Synthesis and characterization of cyclotriphosphazenes containing silicon as single solid-state precursors for the formation of silicon/phosphorus nanostructured materials

The synthesis and characterization of new organosilicon derivatives of N3P3Cl6, N3P3[NH(CH2)3Si(OEt)3]6 (1), N3P3[NH(CH2)3Si(OEt)3]3[NCH3(CH2)3CN]3 (2), and N3P3[NH(CH2)3Si(OEt)3]3[HOC6H4(CH2)CN]3 (3) are reported. Pyrolysis of 1, 2, and 3 in air and at several temperatures results in nanostructured materials whose composition and morphology depend on the temperature of pyrolysis and the substituents of the phosphazenes ring. The products stem from the reaction of SiO2 with P2O5, leading to either crystalline Si5(PO4)6O, SiP2O7 or an amorphous phase as the glass Si5(PO4)6O/3SiO2·2P2O5, depending on the temperature and nature of the trimer precursors. From 1 at 800 °C, core−shell microspheres of SiO2 coated with Si5(PO4)6O are obtained, while in other cases, mesoporous or dense structures are observed. Atomic force microscopy examination after deposition of the materials on monocrystalline silicon wafers evidences morphology strongly dependent on the precursors. Isolated islands of size ∼9 nm are observed from 1, whereas dense nanostructures with a mean height of 13 nm are formed from 3. Brunauer−Emmett−Teller measurements show mesoporous materials with low surface areas. The proposed growth mechanism involves the formation of cross-linking structures and of vacancies by carbonization of the organic matter, where the silicon compounds nucleate. Thus, for the first time, unique silicon nanostructured materials are obtained from cyclic phosphazenes containing silicon.

Mechanochemistry for Active Materials and Devices

The coupling of mechanical stress fields in polymers to covalent chemistry (polymer mechanochemistry) has provided access to previously unattainable chemical reactions and polymer transformations. In the bulk, mechanochemical activation has been used as the basis for new classes of stress-responsive polymers that demonstrate stress/strain sensing, shear-induced intermolecular reactivity for molecular level remodeling and self-strengthening, and the release of acids and other small molecules that are potentially capable of triggering further chemical response. The potential utility of polymer mechanochemistry in functional materials is limited, however, by the fact that to date, all reported covalent activation in the bulk occurs in concert with plastic yield and deformation, so that the structure of the activated object is vastly different from its nascent form. Mechanochemically activated materials have thus been limited to “single use” demonstrations, rather than as multi-functional materials for structural and/or device applications. Here, we report that filled polydimethylsiloxane (PDMS) elastomers provide a robust elastic substrate into which mechanophores can be embedded and activated under conditions from which the sample regains its original shape and properties. Fabrication is straightforward and easily accessible, providing access for the first time to objects and devices that either release or reversibly activate chemical functionality over hundreds of loading cycles.

While the mechanically accelerated ring-opening reaction of spiropyran to merocyanine and associated color change provides a useful method by which to image the molecular scale stress/strain distribution within a polymer, the magnitude of the forces necessary for activation had yet to be quantified. Here, we report single molecule force spectroscopy studies of two spiropyran isomers. Ring opening on the timescale of tens of milliseconds is found to require forces of ~240 pN, well below that of previously characterized covalent mechanophores. The lower threshold force is a combination of a low force-free activation energy and the fact that the change in rate with force (activation length) of each isomer is greater than that inferred in other systems. Importantly, quantifying the magnitude of forces required to activate individual spiropyran-based force-probes enables the probe behave as a “scout” of molecular forces in materials; the observed behavior of which can be extrapolated to predict the reactivity of potential mechanophores within a given material and deformation.

We subsequently translated the design platform to existing dynamic soft technologies to fabricate the first mechanochemically responsive devices; first, by remotely inducing dielectric patterning of an elastic substrate to produce assorted fluorescent patterns in concert with topological changes; and second, by adopting a soft robotic platform to produce a color change from the strains inherent to pneumatically actuated robotic motion. Shown herein, covalent polymer mechanochemistry provides a viable mechanism to convert the same mechanical potential energy used for actuation into value-added, constructive covalent chemical responses. The color change associated with actuation suggests opportunities for not only new color changing or camouflaging strategies, but also the possibility for simultaneous activation of latent chemistry (e.g., release of small molecules, change in mechanical properties, activation of catalysts, etc.) in soft robots. In addition, mechanochromic stress mapping in a functional actuating device might provide a useful design and optimization tool, revealing spatial and temporal force evolution within the actuator in a way that might also be coupled to feedback loops that allow autonomous, self-regulation of activity.

