31 results on '"Rhodri Williams"'
Search Results
2. Abnormal clot microstructure formed in blood containing HIT-like antibodies
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John W. Weisel, M. Rowan Brown, Lubica Rauova, Bethan R. Thomas, P. Rhodri Williams, Karl Hawkins, Nafiseh Badiei, Rebecca J. Hambly, and Catherine A. Thornton
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Pathology ,medicine.medical_specialty ,030204 cardiovascular system & hematology ,Platelet Factor 4 ,Fibrin ,Flow cytometry ,03 medical and health sciences ,0302 clinical medicine ,medicine ,Humans ,Platelet activation ,Whole blood ,medicine.diagnostic_test ,biology ,Chemistry ,Heparin ,Thrombosis ,Hematology ,Microstructure ,medicine.disease ,Thrombocytopenia ,030220 oncology & carcinogenesis ,biology.protein ,Platelet factor 4 ,medicine.drug - Abstract
INTRODUCTION Thrombosis is a severe and frequent complication of heparin-induced thrombocytopenia (HIT). However, there is currently no knowledge of the effects of HIT-like antibodies on the resulting microstructure of the formed clot, despite such information being linked to thrombotic events. We evaluate the effect of the addition of pathogenic HIT-like antibodies to blood on the resulting microstructure of the formed clot. MATERIALS AND METHODS Pathogenic HIT-like antibodies (KKO) and control antibodies (RTO) were added to samples of whole blood containing Unfractionated Heparin and Platelet Factor 4. The formed clot microstructure was investigated by rheological measurements (fractal dimension; df) and scanning electron microscopy (SEM), and platelet activation was measured by flow cytometry. RESULTS AND CONCLUSIONS Our results revealed striking effects of KKO on clot microstructure. A significant difference in df was found between samples containing KKO (df = 1.80) versus RTO (df = 1.74; p
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- 2020
3. Hydrophilic microporous membranes for selective ion separation and flow-battery energy storage
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Xiaoqun Zhou, Rhodri Williams, Clare P. Grey, Richard Malpass-Evans, Neil B. McKeown, Lukas Turcani, Tao Li, Zhiyu Fan, Andrew I. Cooper, Rui Tan, Barbara Primera Darwich, Anqi Wang, Qilei Song, Edward Jackson, Samantha Y. Chong, Evan Wenbo Zhao, Tao Liu, Nigel P. Brandon, Linjiang Chen, Chunchun Ye, Kim E. Jelfs, The Royal Society, Commission of the European Communities, and Engineering & Physical Science Research Council (EPSRC)
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Technology ,INTRINSIC MICROPOROSITY ,Materials Science ,Materials Science, Multidisciplinary ,02 engineering and technology ,010402 general chemistry ,Electrochemistry ,01 natural sciences ,7. Clean energy ,ANION-EXCHANGE MEMBRANES ,FUEL-CELLS ,Energy storage ,Physics, Applied ,General Materials Science ,Nanoscience & Nanotechnology ,Ion transporter ,PIMS ,chemistry.chemical_classification ,Aqueous solution ,Science & Technology ,PACKING ,Chemistry, Physical ,Mechanical Engineering ,Physics ,General Chemistry ,Polymer ,PERFORMANCE ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,Flow battery ,Electrochemical energy conversion ,POLYMER MEMBRANE ,6. Clean water ,TRANSPORT ,0104 chemical sciences ,Chemistry ,Membrane ,chemistry ,Chemical engineering ,Physics, Condensed Matter ,Mechanics of Materials ,Physical Sciences ,0210 nano-technology - Abstract
Membranes with fast and selective ion transport are widely used for water purification and devices for energy conversion and storage including fuel cells, redox flow batteries and electrochemical reactors. However, it remains challenging to design cost-effective, easily processed ion-conductive membranes with well-defined pore architectures. Here, we report a new approach to designing membranes with narrow molecular-sized channels and hydrophilic functionality that enable fast transport of salt ions and high size-exclusion selectivity towards small organic molecules. These membranes, based on polymers of intrinsic microporosity containing Troger’s base or amidoxime groups, demonstrate that exquisite control over subnanometre pore structure, the introduction of hydrophilic functional groups and thickness control all play important roles in achieving fast ion transport combined with high molecular selectivity. These membranes enable aqueous organic flow batteries with high energy efficiency and high capacity retention, suggesting their utility for a variety of energy-related devices and water purification processes. Ion-selective membranes are widely used for water purification and electrochemical energy devices but designing their pore architectures is challenging. Membranes with narrow channels and hydrophilic functionality are shown to exhibit salt ions transport and selectivity towards small organic molecules.
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- 2020
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4. The effects of morpholine pre-treated and carboxymethylated cellulose nanofibrils on the properties of alginate-based hydrogels
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Amaka J. Onyianta, Rhodri Williams, Maila Castellano, Mark Dorris, and Silvia Vicini
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Materials science ,Polymers and Plastics ,Alginates ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,Viscoelasticity ,chemistry.chemical_compound ,Surface modification ,Materials Chemistry ,medicine ,Cellulose ,Porosity ,Aqueous solution ,Organic Chemistry ,technology, industry, and agriculture ,Hydrogels ,QD Chemistry ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Compressive strength ,chemistry ,Chemical engineering ,Compressive modulus ,Self-healing hydrogels ,Carboxymethylation ,Swelling ,medicine.symptom ,0210 nano-technology ,Cellulose nanofibrils (CNF) ,660 Chemical engineering - Abstract
The effects of varying percentage loadings of morpholine pre-treated cellulose nanofibrils (MCNF) and carboxymethylated cellulose nanofibrils (CMCNF) on the aqueous swelling, compressive modulus and viscoelastic properties of calcium-ion-crosslinked alginate hydrogels were investigated. In addition, the pore structures of hydrogels with the highest compressive modulus were studied. The incorporation of 5 wt. % MCNF resulted in a slightly reduced aqueous swelling, a 36% increase in compressive modulus and a layered pore structure when compared with the neat alginate hydrogel. On the other hand, the addition of CMCNF at the same loading led to a slightly improved aqueous swelling, an increase in compressive modulus (17%) and high porosity. Further increases in CNF loadings did not result in significant increase in material properties. The alginate/CNF composite materials have potentials to be used in applications where good swelling and mechanical robustness are required.
