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.

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.

Off-world robotic excavation for Large-scale habitat construction and resource extraction

This paper describes technologies we have developed to perform autonomous large-scale off-world excavation. A scale dragline excavator of size similar to that required for lunar excavation was made capable of autonomous control. Systems have been put in place to allow remote operation of the machine from anywhere in the world. Algorithms have been developed for complete autonomous digging and dumping of material taking into account machine and terrain constraints and regolith variability. Experimental results are presented showing the ability to autonomously excavate and move large amounts of regolith and accurately place it at a specified location.

Fingerprint analysis using wavelet transform with application to compression and feature extraction

The main goal of this research is to design an efficient compression al~ gorithm for fingerprint images. The wavelet transform technique is the principal tool used to reduce interpixel redundancies and to obtain a parsimonious representation for these images. A specific fixed decomposition structure is designed to be used by the wavelet packet in order to save on the computation, transmission, and storage costs. This decomposition structure is based on analysis of information packing performance of several decompositions, two-dimensional power spectral density, effect of each frequency band on the reconstructed image, and the human visual sensitivities. This fixed structure is found to provide the "most" suitable representation for fingerprints, according to the chosen criteria. Different compression techniques are used for different subbands, based on their observed statistics. The decision is based on the effect of each subband on the reconstructed image according to the mean square criteria as well as the sensitivities in human vision. To design an efficient quantization algorithm, a precise model for distribution of the wavelet coefficients is developed. The model is based on the generalized Gaussian distribution. A least squares algorithm on a nonlinear function of the distribution model shape parameter is formulated to estimate the model parameters. A noise shaping bit allocation procedure is then used to assign the bit rate among subbands. To obtain high compression ratios, vector quantization is used. In this work, the lattice vector quantization (LVQ) is chosen because of its superior performance over other types of vector quantizers. The structure of a lattice quantizer is determined by its parameters known as truncation level and scaling factor. In lattice-based compression algorithms reported in the literature the lattice structure is commonly predetermined leading to a nonoptimized quantization approach. In this research, a new technique for determining the lattice parameters is proposed. In the lattice structure design, no assumption about the lattice parameters is made and no training and multi-quantizing is required. The design is based on minimizing the quantization distortion by adapting to the statistical characteristics of the source in each subimage. 11 Abstract Abstract Since LVQ is a multidimensional generalization of uniform quantizers, it produces minimum distortion for inputs with uniform distributions. In order to take advantage of the properties of LVQ and its fast implementation, while considering the i.i.d. nonuniform distribution of wavelet coefficients, the piecewise-uniform pyramid LVQ algorithm is proposed. The proposed algorithm quantizes almost all of source vectors without the need to project these on the lattice outermost shell, while it properly maintains a small codebook size. It also resolves the wedge region problem commonly encountered with sharply distributed random sources. These represent some of the drawbacks of the algorithm proposed by Barlaud [26). The proposed algorithm handles all types of lattices, not only the cubic lattices, as opposed to the algorithms developed by Fischer [29) and Jeong [42). Furthermore, no training and multiquantizing (to determine lattice parameters) is required, as opposed to Powell's algorithm [78). For coefficients with high-frequency content, the positive-negative mean algorithm is proposed to improve the resolution of reconstructed images. For coefficients with low-frequency content, a lossless predictive compression scheme is used to preserve the quality of reconstructed images. A method to reduce bit requirements of necessary side information is also introduced. Lossless entropy coding techniques are subsequently used to remove coding redundancy. The algorithms result in high quality reconstructed images with better compression ratios than other available algorithms. To evaluate the proposed algorithms their objective and subjective performance comparisons with other available techniques are presented. The quality of the reconstructed images is important for a reliable identification. Enhancement and feature extraction on the reconstructed images are also investigated in this research. A structural-based feature extraction algorithm is proposed in which the unique properties of fingerprint textures are used to enhance the images and improve the fidelity of their characteristic features. The ridges are extracted from enhanced grey-level foreground areas based on the local ridge dominant directions. The proposed ridge extraction algorithm, properly preserves the natural shape of grey-level ridges as well as precise locations of the features, as opposed to the ridge extraction algorithm in [81). Furthermore, it is fast and operates only on foreground regions, as opposed to the adaptive floating average thresholding process in [68). Spurious features are subsequently eliminated using the proposed post-processing scheme.

GYAN: A methodology for rule extraction from artificial neural networks

Artificial neural network (ANN) learning methods provide a robust and non-linear approach to approximating the target function for many classification, regression and clustering problems. ANNs have demonstrated good predictive performance in a wide variety of practical problems. However, there are strong arguments as to why ANNs are not sufficient for the general representation of knowledge. The arguments are the poor comprehensibility of the learned ANN, and the inability to represent explanation structures. The overall objective of this thesis is to address these issues by: (1) explanation of the decision process in ANNs in the form of symbolic rules (predicate rules with variables); and (2) provision of explanatory capability by mapping the general conceptual knowledge that is learned by the neural networks into a knowledge base to be used in a rule-based reasoning system. A multi-stage methodology GYAN is developed and evaluated for the task of extracting knowledge from the trained ANNs. The extracted knowledge is represented in the form of restricted first-order logic rules, and subsequently allows user interaction by interfacing with a knowledge based reasoner. The performance of GYAN is demonstrated using a number of real world and artificial data sets. The empirical results demonstrate that: (1) an equivalent symbolic interpretation is derived describing the overall behaviour of the ANN with high accuracy and fidelity, and (2) a concise explanation is given (in terms of rules, facts and predicates activated in a reasoning episode) as to why a particular instance is being classified into a certain category.

