Additives forPesticide Formulations About Us Evonik Industries is the creative industrial group from Germany which operates in three business areas: Chemicals, Energy and Real Estate. Evonik is a global leader in specialty chemicals, an expert in power generation from hard coal and renewable energies, and one of the largest private residential real estate companies in Germany. Our strengths are creativity, specialization, continuous self-renewal, and reliability. Evonik is active in over 100 countries around the world. The Business Line Interface & Performance of Evonik Industries AG has its base in all kinds of organic specialty surfactants and organomodified siloxanes. We hold strong positions with antifoams, emulsifiers, corrosion inhibitors, dispersing aids, hydrophobing and wetting agents, softeners and radiation curable release coatings. Our broad product range, technological background and application know-how addresses several industries like plastics, rubber, label, tape and release liner manufacturing, construction, lubricants, agro, textile and tissue industry. When our flagship product BREAK-THRU® S 240 was introduced in 1992, our focus was on tankmix adjuvants. Since then, we have started to include different surfactant classes into pesticide our portfolio. Drawing upon our in-house pool of surfactants and the in-depth knowledge of interfacial processes and technologies, we have expanded our product portfolio to include additional organomodified siloxanes and other specialty surfactants. BREAK-THRU® is a registered trademark of Evonik Industries AG. 2 we offer a novel package of products and expertise. 3 . and a growing generic market. Contact your representative for the latest information. we are continuing to add new products and develop new guideline formulations. With a decreasing number of new actives specifically in the crop protection area. We also offer unique antifoams with superior compatibility allowing crystal clear formulations or novel additive systems such as our patented thermody- namically stable microemulsions. In this way. anti-caking and milling behaviour In the middle of this decade. we started to develop prototype formulations to provide guidance to the user with respect to product and functionality. it is our goal to provide solutions to meeting the competitive demands of the pesticide industry. packaging and tank-mixing Dispersing Agents Improve the dispersion and suspension of solid particles Emulsifiers Effectively emulsify oils in water Rheology Modifiers Stabilize active ingredients in liquid formulations and adjust to the viscosity Carrier Substances and Flow Agents Are highly efficient for absorption of liquid components and improving the free flow. For us the aim is to give you the ability to differentiate your formulation in the market place by offering superior agrochemical products. Various examples of guideline formulations are given in the end of this document. The effects of our products are not limited to enhancing and safeguarding biological efficacy. Our formulation experts combine decades of experience from the agricultural chemical and other industries and have merged their knowledge with that of our plant physiologists who link it to performance in the field. While this brochure is designed to give an overview of our current agro activities.Our Product Range Oil Enhancers Influence surface tension and spreading of oil Wetting Agents • Trisiloxanes • pH stable polysiloxanes Enhance deposition of pesticides by lowering surface tension of spray water and improving spread Antifoams Suppress or eliminate foam during manufacturing. As oil types and compositions vary globally. 4 . All three BREAK-THRU® OE products are approved for use under 40 CFR 180. phytotoxicity risk and environmental concerns. it is possible to increase pesticide performance and reduce the amount of spray oil. the BREAK-THRU® OE oil spreaders are designed for a broad spectrum of formulation types.Oil Enhancers Many pesticides exhibit limited water solubility. When incorporated into oil-containing formulations such as EC’s.910 and generate only little or no foam. EW’s or OD’s. With the improved performance of these oil-based pesticide formulations. thereby reducing cost. the BREAK-THRU® OE series of organomodified polysiloxanes lowers the bulk surface tension of the oils which leads to improved spreading and distribution of the oil droplets onto and into the target. so mineral and vegetable oils often serve as the carriers to deliver these actives to plants or pests. Cyclohexanone Soluble Soluble Soluble (only in butanol) ® * Registered trademark of Exxon Mobil 5 . Field studies with BREAK-THRU® OE 444 on several fruits confirm that it leads to improved foliar coverage and efficacy with fungicides and insecticides. Since BREAK-THRU® OE 441 is also soluble in water it can be used in SC.g. NMP. EW and SE formulations. soya oil Soluble Dispersible Dispersible Mineral Oil Insoluble Soluble Soluble Paraffinic Oil Insoluble Insoluble Soluble Solvesso 150* Soluble Soluble Soluble Others: Butanol. rapeseed oil. Addition of only 0. Benefits of Oil Enhancers: • Improve pesticide performance • Approved under 40 CFR 180.910 • Benign toxicity & ecotox • Soluble in most common solvents • Low use rates Solubility of selected BREAK-THRU® Oil Enhancers (5 wt%) in different oils Solvent BREAK-THRU® OE 440 BREAK-THRU® OE 441 BREAK-THRU® OE 444 Water Insoluble Soluble Insoluble Methyl soyate. On a hydrophobic surface.Oil enhancers allow oil droplets to move to the back of fruits even though the oil was only sprayed on one side BREAK-THRU® OE 440 is recommended for formulations containing vegetable oils and is typically used between 0.5–5 wt% of the oil. It must be added as a component of the oil phase and not post added to the finished formulations. this product increases the spreading of seed oil droplets by 300 to 500 percent after 30 minutes. BREAK-THRU® OE 441 is recommended for EC or OD formulations containing methylated or ethylated vegetable oils and is effective at concentrations between BREAK-THRU® OE 444 is recommended for formulations containing mineral oils at 0. 