A comparison of theoretically determined and experimentally measured velocity distributions of poly(ethylene terephthalate) flow in a capillary

A streak photographic technique was used to determine the velocity distribution in a capillary produced by the flow of poly(ethylene terephthalate) (PET). This uniquely designed quartz die assembly, which was fitted onto a melt extruder, permitted visualization of polymer flow behavior during melt spinning. Aluminum tracer particles were mixed with polymer chips prior to extrusion. A laser beam was directed through a lens system that illuminated the tracer particles in the melt only in a thin, vertical cross section of the transparent quartz die. A pressure-drop analysis was also performed on PET, under the same experimental conditions, to determine rheological properties of the polymer. By using these rheological properties theoretical velocity distributions were calculated for PET and then compared with the profiles obtained by the streak photographic technique.     

A novel method for making ultra-fine metal fibers and particles

A novel method based on plastic processing and equipment for preparing ultra-fine metal fibers and particles is reported. With this new method, metal fibers and particles can both be produced on the same equipment and the surfaces of the fibers and particles can be protected from oxidation by the polymers or solvents during the preparation process. Metal-alloy powders with lower melt point were filled into polymer by an extruder, followed by a die-drawing process at a temperature lower than the melt temperature of the metal alloy. Metal fibers or particles were obtained after the polymer matrix was washed away. Metal alloy fibers can be obtained when a polymer that strongly interacts with metal alloy, such as a special polyvinyl alcohol with a low alcoholysis degree, is used as the polymer matrix. Metal-alloy particles can be obtained when a polymer with weak interaction with metal alloy, such as polyethylene (PE), is used as the polymer matrix. Based on the principle of this new method, it is possible to produce finer or even nano-sized metal fibers and particles with higher melting points.     

Polypyrrole containers grown on oil microdroplets: encapsulation of fluorescent dyes

Polypyrrole microcapsules were synthesized by the chemical deposition of the polymer onto mineral oil droplets adsorbed onto glass or quartz substrates. The droplets act as a kind of a template that directs the polymer growth into the form of three-dimensional containers. The polymer is deposited on both the surface of oil droplets and the glass or quartz substrate entrapping the oil content. The dissolution of chemical species in oil prior to polymer deposition permits the encapsulation of these species within the cavities of the containers. This phenomenon was demonstrated through the entrapment of the fluorescent dyes, pyrene and perylene, within the polymeric capsules. It was shown that the entrapped molecules can be released from the capsules by controlling the hydration of the polymer, which in turn changes the permeability of the oil content through the polypyrrole shells. The polymer growth and encapsulation phenomena were investigated with a range of complementary physicochemical techniques, including microscopic (AFM, SEM, and confocal microscopy) and spectroscopic (steady-state fluorescence and UV-vis absorption) methods. In particular, the use of optical methods was possible due to the deposition of the capsules on transparent substrates (glass, quartz). As a consequence, the optical information on the interior of the capsules was accessible, for example, dye concentration and local polarity.     

Functional inorganic nanofillers for transparent polymers

The integration of inorganic nanoparticles into polymers has been used for the functionalization of polymer materials with great success. Whereas in traditional polymer composites, micron sized particles or agglomerates typically cause significant light scattering hampering optical applications, in nanocomposites the particle dimensions are small enough for the production of highly transparent composites. A challenge for the generation of such materials is to develop an integrated synthesis strategy adapting particle generation, surface modification and integration inside the polymer. Surface grafting using polymerizable surfactants or capping agents allows for linking the particles to the polymer. Novel techniques such as in situ polymerization and in situ particle processing are beneficial to avoid aggregation of inorganic particles inside the polymer matrix. The functions associated with inorganic fillers are widespread. Layered silicates and related materials are nowadays commercially available for improving mechanical and barrier properties in packaging. With the availability of highly transparent materials, the focus has shifted towards optical functions such as luminescence and UV-protection in transparent polymers. IR-active fillers are used in laser-holography for transparent poly(methyl methacrylate) (PMMA) nanocomposites. Refractive index modulation and ultrahigh refractive index films were developed based on inorganic materials such as PbS. The integration of magnetic nanoparticles has a great potential for applications such as electromagnetic interference shielding and magneto-optical storage.This tutorial review will summarize functions associated with the integration of inorganic nanofillers in polymers with a focus on optical properties.     

