No description available.

Various additions are used in rubber compounds to accelerate mixing with particulate fillers and to improve behaviour in subsequent processing operations. Cationic surfactants of general structure [RNH2(CH2)3NH3]2+ 2[R'COO] can be used in rubber processing as multifunctional additives (MFA) which act as processing aids, accelerators and mould releasing agents. However, with all these beneficial properties an adverse effect of decreased scorch time was observed when N–tallow–1,3 diaminopropane dioleate (EN444) was used in the filled natural rubber compound.

Made available in DSpace on 2014-06-11T19:35:01Z (GMT). No. of bitstreams: 0 Previous issue date: 2001-11Bitstream added on 2014-06-13T20:25:37Z : No. of bitstreams: 1 montorio_ga_dr_botfca.pdf: 2363387 bytes, checksum: e273d7e54b422a27a4c07a085938cd37 (MD5) / O presente trabalho teve por objetivo avaliar a tensão superficial de soluções com diferentes surfatantes. Utilizaram 180 tratamentos combinados de forma fatorial (15x12), correspondendo a quinze surfatantes (Ag-Bem, Agral, Aterbane BR, Agrex, Break Thru, Extravon, Energic, Fixade, Gotafix, Haiten, Herbitensil, Iharaguem, Lanzar, Silwet L-77 e Wil Fix) e 12 concentrações (0; 0,001; 0,0025; 0,005; 0,01; 0,025; 0,05; 0,1; 0,25; 0,5%; 1 e 2%). A análise estatística dos dados foi realizada com auxilio do programa SAS e para análise de regressão, adotou-se o modelo de Mitscherlich com algumas modificações (Y = 72,6 - A .(1 - 10 - C . X )), onde “A” e “C” são constantes, “X” é a concentração e “Y” é a tensão superficial. A expressão “72,6 - A” corresponde a mínima tensão superficial que pode ser alcançada com o surfatante em questão. A tensão mínima alcançada com os surfatantes permite dispo-los na seguinte ordem crescente: Silwet (19,08 mN/m), Break Thru (19,87 mN/m), Wil Fix (24,71 mN/m), Haiten (27,94 mN/m), Fixade (28,23 mN/m), Agrex (29,29 mN/m), Iharaguem (29,55mN/m), Herbitensil (29,66 mN/m), Agral (30,46 mN/m), Extravon (30,47 mN/m), Energic (30,74 mN/m), Gotafix (30,91 mN/m), Lanzar (32,41mN/m), Aterbane (32,68 mN/m) e Ag-Bem (32,71mN/m). Pelo coeficiente de eficácia (constante “C” do modelo de Mitscherlich) na redução da tensão superficial, os surfatantes foram dispostos na seguinte ordem decrescente: Break Thru (169,81), Silwet (143,43), Fixade (89,28), Herbitensil (63,74), Aterbane (46,38), Iharaguem (36,11), Extravon (30,39), Energic (27,81), Agral (24,31), Gotafix (22,68), Haiten (21,28), Ag-Bem (11,24), Lanzar (8,61), Agrex (4,01) e Wil Fix (1,52). Desenvolveu-se um procedimento alternativo para se calcular o coeficiente de micelização, a partir das curvas de tensão superficial em função das concentrações dos surfatantes. / The objective of this research was to evaluate the static surface tension of solutions of the major surfactants used, in Brazil, as adjuvant in pesticide applications. It were considered 180 treatments arranged in a factorial scheme 15 x 12 with 15 surfactants (Break Thru, Silwet L 77, Fixade, Herbitensil, Aterbane, Iharaguem, Extravon, Energic, Agral, Gotafix, Haiten, Ag- Bem, Lanzar, Agrex e Wil Fix) and 12 concentrations v/v (0; 0,001; 0,0025; 0,005; 0,01; 0,025; 0,05; 0,1; 0,25; 0,5%; 1 e 2%). It were performed regression analysis and established models relating surfactant concentration to the surface tensions. The model best fitted to the data was Y = 72,6 - A.(1 - 10 - C . X )), corresponding to a modification of Mitscherlich model, where Y is the surface tension, X is the concentration of the surfactant, A and C are constants of the model. The expression “72,6 - A” is the minimum surface tension that could be achieved by the use of a certain surfactant and “C” was named efficacy coefficient and refers to the potential of each product in reducing the surface tension. The organosilicon surfactants were the most effective in reducing surface tension. The minimum tensions that could be achieved were 19,08 mN/m and 19,87 mN/m respectively for Silwet L 77 and Break-thru. The efficacy coefficients for both products were 143,43 and 169,81, also in a respective way. The other 13 non-organosilicon surfactants could be ranked in the following increasing order of minimum surface tensions: Wil Fix (24,71 mN/m), Haiten (27,94 mN/m), Fixade (28,23 mN/m), Agrex (29,29 mN/m), Iharaguem (29,55mN/m), Herbitensil (29,66 mN/m), Agral (30,46 mN/m), Extravon (30,47 mN/m), Energic (30,74 mN/m), Gotafix (30,91 mN/m), Lanzar (32,41mN/m), Aterbane (32,68 mN/m) and Ag-Bem (32,71mN/m). Considering the efficacy coefficients, the surfactants could be disposed in the following decreasing order... (Complete abstract, click electronic address below).

