species crystallized by material rejected from the primary crystals. This concept arose from our previous work, where it was speculated that increasing the average molecular-weight of PET would enhance molecular entanglement and increase secondary crystallization. This process would give rise to a higher amount of species being rejected from the main crystals, i.e., an increase of secondary crystallization would occur, and as a consequence the second melting endotherm would be enhanced. Similar to the effect of molecular weight, such behavior has been observed as a function of rejected copolymer content. This gives support to our previously proposed step-like crystallization and melting mechanism for PET homopolymers, and has the potential to be extended to other high temperature semicrystalline polymeric systems. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 763-781, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 873-888 
    ISSN: 0887-6266
    Keywords: crystallization ; polymer blends ; pattern formation ; numerical simulation ; syndiotactic polystyrene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of texture which exists in polymer spherulites grown from single phase melts containing an appreciable amount of noncrystallizable material was investigated. This texture generally consists of lamellar bundles separated by amorphous regions, both of which are typically 0.1-1 μm thick. A space-time finite element model previously developed by us was used to simulate the growth of a group of polymer lamellae. The model determines the impurity concentration field in the melt surrounding the growing lamellae and tracks the growth of each lamella. Important variables are the initial melt concentration of noncrystallizable material, the mass diffusion coefficient of noncrystallizable species, lamellar thickness, long period, and the rate of molecular attachment at the growth front. Under certain conditions, bundles did indeed develop during the simulations. These results were used to predict bundle thicknesses. The predictions of bundle texture were compared to actual textures observed in blends of syndiotactic and atactic polystyrene. It was found both experimentally and numerically that bundle thickness was a strong function of crystallization temperature and a relatively weak function of both the initial composition of noncrystallizable species and the degree of crystallinity of the lamellar stack. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 873-888, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 1335-1348 
    ISSN: 0887-6266
    Keywords: PEEK ; growth rate ; crystallization ; kinetics ; regime ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An optical microscope equipped with a video photograph system was used to follow the growth of spherulites. Under nitrogen atmosphere, the growth rates at 290 and 300°C suggest that when the melt of PEEK has been equilibrated for 15 min at 400°C, the subsequent crystallization behavior was nearly independent of the prior thermal history. Linear growth rates of crystallization of PEEK have been measuredin the temperature range of 260-325°C for melt-pressed films and solvent cast films. Detailed kinetic analysis indicated that PEEK exhibited an unmistakable regime II → III transition at 296 ± 1°C. The II → III transition was clearly present irrespective of the rather drastic changes in U*. It is interesting that the branching and crosslinking retarded the growth rate of PEEK, but a transition from regime II to regime III still existed. For melt-pressed films after equilibration at 400°C for 15 min, values of σ and q suggest that U* should be taken nearer to 1500 cal/mol in the case of T∞ = Tg - 30 K and 2000 cal/mol in the case of T∞ = Tg - 51.6 K. The Kg(III)/Kg(II) ratio (1.32) was not as close to the predicted value of 2 as was Hoffman's ratio. For PEEK, the Thomas-Staveley constant (β) should be closer to 0.25 or 0.3 instead of 0.1. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1335-1348, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2401-2412 
    ISSN: 0887-6266
    Keywords: nylon 2 4 ; chain folding ; lamellar crystals ; structure and morphology ; crystallization ; electron microscopy ; Brill transformation ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chain-folded lamellar crystals of nylon 2 4 have been prepared from dilute solution by addition of poor solvent. Two crystal structures are observed at room temperature: a monoclinic form I, precipitated at elevated temperature, and a less-defined, orthorhombic form II, precipitated at room temperature. The unit cell parameters for both forms are similar to those reported for its isomer, nylon 3. Nylon 2 4 form II is a liquid-crystal-like or disordered phase, consisting of hydrogen-bonded sheets in poor register in the hydrogen bond direction. Form I crystals have two characteristic interchain spacings of 0.41 nm and 0.39 nm at room temperature and on heating, exhibit a structural transformation and a Brill temperature (250°C) characteristic of many other even-even nylons. Nylon 2 4 is a member of the nylon 2 Y and nylon 2N 2(N+1) families, and the form I crystals show behavior commensurate with both. We propose they contain a proportion of intersheet hydrogen bonds at room temperature, similar to that for the nylon 2 Y family, and the short dimethylene alkane segments mean that the structure consists of hydrogen-bonded a-sheets, with an amide unit in each fold, similar to that of nylon 4 6. The fold geometry and sheet structure is compared with chain-folded apβ-sheet polypeptides and nylon 3. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2401-2412, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2643-2651 
    ISSN: 0887-6266
    Keywords: poly(ethylene oxide) ; poly(methyl methacrylate) ; blends ; atomic-force microscopy ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The binary blend of poly(ethylene oxide)/atactic poly(methyl methacrylate) is examined using hot-stage atomic-force microscopy (AFM) in conjunction with differential scanning calorimetry and optical microscopy. It was found possible to follow in real time the melting process, which reveals itself to be nonuniform. This effect is ascribed to the presence of lamellae having different thicknesses. The crystallization process of poly(ethylene oxide) from the miscible melt is also followed in real time by AFM, affording detailed images of the impingement of adjacent spherulites and direct observation of lamellar growth and subsequent polymer solidification in the interlamellar space.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2643-2651, 1998
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 737-749 
    ISSN: 0887-6266
    Keywords: poly(ether-ester) ; multiblock ; poly(tetramethylene isophthalate) ; crystallization ; melting ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Morphology development during isothermal annealing of poly(ether-ester) multiblock copolymers with hard segments containing poly(tetramethylene isophthalate) is examined by differential scanning calorimetry (DSC) and small-angle x-ray scattering (SAXS). Reorganization in the solid-state occurs by melting and recrystallization. At temperatures close to the melting point, glass transition measurements after quenching from the annealing temperature suggest microphase mixing follows melting. The temperature of maximum recrystallization rate is elevated relative to that of isothermal crystallization. SAXS experiments suggest that a memory of the initial morphology is retained during annealing. Aspects of the DSC scans related to crystallization on cooling and rescanning also suggest that the morphology at the annealing temperature plays a governing role in the determination of the degree of order possible on cooling. The crystalline regions stable at the annealing temperature are envisioned to function in a dual role, acting as nucleation centers for recrystallization and as a form of “constraint” to ordering on cooling. © 1996 John Wiley & Sons, Inc.