Nanocomposites of polymers and metals or semiconductors: Historical background and optical properties

Upon transmission of visible light through composites comprising of a transparent polymer matrix with embedded particles, the intensity loss by scattering is substantially reduced for particle diameters below 50–100 nm (nanoparticles, nanosized particles). As a consequence, related materials (nanocomposites) have found particular interest in optical studies. The first part of this article deals with a historical survey on nanoparticles and nanocomposites and the importance of small particle sizes on their optical properties. The second part focuses on results from our laboratory concerning nanocomposites with extremely high or low refractive indices and dichroic nanocomposites and their application in bicolored liquid crystal displays (LCD). The inorganic colloids required for these studies (lead sulfide, iron sulfides, gold, and silver) were prepared in situ in presence of a polymer or isolated as redispersable metal colloids modified at the surface with a self‐assembled monolayer (SAM) of an alkanethiol. The nanocomposites themselves were finally obtained by coprecipitation, spin coating, solvent casting or melt extrusion, with poly(ethylene oxide), gelatin, poly(vinyl alcohol) and polyethylene as matrix polymers.     

Study on the melt entry flow characteristics in axisymmetric dies with abrupt contraction by a visualization technique

The die entry characteristics of low density polyethylenes (LDPE) were studied using a 45 mm diameter single-screw extruder. The extruder incorporated a “transparent” die to enable direct visualization to be performed. With the addition of a small percent of red colour masterbatch into the main polymer bulk, melt circulation near the die entry at the wall was clearly observed. The dynamic behaviour of the polymer melt was recorded by a digital video recorder. Upon replaying the films, detailed qualitative and quantitative analysis of the flow characteristics was made. The die entry performance was defined by the dimensionless vortex size which was found to be most susceptible to the contraction ratio of a die. It was found that temperature and length to diameter ratio had little or no effects on the dimensionless vortex size which, in turn, may be estimated by either of the two correlations (one based on theory whereas the other was obtained from curve-fitting) developed.     

High‐pressure rheology of polystyrene melts plasticized with CO2: Experimental measurement and predictive scaling relationships

A high‐pressure extrusion slit die rheometer was constructed to measure the viscosity of polymer melts plasticized by liquid and supercritical CO₂. A novel gas injection system was devised to accurately meter the follow of CO₂ into the extruder barrel. Measurements of pressure drop, within the die, confirm the presence of a one‐phase mixture and a fully developed flow during viscosity measurements. Experimental measurements of viscosity as a function of shear rate, pressure, temperature, and CO₂ concentration were conducted for three commercial polystyrene melts. The CO₂ was shown to be an effective plasticizer for polystyrene, lowering the viscosity of the polymer melt by as much as 80%, depending of the process conditions and CO₂ concentration. Existing theories for viscoelastic scaling of polymer melts and the prediction of T_g depression by a diluent were used to develop a free volume model for predicting the effects of CO₂ concentration and pressure on polymer melt rheology. The free volume model, dependent only on material parameters of the polymer melt and pure CO₂, was shown to accurately collapse the experimental data onto a single master curve independent of pressure and CO₂ concentration for each of the three polystyrene samples. This model constitutes a simple predictive set of equations to quantify the effects of gas‐induced plasticization on molten polymer systems. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3168–3180, 2000     

NEW FLUOROSILOXANE AS A COATING MATERIAL FOR NERVE AGENT SENSORS

Polymer coated quartz crystal microbalance （QCM） sensor based on the frequency shifts due to the adsorption of compounds at the surface of modified quartz crystal electrode is an effective method for detection of sarin （GB） which is a highly toxic nerve warfare agent. A new fluorosiloxane polymer has been synthesized through 6 steps from trifluoromethyl benzene. The synthesis was achieved from trifluoromethyl benzene through nitration, hydrogenation. The obtained m-nitrotrifluoromethyl aniline was treated with NANO2, and then hydrolyzed to m-nitrotrifluoromethyl phenol, m-nitrotrifluoromethyl phenol was reacted with allyl bromide to the ether product. The product was rearranged by Claisen rearrangement, and then reacted with polymethylhydrosiloxane under catalyst of Pt/DVTMS. The fluorosiloxane polymer can be obtained. The polymer has been successfully used as QCM coating material     

Die swell ratio of polystyrene melt from an electro‐magnetized capillary die in an extrusion rheometer: effects of barrel diameter,shear rate and die temperature

