A method for measuring the contact area in instrumented indentation testing by tip scanning probe microscopy imaging

The determination of the contact area is a key step to derive mechanical properties such as hardness or an elastic modulus by instrumented indentation testing. Two families of procedures are dedicated to extracting this area: on the one hand, post mortem measurements that require residual imprint imaging, and on the other hand, direct methods that only rely on the load vs. the penetration depth curve. With the development of built-in scanning probe microscopy imaging capabilities such as atomic force microscopy and indentation tip scanning probe microscopy, last generation indentation devices have made systematic residual imprint imaging much faster and more reliable. In this paper, a new post mortem method is introduced and further compared to three existing classical direct methods by means of a numerical and experimental benchmark covering a large range of materials. It is shown that the new method systematically leads to lower error levels regardless of the type of material. Pros and cons of the new method vs. direct methods are also discussed, demonstrating its efficiency in easily extracting mechanical properties with an enhanced confidence

Functional food science and defence against reactive oxidative species

This paper assesses critically the science base that underpins the argument that oxidative damage is a significant causative factor in the development of human diseases and that antioxidants are capable of preventing or ameliorating these disease processes. The assessment has been carried out under a number of headings, and some recommendations for future research are made based on the present day knowledge base. The knowledge database (1) Consideration of the basic science that underlies understanding of the role of free radicals in causing cellular pathologies, and the role of antioxidants in preventing this, shows that an imbalance of reactive oxygen species and antioxidant defence systems may lead to chemical modifications of biologically relevant macromolecules. This imbalance provides a logical pathobiochemical mechanism for the initiation and development of several disease states. Experimental data obtained in vivo provide evidence that antioxidants function in systems that scavenge reactive oxygen species and that these are relevant to what occurs in vivo. The relevance in vivo of these observations depends inter alia on knowledge of the uptake and distribution of the antioxidant within the human body, and on what tissue levels of the antioxidant may be expected in relation to dietary levels. (2) There is some way to go until validated precise methods are available for measuring biomarkers of oxidative damage in human subjects in vivo under minimally invasive conditions. With respect to oxidative damage in DNa, HPLC and GC-mass spectrophotometry methods have both merits and limitations. Lipid oxidation products in plasma are best measured as isoprostanes or as lipid hydroperoxides using specific HPLC techniques. Development of isoprostane measurement will advance specificity and precision. The measurement of oxidative damage to proteins has some potential but such methods have not been effectively exploited. (3) Epidemiological studies support the hypothesis that the major antioxidant nutrients vitamin E and vitamin C, and beta-carotene (which may or may not be acting as an antioxidant in vivo), may play a beneficial role in prevention of several chronic disorders. More research is needed on the impact of other non-nutrient compounds, such as other carotenoids and flavonoids, on human health. In general, human intervention studies using hard end-points are the gold standard. Trials are restricted mainly to the major antioxidants and do not allow firm conclusions because of inconsistent findings, an insufficient number of studies and the use of varying doses. There is evidence that large doses of beta-carotene may be deleterious to the health of certain subgroups of the population such as heavy habitual smokers. (4) With respect to the safety of administration of supplementary vitamins, vitamin C is safe at levels of supplementation up to 600 mg/d, and higher levels, up to 2000 mg/d, are without risk. Vitamin E has a very low human toxicity and an intake of 1000 mg/d is without risk; 3200 mg/d has been shown to be without any consistent risk. Large intakes of beta-carotene must be viewed with caution because they have been shown to confer detriment to a population at high risk of lung cancer when administered after many years of high risk (smoking) behaviour. Until further work clarifies the situation in heavy smokers with respect to taking supplements, larger doses should be avoided by such individuals. There is little reliable information about the human toxicology of flavonoids and related non-nutrient antioxidant constituents of the diet. (5) The food industry has long experience in the control of oxidative damage in foods and this experience can be used to advantage for the protection of food antioxidants which are beneficial. Some of these, such as vitamins C and E and beta-carotene, are well known, and strategies for their protection in foods are already exploited by food technologies. (ABSTRACT TRUNCATED

Materials characterisation part II: tip geometry of the Vickers indenter for microindentation tests

