Partial to complete wetting transitions in immiscible ternary blends with PLA: the influence of interfacial confinement.

In this study it is shown that the three different intermediate phases in melt blended ternary PLA/PHBV/PBS, PLA/PBAT/PE and PLA/PE/PBAT systems all demonstrate partial wetting, but have very different wetting behaviors as a function of composition and annealing. The interfacial tension of the various components, their spreading coefficients and the contact angles of the confined partially wet droplets at the interface are examined in detail. A wetting transition from partially wet droplets to a complete layer at the interface is observed for both PHBV and PBAT by increasing the concentration and also by annealing. In contrast, in PLA/PE/PBAT, the partially wet droplets of PE at the interface of PLA/PBAT coalesce and grow in size, but remain partially wet even at a high PE concentration of 20% and after 30 min of quiescent annealing. The dewetting speed of the intermediate phase is found to be the principal factor controlling these wetting transitions. This work shows the significant potential for controlled wetting and structuring in ternary polymer systems.

Poly(ε-caprolactone) scaffolds of highly controlled porosity and interconnectivity derived from co-continuous polymer blends: model bead and cell infiltration behavior.

Porous structures destined for tissue engineering applications should ideally show controlled and narrow pore size distributions with fully interconnected pores. This study focuses on the development of novel poly(ε-caprolactone) (PCL) structures with fully connected pores of 84, 116, 141, and 162 µm average diameter, from melt blending of PCL with poly(ethylene oxide) (PEO) at the co-continuous composition, followed by static annealing and selective extraction of PEO. Our results demonstrate a low onset concentration for PEO continuity and a broad region of phase inversion. A novel in vitro assay was used to compare scaffold infiltration by 10-µm diameter polystyrene beads intended to mimic trypsinized human bone marrow stromal cells (hBMSCs). Beads showed a linear increase in the extent of scaffold infiltration with increasing pore size, whereas BMSCs infiltrated 162 and 141 µm pores, below which the cells aggregated and adhered near the seeding area with low infiltration into the porous device. While providing a baseline for non-aggregated systems, the beads closely mimic trypsinized cells at pore sizes equal to or larger than 141 µm, where optimal retention and distribution of hBMSCs are detected. A cytotoxicity assay using L929 cells showed that these scaffolds were cytocompatible and no cell necrosis was detected. This study shows that a melt blending approach produces porous PCL scaffolds of highly controlled pore size, narrow size distribution and complete interconnectivity, while the bead model system reveals the baseline potential for a homogeneous, non-aggregated distribution of hBMSCs at all penetration depths.

Physicochemical Limitations of Capillary Models Applied to High-Concentration Polymer Solutions.

Advances in binder jet printing (BJP) require the development of new binder-powder systems, for example, to increase compatibility with better performance metal alloys or to increase the strength of parts using stronger binders. The dynamics of binder absorption are principally understood through capillary models. However, validation of these models in BJP has focused on variation of powder properties. Using a design-of-experiments approach and an optical observation method to track absorption of droplets, this study tests the influence of fluid properties on absorption time against the predictions of capillary models. Properties specific to polymeric binders, such as molecular weight and entanglement state, are also considered. Capillary models are found to be generally accurate in predicting absorption time in dilute systems; however, these predictions are not accurate for highly concentrated binder solutions. The effect of polymer entanglement becomes prevalent as the solution concentration increases, which can also potentially occur as a result of increased evaporation due to powder bed heating. Specifically, concentrated solutions close to the onset of entanglement will absorb much more slowly than predicted. Future models of BJP systems must account for the possibility of polymer entanglement throughout the absorption process. Improved models will provide a more accurate understanding of the flow and solidification of the binder in the powder, allowing faster development of new binders for improved performance in printing.

Chitosan coatings with distinct innate immune bioactivities differentially stimulate angiogenesis, osteogenesis and chondrogenesis in poly-caprolactone scaffolds with controlled interconnecting pore size.

