A novel profluorescent dinitroxide for imaging polypropylene degradation

Free-radical processes underpin the thermo-oxidative degradation of polyolefins. Thus, to extend the lifetime of these polymers, stabilizers are generally added during processing to scavenge the free radicals formed as the polymer degrades. Nitroxide radical precursors, such as hindered amine stabilizers (HAS),1,2 are common polypropylene additives as the nitroxide moiety is a potent scavenger of polymer alkyl radicals (R¥). Oxidation of HAS by radicals formed during polypropylene degradation yields nitroxide radicals (RRNO¥), which rapidly trap the polymer degradation species to produce alkoxyamines, thus retarding oxidative polymer degradation. This increase in polymer stability is demonstrated by a lengthening of the “induction period” of the polymer (the time prior to a sharp rise in the oxidation of the polymer). Instrumental techniques such as chemiluminescence or infrared spectroscopy are somewhat limited in detecting changes in the polymer during the initial stages of degradation. Therefore, other methods for observing polymer degradation have been sought as the useful life of a polymer does not extend far beyond its “induction period”

Structure–property relationships of silk-modified mesoporous bioglass scaffolds

Porous mesopore-bioglass (MBG) scaffolds have been proposed as a new class of bone regeneration materials due to their apatite-formation and drug-delivery properties; however, the material’s inherent brittleness and high degradation and surface instability are major disadvantages, which compromise its mechanical strength and cytocompatibility as a biological scaffold. Silk, on the other hand, is a native biomaterial and is well characterized with respect to biocompatibility and tensile strength. In this study we set out to investigate what effects blending silk with MBG had on the physiochemical, drug-delivery and biological properties of MBG scaffolds with a view to bone tissue engineering applications. Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were the methods used to analyze the inner microstructure, pore size and morphology, and composition of MBG scaffolds, before and after addition of silk. The effect of silk modification on the mechanical property of MBG scaffolds was determined by testing the compressive strength of the scaffolds and also compressive strength after degradation over time. The drug-delivery potential was evaluated by the release of dexamethasone (DEX) from the scaffolds. Finally, the cytocompatibility of silk-modified scaffolds was investigated by the attachment, morphology, proliferation, differentiation and bone-relative gene expression of bone marrow stromal cells (BMSCs). The results showed that silk modification improved the uniformity and continuity of pore network of MBG scaffolds, and maintained high porosity (94%) and large-pore size (200–400 mm). There was a significant improvement in mechanical strength, mechanical stability, and control of burst release of DEX in silkmodified MBG scaffolds. Silk modification also appeared to provide a better environment for BMSC attachment, spreading, proliferation, and osteogenic differentiation on MBG scaffolds.

New strength : independent television companies in China’s television industry

As most of people know that all of mass media are state-owned in China, television stations are not exceptional to belong to the enormous state-owned system. But to date, with the economic reform in the broadcasting system and China entering into WTO, the television industry has increased greatly and the television market has matured with more and more competition. The players in China’s television industry have changed from the monologue of TV stations to multi roles of TV stations, production companies and overseas television companies, although TV stations are still the majority of China’s TV market. Especially, private television production companies are becoming more and more active in this market. In this paper, I will describe the development process and challenges of this group in China and ask whether the emergence of this group means for the whole China’s TV industry?

Private television production companies in China : new strength in the market

As most people know, all mass media, including television stations, are state-owned in China. However, with the economic reform in the broadcasting system and China entering the World Trade Organization (WTO), the television industry has expanded greatly and the television market has evolved, with an ensuing growth of competition. The players in China’s television industry have changed from a monologue of TV stations to stations that hold multiple roles and a growth of production companies and overseas television companies although the TV stations still dominate China’s television market. Private television production companies are, however, becoming increasingly active in this market.

Experimental tests on structural members fabricated from high strength steel materials

Typical high strength steels (HSS) have exceptional high strengths with improved weldability making the material attractive in modern steel constructions. However, due to lack of understanding, most of the current steel design standards are limited to conventional low strength steels (LSS, i.e. fy ≤ 450 MPa). This paper presents the details of full-scale experimental tests on short beams fabricated from BISPLATE80 HSS materials (nominal fy = 690 MPa). The various slenderness ratios of the plate elements in the test specimens were chosen in the range near the current yield limit (AS4100-1998, etc.). The experimental studies presented in this paper have produced a better understanding of the structural behaviour of HSS members subjected to local instabilities. Comparisons have also presented in the paper regarding to the design predictions from the current steel standards (AS4100-1998). This study has enabled to provide a series of proposals for proper assessment of plate slenderness limits for structural members made of representative HSS materials. This research work also enables the inclusion of further versions in the steel design specifications for typical HSS materials to be used in buildings and bridges. This paper also presents a distribution model of residual stresses in the longitudinal direction for typical HSS I-sections.

