Effect of the average soft-segment length on the morphology and properties of segmented polyurethane nanocomposites

Two organically modified layered silicates (with small and large diameters) were incorporated into three segmented polyurethanes with various degrees of microphase separation. Microphase separation increased with the molecular weight of the poly(hexamethylene oxide) soft segment. The molecular weight of the soft segment did not influence the amount of polyurethane intercalating the interlayer spacing. Small-angle neutron scattering and differential scanning calorimetry data indicated that the layered silicates did not affect the microphase morphology of any host polymer, regardless of the particle diameter. The stiffness enhancement on filler addition increased as the microphase separation of the polyurethane decreased, presumably because a greater number of urethane linkages were available to interact with the filler. For comparison, the small nanofiller was introduced into a polyurethane with a poly(tetramethylene oxide) soft segment, and a significant increase in the tensile strength and a sharper upturn in the stress-strain curve resulted. No such improvement occurred in the host polymers with poly(hexamethylene oxide) soft segments. It is proposed that the nanocomposite containing the more hydrophilic and mobile poly(tetramethylene oxide) soft segment is capable of greater secondary bonding between the polyurethane chains and the organosilicate surface, resulting in improved stress transfer to the filler and reduced molecular slippage. (c) 2006 Wiley Periodicals, Inc.

Synthesis and physical properties of lipid-based poly(ester-urethane)s, I: Effect of varying polyester segment length

Four aliphatic thermoplastic poly(ester-urethane)s (PEUs) with similar molecular weights but varying polyesters molecular weight (534-1488 g/mol) were prepared from polyester diols, obtained by melt condensation of Azelaic acid and 1,9-Nonanediol, and 1,7-heptamethylene di-isocyanate (HPMDI) all sourced from vegetable oil feedstock. The thermal, and mechanical properties, and crystal structure of PEUs were investigated using DSC, TGA, DMA, tensile analysis and WAXD. For sufficiently long polyester chain, WAXD data indicated no hydrogen bonds polyethylene (PE)-like crystalline packing and for short polyester chains, small crystal domains with significant H-bonded polyamide (PA)-like packing. Crystallinity decreased with decreasing polyester molecular weights. The polymorphism of PEUs and consequently their melting characteristics were found to be largely controlled by polyester segment length. TGA of the PEUs indicated improved thermal stability with decreasing polyester chain length, suggesting a stabilization effect by urethane groups. Mechanical properties investigated by DMA and tensile analysis were found to scale predictably with the overall crystallinity of PEUs. (C) 2012 Elsevier Ltd. All rights reserved.

Comparison between polyurethanes containing castor oil (Soft Segment) and cancellous bone autograft in the treatment of segmental bone defect induced in rabbits

The aim of this study is to compare polyurethanes containing castor oil (soft segment) in granular form compared to cancellous bone autograft applied to a segmental bone defect. Norfolk adult female rabbits - approximately 13 months of age with a mean body weight of 4.5 kg - are used. In both radial diaphyses, 1 cm osteoperiosteal segmental defects are created. The defect in the left radius is filled with the castor-oil-based polyurethane, and the right one, filled with cancellous bone autograft, collected from the left proximal humerus. The rabbits are euthanazed at 15, 30, 60, and 120 days postsurgery (5 animals/ period), for histological analyses. By radiographic analyses, at these time points, the bone regeneration is more evident and accelerated in the bone defects treated with the cancellous bone autograft. At 120 days postsurgery, the segmental bone defects treated with the cancellous bone autograft are totally reconstituted and remodeled, while the bone defects treated with polyurethane polymer have bone formation of 79%. Histological study shows that the polyurethane acts as a space filler, minimizing the local production of fibrous tissue. No granule degradation, resorption or any inflammatory reaction is detected. Thus, it is possible to conclude that the castor-oil-plant-based polyurethane - in the granule presentation - is biocompatible and osteointegrated, but does not show the same bone regeneration capacity as the cancellous bone autograft. © 2007 SAGE Publications.