A constant shear‐rate extrusion rheometer with an electro‐magnetized capillary die was utilized to investigate die swell behavior and flow properties of a polystyrene melt as the application of an electro‐magnetic field to the capillary die was relatively novel in polymer processing. The test conditions such as magnetic flux density, barrel diameter, extrusion rate and die temperature were studied. The results suggest that the maximum swelling of the polystyrene melt with application of the electro‐magnetic field could be enhanced up to 2.6 times (260%) whereas that without the electro‐magnetic field was 1.9 times (190%). The barrel diameter of 30 mm was found to be a critical value in the case of the die swell ratio and flow properties of the polystyrene melt were significantly affected by the magnetic flux density. This involved the number and angle of magnetic flux lines around the barrel part. Under the electro‐magnetic field, there were two mechanical forces influencing the die swell ratio and the flow properties; magnetic torque and shearing force. The die swell at wall shear rates less than 11.2 sec^?1 was caused by the magnetic torque, whereas at higher wall shear rates it was dependent on the shearing force. For a given magnetic flux density, the maximum increase in the die swell ratio as a result of the magnetic torque was calculated to be approximately 20%. Increasing the die temperature from 180 to 200°C reduced the overall die swell ratio and suppressed the effect of the magnetic flux density. Copyright © 2004 John Wiley & Sons, Ltd.     

Birefringence control by hydrogen bonding on compatible polymer pair composed of hydrogenated ring‐opening polymer and modified polystyrene

A new polymer blend composed of a hydrogenated ring‐opening polymer (HROP) with an ester group and hydroxyl functionalized polystyrene (HFP) produced the excellent transparent materials which enabled a precise birefringence control in keeping with the other physical properties for optical film use. The blend with a composition from 0.28 to 0.35 for the HFP weight fraction showed an extraordinary wavelength dispersion, transmitting through a zero birefringence point at the critical fraction of 0.45, while each polymer showed an ordinary wavelength dispersion. The observed excellent transparency even above those of the glass transition temperature was attributed to a depressed phase separation that resulted from strong hydrogen bond between the ester and hydroxyl groups. An IR analysis of the film demonstrated a remarkable red‐shift in the carbonyl peak with an increase of the hydroxylated polystyrene content, indicating a strong hydrogen bond between those groups. This new polymer blend provides a useful design to achieve practical demands for film use, both optical and mechanical under the fabrication conditions using the melt extrusion technique. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3132–3143     

Towards stationary phases for chromatography on a microchip: molded porous polymer monoliths prepared in capillaries by photoinitiated in situ polymerization as separation media for electrochromatography

Photoinitiated free radical polymerization has been used for the preparation of porous polymer monoliths within UV transparent fused silica capillaries and quartz tubes. These formats were used as models for the preparation of the separation media within channels of microfabricated devices. A mixture of ethylene dimethacrylate, butyl methacrylate, and 2-acrylamido-2-methyl-1-propanesulfonic acid was polymerized in the presence of a porogenic solvent consisting of 1-propanol, 1,4-butanediol, and water at room temperature under UV irradiation. Modification of the porogen composition enables the tailoring of pore size within the broad range from ca. 100 to 4000 nm. Scanning electron micrographs confirmed the homogeneity of the porous structure of the materials prepared, even in a quartz tube with a diameter as large as 4 mm. Separation properties of the resulting capillary columns were tested in capillary electrochromatography (CEC) mode using a mixture of thiourea and eight aromatic compounds. Plate number as high as 210 000 plates/m were found for a capillary column with optimized porous properties. The monolithic columns were also able to separate mixtures of peptides.     

Melt‐compounded nanocomposites of titanium dioxide atomic‐layer‐deposition‐coated polyamide and polystyrene powders

Polyamide and polystyrene particles were coated with titanium dioxide films by atomic layer deposition (ALD) and then melt‐compounded to form polymer nanocomposites. The rheological properties of the ALD‐created nanocomposite materials were characterized with a melt flow indexer, a melt flow spiral mould, and a rotational rheometer. The results suggest that the melt flow properties of polyamide nanocomposites were markedly better than those of pure polyamide and polystyrene nanocomposites. Such behavior was shown to originate in an uncontrollable decrease in the polyamide molecular weight, likely affected by a high thin‐film impurity content, as shown in gel permeation chromatography (GPC) and scanning electron microscope (SEM) equipped with an energy‐dispersive spectrometer. Transmission electron microscope image showed that a thin film grew on both studied polymer particles, and that subsequent melt‐compounding was successful, producing well dispersed ribbon‐like titanium dioxide with the titanium dioxide filler content ranging from 0.06 to 1.12 wt%. Even though we used nanofillers with a high aspect ratio, they had only a minor effect on the tensile and flexural properties of the polystyrene nanocomposites. The mechanical behavior of polyamide nanocomposites was more complex because of the molecular weight degradation. Our approach here to form polymeric nanocomposites is one way to tailor ceramic nanofillers and form homogenous polymer nanocomposites with minimal work‐related risks in handling powder form nanofillers. However, further research is needed to gauge the commercial potential of ALD‐created nanocomposite materials. Copyright © 2011 John Wiley & Sons, Ltd.     