Foram estudados os efeitos da presença de surfatantes aniônicos (dodecilsulfato de sódio - SDS e dodecilbenzenosssulfonato de sódio - SDBS) e catiônico (cloreto de dodecilamônio - DAC) em diferentes interfases metal/cloreto de sódio, em valores de pH iguais a 5,8 e 3,0 . Platina, cobre e níquel foram utilizados como substratos. Técnicas eletroquímicas (polarizações potenciostáticas catódicas e anódicas; voltametria cíclica; cronoamperometria; impedância eletroquímica, com eletrodo parado e com eletrodo de disco rotativo - EDR) foram empregadas, bem como técnicas não eletroquímicas (espectroscopia Raman \"in situ\" SERS; microscopia eletrônica de varredura (MEV) / espectroscopia de dispersão de energia - EDS) a fim de caracterizar a ação destes surfatantes em processos anódicos e catódicos que ocorrem nas interfases citadas. DAC apresentou ação inibidora acentuada para as reações de oxidação e redução da água, na interfase Pt/NaCl 0,1 mol.L1 , não sendo eletroativo na faixa de potenciais compreendida entre estes dois processos. Utilizando-se eletrodo parado, o surfatante mostrou ação inibidora mais acentuada para os processos anódicos do que para os catódicos. Com convecção forçada empregando EDR, o surfatante apresentou graus de inibição da ordem de 90 % para ambos os processos, sugerindo que o transporte de massa favorece a adsorção do DAC sobre a platina. Tal comportamento pôde também ser comprovado quando se utilizou cobre e níquel como substratos, -1 em meio de pH igual a 5,8. Para a interfase Cu / NaCl 0,1 mol.L-1 pH = 3, com EDR, os três surfatantes tiveram seus efeitos estudados na região catódica, a fim de se verificar a sua atuação na reação de desprendimento de hidrogênio. Os surfatantes aniônicos não apresentaram efeito inibidor sobre a referida reação, aumentando a sua velocidade para potenciais mais negativos + do que -1,0 V / ECS. DAC, ao contrário, inibiu a reação H+ / H2 , com valores de grau de cobertura 2 da ordem de 50 %. A adsorção dos surfatantes sobre cobre foi caracterizada por espectroscopia Raman (SERS), cujos estudos mostraram que os três surfatantes são adsorvidos através da cadeia carbônica (hidrofóbica), no potencial de corrosão (Ecorr ) e a valores de potencial mais positivos e Ecorr . Os resultados espectroscópicos sugerem a presença da parte polar do SDS na interfase, enquanto que, no no caso do DAC, não foi possível caracterizar, por esta técnica, a adsorção do grupamento amônio Foram realizados também estudos sobre o efeito destes surfatantes em processo de eletrodeposição de níquel sobre cobre. SDS apresentou aumento de rendimento de 28% para 43% a um potencial de -1,10 V / ECS, em relação ao processo efetuado em ausência de surfatante. Os depósitos obtidos em presença de SDS e SDBS apresentaram-se mais brilhantes e visualmente mais homogêneos do que aquele obtido em ausência de surfatante, confirmando a ação abrilhantadora destes aditivos utilizados em banhos comerciais de deposição. A presença de DAC inibiu a reação Ni2+ /Ni, obtendo-se depósito de níquel apenas nas bordas do eletrodo de cobre. As superfícies de cobre niqueladas foram caracterizadas por medidas de potencial de circuito aberto, polarização anódica, cronoamperometria, impedância eletroquímica e por MEV / EDS. Os resultados obtidos, empregando as diferentes técnicas, indicaram que a deposição de níquel sobre cobre em meio de NaC1 0,1 mol.L-1, pH = 3, contendo 1,0X10-3 mol.L-1 de SDS foi a apresentou melhores características tanto em relação ao rendimento quanto à qualidade do depósito formado. / The effect of anionic (sodium dodecylsulphate - SDS and sodium dodecylbenzenesulphonate - SDBS) and cationic (dodecylammonium chloride - DAC) surfactants has been studied in different metal / sodium chloride interfaces, at pH = 5.8 and pH = 3.0 . Platinum, copper and nickel have been used as substracts. Electrochemical (anodic and cathodic potentiostatic polarisation, cyclic voltammetry, chronoamperometry, and electrochemical impedance, using stationary and rotating disk electrodes - RDE) and non-electrochemical techniques (\"in situ\" Raman spectroscopy / SERS ; scanning electronic microscopy - SEM / energy dispersion spectroscopy - EDS) have been used to study the action of these surfactants on anodic and cathodic reactions that occur in the interfaces. DAC has shown strong -1 inhibitory action on reduction and oxidation water reactions, on Pt / 0.1 mol.L-1 NaCl interfhace, without electroactivity in all the potential range studied. Stationary electrode, has shown that DAC is more effective as inhibitor for the anodic processes than for the cathodic one. Using rotating disc electrode (RDE), surfactant presents about 90 % of inhibitory efficiency in both processes, suggesting that mass transport favours DAC adsorption on Pt. Furthermore the inhibitory action is the same when using copper and nickel as substract , at pH = 5.8. The three surfactants (SDS, SDBS and DAC) were studied on cathodic potential range, in order to verify their action on hydrogen evolution reaction, in Cu / NaCl 0.1 mol.L-1 , pH = 3.0, using RDE. Anionic surfactants have not shown inhibitory action on the mentioned reaction, increasing its rate at more negative potentials than -1.0 V / ECS. On the other hand, DAC inhibits the same reaction, showing 50 % inhibitory efficiency. Surfactants adsorption on copper have been studied by Raman Spectroscopy (SERS) \"in situ\". These studies have shown the adsorption of DAC, SDS and SDBS through carbonic chain (hydrophobic) at corrosion potential (Ecorr) and at more negative and more positive potentials. The presence of the polar head at the interface have been confirmed for SDS and SDBS. For DAC, however, it was not possible to characterize the ammonium group adsorption from Raman spectra. The effect of these surfactants have also been studied for nickel electrodeposition process on copper. SDS increased the process yield (28 % to 43 %, at E = -1.1 V / ECS), when compared to the results obtained without surfactant. Deposits were brighter and more homogeneous than those obtained in the absence of SDS and SDBS surfactants, confirming the brightening action of these additives in commercial deposition baths. DAC also inhibits Ni /Ni2+ reduction, producing nickel deposit just on the edge of copper electrode. The results, obtained from different techniques, have shown that nickel deposition on copper, in 0.1 mol.L-1 NaC1, pH = 3, containing 1.0X10-3 mol.L-1 SDS, presented the best performance, if it is considered the yield values and the quality of the deposit.

