Reactivity,chemical structure,and molecular mobility of urea–formaldehyde adhesives synthesized under different conditions using FTIR and solid‐state 13C CP/MAS NMR spectroscopy

This study was conducted to investigate the effects of reaction pH condition and hardener type on the reactivity, chemical structure, and molecular mobility of urea–formaldehyde (UF) resins. Three different reaction pH conditions, such as alkaline (7.5), weak acid (4.5), and strong acid (1.0), were used to synthesize UF resins, which were cured by adding four different hardeners (ammonium chloride, ammonium sulfate, ammonium citrate, and zinc nitrate) to measure gel time as the reactivity. FTIR and ¹³C‐NMR spectroscopies were used to study the chemical structure of the resin prepared under three different reaction pH conditions. The gel time of UF resins decreased with an increase in the amount of ammonium chloride, ammonium sulfate, and ammonium citrate added in the resins, whereas the gel time increased when zinc nitrate was added. Both FTIR and ¹³C‐NMR spectroscopies showed that the strong reaction pH condition produced uronic structures in UF resin, whereas both alkaline and weak‐acid conditions produced quite similar chemical species in the resins. The proton rotating‐frame spin–lattice relaxation time (T_1ρH) decreased with a decrease in the reaction pH of UF resin. This result indicates that the molecular mobility of UF resin increases with a decrease in the reaction pH used during its synthesis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2677–2687, 2003     

Preparation and properties of microcapsule with EVA core‐PU shell structure

Microcapsule with poly(ethylene‐co‐vinylacetate) (EVA) core‐polyurethane (PU) shell structure was synthesized by interfacial polymerization in aqueous polyol dispersion with ethylene diamine as the chain extender of toluene diisocyanate in poly(vinyl alcohol) aqueous solution as the stabilizing agent. The effects of polyol constituent on the average particle size and distributions, morphologies, color strength, and friction fastness of core‐shell particles were investigated to design microcapsule. The friction fastness of printed fabrics with EVA core‐PU shell microcapsules became the increase to 4–5 grades. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 893–902, 2007     

Fully aliphatic polyimides from adamantane‐based diamines for enhanced thermal stability,solubility, transparency,and low dielectric constant

We have synthesized a series of fully aliphatic polyimides (APIs) from bicyclo[2,2,2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride (BOCA) and various aliphatic diamines, including linear aliphatic, flexible alicyclic, and rigid adamantyl diamines. We performed the polymerization reactions using one‐step syntheses in m‐cresol at elevated temperatures without the isolation of poly(amic) acid. The chemical composition and structure of the polymers were characterized by nuclear magnetic resonance (NMR) and infrared (IR) spectrometry. The characterization data are reported from analyses using gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), and wide‐angle X‐ray diffraction (WXAD) measurements. The polyimides are also subjected to solubility, solution viscosity, tensile strength, transparency, and dielectric constant measurements. The resultant polyimides possess well‐controlled molecular weight, reasonable intrinsic viscosity, good transparency, enhanced solubility, low dielectric constants, and high glass transition temperature, together with marginal thermal and mechanical stability. These properties were enhanced in copolyimides containing equimolar amounts of rigid and flexible moieties. These rigid‐rod APIs derived from the alicyclic dianhydride and aliphatic diamines are promising candidates as advanced materials for future applications in micro‐ and photoelectronic devices. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3316–3326, 2006     

THERMAL REGENERATION OF ACTIVATED CARBONS

The thermal regeneration of activated carbons loaded with p-nitrophenol (PNP) and other aromatic compounds was studied using a thermal balance. After pyrolysis of the adsorbates in nitrogen at 700°C, the residues were gasified with oxygen at 415 to 500°C or with steam at 840 to 920°C. Residues from PNP were several times more reactive to oxygen than the base carbons and also showed greater chemisorption of oxygen. For steam gasification, only small differences between spent and fresh carbons were found.     

Experimental studies on extrudate swell behavior of PS and LLDPE melts in single and dual capillary dies

Extrudate swell behavior of polystyrene (PS) and linear low‐density polyethylene (LLDPE) melts was investigated using a constant shear rate capillary rheometer. Two capillary dies with different design configurations were used, one being a single flow channel and the other being a dual flow channel. A number of extrudate swell related parameters were examined, and used to explain the discrepancies in the extrudate swell results obtained from the single and dual flow channel dies, the parameters including output rate and output rate ratio, power law index, wall shear rate, wall shear stress, melt residence time, pressure drop induced temperature rise, flow channel position relative to the barrel centerline, and the flow patterns. It was found in this work that the power law index (n value) was the main parameter to determine the output rate ratio and the extrudate swell between the large and small holes for the dual flow channel die: the greater the n value the lower the output rate ratio and thus decreased extrudate swell ratio. The differences in the extrudate swell ratio and flow properties for PS and LLDPE melts resulted from the output rate ratio and the molecular chain structure, respectively. The extrudate swell was observed to increase with wall shear rate. The discrepancies in the extrudate swell results from single and dual dies for a given shear rate were caused by differences in the flow patterns in the barrel and die, and the change in the melt velocities flowing from the barrel and in the die to the die exit. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1713–1722, 2003     

Analysis of the effects of the polymerization route of ethylene‐propylene‐diene rubbers (EPDM) on the properties of polypropylene‐EPDM blends

