Drag reduction is a well-observed phenomenon, it was first observed by the British chemist Toms in 1946, yet its mechanism is still unknown to this day. Polymer Drag reduction has found application in reducing pumping costs for oil pipelines (its use in the Trans Alaska Pipeline has resulted in an increase from 1.44 million bbl./day to 2.1356 million bbl./day), increasing the flow rate in firefighting equipment , and in supporting irrigation and drainage systems. Surfactant drag reducers are used industrially in district heating and cooling systems. Though the fields of Surfactant Drag Reduction and Polymer Drag Reduction are each independently well-developed the effect of their interaction on drag reduction is a less explored phenomenon. Through a well chosen pairing of surfactant and polymer, drag reduction can be maximized while minimizing surfactant and polymer concentrations cutting down on cost and environmental impact. The focus of this work was to determine if there was any positive interaction between the polymers Polyethylene Oxide (PEO) and Anionic PolyAcrylAmide (PAM) and the surfactant Amphosol CG (Cocamidopropyl Betaine) as well as any interaction between the polymers themselves. Both polymers are popular drag reducers while Amphosol is a practically nontoxic (LD50=5g/kg) zwitterionic surfactant and is readily biodegradable. In order to determine if any interaction was present and at what concentration was this most notable 4 techniques were used: Surface tension, Conductivity, Relative Viscosity and Shear Viscosity measurement. From this analysis the polymer Saturation point (PSP), Critical aggregation concentration (CAC) and Critical micelle concentration (CMC) were found as well as the concentrations that optimized the viscosity for the pilot plant runs. The bench scale results were used to pick the optimum concentrations for the polymer surfactant solutions. Pressure readings and flowrate measurements were used to plot the Fanning Friction Factor against the Generalized Reynolds Number for the surfactant polymer mixtures and compared to their pure polymer and surfactant counterparts. The Blasius line was found to hold for water measurements taken and is the base to determine percentage drag reduction. The effect of the presence of amphosol on degradation and overall drag reduction were noted. Other factors considered were pipe diameter and the effect of ionic impurities in the solvent.

Drag reduction is a well-observed phenomenon, it was first observed by the British chemist Toms in 1946, yet its mechanism is still unknown to this day. Polymer Drag reduction has found application in reducing pumping costs for oil pipelines (its use in the Trans Alaska Pipeline has resulted in an increase from 1.44 million bbl./day to 2.1356 million bbl./day), increasing the flow rate in firefighting equipment , and in supporting irrigation and drainage systems. Surfactant drag reducers are used industrially in district heating and cooling systems. Though the fields of Surfactant Drag Reduction and Polymer Drag Reduction are each independently well-developed the effect of their interaction on drag reduction is a less explored phenomenon. Through a well chosen pairing of surfactant and polymer, drag reduction can be maximized while minimizing surfactant and polymer concentrations cutting down on cost and environmental impact. The focus of this work was to determine if there was any positive interaction between the polymers Polyethylene Oxide (PEO) and Anionic PolyAcrylAmide (PAM) and the surfactant Amphosol CG (Cocamidopropyl Betaine) as well as any interaction between the polymers themselves. Both polymers are popular drag reducers while Amphosol is a practically nontoxic (LD50=5g/kg) zwitterionic surfactant and is readily biodegradable. In order to determine if any interaction was present and at what concentration was this most notable 4 techniques were used: Surface tension, Conductivity, Relative Viscosity and Shear Viscosity measurement. From this analysis the polymer Saturation point (PSP), Critical aggregation concentration (CAC) and Critical micelle concentration (CMC) were found as well as the concentrations that optimized the viscosity for the pilot plant runs. The bench scale results were used to pick the optimum concentrations for the polymer surfactant solutions. Pressure readings and flowrate measurements were used to plot the Fanning Friction Factor against the Generalized Reynolds Number for the surfactant polymer mixtures and compared to their pure polymer and surfactant counterparts. The Blasius line was found to hold for water measurements taken and is the base to determine percentage drag reduction. The effect of the presence of amphosol on degradation and overall drag reduction were noted. Other factors considered were pipe diameter and the effect of ionic impurities in the solvent.

No description available.

