Influence of monomeric and polymeric structure on the physical properties of thermoplastic polyesters derived from hydroxy fatty acids

The physical properties of three vegetable oil derived medium and long chain poly(-hydroxy fatty ester)s (P(Me--OHFA)s), namely poly(-hydroxynonanoate) [P(Me--OHC9)], poly(-hydroxytridecanoate) [P(Me--OHC13)] and poly(-hydroxyoctadecanoate) [P(Me--OHC18)] (n = 8, 12 and 17, respectively), of the [-(CH2)(n)-COO-](x) polyester homologous series are presented. The effect of M-n (M-n 10-40 kg mol(-1)) and n on the crystal structure and thermal and mechanical properties of the P(Me--OHFA)s were investigated by wide-angle X-ray diffraction (WAXD), TGA, DSC, dynamic mechanical analysis (DMA) and tensile analysis and are discussed in the context of the [-(CH2)(n)-COO-](x) polyester homologous series, contrasted with linear polyethylene (PE). For all P(Me--OHFA)s the WAXD data indicated an orthorhombic crystal phase reminiscent of linear PE with crystallinity (X-c = 50%-80%) depending strongly on M-n. The glass transition temperature and Young's modulus for P(Me--OHFA)s increased with X-c. The DSC, DMA and TGA studies for P(Me--OHFA)s (n = 8, 12 and 17) indicated strong correlations between the melting, glass transition and thermal degradation behavior and n. The established predictive structure relationships can be used for the custom engineering of polyester materials suitable for specialty and commodity applications. (c) 2014 Society of Chemical Industry

Horse chestnut (Aesculus hippocastanum L.) starch: Basic physico-chemical characteristics and use as thermoplastic material

Starch isolated from non-edible Aesculus hippocastanum seeds was characterized and used for preparing starch-based materials. The apparent amylose content of the isolated starch was 33.1%. The size of starch granules ranged from 0.7 to 35 pm, and correlated with the shape of granules (spherical, oval and irregular). The chain length distribution profile of amylopectin showed two peaks, at polymerization degree (DP) of 12 and 41-43. Around 53% of branch unit chains had DP in the range of 11-20. A. hippocastanum starch displayed a typical C-type pattern and the maximum decomposition temperature was 317 degrees C.Thermoplastic starch (TPS) prepared from A. hippocastanum with glycerol and processed by melt blending exhibited adequate mechanical and thermal properties. In contrast, plasticized TPS with glycerol:malic acid (1:1) showed lower thermal stability and a pasty and sticky behavior, indicating that malic acid accelerates degradation of starch during processing. (C) 2014 Elsevier Ltd. All rights reserved.

Filling of simulated lateral canals with gutta-percha or thermoplastic polymer by warm vertical compaction

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

In situ sonochemical synthesis of ZnO particles embedded in a thermoplastic matrix for biomedical applications

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Biodegradation of Thermoplastic and hermosetting Polyesters from Z-Protected Glutamic Acid

In a previous article,1 the development and molecular characterization of three polyesters from N-carbobenzyloxy-L-glutamic acid (ZGluOH) were reported. The polymers were a linear, heterochain polyester (ZGluOH and ethylene glycol), a crosslinked heterochain polyester (ZGluOH and diglycidyl ether of 1,4-butanediol), and a crosslinked, heterochain aromatic polyester (ZGluOH and diglycidyl ether of bisphenol A). In this manuscript, results of biodegradation studies are reported. The three polymers hydrolyzed to low molecular weight oligomers similar to the monomers with lipase. When exposed to a mixed culture of micro-organisms, the first two resins degraded to biomass and respiratory gases. The crosslinked heterochain aromatic polyester resisted microbial degradation.

Constitutive models for biodegradable thermoplastic ropes for ligament repair

The concept behind a biodegradable ligament device is to temporarily replace the biomechanical functions of the ruptured ligament, while it progressively regenerates its capacities. However, there is a lack of methods to predict the mechanical behaviour evolution of the biodegradable devices during degradation, which is an important aspect of the project. In this work, a hyper elastic constitutive model will be used to predict the mechanical behaviour of a biodegradable rope made of aliphatic polyesters. A numerical approach using ABAQUS is presented, where the material parameters of the model proposal are automatically updated in correspondence to the degradation time, by means of a script in PYTHON. In this method we also use a User Material subroutine (UMAT) to apply a failure criterion base on the strength that decreases according to a first order differential equation. The parameterization of the material model proposal for different degradation times were achieved by fitting the theoretical curves with the experimental data of tensile tests on fibres. To model all the rope behaviour we had considered one step of homogenisation considering the fibres architectures in an elementary volume. (C) 2012 Elsevier Ltd. All rights reserved.

