Low density polyethylene (LDPE) was prepared into micro‐ or submicro‐spheres or nanofibers via melt blending or extrusion of cellulose acetate butyrate (CAB)/LDPE immiscible blends and subsequent removal of the CAB matrix. The sizes of the PE spheres or fibers can be successfully controlled by varying the composition ratio and modifying the interfacial properties of the blends. The surface structures of LDPE micro‐ or submicro‐spheres and nanofibers were analyzed using SEM and FTIR‐ATR spectroscopy. In addition, the crystalline structures of the LDPE nanofibers were characterized.
Temperature‐responsive PVCL homopolymers and functional PVCL polymers containing carboxylic acids are prepared in organic and aqueous solutions. PVCL bulk polymers are characterized using 1H NMR, photometry, ATR‐FTIR, and thermal analysis. A finite phase transition at 37–40 °C occurs in aqueous solutions of PVCL and PVCL‐COOH. PVCL and PVCL‐COOH polymers are electrospun into fibers ranging from 100 to 2300 nm in diameter. PVCL/cellulose bi‐component films are obtained by electrospinning of CA and PVCL followed by alkaline hydrolysis. These tunable thermo‐responsive PVCL/cellulose nanofibers have potential applications in developing affinity membranes.
TMC/LLA copolymers with several TMC/LLA ratios are synthesized and a composite is obtained by reinforcing with short PLGA fibers. In vitro degradation is studied at 37 °C in pH = 7.4 buffer and compared with a PLLA homopolymer. The degradation of the copolymers appears slower than that of PLLA, showing that TMC units are more resistant to hydrolysis than LLA. Compositional changes indicate a preferential degradation of LLA units as compared to TMC ones. Morphological changes with crystallization of degradation by‐products are observed. The composite degrades much faster than the neat copolymer and PLLA because the faster degradation of PLGA fibers speeds up the degradation of the matrix. The composite appears promising for the fabrication of totally bioresorbable stents.
A new class of PLGA‐based materials suitable for the production of biodegradable NPs via free‐radical polymerization is proposed. ROP of lactide and glycolide using HEMA is carried out; macromonomers (HEMA‐LxGyA) with short PLGA chain ends are successfully produced. Afterwards, monomer‐starved semi‐batch emulsion polymerization of these HEMA‐LxGyA macromonomers is performed to obtain NPs with a low polydispersity index and a controlled size. The stability and degradability of NPs is confirmed from degradation studies that verify the possibility of tuning the degradation time by changing macromonomer characteristics such as chain length and composition.
A new completely biodegradable shape‐memory elastomer consisting of PLLCA reinforced by in situ PGA fibrillation is described. The manufacturing processes and shape‐memory effects of the composites are discussed. DMA results reveal a strong interface interaction between in situ PGA fibrillation and PLLCA. Compared with the SMP‐based composites that are commonly used, the shape‐memory test shows that in situ PGA fibrillation can improve the recovery properties of PLLCA; in fact, the shape‐recovery rate increases from 80.5 to 93.2%.
In order to enhance the molecular orientation of electrospun nanofibers, a novel collection technique is proposed and applied to the spinning of polyethylene from high temperature solution. The technique makes use of a parallel‐electrode collector that acts before solidification of the fiber occurs. The resulting multiple‐necking morphology is composed of fine nanofibrils with very small diameter and narrow size distribution. The crystalline orientation of the nanofibrils was analyzed by TED. The formation mechanism of the nanofibrils is discussed. The strong elongational effect of the electric‐field‐induced stretching force in the parallel‐electrode collector is demonstrated by the orientational analysis and by observation of the multiple‐necking morphology.
Continuous and uniform yarns of thermoplastic nanofibers were prepared via direct melt extrusion of immiscible blends of thermoplastic polymers with CAB and subsequent extraction removal of CAB. Ratios of thermoplastic/sacrificial polymers, melt viscosity, and interfacial tensions affect the formation of nanofibers. Dominating sacrificing polymer content in the blends and low interfacial tensions between thermoplastic polymer and CAB are two key factors. This fabrication process possesses features of high productivity, versatility of thermoplastics, controllability, and environment friendliness in manufacturing thermoplastic nanofibers.
A blend composition of poly(3‐hydroxybutyrate‐co‐valerate) and polylactide is used as a bioplastic matrix and reinforced with soy hull to engineer novel green composites. A comparative study with soy‐hull‐reinforced polypropylene composite system is performed. A compatibilizer is used to engineer the novel class of green composites with a balanced stiffness and toughness performance with the target to substitute PP‐based composites. The flexural and impact strength along with hydrophobicity of compatibilized composites are improved significantly over the noncompatibilized counterpart. The fiber/matrix interaction is investigated by SEM. These green composites have the potential to substitute PP‐based composites in some applications.
This work aims at improving the interfacial bonding between polyamide‐12 and CNFs. CNFs were oxidized and dispersed in polyamide‐12 giving rise to polymer nanocomposites. The oxidation caused an increase in the specific surface area and structural defects of the fibers, as indicated by surface area and Fourier‐transform Raman spectroscopy. The nanocomposites exhibited improved thermal and thermo‐oxidative stabilities. The oxidized nanofibers had marginal effect on the crystallinity and crystallization of the polyamide‐12. An over‐proportional enhancement of stiffness due to the fibers could be achieved. In spite of these improvements the fiber/polymer adhesion should be further improved.
