Studying nanostructure gradients in injection-molded polypropylene/montmorillonite composites by microbeam small-angle x-ray scattering.

The core-shell structure in oriented cylindrical rods of polypropylene (PP) and nanoclay composites (NCs) from PP and montmorillonite (MMT) is studied by microbeam small-angle x-ray scattering (SAXS). The structure of neat PP is almost homogeneous across the rod showing regular semicrystalline stacks. In the NCs the discrete SAXS of arranged crystalline PP domains is limited to a skin zone of 300 µm thickness. Even there only frozen-in primary lamellae are detected. The core of the NCs is dominated by diffuse scattering from crystalline domains placed at random. The SAXS of the MMT flakes exhibits a complex skin-core gradient. Both the direction of the symmetry axis and the apparent perfection of flake-orientation are varying. Thus there is no local fiber symmetry, and the structure gradient cannot be reconstructed from a scan across the full rod. To overcome the problem the rods are machined. Scans across the residual webs are performed. For the first time webs have been carved out in two principal directions. Comparison of the corresponding two sets of SAXS patterns demonstrates the complexity of the MMT orientation. Close to the surface (< 1 mm) the flakes cling to the wall. The variation of the orientation distribution widths indicates the presence of both MMT flakes and grains. The grains have not been oriented in the flowing melt. An empirical equation is presented which describes the variation from skin to core of one component of the inclination angle of flake-shaped phyllosilicate filler particles.

Superlattice deformation in quantum dot films on flexible substrates via uniaxial strain.

The superlattice in a quantum dot (QD) film on a flexible substrate deformed by uniaxial strain shows a phase transition in unit cell symmetry. With increasing uniaxial strain, the QD superlattice unit cell changes from tetragonal to cubic to tetragonal phase as measured with in situ grazing-incidence small-angle X-ray scattering (GISAXS). The respective changes in the optoelectronic coupling are probed with photoluminescence (PL) measurements. The PL emission intensity follows the phase transition due to the resulting changing inter-dot distances. The changes in PL intensity accompany a redshift in the emission spectrum, which agrees with the Förster resonance energy transfer (FRET) theory. The results are essential for a fundamental understanding of the impact of strain on the performance of flexible devices based on QD films, such as wearable electronics and next-generation solar cells on flexible substrates.

In-Situ Synchrotron X-ray Study on the Structure Variation of Morphology-Identified Injection-Molded ß-Nucleated iPP under Tensile Deformation.

The deformation behavior of semi-crystalline polymers is strongly dependent on the morphology formed during processing. In this study, in-situ synchrotron X-ray was firstly used to identify the morphological distributions of injection-molded isotactic polypropylene (iPP) with different concentrations of ß-nucleating agent. It was found that under relatively high concentration of ß-nucleating agent (i.e., ≥0.03 wt.%), the outer region (skin and shear region) of the iPP was dominated by mainly highly oriented α-phase as well as certain amount γ-phase, while the core region was rich in ß-crystals with little if any orientation. The addition of the ß-nucleating agent was beneficial for the formation of lamellae with large lamellar stacking distance in the shear layer. Then the synchrotron X-ray was applied to study the structure variation of those morphology-identified samples under tensile deformation. It was found that voids and cavities along the stretching direction existed in the deformed iPP samples and their volume increased with increasing concentration of ß-nucleating agent. The increased volume of void and cavity was associated with the ß to α phase transition, which mainly occurred at the core region. In addition, upon stretching crystalline fragmentation and rearrangement took place following the formation of thinner lamellae.

Thermomechanical Characterization and Modeling of Cold-Drawing of Poly(ethylene Terephthalate).

The tensile testing of amorphous polyethylene terephthalate is observed until failure by IR thermography and optical strain measurement. The deformation can be subdivided in six deformation phases: elastic deformation, neck formation with a localized sharp temperature rise, neck propagation, which is also known as cold-drawing, with heat generation in a transition zone, crack initialization with local heating, crack growth, and rupture. These deformation phases are showing different mechanical and thermal reactions to the deformation. The initial and drawn samples are studied with differential scanning calorimetry. Alongside heating due to the dissipation of mechanical energy, latent heat due to strain-induced crystallization was detected. While the material is cold-drawn, a high dependence on the crosshead speed is found for the heat generation as well as the draw ratio, mechanical response, and morphological changes due to orientation and crystallization. For cold-drawing, a thermomechanical model is introduced, which is based on the first law of thermodynamics and reproduces the temperature distribution along the sample.

Switching of friction by binary polymer brushes.