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  • 43
    ISSN: 0887-6266
    Keywords: crystallization ; random copolymers ; heterogeneous polymerization ; resin beads ; particle morphology ; noncrystallizable units ; SEM ; specific surface area ; vinylidene chloride ; methyl acrylate ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isothermal crystallization kinetics for random copolymers of vinylidene chloride (VDC) with methyl acrylate (MA) is reported. Syntheses of many semicrystalline polymers follow heterogeneous reaction paths in which the macromolecule chains phase separate from the reaction mixtures. The internal particle morphology (the internal structure of the resin bead) from this type of reaction is granular and porous, as a result of the demixing processes accompanying polymer formation. Demixing in these polymers involves either liquid-liquid (L-L) phase separation followed by liquid-solid (L-S) transformation (crystallization) or L-S transformation alone. Crystallization (L-S transformation) must be an indispensable part of the process if a porous granular structure is to be expected. This is because L-S transformation is the most probable means by which the demixed structure can be stabilized against complete coalescence or agglomeration, which would lead to totally fused bead internal structure. This is particularly true if the glass transition temperature (Tg) is lower than the polymerization temperatures, as is the case with the VDC-MA copolymers. Copolymers that crystallize the fastest will have the finest (most porous) resin bead morphology. The result of this work is consistent with expectation. The homopolymer (PVDC) that crystallizes the fastest has the finest resin bead internal morphology. The copolymers show slower crystallization rates with increasing noncrystallizable MA content. Correspondingly, resin morphology measured by specific surface area decreased with increasing amounts of the noncrystallizable (MA) comonomer unit in the copolymer. This is clearly seen in SEM photographs of the internal bead structures of these copolymers. ©1995 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 615-622 
    ISSN: 0887-6266
    Keywords: adhesion ; crystallization ; peeling ; plastic yielding ; polyethylene ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thin strips of crosslinked linear high-density polyethylene were melted and then crystallized in contact by cooling to room temperature. The work required to peel the strips apart by pulling one strip away from the other at 90° was found to be remarkably high, 5 to 30 kJ/m2, and in some cases the strips could not be separated in this way. However, adhesion measured in T-peeling was much lower, about one-tenth as large. Adhesion was also fairly small, 200 to 600 J/m2, using other test methods designed to minimize bending strains. Thus, most of the work of separation is normally expended in bending, probably in plastic yielding of the outer layers of bent strips. However, even when bending energy losses were minimized, the residual adhesion was much greater than expected for Van der Waals bonding (about 0.05 J/m2). Apparently, cocrystallization of molecular strands lying on either side of the interface greatly enhances the intrinsically low level of autohesion of amorphous polyethylene, probably by local yielding processes around the line of separation. Some effects of test temperature were also examined in T-peeling. Adhesion passed through a pronounced maximum at temperatures of 75-100°C before reducing to very low values in the melted state. This maximum was absent in tests with reduced bending. It is, therefore, attributed to extra work expended in plastic bending over a narrow range of temperature, probably due to a lower yield stress at these temperatures and not to an increase in the actual adhesion. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 615-622, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 953-961 
    ISSN: 0887-6266
    Keywords: ethylene-1-hexene copolymer ; polypropylene ; polymer blend ; miscibility ; crystallization ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Morphology and isothermal growth rates of spherulites for the binary blends consisting of an isotactic polypropylene (i-PP) and an ethylene-1-hexene rubber (EHR) were examined as a function of the crystallization temperature ranging from 388 K to 418 K. In this study, two types of EHR's were employed: “ethylene rich” EHR and “1-hexene rich” EHR. The blends of i-PP with the EHR of 51 mol % 1-hexene are miscible in the molten state, whereas the blends with the EHR of 33 mol % 1-hexene are immiscible in the molten state. It is found that the isothermal spherulite growth rate of the miscible i-PP/EHR blends decreases with increasing the EHR fraction, whereas the spherulite growth rate of the immiscible i-PP/EHR blends is independent of the blend composition and is the same as that of the i-PP. Optical microscope observation of the miscible blends crystallized isothermally shows that there are no rubber domains either in the intraspherulitic or in the interspherulitic contact regions. On the other hand, the immiscible i-PP/EHR blends show a phase-separated morphology. Furthermore, the number of tangential lamellae of the miscible i-PP/EHR blends is found to be increased by blending of the EHR, leading to the spherulite with negative birefringence. The sign of birefringence of spherulites is unaffected by the regime transition as well as by the fold surface free energy. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 953-961, 1997
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    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 2393-2407 
    ISSN: 0887-6266
    Keywords: crystallization ; orientation ; flow ; kinetics ; stress ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A model for flow-induced crystallization is developed which is based on ideas from the theory of strain-induced crystallization, coupled with an irreversible thermodynamic formalism based on the continuum Hamiltonian Poisson Brackets. The latter allows accounting for the changing energetics during simultaneous flow deformation and extended-chain crystallization. Input parameters to the model include the molecular relaxation time, a crystallization parameter, and the molecular weight. Calculations of the crystallization rate, chain elongation, stress, and birefringence are presented for a variety of flow kinematics and flow histories, including transient processes following cessation of flow. Induction times based on a reasonable choice for the induction crystallinity follow experimentally observed trends reported in the literature. © 1996 John Wiley & Sons, Inc.
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 253-263 
    ISSN: 0887-6266
    Keywords: thermotropics ; dynamic viscoelasticity ; relaxation peaks ; gelation ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rheological characterization of two commercial thermotropic liquid crystalline polymers based on poly(ethylene terephthalate) (PET) and para-hydroxybenzoic acid (PHB) is carried out. The thermal transitions determined by DMTA are explained by the random character of these copolyesters, in comparison with non-random copolyesters synthesized by Jackson and Kuhfuss. The evolution of the dynamic viscoelastic functions with time in the nematic state is concave in shape for the 20%PET/80%PHB copolymer, a result that leads us to treat this system as a suspension of solid spheres (unmolten crystals) where the volume fraction of crystals increases with time according to an Avrami equation. The response of 40%PET/60%PHB copolymer is similar to a chemical or physical gelation and the hypothesis that the polydomain structure gives rise to a network is considered. Continuous flow, time-independent viscosity results reveal the existence of a three-region flow curve for 40%PET/60%PHB copolymer, but a Newtonian zone followed by a shear thinning region for 20%PET/80%PHB sample. At high temperatures the isotropization of the samples leads to a very strong decrease of the activation energy of flow, which becomes zero for 40%PET/60%PHB. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 253-263, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 403-414 
    ISSN: 0887-6266
    Keywords: P(VDF/TrFE) copolymer ; phase transition ; ferroelectric ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A systematic study was carried out on the effect of the crystallization temperature (Tcr), on the phase transitions presented by P(VDF/TrFE) copolymers cast from dimethylformamide (DMF) solution with molar ratios 60/40, 70/30, and 80/20. The results obtained by differential scanning calorimetry (DSC) showed that two-phase transitions are observed only when the copolymer crystallizes above a certain temperature To, and that the temperatures at which these transitions occur are reduced slightly with Tcr increase. It also was observed that when Tcr increases, the intensity of the endotherm corresponding to the lowest temperature transition is increased, whereas the one corresponding to the highest temperature transition is reduced. In order to explain these phenomena, the existence of two ferroelectric and two paraelectric phases is suggested. The conformational differences between like phases occur due to the distinct origin of each one: the best organized phase crystallizes directly from solution, whereas the least organized is the result of a solid phase transition. Wide angle x-ray diffusion (WAXD) diffractograms corroborate this hypothesis. Phase diagrams for samples crystallized below and above To have been proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 403-414, 1998
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1877-1886 
    ISSN: 0887-6266
    Keywords: temperature-modulated calorimetry ; TMC ; temperature-modulated differential scanning calorimetry ; TMDSC ; melting ; crystallization ; molecular nucleation ; poly(oxyethylene) ; Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Temperature-modulated calorimetry, TMC, is used to evaluate the temperature region of metastability between crystallization and melting. While crystals like indium can be made to melt practically reversibly during a TMC cycle of low amplitude so that sufficient crystal nuclei remain unmelted, linear macromolecules cannot, because of their need to undergo molecular nucleation. Modulation amplitudes varying from ±0.2 to ±3.0 K are used to assess the temperature gap between the slow crystallization region and the melting of metastable crystals of poly(oxyethylene) (PEO) of molar mass 1500 Da. This low molar mass PEO serves as a model compound with a metastable gap of melting/crystallization that can be bridged by TMC with a large modulation amplitude. © 1997 John Wiley & Sons, Inc.This article is a US Government work and, as such, is in the public domain in the United States of America. J Polym Sci B: Polym Phys 35: 1877-1886, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1757-1774 
    ISSN: 0887-6266
    Keywords: polyesters ; crystallization ; melting ; morphology ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting behavior of isothermally crystallized PET has been studied using linear heating in a differential scanning calorimeter (DSC). Variables such as crystallization temperature, crystallization time, heating rate, and average molecular weight are the main focus of the study. On the basis of several experimental techniques, a correlation of the melting behavior of PET with the amount of secondary crystallization was found to exist. It was observed that the triple melting of PET is a function of programmable DSC variables such as crystallization temperature, crystallization time, and heating rate. However, in testing the hypothesis that there was a correlation between melting endotherms and secondary crystallization inside spherulites, it was found necessary to use a DSC-independent variable in order to enhance the observed effects. Therefore, on the basis of a crystallization model that involves secondary branching along the edges of parent lamellar structures, it was speculated that an increase in the average molecular weight could affect the triple melting of PET due to an increase of rejected portions of the macromolecules. It was found that the second melting endotherm increased, apparently, at the expense of the third one as the average molecular weight was increased. The second melting endotherm was also found to correlate proportionally with the amount of secondary crystallization inside spherulites. The results support a model of crystallization which basically consists of parent crystals and at least one population of secondary, probably metastable, crystals. This latter structural component must involve excluded portions of the macromolecules that did not crystallize during the isothermal crystallization period of the parent crystals. An increase of molecular weight gives rise to a higher entanglement density which in turn increases the fraction of initially rejected chain sections and therefore the amount of secondary crystallization. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1757-1774, 1997
