190 resultados para Monatomic chains


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The crystal structure of the 2:1 proton-transfer compound of brucine with biphenyl-4,4’-disulfonate, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate (1) has been determined at 173 K. Crystals are monoclinic, space group P21 with Z = 2 in a cell with a = 8.0314(2), b = 29.3062(9), c = 12.2625(3) Å, β = 101.331(2)o. The crystallographic asymmetric unit comprises two brucinium cations, a biphenyl-4,4'-disulfonate dianion and six water molecules of solvation. The brucinium cations form a variant of the common undulating and overlapping head-to-tail sheet sub-structure. The sulfonate dianions are also linked head-to-tail by hydrogen bonds into parallel zig-zag chains through clusters of six water molecules of which five are inter-associated, featuring conjoint cyclic eight-membered hydrogen-bonded rings [graph sets R33(8) and R34(8)], comprising four of the water molecules and closed by sulfonate O-acceptors. These chain structures occupy the cavities between the brucinium cation sheets and are linked to them peripherally through both brucine N+-H...Osulfonate and Ocarbonyl…H-Owater to sulfonate O bridging hydrogen bonds, forming an overall three-dimensional framework structure. This structure determination confirms the importance of water in the stabilization of certain brucine compounds which have inherent crystal instability.

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The structure of the 1:1 proton-transfer compound from the reaction of L-tartaric acid with the azo-dye precursor aniline yellow [4-(phenylazo)aniline], 4-(phenyldiazenyl)anilinium hydrogen 2R,3R-tartrate C12H12N3+ . C4H6O6- has been determined at 200 K. The asymmetric unit of the compound contains two independent phenylazoanilinium cations and two hydrogen L-tartrate anions. The structure is unusual in that all four phenyl rings of both cations have identical 50% rotational disorder. The two hydrogen L-tartrate anions form independent but similar chains through head-to-tail carboxylic O--H...O~carboxyl~ hydrogen bonds [graph set C7] which are then extended into a two-dimensional hydrogen-bonded sheet structure through hydroxyl O--H...O hydrogen-bonding links. The anilinium groups of the phenyldiazenyl cations are incorporated into the sheets and also provide internal hydrogen-bonding extensions while their aromatic tails layer in the structure without significant interaction except for weak \p--\p interactions [minimum ring centroid separation, 3.844(3) \%A]. The hydrogen L-tartrate residues of both anions have the common short intramolecular hydroxyl O--H...O~carboxyl~ hydogen bonds. This work has provided a solution to the unusual disorder problem inherent in the structure of this salt as well as giving another example of the utility of the hydrogen tartrate in the generation of sheet substructures in molecular assembly processes.

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An adaptive agent improves its performance by learning from experience. This paper describes an approach to adaptation based on modelling dynamic elements of the environment in order to make predictions of likely future state. This approach is akin to an elite sports player being able to “read the play”, allowing for decisions to be made based on predictions of likely future outcomes. Modelling of the agent‟s likely future state is performed using Markov Chains and a technique called “Motion and Occupancy Grids”. The experiments in this paper compare the performance of the planning system with and without the use of this predictive model. The results of the study demonstrate a surprising decrease in performance when using the predictions of agent occupancy. The results are derived from statistical analysis of the agent‟s performance in a high fidelity simulation of a world leading real robot soccer team.

