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Thermoelectric Properties of N-Type Poly (Ether Ether Ketone)/Carbon Nanofiber Melt-Processed Composites
The thermoelectric properties, at temperatures from 30 °C to 100 °C, of melt-processed poly(ether ether ketone) (PEEK) composites prepared with 10 wt.% of carbon nanofibers (CNFs) are discussed in this work. At 30 °C, the PEEK/CNF composites show an electrical conductivity (σ) of ~27 S m−1 and a Seebeck coefficient (S) of −3.4 μV K−1, which means that their majority charge carriers are electrons. The origin of this negative Seebeck is deduced because of the impurities present in the as-received CNFs, which may cause sharply varying and localized states at approximately 0.086 eV above the Fermi energy level (EF) of CNFs. Moreover, the lower S, in absolute value, found in PEEK/CNF composites, when compared with the S of as-received CNFs (−5.3 μV K−1), is attributed to a slight electron withdrawing from the external layers of CNFs by the PEEK matrix. At temperatures from 30 °C to 100 °C, the σ (T) of PEEK/CNF composites, in contrast to the σ (T) of as-received CNFs, shows a negative temperature effect, understood through the 3D variable-range hopping (VRH) model, as a thermally activated hopping mechanism across a random network of potential wells. Moreover, their nonlinear S (T) follows the same behavior reported before for polypropylene composites melt-processed with similar CNFs at the same interval of temperatures.
Influence of Polyvinylpyrrolidone on Thermoelectric Properties of Melt-Mixed Polymer/Carbon Nanotube Composites
For thermoelectric applications, both p- and n-type semi-conductive materials are combined. In melt-mixed composites based on thermoplastic polymers and carbon nanotubes, usually the p-type with a positive Seebeck coefficient (S) is present. One way to produce composites with a negative Seebeck coefficient is to add further additives. In the present study, for the first time, the combination of single-walled carbon nanotubes (SWCNTs) with polyvinylpyrrolidone (PVP) in melt-mixed composites is investigated. Polycarbonate (PC), poly(butylene terephthalate) (PBT), and poly(ether ether ketone) (PEEK) filled with SWCNTs and PVP were melt-mixed in small scales and thermoelectric properties of compression moulded plates were studied. It could be shown that a switch in the S-value from positive to negative values was only possible for PC composites. The addition of 5 wt% PVP shifted the S-value from 37.8 µV/K to −31.5 µV/K (2 wt% SWCNT). For PBT as a matrix, a decrease in the Seebeck coefficient from 59.4 µV/K to 8.0 µV/K (8 wt% PVP, 2 wt% SWCNT) could be found. In PEEK-based composites, the S-value increased slightly with the PVP content from 48.0 µV/K up to 54.3 µV/K (3 wt% PVP, 1 wt% SWCNT). In addition, the long-term stability of the composites was studied. Unfortunately, the achieved properties were not stable over a storage time of 6 or 18 months. Thus, in summary, PVP is not suitable for producing long-term stable, melt-mixed n-type SWCNT composites.
Graphite modified epoxy-based adhesive for joining of aluminium and PP/graphite composites
A graphite-modified adhesive was developed in order to simultaneously enhance the thermal conductivity and the strength of an adhesive joint. The thermal conductivity through the joint was investigated by using highly filled PP/graphite composite substrates, which were joined with an epoxy adhesive of different layer thicknesses. Similar measurements were carried out with a constant adhesive layer thickness, whilst applying an epoxy adhesive modified with expanded graphite (EG) (6, 10, and 20 wt%). By reducing the adhesive layer thickness or modifying the adhesive with conductive fillers, a significant increase of the thermal conductivity through the joint was achieved. The examination of the mechanical properties of the modified adhesives was carried out by tensile tests (adhesive only), lap-shear tests, and fracture energy tests (mode 1) with aluminium substrates. Modification of the adhesive with EG led to an increase of the tensile lap-shear strength and the adhesive fracture energy (mode 1) of the joint. In addition, burst pressure tests were performed to determine the strength of the joint in a complex component. The strength of the joint increased with the graphite content in the PP substrate and in the epoxy adhesive.