This study tested whether osseous integration into poly (ε-caprolactone) (PCL) bioplastic scaffolds with fully-interconnecting 155 ± 8 µm pores is enhanced by an adhesive, non-inflammatory 99% degree of deacetylation (DDA) chitosan coating (99-PCL), or further incorporation of pro-inflammatory 83% DDA chitosan microparticles (83-99-PCL) to accelerate angiogenesis. New Zealand White rabbit osteochondral knee defects were press-fit with PCL, 99-PCL, 83-99-PCL, or allowed to bleed (drill-only). Between day 1 and 6 weeks of repair, drill-only defects repaired by endochondral ossification, with an 8-fold higher bone volume fraction (BVF) versus initial defects, compared to a 2-fold (99-PCL), 1.1-fold (PCL), or 0.4-fold (83-99-PCL) change in BVF. Hematoma innate immune cells swarmed to 83-99-PCL, elicited angiogenesis throughout the pores and induced slight bone resorption. PCL and 99-PCL pores were variably filled with cartilage or avascular mesenchyme near the bone plate, or angiogenic mesenchyme into which repairing trabecular bone infiltrated up to 1 mm deep. More repair cartilage covered the 99-PCL scaffold (65%) than PCL (18%) or 83-99-PCL (0%) (p < 0.005). We report the novel finding that non-inflammatory chitosan coatings promoted cartilage infiltration into and over a bioplastic scaffold, and were compatible with trabecular bone integration. This study also revealed that in vitro osteogenesis assays have limited ability to predict osseous integration into porous scaffolds, because (1) in vivo, woven bone integrates from the leading edge of regenerating trabecular bone and not from mesenchymal cells adhering to scaffold surfaces, and (2) bioactive coatings that attract inflammatory cells induce bone resorption.

Hydrophobic Porous Polypropylene with Hierarchical Structures for Ultrafast and Highly Selective Oil/Water Separation.

Recently, various porous absorbents have been developed and the in situ vacuum/pump-assisted continuous separation process has proven to be the most efficient technique to utilize those absorbents for oil spill cleanup. However, to achieve a high oil removal throughput, a high pumping pressure and/or large absorbent pore sizes are required, which would compromise the selectivity of oil/water separation, as water may penetrate the absorbent beyond a critical external pressure. In this work, this challenge has been circumvented by employing hierarchically porous polypropylene (PP) with controlled pore sizes generated from a tricontinuous heterophase polymer blend system. As compared to unimodal pores, the incorporation of the secondary smaller pores significantly enhances the oil removal throughput by up to 4-5 times without the necessity of raising the pumping pressure or increasing the diameter of the primary pores, which in turn, prevents compromising the oil/water separation selectivity.

Controlling the distribution of nanoparticles in hydrogels via interfacial synthesis.

In this article, a dual-solvent method is presented which allows for precise control over the distribution of nanoparticles (NPs) in hydrogels. The technique is based on the interfacial reaction between a reducing agent (herein THPC) initially solubilized in the hydrogel phase, and an organometallic precursor (herein Au(PPh3)Cl) solubilized in the surrounding organic liquid phase. When the organic phase is completely immiscible with water, the interfacial reaction yields a fragile monolayer film of NPs at the hydrogel surface. Then, the addition of a co-solvent (miscible with both aqueous and organic phases) allows precise tuning over the distribution of NPs, from a fine and well-anchored layer at the interface, to the whole gel volume. As a result, it is possible to independently control the size and concentration of NPs, and their distribution. The impact of such control is demonstrated with the reduction of p-nitrophenol to p-aminophenol catalyzed by gold nanoparticles (AuNPs). When AuNPs are mostly localized at the gel surface, the apparent reaction rate is more than 10× superior compared to AuNPs distributed in the whole gel - at comparable particle content and size. This approach is straightforward, decisive and compatible with broad arrays of NPs and hydrogel chemistries, and solvent combinations.

Nucleation of Poly(lactide) Partially Wet Droplets in Ternary Blends with Poly(butylene succinate) and Poly(ε-caprolactone).