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    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 2757-2764 
    ISSN: 0887-6266
    Keywords: Monte Carlo simulations ; polypropylene ; isotacticity ; sequence distributions ; crystallization ; degrees of crystallinity ; melting points ; mechanical properties ; moduli ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanical properties of polypropylene depend critically on the crystallizability of the chains, which depends in turn on their stereochemical structures. These dependences were investigated using Monte Carlo methods to generate chains having various stereochemical sequences and then scrutinizing parallel arrays of these chains to look for matches in isotactic stereochemistry that could lead to the formation of crystallites. The fraction of such units in matches, for example, gives a direct measure of the degree of crystallinity expected for the specified degree of isotacticity. Other quantities of interest obtainable in this way were the natures of the sequence distributions themselves, melting points, free energies of fusion, interfacial free energies, and moduli (calculated on the basis of the crystallites acting as crosslinks within an elastomeric network structure). © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2757-2764, 1997
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2197-2210 
    ISSN: 0887-6266
    Keywords: polycarbonate ; PMMA ; polyglutarimide ; crystallization ; segregation ; AFM ; SAXS ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The microstructure of amorphous polymer blends has been extensively studied in the past, but now there is a growing interest for polymer blends where one or more of the components can crystallize. In this study we investigate such blends, namely miscible polycarbonate (PC)/acrylic blends. Using small angle X-ray scattering (SAXS) measurements, combined with atomic force microscopy (AFM), electron microscopy (SEM), and optical microscopy, we demonstrate that the amorphous acrylic component mostly segregates inside the spherulites between the lamellar bundles (interfibrillar segregation). Varying the PC molecular weight or the mobility of the amorphous component (by changing its molecular weight and Tg) does not change the mode of segregation. So far qualitative predictions of the mode of segregation in semicrystalline polymer blends have been proposed using the δ parameter (the ratio between the diffusion coefficient D of the amorphous component in the blend and the linear crystallization rate G), introduced by Keith and Padden. Our results suggest that other parameters have to be considered to fully understand the segregation process. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2197-2210, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2311-2325 
    ISSN: 0887-6266
    Keywords: poly(ethylene oxide) ; crystallization ; AFM ; spherulites ; crystal growth ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The atomic force microscope (AFM) has been used to investigate morphological development during the crystallization of poly(ethylene oxide) (PEO) from the melt. PEOs with molecular weights of 1 × 105 and 7 × 106 were used. Height and amplitude images were recorded, using the tapping mode. For both polymers, the mode of spherulite development varied with the velocity of the growth front. For slow growth velocities, the growth of the crystallites was linear, with growth initially occurring by single lamellae, later developing into growth arms by screw dislocation spawning of crystallites. At intermediate growth velocities, stacks of lamellae develop rapidly. The splaying apart of adjacent crystals and growth arms is abundant. The operation of growth spirals was observed directly in this growth velocity range. The crystals formed by the giant screw dislocations diverge immediately from the original growth direction, providing a source of interlamellar splaying. At low and intermediate velocities, the front propagates by the advance of primary growth arms, with the regions between the arms filled in by arms growing behind the primary front. At the highest velocity observed here, the formation of lamellar bundles and immediate splaying results in recognizable spherulites developing at the earliest stages of crystallization. The change from linear growth to splaying and nonlinear growth are qualitatively explained in terms of driving force, elastic resistance and the presence of compositional and/or elastic fields in the melt. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2311-2325, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2393-2399 
    ISSN: 0887-6266
    Keywords: PEEK ; nonisothermal ; growth rate ; crystallization ; kinetics ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: During cooling at a rate of 10°C/min from the melt state of PEEK we have followed the growth of spherulites using an optical microscope equipped with a camera. The isothermal growth rates of crystallization in the temperature range of 266-308°C could be estimated by means of a differential equation. These continuous growth rate data were used further for kinetic analysis, which indicated that PEEK exhibited an unmistakable regime II → III transition at 296°C. The results compared favorably with those obtained by the traditional isothermal method, which is time consuming. Due to chain folding, the Thomas-Staveley constant should be closer to 0.25 instead of 0.1 or 0.3. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2393-2399, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2923-2930 
    ISSN: 0887-6266
    Keywords: polymer blends ; crystallization ; diffusion ; composition inhomogeneities ; internal spherulite structure ; Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Composition profiles develop around growing PVDF spherulites in a blend with PMMA. These profiles assume stationary courses after a certain crystallization time provided that the overall degree of crystallinity is not too high. The composition-dependent growth rate and the diffusion-controlled remove of the surplus PMMA from the spherulite surface are then in a stationary equilibrium. The internal structure of the spherulites will then be homogeneous, too. Upon isothermal crystallization of a PVDF/PMMA = 60/40 (wt %) blend at 160°C for at least 4 h, the spherulites internal degree of crystallinity xc as related to the PVDF fraction obeys the inequality 55 wt % ≤ xc ≤ 84 wt %. The overall PMMA content within the spherulites as averaged over its whole inside has been determined by IR microscopy. It amounts to about 15 wt %. In contrast, the PMMA content of the amorphous phase within the spherulites (averaged again over its whole inside) ranges between 28 and 52 wt %. This composition jumps at the spherulite surface to 52 wt %. From the slope of the composition profiles outside the spherulites that have a width of more than 50 μm, the effective chain diffusion coefficient in blends as averaged over both components can be calculated to amount to (250 ± 100) μm2h-1. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2923-2930, 1998
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    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2573-2585 
    ISSN: 0887-6266
    Keywords: polyethylene ; poly(butylene terephthalate) ; blend ; rheology ; Palierne's model ; morphology ; differential scanning calorimetry ; crystallization ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization at high supercooling of polybutylene terephthalate (PBT) droplets dispersed in a molten polyethylene (PE) matrix was investigated through rheological and DSC experiments. The Palierne's emulsion model was used as a theoretical framework for studying the viscoelastic behavior of the blends in different ranges of temperature: on the one hand, when the two polymers are molten (T 〉 225°C) and on the other hand, when PBT droplets are at high supercooling in the molten PE matrix (130°C 〈 T 〈 205°C). From rheological experimental evidences it was shown that molten and solidified droplets coexist at high supercooling. The Palierne's model was then successfully adapted to take into account the three phases (molten PE, molten PBT droplets, and solidified PBT droplets). The evolution of the behavior with the temperature is consistent with the growing amount of crystallized droplets. Moreover, a calculation taking into account the droplets size distribution and the number of nuclei is introduced to explain the crystallization behavior of three different blend ratios.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2573-2585, 1998
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    Polymer International 37 (1995), S. 249-254 
    ISSN: 0959-8103
    Keywords: poly(ethylene succinate) ; crystallization ; morphology ; electron microscopy ; thermal analysis ; Chemistry ; Polymer and Materials Science
    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 morphology of melt-crystallized poly(ethylene succinate) (PES) was investigated by optical microscopy and scanning electron microscopy, and the melting behaviour of PES was studied by differential scanning calorimetry (DSC). At low crystallization temperature imperfect crystals were formed which could melt and recrystallize during the DSC scan. Triple melting peaks were observed, and the melting behaviour was strongly dependent on crystallization time and scan rate. It was observed that crystallization at high temperature perfected the crystals (dominant and subsidiary lamellae in the spherulitic structure). Increasing the scan rate reduced the chance for reorganization. However, at high crystallization temperature two melting peaks were observed. The material formed was much more perfect, so that the melting process was not dominated by recrystallization. Accordingly, the cause of dual melting is the existence of two kinds of crystal perfection.
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    Polymer International 38 (1995), S. 367-373 
    ISSN: 0959-8103
    Keywords: poly(ethylene terephthalate) ; annealing ; thermal behaviour ; morphology ; crystallization ; Chemistry ; Polymer and Materials Science
    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 influence of annealing conditions on the morphology and melting behaviour of poly(ethylene terephthalate) (PET) was studied. PET annealed under isothermal conditions often shows double melting endotherms depending on the annealing temperature (Ta) and the heating rate of the calorimeter. It was found that the morphological structure and the lower melting peak depend strongly on the annealing temperature, Ta. The increase of the lower melting peak temperature with Ta is due to an increase of the lamellar thickness within the spherulitic structure and to a higher crystallite perfection.
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    Polymer International 38 (1995), S. 381-385 
    ISSN: 0959-8103
    Keywords: poly(vinylidene fluoride) ; crystallization ; thermal behaviour ; morphology ; Chemistry ; Polymer and Materials Science
    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 influence of crystallization temperature on the melting behaviour and the morphology of poly(vinylidene fluoride) (PVF2) has been investigated. The DSC endotherms of PVF2 crystallized from the melt show at least two peaks. The peak areas depend on the thermal history of the samples and the heating scan rate. The area of the first peak was found to increase as the crystallization temperature or the scan rate increased. The double peak configuration was attributed to a melting-recrystallization process. Electron microscopy supports these results, for which only one type of lamella was found in the spherulitic structure.
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  • 60
    ISSN: 0959-8103
    Keywords: copolymers ; ethylene ; α-olefins ; transition metal catalysts ; thermal stability ; crystallization ; Chemistry ; Polymer and Materials Science
    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: Copolymers of ethylene with propylene, butene-1 and hexene-1 were prepared using a titanium-magnesium (TMC) or a vanadium-magnesium catalyst (VMC). The copolymers were examined for thermal stability by TGA, melting and crystallization behaviour by DSC and crystallinity by XRD. Fractionated samples of ethylene-hexene-1 copolymers were also similarly characterized. Results indicate that VMC produces copolymers with a higher degree of crystallinity and greater compositional homogeneity than TMC.