Characterisation and Modelling of Moisture Gradients in Polyamide 6
Polyamide 6 (PA6) is able to absorb water from the surrounding air and bond to it by forming hydrogen bonds between the carbonamide groups of its molecular chains. Diffusion processes cause locally different water concentrations in the (component) cross-section during the sorption process, resulting in locally different mechanical properties due to the water-induced plasticisation effect. However, the water content of PA6 is usually specified as an integral value, so no information about a local water distribution within a component is provided. This paper shows a method to characterise moisture distributions within PA6 samples using low-energy computer tomography (CT) techniques and comparing the reconstructed results with a developed finite elements (FE) modelling method based on Fick’s diffusion laws with concentration-dependent diffusion coefficients. For this purpose, the ageing of the samples at two different water bath temperatures as well as at different integral water contents are considered. The results obtained by CT reconstruction and FE modelling are in very good agreement, so that the concentration distributions by water sorption of PA6 calculated by FEM can be regarded as validated.
Magneto-Mechanical Coupling in Magneto-Active Elastomers
In the present work, the magneto-mechanical coupling in magneto-active elastomers is investigated from two different modeling perspectives: a micro-continuum and a particle–interaction approach. Since both strategies differ significantly in their basic assumptions and the resolution of the problem under investigation, they are introduced in a concise manner and their capabilities are illustrated by means of representative examples. To motivate the application of these strategies within a hybrid multiscale framework for magneto-active elastomers, their interchangeability is then examined in a systematic comparison of the model predictions with regard to the magneto-deformation of chain-like helical structures in an elastomer surrounding. The presented results show a remarkable agreement of both modeling approaches and help to provide an improved understanding of the interactions in magneto-active elastomers with chain-like microstructures.
A Theoretical and Experimental Analysis of the Effect of Nanoclay on Gas Perm-Selectivity of Biodegradable PLA/EVA Blends in the Presence and Absence of Compatibilizer
Poly (lactic acid) (PLA)-based compounds are widely used in thin-film and food packaging industries. Herein, PLA/ethylene vinyl acetate copolymer (EVA)/nanoclay nanocomposites are prepared in various compositions by melt blending. The gas permeability against N2, CO2, and O2 gases is determined as a function of composition and morphology of the nanocomposites. Inclusion of high aspect ratio of platelet-like nanoclay to the blend reduces the gas diffusion. The best barrier properties against all gases is observed on introducing 5 wt% poly(ethylene/n-butyl acrylate glycidyl methacrylate) copolymer as compatibilizer to the PLA/EVA/nanoclay (75/25/5) system. The scanning and transmission electron microscopic analyses and wide-angle X-ray scattering studies reveal that inclusion of compatibilizer to the filled-blends improves the blend morphology, dispersion state, and intercalation level of clay platelets which are preferably localized at the interface of the blend. Analysis of selectivity parameter (a) shows the lowest O2 permeability and the highest aCO2/N2 and aO2/N2 values for the compatibilized filled-blend (75/25/5/5). In situ aspect ratio of clay and the degree of intercalation are theoretically evaluated based on the permeability data using various empirical models. It is found that the compatibilized filled-blend has the highest aspect ratio and intercalation level that are responsible for the optimum perm-selectivity performance. © 2020 The Authors. Published by Wiley-VCH GmbH
Statistical Analysis of Mechanical Stressing in Short Fiber Reinforced Composites by Means of Statistical and Representative Volume Elements
Analyzing representative volume elements with the finite element method is one method to calculate the local stress at the microscale of short fiber reinforced plastics. It can be shown with Monte-Carlo simulations that the stress distribution depends on the local arrangement of the fibers and is therefore unique for each fiber constellation. In this contribution the stress distribution and the effective composite properties are examined as a function of the considered volume of the representative volume elements. Moreover, the influence of locally varying fiber volume fraction is examined, using statistical volume elements. The results show that the average stress probability distribution is independent of the number of fibers and independent of local fluctuation of the fiber volume fraction. Furthermore, it is derived from the stress distributions that the statistical deviation of the effective composite properties should not be neglected in the case of injection molded components. A finite element analysis indicates that the macroscopic stresses and strains on component level are significantly influenced by local, statistical fluctuation of the composite properties.
