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  • 1
    Publication Date: 2017-06-12
    Repository Name: EPIC Alfred Wegener Institut
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  • 2
    Publication Date: 2017-09-13
    Description: This paper investigates new observations from the poorly understood region between the Kara and Laptev Seas in the Eastern Arctic Ocean. We discuss relevant circulation features including riverine freshwater, Atlantic-derived water, and polynya-formed dense water, emphasize Vilkitsky Strait (VS) as an important Kara Sea gateway, and analyze the role of the adjacent 250 km-long submarine Vilkitsky Trough (VT) for the Arctic boundary current. Expeditions in 2013 and 2014 operated closely spaced hydrographic transects and 1 year-long oceanographic mooring near VT’s southern slope, and found persistent annually averaged flow of 0.2 m s21 toward the Nansen Basin. The flow is nearly barotropic from winter through early summer and becomes surface intensified with maximum velocities of 0.35 m s21 from August to October. Thermal wind shear is maximal above the southern flank at 30 m depth, in agreement with basinward flow above VT’s southern slope. The subsurface features a steep front separating warm (–0.58C) Atlantic-derived waters in central VT from cold (〈–1.58C) shelf waters, which episodically migrates across the trough indicated by current reversals and temperature fluctuations. Shelf-transformed waters dominate above VT’s slope, measuring near-freezing temperatures throughout the water column at salinities of 34–35. These dense waters are vigorously advected toward the Eurasian Basin and characterize VT as a conduit for near-freezing waters that could potentially supply the Arctic Ocean’s lower halocline, cool Atlantic water, and ventilate the deeper Arctic Ocean. Our observations from the northwest Laptev Sea highlight a topographically complex region with swift currents, several water masses, narrow fronts, polynyas, and topographically channeled storms.
    Repository Name: EPIC Alfred Wegener Institut
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  • 3
    Publication Date: 2017-09-18
    Description: The mechanisms causing widespread flow acceleration of Jakobshavn Isbræ, West Greenland, remain unclear despite an abundance of observations and modeling studies. Here we simulate the glacier's evolution from 1985 to 2016 using a three-dimensional thermomechanical ice flow model. The model captures the timing and 90% of the observed changes by forcing the calving front. Basal drag in the trough is low, and lateral drag balances the ice stream's driving stress. The calving front position is the dominant control on changes of Jakobshavn Isbræ since the ice viscosity in the shear margins instantaneously drops in response to the stress perturbation caused by calving front retreat, which allows for widespread flow acceleration. Gradual shear margin warming contributes 5 to 10% to the total acceleration. Our simulations suggest that the glacier will contribute to eustatic sea level rise at a rate comparable to or higher than at present.
    Repository Name: EPIC Alfred Wegener Institut
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  • 4
    Publication Date: 2017-12-01
    Description: Greenland's bed topography is a primary control on ice flow, grounding line migration, calving dynamics and subglacial drainage. Moreover, fjord bathymetry regulates the penetration of warm Atlantic Water (AW) that rapidly melts and undercuts Greenland's marine-terminating glaciers. Here, we present a new compilation of Greenland bed topography that assimilates seafloor bathymetry and ice thickness data through a mass conservation (MC) approach. A new 150-m horizontal resolution bed topography/bathymetric map of Greenland is constructed with seamless transitions at the ice/ocean interface, yielding major improvements over previous datasets, particularly in the marine-terminating sectors of northwest and southeast Greenland. Our map reveals the total sea level potential of the Greenland Ice Sheet is 7.42±0.05 m, which is 7 cm greater than previous estimates. Furthermore, it explains recent calving front response of numerous outlet glaciers and reveals new pathways by which AW can access glaciers with marine-based basins, thereby highlighting sectors of Greenland that are most vulnerable to future oceanic forcing.
    Repository Name: EPIC Alfred Wegener Institut
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  • 5
    Publication Date: 2017-05-04
    Description: We present a simulation of Antarctic iceberg drift and melting that includes small, medium-sized, and giant tabular icebergs with a realistic size distribution. For the first time, an iceberg model is initialized with a set of nearly 7000 observed iceberg positions and sizes around Antarctica. The study highlights the necessity to account for larger and giant icebergs in order to obtain accurate melt climatologies. We simulate drift and lateral melt using iceberg-draft averaged ocean currents, temperature, and salinity. A new basal melting scheme, originally applied in ice shelf melting studies, uses in situ temperature, salinity, and relative velocities at an iceberg's bottom. Climatology estimates of Antarctic iceberg melting based on simulations of small (≤ 2.2 km), 'small-to-medium'-sized (≤ 10 km), and small-to-giant icebergs (including icebergs 〉 10 km) exhibit differential characteristics: successive inclusion of larger icebergs leads to a reduced seasonality of the iceberg meltwater flux and a shift of the mass input to the area north of 58 °S, while less meltwater is released into the coastal areas. This suggests that estimates of meltwater input solely based on the simulation of small icebergs introduce a systematic meridional bias; they underestimate the northward mass transport and are, thus, closer to the rather crude treatment of iceberg melting as coastal runoff in models without an interactive iceberg model. Future ocean simulations will benefit from the improved meridional distribution of iceberg melt, especially in climate change scenarios where the impact of iceberg melt is likely to increase due to increased calving from the Antarctic ice sheet.
    Repository Name: EPIC Alfred Wegener Institut
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  • 6
    Publication Date: 2017-09-25
    Repository Name: EPIC Alfred Wegener Institut
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  • 7
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    Wiley
    In:  EPIC3Global Biogeochemical Cycles, Wiley, ISSN: 0886-6236
    Publication Date: 2017-10-27
    Repository Name: EPIC Alfred Wegener Institut
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  • 8
    Publication Date: 2019-12-03
    Description: The Southern Hemisphere Antarctic stratosphere experienced two noteworthy events in 2015: a significant injection of sulfur from the Calbuco volcanic eruption in Chile in April, and a record-large Antarctic ozone hole in October and November. Here, we quantify Calbuco's influence on stratospheric ozone depletion in austral spring 2015 using observations and an earth system model. We analyze ozonesondes, as well as data from the Microwave Limb Sounder. We employ the Community Earth System Model, version 1, with the Whole Atmosphere Community Climate Model (CESM1(WACCM)) in a specified dynamics setup, which includes calculations of volcanic effects. The Cloud Aerosol Lidar with Orthogonal Polarization data indicate enhanced volcanic liquid sulfate 532 nm backscatter values as far poleward as 68°S during October and November (in broad agreement with WACCM). Comparison of the location of the enhanced aerosols to ozone data supports the view that aerosols played a major role in increasing the ozone hole size, especially at pressure levels between 150 and 100 hPa. Ozonesonde vertical ozone profiles from the sites of Syowa, South Pole, and Neumayer, display the lowest individual October or November measurements at 150 hPa since the 1991 Mt. Pinatubo eruption period, with Davis showing similarly low values, but no available 1990s data. The analysis suggests that under the cold conditions ideal for ozone depletion, stratospheric volcanic aerosol particles from the moderate-magnitude eruption of Calbuco in 2015 greatly enhanced austral ozone depletion, particularly at 55–68°S, where liquid binary sulfate aerosols have a large influence on ozone concentrations.
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  • 9
    Publication Date: 2018-01-11
    Description: Near-surface air temperatures close to 0°C were observed in situ over sea ice in the central Arctic during the last three winter seasons. Here we use in situ winter (December–March) temperature observations, such as those from Soviet North Pole drifting stations and ocean buoys, to determine how common Arctic winter warming events are. Observations of winter warming events exist over most of the Arctic Basin. Temperatures exceeding -5°C were observed during 〉30% of winters from 1954 to 2010 by North Pole drifting stations or ocean buoys. Using the ERA-Interim record (1979–2016), we show that the North Pole (NP) region typically experiences 10 warming events (T2m 〉 10°C) per winter, compared with only five in the Pacific Central Arctic (PCA). There is a positive trend in the overall duration of winter warming events for both the NP region (4.25 days/decade) and PCA (1.16 days/decade), due to an increased number of events of longer duration.
    Repository Name: EPIC Alfred Wegener Institut
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  • 10
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    Wiley
    In:  EPIC3Journal of Geophysical Research-Earth Surface, Wiley, 122, pp. 1619-1634, ISSN: 0148-0227
    Publication Date: 2018-08-30
    Description: Retrogressive thaw slumps (RTSs) are among the most active landforms in the Arctic; their number has increased significantly over the past decades. While processes initiating discrete RTSs are well identified, the major terrain controls on the development of coastal RTSs at a regional scale are not yet defined. Our research reveals the main geomorphic factors that determine the development of RTSs along a 238 km segment of the Yukon Coast, Canada. We (1) show the current extent of RTSs, (2) ascertain the factors controlling their activity and initiation, and (3) explain the spatial differences in the density and areal coverage of RTSs. We mapped and classified 287 RTSs using high-resolution satellite images acquired in 2011. We highlighted the main terrain controls over their development using univariate regression trees model. Coastal geomorphology influenced both the activity and initiation of RTSs: active RTSs and RTSs initiated after 1972 occurred primarily on terrains with slope angles greater than 3.9° and 5.9°, respectively. The density and areal coverage of RTSs were constrained by the volume and thickness of massive ice bodies. Differences in rates of coastal change along the coast did not affect the model. We infer that rates of coastal change averaged over a 39 year period are unable to reflect the complex relationship between RTSs and coastline dynamics. We emphasize the need for large-scale studies of RTSs to evaluate their impact on the ecosystem and to measure their contribution to the global carbon budget.
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  • 11
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    Wiley
    In:  EPIC3Tectonics, Wiley, 36, pp. 229-240, ISSN: 0278-7407
    Publication Date: 2019-07-17
    Repository Name: EPIC Alfred Wegener Institut
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  • 12
    Publication Date: 2017-05-30
    Repository Name: EPIC Alfred Wegener Institut
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  • 13
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    Wiley
    In:  EPIC3Geochemistry Geophysics Geosystems, Wiley, 18(1), pp. 457-470, ISSN: 1525-2027
    Publication Date: 2018-02-02
    Description: Digital grids of basement age of the world’s oceans are essential for modern geodynamic and paleoceanographic studies. Any such grid is built using a plate kinematic model, whose accuracy and reli- ability directly influence the accuracy and reliability of the grid. We present a seafloor age grid for the South Atlantic based on a recent high-resolution plate kinematic model. The grid is built from a data set of points whose ages are defined in or for the plate kinematic model, incorporating breaks at tectonic boundaries like fracture zones where the age function is discontinuous. We compare predictions of the new grid and of a previously published one, which is based on an older plate kinematic model, to magnetic isochron pick data sets. The comparison shows the new grid to provide a more reliable depiction of seafloor age in the South Atlantic. Numerical estimates of the new grid’s uncertainty are determined by interpolation between (1) misfits at grid cells coinciding with magnetic isochron ages, (2) misfits implied by locational uncertainties in predicted isochrons propagated from uncertainties in the plate kinematic model, and (3) by the proxim- ities of cells to fracture zone traces or ridge-jump scars. Estimated total uncertainty is 〈10 My for 94% of the grid and 〈5 My for 72%, but much larger in areas where magnetic anomaly data are scarce (such as the Cretaceous Normal Superchron) and in the vicinity of long-offset fracture zones.
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  • 14
    Publication Date: 2018-08-10
    Description: The deep southern component water (SCW), comprising Lower Circumpolar Deep Water (LCDW) and Antarctic Bottom Water (AABW), is a major component of the global oceanic circulation. It has been suggested that the deep Atlantic water mass structure changed significantly during the last glacial/interglacial cycle. However, deep SCW source-proximal records remain sparse. Here we present three coherent deep SCW paleocurrent records from the deep Argentine continental margin shedding light on deep water circulation and deep SCW flow strength in the Southwest Atlantic since the Last Glacial Maximum (LGM). Based on increased sortable silt values, we propose enhanced deep SCW flow strength from 14 to 10 cal ka B.P. relative to the early deglacial/LGM and the Holocene. We propose a direct influence of deep northern component water (NCW) on deep SCW flow strength due to vertical narrowing of deep SCW spreading, concurrent with a migration of the high-energetic LCDW/AABW interface occupying our core sites. We suggest a shoaled NCW until 13 cal ka B.P., thereby providing space for deep SCW spreading that resulted in reduced carbonate preservation at our core sites. Increased carbonate content from 13 cal ka B.P. indicates that the NCW expanded changing deep water properties at our core sites in the deep Southwest Atlantic. However, southern sourced terrigenous sediments continued to be deposited at our core sites, suggesting that deep SCW flow was uninterrupted along the Argentine continental margin since the LGM.
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  • 15
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    Wiley
    In:  EPIC3Journal of Geophysical Research-Biogeosciences, Wiley, ISSN: 0148-0227
    Publication Date: 2019-03-31
    Description: Measurements of late springtime nutrient concentrations in Arctic waters are relatively rare due to the extensive sea ice cover that makes sampling difficult. During the SUBICE cruise in May-June 2014, an extensive survey of hydrography and pre-bloom nutrient concentrations was conducted in the Chukchi Sea. Cold (〈 -1.5°C) winter water was prevalent throughout the Chukchi Sea shelf, and the water column was weakly stratified. Nitrate (NO3-) concentration averaged 12.6±1.92 µM in surface waters and 14.0±1.91 µM near the bottom and was significantly correlated with salinity. The highest NO3- concentrations were associated with winter water within the Central Channel flow path. NO3- concentrations were much reduced near the northern shelfbreak within the upper halocline waters of the Canada Basin and along the eastern side of the shelf near the Alaskan coast. Net community production (NCP), estimated as the difference in depth-integrated NO3- content between spring (this study) and summer (historical), varied from 28-38 g C m-2 a-1. This is much lower than previous NCP estimates using NO3- concentrations from the southeastern Bering Sea as a baseline. These results demonstrate the importance of using local profiles of NO3- measured as close to the beginning of the spring bloom as possible when estimating NCP.
    Repository Name: EPIC Alfred Wegener Institut
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  • 16
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    Wiley-Blackwell
    In:  EPIC3Climate Change Impacts on Fisheries and Aquaculture: A Global Analysis, Climate Change Impacts on Fisheries and Aquaculture: A Global Analysis, Wiley-Blackwell, pp. 663-701, ISBN: 978-1-119-15404-4
    Publication Date: 2017-10-09
    Description: Exploitation of Southern Ocean marine resources began more than 200 years ago with the massive hunt for seals and whales. In the 1960s/70s, fisheries for finfish and krill entered Southern Ocean waters. Within a few years many fish populations were heavily overfished and dramatically depleted, and some of these stocks still did not recover. Today, fish stocks and fisheries activities are managed and monitored by the Commission for the Conservation of Antarctic Marine Living Resources (CCAMLR) which was established in 1982 to ensure sustainable exploitation and protection of the delicate marine ecosystem. Current target species include Mackerel icefish (Champsocephalus gunnari), Patagonian as well as Antarctic toothfish (Dissostichus eleginoides and D. mawsoni) and Antarctic krill (Euphausia superba). Most of these species are vulnerable to overfishing due to slow growth, late age at maturity, and rather low fecundity. This vulnerability might increase, as Southern Ocean living communities are currently also faced with alterations of their environment due to climate change, such as increasing water temperatures and decreasing sea ice. Species, including the ones targetted by fisheries, are well-adapted to their particular environmental conditions and are believed to be highly sensitive to changes because of their cold-adapted physiology, their life history traits, and their direct or indirect dependence on sea ice. The species will be exposed to several stressors at the same time, and fishing pressure, direct abiotic forcing and changes mediated via the food web might act synergistically and result in significant population declines. In particular the strongly sea ice-dependent Antarctic krill, a key species in the food web, might be adversely affected. Fish species seems to have low tolerance towards higher water temperatures and may thus, in the long run, be replaced by lower latitude species.
    Repository Name: EPIC Alfred Wegener Institut
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  • 17
    Publication Date: 2018-03-04
    Description: The Eger Rift is an active element of the European Cenozoic Rift System associated with intense Cenozoic intraplate alkaline volcanism and system of sedimentary basins. The intracontinental Cheb Basin at its western part displays geodynamic activity with fluid emanations, persistent seismicity, Cenozoic volcanism, and neotectonic crustal movements at the intersections of major intraplate faults. In this paper, we study detailed geometry of the crust/mantle boundary and its possible origin in the western Eger Rift. We review existing seismic and seismological studies, provide new interpretation of the reflection profile 9HR, and supplement it by new results from local seismicity. We identify significant lateral variations of the high-velocity lower crust and relate them to the distribution and chemical status of mantle-derived fluids and to xenolith studies from corresponding depths. New interpretation based on combined seismic and isotope study points to a local-scale magmatic emplacement at the base of the continental crust within a new rift environment. This concept of magmatic underplating is supported by detecting two types of the lower crust: a high-velocity lower crust with pronounced reflectivity and a high-velocity reflection-free lower crust. The character of the underplated material enables to differentiate timing and tectonic setting of two episodes with different times of origin of underplating events. The lower crust with high reflectivity evidences magmatic underplating west of the Eger Rift of the Late Variscan age. The reflection-free lower crust together with a strong reflector at its top at depths of ~28–30 km forms a magma body indicating magmatic underplating of the late Cenozoic (middle and upper Miocene) to recent. Spatial and temporal relations to recent geodynamic processes suggest active magmatic underplating in the intracontinental setting.
