Thermoplastic elastomers (TPEs) based on multiblock copolymers are an important class of engineering polymers. They are widely used in many applications where flexibility and durability are required and are seen as a sustainable (recyclable) alternative to thermoset rubbers. While their high-temperature mechanical behavior has received recent interest, few studies have explored their fracture and fatigue behavior. Understanding how the temperature and rate-dependence of the deformation behavior at both a local and global scale influences the fatigue resistance and failure behavior is critical when designing with these materials. In this study, the failure behavior in tensile, fracture, and fatigue of well-characterized, industrially relevant, model block copoly(ether-ester) based TPEEs were evaluated over a wide range of temperatures, deformation rates, and molecular weights. Small changes in temperature or rate are shown to result in a sharp transition between a highly deformable and notch resistant response, to a more brittle and strongly notch-sensitive response. This behavior surprisingly manifests itself as a threshold strain below which the cracks do not propagate in fatigue and increasing deformation rates decreases the materials toughness in fracture tests, whereas in tensile tests the opposite is observed. The change from homogenous to inhomogeneous stress fields for tensile and fracture experiments coupled with the viscoelasticity and strain-dependent morphology of TPEs explains why a different rate dependency is observed. Strain and stress delocalization is key to achieve high toughness. Digital Image Correlation is used to measure the size and time dependence of the process zone. Comparison with micromechanical models developed for soft, elastic, and tough double network gels highlights the dominance of high strain properties for toughness and explains the strong molecular weight dependence. However, to understand the rate dependence, the characteristic times for stress transfer from the crack tip and the time to nucleate failure must be compared. The results presented in this study demonstrate the complex effect of loading conditions on the intrinsic failure mechanisms of the TPE material, and provide a first attempt at rationalizing that behavior.

We discuss the connection between high-temperature mechanics, block structure, and composition of a model series of industrially relevant, soft, thermoplastic elastomers (TPEs) containing polydisperse hard blocks (HBs). The high-strain deformation behavior of these materials results from the combination of multiple dynamics in the system, i.e., the HB associations and the mobile and entangled amorphous phase. Many soft-TPEs show a reduction in toughness with increasing temperature. Molecular weight (Mw) has been shown to improve the temperature-dependent mechanics by increasing network connectivity. In this work, we investigate the possibility to increase the network connectivity by tuning block length at constant Mw and composition. The average number of HBs per chain can be used to quantify network connectivity; however, by using block statistics, we show how increasing this value is not enough to increase the high-temperature mechanics, especially in the case of polydisperse HBs. Since temperature affects the HB ability to associate with each other, only the number of associated HBs per chain determines network connectivity. The experimental results are consistent with modeling predictions, revealing how decreasing the average block length influences the crystal stability, which ultimately controls network connectivity, and how this relationship is affected by temperature.

The mechanical properties of multiblock copolymer thermoplastic elastomers (TPEs) are governed by the interplay of different reversible dynamics [e.g., hard block (HB) association and chain entanglements]. Understanding how these physical processes influence the high-temperature deformation behavior is relevant as many TPEs lose toughness with increasing temperature. Increasing molecular weight (Mw) improves their temperature resistance that is attributed to an increase in network connectivity. Indeed, longer chains are characterized by more HBs per chain and by a longer lifetime of the entanglements in the amorphous phase. Both the associating HB and disentanglement dynamics are temperature and rate dependent. To further understand the interconnected role of Mw, temperature and rate dependencies on the mechanical properties, we perform Temperature Scanning Stress Relaxation (TSSR) tests. The method consists of measuring the stress relaxation of the materials as the temperature monotonically increases, allowing us to probe the stress response as the HBs progressively disassociate due to the increase in temperature. The results show that increasing Mw improves the high-temperature relaxation behavior, allowing the material to retain more stress than its low Mw counterpart as the temperature increases. This distinction does not show itself when performing standard small strain dynamic mechanical thermal analyses. Depending on the deformation experienced before the TSSR is performed, different relaxation behaviors are observed illustrating the importance of the current microstructure in determining the mechanical properties. The TSSR approach is well-suited to benchmark the high-temperature stress-bearing properties of network-based polymers whose morphology and, hence, properties are strongly deformation dependent.

Thermoplastic elastomers (TPEs) combine high elasticity with melt processability due to their structural features being based on physical associations rather than chemical crosslinking. Their mechanical properties are governed by the interplay of the different dynamics present in the system (i.e., hard block associations and soft block mobility) combined with their morphology. Irrespective of their exact chemical structure or type of association (crystals, hydrogen bonds, or glassy domains), many soft TPEs show a reduction in toughness at elevated temperatures. In this study, we investigate the high-temperature mechanical properties of a model series of industrially relevant TPEs via systematically varying composition and molecular weight. The results show an increase in temperature resistance and in large-strain stress response as chain length increases. We underline the key parameters that influence the mechanical behavior and explain the observed effect of molecular weight on both the temperature- and rate-dependent large-strain response. A physical network-based model is presented that can explain the experimental findings assuming an improved network connectivity and extended lifetime of the entangled segments with increasing molecular weight.