聚合物纳米微粒静电组装行为及其表征

使用2,2′-偶氮二异丁基脒二盐酸盐自由基引发剂,改变甲基丙烯酰氧乙基十六烷基二甲基溴化铵阳离子功能单体的量与苯乙烯进行乳液聚合获得不同粒径的阳离子乳胶粒,使用十二烷基硫酸钠为乳化剂和过硫酸钾为引发剂制备阴离子聚合物乳胶粒.采用基于静电相互作用的异凝聚法将以上2种带有相反电荷的乳胶粒组装,获得了表面粗糙程度不同的复合微粒.对异凝聚过程中复合液透光率和微粒大小及分布进行跟踪测试,并用透射电子显微镜表征了阳离子微粒、阴离子微粒以及复合微粒的形态和大小.结果表明,在一定范围内可以通过控制阴离子乳胶粒与阳离子乳胶粒的复合比例改变单个复合微粒表面阳离子小微粒的数目.     

Monte Carlo simulation of structure and nanoscale interactions in polymer nanocomposites

Off-lattice Monte Carlo simulations in the canonical ensemble are used to study polymer-particle interactions in nanocomposite materials. Specifically, nanoscale interactions between long polymer chains (N=550) and strongly adsorbing colloidal particles of comparable size to the polymer coils are quantified and their influence on nanocomposite structure and dynamics investigated. In this work, polymer-particle interactions are computed from the integrated force-distance curve on a pair of particles approaching each other in an isotropic polymer medium. Two distinct contributions to the polymer-particle interaction potential are identified: a damped oscillatory component that is due to chain density fluctuations and a steric repulsive component that arises from polymer confinement between the surfaces of approaching particles. Significantly, in systems where particles are in a dense polymer melt, the latter effect is found to be much stronger than the attractive polymer bridging effect. The polymer-particle interaction potential and the van der Waals potential between particles determine the equilibrium particle structure. Under thermodynamic equilibrium, particle aggregation is observed and there exists a fully developed polymer-particle network at a particle volume fraction of 11.3%. Near-surface polymer chain configurations deduced from our simulations are in good agreement with results from previous simulation studies.     

Polymer sheets with a thin nanocomposite layer acting as a UV filter

A surface layer (thickness 1–10 μm) containing colloidal TiO₂ or ZnO particles was prepared in EVA (a copolymer of ethylene and vinyl acetate). The inorganic particles were formed in situ by hydrolysis of incorporated titanium tetrachloride or diethyl zinc. The resulting materials were analyzed with UV spectroscopy, electron microscopy, X-ray diffraction, thermogravimetric analysis and atomic emission spectroscopy. The average diameter of the embedded TiO₂ particles was 70 nm; these particles absorb UV radiation but also induce opacity in the polymer sheets in the visible wavelengths range. The ZnO particles were smaller (average diameter 15 nm); with a surface layer of embedded ZnO, transparent polymer sheets can be obtained that absorb UV radiation. © 1997 John Wiley & Sons, Ltd.     

基于分子印迹技术的丙溴磷压电石英晶体微天平研制

介绍了一种用于检测丙溴磷农药的分子印迹压电生物传感器的构建方法。采用沉淀聚合法合成了农药丙溴磷的分子印迹聚合物,将其固定于石英晶体微天平电极表面构建传感器;采用环境扫描电镜以及原子力显微镜对聚合物形貌、传感器电极表面形貌特征进行分析,并利用传感器对丙溴磷农药进行检测分析,其质量浓度在10~1000 ng/mL范围内,传感器频率改变与丙溴磷浓度之间的响应呈线性关系,线性方程为y=0.139ρ+2.26(r=0.9984)。结果表明,构建的分子印迹压电生物传感器能够对农药进行初步检测,具有较高的灵敏性和较好的特异识别能力。     

Size‐selective purification of hepatitis B virus‐like particle in flow‐through chromatography: Types of ion exchange adsorbent and grafted polymer architecture