This work presents the first investigation on the crystallization behavior of partially wet droplets in immiscible ternary blends. Poly(lactide), poly(ε-caprolactone), and poly(butylene succinate) (PLA, PCL, and PBS, respectively) were melt blended in a 10/45/45 weight ratio to produce a "partial wetting" morphology with droplets of the PLA minor phase located at the interface between the other two major components. The crystallization process of the higher melting PLA droplets was studied by polarized light optical microscopy, while the other components remain in the molten state. We found that neighboring partially wet droplets nucleate in close sequence. This is unexpected since partially wet droplets display points of three-phase contact and, hence, should not touch each other. Moreover, the onset of poly(lactide) crystallization is frequently observed at the interface with molten PCL or PBS, with a significant preference for the former polymer. The observed sequential droplet-to-droplet crystallization is attributed to the weak partial wetting behavior of the PCL/PLA/PBS ternary system. In fact, the contact between the interfacially confined droplets during crystallization due to their mobility can lead to a transition from a partial to a completely wet state, with the formation of thin continuous layers bridging larger partially wet droplets. This allows crystallization to spread sequentially between neighboring domains. Using a simple heterogeneous nucleation model, it is shown that the nucleation of PLA on either PCL or PBS melts is energetically feasible. This study establishes a clear relationship between the unique partial wetting morphology of ternary blends and the nucleation of the minor component, paving the way to the understanding and control of crystallization in multiphasic polymer blends for advanced applications.

Controlling burst and final drug release times from porous polylactide devices derived from co-continuous polymer blends.

This work has demonstrated that it is possible to exercise a wide range of control over both the initial burst release and the final drug release times from porous polylactide (PLA) devices derived from cocontinuous polymer blends. Two strategies were used: a layer-by-layer polyelectrolyte surface deposition approach on the porous PLA surface and the application of a partially closed-cell protocol. A PLA porous substrate with a pore size of 1.5 microm, derived from a blend of PLA and polystyrene (PS) via selective solvent extraction of the PS phase, was used as the drug delivery device. The surface area and pore dimensions were examined via BET nitrogen adsorption and image analysis. Porous PLA substrates with 0, 3, and 5 layers of polyelectrolytes and with open areas of 100, 12, and 2% were studied both separately and in combination. In vitro release tests were performed to study the release profile of bovine serum albumin (BSA) from the devices via UV spectrophotometry. It is shown that, while both are important, surface modification is more dominant in controlling the release rate than the partially closed cell approach. When a five layer surface modification of the PLA and a partially closed cell approach (2% open area) are combined, denoted as the L5C sample, the synergy is dramatic with a 5x reduction in the first two hour burst release amount and a total release time that is extended by 123x as compared to the 100% open cell, surface unmodified, reference sample. The L5C sample ultimately releases 89% of the total BSA loaded, demonstrating the high level of interconnectivity of the microchannels in the porous PLA. The mechanism of release in this system is clearly diffusion controlled with well-defined concentration gradients, as measured by X-ray photoelectron spectroscopy (XPS), observed in the direction of release. These results point toward a diffusion mechanism combined with a sorption/desorption interaction of the BSA with the modified PLA surface.

Porous devices derived from co-continuous polymer blends as a route for controlled drug release.

In this study we examine the release profile of bovine serum albumin (BSA) from a porous polymer matrix derived from a co-continuous polymer blend. The porosity is generated through the selective extraction of one of the continuous phases. This is the first study to examine the approach of using morphologically tailored co-continuous polymer blends as a template for generating porous polymer materials for use in controlled release. A method for the preparation of polymeric capsules is introduced, and the effect of matrix pore size and surface area on the BSA release profile is investigated. Furthermore, the effect of surface charge on release is examined by surface modification of the porous substrate using layer-by-layer deposition techniques. Synthetic, nonerodible polymer, high-density polyethylene (HDPE), was used as a model substrate prepared by melt blending with two different styrene-ethylene-butylene copolymers. Blends with HDPE allow for the preparation of porous substrates with small pore sizes (300 and 600 nm). A blend of polylactide (PLA) and polystyrene was also used to prepare porous PLA with a larger pore size (1.5 microm). The extents of interconnectivity, surface area, and pore dimension of the prepared porous substrates were examined via gravimetric solvent extraction, BET nitrogen adsorption, mercury porosimetry, and image analysis of scanning electron microscopy micrographs. With a loading protocol into the porous HDPE and PLA involving the alternate application of pressure and vacuum, it is shown that virtually the entire porous network was accessible to BSA loading, and loading efficiencies of between 80% and 96% were obtained depending on the pore size of the carrier and the applied pressure. The release profile of BSA from the microporous structure was monitored by UV spectrophotometry. The influence of pore size, surface area, surface charge, and number of deposited layers is demonstrated. It is shown that an effective closed-cell structure in porous PLA can be prepared, effectively eliminating all short-term BSA release.

