STP 1595 Editors: Craig Pofenberger Justin Heuser Downloaded/printed by Coventry University (Tongji University) pursuant to License Agreement No further reproductions authorized Selected technical PaPerS StP1595 Editors: Craig Pofenberger and Justin Heuser Pesticide Formulation and Delivery Systems: 36th Volume, Emerging Trends Building on a Solid Foundation ASTM STOCK #STP1595 DOI: 10.1520/STP1595-EB ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959 Printed in the U.S.A Library of Congress Cataloging-in-Publication Data ISBN: 978-0-8031-7635-5 ISSN: 1545-9004 Copyright © 2016 ASTM INTERNATIONAL, West Conshohocken, PA All rights reserved This material may not be reproduced or copied, in whole or in part, in any printed, mechanical, electronic, f lm, or other distribution and storage media, without the written consent o f the publisher Photocopy Rights Authorization to photocopy items for internal, personal, or educational classroom use, or the 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the peer reviewers The ASTM International Committee on Publications acknowledges with appreciation their dedication and contribution o f time and efort on behal f o f ASTM International Citation of Papers When citing papers from this publication, the appropriate citation includes the paper authors, “paper title,” STP title, STP number, book editor(s), ASTM International, West Conshohocken, PA, year, page range, paper doi, listed in the footnote o f the paper A citation is provided on page one o f each paper Printed in Bay Shore, NY November, 2016 Foreword THIS COMPILATION OF Selected Technical Papers, STP1595, Pesticide Formulation and Delivery Systems: 36th Volume, Emerging Trends Building on a Solid Foundation, contains peer-reviewed papers that were presented at a symposium held October 27–29, 2015, in Tampa, Florida, USA e symposium was sponsored by ASTM International Committee E35 on Pesticides, Antimicrobials, and Alternative Control Agents and Subcommittee E35.22 on Pesticide Formulations and Delivery Systems T Symposium Chairpersons and STP Editors: Craig Pofenberger Evonik Corporation Richmond, VA, USA Justin Heuser Evonik Corporation Richmond, VA, USA Contents Overview vii Standards OMRI Listing for Pesticides: What You Need to Know Doug Currier ASTM Standard Terminology Related to Biorationals Update Lizbeth Rea and Michael C White 15 Adjuvant Technology Polyglycerol Esters as Adjuvants for Enhanced Pesticidal Activity 18 Lignin-Based Chemicals as Green Dispersants for Liquid Formulation: Better Protection Against Crystal Growth 30 The Afect of Dew on Herbicide and Adjuvant E f cacy 42 Crop Oil Concentrates Comparison: Connecting Chemical Features to Performance 49 E f cacy of Non-Ammonium Sulfate Water Conditioning Adjuvants 65 Justin Heuser, Craig Pofenberger, Rene Haensel, and Ewald Sieverding Jerry Gargulak, Stig Are Gundersen, Frédérik Bierre, and Pauline Rolland Donald Penner and Jan Michael Fernanda de Oliveira B Costa, Cíntia Fávaro, Marcelo Catani F Antunes, and Richard K Zollinger Richard K Zollinger, Bryan G Young, Mark L Bernards, and Dallas E Peterson Formulation Development Novel Nonionic Star Polymeric Stabilizer in Aqueous Dispersion Formulations 76 Polymeric-Based Compatibility Agents for High Electrolyte Systems 90 Ron Kayea, Matthew Secrest, and Greg Lindner Hannah Bo f nger, Sharon Ellis, Susan Sun, and Greg Lindner v I m proved An a l yti ca l M eth o d S tu d y o f th e D eterm i n a ti o n o f La m b d a - Cyh a l oth ri n a s Prem i x i n Wa ter- B a sed , E n vi ro n m en ta l l y Fri en d l y Fo rm u l a ti o n s 02 Shao’e Chen, Zhen Zhu, Dejian Ni, Lidong Wang, and Zhongwen Gao Spray Applications and Delivery Systems M o d e o f Acti o n o f Si l i co n e D ri ft Co n tro l Ag en ts 113 Michael Klostermann, Rene Hänsel, Ewald Sieverding, Joachim Venzmer, Craig Pofenberger, Lars Op fer, Ilia Roisman, and Cameron Tropea Th e E f ect o f Ad j u va n ts a t H i g h Sp y Pressu res fo r Aeri a l Ap p l i ca ti on s 33 Bradley K Fritz, W Clint Hofmann, and Ryan S Henry Th e I n f u en ce o f N ozzl e Typ e, O p era ti n g Pressu re, a n d Ta n k- M i xtu re Co m p o n en ts o n D ro p l et Ch a cteri sti cs a n d th e E PA’ s D ri ft Red u cti o n Ra ti n g 49 Ryan S Henry, Bradley K Fritz, W Clint Hofmann, and Greg R Kruger S p y Ch a cteri za ti o n by O p ti ca l I m a g e An a l ysi s 62 Sounak Sarkar, Surya Kamin, and Greg R Kruger Seed Coatings Co rrel a ti o n of th e M ech a n i ca l Pro p erti es o f S e ed Co a ti n g Fi l m s a n d D u st- O f , Fl owa b i l i ty, a n d Pl a n t a b i l i t y Tests 83 Alan Halecky, Ning Ren, Jie Lu, Jane Q Wang, and Frances E Lockwood Fl owa b l e S e e d Trea tm en ts: A N ew Po l ym eri c D i spersi n g System to I n crea se Acti ve I n g red i en t Co n