The solid and thermally instable azoinitiators V‐65 and VR‐110 were embedded within a polymer particle by using the miniemulsion process and afterwards quickly decomposed by thermal treatment below the glass temperature of the polymer. The resulting nitrogen gas overpressure inside the particles leads to a disruption of the polymer particle and a possible sudden release of encapsulated substances. It is shown, by electron microscopic measurements, that the number of burst particles correlates with the applied temperatures as well as the heating time. The surface deformation could be verified by scanning electron microscope analyses.
Two novel cationic RAFT agents, PCDBAB and DCTBAB, were anchored onto MMT clay to yield RAFT‐MMT clays. The RAFT‐MMT clays were then dispersed in styrene where thermal self‐initiation polymerization of styrene to give rise to exfoliated PS/clay nanocomposites occurred. The RAFT agents anchored onto the clay layers successfully controlled the polymerization process resulting in controlled molecular masses and narrow polydispersity indices. The nanocomposites prepared showed enhanced thermal stability, which was a function of the clay loading, clay morphology, and slightly on molecular mass.
A facile and easily industrialized approach for preparing highly dispersed MMT/polymer nanocomposites is developed by combining the latex compounding method and a spray‐drying process. Clay particles are successfully delaminated into layers, and layer re‐stacking is effectively prevented. HR‐TEM and XRD results confirm that MMT layers achieve exfoliated or nearly exfoliated dispersion in both MMT/styrene‐butadiene rubber and MMT/PS nanocomposites. Compared with melt‐blended MMT/SBR composites, MMT/SBR nanocomposites prepared by this new strategy exhibit extremely high dynamic modulus.
In recent years TPS has attracted more and more research interest as a promising replacement for commodity polymers in some applications. In this paper, a novel manufacturing technology to produce PLA fiber reinforced biodegradable TPS composite, and the microstructure and tensile properties of the composite, were first reported. PLA micro/sub‐micro fibers were generated in situ by elongational flow during die extrusion and subsequent hot stretching. The addition of 10% PLA significantly increased the drawability of TPS. Compared to direct extrusion, hot stretching tripled the tensile strength of the composite to 34 MPa. Extensive PLA fibrillation was evident in the composite. The generated PLA fibers measured ca. 400 nm in diameter with a large L/D ratio.
The influence of the functionalization of fully condensed POSS cages on the properties of POM‐based nanocomposites is studied. POSS with different organic substituents [glycidylethyl, aminopropylisobutyl, and poly(ethylene glycol)] are taken into account and melt mixed with POM. Good dispersion was achieved upon the addition of amino functionalized POSS, leading to an increase on the thermal decomposition temperature under nitrogen atmosphere up to 50 °C. However, µm‐size aggregates were observed for other nanocomposites. There is no significant change in other thermal properties of the nanocomposites. The relationships among these effects and the morphological characteristics of the systems were analyzed.
A new technique for design and preparation of self‐reinforced starch films is introduced. The films were based on a high‐amylose corn starch that was chemically modified in different ways. Hydroxypropylation was used to decrease gelatinization temperature and improve processability. The reinforcing component consisted of cross‐linked starch granules, where the crosslinking increased granule thermal stability and moisture resistance. Distribution of the cross‐linked starch was imaged by CLSM, and the matrix/particle interface was studied by SEM. Modulus and tensile properties of the starch film were increased by about 30 and 20%, respectively, after addition of rigid cross‐linked starch particles. A perfect interface between matrix and reinforce agent was obtained.
Fully exfoliated PS/clay nanocomposites were prepared via FRP in dispersion. Na‐MMT clay was pre‐modified using MPTMS before being used in a dispersion polymerization process. The objective of this study was to determine the impact of the clay concentrations on the monomer conversion, the polymer molecular weight, and the morphology and thermal stability of the nanocomposites prepared via dispersion polymerization. DLS and SEM revealed that the particle size decreased and became more uniformly distributed with increasing clay loading. XRD and TEM revealed that nanocomposites at low clay loading yielded exfoliated structures, while intercalated structures were obtained at higher clay loading.
