This research focused on the characterization of organosilicone surfactants and their effects on sulfonylurea herbicide activity. The project included efficacy tests, rainfastness studies in the greenhouse, radiotracer studies on herbicide uptake, fluorescent dye studies on surface deposition, and various measurements of physico-chemical properties. In measuring physico-chemical properties, a logistic dose response relationship was found between adjuvant concentration and contact angle on parafilm. An AsymSigR relationship existed between adjuvant concentration and surface tension for all the adjuvants. The organosilicones, Silwet L-77, Silwet 408, and Sylgard 309, and Kinetic (a blend of an organosilicone with a nonionic surfactant) gave equilibrium surface tension values around 20 dyne/cm and showed great spreading ability on the foliage of velvetleaf. With the conventional adjuvants, Agri-Dex, methylated soybean oil, Rigo oil concentration, and X-77, and Dyne-Amic (a blend of an organosilicone with a crop oil concentrate), surface tension was rarely below 28 dyne/cm and spreading ability was limited on velvetleaf. In addition, the organosilicone surfactant and Kinetic also lowered dynamic surface tension, which may improve droplet retention on leaf surfaces. The differences in physico-chemical properties between Kinetic and Dyne-Amic confirmed that carefully electing a co-adjuvant for an organosilicone blend is critical to avoid antagonism with trisiloxane molecules and retain the unique physico-chemical properties of organosilicone in the blends. Studies involving structurally-related organosilicones showed that the end structure in the trisiloxane hydrophilic group has little or no effect on surface tension, contact angle, spread pattern, herbicide uptake and translocation, and efficacy of primisulfuron on velvetleaf. It may be suggested that there is not a strict requirement to purify the end structure during the synthesis process, which is time consuming and expensive. When 14C-primisulfuron was combined with organosilicones or the blends, the uptake of 14C at 1 or 2 h after herbicide application was significantly higher than when combined with conventional adjuvants in velvetleaf. In the greenhouse, organosilicone surfactants greatly increased the rainfastness of primisulfuron in velvetleaf. The effect was immediate and dramatic, even when simulated rainfall was applied 0.25 h after treatment. In addition, herbicide efficacy on marginally susceptible weed species, velvetleaf and barnyardgrass, was significantly increased. A very complicated relationship exists between herbicides and adjuvants. The enhancement effects of adjuvants are often herbicide specific, weed species specific, and even environment specific. No one type of adjuvant functions well in all circumstances. Therefore, there is a need to understand the properties and functions of each class of adjuvants and locate the 'right' niche for each individual adjuvant. / Ph. D.

Orientador: Carlos Gilberto Raetano / Banca: Ulisses Rocha Antuniassi / Banca: Cristina Gonçalves de Mendonça / Resumo: Este trabalho teve como objetivo avaliar o efeito de adjuvantes sobre algumas propriedades de soluções aquosas, como tamanho de gotas, tensão superficial dinâmica e ângulo de contato das gotas em diferentes superfícies, natural e artificial, bem como avaliar o efeito desses produtos sobre a deposição e a deriva utilizando como alvo três espécies de plantas daninhas (Euphorbia heterophylla, Ipomoea grandifolia e Brachiaria plantaginea). Seis formulações de adjuvantes (Antideriva®, Uno®, Pronto 3®, Li-700®, Supersil® e Silwet L-77®) foram avaliadas em soluções aquosas contendo a dose recomendada do produto comercial e o dobro dela. As avaliações de tamanho de gotas foram feitas com três diferentes pontas de pulverização (AXI 110 015, 110 02 e 110 03) por um equipamento a laser (Mastersizer, Malvern) na pressão de trabalho de 414 kPa. Os ângulos de contato formados pelas gotas em duas superfícies, uma hidrofílica (vidro) e outra hidrofóbica (óxido de alumínio), foram obtidos por análise de imagens capturadas por uma câmera digital. As avaliações de deposição e deriva das soluções aquosas associadas ou não aos adjuvantes e contendo o traçador azul brilhante (0,15% v/v), foram feitas sobre diferentes espécies vegetais, e com o auxílio de coletores laterais (placas de Petri). A quantificação do traçador foi por feita espectrofotometria. A tensão superficial dinâmica e o ângulo de contato formado sobre as superfícies adaxiais das folhas foram medidos por um tensiômetro. Em relação ao tamanho de gotas, o adjuvante Antideriva, com dobro da dose recomendada, foi o que apresentou os menores valores percentuais de volume de gotas com diâmetro menor que 100 µm e os maiores DMV, para todas as pontas em teste. As soluções que proporcionaram as maiores ...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The aim of this work is to evaluate the effect of adjuvants on droplet size, dynamic surface tension and contact angle formed by the water drops in different surfaces, as well as evaluating the adjuvants effect on the deposit and the spray drift using three species of plants (Euphorbia heterophylla, Ipomoea grandifolia e Brachiaria plantaginea). We studied six adjuvants formulations (Antideriva™, Uno™, Pronto 3™, Li- 700™, Supersil™ and Silwet L-77™) in water solution using the dosage recommended by the manufacturer and twice that dose. The droplet size of three different nozzles (AXI 110 015, 110 02 and 110 03), for a constant pressure of 414 kPa, were evaluated by a laser system. The contact angles of the drops in two surfaces (hydrophilic and hydrophobic) were obtained by the analysis of images captured by a digital camera. The evaluation of deposition and spray drift deposition of the solutions containing brilliant-blue dye (0.15 % v/v) were carried out in different plant species. The solutions were collected laterally using Petri dishes, and the brilliant-blue dye content quantified by absorption spectroscopy. The dynamic surface tension and the angle formed on the surfaces of the leaves were measured by a tensiometer. Regarding the droplet size, for all the nozzles tested the adjuvant Antideriva with twice the recommended dose presented the lowest percentage of spray volume in droplets with diameters smaller than 100µm, and highest VMD. The solutions that provided the highest reductions in the dynamic surface tension and the smallest contact angle were the ones with the adjuvants Silwet L-77 and Supersil for both appraised doses. The largest deposit average for I. grandifolia was obtained by using Uno with double of the dose; for B. ...(Complete abstract click electronic access below) / Mestre