ten t a n d to I m p rove Fl owa b l e S e ed Fo rm u l a ti o n Perfo rm a n ce a n d Fl exi b i l i ty 202 Rocco Di Modugno, Federico De Pellegrini, Brad Eidem, and Andrea Balestrini vi Overview T e 36th Symposium on Pesticide Formulation and Delivery Systems was held in Tampa, Florida, on October 27–29, 201 It was sponsored by ASTM Committee E35 on Pesticides, Antimicrobials, and Alternative Control Agents and was organized by Subcomittee E35.22 on Pesticide Formulations and Delivery Systems posium was titled, “Emerging Trends Building on a Solid Foundation.” f T T e sym- irty-three contributed papers ranged in content rom current topics such as UAVs, pollinator health, and green chemistries to more traditional ones, such as regulatory issues, f spray applications, and ormulation and adjuvant research T f is symposium varied rom previous ones in that there were no traditional key- f note speakers Following the conclusion o the 35th Symposium in New Orleans in f f October 201 4, a brainstorming session provided many insight ul erence topics f Consequently, invited speakers covered a broad range o noteworthy topics: f • Precision Ag with Unmanned Aerial Vehicles (presentation by an actual armer!) • Irrigation and Water Minimization • Pollinater Health and RNAi Technology • Biopesticides • A How-to on OMRI Listing o Pesticides and Adjuvants f f In this publication, the technical papers will be classi fed as ollows: Standards, Adjuvant Technology, Formulation Development, Spray Applications and Delivery Systems, and Seed Coatings STANDARDS f Doug Currier presented the basics on how to gain OMRI listings or pesticides and adjuvants, including required documentation Although not presented, Rea and f White submitted a paper on standard terminology or Biorationals, as this is under review by the E35.22 subcomittee ADjuvANTS Te C h N o Logy f Heuser et al described the application o polyglycerol esters as benign tank-side adju- f f vants, and Gargulak et al detailed the application o ligninsul onates as green disper- f f sants in ungicidal SC ormulations Penner and Michael presented his results on how f dew efects various adjuvants upon the application o glyphosate on post-emergent f weeds Costa et al evaluated the per ormance o vii ff f our crop oil concentrates or drif f potential and in feld trials to: 1) determine the e cacy behavior of a fungicide combination and 2) determine e cacy control of a three-component herbicide blend In a collaboration between four universities, Zollinger et al conducted standardized, uniform studies on several weed species known to show glyphosate antagonism with hard water Te intent is to ultimately develop an ASTM standard for water conditioning agents f Fo Rmu LATI o N D eve Lo Pme NT A new star polymer surfactant was introduced by Kayea et al with benefts including improved emulsion stability and resuspension ability as based on evaluations with multiple formulation types and actives Bofnger et al described how a family of novel amphoteric polymers compatibilizes high electrolyte formulations containing glyphosate, AMS, and fertilizers Chen et al introduced a high-pressure liquid chromatography (HPLC) method for determination of Lambda-cyhalothrin, which overcomes the limitiations of the CIPAC method of quantifcation by GC wherein the technical is prone to isomerization SPRAy APPLICATI o NS AND D e LI ve Ry SyST em S Papers by Klostermann et al and Fritz et al reported on the mode of action of silicone adjuvants as drif-control adjuvants and how adjuvants afect high-speed aerial applications, respectively Henry et al explained how parameters such as nozzle type, pressure, and tank-mix components infuence spray droplet characteristics Optical image analysis was ofered as an alternative to characterize spray droplet size as compared to the traditional laser method by Sarkar et al See D CoATIN g S To address the concerns of dust of of seed coatings, Halecky et al adapted mechanical methods used to predict paint durability in tribological studies with insecticide and fungicide SC formulations Di Modugno et al described a new dispersant approach with a polymeric surfactant which allows for an increased active content in the seed coating and reduced dust of Te editors wish to acknowledge the sincere eforts undertaken by those who presented at the conference, those who followed with a contributed paper, and those who reviewed the papers Session chairs were selected to highlight the dynamic of a new generation of researchers taking the reins of Subcomittee E35.22 on Pesticide Formulations and Delivery Systems Evonik Corporation actively supported the endeavors and time demands imposed on the symposium chairman and editors Dr Craig Pofenberger Evonik Corporation Richmond, Virginia Dr Justin Heuser Evonik