Solid-state complexes between diblock copolymer and amphiphilic surfactant (surf) results in polymers characterized by two length scales with one macroscopic ¡§block copolymer length¡¨ and one mesomorphic ordered ¡§nanoscale¡¨. In this study, the desired polymer was prepared by complexing the surf molecules, i.e., 4-dodecylbenzenesulfonic acid (DBSA), with polystyrene-block-poly(4-vinyl pyridine) (PS-b-P4VP) and a comb-coil A-block-(B-graft-C) type copolymer can be generated through a supramolecular assembly route. On the block copolymer scale, the PS blocks are phase-separation from the P4VP(DBSA)x block, which x denotes the molar ratio between DBSA and pyridine groups. Bonding interaction between PS-b-P4VP and DBSA was conformed by FTIR. PLM was used to detect the mesomorphic structure within P4VP(DBSA)x block. In all cases, we found that birefringent can be only found in copolymer with their comb content exceeding 63 wt%. In the thermal analysis, shows us that the glasses transition temperature(Tgs) of the P4VP(DBSA)x block increases with the increasing DBSA content, a result related to the stiffening of the P4VP main chain due to dense packing. On the mesomorphic nanoscale, wide-angle X-ray diffraction study suggests an ordered supramolecular layer structure was formed in most of the complexation cases, in which the thicknesses of the polymer and surf layers were determined from the one-dimensional correlation function. The result indicates that both layers thickness increase with increasing DBSA amounts due to the stretching of the long alkyl tail in DBSA. Finally, macroscopic morphology varied with the DBSA content according to TEM results.

The interfacial adsorption and bulk properties of a collagenous polypeptide derived from chicken eggshell membranes, the 40 KDa polypeptide, and its mixtures with common low molecular weight (LMW) surfactants, SDS, DTAB and C10E8, have been studied for the first time using surface tension, ζ-potential, foam observations and neutron scattering techniques. The biopolymer has been shown to act as an effective biosurfactant by lowering the surface tension of water below the values commonly achieved with conventional LMW surfactants, i.e. γ = 32 ± 1 mN/m. This capability is maximized at its isoelectric point, pH ~5, and addition of NaCl does not have a major impact upon adsorption. On its own, the 40 KDa polypeptide lacks the ability to foam. When mixed with cationic and anionic surfactants, a positive synergy is observed at low concentrations of both materials that exceeds the expectations from the individual components due to the formation of polypeptide/surfactant complexes with high surface activity and high ability to foam and foam stability. At these concentrations, maximum interfacial adsorption is achieved. The synergy is observed in spite of the type of charges present in the surfactant polar head. However, under the conditions studied, there is a difference in behaviour in regards to colloidal stability and surface film formation between the mixed solutions with the anionic SDS and the cationic DTAB. The non-existence of the synergy in the surface adsorption profile of the mixtures of the polypeptide with the non-ionic surfactant C10E8, as obtained via the plate method, suggests that electrostatic interactions are necessary for this strong synergy to act. ζ-potential has been used to prove the electrostatic nature of the synergy. Specular neutron reflection and SANS measurements offered an insight into the complex size and structure. The 40 KDa polypeptide thus offers a promising alternative to the use of high amounts of LMW surfactants in a range of products in which low surface tension and/or high and stable volumes of foams are needed, by combining small amounts of polypeptide and an ionic surfactant. This could be exploited by industries which have an interest in nanoparticle formation such as personal care or pharmaceutical companies. However, further work is needed to fully characterize these interactions.