In the future, both the specific material and the general approach should be useful in enriching the responsive functionality of soft elastomeric materials and devices. We anticipate the development of new mechanophores that, like the materials, are reversibly and repeatedly activated, expanding the capabilities of soft, active devices and further permitting dynamic control over chemical reactivity that is otherwise inaccessible, each in response to a single remote signal.

THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

Porous Materials with Tunable Structure and Mechanical Properties via Templated Layer-by-Layer Assembly

The deposition of stiff and strong coatings onto porous templates offers a novel strategy for fabricating macroscale materials with controlled architectures at the micro- and nanoscale. Here, layer-by-layer assembly is utilized to fabricate nanocomposite-coated foams with highly customizable properties by depositing polymer–nanoclay coatings onto open-cell foam templates. The compressive mechanical behavior of these materials evolves in a predictable manner that is qualitatively captured by scaling laws for the mechanical properties of cellular materials. The observed and predicted properties span a remarkable range of density-stiffness space, extending from regions of very soft elastomer foams to very stiff, lightweight honeycomb and lattice materials.

Central Stores Inventory: Employing the IBM 1410 Magnetic Tape Computer System

The Property and Equipment Department has a central supply of automotive parts, tools, and maintenance supplies. This central supply is used to supply the repair shop and also to supply parts to the various field garages and all departments of the Commission. The old procedure involved keeping track manually of all of the parts, which involved some 22,000 items. All records, billings, arid re-order points were kept manually. Mani times the re-order points were located by reaching into a bin and finding nothing there. Desiring to improve this situation, an inventory control system was established for use on the computer. A complete record of the supplies that are stored in the central warehouse was prepared and this information was used to make a catalog. Each time an item is issued or received, it is processed through the inventory program. When the re-order point is reached, a notice is given to reorder. The procedure for taking inventory has been improved. A voucher invoice is now prepared by the computer for all issues to departments. These are some of the many benefits that have been de rived from this system.

How does employer support and educational background effect an Ergonomics Practitioner’s awareness of the relationship between ergonomics and psychosocial hazard control?

There is a growning need to address psychological health and safety in the workplace. Ergonomics tends to be widely recognized for its physical applications, such as ¨office¨ and ¨manual materials handling¨ however the other domains of specialization of ergonomics (cognitive and organizational) appear to be less well known. This study evaluates the level of understanding that professionals who practice ergonomics have of the relation between ergonomics and the control of psychosocial hazards in the workplace. A survey was distributed to ergonomics practitioners and asked them about their awareness of the relation between ergonomics and workplace psychosocial hazard control. Ergonomists and human factors specialists demonstrated a greater awareness of this relationship than other allied occupational groups that also practice ergonomics, however they indicated that there may be difficulties in the “real world” applying these areas of knowledge into practice. Participants who demonstrated a high level of awareness of the relation between ergonomics and psychosocial hazard control demonstrated stronger organizational commitment than participants with a low awareness. Ergonomics practitioners who reported having employer support for professional development also demonstrated a higher degree of awareness of the relation between ergonomics and psychosocial hazard control, as did the professionals who had been practicing in the field the longest. This research provides some insight for professional associations for Ergonomists, employers of Ergonomists, and human resource professionals about how ergonomics practitioners perceive the ergonomics field and the profession as well as their employing organization.