Corporation Richmond, Virginia viii PESTICIDE FORMULATION AND DELIVERY SYSTEMS: 36TH VOLUME STP 1595, 2016 / available online at www astm org / doi: 10 1520/STP159520150090 Doug Currier1 OMRI Listing for Pesticides: What You Need to Know Citation Currier, D., “OMRI Listing for Pesticides: What You Need to Know,” Pesticide Formulation and Delivery Systems: 36th Volume, Emerging Trends Building on a Solid Foundation , ASTM STP1595, C Poffenberger and J Heuser, Eds., ASTM International, West Conshohocken, PA, 2016, pp 1–14, http://dx.doi.org/10.1520/STP159520150090 ABSTRACT The regulations that govern the production of certified organic produce in the United States are complex and cover all points of production from start (e.g., seed, input materials, origins of livestock) to finish (e.g., product handling, labeling, delivery) These regulations help ensure that organic produce is meeting a standard that everyone must follow The Organic Materials Review Institute (OMRI) helps clarify this complex regulatory environment by focusing on one piece of certified organic production: input materials Created by organic certifiers in 1997 to conduct this type of work, OMRI has built a reputation over the last 18 years as the leader in material review This paper examines and explains the specific review criteria OMRI uses when evaluating the compliance of pesticide products for use in organic production under the U.S Department of Agriculture’s National Organic Program Keywords pesticides, National Organic Program, Canada Organic Regime, U.S Department of Agriculture (USDA), Canadian Food Inspection Agency (CFIA), Organic Materials Review Institute (OMRI), organic farming Manuscript received October 26, 2015; accepted for publication May 10, 2016 The Organic Materials Review Institute, P O Box 11558, Eugene, OR 97440-3758 ASTM 36th Symposium on Pesticide Formulation and Delivery Systems: Emerging Trends Building on a Solid Foundation on October 27–29, 2015 in Tampa, Florida Copyright VC 2016 by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959 HALECKY ET AL., DOI 10.1520/STP159520160082 [9] The ESTA Standard , “European Seed Treatment Qu al i ty Assurance Scheme for Seed Treatment,” Ag ri cul tu ral I ndu stri es Confederati on (AI C) Req V.6, J une 201 [1 0] Ameri can Seed Trade Associ ati on (ASTA)/CropLi fe Ameri ca, “The G ui d e to Seed Treatment Steward shi p,” 201 3, http: //seed -treatment-gu i de.com (accessed October 3, 201 6) [1 ] Doerge, T., H al l , T., and G ard ner, D., “N ew Research Confi rms Benefi ts of I mproved Pl ant Spaci ng i n Corn,” [1 2] Crop Insights, Vol 2, N o 2, 2002, pp –5 Lau er, J G , “Theoreti cal and Experi mental Eval uati on of Wi thi n-Row Pl ant Spaci ng i n Corn,” Ag ron Abstr., American Soci ety of Agronomy, M ad i son, WI , 2001 [1 3] Okopni k, D L and Fal ate, R., “Usage of the DFRobot RB-DFR-49 I nfrared Sensor to Detect M ze Seed Passag e on a Conveyor Bel t,” ture, Vol 02, 201 4, pp 06–1 1 Computers and Electronics in AgriculProceedings of the Florida [1 4] Sal yani , M , “Dri ft Potenti al of Ci tru s Ai r-Carri er Sprayers,” [1 5] Bhu shan, Bharat, I ntrod u cti on to Tri bol og y Oxford : Wi l ey-Bl ackwel l , Oxford , 201 [1 6] Li , X and Bh ush an , B , “A Revi ew of N an oi nd en tati on Conti nu ou s Sti ffness M easu re- State Horticultural Society, Vol 1 7, pp 30–1 35 men t Tech ni q u e an d I ts Appl i cati on s,” Materials Characterization , Vol 48, N o , 2002, pp 1 –36 [1 7] Beake, B D., H arri s, A J., and Liski ewicz, T W., “Revi ew of Recent Progress i n N anoscratch Testi ng,” Tribology—Materials, Surfaces & Interfaces, Vol 7, N o 2, 201 3, pp 87–96 201 202 PESTICIDE FORMULATION AND DELIVERY SYSTEMS: 36TH VOLUME STP 1595, 2016 / available online at www astm org / doi: 10 1520/STP159520150088 Rocco Di Modugno, Federico De Pellegrini, Brad Eidem, and Andrea Balestrini Flowable Seed Treatments: A New Polymeric Dispersing System to Increase Active Ingredient Content and to Improve Flowable Seed Formulation Performance and Flexibility Citation Di Modugno, R., De Pellegrini, F., Eidem, B., and Balestrini, A., “Flowable Seed Treatments: A New Polymeric Dispersing System to Increase Active Ingredient Content and to Improve Flowable Seed Formulation Performance and Flexibility,” Pesticide Formulation and Delivery Systems: 36th Volume, Emerging Trends Building on a Solid Foundation , ASTM STP1595, C Poffenberger and J Heuser, Eds., ASTM International, West Conshohocken, PA, 2016, pp 202–214, http://dx.doi.org/10.1520/STP159520150088 ABSTRACT The global agrochemical market is continuously offering challenging opportunities to improve the quality and performance of crop protection products, seeds, and equipment in order to increase the yield of cultivated areas the global acreage of which is