Extrusion foaming of semi-crystalline PLA and PLA/thermoplastic starch blends.

Low density open-cell foams were obtained from polylactic acid (PLA) and from blends of PLA with thermoplastic starch (TPS) using CO(2) as a blowing agent. Two unexpected features were found. First, a 2D cavitation process in the fractured cell walls was unveiled. Elliptical cavities with dimensions in the 100-300 nm range were aligned perpendicular to large cell cracks clearly exhibiting 2D crazing prior to macroscopic cell rupture. Secondly, a significant crystallization rate increase associated with the CO(2) foaming of PLA was discovered. While the PLA used in this study crystallized very slowly in isothermal crystallization, the PLA foams exhibited up to 15% crystallinity, providing evidence that CO(2) plasticization and the biaxial stretching upon foam expansion provided conditions that could increase the crystallization rate by several orders of magnitude.

Cationic osteogenic peptide P15-CSP coatings promote 3-D osteogenesis in poly(epsilon-caprolactone) scaffolds of distinct pore size.

P15-CSP is a biomimetic cationic fusion peptide that stimulates osteogenesis and inhibits bacterial biofilm formation when coated on 2-D surfaces. This study tested the hypothesis that P15-CSP coatings enhance 3-D osteogenesis in a porous but otherwise hydrophobic poly-(ɛ-caprolactone) (PCL) scaffold. Scaffolds of 84 µm and 141 µm average pore size were coated or not with Layer-by-Layer polyelectrolytes followed by P15-CSP, seeded with adult primary human mesenchymal stem cells (MSCs), and cultured 10 days in proliferation medium, then 21 days in osteogenic medium. Atomic analyses showed that P15-CSP was successfully captured by LbL. After 2 days of culture, MSCs adhered and spread more on P15-CSP coated pores than PCL-only. At day 10, all constructs contained nonmineralized tissue. At day 31, all constructs became enveloped in a "skin" of tissue that, like 2-D cultures, underwent sporadic mineralization in areas of high cell density that extended into some 141 µm edge pores. By quantitative histomorphometry, 2.5-fold more tissue and biomineral accumulated in edge pores versus inner pores. P15-CSP specifically promoted tissue-scaffold integration, fourfold higher overall biomineralization, and more mineral deposits in the outer 84 µm and inner 141 µm pores than PCL-only (p < 0.05). 3-D Micro-CT revealed asymmetric mineral deposition consistent with histological calcium staining. This study provides proof-of-concept that P15-CSP coatings are osteoconductive in PCL pore surfaces with 3-D topography. Biomineralization deeper than 150 µm from the scaffold edge was optimally attained with the larger 141 µm peptide-coated pores. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 2171-2181, 2017.

Partial and Complete Wetting in Ultralow Interfacial Tension Multiphase Blends with Polylactide.

The control of phase structuring in multiphase blends of polylactide (PLA) with other polymers is a viable approach to promote its broader implementation. In this article, ternary and quaternary blends of PLA with poly(butylene succinate) (PBS), poly(butylene adipate-co-terephthalate) (PBAT), and poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) are prepared by melt blending. The interfacial tensions between components are measured using three different techniques, and a Fourier transform infrared imaging technique is developed for the purpose of unambiguous phase identification. A tricontinuous complete wetting behavior is observed for the ternary 33PLA/33PBS/33PBAT blend before and after quiescent annealing, which correlates closely with spreading theory analysis. In the quaternary PLA/PBS/PBAT/PHBV blend, a concentration-dependent wetting behavior is found. At 10 vol % PBAT, self-assembled partially wet droplets of PBAT are observed at the interface of PBS and PHBV, and they remain stable after quiescent annealing as predicted by spreading theory. In contrast, at 25 vol % PBAT, a quadruple continuous system is observed after mixing, which only transforms to partially wet PBAT droplets after subsequent annealing. These results clearly indicate the potential of composition control during the mixing of multiphase systems to result in a complete change of spreading behavior.

