ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

S&D 1: Fabric Care Performance Boosters and New Benefits Chairs: Kathleen Stanton, American Cleaning Institute, USA; and Tyler Smith, Lightbox Laboratories, LLC, USA Rational Design of Lipases: A Case Study. Jakob detergent formulations protease may negatively Skjold-Jørgensen*, Novozymes A/S, Denmark impact the cellulase activity over time, resulting in When it comes to caring for their clothes, loss of fabric care properties. Therefore, an consumers want to save time and money with a improvement of the storage stability properties of high expectation on performance. With an cellulase is required. DuPont has applied molecular increasing number of consumers using the “Quick modelling software and structure function analysis wash” cycle to save time, water and energy costs, to generate hypotheses about regions of the concerns with incomplete stain removal also arise. enzyme that may be susceptible to instability. Average wash temperatures have been falling Functional studies identified the cleavage sites driven by appliance manufacturers designing where we could influence the properties of machines to meet Energy Star requirements. improved performance and stability. These Colder wash cycles address key consumer needs of improved properties of the new cellulase were fabric care and preservation, but cleaning confirmed in application studies under North efficiency is lower than with warm water. This talk American wash conditions, as well as storage demonstrates how catalytic enzymes enable better stability trials in typical US liquid detergents cleaning with shorter wash cycles and colder wash comprising protease. temperatures. Breakthrough Solution for Odor Reduction in Engineering an Improved Cellulase for Fabric Care Cleaning Products. Anita Augustyniak, and Yvon G. in Liquid Detergents. Christian Adams*1, Andre Durant*,Itaconix, USA Krouwer2, and Arjen J. Hoekstra2,1DuPont Industrial Odor management is a core component of Biosciences, USA; 2DuPont Industrial Biosciences, cleaning functions. Odor in various textiles, such as The Netherlands laundry, sport equipment, upholstery and carpets A global fabric care study carried out by DuPont are assaulted by combinations of odors ranging highlighted considerable consumer dissatisfaction from pet urine to bodily fluids to food waste. Odor with pilling and color fading on garments after management in cleaning products is often a using most detergents. In general, liquid detergents combination of detergency (odor extraction to provide better fabric care properties than laundry solution), oxidation and masking. However, some powders, and in most mature markets, including odors are persistent even after oxidation and recur North America; liquids have become the dominant once masking has dissipated. This is due to the high product format. Cellulase is known for providing susceptibility of the human nose to a set of odors multi cycle fabric care benefits such as pilling that we culturally associate as unwanted. Thiol and prevention and color maintenance. However, liquid amine derivatives are some of the most persistent detergents provide a challenge to the product molecules that can be detected by our noses at sub formulator for delivering robust fabric care ppb level. A breakthrough strategy is to add performance with cellulase, especially in the molecules that have the ability to complex presence of proteolytic enzymes. In liquid malodorants into non-volatile molecules.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

Complexes of Zinc-polyitaconate have the property prevent transfer of bacteria from bio-film to of maintaining zinc ions in solution across a wide clothes during washing. As a result, we found a range of pH, in complex aqueous matrices, while specific enzyme itself and further the combination drying to a non-oily residue. The zinc atom is able of the enzyme with some detergent components to coordinate with thiols or amines, to create Lewis are effective for the purpose. acid-base complexes that are non-volatile, while remaining in solution. Formulated products Laundry Detergency of Solid Non-particulate Soil containing these neutralizing metal-organic or Waxy Solids: Relation to Oily Soil Removal complexes are offering novel performance in odor Above the Melting Point. David A. Sabatini*1, John reduction, while eliminating unwanted residues on Scamehorn1, Jarussri Chanwattanakit2, and fabric. Sumaeth Chavadej2, 1University of Oklahoma, USA; 2Chulalongkorn University, Thailand Study on Bacterial Control During Washing with In this work, methyl palmitate or palmitic acid Laundry Detergent. Nanami Sasaki*, Keisuke Mori, methyl ester, a monoglyceride, was used as both a Takahiro Hayashi, Misa Nakagawa, Masayoshi model solid fat below the melting point and as an Oishi, Hiroaki Shindo, Hiroyuki Masui, and Takahiro oily soil above the melting point. An anionic Okamoto, Lion Corporation, Japan extended surfactant [branched alcohol propoxylate In recent times, awareness on personal hygiene sulfate sodium salt (C123-(PO)4-SO4Na)] was used has been increased year by year, especially, to remove methyl palmitate from cotton and from consumer needs on odor care in daily life has polyester. Above the melting point (~30ºC) of become higher. In response to this needs, many methyl palmitate, the maximum oily soil removal kinds of study on odor care have been conducted was found to correspond to the lowest dynamic in the fabric care field.So far, most of studies have interfacial tension (IFT), as is common with liquid been done focusing on 1) removing sebum soil, soils. Below the melting point, the lower the nutrition for bacteria, from fabric, or 2) preventing contact angle of the wash solution against the soil bacteria growth on fabric as a counter-measure for (indicating higher wettability), the higher the solid bacteria generating malodor. In this study we fat soil detergency. The removed methyl palmitate focused on the effect of bacteria present in was found to be mostly in unsolubilized droplets or washing tubs to reduce fabric malodor. First, we particles with a small fraction of micellar studied bacteria flora of bio-film on washing tub solubilization for both solid and liquid forms. The surfaces in 14 houses by using gene-sequences presence of surfactant can prevent the homology comparison. From this data, we found agglomeration of detached methyl palmitate that some kind of bacteria detected commonly in particles in both liquid and solid forms, reducing most houses have clear relation with malodor of redeposition and enhancing detergency. Below the washing tubs. These bacteria grew up and formed melting point, the surfactant aids the solution bio-film to stick firmly to the surface. These wetting the surfaces, then penetrating the waxy bacteria transferred to clothes during washing solid, causing detachment as small particles, and process then it became a cause of clothes malodor. dispersion of these particles. Unlike particulate soil Next, we tried to reduce the effect of bacteria on detergency, electrostatic forces are not an washing tub surface by approaching 1) to remove important factor in fatty soil detergency. bio-film or to inhibit bio-film forming, and 2) to

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

Polymers and Detergency—A Complex Game of Protect and Care—Silicone Effects for Perceivable Interactions. Keith E. Gutowski1, and Dieter Benefits. John H. Richards*,Wacker Chemical Boeckh*2,1BASF Corporation, USA; 2BASF SE, Corporation, USA Germany Consumers are continually seeking ways to Liquid laundry detergents are formulations maintain, refresh and enhance garment properties. predominantly based on surfactants. Polymers are Silicones utilized as rinse cycle additives generate added at much lower levels serving a variety of many perceivable consumer benefits. Color purposes like hardness- and rheology- fastness and shape retention are two such effects management, soil-dispersion or the prevention of that can be defined and quantified via application redeposition of soils or dyes. Primary and testing. An overview of novel silicone chemistries secondary detergency are areas that can be that protect fabrics will be provided, along with significantly relevant for the application of relevant practical test results. Performance polymers. While initially, when polymers were characteristics of treated garments are highlighted introduced to laundry detergents, the focus was on along with product recommendations for achieving anionic polymers, the scope of polymers applied the desired effects. today has widened and includes functional polymers with cationic character as well as nonionic amphiphilic structures. The variability and characteristics of functional polymers allows choices how the polymer can interact with the complex colloidal and interfacial situation found in a liquid detergent and during laundry. Charge, size and polarity as well as distribution of functionality determine if and how polymers associate with surfactants, interfaces and hardness ions. A study of the colloidal chemistry of selected polymers in mixed polymer-surfactant systems is presented. The influence of the selected surfactant system as well as of water hardness on association concentrations and phase behavior is studied. Examples show how modeling can help understand the solution behavior of these polymers and how they are affected by the presence of surfactant and hardness ions. The influence of observed properties and association phenomena on detergency are discussed and examples are shown that were obtained in model experiments.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

S&D 1.1: New Technologies in Industry Chairs: Eric Theiner, Evonik Corporation, USA; and Hongwei Shen, Colgate Palmolive Co., USA Surface Restoration Achieved Using STEPOSOL® surfactant triethanolamine-based esterquat (TEQ) CITRI-MET via Partial Softening and Cure of as ingredients of softener. We found that the Existing Polymer Coatings Ron A. Masters*, Stepan addition of a non-adsorbed polymer which cannot Company, USA interact with the vesicle membrane is effective in STEPOSOL® CITRI-MET is a concentrated, this system by utilizing the techniques of natural-oil-based cleaning blend that contains rheological measurements, differential scanning Nobel Prize winning metathesis and Stepan calorimetry and dynamic light scattering. Thus, we commercial amidation chemistry. Launched considered that the main factor of structural September 2015, this product serves multiple viscosity is depletion flocculation induced by the applications, depending on dilution, from heavy coexistence of the two different particle sizes oilfield equipment cleaning to household all- represented by the surfactant vesicles and by non- purpose cleaning. At a ten to twenty-fold dilution adsorbed polymers. To understand the flocculation range, a unique restorative effect is observed for behavior of this system more clearly, we examined many surfaces. Originally thought to be a deeper, the effect of the particle size, concentration of more effective cleaning than traditional cleaners, vesicles and non-adsorbed polymers on the further development has revealed that this is a viscoelastic behavior. As a result, the flocculation new technology where existing surface coatings are force calculated from viscoelastic property became slightly softened and mobilized, and when spread strong with increasing size and concentration of and left to dry, provides a restoration effect, as if the non-adsorbed polymer. It can be deduced that the original coating were reapplied. This the flocculation mechanism is based on the theory presentation will include the technical basis for the of depletion interaction. effect, visual examples, and a live demonstration. Potential of Biosurfactants as New Performance Viscosity Control for a Vesicle Suspension System Ingredients in Liquid Laundry Alexander Schulz* with Non-adsorbed Polymer Ryo Inoue*1, Asami and Michael Dreja, Henkel AG & Co. KGaA, Miyajima1, Taku Ogura1, Otto Glatter2, and Norio Germany Tobori1, 1Lion Corporation, Japan; 2University of The main target for a detergent from a Graz, Austria consumer viewpoint is the removal of soil and Consumers’ need of long-lasting fragrance for stains. Since the invention of modern detergents, the fabric-care category has been steadily the consumer goods industry is working to fulfil increasing in recent years. Therefore, a number of those needs. More recently, growing liquid laundry products containing encapsulated environmental awareness of industry, regulators fragrance have been launched. In order to satisfy and customers leads to additional requirements both the prevention of floating capsule particles which can be met today via innovations in and easy pouring in liquid products, it is necessary sustainability. Modern detergents have to work to have a structural viscosity as a solution property. well at low temperatures during the wash, and its In this study, we attempted to control structural ingredients have to be well biodegradable. viscosity for vesicle suspensions formed by cationic Surfactants can be derived from sustainable natural

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

sources, among them biosurfactants produced by Development of a Spherulite Structured Liquid microorganisms. Integrating biosurfactants into Cleanser at Reduced Surfactant Concentrations market-relevant detergent formulations remains Peter R. Hilliard*, Colgate Palmolive Co., USA challenging, due to their availability, performance Delivering moisturizing benefits to the skin’s profile and since the vast majority of consumers surface from a body cleansing liquid presents are reluctant to pay extra for “green” claims. several challenges. One particular challenge is the Indeed, not all biosurfactants are in general more need to deliver significant amounts of oil to the sustainable when e.g. land use, energy skin while maintaining formula stability and consumption and biodegradability are considered. foaming properties. Spherulite based structured Due to these complex requirements, we use surfactant systems can be used to develop several methods to assess the use of biosurfactants cleansing liquids capable of suspending and for liquid laundry applications. We start with the delivering significant concentrations of oil to the evaluation of physico-chemical parameters like the skin. However, these formulations tend to contain critical micellar concentration of the pure significant concentrations of surfactants in order to surfactant, but also of blends with other maintain the spherulite structures and suspension surfactants. At the same time, we evaluate what properties. We will discuss chemistries and the end consumer can perceive by assessing processes that produce structure at lower compatibility, stability and performance, via spherulite based surfactant concentrations. These washing trials with suitable sets of stains. Especially low spherulite concentration structured formulas on various fatty stains like lard, sebum, and oil, are significantly more effective delivering oils to biosurfactants show unique properties, and the skin than normal high concentration spherulite understanding these properties is important for the formulas. In addition, a low concentration creation of future detergents. Correlating these spherulite system is much more effective than a results with the physico-chemical parameters standard oil/water emulsion in delivering oils to enables us to understand underlying interactions the skin’s surface during washing procedures. The and to make predictions about the best detergent hypothesized mode of action is based on formation formulations to fulfil consumer needs. of a unique “honey comb” ordering of the spheruiltes leading to structure at much lower Elucidation of Softening Mechanism in Rinse Cycle surfactant concentrations. This is very different Fabric Softeners Takako Igarashi*, Koichi from that observed in a normal spherulitic system Nakamura, Masato Hoshi, Teruyuki Hara, Hironori based on volume exclusion and tight packing of the Kojima, Masatsugu Itou, Reiko Ikeda, and spherulite structures. The oil is dispersed within Yoshimasa Okamoto, Kao Corporation, Japan the “honey comb” formations, is released during a In our previous study, we proposed that the catastrophic breakdown of the structure upon inhibition of the formation of hydrogen bonding dilution, and potentially presenting a high localized network between single fibers made of bound concentration of the oil to the skin. In addition, water was important. Based on this proposal, we since less surfactant is required to produce a have continued to get a deeper-insight about the structured formula capable of suspending the oil reason why and how the comfortable softening is phase, it is hypothesized that less of the oil will be realized with the point of adsorption status of emulsified during washing and resulting in a further cationic vesicles to the yarns. increase in the amount of oil deposited on the skin.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

Examples of experiments supporting this Hydrotroping Properties of Naturally-derived hypothesis will be discussed. Surfactants in Alkaline Formulations Robert J. Coots*, and Dennis Abbeduto, Colonial Chemical, Noverite™ Polymers for Window and Bathroom Inc., USA Cleaners: Improved Anti-fog, Reduced Hard Water Surfactant chemicals that are classified as Spotting, and Easier Soap Scum Removal Jobiah J. hydrotropes serve an important function in Sabelko*, Chris Cypcar, and Eve De Maesschalck, formulating cleaning products for many different Lubrizol Advanced Materials, Inc., USA applications. The ability of a water insoluble Consumers have increasingly busy lifestyles and detergent ingredient to be solubilized into an desire cleaning products that make the cleaning aqueous alkaline solution, is an important process easier and more effective. Product requirement when formulating such products. In differentiation is also critical to success in this the last few years, we have seen a shift in attitude crowded marketplace and typically requires of both consumer and industrial consumers toward providing innovative functionality to traditional using ingredients that are from natural, renewable products. In response to these market needs, sources. This has given rise to several new products Lubrizol has developed Noverite™ 301, 310 and that are derived from natural feedstocks designed 311 polymers, novel functional additives for to compete in this area of surfactant chemistry. window and bathroom cleaners with long-lasting This talk will give detailed information about effects. These high performance surface- hydrotropes that are derived from natural sources substantive polymers have shown excellent and their performance compared to traditional capability to provide hydrophilic properties to hard hydrotropes, that are derived from petroleum- surfaces. The resulting water sheeting effect based feedstocks. inhibits fogging on glass, reduces the formation of hard water spots, and provides easier removal of soap scum on bathroom surfaces. The Noverite™ polymers are water soluble, easy to use liquid additives that are effective at low dosage levels. They are compatible with a wide range of surfactants and over a broad pH range thereby providing great formulating flexibility and are also suitable for products that demand high clarity. Noverite™ polymers allow for the development of cost-effective cleaners that prevent fogging, hard water spotting and soap scum build up, making the cleaning process easier and less time-consuming.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