The transport of oxygen through silicone-hydrogel (SiHy) materials is of great interest in bio-materials' applications. In this study O2 permeability of hydrogels made from UV-cured polyacrylamide containing different siloxane co-monomers were analyzed through the traditional coulometric flux method, as well as by 1H NMR T1 relaxometry. It was shown by coulometric flux methods that the crosslinked polyacrylamide with short, linear siloxane side chains (polydimethylsiloxane (PDMS)) has higher O2 permeability as well as O2 solubility, as calculated from the composite diffusivity, than that with branched siloxane (tris-(trimethylsiloxysilyl-) (TRIS)). On the other hand, based on direct measurement from NMR T1 analyses, a slightly higher O2 solubility was observed for the samples with branched siloxane as expected from its larger free volume. In order to understand the reason behind this discrepancy, a series of morphological studies using 29Si and 1H NMR T2 relaxometry, as well as small-angle X-ray scattering (SAXS) were undertaken. These results are discussed in the context of molecular dynamic simulations undertaken on the same systems which together strongly suggest that morphology plays a critical role in O2 permeability. It is proposed that samples made from the linear silicone, PDMS, has a more pronounced siloxane phase separation than its bulky counterpart, TRIS. Significantly percolating hydrophobic silicone domains with twice the siloxane content are found for the PDMS sample with reduced tortuosity of the hydrophilic domain's percolating path. The mobility in the linear siloxane was also much higher which can be attributed to the molecular structure and to fewer interfacial and topological constraints arising from the different domain structure. Hence, we propose a framework for O2 permeability in SiHys, emphasizing the importance of percolated hydrophobic domain in designing SiHy with optimized O2 permeability. The study demonstrates that while a simple permeability measurement can be used for materials' comparison, the use of multiple orthogonal techniques is critical for developing a more complete understanding of small molecule transport in heterogeneous materials.

In order to understand the influence of composition on oxygen permeability, the morphology of model silicone hydrogels in both the dry and hydrated states was characterized using a variety of techniques (AFM, HAADF-STEM, solid-state NMR, and X-ray scattering). The model system studied is heterogeneous on length scales below 20 nm and consists of globular silicone-rich domains that rearrange in response to changes in hydration. In contrast to the well-defined morphologies of block copolymer systems, these radically cured amphiphilic networks are less ordered, showing gradual composition fluctuations. Comprehensive morphology characterization rationalizes the transport behavior of these heterogeneous hydrogels: the non-linear permeability increase with increasing silicone monomer content is not only related to changes in the spatial arrangement of silicone-rich domains but also to their mobility. This understanding is needed for further optimizing soft contact lens materials where oxygen transport and optical clarity are critical features. (C) 2017 Elsevier Ltd. All rights reserved.

Hydrophilic silicone monomers (SiO Monomers) with Si-O repeats 13, 9, 3 (Figure 1) were designed and synthesized to use as ingredients for contact lenses. We investigated the effect of silicone chain length and formulation composition on oxygen permeability (Dk) of cured hydrogel films. In addition, films made with SiO Monomers were compared with films made from commercially available silicone monomers, methacrylate PDMS, TRIS and SIGMA. The influence on oxygen permeability (Dk) was studied using presence vs absence of hydrophile spacer and branched silicone vs. linear PDMS.

