The structure of selected magnesium carbonate minerals : a near infrared and mid-infrared spectroscopic study

The approach to remove green house gases by pumping liquid CO2 several kilometres below the ground implies that many carbonate containing minerals will be formed. Among these minerals the formation of dypingite and artinite are possible; thus necessitating a study of such minerals. Two carbonate bearing minerals dypingite and artinite with a hydrotalcite related formulae have been characterised by a combination of infrared and near-infrared spectroscopy. The infrared spectra of both minerals are characterised by OH and water stretching vibrations. Both the first and second fundamental overtones of these bands are observed in the NIR spectra in the 7030 to 7235 cm-1 and 10490 to 10570 cm-1. Intense (CO3)2- symmetric and antisymmetric stretching vibrations confirm the distortion of the carbonate anion. The position of the water bending vibration indicates water is strongly hydrogen bonded to the carbonate anion in the mineral structure. Split NIR bands at around 8675 and 11100 cm-1 indicates that some replacement of magnesium ions by ferrous ions in the mineral structure has occurred.

Smectite flocculation structure modified by AI13 macromolecules; as revealed by the Transmission X-ray Microscopy (TXM)

The aggregate structure which occurs in aqueous smectitic suspensions is responsible for poor water clarification, difficulties in sludge dewatering and the unusual rheological behaviour of smectite rich soils. These macroscopic properties are dictated by the 3-D structural arrangement of smectite finest fraction within flocculated aggregates. Here, we report results from a relatively new technique, Transmission X-ray Microscopy (TXM), which makes it possible to investigate the internal structure and 3-D tomographic reconstruction of the smectite clay aggregates modified by Al13 keggin macro-molecule [Al13(O)4(OH)24(H2O)12 ]7+. Three different treatment methods were shown resulted in three different micro-structural environments of the resulting flocculation.

The structure of the copper(II) complex with 4,5-dichlorophthalic acid: The 1:1 complex 'adduct' salt trans-tetraaqua(2-carboxy-4,5-dichlorobenzoato)(4,5-dichlorobenzene-1,2-dicarboxylic acid)copper(II) 2-carboxy-4,5-dichlorobenzoate

The unusual (1:1) complex ‘adduct’ salt of copper(II) with 4,5-dichlorophthalic acid (H2DCPA), having formula [Cu(H2O)4(C8H3Cl2O4) (C8H4Cl2O4)] . (C8H3Cl2O4) has been synthesized and characterized using single-crystal X-ray diffraction. Crystals are monoclinic, space group P21/c, with Z = 4 in a cell with dimensions a = 20.1376(7), b =12.8408(4) c = 12.1910(4) Å, β = 105.509(4)o. The complex is based on discrete tetragonally distorted octahedral [CuO6] coordination centres with the four water ligands occupying the square planar sites [Cu-O, 1.962(4)-1.987(4) Å] and the monodentate carboxyl-O donors of two DCPA ligand species in the axial sites. The first of these bonds [Cu-O, 2.341(4) Å] is with an oxygen of a HDCPA monoanion, the second with an oxygen of a H2DCPA acid species [Cu-O, 2.418(4) Å]. The un-coordinated ‘adduct’ molecule is a HDCPA counter anion which is strongly hydrogen-bonded to the coordinated H2DCPA ligand [O… O, 2.503(6) Å] while a number of peripheral intra- and intermolecular hydrogen-bonding interactions give a two-dimensional network structure.

Hydrogen bonding in the water stabilized structure of the modified unsymmetrically substituted viologen chromophore, N-ethyl-N'-(2-phosphonomethyl)-4,4'-bipyridylium dichloride

The crystal structure of the modified unsymmetrically N, N'-substituted viologen chromophore, N-ethyl- N'-(2-phosphonoethyl)-4, 4'-bipyridinium dichloride 0.75 hydrate. (1) has been determined. Crystals are triclinic, space group P-1 with Z = 2 in a cell with a = 7.2550(1), b = 13.2038(5), c = 18.5752(7) Å, α = 86.495(3), β = 83.527(2), γ = 88.921(2)o. The two independent but pseudo-symmetrically related cations in the asymmetric unit form one-dimensional hydrogen-bonded chains through short homomeric phosphonic acid O-H...O links [2.455(4), 2.464(4)A] while two of the chloride anions are similarly strongly linked to phosphonic acid groups [O-H…Cl, 2.889(4), 2.896(4)Å]. The other two chloride anions together with the two water molecules of solvation (one with partial occupancy) form unusual cyclic hydrogen-bonded bis(Cl...water) dianion units which lie between the layers of bipyridylium rings of the cation chain structures with which they are weakly associated.