The first part of this thesis is concerned with thestructure-property relationships in nonionic surfactantsystems. The main aim was to investigate how the surfactantstructure influences the adsorption at interfaces andinteractions between surfactant coated interfaces.Particularly, the effect of the structure of the surfactantheadgroups was investigated. These were sugar-based headgroupwith varying size and flexibility and poly(ethylene oxide)based headgroups with or without an additional amide or estergroup. The hydrophobic part of the surfactant consisted mostlyof straight alkyl chains, except for one type of poly(ethyleneoxide) based surfactant with a dehydroabietic hydrophobe. The main technique that was used is the surface forcetechnique, with which the forces acting between two adsorbedsurfactant layers on hydrophilic or hydrophobic surfaces can bemeasured. These forces are important for e.g. the stability ofdispersions. The hydrophilic surfaces employed were glass andmica, whereas the hydrophobic surfaces were silanized glass andhydrophobized mica. The adsorption behavior on hydrophilicsurfaces is highly dependent on the type of headgroup andsurface, whereas similar results were obtained on the two typesof hydrophobic surfaces. To better understand how the surfaceforces are affected by the surfactant structure, measurementsof adsorbed amount and theoretical mean-field latticecalculations were carried out. The results show that the sugarsurfactant layers and poly(ethylene oxide) surfactant layersgive rise to very different surface forces, but that the forcesare more similar within each group. The structure-propertyrelationships for many other physical properties have beenstudied as well. These include equilibrium and dynamicadsorption at the liquid-vapor interface, micelle size, micelledynamics, and wetting. The second part in this thesis is about the aggregationbetween cationic polyelectrolytes and an anionic surfactant.The surface force technique was used to study the adsorption ofa low charged cationic polyelectrolyte on mica, and theaggregation between the adsorbed polyelectrolyte with theanionic surfactant. The aggregation in bulk was studied withturbidimetry, small angle neutron scattering (SANS), and smallangle x-ray scattering (SAXS). An internal hexagonal aggregatestructure was found for some of the bulk aggregates. <b>Keywords:</b>nonionic surfactant, sugar surfactant,poly(ethylene oxide), amide, ester, polyelectrolyte, SDS,hydrophobic surface, glass surface, mica, adsorption,aggregation, micelle size, surface forces, wetting, dynamicsurface tension, NMR, TRFQ, SANS, SAXS, mean-field latticecalculations.

<p>The first part of this thesis is concerned with thestructure-property relationships in nonionic surfactantsystems. The main aim was to investigate how the surfactantstructure influences the adsorption at interfaces andinteractions between surfactant coated interfaces.Particularly, the effect of the structure of the surfactantheadgroups was investigated. These were sugar-based headgroupwith varying size and flexibility and poly(ethylene oxide)based headgroups with or without an additional amide or estergroup. The hydrophobic part of the surfactant consisted mostlyof straight alkyl chains, except for one type of poly(ethyleneoxide) based surfactant with a dehydroabietic hydrophobe.</p><p>The main technique that was used is the surface forcetechnique, with which the forces acting between two adsorbedsurfactant layers on hydrophilic or hydrophobic surfaces can bemeasured. These forces are important for e.g. the stability ofdispersions. The hydrophilic surfaces employed were glass andmica, whereas the hydrophobic surfaces were silanized glass andhydrophobized mica. The adsorption behavior on hydrophilicsurfaces is highly dependent on the type of headgroup andsurface, whereas similar results were obtained on the two typesof hydrophobic surfaces. To better understand how the surfaceforces are affected by the surfactant structure, measurementsof adsorbed amount and theoretical mean-field latticecalculations were carried out. The results show that the sugarsurfactant layers and poly(ethylene oxide) surfactant layersgive rise to very different surface forces, but that the forcesare more similar within each group. The structure-propertyrelationships for many other physical properties have beenstudied as well. These include equilibrium and dynamicadsorption at the liquid-vapor interface, micelle size, micelledynamics, and wetting.</p><p>The second part in this thesis is about the aggregationbetween cationic polyelectrolytes and an anionic surfactant.The surface force technique was used to study the adsorption ofa low charged cationic polyelectrolyte on mica, and theaggregation between the adsorbed polyelectrolyte with theanionic surfactant. The aggregation in bulk was studied withturbidimetry, small angle neutron scattering (SANS), and smallangle x-ray scattering (SAXS). An internal hexagonal aggregatestructure was found for some of the bulk aggregates.</p><p><b>Keywords:</b>nonionic surfactant, sugar surfactant,poly(ethylene oxide), amide, ester, polyelectrolyte, SDS,hydrophobic surface, glass surface, mica, adsorption,aggregation, micelle size, surface forces, wetting, dynamicsurface tension, NMR, TRFQ, SANS, SAXS, mean-field latticecalculations.</p>