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  • 18
    Publication Date: 2019-07-17
    Description: Antarctica is the largest reservoir of ice on Earth. Understanding its ice sheet dynamics is crucial to unraveling past global climate change and making robust climatic and sea level predictions. Of the basic parameters that shape and control ice flow, the most poorly known is geothermal heat flux. Direct observations of heat flux are difficult to obtain in Antarctica, and until now continent-wide heat flux maps have only been derived from low-resolution satellite magnetic and seismological data. We present a high-resolution heat flux map and associated uncertainty derived from spectral analysis of the most advanced continental compilation of airborne magnetic data. Small-scale spatial variability and features consistent with known geology are better reproduced than in previous models, between 36% and 50%. Our high-resolution heat flux map and its uncertainty distribution provide an important new boundary condition to be used in studies on future subglacial hydrology, ice sheet dynamics, and sea level change.
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  • 19
    Publication Date: 2017-12-19
    Description: The evidence from both data and models indicates that specific equilibrium climate sensitivity S[X]—the global annual mean surface temperature change (ΔTg) as a response to a change in radiative forcing X (ΔR[X])—is state dependent. Such a state dependency implies that the best fit in the scatterplot of ΔTg versus ΔR[X] is not a linear regression but can be some nonlinear or even nonsmooth function. While for the conventional linear case the slope (gradient) of the regression is correctly interpreted as the specific equilibrium climate sensitivity S[X], the interpretation is not straightforward in the nonlinear case. We here explain how such a state-dependent scatterplot needs to be interpreted and provide a theoretical understanding—or generalization—how to quantify S[X] in the nonlinear case. Finally, from data covering the last 2.1 Myr we show that—due to state dependency—the specific equilibrium climate sensitivity which considers radiative forcing of CO2 and land ice sheet (LI) albedo, math formula, is larger during interglacial states than during glacial conditions by more than a factor 2.
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  • 20
    Publication Date: 2018-01-09
    Description: We present vertically resolved observations of aerosol composition during pristine summertime Arctic background conditions. The methansulfonic acid (MSA)-to-sulfate ratio peaked near the surface (mean 0.10), indicating a contribution from ocean-derived biogenic sulfur. Similarly, the organic aerosol (OA)-to-sulfate ratio increased toward the surface (mean 2.0). Both MSA-to-sulfate and OA-to-sulfate ratios were significantly correlated with FLEXPART-WRF-predicted air mass residence time over open water, indicating marine-influenced OA. External mixing of sea salt aerosol from a larger number fraction of organic, sulfate, and amine-containing particles, together with low wind speeds (median 4.7 m s−1), suggests a role for secondary organic aerosol formation. Cloud condensation nuclei concentrations were nearly constant (∼120 cm−3) when the OA fraction was 〈60% and increased to 350 cm−3 when the organic fraction was larger and residence times over open water were longer. Our observations illustrate the importance of marine-influenced OA under Arctic background conditions, which are likely to change as the Arctic transitions to larger areas of open water.
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  • 21
    Publication Date: 2018-01-11
    Description: Arctic sea ice has displayed significant thinning as well as an increase in drift speed in recent years. Taken together this suggests an associated rise in sea ice deformation rate. A winter and spring expedition to the sea ice covered region north of Svalbard–the Norwegian young sea ICE2015 expedition (N-ICE2015)—gave an opportunity to deploy extensive buoy arrays and to monitor the deformation of the first-year and secondyear ice now common in the majority of the Arctic Basin. During the 5 month long expedition, the ice cover underwent several strong deformation events, including a powerful storm in early February that damaged the ice cover irreversibly. The values of total deformation measured during N-ICE2015 exceed previously measured values in the Arctic Basin at similar scales: At 100 km scale, N-ICE2015 values averaged above 0.1 d-1, compared to rates of 0.08 d-1 or less for previous buoy arrays. The exponent of the power law between the deformation length scale and total deformation developed over the season from 0.37 to 0.54 with an abrupt increase immediately after the early February storm, indicating a weakened ice cover with more free drift of the sea ice floes. Our results point to a general increase in deformation associated with the younger and thinner Arctic sea ice and to a potentially destructive role of winter storms.
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  • 22
    Publication Date: 2018-11-16
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  • 23
    Publication Date: 2018-03-06
    Description: We investigate the impact of different CO2 levels and different subarctic gateway configurations on the surface temperatures during the latest Cretaceous using the Earth System Model COSMOS. The simulated temperatures are compared with the surface temperature reconstructions based on a recent compilation of the latest Cretaceous proxies. In our numerical experiments, the CO2 level ranges from 1 to 6 times the preindustrial (PI) CO2 level of 280 ppm. On a global scale, the most reasonable match between modeling and proxy data is obtained for the experiments with 3 to 5 × PI CO2 concentrations. However, the simulated low- (high-) latitude temperatures are too high (low) as compared to the proxy data. The moderate CO2 levels scenarios might be more realistic, if we take into account proxy data and the dead zone effect criterion. Furthermore, we test if the model-data discrepancies can be caused by too simplistic proxy-data interpretations. This is distinctly seen at high latitudes, where most proxies are biased toward summer temperatures. Additional sensitivity experiments with different ocean gateway configurations and constant CO2 level indicate only minor surface temperatures changes (〈~1°C) on a global scale, with higher values (up to ~8°C) on a regional scale. These findings imply that modeled and reconstructed temperature gradients are to a large degree only qualitatively comparable, providing challenges for the interpretation of proxy data and/or model sensitivity. With respect to the latter, our results suggest that an assessment of greenhouse worlds is best constrained by temperatures in the midlatitudes.
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  • 24
    Publication Date: 2017-10-18
    Description: State-of-the-art Arctic Ocean mean sea surface (MSS) models and global geoid models (GGMs) are used to support sea ice freeboard estimation from satellite altimeters, as well as in oceanographic studies such as mapping sea level anomalies and mean dynamic ocean topography. However, errors in a given model in the high frequency domain, primarily due to unresolved gravity features, can result in errors in the estimated along-track freeboard. These errors are exacerbated in areas with a sparse lead distribution in consolidated ice pack conditions. Additionally model errors can impact ocean geostrophic currents, derived from satellite altimeter data, while remaining biases in these models may impact longer-term, multi-sensor oceanographic time-series of sea level change in the Arctic. This study focuses on an assessment of five state-of-the-art Arctic MSS models (UCL13/04, DTU15/13/10) and a commonly used GGM (EGM2008). We describe errors due to unresolved gravity features, inter-satellite biases, and remaining satellite orbit errors, and their impact on the derivation of sea ice freeboard. The latest MSS models, incorporating CryoSat-2 sea surface height measurements, show improved definition of gravity features, such as the Gakkel Ridge. The standard deviation between models ranges 0.03-0.25 m. The impact of remaining MSS/GGM errors on freeboard retrieval can reach several decimeters in parts of the Arctic. While the maximum observed freeboard difference found in the central Arctic was 0.59 m (UCL13 MSS minus EGM2008 GGM), the standard deviation in freeboard differences is 0.03-0.06 m.
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  • 25
    Publication Date: 2018-06-14
    Description: Species flocks (SFs) fascinate evolutionary biologists who wonder whether such striking diversification can be driven by normal evolutionary processes. Multiple definitions of SFs have hindered the study of their origins. Previous studies identified a monophyletic taxon as a SF if it displays high speciosity in an area in which it is endemic (criterion 1), high ecological diversity among species (criterion 2), and if it dominates the habitat in terms of biomass (criterion 3); we used these criteria in our analyses. Our starting hypothesis is that normal evolutionary processes may provide a sufficient explanation for most SFs. We thus clearly separate each criterion and identify which biological (intrinsic) and environmental (extrinsic) traits are most favourable to their realization. The first part focuses on evolutionary processes. We highlight that some popular putative causes of SFs, such as key innovations or ecological speciation, are neither necessary nor sufficient to fulfill some or all of the three criteria. Initial differentiation mechanisms are diverse and difficult to identify a posteriori because a primary differentiation of one type (genetic, ecological or geographical) often promotes other types of differentiation. Furthermore, the criteria are not independent: positive feedbacks between speciosity and ecological diversity among species are expected whatever the initial cause of differentiation, and ecological diversity should enhance habitat dominance at the clade level. We then identify intrinsic and extrinsic factors that favour each criterion. Low dispersal emerges as a convincing driver of speciosity. Except for a genomic architecture favouring ecological speciation, for which assessment is difficult, high effective population sizes are the single intrinsic factor that directly enhances speciosity, ecological diversity and habitat dominance. No extrinsic factor appeared to enhance all criteria simultaneously but a combination of factors (insularity, fragmentation and environmental stability) may favour the three criteria, although the effect is indirect for habitat dominance. We then apply this analytical framework to Antarctic marine environments by analysing data from 18 speciose clades belonging to echinoderms (five unrelated clades), notothenioid fishes (five clades) and peracarid crustaceans (eight clades). Antarctic shelf environments and history appear favourable to endemicity and speciosity, but not to ecological specialization. Two main patterns are distinguished among taxa. (i) In echinoderms, many brooding, species‐rich and endemic clades are reported, but without remarkable ecological diversity or habitat dominance. In these taxa, loss of the larval stage is probably a consequence of past Antarctic environmental factors, and brooding is suggested to be responsible for enhanced allopatric speciation (via dispersal limitation). (ii) In notothenioids and peracarids, many clades fulfill all three SF criteria. This could result from unusual features in fish and crustaceans: chromosome instability and key innovations (antifreeze proteins) in notothenioids, ecological opportunity in peracarids, and a genomic architecture favouring ecological speciation in both groups. Therefore, the data do not support our starting point that normal evolutionary factors or processes drive SFs because in these two groups uncommon intrinsic features or ecological opportunity provide the best explanation. The utility of the three‐criterion SF concept is therefore questioned and guidelines are given for future studies.
    Repository Name: EPIC Alfred Wegener Institut
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  • 26
    Publication Date: 2017-09-25
    Description: Our study followed the seasonal cycling of soluble (SFe), colloidal (CFe), dissolved (DFe), total dissolvable (TDFe), labile particulate (LPFe) and total particulate (TPFe) iron in the Celtic Sea (NE Atlantic Ocean). Preferential uptake of SFe occurred during the spring bloom, preceding the removal of CFe. Uptake and export of Fe during the spring bloom, coupled with a reduction in vertical exchange, led to Fe deplete surface waters (〈0.2 nM DFe; 0.11 nM LPFe, 0.45 nM TDFe, 1.84 nM TPFe) during summer stratification. Below the seasonal thermocline, DFe concentrations increased from spring to autumn, mirroring NO3- and consistent with supply from remineralised sinking organic material, and cycled independently of particulate Fe over seasonal timescales. These results demonstrate that summer Fe availability is comparable to the seasonally Fe limited Ross Sea shelf, and therefore is likely low enough to affect phytoplankton growth and species composition.
    Repository Name: EPIC Alfred Wegener Institut
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  • 27
    Publication Date: 2018-01-09
    Repository Name: EPIC Alfred Wegener Institut
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  • 28
    Publication Date: 2017-03-20
    Description: Northwestern Namibia, at the landfall of the Walvis Ridge, was affected by the Tristan da Cunha mantle plume during continental rupture between Africa and South America, as evidenced by the presence of the Etendeka continental flood basalts. Here we use data from a passive-source seismological network to investigate the upper mantle structure and to elucidate the Cretaceous mantle plume-lithosphere interaction. Receiver functions reveal an interface associated with a negative velocity contrast within the lithosphere at an average depth of 80 km. We interpret this interface as the relic of the lithosphereasthenosphere boundary (LAB) formed during the Mesozoic by interaction of the Tristan da Cunha plume head with the pre-existing lithosphere. The velocity contrast might be explained by stagnated and ‘‘frozen’’ melts beneath an intensively depleted and dehydrated peridotitic mantle. The present-day LAB is poorly visible with converted waves, indicating a gradual impedance contrast. Beneath much of the study area, converted phases of the 410 and 660 km mantle transition zone discontinuities arrive 1.5 s earlier than in the landward plume-unaffected continental interior, suggesting high velocities in the upper mantle caused by a thick lithosphere. This indicates that after lithospheric thinning during continental breakup, the lithosphere has increased in thickness during the last 132 Myr. Thermal cooling of the continental lithosphere alone cannot produce the lithospheric thickness required here. We propose that the remnant plume material, which has a higher seismic velocity than the ambient mantle due to melt depletion and dehydration, significantly contributed to the thickening of the mantle lithosphere.
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  • 29
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    Wiley
    In:  EPIC3Journal of Geophysical Research-Oceans, Wiley, 122(3), pp. 2108-2119, ISSN: 0148-0227
    Publication Date: 2017-04-26
    Description: Snow on sea ice alters the properties of the underlying ice cover as well as associated physical and biological processes at the interfaces between atmosphere, sea ice, and ocean. The Antarctic snow cover persists during most of the year and contributes significantly to the sea-ice mass due to the widespread surface flooding and related snow-ice formation. Snow also enhances the sea-ice surface reflectivity of incoming shortwave radiation and determines therefore the amount of light being reflected, absorbed, and transmitted to the upper ocean. Here, we present results of a case study of spectral solar radiation measurements under Antarctic pack ice with an instrumented Remotely Operated Vehicle in the Weddell Sea in 2013. In order to identify the key variables controlling the spatial distribution of the under-ice light regime, we exploit under-ice optical measurements in combination with simultaneous characterization of surface properties, such as sea-ice thickness and snow depth. Our results reveal that the distribution of flooded and nonflooded sea-ice areas dominates the spatial scales of under-ice light variability for areas smaller than 100 m-by-100 m. However, the heterogeneous and highly metamorphous snow on Antarctic pack ice obscures a direct correlation between the under-ice light field and snow depth. Compared to the Arctic, light levels under Antarctic pack ice are extremely low during spring (〈0.1%). This is mostly a result of the distinctly different dominant sea ice and snow properties with seasonal snow cover (including strong surface melt and summer melt ponds) in the Arctic and a year-round snow cover and widespread surface flooding in the Southern Ocean.
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  • 30
    Publication Date: 2021-01-26
    Description: Snow thickness on sea ice is a largely under-sampled parameter, yet of importance for the sea-ice mass balance and for satellite based sea-ice thickness estimates and thus our general understanding of global ice-volume change. Traditional direct thickness measurements with meter sticks can provide accurate but only spot information, referred to as "needles" due to their pinpoint focus and information while airborne and satellite remote sensing snow products, referred to as "the haystack" have large uncertainties due to their scale. We demonstrate the remarkable accuracy and applicability of ground penetrating radar (GPR) snow-thickness measurements by comparing them with in-situ, meter-stick data from two field campaigns to Antarctica in late winter/early spring. The efficiency and millimeter- to centimeter accuracy of GPR enables practitioners to acquire extensive, semi-regional data with the potential to upscale "needles" to "the haystack" and to potentially calibrate satellite remote sensing products that we confirm to derive roughly 30 % of the in-situ thickness. We find the radar wave propagation velocity in snow to be rather constant (+/- 6%), encouraging regional snow-thickness surveys. Snow thinner than 10 cm is under the detection limit with the off-the-shelf GPR setup utilized in our study.
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  • 31
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    Wiley
    In:  EPIC3Journal of Geophysical Research-Oceans, Wiley, 122(8), pp. 6437-6453, ISSN: 0148-0227
    Publication Date: 2019-10-04
    Description: New two-year long records from three moorings, located at 76°S along the eastern flank and shelf of the Filchner Trough, give insight in the seasonal cycle of hydrography to a region where Modified Warm Deep Water (MWDW) enters the southern Weddell Sea continental shelf, possibly reaching the Filchner Ronne Ice Shelf, the biggest ice shelf (by volume) in Antarctica. A persistent northward flow of Ice Shelf Water (ISW) is found along the slope of the trough at 600 m depth, while the data on the shelf indicate a seasonal cycle, characterized by four phases. A distinct warm inflow period (separated in two phases), with maximum temperatures of −1°C, appears to be related to the seasonal heaving of the Antarctic Slope Front thermocline along the continental shelf break further north and a seasonal extension of the ISW layer onto the Eastern Shelf. The density gradients between the ISW in the trough and the MWDW on the adjacent shelf drive the southward flow during these phases. A flow reversal is found in winter, ceasing the southward flow along the eastern flank of the trough. Weaker density gradients between the trough and the shelf during winter allow a westward flow, partly driven by a N-S density gradient, existing across the Eastern Shelf during this time. From spring through to summer the ISW layer in the trough extends onto the eastern shelf where it occupies the bottom layer at our moorings and it is associated with northward flow.
