Examination of the flow rheological and textural properties of polymer gels composed of poly(methylvinylether-co-maleic anhydride) and poly(vinylpyrrolidone): rheological and mathematical interpretation of textural parameters.

The purpose of this study was to mathematically characterize the effects of defined experimental parameters (probe speed and the ratio of the probe diameter to the diameter of sample container) on the textural/mechanical properties of model gel systems. In addition, this study examined the applicability of dimensional analysis for the rheological interpretation of textural data in terms of shear stress and rate of shear. Aqueous gels (pH 7) were prepared containing 15% w/w poly(methylvinylether-co-maleic anhydride) and poly(vinylpyrrolidone) (PVP) (0, 3, 6, or 9% w/w). Texture profile analysis (TPA) was performed using a Stable Micro Systems texture analyzer (model TA-XT 2; Surrey, UK) in which an analytical probe was twice compressed into each formulation to a defined depth (15 mm) and at defined rates (1, 3, 5, 8, and 10 mm s-1), allowing a delay period (15 s) between the end of the first and beginning of the second compressions. Flow rheograms were performed using a Carri-Med CSL2-100 rheometer (TA Instruments, Surrey, UK) with parallel plate geometry under controlled shearing stresses at 20.0°?±?0.1°C. All formulations exhibited pseudoplastic flow with no thixotropy. Increasing concentrations of PVP significantly increased formulation hardness, compressibility, adhesiveness, and consistency. Increased hardness, compressibility, and consistency were ascribed to enhanced polymeric entanglements, thereby increasing the resistance to deformation. Increasing probe speed increased formulation hardness in a linear manner, because of the effects of probe speed on probe displacement and surface area. The relationship between formulation hardness and probe displacement was linear and was dependent on probe speed. Furthermore, the proportionality constant (gel strength) increased as a function of PVP concentration. The relationship between formulation hardness and diameter ratio was biphasic and was statistically defined by two linear relationships relating to diameter ratios from 0 to 0.4 and from 0.4 to 0.563. The dramatically increased hardness, associated with diameter ratios in excess of 0.4, was accredited to boundary effects, that is, the effect of the container wall on product flow. Using dimensional analysis, the hardness and probe displacement in TPA were mathematically transformed into corresponding rheological parameters, namely shearing stress and rate of shear, thereby allowing the application of the power law (??=?k?n) to textural data. Importantly, the consistencies (k) of the formulations, calculated using transformed textural data, were statistically similar to those obtained using flow rheometry. In conclusion, this study has, firstly, characterized the relationships between textural data and two key instrumental parameters in TPA and, secondly, described a method by which rheological information may be derived using this technique. This will enable a greater application of TPA for the rheological characterization of pharmaceutical gels and, in addition, will enable efficient interpretation of textural data under different experimental parameters.

Software Products for Modelling and Simulation in Materials Science

Models and software products have been developed for modelling, simulation and prediction of different correlations in materials science, including 1. the correlation between processing parameters and properties in titanium alloys and ?-titanium aluminides; 2. time–temperature–transformation (TTT) diagrams for titanium alloys; 3. corrosion resistance of titanium alloys; 4. surface hardness and microhardness profile of nitrocarburised layers; 5. fatigue stress life (S–N) diagrams for Ti–6Al–4V alloys. The programs are based on trained artificial neural networks. For each particular case appropriate combination of inputs and outputs is chosen. Very good performances of the models are achieved. Graphical user interfaces (GUI) are created for easy use of the models. In addition interactive text versions are developed. The models designed are combined and integrated in software package that is built up on a modular fashion. The software products are available in versions for different platforms including Windows 95/98/2000/NT, UNIX and Apple Macintosh. Description of the software products is given, to demonstrate that they are convenient and powerful tools for practical applications in solving various problems in materials science. Examples for optimisation of the alloy compositions, processing parameters and working conditions are illustrated. An option for use of the software in materials selection procedure is described.

Formulation and characterisation of tetracycline-containing bioadhesive polymer networks designed for the treatment of periodontal disease.