Assessment and Life-Cycle Analysis of Recycled Materials for Sustainable Highway

Recycled materials replacing part of virgin materials in highway applications has shown great benefits to the society and environment. Beneficial use of recycled materials can save landfill places, sparse natural resources, and energy consumed in milling and hauling virgin materials. Low price of recycled materials is favorable to cost-saving in pavement projects. Considering the availability of recycled materials in the State of Maryland (MD), four abundant recycled materials, recycled concrete aggregate (RCA), recycled asphalt pavement (RAP), foundry sand (FS), and dredged materials (DM), were studied. A survey was conducted to collect the information of current usage of the four recycled materials in States’ Department of Transportation (DOTs). Based on literature review, mechanical and environmental properties, recommendations, and suggested test standards were investigated separately for the four recycled materials in different applications. Constrains in using these materials were further studied in order to provide recommendations for the development of related MD specifications. To measure social and environmental benefits from using recycled materials, life-cycle assessment was carried out with life-cycle analysis (LCA) program, PaLATE, and green highway rating system, BEST-in-Highway. The survey results indicated the wide use of RAP and RCA in hot mix asphalt (HMA) and graded aggregate base (GAB) respectively, while FS and DM are less used in field. Environmental concerns are less, but the possibly low quality and some adverse mechanical characteristics may hinder the widely use of these recycled materials. Technical documents and current specifications provided by State DOTs are good references to the usage of these materials in MD. Literature review showed consistent results with the survey. Studies from experimental research or site tests showed satisfactory performance of these materials in highway applications, when the substitution rate, gradation, temperature, moisture, or usage of additives, etc. meet some requirements. The results from LCA revealed significant cost savings in using recycled materials. Energy and water consumption, gas emission, and hazardous waste generation generally showed reductions to some degree. Use of new recycled technologies will contribute to more sustainable highways.

A PRELIMINARY SURVEY OF ANIMAL HANDLING AND CULTURAL SLAUGHTER PRACTICES AMONG KENYAN COMMUNITIES: POTENTIAL INFLUENCE ON MEAT QUALITY

Kenya is composed of over 40 ethnic communities who practice varied methods of animal handling and slaughter. Socio-cultural and religious traditions have the potential to influence animal handling and slaughter practices. These influences have, however, not been documented in the literature as far as the author is aware. Also, the literature has documented the connection between the manner of animal treatment and meat quality, but this is rarely discussed in the literature in Kenya; this connection is important as it informs modern meat trade practices by Kenyans as they trade in the global arena. This survey aimed to mainly establish and document the animal slaughter practices among Kenyan communities, and, to also highlight any current provisions related to meeting modern animal welfare requirements, animal handling procedures in the meat trade and discuss their potential influence on meat quality available in commerce in Kenya. This preliminary study surveyed the slaughter practices among 10 different Kenyan communities through a semi-structured questionnaire, focus group discussions and individual interviews. The survey demonstrated that different Kenyan communities practice varied methods of animal slaughter depending on whether the animal being slaughtered is for public feasting, domestic consumption or commercial merchandizing. The Kenyan communities surveyed in this study depend mainly on males to slaughter livestock for females preparing it for domestic use using a number of instruments and methods. For small stock for domestic consumption, females may slaughter the animal except for Muslims whose males have to slaughter the animal with a special knife (a Khalef) according to Muslim rites to render it Halal. Large stock is invariably slaughtered by males irrespective of the community, and the manner of use of the carcass. Gender, age, religion, community and the size of the animal were the major determinants of the method of animal slaughter. The animal welfare issues highlighted in the survey and related to the handling and slaughter of livestock have important implications for meat quality during commercial merchandizing. There is an apparent need to provide education to herders, livestock handlers, employees and management in the livestock industry in Kenya on the relationship between animal welfare requirements, animal handling procedures and meat quality. Such awareness can potentially improve the quality and economic value of the meat available in commerce.

