Crystallization of polymer melts under fast cooling. II. High-purity iPP

Samples of a high-purity isotactic polypropylene (iPP) were quenched from the melt so as to monitor cooling history. A continuous variation of morphology and crystal structure was obtained with cooling rate. This is discussed in relation to sample thermal history evidencing that cooling history relevant to quenched samples is in the neighborhood of 90°C. In particular the samples are essentially mesomorphic when at this temperature cooling rates larger than 80°C/s were adopted, while below a few tens of °C/s only α-monocline form is obtained. Densities of quenched samples were compared with predictions of an isokinetic extrapolation of Avrami model of polymer crystallization kinetics.     

Aggregation behaviour of stereoregular poly(methyl methacrylates) in dilute solution: light scattering and proton n.m.r. study

The aggregation behaviour of syndiotactic and isotactic poly(methyl methacrylate) in methyl ethyl ketone, n-butyl acetate, and 2-ethoxyethanol was investigated by light scattering and ¹H n.m.r. spectroscopy. Syndiotactic poly(methyl methacrylate) remains in its molecular form in solution at temperatures above 60°–70°C; on cooling it undergoes aggregation followed by macroscopic separation (precipitation) of the polymer from solution. The rate of these processes depends on temperature, concentration of the polymer, and solvent. Molecular solutions of isotactic poly(methyl methacrylate) can be prepared only by long-term heating at temperatures above 100°–130°C. During cooling, isotactic macromolecules prior to separation form stable associates in the region limited by discrete temperatures, and below this region polymer precipitates. The individual stereo forms of poly(methyl methacrylate) are separated from solution at different temperatures which are above the θ-temperatures of the atactic polymer.     

Crystallization of polymer melts under fast cooling. I: Nucleated polyamide 6

Samples of nucleated polyamide 6 were quenched from the melt so as to monitor cooling histories. Their morphology and crystal structures were discussed in relation to sample thermal history; cooling history relevant to quenched sample morphology was recognized as being confined in the interval 110 to 160°C. In particular, samples were essentially amorphous for cooling rates larger than 200°C/s. The γ-crystalline form was observed for cooling rates in the interval 70 to 200°C/s, whereas α crystalline structure was found dominant for yet lower cooling rates. Crystallinities evaluated from densities of quenched samples were compared with predictions of an isokinetic form of the Avrami model for polymer crystallization kinetics.     

Influence of cooling methods on high-temperature residual mechanical characterization of strain-hardening cementitious composites

Residual strength tests are commonly used to characterize the high-temperature mechanical properties of concrete materials. In these tests, the specimens are heated to a target temperature in a furnace and then cooled down to room temperature, followed by mechanical testing at room temperature. This research investigates the influence of the cooling method on the residual strength of Strain Hardening Cementitious Composites (SHCC) after exposure to 400°C and 600°C. Two types of cooling methods — furnace-cooling (within a closed furnace) and water-cooling (immersed in a water tank) — were adopted. Four different SHCC previously investigated by the authors for high-temperature residual mechanical and bond behavior with steel were studied. Two different specimen sizes were tested under uniaxial compression and flexure to characterize the residual compressive strength and modulus of rupture. The effect of the cooling method was prominent for the normalized residual modulus of rupture at 400°C, but not at 600°C. The cooling method had no effect on the normalized residual compressive strength of any material at either of the two temperatures, except one of the SHCC (PVA-SC) at 400°C. Specimen size also had no effect on the normalized residual compressive strength and modulus of rupture irrespective of the cooling method.     

Polymer aqyeous solutions as quenching media. I. Polyvinylpyrrolidone

The cooling power of aqueous solutions of polyvinylpyrrolidone are studied with a silver standard sample by using two apparatuses quench with injection and quench with agitation. The dependences of the cooling rates at each temperature on polymer concentration and solution viscosity are established and empirical laws of variation are given.     

Structure and properties of hard carbon films depending on heat treatment temperatures via polymer precursor

Phenylcarbyne polymer films were coated on silicon substrates and heat treated in 1 atm pressure of argon at various temperatures. The structural changes occurring during the heat treatment process of the polymer were investigated by Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The Raman and FTIR spectra features of the polymer showed a dependence on the heat treatment temperatures. At low temperatures (below 400°C), the Raman and IR spectra of the polymer were similar to those of the original polymer. The hardness and Young's modulus of the polymer films were below 1 and 50 GPa, respectively. With increasing temperature (above 400°C), thermal decomposition of the polymer occurred, resulting in structural changes of the polymer from soft amorphous hydrocarbon (400–600°C) phases to hard carbon phases (above 600°C). The hardness and Young's modulus increased from 1.5 and 65 GPa at 600°C to 9 and 120 GPa at 1000°C, respectively. It is assumed that the hard carbon film converted from the polymer might contain sp² and sp³ carbon phases; high temperature of heat treatment resulted in increasing sp² (glassy) carbon phase in the films.     