<p>Savremene svetske tendencije upućuju na sve &scaron;iru primenu<br />ekstrakata lekovitog i aromatičnog bilja, kako u prehrambenim<br />proizvodima&ndash; funkcionalna hrana, tako i u proizvodima<br />farmaceutske i kozmetičke industrije. Ekstrakti biljnog<br />materijala, dobijeni primenom ugljendioksida pod pritiskom,<br />sadrže termički nepromenjene aktivne komponente, te se<br />poslednjih godina sve vi&scaron;e primenjuju u farmaceutskoj i<br />prehrambenoj industriji.<br />Cilj ove doktorske disertacije je da se ispita mogućnost<br />inkorporiranja ekstrakta nevena (<em>Calendula officinalis</em> L.), kao<br />farmakolo&scaron;ki aktivne materije, u mikrokapsule sa ciljem za&scaron;tite<br />od spolja&scaron;njih uticaja, produžetka njegovog delovanja i<br />pro&scaron;irenja mogućnosti primene.<br />Za dobijanje ekstrakata nevena primenjeni su postupci<br />ekstrakcije ugljendioksidom u tečnom i superkritičnom stanju.<br />Definisani su uslovi pri kojima je moguće dobiti ekstrakat sa<br />visokim sadržajem etarskog ulja, nosiocem gastro-intestinalnog<br />delovanja (200 bar, 40^oC). Totalni ekstrakt dobijen pod ovim<br />uslovima ekstrakcije je odabran za dobijanje mikrokapsula.<br />Ispitivana je mogućnosti primene polimer&ndash;PAM interakcije<br />nejonskih derivata celuloze- hidroksipropilmetil celuloze<br />(HPMC) i anjonske PAM- natrijum dodecilsulfata (SDS), za<br />formiranje omotača mikrokapsula. Primenom konduktometrijske<br />i viskozimetrijske metode, određene su karakteristične<br />koncentracije pri kojima HPMC&ndash;SDS interakcija započinje i<br />zavr&scaron;ava se. Definisan je uticaj osobina molekula HPMC<br />(molekulska masa, stepen supstitucije, vrsta supstituenta) i<br />temperature na &scaron;irinu intervala interakcije i obja&scaron;njeni<br />mehanizmi njihovog povezivanja, sa osvrtom na strukturu i<br />osobine formiranih HPMC/SDS komleksa. Reolo&scaron;kim<br />ispitivanjima pri različitim uslovima definisane su promene u<br />pona&scaron;anju sistema u zavisnosti od HPMC&ndash;SDS interakcije.<br />Ispitivan je uticaj interakcije na osobine 20% emulzija<br />suncokretovog ulja u vodi određivanjem njihovih reolo&scaron;kih<br />osobina, veličina i raspodela veličina kapi i praćenjem<br />stabilnosti. Utvrđeno je da se u oblasti najizraženije HPMC&ndash;SDS interakcije, odnosno kada se na granici faza ulje-voda<br />nalazi umrežen HPMC/SDS kompleks, dobijaju emulzije<br />najveće stabilnosti, sa njajmanjim srednjim prečnikom kapi.<br />Su&scaron;enjem emulzija, primenom spray drying postupka,<br />dobijene su mikrokapsule uljnog sadržaja, stabilizovane<br />kompleksom HPMC/SDS. Najbolje karakteristike mikrokapsula<br />(mehanička otpornost, morfolo&scaron;ke karakteristike, sposobnost<br />redispergovanja, veličina i raspodela veličina čestica i količina<br />inkapsuliranog ulja), dobijene u oblasti najizraženije interakcije.<br />Dodatak odabranog CO₂ ekstrakta nevena u uljnu fazu<br />emulzija ne menja značajno njihove osobine, kao ni osobine iz<br />njih dobijenih mikrokapsula.<br />Ispitivanja sprovedena u ovoj doktorskoj disertaciji<br />pokazala su da se osobine kompleksa polimer/PAM mogu<br />iskoristiti za mikrokapsulaciju ulja kao nosača farmakolo&scaron;ki<br />aktivnih materija.</p> / <p>Contemporary global trends in food- functional food,<br />pharmaceutical and cosmetic industry as well have been<br />focused on a wider medical plants extracts application during<br />the recent decade. Plant extracts obtained by means of carbon<br />dioxide under high pressure contained all unchanged active<br />compounds from plant, so that they have became more<br />popular for application in food and pharmaceuticals recently.<br />The aim of this thesis was to investigate the possibility to<br />incorporate marigold extract (<em>Calendula officinalis</em> L.), as a<br />pharmacologicaly active compound, into microcapsules in<br />order to protect them from surrounding medium, improve<br />their activity and enlarge application.<br />Marigold extracts were obtained by means of carbon<br />dioxide- CO2 under subcritical and supercritical conditions.<br />Extraction conditions under which obtained extract has high<br />content of essential oil, responsible for gastrointestinal<br />activity, were determined (200bar and 40^oC). Total extract<br />obtained under such conditions, was chosen for microcapsule<br />preparation. Application possibility of polymer&ndash;surfactant<br />interaction between non-ionic cellulose derivativehydroxypropylmethyl<br />cellulose (HPMC) and anionic<br />surfactant- sodium dodecylsulfate (SDS) to microcapsule<br />wall formation was investigated. Characteristic<br />concentrations at which interaction starts and ends were<br />determined by means of conductometric and viscometric<br />measurements. The influence of HPMC molecular<br />characteristics (molecular weight, degree of substitution and<br />substituents kind) and temperature on interaction were<br />determined and, considering the structure and characteristics<br />of HPMC/SDS complexes, binding mechanism was<br />explained. The changes in HPMC-SDS system caused by<br />their interaction were defined by rheological investigations<br />that took place under various conditions.<br />The influence of interaction on the properties of 20%<br />sunflower oil/water emulsion was investigated by rheology<br />measurement, particle size and particle size distribution<br />determination and stability testing. It was provided that<br />emulsions prepared in the region of pronounced HPMC&ndash;SDS<br />interaction, where HPMC/SDS complex is adsorbed at the</p><p>o/w interface, have highest stability and smallest particle<br />mean diameter.<br />Microcapsules were obtained by spray drying of<br />emulsions stabilized with HPMC/SDS complex. The best<br />characteristics (mechanical resistance, morphological<br />characteristics, redispersing ability, particle size and particle<br />size distribution and amount of encapsulated oil) have<br />microcapsules obtained in the region of most pronounced<br />interaction.<br />Addition of marigold CO₂ extract in to the oil phase of<br />emulsions has no significant influence neither on their, nor on<br />corresponding microcapsules characteristics<br />Investigations conducted in this thesis showed that<br />characteristics of polymer/surfactant complexes can be used<br />in microencapsulation of oil as carrier of pharmacologically<br />active compounds</p>