Consumer- and pharmaceutical-based products are a major component of the chemical industry. In the personal care industry, formulations often consist of a mixture of surfactants and fatty alcohols. The addition of surfactants aids the stability of the formulation. The formulated product microstructure depends upon the preparation conditions as well as the ingredients. Controlling which microstructures form during the production of a formulated product is important as different microstructures can have wildly different physical properties, making some far more favourable than others. This thesis examines several of the processes undertaken in the manufacture of formulated products. The dissolution of a surfactant in a bulk water phase is examined. This is examined in a number of ways; firstly, the dissolution times of the surfactants are measured using electrical resistance tomography. It is found that the dissolution time varies with the agitation rate, agitator size, and addition method. The dissolution is also examined using dissipative particle dynamics to gain insight into the dissolution on a molecular scale. It is found that the surfactant breaks into wormlike micelles on dissolution. If an oil is added to the initial bulk then the dissolution process is modified so that long cylinders are produced with some spherical micelles. Finally, the break-up rate is predicted using a breakage model based on the agitator shear rate and a network-of-zones model. This produces good results. The production and post-shear processing of a sample formulated product, hair conditioner, is examined. Firstly, the mixing in a vessel is examined with electrical resistance tomography. Problems are encountered when the production method involves the use of distilled water as the conductivity is very low; however, the mixing time of the final product in the vessel can be determined. It is also shown that the majority of the structural changes in the post-shearing process are caused by the in-line rotor-stator mixer. The viscosity of the product increases in a linear fashion with the shear rate, while the conductivity increases as a function of the shear rate and the recycle rate. This allows the monitoring of the post-shearing process to be carried out using electrical resistance tomography. This thesis also looks at the possibility of producing a multiple frequency electrical resistance tomography device to monitor formulated product production; however, it has been shown that the conductivity does not vary with the voltage frequency over a usable range. This meant that no further effort was put into developing this, as it gave no advantage over the traditional single frequency technique. Nevertheless, important advances towards better understanding of mixing processes resulted due to the investigations carried out.

