Toughness Optimization of SBR Elastomers – Use of Fracture Mechanics Methods for Characterization

Elastomer materials are used in a wide application range and subjected to different loading from which failure of the material results. Because this failure is caused by initiation and propagation of cracks, the application of fracture mechanics methods for the assessment of the material is obvious. A short summary of the methods of technical fracture mechanics including possibilities of determination of crack resistance curves is given. Vulcanizates on the basis of SBR 1500 with various sulfur and carbon black contents were investigated. For describing the crack initiation and crack propagation behavior, several fracture mechanics examination methods were applied. Tear‐analyzer results were used to assess the crack propagation behavior under fatigue‐like loading conditions. Furthermore, for the characterization of the crack resistance of the materials under impact‐like loading conditions, instrumented tensile‐impact tests were performed. To obtain information about the initiation and propagation of a stable crack, quasi‐static fracture mechanics tests were applied. The results of the several tests are discussed in dependence on sulfur and carbon black contents. We found a non‐monotonous behavior of the toughness as a function of carbon black loading. An explanation is given in connection with a percolation‐like transition in filler morphology on larger length scales.

Schematic crack propagation curve for characterizing the fatigue behavior of the vulcanizates recorded in a TFA test.     

Regioselective Alkoxylation of 2,2,4-Trimethyl-1,3-pentanediol

An efficient procedure for the regioselective synthesis of secondary alcohol alkoxylates from 2,2,4-trimethyl-1,3-pentanediol (TMPD) is described. TMPD was reacted with propylene oxide followed by ethylene oxide in the presence of a catalytic amount of alkali metal hydroxide to form secondary alcohol alkoxylates. Instead of a mixture of compounds resulting from the reaction of TMPD and propylene oxide, the primary hydroxyl group of the TMPD reacted to form predominantly 2,2,4-trimethyl-3-hydroxypentylpropoxylate as the major product. On further ethoxylation the less hindered secondary hydroxyl group of the 2,2,4-trimethyl-3-hydroxypentylpropoxylate reacted predominantly. ¹³C NMR indicated that the secondary hydroxyl group (96.2 mol%) of TMPD remained unreacted during alkoxylation.     

Morphology and crack resistance behavior of binary block copolymer blends

Fracture behavior of binary blends comprising of styrene-butadiene block copolymers having star and triblock architectures was studied via instrumented Charpy impact test. The toughness of the ductile blends was characterized by dynamic crack resistance curves (R-curves).This study represents a systematic investigation of crack resistance behavior of nanometer structured binary block copolymer blends and the development of a new material with a combination of high toughness and transparency, usually not observed in incompatible polymer blends. While the lamellar star block copolymer shows an elastic behavior (small-scale yielding and unstable crack growth), adding of 20 wt% of the triblock copolymer leads to a stable crack growth and at 60 wt% of the triblock copolymer the strong increase of toughness values indicate a tough/high-impact transition, demonstrating the existence of novel toughening concepts for polymers based on nanometer structured materials.     

The effect of stoichiometry on the fracture toughness of a liquid crystalline epoxy

The fracture toughness of a liquid crystalline epoxy was compared with that of a standard bisphenol‐A based epoxy to understand how both the liquid crystalline structure and the crosslink density affect fracture toughness. For the liquid crystalline epoxy, the liquid crystalline domain size decreased with increasing temperature of cure and away from the stoichiometric formulation. Quantitative fractography showed that there is a competition between the liquid crystalline domain structure and the stoichiometry in determining the fracture toughness. At some cure conditions the effect of the domains is dominant. When the cure conditions are adjusted to reduce the domain size, the domains become too small to affect the fracture toughness, and thus the effect of the stoichiometry is dominant. The result is that the formation of liquid crystalline structure only increases the fracture toughness relative to that of a traditional epoxy at and near the stoichiometric formulation.     

Engineered Biomolecular Recognition of RDX by Using a Thermostable Alcohol Dehydrogenase as a Protein Scaffold

There are many biotechnology applications that would benefit from simple, stable proteins with engineered biomolecular recognition. Here, we explored the hypothesis that a thermostable alcohol dehydrogenase (AdhD from Pyrococcus furiosus) could be engineered to bind a small molecule instead of a cofactor or molecules involved in the catalytic transition state. We chose the explosive molecule 1,3,5‐trinitro‐1,3,5‐triazine (royal demolition explosive, RDX) as a proof‐of‐concept. Its low solubility in water was exploited for immobilization for biopanning by using ribosome display. Docking simulations were used to identify two potential binding sites in AdhD, and a randomized library focused on tyrosine or serine mutations was used to determine that RDX was binding in the substrate binding pocket of the enzyme. A fully randomized binding pocket library was selected, and affinity maturation by error‐prone PCR led to the identification of a mutant (EP‐16) that gained the ability to bind RDX with an affinity of (73±11) μm . These results underscore the way in which thermostable enzymes can be useful scaffolds for expanding the biomolecular recognition toolbox.     