S&D 2: New Trends in Cleaning: Hard Surface, Detergency, Hand Dish, and Autodish Chairs: Paul Sharko, Shell Global Solutions, Inc., USA; and Masaki Tsumadori, Senior Advisor, R&D, Kao Corporation, Japan

Improving Hand Dishwashing Liquid Cleaning the wash up and still add to the foam mileage of the Performance with Enzymes Lotte J. Jensen-Holm1 and hand dishwashing liquid. In hard surface cleaning short Thomas J. Burns*2, 1Novozymes A/S, Denmark; chain exhibit superior wetting performance. Their 2Novozymes North America, Inc., USA excellent lime scale removal power combined with Hand-dishwashing (HDW) product formulations excellent compatibility with all kind of surfaces, have historically focused on continuous optimization of especially sensitive plastic materials makes them the the surfactant and fragrance systems. Innovation is now ideal solution for bath cleaners. In addition, Glucamides increasingly dependent on more-novel ingredients such leave low residue and streaks on the cleaned surfaces, as enzymes. To benefit from the well-known ability and maintaining their shiny appearance. Finally members of speed of enzymes to quickly break down starch and the Glucamide family are also excellent rinse surfactant protein, HDW formulations require state-of-the-art for automatic dishwashing as they reduce spots and technology to ensure formulation compatibility as well films significantly. as stability. We evaluated the ability of enzymes to enhance performance by dismantling complex burnt-on Novel Dishwashing Process Converting Fatty Soil into and dried-in food-soils. In addition to those results, the Surfactant Mariko Kagaya*, and Takaya Sakai, Kao presentation will focus on how to overcome the Corporation, Japan technical formulation challenges to ensure this Sodium poly (oxyethylene) alkyl ether carboxylate improved performance in hand dishwashing solutions. (EC) is known as a low irritated anionic surfactant and has been applied to many kinds of detergents and Glucamides - Versatile Sugar Surfactants for industrial chemical products. Recently we found that EC Sustainable Cleaning of Hard Surfaces Carsten Cohrs*, performs excellent detergency for fatty soil. In order to Florian Schinle, Gabi Ohlendorf, and Christine Müller, reveal the mechanism for it, we investigated the Clariant, Germany triangle phase diagram of EC, a component of fatty soil To meet the trend of renewable based and and water by means of microscopic observation, small environmentally safe surfactants we investigated angle x-ray scattering (SAXS) and DSC measurement. As Glucamides or N-Methyl-N-Acyl Glucamines as a new a result, EC aqueous solution and oleic acid, which is type of highly renewable, non-ionic sugar surfactants. one of the components of fatty soil, form lamellar liquid They are readily biodegradable and are safe for the crystal (LLC) in very broad composition and aquatic environment. Depending on the hydrophobic concentration range in the phase diagram. The moiety of the molecule wetting ability, foam cleansing mechanism for fatty soil is thought to be that performance and cleaning effect can be modulated to EC solution penetrates into fatty soil and forms LLC with cover a broad field of applications. Therefore we oleic acid. In this LLC, fatty acid, which is soil, also works assumed them to be an ideal new product group for as a surfactant and it becomes high concentrated hard surface applications. In the homecare segment surfactant solution. As high concentrated surfactant they may be used for a variety of applications. In hand solution (LLC) is formed inner soil itself, the other soil dishwashing liquids, green hand dishwashing liquids can components can be removed by liquid crystal formulated without loss in performance against emulsification with much less power than the normal standard products. Highly concentrated liquids are emulsification. In fact, it is confirmed that EC solution accessible without volatile organic solvents. The liquids removes the whole fatty soil without rubbing. From have a very low impact on the environment. Selected above, EC performs not only high detergency but also Glucamides can deliver caring benefits to hands after spontaneous dishwashing for fatty soil converting soil - 7 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

into surfactant. It might lead sustainable process regions, phosphonates. Cleaning: the palette of decreasing the amount of surfactant. Moreover this chemistry the ADW formulator can chose range across cleansing can provide consumer low mechanical power bleach for beverage removal, enzymes (protease for cleansing with mildness to the skin. protein soils such as meat and egg and amylases for starch related pasta and rice), alkalinity for hydration of Increasing the Performance of Automatic Dishwashing burnt soils and surfactant for grease removal. Shine: with Enzymes Roberta Mustacchi1, Lotte J. Jensen- combinations of polymers, builders and crystal growth Holm*1, and Thomas J. Burns2, 1Novozymes A/S, inhibitors are available to deliver shine across the full Denmark; 2Novozymes North America, Inc., USA range of consumer relevant substrate. Yet the top In this presentation we will focus on showing the unmet consumer need continues to be on tough baked ability of enzymes to save time and effort in the wash on soil removal. Delivering against this consumer need process and we will prove how enzymes can will become even more challenging as the industry and significantly increase the overall wash performance on consumers will try to save energy behind lower hard to remove complex soils. We will also illustrate the temperatures and with shorter wash cycles, which pose novel methodology used for evaluating performance new technical challenges such as dissolution of tablets, and the materials available for reproducing such results grease cleaning, organic film formation, and need for in any laboratory. higher levels of enzymes/efficient enzymes under these conditions. In addition there are space constraints Cracking the Code for Spotless Dishes Peter Miller* and within the unit dose form to be compatible with Keith E. Gutowski, BASF Corporation, USA machine dispenser drawers. The ADW formulator will In 2010, a post-phosphate landscape created some need look to increasingly sophisticated chemistries in major challenges for automatic dishwashing detergent order to balance these challenges and, in the process, formulators, and many consumers were left with dirty continue to demonstrate good product stewardship in dishes. Six years later, formulators have come up with the area of human and environmental safety. The inventive ways to replace and even exceed the partnership of the Dishwashing Appliance Industry is a performance gaps left by the removal of phosphate. requisite to achieve these goals. One of the largest gaps has been the spotting and filming performance, largely influenced by the level of In Situ Monitoring of Soil Removal Processes from minerals in the wash water and the degree to which Hard Surfaces Using Quartz Crystal Microbalance these minerals can be sequestered in the wash. Technique Yu Kanasaki*1, Yasuyuki Kobayashi2, and Formulating with the chelating agent sodium Keiko Gotoh3, 1Nara Women's University, Japan; 2Osaka methylglycine diacetate (MGDA), in combination with Municipal Technical Research Institute, Japan; 3National other sequestrants, can virtually eliminate spotting and Institute of Technology, Nara College, Japan filming without major concessions on cost or other The trace-level surface contaminants significantly performance criteria. impact on the quality of the products such as hard disk, silicon wafer and semi-conductor, and therefore their Future Trends in Auto-dish Wash Detergents Mike removal by cleaning should be necessary. To improve Orr*, Nilgun Aksoy, Rob Roggeband, and Graham A. the removal efficiency of the contaminants, the Sorrie, The Procter & Gamble Co., UK mechanism of the removal process should be revealed. Consumers continue to demand outstanding In this study, to investigate removal behavior of trace- cleaning and shine performance from auto-dish level contaminants from various hard surfaces in detergents. To delight the consumer, The ADW aqueous solutions, we performed in-situ monitoring of innovator has to deliver top class cleaning performance contamination removal process using a quartz crystal through a skilled integration of a diverse palette of microbalance (QCM). The QCM electrodes consist of chemistries that does not require phosphate or, in some carbon, silica, and gold, which were used as model hard - 8 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

surface substrates. For comparison, a polymer film, was Methane Sulfonic Acid and Methylglycinediacetic Acid prepared on the QCM. Stearic acid (SA) was deposited Benefits in Acidic Bathroom Cleaning Formulations as trace-level contaminants onto the QCM by the Kevin M. Salmon*, and Stephen F. Gross, BASF Langmuir-Blodgett (LB) technique. Immediately after Corporation, USA immersion of the QCM in the aqueous solution In this presentation, a performance synergy is containing sodium hydroxide (NaOH) or alkyl sulfate explored between a combination of methane sulfonic (AS), the QCM frequency was recorded. The apparent acid (MSA) and methylglycinediacetic acid (MGDA) in an equilibrium removal efficiency and the rate constant of acidic bathroom cleaning formulation. For home care the SA-LB film were determined from the frequency vs. applications, MSA must be partially neutralized to an time curve. In the NaOH solution, the SA-LB film was acceptable pH (>2.3). Buffering of strong acid solutions efficiently removed from all substrates due to to higher pH normally results in loss of primary cleaning neutralization. On the other hand, in the AS solution, performance, due to acid neutralization and acid salt the removal efficiencies of the SA-LB film from the formation. Surprisingly, a significant increase in primary carbon, gold and polymer substrates were small. It cleaning performance vs. calcium stearate is observed seems that the SA-LB film deposited on the substrate in when the pH is adjusted using MGDA as opposed to contact with its hydrophobic part is difficult to remove NaOH. Further development work was performed to by the penetration of the surfactant. As expected, the generate a formulation with improved performance to SA-LB film deposited on the silica substrate in contact market products at a greatly reduced activity. Market with its hydrophilic part was rapidly removed. trends in Hard Surface (specifically bathroom care), test formulations and performance data will be presented. Silicone-free Rubber and Plastic Dressing for Enhanced Carwashing Danielle Goodwin1 and Dave McCall2*, Spontaneously-generated Peeling of Keratin Grime 1Madonna University, USA; 2USA from Hard Surfaces by the Effects of Permeation, Unlike most detergent processes, successful Chelation, and Swelling Yosuke Watanabe*, Asako washing of an automobile involves more than just soil Kawasaki, Yukihiro Kaneko, and Ryoji Yasue, Lion removal. Once clean, the various surfaces of the vehicle Corporation, Japan are expected to have a high gloss. Achieving sufficient In a bathroom, various grime stick and accumulate shine usually requires the application of an additional to the hard surfaces easily and strongly by repeating product. Rubber and plastic surfaces are generally dipping and drying with soiled bathtub and showering treated with a silicone blend, which produces a very water. In this study, we report a new mechanism of high gloss. However, the silicone film is wet and tends bath cleaning whereby the detergent can wash out the to sling off the surface when the car is in motion and is grime from hard surfaces without a great deal of time prone to quick resoiling when dirt impacts the wet film. and effort. For easy cleaning, we focused on the binding A new rubber and plastic dressing product has been state between the bath grime and the hard surfaces, formulated which produces a durable, glossy film on and tried to weaken the bond strength by permeating treated surfaces in the form of a dry film. The film is a and chelate effects of detergents. We confirmed that a blend of polymers and waxes and includes an exclusive main component of the bathtub grime is a complex of gloss agent specifically synthesized for this application. calcium and a keratin protein derived from human skin Since the film is dry, it remains in place after by using FT-IR and EDS-SEM measurements, and keratin application, resists soil, and survives multiple cleaning grime is remarkably swollen with water by depriving it cycles. of calcium ion with chelating agents by using ICP and FT- IR measurements. Further, we found that the swelling rate is increased by permeating effect of anionic surfactants and glycol solvent by using dynamic surface tension measurement and the advanced swelling - 9 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

induces spontaneously-generated peeling of keratin grime from the hard surfaces by using video microscope measurement. The results demonstrate that the binding state between the bath grime and the hard surfaces can be weakened by permeating effect of surfactants / glycol solvent and swelling effect of chelating agents.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

S&D 2.1: General Surfactants Chairs: Sanja Natali, USA; and Phillip Vinson, The Procter & Gamble Co., USA A New Approach to Developing Surfactants photo-transition in 5 days post-fertilization (dpf) Soluble in Highly Alkaline Systems Renae Bennett, larvae. Larval zebrafish are exposed to test Eric Theiner*, Khalil Yacoub, Brian Smith, and Larry materials beginning at 5 dpf and locomotor activity Meyers, Evonik Corporation, USA assessed using video tracking. Locomotor activity is Cleaning systems with high levels of actives stimulated using alternating 3 minute light/dark allow more economical distribution of periods and activity recorded for 8 light/dark concentrated products as well as the benefit of cycles. Narcotic potency is determined as the bringing high performance products to bear in concentration at which locomotor activity is difficult soil removal systems such as those found reduced by 50% (IC50). A variety of test materials in food and beverage plants. To date, there have have been evaluated including linear alcohols and not been many materials that provide a high surfactants. The narcotic potency of linear alcohols degree of solubility in heavily built alkaline systems (C2 to C12) was observed to increase with carbon while maintaining the performance that results number. Ethoxylation (EO) of alcohols to produce from good surface and kinetic action. This alcohol ethoxylate (AE) surfactants altered narcotic presentation will discuss a new approach to the potency in a biphasic manner, increasing narcotic problem and the resulting surfactants that are potency at low EO but decreasing narcotic potency unique to the industry. at high EO. Anionic surfactants (alkyl ethoxy sulfates, linear alkylbenzene sulfonates) were an Assessment of Narcotic-like Effects of Surfactants order magnitude less potent narcotic agents in Using a Larval Zebrafish Neurobehavioral Assay comparison to AEs. These studies collectively Harry W. Broening*1, Lisa Truong2, Jane K. La Du2, demonstrate the utility of the larval zebrafish Greg J. Carr1, J. F. Nash1, George P. Daston1, and model to detect and characterize narcotic agents. Robert L. Tanguay2, 1The Procter & Gamble Co., USA; 2Oregon State University, USA Counterion Binding on Coacervation of Dioctyl The intoxicating (narcotic) potential of Sulfosuccinate in Aqueous Sodium Chloride ingredients used in consumer products can result in Shengbo Wang, Changlong Chen*, Ben Shiau, and adverse outcomes following accidental exposures. Jeffrey Harwell, University of Oklahoma, USA These effects are often characterized as Large amounts of surfactant coacervation work drowsiness, lethargy, or non-responsiveness in focused on complex coacervation, such as mixture emergency treatment situations. Thus, it is of surfactant and polymer, or mixture of different important to identify ingredients with narcotic species of surfactants, seldom on the simple potential in order to assess the likelihood that a coacervation of single conventional surfactant in formulation may produce symptoms of narcosis aqueous phase. This study aims to investigate following accidental ingestion. To rapidly screen evolution of dioctyl sulfosuccinate (AOT) /sodium and evaluate the narcotic-like effects of chemicals, chloride coavervation in aqueous solution a neurobehavioral assay was developed using early associated with change in counterion binding life-stage zebrafish. The assay is based on degree. In this work, coacervation phase boundary locomotor responses stimulated by a light-to-dark of AOT in the presence of sodium chloride was