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The structures of proton-transfer compounds of 4,5-dichlorophthalic acid (DCPA) with the aliphatic Lewis bases triethylamine, diethylamine, n-butylamine and piperidine, namely triethylaminium 2-carboxy-4,5-dichlorobenzoate C~6~H~16~N^+^ C~8~H~3~Cl~2~O~4~^-^ (I), diethylaminium 2-carboxy-4,5-dichlorobenzoate C~4~H~12~N^+^ C~8~H~3~Cl~2~O~4~^-^ (II), bis(n-butylaminium) 4,5-dichlorophthalate monohydrate 2(C~4~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (III) and bis(piperidinium) 4,5-dichlorophthalate monohydrate 2(C~5~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (IV)have been determined at 200 K. All compounds have hydrogen-bonding associations giving in (I) discrete cation-anion units, linear chains in (II) while (III) and (IV) both have two-dimensional structures. In (I) a discrete cation-anion unit is formed through an asymmetric R2/1(4) N+-H...O,O' hydrogen-bonding association whereas in (II), one-dimensional chains are formed through linear N-H...O associations by both aminium H donors. In compounds (III) and (IV) the primary N-H...O linked cation-anion units are extended into a two-dimensional sheet structure via amide N-H...O(carboxyl) and ...O(carbonyl) interactions. In the 1:1 salts [(I) and (II)], the hydrogen 4,5-dichlorophthalate anions are essentially planar with short intramolecular carboxylic acid O-H...O(carboxyl) hydrogen bonds [O...O, 2.4223(14) and 2.388(2)A respectively]. This work provides a further example of the uncommon zero-dimensional hydrogen-bonded DCPA-Lewis base salt and the one-dimensional chain structure type, while even with the hydrate structures of the 1:2 salts with the primary and secondary amines, the low dimensionality generally associated with 1:1 DCPA salts is also found.

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The radiation chemistry and the grafting of a fluoropolymer, poly(tetrafluoroethylene-coperfluoropropyl vinyl ether) (PFA), was investigated with the aim of developing a highly stable grafted support for use in solid phase organic chemistry (SPOC). A radiation-induced grafting method was used whereby the PFA was exposed to ionizing radiation to form free radicals capable of initiating graft copolymerization of styrene. To fully investigate this process, both the radiation chemistry of PFA and the grafting of styrene to PFA were examined. Radiation alone was found to have a detrimental effect on PFA when irradiated at 303 K. This was evident from the loss in the mechanical properties due to chain scission reactions. This meant that when radiation was used for the grafting reactions, the total radiation dose needed to be kept as low as possible. The radicals produced when PFA was exposed to radiation were examined using electron spin resonance spectroscopy. Both main-chain (–CF2–C.F–CF2-) and end-chain (–CF2–C.F2) radicals were identified. The stability of the majority of the main-chain radicals when the polymer was heated above the glass transition temperature suggested that they were present mainly in the crystalline regions of the polymer, while the end-chain radicals were predominately located in the amorphous regions. The radical yield at 77 K was lower than the radical yield at 303 K suggesting that cage recombination at low temperatures inhibited free radicals from stabilizing. High-speed MAS 19F NMR was used to identify the non-volatile products after irradiation of PFA over a wide temperature range. The major products observed over the irradiation temperature 303 to 633 K included new saturated chain ends, short fluoromethyl side chains in both the amorphous and crystalline regions, and long branch points. The proportion of the radiolytic products shifted from mainly chain scission products at low irradiation temperatures to extensive branching at higher irradiation temperatures. Calculations of G values revealed that net crosslinking only occurred when PFA was irradiated in the melt. Minor products after irradiation at elevated temperatures included internal and terminal double bonds and CF3 groups adjacent to double bonds. The volatile products after irradiation at 303 K included tetrafluoromethane (CF4) and oxygen-containing species from loss of the perfluoropropyl ether side chains of PFA as identified by mass spectrometry and FTIR spectroscopy. The chemical changes induced by radiation exposure were accompanied by changes in the thermal properties of the polymer. Changes in the crystallinity and thermal stability of PFA after irradiation were examined using DSC and TGA techniques. The equilibrium melting temperature of untreated PFA was 599 K as determined using a method of extrapolation of the melting temperatures of imperfectly formed crystals. After low temperature irradiation, radiation- induced crystallization was prevalent due to scission of strained tie molecules, loss of perfluoropropyl ether side chains, and lowering of the molecular weight which promoted chain alignment and hence higher crystallinity. After irradiation at high temperatures, the presence of short and long branches hindered crystallization, lowering the overall crystallinity. The thermal stability of the PFA decreased with increasing radiation dose and temperature due to the introduction of defect groups. Styrene was graft copolymerized to PFA using -radiation as the initiation source with the aim of preparing a graft copolymer suitable as a support for SPOC. Various grafting conditions were studied, such as the total dose, dose rate, solvent effects and addition of nitroxides to create “living” graft chains. The effect of dose rate was examined when grafting styrene vapour to PFA using the simultaneous grafting method. The initial rate of grafting was found to be independent of the dose rate which implied that the reaction was diffusion controlled. When the styrene was dissolved in various solvents for the grafting reaction, the graft yield was strongly dependent of the type and concentration of the solvent used. The greatest graft yield was observed when the solvent swelled the grafted layers and the substrate. Microprobe Raman spectroscopy was used to map the penetration of the graft into the substrate. The grafted layer was found to contain both poly(styrene) (PS) and PFA and became thicker with increasing radiation dose and graft yield which showed that grafting began at the surface and progressively penetrated the substrate as the grafted layer was swollen. The molecular weight of the grafted PS was estimated by measuring the molecular weight of the non-covalently bonded homopolymer formed in the grafted layers using SEC. The molecular weight of the occluded homopolymer was an order of magnitude greater than the free homopolymer formed in the surrounding solution suggesting that the high viscosity in the grafted regions led to long PS grafts. When a nitroxide mediated free radical polymerization was used, grafting occurred within the substrate and not on the surface due to diffusion of styrene into the substrate at the high temperatures needed for the reaction to proceed. Loading tests were used to measure the capacity of the PS graft to be functionialized with aminomethyl groups then further derivatized. These loading tests showed that samples grafted in a solution of styrene and methanol had superior loading capacity over samples graft using other solvents due to the shallow penetration and hence better accessibility of the graft when methanol was used as a solvent.

