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Abstract  

Three glass reinforced polymers of Nylon 66, PET and HT-Nylon with glass transitions of 58, 72, and 132°C are selected for checking the necessity of high temperature annealing and degree of its impact on creep strains. The improvement after annealing depends on the polymer type of whether it is fast or slow crystallizing at molding process and whether it has hydrogen bonded sheets. The physical property changes observed of these materials before and after annealing support the explanation of crystal reorganization through crystallization, free volume reduction through densification and crystal perfection through better chain packing. The prediction of long-term creep strains up to 10 years using time-temperature superposition technique has been the practice for last 13 years in our laboratory. The accuracy of the prediction are shown in confidence level of about 90%.

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Journal of Thermal Analysis and Calorimetry
Authors:
M. Keating
,
K. Gardner
,
H. Ng
,
D. Marks
,
W. Yung
,
P. Avakian
, and
H. Starkweather

Abstract  

Our X-ray work of Dytek-A, 2-methyl-pentamethylenediamine, containing polyamides shows polymorphism, whereas the polyamides with linear diamines do not. The polyamide of Dytek-A and dodecanedioic acid, MPMD-12, is singled out for discussion and compared with the unbranched analogs of polyamides 6,12 and 5,12. Due to the presence of the -CH3 side group in the 2-position of the diamine, the polyamide MPMD-12 exhibits two stable crystal conformations. The new δ polymorph is not seen in linear polyamides 6,12 and 5,12. Studies by DSC polyamide MPMD-12 clearly illustrates at least two crystal forms, γ and δ, coexisting over a wide temperature range, and the isolation of each phase is possible by controlling temperature and time. The DMA modulus in the temperature region between the glass transition (or alpha relaxation) and melting transition shows strong dependence on the thermal history as demonstrated in a study of crystallization kinetics.

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Abstract  

The polyamide from 2-methylpentamethylenediamine and dodecanedioic acid (MPMD-12) has been studied by differential scanning calorimetry, dynamic mechanical analysis, dielectric analysis, X-ray crystallography, and simultaneous small and wide-angle X-ray scattering using synchrotron radiation. The polymer exhibits polymorphism which is shown to be associated with the incorporation of the branched diamine. At relatively low temperatures, the crystal structure is similar to the gamma form which has been found in many other polyamides. At higher temperatures, a new delta form appears in which the diamine moiety adopts a bent conformation. In this form, the chains follow a zig-zag pattern with two chemical repeats units per crystallographic repeat with a shortening of about 10% along the c-axis.

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Journal of Thermal Analysis and Calorimetry
Authors:
W. Liu
,
S. Kim
,
J. Lopez
,
B. Hsiao
,
M. Keating
,
I.-H. Lee
,
B. Landes
, and
R. Stein

Abstract  

In this study, the stepwise isothermal crystallization or thermal fractionation of Ziegler—Natta and metallocene based polyethylenes (ZN-PE and m-PE) with two kinds of branch lengths (ethyl and hexyl) and branch compositions were studied using simultaneous synchrotron small-angle X-ray scattering (SAXS)/wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The crystal long period and the invariant were determined by SAXS, and the variations of crystal unit cell parameters and the degree of crystallinity were determined by WAXD. The arithmetic mean length (Ln), the weightedmean length (Lw) and the broadness index (Lw/Ln) of the studied polyethylenes were previously determined by DSC. Results from these studies were interpreted using the model of branch exclusion, which affects the ability of the chain-reentry into the crystal phase. Multiple SAXS peaks and step-change in crystallinity change (WAXD) were seen during heating, which corresponded well with the crystal thickness distribution induced by stepwise crystallization. The effects of the heterogeneity of the 1-olefin branch length and the distribution on the crystal long period and the invariant as well as the degree of crystallinity were discussed.

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