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  • 32
    Publication Date: 2017-12-11
    Description: In this study we applied a multidisciplinary approach, coupling geophysical and geochemical measurements, to unveil the provenance of 170 obsidian flakes, collected on the volcanic island of Ustica (Sicily). On this island there are some prehistoric settlements dated from the Neolithic to the Middle Bronze Age. Despite not having geological outcrops of obsidian rocks, the countryside of Ustica is rich in fragments of this volcanic glass, imported from other source areas. The study of obsidian findings was carried out first through visual observations and density measurements. At least two different obsidian families have been distinguished, probably imported from Lipari and Pantelleria islands. Analysing the magnetic properties of the samples, these two main sources were confirmed, but the possibility of other provenances was inferred. Finally, we characterized the geochemical signature of the Ustica obsidians by performing microchemical analyses through electron microprobe (EMPA) and laser ablation (LA–ICP–MS). The results were compared with literature data, confirming the presence of the Lipari and Pantelleria sources (Sicily) and indicating for the first time in this part of Italy a third provenance from Palmarola island (Latium). Our results shed new light on the commercial exchanges in the peri-Tyrrhenian area during the prehistoric age.
    Description: Published
    Description: 435–454
    Description: 1SR. TERREMOTI - Servizi e ricerca per la Società
    Description: 2SR. VULCANI - Servizi e ricerca per la Società
    Description: 3SR. AMBIENTE - Servizi e ricerca per la Società
    Description: JCR Journal
    Description: restricted
    Keywords: obsdian provenance ; LA-ICPMS ; 05. General::05.04. Instrumentation and techniques of general interest::05.04.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 33
    Publication Date: 2017-07-21
    Repository Name: EPIC Alfred Wegener Institut
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  • 34
    Publication Date: 2020-03-05
    Description: The Norwegian young sea ICE (N-ICE2015) expedition was designed to investigate the atmosphere-snow-ice-ocean interactions in the young and thin sea ice regime north of Svalbard. Radiosondes were launched twice daily during the expedition from January to June 2015. Here we use these upper air measurements to study the multiple cyclonic events observed during N-ICE2015 with respect to changes in the vertical thermodynamic structure, moisture content, and boundary layer characteristics. We provide statistics of temperature inversion characteristics, static stability, and boundary layer extent. During winter, when radiative cooling is most effective, we find the strongest impact of synoptic cyclones. Changes to thermodynamic characteristics of the boundary layer are associated with transitions between the radiatively “clear” and “opaque” atmospheric states. In spring, radiative fluxes warm the surface leading to lifted temperature inversions and a statically unstable boundary layer. Further, we compare the N-ICE2015 static stability distributions to corresponding profiles from ERA-Interim reanalysis, from the closest land station in the Arctic North Atlantic sector, Ny-Ålesund, and to soundings from the SHEBA expedition (1997/1998). We find similar stability characteristics for N-ICE2015 and SHEBA throughout the troposphere, despite differences in location, sea ice thickness, and snow cover. For Ny-Ålesund, we observe similar characteristics above 1000 m, while the topography and ice-free fjord surrounding Ny-Ålesund generate great differences below. The long-term radiosonde record (1993–2014) from Ny-Ålesund indicates that during the N-ICE2015 spring period, temperatures were close to the climatological mean, while the lowest 3000 m were 1–3∘C warmer than the climatology during winter.
    Repository Name: EPIC Alfred Wegener Institut
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  • 35
    Publication Date: 2019-07-17
    Description: Focused research on the Pine Island and Thwaites glaciers, which drain the West Antarctic Ice Shelf (WAIS) into the Amundsen Sea Embayment (ASE), revealed strong signs of instability in recent decades that result from variety of reasons, such as inflow of warmer ocean currents and reverse bedrock topogra- phy, and has been established as the Marine Ice Sheet Instability hypothesis. Geothermal heat flux (GHF) is a poorly constrained parameter in Antarctica and suspected to affect basal conditions of ice sheets, i.e., basal melting and subglacial hydrology. Thermomechanical models demonstrate the influential boundary condition of geothermal heat flux for (paleo) ice sheet stability. Due to a complex tectonic and magmatic history of West Antarctica, the region is suspected to exhibit strong heterogeneous geothermal heat flux variations. We present an approach to investigate ranges of realistic heat fluxes in the ASE by different methods, discuss direct observations, and 3-D numerical models that incorporate boundary conditions derived from various geophysical studies, including our new Depth to the Bottom of the Magnetic Source (DBMS) estimates. Our in situ temperature measurements at 26 sites in the ASE more than triples the number of direct GHF observations in West Antarctica. We demonstrate by our numerical 3-D models that GHF spatially varies from 68 up to 110 mW m-2.
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  • 36
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    Wiley
    In:  EPIC3Journal of Geophysical Research-Oceans, Wiley, 122(2), pp. 1497-1512, ISSN: 0148-0227
    Publication Date: 2017-10-10
    Description: The Barents Sea is one of the fastest changing regions of the Arctic, and has experienced the strongest decline in winter-time sea-ice area in the Arctic, at -23 +/- 4% per decade. Sea-ice thickness in the Barents Sea is not well studied. We present two previously unpublished helicopter-borne electromagnetic (HEM) ice thickness measurements from the northwestern Barents Sea acquired in March 2003 and 2014. The HEM data are compared to ice thickness calculated from ice draft measured by ULS deployed between 1994 and 1996. These data show that ice thickness varies greatly from year to year; influenced by the thermodynamic and dynamic processes that govern local formation vs long-range advection. In a year with a large inflow of sea-ice from the Arctic Basin, the Barents Sea ice cover is dominated by thick multiyear ice; as was the case in 2003 and 1995. In a year with an ice cover that was mainly grown in situ, the ice will be thin and mechanically unstable; as was the case in 2014. The HEM data allow us to explore the spatial and temporal variability in ice thickness. In 2003 the dominant ice class was more than 2 years old; and modal sea-ice thickness varied regionally from 0.6 to 1.4 m, with the thinner ice being either first-year ice, or multiyear ice which had come into contact with warm Atlantic water. In 2014 the ice cover was predominantly locally grown ice less than 1 month old (regional modes of 0.5–0.8 m). These two situations represent two extremes of a range of possible ice thickness distributions that can present very different conditions for shipping traffic; or have a different impact on heat transport from ocean to atmosphere.
    Repository Name: EPIC Alfred Wegener Institut
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  • 37
    Publication Date: 2017-10-24
    Repository Name: EPIC Alfred Wegener Institut
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  • 38
    Publication Date: 2017-09-20
    Description: Antarctic pack ice serves as habitat for microalgae which contribute to Southern Ocean primary production and serve as important food source for pelagic herbivores. Ice algal biomass is highly patchy and remains severely undersampled by classical methods such as spatially restricted ice coring surveys. Here we provide an unprecedented view of ice algal biomass distribution, mapped (as chlorophyll a) in a 100 m by 100 m area of a Weddell Sea pack ice floe, using under-ice irradiance measurements taken with an instrumented remotely operated vehicle. We identified significant correlations (p 〈 0.001) between algal biomass and concomitant in situ surface measurements of snow depth, ice thickness, and estimated sea ice freeboard levels using a statistical model. The model’s explanatory power (r2 = 0.30) indicates that these parameters alone may provide a first basis for spatial prediction of ice algal biomass, but parameterization of additional determinants is needed to inform more robust upscaling efforts.
    Repository Name: EPIC Alfred Wegener Institut
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  • 39
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    Wiley
    In:  EPIC3Paleoceanography, Wiley, 32, ISSN: 0883-8305
    Publication Date: 2017-04-25
    Description: The global ocean state for the modern age and for the Last Glacial Maximum (LGM) was dynamically reconstructed with a sophisticated data assimilation technique. A substantial amount of data including global seawater temperature, salinity (only for the modern estimate), and the isotopic composition of oxygen and carbon (only in the Atlantic for the LGM) were integrated into an ocean general circulation model with the help of the adjoint method, thereby the model was optimized to reconstruct plausible continuous fields of tracers, overturning circulation and water mass distribution. The adjoint-based LGM state estimation of this study represents the state of the art in terms of the length of forward model runs, the number of observations assimilated, and the model domain. Compared to the modern state, the reconstructed continuous sea-surface temperature field for the LGM shows a global-mean cooling of 2.2 K, and the reconstructed LGM ocean has a more vigorous Atlantic meridional overturning circulation, shallower North Atlantic Deep Water (NADW) equivalent, stronger stratification, and more saline deep water.
    Repository Name: EPIC Alfred Wegener Institut
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  • 40
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    Wiley
    In:  EPIC3Journal of Geophysical Research-Oceans, Wiley, 122(5), pp. 4004-4020, ISSN: 0148-0227
    Publication Date: 2018-01-02
    Description: Nioghalvfjerdsfjorden Glacier (79NG) is the largest of three marine-terminating outlet glaciers draining the Northeast Greenland Ice Stream. To understand how Atlantic waters supply waters in the cavity beneath the floating 79NG, we analyze historic and recent bathymetric, hydrographic, and velocity observations obtained on the Northeast Greenland continental shelf. The bathymetry is characterized by a trough system, consisting of the Westwind Trough and the Norske Trough in the northern and southern part of the continental shelf, respectively. Atlantic waters recirculating in Fram Strait cross the shelf break and enter the trough system at its southeastern inlet toward the inner shelf. Warm Atlantic Intermediate Water (AIW) present below 200 m in the Norske Trough shows large contributions of the recirculating Atlantic water. We found that the bathymetry is sufficiently deep to provide a direct subsurface pathway for warm AIW between the shelf break and the 79NG cavity via the Norske Trough. Likewise, based on the hydrographic data, we show that the Norske Trough supplies AIW warmer than 1°C to the 79NG, which is not present in the Westwind Trough. Our moored and lowered velocity measurements indicate that a boundary current carries warm AIW along the northeastern slope of Norske Trough toward the 79NG. We suggest that anomalies in Atlantic water temperatures in Fram Strait could reach 79NG within less than 1.5 years, thereby modifying the glacier's basal melt rates.
    Repository Name: EPIC Alfred Wegener Institut
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  • 41
    Publication Date: 2018-08-10
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  • 42
    Publication Date: 2022-03-28
    Description: The Central Yakutian permafrost landscape is rapidly being modified by land use and global warming, but small-scale thermokarst process variability and hydrological conditions are poorly understood. We analyze lake-area changes and thaw subsidence of young thermokarst lakes on ice-complex deposits (yedoma lakes) in comparison to residual lakes in alas basins during the last 70 years for a local study site and we record regional lake size and distribution on different ice-rich permafrost terraces using satellite and historical airborne imagery. Statistical analysis of climatic and ground-temperature data identified driving factors of yedoma- and alas-lake changes. Overall, lake area is larger today than in 1944 but alas-lake levels have oscillated greatly over 70 years, with a mean alas-lake-radius change rate of 1.663.0 m/yr. Anthropogenic disturbance and forest degradation initiated, and climate forced rapid, continuous yedoma-lake growth. The mean yedoma lake-radius change rate equals 1.261.0 m/yr over the whole observation period. Mean thaw subsidence below yedoma lakes is 6.261.4 cm/yr. Multiple regression analysis suggests that winter precipitation, winter temperature, and active-layer properties are primary controllers of area changes in both lake types; summer weather and permafrost conditions additionally influence yedoma-lake growth rates. The main controlling factors of alas-lake changes are unclear due to larger catchment areas and subsurface hydrological conditions. Increasing thermokarst activity is currently linked to older terraces with higher ground-ice contents, but thermokarst activity will likely stay high and wet conditions will persist within the near future in Central Yakutian alas basins.
    Repository Name: EPIC Alfred Wegener Institut
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  • 43
    Publication Date: 2022-05-24
    Description: Continuous GPS (CGPS) data, collected at Mt. Etna between April 2012 and October 2013, clearly define inflation/deflation processes typically observed before/after an eruption onset. During the inflationary process from May to October 2013, a particular deformation pattern localised in the upper North Eastern sector of the volcano suggests that a magma intrusion had occurred a few km away from the axis of the summit craters, beneath the NE Rift system. This is the first time that this pattern has been recorded by CGPS data at Mt. Etna. We believe that this inflation process might have taken place periodically at Mt. Etna and might be associated with the intrusion of batches of magma that are separate from the main feeding system. We provide a model to explain this unusual behaviour and the eruptive regime of this rift zone, which is characterised by long periods of quiescence followed by often dangerous eruptions in which vents can open at low elevation and thus threaten the villages in this sector of the volcano.
    Description: Published
    Description: 356-363
    Description: 2V. Dinamiche di unrest e scenari pre-eruttivi
    Description: JCR Journal
    Description: restricted
    Keywords: Shallow intrusion beneath NE Rift system ; Mt. Etna volcano ; CGPS data ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 44
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    Wiley
    In:  EPIC3Ecosphere, Wiley, 8(3), pp. e01742-e01742, ISSN: 2150-8925
    Publication Date: 2023-09-22
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  • 45
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 139-150 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine Reihe makroporöser Glycidylmethacrylat-Ethylendimethacrylat-Copolymerer (GMA-co-EDMA) wurde durch Suspensionspolymerisation hergestellt; dabei wurden nach einer statistisch geplanten experimentellen Durchführung die Ethylendimethacrylatkonzentration und die Heizrate der Polymerisationstemperatur von 20 auf 70°C variiert. Die Porositätseigenschaften der hydrolysierten Copolymeren wurden mit Hilfe der Größenausschlußchromatographie unter Verwendung von Polystyrolstandards in Tetrahydrofuran charakterisiert. Das Porenvolumen, die spezifische Oberfläche und die Porengröße werden dabei durch die Konzentration des Vernetzungsmittels stärker beEinflußt als durch die Heizrate während der Polymerisation.
    Notes: A series of macroporous glycidyl methacrylate-ethylene dimethacrylate copolymers have been prepared by the suspension polymerization according to a statistical design of experimental approach in which concentration of ethylene dimethacrylate and time needed for raising the polymerization temperature from 20 to 70°C have been varied. The porous properties of hydrolyzed copolymers have been characterized by means of size exclusion chromatography using polystyrene standards in tetrahydrofuran. Pore volume, specific surface area, and pore size are affected by the crosslinking agent concentration rather than by the rate of temperature increase during the polymerization reaction.
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  • 46
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 171-190 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Copolymers of AN were prepared with variable molecular masses and with variable contents of methylacrylate (ASME) and sodiumallylsulfonate (NaAS), acrylamide (AA), itaconic acid (IS), polyethyleneglycol acrylate (600) (PEGA), vinylacetate (VA), 2-hydroxyethyl acrylate, (HEE) or sodium acrylamido-2-methylpropanesulfonate (NaAMPS), respectively, by using a mathematical model for the calculation of the polymerization conditions needed. Precipitation studies by light scattering showed the predominant influence of NaAS and NaAMPS on the precipitation properties. Acrylonitrile homopolymers show a hard precipitation behaviour. The originating particles have a density of between 0.2 and 0.4 g/cm3. An increasing content of NaAS or NaAMPS leads for example beginning from 0.8 wt.-% NaAS in the monomer composition to a soft precipitation behaviour and to highly swollen particles possessing a density of less than 1 · 10-2 g/cm3. The molar mass and the ASME-content show no significant influence. For the acrylonitrile/acrylamide system already 0.5 wt.-% allylsulfonate is sufficient to get a soft precipitation behaviour with formation of highly swollen particles. All samples with the other cocomponents and without NaAS- or NaAMPS-comonomer show a hard precipitation behaviour with little swollen particles.