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- 2018
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5. In vitro clot model to evaluate fibrin-thrombin effects on fractal dimension of incipient blood clot
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D. J. Curtis, Phillip A. Evans, Ahmed Sabra, Phylip Rhodri Williams, Matthew Lawrence, and Karl Hawkins
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medicine.medical_specialty ,Physiology ,030204 cardiovascular system & hematology ,Fibrinogen ,Fractal dimension ,Fibrin ,030218 nuclear medicine & medical imaging ,03 medical and health sciences ,Fibrinogen levels ,0302 clinical medicine ,Thrombin ,Physiology (medical) ,Internal medicine ,medicine ,Humans ,Blood Coagulation ,Whole blood ,biology ,Chemistry ,Thrombosis ,Hematology ,Clot formation ,In vitro ,Endocrinology ,biology.protein ,Blood Coagulation Tests ,Cardiology and Cardiovascular Medicine ,circulatory and respiratory physiology ,medicine.drug - Abstract
INTRODUCTION This aim of this study is to investigate the individual effects of varying concentrations of thrombin and fibrinogen on clot microstructure (characterised through the fractal dimension of the incipient clot network, df) and clot formation time (TGP) using a fibrin-thrombin clot model. df and TGP markers are measured using a haemorheological method that has already been investigated for whole blood. METHODS This is an in vitro study using three thrombin concentrations (0.1, 0.05 and 0.02 NIH/ml) and two fibrinogen concentrations (8 mg/ml and 12 mg/ml) to investigate a fibrin-thrombin clot model. The haemorheological changes were measured at the gel point using df and TGP. RESULTS Fractal dimension (df) increased with increasing concentrations of thrombin both at 8 mg/ml (1.60±0.024, 1.67±0.022, 1.74±0.079) and 12 mg/ml fibrinogen concentrations (1.63±0.02, 1.87±0.019, 1.95±0.014). On the other hand, TGP decreased for both 8 mg/ml (1089±265, 637±80, 223±22 seconds) and 12 mg/ml fibrinogen concentrations (2008±247, 776±20, 410±20 seconds). In contrast to previous studies investigating whole blood, TGP increased with higher fibrinogen levels. CONCLUSIONS The findings from this fibrin-thrombin clot model confirmed that df and TGP can detect changes in the incipient clot following manipulation of fibrinogen and thrombin concentration. df increases (indicating stronger clot) with higher concentrations of thrombin and fibrinogen. On the other hand, TGP decreased as expected with higher thrombin level but not with higher fibrinogen concentrations.
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- 2019
6. Characterization of hyaluronic acid by dynamic light scattering and rheological techniques
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Maila Castellano, Marina Alloisio, Silvia Vicini, Rhodri Williams, Simona Gagliardi, and Andrea Dodero
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chemistry.chemical_classification ,Materials science ,chemistry ,Rheology ,Rheometry ,Chemical engineering ,Dynamic light scattering ,Biomolecule ,Dynamic modulus ,Polymer ,Dynamic mechanical analysis ,Characterization (materials science) - Abstract
Hyaluronic acid (HA) solutions represent an important class of biomedical products, mostly used in viscosupplementation of joints and as fillers. In the present work the hydrodynamic and rheological properties of hyaluronic acid, of differing MW(90-4000 kDa), in physiological saline were investigated. Firstly, the effective conformation taken by the polymer chains was studied using dynamic light scattering. It was observed that they behaved like random coils which dimension is higher increasing the molecular weight of the material. Secondly, combining a novel microrheological technique, based on the dynamic light scattering of tracer particles, with conventional rheometry, it was possible to study in which way the molecular weight and the concentration of the polymer influence the storage modulus (G’), loss modulus (G”) and complex viscosity (η*) of its solutions, over an extended frequency range (typically 0.01-10000 Hz). This extended characterization allowed determination of the mesh size ξ of the physical network, created by the entangled polymer chains. Calculated mesh sizes in the range 200-700 nm were observed, demonstrating the possibility to use these systems as injectable carriers of biomolecules with an appropriate dimension.
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- 2018
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7. A highly rigid and gas selective methanopentacene-based polymer of intrinsic microporosity derived from Tröger's base polymerization
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Luke A. Burt, Neil B. McKeown, Johannes C. Jansen, Marek Lanč, Elisa Esposito, Mariolino Carta, Carmen Rizzuto, Rhodri Williams, and Elena Tocci
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chemistry.chemical_classification ,Flue gas ,Materials science ,Renewable Energy, Sustainability and the Environment ,Intrinsic microporosity ,Gas permeability ,Gas separation ,02 engineering and technology ,General Chemistry ,Polymer ,Permeation ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Membrane ,Polymerization ,chemistry ,Chemical engineering ,Carbon dioxide ,Barrer ,General Materials Science ,0210 nano-technology ,Selectivity ,BET theory - Abstract
Polymers of intrinsic microporosity (PIMs) have been identified as potential next generation membrane materials for the separation of gas mixtures of industrial and environmental relevance. Based on the exceptionally rigid methanopentacene (MP) structural unit, a Polymer of Intrinsic Microporosity (PIM-MP-TB) was designed to demonstrate high selectivity for gasseparations. PIM-MP-TB was prepared using a polymerisation reaction involving the formation of Tröger’s base linking groups and demonstrated an apparent BET surface area of 743 m2 g-1 as a powder. The microporosity of PIM-MP-TB was also characterized by chain packing simulations. PIM-MP-TB proved soluble in chlorinated solvents and was cast as a robust, free-standing film suitable for gas permeation measurements. Despite lower gas permeability as compared to previously reported PIMs, high selectivities for industrially relevant gas pairs were obtained, surpassing the 2008 Robeson upper bound for H2/CH4 and O2/N2, (e.g., PO2=999 Barrer; αO2/N2= 5.0) and demonstrating a clear link between polymer rigidity and selectivity. Upon aging, the permeability data move parallel to the Robeson upper bounds with a decrease of permeability,compensated by a related increase in selectivity. Mixed gas permeation measurement for CO2/CH4 and CO2/N2 mixtures confirmed the excellent selectivity of PIM-MP-TB for potentially relevant separations such as biogas upgrading and CO2 capture from flue gas. Importantly, unlike other high perfoming PIMs, PIM-MP-TB is prepared in four simple steps from acheap starting material.