archives@tulane.edu / 1 / Olakunle Francis Ojo

Yes / Colloidal nanoparticles, such as gold nanoparticles (AuNPs), are promising materials for the delivery of hydrophilic drugs via the pulmonary route. The inhaled nanoparticle drug carriers primarily deposit in lung alveoli and interact with the alveolar surface known as lung surfactants. Therefore, it is vital to understand the interactions of nanocarriers with the surfactant layer. To understand the interactions at the molecular level, here we simulated model lung surfactant monolayers with phospholipid (PL)-wrapped AuNPs at the vacuum-water interface using coarse-grained molecular dynamics simulations. The PL-wrapped AuNPs quickly adsorbed into the surfactant layer, altered the structural properties of the monolayer, and at high concentrations initiated the compressed monolayer to collapse/buckle. Among the surfactant monolayer lipid components, cholesterol adsorbed to the AuNPs preferentially over PL species. The position of the adsorbed PL-AuNPs within the monolayer, and subsequent monolayer perturbation, vary depending on the monolayer phase, monolayer composition, and species of PL used as a ligand. Information provided by these molecular dynamic simulations helps to rationalize why some colloidal nanoparticles work better as nanocarriers than others and aid the design of new ones, to avoid biological toxicity and improve efficacy for pulmonary drug delivery.

No description available.

Calculating the solvation energies of surfactants is a way to predict the cmc. The solvation energies were determined for a homologous series of betaines, (CH₃)₃N+(CH₂)nCOO- where n = 1 to 6. Their structure is composed of only the hydrophilic head group of a surfactant. The solvation energies were determined from both the gas phase energy and free energy of solution. Conformational analysis was performed on each molecule to locate the lowest energy structures and determine the Boltzmann population of each conformation for each molecule. The final solvation energies for each molecule are expectation values based on their energies and Boltzmann populations. The plotted solvation energies versus n form a parabolic curve that is similar to the literature cmc data where the betaine has a long hydrocarbon tail. However, the solvation energies peak at n = 3 and the cmc data peaks at n = 4. The dipole moments were also examined. The gas phase dipole moments were graphed and have a maximum at n = 3, similar to the solvation energy. The solution dipole moments have a linear graph, not comparable to the solvation energies. Therefore, the stability of the gas phase structures contributes more to the final solvation energy than the stability of the molecule in water. The correlation between the plots of log cmc vs n and solvation energy vs n indicates that it is possible to computationally predict the cmc with this method. The hydrophobic contribution can be accounted for based on a known correlation between chain length and the cmc, and the hydrophilic contribution can be examined with this method. Therefore, it is possible to design a new surfactant molecule that has a cmc within the range of the biological activity to be sent for synthesis. / Master of Science