This is the second of two papers by the authors associated with materials characterisation methods based on hardness testing. It is important to have knowledge of the tip geometry of the indenter employed in the hardness test as this affects the correctness of the value of contact area parameter used to determine the mechanical properties. In this paper, outcomes of a study concerned with the tip geometry of the Vickers microindenter are presented. Results from experiment are compared with results from published works and the most current accepted analytical models. A new non-contact methodology based on a residual imprint imaging process is developed and further compared with other methods using experimental and numerical analyses over a wide range of material properties. For confirmation, an assessment was undertaken using numerical dimensional analysis which permitted a large range of materials to be explored. It is shown that the proposed method is more accurate compared with other methods regardless of the mechanical properties of the material. The outcomes demonstrate that measuring contact area with the new method enhanced the overall relative error in the resulting mechanical properties including hardness and Young’s modulus of elasticity. It is also shown that the value of the contact area using actual indenter geometry obtained from experimental load-displacement analysis or FEM numerical analysis is more accurate than the value obtained from the assumption of perfect indenter geometry and hence can be used for materials with low strain hardening property. © 2017 Springer-Verlag Londo

End-group ionisation enables the use of poly(N-(2-methacryloyloxy)ethyl pyrrolidone) as an electrosteric stabiliser block for polymerisation-induced self-assembly in aqueous media

A series of near-monodisperse poly(N-2-(methacryloyloxy)ethyl pyrrolidone) (PNMEP) homopolymers was prepared via reversible addition-fragmentation chain transfer (RAFT) solution polymerisation of NMEP in ethanol at 70 °C using a carboxylic acid-functional RAFT agent. The mean degree of polymerisation (DP) was varied from 19 to 89 and acid titration indicated end-group pK a values of 5.07-5.44. Turbidimetry studies indicated that homopolymer cloud points were significantly higher at pH 7 (anionic carboxylate) than at pH 3 (neutral carboxylic acid). Moreover, this enhanced hydrophilic character enabled PNMEP to be used as a steric stabiliser for aqueous polymerisation-induced self-assembly (PISA) syntheses. Thus, a PNMEP 42 precursor was chain-extended via RAFT aqueous dispersion polymerisation of 2-hydroxypropyl methacrylate (HPMA) at 44 °C. A series of PNMEP 42 -PHPMA x diblock copolymers were synthesised using this protocol, with target PHPMA DPs of 150 to 400. High conversions were achieved and a linear evolution in M n with increasing PHPMA DP was observed. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) studies confirmed a spherical morphology in all cases. The nanoparticles flocculated either below pH 4.5 (owing to protonation) or on addition of 60 mM KCl (as a result of charge screening). Thus the anionic end-groups on the PNMEP stabiliser chains make an important contribution to the overall colloidal stability. Similarly, a PNMEP 53 macro-CTA was chain-extended via RAFT aqueous emulsion polymerisation of 2-ethoxyethyl methacrylate (EEMA) at 44 °C. Again, a neutral solution pH was critical for the synthesis of colloidally stable nanoparticles. High conversions were achieved as the target PEEMA DP was varied between 100 and 600 and a linear evolution in molecular weight with PEEMA DP was confirmed by chloroform GPC studies. DLS experiments indicated a monotonic increase in nanoparticle diameter with PEEMA DP and TEM studies confirmed a spherical morphology in each case. In summary, PNMEP can be used as a water-soluble steric stabiliser for aqueous PISA syntheses provided that it contains an anionic carboxylate end-group to enhance its hydrophilic character

