Le reologia dei leganti bituminosi stradali: studio delle proprietà meccaniche a seguito di processi di “aging” in laboratorio

Lo studio effettuato pone le sue basi sulla ricerca di materiali stradali che combinino ad elevati standard prestazionali, la riduzione dell’impatto ambientale in fase realizzativa e manutentiva. In particolare il seguente lavoro si occupa dello studio di 7 leganti modificati con polimeri ed additivati con cere. I primi infatti conferiscono alla miscela maggiore elastoplasticità, incrementandone la durabilità e la resistenza a fatica. Nei secondi la presenza del materiale paraffinico contribuisce a ridurre la viscosità del bitume, consentendo un notevole abbassamento della temperatura di produzione e stesa della miscela. Numerosi studi hanno dimostrato che le caratteristiche meccaniche della pavimentazione sono fortemente influenzate dal grado di ossidazione delle componenti organiche del bitume, ovvero dal fenomeno dell’invecchiamento o aging. Pertanto allo studio reologico del bitume, si sono affiancate prove di simulazione dell’ invecchiamento nel breve e lungo termine. In fase di ricerca sperimentale si sono analizzati i leganti modificati ed additivati secondo la teoria della viscoelasticità, simulando le reali condizioni di carico ed invecchiamento alle quali il bitume è sottoposto. Tutte le prove di caratterizzazione reologica avanzata sono state effettuate mediante l’utilizzo del DSR (Dynamic Shear Rheometer - UNI EN 14770 ) in varie configurazioni di prova e l’invecchiamento a breve termine è stato simulato mediante RTFOT (Rolling thin film oven test -UNI EN 12607-1). Si è proposto inoltre una nuova procedura di aging invecchiando il bitume alla temperatura di Twork, ovvero a quel valore della temperatura tale per cui, in fase di messa in opera, si avrà una distribuzione molecolare omogenea del modificante all’interno del bitume.

Structure property relations in complex copolymer systems

A thorough investigation was made of the structure-property relation of well-defined statistical, gradient and block copolymers of various compositions. Among the copolymers studied were those which were synthesized using isobornyl acrylate (IBA) and n-butyl acrylate (nBA) monomer units. The copolymers exhibited several unique properties that make them suitable materials for a range of applications. The thermomechanical properties of these new materials were compared to acrylate homopolymers. By the proper choice of the IBA/nBA monomer ratio, it was possible to tune the glass transition temperature of the statistical P(IBA-co-nBA) copolymers. The measured Tg’s of the copolymers with different IBA/nBA monomer ratios followed a trend that fitted well with the Fox equation prediction. While statistical copolymers showed a single glass transition (Tg between -50 and 90 ºC depending on composition), DSC block copolymers showed two Tg’s and the gradient copolymer showed a single, but very broad, glass transition. PMBL-PBA-PMBL triblock copolymers of different composition ratios were also studied and revealed a microphase separated morphology of mostly cylindrical PMBL domains hexagonally arranged in the PBA matrix. DMA studies confirmed the phase separated morphology of the copolymers. Tensile studies showed the linear PMBL-PBA-PMBL triblock copolymers having a relatively low elongation at break that was increased by replacing the PMBL hard blocks with the less brittle random PMBL-r-PMMA blocks. The 10- and 20-arm PBA-PMBL copolymers which were studied revealed even more unique properties. SAXS results showed a mixture of cylindrical PMBL domains hexagonally arranged in the PBA matrix, as well as lamellar. Despite PMBL’s brittleness, the triblock and multi-arm PBA-PMBL copolymers could become suitable materials for high temperature applications due to PMBL’s high glass transition temperature and high thermal stability. The structure-property relation of multi-arm star PBA-PMMA block copolymers was also investigated. Small-angle X-ray scattering revealed a phase separated morphology of cylindrical PMMA domains hexagonally arranged in the PBA matrix. DMA studies found that these materials possess typical elastomeric behavior in a broad range of service temperatures up to at least 250°C. The ultimate tensile strength and the elastic modulus of the 10- and 20-arm star PBA-PMMA block copolymers are significantly higher than those of their 3-arm or linear ABA type counterparts with similar composition, indicating a strong effect of the number of arms on the tensile properties. Siloxane-based copolymers were also studied and one of the main objectives here was to examine the possibility to synthesize trifluoropropyl-containing siloxane copolymers of gradient distribution of trifluoropropyl groups along the chain. DMA results of the PDMS-PMTFPS siloxane copolymers synthesized via simultaneous copolymerization showed that due to the large difference in reactivity rates of 2,4,6-tris(3,3,3-trifluoropropyl)-2,4,6-trimethylcyclotrisiloxane (F) and hexamethylcyclotrisiloxane (D), a copolymer of almost block structure containing only a narrow intermediate fragment with gradient distribution of the component units was obtained. A more dispersed distribution of the trifluoropropyl groups was obtained by the semi-batch copolymerization process, as the DMA results revealed more ‘‘pure gradient type’’ features for the siloxane copolymers which were synthesized by adding F at a controlled rate to the polymerization of the less reactive D. As with trifluoropropyl-containing siloxane copolymers, vinyl-containing polysiloxanes may be converted to a variety of useful polysiloxane materials by chemical modification. But much like the trifluoropropyl-containing siloxane copolymers, as a result of so much difference in the reactivities between the component units 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane (V) and hexamethylcyclotrisiloxane (D), thermal and mechanical properties of the PDMS-PMVS copolymers obtained by simultaneous copolymerization was similar to those of block copolymers. Only the copolymers obtained by semi-batch method showed properties typical for gradient copolymers.

