Peroxide-cured HFP boosts cure rate, demolding

Executive summary Fluoroelastomers having a monomer composition of tetrafluoroethylene (TFE), hexafluoropropylene (HFP) and vinylidene fluoride (VF2) with an incorporated cure site monomer that allows peroxide crosslinking have grown in commercial significance in the past 20 years since the introduction of Viton GF in 1980. While these FKM terpolymers show improved water, steam and acid resistance, the need to peroxide crosslink them has caused processing problems such as mold sticking and poor hot tear resistance. This paper will introduce a new generation of peroxide-cured HFP-containing fluoroelastomers, which use a new, unique improved cure site monomer system. These ICSM containing products give much faster cure rates, low mold fouling and improved hot-demolding properties. In addition, they provide improved compression set resistance, even when not postcured, and enhanced aqueous media resistance. Processing and end-use data will highlight the utility of these new type fluoroelastomers. TECHNICAL NOTEBOOK Edited by Harold Herzlich Fluoroelastomer terpolymers having a structure of hexafluoroproplyene (HFP), tetrafluoroethylene (TFE) and vinylidene fluoride (VF2) have been used since the 1960s in a variety of industrial and automotive applications. The general chemical structure of these polymers is shown in In the mid-1970s a breakthrough in cure systems became available to the fluoroelastomer chemist, an FKM terpolymer with incorporated cure site monomer (CSM) that was sensitive to a peroxide/coagent cure system These peroxide-cured types of FKM were introduced at the San Francisco Rubber Division/ACS meeting by Finlay, MacLachlan and Hallenbeck1,2 in 1976, and in 1980, Bauerle and Finlay3 introduced an improved ~70-percent fluorine version of this type of FKM called Viton GF. Later, 68-percent fluorine versions of these elastomers called GBL900 and GBL200 were introduced by Tabb and Stevens4 at the Los Angeles Rubber Division/ACS meeting in 1985. These new peroxide-cured types of fluoroelastomer had several advantages in end-use properties, specifically in the area of fluids resistance. The peroxidecured polymers do not depend on strong metal bases such as magnesium oxide to dehydrohalogenate the backbone at the VF2-HPF site to initiate a double bond for the crosslinking reaction, rather they crosslink through a cure site monomer by use of a coagent that is activated by a peroxide. These peroxide-cured FKMs are known to have improved water, steam, acid and amine additive resistance when compared to conventional bisphenol-cured types of fluoroelastomers. While the end-use properties of peroxide-cured FKM are quite impressive, the processability of compounds suffers from the use of this cure system. Mold sticking and reduced hot tear strength are two problems that can be observed when processing peroxide-cured FKM. These problems led to more production scrap and higher part costs for peroxidecured FKMs

X-ray and Multiwavelength Insights into the Nature of Weak Emission-Line Quasars at Low Redshift

(Abridged) We report on the X-ray and multiwavelength properties of 11 radio-quiet quasars with weak or no emission lines identified by the Sloan Digital Sky Survey (SDSS) with redshift z=0.4-2.5. The distribution of relative X-ray brightness for our low-redshift weak-line quasar (WLQ) candidates is significantly different from that of typical radio-quiet quasars, having an excess of X-ray weak sources, but it is consistent with that of high-redshift WLQs. The X-ray weak sources generally show similar UV emission-line properties to those of the X-ray weak quasar PHL 1811; they may belong to the notable class of PHL 1811 analogs. The average X-ray spectrum of these sources is somewhat harder than that of typical radio-quiet quasars. Several other low-redshift WLQ candidates have normal ratios of X-ray-to-optical/UV flux, and their average X-ray spectral properties are also similar to those of typical radio-quiet quasars. The X-ray weak and X-ray normal WLQ candidates may belong to the same subset of quasars having high-ionization "shielding gas" covering most of the wind-dominated broad emission-line region, but be viewed at different inclinations. The mid-infrared-to-X-ray spectral energy distributions (SEDs) of these sources are generally consistent with those of typical SDSS quasars, showing that they are not likely to be BL Lac objects with relativistically boosted continua and diluted emission lines. However, one source in our X-ray observed sample is remarkably strong in X-rays, indicating that a small fraction of low-redshift WLQ candidates may actually be BL Lacs residing in the radio-faint tail of the BL Lac population. We also investigate universal selection criteria for WLQs over a wide range of redshift, finding that it is not possible to select WLQ candidates in a fully consistent way using different prominent emission lines as a function of redshift.Comment: ApJ in press; 26 pages, 11 figures and 7 tables. The full Table 3 is available upon reques