unlikely to increase One of the most challenging applications is seed treatment because most seed companies not only consider seeds as their core technology but also as delivery systems for chemical or biological products (or both) that further enhance seed germination and crop yields It is for these reasons that Lamberti developed a new dispersing system capable of providing greater flexibility Manuscript received October 22, 2015; accepted for publication July 28, 2016 Lamberti CST-PPC, 14622 Exxon Rd., Conroe, TX 77302 Lamberti SpA, Via Piave 18, Albizzate, 21041 VA, Italy Lamberti USA, County Rd 212, Hungerford, TX 77448 ASTM 36th Symposium on Pesticide Formulation and Delivery Systems: Emerging Trends Building on a Solid Foundation on October 27–29, 2015 in Tampa, Florida Copyright VC 2016 by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959 DI MODUGNO ET AL., DOI 10.1520/STP159520150088 in com pa ri son n a ph th a l en e n ew to tech n ol og y speci a l ben efi ts red u ced severa l sta n d a rd su l ph on a te-ba sed , d u st to bu i l d for off, th e h i g h er trea ted a d d ed or a pproa ch es (su ch tri styri l ph en ol -ba sed ) a cti ve seed i n g red i en t i n to m i cron u tri en ts, th ei r etc ) (AI ) n onyl ph en ol -ba sed , g i vi n g form u l a ti on s exi sti n g Th e as and prod u cts d i spersi n g form u l a tors or to (better system a i n trod u ce fl owa bi l i ty, d escri bed is ba sed on a n ew pol ym eri c su rfa cta n t th a t i s a bl e to i n tera ct wi th AI s, very effecti vel y provi d i n g i m proved d i spersi n g oth er a d d i ti ves ( ? d i spersi n g properti es th a t en a bl e offer perform a n ce i n crea sed g rea ter AI and ten t covera g e, better excel l en t ( ỵ 20 sta bi l i ty %) and fl owa bi l i ty, Th e i n -ca n and i m proved a d d i ti on red u ced d u st 50 %) Fl exi bi l i ty i s th e pri m a ry ben efi t of th i s n ew fa m i l y of pol ym eri c su rfa cta n ts beca u se m u l ti com pon en t form u l a ti on s ta i n i n g th ree to fi ve d i fferen t AI s ca n d evel oped even i f th e AI s beh ave i n very d i fferen t ways (e g , wa ter sol u bi l i ty, Log P or of off m el ti ng poi n t) Th i s re s u l t s in m ore e ffi ci en t s e ed t re a tm e n t s a nd in be , o/w p ro ce s s s a vi n g s d u ri n g t h e we t - m i l l i n g o f t h e fl owa bl e co n ce n tra te s for s e ed t re a tm e n t Keywords flowable seed treatments, polymeric surfactants, high load formulations Introduction Plant protection products (PPPs) have been continuously improved and developed over many decades It is well known that organochlorines, and DDT in particular, were among the earliest synthetically produced pesticide categories available for growers, although soon after their introduction, other active ingredient classes—such as organophosphate insecticides, phenoxy herbicides, and carbamate insecticides— were introduced [1] Most were formulated as soluble liquids, emulsifiable concentrates, or wettable powders (WPs) In 1947, one of the first patents was issued where a fungicide, specifically a thiocarbamate, was used in the spray tank solution in combination with a dispersing agent to make it homogeneously available [2] In the mid-1970s, formulators found that powders could be predispersed in water, building up suspension concentrates (SCs) These aqueous compositions frequently contain about 10 % to 80 %, by weight, of a solid pesticide or a mixture of solid pesticides in an aqueous medium When compared to solid formulations such as WPs or water-dispersible granules, SC formulations show desirable characteristics of a viscous liquid that is easily pourable and pumpable Compared to older solid formulations, this results in safer and more desirable handling because both dusting and accidental contaminations are minimized In many instances, SC/flowables for seed (FS) formulations initially appeared to be suitable, but some of them were actually metastable and experienced stability problems upon storage (such as claying, caking, and settling) as well as problems such as crystal growth and high water solubility Those problems became more common when multiple active ingredients (AIs) with different chemical behaviors were present in the same formulation In an effort 203 204 STP 1595 On Pesticide Formulation and Delivery Systems to stabilize solid/liquid formulations, the coformulant industry developed several different categories of dispersing agents (such as lignin sulphonates, acrylic nongrafted polymers, condensate naphthalene sulphonates, alkylphenol derivatives, fatty alcohol derivatives, and tristyrylphenol derivatives) [3–5] As formulations with more difficult and challenging requirements began to evolve, polymeric surfactants such as ethylene oxide/propylene oxide (EO/PO) block polymers and comb-grafted copolymers came into use Comb-grafted copolymers allowed formulators to optimize their formulations so that they would have the following [6] : • Improved stability against flocculation • Stronger, nearly irreversible adsorption on particles (reduced desorption) • Optimized coverage, reducing Van der Waal force effects (attraction) More specifically, the way those desirable effects are maximized relates to the nature of copolymers They are a combination of several monomers having different interactions with solid/liquid interfaces Essentially, inside the same molecules they present parts that are less soluble in the liquid phase but fully compatible with particle surfaces as well as with parts that can be easily surrounded by solvent molecules, such as water, and solubilized The excellent performance of several polymeric surfactants available on the market allowed the development of formulations where: • Multiple active ingredients are present • The slurry out of the wet-mill potentially has a concentration above 700 g/L • Formulations may contain post-mill additives such as stickers, pigments, (volume fraction [ / ] above 0.5) built-in adj uvants, and so on All the aforementioned characteristics are often present in FS formulations and, in many cases, neonicotinoid insecticides are involved Beginning around 201 3, a lot of pressure was placed on certain growers (European Union, Brazil, United States, and Canada) to limit the use of neonicotinoids, thereby pushing them to use older active ingredients such as pyrethroids, organophosphates, and carbamates [7–1 ] Neonicotinoid applications have become more challenging for growers and for- V mulators, making the use of polymeric dispersing technologies (e.g., ENVI-POL R 871 ) in combination with post-mill “in-can” additives essential or reducing or eliminating off- target or beneficial species’ exposure Materials and Methods MAIN ACTIVE INGREDIENTS AND CO-FORMULANT DESCRIPTIONS V ENVI-POL R 871 dispersant (from Lamberti) is a unique water-soluble comb- grafted copolymer where the backbone is a combination of Component (carboxylated ethylenically unsaturated monomer) and Component (noncarboxylated ethylenically unsaturated monomer) The comb-grafted configuration is achieved using polyalkoxylated capped derivatives This polymeric surfactant shows certain chemical–physical properties, which are reported in Table DI MODUGNO ET AL., DOI 10.1520/STP159520150088 TABLE Chemical–physical behaviors of ENVI-POLV 871 R Parameters Results Description: Viscosity(@ 68 ? F, S02 – 20 RPM) Density (@ 68 ? F) Surface tension (@ 68 ? F – 0.1 % w/w) Water solubility pH (@ % in water) polymeric surfactant 25,000 mPa ? s 9.4 lb/gal 49 dynes/cm soluble 6–8 FS formulations were prepared using two different dispersing systems; in particular, tristyrylphenol esters (CAS# 105362-40-1), existing crystal growth inhibitors, and EO/PO block copolymers were used as comparative or synergistic co-dispersing agents (see Table ) Different post-mill additives were incorporated to improve the performance of FS formulations; these were acrylic polymer film-forming agents, antifriction agents, pigments, and antifoaming agents and stabilizers such as: • Sticker is EmulsonV Ag Coat, acrylic latex in emulsion, about 40 % active R • • • • • • • matter, available from Lamberti Sticker is EmulsonV Ag Coat 80, acrylic latex in emulsion, available from Lamberti Sticker is EmulsonV Ag STFS, acrylic latex in emulsion, about 45 % active matter, available from Lamberti Sticker is EmulsonV Ag Coat SC, acrylic latex in emulsion, about 40 % active matter, available from Lamberti Antifriction Agent is EmulsonV Ag W6, solid polymer 100 % active matter, available from Lamberti Dow CorningV Antifoam 1410 is silicon-based emulsion, about 10 % active matter, available from Dow Corning Red Neprint D-GR is red pigment in dispersion available from Lamberti Titanium Dioxide is a white powder, 100 % active matter R R R R R Active ingredients used in these studies are shown in Table [1 2] TABLE Composition of dispersing systems Code LDP-17245 LDP-17871 Composition 60 % - Emulson Ag TRST/HA (Cas# 105362-40-1) 40 % - Emulson Ag TRN 141-05 50 % - ENVI-POLV 871 50 % - Emulson Ag TRN 141-05 R Note: Emulson Ag TRST/HA is tristyrylphenol ethoxylate (16EO) phosphate ester TEA salt Emulson Ag TRN 141-05 is acrylic comb graft copolymer 205 206 STP 1595 On Pesticide Formulation and Delivery Systems TABLE List of tested active ingredients Pesticides Type Category Mode of Action Fipronil insecticide phenylpirazole Insecticide toxic by contact and ingestion Imidacloprid insecticide neonicotinoid Systemic insecticide with translaminar activity Azoxystrobin fungicide strobilurin Fungicide with protectant, curative, eradicant, Thiophanate-M