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

obtained by spectrophotometer in terms of selecting the suitable surfactants. The objective of turbidity measurement. The activity of counterion this research is to investigate the salt-viscosity was measured by sodium ion electrode probe. response of alcohol ethoxylate sulfate anionic Electro kinetic parameters such as Zeta potential surfactants, alcohol ethoxylate nonionic surfactants and hydrodynamic aggregate size were and mixtures of the two. These surfactants are also investigated by dynamic lighting scattering (DLS). tested in different laundry detergent formulations Also, the formation of coacervate, an for their viscosity performance. Parameters electrostatically-driven phase separation, is affecting the salt-viscosity response to be studied mathematically illustrated through DLVO theory, include the degree of ethoxylation, the essentially a balance between electrostatic hydrophobe structure of the surfactants and the repulsion and van der waals attraction for colloid anionic/nonionic surfactant ratio. The viscosity is system. A monotonic decreasing AOT coacervate measured using a Brookfield viscosmeter at room boundary was observed with increase in NaCl temperature. The stability of the laundry detergent concentration. The degree of counterion binding, formulas is evaluated visually based on the calculated by modified Corrin-Harkins equations, formulation clarity and homogeneity at 4 and 40oC. revealed a 3-segment behavior of AOT in salt As different formulations require different solution. Colloid size distribution was conducted viscosities, the finding of this study will provide with DLS, where a micelle-vesicle-coavervation guidance for screening potential alcohol ethoxylate process was observed in according with a sharp sulfate/alcohol ethoxylate surfactants individually change in zeta potential. Electron microscopy also or in combination for a new formulation as well as verified the evolution of coacervation in aspect of selecting a drop-in replacement of each surfactant morphology. DLVO theory calculation shed lights or surfactant combination in an existing on how to promote or avoid coacervate. formulation to achieve the desirable formula Counterion binding degree plays an important role viscosity. in the formation of surfactant aggregates. A further study of binding degree facilitates to understand Synthesis, Characterisation, and Surface Activity coacervation. of Purified Sodium Lauroyl Isethionate. Mohammed I. Jeraal*, David Harbottle, and Kevin Strategies for Drop-in Replacements for Active Roberts, University of Leeds, UK Ingredients in Existing Liquid Laundry Detergent In recent decades, synthetic detergents such Formulations Thu Nguyen, Christian Jones*, and as sodium cocoyl isethionate (SCI) have become a Tamra Weemes, Sasol Performance Chemicals, USA popular alternative to saponified soaps as a result Viscosity control plays an important role in of their comparatively higher stability in hard water creating a liquid laundry detergent product that and increased mildness. Despite widespread meets consumer needs. Beside the reason for the adoption by the personal care industry, there is a appearance of the liquid detergent, high viscosity notable lack of knowledge with respect to their can cause liquid flow and stability problem while fundamental chemical and physical properties. In low viscosity can cause mechanical loss of the the current study, a compositional analysis was detergent during the machine washing process. executed on a hydrolysed coconut oil blend Therefore, it is important to formulate a liquid typically used to synthesise SCI. The most abundant laundry detergent with reasonable viscosity by lauryl constituent was subsequently synthesised at

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

the 1L scale. The crude isethionate product was phenyl linear alkylbenzenes and 2-phenyl linear purified by repeat recrystallisation in methanol and alkylbenzene sulfonates. A series of 2-PhLAS were any incremental increase in purity was measured synthesized with chain lengths ranging from 10 to by titration with benzethonium chloride. The 16 carbons. These isomerically pure 2-PhLAS chemical identity of the resulting surfactant was compounds were independently tested to verified by FTIR, NMR and LC-MS. A combined TGA- determine if enhanced detergency performance DSC thermal analysis was used to determine the was achieved when compared to commercial LAS. solid-liquid phase behaviour of the pure Results from the detergency tests will be included isethionate species. Sodium lauroyl isethionate was in this presentation. isolated to a purity of 97% by LC MS. The thermal analyses indicated a melting temperature range of The Effect of Regular Surface Patterning on 223-225°C with significant decomposition beyond Surfactant Adsorption Brian P. Grady* and Joshua 300°C. A critical micellar concentration of 5.4 mM J. Hamon, University of Oklahoma, USA at 18°C was determined by tensiometric analysis, Using e-beam lithography and reactive ion thus confirming the surface activity of the etching, we have created surfaces that we have isethionate ester derivative. Commercial termed pillars (a relatively flat surface with isethionate esters typically range between 70 and nanoscale size) and troughs (a relatively flat surface 85% so this research provides an insight into the with nanoscale size with walls on either side). Using preparation and performance of isethionate esters atomic force microscopy, we have examined these of a higher purity. Future research aims to blend surfaces in water after surfactant adsorption and different purified isethionates to determine the compared those to the same surfaces with no effect of varying chain length distributions on the confinement. Results in terms of the thickness of phase behaviour of naturally derived synthetic the layers will be presented, and molecular detergents. dynamic simulations under similar confinement will also be presented.

Synthesis of Isomerically Pure 2-Phenyl Linear Rheology Modifications for Functional Markets Alkyl Benzene Sulfonates Richard L. Pederson*, David R. Allen, Aaron W. Sanders*, Elodie Shaw, Materia Inc., USA Ginger Wren, Dawn Friesen, Eric Weber, and Kelly Linear alkylbenzenes are primary surfactants Buchek, Stepan Company, USA used in household cleaners and detergents. The The use of rheology modifiers is widespread in demand for linear alkyl benzene sulfonates the functional additives markets. Surfactant based continues to grow because of their low cost, strong solutions can offer alternatives to the traditional performance, and biodegradability. One of the polymeric based systems. In the oilfield viscoelastic "holy grails" of the detergent industry is more surfactant formulations and foamed fluids have concentrated cleaning power. Industrial experts found several niche applications, including have described the superior cleaning performance hydraulic fracturing, gas well deliquification, and of the 2-phenyl linear alkyl benzene sulfonate (2- EOR. Viscoelastic surfactants form a self healing PhLAS) isomer over the other LAS isomers (e.g., the “pseudo polymer” that can be easily broken down 1-, 3-, 4-, 5- and 6-PhLAS). This presentation will when required. Foams create a novel shear describe the synthesis of isomerically pure 2- thinning or thickening fluid, that can modify the

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

density of a liquid making it easier to lift, but also The Effect of Small Molecules on Cetylpyridinium can slow the propagation of gas in porous media. In Chloride’s Behavior in Solution and at Interface the agrochemical area, formation of nano-sized Hongwei Shen*, Chi-Yuan Cheng, Kevin Chi, vesicles through a self-assembly process using at Donghui Wu, Venda P. Maloney, and Ravi least two surfactants can provide liquids which are Subramanyam, Colgate Palmolive Co., USA both shear thinning and have high elasticity. These Cetylpyridinium chloride (CPC) has been widely properties are the basis for strong suspensive used in many consumer products as emulsifier, systems which can be utilized in agrochemical antibacterial agent, and / or preservative. suspension concentrate or suspoemulsion delivery Understanding how small molecules in the systems. This talk discusses some of the recent formulations impact CPC’s behavior and activity is advances in the rheology of surfactant systems and critical for developing efficacious new products for foams in the functional products area. consumers. In this study, the effects of two small molecules, sodium benzoate and benzyl alcohol on Development and Characterization of a New Class CPC’s behavior in solution and at interfaces were of Castor Oil Ethoxylates Cornell Stanciu*, Jorge M. investigated by NMR, dynamic light scattering Fernandez, and Ning Xie, Sasol North America, USA (DLS), and surface/interfacial tension (SFT/IFT) A new class of castor oil ethoxylates with techniques. It was found that sodium benzoate significantly improved efficacy has been developed significantly altered the size and dynamics of CPC using a narrow range catalyst. The unique structure aggregates, while benzyl alcohol had minimum of the castor oil tricglyceride allows for the effect. In an effort to understand the observed CPC formation of highly effective surfactants especially behavior change, the interaction of these small when saponification can be mitigated through the molecules and CPC at molecular level was use of a very selective catalyst. These products investigated by Nuclear Overhauser Effect NMR display distinct features compared to other Spectroscopy (NOESY). NOESY results suggest that traditionally base-catalyzed analogs on the market, the aromatic ring of negatively charged sodium making them particularly suitable for agricultural benzoate strongly interacted with CPC while benzyl and oilfield applications. This paper describes the alcohol did not. It is believed that electro-static thorough analytical characterization (NMR, wet interaction dominates the effect of small molecules chemistry, HPLC, MALDI-TOF) we pursued in order on CPC in aqueous formulations and results in to understand the noticeable differences in observed behavior change. behavior compared to similar products manufactured via alternative catalytic methods. It also shows the main surfactant characterization methods (ST, IFT) utilized for the product. A report on the performance of these molecules in agricultural and oilfield markets with the new applications developed is also presented.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

S&D 3: Journal of Surfactants and Detergents—20th Volume Celebration Honoring Milton Rosen Chairs: Dennis Murphy, Stepan Company, USA; and Arun Ramchandran, University of Toronto, Canada Gemini Surfactants Based on Linear Alkylbenzene salt. Detergent properties are also superior to LAS Sulfonate for Use in Liquid Laundry Detergents on a variety of soil types. The presentation will George A. Smith*, Huntsman Corporation, USA discuss the physiochemical and performance Linear Alkylbenzene sulfonate (LAS) is the properties of gemini and oligomeric surfactants largest production volume anionic surfactant in the based on LAS. world. It has a clean bill of health in terms of environmental and ecotoxicity and is the main Silicone Surfactants in Oil Based Systems Tony frame surfactant in most laundry powder O'Lenick*, Siltech LLC, USA formulations. LAS suffers from some deficiencies Over the years Dr. Rosen has examined, including poor hard water tolerance and limited characterized, and evaluated many different types solubility in aqueous solution because of it of surfactants and their ability to function for very propensity to form lamellar phases. With the shift specialized applications. His in approach to the in from powders to liquids in many countries, the depth studies that provide structure/ function demand for LAS has decreased. To obtain better insights into surfactants in which traditional fatty performance in liquid formulations, Huntsman has surfactants are placed into water has inspired been investigating the use of gemini and oligomer expansion into non-traditional systems. Professor surfactants based on LAS. A gemini surfactant is Rosen’s approach to evaluating standard two has two hydrophilic headgroups and two surfactants has been expanded into looking non- hydrophobic tails chemically connected by a spacer traditional surfactant systems. Such systems are group close to the headgroups. In general, gemini those in which silicone / hydrocarbon surfactants surfactants have very low critical micelle are added to oil based systems. Our laboratory has concentrations (CMC), have better foaming, become increasingly interested in understanding wetting and emulsification properties than the function of such surfactants in anhydrous conventional single chain surfactants. Huntsman systems. These systems take advantage of the fact has been looking at using electrostatic interactions that hydrocarbon and silicone are immiscible in rather than covalent bonds to form gemini each other and have surface activity. These surfactant structures for use in liquid formulations. surfactants, when properly chosen will lower A number of different commercial bola-type surface tension, provide wetting, foam and connecting molecules can be used to form gemini- function that are directly analogous to what fatty like surfactants. Ethyleneamines and surfactants do in aqueous systems. It is perfectly multifunctional polyetheramines are very effective legitimate to ask what is the CMC of cetyl at forming gemini and oligomeric surfactant dimethicone in mineral oil or in olive oil. Using the structures in aqueous solution by simple mixing. techniques that have allowed us to understand These structures have much reduced CMC, foaming traditional surfactants it is possible to understand properties and can build viscosity in low active the function of non-traditional systems that are detergent formulations without the need for added already in use in several industries. This paper will - 15 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

discuss the properties of silicone surfactants used Microemulsions, and Detergency David A. in oil based anhydrous systems and compare them Sabatini*, University of Oklahoma, USA to standard surfactants in aqueous systems. Journal of Surfactants and Detergents – 20th Volume Celebration (in honor of Milt Rosen) Synergism and Interaction of Surfactants in Surfactant mixtures have the potential to achieve Enhancing Performance in Personal Care and ultra-low CMC values, greatly enhance Industrial Formulations Manilal Dahanayake*, solubilization, produce middle phase Surfactant Solution Experts LLC, USA microemulsions, and corresponding ultra-low IFTs, The interfacial and colloidal properties of a and thus enhance system performance in a range solution of two or more surfactants may be quite of applications. This presentation will summarize different from those of the individual surfactants in research published in JSD that focused on solution. Mixtures of surfactants can exhibit surfactant mixtures to achieve these objectives, synergy if the surfactants attract each other including anionic-cationic surfactant mixtures as sufficiently, either through mutual electrostatic well as other mixtures. The role of surfactant attraction of oppositely charged hydrophilic groups mixtures in detergency will discussed as well. or through van der Waals attraction of their hydrophobes. The interactions between Surfactant-polymer Interaction Yun-Peng Zhu*, surfactants can be measured and quantified by the Lubrizol Advanced Materials, Inc., USA so called "beta"parameters related to their activity Polymers are widely used together with coefficients in the mixture. Mixing different charge surfactants in many applications. To understand types of surfactant that exhibit synergism is an the interaction of surfactants and polymers is of important method in enhancing performance great significance to developing the beneficial properties. Synergism in surfactant mixtures leads properties while avoiding unwanted problems. to less surfactant utilized to obtain the same level Here, a study to investigate the interaction of of performance, with consequent economic and common surfactants with polymers was carried out environmental benefits as well as enhancing and the properties including rheology control, surface activity, spreading, wetting, foaming, viscosity enhancement, and water solubility detergency and many other phenomena. Recent improvement were discussed in terms of the advances in design of surfactants to optimize interaction between surfactant-polymer. interactions and synergism in surfactant Furthermore, a brief introduction of the application mixtures has further led to several new and novel of polymer with surfactants to detergents was opportunities in practical applications. Some of provided. these developments such as mitigating the irritancy in personal care formulations, use of bio-enhanced Improve Low Tension Formulation Robustness in surfactant-adjuvants to reduce usage levels of Enhanced Oil Recovery with Properly Optimized many highly toxic agrochemicals and enhanced Surfactant Mixture Jean-Louis Salager*, and Ana recovery of oil and gas (EOR) by the use of M. Forgiarini, Universidad de Los Andes, Venezuela viscoelastic surfactants will be highlighted in this Enhanced Oil Recovery requires the attainment talk. of ultra low interfacial tension between crude oil and the injected aqueous phase. It is known that Surfactant Mixtures: Synergism in Solubilization, the lower the minimum tension is, the narrower