Physico-chemical and microstructural properties of food dispersions

The macroscopic properties of oily food dispersions, such as rheology, mechanical strength, sensory attributes (e.g. mouth feel, texture and even flavour release) and as well as engineering properties are strongly determined by their microstructure, that is considered a key parameter in the understanding of the foods behaviour . In particular the rheological properties of these matrices are largely influenced by their processing techniques, particle size distribution and composition of ingredients. During chocolate manufacturing, mixtures of sugar, cocoa and fat are heated, cooled, pressurized and refined. These steps not only affect particle size reduction, but also break agglomerates and distribute lipid and lecithin-coated particles through the continuous phase, this considerably modify the microstructure of final chocolate. The interactions between the suspended particles and the continuous phase provide information about the existing network and consequently can be associated to the properties and characteristics of the final dispersions. Moreover since the macroscopic properties of food materials, are strongly determined by their microstructure, the evaluation and study of the microstructural characteristics, can be very important for a through understanding of the food matrices characteristics and to get detailed information on their complexity. The aim of this study was investigate the influence of formulation and each process step on the microstructural properties of: chocolate type model systems, dark milk and white chocolate types, and cocoa creams. At the same time the relationships between microstructural changes and the resulting physico-chemical properties of: chocolate type dispersions model systems dark milk and white chocolate were investigated.

Synthesis and application of stimuli responsive tunable systems based on physical interactions