fungicide benzimidazole Systemic fungicide with protective and Thiamethoxam insecticide neonicotinoid Insecticide with contact, stomach, and and with contact and stomach action translaminar, and systemic properties curative action systemic activity PERFORMED TESTS ON FS FORMULATIONS Tests used to characterize formulation performances are reported in Table TABLE Chemical and physical tests Parameters Unit Description/Expected Behavior Appearance Visual The FS formulations should be homogeneous Viscosity mPa*s The test was measured @20 ? C S02 @20 rpm The viscometer lm Corresponds to 90 % of the cumulative distribution by volume (no sedimentation) and pourable was a Brookfield Digital Model DV-I Particle size (D90) as defined by ISO 13320-1 The particle size analyzer was a Malvern Mastersizer Hydro 2000 S Spontaneity % Based on the preparation of 250 mL of a mixture of the SC (5 %) and water (342 ppm), mixed with only one inversion of the measuring cylinder After standing under defined conditions, the top nine-tenths is removed, and the remaining tenth assayed chemically, gravimetrically, or by solvent extraction The method gives an index of the immediate homogeneity of the diluted SC Complete immediate homogeneity of the diluted formulation corresponds to 100 % [13] Suspensibility % Based on preparation of 250 ml of the SC (2 %) and water (342 ppm) mixed with 30 inversions of the measuring cylinder, allowing it to stand for a specified time in the cylinder (1 h) under defined conditions and removing the top nine-tenths The remaining tenth is then assayed chemically, gravimetrically, or by solvent extraction The method gives an index of the stability of the homogeneity of the diluted SC over time Complete stability and homogeneity correspond to 100 % [14] Storage stability Pass/ Evaluated by storing them at 40 ? C for eight weeks or at Not Pass 54 ? C for two weeks (according MT 46.1.3, CIPAC Content Handbook F) and repeating the relevant tests DI MODUGNO ET AL., DOI 10.1520/STP159520150088 TABLE Settings related to application on seeds Seed Weight lb 10 oz (FS ỵ waterỵ pigment) per 100-lb seed (CWT) Slurry applied to seeds Injection time 7s Coat time 14 s Discharge time 10 s Rotor speed 7,600 RPM TESTS PERFORMED ON SEEDS Application of the SCs on seeds was done using an Aginnovation Rotary-12 with the settings reported in Table A description of performance tests used on seeds is reported in Table TABLE Performance tests on seeds Test Dust off Unit g/100,000 seeds Description/Expected Behavior Dust-off testing is performed in accordance with good laboratory practice standards Samples are collected and allowed to acclimate to the environment for 48 h Samples are then separated into four repetitions of 100 g and tested V using the Heubach Dustmeter In this process, the seed is R agitated as a vacuum forces air through the seed and across V a 50-mm Whatman Glass Fiber Filter The dust created by R the agitation of the seed is collected on the filter The final weight of the dust and filter is recorded less the original filter weight Experiments normally are performed at a temperature of 22.5 ? C and a relative humidity of 35 % Flowability s Samples are treated with test solutions and immediately transferred to a seed flow assessment device The seed flow device is an acrylic container holding a minimum of lb of seed with an angled floor of approximately 45 ? The discharge opening width is the same as the unit width, and the opening height is limited to in After 60 of retention in the seed flow device, the opening is set at 100 % open, and the discharge is timed Any bridging to prevent discharge is noted Residual seed that does not flow from the device is collected and weighed If possible, discharge is video-recorded to capture the accurate time of discharge, and there is repeated visual observation of flow characteristics 207 208 STP 1595 On Pesticide Formulation and Delivery Systems TABLE (Continued) Test Unit Plantability Description/Expected Behavior Number of skips over Plantability testing is performed on a Big John Computrol III 1,000 seeds Test Stand with two planting modes—finger pick up and vacuum pick up Seed samples are divided into a minimum of three repetitions of 1,000 seeds each The Computrol III is set to a standard setting of 13, with a seeds/acre count of 30,000, a speed of mph, rotation at 46–48 RPM, and a vacuum rate of 15 The Big John Computrol III records and digitally prints a report that indicates the number of instances of two seeds being discharged (planted) at the same time (recorded as “doubles”), the number of instances when no seed was discharged (recorded as “skips”), and then calculates the percentage of seed that is discharged within % of the intended planting distance, recorded as “% center