Designing acid- and ion-containing polymers for optimal proton, ion, or water transport would benefit profoundly from predictive models or theories that relate polymer structures with ionomer morphologies. Recently, atomistic molecular dynamics (MD) simulations were performed to study the morphologies of precise poly(ethylene-co-acrylic acid) copolymer and ionomer melts. Here, we present the first direct comparisons between scattering profiles, I(q), calculated from these atomistic MD simulations and experimental X-ray data for 11 materials. This set of precise polymers has spacers of exactly 9, 15, or 21 carbons between acid groups and has been partially neutralized with Li, Na, Cs, or Zn. In these polymers, the simulations at 120 degrees C reveal ionic aggregates with a range of morphologies, from compact, isolated aggregates (type 1) to branched, stringy aggregates (type 2) to branched, stringy aggregates that percolate through the simulation box (type 3). Excellent agreement is found between the simulated and experimental scattering peak positions across all polymer types and aggregate morphologies. The shape of the amorphous halo in the simulated I(q) profile is in excellent agreement with experimental I(q). The modified hard-sphere scattering model fits both the simulation and experimental I(q) data for type 1 aggregate morphologies, and the aggregate sizes and separations are in agreement. Given the stringy structure in types 2 and 3, we develop a scattering model based on cylindrical aggregates. Both the spherical and cylindrical scattering models fit I(q) data from the polymers with type 2 and 3 aggregates equally well, and the extracted aggregate radii and inter- and intra-aggregate spacings are in agreement between simulation and experiment. Furthermore, these dimensions are consistent with real-space analyses of the atomistic MD simulations. By combining simulations and experiments, the ionomer scattering peak can be associated with the average distance between branches of type 2 or 3 aggregates. This direct comparison of X-ray scattering data to the atomistic MD simulations is a substantive step toward providing a comprehensive, predictive model for ionomer morphology, gives substantial support for this atomistic MD model, and provides new credibility to the presence of stringy, branched, and percolated ionic aggregates in precise ionomer melts.

We perform a comprehensive set of coarse-grained molecular dynamics simulations of ionomer melts with varying polymer architectures and compare the results to experiments in order to understand ionic aggregation on a molecular level. The model ionomers contain periodically or randomly spaced charged beads, placed either within or pendant to the polymer backbone, with the counterions treated explicitly. The ionic aggregate structure was determined as a function of the spacing of charged beads and also depends on whether the charged beads are in the polymer backbone or pendant to the backbone. The low wavevector ionomer peak in the counterion scattering is observed for all systems, and it is sharpest for ionomers with periodically spaced pendant charged beads with a large spacing between charged beads. Changing to a random or a shorter spacing moves the peak to lower wavevector. We present new experimental X-ray scattering data on Na+-neutralized poly(ethylene-co-acrylic acid) ionomers that show the same two trends in the ionomer peak, for similarly structured ionomers. The order within and between aggregates, and how this relates to various models used to fit the ionomer peak, is quantified and discussed.

Solid-state 13C NMR experiments were performed on a series of linear poly(ethylene-co-acrylic acid) (E-AA) copolymers with the carboxylic acid group spaced precisely or randomly along the polyethylene backbone in order to determine the impact that molar percent acid content and acid group spacing have on the structure and dynamics of these materials. The impact of Zn-neutralization is investigated in precise E-AA ionomers. 13C cross-polarization (CP) NMR experiments with 1H dipolar or 1H spin-lock filters were utilized to identify the amorphous or crystalline components in the materials. Constraints extracted from the filtering experiments were used to fit quantitative NMR data for samples that contained both crystalline and amorphous regions. All random copolymers contained crystalline phases, while only the precise sample with the longest polyethylene run between acid groups (twenty CH2 groups) contained a crystalline component. The crystalline phase in this precise copolymer decreased with increasing zinc content.

ADVERTISEMENT RETURN TO ISSUEPREVCommunication to the...Communication to the EditorNEXTPolymer Tracer Diffusion Exhibits a Minimum in Nanocomposites Containing Spherical NanoparticlesMinfang Mu†, Michelle E. Seitz†, Nigel Clarke‡, Russell J. Composto†, and Karen I. Winey*†View Author Information† Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6272, United States‡ Department of Chemistry, Durham University, Durham DH1 3LE, England*Corresponding author. E-mail: [email protected]Cite this: Macromolecules 2011, 44, 2, 191–193Publication Date (Web):December 20, 2010Publication History Received26 August 2010Revised25 October 2010Published online20 December 2010Published inissue 25 January 2011https://pubs.acs.org/doi/10.1021/ma1019818https://doi.org/10.1021/ma1019818rapid-communicationACS PublicationsCopyright © 2010 American Chemical SocietyRequest reuse permissionsArticle Views1146Altmetric-Citations26LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Carbon nanotubes,Diffusion,Nanocomposites,Nanoparticles,Transport properties Get e-Alerts

This article simulates highly overlapped projections of spherical particles that are distributed randomly in space. The size and number of the features in the projections are examined as well as how these features change with particle size and concentration. First, there are discernable features in projection even when particles overlap extensively, and the size of these discernable features is the expected size of an individual particle. Second, the number of features increases with specimen thickness at a rate of t 0.543 when the specimen thickness is below a critical value and becomes independent of specimen thickness at higher thicknesses. A criterion is established for the critical thickness based on particle size and particle volume fraction. When the specimen thickness is known and smaller than the critical thickness, a single representative transmission electron microscopy (TEM) (or scanning TEM) image exhibiting extensive particle overlap can be used to determine the size and number density of the spherical particles.