Novel single step synthetic procedure for hydrophobically modified alkali soluble latexes (HASE) via a miniemulsion-analogous method is presented. This facile method simplifies the copolymerization of the monomers with basically “opposite” character in terms of their hydrophilic/hydrophobic nature, which represent one of the main challenges in water based systems. Considered systems do not represent classical miniemulsions due to a high content of water soluble monomers. However, the polymerization mechanism was found to be rather similar to miniemulsion polymerization process.rnThe influence of the different factors on the system stability has been investigated. The copolymerization behavior studies typically showed strong composition drifts during copolymerization. It was found that the copolymer composition drift can be suppressed via changing the initial monomer ratio.rnThe neutralization behavior of the obtained HASE systems was investigated via potentiometric titration. The rheological behavior of the obtained systems as a function of the different parameters, such as pH, composition (ultrahydrophobe content) and additive type and content has also been investigated.rnDetailed investigation of the storage and loss moduli, damping factor and the crossover frequencies of the samples showed that at the initial stages of the neutralization the systems show microgel-like behavior.rnThe dependence of the rheological properties on the content and the type of the ultrahydrophobe showed that the tuning of the mechanical properties can be easily achieved via minor (few percent) but significant changes in the content of the latter. Besides, changing the hydrophobicity of the ultrahydrophobe via increasing the carbon chain length represents another simple method for achieving the same results.rnThe influence of amphiphilic additives (especially alcohols) on the rheological behavior of the obtained systems has been studied. An analogy was made between micellation of surfactants and the formation of hydrophobic domains between hydrophobic groups of the polymer side chain.rnDilution induced viscosity reduction was investigated in different systems, without or with different amounts or types of the amphiphilic additive. Possibility of the controlled response to dilution was explored. It was concluded that the sensitivity towards dilution can be reduced, and in extreme cases even the increase of the dynamic modulus can be observed, which is of high importance for the setting behavior of the adhesive material.rnIn the last part of this work, the adhesive behavior of the obtained HASE systems was investigated on different substrates (polypropylene and glass) for the standard labeling paper. Wet tack and setting behavior was studied and the trends for possible applications have been evaluated.rnThe novel synthetic procedure, investigation of rheological properties and the possibility of the tuning via additives, investigated in this work create a firm background for the development of the HASE based adhesives as well as rheology modifiers with vast variety of possible applications due to ease of tuning the mechanical and rheological properties of the systems.

Investigation into the enhancement of polycarbonate with conductive nanomaterials

Polymers are typically electrically and thermally insulating materials. The electrical and thermal conductivities of polymers can be increased by the addition conductive fillers such as carbons. Once the polymer composites have been made electrically and thermally conductive, they can be used in applications where these conductivities are desired such as electromagnetic shielding and static dissipation. In this project, three carbon nanomaterials are added to polycarbonate to enhance the electrical and thermal conductivity of the resulting composite. Hyperion Catalysis FIBRILs carbon nanotubes were added to a maximum loading of 8 wt%. Ketjenblack EC-600 JD carbon black was added to a maximum loading of 10 wt%. XG Sciences xGnP™ graphene nanoplatelets were added to a maximum loading of 15 wt%. These three materials have drastically different morphologies and will have varying effects on the various properties of polycarbonate composites. It was determined that carbon nanotubes have the largest effect on electrical conductivity with an 8 wt% carbon nanotube in polycarbonate composite having an electrical conductivity of 0.128 S/cm (from a pure polycarbonate value of 10-17 S/cm). Carbon black has the next largest effect with an 8 wt% carbon black in polycarbonate composite having an electrical conductivity of 0.008 S/cm. Graphene nanoplatelets have the least effect with an 8 wt% graphene nanoplatelet in polycarbonate having an electrical conductivity of 2.53 x 10-8 S/cm. Graphene nanoplatelets show a significantly higher effect on increasing thermal conductivity than either carbon nanotubes or carbon black. Mechanically, all three materials have similar effects with graphene nanoplatelets being somewhat more effective at increasing the tensile modulus of the composite than the other fillers. Carbon black and graphene nanoplatelets show standard carbon-filler rheology where the addition of filler increases the viscosity of the resulting composite. Carbon nanotubes, on the other hand, show an unexpected rheology. As carbon nanotubes are added to polycarbonate the viscosity of the composite is reduced below that of the original polycarbonate. It was seen that the addition of carbon nanotubes offsets the increased viscosity from a second filler, such as carbon black or graphene nanoplatelets.