Chemical modification of EVOH in the molten state at 185 °C by a grafting from process of poly(ε‐caprolactone) in batch was studied. 1H NMR was used to characterize the structure evolutions of PCL grafts. In addition to grafting reactions, dynamic covalent transesterification reactions between EVOH residual alcohols and the polyester grafts led to a redistribution of the PCL grafts length. up to 27 and SR up to 80% were obtained. Experiments made in a corotating mini twin‐screw extruder also confirmed these results. The effect of the alcohol to caprolactone ratio and catalyst concentration (SnOct2) on kinetic evolution showed that few minutes were necessary to complete the polymerization. A kinetic model was proposed and adequate conditions for the synthesis by reactive extrusion were defined.
This study concerns with the investigation of the effect of irradiation conditions on grafting of styrene into FEP films by the pre‐irradiation method. EPR spectroscopy was used to characterize the base polymer material regarding the trapped radical species and their concentration. Radiation‐induced changes in the chemical structure were studied by IR spectroscopy. Tensile strength and elongation at break as well as yield of grafting were found to be strongly influenced by irradiation temperature. Main‐chain scissions were identified to be the reason for the deterioration of the mechanical properties after radiation treatment at temperatures below glass transition temperature.
The application of computationally inexpensive modeling methods for a predictive study of powder mixing is discussed. A multidimensional population balance model is formulated to track the evolution of the distribution of a mixture of particle populations with respect to position and time. Integrating knowledge derived from a discrete element model, this method can be used to predict residence time distribution, mean and relative standard deviation of the API concentration in a continuous mixer. Low‐order statistical models, including response surface methods, kriging, and high‐dimensional model representations are also presented. Their efficiency for design optimization and process design space identification with respect to operating and design variables is illustrated.
The first reported use of two‐dimensional mesh thermoplastic fibers in an epoxy matrix for mendable composites is presented, yielding 100% restoration of GIC, failure energy, and peak loads over repeated damage‐healing cycles. SEM imaging and EDS mapping showed different surface structures between CFRPp and CFRPf and confirmed strength recoveries were attained by delivery of EMAA to the fracture plane which enabled the fractured surfaces to rebind after heating to 150 °C for 30 min.
Polymerization rate and copolymerization parameters of the free‐radical copolymerization of AMPS with 1‐VIm was studied as a function of the monomer feed and the pH value in ethanol. It was found that neutral and basic monomer mixtures containing the sodium salt of AMPS polymerized faster and led to polymers with a higher proportion of NaAMPS incorporated than those monomer mixtures containing the free acid. Additionally, based on the experimental data, copolymerization parameters of rAMPS = 0.3 and r1‐VIm = 0.13 were calculated for polymerization in acidic solution and rAMPS = 4.1 and r1‐VIm = 0.1 for polymerization in basic and neutral solutions. Finally, the thermal stability, rheological behavior, and intrinsic viscosity were determined for the polymers.
Biodegradable hyperbranched poly(ester amide) (HBP) was used as a compatibilizer to modify PLA/SiO2 nanocomposites for the first time. The ternary composites displayed dramatically improved mechanical properties including excellent toughness and fairly high stiffness. TEM images revealed that an encapsulation structure was formed by HBP surrounding SiO2 nanoparticles, and their surfaces became flocculent due to the migration process of silica. The linear viscoelastic behavior of the nanocomposites measured by parallel plate rheometer indicated that strong interface adhesion existed between PLA matrix and silica nanofiller after incorporating of HBP. The compatibilization effect of HBP and the enhanced mobility of nanoparticles contributed to the improved mechanical properties.
Toughness enhancement of S‐(S/B)‐S triblock copolymers via a molecular‐weight‐controlled pathway is demonstrated. The post‐yield crack toughness behavior of the triblock copolymers uniquely reveal a brittle‐to‐semiductile‐to‐ductile transition with increasing while keeping the basic molecular architecture fixed. TEM and SAXS investigations indicated three distinct morphologies as a function of χeffN as a consequence of the increase in : (i) a homogeneous structure without phase‐separation, (ii) a weakly segregated structure, and (iii) a lamellar structure. The increase in crack toughness is also reaffirmed from kinetic and strain field analysis studies concerning dynamics of crack growth in block copolymers with high PS content.