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- 2018
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8. Aqueous morpholine pre-treatment in cellulose nanofibril (CNF) production: comparison with carboxymethylation and TEMPO oxidisation pre-treatment methods
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Mark Dorris, Amaka J. Onyianta, and Rhodri Williams
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572 Biochemistry ,Aqueous solution ,Polymers and Plastics ,Culture and Communities ,Dispersity ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,chemistry.chemical_compound ,Crystallinity ,chemistry ,Chemical engineering ,Morpholine ,Reagent ,medicine ,Thermal stability ,Cellulose nanofibrils (CNF), Morpholine pre-treatment, carboxymethylation, TEMPO-oxidation, surface modification, mechanical fibrillation, sedimentation ,Cellulose ,Swelling ,medicine.symptom ,0210 nano-technology ,QD415-436 Biochemistry ,Materials - Abstract
In this study, pulped cellulose fibres were pre-treated with aqueous morpholine prior to mechanical disruption in the production of cellulose nanofibrils (CNF). The properties of the morpholine pre-treated CNF (MCNF) were closely compared with CNF obtained from carboxymethylation (CMCNF) and TEMPO-oxidation (TCNF) pre-treatment methods. An investigation of the swelling behaviours of cellulose in varying concentrations of morpholine revealed that there is a synergistic behaviour between morpholine and water in its ability to swell cellulose. As a result, cellulose pulp dispersed in 1:1 mole ratio of morpholine to water was well swollen and readily fibrillated by mechanical shear. Surface chemistry analyses indicated that the surface of the MCNF remained unmodified, compared to the CMCNF and TCNF which were modified with anionic groups. This resulted in only a slight decrease in crystallinity index and a minimal effect on the thermal stability of MCNF, compared to CMCNF and TCNF which showed marked decreases in crystallinity indices and thermal stabilities. The average widths of MCNF, CMCNF and TCNF, as measured from electron microscopic images, were broadly similar. The higher polydispersity of MCNF widths however led to a differential sedimentation and subsequent lower aspect ratio in comparison with CMCNF and TCNF as estimated using the sedimentation approach. Also, the presence of electrostatic repulsive forces, physical interactions/entanglements and lower rigidity threshold of the CMCNF and TCNF resulted in higher storage moduli compared to the MCNF, whose elasticity is controlled by physical interactions and entanglements. Aqueous morpholine pre-treatment can potentially be regarded as an ecologically sustainable process for unmodified CNF production, since the chemical reagent is not consumed and can be recovered and reused.
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- 2017
9. The Use of Sedimentation for the Estimation of Aspect Ratios of Charged Cellulose Nanofibrils
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Amaka J. Onyianta and Rhodri Williams
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chemistry.chemical_classification ,Gel point ,Flocculation ,Aqueous solution ,Materials science ,010405 organic chemistry ,Sediment ,Salt (chemistry) ,02 engineering and technology ,Sedimentation ,021001 nanoscience & nanotechnology ,01 natural sciences ,Aspect ratio (image) ,0104 chemical sciences ,chemistry.chemical_compound ,chemistry ,Chemical engineering ,Cellulose ,Composite material ,0210 nano-technology - Abstract
In this study, the aspect ratios of carboxymethylated and TEMPO-oxidised cellulose nanofibrils (CNF) were estimated by gel point analysis using a sedimentation approach. The flocculation and subsequent sedimentation of the CNF aqueous suspensions, which were stabilised by negative repulsive forces, were made possible after screening in concentrated salt media. The aspect ratios of the CNFs were then calculated from the linear fit (gel point) of the plot of concentration of the CNFs against the relative sediment height, using the crowding number theory.
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- 2017
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10. A redox hydrogel protects hydrogenase from high-potential deactivation and oxygen damage
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Nicolas Plumeré, Jeevanthi Vivekananthan, Sascha Pöller, Wolfgang Schuhmann, Olaf Rüdiger, Wolfgang Lubitz, Rhodri Williams, and Alaa A. Oughli
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Binding Sites ,Hydrogenase ,biology ,Hydrogen ,Bioelectric Energy Sources ,Chemistry ,General Chemical Engineering ,Active site ,chemistry.chemical_element ,Viologen ,General Chemistry ,Photochemistry ,Electron transport chain ,Redox ,Hydrogel, Polyethylene Glycol Dimethacrylate ,Viologens ,Catalysis ,Electron Transport ,Oxygen ,Electron transfer ,biology.protein ,medicine ,Oxidation-Reduction ,medicine.drug - Abstract
Hydrogenases are nature's efficient catalysts for both the generation of energy via oxidation of molecular hydrogen and the production of hydrogen via the reduction of protons. However, their O2 sensitivity and deactivation at high potential limit their applications in practical devices, such as fuel cells. Here, we show that the integration of an O2-sensitive hydrogenase into a specifically designed viologen-based redox polymer protects the enzyme from O2 damage and high-potential deactivation. Electron transfer between the polymer-bound viologen moieties controls the potential applied to the active site of the hydrogenase and thus insulates the enzyme from excessive oxidative stress. Under catalytic turnover, electrons provided from the hydrogen oxidation reaction induce viologen-catalysed O2 reduction at the polymer surface, thus providing self-activated protection from O2. The advantages of this tandem protection are demonstrated using a single-compartment biofuel cell based on an O2-sensitive hydrogenase and H2/O2 mixed feed under anode-limiting conditions.