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  • 61
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    Bioelectromagnetics 15 (1994), S. 483-487 
    ISSN: 0197-8462
    Keywords: ELF magnetic field ; dosimetry ; electric field probe ; tissue conductivity ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Measuring internal induced electric fields in animals with a miniaturized probe involves a potential error related to the difference between the hole conductivity (σh) and the surrounding tissue conductivity (σt). Theory was developed to describe this phenomenon and checked by probe measurements in agar-filled petri dishes. The value measured in the hole is 2σt/(σh + σt) times the actual field in the tissue. For example, a probe hole in muscle, which is filled with blood, could yield a measurement only about 22% of the true value in the muscle. This potential source of error can be mitigated to some extent by not actually cutting a hole, by using a low-conductivity (e.g., 0.2 S/m) coupling medium in the hole, or by ensuring contact between the probe's electrodes and the tissue. © 1994 Wiley-Liss, Inc.
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    Bioelectromagnetics 15 (1994), S. 513-518 
    ISSN: 0197-8462
    Keywords: subchronic exposure ; rotating magnetic fields ; neuroendocrine hormone ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: We exposed rats to circularly polarized 50 Hz magnetic fields to determine if plasma testosterone concentration was affected. Previous experiments indicate that magnetic fields suppress the nighttime rise in melatonin, suggesting that other neuroendocrine changes might occur as well. Male Wistar-King rats were exposed almost continuously for 6 weeks to magnetic flux densities of 1,5, or 50 μT. Blood samples were obtained by decapitation at 12:00 h and 24:00 h. Plasma testosterone concentration showed a significant day-night difference, with a higher level at 12:00 h when studied in July and December, but the day-night difference disappeared when concentrations were studied in April. In three experiments, magnetic field exposure had no statistically significant effect on plasma testosterone levels compared with the sham-exposed groups. These findings indicate that 6 weeks of nearly continuous exposure to circularly polarized, 50 Hz magnetic fields did not change plasma testosterone concentration in rats. © 1994 Wiley-Liss, Inc.
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  • 63
    ISSN: 0197-8462
    Keywords: magnetic fields ; micelles ; photolysis ; triplet radical pair ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The influence of 60-Hz magnetic fields on free radical reactions can be quantitatively predicted from the knowledge of the effect of static fields on free radical behavior. Studies of radical reactions in micellar systems show that the behavior under a 60-Hz field is identical to that under a static field at any given point in time. © 1994 Wiley-Liss, Inc.
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  • 64
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    Bioelectromagnetics 15 (1994), S. 519-529 
    ISSN: 0197-8462
    Keywords: electromagnetic fields ; occupational hazards ; fetal development ; carcinogenesis ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Given the current interest in potential carcinogenic and developmental effects of exposure to extremely-low-frequency electromagnetic fields, there is a need to identify cohorts of exposed female workers for future epidemiologic investigations. This study was designed to test the hypothesis that nurses working in neonatal intensive care units (NICU) may be significantly exposed to power-frequency magnetic fields. An electromagnetic field monitor was used to measure magnetic fields at distances of 5, 15, 30, and 60 cm from the surfaces of each device used in the NICU. Six female nurses assigned to the NICU (the “exposed” group) and six female nurses working in the normal newborn nursery (the “referent” group) wore EMDEX dosimeters for the entire duration of their 12 h shifts. An investigator kept a detailed log of each NICU subject's whereabouts for the first one-third of her shift. Magnetic fields at 5 cm from the front (defined by the nurses' usual work area) of the NICU devices ranged from less than 0.1 to 114 μT and in all cases decreased considerably with increasing distance. The geometric mean of the shift-time-weighted average exposure of the NICU nurses was 0.17 μT compared with 0.11 μT for the normal newborn nurses. The percentage of time when subjects were exposed to magnetic fields of 0.4 μT or greater ranged from 5.8% to 15.6% for the NICU nurses, 0.4% to 2.9% for five of the comparison group nurses, and was 9.4% for one of the normal newborn nurses with unidentified aberrantly high exposures. Log data revealed that the vast majority of observed peaks among NICU nurses occurred while subjects were in close proximity to infant bed units. We conclude that NICU nurses represent one female-intensive job sector with intermittent high exposures to ELF magnetic fields and encourage larger exposure studies of nurses in a variety of medical settings. © 1994 Wiley-Liss, Inc.
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  • 65
    ISSN: 0197-8462
    Keywords: cancer promotion ; initiation ; tumor incidence ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The purpose of this study was to investigate the effects of 2.45 GHz microwave (MW) radiation on dimethylhydrazine (DMH)-induced colon cancer in mice. The subjects were 115 Balb/c mice 4 weeks of age. The animals were divided into group A (control), group B (DMH), group C (DMH + MW), and group D [DMH + 12-O-tetradecanoylphorbol-13-acetate (TPA)]. Radiation (10 mW/cm2) was delivered dorsally with the E field parallel to the mouse's long body axis in an anechoic chamber. Radiations were administered 3 hr daily, 6 days per week, over a period of 5 months. The average SAR was estimated to be 10-12 W/kg. During the course of radiation treatments, DMH was injected once per week. The tumor promoter TPA was administered once per week for 10 weeks, from the third week on, after the initial treatment. The incidence of tumors did not significantly differ between the three test groups (groups B, C, and D; P 〉 0.25). However, the number of tumors, the size of the tumors, and the incidence of protuberant and infiltrative types in tumor-bearing animals were higher in group D compared to groups B and C (P 〈 0.05). No difference was found between groups B and C (P 〉 0.25). The study indicates that 2.45 GHz microwave radiation at 10 mW/cm2 power density did not promote DMH-induced colon cancers in young mice. The study also showed that TPA could accelerate colon tumor production if a tumor was initiated. © 1994 Wiley-Liss, Inc.
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    Bioelectromagnetics 17 (1996), S. 33-36 
    ISSN: 0197-8462
    Keywords: static magnetic field ; poly-L-lysine ; Raman spectroscopy ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: We have explored the mechanism of coupling of an approximately 50 mT static magnetic field with the α helices of poly-L-lysine. Structural changes in poly-L-lysine were determined by Raman spectroscopy. Our testable hypothesis is that static magnetic fields of this magnitude can couple with the α-helical segments of the polypeptide, and, as a result, the structure of the polypeptide is significantly altered. Our model further suggests that a static magnetic field can promote protein unfolding and can prevent refolding. © 1996 Wiley-Liss, Inc.
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  • 67
    ISSN: 0197-8462
    Keywords: AC/DC magnetic fields ; IPR ; proton ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: PC-12 cells primed with nerve growth factor (NGF) were exposed to sinusoidal extremely-low-frequency (ELF) magnetic fields (MFs) selected to test the predictions of the ion parametric resonance (IPR) model under resonance conditions for a single ion (hydrogen). We examined the field effects on the neurite outgrowth (NO) induced by NGF using three different combinations of flux densities of the parallel components of the AC MF (Bac) and the static MF (Bdc). The first test examined the NO response in cells exposed to 45 Hz at a Bdc of 2.96 μT with resonant conditions for H+ according to the model. The Bac values ranged from 0.29 to 4.11 μT root-mean-square (rms). In the second test, the MF effects at off-resonance conditions (i.e., no biologically significant ion at resonance) were examined using the frequency of 45 Hz with a Bdc of 1.97 μT and covering a Bac range between 0.79 and 2.05 μT rms. In the third test, the AC frequency was changed to 30 Hz with the subsequent change in Bdc to 1.97 μT to tune for H+ as in the first test. The Bac values ranged from 0.79 to 2.05 μT rms. After a 23 h incubation and exposure to the MF in the presence of NGF (5 ng/ml), the NO was analyzed using a stereoscopic microscope. The results showed that the NGF stimulation of neurite outgrowth (NSNO) was affected by MF combinations over most of the Bac exposure range generally consistent with the predictions of the IPR model. However, for a distinct range of Bac where the IPR model predicted maximal ionic influence, the observed pattern of NSNO contrasted sharply with those predictions. The symmetry of this response suggests that values of Bac within this distinct range may trigger alternate or additional cellular mechanisms that lead to an apparent lack of response to the MF stimulus. © 1996 Wiley-Liss, Inc.
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  • 68
    ISSN: 0197-8462
    Keywords: cohort ; electrolysis ; pot room ; sick leave ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: This is a study of the relationship between occupational exposure to magnetic fields in pot rooms and occurrence of sick leave caused by musculoskeletal disorders. The average exposure to static magnetic fields was 8 mT in the pot rooms. Ripple fields were recorded as well. A cohort of 342 exposed workers and 222 unexposed workers from the same electrolysis plant was retrospectively followed for 5 years. The reference group had a type of work similar to the exposed group except for the exposure to magnetic fields. The occurrence of sick leave and the diagnoses causing the sick leave were obtained from the Occupational Health Care Unit: these data were stored in their computer files. The data were complete. No relationship between the occurrence of sick leave caused by musculoskeletal disorders and exposure to magnetic fields was found. This was the case for both the annual number of periods of sick leave and the total number of days with sick leave. The results must be interpreted with caution due to limitations in the design and available data. Also, static magnetic fields constituted the major exposure, and the results may be different when related to work in other types of magnetic-field exposure. © 1996 Wiley-Liss, Inc.
