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.

Charge transport in a blue-emitting alternating block copolymer with a small spacer to conjugated segment length ratio

We analyze current versus voltage data obtained using single carrier injection in several metal/polymer/metal sandwich structures. The polymer used in each case is a soluble blue-emitting alternating block copolymer. Our experimental results demonstrate that the electron transport is space-charge limited by the high density of traps having an exponential energy distribution (temperature dependent characteristic energy) in the copolymer. The electron mobility of 8x10(-10) cm(2)/V s is directly determined using space-charge-limited current analytical expressions. Hole transport is also space-charge limited, with a mobility of 2x10(-6) cm(2)/V s. A hole trap with energy 0.17 eV is observed. We compare these results with those obtained for related block copolymers with different spacer and conjugated segment lengths and discuss the influence of spacer length and conjugated segment length on the charge transport properties. (C) 2000 American Institute of Physics. [S0021-8979(00)04501-1].

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.

Isothermal crystallization kinetics of PEO in poly(ethylene terephthalate)-poly(ethylene oxide) segmented copolymers. I. Effect of the sofi-block length

The isothermal crystallization kinetics of poly(ethylene oxide) (PEO) block in two poly(ethylene terephthalate) (PET)-PEO segmented copolymers was studied with differential scanning calorimetry. The Avrami equation failed to describe the overall crystallization process, but a modified Avrami equation, the Q equation, did. The crystallizability of the PET block and the different lengths of the PEO block exerted strong influences on the crystallization process, the crystallinity, and time final morphology of the PEO block. The mechanism of nucleation and the growth dimension of the PEG block were different because of the crystallizability of time PET block and the compositional heterogeneity. The crystallization of the PEO block was physically constrained by the microstructure of time PET crystalline phase, which resulted in a lower crystallization rate. However, this influence became weak with the increase in the soft-block length. (C) 2000 John Wiley & Sons, Inc.

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.

Implementing low intensity CBT in case management of clients with severe mental illness

In a previous chapter (Dean and Kavanagh, Chapter 37), the authors made a case for applying low intensity (LI) cognitive behaviour therapy (CBT) to people with serious mental illness (SMI). As in other populations, LI CBT interventions typically deal with circumscribed problems or behaviours. LI CBT retains an emphasis on self-management, has restricted content and segment length, and does not necessarily require extensive CBT training. In applying these interventions to SMI, adjustments may be needed to address cognitive and symptomatic difficulties often faced by these groups. What may take a single session in a less affected population may require several sessions or a thematic application of the strategy within case management. In some cases, the LI CBT may begin to appear more like a high-intensity (HI) intervention, albeit simple and with many LI CBT characteristics still retained. So, if goal setting were introduced in one or two sessions, it could clearly be seen as an LI intervention. When applied to several different situations and across many sessions, it may be indistinguishable from a simple HI treatment, even if it retains the same format and is effectively applied by a practitioner with limited CBT training. ----- ----- In some ways, LI CBT should be well suited to case management of patients with SMI. treating staff typically have heavy workloads, and find it difficult to apply time-consuming treatments (Singh et al. 2003). LI CBT may allow provision of support to greater numbers of service users, and allow staff to spend more time on those who need intensive and sustained support. However, the introduction of any change in practice has to address significant challenges, and LI CBT is no exception. ----- ----- Many of the issues that we face in applying LI CBT to routine case management in a mnetal health service and their potential solutions are essentially the same as in a range of other problem domains (Turner and Sanders 2006)- and, indeed, are similar to those in any adoption of innovation (Rogers 2003). Over the last 20 years, several commentators have described barriers to implementing evidence-based innovations in mental health services (Corrigan et al. 1992; Deane et al. 2006; Kavanagh et al. 1993). The aim of the current chapter is to present a cognitive behavioural conceptualisation of problems and potential solutions for dissemination of LI CBT.

Adapting low intensity CBT interventions for clients with severe mental illness

Many people with severe mental illness (SMI) such as schizophrenia, whose psychotic symptoms are effectively managed, continue to experience significant functional problems. This chapter argues that low intensity (LI) cognitive behaviour therapy (CBT; e.g. for depression, anxiety, or other issues) is applicable to these clients, and that LI CBT can be consistent with long-term case management. However, adjustments to LI CBT strategies are often necessary and boundaries between LI CBT and high intensity (HI) CBT (with more extensive practitioner contact and complexity) may become blurred. Our focus is on LI CBT's self-management emphasis, its restricted content and segment length, and potential use after limited training. In addition to exploring these issues, it draws on the authors' Collaborative Recovery (CR; Oades et al. 2005) and 'Start Over and Survive' programs (Kavanagh et al. 2004) as examples. ----- ----- Evidence for the effectiveness of LI CBT with severe mental illness is often embedded within multicomponent programs. For example, goal setting and therapeutic homework are common components of such programs, but they can also be used as discrete LI CBT interventions. A review of 40 randomised controlled trials involving recipients with schizophrenia or other sever mental illnesses has identified key components of illness management programs (Mueser et al. 2002). However, it is relatively rare for specific components of these complex interventions to be assessed in isolation. Given these constraints, the evidence for specific LI CBT interventions with severe mental ilnness is relatively limited.

MRI study of the changes in crystalline lens shape with accommodation and ageing in humans

Magnetic Resonance Imaging was used to study changes in the crystalline lens and ciliary body with accommodation and aging. Monocular images were obtained in 15 young (19-29 years) and 15 older (60-70 years) emmetropes when viewing at far (6m) and at individual near points (14.5 to 20.9 cm) in the younger group. With accommodation, lens thickness increased (mean±95% CI: 0.33±0.06mm) by a similar magnitude to the decrease in anterior chamber depth (0.31±0.07mm) and equatorial diameter (0.32±0.04mm) with a decrease in the radius of curvature of the posterior lens surface (0.58±0.30mm). Anterior lens surface shape could not be determined due to the overlapping region with the iris. Ciliary ring diameter decreased (0.44±0.17mm) with no decrease in circumlental space or forward ciliary body movement. With aging, lens thickness increased (mean±95% CI: 0.97±0.24mm) similar in magnitude to the sum of the decrease in anterior chamber depth (0.45±0.21mm) and increase in anterior segment depth (0.52±0.23mm). Equatorial lens diameter increased (0.28±0.23mm) with no change in the posterior lens surface radius of curvature. Ciliary ring diameter decreased (0.57±0.41mm) with reduced circumlental space (0.43±0.15mm) and no forward ciliary body movement. Accommodative changes support the Helmholtz theory of accommodation including an increase in posterior lens surface curvature. Certain aspects of aging changes mimic accommodation.

A cluster-voting approach for speaker diarization and linking of Australian broadcast news recordings

We present a clustering-only approach to the problem of speaker diarization to eliminate the need for the commonly employed and computationally expensive Viterbi segmentation and realignment stage. We use multiple linear segmentations of a recording and carry out complete-linkage clustering within each segmentation scenario to obtain a set of clustering decisions for each case. We then collect all clustering decisions, across all cases, to compute a pairwise vote between the segments and conduct complete-linkage clustering to cluster them at a resolution equal to the minimum segment length used in the linear segmentations. We use our proposed cluster-voting approach to carry out speaker diarization and linking across the SAIVT-BNEWS corpus of Australian broadcast news data. We compare our technique to an equivalent baseline system with Viterbi realignment and show that our approach can outperform the baseline technique with respect to the diarization error rate (DER) and attribution error rate (AER).