X-ray Insights into the Nature of Weak Emission-Line Quasars at High Redshift

We present Chandra observations of nine high-redshift quasars (z=2.7-5.9) discovered by the Sloan Digital Sky Survey with weak or undetectable high-ionization emission lines in their UV spectra (WLQs). Adding archival X-ray observations of six additional sources of this class has enabled us to place the strongest constraints yet on the X-ray properties of this remarkable class of AGNs. Although our data cannot rule out the possibility that the emission lines are overwhelmed by a relativistically boosted continuum, as manifested by BL Lac objects, we find that WLQs are considerably weaker in the X-ray and radio bands than the majority of BL Lacs found at much lower redshifts. If WLQs are high-redshift BL Lacs, then it is difficult to explain the lack of a large parent population of X-ray and radio bright weak-lined sources at high redshift. We also consider the possibility that WLQs are quasars with extreme properties, and in particular that the emission lines are suppressed by high accretion rates. Using joint spectral fitting of the X-ray spectra of 11 WLQs we find that the mean photon index in the hard X-ray band is consistent with those observed in typical radio-quiet AGNs with no hint of an unusually steep hard-X-ray spectrum. This result poses a challenge to the hypothesis that WLQs have extremely high accretion rates, and we discuss additional observations required to test this idea.Comment: 13 pages (emulateapj), 7 figures. Accepted for publication in Ap

A High Yield of New Sightlines for the Study of Intergalactic Helium: Far-UV-Bright Quasars from SDSS, GALEX, and HST

Investigations of He II Ly-alpha (304 A rest) absorption toward a half-dozen quasars at z~3-4 have demonstrated the great potential of helium studies of the IGM, but the current critically small sample size of clean sightlines for the He II Gunn-Peterson test limits confidence in cosmological inferences, and a larger sample is required. Although the unobscured quasar sightlines to high redshift are extremely rare, SDSS DR6 provides thousands of z>2.8 quasars. We have cross-correlated these SDSS quasars with GALEX GR2/GR3 to establish a catalog of 200 higher-confidence (~70% secure) cases of quasars at z=2.8-5.1 potentially having surviving far-UV (restframe) flux. We also catalog another 112 likely far-UV-bright quasars from GALEX cross-correlation with other (non-SDSS) quasar compilations. Reconnaissance UV prism observations with HST of 24 of our SDSS/GALEX candidates confirm 12 as detected in the far-UV, with at least 9 having flux extending to very near the He II break; with refinements our success rate is even higher. Our SDSS/GALEX selection approach is thereby confirmed to be an order of magnitude more efficient than previous He II quasar searches, more than doubles the number of spectroscopically confirmed clean sightlines to high redshift, and provides a resource list of hundreds of high-confidence sightlines for upcoming He II and other far-UV studies from HST. Our reconnaissance HST prism spectra suggest some far-UV diversity, confirming the need to obtain a large sample of independent quasar sightlines across a broad redshift range to assess such issues as the epoch(s) of helium reionization, while averaging over individual-object pathology and/or cosmic variance.Comment: 32 pages, 7 figures, accepted by Ap

Quantifying Avian Predation on Fish Populations: Integrating Predator-Specific Deposition Probabilities in Tag Recovery Studies

Accurate assessment of specific mortality factors is vital to prioritize recovery actions for threatened and endangered species. For decades, tag recovery methods have been used to estimate fish mortality due to avian predation. Predation probabilities derived from fish tag recoveries on piscivorous waterbird colonies typically reflect minimum estimates of predation due to an unknown and unaccounted-for fraction of tags that are consumed but not deposited on-colony (i.e., deposition probability). We applied an integrated tag recovery modeling approach in a Bayesian context to estimate predation probabilities that accounted for predator-specific tag detection and deposition probabilities in a multiple-predator system. Studies of PIT tag deposition were conducted across three bird species nesting at seven different colonies in the Columbia River basin, USA. Tag deposition probabilities differed significantly among predator species (Caspian terns Hydroprogne caspia: deposition probability = 0.71, 95% credible interval [CRI] = 0.51–0.89; double-crested cormorants Phalacrocorax auritus: 0.51, 95% CRI = 0.34–0.70; California gulls Larus californicus: 0.15, 95% CRI = 0.11–0.21) but showed little variation across trials within a species or across years. Data from a 6-year study (2008–2013) of PIT-tagged juvenile Snake River steelhead Oncorhynchus mykiss (listed as threatened under the Endangered Species Act) indicated that colony-specific predation probabilities ranged from less than 0.01 to 0.17 and varied by predator species, colony location, and year. Integrating the predator-specific deposition probabilities increased the predation probabilities by a factor of approximately 1.4 for Caspian terns, 2.0 for double-crested cormorants, and 6.7 for California gulls compared with traditional minimum predation rate methods, which do not account for deposition probabilities. Results supported previous findings on the high predation impacts from strictly piscivorous waterbirds nesting in the Columbia River estuary (i.e., terns and cormorants), but our findings also revealed greater impacts of a generalist predator species (i.e., California gulls) than were previously documented. Approaches used in this study allow for direct comparisons among multiple fish mortality factors and considerably improve the reliability of tag recovery models for estimating predation probabilities in multiple-predator systems