Morphology and properties of thermoplastic polyurethane nancomposites incorporating hydrophilic layered silicates

Hydrophilic layered silicate/polyurethane nanocomposites were prepared via twin screw extrusion and solvent casting. Good dispersion and delamination was achieved-regardless of processing route, illustrating that the need for optimised processing conditions diminishes when there is a strong driving for de for intercalation between the polymer and organosilicate. Evidence for altered polyurethane microphase morphology in the nanocomposites was provided by DMTA and DSC. WAXD results suggested that the appearance of an additional high temperature melting endotherm in some melt-compounded nanocomposites was not due to the formation of a second crystal polymorph, but rather due to more well-ordered hard microdomains. Solvent casting was found to be the preferred processing route due to the avoidance of polyurethane and surfactant degradation associated with melt processing. While tensile strength and elongation were not improved on organosilicate addition, large increases in stiffness were observed. At a 7 wt% organosilicate loading, a 3.2-fold increase in Young's modulus was achieved by solvent casting. The nanocomposites also displayed higher hysteresis and permanent set. (C) 2004 Elsevier Ltd. All rights reserved.

Influence of cellulose nanofibrils on soft and hard segments of polyurethane/cellulose nanocomposites and effect of humidity on their mechanical properties

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Speech production in Parkinson's disease: II. Acoustic and electropalatographic investigation of sentence, word and segment durations

Previous investigations employing electropalatography (EPG) have identified articulatory timing deficits in individuals with acquired dysarthria. However, this technology is yet to be applied to the articulatory timing disturbance present in Parkinson's disease (PD). As a result, the current investigation aimed to use EPG to comprehensively examine the temporal aspects of articulation in a group of nine individuals with PD at sentence, word and segment level. This investigation followed on from a prior study (McAuliffe, Ward and Murdoch) and similarly, aimed to compare the results of the participants with PD to a group of aged (n=7) and young controls (n=8) to determine if ageing contributed to any articulatory timing deficits observed. Participants were required to read aloud the phrase I saw a ___ today'' with the EPG palate in-situ. Target words included the consonants /1/, /s/ and /t/ in initial position in both the /i/ and /a/ vowel environments. Perceptual investigation of speech rate was conducted in addition to objective measurement of sentence, word and segment duration. Segment durations included the total segment length and duration of the approach, closure/constriction and release phases of EPG consonant production. Results of the present study revealed impaired speech rate, perceptually, in the group with PD. However, this was not confirmed objectively. Electropalatographic investigation of segment durations indicated that, in general, the group with PD demonstrated segment durations consistent with the control groups. Only one significant difference was noted, with the group with PD exhibiting significantly increased duration of the release phase for /1a/ when compared to both the control groups. It is, therefore, possible that EPG failed to detect lingual movement impairment as it does not measure the complete tongue movement towards and away from the hard palate. Furthermore, the contribution of individual variation to the present findings should not be overlooked.

Variability of marine climate on the North Icelandic Shelf in a 1357-year proxy archive based on growth increments in the bivalve Arctica islandica

A multicentennial and absolutely-dated shell-based chronology for the marine environment of the North Icelandic Shelf has been constructed using annual growth increments in the shell of the long-lived bivalve clam Arctica islandica. The region from which the shells were collected is close to the North Atlantic Polar Front and is highly sensitive to the varying influences of Atlantic and Arctic water masses. A strong common environmental signal is apparent in the increment widths, and although the correlations between the growth increment indices and regional sea surface temperatures are significant at the 95% confidence level, they are low (r ~ 0.2), indicating that a more complex combination of environmental forcings is driving growth. Remarkable longevities of individual animals are apparent in the increment-width series used in the chronology, with several animals having lifetimes in excess of 300 years and one, at 507 years, being the longest-lived non-colonial animal so far reported whose age at death can be accurately determined. The sample depth is at least three shells after AD 1175, and the time series has been extended back to AD 649 with a sample depth of one or two by the addition of two further series, thus providing a 1357-year archive of dated shell material. The statistical and spectral characteristics of the chronology are investigated by using two different methods of removing the age-related trend in shell growth. Comparison with other proxy archives from the same region reveals several similarities in variability on multidecadal timescales, particularly during the period surrounding the transition from the Medieval Climate Anomaly to the Little Ice Age.

A pictorial field guide for the rapid identification of sandflies (DIPTERA: PSYCHODIDAE), commonly encountered in Pará state, Brazil.