Pore size and LbL chitosan coating influence mesenchymal stem cell in vitro fibrosis and biomineralization in 3D porous poly(epsilon-caprolactone) scaffolds.

Poly(epsilon-caprolactone) (PCL) is a hydrophobic bioplastic under development for bone tissue engineering applications. Limited information is available on the role of internal geometry and cell-surface attachment on osseous integration potential. We tested the hypothesis that human bone marrow mesenchymal stem cells (MSCs) deposit more mineral inside porous 3D PCL scaffolds with fully interconnected 84 or 141 µm pores, when the surfaces are coated with chitosan via Layer-by-Layer (LbL)-deposited polyelectrolytes. Freshly trypsinized MSCs were seeded on PCL 3D cylinders using a novel static cold seeding method in 2% serum to optimally populate all depths of the scaffold discs, followed by 10 days of culture in proliferation medium and 21 additional days in osteogenic medium. MSCs were observed by SEM and histology to spread faster and to proliferate more on chitosan-coated pore surfaces. Most pores, with or without chitosan, became filled by collagen networks sparsely populated with fibroblast-like cells. After 21 days of culture in osteogenic medium, sporadic matrix mineralization was detected histologically and by micro-CT in highly cellular surface layers that enveloped all scaffolds and in cell aggregates in 141 µm pores near the edges. LbL-chitosan promoted punctate mineral deposition on the surfaces of 84 µm pores (p < 0.05 vs. PCL-only) but not the 141 µm pores. This study revealed that LbL-chitosan coatings are sufficient to promote MSC attachment to PCL but only enhance mineral formation in 84 µm pores, suggesting a potential inhibitory role for MSC-derived fibroblasts in osteoblast terminal differentiation.

Macroporous poly(L-lactide) of controlled pore size derived from the annealing of co-continuous polystyrene/poly(L-lactide) blends.

A detailed study on the static annealing of co-continuous polystyrene/poly(L-lactide) (PLLA) blends is presented. The effects of temperature, time at temperature, viscosity of the phases and interfacial modification on the coarsening of the blend are discussed. In this paper, polystyrene and PLLA are blended at compositions of 50/50 and 60/40 to form co-continuous morphologies. These co-continuous morphologies are coarsened under quiescent annealing conditions, and the subsequent removal of the polystyrene phase leaves a macroporous PLLA structure. The microstructure is analyzed using three different techniques: the BET nitrogen adsorption technique, mercury intrusion porosimetry and SEM combined with image analysis. It is shown that static annealing can be used to generate a series of co-continuous networks with controlled pore sizes ranging from 1 to hundreds of microns. A non-linear pore size growth rate is observed for these systems due to the degradation of PLLA and this study indicates that controlled degradation can be used as an additional tool for morphology control. Compatibilized polystyrene/PLLA blends demonstrate significantly reduced coarsening effects due to the reduction of interfacial tension. The coarsening rate of the co-continuous structure was examined in terms of the pore size, R and this growth rate is discussed in terms of a previously proposed coarsening mechanism. This approach is a route towards the preparation of a macroporous PLLA structure with pore sizes in the range required for scaffolds for tissue regeneration.

Controlled preparation and properties of porous poly(L-lactide) obtained from a co-continuous blend of two biodegradable polymers.