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

the range of formulation over which it would take optimal salinity. We have observed large changes place. Consequently, the general rule is that the in optimal salinity when varying the cation of an lower the tension, the more accurate should be the added salt. Results with potassium, calcium, surfactant formula, and the worse will be the magnesium, cesium, rubidium and lithium chloride robustness. This is a very serious problem since the salts are presented. The observed shifts in optimal injected formulation is likely to be altered as the salinity are consistent with the Hofmeister series; surfactant slug progresses through the petroleum for example, potassium, the weakest chaotrope, reservoir. However, there are two ways to avoid it. reduces the optimal salinity, while lithium, the The first one is to use an injected formula as strongest kosmotrope, increases the optimal insensitive as possible from the variable likely to be salinity. These results suggest additional strategies altered like the salinity, temperature, or surfactant for formulators in a variety of application areas mixture characteristics. This can be attained in from enhanced oil recovery, to cleaning systems, to some cases with complex surfactant mixtures drug delivery. We present suggested adjustments whose components partitioning may be used to to the calculation of the optimal salinity in the HLD counteract the spontaneous change. The second equation to account for these effects. way to improve robustness is to use an artifact in which the spontaneous alteration will result in a Use of High Throughput Technologies to transition followed by the opposite retrograde Accelerate Formulation Development Christopher transition, thus producing two optimum J. Tucker*, Michael Tate, and John Ell, The Dow formulation zones taking place one after the other. Chemical Company, USA It is shown that such an extended low tension zone Colloid and interface science is a may be attained to compensate a spontaneous multidisciplinary field at the intersection of change in aqueous pH, in brine salinity, and in chemistry and physics. Many of the most surfactant originally injected composition. interesting aspects of the field occur in multiphase materials or systems at or near phase transitions. Accounting for Ion Specific Effects in the We have utilized fundamental studies of the Hydrophilic/Lipophilic Difference (HLD) Equation properties and phase behavior of complex systems Brock A. Trotter, Mohannad Kadhum, Ben Shiau, such as emulsions, microemulsions and surfactant and Jeffrey Harwell*, University of Oklahoma, USA blends with polymers and other materials to The Hydrophilic/Lipophilic Difference (HLD) impact performance of formulated products in Equation correlates the phase behavior of multiple applications. In order to facilitate these surfactant/oil/water systems with temperature, studies, we have developed a range of high electrolyte concentration, oil type, and surfactant throughput formulation and characterization selection. A Winsor Type III microemulsion is a methods that have reduced the experimental time separate, surfactant-rich phase that forms in required to study structure property relationships equilibrium with excess oil and water. Varying the and generate complex phase diagrams. The amount of an added simple electrolyte can induce effectiveness of these tools and methods can be the formation of a Type III microemulsion from an maximized if they are combined with experimental oil/water/surfactant system. The concentration of design approaches to generate predictive models sodium chloride at which equal volumes of oil and to optimize performance in different applications. water partition into the middle phase is called the The products impacted are diverse and include

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

consumer and personal care products, paints and coatings, food additives, drug and Agricultural products, and microelectronic device fabrication.

Samuel Rosen, Milton Rosen, and Visions of a Future Honoring a Legacy Charles E. Hammond*, Flotek Chemistry, USA "Surfactants and Interfacial Phenomena", 4th Edition, was published by Wiley in 2012. The book includes many tables that painstaking tabulated references of data. As the number of surfactant publications per year continues to grow, how will similar data be collated and tabulated in the future? This presentation will briefly discuss how the world of surfactant oil water systems may be augmented by "big data".

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

S&D 3.1: New Encapsulation and Delivery Systems Chairs: Sam Adamy, Church & Dwight Co. Inc., USA; and Michael Miguez, Shell Global Solutions, Inc., USA HLD-based Method to Customize Lecithin-linker Study of Fragrance Bloom, Release, and Retention SMEDS Delivery Systems Mehdi Nouraei*, and on Substrate from Surfactant-rich Cosmetics Edgar Acosta, University of Toronto, Canada Martin S. Vethamuthu*, Sergio Lira, Edward Lecithin-linker microemulsions have been used DiAntonio, and Hani Fares, Ashland Specialty as platform for designing fully dilutable self- Ingredients G.P., USA microemulsifying delivery systems (SMEDS). A Objective: This study discusses a new and platform SMEDS formulation composed of ethyl effective in vivo method to study fragrance bloom caprate (oil), lecithin (surfactant), glycerol and release kinetics from formulations containing monooleate (lipophilic linker, LL) and polyglycerol neat and encapsulated fragrance oils in surfactant caprylate (hydrophilic linker, HL) displayed a fully rich cosmetics. Method: The instrument used to dilutable path suitable in the absence of active screen cosmetic compositions for improved ingredient. Introducing ibuprofen as a model active fragrance retention components is an Agilent ingredient resulted in a phase separation along the HP7890B GC/5977C MSD with GERSTEL MPS dilution line. To address this issue, the Hydrophilic robotic sampler, equipped with a DB-624 capillary Lipophilic Difference (HLD) framework was used to column (30m, 250 mm and 1.40µm film thickness). quantify the effect of ibuprofen on the An area of 18cm2 of the inside arm was washed lipophilicity/hydrophilicity of the formulation. with 3.3 mg/cm2 of a shower gel formulation and Using this methodology, the SMEDS-drug rinsed with tap water for 30 seconds and dried. interaction was quantified by calculating the shift Subsequently the area of the arm was exposed to in optimum salinity for loaded and unloaded the twister bar or SPME fiber for 15 minutes, this systems over a phase scan. It was determined that step is repeated at intervals of 1 hour for a total introducing ibuprofen produces a positive HLD time of four hours, after extraction the twister bar shift. The HLD framework was then used to predict / fiber is removed and placed into a clean glass the required type of hydrophilic linker and the thermal desorption tube for GCMS analysis. proportions of LL: Lecithin: HL to restore (recover) Results: The technology screening process helps the fully dilutable path. Implementing the identify fragrance encapsulates and polymeric proposed changes resulted in a fully dilutable deposition aids that capture, interact and retain SMEDS loaded with ibuprofen upon exposure to fragrance ingredients on skin during the wash simulated intestinal fluid (SIF). The results of this process. Discussion and Conclusion: The headspace study suggest that the HLD is a useful tool to GC instrumentation coupled with the appropriate quantify the impact of active-formulation SPME fiber or twister bar is capable of monitoring interaction and prescribe the necessary changes to the time dependent release/ retention profiles of restore the formulation. Although the active in this fragrance ingredients from the substrate. The formulation was a drug, the concept could also be results from this study show polymeric deposition used in the delivery of nutraceuticals, technology when combined with micro- cosmeceuticals, and active ingredients for encapsulation routes provides the best approach to agrochemicals. significantly improve fragrance delivery from rinse- off cosmetics.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

Microencapsulation Robert S. Bobnock*, Encapsys, elastomers as delivery medium, and various Si USA specific encapsulation routes will also be discussed. Microencapsulation can be defined in a myriad of ways usually closely related to the core, wall Delivery Systems in Detergent Products Johan material and/or release mechanism being utilized. Smets*, The Procter & Gamble Co., USA The technology has been around for many decades The freshness experience from fabrics and it continues to experience new advances during/after the laundry process is of outermost followed by patent protection as more and more importance of the appreciation of the detergent companies and their researchers test the products being used for the laundry process. The boundaries of encapsulation chemistry and physics. detergent industry is one of the biggest customers Microcapsules are common in many of the major of the perfume business. The optimal use of markets including but not limited to consumer perfume materials is of outermost importance in products, pharmaceutical, paper, agrochemical, the strive for efficient material use and can be food, microorganisms and many others. This effectively done via several approaches as review will explore wall materials, core materials, evidenced by the huge amount of patent activity in release mechanisms, and the reality of using this domain since the late ‘80s. In the strive for microencapsulation for a new benefit with the optimal use of perfume materials in the detergent possibility of creating a competitive advantage. business, multiple factors are into play, for most i) bring the signal perfume materials to places where Waterborne Silicone Delivery Brett L. it matters and ii) release at the appropriate time in Zimmerman*1, and Leon Marteaux2, 1Dow the appropriate amounts. We will present a Performance Silicones, USA; 2Dow Performance showcase on a perfume delivery technology being Silicones, Belgium used in detergent business. We will describe the The targeted delivery of actives has generated various aspects that were important to the significant interest globally, largely driven by ever commercialization path of the perfume delivery changing and demanding consumer perceived technology, what was important for deposition, needs. Whether from environment concerns and for headspace release in combination with the (solvent and waste minimization) or just perfume material choice. The perfume delivery application performance optimization, the technology is based upon the use cationic polymers waterborne delivery of silicone and other high with substantivity to specific perfume raw value actives are becoming prominent fixtures in materials. It has been evidenced that the approach academic and industrial project lists. The can enhance dramatically perfume deposition and purposeful use of surfactants to stabilize droplets, the head space release above dry fabrics can be to direct actives to surfaces, and to provide a significantly increased by the technology approach. template for interfacial polymerization once only We have also been researching the impact of the prevalent in applications like beauty care are now rheological parameters of the technology versus finding utility in textiles, construction, and even the efficiency of the technology. We will present electronics. Silicone emulsions, water based how these rheology aspects of the technology elastomers, and encapsulation in general will be represented a huge challenge that was turned into covered. The inherent properties of silicones and an opportunity. Furthermore, we will cover how how they are delivered, possible use of silicone scale up and process challenges were overcome to

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

implement the technology for a wide range of coverage of traditional encapsulated fragrance and businesses. the malodor elimination of a physico-chemical absorber. Malodor coverage efficacy is quantified Dual Action Malodor Benefit Capsules for using ratings of malodor reduction reported by Enhanced Freshness Evan Beach*, Ron Gabbard, trained sensory panelists and application relevant Yabin Lei, Sean Wetterer, and Li Xu, International standardized malodor mixtures. Elimination Flavors & Fragrances Inc., USA efficacy against a series of malodor molecules of Superior, long-lasting fabric freshness is interest is demonstrated using instrumental increasingly demanded by modern consumers of testing. The resulting combination results in an laundry detergents. Often, delivering this benefit is enhancement of freshness over standard detergent dependent on covering or reducing undesirable or benchmarks in application testing that simulates a unpleasant odors – malodors - that may arise as a full laundry cycle. Secondary benefits of the new result of washing practices, the environment, or technology include a long-lasting fragrance delivery wear. To that end, innovative scent and delivery profile and the potential for activated release of technologies have been developed to ensure a fragrance during periods of motion or exertion, preferred sensorial experience in this technically which may precede malodor development. challenging application. In this presentation, we report on the additional malodor reduction benefits of a novel capsule system that combines two proven modes of action: the perceptual

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

S&D 4: Chemicals and Surfactants in Enhanced Oil Recovery Chairs: Upali Weerasooriya, University of Texas, Harcros Chemicals & Ultimate EOR Services, USA; and Ben Shiau, University of Oklahoma, USA Enhanced Oil Recovery via Targeted Emulsified Highly Branched Heavy Guerbet Alkoxylate Solvent Injection (TESI) Aurelio Stammitti*, and Sulfates as EOR Surfactants and Crude Oil IFT Edgar Acosta, University of Toronto, Canada Reduction Thu Nguyen*1, Christian Jones1, and Based on 2013 Canadian oil production Greg Trahan2, 1Sasol Performance Chemicals, USA; statistics, surface mining and steam injection are 2Sasol North America, USA the two main recovery methods from oil sands. The This study focuses on evaluating the performance former is used up to 70m depth, and the latter for of highly branched heavy Guerbet alkoxylate depths greater than 150m. However, no method is sulfates as EOR surfactants and finding a new implemented to recover heavy oil within 70 to effective method of selecting appropriate 150m in depth. In this work, emulsified-solvent surfactant systems for crude oil IFT reduction. formulations near the phase inversion point or PIP Therefore, this research has two objectives. The (exhibiting ultralow interfacial tension) were first objective is to compare the IFT reducing injected into a column packed with bitumen-coated capability of highly branched heavy Guerbet sand. Five emulsified-solvent formulations around alkoxylate sulfates to that of conventional light the PIP having a water-to-solvent volumetric ratio alkoxylate sulfates. The second objective is to of 10 were injected into artificial oil-sand packed develop a method for identifying an effective columns at 9.2 m/day. The effluent was collected in surfactant system for a new crude oil based on its a fraction collector and the overall recovery was SARA (saturates, aromatics, resins and asphaltenes) determined by mass balance in each experiment. analysis. Our previous study showed that heavy Our preliminary results showed that at least 90% of Guerbet alkoxylate sulfates have higher the original oil in place can be recovered using solubilization capacity for oils than light alkoxylate surfactant concentrations below 1% and salinities sulfates. This study further demonstrates that close to 1% NaCl. The proximity to the PIP (as highly branched Guerbet alkoxylates with proper determined via the Hydrophilic-Lipophilic- PO/EO ratios can lower the IFT for crude oils as Difference or HLD framework) influenced not only much as light alkoxylate sulfates. A number of the fraction of oil recovery, but also the pressure crude oils were also studied and characterized into drop observed in the process. The results will be two groups based on their SARA analysis. The discussed in light of dimensionless number, crude oils that have the ratios of each of light particularly the capillary number that relates the hydrocarbon (

are considered as light crudes. It was found that the IFT for all crude oils with composition ratios of