Three-Dimensional Mechanics of Yakutat Convergence in the Southern Alaskan Plate Corner

Three-dimensional numerical models are used to investigate the mechanical evolution of the southern Alaskan plate corner where the Yakutat and the Pacific plates converge on the North American plate. The evolving model plate boundary consists of Convergent, Lateral, and Subduction subboundaries with flow separation of incoming material into upward or downward trajectories forming dual, nonlinear advective thermal/mechanical anomalies that fix the position of major subaerial mountain belts. The model convergent subboundary evolves into two teleconnected orogens: Inlet and Outlet orogens form at locations that correspond with the St. Elias and the Central Alaska Range, respectively, linked to the East by the Lateral boundary. Basins form parallel to the orogens in response to the downward component of velocity associated with subduction. Strain along the Lateral subboundary varies as a function of orogen rheology and magnitude and distribution of erosion. Strain-dependent shear resistance of the plate boundary associated with the shallow subduction zone controls the position of the Inlet orogen. The linkages among these plate boundaries display maximum shear strain rates in the horizontal and vertical planes where the Lateral subboundary joins the Inlet and Outlet orogens. The location of the strain maxima shifts with time as the separation of the Inlet and Outlet orogens increases. The spatiotemporal predictions of the model are consistent with observed exhumation histories deduced from thermochronology, as well as stratigraphic studies of synorogenic deposits. In addition, the complex structural evolution of the St Elias region is broadly consistent with the predicted strain field evolution. Citation: Koons, P. O., B. P. Hooks, T. Pavlis, P. Upton, and A. D. Barker (2010), Three-dimensional mechanics of Yakutat convergence in the southern Alaskan plate corner, Tectonics, 29, TC4008, doi: 10.1029/2009TC002463.

Buckling Rate and Overhang Development at a Calving Face

Using the finite-element we have modeled the stress field near the calving face of an idealized tidewater glacier under a variety of assumptions about submarine calving-face height, subaerial calving-face height, and ice rheology These simulations all suggest that a speed maximum should be present at the calving face near the waterline. In experiments without crevassing, the decrease in horizontal velocity above this maximum culminates in a zone of longitudinal compression at the surface somewhat Up-glacier from the face. This zone of compression appears to be a consequence of the non-linear rheology of ice. It disappears when a linear rheology is assumed. Explorations of the near-surface stress field indicate that when pervasive crevassing of the surface ice is accounted for in the simulations (by rheological softening), the zone of compressive strain rates does not develop. Variations in the pattern of horizontal velocity with glacier thickness support the contention that calving rates should increase with water depth at the calving face. In addition, the height of the subaerial calving face may have an importance that is not visible ill Current field data owing to the lack of variation in height of such faces in nature. Glaciers with lower calving faces may not have sufficient tensile stress to calve actively, while tensile stresses in simulated higher faces are sufficiently high that such faces will be unlikely to build in nature.

Sliding of Ice Past an Obstacle at Engabreen, Norway

At Engabreen, Norway, an instrumented panel containing a decimetric obstacle was mounted flush With the bed surface beneath 210 m of ice. Simultaneous measurements of normal and shear stresses, ice velocity and temperature were obtained as dirty basal ice flowed past the obstacle. Our measurements were broadly consistent with ice thickness, flow conditions and bedrock topography near the site of the experiment. Ice speed 0.45 m above the bed was about 130 mm d(-1), much less than the surface velocity of 800 mm d(-1) Average normal stress on the panel was 1.0-1.6 MPa, smaller than the expected ice overburden pressure. Normal stress was larger and temperature was lower on the stoss side than on the lee side, in accord with flow dynamics and equilibrium thermodynamics. Annual differences in normal stresses were correlated with changes in sliding speed and ice-flow direction. These temporal variations may have been caused by changes in ice rheology associated with changes in sediment concentration, water content or both. Temperature and normal stress were generally correlated, except when clasts presumably collided with the panel. Temperature gradients in the obstacle indicated that regelation was negligible, consistent with the obstacle size. Melt rate was about 10% of the sliding speed. Despite high sliding speed, no significant ice/bed separation was observed in the lee of the obstacle. Frictional forces between sediment particles in the ice and the panel, estimated from Hallet's (1981) model, indicated that friction accounted for about 5% of the measured bed-parallel force. This value is uncertain, as friction theories are largely untested. Some of these findings agree with sliding theories, others do not.