Customer-oriented deviance (COD) : a conceptualisation, development and validation of a behavioural measure

Frontline employee behaviours are recognised as vital for achieving a competitive advantage for service organisations. The services marketing literature has comprehensively examined ways to improve frontline employee behaviours in service delivery and recovery. However, limited attention has been paid to frontline employee behaviours that favour customers in ways that go against organisational norms or rules. This study examines these behaviours by introducing a behavioural concept of Customer-Oriented Deviance (COD). COD is defined as, “frontline employees exhibiting extra-role behaviours that they perceive to defy existing expectations or prescribed rules of higher authority through service adaptation, communication and use of resources to benefit customers during interpersonal service encounters.” This thesis develops a COD measure and examines the key determinants of these behaviours from a frontline employee perspective. Existing research on similar behaviours that has originated in the positive deviance and pro-social behaviour domains has limitations and is considered inadequate to examine COD in the services context. The absence of a well-developed body of knowledge on non-conforming service behaviours has implications for both theory and practice. The provision of ‘special favours’ increases customer satisfaction but the over-servicing of customers is also counterproductive for the service delivery and costly for the organisation. Despite these implications of non-conforming service behaviours, there is little understanding about the nature of these behaviours and its key drivers. This research builds on inadequacies in prior research on positive deviance, pro-social and pro-customer literature to develop the theoretical foundation of COD. The concept of positive deviance which has predominantly been used to study organisational behaviours is applied within a services marketing setting. Further, it addresses previous limitations in pro-social and pro-customer behavioural literature that has examined limited forms of behaviours with no clear understanding on the nature of these behaviours. Building upon these literature streams, this research adopts a holistic approach towards the conceptualisation of COD. It addresses previous shortcomings in the literature by providing a well bounded definition, developing a psychometrically sound measure of COD and a conceptually well-founded model of COD. The concept of COD was examined across three separate studies and based on the theoretical foundations of role theory and social identity theory. Study 1 was exploratory and based on in-depth interviews using the Critical Incident Technique (CIT). The aim of Study 1 was to understand the nature of COD and qualitatively identify its key drivers. Thematic analysis was conducted to analyse the data and the two potential dimensions of COD behaviours of Deviant Service Adaptation (DSA) and Deviant Service Communication (DSC) were revealed in the analysis. In addition, themes representing the potential influences of COD were broadly classified as individual factors, situational factors, and organisational factors. Study 2 was a scale development procedure that involved the generation and purification of items for the measure based on two student samples working in customer service roles (Pilot sample, N=278; Initial validation sample, N=231). The results for the reliability and Exploratory Factor Analyses (EFA) on the pilot sample suggested the scale had poor psychometric properties. As a result, major revisions were made in terms of item wordings and new items were developed based on the literature to reflect a new dimension, Deviant Use of Resources (DUR). The revised items were tested on the initial validation sample with the EFA analysis suggesting a four-factor structure of COD. The aim of Study 3 was to further purify the COD measure and test for nomological validity based on its theoretical relationships with key antecedents and similar constructs (key correlates). The theoretical model of COD consisting of nine hypotheses was tested on a retail and hospitality sample of frontline employees (Retail N=311; Hospitality N=305) of a market research panel using an online survey. The data was analysed using Structural Equation Modelling (SEM). The results provided support for a re-specified second-order three-factor model of COD which consists of 11 items. Overall, the COD measure was found to be reliable and valid, demonstrating convergent validity, discriminant validity and marginal partial invariance for the factor loadings. The results showed support for nomological validity, although the antecedents had differing impact on COD across samples. Specifically, empathy and perspective-taking, role conflict, and job autonomy significantly influenced COD in the retail sample, whereas empathy and perspective-taking, risk-taking propensity and role conflict were significant predictors in the hospitality sample. In addition, customer orientation-selling orientation, the altruistic dimension of organisational citizenship behaviours, workplace deviance, and social desirability responding were found to correlate with COD. This research makes several contributions to theory. First, the findings of this thesis extend the literature on positive deviance, pro-social and pro-customer behaviours. Second, the research provides an empirically tested model which describes the antecedents of COD. Third, this research contributes by providing a reliable and valid measure of COD. Finally, the research investigates the differential effects of the key antecedents in different service sectors on COD. The research findings also contribute to services marketing practice. Based on the research findings, service practitioners can better understand the phenomenon of COD and utilise the measurement tool to calibrate COD levels within their organisations. Knowledge on the key determinants of COD will help improve recruitment and training programs and drive internal initiatives within the firm.