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

less than 10 was similar by the same surfactant Oil-induced Formation of Wormlike Micelles and system. Their Use in Nanoparticle Stabilization Francis Choi*, and Edgar Acosta, University of Toronto, A Novel Approach to Determine HLD Parameters Canada Demonstrated with Internal Olefin Sulfonates Controlled nanoparticle synthesis using self- Chien-Yuan Su1, Ben Shiau2, and Jeffrey Harwell2, assembled structures produced with surfactants 1Institute of Applied Surfactant Research, University and microemulsions have been widely used due to of Oklahoma, USA; 2University of Oklahoma, USA their consistency in structure, and tunability. The hydrophilic-lipophilic difference (HLD) Though effective in synthesis, the stability of the equation has shown utility in guiding surfactant resulting suspensions is relatively poor. The ease in formulations for Winsor I, II and III microemulsions modifying the structures of lyotropic liquid crystals in various applications. A major limitation, into wormlike micelles (WLMs) through however, is the difficulty of obtaining the head composition, however, provides flexibility in group constant (K), the characteristic curvature nanoparticle stabilization after synthesis. We have (Cc), and the temperature dependence (αT) of the studied the formation of WLMs in microemulsions surfactants. This paper illustrates the facile and their application in nanoparticle stability. determination of these parameters using a WLMs have typically been produced using systems reference surfactant with a series of internal olefin of surfactant, water, and salt. Recently, we found sulfonates (IOS). IOS surfactants are a the addition of a fatty acid ester to an extended multicomponent mixture of hydroxyalkane anionic surfactant-water-NaCl system containing sulfonate, alkene sulfonate, and di-sulfonate spherical micelles, induces the formation of oil- molecules with twin-tailed structures, which are swollen WLMs and liquid crystals. The construction unable to form middle-phase microemulsions of phase diagrams show WLM formation requires without introducing alcohols at ambient two conditions: a low oil content, and surfactant- temperature. In this work, the IOS surfactants were oil-water systems with a hydrophilic-lipophilic- blended with a reference surfactant, an alkyl difference (HLD) value equal or greater than zero. propoxysulfate, C10-(PO)4-SO4Na, to aid in the Rheological measurements also indicate a large formation of middle-phase microemulsions with a increase in the storage modulus (G’) from liquid- series of alkanes at room temperature. From these like to solid-like behavior when these conditions studies the K and Cc values of the IOS surfactants are satisfied. Sedimentation tests for iron oxide were individually determined by the plots of and titanium dioxide suspensions show that the optimal salinity against alkane carbon number stability occurs in regions of the phase diagram (ACN) combined assuming the applicability of a containing WLMs. The G’ of these suspensions liner mixing rule. In addition, the determination of increase upon the addition of particles, suggesting the temperature constant (αT) of one IOS the particles act as junctions in networks of surfactant was shown using this novel approach. entangled WLMs that further increase the Finally, the practical application of the HLD viscoelasticity to achieve exceptional stability. This parameters combined with the HLD equation was phenomenon offers the possibility of formulating demonstrated for guiding the optimal wormlike micelles from a variety of surfactant- microemulsion formulation at high temperature. water systems previously incapable of producing The accuracy of the HLD parameters determined in this work was thus demonstrated. - 23 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

these phases, leading to an increased flexibility in Enhancing Foam Stability in Porous Media by the formulation of nanoparticle suspensions. Applying Nanoparticles Shengbo Wang*, Changlong Chen, Mohannad Kadhum, Ben Shiau, Interaction of Alkalis with Acidic Crude Oils and Jeffrey Harwell, University of Oklahoma, USA 1 1 2 Himanshu Sharma* , Krishna Panthi , Jun Lu , Upali The utilization of nanoparticles dispersions Weerasooriya3, Gary A. Pope1, and Kishore K. in foam flooding has become an attractive chemical Mohanty1, 1University of Texas, Austin, USA; EOR technique as compared to the conventional 2University of Tulsa, USA; 3University of Texas, surfactant only foaming system. This study is to Harcros Chemicals & Ultimate EOR Services , USA expand our understanding of utilizing multi wall A large amount of oil is left unrecovered after carbon nanotube (MWNT) on foam stability in primary and secondary floods due to high capillary porous media. We developed several foaming forces. Low IFT surfactants can recover this trapped agent formulations (surfactant and polymer) in the oil by lowering the interfacial tension. An alkali is presence of MWNT in 3% salinity (NaCl, 2.4wt%, CaCl2, 0.6wt %). The dispersion stability of the added with surfactants to lower their adsorption MWNT and the viscosity of the solutions were on the rock surface and generate in-situ soap with measured. Foam was generated in-situ, one- acidic crude oils. The objective of this study is to dimensional flow-through tests were performed by investigate the interactions of alkalis with acidic co-injecting air and foaming solution containing crude oils (NH3, NaOH, Na2CO3, and NaBO2). Alkali either the foaming agents-only or the foaming scans with acidic crude oils were performed, with agents in the presence of MWNT. During each and without adding cosolvents, and low IFT regions experiment, the pressure drop (Δp) and the were identified. An organic alkali was studied, in nanoparticles recovered across the sand-pack were addition to conventional alkalis, for performing ACP monitored. Injection rate, gas fraction and the floods. The type and amount of soap formed with effect of MWNT stabilized foams in porous media different alkalis were investigated. The effect of were investigated. The results reveal that foams cosolvent type was studied. Oil recovery corefloods stabilized by nanoparticles are able to generate stronger foams leading to apparent higher ∆p by were performed to compare ACP floods with ASP introducing MWNT total concentration as low as floods for the same oil. ACP formulations 60ppm. ∆p profile varies with gas fraction which developed using ammonia and sodium hydroxide largely affects the foam texture. Also, our data were found to be similar; showing low IFT at lower indicate the viscosity of foaming agent solutions salinities. An incremental addition of calcium ions influences ∆p values. Adding MWNT to the foaming resulted in gradually transforming the phase agent solutions appears beneficial to the flooding behavior towards Winsor type II. Favorable ACP as surfactants adsorb to nanoparticles which phase behaviors were obtained on adding a more facilitates surfactants partitioning to the G/L hydrophilic cosolvent. Good oil recoveries were interface. Thus, addition of nanoparticles in the observed during ACP corefloods in sandstone developed surfactant-polymer foam formulations cores. The results of ACP floods were found to be can lead to formation of stronger high-quality as good as those of the ASP corefloods in some foams in porous media, which improves the sweep cases. The interaction of alkalis with acidic crude efficiency and increases the oil recovery. oils is not well understood. This study is aimed at improving that understanding so that ACP and ASP floods can be designed effectively.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

New Surfactants and Cosolvents for Chemical EOR synergistically with traditionally used surfactants, Processes Pinaki Ghosh, Krishna Panthi, Himanshu give ultralow IFT ASP/SP/ACP formulations and Sharma, Upali P. Weerasooriya, and Kishore K. show enhanced foam stability in high- Mohanty, University of Texas, Austin, USA temperature/high-salinity environment. A large amount of oil is left unrecovered from oil reservoirs after primary and secondary Solid-Liquid-Liquid Wettability and Its Prediction floods due to various reasons. Among these with Surface Free Energy Models Aurelio factors, high capillary forces (between oil and Stammitti*, and Edgar Acosta, University of water) and poor sweep efficiency are largely Toronto, Canada responsible for trapping of oil in the porous media. Understanding wettability of immersed solids is Surfactants that can lower the interfacial tension important for applications such as enhanced oil with oil have traditionally been studied to improve recovery, multiphase flow in pipes and porous the oil recovery. Studies have shown that a media, oil-water separation, and bacterial significant improvement in oil recovery can be attachment. Significant research efforts have been achieved by injecting suitable surfactants in the undertaken to characterize wettability of low- reservoir. However, traditionally used surfactants energy surfaces like polymers and coatings exposed suffer from severe limitations due to their limited to air, and to a lower extent under immersed applicability in a high salinity/hardness and a high- conditions. Furthermore, wettability alteration temperature environment. These surfactants tend through structured/functionalized surfaces has to be unstable (not soluble) under these conditions been the focus of recent experimental and therefore cannot be used for improving the oil development. However, little attention has been recovery. Novel surfactants that are stable under a paid to immersed high-energy surfaces and no high salinity/hardness/temperature environment models are available to predict their wetting would expand the applicability of surfactant EOR to behavior. In this work, the solid-liquid-liquid such reservoirs. In addition to an ultralow wettability of glass, mica, stainless steel, PTFE and interfacial tension, a favorable microemulsion PMMA immersed in isopropyl alcohol (IPA) rheology is critical in lowering the surfactant aqueous solutions equilibrated with toluene was requirement. Cosolvents have shown to lower the determined via the contact angle (θ) of toluene microemulsion viscosity, lower surfactant retention drops (measured through the toluene phase) and improve the oil recovery. Alkali cosolvent deposited using the inverted sessile drop method. polymer (ACP) floods have been developed The Geometric Mean and Neumann’s Equation-of- recently for acidic crude oils, employing in-situ State (EQS) models were assessed for the generated Naphthenic soap as the surfactant. prediction of θ using a fitted or assigned solid- Improved cosolvents are critical to the success of aqueous phase interfacial energy (γSW). Results the above-mentioned processes. In this study, new plotted as IFT·cosθ vs. IFT show a smooth wetting surfactants and cosolvents for chemical EOR were transition from hydrophilic to hydrophobic with developed and their applicability in chemical EOR decreasing IFT for stainless steel and glass. Mica processes such as ASP/SP floods, ACP floods, and remained hydrophilic, while PTFE and PMMA foam floods was investigated. Promising results hydrophobic running parallel to the θ=0° line, were obtained using these new surfactants and consistent with literature data. Neumann’s EQS cosolvents. They were found to interact was able to describe the trends for glass, stainless steel and mica, suggesting that probably γSW is - 25 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

approximately constant for these systems. Medium Sachin Goel*1, Samson Ng2, and Arun Neumann’s EQS offers a promising simple Ramchandran3, 1Dept. of Chemical Engineering and prediction tool for immersed high-energy surfaces. Applied Chemistry, University of Toronto, Canada; 2Syncrude Canada Limited, Canada; 3University of Static Adsorption Study of Alcohol Propoxy Toronto, Canada Sulfate Surfactants onto Crushed Berea Sandstone It is well known that the dissolution rate and Daniel F. Wilson*, Laurie A. Poindexter, and Greg solubility of drops of one liquid emulsified in a Trahan, Sasol North America, USA second, immiscible liquid phase can be enhanced For chemical enhanced oil recovery (CEOR) significantly by the presence of surfactants in the applications, surfactant adsorption in porous media continuous phase. While methods for measuring is one of the major criteria which determine both solubility abound in the literature, measurement the technical and economic viability of surfactant techniques for the dissolution rate are rare. In this based flooding applications. In this study, static study, we present a new, robust microfluidic adsorption measurements were carried out with platform for determining the dissolution dynamics several representatives of anionic alcohol propoxy of an individual drop in an immiscible suspending sulfate surfactants onto crushed Berea sandstone. medium. We demonstrate this technique for Although there are other studies in the literature emulsions of water in bitumen, which contains that independently evaluate the strong roles that natural surfactants that enhance water mineralogy, temperature, pH, inclusion of other solubilization. This is a difficult system for chemicals, and brine salinity play on the adsorption dissolution measurements due to the opacity of capacity of surfactant on a solid surface, these bitumen, but our shallow microfluidic channels parameters were maintained as constants for this allow us to clearly image the water-bitumen work. The focus for this study was instead placed interface. We show that depending on the bitumen solely on the surfactants being evaluated with composition, water chemistry, and flow conditions, regard to alcohol structure, length of the the time for water dissolution in bitumen is hydrophobe, neutralization process, and variable governed either by interfacial phenomena or by PO extensions available. Chemical-flooding mass transfer between the bulk bitumen phase and schemes for recovering residual crude oil the water-bitumen interface. In the latter case, we saturation from reservoirs have often struggled can also calculate the solubility of water in due to loss of chemicals by adsorption to the bitumen, provided an independent measure of the reservoir rock. An increased understanding on how size of the water-carrying species is available. various surfactant parameters may affect Water-in-bitumen emulsions are extremely stable, surfactant adsorption are helping lead to and any sub-micron emulsified water droplets, enhancements in manufacturing, minimizing which are difficult to remove even by surfactant loss, and improving the overall ultracentrifugation, are also counted as solubilized economic efficiency of surfactant based CEOR water in traditional solubility measurements. Our processes in the field. single drop dissolution technique avoids this

complication. Lastly, our microscale results can also A Novel Microfluidic Platform to Measure the predict the time required to completely solubilize a Dissolution Rate of Drops Emulsified in an spherical drop in a suspending medium at the Immiscible, Surfactant-containing Suspending macroscale

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

BIO 4.1 / S&D 4.1: Biosurfactants, Bio-derived Surfactants, and Biodetergents Chairs: Heather Byrne, Huntsman Performance Products, USA; Douglas G. Hayes, University of Tennessee, USA; and Daniel Solaiman, USDA, ARS, ERRC, USA Tailoring of Mannosylerythritol Lipids by biosurfactants in sufficient amounts and desired Pseudozyma Species Using Different Renewable performance available, we are developing scalable Feedstocks Susanne Zibek*, Fraunhofer IGB production processes (fermentation and Institute for Interfacial Engineering and downstream processing) for several glycolipids. Biotechnology , Germany Our current optimized fermentation processes Currently, sustainable surfactant products with deliver product concentrations more than 120 g/L decreased carbon footprint and complete for mannosylerythritol lipids. biodegradability are highly demanded. This requires the introduction of new compounds and Integrated Bioprocess Design for the Production production processes based on renewable of Tailor-made Glycolipids Using Starmerella resources. Microbial biosurfactants meets organic bombicola: Promising Results from Application criteria and shows also a broad spectrum of Testing Lisa Van Renterghem1*, S. Roelants1,2, N. molecule diversity. Mannosylerythritol lipids (MEL), Baccile3, K. De Schamphelaere4, M. Höfte5, Q. produced by fungi of the genus Pseudozyma and Christiaens1, M. Hartmann1, S. Verweire1, and W. Ustilago, are among the most promising microbial Soetaert1,2,1Ghent University, Centre for Industrial biosurfactants with application potential in Biotechnology and Biocatalysis, Ghent, Belgium, personal care, technical uses and pharmaceuticals. 2Bio Base Europe Pilot Plant, Ghent, Belgium, MEL can be composed of a group of four variants 3Université Pierre et Marie Curie, Laboratoire de (A to D), which are classified by the degree of Chimie de la Matière Condensée, Paris, France, acetylation, which affects the polarity of the 4Ghent University, Environmental Toxicology Unit, biosurfactant and by that, their spectrum of Ghent, Belgium, 5Ghent University, Phytopathology application. Depending on the strain and feedstock Unit, Ghent, Belgium (fatty acid chain length, unsaturation), unique MEL Biosurfactants are an emerging class of mixtures can be produced. Therefore, we surfactants produced by microorganisms, offering a evaluated the effect of different feedstocks on the more environmentally friendly alternative production of MEL by various Pseudozyma strains. compared to traditional surfactants. One type of The results are used to develop strategies for glycolipid biosurfactants are sophorolipids (SLs), structure-tailoring of the surfactants by enzymatic, naturally produced by the non-pathogenic yeasts process engineering or metabolic engineering from the Starmerella clade in high amounts (> 200 methods. This way a portfolio of MEL-derivatives g/L), explaining its large industrial interest. Due to with enhanced hydrophilicity or hydrophobicity unique expertise gathered at InBio.be, Starmerella was generated. The created portfolio of MEL- bombicola can be genetically engineered to alter derivatives ranges from diacylated and acetylated the production towards one specific sophorolipid molecules with hydrophobic properties especially or novel glycolipid, transforming S. bombicola into suitable as emulsifier and cosmetic ingredients to a real platform organism. This research focuses on developing an monoacylated hydrophilic MEL for applications in integrated bioprocess design (IBPD) strategy for aqueous solution. In order to make more types of the production of new-to-nature glycolipids using - 27 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

genetically engineered S. bombicola strains. In this few products can actually be found on the market strategy, the entire innovation chain is considered: today. Dedicated and valorization oriented from genetic engineering to medium optimization, research at Universities on the other hand has fermentation and downstream processing, to final enabled the generation of potent microbial strains, application testing. ready to move ahead in the innovation chain. In The application testing is very important to this paper, we will use an example to show how define possible applications of the tailor-made the integration of process (fermentation and molecules. Since biosurfactants can be employed in purification) development, optimization, scale up so many fields of industry, this is a complicated task, and therefore a multidisciplinary and application testing has been key for collaboration was set up. Different possible biosurfactant technologies to move further ahead applications of tailor-made glycolipids were in the innovation chain. The production of a new assessed and some very interesting leads were type of sophorolipid, by a strain with lower found, showing that there are real opportunities in inherent productivities compared to the wild type various markets/applications. For example, a new sophorolipid producing organism, was optimized by method to encapsulate iron oxide nanoparticles process development and scale up. This resulted in into liposomes was discovered. Antimicrobial a substantial (x4) increase of the productivity and characteristics were assessed for various tailor- thus a significant reduction of the production price. made glycolipid molecules for selected bacteria Moreover, scaling up the process enabled us to and fungi. An ecotoxicological evaluation of the generate large samples for dedicated application novel-made glycolipids display much higher (or testing and perform both a techno economic even not-determinable) EC50 concentrations analysis (TEA) as a life cycle assessment (LCA), compared to traditional surfactants, making them very promising alternatives. sometimes resulting in surprising findings. This portfolio of tailor-made sophorolipid Sensitivity analysis of the TEA and LCA studies biosurfactants with varying characteristics and enabled us to identify hotspots for price and properties will lead to an improved market impact reduction respectively. The combination of penetration of biosurfactants in the future. the described efforts and strain engineering is expected to result in a real commercial Microbial Biosurfactants, from Lab to Market: breakthrough of microbial biosurfactant the Hurdles and How to Take Them Sophie LKW coming years. Roelants*1, Bernd Everaert1, Emile Redant1, Brecht Vanlerberghe1, and Wim Soetaert2, 1Bio Base Sophorolipids in Hard Surface Cleaning Europe Pilot Plant, Belgium; 2Centre for Industrial Applications Zheng Xue*, Dennis Parrish, Jeff Biotechnology and Biocatalysis (InBio.be), Ghent Davidson, Samuel Christry, Andras Nagy, Miyako University, Belgium Hisamoto, and Terrence Everson, Evonik Microbial biosurfactants have been holding the Corporation, USA promise as thé environmental friendly alternative Microbial biosurfactants produced by for petrochemical derived surfactants for many fermentation exhibit favorable properties such as years. The real lift off of this technology is still low toxicity, skin mildness, and biodegradability. In expected, but some important recent particular, there is significant commercial interest developments were done. On one hand, large in sophorolipids, owing to the nonpathogenic companies are investing in this technology and a character of the production host and the high