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    Bioelectromagnetics 17 (1996), S. 21-32 
    ISSN: 0197-8462
    Keywords: blood flow ; static magnetic field ; magnetohydrodynamic interactions ; finite element analysis ; sinuatrial node ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The flow of blood in the presence of a magnetic field gives rise to induced voltages in the major arteries of the central circulatory system. Under certain simplifying conditions, such as the assumption that the length of major arteries (e.g., the aorta) is infinite and that the vessel walls are not electrically conductive, the distribution of induced voltages and currents within these blood vessels can be calculated with reasonable precision. However, the propagation of magnetically induced voltages and currents from the aorta into neighboring tissue structures such as the sinuatrial node of the heart has not been previously determined by any experimental or theoretical technique. In the analysis presented in this paper, a solution of the complete Navier-Stokes equation was obtained by the finite element technique for blood flow through the ascending and descending aortic vessels in the presence of a uniform static magnetic field. Spatial distributions of the magnetically induced voltage and current were obtained for the aortic vessel and surrounding tissues under the assumption that the wall of the aorta is electrically conductive. Results are presented for the calculated values of magnetically induced voltages and current densities in the aorta and surrounding tissue structures, including the sinuatrial node, and for their field-strength dependence. In addition, an analysis is presented of magnetohydrodynamic interactions that lead to a small reduction of blood volume flow at high field levels above approximately 10 tesla (T). Quantitative results are presented on the offsetting effects of oppositely directed blood flows in the ascending and descending aortic segments, and a quantitative estimate is made of the effects of assuming an infinite vs. a finite length of the aortic vessel in calculating the magnetically induced voltage and current density distribution in tissue. © 1996 Wiley-Liss, Inc.
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    Bioelectromagnetics 17 (1996), S. 44-47 
    ISSN: 0197-8462
    Keywords: regeneration ; rat sciatic nerve ; microsurgical suture ; millimeter wave radiation ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The effect of low-intensity millimeter wave electromagnetic radiation (MWR) on regeneration of the rat sciatic nerve after transection and microsurgical reapproximation was examined. Rats were exposed to 54 GHz MWR at a power density of 4 mW/cm2. It was found that MWR treatment of the femoral skin in the area of suture accelerated the regeneration of nerve fibers. At the twentieth postoperative day, the MWR-treated animals had a 32% increase in the regeneration distance compared to the control animals. The conduction velocity showed a 26% increase in the MWR-treated animals. © 1996 Wiley-Liss, Inc.
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    Bioelectromagnetics 17 (1996) 
    ISSN: 0197-8462
    Keywords: Life and Medical Sciences ; Occupational Health and Environmental Toxicology
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    Bioelectromagnetics 17 (1996), S. 48-57 
    ISSN: 0197-8462
    Keywords: ELF fields ; modeling ; induced current ; induced electric field ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Calculations of the current density and electric field distributions induced in cell cultures by an applied low-frequency magnetic field have assumed that the medium is uniform. This paper calculates these distributions for a more realistic, inhomogeneous, anisotropic model in which the cells are regarded as conducting squares surrounded by insulating membranes. Separate parameters are used to specify the resistivities of the cell interior, the cell membrane parallel to its surface, the cell membrane perpendicular to its surface, and the intercellular junction parallel to the membrane. The presence of gap junctions connecting the interiors of adjacent cells is also considered. For vertical applied magnetic fields, the induced currents and field distributions may deviate considerably from the homogeneous medium model if there is sufficiently tight binding of the cells to each other. The presence of gap junctions can produce relatively large transmembrane electric fields or intracellular current densities. These considerations are generally less important for horizontal applied fields. A simple microscopic model of the cell surface is also discussed. © 1996 Wiley-Liss, Inc.
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    Bioelectromagnetics 17 (1996), S. 1-2 
    ISSN: 0197-8462
    Keywords: Life and Medical Sciences ; Occupational Health and Environmental Toxicology
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    Bioelectromagnetics 17 (1996), S. 58-70 
    ISSN: 0197-8462
    Keywords: ion parametric resonance ; AC/DC magnetic fields ; excitation and deexcitation mechanisms ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: This paper presents a further development of the mechanism for the detection of weak magnetic fields proposed by [Lednev (1991): Bioelectromagnetics 12:71-75]. The fraction of excited oscillator states of an unhydrated ion is studied in a dynamic model driven by the predicted (time-varying) transition probability in the presence of thermal noise and an unspecified excitation mechanism. The main results of Lednev are confirmed. In addition, I conclude that ultraharmonic and ultrasubharmonic resonances may also be observed, provided that the response time of the dynamic system is similar to the period of the oscillating magnetic field. I discuss the time scales involved in the mechanism and present theoretical constraints on these parameters. The crucial requirement for the theory's applicability is that the lifetime of the excited states of the affected ion oscillator exceeds the period of the applied magnetic field. Numerical solutions of the dynamic system are given and are shown to correspond well to theoretical expectations. The main discrepancy between the theories of Lednev and of Blanchard and Blackman [Blanchard and Blackman (1994): Bioelectromagnetics 15:217-238] appears to be due to an inconsistency in the latter paper. The general problem of robust analysis of experimental data is discussed, and I suggest a test of compliance with the Lednev model that is independent of all parameters except for the ratio of oscillating and static field strength (B1/B0) for many resonance conditions and experimental models. © 1996 Wiley-Liss, Inc.
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    Bioelectromagnetics 17 (1996), S. 85-88 
    ISSN: 0197-8462
    Keywords: brain tumor ; coagulation ; bleeding ; hemostasis ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Implantable microwave coagulation was used to perform resection on 62 patients that had intracranial meningiomas. When 20-60 W microwave power was applied for 15 s, the temperature at the center of the tumor tissue was 43-63°C; 30 mm from the center, the temperature was under 40°C. Histological changes in the center of the tumor showed coagulative necrosis, diminished nuclei, and obliterated blood vessels. The changes at 10-20 mm from the center of the tumor showed coagulative necrosis and degeneration and, 30-50 mm from the center of the tumor, showed normal cell morphology after microwave coagulation. The thermal field in brain tumor has an effective diameter of about 40 mm. No side effects on the normal brain tissues were observed. The amount of blood loss during the operation was minimal while the meningioma was coagulated, especially when the meningioma was located at the skull base or in the parasagittal or cerebral convexity region. After microwave coagulation, the entire tumor could easily be removed. Among the 62 surgically treated cases, gross total tumor excision was 85%. No postoperative complications occurred after microwave coagulation, and there was no operative mortality in the series. We believe that this new technique has the advantage of simplicity, less blood loss, and smooth postoperative procedures. Hemostatic effects during the operation are satisfactory, and blood transfusion can be reduced by 50-60%. © 1996 Wiley-Liss, Inc.
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    Bioelectromagnetics 17 (1996), S. 71-84 
    ISSN: 0197-8462
    Keywords: decision analysis ; grounding systems ; residential EMFs ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Several epidemiological studies have linked exposure to electromagnetic fields (EMFs) with health effects, including leukemia and brain cancer, but the research is still inconclusive. In particular, no clear causal mechanism has been identified by which EMFs may promote cancers. Nevertheless, the concerns raised by the positive epidemiological studies have led to increasing efforts to reduce EMFs from a number of sources. One source of EMFs are home grounding systems that are connected through water pipes in homes to water mains. This paper analyzes whether home owners who are concerned about electromagnetic fields exposure from home grounding systems should take any action to reduce fields. Assuming that the grounding system produces elevated magnetic fields (e.g., 2-3 mG or higher), this study investigates several readily available alternatives and evaluates them with respect to five criteria: risk reduction, cost, fire risk increase, worker risk, and electrical shock risk. Because of the lack of conclusive evidence about an EMF-cancer relationship, this study uses a parameterized approach that makes conditional estimates of health risk depending on future research outcomes and on the nature of the EMF/health effects relationship. This type of analysis, which is called predecision analysis because of its preliminary nature, is therefore highly dependent on a set of assumptions. Nevertheless, this predecision analysis had some fairly clear results. First, waiting for more research or taking a fairly inexpensive corrective action (insulating the water pipe to reduce ground current flow) seem to be the main contenders for the best decision for many different assumptions and parameters. Second, the choice between these two actions is very sensitive to variations in assumptions and parameters. Homeowners who accept the base-case assumptions and parameters of this study should prefer to wait. If any of the base-case parameters are changed to more pessimistic estimates or if psychological concerns (like worry and regret) are considered, then the best action is to insulate the pipe to reduce the current flow through the water pipes. © 1996 Wiley-Liss, Inc.