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In 2009, Religious Education is a designated key learning area in Catholic schools in the Archdiocese of Brisbane and, indeed, across Australia. Over the years, though, different conceptualisations of the nature and purpose of religious education have led to the construction of different approaches to the classroom teaching of religion. By investigating the development of religious education policy in the Archdiocese of Brisbane from 1984 to 2003, the study seeks to trace the emergence of new discourses on religious education. The study understands religious education to refer to a lifelong process that occurs through a variety of forms (Moran, 1989). In Catholic schools, it refers both to co-curricula activities, such as retreats and school liturgies, and the classroom teaching of religion. It is the policy framework for the classroom teaching of religion that this study explores. The research was undertaken using a policy case study approach to gain a detailed understanding of how new conceptualisations of religious education emerged at a particular site of policy production, in this case, the Archdiocese of Brisbane. The study draws upon Yeatman’s (1998) description of policy as occurring “when social actors think about what they are doing and why in relation to different and alternative possible futures” (p. 19) and views policy as consisting of more than texts themselves. Policy texts result from struggles over meaning (Taylor, 2004) in which specific discourses are mobilised to support particular views. The study has a particular interest in the analysis of Brisbane religious education policy texts, the discursive practices that surrounded them, and the contexts in which they arose. Policy texts are conceptualised in the study as representing “temporary settlements” (Gale, 1999). Such settlements are asymmetrical, temporary and dependent on context: asymmetrical in that dominant actors are favoured; temporary because dominant actors are always under challenge by other actors in the policy arena; and context - dependent because new situations require new settlements. To investigate the official policy documents, the study used Critical Discourse Analysis (hereafter referred to as CDA) as a research tool that affords the opportunity for researchers to map and chart the emergence of new discourses within the policy arena. As developed by Fairclough (2001), CDA is a three-dimensional application of critical analysis to language. In the Brisbane religious education arena, policy texts formed a genre chain (Fairclough, 2004; Taylor, 2004) which was a focus of the study. There are two features of texts that form genre chains: texts are systematically linked to one another; and, systematic relations of recontextualisation exist between the texts. Fairclough’s (2005) concepts of “imaginary space” and “frameworks for action” (p. 65) within the policy arena were applied to the Brisbane policy arena to investigate the relationship between policy statements and subsequent guidelines documents. Five key findings emerged from the study. First, application of CDA to policy documents revealed that a fundamental reconceptualisation of the nature and purpose of classroom religious education in Catholic schools occurred in the Brisbane policy arena over the last twenty-five years. Second, a disjuncture existed between catechetical discourses that continued to shape religious education policy statements, and educational discourses that increasingly shaped guidelines documents. Third, recontextualisation between policy documents was evident and dependent on the particular context in which religious education occurred. Fourth, at subsequent links in the chain, actors created their own “imaginary space”, thereby altering orders of discourse within the policy arena, with different actors being either foregrounded or marginalised. Fifth, intertextuality was more evident in the later links in the genre chain (i.e. 1994 policy statement and 1997 guidelines document) than in earlier documents. On the basis of the findings of the study, six recommendations are made. First, the institutional Church should carefully consider the contribution that the Catholic school can make to the overall pastoral mission of the diocese in twenty-first century Australia. Second, policymakers should articulate a nuanced understanding of the relationship between catechesis and education with regard to the religion classroom. Third, there should be greater awareness of the connections among policies relating to Catholic schools – especially the connection between enrolment policy and religious education policy. Fourth, there should be greater consistency between policy documents. Fifth, policy documents should be helpful for those to whom they are directed (i.e. Catholic schools, teachers). Sixth, “imaginary space” (Fairclough, 2005) in policy documents needs to be constructed in a way that allows for multiple “frameworks for action” (Fairclough, 2005) through recontextualisation. The findings of this study are significant in a number of ways. For religious educators, the study highlights the need to develop a shared understanding of the nature and purpose of classroom religious education. It argues that this understanding must take into account the multifaith nature of Australian society and the changing social composition of Catholic schools themselves. Greater recognition should be given to the contribution that religious studies courses such as Study of Religion make to the overall religious development of a person. In view of the social composition of Catholic schools, there is also an issue of ecclesiological significance concerning the conceptualisation of the relationship between the institutional Catholic Church and Catholic schools. Finally, the study is of significance because of its application of CDA to religious education policy documents. Use of CDA reveals the foregrounding, marginalising, or excluding of various actors in the policy arena.