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

yields. Sophorolipids are glycolipids biosurfactants cell lysis; S. mutans (at SL=130 μg/ml) showed consisting of a sophorose sugar head and a extensive lesions on cell surface but no lysis. SL (at hydrophobic fatty acid tail. The carboxylic end of Lactococci, as shown by increased cell-doubling this fatty acid can be free, forming the acidic time (Td) and decreased final cell density (by structure, or internally esterified at the 4 position A600nm) in concentration-dependent manner. SL at of the sophorose head, forming the lactone Streptococci, as evidenced by a prolonged lag-time structure. The lactone form is only stable at neutral of growth curves in a concentration-dependent or slightly acidic conditions due to the hydrolysis of manner but no differences in Td and the final ester bond at high alkalinity. The narrow pH range A600nm. Standard Minimal Inhibitory Concentration for stability against hydrolysis poses significant (MIC) test was also performed towards a broad challenges for utilizing sophorolipids in hard array of oral and skin bacteria. Superior surface cleaning formulations, which are usually antibacterial properties were achieved against 3 formulated at alkaline conditions of pH ≥ 10 to oral Streptococci species tested (MIC < 4ppm). saponify fatty deposits. Sophorolipids formulation Good antibacterial properties (MIC=19-39 ppm) at neutral pH with cleaning performance were also achieved towards some Gram-positive comparable to conventional high pH cleaners were skin bacteria such as S. haemolyticus, C. striatus developed, through tuning the hydrophilic- and pathogenic S. aureus. However, its efficacy lipophilic balance of the formulation to obtain towards Gram-negative E. coli is only moderate strong emulsification. The effects of sophorolipids (MIC=312-625 ppm). In conclusion, the results on detergency are investigated using interfacial presented demonstrated the high value of SL as rheology and interfacial tension measurements. antimicrobials for applications in oral and skin care Formulation procedures and comparative results industries. will be discussed. A Journey to Standardisation of Bio-based Sophorolipid Biosurfactant Against Bacteria Surfactants in Europe Juergen G. Tropsch*1, Relevant to Tooth Caries and Skin Hygiene Daniel Christophe Sené2, Thierry Beaudouin2, Stephen K.Y.Solaiman*1, Richard D. Ashby1, Joseph Uknalis2, Mudge3, and Horacio Hormazabal4, 1BASF SE, Aixing Fan3, and Laurence Du-Thumm3, 1USDA, ARS, Germany; 2Stepan, France; 3BSI, UK; 4AFNOR, ERRC, USA; 2USDA, ARS, ERRCA, USA; 3Colgate France Palmolive Co., USA The European Commission has decided in 2011 Sophorolipid (SL) is glycolipid biosurfactant to become the first bio-based economy. In the produced by yeast. Its general antimicrobial activity following, the EU issued a mandate to CEN to was previously reported. In this paper, we present develop a standard on bio-based surfactants the antimicrobial activity of SL specifically against among other product groups. A new working group oral and skin bacteria. Using a microplate to within CEN was created to deal with the continuously monitor cell growth, we found standardization process (CEN/TC-276 WG3). The complete inhibition of cell growth at SL working group issued the technical specification concentrations ≥1 mg/ml (1,000 ppm) for oral CEN/TS 17035 which will be published in April Lactobacilli tested and ≥50 μg/ml (50 ppm) for the 2017. The CEN/TS 17035 specifies the thresholds oral Streptococci. SEM study of SL-treated L. on the biomass content (5%, 50% and 95%) and the acidophilus (overnight; 1 mg/ml) suffered extensive naming as well as the methods to determine the

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

thresholds (e.g. radiocarbon method according to products. Our clinical studies demonstrated EN 16640). The reasoning for the thresholds als oleosomes are hypoallergenic and emollient with well as our approach on the environmental and high water resistance. When applied for sun societal criteria will also be explained. Further work protection products, where active ingredients are of the working group will include the finalization of oil soluble UV filters, oleosomes resulted in great a European Norm (EN) and a Technical Report (TR) emulsion stability and outstanding functionality, in 2017. There is planed also an ISO standard on specifically boosting sun protection factor (SPF) bio-based surfactants. The standard might be used significantly. This outcome was delivered by in European ecolabels and in public procurement. diminishing the use of the aggressive UV filters by up to 9 - 10 folds, achieving the same levels of SPF Oil Seed-extracted Oleosome Emulsifiers for Sun as market-leading products. Protection Products Soo In Yang*1, Shuanghui Liu1, Geoffrey Brooks1, Yves Lanctot1, and James V. The Antibacterial Property of Fatty Acyl Glutamic Gruber2, 1Botaneco Inc., Canada; 2Botaneco Inc., Acid and Proposed Mechanism Buddhi Lamsal, and USA Kangzi Ren*, Iowa State University, USA As a repository of new life energy source in oil Fatty acyl Glutamic acid (FA-Glu), a highly seeds, oil bodies or oleosomes are structurally water-soluble acyl lipoprotein biosurfactant unique due to their uniformly embedded protein produced by bacterial fermentation, was studied as stabilizers into the phospholipid-surrounded an antibacterial agent against foodborne- triacylglycerol core. This naturally-engineered pathogens. The objective of this study was to structure provides a foundation for the determine the how the FA-Glu interacted with biochemically programed collapse and release of bacterial cell membrane to achieve bactericidal oil from the oleosomes in a tightly controlled effect. The minimum inhibitory concentrations of manner. The oil in the oleosomes are dispersed in FA-Glu and other bio-based surfactants against the aqueous phase of the cells with the help of the E.coli O157:H7, Salmonella enteria and Listeria physically stabilized structure by the surface monocytogenes were determined and compared. proteins. This structural benefit yields a protective The mechanism of FA-Glu antibacterial property mechanism against coalescence of oil droplets; was studied. Cell content leakage test by thus, also increasing the surface area. These spectrometry indicated FA-Glu caused significant physico-chemical barriers provide steric and leakage of cytoplasmic protein and DNA. The electrostatic stabilization to the oleosomes, leading differential scanning calorimetry study of FA-Glu to a stable emulsion system. Oleosome itself is an interaction with artificial cell membrane revealed oil-in-water emulsion, but it also possesses an that FA-Glu disrupted the cooperativity of excellent surface active characteristic, thus phospholipid bilayer structure by interacting with suggesting its great potential as an emulsifier. We the hydrocarbon chain, reducing phase transition extracted oleosomes using a patented non-solvent- temperature and enthalpy change. The interaction based aqueous extraction process. The purified with different types of phospholipids indicated that mixture of oleosome-containing liquid fraction in bio-based surfactant were more effective against water with D-glucono-1,5-Lactone, sodium Gram-positive bacteria compared to Gram- benzoate, and citric acid, has been studied for its negative ones. The major phospholipid (DPPE) in potential use as an emulsifier for sun protection Gram-negative E.coli O157:H7 is harder to disturb

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

than the major phospholipid (DMPG) in Gram- such as agriculture, metal working and personal positive Listeria monocytogenes. Composition of care. The main technology available on the market various proteins (from cytoplasma, cell membrane uses direct ethoxylation on castor oil to obtain this and cell wall) of FA-Glu treated and control vegetable based surfactant. Although the older bacteria will be examined by SDS-PAGE to technology is still used today, in the more recent determine whether FA-Glu interacted with a years, it was found that you could obtain castor oil specific protein or show the detergent ethoxylates by scrambling ethoxylated glycerin and solubilization effect. The study will provide castor oil triglycerides. Compared to the old information on possible development of technology, this new route helps to keep both the disinfectant formulation using this novel bio-based hydroxyl group intact and the levels of 1,4-dioxane surfactant. low. Investigations showed benefits to these newer castor oil ethoxylates which in turn led to further Triglyceride Derived Surfactants and experimentation in order to see if we could derive Interesterification: Synthesis and Performance an estolide with this generation of COE. Once able Properties Heather E. Byrne*1, George A. Smith2, to synthesize the interester of the castor oil and Angela Garibay-Lewis2, 1Huntsman ethoxylate, several performance tests were run to Performance Products, USA; 2Huntsman see what benefits, if any, were seen. This data Corporation, USA along with other comparison data will be discussed Castor oil ethoxylates (COEs) have been widely in depth. used for emulsification properties in industries

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

S&D 5: Foam Boosting and Control Chairs: Warren Schmidt, Consultant, USA; and Martin Severance, Dow Corning Corporation, USA Mechanism of Action of Silicone-based Foam this in mind, BASF has evaluated several low Control Agents Jacqueline L'hostis*, Chamee Chao, foaming nonionic surfactants for use in HE laundry and Stéphanie Lobry, Dow Corning, Belgium detergents. Both structure-property trends with In recent years, the “High-Efficiency” (HE) home respect to defoaming will be explored and washing machines have increased in usage in North synergistic combinations of defoamers will be America. This design of the machine (horizontal reported. drum), combined with more concentrated and anionic-rich detergent formulations is leading to High Performance Surfactant Blends with High increased foaming conditions. This high foam Bio-based Content Scott Jaynes*, Croda, Inc., USA ability needs to be efficiently controlled to avoid Domestic production of bio-based ethylene interference with the cleaning action, and even an oxide (EO) made from corn ethanol will begin in undesirable overflow of the washing liquor out of late 2017 at Croda’s Delaware manufacturing site. the machines. The mechanism of action of Silicone- This renewable EO will be utilized on-site to based foam control agents will be discussed, produce ethoxylated surfactants with high levels of explaining their ability to control foam at very low bio-based content. The availability of these plant- dosage in an extremely large scope of detergent based surfactants will allow home care product concentrations, formulations and foaming formulators to more easily meet the rising demand conditions due to their inherent silicone properties. from their customers for products made with bio- This specific foam control mechanism, different based materials. As an example of products from soap, makes silicones extremely attractive available with increased bio-based content, a especially when formulation space is needed such family of high performance surfactant blends will as in highly concentrated detergent formulations. be presented. These surfactant blends have been carefully designed to give optimal performance in Nonionic Surfactant Foam Control Technology for specific application areas, saving time for HE Laundry Michael D. Capracotta*, Shakera formulators who would otherwise need to prepare Thamanna, Kevin M. Salmon, and Stephen F. Gross, and test numerous blends of individual surfactants. BASF Corporation, USA “Blend NC” is a blend of nonionic alcohol Foam control in machine washing applications ethoxylates and a cationic surfactant, delivering a has long been important in enabling optimal highly effective grease cutting product for cleaning, but is even more important in modern household or I&I degreasers. “Blend CS” is a blend appliances that apply “smart” technology during of an alkylpolyglucoside (APG) with an alcohol cleaning cycles. For example, HE laundry machines ethoxylate that has the high caustic compatibility can detect foam present in the drum and will of an APG, but with the added cleaning power of continue to rinse until the foam is dissipated. As a an ethoxylate. Lastly, a new “Blend CIP” will be result, foam control technology in detergent introduced for application in Clean-in-Place (CIP) formulations is a key factor in minimizing rinsing and other I&I areas, with excellent caustic stability times, impacting both water and energy use. With and very low foaming. All of these products will

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

have bio-based content of >60% when Croda’s bio- selection for a given foam profile. based EO manufacturing plant comes on line in late 2017. Foam Optimization Strategies in Various Consumer Relevant Applications Shui P. Zhu*, and Driving Foam Performance with Surfactant Sangeeta Ganguly-Mink, Stepan Company, USA Interactions Eric Theiner* and Renae Bennett, It is well established that each distinct Evonik Corporation, USA application formulation or product needs a suitable It is common to report foaming properties for foam profile. Some need high and sustainable foam neat surfactants in dilute solutions, but it is less such as hand dish washing detergents and common to report foaming characteristics for shampoos, and some need low and fast-collapsing combined surfactant systems. Unfortunately, foam such as auto dishwasher detergents and surfactant systems are rarely used as neat swimming pool disinfectants. This presentation materials. The presented study presents a large introduces some basic foam optimization body of data developed from High Throughput principles, technologies and formulations with Experimentation to determine foam behavior for a ingredients such as anionic, nonionic, amphoteric, base set of combined surfactants. Also to be and cationic surfactants, cosurfactants, presented is the analysis undertaken in an attempt specific/multivalent counterions etc. to develop a set of rules to guide surfactant

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

S&D 5.1: Sustainability in Surfactants, Polymers, and Detergent Chemicals Chairs: Keith Genco, Arkema Inc., USA; and Troy Graham, Lightbox Laboratories, LLC, USA