Study of the thermal-oxidative stability of polybenzoheterocyclic binder

The results of investigating highly thermostable polymer matrices with softening temperatures of 400–450°C are reported. Binders based on a tetranitrile of an aromatic tetracarboxylic acid and bis(o-cyanoamine) are used as polymer matrices. Traditional antioxidants, such as aromatic amines, phenols, and alkyl aryl phosphites, cannot be applied as thermostabilizers. Detailed tests of an efficient stabilizer carborane-containing dinitrile were also unsuccessful because the initial period of retardation in the thermal-oxidative degradation is followed by irreversible changes in the polymer at 350–400°C. Only a new thermostabilizing system based on carborane-containing aromatic compounds with a set of conjugated bonds demonstrates a positive effect. It is established that the developed thermostabilizing system retards the thermal-oxidative degradation and makes it possible to obtain the polymer matrix with a thermal stability of 350–400°C.     

Solidification of poly(ethylene terephthalate) with incomplete crystallization

Cooling is a critical step in any crystalline polymer molding or extrusion process. A simulation is proposed which will predict the transient temperature and crystallinity profiles developed when a finite polymeric slab comes in contact with a cooling fluid. A generalized, phenomenological model of the crystallization kinetics of polymers is incorporated to account for the effect of the latent heat of crystallization on the thermal history as well as on the crystalline structure at any point in the slab. The model assumes heterogeneous nucleation and temperature-dependent radial growth of spherulites. DSC cooling thermograms for the polymer are used to verify the kinetic model for comparing experimental measurements against simulated results. Observed spherulite sizes should also be matched by the simulation. Kinetic data have been obtained for two grades of poly(ethylene terephthalate) which have the same growth rate expression but different nucleation characteristics. Crystallinity of these two polymers decreases rapidly as either quench temperatures or nucleation densities are decreased independently. Calculations have been carried out for 1/16 in. thick sheets of polymer exposed to a cooling medium with a heat transfer coefficient of 100 Btu/hr/ft²/°F. Temperature gradients are also presented. The simulation can be used for optimizing quench conditions in polyester film extrusion.     

Polymers from renewable resources. IX. Interpenetrating polymer networks based on castor oil polyurethane poly(hydroxyethyl methacrylate): Synthesis,chemical, thermal,and mechanical properties

A number of polyurethanes were synthesized by reacting castor oil with hexamethylene diisocyanate, varying the NCO/OH ratio. The polyurethanes were reacted with 2-hydroxyethyl methacrylate (HEMA) to prepare the interpenetrating polymer networks (IPNs) using benzoyl peroxide as the initiator and ethylene glycol dimethacrylate (EGDM) as the crosslinker. The IPNs are partly soluble in some of the solvents and are less resistant to alkali, but more resistant to acid. The solvent absorption is more pronounced in benzene than in toluene. A novel computerized LOTUS package was used to calculate the kinetic parameters. All the IPNs decomposed with 2–4% weight in the temperature range of 0 to 200°C; 10% weight loss occurs at 300°C and 40% weight loss occurs at 400°C. There is a rapid weight loss from 10 to 90% in the temperature range of 400–500°C. From the kinetic data, it is clear that the degradation process of the IPNs is slower in the temperature range 300–400°C and faster in the temperature range of 440–560°C. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 671–679, 1997     

Transport properties of dichloromethane in glassy polymers. II. Amorphous syndiotactic polystyrene films

Sorption and diffusion of dichloromethane vapor were measured in amorphous syndiotactic polystyrene films, obtained with different cooling conditions and after controlled aging times at different temperatures. The diffusional behavior, at the temperature of 25°C, was characterized by three stages, depending on penetrant activity. In the first stage, at low activity, the diffusion coefficient was independent of vapor concentration; the second stage was characterized by concentration-dependent diffusion, whereas in the third stage, at high activity, the strong interaction solvent–polymer increased the mobility, allowing the polymer crystallization. The different cooling conditions neither have an effect on the diffusional behavior nor on the sorption curve. The aging, both at room temperature and at 70°C, did not change the diffusion parameters, but led to the appearance of more and more anomalous sorption behavior. The sorption curve, as a function of vapor activity, did not show any difference for the fresh and the aged-at-room temperature samples, whereas the samples aged at 70°C presented a lower sorption at low activity. The presence of ordered domains, impermeable to the penetrant at low activity, was suggested on the basis of sorption results. The solvent-induced crystallization was investigated for all the samples. Crystallization was induced at an activity of 0.45 for the fresh and the aged-at-room temperature samples; at variance, the samples aged at 70°C crystallize at a slightly higher activity, reaching, nevertheless, a higher level of crystallinity. © 1993 John Wiley & Sons, Inc.     

