Designed poly(ethylene glycol)/poly(D,L-lactide)-based hydrogel structures prepared by stereolithography

Three-dimensional biodegradable poly(ethylene glycol)/poly(D,L-lactide) hydrogel structures were prepared by stereolithography. A photo-polymerisable liquid resin comprising PDLLA-PEG-PDLLA-based macromer, visible light photo-initiator, dye and inhibitor in DMSO/water was used to build the structures. Hydrogels with welldefined architectures and good mechanical properties were prepared. Hydrogel structures with a gyroid pore network architecture showed narrow pore size distributions, excellent pore interconnectivity and good mechanical properties. The structures showed good cell seeding characteristics, and human mesenchymal stem cells adhered and proliferated on these materials.

New stress and velocity fields for highly frictional granular materials

The idealised theory for the quasi-static flow of granular materials which satisfy the Coulomb-Mohr hypothesis is considered. This theory arises in the limit that the angle of internal friction approaches $\pi/2$, and accordingly these materials may be referred to as being `highly frictional'. In this limit, the stress field for both two-dimensional and axially symmetric flows may be formulated in terms of a single nonlinear second order partial differential equation for the stress angle. To obtain an accompanying velocity field, a flow rule must be employed. Assuming the non-dilatant double-shearing flow rule, a further partial differential equation may be derived in each case, this time for the streamfunction. Using Lie symmetry methods, a complete set of group-invariant solutions is derived for both systems, and through this process new exact solutions are constructed. Only a limited number of exact solutions for gravity driven granular flows are known, so these results are potentially important in many practical applications. The problem of mass flow through a two-dimensional wedge hopper is examined as an illustration.

Near infrared optical materials from polymeric amorphous carbon synthesized by collisional plasma process

The synthesis of polymerlike amorphous carbon(a-C:H) thin-films by microwave excited collisional hydrocarbon plasma process is reported. Stable and highly aromatic a-C:H were obtained containing significant inclusions of poly(p-phenylene vinylene) (PPV). PPV confers universal optoelectronic properties to the synthesized material. That is a-C:H with tailor-made refractive index are capable of becoming absorption-free in visible (red)-near infrared wavelength range. Production of large aromatic hydrocarbon including phenyl clusters and/or particles is attributed to enhanced coagulation of elemental plasma species under collisional plasma conditions. Detailed structural and morphological changes that occur in a-C:H during the plasma synthesis are also described.

Formation of nanoporous materials via mild retro-Diels–Alder chemistry

Poly(styrene)-block-poly(ethylene oxide) copolymers synthesized via the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and hetero Diels–Alder (HDA) cycloaddition can be cleaved in the solid state by a retro-HDA reaction occurring at 90 °C. Nanoporous films can be prepared from these polymers using a simple heating and washing procedure.