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- 2014
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11. Roles of the molecular weight of n -ethylene glycol diacrylates and UV irradiance on the mechanical properties at the gel point of acrylic acid based hydrogels
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Saminu M. Magami and Rhodri Williams
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Gel point ,Materials science ,Polymers and Plastics ,Irradiance ,General Chemistry ,Surfaces, Coatings and Films ,chemistry.chemical_compound ,chemistry ,Rheology ,Chemical engineering ,Self-healing hydrogels ,Materials Chemistry ,Irradiation ,Ethylene glycol ,Acrylic acid - Published
- 2019
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12. An electric-field responsive microsystem for controllable miniaturised drug delivery applications
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Yufei Liu, A. Servant, Khuloud T. Al-Jamal, Owen J. Guy, Phylip Rhodri Williams, Kostas Kostarelos, and Karl Hawkins
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chemistry.chemical_classification ,Microelectromechanical systems ,Materials science ,Metals and Alloys ,Nanotechnology ,02 engineering and technology ,Polymer ,010402 general chemistry ,021001 nanoscience & nanotechnology ,Condensed Matter Physics ,01 natural sciences ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,chemistry ,Microsystem ,Electric field ,Drug delivery ,Self-healing hydrogels ,Materials Chemistry ,Wafer ,Electrical and Electronic Engineering ,0210 nano-technology ,Instrumentation ,Voltage - Abstract
A novel MEMS based drug delivery device has been developed, consisting of an array of metallic contacts on silicon and Pyrex glass wafers. The meander structured device creates a uniform electric field which stimulates drug release. An electro-active hydrogel based polymer matrix has also been developed, which responds to an electrical stimulus and shrinks or de-swells on application of an electric field from the fabricated device. Different drug candidates can be encapsulated within the polymer matrix. The de-swelling of the polymer enables the encapsulated drug to be released from the matrix. The gel is able to recover its original size once electric stimulation is ceased. By controlling the applied voltage and its duration, the drug release rate and dose can be precisely controlled. Controlled drug delivery devices may be integrated with sensor technology in combined diagnostic/therapeutic point of care devices.
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- 2012
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13. Rheometrical and molecular dynamics simulation studies of incipient clot formation in fibrin-thrombin gels: An activation limited aggregation approach
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M. R. Brown, Matthew Lawrence, Phillip A. Evans, D. J. Curtis, Paul Rees, Phylip Rhodri Williams, and Karl Hawkins
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Gel point ,Rheometry ,biology ,Applied Mathematics ,Mechanical Engineering ,General Chemical Engineering ,Diffusion ,Kinetics ,Nanotechnology ,Condensed Matter Physics ,Fractal dimension ,Fibrin ,chemistry.chemical_compound ,Molecular dynamics ,Monomer ,chemistry ,biology.protein ,Biophysics ,General Materials Science - Abstract
A rheometrical investigation of incipient clots formed in fibrin-thrombin gels is reported in which the Gel Point (GP) is characterised by frequency independence of the loss tangent in small amplitude oscillatory shear measurements over a wide range of thrombin concentration. Values of the fractal dimension (Df) of the GP network calculated from measurements are consistent with those reported in simulations of diffusion limited cluster–cluster aggregation (DLCCA) and reaction limited cluster–cluster aggregation (RLCCA), but differ insofar as the values of Df calculated from the present experiments increase progressively with a reduction in gel formation time. A molecular dynamics simulation (MDS) of systems of rod-like particles was designed to (i) test the hypothesis that the presence of an activation profile in a cluster aggregation model could account for the trend of Df as a function of gel formation time observed experimentally in fibrin-thrombin gels and whole heparinised blood without recourse to the inclusion of fibrinogen-specific interactions; and (ii) to explore the effect of monomer activation kinetics on the microstructure of fractal clusters formed in systems of rigid rod-like particles. The results identify two possible mechanisms for the increase in Df as the gel formation time decreases, both being a consequence of altering the evolution of the clustering dynamics by a process referred to herein as activation limited aggregation (ALA). This ALA-based MDS substantiates the experimental findings by confirming the trend evident in the formation of incipient clots in fibrin-thrombin gels and in whole heparinised blood. A mechanism for ALA involving the aggregation of pre-GP sub-clusters is proposed.
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- 2011
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14. Measuring maximum tensile strength of liquids at low stressing rates
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Davide Deganello, A. S. Lubansky, R. Brad, Tim Claypole, and Phylip Rhodri Williams
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Materials science ,Capillary action ,Applied Mathematics ,Mechanical Engineering ,General Chemical Engineering ,Polyethylene glycol ,Condensed Matter Physics ,law.invention ,chemistry.chemical_compound ,Piston ,Compressive strength ,chemistry ,law ,Cavitation ,Ultimate tensile strength ,General Materials Science ,Composite material ,Tensile testing - Abstract
A technique is presented for determining the maximum tensile strength of a given fluid through the analysis of the break-up at the end of a capillary-thinning experiment. This technique allows the characterisation of the tensile strength, an important parameter for understanding cavitation, of a fluid at lower stressing rates than previous methods, such as bullet-piston apparatus. The method was validated by tests on a range of concentrations and molecular weights of polyethylene glycol, comparing the results with the values and behaviours observed from the bullet piston apparatus. Excellent agreement was observed between the two techniques, with quantitative differences corresponding to the differences in stressing rates. The results from the capillary break-up experiments were also used to investigate the effect of concentration and molecular-weight on tensile strength.
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- 2011
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15. Gelation studies on acrylic acid-based hydrogels via in situ photo-crosslinking and rheology
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Saminu M. Magami and Rhodri Williams
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In situ ,Materials science ,Polymers and Plastics ,02 engineering and technology ,General Chemistry ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Surfaces, Coatings and Films ,chemistry.chemical_compound ,chemistry ,Rheology ,Chemical engineering ,Self-healing hydrogels ,Photo crosslinking ,Materials Chemistry ,0210 nano-technology ,Acrylic acid - Published
- 2018
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16. Fractal analysis of viscoelastic data with automated gel point location and its potential application in the investigation of therapeutically modified blood coagulation
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P. Adrian Evans, P. Rhodri Williams, Lisa J. Wakeman, Andrew Beddel, N. Thirumalai, Karl Hawkins, Roger C. Munro, M. S. Barrow, R. H. Keith Morris, Matthew Lawrence, D. J. Curtis, and M. Rowan Brown
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Gel point ,medicine.diagnostic_test ,medicine.drug_class ,Chemistry ,Anticoagulant ,Analytical chemistry ,Heparin ,Condensed Matter Physics ,Fractal analysis ,Thromboelastography ,Viscoelasticity ,medicine ,Coagulation (water treatment) ,General Materials Science ,Whole blood ,Biomedical engineering ,medicine.drug - Abstract
This study reports an automated numerical method for the location of the gel point in oscillatory shear data and demonstrates its potential application in measurements on therapeutically modified (heparinised) samples of healthy coagulating blood. Heparin prolongs the onset of clot formation and has a significant effect on the microstructure of the clot which is eventually formed. The results demonstrate the potential of this rheometrical technique as a new tool for monitoring the effect of heparin on samples of whole blood with significantly better linearity of response within the therapeutic range than another global coagulation monitoring technique (thromboelastography) which has previously been used.