Thermo-responsive Diblock Copolymer Worm Gels in Non-polar Solvents

Benzyl methacrylate (BzMA) is polymerized using a poly(lauryl methacrylate) macromolecular chain transfer agent (PLMA macro-CTA) using reversible addition–fragmentation chain transfer (RAFT) polymerization at 70 °C in n-dodecane. This choice of solvent leads to an efficient dispersion polymerization, with polymerization-induced self-assembly (PISA) occurring via the growing PBzMA block to produce a range of PLMA–PBzMA diblock copolymer nano-objects, including spheres, worms, and vesicles. In the present study, particular attention is paid to the worm phase, which forms soft free-standing gels at 20 °C due to multiple inter-worm contacts. Such worm gels exhibit thermo-responsive behavior: heating above 50 °C causes degelation due to the onset of a worm-to-sphere transition. Degelation occurs because isotropic spheres interact with each other much less efficiently than the highly anisotropic worms. This worm-to-sphere thermal transition is essentially irreversible on heating a dilute solution (0.10% w/w) but is more or less reversible on heating a more concentrated dispersion (20% w/w). The relatively low volatility of n-dodecane facilitates variable-temperature rheological studies, which are consistent with eventual reconstitution of the worm phase on cooling to 20 °C. Variable-temperature 1H NMR studies conducted in d26-dodecane confirm partial solvation of the PBzMA block at elevated temperature: surface plasticization of the worm cores is invoked to account for the observed change in morphology, because this is sufficient to increase the copolymer curvature and hence induce a worm-to-sphere transition. Small-angle X-ray scattering and TEM are used to investigate the structural changes that occur during the worm-to-sphere-to-worm thermal cycle; experiments conducted at 1.0 and 5.0% w/w demonstrate the concentration-dependent (ir)reversibility of these morphological transitions

RAFT aqueous dispersion polymerization yields poly(ethylene glycol)-based diblock copolymer nano-objects with predictable single phase morphologies

A poly(ethylene glycol) (PEG) macromolecular chain transfer agent (macro-CTA) is prepared in high yield (>95%) with 97% dithiobenzoate chain-end functionality in a three-step synthesis starting from a monohydroxy PEG113 precursor. This PEG113-dithiobenzoate is then used for the reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). Polymerizations conducted under optimized conditions at 50 °C led to high conversions as judged by 1H NMR spectroscopy and relatively low diblock copolymer polydispersities (Mw/Mn < 1.25) as judged by GPC. The latter technique also indicated good blocking efficiencies, since there was minimal PEG113 macro-CTA contamination. Systematic variation of the mean degree of polymerization of the core-forming PHPMA block allowed PEG113-PHPMAx diblock copolymer spheres, worms, or vesicles to be prepared at up to 17.5% w/w solids, as judged by dynamic light scattering and transmission electron microscopy studies. Small-angle X-ray scattering (SAXS) analysis revealed that more exotic oligolamellar vesicles were observed at 20% w/w solids when targeting highly asymmetric diblock compositions. Detailed analysis of SAXS curves indicated that the mean number of membranes per oligolamellar vesicle is approximately three. A PEG 113-PHPMAx phase diagram was constructed to enable the reproducible targeting of pure phases, as opposed to mixed morphologies (e.g., spheres plus worms or worms plus vesicles). This new RAFT PISA formulation is expected to be important for the rational and efficient synthesis of a wide range of biocompatible, thermo-responsive PEGylated diblock copolymer nano-objects for various biomedical applications

Polymerization-Induced Self-Assembly of Block Copolymer Nano-objects via RAFT Aqueous Dispersion Polymerization

In this Perspective, we discuss the recent development of polymerization-induced self-assembly mediated by reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization. This approach has quickly become a powerful and versatile technique for the synthesis of a wide range of bespoke organic diblock copolymer nano-objects of controllable size, morphology, and surface functionality. Given its potential scalability, such environmentally-friendly formulations are expected to offer many potential applications, such as novel Pickering emulsifiers, efficient microencapsulation vehicles, and sterilizable thermo-responsive hydrogels for the cost-effective long-term storage of mammalian cells

Strengthening mechanisms in thermomechanically processed NbTi-microalloyed steel

The effect of deformation temperature on microstructure and mechanical properties was investigated for thermomechanically processed NbTi-microalloyed steel with ferrite-pearlite microstructure. With a decrease in the finish deformation temperature at 1348 K to 1098 K (1075 °C to 825 °C) temperature range, the ambient temperature yield stress did not vary significantly, work hardening rate decreased, ultimate tensile strength decreased, and elongation to failure increased. These variations in mechanical properties were correlated to the variations in microstructural parameters (such as ferrite grain size, solid solution concentrations, precipitate number density and dislocation density). Calculations based on the measured microstructural parameters suggested the grain refinement, solid solution strengthening, precipitation strengthening, and work hardening contributed up to 32 pct, up to 48 pct, up to 25 pct, and less than 3 pct to the yield stress, respectively. With a decrease in the finish deformation temperature, both the grain size strengthening and solid solution strengthening increased, the precipitation strengthening decreased, and the work hardening contribution did not vary significantly