Infrared spectroscopic investigation of the effects of titania photocatalyst on the degradation of linear low density polyethylene film for commercial applications

There is a need in industry for a commodity polyethylene film with controllable degradation properties that will degrade in an environmentally neutral way, for applications such as shopping bags and packaging film. Additives such as starch have been shown to accelerate the degradation of plastic films, however control of degradation is required so that the film will retain its mechanical properties during storage and use, and then degrade when no longer required. By the addition of a photocatalyst it is hoped that polymer film will breakdown with exposure to sunlight. Furthermore, it is desired that the polymer film will degrade in the dark, after a short initial exposure to sunlight. Research has been undertaken into the photo- and thermo-oxidative degradation processes of 25 ìm thick LLDPE (linear low density polyethylene) film containing titania from different manufacturers. Films were aged in a suntest or in an oven at 50 °C, and the oxidation product formation was followed using IR spectroscopy. Degussa P25, Kronos 1002, and various organic-modified and doped titanias of the types Satchleben Hombitan and Hunstsman Tioxide incorporated into LLDPE films were assessed for photoactivity. Degussa P25 was found to be the most photoactive with UVA and UVC exposure. Surface modification of titania was found to reduce photoactivity. Crystal phase is thought to be among the most important factors when assessing the photoactivity of titania as a photocatalyst for degradation. Pre-irradiation with UVA or UVC for 24 hours of the film containing 3% Degussa P25 titania prior to aging in an oven resulted in embrittlement in ca. 200 days. The multivariate data analysis technique PCA (principal component analysis) was used as an exploratory tool to investigate the IR spectral data. Oxidation products formed in similar relative concentrations across all samples, confirming that titania was catalysing the oxidation of the LLDPE film without changing the oxidation pathway. PCA was also employed to compare rates of degradation in different films. PCA enabled the discovery of water vapour trapped inside cavities formed by oxidation by titania particles. Imaging ATR/FTIR spectroscopy with high lateral resolution was used in a novel experiment to examine the heterogeneous nature of oxidation of a model polymer compound caused by the presence of titania particles. A model polymer containing Degussa P25 titania was solvent cast onto the internal reflection element of the imaging ATR/FTIR and the oxidation under UVC was examined over time. Sensitisation of 5 ìm domains by titania resulted in areas of relatively high oxidation product concentration. The suitability of transmission IR with a synchrotron light source to the study of polymer film oxidation was assessed as the Australian Synchrotron in Melbourne, Australia. Challenges such as interference fringes and poor signal-to-noise ratio need to be addressed before this can become a routine technique.

Combined marrow stromal cell-sheet techniques and high-strength biodegradable composite scaffolds for engineered functional bone grafts

In this study, cell sheets comprising multilayered porcine bone marrow stromal cells (BMSC) were assembled with fully interconnected scaffolds made from medical-grade polycaprolactone–calcium phosphate (mPCL–CaP), for the engineering of structural and functional bone grafts. The BMSC sheets were harvested from culture flasks and wrapped around pre-seeded composite scaffolds. The layered cell sheets integrated well with the scaffold/cell construct and remained viable, with mineralized nodules visible both inside and outside the scaffold for up to 8 weeks culture. Cells within the constructs underwent classical in vitro osteogenic differentiation with the associated elevation of alkaline phosphatase activity and bone-related protein expression. In vivo, two sets of cell-sheet-scaffold/cell constructs were transplanted under the skin of nude rats. The first set of constructs (554mm3) were assembled with BMSC sheets and cultured for 8 weeks before implantation. The second set of constructs (10104mm3) was implanted immediately after assembly with BMSC sheets, with no further in vitro culture. For both groups, neo cortical and well-vascularised cancellous bone were formed within the constructs with up to 40% bone volume. Histological and immunohistochemical examination revealed that neo bone tissue formed from the pool of seeded BMSC and the bone formation followed predominantly an endochondral pathway, with woven bone matrix subsequently maturing into fully mineralized compact bone; exhibiting the histological markers of native bone. These findings demonstrate that large bone tissues similar to native bone can be regenerated utilizing BMSC sheet techniques in conjunction with composite scaffolds whose structures are optimized from a mechanical, nutrient transport and vascularization perspective.