This study described the drug release, rheological (dynamic and flow) and textural/mechanical properties of a series of formulations composed of 15% w/w polymethylvinylether-co-maleic anhydride (PMVE-MA), 0-9% w/w polyvinylpyrrolidone (PVP) and containing 1-5% w/w tetracycline hydrochloride, designed for the treatment of periodontal disease. All formulations exhibited pseudoplastic flow with minimal thixotropy. Increasing the concentration of PVP sequentially increased the zero-rate viscosity (derived from the Cross model) and the hardness and compressibility of the formulations (derived from texture profile analysis). These affects may be accredited to increased polymer entanglement and, in light of the observed synergy between the two polymers with respect to their textural and rheological properties, interaction between PVP and PMVE-MA. Increasing the concentration of PVP increased the storage and loss moduli yet decreased the loss tangent of all formulations, indicative of increased elastic behaviour. Synergy between the two polymers with respect to their viscoelastic properties was observed. Increased adhesiveness, associated with increased concentrations of PVP was ascribed to the increasing bioadhesion and tack of the formulations. The effect of increasing drug concentration on the rheological and textural properties was dependent on PVP concentration. At lower concentrations (0, 3% w/w) no effect was observed whereas, in the presence of 9% w/w PVP, increasing drug concentration increased formulation elasticity, zero rate viscosity, hardness and compressibility. These observations were ascribed to the greater mass of suspended drug in formulations containing the highest concentration of PVP. Drug release from formulations containing 6 and 9% PVP (and 5% w/w drug) was prolonged and swelling/diffusion controlled. Based on the drug release, rheological and textural properties, it is suggested that the formulation containing 15% w/w PMVE-MA, 6% w/w PVP and tetracycline hydrochloride (5% w/w) may be useful for the treatment of periodontal disease.

Design, characterisation and preliminary clinical evaluation of a novel mucoadhesive topical formulation containing tetracycline for the treatment of periodontal disease

This study describes the formulation, characterisation and preliminary clinical evaluation of mucoadhesive, semi-solid formulations containing hydroxyethylcellulose (HEC, 1-5%, w/w), polyvinylpyrrolidine (PVP, 2 or 3%, w/w), poly carbophil (PC, 1 or 3%, w/w) and tetracycline (5%, w/w, as the hydrochloride). Each formulation was characterised in terms of drug release, hardness, compressibility, adhesiveness (using a texture analyser in texture profile analysis mode), syringeability (using a texture analyser in compression mode) and adhesion to a mucin disc (measured as a detachment force using the texture analyser in tensile mode). The release exponent for the formulations ranged from 0.78+/-0.02 to 1.27+/-0.07, indicating that drug release was non-diffusion controlled. Increasing the concentrations of each polymeric component significantly increased the time required for 10 and 30% release of the original mass of tetracycline, due to both increased viscosity and, additionally, the unique swelling properties of the formulations. Increasing concentrations of each polymeric component also increased the hardness, compressibility, adhesiveness, syringeability and mucoadhesion of the formulations. The effects on product hardness, compressibility and syringeability may be due to increased product viscosity and, hence, increased resistance to compression. Similarly, the effects of these polymers on adhesiveness/mucoadhesion highlight their mucoadhesive nature and, importantly, the effects of polymer state (particularly PC) on these properties. Thus, in formulations where the neutralisation of PC was maximally suppressed, adhesiveness and mucoadhesion were also maximal. Interestingly, statistical interactions were primarily observed between the effects of HEC and PC on drug release, mechanical and mucoadhesive properties. These were explained by the effects of HEC on the physical state of PC, namely swollen or unswollen. In the preliminary clinical evaluation, a formulation was selected that offered an appropriate balance of the above physical properties and contained 3% HEC, 3% PVP and 1% PC, in addition to tetracycline 5% (as the hydrochloride). The clinical efficacy of this (test) formulation was compared to an identical tetracycline-devoid (control) formulation in nine periodontal pockets (greater than or equal to 5 mm depth). One week following administration of the test formulation, there was a significant improvement in periodontal health as identified by reduced numbers of sub-gingival microbial pathogens. Therefore, it can be concluded that, when used in combination with mechanical plaque removal, the tetracycline-containing semi-solid systems described in this study would augment such therapy by enhancing the removal of pathogens, thus improving periodontal health. (C) 2000 Elsevier Science B.V. All rights reserved.