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Environmental education is a field which has only come of age since the late nineteen sixties. While its content and practice have been widely debated and researched, its leadership has been minimally studied and, therefore, is only partially understood. The role of mentoring in the development of leaders has been alluded to, but has attracted scant research. Therefore, this study explores the importance of mentoring during the personal and professional development of leaders in environmental education. Four major research questions were investigated. Firstly, have leaders been men to red during their involvement with environmental education? Secondly, when and how has that mentoring taken place? Thirdly, what was the personal and professional effectiveness of the mentoring relationship? Fourthly, is there any continuation of the mentoring process which might be appropriate for professional development within the field of environmental education? Leaders were solicited from a broad field of environmental educators including teachers, administrators, academics, natural resource personnel, business and community persons. They had to be recognized as active leaders across several environmental education networks. The research elicited qualitative and quantitative survey data from fifty seven persons in Queensland, Australia and Colorado, USA. Seventeen semi-structured interviews were subsequently conducted with selected leaders who had nominated their mentors. This led to a further thirteen 'linked interviews' with some of the mentors' mentors and new mentorees. The interview data is presented as four cases reflecting pairs, triads, chains and webs of relationships- a major finding of the research process. The analysis of the data from the interviews and the surveys was conducted according to a grounded theory approach and was facilitated by NUD.IST, a computer program for non-numerical text analysis. The findings of the study revealed many variations on the classical mentoring patterns found in the literature. Gender and age were not seen as mportant factors, as there were examples of contemporaries in age, older men to younger women, older women to younger men, and women to women. Personal compatibility, professional respect and philosophical congruence were critical. Mentoring was initiated from early, mid and late career stages with the average length of the relationship being fourteen years. There was seldom an example of the mentoree using the mentor for hierarchical career climbing, although frequent career changes were made. However, leadership actions were found to increase after the intervention of a mentoring relationship. Three major categories of informal mentoring were revealed - perceived,acknowledged and deliberate. Further analysis led to the evolution of the core concept, a 'cascade of influence'. The major finding of this study was that this sample of leaders, mentors and new mentorees moved from the perception of having been mentored to the acknowledgment of these relationships and an affirmation of their efficacy for both personal and professional growth. Hence, the participants were more likely to continue future mentoring, not as a serendipitous happening, but through a deliberate choice. Heightened awareness and more frequent 'cascading' of mentoring have positive implications for the professional development of future leaders in environmental education in both formal and informal settings. Effective mentoring in environmental education does not seek to create 'clones' of the mentors, but rather to foster the development of autonomous mentorees who share a philosophical grounding. It is a deliberate invitation to 'join the clan'.