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    Bioelectromagnetics 17 (1996), S. 100-110 
    ISSN: 0197-8462
    Keywords: extremely low frequency ; electric fields ; rhythm ; synchronization ; period changes ; Musca domestica ; Calliphora ; Diptera ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Musca domestica flies that were exposed to a uniform vertical 10 Hz electric square-wave field of 1 kVm-1 changed the period length of their circadian locomotor activity rhythm. Under constant conditions, the clock of short-period flies was slowed down by the field, whereas the clock of long-period flies either was affected only scarcely (experiments at about 19°C) or ran faster (experiments at 25°C). If the field was applied for only 12 h daily, then 30-40% of the flies were synchronized. Thus, the field could function as a weak “Zeitgeber” (synchronizer). If the field was increased to 10 kVm-1, then 50-70% of the flies were synchronized. Flies avoided becoming active around the onset of the 12 h period of exposure to a 10 Hz field. The results of these experiments are discussed with respect to similar experiments by Wever on the effects of exposure to a 10 Hz field on the circadian system of man. © 1996 Wiley-Liss, Inc.
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    Bioelectromagnetics 17 (1996), S. 89-99 
    ISSN: 0197-8462
    Keywords: EMF ; linear oscillator ; ion binding ; thermal noise ; spectral density ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The present study characterizes an ion-binding site, a molecular cleft in a signalling molecule such as calmodulin or troponin C, as a damped linear isotropic oscillator potential for small displacements about the origin. Quantitative assessments of the effects of thermal noise and exogenous static magnetic fields are made through a statistical mechanical treatment of the Lorentz-Langevin equation for an ion bound in a molecular cleft. Thermal noise causes a bound ion to be ejected from the site after a bound lifetime dependent upon the thermal noise spectral density. It is shown that the Lorentz-Langevin model requires values of the viscous damping parameter many orders of magnitude below those for bulk water in order to characterize the binding site and to obtain realistic lifetimes for a bound ion. The model predicts that milliTesla-range magnetic fields are required for static field effects on dissociation kinetics. The Lorentz equation also yields a classic coherent solution describing precession of the boundion oscillator orientation at the Larmor frequency. The bound-ion dynamics described by this coherent solution are sensitive to micro Tesla-range static magnetic fields in the presence of thermal noise. Numerical integration of the contribution of thermal noise forces to these dynamics is in good agreement with the results of statistical mechanical analysis, also producing realistic bound lifetimes for only very low viscous damping values. The mechanisms by which modulation of precessional motion might enable a signalling molecule such as calmodulin to detect an exogenous magnetic field are presently unclear. © 1996 Wiley-Liss, Inc.
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  • 79
    ISSN: 0197-8462
    Keywords: high-frequency inductive power distribution ; mice ; acute ; subchronic ; toxicity ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: A high-frequency inductive power distribution (HID) technology has been developed that generates sinusoidal magnetic fields at a frequency of 10 kHz. In typical industrial applications, field intensities in the order of 0.2 mT can be expected between the current-carrying coils. Because the possible health effects of 10 kHz sinusoidal magnetic fields of this type had never been investigated, a broad evaluation of possible effects on animal health was made in a preliminary 14 day acute study and in a 90 day subchronic study using male and female B6C3F1 mice. Exposures were at 0.08, 0.28, and 1.0 mT vs. a background exposure of 3.7 μT and were essentially continuous.These studies failed to demonstrate any health effects that can be clearly related to the magnetic field exposure. No changes in animal behaviour or indications of morbidity were detected during the initial exposure to the fields. There were no significant differences in body weight between exposed and unexposed (control) mice at any time in the study, and the clinical chemistry and hematology parameters were essentially unchanged. Although minor differences in some clinical chemistry and hematology parameters were seen between control and exposure groups, the lack of exposure dependence, the lack of consistency between sexes, and the lack of correspondence with the results of the two studies all suggest that these were chance associations. Even if the changes were real, the magnitude of the changes was very small and does not indicate serious biological effects. Finally, all organs were macroscopically and microscopically normal except for isolated, generally mild, histological lesions and lesions that were ascribed to fighting among males. There was no obvious association with field intensity. © 1996 Wiley-Liss, Inc.
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    Bioelectromagnetics 17 (1996), S. 131-137 
    ISSN: 0197-8462
    Keywords: statistical power ; duration discrimination ; blood pressure ; heart rate ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: One hundred subjects, males and females with ages ranging between 18 and 48 years, were studied under both field-exposed and sham-exposed conditions. A 50 Hz, 100 μT magnetic field (MF) was used. To examine the effect of field exposure on performance, a two-alternative, forced-choice, duration-discrimination task with three levels of difficulty was used. The subject's task was to decide which of two sequentially presented light flashes had the longer duration. The standard duration was 50 ms, and the alternative durations were 65, 100, or 125 ms. Both reaction time and percentage of correct responses were recorded for each subject. MF and sham exposure were for 9 min each. Blood pressure and heart rate were also measured before and following MF exposure and sham-exposure trials. The study was performed double blind, with the exposure order counterbalanced. Compared to sham exposure, MF exposure significantly decreased reaction time on the hardest level of the performance task. MF exposure did not reliably affect percentage correct or cardiovascular performance. It was demonstrated that a relatively high level of statistical power was the basis for the observed MF effect, and the need to pay closer attention to power levels in future research is discussed. © 1996 Wiley-Liss, Inc.
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  • 81
    ISSN: 0197-8462
    Keywords: ELF bioeffects ; attenuation of opioid-induced analgaesia ; biophysical mechanisms ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Although extremely low frequency (ELF) magnetic fields (〈300 Hz) appear to exert a variety of biological effects, the magnetic field sensing/transduction mechanism(s) remains to be established. Here, using the inhibitory effects of magnetic fields on endogenous opioid peptide-mediated “analgaesic” response of the land snail. Cepaea nemoralis, we addressed the mechanism(s) of action of ELF magnetic fields. Indirect mechanisms involving both induced electric fields and direct magnetic field detection mechanisms (e.g., magnetite, parametric resonance) were evaluated. Snails were exposed to a static magnetic field (BDC=78±1 μT) and to a 60 Hz magnetic field (BAC=299±1 μT peak) with the angle between the static and 60 Hz magnetic fields varied in eight steps between 0° and 90°. At 0° and 90°, the magnetic field reduced opioid-induced analgaesia by approximately 20%, and this inhibition was increased to a maximum of 50% when the angle was between 50° and 70°. Because BAC was fixed in amplitude, direction, and frequency, any induced electric currents would be constant independent of the BAC/BDC angle. Also, an energy transduction mechanism involving magnetite should show greatest sensitivity at 90°. Therefore, the energy transduction mechanism probably does not involve induced electric currents or magnetite. Rather, our results suggest a direct magnetic field detection mechanism consistent with the parametric resonance model proposed by Lednev. © 1996 Wiley-Liss, Inc.
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  • 82
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    Bioelectromagnetics 17 (1996), S. 138-143 
    ISSN: 0197-8462
    Keywords: epidemiology ; pregnancy ; exposure assessment ; generalized additive modelling ; exposure-response relationship ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Choosing the right exposure index for epidemiological studies on 50-60 Hz magnetic fields is difficult due to the lack of knowledge about critical exposure parameters for the biological effects of magnetic fields. This paper uses data from a previously published epidemiological investigation on early pregnancy loss (EPL) to study the methods of evaluating the exposure-response relationship of 50 Hz magnetic fields. Two approaches were used. The first approach was to apply generalized additive modeling to suggest the functional form of the relationship between EPL and magnetic field strength. The second approach evaluated the goodness of fit of the EPL data with eight alternative exposure indices: the 24 h average of magnetic field strength, three indices measuring the proportion of time above specified thresholds, and four indices measuring the proportion of time within specified intensity windows. Because the original exposure data included only spot measurements, estimates for the selected exposure indices were calculated indirectly from the spot measurements using empirical nonlinear equations derived from 24 h recordings in 60 residences. The results did not support intensity windows, and a threshold-type dependence on field strength appeared to be more plausible than a linear relationship. In addition, the study produced data suggesting that spot measurements may be used as surrogates for other exposure indices besides the time average field strength. No final conclusions should be drawn from this study alone, but we hope that this exercise stimulates evaluation of alternative exposure indices in other planned and ongoing epidemiological studies. © 1996 Wiley-Liss, Inc.
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  • 83
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    Bioelectromagnetics 17 (1996), S. 165-165 
    ISSN: 0197-8462
    Keywords: Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: No abstract.
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  • 84
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    Bioelectromagnetics 17 (1996), S. 162-164 
    ISSN: 0197-8462
    Keywords: coaxial cable ; power distribution ; magnetic field ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: A coaxial cable can be used to reduce the magnetic and electric fields that extend into environments in the vicinity of transmission lines and distribution lines and in-house or building wiring for power distribution systems. The use of the coaxial geometry may prove useful in cases where there are environmental concerns with respect to health effects and in cases where there is a need to run high-speed data communications in close proximity to power distribution systems. © 1996 Wiley-Liss, Inc.