drop.” Results and Discussions In the first study, LDP- 7871 was tested in a “multicomponent” FS formulation The four AIs were Fipronil, Imidacloprid, Azoxystrobin, and Thiophanate methyl Figs 1–3 report the main chemical–physical properties of those AIs Water solubility is significantly greater for Imidacloprid when compared to the other components This may result in particle size growth due to a strong Ostwald ripening effect during the aging process In Fig , ? graphically represented melting point data show a 70 to 80 C differ- ence between the highest and the lowest values reported This can result in in an inhomogeneous milled product and likely an undesirable bimodal particle size distribution if the milling process is not optimized (low milling temperature and pressure working conditions, very thin slurry) FIG Water solubility of active ingredients DI MODUGNO ET AL., DOI 10.1520/STP159520150088 FIG Melting points of active ingredients Log P o/w values vary greatly and range from Imidacloprid, which is very hydrophilic, to Fipronil, which is very hydrophobic These conditions require a dispersing system that is very flexible and able to effectively work at the solid/liquid interface Formulation preparation consisted of two steps: (1) milling process and (2) postmill completion Active ingredients were milled using a DynoV-Mill Multilab bead mill with different formulations, reported in Table FS1 did not show any percentages for post-mill additives because the slurry gelled into the milling chamber, and the milling process was abandoned Most likely the dispersing system was not able to interact properly with the AI mixture FS2 and FS3 were processed successfully, with physical characterizations reported in Table FS2 and FS3 both showed very good appearance and viscosity inside the expected range (800–1200 mPa*s) Particle size was measured out of the wet-mill and before post-mill additive addition Both spontaneity and suspensibility were R FIG Log Po/w of active ingredients 209 210 STP 1595 On Pesticide Formulation and Delivery Systems TABLE Recipes for different multicomponent FS formulations Ingredient Fipronil, Imidacloprid, Azoxystrobin, Thiophanate-M Glycol LDP-17245 LDP-17871 Antifoam 1410 Citric Acid Sticker Red Neoprint D-GR Gel (Xanthan Gum) % Water FS1 FS2 FS3 %-Weight %-Weight %-Weight 55.4 2.5 3.5 55.4 2.5 55.4 2.5 2.4 0.4 0.1 0.0 9.5 5.0 24.7 2.4 0.4 0.1 4.9 9.5 5.0 19.8 0.4 0.1 Post-mill Post-mill Post-mill 24.8 greater than 90 %, indicating that FS2 and FS3 can match application standards For this reason, they were applied to corn seeds to test performance ( Table ) FS2 did not contain any specific post-mill additives that might have been able to improve seed applied performance, so it was considered as “control.” FS3 contains Sticker , and it resulted in a suitable dust-off reduction of close to 60 % This favorable performance was achieved without compromising flowability and plantability In the second study, LDP-1 7871 was tested in “high solid content” FS formulations It was tested in two different formulations (FS5 and FS6) and compared to a third formulation based on a tristyrylphenol type dispersing system (FS4) In this specific case, the goal was to mill slurry with at least 70 % solid content Table 10 reports the compositions of the different FS formulations FS4, formulated with LDP-1 7245, did not succeed.The milling process was abandoned because pressure and temperature became too high Both FS4 and FS5 TABLE Physical characterization of multicomponent FS formulations Test Appearance Viscosity, mPa ? s Particle size D90, lm Spontaneity, % Suspensibility, % Storage stability FS1 FS2 FS3 Paste - Fluid suspension 1,100 90 > 90 Passed Fluid suspension 1,200 90 > 90 Passed DI MODUGNO ET AL., DOI 10.1520/STP159520150088 TABLE Corn seed after treatment with multicomponent FS formulations Seed Treatment Parameters Seeds-FS2 Seeds-FS3 0.95 0.97 Skips 28.5 29.25 Doubles 1.25 0.787 0.315 Flowability, s Plantability Dust off, g/100 K seeds included post-mill additives; in particular, FS5 was formulated with Sticker in an effort to reduce dustoff Table 11 shows physical analyses of FS5 and FS6 These results confirmed the anticipated good performance of LDP- 7871 as a dispersing agent and its compatibility with post- mill additives As a further step, six additional FS formulations were prepared to develop a more complex post- mill additive system containing antifriction agent The scope was to reduce seed/seed friction occurring when seeds are moved or planted because this is one of the maj or causes of dust off Several stickers having different glass transition temperatures (Tgs) were tested to describe how dust off is affected by the sticker’ s properties Table 12 reports these compositions In FS1 and FS1 2, we introduced