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In order to examine time allocation patterns within household-level trip-chaining, simultaneous doubly-censored Tobit models are applied to model time-use behavior within the context of household activity participation. Using the entire sample and a sub-sample of worker households from Tucson's Household Travel Survey, two sets of models are developed to better understand the phenomena of trip-chaining behavior among five types of households: single non-worker households, single worker households, couple non-worker households, couple one-worker households, and couple two-worker households. Durations of out-of-home subsistence, maintenance, and discretionary activities within trip chains are examined. Factors found to be associated with trip-chaining behavior include intra-household interactions with the household types and their structure and household head attributes.

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Exchange reactions between the isoindoline profluorescent nitroxide 1,1,3,3-tetramethyldibenzo[e,g]isoindolin-2-yloxyl (TMDBIO) and a TEMPO capped polystyrene were carried out. High conversions to the desired products were achieved using only stoichiometric ratios of nitroxide relative to polymer. The scope of this study was expanded by exploiting a di-nitroxide 9,10-bis(5-[1,1,3,3-tetramethylisoindolin-2-yloxy])anthracene (BTMIOA) as a connector between two polymer chains forming PS–nitroxide–PS systems.

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This research uses confirmatory factor analysis and structural equation modelling to examine how organizational size - made up of four dimensions - control, resources, trust and complexity - impacts on utilization of industry-led supply chain innovation capacity in a traditional agribusiness industry, the Australian beef industry. It confirms small business rather than larger business accords greater importance to exploiting supply chain dynamic capabilities, particularly in relation to utilizing industry –led supply chain innovation capacity. For small business in Australian beef supply chains, being agile and able to adapt and align their business practices with supply chain partners is integral to ensuring these businesses remain relevant and competitive in this market. In theoretical terms this is supported by authors in the dynamic capabilities literature as they argue these types of capabilities enable organizations to innovate faster (or better), often leading to the creation of newer sources of competitive advantage.

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To date, biodegradable networks and particularly their kinetic chain lengths have been characterized by analysis of their degradation products in solution. We characterize the network itself by NMR analysis in the solvent-swollen state under magic angle spinning conditions. The networks were prepared by photoinitiated cross-linking of poly(dl-lactide)−dimethacrylate macromers (5 kg/mol) in the presence of an unreactive diluent. Using diffusion filtering and 2D correlation spectroscopy techniques, all network components are identified. By quantification of network-bound photoinitiator fragments, an average kinetic chain length of 9 ± 2 methacrylate units is determined. The PDLLA macromer solution was also used with a dye to prepare computer-designed structures by stereolithography. For these networks structures, the average kinetic chain length is 24 ± 4 methacrylate units. In all cases the calculated molecular weights of the polymethacrylate chains after degradation are maximally 8.8 kg/mol, which is far below the threshold for renal clearance. Upon incubation in phosphate buffered saline at 37 °C, the networks show a similar mass loss profile in time as linear high-molecular-weight PDLLA (HMW PDLLA). The mechanical properties are preserved longer for the PDLLA networks than for HMW PDLLA. The initial tensile strength of 47 ± 2 MPa does not decrease significantly for the first 15 weeks, while HMW PDLLA lost 85 ± 5% of its strength within 5 weeks. The physical properties, kinetic chain length, and degradation profile of these photo-cross-linked PDLLA networks make them most suited materials for orthopedic applications and use in (bone) tissue engineering.

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In the structure of the title compound, C6H13N2O+ C7H4NO5-, the isonipecotamide cations and the 5-nitrosalicylate anions form hydrogen-bonded chain substructures through head-to-tail piperidinium N---H...O(carboxyl) hydrogen bonds and through centrosymmetric cyclic head-to-head amide-amide hydrogen-bonding associations [graph set R2/2(8)]. These chains are cross linked by amide N---H...O~carboxyl~ and piperidinium N-H...O(nitro) associations to give a two-dimensional sheet structure.