    Notes: Copolymere des Acrylnitrils (AN) mit variabler Molmasse bzw. mit variablem Anteil von Acrylsäuremethylester (ASME) und Natriumallylsulfonat (NaAS), Acrylamid (AA), Itaconsäure (IS), Polyethylenglykolacrylat (600) (PEGA), Vinylacetat (VA), Acrylsäure-2-hydroxyethylester (HEE) oder Natrium-2-acrylamido-2-methylpropansulfonat (NaAMPS) wurden hergestellt, wobei die erforderlichen Polymerisations-bedingungen mit Hilfe eines mathematischen Polymerisationsmodells ermittelt wurden.Die Fällungsuntersuchungen mit der Methode der Lichtstreuung zeigten, daß NaAS und NaAMPS einen dominierenden Einfluß haben. Bei Acrylnitril-Homopolymeren tritt eine harte Fällung auf, und die entstehenden Partikel haben eine Dichte zwischen 0,2 und 0,4 g/cm3. Zunehmender NaAS-bzw. NaAMPS-Gehalt führt ab einem Gehalt von beispielsweise ca. 0,8 Gew.-% NaAS im Monomergemisch zu einer weichen Fällung, bei der hochgequollene Partikel mit einer Dichte in der Größenordnung von 〈 1.10-2 g/cm3 entstehen. Ein Einfluß der Molmassen und des ASME-Gehaltes Konnte nicht nachgewiesen werden. Beim Acrylnitril/Acrylamid-System genügen offensichtlich 0,5 Gew.-% Allylsulfonat im Monomeransatz, um eine stabile, weiche Fällung unter Bildung hochgequollener Strukturen zu gewährleisten. Alle Proben mit den übrigen hydrophilen Cokomponenten zeigen ohne NaAS bzw. NaAMPS-Comonomer ein hartes Fäungsverhalten mit wenig gequollenen Partikeln.
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  • 47
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 195 (1992), S. 213-213 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 48
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    Angewandte Makromolekulare Chemie 195 (1992), S. 191-204 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Photovernetzung von Poly(p-hydroxystyrol) (PPHS) wird durch O2 beachtlich beschleunigt. Dies ergab sich aus der Bestimmung der Molmasse (mit Hilfe der Lichtstreumethode) und des Gelanteils nach kontinuierlicher Bestrahlung bei λinc = 254 nm. Aufgrund von Ergebnissen aus Blitzphotolyseversuchen wird der folgende Reaktionsmechanismus aufgestellt: Die Vernetzung sowohl in An-als auch Abwesenheit von O2 kommt im wesentlichen durch Kombination von Radikalen des Phenoxyltyps zustande. In Abwesenheit von O2 werden Phenoxylradikale ausschließlich durch Spaltung von O—H-Bindungen phenolischer Gruppen, die sich im angeregten Singulettzustand befinden, erzeugt. Triplett-angeregte phenolische Gruppen, die sich auch bilden, desaktivieren nicht durch Spaltung der O—H-Bindungen. Sie reagieren allerdings sehr effektiv, sofern vorhanden, mit O2. Bei dieser Reaktion entstehen HO·2- und zusätzliche Phenoxylradikale. Alle handelsüblichen und die meisten im Labor synthetisierten PPHS-Proben enthalten chemisch gebundene, chinoidartige Verunreinigungen. Durch Versuche mit niedermolekularen Modellverbindungen wurde nachgewiesen, daß triplett-angeregte chinoide Gruppen einerseits mit phenolischen Gruppen unter Bildung von Phenoxylradikalen reagieren und daß sie andererseits unreaktiv sind bezüglich der Abstraktion aliphatischer Wasserstoffatome. Die Bestrahlung von PPHS bei λinc = 254 nm bewirkt die Bildung chinoider Gruppen, die bei dieser Wellenlänge auch stark absorbieren. Die Lichtabsorption dieser Gruppen wird im Laufe der weiteren Bestrahlung zum bestimmenden Faktor hinsichtlich der photochemischen Veränderung des Polymeren.
    Notes: Light-induced crosslinking of poly(p-hydroxystyrene) (PPHS) is significantly enhanced by O2. This was evidenced by molar mass (light scattering measurements) and by gel content determinations which were performed on various polymer samples before and after continuous irradiation at λinc = 254 nm. The following mechanism was elucidated with the aid of flash photolysis studies: Crosslinking in the absence or presence of O2 is mainly due to the combination of phenoxyl type radicals. In the absence of O2 the latter are exclusively formed by O—H bond cleavage of singlet excited phenolic groups. Triplet excited phenolic groups which are also formed do not deactivate via O—H bond cleavage but react very effectively with O2. This reaction leads to the formation of HO2· and additional phenoxyl type radicals. All Commercial and most laboratory-prepared PPHS samples contain chemically bound impurities of quinoid nature. On the basis of results performed with model compounds of low molar mass, it is concluded that triplet excited quinoid groups react effectively with phenolic groups forming phenoxyl type radicals and that they are quite unreactive with respect to the abstraction of alphatic hydrogen atoms. Irradiation of PPHS at λinc = 254 nm causes the formation of quinoid groups which absorb strongly at this wavelength. Light absorption by these groups becomes a determining factor with respect to photochemical alteration in the course of further irradiation.
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  • 49
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    Angewandte Makromolekulare Chemie 196 (1992), S. 21-35 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die verschiedenartigen Eigenschaften von Polymerlegierungen aus Polyoxymethylen (POM) und bis zu 20 Gew.-% chemische oberf;ächenbehandeltem Poly(tetrafluorethylen) (CPTFE) wurden untersucht und denen unbahandelter POM/PTFE- Blends gegenübergestellt. PTFE iwrd POM zugesetzt, um dessen Oberflächenabriebseigenschaften Anteil zunehmend verschlechtert. Durch die bessere Phasenanbindung in den oberflächenbehandelten POM/CPTFE- Blends konnten die doppelten Zugfestigkeiten und EModuli wie bei unbehandelten POM/PTEF- Blends erreicht werden. Mit Hilfe der Elektronenmikroskopie (SEM) konnte gezeigt werden, daß die PTEF-Agglomerate in der POM-Matrix eine Größe von 30 bis 100 μm haben, während die CPTFE-Teilchengrößbe unter 1 μum liegt.
    Notes: The various properties of the blends of polyacetal (POM) with up to 20 wt.-% chemically surface-treated poly(tetrafluoroethylene) (CPTFE) were investigated and compared with those of POM/PTFE blends. The PTFE is added to POM to improve the wear properties, however, the mechanical properties of POM/PTFE blends decrease with increasing PTFE content, but tensile strength and Young's modulus of POM/CPTFE blends are more than 2 times higher than that of the POM/PTFE blends. SEM shows that the size of inherent agglomerative PTFE is in the range of 30 to 100 μm. The particle size of major CPTFE dispersed in POM is smaller than 1 μm.
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  • 50
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    Angewandte Makromolekulare Chemie 196 (1992), S. 49-61 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Hydrogele wurden aus methylmethacrylat (MMA) and N-Vinyl-2-pyrrolidon (NVP) mit 1,2,2-Trimethylolpropantrimethacrylat (TPTA) als Vernetzungsmittel hergestellt. Die Terplymerisation wurden mittels UV-strahlung (365 nm) initiiert, wobei kleine Mengen an Diethoxycetophenon (DEAP) als Photosensibilisator sowie Triethanolamin(TEA)als Beschleuniger und Verdünner verwendet wurden. Die Hydrogele wurden durch Messung des Wasserrückhaltevermögens, der Sauerstodiffusions- und permitionskoeffizienten, der mechanischen Eigenschaften und der Lichtdurchlässigkeit charakterisiert. Dabei zeigte sich, daß die Hydrogele bis zu 80 Gew.-% Wasser aufnehmen können, wobei mit steigendem Wassergtehalt deren mechanische Festigkeit drastisch sinkt. Der Ssuerstoffdiffusionskoeffizient der gequollenen Hydrogele beträgt 10-6 cm2s-1, der Sauerstoffpermeationskoeffizient 1013 cm2s-1Pa-1, und die Lichtdurchlässigkeit liegt im Bereich von 500 bis 700 nm bei über 90%.
    Notes: Hydrogels are synthesized from methyl methacrylate (MMA) and N-vinyl-2-pyrrolidone (NVP) with 1,1,1-trimethylol propane trimethacrylate (TPTA) as a crosslinking agent. It was polymerized under UV radiation (365nm) with a small amount of photosensitizer, diethoxy acetophenone (DEAP), acclerator and diluent, triethanol amine (TEA). The hydrogels were characterized by measuring the water retention, dissolved oxygen diffusivity and permeability, mechanical strength, and light transparency. The hydrogels can retain water up to 80 wt.-% and the mechanical strenght is weakened as the water content is increased in the gel. The dissolved oxygen diffusivity and permeability in the swelling hydrogels are determined to be 10-6 cm2/sec and 1013 cm2s-1 Pa-1, respectively. The light transparency is over 90% in the wave lenght ranging from 500 to 700 nm.
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  • 51
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein Bisphenol-A-Epoxidharz wurde zunächst mit Toluylendiisocyanat, dessen eine Isocyanatgruppe mit 2-Ethylhexanol blockiert war, und dann mit unterschiedlichen Mischungen on Diethanolamin und Bis(2-methyl-isobutylketiminoethyl)amin (DKI)umgesetzt. Aus diesen Harzen mit Triethanolamin- und DKI-Endgruppen wurden durch Hydrolyse und Neutralisieren mit Essigsäure kationische Harze mit primären Amin-Endgruppen erhalten, aus denen mit geeigneten Lösungsmitteln und deionisiertem Wasser Emulsionen hergestellt wurden. Deren Eigenschaften und die Elektroabscheidung der Harze aus den Emulsionen wurden untrsucht. Der Effekt der Zugabe von hydrophoben Lösungsmitteln wie Toluol oder Hexylcellosolv (HCS) auf die Abscheidungseigenschaften wird diskutiert.
    Notes: A diglycidylether of bisphenol A epoxy resin (DGEBA) was first reacted with 2,4-toluene diisocyanate partially blocked with 2-ethylhexanol (2-EH P. B. TDI) to form modified epoxy resins, and subsequently reacted with different molar ratios of diethanolamine and bis(2-methylisobutylketiminoethyl)amine (DKI) (used as ring opening agents) to give diethanolamine/diketimine terminated resins. These resins were hydrolyzed and neutralized with acetic acid to give cationic resins containing various contents of primary amine groups in the terminal polymeric chain. These cationic resins can be dissolved in a suitable solvent and mixed with deionized water to obtain emulsions. The electrodeposition properties and characteristics of the resulting cationic resins were investigated in detail. The effects of hydrophobic solvents, such as hexyl cellosolve (HCS) and toluene, on the deposition properties of the emulsions are discussed.
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  • 52
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    Angewandte Makromolekulare Chemie 196 (1992), S. 107-111 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die radikalische Polymerisation von Acrylnitril in Gegonwart verschiedener ungesättigter optischer Aufheller (FB) (Derivate des 1,3,5-Triazins) wurde untersucht. Kolorimetrische Messungen ergaben, daß mehr als 80% des optischen Aufhellers in die Polymerkette eingebaut werden. Zur Erzielung eines intensiven optischen Effektes genügt eine FB-Anfangskonzentration von 0,1 Gew.-%, bezogen auf Acrylnitril.
    Notes: The polymerization of acrylonitrile in the presence of some unsaturated, triazinebased fluorescent brighteners (FB) has been investigated. It was found colourimetrically that more than 80% of the FB is incorporated in the polymer. The initial concentration of 0.1 wt.-% is sufficient to obtain a good bleaching effect without significant decrease of the molecular weight.
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  • 53
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Les polyesters thermoplastiques (PBT et PET) sont des polymères fragiles avec une résistance au choc entaillée faible. Leur renforcement peut être obtenu par extrusion réactive avec dirrérents types de copolymères élastomères de l'éthylène, contenant des fonctons à réactivité potentielle avec extrémités de chaîne acide et hydroxyle des polyesters.Deux types de copolymères ont été étudiés: Ethylène(acrylate d'éthyle/méthacrylate de glycidyle (E/EA/GMA), et éthylène/acrylate d'éthyle/anhydride maléique (E/EA/MAH). Les alliages ont été obtenu par malaxage de 10 à 25% de coppolymères avec du PBT.Le PBT présente une transition fragile, ductile lorsqu'on passe de 10 à 20% de particules dispersées de copolymère au GMA. Les gains les plus importants en résistance au choc sont obtenus en réticulant partiellement la phase dispersée, par association de copolymères en GMA et de copolymères avec MAH et catalyseur de réaction.
    Notes: Poly(butylene terephthalate) (PBT) and poly(ethylene terephthalate) (PET) are brittle polymers with poor notched impact strength. Their toughening can be achieved by melt blending with different types of rubbery ethylene copolymers containing functions having potential reactivity with the hydroxy and carboxy end groups in polyesters.Two types of ethylene copolymers were investigated: ethylene/ethyle acrylate/glycidyl methacrylate (E/EA/GMA) and ethylene/ethyl acrylate/maleic anhydride (E/EA/MAH) copolymers. The blends were obtained by reactive extrusion of PBT with 10 to 25% of copolymers.PBT blends undergo a brittle to ductile transition by toughening with GMA copolymer between 10 and 20% of rubbery phase. The most effective toughening could be achieved by a partial crosslinking of the rubbery particles obtained by associating GMA and MAH copolymers and a reaction catalyst.
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  • 54
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    Angewandte Makromolekulare Chemie 196 (1992), S. 101-106 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Orientierung (Neigungswinkel ϕ) von thermotropen Flüssigkristallen (LC) an der Grenzfläche zu polymerbeschichteten Substraten wird nicht nur durch den numerischen Wert der Oberflächenspannung \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm \gamma }_{\rm S} {\rm = \gamma }_{\rm S}^{\rm d} {\rm + \gamma }_{\rm S}^{\rm p} } \right)$\end{document} bestimmt. Das Verhältnis zwischenden dispersiven und polaren Anteilen an \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm \gamma }_{\rm S}^{\rm d} {\rm : \gamma }_{\rm S}^{\rm p} } \right)$\end{document} beeinflußt ebenfalls die Orientierung der LC-Moleküle an der Substratoberfläche. Als Polymere wurden ein Polyimid und ein Midgruppenhaltiges Styrol/Maleinsäureanhydrid-Copolymeres verwendet.
    Notes: The orientation (tilt angle ϕ) of thermotropic liquid crystals (LC) on the interface to a polymer-coated surface is not only determined by the numerical value \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm \gamma }_{\rm S} {\rm = \gamma }_{\rm S}^{\rm d} {\rm + \gamma }_{\rm S}^{\rm p} } \right)$\end{document} of the substrate surface tension. However, the ratio between the dispersive and the polar part of \documentclass{article}\pagestyle{empty}\begin{document}${\rm \gamma }_{\rm S} {\rm }\left( {{\rm\gamma }_{\rm S}^{\rm d} {\rm : \gamma }_{\rm S}^{\rm p} } \right)$\end{document} also influences the LC orientation on the substrate surface. A polyimide and an amide-modified styrene/maleic anhydride copolymer were used as polymers.
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  • 55
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    Angewandte Makromolekulare Chemie 195 (1992), S. 129-137 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Epoxidharze aus Bisphenol A wurden mit neuen Diphenolen, die Imidgruppen enthalten, modifiziert, um die thermischen Eigenschaften zu verbessern. Die verwendeten Diimiddiphenole wurden aus Dianhydriden und Aminophenolen durch Kondensation hergestellt. Die Diimiddiphenole und die modifizierten Harze wurden durch IR- und NMR-spektroskopische Messungen charakterisiert. Das thermische Verhalten wurde anhand von DSC- und TGA-Messungen untersucht.
    Notes: Epoxy resins derived from Bisphenol A have been modified with new diphenols containing imide moieties in order to improve their thermal properties. The diphenols have been synthesized from dianhydrides and aminophenols by condensation reactions. Diphenols as well as modified resins have been characterized by IR and NMR spectroscopy. The thermal characteristics were evaluated by DSC and TGA.
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  • 56
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    Angewandte Makromolekulare Chemie 195 (1992), S. 165-170 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The structural transformation of a molecular complex (MC) of polyoxyethylene and urea on cooling from the molten state has been investigated by DSC and X-ray analysis. A high-temperature polymorphic from of the MC was found to be formed, which transforms into the known crystal form of the MC with a hexagonal crystal modification on cooling.
    Notes: Die Strukturveränderungen eines Molekülkomplexes (MK) aus Polyoxyethylen und Harnstoff beim Abkühlen aus dem geschmolzenen Zustand werden kalorimetrisch und röntgenographisch untersucht. Es wird festgestellt, daß eine polymorphe Hochtemperaturform des MK entsteht, die beim Abkühlen in die bekannte Kristallform des MK mit hexagonaler Kristallmodifikation übergeht.
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  • 57
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    Angewandte Makromolekulare Chemie 196 (1992), S. 143-154 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Anfangsstadium der Oxidation von Lactamen wurden im Temperaturbereich 70-120°C Cuntersucht. Es wurde festgestellt, daß Pyrrolidon und Piperidon bedeutend schneller oxidiert werden als die sieben-, acht- und dreizehngliedrigen Lactame sowie lineare N-Alkylamide. Die hohe Oxidierbarkeit der fünf- und sechsgliedrigen Lactame kann der leichteren homolytischen Spaltung der N- vicinalen C—H Bindung und der unterschiedlichen Reaktivität der Lactamradikale im Wachstuschritt der Kettenoxidation zugeschrieben werden.