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  • 85
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    Bioelectromagnetics 15 (1994), S. 217-238 
    ISSN: 0197-8462
    Keywords: AC/DC magnetic fields ; mathematical models ; ionic resonance ; IPR ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Theoretical models proposed to date have been unable to clearly predict biological results from exposure to low-intensity electric and magnetic fields (EMF). Recently a predictive ionic resonance model was proposed by Lednev, based on an earlier atomic spectroscopy theory described by Podgoretskii and Podgoretskii and Khrustalev. The ion parametric resonance (IPR) model developed in this paper corrects mathematical errors in the earlier Lednev model and extends that model to give explicit predictions of biological responses to parallel AC and DC magnetic fields caused by field-induced changes in combinations of ions within the biological system. Distinct response forms predicted by the IPR model depend explicitly on the experimentally controlled variables: magnetic flux densities of the AC and DC magnetic fields (Bac and Bdc, respectively); AC frequency (fac); and, implicitly, charge to mass ratio of target ions. After clarifying the IPR model and extending it to combinations of different resonant ions, this paper proposes a basic set of experiments to test the IPR model directly which do not rely on the choice of a particular specimen or endpoint. While the fundamental bases of the model are supported by a variety of other studies, the IPR model is necessarily heuristic when applied to biological systems, because it is based on the premise that the magnitude and form of magnetic field interactions with unhydrated resonant ions in critical biological structures alter ion-associated biological activities that may in turn be correlated with observable effects in living systems. © 1994 Wiley-Liss, Inc.
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  • 86
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    Bioelectromagnetics 15 (1994), S. 239-260 
    ISSN: 0197-8462
    Keywords: AC/DC magnetic fields ; neurite outgrowth ; nerve growth factor ; IPR ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: A companion paper describes a predictive ion parametric resonance (IPR) model of magnetic field interactions with biological systems based on a selective relation between the ratio of the flux density of the static magnetic field to the AC magnetic field and the charge-to-mass ratio of ions of biological relevance. Previous studies demonstrated that nerve growth factor (NGF)-stimulated neurite outgrowth (NO) in PC-12 cells can be inhibited by exposure to magnetic fields as a function of either magnetic field flux density or AC magnetic field frequency. The present work examines whether the PC-12 cell response to magnetic fields is consistent with the quasiperiodic, resonance-based predictions of the IPR model. We tested changes in each of the experimentally controllable variables [flux densities of the parallel components of the AC magnetic field (Bac) and the static magnetic field (Bdc) and the frequency of the AC magnetic field] over a range of exposure conditions sufficient to determine whether the IPR model is applicable. A multiple-coil exposure system independently controlled each of these critical quantities. The perpendicular static magnetic field was controlled to less than 2 mG for all tests. The first set of tests examined the NO response in cells exposed to 45 Hz Bac from 77 to 468 mG(rms) at a Bdc of 366 mG. Next, we examined an off-resonance condition using 20 mG Bdc with a 45 Hz AC field across a range of Bac between 7.9 and 21 mG(rms). Finally, we changed the AC frequency to 25 Hz, with a corresponding change in Bdc to 203 mG (to tune for the same set of ions as in the first test) and a Bac range from 78 to 181 mG(rms). In all cases the observed responses were consistent with predictions of the IPR model. These experimental results are the first to support in detail the validity of the fundamental relationships embodied in the IPR model. © 1994 Wiley-Liss, Inc.
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  • 87
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    Bioelectromagnetics 15 (1994) 
    ISSN: 0197-8462
    Keywords: Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 88
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    Bioelectromagnetics 15 (1994), S. 275-282 
    ISSN: 0197-8462
    Keywords: EMF ; exposure assessment ; wire codes ; 60 Hz ; epidemiology ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Wire codes, introduced by Wertheimer and Leeper as a surrogate for residential magnetic fields, divide imputed exposure into several categories based on the configurations of electrical wiring within 40 m of homes. Using the data set gathered by Savitz et al. in the Denver, Colorado, area of the United States, we determined which of the wiring attributes that contribute to Wertheimer-Leeper coding are actually associated with lowpower magnetic fields measured in bedrooms of subjects. The results led us to propose a considerably simplified three-category form of the Wertheimer-Leeper code that 1) drops the distinctions between thick and thin primary wires and between first-span and other secondary lines, 2) adds a new distinction between open (i.e., conductors not in physical contact) and spun secondaries, and 3) explains as much of the between-home variability in log-transformed bedroom fields as does the five categories of the original Wertheimer-Leeper code. The data necessary to classify residences using the modified code are considerably simpler to obtain and should lead to more reliable results. A separate reanalysis of the Denver data set of Savitz et al. shows that the modified code yields risk estimates that are both precise and markedly elevated for the highest exposure category, suggesting that this code may be useful in other studies. © 1994 Wiley-Liss, Inc.
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  • 89
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    Bioelectromagnetics 15 (1994), S. 283-291 
    ISSN: 0197-8462
    Keywords: electromagnetic field ; protein synthesis ; Escherichia coli ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Escherichia coli JM83 {F- ara Δ(lac-proAB) rpsL [φ80dΔ(lacZ)M15]} in midlog growth phase at 30 °C were exposed to 60 Hz sinusoidal magnetic field of 3 mT of nonuniform diverging flux, inducing a nonuniform electric field with a maximum intensity of 32 μV/cm using an inductor coil. Exposed and unexposed control cells were maintained at 30.8 ± 0.1 °C and 30.5 ± 0.1 °C, respectively. Quadruplicate samples of exposed and unexposed E. coli cells were simultaneously radiolabeled with 35S-L-methionine at 10 min intervals over 2 hr. Radiochemical incorporation into proteins was analyzed via liquid scintillation counting and by denaturing 12.5% polyacrylamide gel electrophoresis. The results showed that E. coli exposed to a 60 Hz magnetic field of 3 mT exhibited no qualitative or quantitative changes in protein synthesis compared to unexposed cells. Thus small prokaryotic cells (less than 2 μm × 0.5 μm) under constant-temperature conditions do not alter their protein synthesis following exposure to 60 Hz magnetic fields at levels at 3 mT. © 1994 Wiley-Liss, Inc.
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  • 90
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    Bioelectromagnetics 15 (1994), S. 293-301 
    ISSN: 0197-8462
    Keywords: sinusoidal ; weak ELF magnetic field ; cultured fetal cells ; clastogenic effect ; chromatid and chromosome gaps ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Our recent studies have shown a significant increase in the frequency of chromosomal aberrations in human amniotic cells after exposure to a sinusoidal 50 Hz, 30 μT (rms) magnetic field. To evaluate further interactions between chromosomes and electromagnetic fields, we have analyzed the effects of intermittent exposure. Amniotic cells were exposed for 72 h to a 50 Hz, 30 μT (rms) magnetic field in a 15 s on and 15 s off fashion. Eight experiments with cells from different fetuses were performed. The results show a 4% mean frequency of aberrations among exposed cells compared to 2% in sham-exposed cells. The difference is statistically significant, with P 〈 0.05 both excluding and including gaps. In another series of eight experiments, the cells were exposed in the same way but with the field on for 2 s and off for 20 s. Also in these experiments a similar increase in the frequency of chromosomal aberrations was seen, but only when the analysis included gaps. Continuous exposure for 72 h to 300 μT, 50 Hz, did not increase the frequency of chromosomal aberrations. The background electromagnetic fields at different locations within the two incubators used was carefully checked and was nowhere found to exceed 120 nT. Likewise, the background level of chromosomal aberrations in cells cultured at different locations in the incubators showed no significant interculture differences. © 1994 Wiley-Liss, Inc.
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  • 91
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    Bioelectromagnetics 15 (1994), S. 315-328 
    ISSN: 0197-8462
    Keywords: cancer cells ; thermochemiluminescence ; dosimetry ; melanin ; microwave radiation ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Chemical and bacterial synthesis of a thermochemiluminescent polymer known as diazoluminomelanin (DALM) has been previously reported. This paper focuses on the intracellular synthesis of aminomelanin (AM) in mammalian cell lines and subsequent DALM synthesis from this core molecule. B16 melanoma cells, HL-60 myeloid leukemia cells, and RAW 264.7 macrophages show AM and DALM production. Macroscopic image analysis of HL-60 cell lysates containing DALM using the Quantitative Luminescence Imaging System (QLIS) showed increased chemiluminescence (CL) with increased microwave power input and increased temperature. This work represents a first step toward the goal of microscopic radiofrequency dosimetry of individual DALM-loaded cells using image analysis. © 1994 Wiley-Liss, Inc.