The Unbeatable Beet: The Power of cleaners MCF has the capability to suspend Microcellulosic Fibers Unraveled Robert Nolles*, particles, preventing sedimentation in the bottle. Cosun Biobased Products, USA Co-valorisation of Palm Oil Processing By-products Royal Cosun invested in an integrated cascading as Soaps Teerasak Punvichai*, Prince of Songkla biorefinery to refine sugar beet pulp and isolate University, Thailand high-value components. The patented The palm oil refining industry generates spent microcellulosic fibers (MCF) obtained from this bleaching clay (SBC) and palm fatty acid distillate biorefinery is a particulate cellulose material (PFAD) as by-products. Both containing fatty acids containing at least 60% cellulose, 0.5-10% pectin and/or acylglycerols (22.4% of waste oil in SBC), the and 1-15% hemicellulose, and has typical particle study concerns the co-valorization through the dimensions within the range of 25-75 µm. This manufacture of soap. The analysis showed free parenchymal cellulose based material, which fatty acid content and saponification value of comprise cell wall derived networks of cellulose 60.5% and 182 mg KOH/g, and 88.4% and 204.5 mg based fibers and nanofibrils, can be used to KOH/g respectively. This data was used for structure liquids and for stabilization of suspended computing the stoichiometric amount of NaOH to particles. In an aqueous environment MCF forms a be used for producing soap at 40ºC with a varying particle gel and creates a physical 3D network that proportion of water introduced through the basic shows superior particle carrying properties. This solution. From SBC the maximum soap content physical network tends to be stronger than 43.9% (dry weight) was obtained by reacting it with chemical networks being built by nano-fibers. 13% w/w of NaOH (based on waste oil content) Hence, the yield point of MCF exceeds the yield and using 30% w/w of water (both forming the point of well-known viscosifiers like CMC, xanthan basic reacting solution). With PFAD the maximum gum and acrylics. More importantly, the properties soap content 89.2% was obtained with 14.6% of of the network built are maintained under a broad NaOH and 15% w/w of water. In the case of pH range, at elevated temperature levels and are mixtures of both by-products, the maximum yield virtually unaffected by electrolytes known to 92.5% was obtained for a SBC:PFAD ratio of 1:5 disrupt chemical networks. Introduced in liquid w/w and with 14.3% of NaOH and 35% of water, compositions MCF delivers high zero shear viscosity and it was found that the maximum yield required and strong shear thinning behavior. MCF is suitable an increasing amount of water when decreasing to structure laundry detergents, fabric softeners, the SBC:PFAD ratio. Soaps with maximum content abrasive cleaners and personal care products like were tested for cleaning efficiency. PFAD and shampoos and body washes. In laundry detergent waste oil soaps gave the lowest reduction of MCF will enable effective suspension of microbial count after hand washing (37 and 30% encapsulated fragrances. In toilet bowl cleaners, respectively), while it was improved to 49% in the strong shear thinning behavior allows easy case of SBC-soap. The best score, 74%, was application using a spray bottle and high zero shear measured when using soaps made from SBC and viscosity supports vertical cling. In abrasive - 34 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

PFAD mixtures. This synergy could be due to biodegradable builders to choose from. Narrowing abrasive or absorption effect of the clay combined the field of choices prior to formulation to the high soap content. development is an important 1st step in the process. Besides safety and regulatory implications, Sustainable Suds Manufacturing Kaj A. Johnson*, and ‘green’ and biobased certifications, several People Against Dirty (Method/Ecover), USA important physical / chemical properties to Most of us spend our days working hard to consider are strength of binding with Ca and other select the very best ingredients, mix and rigorously metal ions as well as Ca chelation value, if a solid or test them. We strive to make awesome products liquid / gel is needed, solubility of the builder at a that delight our consumers, families, and friends. specific pH and other considerations. A review of We do all of this using years of experience with the attributes and properties of ‘green’ commercial ingredients, with input from suppliers and builders – including citrate, MGDA, GLDA, IDS, partners, and innovation from conferences just like EDDS and polyitaconic acid will be presented. this. We consider where these ingredients come Acceptance and use of these products in from, how they will be used, and what happens to commercial formulations is growing rapidly with them after they are finished. We want to be certain their specific usage tending to fall into specific that we are making valuable & high performance cleaning products and applications – such as gel products that are truly sustainable. With all this and solid ADW products, I&I cleaning and water focus on optimizing our products, it’s easy to softening. neglect the role that manufacturing plays in sustainability. A couple of years ago, People How to Improve the Long Term Performance of Against Dirty (Method & Ecover Brands) had the Autodish Washer Formulations Yvon G. Durant*1 opportunity to build a sustainable manufacturing and David A. Pears2, 1Itaconix, USA; 2Revolymer, UK plant from the ground up. This opened the Itaconic acid polymers have been used in opportunity to start from scratch- what ideas make recent years as a cost effective and sustainable sense? how do we do them? And, most alternative solution to amino carboxylate based importantly, how can we drive benefits as a B- builders. We have recently improved these Corp? We wanted to drive practices that reflect our polymeric chelants through the copolymerization company philosophy to make a positive impact on of itaconic acid with sodium styrene sulfonate for the environment and consumers. We certainly optimal performance in ADW formulas. We have made a few mistakes along the way but we also previously presented in-formula performance learned a lot. Here is a fun look at some things we results. These new copolymers are showing a would like to share with you today about our South significant advantage regarding metal erosion. Side Soap Box, our sustainable factory. Polyitaconate have high binding constants for calcium, but relatively low binding for metals such Readily Biodegradable Builders—Selecting the as iron, aluminum, nickel, copper and gold. We Right One(s) Patrick Kincaid*, Butch Dery, James N. have conducted a study of these metals in the LePage, Kuntal Chatterjee, and Jeanne-Marie presence of chelants relevant to ADW McVeigh, AkzoNobel, USA formulations. Upon extended exposure of glasses Today’s cleaning formulators are fortunate to and dinnerware with metal decorations, we have a wide range of safe and readily recorded significant reduction in metal erosion.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

The use of polyitaconate chelants in ADW provided exceptional spot reducing performance practically eliminates the long term performance on glassware and stainless steel, regardless of concerns associated with some amino carboxylate other changes made to the formulation (dispersant builders. type/loading, surfactant type/loading). This novel benefit would allow formulators to achieve Dispersants for Reduction of Spotting in maximum shine utilizing a dispersant alone, while Automatic Dishwashing Paul P. Mercando1, Eric P. optimizing the surfactant system for primary Wasserman1, Severine S. Ferrieux2, and Scott A. cleaning and other benefits. Best performance was Backer*1, 1The Dow Chemical Company, USA; 2The obtained from mixtures of the terpolymer with a Dow Chemical Company, France second specialty dispersant. Dow Home Institutional and Personal Care has been developing and evaluating a series of acrylic polymers to act as next generation dispersants for Advancing Sustainable Chemistry: Chemical automatic dishwashing formulations. The Footprint Reduction at GOJO Antonio Quinones- performance requirements for dispersants have Rivera*, GOJO Industries, USA changed significantly as classical phosphate-based In 2015, at the 10th Annual BizNGO Chemical formulations are being phased out due to Footprint Project Conference in Boston, GOJO environmental regulations in Western Europe. announced its commitment to reduce its Chemical Currently, no single performance replacement for Footprint by 50% by the year 2020. In this phosphates has been identified, and new materials presentation we will discuss the definition of and formulations are currently being developed at Chemical Footprint, share some of the strategies all levels of the market in order to meet this need. we have implemented to determine and reduce A series of terpolymers containing acrylic acid, our Chemical Footprint, and describe some of the AMPS, and a dicarboxylic vinyl monomer (maleic tools we have developed to communicate our acid, itaconic acid) at specific ratios was prepared progress in reducing our Chemical Footprint. and tested in several ADW formulations under various conditions (temperature, water hardness, machine model). Several of the tested terpolymers

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

EAT 5 / S&D 5.2: Interfacial Phenomena in Complex Food Systems Chairs: Nitin Nitin, University of California, Davis, USA; and Ozan Ciftci, University of Nebraska- Lincoln, USA

Effect of Membrane-associated Peptide on the the oil-water interface, which can strongly impact Dynamics of Bicontinuous Microemulsions via Quasi- emulsion kinetic stability against coalescence and phase elastic Neutron Scattering and Neutron Spin-echo separation, functionality and rheology. This Douglas G. Hayes*1, Veerendra K. Sharma2, Volker S. presentation outlines some of the factors that govern Urban2, Hugh M. O'Neill2, S. Venkatesh Pingali2, Michael interfacial crystallization, notably emulsion dispersed E. Ohl2, Eugene Mamatov2, and Madhusudan Tyagi3, phase volume fraction, lipid surface activity and liquid- 1University of Tennessee, USA; 2Oak Ridge National solid phase transition temperature as well as molecular Laboratory, USA; 3National Institute of Standards and complementarity between the crystallizing lipid and Technology, USA interfacially-bound emulsifier. Specific examples of the A grand challenge for the soft matter scientific impact of interfacial crystallization discussed include the community is to obtain a deeper understanding of ability of crystalline shells to transform water-in-oil dynamics at several different length and time scales. emulsions into reservoirs for the controlled release of This paper will describe the short- and long-range aqueous compounds as well as their capacity to protect dynamics of bicontinuous microemulsions (BMEs), a oil cargos during in vitro digestion of oil-in-water potentially useful biomembrane mimetic system, by emulsions. quasi-elastic neutron scattering (QENS)and neutron spin echo (NSE), respectively. The investigation focuses upon The Effect of Interfaces in Nanodroplets Loaded With the effect of melittin on BMEs formed by water/sodium Nutraceuticals on Their Release from Drinks to Human dodecyl sulfate (SDS)/1-pentanol/dedecane. Melittin is System Nissim Garti*, Hebrew University, Israel an antimicrobial peptide (AMP) with potential utility as Dilutable microemulsions (DME) are nanodroplets an agent against antibiotic-resistant microorganism and composed of oil phase, surfactants, cosurfactants and cancer, among others, and penetrates within the cosolvents (no water) and other ingredients that surfactant monolayers of the BMEs. (BMEs may be a facilitate formation of concentrates with the capability potentially valuable delivery system for AMPs.) QENS of being diluted with any amount of water and inverting analysis indicated two distinct motions of the BME from W/O to bicontinuous and to O/W nano structures. surfactant monolayers, namely (i) lateral motion of the The phase diagrams describing these formulations are surfactant on the surface of the oil channels and (ii) termed "U-typephase diagrams" and the structures are internal motion of the surfactants. It is found that termed "umbrella type droplets". The concentrates are melittin hindered both the lateral and the internal loaded (solubilized) with bioactives (guest molecules) motion, thereby acting as a stiffening agent. NSE that are lipophilic and insoluble in water. The systems analysis indicated that melittin has a slight, lesser, are transparent, Newtonian and thermodynamically impact on the long-range dynamics. stable. The bioactives are, in most cases, located at the interface of the structures along any dilution stage. The Structuring Food Emulsions Through Lipid loaded nutraceuticals are, upon dilution, forming soft Crystallization at the Oil-Water Interface Dérick drinks. The structures are consisting also of additional Rousseau*, Ryerson University, Canada ingredients allowing the bioactives to 'survive' the acidic Incorporation of emulsions into processed foods conditions of the human stomach and are aimed to be offers significant possibilities in regards to texture released from the guts jejunum membrane "on improvement, cost reduction, and health enhancement. demand" to the blood stream. We will bring few such In both oil-in-water and water-in-oil emulsions, an examples including CBD (the non narcotic fraction of emerging tool is the use of direct lipid crystallization at Cannabis) and other antioxidants and nutraceuticals. - 37 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

The formulations are derived from Monte Carlo Thermodynamics and Adsorption Mechanisms for Dynamic Simulations calculations, and advanced Hydrophobic Food Surfactants at Interfaces Stephanie analytical tools, to determine the location of the R. Dungan*, University of California, Davis, USA solubilized nutraceuticals at any stage of its dilution and Lipid amphiphiles are found widely in foods and across the guts membrane. other biological materials. Their tendency to accumulate and lower the energy of interfaces plays a In situ Observation of Template Effects of Emulsifiers critical role in food processing and ing metabolic actions with Different Fatty Acid Moieties Chinami Ishibashi*1, such as digestion and cellular transport. Interpretation Hondoh Hironori2, and Satoru Ueno2, 1Hiroshima of interfacial phenomena is often based on studies of University, Japan; 2Graduate School of Biosphere water-soluble molecules, whose behavior is heavily Science, Hiroshima University, Japan influenced by the hydrophobic effect. Instead, in this Template effect is the promotion of fat presentation, the behavior of water-insoluble crystallization by crystallized emulsifiers that were surfactants at oil/air, oil/water and air/water interfaces nucleated prior to fat. Although an impurity effect also will be discussed. Equilibrium surface tension (oil/vapor) promotes a nucleation of fat crystals on the surface of measurements of various triacylglycerol or free fatty an emulsifier, the crystallization mechanism is different acid molecules as a function of temperature were used between template and impurity effects. Many previous to assess surface excess internal energy and entropy. studies reported that the similarity in fatty acid Length of the acyl chain is the main feature to influence composition between a fat and an emulsifier should be surface excess energy, in contrast to degree of important for the template effect. An emulsifier crystal saturation or triacyl or monoacyl character. These having similar fatty acid packing to a fat crystal would findings clarify the very subtle effects of composition on provide a favorable spot for fat crystal nucleation. The surface tension of food oil mixtures. Our understanding molecular interaction at the fat-emulsifier interface will of the behavior of lipid phases alone can then be promote the orientation of fat crystals. However, there extended to oil/water mixtures, where lipid amphiphiles are few reports about the fat crystal orientation have a much more pronounced and complex effect on promoted by the template effect, and the difference interfacial tension. Dynamic interfacial and surface between template and impurity effects are not tensions were also probed, using drop profile concerned so much. The purpose of this study is in situ tensiometry, for caprylic acid, monocaprylin and observation of crystallization behavior of fat crystals on phosphatidylcholine. When the amphiphile is dissolved an emulsifier crystal in order to reveal the difference as individual molecules in a triglyceride or water phase, between the template and the impurity effects. We transport to the interface is driven by diffusive used palm-mid-fraction (PMF) as an oil phase and mechanisms. Phospholipid transport kinetics are more sorbitan tripalmitate (STP), sorbitan tristearate (STS) complex, as these molecules are nearly soluble in both and sorbitan tribehenate (STB) as an emulsifier. The triglyceride and water. Their adsorption kinetics are results were as follows; (i) When fatty acid moiety of much slower, and heavily dependent on the structure of emulsifier were similar to those of fat, PMF crystals the vesicle dispersion. oriented along the STP or STS crystals, suggesting template effect. (ii) When fatty acid moiety of An In-depth Look at Bakery Applications of a emulsifier did not show the similarity to those of fat, Structured Monoglyceride Gel Alejandro G. PMF randomly crystallized around STB crystals, Marangoni1, and Kaustuv Bhattacharya*2, 1University of suggesting impurity effect. Guelph, Canada; 2DuPont Nutrition & Biosciences ApS, Denmark After successfully addressing the use of trans fat in the food industry the focus is now on reduction of saturated fats and in certain parts of the world palm oil - 38 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