No description available.

Les mousses extinctrices sont utilisées sur les feux de catégorie B (solvants inflammables). L’efficacité des mousses actuelles contenant des agents moussants fluorés est apportée par la formation d’un film aqueux à la surface du carburant enflammé. Les entreprises recherchent et développent de nouveaux agents moussants sans fluor car ce type de tensioactif est nocif pour l’environnement et la santé. Des mousses très stables sont nécessaires pour qu'une couche épaisse de mousse résiste aux températures élevées et au démoussage par le solvant et évite ainsi la ré-inflammation.Dans ce travail, l’amélioration de la stabilité de la mousse a été réalisée en utilisant des épaississants dans une solution moussante avec des tensioactifs non fluorés. Des polysaccharides tels que la gomme xanthane ont été utilisés et ses interactions avec des tensioactifs ont été étudiés. Les complexes formés par ces interactions ont été utilisés dans le but d’améliorer la stabilité de la mousse et sa résistance aux flammes. Ceci engendre des mousses de plus faible moussabilité mais de plus grande stabilité. Des tests à échelle réduite ont été réalisés selon la norme EN1568 et ont montré l’efficacité de l’addition de gomme xanthane. Ces formulations innovantes associant des polysaccharides et des agents moussants sont de bonnes alternatives aux formules contenant des tensioactifs fluorés. Le mécanisme d’action des hydrotropes améliorant la moussabilité a aussi été étudié / Firefighting foams are used on class B fires (flammable solvents). The efficiency of currently used foams containing fluorinated foaming agents is ensured by the formation of an aqueous thin film on top of the burning solvent. The formation of such film requires the use of fluorinated surfactants that specifically adsorb at the water-air interface. Companies currently develop fluorine-free products for firefighting foams because this kind of surfactants is harmful for the environment and health. Very stable foams are necessary to the formation of a thick layer of foam that resists high temperatures and defoaming by the solvent, preventing fire re-ignition.In this work, improved foam stability was achieved by using thickeners in the foaming fluid together with the non-fluorinated surfactants. Polysaccharides such as xanthan gum were used and their interactions with surfactants were investigated. Complex species formed by such interactions were used in order to improve foam stability and resistance against flames. This causes a lower foamability but higher stability of foams. Small scale fires extinguishing experiments performed following the standard EN1568 showed the efficiency of xanthan gum addition. These innovative formulations combining polysaccharides and foaming agents are suitable alternatives to those containing fluorinated surfactants. The action mechanism of hydrotropes improving foamability has also been studied