Natural fiber-reinforced thermoplastic starch composites obtained by melt processing

Thermoplastic starch (TPS) from industrial non-modified corn starch was obtained and reinforced with natural strands. The influence of the reinforcement on physical-chemical properties of the composites obtained by melt processing has been analyzed. For this purpose, composites reinforced with different amounts of either sisal or hemp strands have been prepared and evaluated in terms of crystallinity, water sorption, thermal and mechanical properties. The results showed that the incorporation of sisal or hemp strands caused an increase in the glass transition temperature (T-g) of the TPS as determined by DMTA. The reinforcement also increased the stiffness of the material, as reflected in both the storage modulus and the Young's modulus. Intrinsic mechanical properties of the reinforcing fibers showed a lower effect on the final mechanical properties of the materials than their homogeneity and distribution within the matrix. Additionally, the addition of a natural latex plasticizer to the composite decreased the water absorption kinetics without affecting significantly the thermal and mechanical properties of the material. (c) 2012 Elsevier Ltd. All rights reserved.

Compatible blends of thermoplastic starch and hydrolyzed ethylene-vinyl acetate copolymers

Ethylene-vinyl acetate copolymer (EVA) with 19% of vinyl acetate and its derivatives modified by hydrolysis of 50 and 100% of the initial vinyl acetate groups were used to produce blends with thermoplastic starch (TPS) plasticized with 30 wt% glycerol. The blends were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy. X-ray diffraction, water absorption, stress-strain mechanical tests, dynamic mechanical analysis and thermogravimetric analysis. In contrast to the blends with unmodified EVA. those made with hydrolyzed EVA were compatible, as demonstrated by the brittle fracture surface analysis and the results of thermal and mechanical tests. The mechanical characteristics and water absorption of the TPS were improved even with a small addition (2.5 wt%) of hydrolyzed EVA. The glass transition temperature rose with the degree of hydrolysis of EVA by 40 and 50 degrees, for the EVA with 50 and 100% hydrolysis, respectively. The addition of hydrolyzed EVA proved to be an interesting approach to improving TPS properties, even when very small quantities were used, such as 2.5 wt%. (C) 2012 Elsevier Ltd. All rights reserved.

On Designing Compliant Actuators Based On Dielectric Elastomers

Dielectric Elastomers (DE) are incompressible dielectrics which can experience deviatoric (isochoric) finite deformations in response to applied large electric fields. Thanks to the strong electro-mechanical coupling, DE intrinsically offer great potentialities for conceiving novel solid-state mechatronic devices, in particular linear actuators, which are more integrated, lightweight, economic, silent, resilient and disposable than equivalent devices based on traditional technologies. Such systems may have a huge impact in applications where the traditional technology does not allow coping with the limits of weight or encumbrance, and with problems involving interaction with humans or unknown environments. Fields such as medicine, domotic, entertainment, aerospace and transportation may profit. For actuation usage, DE are typically shaped in thin films coated with compliant electrodes on both sides and piled one on the other to form a multilayered DE. DE-based Linear Actuators (DELA) are entirely constituted by polymeric materials and their overall performance is highly influenced by several interacting factors; firstly by the electromechanical properties of the film, secondly by the mechanical properties and geometry of the polymeric frame designed to support the film, and finally by the driving circuits and activation strategies. In the last decade, much effort has been focused in the devolvement of analytical and numerical models that could explain and predict the hyperelastic behavior of different types of DE materials. Nevertheless, at present, the use of DELA is limited. The main reasons are 1) the lack of quantitative and qualitative models of the actuator as a whole system 2) the lack of a simple and reliable design methodology. In this thesis, a new point of view in the study of DELA is presented which takes into account the interaction between the DE film and the film supporting frame. Hyperelastic models of the DE film are reported which are capable of modeling the DE and the compliant electrodes. The supporting frames are analyzed and designed as compliant mechanisms using pseudo-rigid body models and subsequent finite element analysis. A new design methodology is reported which optimize the actuator performances allowing to specifically choose its inherent stiffness. As a particular case, the methodology focuses on the design of constant force actuators. This class of actuators are an example of how the force control could be highly simplified. Three new DE actuator concepts are proposed which highlight the goodness of the proposed method.