This study prepares porous PLLA from a blend of two biodegradable polymers. This approach is based on a detailed and quantitative morphology control of the blends. Co-continuous blends comprised of poly(L-lactide)/poly(epsilon-caprolactone) PLLA/PCL, were prepared via melt processing. Through a judicious combination of concentration control and a subsequent annealing step it is possible to generate a wide range of sizes for the co-continuous phases. Subsequent extraction of the PCL porogen phase generates a fully interconnected porous PLLA material with a void volume between 50% and 60%. The volume average pore diameter is controlled from 1.5 to 88 microm as measured by mercury intrusion porosimetry. Through static annealing it is also possible to generate porous structures well beyond that upper limit of pore size. The upper limit of pore size reported above is in the range required for scaffolds for tissue engineering. Micrographs of porous polyglycolide and PCL derived from co-continuous blends of PLLA/polyglycolide and PCL/poly(ethylene oxide) are also shown and demonstrate the versatility and wide applicability of this preparation protocol. The porous structures produced from PLLA/PCL blends possess a high level of mechanical integrity and a degree of crystallinity between 25% and 38%. High values of both compressive modulus and strength at 10%-strain are obtained, greater than 190 and 11 MPa, respectively. The compressive modulus is found to be from 10% to 20% of that of the pure PLLA material. A series of loading studies were also carried out and it was shown that under a pressure of 40 atm applied for 1 h, the pores of a 1.5 microm porous PLLA structure were filled to approximately 80% by water. In addition, the loading of an aqueous solution of a model drug compound, bovine serum albumin (BSA), was carried out at 40 atm and the results indicate that large quantities of BSA (up to 25% of the weight of the original porous capsule) can be driven into the pores. These results indicate that the internal porous structure is accessible to aqueous solution and that this material also has potential as a substrate for controlled release applications.

Toughening mechanisms in interfacially modified HDPE/thermoplastic starch blends.

The mechanical behavior of polymer blends containing 80 wt% of HDPE and 20 wt% of TPS and compatibilized with HDPE-g-MA grafted copolymer was investigated. Unmodified HDPE/TPS blends exhibit high fracture resistance, however, the interfacial modification of those blends by addition of HDPE-g-MA leads to a dramatic drop in fracture resistance. The compatibilization of HDPE/TPS blends increases the surface area of TPS particles by decreasing their size. It was postulated that the addition of HDPE-g-MA induces a reaction between maleic anhydride and hydroxyl groups of the glycerol leading to a decrease of the glycerol content in the TPS phase. This phenomenon increases the stiffness of the modified TPS particles and stiffer TPS particles leading to an important reduction in toughness and plastic deformation, as measured by the EWF method. It is shown that the main toughening mechanism in HDPE/TPS blends is shear-yielding. This article demonstrates that stiff, low diameter TPS particles reduce shear band formation and consequently decrease the resistance to crack propagation.

Effect of high molecular weight plasticizers on the gelatinization of starch under static and shear conditions.

Starch gelatinization in the presence of high molecular weight polyol plasticizers and water was studied under static and dynamic conditions and was compared to a glycerol reference. For static gelatinization, glycerol, sorbitol, diglycerol and polyglycerol were examined using polarized light microscopy and differential scanning calorimetry. A wide range of starch/water/plasticizer compositions were prepared to explore the gelatinization regime for each plasticizer. The plasticizers show that the onset and conclusion temperatures for sorbitol and glycerol are in the same range and are lower than the other two plasticizers. On the other hand, polyglycerol shows a higher gelatinization temperature than diglycerol because of its higher molecular weight and viscosity. The results indicate that in the case of all plasticizers, increasing the water content tends to decrease the gelatinization temperature and, except for polyglycerol, increasing the plasticizer content increases the gelatinization temperature. In the case of polyglycerol, however, increasing the plasticizer content had the opposite effect and this was found to be related to the borderline solubility of polyglycerol in water. When the polyglycerol/water solubility was increased by increasing the temperature of the water/plasticizer/starch slurry, the gelatinization temperature dependence was found to be similar to the other polyols. A rheological technique was developed to study the dynamic gelatinization process by tracking the influence of shear on the complex viscosity in a couette flow system. Glycerol, diglycerol and sorbitol were subjected to different dynamic gelatinization treatments and the results were compared with static gelatinization. It is quantitatively shown that shear has a major effect on the gelatinization process. The conclusion temperature of gelatinization is significantly diminished (up to 21 °C) in the presence of shear whereas the onset temperature of gelatinization remains virtually unchanged as compared to static conditions. By comparing glycerol, diglycerol and sorbitol data, it is shown that the molecular weight or structure did not qualitatively affect the changes shear imposed on dynamic gelatinization. Shear had a relatively more pronounced effect on diglycerol as the plasticizer with less hydrogen bonding ability.