A novel method is described to functionalize nanofibers to form a nanocomposite with core/shell particles in order to control protein release. The nanocomposite is produced by electrically neutralizing negatively charged poly(lactic acid) nanofibers with positively charged poly[(lactic acid)‐co‐(glycolic acid)] particles via a one‐step electrohydrodynamic jetting process. The protein‐encapsulated core/shell particles exhibited no significant initial burst release or denaturation. The protein release profile was controlled by porosity and protein/polymer interactions. The method may be promising to engineer intelligent scaffolds that can fulfill the needs of biomimetic materials.
Poly(lactic acid) plasticized with 15 and 20 wt.‐% of polyadipate was melt‐blended with different amounts of an O‐MMT (1–5 wt.‐%) to prepare nano‐biocomposites. The effect of plasticizer and nanofiller contents on the morphology and on thermal, mechanical and barrier properties of PLA‐based nano‐biocomposites was evaluated in order to understand their structure‐properties relationships. The oxygen transmission rate was notably reduced (around 45%) with increasing amount of clay due to an increased tortuosity. However, for clay concentrations above 3 wt.‐%, a significant detriment in ductile properties could also be observed. For a given amount of nanofiller, the increasing plasticizer concentration improved the clay dispersion through the polymeric matrix.
The thermal behavior of cellulose dissolved in ionic liquids was studied in comparison to NMMO solutions. The cellulose solutions were characterized by reaction calorimetry and UV‐vis spectroscopy. Generation of chromophoric substances in cellulose/IL solutions is minimized by exposing to temperatures of above 100 °C for longer time periods. Dynamic calorimetric investigations revealed first thermal activities above 180 °C applying EMIMac and above 200 °C for BMIMCl and five other ILs tested. Moreover, even in the case of modified cellulose/IL solutions, e.g., activated charcoal, only a slight decline of onset temperatures was registered compared to modified cellulose/NMMO solutions.
A variety of polymer parts used in microsystems technology is produced by injection molding. For dimensioning and design of these products, both the material properties and changes during the life cycle have to be taken into account. The aging behavior of parts with decreasing dimensions or of parts processed under different cooling conditions is discussed in terms of their morphological and mechanical long‐term properties. The results indicate that a decreasing part size leads to higher post‐crystallization and higher thermo‐oxidative degradation. This leads to size‐dependent changes in mechanical properties. Adjusted process conditions by application of thermal low‐conductive mold materials can favor the process‐related properties and thus the long term properties can be improved.
A method that combines UV irradiation and pausing was developed to manipulate the regularity and the length scales of the morphology generated by phase separation in full‐interpenetrating polymer networks of polystyrene and poly(methyl methacrylate). Upon increasing the pause time of photopolymerization and photo‐crosslink processes, the morphology gradually changes from hexagonal‐like packing to random structures. The width of the loss tan δ obtained for these phase‐separated materials changes with the morphological regularity, suggesting a potential technique for fabrication of mechanical bandgap materials.
The influence of talc loading on phase morphology of PLA/PCL/talc composites and improvement in resulting properties are reported. Talc‐based composites of PLA/PCL blends were prepared by melt blending. SEM analysis demonstrates that PLA appears as discrete domain phase, while PCL acts as a bulk phase in the blend. Talc addition decreases PLA domain sizes and voids in the matrix. This results in significant improvement of oxygen and water vapor barrier properties of composite by 33 and 25%, respectively, at 3 wt.‐% talc loading. DSC shows that talc acted as nucleating agent for PCL phase in the composite and improves its crystallinity. Various theoretical models based on dispersion and filler geometry are used to predict the tensile modulus and oxygen permeability.
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.
The formation of an integral asymmetric membrane composed of a cylinder‐forming polystyrene‐block‐poly(2‐vinylpyridine) on a nonwoven by using solvent casting followed by solvent/nonsolvent exchange (phase inversion) is reported for the first time. The influence of parameters such as solvent composition, evaporation time of the solution‐cast block copolymer film before phase inversion, and immersion bath temperature is demonstrated. The optimized membranes are characterized in terms of stimuli‐responsive water flux properties. The morphologies of the membranes as well as of the bulk of the block copolymer are imaged by scanning force microscopy, scanning electron microscopy, and transmission electron microscopy.
Low‐crystalline random and gradient P(EO‐co‐PO) copolymers and amorphous PPO and PBO of high molecular weight were synthesized by anionic coordination polymerization. Polymer gel electrolytes based on these (co)polymers were prepared and tested for long‐term performance of DSSC. The DSSC based on P(EO‐co‐PO) copolymers have longer life time compared to the homo‐PEO‐ and homo‐PPO‐based DSSC, respectively. The cells containing the chemically crosslinked copolymer gel exhibited a high efficiency of 6% after 25 d performance, whereas the solar cells based on physically crosslinked copolymer gel showed fast degradation.
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.
The effect of a rigid filler on the elastic properties of starch‐based composites is investigated. Thermomolding of the targeted composite is conducted using a starch matrix with varying silicone carbide content. Mechanical testing reveals that the composite's Young modulus cannot be rationalized using two‐phase analytical models. The effect of a weak interphase region is highlighted using a finite‐element model that assumes the generation of virtual microstructures. Numerical results are discussed by describing the influence of the structural and interphase parameters on the composite's elastic modulus. Identification of optimal interphase parameters quantitatively demonstrates the weak adhesion between intrinsic phases for all studied filler fractions.