MANIPULATION OF IONS, ELECTRONS, AND PHOTONS IN 2D MATERIALS BY ION INTERCALATION

2D materials have attracted tremendous attention due to their unique physical and chemical properties since the discovery of graphene. Despite these intrinsic properties, various modification methods have been applied to 2D materials that yield even more exciting results. Among all modification methods, the intercalation of 2D materials provides the highest possible doping and/or phase change to the pristine 2D materials. This doping effect highly modifies 2D materials, with extraordinary electrical transport as well as optical, thermal, magnetic, and catalytic properties, which are advantageous for optoelectronics, superconductors, thermoelectronics, catalysis and energy storage applications. To study the property changes of 2D materials, we designed and built a planar nanobattery that allows electrochemical ion intercalation in 2D materials. More importantly, this planar nanobattery enables characterization of electrical, optical and structural properties of 2D materials in situ and real time upon ion intercalation. With this device, we successfully intercalated Li-ions into few layer graphene (FLG) and ultrathin graphite, heavily dopes the graphene to 0.6 x 10^15 /cm2, which simultaneously increased its conductivity and transmittance in the visible range. The intercalated LiC6 single crystallite achieved extraordinary optoelectronic properties, in which an eight-layered Li intercalated FLG achieved transmittance of 91.7% (at 550 nm) and sheet resistance of 3 ohm/sq. We extend the research to obtain scalable, printable graphene based transparent conductors with ion intercalation. Surfactant free, printed reduced graphene oxide transparent conductor thin film with Na-ion intercalation is obtained with transmittance of 79% and sheet resistance of 300 ohm/sq (at 550 nm). The figure of merit is calculated as the best pure rGO based transparent conductors. We further improved the tunability of the reduced graphene oxide film by using two layers of CNT films to sandwich it. The tunable range of rGO film is demonstrated from 0.9 um to 10 um in wavelength. Other ions such as K-ion is also studied of its intercalation chemistry and optical properties in graphitic materials. We also used the in situ characterization tools to understand the fundamental properties and improve the performance of battery electrode materials. We investigated the Na-ion interaction with rGO by in situ Transmission electron microscopy (TEM). For the first time, we observed reversible Na metal cluster (with diameter larger than 10 nm) deposition on rGO surface, which we evidenced with atom-resolved HRTEM image of Na metal and electron diffraction pattern. This discovery leads to a porous reduced graphene oxide sodium ion battery anode with record high reversible specific capacity around 450 mAh/g at 25mA/g, a high rate performance of 200 mAh/g at 250 mA/g, and stable cycling performance up to 750 cycles. In addition, direct observation of irreversible formation of Na2O on rGO unveils the origin of commonly observed low 1st Columbic Efficiency of rGO containing electrodes. Another example for in situ characterization for battery electrode is using the planar nanobattery for 2D MoS2 crystallite. Planar nanobattery allows the intrinsic electrical conductivity measurement with single crystalline 2D battery electrode upon ion intercalation and deintercalation process, which is lacking in conventional battery characterization techniques. We discovered that with a “rapid-charging” process at the first cycle, the lithiated MoS2 undergoes a drastic resistance decrease, which in a regular lithiation process, the resistance always increases after lithiation at its final stage. This discovery leads to a 2- fold increase in specific capacity with with rapid first lithiated MoS2 composite electrode material, compare with the regular first lithiated MoS2 composite electrode material, at current density of 250 mA/g.

Characterization of MSW rejected fractions to fulfill RDF requirements and utilization

In order to fulfil European and Portuguese legal requirements, adequate alternatives to traditional municipal waste landfilling must be found namely concerning organic wastes and others susceptible of valorisation. According to the Portuguese Standard NP 4486:2008, refuse derived fuels (RDF) classification is based on three main parameters: lower heating value (considered as an economic parameter), chlorine content (considered as a technical parameter) and mercury content (considered as an environmental parameter). The purpose of this study was to characterize the rejected streams resulting from the mechanical treatment of unsorted municipal solid waste, from the plastic municipal selective collection and from the composting process, in order to evaluate their potential as RDF. To accomplish this purpose six sampling campaigns were performed. Chemical characterization comprised the proximate analysis – moisture content, volatile matter, ashes and fixed carbon, as well as trace elements. Physical characterization was also done. To evaluate their potential as RDF, the following parameters established in the Portuguese standard were also evaluated: heating value and chlorine content. As expected, results show that the refused stream from mechanical treatment is rather different from the selective collection rejected stream and from the rejected from the compost screening in terms of moisture, energetic matter and ashes, as well as heating value and chlorine. Preliminary data allows us to conclude that studied materials have a very interesting potential to be used as RDF. In fact, the rejected from selective collection and the one from composting have a heating value not very different from coal. Therefore, an important key factor may be the blending of these materials with others of higher heating values, after pre-processing, in order to get fuel pellets with good consistency, storage and handling characteristics and, therefore, combustion behavior.

