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EN
Abstract: The polymorphic transition of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo[5.5.0.05,9.03,11]dodecane (CL-20) is influenced by the materials and conditions used in the preparation of propellants, and limits the application of ε-CL-20 in solid propellants. In the present work, the effect of dinitroxydiethylnitramine (DINA) on the polymorphic transition of ε-CL-20 in CMDB propellants was investigated by Raman spectroscopy and the Calvet microcalorimeter method. The performance of propellants with CL-20 as affected by DINA was studied by the theoretical prediction of their energetic parameters, stability, combustion, and mechanical tests, respectively. The results showed that the polymorphic transition temperature of ε-CL-20 to α-CL-20 can be reduced to 75 °C by DINA. Expansion of the crystal volume during the process of the ε-CL-20 to α-CL-20 transition will produce obvious cracks in the surface of the crystals. NC/NG can inhibit the effect of DINA on the polymorphic transition of ε-CL-20. The theoretically predicted results indicated that adding DINA will not lower the energy level of CMDB propellants containing CL-20. The DSC and VST results showed that CL-20 has good compatibility and thermal stability with DINA. The burning rate tests revealed that adding DINA decreases the burning rates of CMDB propellants containing CL-20. Mechanical property testing showed that adding DINA can clearly improve the mechanical properties of CMDB propellants containing CL-20. The results of these investigations suggested that DINA has no effect on the crystalline stability of ε-CL-20 in the solventless extrusion process, which contributes to a significant understanding of practical applications and provides guidance for applied research on the use of CL-20 in propellants.
EN
In order to explore the polymorphic transition law for ε-CL-20 in composite systems, the polymorphic transition process of pure ε-CL-20 crystals stimulated by heat was investigated by the X-ray Diffraction (XRD) method, and the kinetic parameters of the polymorphic transition process were calculated (including the apparent activation energy Ea and the pre-exponential factor lnA). Meanwhile the effects of different additives on the polymorphic transition process and kinetics of ε-CL-20 were explored in detail. The experimental results showed that the ε-form tends to transform into the γ- form on heating and that the Ea and lnA for the transition process were 209.97 kJ/mol and 57.47, respectively. The first group of additives clearly promoted the polymorphic transition of ε-CL-20 and lowered the initial transition temperature and the activation energy. The second and third groups of additives inhibited the polymorphic transition of ε-CL-20 and raised the initial transition temperature and the activation energy.
EN
The aim of this research project was to investigate the mercerisation process of natural rapeseed straw used to manufacture composites with thermoplastic polymers. Alkali treatment of the native cellulose causes polymorphic transition to cellulose II and, consequently, improvement of mechanical properties of natural lignocellulosic materials. Different concentrations of alkali solutions were employed in the course of the rape (Brassica napus) mercerisation of Kaszub and Californium varieties: 5, 10, 12.5, 15, 17.5, 20, & 25%, and the process lasted for 1, 2, 3 4, 5, 7.5, 10, 15, 30, 60, 90 and 120 minutes, respectively. The structural transformation from cellulose I to cellulose II for rapeseed straw after alkali treatment with sodium hydroxide was investigated by means of the wide-angle X-ray scattering (WAXS) method. The X-ray diffraction pattern was recorded within the angle range of 5 - 30° 2Θ. The polymorphic transition was calculated on the basis of the individual areas under the peaks of both cellulosic forms. It was found that the amount of cellulose II in wooden parts of rapeseed straw depended on the concentration of alkali solution as well as on the time of chemical treatment. It was further found that the great efficiency of Cellulose I → Cellulose II transition (over 50%) was observed for both experimental varieties at a wide range of the concentrations applied, from 12.5 to 20%, when the process was conducted for at least 5 minutes. This result indicates a different behaviour of rapeseed straw in comparison with such other lignocellulosic materials as wood or natural fibres. There were no structural differences found between various rapeseed straw varieties in the mercerisation process. On the basis of the degree of cellulose crystallinity in rapeseed straw after alkali treatment, no degradation of lignocellulosic material was found to occur in the above-mentioned conditions.
PL
Celem pracy było zbadanie procesu merceryzacji rozdrobnionej słomy rzepakowej mogącej znaleźć zastosowanie jako lignocelulozowy napełniacz kompozytów z termoplastyczną osnową. Proces ten powoduje przemianę polimorficzną celulozy natywnej w celulozę II cechującą się lepszymi właściwościami mechanicznymi. Badaniom poddano słomę rzepakową dwóch odmian Kaszub oraz Californium, stosując stężenia zasady NaOH od 5 do 25% w czasie prowadzenia procesu od 1 minuty do 120 minut. Badania przemiany polimorficznej przeprowadzono metodą szerokokątowej dyfrakcji promieni rentgenowskich. Stwierdzono, że zawartość celulozy II w zdrewniałych częściach słomy rzepakowej zależy zarówno od zastosowanego stężenia zasady jak i od czasu prowadzenia procesu. Największa efektywność przejścia fazowego Celuloza I → Celuloza II (ponad 50%) została stwierdzona przy stosowaniu stężeń w zakresie 12,5 – 20%, przy procesie alkalizacji trwającym nie mniej niż 5 minut. Wyniki badań wskazują, że proces merceryzacji słomy rzepakowej zachodzi w odmienny sposób niż dla innych materiałów lignocelulozowych, na przykład dla naturalnych włókien czy drewna. Ponadto na podstawie wyznaczonego stopnia krystaliczności celulozy stwierdzono, że w stosowanych warunkach nie wystąpiły procesy degradacji słomy rzepakowej pod wpływem środowiska alkalicznego.
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