Optimization of the thermomechanical behavior of a poly(chromium(III) trisphosphinate)

A two-component reactive system consisting of a poly(chromium(III) bisphosphinate) and dioctylphosphinic acid reacts to form a poly(chromium(III) trisphosphinate). Extensive thermomechanical hysteresis is displayed throughout the temperature range ?180°C to >300°C by specimens containing filaments of glass. Thermal pretreatment to about 400°C (the limit of thermal stability) eliminated these instabilities. These results correlate with the reported brittle and tough character of films of the poly(chromium (III) bisphosphinate) and poly(chromium (III) trisphosphinate), respectively. Regardless of thermal history (between 200°C and 400°C), the polymer system displayed three major transition regions: the glass transition centered at about 0°C, another centered at about 230°C, and a third at about ?200°C.     

Effect of process parameters on phase behavior and particle size of aspirin during freeze concentration

Abstract

The present work investigated effect of process parameters on phase behavior of aspirin (ASP) solution and ASP particle size during freeze concentration. ASP solution (3% w/w in 40% w/w TBA in water) was studied using differential scanning calorimetry (DSC) and cold stage polarized light microscopy (CSPLM) at cooling rates of 0.1, 0.5, 1, 3, 5, 10, 20, and 30?°C/min. Significant reduction in D₉₀ of ASP crystals (from 45.6?µm to 3.0?µm) was observed for ASP crystals in frozen solution with increase in cooling rate. Non-isothermal crystallization kinetics (NITC) of ASP in frozen solution using CSPLM revealed linear increase and an exponential increase in Avrami exponent and crystallization rate constant, respectively. NITC results indicated generation of higher nucleation sites and localized multidimensional crystallization with increase in cooling rate. Moreover, the high degree of supercooling and higher supersaturation achieved with increasing the cooling rate further supported the generation of more nuclei and smaller ASP crystals. Finally, the implication of phase behavior was established using lab scale freeze dryer, where particle size (D₉₀) of 41.8, 14.8, and 7.1?µm was obtained with cooling rate of 1?°C/min, 15?°C/min and quench cooling, respectively. The proposed strategy can be applied for development of lyophilized product that can generate parenteral suspension upon reconstitution.     

Free radicals in coal and coal conversions. 6. Effects of liquefaction process variables on the in-situ observation of free radicals

To determine the effects and relative importance of process variables in coal liquefaction, a uniquely designed and fabricated high-pressure/high-temperature electron spin resonance (e.s.r.) apparatus is used to monitor the in-situ formation and behaviour of free radicals, which are generally assumed to be the key factor. It is concluded that the temperature is the most significant single process variable that affects free radical formation; for Powhatan No. 5 coal there is a 9-fold increase in going from 400 to 460 °C. At 460 °C the other process variables tested can affect significantly the free radicals significantly, but at 400 °C these variables have essentially no effect on free radicals formation. The next most significant effect is due to the combination of solvent nature and residence time. Tetralin and the SRC-II heavy distillate quench the free radicals from Powhatan No. 5 to the same extent with one significant difference. In tetralin the maximum concentration is observed shortly after the slurry achieves its highest temperature, whereas in the SRC-II heavy distillate experiments the concentration is still increasing, at 460 °C, even after 1 h of reaction. The heating time, pressures and types of gas used affect the free radical concentration to a much smaller extent. The conversions obtained in the in-situ e.s.r. experiments using SRC-II heavy distillate as the solvent are somewhat lower than those obtained with tetralin as the solvent. The corresponding oil yields with tetralin are considerably higher than with SRC-II heavy distillate.     

Effect of cooling methods on residual compressive strength and cracking behavior of fly ash concretes exposed at elevated temperatures

This paper presents the effects of cooling methods on residual compressive strength and cracking behavior of concretes containing four different class F fly ash contents of 10%, 20%, 30% and 40% as partial replacement of cement at various elevated temperatures. The residual compressive strength of the aforementioned fly ash concretes is measured after being exposed to 200, 400, 600 and 800 °C temperatures and two different cooling methods, for example, slow cooling and rapid water cooling. Results show that the residual compressive strengths of all fly ash concretes decrease with increase in temperatures irrespective of cooling regimes, which is similar to that of ordinary concrete. Generally, control ordinary concrete and all fly ash concretes exhibited between 10% and 35% more reduction in residual compressive strength because of rapid cooling than slow cooling except few cases. Cracks are observed over concrete specimens after being exposed to temperatures ranging from 400 to 800 °C. Samples that are slowly cooled developed smaller cracks than those rapidly cooled. At 800 °C, all fly ash concretes that are exposed to rapid cooling showed the most severe cracking. X‐ray diffraction analysis shows reduction of Ca(OH)₂ peak and formation of new calcium silicate peak in concretes containing 20% and 40% fly ash when subjected to 800 °C in both cooling methods. Thermo gravimetric analysis and differential thermal analysis results show increase in thermal stability of concrete with increase in fly ash contents. The existing Eurocode also predicted the compressive strength of fly ash concretes with reasonable accuracy when subjected to the aforementioned elevated temperatures and cooling methods. Copyright © 2014 John Wiley & Sons, Ltd.     