a suitable amount of antifriction agent FS1 was formulated to maximize the amount of Sticker FS7 through FS1 were tested, and the results are reported in As shown in iations ( Table 13 , Table 13 when only the sticker is present, viscosityhas limited var- 00 mPa) in comparison to the control (FS5) The addition of an antifric- tion agent resulted in greater viscosity (up to 800–1 900 mPa*s) , which begins to TABLE 10 Compositions of high solid content FS formulations FS4 FS5 FS6 %-Weight %-Weight %-Weight Thiamethoxam 47.6 47.6 47.6 LDP-17245 6.0 LDP-17871 Antifoam 1410 0.4 4.5 4.5 0.4 % 0.4 Titanium Oxide 2.0 2.0 % 2.0 Pre-mill water 24.0 25.5 % 25.5 1.7 Sticker Post-mill Gel (2 % Xanthan Gum) Post-mill 1.7 % Post-mill water Post-mill 18.3 % 8.3 80.0 % 100.0 100.0 Total 10 211 212 STP 1595 On Pesticide Formulation and Delivery Systems TABLE 11 Physical characterization of FS formulations Test Appearance Viscosity, mPa ? s Particle Size D90, lm Spontaneity, % Suspensibility, % Storage Stability FS4 FS5 (control) FS6 Paste - Fluid suspension 1,100 90 > 90 Passed Fluid suspension 1,300 90 > 90 Passed TABLE 12 Compositions of FS formulations containing post-mill additives to improve performance Thiamethoxam LDP-17871 Antifoam 1410 Titanium Dioxide Pre-mill water Sticker Sticker Sticker Sticker Antifriction agent Gel (2 % Xanthan Gum) Water Total FS7 FS8 FS9 FS10 FS11 FS12 %-Weight %-Weight %-Weight %-Weight %-Weight %-Weight 47.6 4.5 0.4 2.0 25.5 47.6 4.5 0.4 2.0 25.5 47.6 4.5 0.4 2.0 25.5 47.6 4.5 0.4 2.0 25.5 47.6 4.5 0.4 2.0 25.5 47.6 4.5 0.4 2.0 25.5 10.0 10.0 10.0 2.0 1.7 6.3 100.0 15.0 10.0 10.0 1.7 8.3 100.0 1.7 8.3 100.0 1.7 8.3 100.0 5.0 100.0 2.0 1.7 6.3 100.0 TABLE 13 Chemical–physical characterizations of FS formulations Test Appearance Viscosity, mPa ? s Particle Size D90, lm Spontaneity, % Suspensibility, % Storage stability FS7 FS8 FS9 FS10 FS11 FS12 Fliud 1,300 90 > 90 Passed Fliud 1,400 90 > 90 Passed Fliud 1,300 90 > 90 Passed Fliud 1,800 90 > 90 Passed Fliud 2,100 90 > 90 Passed Fliud 1,900 90 > 90 Passed DI MODUGNO ET AL., DOI 10.1520/STP159520150088 TABLE 14 Seed applied performance Seed Treatment Seeds Benchmark Seeds Control Seeds FS6 Seeds FS7 Seeds FS8 Seeds FS9 Seeds FS10 Seeds FS11 Seeds FS12 0.92 0.90 0.91 0.88 0.92 0.90 0.88 0.89 0.89 28.5 Flowability, s Plantability Skips 27.5 28.25 28.5 28.75 28.25 27.5 28.5 28.75 Doubles 1.25 1.5 1.75 1.5 1.5 1.25 1.5 Dust off, 0.483 0.497 0.154 0.311 0.087 0.182 0.056 0.134 0.078 g/100 K seeds Reduction % (referred to control) ? 69 % ? 37 % ? 82 % ? 63 % ? 89 % ? 73 % ? 84 % be difficult to handle Increasing the amount of sticker from % to 15 % resulted in a viscosity above 2,000 mPa*s without any stabilizer added (such as xanthan gum as a thickening agent) The particle size distribution was measured out of the mill Spontaneity and suspensibility values were above 90 % for all tested formulations, which means the dispersing system is working properly and the quality of the milling process is acceptable Some of the more viscous formulations were tested after storage at 40 ?C for weeks instead of 54?C for weeks All formulations passed the storage stability test Seeds’ applied performance of different FS formulations is reported in Table 14 In this specific case, the benchmark is a commercially available Thiamethoxam lb/gal formulation Flowability did not show any big variation, and the highest value, 0.92 s, was for FS8 and may be due to the low Tg of Sticker Plantability also showed very little variation The biggest differences were noticed in the dustoff test When compared to the benchmark and control, all formulations showed improved performance Different Tgs resulted in different dust-off reduction performances FS8 Sticker showed the greatest reduction of dust off without any antifriction agent added Overall, the best formulation was FS10, containing both Sticker and an antifriction agent Increasing the sticker from 10 % to % did not provide the expected benefit because the viscosity of the final formulation became too high Conclusions V The ENVI-POL polymeric dispersing agent showed very good performance in fully formulated seed coatings It has been developed to provide benefit when used in SCs, FS, and SEs Its main function as a high-performance dispersing agent and milling aid allows formulators to mill highly concentrated slurries, thereby improving formulation flexibility The data provided suggest they may be able to design more complex formulations and, by adding post-mill additives, improve the efficacy of PPPs Improved efficacy may result in higher crop yield, better seed protection, or more “on-target” application R 213 214 STP 1595 On Pesticide Formulation and Delivery Systems Acknowledgments The authors 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