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  • 92
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    Bioelectromagnetics 15 (1994), S. 329-336 
    ISSN: 0197-8462
    Keywords: transcription ; translation ; SV-40 ; large T-antigen ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: In its integrated form, SV-40 DNA offers an opportunity to observe the behavior of what is in effect a viral genome within a cellular genome, with transcriptional and translational products that can be clearly distinguished from those of the host cell. Exposure of SV40-transformed human fibroblasts to a 60 Hz continuous-wave sinusoidal electromagnetic (EM) field resulted in increased levels of virally derived mRNA and protein of large T-antigen. These findings provide evidence that a foreign DNA integrated into cells can be affected by EM fields under conditions known to cause increased transcripts from endogenous cellular genes. © 1994 Wiley-Liss, Inc.
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  • 93
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    Bioelectromagnetics 15 (1994), S. 337-347 
    ISSN: 0197-8462
    Keywords: ELF magnetic fields ; exposure assessment ; epidemiology ; misclassification ; statistical power ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The development of a wire code protocol based on a study of electrical installations in Melbourne, Australia, is described. Because of very significant differences between the Melbourne power distribution system and that used in Denver, Colorado, an approach different from that used by Wertheimer and Leeper was required. A combined practical and theoretical approach was used to determine a continuous exposure index, defined as a measure of the potential for exposure due to external electrical installations. The protocol was tested on a convenient sample of 41 homes in which the field was monitored over a 12 hour overnight period. A correlation of 0.85 (95% CI 0.74-0.92, P 〈 .0001) was obtained between the measured time-weighted average and the wire coding exposure index. To assess the efficacy of the wiring configuration index, a computer simulation of a case-control study was then performed. It was concluded that, using the same basic reasoning of the Wertheimer and Leeper code, it is possible to develop a location-specific code that provides a good correlation with the residential time-weighted average and an acceptable degree of exposure misclassification. © 1994 Wiley-Liss, Inc.
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  • 94
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    Bioelectromagnetics 15 (1994), S. 539-547 
    ISSN: 0197-8462
    Keywords: electromagnetic fields ; signal-to-noise ratio ; stochastic resonance ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: The most important but still unresolved problem in bioelectromagnetics is the interaction of weak electromagnetic fields (EMFs) with living cells. Thermal and other types of noise pose restrictions in cell detection of weak signals. As a consequence, some extant experimental results that indicate low-intensity field effects cannot be accounted for, and this renders the results themselves questionable. One way out of this dead end is to search for possible mechanisms of signal amplification. In this paper, we discuss a general mechanism in which a weak signal is amplified by system noise itself. This mechanism was discovered several years ago in physics and is known, in its simplest form, as a stochastic resonance. It was shown that signal amplification may exceed a factor of 1000, which renders existing estimations of EMF thresholds highly speculative. The applicability of the stochastic resonance concept to cells is discussed particularly with respect to the possible role of the cell membrane in the amplification process. © 1994 Wiley-Liss, Inc.
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  • 95
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    Bioelectromagnetics 15 (1994), S. 555-561 
    ISSN: 0197-8462
    Keywords: frog ; ventricular muscle ; conduction velocity ; 2,450 MHz ; microwave thermal effect ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Thirty-two frog hearts were divided into four groups and placed individually in temperature-controlled waveguides filled with Ringer's solution. The pacemaker was removed, and stimulation was provided at 0.3 Hz by three carbon-loaded Teflon electrodes located on the aorta and the ventricular muscle. Conduction velocity was measured from the difference between two action potentials. One group served as control; the three other groups were exposed for 2 h to pulsed 2,450 MHz microwave fields (10 μs, 0.001 duty cycle, 16 Hz modulation) at specific absorption rates (SARs) of 0.003, 2, and 6 W/kg, respectively. No significant difference in conduction velocity was found between the control and the exposed groups. © 1994 Wiley-Liss, Inc.
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  • 96
    ISSN: 0197-8462
    Keywords: ELF ; magnetic fields ; cyclotron resonance ; calcium transport ; potassium transport ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: We have investigated the effects of sinusoidal electromagnetic fields (EMF) on ion transport (Ca2+, Na+, K+, and H+) in several cell types (red blood cells, thymocytes, Ehrlich ascites tumor cells, and HL60 and U937 human leukemia cells). The effects on the uptake of radioactive tracers as well as on the cytosolic Ca2+ concentration ([Ca2+]i), the intracellular pH (pHi), and the transmembrane potentsial (TMP) were studied. Exposure to EMF at 50 Hz and 100-2000 μT (rms) had no significant effects on any of these parameters. Exposure to EMF of 20-1200 μT (rms) at the estimated cyclotron magnetic resonance frequencies for the respective ions had no significant effects except for a 12-32% increase of the uptake of 42K within a window at 14.5-15.5 Hz and 100-200 μT (rms), which was found in U937 and Ehrlich cells but not in the other cell types. © 1994 Wiley-Liss, Inc.
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  • 97
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    Bioelectromagnetics 15 (1994), S. 589-591 
    ISSN: 0197-8462
    Keywords: dielectric measurement ; human blood ; age ; temperature ; permittivity ; conductivity ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Dielectric properties of human red blood cells (RBCs) in suspension (hematocrit 50%) from 243 healthy persons (120 males, 123 females) were measured at 25 °C in a frequency range of 1-500 MHz, with a coaxial transmission line reflection method (one-side measurement). The measuring system, controlled by an IBM-PC computer, was composed of a network analyzer (HP4195A), an impedance test adapter (HP41951-61001), a coaxial line sensor, and a temperature-controlling set. The data measured revealed a statistically significant age dependence, with a critical age of about 49 years, above which permittivity and conductivity of human RBCs in suspension decreased significantly. © 1994 Wiley-Liss, Inc.
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  • 98
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    Bioelectromagnetics 16 (1995) 
    ISSN: 0197-8462
    Keywords: Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 99
    ISSN: 0197-8462
    Keywords: magnetic fields ; exposure system ; stray fields ; Merritt coils ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Exposure systems that provide good magnetic field uniformity, minimum stray fields, and minimal heating, vibration, and hum, as well as capability for true sham exposure in which current flows in the coils, are needed to determine rigorously the biological effects of weak magnetic fields. Designs based on acrylic polymer coil support structures and twisted pair bifilary coil windings were employed to fabricate several different systems for the exposure of laboratory animals and cell cultures to magnetic fields. These systems exhibit excellent performance characteristics in terms of exposure field uniformity, stray field containment, and exposure field cancellation in the sham exposure mode. A custom-written computer program was used to determine the best arrangement for coils with regard to field uniformity in the exposure volume and stray field containment. For in vivo exposures, modules were made up of four Merritt four-coil sets, built into a single structure and positioned to form an octapole with fields directed in the horizontal plane. For in vitro applications, two different coil configurations were selected to produce the vertical fields required. A quadrupole system, comprising modules consisting of two Merritt four-coil sets arranged side by side to limit stray fields, was built as a prototype. In the second configuration, one Merritt four-coil set was positioned inside the other to form a concentric coil set. In both in vitro systems, exposure chambers were connected to remote commercial incubators in order to reduce ambient magnetic fields in the exposure volume. An active field cancellation circuit was developed for reducing ambient AC magnetic fields in the in vitro sham exposure chamber, when necessary. These design and fabrication approaches provide systems that offer uniform field exposures and excellent stray field containment when needed and are portable, washable, and relatively inexpensive. © 1994 Wiley-Liss, Inc.This article is a US Government work and, as such, is in the public domain in the United States of America.
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  • 100
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    Bioelectromagnetics 15 (1994), S. 593-597 
    ISSN: 0197-8462
    Keywords: magnetic fields ; AMEX ; average magnetic field exposure system ; Life and Medical Sciences ; Occupational Health and Environmental Toxicology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: Two types of dosimeters for measuring human exposure to 60 Hz magnetic fields were compared. Fifty adults wore the single-axis, wrist model AMEX (average magnetic field exposure system) and the triple axis, hip-pocket or pouch model AMEX-3D meters for 2 days. Ninety-six percent of the tests were accomplished without apparent dosimeter failure. The average root mean square magnetic flux density measurements with the AMEX3D (mean = 0.10 μT, S.D. = 0.07, range = 0.03 - 0.31) were significantly higher than with the AMEX meter (mean = 0.07 μT, S.D. 0.05, range = 0.02 - 0.27 μT) (t test, P 〈 0.01). There was substantial correlation between the AMEX and the AMEX-3D measurements (Pearson's correlation coefficient = 0.65, P 〈 0.01) but poor concordance (Intraclass correlation coefficient = - 0.25). These results suggest that there is a wide variation in exposure to extremely low frequency magnetic fields in the population. Magnetic field measurements with the AMEX-3D are nearly always higher than with the AMEX dosimeters. Caution is advised when comparing magnetic field measurements made with different types of dosimeters. © 1994 Wiley-Liss, Inc.
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