Modelling the correlation between processing parameters and properties of maraging steels using artificial neural network

An artificial neural network (ANN) model is developed for the analysis and simulation of the correlation between the properties of maraging steels and composition, processing and working conditions. The input parameters of the model consist of alloy composition, processing parameters (including cold deformation degree, ageing temperature, and ageing time), and working temperature. The outputs of the ANN model include property parameters namely: ultimate tensile strength, yield strength, elongation, reduction in area, hardness, notched tensile strength, Charpy impact energy, fracture toughness, and martensitic transformation start temperature. Good performance of the ANN model is achieved. The model can be used to calculate properties of maraging steels as functions of alloy composition, processing parameters, and working condition. The combined influence of Co and Mo on the properties of maraging steels is simulated using the model. The results are in agreement with experimental data. Explanation of the calculated results from the metallurgical point of view is attempted. The model can be used as a guide for further alloy development.

Reactivity of the 4d transition metals toward N hydrogenation and NH dissociation: A DFT-based HSAB analysis

The density functional theory (DFT) based hard-soft acid-base (HSAB) reactivity indices, including the electrophilicity index, have been successfully applied to many areas of molecular chemistry. In this work we test the applicability of such an approach to fundamental surface chemistry. We have considered, as prototypical surface reactions, both the hydrogenation of atomic nitrogen and the dissociative adsorption of the NH molecular radical. By use of a DFT methodology, the minimum energy reaction pathways, and corresponding reaction barriers, of the above reactions over Zr(001), Nb(110), Mo(110), Tc(001), Ru(001), Rh(111), and Pd(111) have been determined. By consideration of the chemical potential and chemical hardness of the surface metal atoms, and the principle of electronegativity equalization, it is found that the charge transferred to the NH radical during the process of dissociative adsorption correlates very well with that determined by Mulliken population analysis. Furthermore, it is found that the stability of the NH/surface transition state complex relates directly to this charge transfer and that the trend in transition state stability predicted by a HSAB; treatment correlates very strongly with that determined by DFT calculations. With regards to N hydrogenation, we find that during the course of the reaction, H loses cohesion to the surface, as it must migrate from a 3-fold hollow site to either a bridge or top site, to react with N. Partial density of states (PDOS) and Mulliken population analysis reveal that this loss of bonding is accompanied by charge transfer from H to the surface metal atoms. Moreover, by simple modeling, we show that the reaction barriers are directly proportional to this mandatory charge transfer. Indeed, it is found that the reaction barriers correlate very well with the electrophilicity index of the metal atoms.

Origin of Ferroelastic domains in Free-Standing Single Crystal Ferroelectric Films

The origin of the unusual 90 degrees ferroelectric/ferroelastic domains, consistently observed in recent studies on mesoscale and nanoscale free-standing single crystals of BaTiO3 [Schilling , Phys. Rev. B 74, 024115 (2006); Schilling , Nano Lett. 7, 3787 (2007)], has been considered. A model has been developed which postulates that the domains form as a response to elastic stress induced by a surface layer which does not undergo the paraelectric-ferroelectric cubic-tetragonal phase transition. This model was found to accurately account for the changes in domain periodicity as a function of size that had been observed experimentally. The physical origin of the surface layer might readily be associated with patterning damage, seen in experiment; however, when all evidence of physical damage is removed from the BaTiO3 surfaces by thermal annealing, the domain configuration remains practically unchanged. This suggests a more intrinsic origin, such as the increased importance of surface tension at small dimensions. The effect of surface tension is also shown to be proportional to the difference in hardness between the surface and the interior of the ferroelectric. The present model for surface-tension induced twinning should also be relevant for finely grained or core-shell structured ceramics.

