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     

杂色云芝漆酶的分离、纯化和酶学特性研究

杂色云芝发酵液,经超滤、DEAE-Sephadex A250柱层析两步分离、纯化出两型漆酶。以愈创木酚与酶带在适当条件下反应呈棕红色谱带鉴定出漆酶谱带。两型漆酶分别命名为LacA和LacB。经测定两漆酶亚基的分子量分别为66.0kDa和30.7kDa;等电点pI分别为4.79和5.18;LacA的最适作用温度是40℃,LacB为50℃;保温2h, LacA的半失活温度为60℃,LacB为90℃;LacA和LacB催化愈创木酚的酶活最适pH值均为4.0; 二者的稳定pH值也都在2.5~5.5之间。LacA催化氧化愈创木酚的Km和Vmax分别为286.5molL-1和292.4nmol mL-1 min-1;LacB催化氧化愈创木酚的Km和Vmax分别为813.0mol L-1和127.4nmol mL-1 min-1。     

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 growth mark method for studying growth mechanism of carbon nanotube arrays

A novel and simple growth mark method was developed to make marks during the growth process of carbon nanotube arrays. These marks can be read out under scanning electron microscope or optical microscope. Based on this method, the growth rates at different temperatures and under different acetylene partial pressures were measured, from which the activation energy and the order of reaction were determined. Based on our experimental results, the growth of carbon nanotube arrays in our experimental condition could not be diffusion-limited. The measured activation energy could possibly be attributed to the heterogeneous decomposition of acetylene over the catalyst particle. Furthermore the marked array with special segmental structure may be found some applications in the future.     

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.     

Toughening of cycloaliphatic epoxy resins by poly(ethylene phthalate) and related copolyesters

Poly(ethylene phthalate) (PEP) and poly(ethylene phthalate–co‐ethylene terephthalate) were used to improve the brittleness of the cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate (Celoxide 2021?), cured with methyl hexahydrophthalic anhydride. The aromatic polyesters used were soluble in the epoxy resin without solvents and effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PEP (MW, 7400) led to a 130% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 388–399, 2002; DOI 10.1002/app.10363     

Crosslink reaction of natural rubber with thiuram sulphur donors in the presence of a thiuram monosulfide

The vulcanization of natural rubber was studied with the sulfurating agents dipentamethylene thiuram tetrasulfide (DPTT) and tetramethylene thiuram disulfide (TMTD) in the presence of tetramethyl thiuram monosulfide (TMTM). This last accelerant affects the rate and efficiency of the vulcanization as well as the structures of crosslinks formed by the two sulphur donors. It may give rise to a polymerization between adjacent double bonds and generate a inhomogeneous crosslink distribution with an adverse effect on physical properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 491–499, 2002     

A Unified Model for the Mixing of Non‐Newtonian Fluids in the Laminar,Transition, and Turbulent Region

Summary: Non‐Newtonian fluid behavior has significant influence on quantities in chemical engineering like power input, mixing time, heat transfer etc. In the laminar flow region, the concept of effective viscosity by Metzner and Otto is well established. In the transition region between laminar and turbulent flow, the existing concepts use three and even more empirical parameters to determine the specific power input. Here, a unified and general but simple approach is introduced to calculate the power input for shear thinning fluids over the whole flow region using just one empirical parameter. The Metzner‐Otto relation is obtained as a limiting case for the laminar region. The empirical parameter of the new approach is related to the Metzner‐Otto constant. The concept is validated for eight different stirrer systems. Mixing time and maximum shear rate and heat transfer can also be calculated using this approach. The new concept presented should also be applicable for other apparatuses, e.g., static mixers.

Comparison of experimental data and a curve calculated according to the new method (solid line).