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A series of thermally crosslinkable polyester copolymers were synthesized by incorporation of a benzocyclobutene-containing terephthalit acid derivative (XTA) into polyethylene terephthalate (PET). The cyclobutene moiety on the XTA monomer allows for reactive crosslinking at temperatures -350°C requiring no catalyst and causing no change in mass. Copolymers were synthesized containing 1,5, 10,20, 50, and 100 mol% XTA. Crosslinking occurred above the melting temperature (-250°C) yet below the degradation temperature (--4OO”C), providing a window for melt processing of the copolymer. To demonstrate this point fibres were melt spun. The PET-co-XTA copolymers show systematic variations in the glass transition, recrystallization, melting and degradation temperatures as a function of benzocyclobutene content. The degradation and melting temperature both decrease slightly with increased XTA, while the recrystallization and glass transition temperature were relatively insensitive to XTA content. Thermal gravimetric analysis (TGA) indicated a decrease in the degradation temperature as higher amounts of XTA were incorporated, although an increase in the %char at 800°C was seen. This decrease in degradation temperature may be due to the generation of free radicals. Limiting Oxygen Index (LOI) measurements showed an increase in the oxygen content required to maintain a stable flame in copolymers with increasing amounts of XTA. LO1 values ranged from 18 for neat PET to 35 for the copolymer containing 20 mol % XTA. Wide-angle X-ray scattering data showed little change in the crystalline structure, but decreasing crystallinity for PET for blends containing up to 20 mol% XTA. The 50 mol% XTA copolymer was amorphous, while the 100% XTA homopolymer (PEXTA) showed evidence of a new crystalline structure. Crystalline diffraction peaks showed reduced intensities in data recorded for heat treated samples, and there was evidence for new peaks in the copolymer containing 20 mol% XTA when heated near 300°C. Transmission electron microscopy of cross-sections through burned samples showed a highly crystalline char at the surface of XTA copolyesters. This crystalline char appeared to protect the underlying copolymer from further flame-induced degradation. Evidence for significantly increased adhesion of the copolymers to polyimide films was also obtained

Детальніше...  

Neutron reflectivity (NR) and dynamic secondary ion mass spectroscopy (DSIMS) were used to study compositional variations as a function of film depth in thin polymeric nanofoam films formed from triblock copolymers containing 15 wt%, 13 kg/mol polypropylene oxide end blocks with a fluorinated polyimide center block. The triblock copolymer films were spun cast and imidized on silicon substrates and showed an excess amount of polyimide present at both the air/film and film/substrate interfaces. Upon foaming the films showed a slight densification, and the formation of a 50–150 Å thick polyimide skin at the air interface. The final nanofoam materials had a calculated porosity of roughly 20 vol.% in the center portion of the film.

Детальніше...  

Blends of poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP) were studied by dynamic-mechanical analysis (DMA). PVA with different degrees of hydrolysis (88 and 99 wt%) and PVP with different molecular weights (10.000 and 360.000 g/mol) were used to prepare the blends. DMA results showed that blends were miscible over the whole composition range studied. However, the E 00 modulus curves exhibit relaxations at the same temperature range below Tg for all blends, suggesting the presence of microenvironments in the blends. These microenvironments are associated to the hydrogen bonding between PVA–PVA in the crystalline and amorphous phase and PVP–PVA in the amorphous phase and in the amorphous–crystalline interface. The stiffness and the flexibility of these blends at 200°C depend strongly on the blends composition, the molecular weight of PVP and the hydrolysis degree of the PVA as determined by the E 0 modulus curves.

Детальніше...  

Ultimate mechanical properties of polyethylene fibers were measured. Results are in close agreement with the stress-induced melting theory of fracture (for finite molecular weight polymers). The perfect fiber work of rupture Wc, modulus Kc, strength s c, and strain 1 c are found to be Wc ˆ 0.084 ^ 0.003 GPa; s c ˆ 7.5 GPa; Kc ˆ 335 ^ 12 GPa; 1 c ˆ 0.0225 ^ 0.0005. The activation energy of fracture is measured as < 108 kJ/mol—the activation energy of polyethylene fusion and one-third the activation energy of bond scission. Nonuniformity of fibers necessitates averaging properties over several test lengths. Actual stress-strain curves are decomposed into thermodynamic and irreversible components. Fusion theory applies to the thermodynamic component..