Characterization of the Rheological, Mucoadhesive, and Drug Release Properties of Highly Structured Gel Platforms for Intravaginal Drug Delivery

This investigation describes the formulation and characterization of theologically structured vehicles (RSVs) designed for improved drug delivery to the vagina. Interactive, multicomponent, polymeric platforms were manufactured containing hydroxyethylcellulose (HEC, 5% w/w) polyvinylpyrrolidone (PVP, 4% w/w), Pluronic (PL, 0 or 10% w/w), and either polycarbophil (PC, 3% w/w) or poly(methylvinylether-co-maleic anhydride) (Gantrez S97, 3% w/w) as a mucoadhesive agent. The rheological (torsional and dynamic), mechanical (compressional), and mucoadhesive properties were characterized and shown to be dependent upon the mucoadhesive agent used and the inclusion/exclusion of PL. The dynamic theological properties of the gel platforms were also assessed following dilution with simulated vaginal fluid (to mimic in vivo dilution). RSVs containing PC were more rheologically structured than comparator formulations containing GAN. This trend was also reflected in formulation hardness, compressibility, consistency, and syringeability. Moreover, formulations containing PL (10% w/w) were more theologically structured than formulations devoid of PL. Dilution with simulated vaginal fluids significantly decreased rheological structure, although RSVs still retained a highly elastic stnicture (G' > G '' and tan delta <1). Furthermore, RSVs exhibited sustained drug release properties that were shown to be dependent upon their rheological structure. It is considered that these semisolid drug delivery systems may be useful as site-retentive platforms for the sustained delivery of therapeutic agents to the vagina.

The influence of reusing ‘Formtex’ controlled permeability

The effects of the reuse of ‘Formtex’ Controlled Permeability Formwork (CPF) liner on strength and durability properties of concrete were investigated at two different water-cement ratios and the results are reported in this paper. Test blocks were cast using the CPF on one side and impermeable formwork (IF) on the opposite side of the mould so that direct comparisons could be made between the two. The strength was assessed using the Limpet pulloff tester and both the air permeability and the water absorption (sorptivity) were measured using the Autoclam Permeability System. Both these instruments measured the ‘covercrete’ properties. In addition, cores cut from the test specimens were subjected to an accelerated carbonation test and a chloride exposure test. The results showed that the ‘Formtex’ CPF increases the surface strength and the durability of concrete compared to the IF. There was an almost complete elimination of blowholes. The permeability of concrete decreased and its resistance to the ingress of both carbon dioxide and chlorides increased when CPF was used. The beneficial effects of the Formtex CPF were most evident in concrete of higher water-cement ratio. With the reuse of the Formtex liner twice, that is a total of three uses, the performance of the CPF to improve the properties of concrete remained almost the same. In this research the CPF liner was cleaned thoroughly between each use, which must be adhered to for site applications for reproducing the beneficial effects observed in the laboratory.

Validity and reliability of cardiorespiratory measurements recorded by the LifeShirt during exercise tests

The LifeShirt is a novel ambulatory monitoring system that records cardio respiratory measurements outside the laboratory. Validity and reliability of cardiorespiratory measurements recorded by the LifeShirt were assessed and two methods of calibrating the LifeShirt were compared. Participants performed an incremental treadmill test and a constant work rate test (65% peak oxygen uptake) on four occasions (>48 In apart) and wore the LifeShirt, COSMED system and Polar Sport Tester simultaneously. The LifeShirt was calibrated using two methods: comparison to a spirometer; and 800 ml fixed-volume bag. Ventilation, respiratory rate, expiratory time and heart rate recorded by the LifeShirt were compared to measurements recorded by laboratory equipment. Sixteen adults participated (6M: 10F); mean (SD) age 23.1 (2.9) years. Agreement between the LifeShirt and laboratory equipment was acceptable. Agreement for ventilation was improved by calibrating the LifeShirt using a spirometer. Reliability was similar for the LifeShirt and the laboratory equipment. This study suggests that the LifeShirt provides a valid and reliable method of ambulatory monitoring. (C) 2009 Elsevier B.V. All rights reserved.

Thermal study of selectively plated nickel sulfamate coatings

Nickel sulfamate solution was applied to mild steel substrates by the process of selective plating. The coated samples were heated to temperatures in the range of 50–1000 °C. Thermal analysis, X-ray diffraction and microscopy techniques were used to investigate the effect of secondary heating on the microstructure, mechanical properties and the composition of the surface coatings.

