Velocity fluctuations of fracturelike disruptions of associating polymer solutions

Velocity has been measured as a function of time for propagating crack tips as water is injected into solutions of end-capped associating polymers in a rectanguar Hele-Shaw cell. Measurements were performed for flows with different values of cell gap, channel width, polymer molecular weight, and polymer concentration. The condition for the onset of fracturelike behavior is well described by a Deborah number which uses the shear-thinning shear rate of the polymer solution as a characteristic frequency for network relaxation. At low molecular weight, the onset of fracturelike pattern evolution is accompanied by an abrupt jump in tip velocity, followed by a lower and approximately constant acceleration. At high molecular weight, the transition to fracturelike behavior involves passing through a regime that may be understood in terms of stick-slip dynamics. The crack-tip wanders from side to side and fluctuates (in both speed and velocity along the channel) with a characteristic frequency which depends linearly on the invading fluid injection rate.

Velocity-jump instabilities in Hele-Shaw flow of associating polymer solutions

We study fracturelike flow instabilities that arise when water is injected into a Hele-Shaw cell filled with aqueous solutions of associating polymers. We explore various polymer architectures, molecular weights, and solution concentrations. Simultaneous measurements of the finger tip velocity and of the pressure at the injection point allow us to describe the dynamics of the finger in terms of the finger mobility, which relates the velocity to the pressure gradient. The flow discontinuities, characterized by jumps in the finger tip velocity, which are observed in experiments with some of the polymer solutions, can be modeled by using a nonmonotonic dependence between a characteristic shear stress and the shear rate at the tip of the finger. A simple model, which is based on a viscosity function containing both a Newtonian and a non-Newtonian component, and which predicts nonmonotonic regions when the non-Newtonian component of the viscosity dominates, is shown to agree with the experimental data.

Laboratory Evaluation of Polymer and Multi-Grade Asphalt Binders, MLR-90-5, 1992

A number of claims have been made that polymer modified asphalt cements, multi-grade asphalt cements, and other modifications of the liquid asphalt will prevent rutting and other deterioration of asphalt mixes, thereby, extending the service life of asphalt pavements. This laboratory study evaluates regular AC-20 asphalt cement, PAC-30 polymer modified asphalt cement and AC-10-30 multi-grade asphalt cement. PAC-30 was also evaluated with 15% Gilsonite and 15% Witcurb in a 75% crushed stone - 25% sand mix. These mixtures were evaluated for all Marshall properties along with indirect tensile, resilient modulus, and creep resistance.

Polydispersity index from linear viscoelastic data: Unimodal and bimodal linear polymer melts

This article describes a method for determining the polydispersity index Ip2=Mz/Mw of the molecular weight distribution (MWD) of linear polymeric materials from linear viscoelastic data. The method uses the Mellin transform of the relaxation modulus of a simple molecular rheological model. One of the main features of this technique is that it enables interesting MWD information to be obtained directly from dynamic shear experiments. It is not necessary to achieve the relaxation spectrum, so the ill-posed problem is avoided. Furthermore, a determinate shape of the continuous MWD does not have to be assumed in order to obtain the polydispersity index. The technique has been developed to deal with entangled linear polymers, whatever the form of the MWD is. The rheological information required to obtain the polydispersity index is the storage G′(ω) and loss G″(ω) moduli, extending from the terminal zone to the plateau region. The method provides a good agreement between the proposed theoretical approach and the experimental polydispersity indices of several linear polymers for a wide range of average molecular weights and polydispersity indices. It is also applicable to binary blends.

Casparian strip diffusion barrier in Arabidopsis is made of a lignin polymer without suberin.

Casparian strips are ring-like cell-wall modifications in the root endodermis of vascular plants. Their presence generates a paracellular barrier, analogous to animal tight junctions, that is thought to be crucial for selective nutrient uptake, exclusion of pathogens, and many other processes. Despite their importance, the chemical nature of Casparian strips has remained a matter of debate, confounding further molecular analysis. Suberin, lignin, lignin-like polymers, or both, have been claimed to make up Casparian strips. Here we show that, in Arabidopsis, suberin is produced much too late to take part in Casparian strip formation. In addition, we have generated plants devoid of any detectable suberin, which still establish functional Casparian strips. In contrast, manipulating lignin biosynthesis abrogates Casparian strip formation. Finally, monolignol feeding and lignin-specific chemical analysis indicates the presence of archetypal lignin in Casparian strips. Our findings establish the chemical nature of the primary root-diffusion barrier in Arabidopsis and enable a mechanistic dissection of the formation of Casparian strips, which are an independent way of generating tight junctions in eukaryotes.