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- 2010
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17. STUDIES OF THE FORMATION OF MICROPOROUS POLYMER FILMS IN 'BREATH FIGURE' CONDENSATION PROCESSES
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Chris J. Wright, M. S. Barrow, R. L. Jones, Jung Ok Park, Mohan Srinivasarao, and Phylip Rhodri Williams
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chemistry.chemical_classification ,Materials science ,Condensation ,Dispersity ,Evaporation ,Statistical and Nonlinear Physics ,Nanotechnology ,Microporous material ,Polymer ,Condensed Matter Physics ,Solvent ,Colloid ,Chemical engineering ,chemistry ,Monolayer - Abstract
We report studies of the formation of ordered microporous polymer films by the evaporation of polymer solutions following exposure to a humid atmosphere. High-speed microphotographic (HSMP) studies of the formation process reveal that near the surface of the polymer solution, vapor condensation produces near monodisperse water droplets which crystallize to form a close-packed array. Following the evaporation of the solvent, characterization of the solid by Atomic Force Microscopy, confocal microscopy and white light interferometry reveals that the surface of the polymer film features extensive regions of hexagonally close-packed microscopic pores, whose spatial arrangement replicates that of the initial droplet monolayer. Defects recorded by HSMP in the packing of the colloidal monolayer of liquid droplets formed above the surface of the polymer solution are found to correspond to those transferred into the eventual solid film, providing the first direct evidence of the structure templating role of the droplet monolayer.
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- 2008
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18. Cavitation erosion in polymer aqueous solutions
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Emil-Alexandru Brujan, A. Al-Hussany, Phylip Rhodri Williams, and R. L. Williams
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chemistry.chemical_classification ,Materials science ,Aqueous solution ,business.industry ,Scanning electron microscope ,Bubble ,Ultrasound ,Mineralogy ,Surfaces and Interfaces ,Polymer ,Condensed Matter Physics ,Surfaces, Coatings and Films ,Viscosity ,chemistry ,Mechanics of Materials ,Cavitation ,Materials Chemistry ,Extensional viscosity ,Composite material ,business - Abstract
We report the results of experiments designed to test the hypothesis that the enhanced levels of extensional viscosity conferred upon a liquid due to a polymer additive substantially mitigate cavitation damage, in addition to substantially increasing the liquid's cavitation threshold stress. As far as we are aware, these issues have never been directly addressed in a single investigation, involving samples of the same polymer system, in complementary experiments expressly designed for these purposes. The cavitation thresholds of aqueous PAA solutions are measured under dynamic stressing by pulses of tension and cavitation erosion experiments involving solid target specimens are also reported. The cavitation threshold of the solutions is found to be substantially enhanced by the presence of the polymer and the damage patterns recorded by scanning electron microscopy after 80 min exposure to cavitation in polymer solutions differ significantly from those in water. Whereas in water the surface presents heavily eroded areas with deep pitting cavities, in the 1% PAA solution the damage appears only in the form of individual craters that accumulate along specific lines and large undamaged areas (a stringy damage pattern). The weight loss decreases with increasing the polymer concentration and is one order of magnitude smaller in the 1% PAA solution than in the case of water. The present results suggest that the reduction of the maximum pressure inside the bubble at its minimum volume upon addition of polymer is the dominant mechanism of the observed suppression of cavitation damage in polymer solutions. The implications of the results are discussed with respect to the reduction of collateral damage in ultrasound phacoemulsification.
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- 2008
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19. Cavitation Properties of Oils Under Dynamic Stressing by Tension
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Phylip Rhodri Williams and R. L. Williams
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Shear (sheet metal) ,chemistry.chemical_compound ,Viscosity ,Materials science ,chemistry ,Tension (physics) ,Mechanical Engineering ,Cavitation ,Ultimate tensile strength ,Newtonian fluid ,Lubricant ,Composite material ,Silicone oil - Abstract
We report measurements of the effective tensile strength Fc of commercial “multigrade” oils (in the SAE viscosity grades 5W-30 and 10W-40) over a range of temperatures T, which are representative of those encountered under their normal operating conditions (in the range 20°C⩽T⩽140°C). Also reported are the values of Fc that are obtained for Newtonian silicone oils over a range of shear viscosities. In the experiments reported herein, samples of liquid are subjected to dynamic stressing by a pressure-tension cycle, this being a feature of the conditions experienced by a lubricant within a dynamically loaded journal bearing and the method used to estimate Fc avoids reliance on direct measurements of substantial dynamic tensions using conventional pressure transducers.
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- 2004
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20. The tensile behaviour of elastic liquids under dynamic stressing
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Phylip Rhodri Williams and S W J Brown
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chemistry.chemical_classification ,Materials science ,Aqueous solution ,Tension (physics) ,Applied Mathematics ,Mechanical Engineering ,General Chemical Engineering ,Bubble ,Polyacrylamide ,Concentration effect ,Polymer ,Condensed Matter Physics ,chemistry.chemical_compound ,chemistry ,Cavitation ,Ultimate tensile strength ,General Materials Science ,Composite material - Abstract
We report measurements of the tensile strength, F c , of dilute polymer solutions, involving tension pulses of ca. 200–300 μs duration, and stressing rates of ca. 1–10 bar/μs: Contrary to previous indications in the literature, the tensile strength of polyacrylamide (PAA) solutions under pulsed dynamic stressing is found to increase with increasing polymer concentration. This accords with the results of a study of the effect of PAA concentration on the development of liquid jets, which are formed by bubble collapse in dilute PAA solutions: a marked reduction in jet length and velocity is found due to the presence of PAA. Estimates of the tensile stresses supported by the stretching jets are commensurate with the results obtained in measurements of F c .