The microscopy analysis showed that the secondary heating caused diffusion within the coating itself and diffusion between the coating and the substrate as concentrations of iron increased in the coating and nickel appeared in the substrate. This diffusion redistribution also caused a phase transformation in the coating as NiO formed on the surface when the coating was heated in a furnace fitted with a nitrogen flow. However this transformation was found not to occur when the coating was heated in a sealed helium environment. Layer and grain growth occurred as temperature increased with the grains taking their preferred orientation as they were heated.

The surface hardness was found to initially rise up from 565 HV to 600 HV when heated to 200 °C. After 200 °C the surface hardness decreased in two stages before falling to 110 HV by 1000 °C. During tensile testing the coated samples performed marginally better in tension than the uncoated samples, however the temperatures used were not elevated high enough to show any real degradation during the tensile testing of the nickel coating that was shown during hardness testing and the microscopy analysis

Nitride-strengthened reduced activation ferritic/martensitic steels

Two nitride-strengthened reduced activation ferritic/martensitic (RAFM) steels with different Mn contents were investigated. The experimental steels were designed based on the chemical composition of Eurofer 97 steel but the C content was reduced to an extremely low level. Microstructure observation and hardness tests showed that the steel with low Mn content (0.47 wt.%) could not obtain a full martensitic microstructure due to the inevitable δ-ferrite independent of cooling rate after soaking. This steel showed similar room temperature strength and higher strength at 600 °C, but lower impact toughness, compared with Eurofer 97 steel. Fractography of the Charpy impact specimen revealed that the low room temperature toughness should be related to the Ta-rich inclusions initiating the cleavage fracture. The larger amount of V-rich nitrides and more dissolved Cr in the matrix could be responsible for the strength being similar to Eurofer 97 steel. In the second steel developed from the first steel by increasing the Mn content from 0.47 wt.% to 3.73 wt.%, a microstructure of full martensite could be obtained.

Precipitation, microstructure and mechanical properties of low nickel maraging steel

A maraging steel with a composition of Fe–12·94Ni–1·61Al–1·01Mo–0·23Nb (wt-%) was investigated. Optical, scanning electron and transmission electron microscopy and X-ray diffraction analysis were employed to study the microstructure of the steel after different aging periods at temperatures of 450–600°C. Hardness and Charpy impact toughness of the steel were measured. The study of microstructure and mechanical properties showed that nanosized precipitates were formed homogeneously during the aging process, which resulted in high hardness. As the aging time is prolonged, precipitates grow and hardness increases. Fractography of the as forged steel has shown mixed ductile and brittle fracture and has indicated that the steel has good toughness. Relationships among heat treatment, microstructure and mechanical properties are discussed. Further experiments using tensile testing and impact testing for aged steel were carried out.

Microstructure evolution of a 10Cr heat-resistant steel during high temperature creep

The microstructure evolution of a 10Cr ferritic/martensitic heat-resistant steel during creep at 600°C was investigated in this work. Creep tests demonstrated that the 10Cr steel had higher creep strength than conventional ASME-P92 steel at 600°C. The microstructure after creep was studied by transmission electron microscopy, scanning electron microscopy and electron probe microanalysis. It was revealed that the martensitic laths were coarsened with time and eventually developed into subgrains after 8354 h. Laves phase was observed to grow and cluster along the prior austenite grain boundaries during creep and caused the fluctuation of solution and precipitation strengthening effects, which was responsible for the two slope changes on the creep rupture strength vs rupture time curve. It was also revealed that the microstructure evolution could be accelerated by stress, which resulted in the lower hardness in the deformed part of the creep specimen, compared with the aging part.

SEM-EDX of morphology of electroless nickel coatings with tin and tungsten

Electroless plating of binary Ni-P, ternary Ni-Sn-P and Ni-W-P, and quaternary Ni-W-Sn-P alloy coatings was carried out in alkalicitrate baths. After the plating, several kinds of test were carried out to determine the improvement in the characteristics and properties due to the additional elements as well as to study the change in behaviour when heat treatment was applied to these coatings. The coatings were subjected to X-ray diffraction analysis where it was found that all the coatings were amorphous. Interesting surface morphology features were examined using scanning electron microscopy. Addition of a third element improved the hardness.