Building a successful partnership to increase affordable rental housing supply in Queensland

Accessibility to housing for low to moderate income groups in Australia has been experiencing a severe decline since 2001. On the supply side, the public sector has been reducing its commitment to the direct provision of public housing. Despite high demand for affordable housing, there has been limited supply generated by non-government housing providers. One possible solution to promote an increase in affordable housing supply, like other infrastructure, is through the development of multi-stakeholder partnerships and private financing. This research aims to identify current issues underlying decision-making criteria for building multi-stakeholder partnerships to deliver affordable housing projects. It also investigates strategies for minimising risk and ensuring the financial outcomes of these partnership arrangements. A mix of qualitative in-depth interviews and quantitative surveys has been used as the main method to explore stakeholder experiences regarding their involvement in partnership arrangements in the affordable housing sector in Queensland. Two sets of interviews were conducted following an exploratory pilot study: one set in 2003-2004 and the other in 2007-2008. There were nineteen respondents representing government, private and not-for-profit organisations in the first stage interviews and surveys. The second stage interviews were focussed on twenty-two housing providers in South East Queensland. Initial analyses have been conducted using thematic and statistical analyses. This study extends the use of existing decision making tools and combines the use of a Soft System Framework to analyse the ideal state questionnaires using qualitative thematic analysis. Soft System Methodology (SSM) has been used to analyse this unstructured complex problem by using systematic thinking to develop a conceptual model and carrying it to the real world situations to solve the problem. This research found that the diversity of stakeholder capability and their level of risk acceptance will allow partnerships to develop the best synergies and a degree of collaboration which achieves the required financial return within acceptable risk parameters. However, some of the negativity attached to future commitment to such partnerships has been found to be the anticipation of a worse outcome than that expected from independent action. Many interviewees agree that housing providers' fear of financial risk and community rejection has been central to dampening their enthusiasm for entering such investment projects. The creation of a mixed-use development structure will mitigate both risk and return as the commercial income will subsidise the affordable housing development and will normalise concentration of marginalised low-income people who live in a prime location with an award winning design. In addition, tenant support schemes and rent-to-buy incentive programs will encourage them to secure their tenancies and significantly reduce the risk of rent arrears and property damage. There is also a breakthrough investment vehicle offered by the social developer which sells the non-physical but financial product to individual and institutional investors to mitigate further financial risk. Finally, this study recommends modification of the current value-for-money framework in favour of broader partnership arrangements which are more closely aligned with risk minimisation strategies.

Influence of smectite suspension structure on sheet orientation in dry sediments : XRD and AFM applications

The structure-building phenomena within clay aggregates are governed by forces acting between clay particles. Measurements of such forces are important to understand in order to manipulate the aggregate structure for applications such as dewatering of mineral processing tailings. A parallel particle orientation is required when conducting XRD investigation on the oriented samples and conduct force measurements acting between basal planes of clay mineral platelets using at. force microscopy (AFM). To investigate how smectite clay platelets were oriented on silicon wafer substrate when dried from suspension range of methods like SEM, XRD and AFM were employed. From these investigations, we conclude that high clay concns. and larger particle diams. (up to 5 μm) in suspension result in random orientation of platelets in the substrate. The best possible laminar orientation in the clay dry film, represented in the XRD 0 0 1/0 2 0 intensity ratio of 47 was obtained by drying thin layers from 0.02 wt.% clay suspensions of the natural pH. Conducted AFM investigations show that smectite studied in water based electrolytes show very long-range repulsive forces lower in strength than electrostatic forces from double-layer repulsion. It was suggested that these forces may have structural nature. Smectite surface layers rehydrate in water environment forms surface gel with spongy and cellular texture which cushion approaching AFM probe. This structural effect can be measured in distances larger than 1000 nm from substrate surface and when probe penetrate this gel layer, structural linkages are forming between substrate and clay covered probe. These linkages prevent subsequently smooth detachments of AFM probe on way back when retrieval. This effect of tearing new formed structure apart involves larger adhesion-like forces measured in retrieval. It is also suggested that these effect may be enhanced by the nano-clay particles interaction.

Hydrate stabilization in the three-dimensional hydrogen-bonded structure of the brucinium compound, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate

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.

Understanding parental physical activity : meanings, habits, and social role influence

Objectives: The research aimed to explore parents’ understandings of physical activity (PA), patterns of PA-related behaviour, and how constructions of social role expectations might influence their PA behaviour. Design and Method: Using a qualitative descriptive design and adopting a social constructionism approach to broaden interpretations of parents’ understandings, 40 adults (21 mothers, 19 fathers; aged 23 to 49 years) living in South East Queensland, Australia participated in semi-structured individual and group interviews. The interviews were analysed using thematic analysis. Results: Parents had clear understandings of what constitutes PA and engaged in various activities which were integrated with or independent of the children. Being active with children, however, was not always constructed favourably in which many parents described the difficulties of being active with their children. All individuals experienced changes in their PA behaviours after having children. For most, a decline in PA level, intensity, and structure was experienced; however, some did experience parenthood as a time to be active. A level of acceptance for the lack of activity performed was also expressed as were feelings of resentment and envy for those who maintained previous activity habits. Parenting and partner roles were considered most influential on PA-related behaviour and were constructed in ways that had both positive and negative influences on activity performance. Parents, however, were empowered to construct strategies to resolve conflicts between social role performance and being active. Conclusion: Results show that parents experience unique difficulties that intervention work should consider when designing programs aimed at increasing parental PA.