and its derivatives due to sustainable issues. The cleaners. Additionally these naturally derived cellulosic primary approach has been replacing fats rich in polymers build rheology, improve skin feel, and saturated fatty acids with structured liquid oils using mildness of cleansing compositions in which they are different ingredients and techniques. But not all incorporated. Research will be presented to validate solutions are food approved or have wide range equivalent foamability at reduced surfactant acceptable application opportunities. The present work concentration. The data to confirm the foam enhancing is based on oleogel emulsion technology using an properties of a multifunctional naturally derived emulsion structured by crystalline multi-layers of modified hydroxypropyl methyl cellulose polymer. monoglyceride interspersed with water in presence of anionic co-emulsifiers in the alpha polymorphic form. Interfacial Interaction and Emulsification Behaviour of This technology is appropriate for manufacturers of oils Lentil Protein Isolate and Fenugreek Gum Complexes and fats, bakery products, and others, who want to Supratim Ghosh* and Natalie Longmore, University of improve the sustainability footprint and health benefits Saskatchewan, Canada of their existing products. By using this technology, The aim of this work was to improve solubility and ‘palm free’, zero trans and reduced saturated fats can emulsification behaviour of lentil protein isolates (LPI) be claimed. The solution is oil source independent by their interaction with fenugreek gum (FG). Complex providing freedom of choice for the manufacturer. A formation between the protein and polysaccharide diverse range of bakery applications including analytical molecules was studied as a function of pH (7 to 1.5), data on the emulsion oleogel and dough containing and mixing ratios (1:3 to 3:1). The soluble complexes at such using NMR, Confocal laser imaging and Rheology pH 2 and 7 were further used to investigate the will also be highlighted. interfacial and emulsification behaviour. At a total biopolymer concentration of 0.1 wt% significant Improve Foam Properties—Multifunctional Cellulose decrease in oil/water interfacial tension was observed. Polymer Terry Crutcher*1 and Bert Kroon2, 1Ashland From 23.9 mN/m for pure oil/water interface, it Specialty Ingredients G.P., USA; 2Ashland Specialty decreased to ~17 and ~13 mN/m, at pH 2 and 7, Ingredients, The Netherlands respectively. No significant change in interfacial tension Many household and personal care wash between the LPI-FG complex and pure LPI was applications exhibit trade mark foamability and observed. In contrast, presence of FG significantly rheological aesthetics that consumers have come to decreased interfacial storage modulus and the values expect and enjoy. The foam profile of a consumer were higher at pH 2 compared to pH 7, which was product may serve as an indicator of its performance in ascribed to strong –ve charge on both the biopolymers the minds of many end users. It is becoming more of a at pH 7 leading to a weaker interfacial interaction. The challenge to deliver cost efficient and robust foam mixed biopolymer solutions were used to prepare 1 performance as traditional foaming ingredients like wt% oil-in-water emulsions using multiple passes alkanolamides and alkyl sulfates are of toxicological through a high pressure homogenizer at pH 2 and 7. concern. Today there is a need for better more efficient Stable emulsions were generated at both pHs where the eco-friendly foaming technologies that satisfy finished average droplet diameters were less 500 nm. Results goods manufacturers’ desire for more sustainable high showed that presence of FG significantly improved performance products with reduced emulsification behaviour of LPI due to improved surfactant/chemical content in the effluent. It has been solubility, and lowering of the interfacial modulus of the found that a modified polysaccharide derivative reduces complex. Interfacial complexation between LPI and FG the surface tension at the air liquid interface sufficiently could be a novel way to utilize natural ingredients in the to boost and stabilize foaming in care compositions like development of food emulsions for beverage hand dish detergent, hand soap, and hard surface application.

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

S&D-P: Surfactants and Detergents Poster Session Chair: Mike Wint, Amway Corporation, USA 1. Studies on Dispersion of Various Size of Ethyl were prepared by acid-catalyzed condensation of Cellulose in Colloidal Solution and Their Foam diethyl tartrate with fatty ketones, followed by a Ability Hongche Noh*,Hanyang University, South reaction with mono-dispersed polyethylene glycol. Korea We confirmed that they have good surface-active Foam has been studied in various fields, such as properties. The emulsion stability of these household goods and foods, in addition to surfactants was similar to that of typical surfactants. In this paper, the stability and surfactants. The biodegradabilities of these structure of foam were studied using cleavable surfactants after 28 days are more than nanoparticles. Ethyl cellulose (EC) colloidal solution 60 % according to guideline OECD 301C with with high dispersibility was prepared by anti- activated sludge. Their detergency on artificially solvent precipitation. Especially, the particle size soiled cotton cloth was better than the reference was controlled by changing the concentration and detergent according to the Japan Industrial temperature. This EC colloidal solution was mixed Standard Method. The reference detergent with sodium dodecyl sulfate to study the stability consisted of sodium n-dodecylbenzenesulfonate, and structure of foam. EC was measured by which is a popular component in commercial dynamic light scattering (DLS), zeta potential and detergents. The new surfactants do not require any scanning electron microscope (SEM). Foam ability expensive reagents or special equipments for their was analyzed by dynamic foam analyzer. preparation and might improve the efficiency of waste water treatment and of polymer purification 2. Chemocleavable Nonionic Surfactants Bearing in the emulsion polymerization process. Mono-dispersed Polyethylene Glycol Derived from Diethyl Tartrate Daisuke Ono*1, Makoto 3. Thermogravimetric and Rheological Evaluation Okumura2, Shintaro Kawano1, Hirofumi Sato1, of Mucilage Flax with Potential Application in Motohiro Shizuma1, and Araki Masuyama2,1Osaka Microencapsulation of Bioactives Substances Municipal Technical Research Institute, Japan; Jaime Reyes Hernandez*, Concepción Lopez 2Osaka Institute of Technology, Japan Padilla, Josefina Gallegos Martinez, and Paola It has become of special interest to develop the Algara Suarez, Universidad Autónoma de San Luis "chemocleavable" surfactants which are designed Potosí, Mexico to be decomposed into nonsurface-active species The goal of this study was evaluated rheological under mild conditions after fulfilling their original (G´), termogravimetric parameters (weight loss) functions such as emulsification, detergency, and pH sensibility of mucilage flaxseed for micellar catalytic activity, and so on. We have been application in microencapsulation. Methods: investigating the preparation and properties of a Thermogravimetric analysis (weight loss) of series of acid- and alkali-cleavable surfactants and mucilage flax (MF) was performed in a TGA TA- reported that they were applicable as detergent Q500, Samples (~5mg) were heated from 35°C to and emulsifier of emulsion polymerization. In this 600ºC at 10ºC/min in N2 atmosphere. The gelation work, one-chain and double-chain chemocleavable of systems with MF was developed with ramp 80°C nonionic surfactants bearing a 1,3-dioxolane ring to 25°C at 1°C/min. Rheological analysis was

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

developed in mechanical spectrometer MCR 101 secondary alkane sulfonates (SAS) provide limited with parallel-plate geometry (PP-50) under static Ross-Miles foaming performance but show good conditions at 25°C and 37°C. Gel sensibility to pH chlorine bleach stability, Draves wetting, and was developed at pH of 2 and 7. Results: surface tension reduction performance. By Thermogravimetric analysis of mucilage flax modifying a secondary alkane sulfonate, a high showed two important weight loss; the first was at foaming, chlorine bleach stable surfactant was temperature of 255.7°C and was associated to created. This product retains chlorine bleach breakdown and weight loss of monosaccharide and stability equal to LAO and has improved Ross-Miles disaccharides. The second weight loss was foaming, Draves wetting and surface tension observed at 297°C, these temperatures can be reduction performance over LAO at both room associated to different composition of proteins temperature and at reduced temperature. When present in MF. Storage module values (G´) formulated at equal actives to LAO it exhibits increased as the concentration of MF increased, improved performance and equal performance at however G´ values was considerably higher at 2 75% of LAO active. The modified secondary alkane and 3% of MF (G´≈ 500 MPa) than 1% (G´≈ 5 MPa). sulfonate product provides the opportunity for The higher resistance structural of gel was manufacturers of cleaning and detergent products observed at pH 2 than pH 7. Conclusions: to either enhance the performance of existing LAO Concentrations higher of 2% suggested the containing formulations and/or reduce the overall possibility of developing gels with good viscoelastic surfactant loading (cost) in cleaning formulations. properties and higher resistance to pH 2 for be used in microencapsulation of bioactives 7. Selective Synthesis of Sugar Mono Fatty Acid substances. Knowledge of these mechanisms may Ester Using Ion-exchange Resin as Catalyst be helpful for the understanding of these Tomone Sasayama*1, Yuto Kamikanda2, and Naomi phenomena and improving the control of the Shibasaki-Kitakawa3, 1Dept. of Chemical viscoelastic properties and therefore their Engineering, Tohoku University, Japan; 2Tohoku functionality. University, Japan; 3Graduate School of Engineering, Tohoku University, Japan 5. High Foaming, Bleach Stable Surfactant Sugar fatty acid ester has been received much Alternative to Laurylamine Oxide Benjamin J. attention as a bio-based surfactant. It is industrially Markovitz, Ryan C. Vikan, Tenu A. Adeosun, William produced by transesterification of sucrose and B. Hehemann, and Philip C. Benes*, Nease Co., USA fatty acid methyl ester using homogeneous alkali This poster for the surfactants and detergent catalyst such as Na2CO3. However, reduced division, foam boosting and control session, will pressure condition for removing by-product, focus on a high foaming, bleach stable alternative methanol, is required to shift the equilibrium to laurylamine oxide (LAO). LAO has been a toward the product and a complicated operation workhorse surfactant in the field of chlorine bleach for removing the catalyst from the product is also stable foaming cleaners. However, while LAO offers necessary. These cause an increase in the good bleach stability and Ross-Miles foaming production cost. We have proposed that the performance, it only provides somewhat limited porous type anion-exchange resin has a high Draves wetting and surface tension reduction catalytic activity for transesterification of performance in cleaning formulations. In contrast, acylglycerols under mild condition. In this research,

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ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

sugar ester is synthesized using the resin catalyst at 9. Manufacturing of Detergent Tablet Rohan S. 60°C under atmospheric pressure. Sucrose and Mestri*, Institute of Chemical Technology, India methyl oleate are used as model feedstocks, A soap or detergent is a material which when dimethyl sulfoxide, as solvent. In the batch dissolved in water, aids the removal of dirt or experiments, we find that sugar ester is rapidly foreign matter from surface. The tablet form of the produced under the specific condition that the detergent powder is one of the new formats of the resin is first added to the sucrose solution and then detergent. It is the compact form of detergent methyl oleate is added to the solution. In the powder with highly active ingredients. The continuous experiments using the reactor packed tabulated form of detergent will reduce the volume with the resin, sucrose solution is first supplied to of the powder due to compact format it affects the the reactor for saturation and then the mixed transportation and packing cost. The detergent solution of sucrose and methyl oleate is fed to the formulation content the Linear alkyl Benzene reactor for ester synthesis. At steady state, the Sulphonate (LABSA), Sodium Tripolyphophate conversion of 50% is obtained at the residence (STPP), Sodium hydroxide (NaOH), Sodium Silicate, time of 1.5 h and mono ester is selectively Sodium Sulphate. The tablet form of the detergent produced (>95wt%). powder is comparatively new. It is the compact form of detergent powder with highly active 8. Synthesis of Mild Natural Micro Beads Face ingredients. The tabulated form of detergent is Scrubber Rohan S. Mestri*, Harshada S. Patil, and expected to reduce the volume of powder due to Amit P. Pratap, Institute of Chemical Technology, compactness. The detergent formulation contains India Linear Alkylbenzene Sulphonate (LABSA), Sodium Daily cleansing does not remove dead epithelial Tripolyphophate (STPP), Sodium hydroxide (NaOH), cells and impurities which are trapped in pores of Sodium Silicate, sodium sulphate etc. Detergent skin. These dead cells and impurities affect the skin powder is mixed with various disintegrating agents life if it is trapped in pores of skin, resulting in the like corn starch, sodium carboxy methyl cellulose less life of skin, problems of acne and blackheads. (Sodium CMC). Detergent tablet is instantly Solution of these problems is use of face scrubbers disintegrated when contacted with water. It is less ones or twice a week which is exfoliating, mild and or no hydroscopic in nature and one or two tablets contains natural traditional ingredients. The mild are enough for the washing instead of one scoop. micro beads face scrubber contains Gram flour, 11. Salt-thickening Effect in the Quaternary aloe vera, sugar, starch, milk, skin care oil etc. in Ammonium/Carboxylate Surfactants Mixtures by this scrubber-beads are outer cover with Gram Forming Entangled Wormlike Micelles Liming flour and inside is oil. When we massage with this Zhang*, Wanli Kang, Derong Xu, Meng Yang, Qiong beads outer layer are exfoliate dead skin and black Zhou, Jiatong Jiang, and Hairong Wu, China heads and inside oils is spread on skin which will University of Petroleum (Beijing), China help to growth of new fresh cells. The result is ever Surfactants impact a lot on fracturing fluids youthful and fresh look. which play a critical role in the effect of the

hydraulic fracturing. However, formation fluids contain large quantities of inorganic salts. When the fracturing fluids are injected into the formations, precipitation appears, leading to a loss - 42 -

ABSTRACTS 2017 AOCS ANNUAL MEETING AND INDUSTRY SHOWCASES April 30–May 3, 2017

to the fracturing effect and damages to the micelles. It provides guidance for the application to formations. Thus, compatibility with the formation EOR as well as other industries. fluids is essential to EOR. The rheological behaviors of the mixtures are measured by the mechanical 12. Turkish Demographic Profile, Homecare Rheometer, and the morphologies of the Detergent Market Volumes and Customer aggregates in the solutions are observed with Cryo- Expectations Kutluay Kabaday*, Saruhan kimya, transmission electron microscopy (Cryo-TEM) and Turkey Freeze-fracture transmission electron microscopy Turkish demographic profile, specifications, (FF-TEM). The results show that viscosities of the population, median ages, houswife profiles, house mixed solutions are quite low when the total mass profile and economical data, GDP per capita values concentrations are lower than 3.0%. They behave among years and forecasted values also like Newtonian fluids. After adding NaCl and CaCl2, comparison to some other countries. Turkish retail there is an obvious increase in viscosity and prospect , market types , market share details, viscoelasticity. Moreover, the salt-thickening effect product groups, tonnages , incomes and strategies, becomes better with the increasing inorganic salt yearly chancing market share values. Discount to some extent. NaCl has an outstanding viscosity- market types, numbers. Total Turkish homecare thickening ability than that of CaCl2. Importantly, detergent sector economical values and product no precipitation appears until the NaCl groups .Homecare detergents as laundry, concentration reaches 25%. In addition, dishwashing, surface group and softener volumes, micrographs exhibit that transformation occurs annual growing rates, forecasts for each group as from spherical micelles to the wormlike micelles. income and tonnages, customer expectation in The larger of the inorganic salt concentration, the homecare detergent business, marketing closer of the entangled wormlike micelles pack. strategies. Also there are a detailed customer The microstructures are in accordance with the profile survey analyzes of customer purchasing salt-thickening effect in theory, indicating a good behaviours. compatibility with the formation fluids. This work has extended the understanding of salt-thickening effect which is related to the forming of wormlike

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