A pictorial field guide to the 30 species of sandfly most commonly encountered in Pará State is presented, based on the easily recognised external characters of the length of the 5th palpal segment, thoracic infuscation, abdominal colour and head and body size. In most cases this allows identification to the species. In others, especially with females, it gives an indication of the species, which may then be confirmed with data from more detailed taxanomix studies. This type of field guide helps in teaching, rapid sorting of flies prior to dissection and in acquainting visitors with the variety of species present in a given area.A rapid technique for the taxonomic sorting of unmounted, freshly killed female sandflies is required, prior to the dissection of large numbers of a particular species. Such a method is useful in areas where numerous species occur in studies on natural flagellate infections, age determination and for ecological studies. With the above points in mind a pictorial field guide has been designed that enables the identification of unmounted, unmacerated specimens of the 30 more commonly encountered species of phleboto-mine sandflies (***) in Pará State, North Brazil. It is based on the easily recognised external characters of the length of the 5th palpal segment, thoracic infuscation, ad-dominal colour and proboscis and body size.Taxonomy of male phlebotomine sandflies is based on the structure of the genitalia and, as most of this is external, a wholly external character key is readily made. Female taxonomy, however, is based on the internal character of the cibarium, pharynx and sperma thecae. In order to produce an external character key we therefore return to an unso phisticated "phlebotometry" (see Martins et al., 1978 p. 3 for review), using relative lengths of the proboscis, palpal segments and body, along with the degree of infuscation. Ihis idea is not new; indeed many sandfly specialists presently use external characters to separate certain species (H. Fraiha, R. P. Lane, P. D. Ready, D. G. Young and R. D. Ward personal communications 1983 & 1984).A key used to separate five anthropophillic sandflies by Biagi (1966), in Mexico, was based mainly on palpal segment length and infuscation. Floch and Abonnenc (1952) stressed the use of relative lengths of palpal segments in their keys to the sandflies of French Guiana, and four members of the shannoni group have been similarly separated according to the degree of infuscation by Morales et al. (1982). The use of thoracic infuscation as a reliable character seems to be gaining favour, having been used by young & Fairchild (1974) and Ready & Fraiha (1981). Indeed Chariotis 1974) showed the usefulness of thoracic infuscation to sepenate 7 anthropophillic species, during studies onvesicular stomatitis in Panama. Identification using external characters is essential for work on viral isolations from sandflies, where bulk samples of whole sandflies are used.Perhaps the major advantage of a simple visual guide is for teaching purposes. Technical staff in this lnstitute are able to identify most of the species they encounter without having to use the standard, more unwieldly (and in many cases unavailable) internal character keys, and the guides presented below have allowed rapid species sorting prior to the dissection of sandflies in our leismaniasis study areas (Ryan et at. ,1985).

Self-avoiding random walks and Olbers' paradox

In this paper, we prove that a self-avoiding walk of infinite length provides a structure that would resolve Olbers' paradox. That is, if the stars of a universe were distributed like the vertices of an infinite random walk with each segment length of about a parsec, then the night sky could be as dark as actually observed on the Earth. Self-avoiding random walk structure can therefore resolve the Olbers' paradox even in a static universe.

Economic optimization method to design telescope irrigation of multiples outlets

In this study is presented an economic optimization method to design telescope irrigation laterals (multidiameter) with regular spaced outlets. The proposed analytical hydraulic solution was validated by means of a pipeline composed of three different diameters. The minimum acquisition cost of the telescope pipeline was determined by an ideal arrangement of lengths and respective diameters for each one of the three segments. The mathematical optimization method based on the Lagrange multipliers provides a strategy for finding the maximum or minimum of a function subject to certain constraints. In this case, the objective function describes the acquisition cost of pipes, and the constraints are determined from hydraulic parameters as length of irrigation laterals and total head loss permitted. The developed analytical solution provides the ideal combination of each pipe segment length and respective diameter, resulting in a decreased of the acquisition cost.