Hepatitis B virus‐like particles expressed in Escherichia coli were purified using anion exchange adsorbents grafted with polymer poly(oligo(ethylene glycol) methacrylate) in flow‐through chromatography mode. The virus‐like particles were selectively excluded, while the relatively smaller sized host cell proteins were absorbed. The exclusion of virus‐like particles was governed by the accessibility of binding sites (the size of adsorbents and the charge of grafted dextran chains) as well as the architecture (branch‐chain length) of the grafted polymer. The branch‐chain length of grafted polymer was altered by changing the type of monomers used. The larger adsorbent (90 μm) had an approximately twofold increase in the flow‐through recovery, as compared to the smaller adsorbent (30 μm). Generally, polymer‐grafted adsorbents improved the exclusion of the virus‐like particles. Overall, the middle branch‐chain length polymer grafted on larger adsorbent showed optimal performance at 92% flow‐through recovery with a purification factor of 1.53. A comparative study between the adsorbent with dextran grafts and the polymer‐grafted adsorbent showed that a better exclusion of virus‐like particles was achieved with the absorbent grafted with inert polymer. The grafted polymer was also shown to reduce strong interaction between binding sites and virus‐like particles, which preserved the particles’ structure.     

Hydrophobic and Melt Processable Starch-Laurate Esters: Synthesis,Structure–Property Correlations

A controlled esterification of starch to replace the  OH moieties with bio-derived medium chain fatty acids, and the changes in the polymer structure and properties for material applications is investigated in this research. The esterification is conducted via a homogeneous esterification process using an activated lauric acid (C₁₂) in the presence of a base catalyst. The degree of esterification through the replacement of hydroxyl groups of starch was estimated using elemental analysis (EA) and proton NMR. The effect of the modification on the structural and material properties of the modified starch polymer is elucidated by evaluating the changes in morphology, network thermal stability, hydrophobicity, solubility profile, and thermal transition events. Scanning electron microscopy imaging reveals structural changes ranging from surface roughness to complete disruption depending on the degree of substitution. This is confirmed by XRD. Because of the esterification of starch, the resulting polymers become melt processable thermoplastic that forms a transparent film with an elastic storage modulus of up to 226 MPa at room temperature. This shows that the starch–fatty acid polymer can be used for various industrial and advanced material applications without any other plasticizers or modifiers. The final material is completely bio-based, and is expected to be biodegradable in the environment. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2611–2622     

Sustainable composites of surface-modified cellulose with low–melting point polyamide

The present study proposed a series of sustainable polyamide/cellulose composites with up to 60% bio-based content to address environmental issues arising from using fossil-based polymers. Furthermore, it addressed one of the most challenging cellulose/polymer composites' issues, filler/matrix compatibility. Accordingly, the microcrystalline cellulose (MCC) surface was treated through the grafting of n-octadecyl isocyanate (ODI) molecules. The elemental analysis confirmed the substitution of approximately 9 ODI molecules per 100 anhydroglucose units, resulting in superhydrophobic MCC formation with a water contact angle of 130°. The surface-modified MCC was melt blended with a bio-based low–melting point polyamide, developed through copolymerization of 11-aminoundecanoic acid and 12-aminolauric acid. Scanning electron microscopy images confirmed no evidence of surface-modified MCC agglomeration, even at a high loading of 30 wt%, suggesting a uniform dispersion of the filler particles and excellent compatibility between two phases. Consequently, the storage modulus, tensile modulus, and yield stress were enhanced by 40%, 100%, and 50%, respectively, in the composite sample with 30 wt% of MCC, proving excellent stress transformation from the matrix to particles arose from good adhesion between cellulose particles and polyamide chains. Furthermore, all samples revealed suitable melt flowability and viscoelastic performances, suggesting their excellent processability, a critical property for engineered thermoplastics. On top of that, the presence of the surface-modified particles considerably decreased water uptake capacity and water vapor transmission of the polymer matrix, making it interesting for specific applications like packaging films.     

New method for post-processing crosslinking reaction

A new processing method to process functionalized polymer materials that are able to crosslink has been developed. The crosslinking reaction occurs after the melt processing stage at moderate temperature and without the addition of external reagents. Maleic anhydride-ethylene copolymer was processed with 1,4-butanediol in the presence of para-toluene sulfonic acid as catalyst. To prevent the reaction in the melt, it was chosen to trap the 1,4-butanediol onto vector particles. The extent of the crosslinking reaction during the mixing at 110 °C has been studied for three different particles taken as vector particles. It was found that Orgasol^® polyamide particles are efficient to inhibit the crosslinking reaction in the mixer. The reaction then takes place at 40 °C and after 100 h the cured samples appeared to be highly and homogeneously crosslinked with a gel content above 90%.