Surface force studies on polystyrene-poly(2-vinylpyridine) (1 : 1) mixed polymer brushes and corresponding monobrushes were carried out in dried state under a controlled environment. The aim was to explore possibilities to control adhesion and friction between inorganic or polymeric surfaces by use of polymer brushes. The effect of switching of chemical composition of binary brush surfaces (on treatment with suitable solvents) on wettability, surface roughness, and hence the adhesion and friction properties of the surfaces were determined. Atomic force microscopy (AFM) with silicon tips, silicon nitride tips, and colloidal probes with silica particles were employed to investigate the interactions between inorganic surfaces and polymer brushes. To study the interactions between different polymer brush surfaces colloidal probes were covered with polystyrene and poly(acrylic acid) brushes on the surface. For all the dry polymer brushes samples, surface roughness values were in the range of 0.35-1.0 nm only. Adhesion and friction forces of polymer brush samples were reduced in comparison to the silicon wafer and were correlated with each other (except for the silicon tip). Switching in adhesion and friction forces up to a factor of 4.5 was possible by switching of the conformation of mixed brushes on treatment with selective solvents. The friction force on a PS + P2VP gradient polymer brush layer varied laterally and increased with increase in the P2VP content. Friction depends on wettability, scan velocity of the AFM tip, grafting density, and composition gradient of polymer brushes. Moreover, for PS and P2VP monobrushes, friction forces were shown to increase with increasing grafting density. Polymer brush layers thus may be used to control the adhesion and friction behavior of solid surfaces in different ways.

Healing properties of surface-coated polycaprolactone-co-lactide scaffolds: a pilot study in sheep.

The aim of this pilot study was to evaluate the bioactive, surface-coated polycaprolactone-co-lactide scaffolds as bone implants in a tibia critical size defect model. Polycaprolactone-co-lactide scaffolds were coated with collagen type I and chondroitin sulfate and 30 piled up polycaprolactone-co-lactide scaffolds were implanted into a 3 cm sheep tibia critical size defect for 3 or 12 months (n = 5 each). Bone healing was estimated by quantification of bone volume in the defects on computer tomography and microcomputer tomography scans, plain radiographs, biomechanical testing as well as by histological evaluations. New bone formation occurred at the proximal and distal ends of the tibia in both groups. The current pilot study revealed a mean new bone formation of 63% and 172% after 3 and 12 months, respectively. The bioactive, surface coated, highly porous three-dimensional polycaprolactone-co-lactide scaffold stack itself acted as a guide rail for new bone formation along and into the implant. These preliminary data are encouraging for future experiments with a larger group of animals.

Comparative evaluation of ten different condylar base fracture osteosynthesis techniques.

The aim of this study on the mandibles of minipigs was to compare the biomechanical stability of different methods of osteosynthesis that are used in the operative treatment of fractures of the base of the condyle. Ten different systems of osteosynthesis were used to fix 164 fractures, which were tested by a two-point bending test after repositioning and fixing. This stress test was applied in four directions: lateral to medial, anterior to distal, distal to anterior, and medial to lateral. The Eckelt lag screw, one or two 2.0mm miniplates, one miniplate with bar (KLS Martin), minicompression plates (Medicon), zygoma compression plates (Medartis), condylus fracture plates (Medartis), square 4-hole plates (KLS Martin), and either one or two resorbable 4-hole miniplates (Resorb-X, Martin) were used for osteosynthesis. A total of 164 tests were done using a universal test machine that measured forces until the osteosynthesis failed. Advantages in mechanical load capacity were also measured for the Eckelt lag screw when force was applied from medial to lateral. Fixation with one resorbable miniplate was not functionally stable. Irrespective of the direction of force applied, two miniplates were the most stable technique. There were pronounced differences depending on the direction of force applied. The results suggest that treatment with a single resorbable miniplate is not functionally stable.

Nanowear studies in reversibly switchable polystyrene-poly(acrylic acid) mixed brushes.

Wear studies were performed on polystyrene (PS)-poly(acrylic acid) (PAA) mixed polymer brushes and corresponding monobrushes in a dried state. The aim was to study the wear mechanism in polymer brush surfaces as well as to investigate the effect of switching of PS + PAA binary brush surfaces (on treatment with the selective solvents for the PS and PAA) on the wear process. Wear experiments were carried out using atomic force microscopy (AFM) under a controlled environment. The wear experiments were performed as a function of scan number using a sharp silicon nitride tip to induce the wear on the sample surfaces. The wear mechanism on different brush surfaces was influenced by molecular entanglement as well as adhesion and friction on the sample surface. The wear process on the PS monobrush surface treated with toluene took place via formation of the ripples. On the other hand, a typical wear mode observed on the PAA monobrushes was removal of the polymeric material from the surface. For the mixed brush surface treated with toluene (selective solvent for PS) where PS chains dominated the top of the sample surface, the typical wear mode observed was ripple formation similar to that observed for the PS monobrushes. However, when a mixed brush was treated with ethanol and pH 10 water so that PAA chains dominated the top layer, wear occurred via removal of material. The amount of wear on the surfaces increased with the number of scans. Furthermore, the load and scan velocity dependence of the wear process was also investigated. Wear on polymer brush surfaces increased on increasing the load and/or decreasing the scan speed. The present study shows that wear can be controlled/tuned using mixed responsive brushes.