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Operations management is an area concerned with the production of goods and services ensuring that business operations are efficient in utilizing resource and effective to meet customer requirements. It deals with the design and management of products, processes, services and supply chains and considers the acquisition, development, and effective and efficient utilization of resources. Unlike other engineering subjects, content of these units could be very wide and vast. It is therefore necessary to cover the content that is most related to the contemporary industries. It is also necessary to understand what engineering management skills are critical for engineers working in the contemporary organisations. Most of the operations management books contain traditional Operations Management techniques. For example ‘inventory management’ is an important topic in operations management. All OM books deal with effective method of inventory management. However, new trend in OM is Just in time (JIT) delivery or minimization of inventory. It is therefore important to decide whether to emphasise on keeping inventory (as suggested by most books) or minimization of inventory. Similarly, for OM decisions like forecasting, optimization and linear programming most organisations now a day’s use software. Now it is important for us to determine whether some of these software need to be introduced in tutorial/ lab classes. If so, what software? It is established in the Teaching and Learning literature that there must be a strong alignment between unit objectives, assessment and learning activities to engage students in learning. Literature also established that engaging students is vital for learning. However, engineering units (more specifically Operations management) is quite different from other majors. Only alignment between objectives, assessment and learning activities cannot guarantee student engagement. Unit content must be practical oriented and skills to be developed should be those demanded by the industry. Present active learning research, using a multi-method research approach, redesigned the operations management content based on latest developments in Engineering Management area and the necessity of Australian industries. The redesigned unit has significantly helped better student engagement and better learning. It was found that students are engaged in the learning if they find the contents are helpful in developing skills that are necessary in their practical life.

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We have used a scanning tunneling microscope to manipulate heteroleptic phthalocyaninato, naphthalocyaninato, porphyrinato double-decker molecules at the liquid/solid interface between 1-phenyloctane solvent and graphite. We employed nano-grafting of phthalocyanines with eight octyl chains to place these molecules into a matrix of heteroleptic double-decker molecules; the overlayer structure is epitaxial on graphite. We have also used nano-grafting to place double-decker molecules in matrices of single-layer phthalocyanines with octyl chains. Rectangular scans with a scanning tunneling microscope at low bias voltage resulted in the removal of the adsorbed doubledecker molecular layer and substituted the double-decker molecules with bilayer-stacked phthalocyanines from phenyloctane solution. Single heteroleptic double-decker molecules with lutetium sandwiched between naphthalocyanine and octaethylporphyrin were decomposed with voltage pulses from the probe tip; the top octaethylporphyrin ligand was removed and the bottom naphthalocyanine ligand remained on the surface. A domain of decomposed molecules was formed within the double-decker molecular domain, and the boundary of the decomposed molecular domain self-cured to become rectangular. We demonstrated a molecular “sliding block puzzle” with cascades of double-decker molecules on the graphite surface.

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This paper presents a method for calculating the in-bucket payload volume on a dragline for the purpose of estimating the material’s bulk density in real-time. Knowledge of the bulk density can provide instant feedback to mine planning and scheduling to improve blasting and in turn provide a more uniform bulk density across the excavation site. Furthermore costs and emissions in dragline operation, maintenance and downstream material processing can be reduced. The main challenge is to determine an accurate position and orientation of the bucket with the constraint of real-time performance. The proposed solution uses a range bearing and tilt sensor to locate and scan the bucket between the lift and dump stages of the dragline cycle. Various scanning strategies are investigated for their benefits in this real-time application. The bucket is segmented from the scene using cluster analysis while the pose of the bucket is calculated using the iterative closest point (ICP) algorithm. Payload points are segmented from the bucket by a fixed distance neighbour clustering method to preserve boundary points and exclude low density clusters introduced by overhead chains and the spreader bar. A height grid is then used to represent the payload from which the volume can be calculated by summing over the grid cells. We show volume calculated on a scaled system with an accuracy of greater than 95 per cent.