Детальніше...  

The thermal degradation of poly(3-nitratomethyl-3-methyloxetane), also called polynimmo, an important high-energy binder used in propellant formulations, has been examined by a variety of spectroscopic methods combined with exhaustive chromatography. Degradation results in the gradual increase in intensity of two main new absorptions around 1729 and 1550 cm-1 in the solution infrared (ir.) spectrum of polynimmo. The band at 1729 cm-1 is attributed to the carbonyl group in a formate ester of which the associated formate proton and carbonyl carbon are clearly visible in the 'H and 13Cn.m.r. spectra at 8.1 and 162 ppm, respectively, and can be cross-correlated by two-dimensional n.m.r. The absorption at 1550 cm-1 is attributed to the asymmetric stretch of a nitro group attached to a tertiary carbon. We propose that this nitro species is formed by the recombination of NOa, following the loss of NO* and subsequent elimination of CHPO from the polynimmo side-chains, with the resulting carbon radical. The assignment of this nitroalkane was confirmed by electrospray mass spectrometry, (including collision-induced decomposition studies) and n.m.r. spectroscopic characterization of a nearly pure sample of the cyclic tetrameric nitro species isolated from pyrolysed polynimmo using column chromatography. Degradation also results in the development of a strong electron spin resonance absorption attributed to a nitroxide radical produced in a secondary reaction

Детальніше...  

Poly(octadecyl acrylate), ODA n, with a trimethoxysilyl group at one side of the terminal group was immobilized onto porous silica by using the reactive terminal group. The silica-supported ODA n underwent crystalline-to-isotropic phase transition. Interaction between ODA n and azobenzenes were evaluated by retention time in the liquid chromatography using the column packed with silica-supported ODA n. The chromatograph showed complete separation against the geometrical isomers of azobenzenes in methanol–water. The temperature dependence of the separation factor indicated that the selectivity increased with the molecular orientation of ODA n. Effect of carbonyl–p interaction due to the acrylate moiety on the selectivity was examined using seven kinds of p-substituted phenylazobenzenes with various Hammett’s substituent constants.

Детальніше...  

The volume phase transitions in hydrogen bonded polymer gels are investigated. The elastic contribution is obtained by a modification of the Flory–Rehner approach proposed previously, where the affine deformation assumption is abandoned and instead the assumptions of the c* model of de Gennes are adopted. The mixing term is modified to account for hydrogen bonding. The calculations (both binary and ternary) clearly indicate the possibility of abrupt volume phase transition. Also the existence of LCST and UCST within an accessible temperature range is predicted for gels in mixed solvent systems involving hydrogen bonding.

Детальніше...  

Maleic anhydride (MA) compatibilized polypropylene (MPP) hybrid composites reinforced with potassium titanate whiskers (K2Ti6O13) and liquid crystalline polymer (LCP) were prepared in a twin-screw extruder followed by injection molding. The surface of whiskers were treated with tetrabutyl orthotitanate before blending. Scanning electron microscopic (SEM) examination showed that elongated LCP fibrils are formed in the skin section of hybrids reinforced with whiskers of various concentrations. Consequently, the hybrids reinforced with both LCP fibrils and whiskers exhibited anisotropic mechanical properties. Tensile test showed that longitudinal Young’s modulus and tensile strength of hybrids tend to increase with increasing whisker content. Moreover, the stiffness and tensile strength of hybrids were higher than those of MPP/K2Ti6O13 composites. Such enhancement in mechanical properties resulted from the compatibilizing effect of MA-grafted-PP, and from the hybrid reinforcing effect of LCP fibrils and K2Ti6O13 whiskers. Torque measurements revealed that LCP addition is beneficial in reducing the melt viscosity of MPP/K2Ti6O13/LCP hybrids. The results of SEM observations generally correlate well with the mechanical measurements. The effects of MA compatibilization on the microstructure and mechanical properties of hybrids are discussed.

Детальніше...  