The aim of this thesis work is to study the physico-chemical properties of poly(ethylene oxide), PEO, based brush polymers both in solution and at solid/aqueous interfaces. The importance of studying the surface properties of brush polymers can be related to a broad spectrum of interfacial-related applications such as colloidal stability, lubrication, detergency, protein repellency to name a few. In many applications it is desirable to form brush-like structures through simple physisorption. In this context the surface properties of PEO based brush polymers differing in molecular architecture were studied, using ellipsometry and surface force apparatus (SFA), to gain some understanding regarding the effect of molecular architecture on the formation of brush structures. The molecular architecture was varied by varying the charge/PEO ratio along the backbone. This study demonstrates that the formation of a brush structure at solid/aqueous interface is due to interplay between the attraction of the backbone to the surface and the repulsions between the PEO side chains. An optimal balance between the two antagonistic factors is required if one aims to build a well-defined brush structure at the interface. In this study the brush-like structures are formed when 25-50% of the backbone segments carry poly(ethylene oxide) side chains. Scattering techniques such as light and neutron reveal that these brush polymers are stiff-rods up to a charge to PEO ratio of 75:25. These stiff PEO brush polymer easily replace the more flexible linear PEO at the silica/water interface, the reason being that the entropy loss on adsorption is smaller for the brush polymer due to its stiff nature.  Polymer-surfactant systems play a ubiquitous role in many technical formulations. It is well known that linear PEO, which adopts random coil conformation in aqueous solution, interact strongly with the anionic surfactant, Sodium Dodecyl Sulphate (SDS). It is of interest to study the interaction between SDS and brush PEO owing to the fact that the PEO side chains have limited flexibility as compared to the linear PEO.  The interaction between brush PEO and the anionic surfactant SDS in solution are studied using different techniques such as NMR, tensiometry, SANS and light scattering. The main finding of this study is that the interaction is weaker compared to the linear PEO-SDS interactions which poses an interesting question regarding the role of chain flexibility in polymer-surfactant interactions. / QC 20100813

Διερευνήθηκε η δέσμευση/αποδέσμευση ιόντων Cu(II) ή/και αντίθετα φορτισμένων επιφανειοδραστικών ενώσεων από συμπολυμερή τύπου κτένας. Ο κεντρικός σκελετός ήταν το πολυ(ακρυλικό νάτριο), PANa, ενώ οι πλευρικές αλυσίδες ήταν το Πολυ(Ν,Ν-διμεθυλακρυλαμίδιο) και το πολυ(Ν-Ισοπροπυλακρυλαμίδιο). Η συμπλοκοποίηση των συμπολυμερών με τα ιόντα Cu(II)σε υδατικό περιβάλλον διερευνήθηκε με θολομετρία, ιξωδομετρία, φασματοφωτομετρία UV-Vis, δυναμική σκέδαση φωτός, ιχνηθέτηση με φθορίζοντες ιχνηθέτες και προσδιορισμό του ζ-δυναμικού. Σε επόμενο στάδιο διερευνήθηκε η δυνατότητα σχηματισμού τριμερών συμπλόκων ΡAΝa/Cu(II)/επιφανειοδραστικής ένωσης σε υδατικό περιβάλλον. Από τη φυσικοχημική μελέτη των συστημάτων σε συνάρτηση του pΗ, ελήφθησαν σημαντικές πληροφορίες σχετικά με τον ανταγωνισμό των δύο ειδών (ιόντα Cu(II)ή ιόντα επιφανειοδραστικής ένωσης) να σχηματίσουν σύμπλοκα με το PANa. Ως τελικό στάδιο, παρασκευάστηκαν αδιάλυτα στο νερό υβριδικά υλικά πολυμερούς/Cu(II)ή πολυμερούς/Cu(II)/επιφανειοδραστικής ένωσης. Έπειτα από διερεύνηση της συμβατότητας/αναμιξιμότητάς τους με εμπορικές μήτρες που χρησιμοποιούνται συνήθως στη βιομηχανία χρωμάτων, ορισμένα από αυτά ενσωματώθηκαν σε πραγματικά χρώματα. / The binding/release of Cu(II) ions or/and surfactants from comb-type copolymers was studied. The backbone was poly(sodium acrylate), PANa, whereas the side chains were poly(N, N-Dimethylacrylamide) and Poly9N-Isopropylacrylamide). The complexation of these copolymers with Cu(II) ions in water, was studied by turbidimetry, viscometry, UV-Vis fasmatophotometry, dynamic light scattering, fluorescense probing and ζ-potential. As a next step, the possible formation of ternary PANa/Cu(II)/surfactant complexes in water was studied. From the physiocochemical studies with pH, important information was taken as far as the competition of the two species (Cu(II) ions and surfactant) to form complexes with PANa is concerned. As a next step, water-insoluble hybrid polymer/Cu(II) or polymer/Cu(II)/surfactant materials were produced. After studies upon the compatibility/mischibility of the hybrid materials with matrices that are usually used in paints, some of the materials were incorporated to paints.