Design and application of experimental methods for steel sheet shearing

Shearing is the process where sheet metal is mechanically cut between two tools. Various shearing technologies are commonly used in the sheet metal industry, for example, in cut to length lines, slitting lines, end cropping etc. Shearing has speed and cost advantages over competing cutting methods like laser and plasma cutting, but involves large forces on the equipment and large strains in the sheet material. The constant development of sheet metals toward higher strength and formability leads to increased forces on the shearing equipment and tools. Shearing of new sheet materials imply new suitable shearing parameters. Investigations of the shearing parameters through live tests in the production are expensive and separate experiments are time consuming and requires specialized equipment. Studies involving a large number of parameters and coupled effects are therefore preferably performed by finite element based simulations. Accurate experimental data is still a prerequisite to validate such simulations. There is, however, a shortage of accurate experimental data to validate such simulations. In industrial shearing processes, measured forces are always larger than the actual forces acting on the sheet, due to friction losses. Shearing also generates a force that attempts to separate the two tools with changed shearing conditions through increased clearance between the tools as result. Tool clearance is also the most common shearing parameter to adjust, depending on material grade and sheet thickness, to moderate the required force and to control the final sheared edge geometry. In this work, an experimental procedure that provides a stable tool clearance together with accurate measurements of tool forces and tool displacements, was designed, built and evaluated. Important shearing parameters and demands on the experimental set-up were identified in a sensitivity analysis performed with finite element simulations under the assumption of plane strain. With respect to large tool clearance stability and accurate force measurements, a symmetric experiment with two simultaneous shears and internal balancing of forces attempting to separate the tools was constructed. Steel sheets of different strength levels were sheared using the above mentioned experimental set-up, with various tool clearances, sheet clamping and rake angles. Results showed that tool penetration before fracture decreased with increased material strength. When one side of the sheet was left unclamped and free to move, the required shearing force decreased but instead the force attempting to separate the two tools increased. Further, the maximum shearing force decreased and the rollover increased with increased tool clearance. Digital image correlation was applied to measure strains on the sheet surface. The obtained strain fields, together with a material model, were used to compute the stress state in the sheet. A comparison, up to crack initiation, of these experimental results with corresponding results from finite element simulations in three dimensions and at a plane strain approximation showed that effective strains on the surface are representative also for the bulk material. A simple model was successfully applied to calculate the tool forces in shearing with angled tools from forces measured with parallel tools. These results suggest that, with respect to tool forces, a plane strain approximation is valid also at angled tools, at least for small rake angles. In general terms, this study provide a stable symmetric experimental set-up with internal balancing of lateral forces, for accurate measurements of tool forces, tool displacements, and sheet deformations, to study the effects of important shearing parameters. The results give further insight to the strain and stress conditions at crack initiation during shearing, and can also be used to validate models of the shearing process.

Manufacturing challenges with fabrication of large size mechanical harmonic drives

Mechanical harmonic transmissions are relatively new kind of drives having several unusual features. For example, they can provide reduction ratio up to 500:1 in one stage, have very small teeth module compared to conventional drives and very large number of teeth (up to 1000) on a flexible gear. If for conventional drives manufacturing methods are well-developed, fabrication of large size harmonic drives presents a challenge. For example, how to fabricate a thin shell of 1.7m in diameter and wall thickness of 30mm having high precision external teeth at one end and internal splines at the other end? It is so flexible that conventional fabrication methods become unsuitable. In this paper special fabrication methods are discussed that can be used for manufacturing of large size harmonic drive components. They include electro-slag welding and refining, the use of special expandable devices to locate and hold a flexible gear, welding peripheral parts of disks with wear resistant materials with subsequent machining and others. These fabrication methods proved to be effective and harmonic drives built with the use of these innovative technologies have been installed on heavy metallurgical equipment and successfully tested.

Estimating indoor air quality using integrated 3D CAD building models

The indoor air quality (IAQ) in buildings is currently assessed by measurement of pollutants during building operation for comparison with air quality standards. Current practice at the design stage tries to minimise potential indoor air quality impacts of new building materials and contents by selecting low-emission materials. However low-emission materials are not always available, and even when used the aggregated pollutant concentrations from such materials are generally overlooked. This paper presents an innovative tool for estimating indoor air pollutant concentrations at the design stage, based on emissions over time from large area building materials, furniture and office equipment. The estimator considers volatile organic compounds, formaldehyde and airborne particles from indoor materials and office equipment and the contribution of outdoor urban air pollutants affected by urban location and ventilation system filtration. The estimated pollutants are for a single, fully mixed and ventilated zone in an office building with acceptable levels derived from Australian and international health-based standards. The model acquires its dimensional data for the indoor spaces from a 3D CAD model via IFC files and the emission data from a building products/contents emissions database. This paper describes the underlying approach to estimating indoor air quality and discusses the benefits of such an approach for designers and the occupants of buildings.