Liquid crystalline elastomers as stimuli-responsive microactuators

Liquid crystalline elastomers (LCEs) are known to perform a reversible change of shape upon the phase transition from the semi-ordered liquid crystalline state to the chaotic isotropic state. This unique behavior of these “artificial muscles” arises from the self-organizing properties of liquid crystals (mesogens) in combination with the entropy-elasticity of the slightly crosslinked elastomer network. In this work, micrometer-sized LCE actuators are fabricated in a microfluidic setup. The microtubular shear flow provides for a uniform orientation of the mesogens during the crosslinking, a perquisite for obtaining actuating LCE samples. The scope of this work was to design different actuator geometries and to broaden the applicability of the microfluidic device for different types of liquid crystalline mesogens, ranging from side-chain to main-chain systems, as well as monomer and polymer precursors. For example, the thiol-ene “click” mechanism was used for the polymerization and crosslinking of main-chain LCE actuators. The main focus was, however, placed on acrylate monomers and polymers with LC side chains. A LC polymer precursor, comprising mesogenic and crosslinkable side-chains was synthesized. Used in combination with an LC monomer, the polymeric crosslinker promoted a stable LC phase, which allowed the mixture to be isothermally handled in the microfluidic reactor. If processed without the additional LC components, the polymer precursor yielded actuating fibers. A suitable co-flowing continuous phase facilitates the formation of a liquid jet and lowers the tendency for drop formation. By modification of the microfluidic device, it was further possible to prepare core-shell particles, comprised of an LCE shell and filled with an isotropic liquid. In analogy to the heart, a hollow muscle, the elastomer shell expels the inner liquid core upon its contraction. The feasibility of the core-shell particles as micropumps was demonstrated. In general, the synthesized LCE microactuators may be utilized as active components in micromechanical and lab-on-chip systems.

The fabrication and application of semi-crystalline and thermoset-thermoplastic composite colloidal particles with well-defined microstructures

Die Zielsetzung der Arbeit besteht darin, neue Ansätze zur Herstellung strukturierter Kompositpartikel in wässrigem Medium zu entwickeln, welche als die Bildung genau definierter heterogener Strukturen in Kolloidsystemen angesehen werden können. Im Allgemeinen wurden zwei verschiedene Herangehensweisen entwickelt, die sich aufgrund des Ursprungs der gebildeten heterogenen Strukturen unterscheiden: Heterogenität oder Homogenität. Der Erste Ansatz basiert auf der Aggregation heterogener Phasen zur Bildung strukturierter Kolloidpartikel mit Heterogenität in der zugrunde liegenden Chemie, während der Zweite Ansatz auf der Bildung heterogener Phasen in Kolloidpartikeln aus homogenen Mischungen heraus durch kontrollierte Phasenseparation beruht.rnIm Detail beschäftigt sich der erste Teil der Dissertation mit einer neuen Herstellungsmethode für teilkristalline Komposit-Kolloidpartikel mit hoher Stabilität basierend auf der Aggregation flüssiger Monomertropfen an teilkristalline Polyacrylnitrilpartikel. Nach der Aggregation wurden hochstabile Dispersionen bestehend aus strukturierten, teilkristallinen Kompositpartikeln durch freie radikalische Polymerisation erhalten, während ein direktes Mischen der PAN Dispersionen mit Methacrylat-Polymerdispersionen zur unmittelbaren Koagulation führte. In Abhängigkeit von der Glastemperatur des Methacrylatpolymers führt die anschließende freie radikalische Polymerisation zur Bildung von Rasberry oder Kern-Schale Partikeln. Die auf diese Weise hergestellten Partikel sind dazu in der Lage, kontinuierliche Filme mit eingebetteten teilkristallinen Phasen zu bilden, welche als Sauerstoffbarriere Anwendung finden können.rnDer zweite Teil der Dissertation beschreibt eine neue Methode zur Herstellung strukturierter Duroplast-Thermoplast Komposit-Kolloidpartikel. Die Bildung eines Duroplastnetzwerks mit einer thermoplastischen Hülle wurde in zwei Schritten durch verschiedene, separate Polymerisationsmechanismen erreicht: Polyaddition und freie radikalische Polymerisation. Es wurden stabile Miniemulsionen erhalten, welche aus Bisphenol-F basiertem Epoxidharz, Phenalkamin-basiertem Härter und Vinlymonomere bestehen. Sie wurden durch Ultraschall mit nachfolgender Härtung bei verschiedenen Temperaturen als sogenannte Seed-Emulsionen hergestellt. Weitere Vinylmonomere wurden hinzugegeben und nachfolgend polymerisiert, was zur Bildung von Kern-Schale, beziehungsweise Duroplast-Thermoplast Kolloidpartikeln führte. Dabei findet in beiden Fällen zwischen der duroplastischen und der thermoplastischen Phase eine chemisch induzierte Phasenseparation statt, welche essenziell für die Bildung heterogener Strukturen ist. Die auf diese Weise hergestellten Kompositpartikel sind dazu in der Lage, transparente Filme zu bilden, welche unter geeigneten Bedingungen deutlich verbesserte mechanische Eigenschaften im Vergleich zu reinen Duroplastfilmen bereitstellen.rn