In vivo ligamentogenesis in embroidered poly(lactic-co-ε-caprolactone) / polylactic acid scaffolds functionalized by fluorination and hexamethylene diisocyanate cross-linked collagen foams
Although autografts represent the gold standard for anterior cruciate ligament (ACL) reconstruction, tissue-engineered ACLs provide a prospect to minimize donor site morbidity and limited graft availability. This study characterizes the ligamentogenesis in embroidered poly(L-lactide-co-epsilon-caprolactone) (P(LA-CL)) / polylactic acid (PLA) constructs using a dynamic nude mice xenograft model. (P(LA-CL))/PLA scaffolds remained either untreated (co) or were functionalized by gas fluorination (F), collagen foam cross-linked with hexamethylene diisocyanate (HMDI) (coll), or F combined with the foam (F+coll). Cell-free constructs or those seeded for 1 week with lapine ACL ligamentocytes were implanted into nude mice for 12 weeks. Following explantation, cell vitality and content, histo(patho)logy of scaffolds (including organs: liver, kidney, spleen), sulphated glycosaminoglycan (sGAG) contents and biomechanical properties were assessed. Scaffolds did not affect mice weight development and organs, indicating no organ toxicity. Moreover, scaffolds maintained their size and shape and reflected a high cell viability prior to and following implantation. Coll or F+coll scaffolds seeded with cells yielded superior macroscopic properties compared to the controls. Mild signs of inflammation (foreign-body giant cells and hyperemia) were limited to scaffolds without collagen. Microscopical score values and sGAG content did not differ significantly. Although remaining stable after explantation, elastic modulus, maximum force, tensile strength and strain at F-max were significantly lower in explanted scaffolds compared to those before implantation, with no significant differences between scaffold subtypes, except for a higher maximum force in F+coll compared with F samples (in vivo). Scaffold functionalization with fluorinated collagen foam provides a promising approach for ACL tissue engineering.
Photo-Ordering and Deformation in Azobenzene-Containing Polymer Networks under Irradiation with Elliptically Polarized Light
Azobenzene-containing polymers (azo-polymers) have been a subject of extensive investigations during the last two and half decades, due to their remarkable ability to undergo pronounced alignment and deformation under irradiation with light. The molecular ordering and deformation in azo-polymers of various structures under irradiation with linearly polarized light was described in a series of theoretical works, based on the effect of the reorientation of azobenzene moieties due to the anisotropic character of the photoisomerization processes. In the present study, we generalize the previous orientation approach to describe the photo-alignment and deformation of azo-polymer networks under irradiation with elliptically polarized light. We demonstrate that, in general, the light-induced ordering and deformation have a biaxial symmetry defined by the polarization ellipse. Azobenzene chromophores have a tendency to align along the direction of light propagation, the orientation in the other two directions being dependent of the aspect ratio of the polarization ellipse. This causes deformation of azo-polymer networks along the direction of light propagation, the sign of which (expansion/contraction) is defined by a chemical structure of network strands. Theoretical results are in agreement with experiments and have a practical importance to predict the photo-mechanical response of azo-polymers depending on their structure and on the polarization of light.
Enhanced growth of lapine anterior cruciate ligament-derived fibroblasts on scaffolds embroidered from poly(L-lactide-co-ε-caprolactone) and polylactic acid threads functionalized by fluorination and hexamethylene diisocyanate cross-linked collagen foams
Reconstruction of ruptured anterior cruciate ligaments (ACLs) is limited by the availability and donor site morbidity of autografts. Hence, a tissue engineered graft could present an alternative in the future. This study was undertaken to determine the performance of lapine (L) ACL-derived fibroblasts on embroidered poly(l-lactide-co-e-caprolactone) (P(LA-CL)) and polylactic acid (PLA) scaffolds in regard to a tissue engineering approach for ACL reconstruction. Surface modifications of P(LA-CL)/PLA by gas-phase fluorination and cross-linking of a collagen foam using either ethylcarbodiimide (EDC) or hexamethylene diisocyanate (HMDI) were tested regarding their influence on cell adhesion, growth and gene expression. The experiments were performed using embroidered P(LA-CL)/PLA scaffolds that were seeded dynamically or statically with LACL-derived fibroblasts. Scaffold cytocompatibility, cell survival, numbers, metabolic activity, ultrastructure and sulfated glycosaminoglycan (sGAG) synthesis were evaluated. Quantitative real-time polymerase chain reaction (QPCR) revealed gene expression of collagen type I (COL1A1), decorin (DCN), tenascin C (TNC), Mohawk (MKX) and tenomodulin (TNMD). All tested scaffolds were highly cytocompatible. A significantly higher cellularity and larger scaffold surface areas colonized by cells were detected in HMDI cross-linked and fluorinated scaffolds compared to those cross-linked with EDC or without any functionalization. By contrast, sGAG synthesis was higher in controls. Despite the fact that the significance level was not reached, gene expressions of ligament extracellular matrix components and differentiation markers were generally higher in fluorinated scaffolds with cross-linked collagen foams. LACL-derived fibroblasts maintained their differentiated phenotype on fluorinated scaffolds supplemented with a HMDI cross-linked collagen foam, making them a promising tool for ACL tissue engineering. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.