Controls on the Basal Water Pressure in Subglacial Channels Near the Margin of the Greenland Ice Sheet

Assuming a channelized drainage system in steady state, we investigate the influence of enhanced surface melting on the water pressure in subglacial channels, compared to that of changes in conduit geometry, ice rheology and catchment variations. The analysis is carried out for a specific part of the western Greenland ice-sheet margin between 66 degrees N and 66 degrees 30' N using new high-resolution digital elevation models of the subglacial topography and the ice-sheet surface, based on an airborne ice-penetrating radar survey in 2003 and satellite repeat-track interferometric synthetic aperture radar analysis of European Remote-sensing Satellite 1 and 2 (ERS-1/-2) imagery, respectively. The water pressure is calculated up-glacier along a likely subglacial channel at distances of 1, 5 and 9 km from the outlet at the ice margin, using a modified version of Rothlisberger's equation. Our results show that for the margin of the western Greenland ice sheet, the water pressure in subglacial channels is not sensitive to realistic variations in catchment size and mean surface water input compared to small changes in conduit geometry and ice rheology.

Ultimate and failure strengths of normal muds and serpentinite muds of ODP Leg 125 samples

Serpentinite seamounts in the Mariana forearc have been explained as diapirs rising from the Benioff zone. This hypothesis predicts that the serpentinites should have low strengths as well as low densities relative to the surrounding rocks. Drilling during Leg 125 showed that the materials forming Conical Seamount in the Mariana forearc and Torishima Forearc Seamount in the Izu-Bonin forearc are water-charged serpentinite muds of density <2 g/cm**3. Wykeham-Farrance torsion-vane tests showed that they are plastic solids with a rheology that bears many similarities to the idealized Cam clay soil model and is well described by critical-state soil mechanics. The serpentinite muds have ultimate strengths of 1.3 to 273.7 kPa and yield strengths of approximately 1.0 to 50 kPa. These muds thus are orders of magnitude weaker than salt and are, in fact, comparable in density and strength to common deep-sea clay muds. Such weak and low-density materials easily become diapiric. Serpentinite muds from the summit of Conical Seamount are weaker and more ductile than those on its flanks or on Torishima Forearc Seamount. Moreover, the summit muds do not contain the pronounced pure- and simple-shear fabrics that characterize those on the seamount flanks. The seamounts are morphologically similar to shield volcanoes, and anastomosing serpentinite debris flows descending from their summits are similar in map view to pahoehoe flows. These morphologic features, together with the physical properties of the muds and their similarities to other oceanic muds and the geochemistry of the entrained waters, suggest that many forearc serpentinite seamounts are gigantic (10-20 km wide, 1.5-2.0 km high) mud volcanoes that formed by the eruption of highly liquid serpentinite muds. Torishima Forearc Seamount, which is blanketed by more ìnormalî pelagic/volcaniclastic sediment, has probably been inactive since the Miocene. Conical Seamount, which seems to consist entirely of serpentinite mud and is venting fresh water of unusual chemistry from its summit, is presently active. Muds from the flanks of Conical Seamount are stronger and more brittle than those from the summit site, and muds from Torishima Forearc Seamount are stronger yet; this suggests that the serpentinite debris flows are compacted and dewatered as they mature. The shear fabrics probably result from downslope creep and flow, but may also be inherited.