    Notes: The initial stage of oxidation of lactams was studied in the temperature range 70-120°C. It was found that pyrrolidone and piperidone are oxidized essentially more easily than the seven-, eight-, nine- and thirteen-membered lactams as well as linear N-alkylamides. The high oxidizability of the five- and six-membered lactams may be attributed to the easier homolytic splitting of the N-vicinal C—H bond and to the different reactivity of lactam radicals in the propagation step of the chain oxidation.
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  • 58
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    Angewandte Makromolekulare Chemie 196 (1992), S. 127-141 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The relative chain transfer constant for sodium allylsulfonate (NaAS) in the copolymer system acrylonitrile (AN)/methylacrylate (MA) in dimethylformamide (DMF) was determined to be Cx = 0,04 ± 0.01, independent of the initiator used (azoisobutyronitrile, ammoniumperoxodisulfate).The chain transfer reaction explains the influence of NaAS on the polymerization degree, but not the concentration dependence of the copolymerization reactivity ratio r1 · r1 depends on the transfer reaction only in a range of 1 - 5%.The extended Debye-Hückel theory for dilute electrolytes has been successfully tested for a quantitative dependence of r1 from NaAS concentration. The resultant r10-value for infinite dilution of NaAS obviously depends on the acrylonitrile concentration, but only to a small extent (e.g. r10 = 0.32 for [AN] =- 4.26 mol/l). This theory provides comfortable access to resolve the nonideal AN/NaAS copolymerization. This approach may be generally applicable to copolymerizations of monomers with dissociated groups.
    Notes: Im Copolymerisationssystem Acrylnitril (AN)/Methylacrylat(MA) mit Natriumallylsulfonat (NaAS) in Dimethylformamid wurde die relative Übertragunskonstante zum NaAS Cx = 0,04 ± 0,01 unabhängig vom verwendeten Initiator (Azoisobuttyronitril, Ammoniumperoxodisulfat) ermittelt. Die Übertragunsreaktion beschreibt den Einfluß des NaAS auf den Polymerisationsgrad, sie beeinflußt jedoch den Copolymerisationsparameter r1 nur in der Größenordung von 1 bis 5% und kann damit die Konzentrationsabhängigkeit von r1 nicht erklären.Mit Hilfe der erweiterten Debye-Hückel-Theorie für verdünnte Elektrolyte wird die Abhängigkiet des r1-Wertes von der NaAS- Konzentration beschrieben. Der sich daraus für unendliche Verünnung des NaAS ergebende r10-Wert ist offensichtlich noch gerinfügig von der Acrylnitrilkonzentration abhägig. Er liegt beispielsweise für [AN] = 4, 26 mol/1 bei r10 = 0, 32. Damit wurde zum ersten Mal das nichtideale Copolymerisationsverhalten im untersuchten System erkärl. Das Vorgehen sollte verallemeinerungsfähig sein und generell auf das Copolymerisationsverhalten von Monomeren mitdissoziierten Gruppen angewendet werden können.
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  • 59
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    Angewandte Makromolekulare Chemie 196 (1992), S. 169-177 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Katalase wurde durch photoinduzeirte Propfpolymerisation auf mikroporöse polymere Trägermembranen immobilisiert. Die katalytische Aktivität für Zersetzung von Wasserstoffperoxid unter Ultrafitrationsbedingungen wurde mittels eines Rezirkulationsapparates untersucht. Die Membranen zeigten ein sehr gutes katalytisches Verhalten; die Enzymreaktion fand ausschließlich in der Membranstruktur statt. Anfangsreaktionsgeschwindigkeiten, gemessen in einem Temperaturbereich von 5-35°C als Funkation der Substratkonzentration und der Menge des immobilisierten Enzyms pro Einheit Membranoberfäche zeigten, daß sich der Reaktionsmechanismus der Katalase durch die Immobilisierung nicht verädert.
    Notes: Catalase has been immobilized in membranes prepared by photoinduced grafting onto microporous polymeric supports and its catalytic activity on hydrogen peroxide decomposition has been studied under ultrafiltration conditions by means of a recirculation apparatus. The membranes showed a very good catalytic performance and the enzyme reaction took place exclusively within the membrane structure. Initial reaction rates measured in the temperature range 5 - 35°C as a function of both substrate concentration and enzyme amount immobilized per unit membrane surface indicate that the mechanism of action of catalase is not altered after immobilization.
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  • 60
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The network formation process of bisphenol A-diglycidylether and 4,4′-diaminodiphenylmethane was investigated by measuring the torque, the conductivity and the soluble part of the crosslinking system. The activation energy for the curing process was estimated from gel time. The volume shrinkage during network formation was measured. The influence of N,N-dimethylbenzylamine as accelerator was discussed.
    Notes: Der Aufbau von Netwerken aus Bisphenol A-Diglycidylether und 4,4′-Diaminodiphenylmethan wurde durch Messung des Drehmomentes, der Leitfähigkeit und durch Bestimmung der löslichen Anteile des vernetzenden System untersucht. Aus den Gelzeiten wurden die Aktivierungsenergie für den Vernetzungsprozeß bestimmt. Außerdem wurde die während der Vernetzung aufretende Volumenschwindung gemessen. Der Einfluß von N, N-Dimethylbenzylamin als Beschleuniger auf den Vernetzungsprozeß wird diskutiert.
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  • 61
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The UV-laser induced surface modification of various types of high-performance fibers is investigated. Due to the high UV-absorption coefficients, the well-known effect of UV-laser induced etching (ablation) is observed with all fiber types. Furthermore, the relaxation of orientated macromolecules leads to a characteristic structuring of the fiber surface. For a possible controlled use of this physical surface modification, exact conditions for the treatment in view of textile applications are determined. Useful constants like threshold of ablation, etching rate and structuring constants are measured for all fiber types.
    Notes: Die Oberflächenbehandlung von unterschiedlichen Hochleistungsfasertypen mit gepulstem UV- Laserlicht wird untersucht. Bedingt durch die hohen UV-Absorptionskoeffizienten dieser Materialien wird der bekannte Effekt des UV-laserinduzierten Abtrags (Ablation) bei allen Fasern beobachtet. Zusätzlich werden durch die Relaxation der orientierten Makromoleküle charakteristische Strukturierungen auf der Faseroberfläche ausgebildet. Für einen möglichen kontrollierten und gezielten Einsatz dieser physikalischen Oberflächenmodifizierung in textilen Anwendungen werden die gnaunen Bedingungen der Laserbestrahlung ermittelt und beschieben. Darüber hinaus werden geeignete Konstanten der Laserbearbeitung wie Ablationsschwellenenergie, Ätzraten und Strukturierungskonstanten für verschiedene Fasertypen bestimmt.
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  • 62
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    Angewandte Makromolekulare Chemie 198 (1992), S. 165-178 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Polymerisation von Dimethyl-diallyl-ammoniumchlorid in konzentrierter wäßriger Lösung mit Persulfat als Initiator kann bis zu hohen Umsätzen mit einem Modell beschrieben werden, in dem folgende Teilreaktionen berücksichtigt werden: a)Primärradikalbildung durch aktivierten Initiatorzerfall sowie Redoxreaktion von S2O2-8 und Cl-b)Kettenwachstum über Monomerkationassoziate undc)Kettenabbruch durch Kombination von cyclisierten Polymerradikalen untereinan der und mit Chloratomen.Für die Polymerisationsgeschwindigkeit wird ein Zeitgesetz hergeleitet, für dessen Konstanten und Parameter numerische Werte ermittelt wurden.
    Notes: The polymerization of dimethyl diallyl ammonium chloride in concentrated aqueous solution with persulfate as an initiator can be described up to high conversion by a kinetic model including a)formation of primary radicals by activated initiator decomposition as well as by redox reaction of S2O82- and Cl-,b)chain propagation via monomer cation associates andc)termination by combination of cyclized polymer radicals between each other or with chlorine atoms.A kinetic expression for the rate of polymerization is presented; rate constants and model parameters have been determined.
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    Angewandte Makromolekulare Chemie 198 (1992), S. 199-199 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 64
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    Angewandte Makromolekulare Chemie 198 (1992), S. 179-190 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polymere mit über eine C—C-Verknüpfung an hochvernetztem Polystyrol kovalent gebundenen, makrocyclischen Amiden wurden durch die Reaktion polymergebundener Malonsäureester-Gruppen mit offenkettigen Diaminen dargestellt. Die Reaktion von vernetztem, chlormethyliertem Polystyrol mit makrocyclischen und offenkettigen Aminen führt zu Polymeren mit kovalenter Bindung über eine C—N-Verknüpfung. Die erhaltenen funktionalisierten Polymeren wurden hinsichtlich der Adsorption von Cu(II)-, Ni(II)- und Co(II)-Ionen aus wäßriger Lösung untersucht.
    Notes: Polymers containing moieties of amides covalently bound to highly crosslinked polystyrene by C—C connections were prepared via a polymer-bound malonic ester group in the reaction with open-chain diamines. The reaction of crosslinked, chloromethylated polystyrene with macrocyclic and open-chain amines results in covalent binding by C—N-connection. The synthesized functionalized polymers were investigated for uptake of Cu(II), Ni(II) and Co(II) ions from aqueous solutions.
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  • 65
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    Angewandte Makromolekulare Chemie 199 (1992), S. 1-6 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(phenylphosphindiylterephthaloyl), ein neues phosphorhaltiges Polymeres, wurde durch Lösungspolykondensation von Dilithium(phenyl)phosphin mit Terephthaloylchlorid bei niedriger Temperatur hergestellt. Es ist in polaren aprotischen Lösungsmitteln löslich; die inhärente Viskosität in DMF bei 30°C beträgt 19 ml/g. Das Polymere wurde mittels Elementaranalyse sowie IR- und 1H-NMR-Spektroskopie charakterisiert. TGA-Messungen ergeben, daß das Polymere in Luft bis 250°C stabil ist; es ist selbstverlöschend.
    Notes: Poly(phenylphosphinediylterephthaloyl), a novel phosphorus-containing polymer, was synthesized by low-temperature solution polycondensation of dilithio(phenyl)-phosphine with terephthaloyl chloride. The resulting polymer is soluble in polar aprotic solvents, having inherent viscosity of 19 ml/g in DMF at 30°C. The polymer was characterized by elemental analysis, IR and 1H-NMR spectroscopy. TGA data show that the polymer is stable up to 250°C in air. The polymer was found to be self-extinguishing.
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  • 66
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird eine neue Methode für die Erweiterung des Meßbereiches der Ausschlußchromatographie, gekoppelt mit Lichtstreuung (SEC/LALLS), zu höherer molarer Masse, vorgestellt. Diese Methode nützt den Effekt, daß das Lichtstreusignal oft schon bei wesentlich kleineren Werten des Elutionsvolumens, also hoheren Werten der molaren Masse erfaßbar ist als das Konzentrationssignal und berücksichtigt dabei die Peakverbreiterung in der SEC. Das betreffende Rechenverfahren wird für den Fall einer logarithmischen Normalverteiung und einer wahrscheinlichsten Verteilung getestet. Im Falle von Polypropylen mit logarithmischer Normalverteilung (M̄W = 420 000 und M̄n = 99 000) kann der durch SEC/LALLS erfaßte Bereich der molaren Masse um einen Faktor von ca. 10 erweitert werden; bei einer wahrscheinlichsten Verteilung (M̄n = 100 000) liegt die erreichbare Erweiterung des Meßbereiches der molaren Masse beieinem Faktor von ca. 2.
    Notes: A new method for the extension of the measuring range of size exclusion chromatography coupled with light scattering (SEC/LALLS) to higher molar mass is presented. This method uses the fact that the light scattering signal can often be detected already at considerable smaller values of the elution volume (i. e. higher values of molar mass) than the concentration signal; furthermore, it takes into account the peak broadening effect in SEC. This procedure is tested for the case of a logarithmic normal distribution and a most probable distribution of molar mass. In the case of polypropylene with a logarithmic normal distribution (M̄w = 420 000, M̄n = 99 000), the range of molar mass covered by SEC/LALLS can be extended by a factor of about 10; with a most probable distribution (M̄n = 100 000), the attainable extension in molar mass assumes a factor of about 2.
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  • 67
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    Angewandte Makromolekulare Chemie 199 (1992), S. 45-63 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Because of the interest in their possible application as biologically degradable polymers, the isotherms of sorption of water vapour by native and thermoplastic starch were measured. The thermomechanical treatment of starch and the insertion of glycerol as softener lead to the disappearance of the hysteresis and to the transition from a Type II to Type III isotherm. A theory, describing the sorption behaviour of swellable sorbents, is introduced and its statements are discussed by means of experimental results. The theory allows to draw conclusions on the molecular behaviour during sorption.
    Notes: Es wurden Wasserdampf-Sorptionsisothermen von nativer und thermoplastischer Stärke gemessen. Die thermisch-mechanische Behandlung der Stärke und das Einfähren von Glyzerin als Weichmacher fährt zum Verschwinden der Hysterese und zum Übergang von der Typ II in eine Typ III Isotherme. Eine Theorie, welche das Sorptionsverhalten von quellbaren Sorbentien gut beschreibt, wird kurz eingeführt und anhand der experimentellen Daten ihre Aussagen diskutiert. Die vorgestellte Theorie erlaubt wegen der physikalischen Bedeutung der Parameter Rückschlüsse auf die molekularen Vorgänge während der Sorption. Die Motivation zur Untersuchung des Sorptionsverhaltens von thermoplastischer Stärke ist deren möglicher Einsatz als biologisch abbaubarer Kunststoff.
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  • 68
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In order to solve the problem of polymer swelling which limits the resolution of negative resists, we have developed new resists where the swelling does not appear. For our study, we developed resists including polymers containing the tetrathiafulvalenylcarbonyloxymethyl radical and dibromotetrachloroethane. In order to study the influence of the nature of the radical bearing the tetrathiafulvalene unit in the polymers on the microlithographic properties of these resists, we also studied polymers containing the tetrathiafulvalenylphenoxymethyl radical. The resists have been tested under UV irradiation. The dependence of resist sensitivity on molecular weight is reported.
    Notes: Pour résoudre le phéomène de gonflement qui limite la résolution des résines microlithographiques classiques, nous nous sommes intéressés à de nouvelles résines avec lesquelles ce phénomène n'apparait pas. Nous avons retenu pour notre étude les résines R qui renferment en mélange un polymère porteur de radicaux tétrathiafulvalénylcarbonyloxyméthyles et le dibromotétrachloroéthane. Afin de voir l'influence de la nature du radical porteur de l'unité tétrathiafulvalène dans le polymtrè sur les propriétés microlithographiques des résines R, nous nous sommes également intéressés aux polymères renfermant des radicaux tétrathiafulvalénylphénoxymethyles. Les résines R ont été testées sous irradiation UV. Leurs sensibilités dépendent en outre de la valeur de la masse molaire du polymèr.
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  • 69
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    Angewandte Makromolekulare Chemie 199 (1992), S. 33-44 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Hochfeste Polyethylen- (HSPE), Polypropylen- (PP), Polyethylenterephthalat-(PET) und Polyvinylalkohol-(PVA) Textilgarne wurden unter Anwendung des entwickelten kontinuierlichen Einweichprozesses mit verschiedenen funktionellen Monomeren, wie beispielsweise Acrylsäure (AA), Acrylamid (AM), Glycidylacrylat (GA) und 4-Vinylpyridin (VP) oberflächenfotogepfropft. Die Einfärbbarkeit der oberflächenmodifizierten Garne mit verschiedenen Textilfarbstoffen wurde untersucht. Im allgemeinen wurde eine erhebliche Verbesserung der Einfärbbarkeit beobachtet. Die Farbstoffaufnahme der oberflächenfotogepfropften Fasern wird von vielen Faktoren beeinflußt, beispielsweise von der Art der Faser, der Menge und den Eigenschaften des auf die Oberfläche der Fasern gepfropften funktionellen Monomeren, der Art des Textilfarbstoffs usw. Die Faseroberflächen, auf die ein Monomeres mit basischen Gruppen wie Acrylamid und 4-Vinylpyridin gepfropft wurde, lassen sich mit einem sauren Farbstoff wirkungsvoll einfärben. Dagegen läßt sich eine Faseroberfläche, auf die ein saures funktionelles Monomeres gepfropft wurde, leicht mit basischen Farbstoffen in tiefen Farbtönen einfärben. Die Farbstoffaufnahme steigt stetig mit zunehmender Pfropfung, in ESCA-Spectren als relative Intensitaten relevanter Linien gemessen. Die nicht gepfropften HSPE-, PP-, und PET-Fasern können mit bestimmten Farbstoffen in gewissem Maße eingefärbt werden. Bei der vorliegenden Arbeit erhöhte sich die Farbstoffaufnahme bei HSPE-Fasern, die mit GA gepfropft und mit dem Metallkomplexfarbstoff IO eingefärbt wurden, um das 3,4fache, bei PP-Fasern, die mit AA gepfropft und mit dem basischen Farbstoff MB eingefärbt wurden, um das 7,9fache, bei PET mit AM und dem Direktfarbstoff SL um das 6,1fache, bei PVA mit VP und dem sauren Farbstoff TE um das 15,3fache.