Evaluating the reinforcement of inorganic fullerene-like nanoparticles in thermoplastic matrices by depth-sensing indentation

The reinforcing effect of inorganic fullerene-like tungsten disulfide (IF-WS2) nanoparticles in two different polymer matrices, isotactic polypropylene (iPP) and polyphenylene sulfide (PPS), has been investigated by means of dynamic depth-sensing indentation. The hardness and elastic modulus enhancement upon filler addition is analyzed in terms of two main contributions: changes in the polymer matrix nanostructure and intrinsic properties of the filler including matrix-particle load transfer. It is found that the latter mainly determines the overall mechanical improvement, whereas the nanostructural changes induced in the polymer matrix only contribute to a minor extent. Important differences are suggested between the mechanisms of deformation in the two nanocomposites, resulting in a moderate mechanical enhancement in case of iPP (20% for a filler loading of 1%), and a remarkable hardness increase in case of PPS (60% for the same filler content). The nature of the polymer amorphous phase, whether in the glassy or rubbery state, seems to play here an important role. Finally, nanoindentation and dynamic mechanical analysis measurements are compared and discussed in terms of the different directionality of the stresses applied.

Thermoplastic Polymer Nanocomposites Based on Inorganic Fullerene-like Nanoparticles and Inorganic Nanotubes

Using inorganic fullerene-like (IF) nanoparticles and inorganic nanotubes (INT) in organic-inorganic hybrid composite, materials provide the potential for improving thermal, mechanical, and tribological properties of conventional composites. The processing of such high-performance hybrid thermoplastic polymer nanocomposites is achieved via melt-blending without the aid of any modifier or compatibilizing agent. The incorporation of small quantities (0.1-4 wt.%) of IF/INTs (tungsten disulfide, IF-WS2 or molybdenum disulfide, MoS2) generates notable performance enhancements through reinforcement effects and excellent lubricating ability in comparison with promising carbon nanotubes or other inorganic nanoscale fillers. It was shown that these IF/INT nanocomposites can provide an effective balance between performance, cost effectiveness, and processability, which is of significant importance for extending the practical applications of diverse hierarchical thermoplastic-based composites.

Multiscale-fiber-reinforced thermoplastic composites incorporating carbon nanotubes: A review

This article reviews recent literature on hierarchical thermoplastic-based composites that simultaneously incorporate carbon nanotubes (CNTs) and conventional microscale fibers, and discusses the structure?property relationships of the resulting hybrids. The mixing of multiple and multiscale constituents enables the preparation of materials with new or improved properties due to synergistic effects. By exploiting the outstanding mechanical, thermal and electrical properties of CNTs, a new generation of multifunctional high-performance composites suitable for a wide variety of applications can be developed.