The solution rheological and electrospinning behavior of a series of charge-containing polymers, surface-active agents, and carbon nanotube composites was studied to investigate the effect of intermolecular interactions, including electrostatic interactions, hydrogen bonding, surface activity, and surface functionalization of carbon nanotubes. The synthesis of novel polyelectrolytes with varied topologies, charge content, and counterions tailored the charged macromolecules to elucidate structure-rheology and structure-processing relationships. In addition, the use of additives for electrospinning, including surfactants and nanofillers, allows us to tailor the functionality of electrospun nanofibers for high-performance applications. Novel polyelectrolytes based on poly(2-(N,N-dimethyl)aminoethyl methacrylate) (DMAEMA) were synthesized with the counteranions Cl-, NO3-, (CN)2N-, BF4-, PF6-, triflate (TfO-), and bis(trifluoromethanesulfonyl)imide (Tf2N-). The counteranion selection controlled the thermal transitions and degradation; the larger and more charge-delocalized anions typically resulted in lower Tg and higher decomposition temperature. The polyelectrolyte behavior in solution was nearly independent of anion choice, though solution conductivity depended on the electrophoretic mobility of the counterion. Charge containing copolymers of DMAEMA and di(ethylene glycol) methyl ether methacrylate (MEO2MA) were synthesized and demonstrated that polyelectrolyte behavior in solution was also nearly independent of charge content. Low ionic contents resulted in extended solution conformations and high conductivities. Controlled atom-transfer radical polymerization allowed the synthesis of star-shaped polyelectrolytes with varying arm numbers and lengths. The solution behavior of the stars deviated slightly from the linear polyelectrolytes due to significant counterion condensation within the star core and constrained polymer conformations. The linear and star-shaped polyelectrolytes were electrospun to understand the interplay between polyelectrolyte structure and electrospinnability. Similar to other strong polyelectrolytes described in the literature, PDMAEMA-based polyelectrolytes with polar anions (e.g. Cl-) experienced significant instabilities during electrospinning, requiring high concentrations and viscosities to stabilize the electrospinning jet. The use of large, more hydrophobic anions (BF4-, TfO-) led to increased electrospinnability. Unlike neutral branched polymers, which electrospin nearly identically to linear polymers of similar molecular weight, the star-shaped PDMAEMA-based polyelectrolytes required even higher viscosities than linear polyelectrolytes for stable electrospinning. The correlations between electrospinnability and solution rheological analysis are detailed. The use of surfactants facilitates the electrospinning of neutral polymers at lower concentrations. However, we have demonstrated that specific cylindrical aggregates of surfactants (wormlike micelles) can be electrospun into microfibers under the proper conditions. Ammonium and phospholipids surfactants as well as organogelators were studied using solution rheology and DLS to determine the effects of micellar structure and solution viscosity on the electrospinnability of low molar mass surfactants. In addition, the effects of charged and uncharged surfactants on the electrospinning behavior of poly(methyl methacrylate) were determined. Added surfactant facilitated uniform fiber formation at lower PMMA concentrations. XPS analysis demonstrated the formation of core-shell fibrous structures resulting from the self-migration of surfactants to the fiber surface. Hydrogen bonding also influences fiber formation through electrospinning. Star-shaped poly(D,L-lactide)s (PDLLAs) were end-functionalized with adenine (A) or thymine (T) units. The complementary hydrogen bonding between the adenine and thymine lead to thermoresponsive rheological behavior for mixtures of PDLLA-A and PDLLA-T. The mixtures could be electrospun above the hydrogen bond dissociation temperature and resulted in thicker fibers compared to unfunctionalized PDLLA stars. The hydrogen bonding allows the preparation of polymers with a combination desirable solid-state properties and very low processing viscosities. The effects of carbon nanotube incorporation on electrospinning behavior and fiber morphology were also investigated. Nonfuntionalized and carboxylic-acid functionalized carbon nanotubes were electrospun into polyurethane nanofibers. The nonfunctionalized nanotubes required high-shear melt mixing to disperse within the polyurethane, but remained well dispersed through electrospinning. The surface functionalization with acid groups produced nanotubes which dispersed more readily into the polyurethane solutions. TEM analysis revealed that nanotube dispersion and alignment within the nanofibers was similar for both nonfunctionalized and acid-functionalized nanotubes. / Ph. D.