    Notes: High-strength polyethylene (HSPE), polypropylene (PP), poly(ethylene terephthalate) (PET), and poly(vinyl alcohol) (PVA) textile yarns have been surface-photografted with various functional monomers, such as acrylic acid (AA), acrylamide (AM), glycidyl acrylate (GA) and 4-vinyl pyridine (VP), by means of the continuous presoaking process developed. The dyeing of these surface-modified yarns with various textile dyes has been investigated. In general, considerable improvements of dyeability have been observed. The dye adsorption of the surface-photografted fibers is influenced by many factors, such as type of fiber, amount and properties of the functional monomer grafted on the surface of the fibers, type of textile dye, etc. The fibers surface-grafted with a monomer containing basic groups, such as acrylamide and 4-vinyl pyridine, are efficiently dyed with an acid dye. Conversely, a fiber surface-grafted with acidic functional monomer is easily dyed to deep shades with basic dyes. The dye adsorption increases monotonically with increasing grafting measured in ESCA spectra as relative intensities of relevant lines. The ungrafted HSPE, PP and PET fibers can be dyed to some extent with certain dyes. In the present work, the dye adsorption increased by 3.4 times for HSPE fiber grafted with GA and dyed with the metal complex dye IO, by 7.9 times for PP fiber grafted with AA and dyed with the basic dye MB, by 6.1 times for PET with AM and with the direct dye SL, and by about 15.3 times for PVA with VP and with the acid dye TE.
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  • 70
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    Angewandte Makromolekulare Chemie 199 (1992), S. 65-74 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die thermische Stabilität von Acrylnitril-Copolymeren wurde mittels DSC untersucht, um den Einfluß von halogenierten Comonomeren mit Carboxygruppen auf die Stabilisierung von PAN zu präfen. Es wird gezeigt, daß die Aktivierungsenergie fär die Cyclisierung des AN/Bromacrylsäure(BrAA)-Copolymeren (86,2 kJ/mol) deutlich niedriger als die der Copolymeren mit Chloracrylsäure (ClAA, 158 kJ/mol), Acrylsäure (AA, 128 kJ/mol) und Itaconsäure (IA, 102 kJ/mol) ist. Das erlaubt eine Stabilisierung bei häherer Temperatur und eine Verkürzung der Stabilisierungszeit. ClAA ist BrAA bezäglich der Stabilisierungseffektivität nicht überlegen. Der Mechanismus der Cyclisierung von AN-Copolymeren mit halogenierten, carboxygruppenhaltigen Comonomeren wird diskutiert.
    Notes: The thermal stability of AN copolymers was studied by DSC technique in order to get information on the influence of comonomers containing halogenated carboxylic acid on the stabilization of PAN. It is shown that the activation energy of cyclization is reduced in the case of the copolymer with bromoacrylic acid (BrAA, 86.2 kJ/mol) compared with chloroacrylic acid (ClAA, 158 kJ/mol), acrylic acid (AA, 128 kJ/mol) and itaconic acid (IA, 102 kJ/mol). Copolymer AN/BrAA permits the stabilization at higher temperature than AN/IA and AN/AA, helping to shorten the stabilization time. It is proved that comonomer ClAA is not superior to BrAA in the effectiveness of thermal stabilization. The mechanism of the cyclization reaction of AN copolymer containing halogenated carboxylic acid is discussed.
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  • 71
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    Angewandte Makromolekulare Chemie 199 (1992), S. 75-85 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden neue unsymmetrische cycloaliphatische Bisepoxyderivative hergestellt. Die unterschiedliche Reaktionsfahigkeit der zwei Oxiranringe (cycloaliphatisch und glycidylisch) gegenüber Carbonsäure wurde untersucht, wobei eine normale und anomale Ringöffnung der Glycidylgruppen beobachtet wurde. Eine Homopolymerisation des Oxirans wurde ebenfalls beobachtet. Mit Hilfe der 13C-NMR-Spektroskopie wurde die Struktur der Polymeren ermittelt. Die neuen Epoxidharze zeigen gute thermische Eigenschaften.
    Notes: New bisepoxy unsymmetrical cycloaliphatic derivatives have been synthesized. The different reactivity of both oxirane rings (cycloaliphatic and glycidylic) has been tested against carboxylic acids giving rise to normal and abnormal opening to the glycidyl group. Homopolymerization reaction was also observed. Polymer structures were identified by 13C-NMR spectroscopy. Thermal analysis carried out allowed to confirm their good thermal properties.
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  • 72
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    Angewandte Makromolekulare Chemie 194 (1992), S. 119-131 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: N,N′-4,4′-Diphenylmethane-bismaleimide (BMI) was oligomerized in semisolid phenolnovolak epoxide-resin (EP) up to P̄n = 10. The morphology of the novolakcured EP-BMI solid resins is a two-phase structure. It consists in a homogeneous EP-BMI phase of an interpenetrating polymer network (IPN) and a BMI phase. The dynamic-mechanical properties depend on the overall weight fraction w2 of BMI and on the degree of oligomerization (P̄)n of BMI. The relative shear modulus of the EP-EMI resin in the rubber state shows that both phases can be coherent. The glass transition temperature (Tg) can be correlated with the degree of oligomerization of the BMI, for instance Δ P̄n ≡ 10 corresponds to Δ Tg ≡ 35 K and Δ wx2 ≡ 0,25 (weight fraction of BMI in the homogeneous EP-BMI phase). Surprisingly, the breaking strength remains constant.
    Notes: N,N′-4,4′-Diphenylmethan-bismaleimid (BMI) wurde in halbfesten Phenolnovolak-Epoxidharzen (EP) bis P̄, = 10 oligomerisiert. Die novolakgehärteten EP-BMI-Festharze bilden eine Zweiphasenstruktur, bestehend aus einer EP-BMI-Mischphase der beiden sich durchdringenden Netzwerke (interpenetrating polymer network, IPN) und einer BMI-Phase. Die dynamisch-mechanischen Eigenschaften hängen vom Gesamt-BMI-Anteil w2 und vom Oligomerisierungsgrad P̄n des BMI ab. Der relative Schubmodul des EP-BMI-Harzes im kautschukelastischen Zustand zeigt, daß beide Phasen kohärent sein können. Die Glastemperatur Tg korreliert mit dem Oligomerisierungsgrad, z. B. entspricht ΔPn ≡ 10 einem ΔTg ≡ 35 K und einem BMI-Anteil Δ wx2 ≡ 0,25 in der Mischphase. Die Bruchzahigkeit bleibt unerwartet konstant.
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  • 73
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Handelsübliche Araldit™-Polymere wurden mit Zimtsäure- bzw. Furanacrylsäurechlorid modifiziert und über [2 + 2]-Cycloaddition photochemisch vernetzt. Die Glasübergangstemperaturen der entstandenen Polymeren betragen bis zu 130°C bei Dielektrizitätskonstanten von ∊r = 3.0. Daher können diese Polymeren in Mehrlagenmikroverdrahtungen verwendet werden. Zahlreiche wohldefinierte, multifunktionelle Modifikatoren wurden synthetisiert und deren Einfluß auf die Polymerisation und die Eigenschaften der Araldit™-Polymeren eingehend untersucht.
    Notes: Commercially available Araldite™-type polymers have been modified with cinnamic and furan acrylic acid chlorides. The polymers were photochemically crosslinked via a [2 + 2] cycloaddition. The resulting polymers show glass transition temperatures up to 130°C and dielectrical constants of ∊r = 3.0. Therefore, these polymers can be applied as permanent resists in multi-layered wiring structures. Numerous well-defined multifunctional modifiers have been synthesized. The effect of those modifiers on the polymerization and properties of the araldite-type polymers has been studied in some detail.
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  • 74
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    Angewandte Makromolekulare Chemie 200 (1992), S. 61-76 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The photoinduced free radical crosslinking of silicone containing pendent acrylate or methacrylate groups was investigated by swelling measurements. A modified swelling test was applied to observe the network formation as a function of several parameters. The results show that the network density of the crosslinked polymers is a function of the light intensity, the exposure time, the acrylate content, the molecular weight of the uncrosslinked silicone acrylate and also of the length of the spacer group between the acrylate unit and the silicone backbone. Oxygen has only an influence on the polymerization kinetics, but it does not influence the network density.From the δB, -values of crosslinked silicone acrylates and silicone containing vinyl groups it is possible to analyze the structure of the network as a function of the olefinic group. The χ-parameters of both silicone types are of the same magnitude in the same concentration range.Kinetics investigations demonstrate that the order of the network formation is nearly unity. This result agrees with the polymerization kinetics.By means of swelling measurements it is also possible to study the influence of hydrogen siloxane additives as hydrogen transfer reagents.
    Notes: Die photoinduzierte radikalische Vernetzung von Siliconacrylaten bzw. -methacrylaten wurde mit Hilfe von Quellungsmessungen untersucht, wobei ein modifizierter Quellungstest erlaubt, die Netzwerkbildung als Funktion verschiedener Parameter zu betrachten. Die Ergebnisse zeigen, daß die Netzwerkdichte eine Funktion der Lichtintensität, der Bestrahlungszeit, des Acrylatgehalts, der Molmasse des unvernetzten Silicons und auch der Länge der Spacergruppe zwischen Acrylateinheit und dem Siliconrückgrat ist. Sauerstoff besitzt dagegen nur einen Einfluß auf die Polymerisationskinetik, nicht aber auf die Netzwerkdichte.Aus dem Vergleich der δB, -Werte der vernetzten Siliconacrylate und der vernetzten Vinylsilicone kann geschlossen werden, daß die Netzwerkstruktur auch vom Typ der olefinischen Gruppen abhängt. Die χ-Parameter besitzen jedoch im gleichen Konzentrationsbereich die gleiche Größe.Kinetische Untersuchungen zeigen, daß die Netzwerkbildung nach einem Zeitgesetz erster Ordnung verläuft. Dieses Ergebnis steht im Einklang mit der Polymerisationskinetik.Mit Hilfe der Quellexperimente ist es auch moglich, den Einfluß von H-Siloxanzusätzen als Wasserstoffüberträger zu untersuchen.
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  • 75
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    Angewandte Makromolekulare Chemie 194 (1992), S. 133-148 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The copolymerization of butadiene with a technical divinylbenzene fraction was investigated to study the modification of cis-1,4 polybutadiene. Beside the Ziegler-Natta-catalyst nickeloctanoate/bortrifluoride/aluminiumtriethyl, another catalytic system consisting of nickeloctanoate/titaniumtetrachloride/aluminiumtriethyl was used, which allows to polymerize more divinylbenzene because of its higher activity toward vinylaromates. With the help of spectroscopical, pyrolysis-gaschromatographical and thermoanalytical methods one can obtain relations between glass-, crystallization- and melting temperature and the microstructure of the polymer. It can be shown that not only the divinylbenzene but also the trans-1,4- and the 1,2-vinyl units are statistically distributed in the polymer. By this, beside the pyrolysis-gaschromatography, particularly the differential scanning calorimetry is a useful tool to characterize the structure of partially crosslinked polymers obtained from polymerization of technical fractions.
    Notes: Im Rahmen von Arbeiten zur Modifizierung des cis-1,6Polybutadiens wurde die Copolymerisation von Butadien und einer Divinylbenzolfraktion, insbesondere der Bereich mit kleinen Divinylbenzolgehalten, untersucht. Neben dem Ziegler-Natta-Katalysator Nickeloctanoat/Bortrifluoridetherat/Aluminiumtriethyl kam auch ein Nickeloctanoat/Titantetrachlorid/Aluminiumtriethyl-System zur Anwendung, welches es durch seine höhere Aktivität gegenüber Vinylaromaten ermöglicht, großere Mengen der Divinylbenzolfraktion zu polymerisieren. Durch die Anwendung von spektroskopischen, pyrolysegaschromatographischen und thermoanalytischen Charakterisierungsmethoden können Beziehungen zwischen den erhaltenen Glas-, Kristallisations- und Schmelztemperaturen und der Mikrostruktur des Polymeren hergestellt werden. Es zeigt sich, daß sowohl das Divinylbenzol als auch die trans-1,4 bzw. die 1,2-Vinyl-Einheiten statistisch in das Polymere eingebaut werden. Damit eignet sich neben der Pyrolysegaschromatographie besonders die Differential Scanning Calorimetry als eine einfache Methode zur Charakterisierung der Struktur von aus technischen Fraktionen erhaltenen und teilweise vernetzten Polymerproben.
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  • 76
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Optisch hochreine Gläser wurden aus Polystyrol (PS), Polymethylmethacrylat (PMMA) und statistischen Styrol-Methylmethacrylat-Copolymeren (S-MMA) hergestellt. Die an diesen Gläsern gemessene Lichtstreuung hängt von der chemischen Zusammensetzung des Polymeren und dem Brechungsindex des zugesetzten Weichmachers ab. Ein isorefraktiver Weichmacher verringert die Streuwerte der S-MMA-Copolymeren, hat aber keinen signifikanten Einfluß auf das Streuverhalten von PMMA. Ein Weichmacher mit einem vom Polymeren verschiedenen Brechungsindex verschlechtert die Streuwerte in allen untersuchten Fällen. Es wird gezeigt, daß ein isorefraktiver Weichmacher die Dämpfungseigenschaften von aus dem Copolymeren S-MMA 2/1 gezogenen polymeren Lichtleitern verbessert.
    Notes: High optical purity polystyrene (PS), poly(methyl methacrylate) (PMMA) and styrene-methyl methacrylate statistical copolymers (S-MMA) were prepared. Light scattering measured on polymeric glasses depends on the chemical composition of the polymer and on the refractive index of the plastifier added. An isorefractive plastifier reduces considerably the scattering values for the copolymers S-MMA, while having no significant effect on the scattering of PMMA. A plastifier with a refractive index different from that of the polymer raises distinctly the light scattering values in all cases. It has been shown that the isorefractive plastifier has a favourable effect on attenuation loss of polymeric optical fibers (POF) obtained from the copolymer S-MMA 2/1.
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  • 77
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: ABS/TPU- und SAN/TPU-blends were investigated on the basis of the analysis of viscoelastic behaviour of the components for characterization of the formation of morphology in melt mixing processes. Blends mixed in a laboratory kneeder and extruded from a high pressure capillary viscosimeter under definite conditions were characterized concerning their phase morphology by transmission electron microscopy. The types of morphology predicted by the help of rheological analysis could be confirmed by electron micrographs and quantitative analysis of morphology. It becomes evident, that the ratio of viscosity of the components has the primary influence on the formation of morphology in the blends. But also thermomechanically induced molecular destruction processes and thermodynamic interactions as well as connecting crystallisation conditions for the TPU-phase are not negligible with regard to resulting phase morphology.
    Notes: An ABS/TPU- bzw. SAN/TPU-Blends wurden Untersuchungen zur Morphologiebildung beim Schmelzemischen auf der Basis der Analyse des viskoelastischen Verhaltens der Komponenten angestellt. Unter definierten Bedingungen im Laborkneter gemischte und unter definierten Bedingungen mittels Hochdruckkapillarviskosimeter extrudierte Blendproben wurden hinsichtlich ihrer Phasenmorphologie elektronenmikroskopisch charakterisiert. Die mittels der rheologischen Analyse prognostizierten Morphologietypen und Morphologiebildungsmechanismen konnten anhand der elektronenmikroskopischen Aufnahmen und der quantitativen Morphologieanalyse bestätigt werden. Es zeigte sich, daß das Viskositätsverhältnis der Komponenten primären Einfluß auf die Morphologiebildung ausübt. Darüber hinaus sind auch thermomechanisch induzierte molekulare Abbauvorgänge und thermodynamische Wechselwirkungen sowie damit im Zusammenhang stehende Kristallisationsbedingungen für die TPU-Phase hinsichtlich der resultierenden Phasenmorphologie nicht zu vernachlässigen.