Water-Compatible Lewis Acid-Catalyzed Conversion of Carbohydrates to 5-Hydroxymethylfurfural in a Biphasic Solvent System

Water-compatible lanthanide-based Lewis acids for the efficient conversion of glucose and other carbohydrates to produce 5-hydroxymethylfurfural (HMF) were demonstrated in a biphasic reactor using sec-butyl phenol as the extracting solvent. The reaction of glucose dehydration to HMF was found to proceed under near-neutral conditions (pH?=?5.5) and a moderately high yield of 42?mol?% could be obtained. The combined catalytic system also showed effectiveness to convert other polysaccharides to HMF. Furthermore, the aqueous phase was recycled and used for multiple times without significant loss of catalytic performance.     

A simple intrinsic measure for rapid crack propagation in bimodal polyethylene pipe grades validated by elastic–plastic fracture mechanics analysis of data from instrumented Charpy impact test

Conventional test procedures, such as the S4 test to analyze the resistance against rapid crack propagation (RCP) of plastic pipe materials are characterized by usage of a lot of material, are far from saving of time and they are‐in need of special experimental set‐ups. Therefore, in the last decade, small‐scale accelerated reliable tests (SMART) are developed ‐ worldwide to overcome the disadvantage of such conventional tests. In this article, fracture mechanics based analysis of instrumented Charpy impact test data for a set of bimodal high‐density polyethylene pipe grades are compared with data of the conventional Charpy impact test. From this comparison the Charpy impact strength at ?30°C comes forth as a robust reproducible measure of the resistance to RCP and it is therefore proposed as a SMART method to rank materials with respect to RCP resistance. POLYM. ENG. SCI., 57:13–21, 2017. © 2016 Society of Plastics Engineers     

Effects of particle arrangement and particle damage on the mechanical response of metal matrix nanocomposites: A numerical analysis

The spatial distribution of reinforcement particles has a significant effect on the mechanical response and damage evolution of metal matrix composites (MMCs). It is observed that particle clustering leads to higher flow stress, earlier particle damage, as well as lower overall failure strain. In recent years, experimental studies have shown that reducing the size of particles to the nanoscale dramatically increases the mechanical strength of MMCs even at low particle volume fractions. However, the effects of particle distribution and particle damage on the mechanical response of these metal matrix nanocomposites, which may be different from that observed in normal MMCs, has not been widely explored. In this paper, these effects are investigated numerically using plane strain discrete dislocation simulations. The results show that non-clustered random and highly clustered particle arrangements result in the highest and lowest flow stress, respectively. The effect of particle fracture on the overall response of the nanocomposite is also more significant for non-clustered random and mildly clustered particle arrangements, in which particle damage begins earlier and the fraction of damaged particles is higher, compared to regular rectangular and highly clustered arrangements.     

Increasing recyclability of PC,ABS and PMMA: Morphology and fracture behavior of binary and ternary blends

Binary and ternary blends of PC, ABS, and PMMA were studied. The blends were produced from original and recycled materials by melt mixing in a wide range of compositions. Instrumented Charpy impact testing, tensile testing, rheology investigations, and electron microscopy were carried out to determine the relationship between the deformation and fracture behavior, blend composition, morphology, and processing parameters. Resistance against unstable crack propagation was evaluated using the concepts of J‐integral and crack‐tip‐opening displacement (CTOD). The transition from ductile elastic‐plastic to brittle‐linear elastic fracture behavior was observed in the case of PC/ABS/PMMA blend at 10% of PMMA. Reprocessing had only a slight influence on the deformation and fracture behavior of the recycled blends. The blends produced from recycled materials proved to be competitive with the original pure materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Impact of precursor preparation on density of gadolinium iron garnets synthesized via reactive sintering

Gadolinium iron garnet was obtained from two different precursors, homogenized in isopropyl alcohol and in an aqueous environment with a fixed pH. In the first case, it was a mixture of goethite (FeO(OH)) and gadolinium oxide (Gd₂O₃); in the second, a mixture of GdIP (GdFeO₃) and α-Fe₂O₃. Conditions of homogenization in the aqueous environment were selected based on the zeta (ξ) potential measurements as the function of pH. DSC measurements of the output powder mixtures allowed the identification of the effects observed during the temperature rise. In the case of the material obtained from a mixture of goethite (FeO(OH)) and gadolinium oxide, with the increasing temperature, we observe three effects, the first of which corresponds to the phase transformation of goethite into α-Fe₂O₃, the second corresponds to the reaction of gadolinium iron perovskite (GdIP) formation, and the third to the reaction in which a gadolinium iron garnet (GdIG) is formed. However, in the case of heat treatment of the mixture of GdIP and α-Fe₂O₃, we only observe the effect responsible for a solid state reaction leading to the formation of gadolinium iron garnet. Dilatometric measurements allowed to determine the changes in linear dimensions at various stages of reaction sintering. The resulting materials were sintered at temperatures of 1200, 1300, and 1400 °C. In the case of the material obtained from a mixture of perovskite and iron (III) oxide, already at the temperature of 1300 °C, a density has been obtained at around 95% of the theoretical density, and the temperature of 1400 °C allowed achieving a density of 97% of the theoretical density. Whereas, for the material obtained from a mixture of goethite (FeO(OH)) and gadolinium oxide, a density above 95% of theoretical density was achieved only at 1400 °C.