The flammability of metallic materials in normal and reduced gravity

Metallic materials exposed to oxygen-enriched atmospheres – as commonly used in the medical, aerospace, aviation and numerous chemical processing industries – represent a significant fire hazard which must be addressed during design, maintenance and operation. Hence, accurate knowledge of metallic materials flammability is required. Reduced gravity (i.e. space-based) operations present additional unique concerns, where the absence of gravity must also be taken into account. The flammability of metallic materials has historically been quantified using three standardised test methods developed by NASA, ASTM and ISO. These tests typically involve the forceful (promoted) ignition of a test sample (typically a 3.2 mm diameter cylindrical rod) in pressurised oxygen. A test sample is defined as flammable when it undergoes burning that is independent of the ignition process utilised. In the standardised tests, this is indicated by the propagation of burning further than a defined amount, or „burn criterion.. The burn criterion in use at the onset of this project was arbitrarily selected, and did not accurately reflect the length a sample must burn in order to be burning independent of the ignition event and, in some cases, required complete consumption of the test sample for a metallic material to be considered flammable. It has been demonstrated that a) a metallic material.s propensity to support burning is altered by any increase in test sample temperature greater than ~250-300 oC and b) promoted ignition causes an increase in temperature of the test sample in the region closest to the igniter, a region referred to as the Heat Affected Zone (HAZ). If a test sample continues to burn past the HAZ (where the HAZ is defined as the region of the test sample above the igniter that undergoes an increase in temperature of greater than or equal to 250 oC by the end of the ignition event), it is burning independent of the igniter, and should be considered flammable. The extent of the HAZ, therefore, can be used to justify the selection of the burn criterion. A two dimensional mathematical model was developed in order to predict the extent of the HAZ created in a standard test sample by a typical igniter. The model was validated against previous theoretical and experimental work performed in collaboration with NASA, and then used to predict the extent of the HAZ for different metallic materials in several configurations. The extent of HAZ predicted varied significantly, ranging from ~2-27 mm depending on the test sample thermal properties and test conditions (i.e. pressure). The magnitude of the HAZ was found to increase with increasing thermal diffusivity, and decreasing pressure (due to slower ignition times). Based upon the findings of this work, a new burn criterion requiring 30 mm of the test sample to be consumed (from the top of the ignition promoter) was recommended and validated. This new burn criterion was subsequently included in the latest revision of the ASTM G124 and NASA 6001B international test standards that are used to evaluate metallic material flammability in oxygen. These revisions also have the added benefit of enabling the conduct of reduced gravity metallic material flammability testing in strict accordance with the ASTM G124 standard, allowing measurement and comparison of the relative flammability (i.e. Lowest Burn Pressure (LBP), Highest No-Burn Pressure (HNBP) and average Regression Rate of the Melting Interface(RRMI)) of metallic materials in normal and reduced gravity, as well as determination of the applicability of normal gravity test results to reduced gravity use environments. This is important, as currently most space-based applications will typically use normal gravity information in order to qualify systems and/or components for reduced gravity use. This is shown here to be non-conservative for metallic materials which are more flammable in reduced gravity. The flammability of two metallic materials, Inconel® 718 and 316 stainless steel (both commonly used to manufacture components for oxygen service in both terrestrial and space-based systems) was evaluated in normal and reduced gravity using the new ASTM G124-10 test standard. This allowed direct comparison of the flammability of the two metallic materials in normal gravity and reduced gravity respectively. The results of this work clearly show, for the first time, that metallic materials are more flammable in reduced gravity than in normal gravity when testing is conducted as described in the ASTM G124-10 test standard. This was shown to be the case in terms of both higher regression rates (i.e. faster consumption of the test sample – fuel), and burning at lower pressures in reduced gravity. Specifically, it was found that the LBP for 3.2 mm diameter Inconel® 718 and 316 stainless steel test samples decreased by 50% from 3.45 MPa (500 psia) in normal gravity to 1.72 MPa (250 psia) in reduced gravity for the Inconel® 718, and 25% from 3.45 MPa (500 psia) in normal gravity to 2.76 MPa (400 psia) in reduced gravity for the 316 stainless steel. The average RRMI increased by factors of 2.2 (27.2 mm/s in 2.24 MPa (325 psia) oxygen in reduced gravity compared to 12.8 mm/s in 4.48 MPa (650 psia) oxygen in normal gravity) for the Inconel® 718 and 1.6 (15.0 mm/s in 2.76 MPa (400 psia) oxygen in reduced gravity compared to 9.5 mm/s in 5.17 MPa (750 psia) oxygen in normal gravity) for the 316 stainless steel. Reasons for the increased flammability of metallic materials in reduced gravity compared to normal gravity are discussed, based upon the observations made during reduced gravity testing and previous work. Finally, the implications (for fire safety and engineering applications) of these results are presented and discussed, in particular, examining methods for mitigating the risk of a fire in reduced gravity.

Calcium ions promote osteogenic differentiation and mineralization of human dental pulp cells : implication for pulp capping materials

Calcium (Ca) is the main element of most pulp capping materials and plays an essential role in mineralization. Different pulp capping materials can release various concentrations of Ca ions leading to different clinical outcomes. The purpose of this study was to investigate the effects of various concentrations of Ca ions on the growth and osteogenic differentiation of human dental pulp cells (hDPCs). Different concentrations of Ca ions were added to growth culture medium and osteogenic inductive culture medium. A Cell Counting Kit-8 (CCK-8) was used to determine the proliferation of hDPCs in growth culture medium. Osteogenic differentiation and mineralization were measured by alkaline phosphatase (ALP) assay, Alizarin red S/von kossa staining, calcium content quantitative assay. The selected osteogenic differentiation markers were investigated by quantitative real-time polymerase chain reaction (qRT-PCR). Within the range of 1.8–16.2 mM, increased concentrations of Ca ions had no effect on cell proliferation, but led to changes in osteogenic differentiation. It was noted that enhanced mineralized matrix nodule formation was found in higher Ca ions concentrations; however, ALP activity and gene expression were reduced. qRT-PCR results showed a trend towards down-regulated mRNA expression of type I collagen (COL1A2) and Runx2 at elevated concentrations of Ca ions, whereas osteopontin (OPN) and osteocalcin (OCN) mRNA expression was significantly up-regulated. Ca ions content in the culture media can significantly influence the osteogenic properties of hDPCs, indicating the importance of optimizing Ca ions release from dental pulp capping materials in order to achieve desirable clinical outcomes.

Infrared and Raman spectroscopic studies of archaeological materials

The use of vibrational spectroscopic techniques to characterise historical artefacts and art works continues to grow and to provide the archaeologist and art historian with significant information with which to understand the nature and activities of previous peoples and civilizations. In addition, conservators can gain knowledge of the composition of artworks or historical objects and so are better equipped to ensure their preservation. Both infrared and Raman have been widely used. Microspectroscopy is the preferred sampling technique as it requires only a very small sample, which often can be recovered. The use of synchrotron radiation in conjunction with IR microspectroscopy is increasing because of the substantial benefits in terms of improved spatial resolution and signal-to-noise ratio. The key trend for the future is the growth in the use of portable instruments, both IR and Raman, which are becoming important because they allow non-destructive measurements to be made in situ, for example at an archaeological site or at a museum.