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- 2000
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21. Dynamic stressing of a liquid-liquid interface by tension
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S W J Brown, Phylip Rhodri Williams, P M Williams, and K Papadopoulou
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Work (thermodynamics) ,Acoustics and Ultrasonics ,Chemistry ,Tension (physics) ,Interface (computing) ,Mechanics ,Condensed Matter Physics ,Capillary number ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Surface tension ,Cavitation ,Ultimate tensile strength ,Longitudinal wave - Abstract
We report experiments in which the interface between two immiscible liquids is subjected to tension by dynamic stressing. During the course of these experiments, cavitation is only observed in the stronger of the two liquids (in terms of their tensile strength). The results are explained in terms of the failure of the liquid-liquid interface under tension, and the ability of the vapour layer so created to reflect subsequent compressional waves as tension. The findings reported here support the results of earlier work in this area and their technological implications are briefly discussed.
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- 1999
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22. Tensile properties of liquid mercury under pulsed dynamic stressing
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S W J Brown, Phylip Rhodri Williams, and P M Williams
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Materials science ,Acoustics and Ultrasonics ,Liquid phase ,chemistry.chemical_element ,Condensed Matter Physics ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Mercury (element) ,Transition metal ,chemistry ,Mechanical strength ,Ultimate tensile strength ,Composite material ,Bar (unit) - Abstract
We report experiments in which liquid mercury is subjected to tension by dynamic stressing, involving pulses of ca s duration, and stressing rates of approximately 1 bar . Under these conditions, the tensile strength of liquid mercury is found to be ca 2500 bar. These results are markedly lower than those obtained in experiments involving shorter pulse durations, and support the conclusion of other workers that in the dynamic stressing of liquids by tension, the higher the rate of stressing, the higher the measured value of tensile strength.
- Published
- 1998
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23. Simultaneous measurements of photocurrents and H2O2 evolution from solvent exposed photosystem 2 complexes
- Author
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En Ning Saw, Matthias Rögner, Tobias Vöpel, Volker Hartmann, Frank Müller, Nicolas Plumeré, Rhodri Williams, Simon Ebbinghaus, Wolfgang Schuhmann, and Marc M. Nowaczyk
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Light ,Photosystem II ,Inorganic chemistry ,General Physics and Astronomy ,chemistry.chemical_element ,02 engineering and technology ,Cyanobacteria ,010402 general chemistry ,Photochemistry ,Photosynthesis ,01 natural sciences ,Oxygen ,General Biochemistry, Genetics and Molecular Biology ,Biomaterials ,chemistry.chemical_compound ,Electricity ,General Materials Science ,skin and connective tissue diseases ,Hydrogen peroxide ,Electrolysis of water ,Oxygen evolution ,Photosystem II Protein Complex ,Electrochemical Techniques ,Hydrogen Peroxide ,General Chemistry ,Chronoamperometry ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,Microscopy, Fluorescence ,chemistry ,Solvents ,Water splitting ,0210 nano-technology ,hormones, hormone substitutes, and hormone antagonists - Abstract
In plants, algae, and cyanobacteria, photosystem 2 (PS2) catalyzes the light driven oxidation of water. The main products of this reaction are protons and molecular oxygen. In vitro, however, it was demonstrated that reactive oxygen species like hydrogen peroxide are obtained as partially reduced side products. The transition from oxygen to hydrogen peroxide evolution might be induced by light triggered degradation of PS2's active center. Herein, the authors propose an analytical approach to investigate light induced bioelectrocatalytic processes such as PS2 catalyzed water splitting. By combining chronoamperometry and fluorescence microscopy, the authors can simultaneously monitor the photocurrent and the hydrogen peroxide evolution of light activated, solvent exposed PS2 complexes, which have been immobilized on a functionalized gold electrode. The authors show that under limited electron mediation PS2 displays a lower photostability that correlates with an enhanced H2O2 generation as a side product of the light induced water oxidation.
- Published
- 2016
- Full Text
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24. Studies of cavitation and ice nucleation in 'doubly-metastable' water: time-lapse photography and neutron diffraction
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Marie-Claire Bellissent-Funel, John C. Dore, M. S. Barrow, Hoi-Houng Chan, and P. Rhodri Williams
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Phase transition ,business.industry ,Chemistry ,Neutron diffraction ,Nucleation ,General Physics and Astronomy ,Optics ,Chemical physics ,Phase (matter) ,Cavitation ,Amorphous ice ,Ice nucleus ,Physical and Theoretical Chemistry ,Supercooling ,business ,Physics::Atmospheric and Oceanic Physics - Abstract
High-speed photographic studies and neutron diffraction measurements have been made of water under tension in a Berthelot tube. Liquid water was cooled below the normal ice-nucleation temperature and was in a doubly-metastable state prior to a collapse of the liquid state. This transition was accompanied by an exothermic heat release corresponding with the rapid production of a solid phase nucleated by cavitation. Photographic techniques have been used to observe the phase transition over short time scales in which a solidification front is observed to propagate through the sample. Significantly, other images at a shorter time interval reveal the prior formation of cavitation bubbles at the beginning of the process. The ice-nucleation process is explained in terms of a mechanism involving hydrodynamically-induced changes in tension in supercooled water in the near vicinity of an expanding cavitation bubble. Previous explanations have attributed the nucleation of the solid phase to the production of high positive pressures. Corresponding results are presented which show the initial neutron diffraction pattern after ice-nucleation. The observed pattern does not exhibit the usual crystalline pattern of hexagonal ice [I(h)] that is formed under ambient conditions, but indicates the presence of other ice forms. The composite features can be attributed to a mixture of amorphous ice, ice-I(h)/I(c) and the high-pressure form, ice-III, and the diffraction pattern continues to evolve over a time period of about an hour.