Systemwide Evaluation of Avian Predation on Juvenile Salmonids from the Columbia River Based on Recoveries of Passive Integrated Transponder Tags

We recovered passive integrated transponder (PIT) tags from nine piscivorous waterbird colonies in the Columbia River basin to evaluate avian predation on Endangered Species Act (ESA)-listed salmonid Oncorhynchus spp. populations during 2007–2010. Avian predation rates were calculated based on the percentage of PIT-tagged juvenile salmonids that were detected as passing hydroelectric dams and subsequently were consumed and deposited by birds on their nesting colonies. Caspian terns Hydroprogne caspia (hereafter, “terns”) and double-crested cormorants Phalacrocorax auritus (hereafter, “cormorants”) nesting on East Sand Island in the Columbia River estuary consumed the highest proportions of available PIT-tagged salmonids, with minimum predation rates ranging from 2.5% for Willamette River spring Chinook salmon O. tshawytscha to 16.0% for Snake River steelhead O. mykiss. Estimated predation rates by terns, cormorants, gulls of two species (California gull Larus californicus and ring-billed gull L. delawarensis), and American white pelicans Pelecanus erythrorhynchos nesting near the confluence of the Snake and Columbia rivers were also substantial; minimum predation rates ranged from 1.4% for Snake River fall Chinook salmon to 13.2% for upper Columbia River steelhead. Predation on ESA-listed salmonids by gulls and American white pelicans were minor (<2.0% per ESA-listed salmonid population) relative to predation by terns and cormorants. Cumulative impacts were greater for Snake River and upper Columbia River salmonids than for salmonids originating closer to the estuary because upriver salmonids must migrate past more bird colonies to reach the ocean. Predation rates adjusted for colony size (per capita rates) were significantly higher for terns and cormorants nesting at inland colonies (upstream of Bonneville Dam) than for those nesting in the estuary, suggesting that inland colonies have a greater reliance on salmonids as a food source. Management actions to increase salmonid survival by reducing avian predation in the estuary could be offset if birds that disperse from the estuary relocate to inland nesting sites on or near the Columbia River.This is the publisher’s final pdf. The article is copyrighted by the American Fisheries Society and published by Taylor & Francis. It can be found at: http://www.tandfonline.com/toc/utaf20/curren

Intensity modulated radiotherapy (IMRT) in patients with carcinomas of the paranasal sinuses: clinical benefit for complex shaped target volumes

INTRODUCTION: The aim of the study was to evaluate the clinical outcome of intensity modulated radiotherapy (IMRT) in 46 patients with paranasal sinus tumors with special respect to treatment-related toxicity. PATIENTS AND METHODS: We treated 46 patients with histologically proven tumors of the paranasal sinuses with IMRT. Histological classification included squamous cell carcinoma in 6, adenocarcinoma in 8, adenoidcystic carcinoma in 20 and melanoma in 8 patients, respectively. Six patients had been treated with RT during initial therapy after primary diagnosis, and IMRT was performed for the treatment of tumor progression as re-irradiation. RESULTS: Overall survival rates were 96% at 1 year, 90% at 3 years. Calculated from the initiation of IMRT as primary radiotherapy, survival rates at 1 and 3 years were 95% and 80%. In six patients IMRT was performed as re-irradiation, and survival rate calculated from re-irradiation was 63% at 1 year. Local control rates were 85% at 1, 81% at 2 and 49% at 3 years after primary RT and 50% at 1 year after re-irradiation. Distant metastases-free survival in patients treated with IMRT as primary RT was 83% after 1 and 64% after 3 years. For patients treated as primary irradiation with IMRT, the distant control rate was 83% at 1 year and 0% at 2 years. No severe radiation-induced side-effects could be observed. CONCLUSION: IMRT for tumors of the paranasal sinuses is associated with very good tumor control rates. Treatment-related acute and long-term toxicity can be minimized as compared to historical results with conventional RT