Planimetric ice-flow convergence and flow-orthonormal strain rate across the Antarctic Ice Sheet, with links to model result files

Fast-flowing ice streams discharge most of the ice from the interior of the Antarctic Ice Sheet coastward. Understanding how their tributary organisation is governed and evolves is essential for developing reliable models of the ice sheet's response to climate change. Despite much research on ice-stream mechanics, this problem is unsolved, because the complexity of flow within and across the tributary networks has hardly been interrogated. Here I present the first map of planimetric flow convergence across the ice sheet, calculated from satellite measurements of ice surface velocity, and use it to explore this complexity. The convergence map of Antarctica elucidates how ice-stream tributaries draw ice from the interior. It also reveals curvilinear zones of convergence along lateral shear margins of streaming, and abundant convergence ripples associated with nonlinear ice rheology and changes in bed topography and friction. Flow convergence on ice-stream tributaries and their feeding zones is markedly uneven, and interspersed with divergence at distances of the order of kilometres. For individual drainage basins as well as the ice sheet as a whole, the range of convergence and divergence decreases systematically with flow speed, implying that fast flow cannot converge or diverge as much as slow flow. I therefore deduce that flow in ice-stream networks is subject to mechanical regulation that limits flow-orthonormal strain rates. These properties and the gridded data of convergence and flow-orthonormal strain rate in this archive provide targets for ice- sheet simulations and motivate more research into the origin and dynamics of tributarization.

A numerical discrete element study on the influence of an embedded viscoelastic-plastic layer at different viscosity values

The major aim of this study was to examine the influence of an embedded viscoelastic-plastic layer at different viscosity values on accretionary wedges at subduction zones. To quantify the effects of the layer viscosity, we analysed the wedge geometry, accretion mode, thrust systems and mass transport pattern. Therefore, we developed a numerical 2D 'sandbox' model utilising the Discrete Element Method. Starting with a simple pure Mohr Coulomb sequence, we added an embedded viscoelastic-plastic layer within the brittle, undeformed 'sediment' package. This layer followed Burger's rheology, which simulates the creep behaviour of natural rocks, such as evaporites. This layer got thrusted and folded during the subduction process. The testing of different bulk viscosity values, from 1 × 10**13 to 1 × 10**14 (Pa s), revealed a certain range where an active detachment evolved within the viscoelastic-plastic layer that decoupled the over- and the underlying brittle strata. This mid-level detachment caused the evolution of a frontally accreted wedge above it and a long underthrusted and subsequently basally accreted sequence beneath it. Both sequences were characterised by specific mass transport patterns depending on the used viscosity value. With decreasing bulk viscosities, thrust systems above this weak mid-level detachment became increasingly symmetrical and the particle uplift was reduced, as would be expected for a salt controlled forearc in nature. Simultaneously, antiformal stacking was favoured over hinterland dipping in the lower brittle layer and overturning of the uplifted material increased. Hence, we validated that the viscosity of an embedded detachment strongly influences the whole wedge mechanics, both the respective lower slope and the upper slope duplex, shown by e.g. the mass transport pattern.

Two-way traveltimes of internal layers and ice thickness between Dome C - Vostok - Dome A

Chinese scientists will start to drill a deep ice core at Kunlun station near Dome A in the near future. Recent work has predicted that Dome A is a location where ice older than 1 million years can be found. We model flow, temperature and the age of the ice by applying a three-dimensional, thermomechanically coupled full-Stokes model to a 70 × 70 km**2 domain around Kunlun station, using isotropic non-linear rheology and different prescribed anisotropic ice fabrics that vary the evolution from isotropic to single maximum at 1/3 or 2/3 depths. The variation in fabric is about as important as the uncertainties in geothermal heat flux in determining the vertical advection which in consequence controls both the basal temperature and the age profile. We find strongly variable basal ages across the domain since the ice varies greatly in thickness, and any basal melting effectively removes very old ice in the deepest parts of the subglacial valleys. Comparison with dated radar isochrones in the upper one third of the ice sheet cannot sufficiently constrain the age of the deeper ice, with uncertainties as large as 500 000 years in the basal age. We also assess basal age and thermal state sensitivities to geothermal heat flux and surface conditions. Despite expectations of modest changes in surface height over a glacial cycle at Dome A, even small variations in the evolution of surface conditions cause large variation in basal conditions, which is consistent with basal accretion features seen in radar surveys.