- Published
- 2012
25. Fractal discrimination of random fractal aggregates and its application in biomarker analysis for blood coagulation
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Karl Hawkins, Paul Rees, Phillip A. Evans, M. R. Brown, D. J. Curtis, Huw D. Summers, and Phylip Rhodri Williams
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Chemistry ,General Mathematics ,Applied Mathematics ,Random fractal ,General Physics and Astronomy ,Statistical and Nonlinear Physics ,Nanotechnology ,Fractal dimension ,Fractal ,Coagulation ,Spectral dimension ,Narrow range ,Statistical analysis ,Biomarker Analysis ,circulatory and respiratory physiology ,Biomedical engineering - Abstract
A recent rheological study has established that the fractal dimension, df, of an incipient clot, formed at the Gel Point (sol–gel transition) of coagulating blood is a significant new biomarker of haemostasis. In whole healthy blood, incipient clots show a clearly defined value of df = 1.7 within a narrow range, which represents a new ‘healthy index’ for normal clotting. The addition of unfractionated heparin significantly prolongs the onset of clot formation with a corresponding reduction of df as a function of heparin dose. However, as clots mature they exhibit (i) an expected increase in df and (ii) a significant increase to spread of these values, i.e. df’s in the range 2.0–2.5, limiting the use of df as a discriminant of clot microstructure. The present study, details how and why the spectral dimension, ds, can be used to accommodate this shortcoming and allow discrimination of mature forms of clot microstructure in indistinguishable in terms of their fractal dimension. To elucidate why ds permits discrimination a numerical experiment was conducted on computationally generated random fractal aggregates (RFAs) with a priori set value of df. Starting from RFAs with a df of 1.7, mature RFAs are evolved from these incipient templates by two differing growth processes achieving a final df of 2.1. Fractal and statistical analysis of the mature RFAs reveals, for the first time, that their differing internal structure is manifest in the magnitude of ds. The potential clinical significance of these findings is discussed in terms of the possibility of exploiting the incipient clot’s ability to template the internal arrangement of the mature clot to better predict long term clot susceptibility to lysis.
- Published
- 2012
26. The development of rheometry for strain-sensitive gelling systems and its application in a study of fibrin–thrombin gel formation
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P. Rhodri Williams, Matthew Lawrence, Marc Davies, P. Adrian Evans, Karl Hawkins, and D. J. Curtis
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Gel point ,biology ,Rheometry ,Chemistry ,Analytical chemistry ,Condensed Matter Physics ,Fractal dimension ,Fibrin ,Viscoelasticity ,Fractal ,Rheology ,biology.protein ,Stress relaxation ,General Materials Science ,Composite material ,circulatory and respiratory physiology - Abstract
This paper reports simulated sequential frequency sweep data which have been reconstructed from time resolved viscoelastic data obtained by Fourier transform mechanical spectroscopy. Comparisons of the results show that the recording of anomalous values of the stress relaxation power law exponent α at the Gel Point under ‘rapid’ gelling conditions may be due to inappropriate rheological techniques. An appropriate rheometrical criterion is established for the application of sequential frequency sweeps in order to obtain accurate values of α in the formation of strain-sensitive, rapidly formed gels. Furthermore, using appropriate rheometry, we report values of α for fibrin–thrombin gels formed by the addition of thrombin to a physiologically relevant level of human fibrinogen, and relate these values to the microstructure of the fibrin gel network in terms of a fractal dimension. The present study is the first to report a modification of the fractal characteristics of incipient clots in fibrin–thrombin gels due to the availability of thrombin. This work confirms the hypothesis that the self-similar (fractal) stress relaxation behaviour recorded at the Gel Point of samples of coagulating blood (Evans et al. 2010a, b) is associated with the microstructural characteristics of the incipient blood clot’s fibrin network.
- Published
- 2010
27. Application of atomic force microscopy to the study of natural and model soil particles
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P. Rhodri Williams, R. Bryant, Chris J. Wright, Shuying Cheng, and Stefan H. Doerr
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chemistry.chemical_classification ,Histology ,Materials science ,Capillary action ,Analytical chemistry ,Surface finish ,complex mixtures ,Pathology and Forensic Medicine ,Adsorption ,chemistry ,Chemical physics ,Soil water ,Surface roughness ,Particle ,Humic acid ,Wetting - Abstract
The structure and surface chemistry of soil particles has extensive impact on many bulk scale properties and processes of soil systems and consequently the environments that they support. There are a number of physiochemical mechanisms that operate at the nanoscale which affect the soil's capability to maintain native vegetation and crops; this includes soil hydrophobicity and the soil's capacity to hold water and nutrients. The present study used atomic force microscopy in a novel approach to provide unique insight into the nanoscale properties of natural soil particles that control the physiochemical interaction of material within the soil column. There have been few atomic force microscopy studies of soil, perhaps a reflection of the heterogeneous nature of the system. The present study adopted an imaging and force measurement research strategy that accounted for the heterogeneity and used model systems to aid interpretation. The surface roughness of natural soil particles increased with depth in the soil column a consequence of the attachment of organic material within the crevices of the soil particles. The roughness root mean square calculated from ten 25 microm(2) images for five different soil particles from a Netherlands soil was 53.0 nm, 68.0 nm, 92.2 nm and 106.4 nm for the respective soil depths of 0-10 cm, 10-20 cm, 20-30 cm and 30-40 cm. A novel analysis method of atomic force microscopy phase images based on phase angle distribution across a surface was used to interpret the nanoscale distribution of organic material attached to natural and model soil particles. Phase angle distributions obtained from phase images of model surfaces were found to be bimodal, indicating multiple layers of material, which changed with the concentration of adsorbed humic acid. Phase angle distributions obtained from phase images of natural soil particles indicated a trend of decreasing surface coverage with increasing depth in the soil column. This was consistent with previous macroscopic determination of the proportions of organic material chemically extracted from bulk samples of the soils from which specimen particles were drawn. Interaction forces were measured between atomic force microscopy cantilever tips (Si(3)N(4)) and natural soil and model surfaces. Adhesion forces at humic acid free specimen surfaces (Av. 20.0 nN), which are primarily hydrophilic and whose interactions are subject to a significant contribution from the capillary forces, were found to be larger than those of specimen surfaces with adsorbed humic acid (Av. 6.5 nN). This suggests that adsorbed humic acid increased surface hydrophobicity. The magnitude and distribution of adhesion forces between atomic force microscopy tips and the natural particle surfaces was affected by both local surface roughness and the presence of adsorbed organic material. The present study has correlated nanoscale measurements with established macroscale methods of soil study. Thus, the research demonstrates that atomic force microscopy is an important addition to soil science that permits a multiscale analysis of the multifactorial phenomena of soil hydrophobicity and wetting.