Polymer Additive Ductilad D1002 in a Bituminous Seal Coat, HR-2035, 1994

Seal coat and chip seal treatments are commonly used as an economical treatment to provide a new surface to an old asphalt roadway. To be successful, the aggregate or chips must be held in place on the roadway by the asphalt binder over a long period of time. It is common, over time, that the binder becomes aged and brittle and loses its ability to be flexible and hold the aggregate in place. Modifiers have been introduced to extend the life and adhesion characteristics of asphaltic binders.

Comment on ‘‘Relaxation Kinetics of Nanoscale Indents in a Polymer Glass’’

A Comment on the Letter by A. Knoll, D. Wiesmann, B. Gotsmann, and U. Duerig, published in Physical Review Letter, 2009, vol. 102, p.117801

Surface assembly of poly(I:C) on PEGylated microspheres to shield from adverse interactions with fibroblasts.

By expressing an array of pattern recognition receptors (PRRs), fibroblasts play an important role in stimulating and modulating the response of the innate immune system. The TLR3 ligand polyriboinosinic acid-polyribocytidylic acid, poly(I:C), a mimic of viral dsRNA, is a vaccine adjuvant candidate to activate professional antigen presenting cells (APCs). However, owing to its ligation with extracellular TLR3 on fibroblasts, subcutaneously administered poly(I:C) bears danger towards autoimmunity. It is thus in the interest of its clinical safety to deliver poly(I:C) in such a way that its activation of professional APCs is as efficacious as possible, whereas its interference with non-immune cells such as fibroblasts is controlled or even avoided. Complementary to our previous work with monocyte-derived dendritic cells (MoDCs), here we sought to control the delivery of poly(I:C) surface-assembled on microspheres to human foreskin fibroblasts (HFFs). Negatively charged polystyrene (PS) microspheres were equipped with a poly(ethylene glycol) (PEG) corona through electrostatically driven coatings with a series of polycationic poly(L-lysine)-graft-poly(ethylene glycol) copolymers, PLL-g-PEG, of varying grafting ratios g from 2.2 up to 22.7. Stable surface assembly of poly(I:C) was achieved by incubation of polymer-coated microspheres with aqueous poly(I:C) solutions. Notably, recognition of both surface-assembled and free poly(I:C) by extracellular TLR3 on HFFs halted their phagocytic activity. Ligation of surface-assembled poly(I:C) with extracellular TLR3 on HFFs could be controlled by tuning the grafting ratio g and thus the chain density of the PEG corona. When assembled on PLL-5.7-PEG-coated microspheres, poly(I:C) was blocked from triggering class I MHC molecule expression on HFFs. Secretion of interleukin (IL)-6 by HFFs after exposure to surface-assembled poly(I:C) was distinctly lower as compared to free poly(I:C). Overall, surface assembly of poly(I:C) may have potential to contribute to the clinical safety of this vaccine adjuvant candidate.

From caging to rouse dynamics in polymer melts with intramolecular barriers: a critical test of the mode coupling theory

By means of computer simulations and solution of the equations of the mode coupling theory (MCT),we investigate the role of the intramolecular barriers on several dynamic aspects of nonentangled polymers. The investigated dynamic range extends from the caging regime characteristic of glass-formers to the relaxation of the chain Rouse modes. We review our recent work on this question,provide new results, and critically discuss the limitations of the theory. Solutions of the MCT for the structural relaxation reproduce qualitative trends of simulations for weak and moderate barriers. However, a progressive discrepancy is revealed as the limit of stiff chains is approached. This dis-agreement does not seem related with dynamic heterogeneities, which indeed are not enhanced by increasing barrier strength. It is not connected either with the breakdown of the convolution approximation for three-point static correlations, which retains its validity for stiff chains. These findings suggest the need of an improvement of the MCT equations for polymer melts. Concerning the relaxation of the chain degrees of freedom, MCT provides a microscopic basis for time scales from chain reorientation down to the caging regime. It rationalizes, from first principles, the observed deviations from the Rouse model on increasing the barrier strength. These include anomalous scaling of relaxation times, long-time plateaux, and nonmonotonous wavelength dependence of the mode correlators.