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  • 78
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    Angewandte Makromolekulare Chemie 194 (1992), S. 189-200 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Stabilität von Verbindungen von Polypropylen (PP) und Polycarbonat (PC) mit einem Acryl-Kleber wurde mit einer thermodynamischen, auf der Messung von Oberflächenspannungen beruhenden Methode bestimmt.Die Charakterisierung der Oberflächen zeigte, daß eine Plasmabehandlung die Bildung einer sauerstoffreichen Oberflächenschicht bewirkt. Eine Lagerung in Wasser führt bei PP zu keiner Veränderung dieser Schicht, während bei PC niedermolekulare, oxidierte Verbindungen ausgewaschen werden.Sowohl unbehandelte als auch mit Plasma behandelte PP-Verbindungen wiesen bei Lagerung in Wasser eine annehmbare Stabilität auf. Zwar wurde eine geringe Abnahme der Scherfestigkeit gemessen, aber unbehandeltes und plasmabehandeltes PP zeigten weiterhin adhäsives bzw. kohäsives Bruchverhalten.Im Falle von PC blieben nur die aus unbehandeltem PC hergestellten Verbindungen ausreichend stabil, während die aus plasmabehandeltem PC hergestellten Verbindungen stark abgebaut wurden. Bei den letzteren wanderte der Versagensort an die Polymer/Kleber-Grenzfläche, was auf die Ausbildung einer sehr hydrophilen, niedermolekularen Schicht zurückgeführt wird.
    Notes: The stability of PP and PC/acrylic adhesive joints has been assessed using a thermodynamic method based on surface tension components.Surface characterization showed that plasma treatment induces the formation of an oxygen-rich layer on treated surfaces. In the case of PP this layer does not change its composition upon immersion in water, while for PC leaching of oxidized species with low molecular weight was observed.Both untreated and plasma treated PP joints showed reasonable stability against immersion in water. A small reduction of shear strength was observed, but the fracture remained adhesive for untreated PP and cohesive for plasma treated PP.In the case of PC, only joints made from untreated PC showed fair sensitivity against immersion in water, while those made from plasma treated specimens degraded dramatically. In the latter case the locus of failure moved to the adhesive/adherend interface, the presence of a very hydrophilic, low molecular weight layer being suggested as responsible for this behavior.
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  • 79
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The chloromethylated polystyrenes bearing tetrathiafulvalenylcarbonyloxymethyl groups can be oxidized. We have shown that ion radical salts are obtained from these polymers and carbon tetrabromide after irradiation with UV light. Charge transfer complexes were prepared by mixing these polymers and 2,3-dichloro-5,6-dicyanobenzoquinone. The possible presence of sulfoxides as a result of oxidation of some tetrathiafulvalene units could explain the difficulties we have observed to filter solutions of these polymers.
    Notes: Les polystyrènes chlorométhylés renfermant des radicaux tétrathiafulvalénylcarbonyloxyméthyles peuvent être oxydés. Ainsi la formation de sels d'ions radicaux obtenus à partir de ces polymères et de tétrabromure de carbone, irradiés sous UV, a été mise en évidence. Des complexes de transfert de charge ont été préparés en mettant en présence ces polymères et de la 2,3-dichloro-5,6-dicyanobenzoquinone. La présence de sulfoxydes non décelés et résultant de l'oxydation de certaines unités de tetrathiafulvalène contenus dans ces polymères pourrait expliquer les problèmes rencontrés lors de la filtration de leurs solutions.
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  • 80
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Metallkomplexierung von wasserloslichem Poly[1-(2-hydroxyethyl)aziridin-co-2-methyl-2-oxazolin] mit Co(II), Zn(II), Ni(II), Cu(II), Cr(III), Fe(III), Cd(II), Pb(II) und Sr(II)-Ionen wurde in wäßriger Phase mit der Methode der Liquid-Phase Polymer-Based Retention (LPR) untersucht. Die Studie zeigt, daß alle Metallionen, außer Co(II) und Zn(II), bei pH 5 komplexiert wurden. Im Gegensatz zu Sr(II), das nur eine schwache Wechselwirkung in einem pH-Bereich von 3 bis 7 zeigte, wurden bei pH 7 94% Co(II) und 88% Zn(II) retentiert. Bei pH 3 zeigten nur Cu(II) und Cr(III) eine Wechselwirkung mit dem Polymeren, wobei die Retentionswerte 76% für Cu(II) und 52% für Cr(III) betrugen. Viskositätsmessungen des Copolymeren in Gegenwart von Metallionen wurden bei verschiedenen pH-Werten durchgeführt.
    Notes: The metal complexation of water-soluble poly[1-(2-hydroxyethyl)aziridine-co-2-methyl-2-oxazoline] with Co(II), Zn(II), Ni(II), Cu(II), Cr(III), Fe(III), Cd(II), Pb(II), and Sr(II) ions was investigated in aqueous phase using Liquid-Phase Polymer-Based Retention (LPR). The study shows that all metal ions are complexed at pH 5, except Co(II) and Zn(II). In contrast to Sr(II), which showed only a slight interaction over a pH range of 3 to 7, 94% of Co(II) and 88% of Zn(II) were retained at pH 7. At pH 3, only Cu(II) and Cr(III) ions interacted with the copolymer with retention values of 76% for Cu(II) and 52% for Cr(III). Viscosimetric measurements of the copolymer were performed in the presence of metal ions at different pH values.
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  • 81
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    Angewandte Makromolekulare Chemie 197 (1992), S. 117-129 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Makroretikulare Copolymerperlen wurden durch Suspensionspolymerisation von Styrol, Bis(2-chlorethyl)vinylphosphonat (CEVP) und Divinylbenzol (DVB) in Gegenwart von Toluol als Verdünnungsmittel hergestellt. Die auf der Perlenoberfläche vorhandenen 2-Chlorethylphosphonat-Gruppen wurden durch Hydrolyse mit verdünnter Salpetersäure in Phosphon-Gruppen transformiert. Für die Einführung zusätzlicher Phosphon-Gruppen wurden die Copolymeren in Gegenwart von Aluminiumchlorid-Katalysator mit Phosphortrichlorid phosphoryliert, und die dabei entstandenen Dichlorphosphingruppen wurden mit verdünnter Salpetersäure verseift und oxidiert. Die Untersuchungen zur Chelatbildung der Copolymeren mit Metallionen zeigten, daß sie ein hohes Adsorptionsvermögen für Uranylionen und gute Stabilität gegen Chemikalien wie Säuren und Alkalien aufweisen. Es wurde auch gefunden, daß die Phosphongruppen enthaltenden Copolymeren recht effektive Adsorbentien für eine Vielzahl von Schwermetalionen wie Pb2+, Hg2+, Cd2+ und Cu2+ sind.
    Notes: Macroreticular copolymer beads were prepared by suspension polymerization of styrene, bis(2-chloroethyl) vinyl phosphonate (CEVP) and divinylbenzene (DVB) in the presence of toluene as diluent. The bis(2-chloroethyl) phosphonate groups on the bead surface were converted into phosphono groups by hydrolysis with dilute nitric acid. For the additional enrichment of phosphono groups, the copolymers were phosphorylated at the phenyl rings with phosphorus trichloride in the presence of aluminum chloride and hydrolyzed and oxidized with dilute nitrics acid. The investigations on metal ion chelation characteristics of the bead-type copolymers revealed that they have very high adsorptivity toward uranyl ions and good chemical resistance under acidic and alkaline media. It was also found that the phosphono group-containing copolymer beads are effective adsorbents for other heavy metal ions such as Pb2+, Hg2+, Cd2+, and Cu2+.
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  • 82
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    Angewandte Makromolekulare Chemie 197 (1992), S. 131-139 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Lösungen von Phenylisocyanat (I) in DMF wurden sowohl bei verschiedenen Temperaturen als auch in Gegenwart von Polyurethankatalysatoren und/oder 1,3-Diphenylharnstoff (II) gelagert. Die Reaktionsprodukte wurden mit Hilfe der HPLC quantifiziert. Neben der Hydrolyse von I zu II wird bei 20°C eine signifikante Reaktion von I mit II zu 1,3,5-Triphenylbiuret (III) beobachtet.Oberhalb 60°C reagiert I mit dem Lösungsmittel zu N,N-Dimethyl-N′-phenylformamidin (V). In DMF dissoziiert III bereits bei Temperaturen 〉 40°C zu I und II.
    Notes: Solutions of phenylisocyanate (I) in DMF were stored at different temperatures in the presence of both polyurethane catalysts and 1,3-diphenylurea (II). The reaction products were determined by HPLC. Beside the hydrolysis of I to II, a significant reaction of I with II to 1,3,5-triphenylbiuret (III) was observed at 20°C. Above 60°C, I reacted with the solvent to form N,N-dimethyl-N′-phenylformamidine (V). In DMF, III dissociated to I and II already at temperatures 〉40°C.
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  • 83
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    Angewandte Makromolekulare Chemie 197 (1992), S. 141-147 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Glasfaserverstärkte Epoxidlaminate wurden aus den Matrixharzen Tetraglycidyldiaminodiphenylmethan (TGDDM) und Tetraglycidylbis(o-toluidino)methan (TGMBT) unter Verwendung von Härtern wie 4,4′-Diaminodiphenylmethan (DDM), 4,4′-Diaminodiphenylsulfon (DDS) und Diethylentriamin (DETA) hergestellt. Die mechanischen und dielektrischen Eigenschaften sowie die Chemikalienresistenz der Laminate wurden untersucht. Die Zugabe eines Epoxyverstärkers (20 Gew.-%, bezogen auf das Matrixharz) ergab eine Verbesserung der mechanischen Eigenschaften.
    Notes: Glass fiber-reinforced epoxy composites were prepared from the matrix resins tetraglycidyl diaminodiphenylmethaneSystematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-diaminodiphenylmethane. (TGDDM) and tetraglycidyl bis(o-toluidino)-methaneSystematic name: N,N,N′,N′-Tetrakis(2,3-epoxypropyl)-4,4′-bis(o-toluidino)methane. (TGMBT) using various amines like 4,4′-diaminodiphenylmethane (DDM), 4,4′-diaminodiphenylsulfone (DDS) and diethylene triamine (DETA) as curing agents. The fabricated laminates were evaluated for their mechanical and dielectrical properties and chemical resistance. The composites prepared using an epoxy fortifier (20 phr) showed significant improvement in the mechanical properties.
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  • 84
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    Angewandte Makromolekulare Chemie 197 (1992), S. 149-157 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: In 1 μm layers of different polymers containing 10 wt.-% 4,4′-diazidobiphenyl, the network formation under the influence of UV-irradiation was estimated by solvent treatment. The high activity of poly(glycidyl methacrylate) against the nitrenes formed is caused by its 1,2-epoxypropyl groups. As confirmed by IR-spectroscopy, the oxirane ring itself is not affected; NMR spectroscopic results indicate reactions between nitrenes and exocyclic CH2-groups.
    Notes: Die UV-Vernetzung in 1 μm-Schichten aus Polymeren verschiedener Konstitution, die 10 Gew.-% 4,4′-Diazidobiphenyl (DABP) enthalten, wird zeitabhängig anhand der reduzierten Schichtdicke nach Lösungsmittelbehandlung verglichen. Für die hohe Vernetzungsgeschwindigkeit von Polyglycidylmethacrylat mit den photolytisch gebildeten Bisnitrenen sind die 1,2-Epoxypropylgruppen verantwortlich. Der Oxiranring bleibt erhalten (IR-Spektroskopie). Wahrscheinlicher Reaktionsort ist die exocyclische CH2-Gruppe (13C-Festkörper-NMR-Spektroskopie).
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  • 85
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    Angewandte Makromolekulare Chemie 197 (1992), S. 159-173 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ausgehend von 10 unterschiedlich 4′-substituierten 4-[N,N-dihydroxyethyl]aminoazobenzolen wurden durch Umsetzung mit Hexamethylendiisocyanat polymere Azofarbstoffe (M̄n 4200-10200) synthetisiert und die Substituentenabhängigkeit der spektralen Eigenschaften, der Redoxpotentiale und des Ausbleichverhaltens mit entsprechenden monomeren und dimeren Modellverbindungen verglichen. Die Ausbleichung erfolgt durch einen photooxidativen Prozeß. In der Reihenfolge monomerer 〉 dimerer 〉 polymerer Azofarbstoff sinkt die Lichtstabilität durch die Verringerung thermischer Desaktivierungsprozesse sowie durch einen möglichen intramolekularen Energietransfer.
    Notes: Starting from 10 different 4′-substituted 4-[N,N-dihydroxyethyl]aminoazobenzenes, polymeric urethane-azo dyes (M̄n 42000-10200) were prepared by reacting those with hexamethylene diisocyanate. The dependence of spectral properties, redox potentials and photofading behaviour on the kind of substitutents was determined and then compared with corresponding monomer and dimer model compounds. Photofading is caused by a photooxidative process. In the sequence of monomeric 〉 dimeric 〉 polymeric azo dyes, light stability decreases due to a diminution in thermal disactivation processes and in a possible intramolecular energy transfer.
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    Angewandte Makromolekulare Chemie 197 (1992), S. 207-208 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 87
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    Angewandte Makromolekulare Chemie 197 (1992), S. 201-206 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Bead cellulose, particle diameter 0.1 - 2.7 mm, was prepared from dispersions of viscose in chlorobenzene by applying the thermal sol-gel transition. Technical viscose containing modifiers Berol Visco 32, Berol Glyco 1540 and Kordamin V was used. The size of cellulose beads can be controlled by means of the amount of oleic acid in the dispersion medium. The optimal result was reached at 5 - 6 mg oleic acid in 90 ml chlorobenzene.
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  • 88
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    Angewandte Makromolekulare Chemie 197 (1992), S. 185-199 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: PET- und PA 66-Textilien wurden unter normalen Bedingungen mit verschiedenen Dispersionsfarbstoffen gefärbt. Die gefärbten Textilien wurden mit 180 kV Elektronenstrahlung bestrahlt. Es wurde beobachtet, daß, verglichen mit den unbestrahlten Materialien, zunehmende Strahlungsdosen zu einer Zunahme des Gesamtfarbabstandes dE führten. Diese Farbunterschiede werden hauptsächlich von zwei Reaktionen verursacht: Erstens von der reversiblen Bildung von Farbstoffradikalen, die (an Luft) wieder zu den Ausgangsfarbstoffen reoxidiert werden können und zweitens durch die irreversible Reaktion von Farbstoffmolekülen mit dem Faserpolymeren. Die zweite Reaktion ruft eine permanente Farbänderung des Textils hervor, die bei entsprechenden Bestrahlungsbedingungen klein gehalten werden kann. Die Entscheidung, ob diese Veränderung toleriert werden kann, hängt von der weiteren Verwendung des Textils ab.
    Notes: PET and PA 66 fabrics were dyed with different disperse dyes under regular conditions. The dyed fabrics were irradiated with 180 kV electron radiation. It was observed that increasing radiation doses led to increasing total color differences dE if compared to the unirradiated materials.These color differences are mainly caused by two types of reactions. First by the reversible formation of dye radicals, which can be reoxidized (in air) to the original dye molecules, and second by the irreversible reaction of dye molecules with the fiber polymer. The latter reaction causes a permanent change of the color of the fabric, which can be kept low with the proper irradiation conditions. The decision whether or not this change can be tolerated depends on the further use of the textile.
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  • 89
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    Angewandte Makromolekulare Chemie 197 (1992), S. 175-184 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Unterschiedlich 4′-substituierte 4-[N-Ethyl-N-(2-acryloyloxy)ethyl]aminoazobenzole dienten als Ausgangsmonomere für Homopolymerisationen und Copolymerisationen mit Styrol und Methylmethacrylat. Die Photobleichung der erhaltenen polymeren Azofarbstoffe (M̄ 4200-9000) wurde mittels einer Xenotest-Apparatur untersucht und mit den entsprechenden Monomeren verglichen. Es wird angenommen, daß die in der Reihenfolge monomerer  -  copolymerisierter  -  homopolymerisierter Azofarbstoff sinkende Photostabilität durch zunehmenden Energietransfer in der Matrix verursacht wird.
    Notes: Different 4′-substituted 4-[N-ethyl-N-(2-acryloyloxy)ethyl]aminoazobenzenes were used as starting monomers for homopolymerization and copolymerization reactions with styrene and methyl methacrylate. The photofading behaviour of the obtained polymeric azo dyes (M̄n 4200 - 9000) was investigated by means of a Xenotest device and compared with that of the corresponding monomers. The decreased photostability in the order monomer  -  copolymer  -  homopolymer was assumed to be caused by an increasing energy transfer in the matrix.
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  • 90
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    Angewandte Makromolekulare Chemie 198 (1992), S. 31-38 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: N-Methacryloyloxyphthalimid und N-Methacryloyloxytetrabromphthalimid wurden durch Reaktion von Methacrylsäure bzw. Methacryloylchlorid mit N-Hydroxyphthalimid bzw. N-Hydroxytetrabromphthalimid hergestellt und homopolymerisiert. Die Austauschreaktionen der Polymeren mit Hydroxy- und Amin-Verbindungen wurden untersucht.