Liquid crystalline aromatic polyesters formed with terephthalic acid,phenyl hydroquinone,and napthalene or anthracene diols

The synthesis and characterization of aromatic copolyesters containing terephthalic acid and phenyl hydroquinone as the major constituents and either 1,4-napthalene diol or 1,4-anthracene diol as the minority comonomer is described. Both polymers melted in the vicinity of 300°C, giving birefringent fluids. Optical microscopy showed Schlieren textures consisting predominantly of inversion walls characteristic of the nematic phase. The clearing temperature was in the vicinity of 460°C, but was accompanied by charring. DSC experiments showed a high glass transition temperature of 130–160°C for both polymers. Crystalnematic and nematic-isotropic endotherms were observed on heating; however, degradation took place near the isotropization temperature. Thus, on cooling, the sequence was reversible only if the previous heating was beyond the crystal-nematic but below the isotropization temperature. The polymers were stable in terms of gross weight loss until about 450°C, though there were indications that crosslinking occurred above about 400°C over a short period of time. The polymers formed low-viscosity injection-molding compounds, but to use them effectively, it would require mold-gate designs that reduce the “jetting” tendency for liquid crystal polymer melts, which result in weld lines. © 1995 John Wiley & Sons, Inc.     

Preparation of diamine-POSS/Ag hybrid microspheres and its application in epoxy resin

Carbon nanowires having different functionality has been synthesized through the template assisted approach using poly(vinyl alcohol) (PVA) as precursor polymer at 400?°C, 600?°C, 700?°C and 800?°C in the absence of any catalyst. Carbon nanowires with a diameter range of about 90?C120?nm have been obtained. Scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy are been adopted to characterize the morphology, thermal properties and chemical configuration of the synthesized samples. Raman spectroscopy indicates carbonization of the samples upto 600?°C. Above that carbon-cluster formation is observed at 700?°C and 800?°C. SEM images show the formation of nanowires in alumite template by infiltration of PVA into the pores at 400?°C. The nanowires produced are very flexible at about 700?°C, above which the nanowires tended to retain their rigidity due to the formation of graphite clusters / crystallites.     

Effect of heat treatment on the structure and photocatalytic properties of BiYO3 and BiY0.995Ni0.005O3 ceramic powders

BiYO₃ powders were synthesized by the Pechini method under low-temperature conditions. When the heat treatment was performed at T < 600 °C, a mixture of tetragonal and cubic phases was obtained, while for T ≥ 600 °C, only the fluorite-like cubic phase was observed. Based on the Rietveld refinement, approximately 2% and 1% of the tetragonal phase remained in samples calcined at 400 °C and 500 °C for 1 h, respectively. The crystal size calculated for these samples was 4.4–48.1 nm, depending on the calcination temperature. The specific surface area of the samples diminished with heat treatment and reached a minimum at 800 °C. The band gap of samples with mixed phases was close to 2.16 eV and was ~2 eV for samples with a cubic phase. Photocatalytic tests demonstrate that BiY_0.995Ni_0.005O₃ calcined at 800 °C had the best performance: it degraded more than 80% of the antibiotic oxytetracycline when irradiated with visible light. The Ni-doped BiYO₃ material could degrade the antibiotic in tap water at an environmentally relevant concentration (μg L⁻¹ levels) and showed steady activity throughout four reaction cycles.     

Zur thermolyse von acrylnitril-vinylidenchlorid-copolymeren

The thermal degradation of random acrylonitrile-vinylidene chloride copolymers under nitrogen was studied at programmed temperature between 25 and 400°C. The following results were obtained: The initiation of dehydrochlorination, studied conductometrically, depends on the polymer composition and ranges from 70 (for copolymers with medium composition) to 130°C (for copolymers rich in acrylonitrile or vinylidene chloride). The total amount of hydrogen chloride evolved (up to 400°C, referred to the vinylidene chloride content) increases with the acrylonitrile content of the copolymers and is larger than that of polyvinylidene chloride. In the temperature range studied, the evolution of hydrogen chloride accounts for approx. 75% of the loss of weight, even with copolymers rich in acrylonitrile. Thc evolution of hydrogen cyanide, as detected by gas chromatography, starts between 150 and 190°C. The total amount of hydrogen cyanide evolved (up to 400°C, referred to the acrylonitrile content) increases with the vinylidene chloride content of the copolymers. Short oligomerized nitrile sequences were detected in the copolymers at 160°C by UV-spectroscopy. The results are discussed with respect to the sequence distribution obtained kinetically.