Carbon nanotubes in blends of polycaprolactone/thermoplastic starch.

Despite the importance of polymer-polymer multiphase systems, very little work has been carried out on the preferred localization of solid inclusions in such multiphase systems. In this work, carbon nanotubes (CNT) are dispersed with polycaprolactone (PCL) and thermoplastic starch (TPS) at several CNT contents via a combined solution/twin-screw extrusion melt mixing method. A PCL/CNT masterbatch was first prepared and then blended with 20 wt% TPS. Transmission and scanning electron microscopy images reveal a CNT localization principally in the TPS phase and partly at the PCL/TPS interface, with no further change by annealing. This indicates a strong driving force for the CNTs toward TPS. Young's model predicts that the nanotubes should be located at the interface. X-ray photoelectron spectroscopy (XPS) of extracted CNTs quantitatively confirms an encapsulation by TPS and reveals a covalent bonding of CNTs with thermoplastic starch. It appears likely that the nanotubes migrate to the interface, react with TPS and then are subsequently drawn into the low viscosity TPS phase. In a low shear rate/low shear stress internal mixer the nanotubes are found both in the PCL phase and at the PCL/TPS interface and have not completed the transit to the TPS phase. This latter result indicates the importance of choosing appropriate processing conditions in order to minimize kinetic effects. The addition of CNTs to PCL results in an increase in the crystallization temperature and a decrease in the percent crystallinity confirming the heterogeneous nucleating effect of the nanotubes. Finally, DMA analysis reveals a dramatic decrease in the starch rich phase transition temperature (~26 °C), for the system with nanotubes located in the TPS phase.

High performance polyethylene/thermoplastic starch blends through controlled emulsification phenomena.

The emulsification efficacies of a range of compatibilizers for polyethylene/thermoplastic starch blends have been studied and a detailed morphological and mechanical analysis has been conducted. It is shown that polyethylene-maleic anhydride terpolymers containing elastomeric segments provided excellent emulsification of PE/TPS blends with a fine morphology (volume diameter of 1.4 µm; number average diameter of 600 nm). The blends compatibilized with these copolymers exhibit a very high elongation at break of about 800%, the highest value ever reported for PE/TPS systems. Also, significant improvement in notched impact strength performance at interfacial saturation was found for these systems leading to specimens with an equivalent performance to pure polyethylene. An excellent correlation was found between the critical concentration for interfacial saturation and the mechanical properties, indicating the key role of morphology.

Morphology control in co-continuous poly(L-lactide)/polystyrene blends: a route towards highly structured and interconnected porosity in poly(L-lactide) materials.

Poly(L-lactide) is a biodegradable polymer primarily used in biomedical applications. In this paper, both the microstructure and the region of dual-phase continuity are examined for binary and compatibilized poly(L-lactide)/polystyrene blends (PLLA/PS) prepared by melt mixing. The blends are shown to be completely immiscible with an interfacial tension of 6.1 mN/m. The PS-b-PLLA (24,000-b-28,000) diblock copolymer compatibilizer has an asymmetric effect on the blend. It is effective at compatibilizing 50/50 PLLA/PS blends but is only a marginal emulsifier for blends where PLLA is the dominant matrix. Percent continuity, as estimated by solvent extraction/gravimetry and also torque/composition diagrams clearly indicate an onset of the region of dual-phase continuity at 40-45%PS. It is demonstrated that highly percolated blends of the above materials exist from 40 to 75% PS and 40 to 60% PS for the binary and compatibilized blends, respectively. The scale of the microstructure of the continuous morphology is measured using BET and mercury intrusion porosimetry techniques, after extraction of the PS phase. Both the pore size and extent of continuity can be controlled through composition and interfacial modification. Static annealing of the blend after melt mixing can also be used to substantially increase the pore size of the system. Extraction of the PS phase in the blend, carried out after the above preparation protocols, is a route to generating completely interconnected porosity of highly controlled morphologies (pore size, void volume) in poly(L-lactide) materials. In this study, the pore diameter was controlled from 0.9 to 72 microm for a constant void volume of 45-47%, and the void volume was modified from 35 to 74% depending on the blend composition.