    Notes: N-Methacryloyloxyphthalimide (NMPI) and N-methacryloyloxytetrabromophthalimide (NMTPI) were prepared by the reaction of methacrylic acid with N-hydroxy-phthalimide and N-hydroxytetrabromophthalimide, respectively. The resulting monomers were polymerized. The reactions of the resulting polymers with hydroxy and amine compounds have been studied.
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  • 91
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    Angewandte Makromolekulare Chemie 198 (1992), S. 15-29 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das Tempern von Poly(etheretherketonketon) zwischen Glasübergangs- und Schmelztemperatur erzeugt normalerweise einen ausgeprägten Doppelschmelzpeak in der DSC-Kurve dieses Polymeren. Die eingehende Untersuchung dieses Doppelschmelzverhaltens in Abhängigkeit von Temperbedingungen und experimentellen Parametern zeigt, daß die Kristallisation als ein in zwei Stufen mit unterschiedlichen Zeitskalen ablaufender Prozeß beschrieben werden kann. Eine Rekristallisation als Ursache des Doppelpeaks kann widerlegt werden.
    Notes: Annealing poly(ether ether ketone ketone) (PEEKK) between glass transition and melting temperature generally results in a pronounced double peak melting behavior as obtained by DSC. Detailed investigations of the dependence of this double peak melting behavior on annealing conditions and experimental parameters clearly reveal that the crystallization can be described by a two-stage process occurring on different time scales. A recrystallization model as origin for the double peak melting curves can be disproved.
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  • 92
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    Angewandte Makromolekulare Chemie 198 (1992), S. 1-14 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Nitrilkautschuk (NBR) wurde mit trans-Chlorcarbonylbis(tripheny1phosphin)rhodium(1) [trans-RhCI(CO)(PPh3)2] und Hydridocarbonyltris(triphenylphosphin)rhodium(1) [RhH (CO)(PPh3)3] als Katalysatoren in homogener Lösung selektiv hydroformyliert. Bei der Hydroformylierung von NBR mit 40 mol-% Acrylnitril bei 363 K, 5,6 MPa Gasdruck (CO:H2 = 1:1) und mit 0,43 mmol Katalysator werden mit trans-RhCl(CO)(PPh3)2 25% und mit RhH (CO)(PPh3)3 30% Umsatz erreicht. Beide Reaktionen sind bezüglich der Olefin- und Katalysatorkonzentration pseudo-erster Ordnung. Mit RhH (CO)(PPh3)3 wird eine höhere Reaktionsgeschwindigkeit erhalten. Die IR- und NMR-spektroskopische Charakterisierung der Produkte zeigt, daß sowohl die 1,4- als auch die 1,2-Butadieneinheiten hydroformyliert werden. Mit steigendem Aldehydgruppengehalt sinkt die Grenzviskositatszahl [q] und steigt die Glastemperatur. Bei hoheren Hydroformylierungsgraden wird Gelbildung beobachtet.
    Notes: Selective homogeneous catalytic hydroformylation of nitrile rubber (NBR) has been carried out in presence of trans-chlorocarbonylbis(triphenylphosphine)rhodium(I) [trans-RhCl(CO)(PPh3)3] and hydridocarbonyltris(triphenylphosphine)rhodium(I) [RhH(CO)(PPh3)3] as catalysts. At 363 K, under 5.6 MPa pressure (CO:H2 = 1:1) in presence of 0.43 mmol/l catalyst, the amount of hydroformylation is 25% in the case of trans-RhCl(CO)(PPh3)2 and 30% in the case of RhH (CO)(PPh3)3 for NBR with 40 mol-% acrylonitrile. Reaction kinetics suggest that both the reactions are pseudo-first order with respect to olefinic substrate and catalyst concentration. The rate of the reaction is higher in the case of RhH(CO)(PPh3)3. The characterization of the products by IR and NMR spectroscopy shows the formation of internal aldehyde groups from 1,4-units and terminal branched aldehyde groups from 1,2-units of the copolymer. Measurements on intrinsic viscosity [η] and glass transition temperature (Tg) suggest a decrease in [η] and an increase in Tg with the degree of formyl functionalization. Gel formation has been observed at higher degree of hydroformylation.
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    Angewandte Makromolekulare Chemie 198 (1992), S. 61-70 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Komplexierung von Rhenium in einer polymeren Methacrylat-Matrix mit funktionellen Diethylentriaminpentaessigsäure-Gruppen wurde untersucht. Es werden diamagnetische Komplexe gebildet, wobei Rhenium in einer heterogenen Koordinationssphäre gebunden wird, bestehend aus Chlor und mehrfach gebundenem Sauerstoffsowie Carboxygruppen, die als einzige funktionelle Gruppe des polymeren Trägers als Ligand des Metallatoms wirken. Die Rhenium-Komplexe wurden durch IR- und UV-VIS-Spektroskopie sowie durch Messung ihrer magnetischen Momente charakterisiert.
    Notes: The bonding of rhenium to diethylenetriaminepentaacetic acid functional groups of a polymeric methacrylate matrix was studied. Diamagnetic complexes were formed of Re(V) with the heterogeneous coordination sphere containing atoms of chlorine and multiply bonded oxygen in addition to carboxylic groups, which are the only groups of the polymeric support functioning as ligands in the bonding to the metal. The rhenium complexes were examined by IR and UV-VIS spectroscopy and by magnetic moment measurements.
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  • 94
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 51-60 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Meta-halogenierte Phenole sind bekanntermaßen chemisch und thermisch stabiler als ihre ortho- oder para-halogenierten Analoga. Die Verwendung eines reaktiven Zwischenproduktes, hergestellt durch Bromierung von 2,4,6-Trimethylphenol, als Alkylierungsmittel für den Einbau der stabilen m-Bromphenol-Einheit in verschiedene organische Substanzen und Polymere wird beschrieben. Bei der Anwendung als Verkapselungsmaterialien für elektronische Bauteile zeigten sich Epoxid-Derivate von Novolaken mit m-Bromphenol-Einheiten bezüglich hydrolytischer und thermischer Stabilität den konventionellen Tetrabrombisphenol-A-Epoxidharzen, die ortho- und para-bromiert sind, überlegen. Die m-Bromphenolgruppe verbessert die Bauteilzuverlässigkeit bei gleichzeitiger Erfüllung der Anforderungen an das Brandverhalten.
    Notes: Meta-halogenated phenols are generally known to be more chemically and thermally stable than their ortho- or para-halogenated counterparts. A reactive intermediate, produced by the bromination of 2,4,6-trimethylphenol is being used as an alkylating agent to incorporate this stable m-bromophenol moiety into varieties of organic compounds and polymers. In electronic encapsulation applications, epoxy derivatives of novolacs containing m-bromophenol have exhibited superior hydrolytic and thermal stability as compared with the conventional tetrabromo bisphenol-A epoxies which are ortho-brominated phenolics. The m-bromophenol moiety contributes to the extended device reliability while meeting flame retardency requirements as well.
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  • 95
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Additionspolymere aus Bisphenol-A und Epichlorhydrin lassen sich mit Arylacryloylchloriden verestern. Die gebildeten Photoresists können mit UV-Licht (λ ≥ 280 nm) gehärtet werden. Aus FT-IR Messungen ergibt sich, daß die Netzwerkbildungsreaktion einem Zeitgesetz zweiter Ordnung gehorcht. DSC- und TGA-Messungen wurden durchgeführt. Die photovernetzten Polymeren weisen Glastemperaturen bis zu 171 °C auf und sind bis mindestens 350 °C thermisch stabil. Spektroskopische Daten werden aufgeführt.
    Notes: Addition polymers of bisphenol-A and epichlorohydrin can easily be esterified with aryl acryloyl chlorides to yield photosensitive polymers. The photoresists are curable with UV-irradiation (λ ≥ 280 nm). FT-IR measurements indicate that the network formation fonforms to second order kinetics. DSC and TGA measurements were carried out. The glass transition temperature of irradiated material is up to 171oC; the material is thermally stable up to 350oC. Spectral data are given.
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  • 96
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 39-49 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wird eine Ultraschall-Meßmethode vorgestellt, mit der sich fünf voneinander unäbhangige Elästizitatskonstanten von uniaxial symmetrischem Material bestimmen lassen. Für die Messung werden nur fünf Ultraschallausbreitungsgeschwindigkeiten benötigt. Vermessen wurden spritzgegossene Composite aus Polyphenylensulfid, Polyarylethersulfon mit Cardo-Seitengruppen, kurzen Kohlefasern und RUB. Die Ergebnisse zeigen eine enge Beziehung zwischen den elastischen Eigenschaften und der Struktur der Materialien auf.
    Notes: The paper makes an approach to the determination of the five independent elastic constants of uniaxial symmetric material with the ultrasonic immersion technique. Only five ultrasonic wave velocities are required during measurement. The elastic constants of the moulded composites comprised of poly(phenylene sulfide), poly(aryl ether sulfone) with cardo side groups, short carbon fiber and carbon black are measured by using the suggested treatment. The results exhibit a close relationship between the elastic properties and the structure of the materials.
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  • 97
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 83-89 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Membranen aus interpenetrierenden Netzwerken (IPN) wurden auf ihre Eignung für die Anwendung als Piezodialyse-Membranen untersucht. Bei diesen IPN-Membrane? handelt es sich nicht um Mosaik-Membranen. Bei zwei der IPN-Membranen enthielten die Permeate eine höhere NaCl-Konzentration als die Ausgangslösung (differentialrefraktometrisch bestimmt). Für eine dieser Membranen wurden die Salzgehalte auchtitrimetrisch mit AgNO3 ermittelt; die Ergebnisse belegen den positiven Piezodialyse-Effekt.
    Notes: In the present study, interpenetrating polymer network (IPN) membranes were investigated for their potential application as piezodialysis membranes. These IPN membranes are not mosaic membranes. It was found that some of these membranes did show piezodialysis effects. Two of the membranes tested under high pressure gave permeates which were found to be more concentrated in sodium chloride than the initial feed solution, when analyzed by differential refractometry. The permeates from one membrane were double checked by titrating the chloride ion with silver nitrate solution. The results of the titration also indicated a positive effect.
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  • 98
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    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 91-110 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurden Untersuchungen zum Flüssig-Dampf- und Flüssig-Fliissig-Gleichgewicht in Mischungen aus den Monomeren Ethen, 1-Buten, 4-Methyl-1 -penten und einem Polyethylenwachs bei mittleren Drücken durchgeführt. Auf der Basis der Chain-of-Rotators (COR) Zustandsgleichung, die mit einem Gruppenbeitragsmodell modifiziert wurde, wurden die Phasendiagramme der binaren und ternären Subsysteme sowie für das quaternare Gesamtsystem berechnet. Die Berechnungen ergeben eine zufriedenstellende Beschreibung des Flussig-Dampf-Gleichgewichtes und dessen Überlappung mit einem Flüssig-Flussig-Gleichgewicht bei höheren Drücken und Temperaturen. Die Mischungslücken in den beiden Systemen aus dem Polyethylenwachs mit 1 -Buten bzw. 4-Methyl-1 -penten werden auch nach Zugabe von Ethen zu den binären Mischungen beobachtet. Die Berechnungen zeigen ein kleines Dreiphasengebiet in allen entsprechenden ternären Mischungen. Eine Flüssig-Flüssig-Mischungslücke, die das Flüssig-Dampf-Gebiet schneidet, wird auch im quäternaren Gesamtsystem durch die Berechnungen mit dem modifizierten COR-Model1 gefunden. Diese doch überraschend komplizierten Phasenverhältnisse rnüssen bei der Abscheidung der Monomeren nach dem Syntheseschritt ausreichend beachtet werden.
    Notes: Some measurements of the vapour-liquid and/or the demixing equilibrium at moderate pressures were carried out in systems containing the monomers ethene, 1-butene, 4-methyl-1-pentene and a polyethylene wax. A group-contribution-modified chain-of-rotators (COR) equation of state was used to calculate the phase diagrams in all binary and ternary subsystems and in the whole quarternary mixture. The calculations lead to a satisfying description of the vapour-liquid equilibrium and its intersection by a liquid-liquid region at higher pressures and temperatures. The miscibility gaps in both mixtures of the polyethylene wax with 1-butene and 4-methyl-1-pentene, respectively, were observed again after adding ethene to these binary mixtures. The calculations indicate a small three phase triangle in all corresponding ternary mixtures. A liquid-liquid demixing region intersecting the vapour-liquid surface could also be found in the whole quaternary system by calculation with the modified COR model. This surprisingly complicated phase behaviour has properly to be taken into account during the separation of the monomers after the co- or terpolymerization process.
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 198 (1992), S. 111-122 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Optisch aktives (+)-2-endo-Acetoxy-5-endo-bornylmethacrylat (ABMA) wurde aus (+)-Campher hergestellt und in Benzol radikalisch homo- bzw. mit achiralem Methyl-methacrylat (MMA) bzw. Styrol (St) copolymerisiert. Der EinfluB von Temperatur und Reaktionszeit auf den Polymerisationsverlauf wird diskutiert. Die Copolymerisations-parameter (r1 und r2, nach Fineman-Ross) für Poly(ABMA-co-MMA) und Poly(ABMA-co-St) sowie die Q- und e-Werte für ABMA wurden berechnet.Der Absolutwert der spezifischen Drehung von Poly(ABMA-co-MMA) nimmt mit steigendem ABMA-Gehalt im Copolymeren zu. Eine geringe Abweichung von der Linearität deutet darauf hin, daß die Copolymerhauptkette nicht asymmetrisch ist. Aus der Temperatur- und Löjsungsmittelabhangigkeit der spezifischen Drehung der beschriebenen Homo- und Copolymeren laßt sich schlierjen, daß diese nicht in einer speziellen helikalen Konformation vorliegen. Die Eignung der chiralen Polymeren als Katalysatoren für die asymmetrische Addition von Butyllithium an verschiedene Aldehyde in Abhängigkeit von der Temperatur wurde untersucht.
    Notes: Optically active (+)-2-endo-acetoxy-5-endo-bornyl methacrylate (ABMA) was prepared from (+)-camphor. The free-radical homopolymerization of ABMA and its copolymerization with achiral methyl methacrylate (MMA) or styrene (St) were carried out with 2,2′-azoisobutyronitrile in benzene. Effects of temperature and reaction time on the copolymerization were discussed. The monomer reactivity ratios (r1, r2) for poly(ABMA-co-MMA) and poly(ABMA-co-St) as well as Q and e values for the chiral ABMA in the copolymerization systems were evaluated by the Fineman-Ross method. It was found that the absolute value of the specific rotation of poly(ABMA-co-MMA) increased with increasing ABMA unit content. A small deviation from linearity was observed, which suggests that asymmetry is not introduced into the copolymer main chain. Temperature and solvent effects on the specific rotation of the chiral homopolymer and copolymers were investigated. The results suggest that the chiral polymers synthesized in this investigation did not show a strong preference for a particular helical conformation. Applications of the chiral polymers on the asymmetric addition of n-butyllithium to aldehydes were investigated. The effect of temperature and aldehydes on the asymmetric addition were also discussed.
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  • 100
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Verschiedene α-oxoethylierte und α-hydroxyethylierte Styrol-Divinylbenzol-Copolymere (St-DVB) mit Unterschieden in Vernetzungsgrad und Porosität wurden hergestellt und auf ihre Eignung als Adsorbentien für ein nichtionisches Detergens (Nonaethylenglycol-mono-nonylphenylether) untersucht. Die durch Einführung der α-Hydroxy-ethylgruppen erreichte Verbesserung der Adsorptionskapazität war in den wenig vernetzten Harzen beträchtlich. Die mit 10 Vo1.-% DVB in Gegenwart von 100-120 Vo1.-% 2,2,4-Trimethylpentan hergestellten α-hydroxyethylierten Harze wiesen das höchste Adsorptionsvermögen auf, das sowohl von der Makroporosität als auch der Gelporosität abhängt. Die Anwendung der Harze als Säulenmaterial wurde geprüft und ihre Adsorptionseigenschaft als “Durchbruch”-Kapazität ermittelt.
    Notes: Several α-oxoethylated and α-hydroxyethylated styrene-divinylbenzene (St-DVB) resins having different degrees of crosslinking and porosity were prepared and their adsorption behaviour toward a nonionic surfactant, decaethyleneglycol nonylphenyl monoether, was investigated. The increment of the adsorption capacity caused by the introduction of the α-hydroxyethyl groups was remarkable in the less crosslinked resin. The α-hydroxyethylated resin derived from the St-DVB resin synthesized with 10 vol.-% DVB and 100 - 120 vol.-% of 2,2,4-trimethylpentane showed the highest capacity among the resins tested. The significance of both macroporosity and gel porosity in the effective adsorption of the nonionic surfactant was elucidated. A column operation using proposed resins was carried out and versatility was evaluated in terms of the breakthrough capacity.
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