Cambios maculares y de capa de fibras nerviosas ganglionares posterior a la vitrectomía pars plana y sus factores pronósticos en la fundación oftalmológica nacional

OBJETIVOS: Determinar los factores pronóstico, cambios maculares morfológicos y de capa de fibras nerviosas ganglionares posterior a vitrectomía pars plana, en la Fundación Oftalmológica Nacional. MATERIALES Y MÉTODOS: Estudio longitudinal de antes y después (3y6 meses) de la vitrectomía pars plana (VPP) en pacientes con membrana epirretiniana, agujero macular, síndrome de tracción vítreo macular y opacidades vítreas no-inflamatorias. Se realizó seguimiento clínico y con tomografía de coherencia óptica. RESULTADOS: Grupo de 60 pacientes (mujeres 65.0%), edad promedio 65.45+9.49años y tiempo de enfermedad promedio 23+29.79meses. Las indicaciones de VPP (n=60ojos) fueron agujero macular (38.3%) y membrana epirretiniana (36.7%). Se encontró diferencia significativa entre grosor del complejo capa de células ganglionares (CCG)+capa plexiforme interna (CPI) inicial y 3 meses (p=0.039), correlación entre grosor del complejo CCG+CPI al tercer y sexto mes (r=0.704,p<0.001) y grosor del complejo CCG+CPI al tercer mes con grosor foveal central (CFT) al tercer y sexto mes (r=–0.594,p<0.001 y r=–0.595,p=0.001). Mayores de 65años tenían menor grosor de CFNG a 6meses (r=-0.528,p=0.007). El grosor de CFNG promedio y la presencia de la zona elipsoide inicial fueron factores pronósticos de buena agudeza visual al tercer mes de VPP (r2=0.414,p=0.018, y r2=0.414,p=0.010). CONCLUSIÓN: El grosor de CFNG y la presencia de la zona elipsoide inicial tienen alta capacidad predictiva de buena agudeza visual al tercer mes de VPP, y, correlación inversa entre grosor del complejo CCG+CPI con CFT al tercer y sexto mes de VPP.

Structural control of photoluminescence of four poly(urethane-urea-co-1,3,5-triazine)s: Synthesis and characterization

A series of segmented poly(urethane-urea)s containing 1,3,5 triazine in the hard block and hexamethylene spacers in the soft block was prepared. The hard to soft segment ratio was varied systematically, to afford a series of polymers in which the chromophore concentration varied from 4.2% to 18.1%. Although triazine emission is located in the UV region, the films with higher content of the chromophore emitted a visible blue light (425 nm) when excited at the very red-edge of the absorption band. The photophysical properties of the materials were strongly dependent on the relative amount of triazine moieties along the main chain. Isolated moieties emit in copolymers with small amount of triazine groups, indicating that even though in solid state, these moieties tend to be apart. Two photophysical consequences were observed when the amount of triazine increases: there is some energy transfer process involving isolated moieties with consequent decrease of the lifetime and an additional red-edge emission attributed to aggregated lumophores. The mono-exponential decay observed for the isolated form is substituted by a bi-exponential decay of the aggregated species. The materials were not strong emitters, but since the N-containing triazine moieties are good electron transport groups, the polymers have potential application as electron transport enhancers in various applications. © 2006 Elsevier B.V. All rights reserved.

Cephalometric analysis for the diagnosis of sleep apnea: a comparative study between reference values and measurements obtained for Brazilian subjects

OBJECTIVE: To verify if the reference values of Sleep Apnea cephalometric analysis of North American individuals are similar to the ones of Brazilian individuals presenting no craniofacial anomalies. The study also aimed to identify craniofacial alterations in Obstructive Sleep Apnea-Hypopnea Syndrome (OSAHS) patients in relation to individuals without clinical characteristics of the disease through this cephalometric analysis. METHOD: It were used 55 lateral cephalograms consisting of 29 for the control group of adult individuals without clinical characteristics of OSAHS and 26 apneic adults. All radiographs were submitted to Sleep Apnea cephalometric analysis through Radiocef Studio 2.0. The standard values of this analysis were compared, by means of z test, to the ones obtained from the control group and these were compared to values from apneic group through Student's t test. RESULTS: There were no significant differences between values obtained from control group and standard values. On the group of OSAHS patients it was observed a decrease on the dimensions of upper airways and an increase on the soft palate length. CONCLUSIONS: The standard values of Sleep Apnea analysis can be used as reference in Brazilian individuals. Besides, through lateral cephalograms it was possible to identify craniofacial alterations in OSAHS patients.