- Published
- 2008
28. Rheometrical studies of blood clot formation by oscillatory shear, thromboelastography, sonoclot analysis and free oscillation rheometry
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P. Adrian Evans, Karl M. Hawkins, Matthew J. Lawrence, P. Rhodri Williams, Rhodri L. Williams, Albert Co, Gary L. Leal, Ralph H. Colby, and A. Jeffrey Giacomin
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Oscillatory shear ,Free oscillation ,Rheometry ,medicine.diagnostic_test ,Chemistry ,Rheometer ,medicine ,Analytical chemistry ,Coagulation (water treatment) ,Clot formation ,Biorheology ,Thromboelastography ,Biomedical engineering - Abstract
We report studies of the coagulation of samples of whole human blood by oscillatory shear techniques, including Fourier Transform Mechanical Spectroscopy (FTMS). These techniques are used herein to identify the Gel Point of coagulating blood in terms of the Chambon‐Winter Gel Point criterion which provides a rheometrical basis for detecting the establishment of an incipient clot. A comparison of the results of FTMS with those obtained from measurements involving a Thromboelastograph (TEG), a Sonoclot Analyzer and a Free Oscillation Rheometer (FOR) indicate that the latter techniques are not capable of detecting the incipient clot, whose establishment occurs several minutes prior to TEG or FOR‐based assessments of clot formation time. The results of the present study suggest that FTMS is a useful tool in blood clotting research, being capable of providing a global coagulation profile in addition to detecting the instant of incipient clot formation.
- Published
- 2008
29. The Tensile Strength of Water as a Function of Temperature
- Author
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P. Rhodri Williams, R. L. Williams, and A. Al-Hussany
- Subjects
Work (thermodynamics) ,Tension (physics) ,Chemistry ,Cavitation ,Ultimate tensile strength ,Forensic engineering ,Reflection (physics) ,Atmospheric temperature range ,Composite material ,Order of magnitude ,Pulse (physics) - Abstract
This paper reports the results of measurements of the effective tensile strength Fc of water, in experiments involving a pulse of tension (‘negative pressure’) created by the reflection of a pressure pulse at a boundary, as a function of temperature. Using a modified ‘Bullet-Piston’ (B-P) pulse reflection apparatus, measurements presented herein show that degassed, deionised water is capable of sustaining tensions an order of magnitude greater than previously reported in B-P work. A theoretical explanation is developed indicating that the pressure records arising in B-P experiments are the result of cavitation due to a pulse of tension. Results are reported for measurements of Fc made over the temperature range 1°C ≤ T ≤ 95°C.Copyright © 2005 by ASME
- Published
- 2005
- Full Text
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30. Measurements of the Effective Tensile Strength of Newtonian and Non-Newtonian Fluids Under Dynamic Stressing
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Stephen Warwick James Brown, R. L. Williams, and P. Rhodri Williams
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Viscosity ,chemistry.chemical_compound ,Materials science ,chemistry ,Polyacrylamide ,Ultimate tensile strength ,Newtonian fluid ,Thermodynamics ,Apparent viscosity ,Composite material ,Power law ,Silicone oil ,Non-Newtonian fluid - Abstract
The ‘Bullet-Piston’ (B-P) dynamic stressing technique has been used to study the tensile strength, Fc , of Newtonian and non-Newtonian fluids. A comparative study of the effects of viscosity on Fc for silicone oils (Newtonian) and aqueous polyacrylamide (PAA) solutions (non-Newtonian) was made. Both systems exhibited a power law dependency of the form Fc ∝ µn , where µ is the viscosity and n is the power index. For the Newtonian system, n was found to be 0.09 in close agreement with the findings of Couzens and Trevena (1974) for silicone oils whilst a value of 0.16 was found for the PAA solutions.Copyright © 2002 by ASME
- Published
- 2002
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31. Effect of solvent choice on breath-figure-templated assembly of 'holey' polymer films
- Author
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Mohan Srinivasarao, Vivek Sharma, Richard A. L. Jones, Lulu Song, M. S. Barrow, and P. Rhodri Williams
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chemistry.chemical_classification ,Materials science ,Dispersity ,Condensation ,Airflow ,General Physics and Astronomy ,Humidity ,Polymer ,Solvent ,chemistry.chemical_compound ,chemistry ,Chemical engineering ,Polystyrene ,Evaporative cooler - Abstract
Dew or breath figures is a disordered pattern formed by polydisperse water drops that form when a cold surface comes in contact with breath or moist air. Unexpectedly, self-assembled arrays of non-coalescent monodisperse water drops form when dilute solutions of polymers in volatile organic solvents are exposed to moist air. After solvent evaporation is complete, these condensation figures dry out as well, leaving "holey" polymer films, containing hexagonally ordered arrays of pores (0.2 to 10 μm). While the macroporous films are produced easily for a wide variety of solvents and polymers, there is no existing theory that describes how the pore size depends upon tunable parameters like humidity, air temperature and velocity as well as on the choice of solvent and polymer. In this study, we propose a transport model to elucidate the role of the solvent and airflow in determining the rate and extent of evaporative cooling, and contrast our model results with the corresponding experimental measurements for polystyrene/carbon disulfide solutions. We describe how modeling evaporative cooling is essential for the quantitative understanding of dominant processes that lead to growth, non-coalescence and self-assembly of water drops, and the subsequent formation of ordered arrays of pores.
- Published
- 2010
- Full Text
- View/download PDF
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