Randomized comparison of biodegradable polymer sirolimus-eluting stents versus durable polymer everolimus-eluting stents for percutaneous coronary revascularization: Rationale and design of the BIOSCIENCE trial.

BACKGROUND: Biodegradable polymers for release of antiproliferative drugs from metallic drug-eluting stents aim to improve long-term vascular healing and efficacy. We designed a large scale clinical trial to compare a novel thin strut, cobalt-chromium drug-eluting stent with silicon carbide-coating releasing sirolimus from a biodegradable polymer (O-SES, Orsiro; Biotronik, Bülach, Switzerland) with the durable polymer-based Xience Prime/Xpedition everolimus-eluting stent (EES) (Xience Prime/Xpedition stent, Abbott Vascular, IL) in an all-comers patient population. DESIGN: The multicenter BIOSCIENCE trial (NCT01443104) randomly assigned 2,119 patients to treatment with biodegradable polymer sirolimus-eluting stents (SES) or durable polymer EES at 9 sites in Switzerland. Patients with chronic stable coronary artery disease or acute coronary syndromes, including non-ST-elevation and ST-elevation myocardial infarction, were eligible for the trial if they had at least 1 lesion with a diameter stenosis >50% appropriate for coronary stent implantation. The primary end point target lesion failure (TLF) is a composite of cardiac death, target vessel myocardial infarction, and clinically driven target lesion revascularization within 12 months. Assuming a TLF rate of 8% at 12 months in both treatment arms and accepting 3.5% as a margin for noninferiority, inclusion of 2,060 patients would provide more than 80% power to detect noninferiority of the biodegradable polymer SES compared with the durable polymer EES at a 1-sided type I error of 0.05. Clinical follow-up will be continued through 5 years. CONCLUSION: The BIOSCIENCE trial will determine whether the biodegradable polymer SES is noninferior to the durable polymer EES with respect to TLF.

Effect of knotting on polymer shapes and their enveloping ellipsoids.

We simulate freely jointed chains to investigate how knotting affects the overall shapes of freely fluctuating circular polymeric chains. To characterize the shapes of knotted polygons, we construct enveloping ellipsoids that minimize volume while containing the entire polygon. The lengths of the three principal axes of the enveloping ellipsoids are used to define universal size and shape descriptors analogous to the squared radius of gyration and the inertial asphericity and prolateness. We observe that polymeric chains forming more complex knots are more spherical and also more prolate than chains forming less complex knots with the same number of edges. We compare the shape measures, determined by the enveloping ellipsoids, with those based on constructing inertial ellipsoids and explain the differences between these two measures of polymer shape.

From caging to rouse dynamics in polymer melts with intramolecular barriers: a critical test of the mode coupling theory

By means of computer simulations and solution of the equations of the mode coupling theory (MCT),we investigate the role of the intramolecular barriers on several dynamic aspects of nonentangled polymers. The investigated dynamic range extends from the caging regime characteristic of glass-formers to the relaxation of the chain Rouse modes. We review our recent work on this question,provide new results, and critically discuss the limitations of the theory. Solutions of the MCT for the structural relaxation reproduce qualitative trends of simulations for weak and moderate barriers. However, a progressive discrepancy is revealed as the limit of stiff chains is approached. This dis-agreement does not seem related with dynamic heterogeneities, which indeed are not enhanced by increasing barrier strength. It is not connected either with the breakdown of the convolution approximation for three-point static correlations, which retains its validity for stiff chains. These findings suggest the need of an improvement of the MCT equations for polymer melts. Concerning the relaxation of the chain degrees of freedom, MCT provides a microscopic basis for time scales from chain reorientation down to the caging regime. It rationalizes, from first principles, the observed deviations from the Rouse model on increasing the barrier strength. These include anomalous scaling of relaxation times, long-time plateaux, and nonmonotonous wavelength dependence of the mode correlators.