Accelerated Partial Breast Irradiation (APBI) : a review of available techniques

Breast conservation therapy (BCT) is the procedure of choice for the management of the early stage breast cancer. However, its utilization has not been maximized because of logistics issues associated with the protracted treatment involved with the radiation treatment. Accelerated Partial Breast Irradiation (APBI) is an approach that treats only the lumpectomy bed plus a 1-2 cm margin, rather than the whole breast. Hence because of the small volume of irradiation a higher dose can be delivered in a shorter period of time. There has been growing interest for APBI and various approaches have been developed under phase I-III clinical studies; these include multicatheter interstitial brachytherapy, balloon catheter brachytherapy, conformal external beam radiation therapy and intra-operative radiation therapy (IORT). Balloon-based brachytherapy approaches include Mammosite, Axxent electronic brachytherapy and Contura, Hybrid brachytherapy devices include SAVI and ClearPath. This paper reviews the different techniques, identifying the weaknesses and strength of each approach and proposes a direction for future research and development. It is evident that APBI will play a role in the management of a selected group of early breast cancer. However, the relative role of the different techniques is yet to be clearly identified.

Anhydrous 1:1 proton-transfer compounds of isonipecotamide with picric acid and 3,5-dinitrosalicylic acid: 4-carbamoylpiperidinium 2,4,6-trinitrophenolate and two polymorphs of 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate

The structures of the anhydrous 1:1 proton-transfer compounds of isonipecotamide (4-carbamoylpiperidine) with picric acid and 3,5-dinitrosalicylic acid, namely 4-carbamoylpiperidinium 2,4,6-trinitrophenolate, C6H13N2O8+ C6H2N3O7- (I) and 4-carbamoylpiperidinium 2-carboxy-4,6-dinitrophenolate, C6H13N2O8+ C7H3N2O7-: two forms, the monoclinic alpha-polymorph (II) and the triclinic beta-polymorph (III) have been determined at 200 K. All compounds form hydrogen-bonded structures, one-dimensional in (II), two-dimensional in (I) and three-dimensional in (III). In (I), the cations form centrosymmetric cyclic head-to-tail hydrogen-bonded homodimers [graph set R2/2(14)] through lateral duplex piperidinium N---H...O(amide) interactions. These dimers are extended into a two-dimensional network structure through further interactions with anion phenolate-O and nitro-O acceptors, including a direct symmetric piperidinium N-H...O(phenol),O(nitro) cation--anion association [graph set R2/1(6)]. The monoclinic polymorph (II) has a similar R2/1(6) cation-anion hydrogen-bonding interaction to (I) but with an additional conjoint symmetrical R1/2(4) interaction as well as head-to-tail piperidinium N-H...O(amide) O hydrogen bonds and amide N-H...O(carboxyl) hydrogen bonds, give a network structure which include large R3/4(20) rings. The hydrogen bonding in the triclinic polymorph (III) is markedly different from that of monoclinic (II). The asymmetric unit contains two independent cation-anion pairs which associate through cyclic piperidinium N-H...O,O'(carboxyl) interactions [graph set R2/1(4)]. The cations also show the zig-zag head-to-tail piperidinium N-H...O(amide) hydrogen-bonded chain substructures found in (II) but in addition feature amide N-H...O(nitro) and O(phenolate) and amide N-H...O(nitro) associations. As well there is a centrosymmetric double-amide N-H...O(carboxyl) bridged bis(cation-anion) ring system [graph set R2/4(8)] in the three-dimensional framework. The structures reported here demonstrate the utility of the isonipecotamide cation as a synthon with previously unrecognized potential for structure assembly applications. Furthermore, the structures of the two polymorphic 3,5-dinitrosalicylic acid salts show an unusual dissimilarity in hydrogen-bonding characteristics, considering that both were obtained from identical solvent systems.

Automatic domain ontology extraction for context-sensitive opinion mining

Automated analysis of the sentiments presented in online consumer feedbacks can facilitate both organizations’ business strategy development and individual consumers’ comparison shopping. Nevertheless, existing opinion mining methods either adopt a context-free sentiment classification approach or rely on a large number of manually annotated training examples to perform context sensitive sentiment classification. Guided by the design science research methodology, we illustrate the design, development, and evaluation of a novel fuzzy domain ontology based contextsensitive opinion mining system. Our novel ontology extraction mechanism underpinned by a variant of Kullback-Leibler divergence can automatically acquire contextual sentiment knowledge across various product domains to improve the sentiment analysis processes. Evaluated based on a benchmark dataset and real consumer reviews collected from Amazon.com, our system shows remarkable performance improvement over the context-free baseline.

Spectral–texture feature extraction using statistical moments with application to object-based vegetation species classification

The use of appropriate features to characterise an output class or object is critical for all classification problems. In order to find optimal feature descriptors for vegetation species classification in a power line corridor monitoring application, this article evaluates the capability of several spectral and texture features. A new idea of spectral–texture feature descriptor is proposed by incorporating spectral vegetation indices in statistical moment features. The proposed method is evaluated against several classic texture feature descriptors. Object-based classification method is used and a support vector machine is employed as the benchmark classifier. Individual tree crowns are first detected and segmented from aerial images and different feature vectors are extracted to represent each tree crown. The experimental results showed that the proposed spectral moment features outperform or can at least compare with the state-of-the-art texture descriptors in terms of classification accuracy. A comprehensive quantitative evaluation using receiver operating characteristic space analysis further demonstrates the strength of the proposed feature descriptors.