Improving the conductivity of electrospinning solutions is often achieved by adding small amounts of conductive additives. HMIMCl, a room temperature ionic liquid, and TEBAC, a quaternary ammonium salt, were added to polylactic acid in chloroform and their effects on solution properties, electrospinning, and fiber properties were investigated. Both additives increased the conductivity which decreased the fiber diameter, but differences were observed on the fiber dispersity and fiber morphology. The conductive solutions caused fiber backbuilding with aggregation and fiber fusion. Reasons for the differences in fiber diameter and fiber morphology are discussed.
Microcellular biodegradable polymer foam with an open porous structure was prepared from amorphous poly‐L,D ‐lactic acid (PL ,D LA) blended with polystyrene (PS), or polymethyl methacrylate (PMMA). The blends were prepared by polymerizing either styrene or methyl methacrylate (MMA) in a PL ,D LA matrix. The styrene and MMA monomers are good cell‐opening agents and constituents for an IPN. Pressure‐quench batch foaming was conducted using carbon dioxide as a foaming agent at 80 °C under 10 MPa. The effects of monomers and a cross‐linking agent on the foamability and OCC were investigated. Manipulation of the monomer and the cross‐linking agent concentrations was able to change the viscoelasticity and partial miscibility of the blend and control the cell size at the micron scale as well as open pore content in the range of 20–90%.
Silane coatings with different thicknesses were synthesized on CNFs for reinforcement of polyethylene composites. The thickness of the silane coating was adjusted by using a basic catalyst to increase the overall reactivity of the silane groups, resulting in a thick coating of ≈46 nm (ca. 90% increase in fiber diameter). DMA performed on the polyethylene composites showed a substantial increase in storage modulus from 1.68 to 2.34 GPa (40%) at low temperatures in the composite with the thick silane coating (≈46 nm) at a low loading of 0.4 wt.‐%. We believe that the silane‐treated nanofillers with thick coatings are very promising for high‐performance nanocomposites with non‐polar polymer matrices.
The inherent properties of poly(lactide), a biocompatible and biodegradable polymer, are concurrently improved by the incorporation of a small amount of surface functionalized carbon nanotubes. A new method has been used to functionalize the CNTs' outer surface with hexadecylamine. A composite of PLA with functionalized CNTs has been prepared by melt‐extrusion. FT‐IR spectroscopy, Raman spectroscopy, DSC, and optical microscopy are used to investigate the thermal and mechanical property improvement mechanism in f‐CNTs containing PLA composite.
In this study, the sol‐gel transition temperature of a thermosensitive chitosan system was measured using SAOS, in‐real time FTR and multi‐frequency SAOS excitation. From FT analysis, we found that the intensity of the harmonics stayed constant while the chitosan system remained in the solution state, while it increased passed the gelation point. Multi‐frequency SAOS excitation was also carried out using a summation function of sine waves that allowed performing the measurements in the LVR. This last technique could determine the unique (frequency independent) critical sol‐gel transition temperature, and was found to be less tedious than the application of the traditional Chambon and Winter's method.
The role of polymer/filler interactions on the mechanical and electrical properties of elastomer nanocomposites is analyzed using dielectric spectroscopy, cyclic stress/strain tests, and online dc‐conductivity measurements. Pristine and deactivated (graphitized) CBs are studied in different rubber matrices. Due to confinement effects, an interphase of strongly immobilized polymer is present between adjacent filler particles, representing stiff but flexible mechanical bonds of the filler network. Under deformation of the sample, these bonds bend and finally break. Cyclic stress/strain measurements are analyzed by fitting the data to a microstructure‐based material model that allows for the evaluation of microscopic parameters of the polymer and filler network.