A comparative study of two ethylene‐propylene‐diene rubbers (EPDM) polymerized by both conventional (Ziegler–Natta catalysts) and new techniques (metallocene catalysts) is presented. For this purpose, thermoplastic elastomers based on isotactic polypropylene (iPP) and EPDM blends at different percentages were prepared and their properties examined. In particular, the processing behavior and mechanical properties are reported. So, the flow properties analyzed by torque value, melt index, and rheological study reveal that the blends containing EPDM synthesized by metallocene catalyst present a smaller viscosity, thus offering better processing behavior. On the other hand, the mechanical properties show that metallocene EPDM rubbers give rise to more elastic materials with a higher deformation at break and resilience as well as a lower compression set. Moreover, the effectiveness of these innovative EPDM rubbers as impact modifiers for PP is demonstrated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 25–37, 2002     

Manipulating the microstructure and rheology in polymer‐organoclay composites

A series of nanocomposites prepared by melt‐blending of cloisite‐based organoclays with poly(ethylene‐vinylacetate) (EVA) and neutralized poly (ethylene‐methacrylic acid) (EMA) copolymers were investigated via DSC, small‐angle X‐ray scattering (SAXS), and rheological techniques. SAXS results indicated partial clay exfoliation in all samples. In both EMA and EVA systems, the nominal melting temperature T_m and bulk crystallinity are not significantly affected by the presence of organoclays, suggesting that clay particles are predominantly confined in the amorphous phase. In rheological measurements (above T_m), the EVA‐clay system demonstrated a solid‐like rheological behavior under the small‐strain oscillatory shear, yet it was able to yield and flow under a steady shear, which is the characteristic of physical crosslinking. In contrast, the EMA‐clay system exhibited a melt‐like rheological behavior, where the influence of organoclay on the thermorheological behavior of the EMA composite was quite minimal. We propose that the carbonyl groups of vinylacetate in EVA interact with the clay surface, resulting in a strong physically crosslinking like interaction in the melt. On the other hand, the interaction between EMA and clay is weak because of repulsion between carboxyl anions and negatively charged clay surface.     

Studies on crystal morphology and crystallization kinetics of polypropylene filled with CaCO3 of different size and size distribution

Changes in the crystal morphology, crystallinity, and the melting temperature of thermoplastics resulted in significant changes in the mechanical behavior of composites containing them. For this reason, the research of crystal morphology and crystallization kinetics in thermoplastic composites became an important requirement. The thermoplastic filled with the filler of different size gradation was a new method for improving processability of thermoplastic composites. We have previously reported that the melt viscosity of polypropylene (PP) composites, which were filled with 30 wt % CaCO₃ of effective size gradation, could be evidently declined. In this study, two sizes of CaCO₃, 325 meshes and 1500 meshes, were blended by different proportions and filled into PP matrix with 30 wt %. Crystal morphology and isothermal crystallization kinetics of a series of composites were characterized by differential scanning calorimeter (DSC) and polarizing microscope. The results showed that composites filled with CaCO₃ of effective size gradation leaded to a well‐crystalline order and a large crystal size, while their isothermal crystallization kinetics and crystallization rate constant (k) were declined, and their Avrami exponents (n) and crystallization half‐life (t_1/2) were increased compared with the composites filled with single size CaCO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2437–2444, 2006     

A colorimetric determination of fatty acids as a new assay of lipases in reverse micelles

A new simple spectrophotometric method is described for the determination of the free fatty acid content in triglyceride oils or other lipophilic samples. The method utilizes phenol red as fatty acid indicator, which is solubilized phenol red as fatty acid indicator, which is solubilized in reverse micelles formed by AOT [sodiumbis(2-ethylhexyl) sulfosuccinate] in isooctane. Fatty acid determinations in vegetable oils can be carried out rapidly with oil samples of less than 100 mg. The acid value of three different oils tested agreed quite well with the acid value obtained for the same samples with another colorimetric determination using cupric acetate. The method can be extended to a continuous determination of fatty acids which are released during the initial stage of a lipase catalyzed hydrolysis of triglyceride substrates in reverse micelles. This new sensitive lipase assay has been applied for a lipase ofPseudomonas bacteria with lipase concentrations as low as 0.1 μg/ml. Using trioctanoylglycerol as substrate in 50 mM AOT/isooctane with w_o=[H₂O]/[AOT]=11.1 (pH 9.0), the apparent overall Michaelis-Menten constant (K_m′app,ov) is 27 mM and the turnover number (k_cat) 44 sec⁻¹.     

Fatty acid esters with short‐chain alcohols in two‐phase olive pomace oils

Two‐phase decanter olive pomace (TPOP) is the by‐product of a centrifugation system, used to produce olive oil, that separates olive oil and moist pomace. The water content in these olive pomaces is about 70%, while it was 45‐50% in the olive pomace stemming from three‐phase systems (oil, water, and pomace) and 30% in the old press system. The aim of this work is focused on quantification and changes undergone during olive pomace storage in ponds of esters of fatty acids with short‐chain linear alcohols, which can be considered as a refining loss. The results indicate that oil deterioration increases very rapidly, in particular when oil is extracted from the TPOP surface. Special attention should be paid to the storage of TPOP, establishing a maximum of 2 months in all cases.