Plasticity and damage mechanisms have been investigated at the lamellar level by scanning force microscopy in bulk isotactic polypropylene under moderate applied shear stresses. The polypropylene under study contains both a! and /3 spherulites. The SPM micrographs show clearly that the local mechanisms are basically the same for both a! and p spherulites, but their intensity is much less lower in the cr spherulites than in the p ones due to the presence of the daughter lamellae in the former case. The main deformation mechanisms which have been observed are: (i) kinking of the lamellae which lie along the principal compressive axis; (ii) nanocracks across the lamellae lying along the principal tensile axis; (iii) fragmentations of the lamellae which are parallel to the shear axis; (iv) fragmentations of the lamellae which are perpendicular to the shear axis

Детальніше...  

A new class of chiral liquid-crystalline polysiloxanes was synthesised, and their thermotropic behaviour and mesophase structure were investigated. The mesogenic side chains consisting of a three-phenyl core were connected to the siloxane polymer backbone by an alkylene spacer segment of varying number m of methylene units and of a chiral sulphide substituent. An X-ray diffraction study of powder and fibre specimens permitted to elucidate the structure of the mesophases, which in any case resulted in tilted, monolayer types. Polysiloxanes P8, P10 and P11 incorporating longer spacers with m ¼ 8, 10, and 11, respectively, exhibited a rich variety of smectic mesophases. The smectic I–smectic F–smectic C phase sequence with rising temperature was identified in all three samples by analysis of the wide-angle diffraction. Three-dimensionally ordered structures were also formed at low temperatures. The various low-angle reflections on the smectic layers were used to evaluate the projections of the electron density profiles along the layer normal, and the most physically acceptable profiles were selected from the numerous possibilities for each smectic mesophase.

Детальніше...  

Корисні статті

Як стати інженером?

Кожна людина в процесі свідомого життя стикається з проблемою вибору професії. Найбільш актуальною ця проблема є для учнів старших класів – випускників, які добровільно або примусово здають шкільні іспити та зовнішнє незалежне оцінювання, за результатами чого приймають участь в конкурсному відборі на навчання у ВНЗ. Щоб обрана професія не стала важким випробовуванням, потрібно ще у шкільні роки зважити всі «за» і «проти», оцінити свої здібності, схильності, можливості.

Хто такий інженер

Інженер - професія нелегка, але одночасно з цим дуже цікава і захоплююча. Адже інженер це людина, у якого народжуються в голові нові ідеї і тому він здатний винаходити.

У багатьох виникає питання: хто такі інженери? Інженер (франц. Ingénieur) - фахівець з вищою технічною освітою. Спочатку інженерами називали людей, які керували військовими машинами. Поняття громадський інженер з'явилося в XVI столітті в Голландії, застосовано до сфери будівництва мостів і доріг, потім інженери з'явилися в Англії, а потім в інших країнах.

Види та функції сучасної упаковки

Різноманітна упаковка щільно увішла у життя кожної людини. На полицях магазинів, в інтер'єрах помешкань можна побачити десятки пляшочок, коробок, аерозольних болончиків. Термін існування упаковки в нашому житті може продовжуватися від кількох хвилин до кількох років. Що ж таке сучасна упаковка? Чому вона займає стільки місця в нашому житті?

ВНЗ України

Вища освіта є невід'ємним елементом перспективного кар'єрного росту, тому перед кожним абітурієнтом виникає проблема, в які інститути подавати документи. Варто відзначити, що в Україні існує велика кількість вузів. Всі навчальні заклади поділяються на державні та приватні, пропонуючи різноманітні освітні програми по різних профілів. Щоб пошук інститутів дав задовільні результати, слід визначитися з найбільш прийнятними спеціальностями. Також підбір університету передбачає вибір підходящої форми навчання, наявність високої акредитації у вузу і рівень його престижності.

Комп'ютер для інженера

У сучасному світі комп'ютери дуже поширені. Складно уявити людину, не знайому з цим поняттям. Багато професій зобов'язані своїм виникненням саме комп'ютеру, вони б просто не з'явилися без створення електронно-обчислювальної техніки.

І хоча відносно недавно, на початку XX століття, комп'ютери були розкішшю і використовувалися лише для самих складних розрахунків, у наш час комп'ютери та комп'ютерна техніка дуже глибоко інтегрувалися у наше життя. Сучасне людство залежить від комп'ютерів, що викликає подиву, якщо розглянути, коли і в яких випадках вони використовуються.