Unsaturated Polyester Coatings containing Biocides

Vesistöissä laivojen pintaan tarttuvat eliöt ovat sekä taloudellinen että kosmeettinen ongelma. Kontrolloimattoman eliöiden kiinnittymisen seurauksena aiheutuu kitkaa, joka puolestaan hidastaa laivan nopeutta ja aiheuttaa polttoaineen kulutuksen kasvua. Tavallisesti eliöiden kiinnittymistä ehkäistään kiinnittymisenestomaalien avulla. Niiden toiminta perustuu biosidien liukenemiseen, jolloin veden ja pinnoitteen väliselle rajapinnalle muodostuu korkea biosidipitoisuus, joka estää eliöiden kiinnittymistä pinnalle. Maailmanlaajuinen orgaanisten tinayhdisteiden käyttökielto kiinnittymisen-estomaaleissa tulee voimaan vuoden 2003 alusta. Tällä hetkellä 70 % maailman laivastoista on suojattu orgaanista tinayhdistettä sisältävällä kiinnittymisenestomaalilla. Nyt onkin kasvava tarve kehittää uusia ympäristöystävällisempiä kiinnittymisenesto-pinnoitteita. Todennäköisesti tinayhdisteet tullaan korvaamaan synteettisillä orgaanisilla yhdisteillä käytettyinä yhdessä kuparin kanssa. Työn tarkoituksena oli valmistaa ympäristöystävällisempi tyydyttämätön polyesteripinnoite, joka itsessään ehkäisisi eliöiden kiinnittymistä. Kirjallisuusosassa tutustuttiin markkinoilla oleviin biosideihin, niiden myrkyllisyyteen ja vaikutuksiin ympäristölle sekä muuttuvaan lainsäädäntöön. Työssä tarkasteltiin myös tällä hetkellä markkinoilla olevia pinnoitteita ja niiden toimintamekanismeja sekä myrkyttömiä vaihtoehtopinnoitteita kiinnittymisenestoon. Kokeellinen osa koostui kahdesta osasta. Ensimmäisessä osassa tutkittiin biosidien sopivuutta käytettäväksi yhdessä tyydyttymättömän polyesterin kanssa. Yhteensopivuutta määritettiin applikaatiotesteillä ja pinnoitteen käyttäytymisen perusteella. Toinen vaihe oli selvittää pinnoitteen tehokkuus leväntarttumista vastaan. Tyydyttymätön polyesteri gel coat kiinnittymisenesto-ominaisuuksilla valmistettiin dispergoimalla biosideja tyydyttymättömään polyesterigeeliin. Yhteensopivuustestien tulosten perusteella huomattiin, ettei biosidien lisääminen geeliin vaikuta mainittavasti applikaatio-ominaisuuksien huononemiseen. Brookfield viskositeetin stabiilisuus jopa paranee ja yksi työssä käytetyistä biosideista parantaa pinnoitteen säänkestoominaisuuksia. Tässä työssä ei pystytty määrittämään eri biosidien välisiä eroja tehokkuudessa levää vastaan.

Dynamic arrest in polymer melts: competition between packing and intramolecular barriers

We present molecular dynamics simulations of a simple model for polymer melts with intramolecular barriers. We investigate structural relaxation as a function of the barrier strength. Dynamic correlators can be consistently analyzed within the framework of the mode coupling theory of the glass transition. Control parameters are tuned in order to induce a competition between general packing effects and polymer-specific intramolecular barriers as mechanisms for dynamic arrest. This competition yields unusually large values of the so-called mode coupling theory exponent parameter and rationalizes qualitatively different observations for simple bead-spring and realistic polymers. The systematic study of the effect of intramolecular barriers presented here also establishes a fundamental difference between the nature of the glass transition in polymers and in simple glass formers.

Antireflection coatings from analogy between electron scattering and spin precession

We use the analogy between scattering of a wave from a potential, and the precession of a spin-half particle in a magnetic field, to gain insight into the design of an antireflection coating for electrons in a semiconductor superlattice. It is shown that the classic recipes derived for optics are generally not applicable due to the different dispersion law for electrons. Using the stability conditions we show that a Poisson distribution of impedance steps is a better approximation than is a Gaussian distribution. Examples are given of filters with average transmissivity exceeding 95% over an allowed band.