Electrodeionization Using Microseparated Bipolar Membranes

An electrochemical technique for deionizing water, now under development, is intended to overcome a major limitation of prior electrically-based water-purification techniques. The limitation in question is caused by the desired decrease in the concentration of ions during purification: As the concentration of ions decreases, the electrical resistivity of the water increases, posing an electrical barrier to the removal of the remaining ions. In the present technique, this limitation is overcome by use of electrodes, a flowfield structure, and solid electrolytes configured to provide conductive paths for the removal of ions from the water to be deionized, even when the water has already been purified to a high degree. The technique involves the use of a bipolar membrane unit (BMU), which includes a cation-exchange membrane and an anion-exchange membrane separated by a nonconductive mesh that has been coated by an ionically conductive material (see figure). The mesh ensures the desired microseparation between the ion-exchange membranes: The interstices bounded by the inner surfaces of the membranes and the outer surfaces of the coated mesh constitute a flow-field structure that allows the water that one seeks to deionize (hereafter called "process water" for short) to flow through the BMU with a low pressure drop. The flow-field structure is such that the distance between any point in the flow field and an ionically conductive material is small; thus, the flow-field structure facilitates the diffusion of molecules and ions to and from the ion-exchange membranes. The BMU is placed between an anode and a cathode, but not in direct contact with these electrodes. Instead, the space between the anion-exchange membrane and the anode is denoted the anode compartment and is filled with an ionic solution. Similarly, the space between the cation-exchange membrane and the cathode is denoted the cathode compartment and is filled with a different ionic solution. The electrodes are made of titanium coated with platinum

Study protocol: a randomized controlled trial of a computer-based depression and substance abuse intervention for people attending residential substance abuse treatment

Background: A large proportion of people attending residential alcohol and other substance abuse treatment have a co-occurring mental illness. Empirical evidence suggests that it is important to treat both the substance abuse problem and co-occurring mental illness concurrently and in an integrated fashion. However, the majority of residential alcohol and other substance abuse services do not address mental illness in a systematic way. It is likely that computer delivered interventions could improve the ability of substance abuse services to address co-occurring mental illness. This protocol describes a study in which we will assess the effectiveness of adding a computer delivered depression and substance abuse intervention for people who are attending residential alcohol and other substance abuse treatment. Methods/Design. Participants will be recruited from residential rehabilitation programs operated by the Australian Salvation Army. All participants who satisfy the diagnostic criteria for an alcohol or other substance dependence disorder will be asked to participate in the study. After completion of a baseline assessment, participants will be randomly assigned to either a computer delivered substance abuse and depression intervention (treatment condition) or to a computer-delivered typing tutorial (active control condition). All participants will continue to complete The Salvation Army residential program, a predominantly 12-step based treatment facility. Randomisation will be stratified by gender (Male, Female), length of time the participant has been in the program at the commencement of the study (4 weeks or less, 4 weeks or more), and use of anti-depressant medication (currently prescribed medication, not prescribed medication). Participants in both conditions will complete computer sessions twice per week, over a five-week period. Research staff blind to treatment allocation will complete the assessments at baseline, and then 3, 6, 9, and 12 months post intervention. Participants will also complete weekly self-report measures during the treatment period. Discussion. This study will provide comprehensive data on the effect of introducing a computer delivered, cognitive behavioral therapy based co-morbidity treatment program within a residential substance abuse setting. If shown to be effective, this intervention can be disseminated within other residential substance abuse programs. Trial registration. Australia and New Zealand Clinical Trials Register (ANZCTR): ACTRN12611000618954

Simulated Atmospheric N Deposition Alters Fungal Community Composition and Suppresses Ligninolytic Gene Expression in a Northern Hardwood Forest

High levels of atmospheric nitrogen (N) deposition may result in greater terrestrial carbon (C) storage. In a northern hardwood ecosystem, exposure to over a decade of simulated N deposition increased C storage in soil by slowing litter decay rates, rather than increasing detrital inputs. To understand the mechanisms underlying this response, we focused on the saprotrophic fungal community residing in the forest floor and employed molecular genetic approaches to determine if the slower decomposition rates resulted from down-regulation of the transcription of key lignocellulolytic genes, by a change in fungal community composition, or by a combination of the two mechanisms. Our results indicate that across four Acer-dominated forest stands spanning a 500-km transect, community-scale expression of the cellulolytic gene cbhI under elevated N deposition did not differ significantly from that under ambient levels of N deposition. In contrast, expression of the ligninolytic gene lcc was significantly down-regulated by a factor of 2–4 fold relative to its expression under ambient N deposition. Fungal community composition was examined at the most southerly of the four sites, in which consistently lower levels of cbhI and lcc gene expression were observed over a two-year period. We recovered 19 basidiomycete and 28 ascomycete rDNA 28S operational taxonomic units; Athelia, Sistotrema, Ceratobasidium and Ceratosebacina taxa dominated the basidiomycete assemblage, and Leotiomycetes dominated the ascomycetes. Simulated N deposition increased the proportion of basidiomycete sequences recovered from forest floor, whereas the proportion of ascomycetes in the community was significantly lower under elevated N deposition. Our results suggest that chronic atmospheric N deposition may lower decomposition rates through a combination of reduced expression of ligninolytic genes such as lcc, and compositional changes in the fungal community