Ultimate shear strength of LiteSteel beams

This paper presents the details of an investigation on the shear behaviour of a recently developed, cold-formed steel beam known as LiteSteel Beam (LSB).The LSB section has a unique shape of a channel beam with two rectangular hollow flanges and is produced by a patented manufacturing process involving simultaneous cold-forming and dual electric resistance welding. In the present investigation, a series of numerical analyses based on three-dimensional finite element modeling and an experimental study were carried out to investigate the shear behaviour of 10 different LSB sections. It was found that the current design rules in cold-formed steel structures design codes are very conservative for the shear design of LiteSteel beams. Significant improvements to web shear buckling occurred due to the presence of rectangular hollow flanges while considerable post-buckling strength was also observed. Therefore the design rules were further modified to include the available post-buckling strength. Suitable design rules were also developed under the direct strength method format. This paper presents the details of this investigation and the results including the final design rules for the shear capacity of LSBs. It also presents new shear strength formulae for lipped channel beams based on the current design equations for shear strength given in AISI (2007) using the same approach used for LSBs.

Degradation of piezoelectric fluropolymers in space environments

The performance criteria of piezoelectric polymers based on polyvinylidene flouride (PVDF) in complex space environments have been evaluated. Thin films of these materials are being explored as in-situ responsive materials for large aperture space-based telescopes with the shape deformation and optical features dependent on long-term deformation and optical features dependent on long-term degradation effects, mainly due to thermal cycling, vacuum UV exposure and atomic oxygen. A summary of previous studies related to materials testing and performance prediction based on a laboratory environment is presented. The degradation pathways are a combination of molecular chemical changes primarily induced via radiative damage and physical degradation processes due to temperature and atomic oxygen exposure resulting in depoling, loss of orientation and surface erosing. Experimental validation for these materials to be used in space is being conducted as part of MISSE-6 (Materials International Space Station Experiment) with an overview of the experimental strategies discussed here.

Dynamics of in vitro polymer degradation of polycaprolactone-based scaffolds : accelerated versus simulated physiological conditions

The increasing use of biodegradable devices in tissue engineering and regenerative medicine means it is essential to study and understand their degradation behaviour. Accelerated degradation systems aim to achieve similar degradation profiles within a shorter period of time, compared with standard conditions. However, these conditions only partially mimic the actual situation, and subsequent analyses and derived mechanisms must be treated with caution and should always be supported by actual long-term degradation data obtained under physiological conditions. Our studies revealed that polycaprolactone (PCL) and PCL-composite scaffolds degrade very differently under these different degradation conditions, whilst still undergoing hydrolysis. Molecular weight and mass loss results differ due to the different degradation pathways followed (surface degradation pathway for accelerated conditions and bulk degradation pathway for simulated physiological conditions). Crystallinity studies revealed similar patterns of recrystallization dynamics, and mechanical data indicated that the scaffolds retained their functional stability, in both instances, over the course of degradation. Ultimately, polymer degradation was shown to be chiefly governed by molecular weight, crystallinity susceptibility to hydrolysis and device architecture considerations whilst maintaining its thermodynamic equilibrium.

The strength and failure of silica optical fibers

The mechanical strength and failure behavior of conventional and microstructured silica optical fibers was investigated using a tensile test and fracture mechanics and numerical analyses. The effect of polymer coating on failure behavior was also studied. The results indicate that all these fibers fail in a brittle manner and failure normally starts from fiber surfaces. The failure loads observed in coated fibers are higher than those in bare fibers. The introduction of air holes reduces fiber strength and their geometrical arrangements have a remarkable effect on stress distribution in the longitudinal direction. These results are potentially useful for the design, fabrication and evaluation of optical fibers for a wide range of applications.

Behaviour of image degradation model in multiresolution

Multiresolution techniques are being extensively used in signal processing literature. This paper has two parts, in the first part we derive a relationship between the general degradation model (Y=BX+W) at coarse and fine resolutions. In the second part we develop a signal restoration scheme in a multiresolution framework and demonstrate through experiments that the knowledge of the relationship between the degradation model at different resolutions helps in obtaining computationally efficient restoration scheme.

New strength of competition and innovation : China’s independent television production

The state-owned media system in China has evolved considerably since 1994 when the first independent TV production company was officially registered. Today, there are thousands of independent TV production companies looking for market opportunities in China. Independent production companies have facilitated the circulation of program trade and investment, and in the process have encouraged innovation and professionalization. This paper focuses on the evolution of independents and the changing face of the television market. It discusses the ecology of independent television companies in China and how government regulations are impacting on the TV production market. It argues that independent TV is providing a new strength for China‟s TV market, one often suspected of being imitative, propagandistic and lacking colour.