2–5 wt% of the oil phase. this product at 5 wt% enhances methylated seed oil to improve spreading five fold. Accelerated studies at pH 4–9 refute the concerns of hydrolytic instability for this robust product. methylated rape seed oil Soluble Soluble Soluble Vegetable Oil e. On a hydrophobic surface.5–5 wt% of the oil phase. SL.5 wt% to a mineral oil or paraffinic oil results in spreading up to a five fold increase after thirty minutes. and increase pesticide up-take. are shown in Diagram 1. BREAK-THRU® S 233. trisiloxane surfactants can provide superior spray coverage and are unique among surfactants in their ability to impart phenomenal spreading characteristics to formulations. Despite a lower amount of pesticide. it can also be caused by the reduction in surface tension of the spray mixture and is critical for enhanced active ingredient uptake. These products can also be instrumental in enabling stomatal flooding and cuticular penetration. Example of a trisiloxane based Super Penetrant Improved penetration of a pesticide is not necessarily the result of super spreading. allow for better targeting.02 to 0. In the case of the non-spreading trisiloxane surfactant.15 wt%. and the lower spray volume of only 250 l/ha the efficacy was equal or better than the full rate of the fungicide (Ortiva® = azoxystrobin*) at the higher water volume. Owing to their ultra low static surface tensions. our organomodified siloxanes are perfectly suited to meet varying requirements. Example of a trisiloxane based Super Spreader The results of field trials on grapes in Italy with the super spreader BREAK-THRU® S 240. For highperformance applications. silicone wetting agents stand out in their ability to do so at concentrations between 0. up-take of glyphosate is faster and more pronounced compared to a super spreader *Registered trademark of Syngenta Water treated with a trisiloxane surfactant can penetrate dense and hydrophobic surfaces like broccoli.Wetting Agents Trisiloxane based Wetting Agents While all wetting agents have the ability to decrease surface tension. used as tank-mix adjuvant. Some of them also cause super spreading of the spray solutions whereas others – designed solely to reduce surface tension – behave as penetrants. 6 . These surfactants can decrease the spray volume required for a particular pesticide application. 5 l/ha Ortiva® 0.g. The speed of uptake was analysed with radiolabeled glyphosate (see Diagram 2). BREAK-THRU® S 240.05 7 . 55. even though both products decrease the surface tension of the spray mixture down to 21 mN/m. is most suitable for actives with systemic action.1 % BREAK-THRU® S 240 + 0.5 l/ha •250 l/ha Ortiva® 0. such as BREAKTHRU® S 233.5 l/ha a 90 85 80 b b* 75 c 70 65 without additional surfactant + 200 ml/ha BREAK-THRU® S240 Diagram 2: Up-take [%] of 14C labeled glyphosate in bean leaves as a function of time: Comparison of different mode of action between BREAK-THRU® S 240 and S 233 Time after application Glyphosate up-take [%] 10 min 24 h d 90 80 70 c 60 50 40 30 20 10 b* a 0 + 0. p. Used with glyphosate. improving rainfastness and efficacy. BREAK-THRU® S 233 can enhance the speed and volume of uptake. Bean leaves were washed at different time intervals to quantify the rate of uptake (Ref.75 l/ha Ortiva® 0.1 % BREAK-THRU® S 233 * All values with the same letter are statistically not different at P = 0. This class of super penetrants. Weed Science 2007.e. 406-411). Diagram 1: Increased efficacy with BREAK-THRU® S 240 with reduced spray volumes Spray volume •500 l/ha Efficacy against grape powdery mildew (%) Ortiva® 0. The reduction in surface tension of these products is not so dramatic as for trisiloxanes.910 BREAK-THRU® S 279 Organomodified Trisiloxane 5–8 21 High 40 CFR 180. thus improved rainfastness times the combination of a trisiloxane Stability of BREAK-THRU® OE 441 in water static surface tension [mN/m] pH 3 pH 4 pH 9 pH 11 1 wt% solution (0 h) 38 38 37 38 1 wt% solution (7d at 54 °C) 40 39 38 41 Static surface tension @ 0. Details are available upon request. These products display solubility in either oil or water.910 BREAK-THRU® S 240 Organomodified Trisiloxane 5–8 22 High 40 CFR 180. • Allow wetting of dusty or hard to wet plants Compatibilty and mode of action drive the selection of the most suitable wetting • Allow reduction of spray volumes by up to 30–50 % agent.910 8 with a solubilizer or amphoteric surfactant is advantageous. the stability towards hydrolysis was analysed by monitoring the • Safeguarding the performance of pesticides static surface tension (mN/m). • Greater or equal up-take of pesticide Specifically for SL formulations somein less time. but polysiloxanes have a great impact on the properties of oils (see oil enhancer section).910 BREAK-THRU® S 200 Organomodified Trisiloxane 5–8 22 High 40 CFR 180. Benefits of Wetting Agents: In the table below. For more detailed recommendations please contact us.pH stable Polysiloxane based Spreaders Due to their extended siloxane backbone.910 BREAK-THRU® S 243 Organomodified Polysiloxane 4–9 47 High 40 CFR 180.910 BREAK-THRU® S 233 Organomodified Trisiloxane 5–8 23 High 40 CFR 180. The mode of action of these products is similar to that of penetrants. the silicone character of BREAK-THRU® OE 441 and BREAK-THRU® S 243 is pronounced. While organomodified trisiloxanes require relatively neutral formulating conditions. organomodified polysiloxanes do not and BREAK-THRU® OE 441 and BREAK-THRU® S 243 are stable in water at pH values between 4 – 9. .1 % in water Foam tendency EPA FIFRA status Properties of our wetting agents Product Chemical description Stable within pH range BREAK-THRU® OE 441 Organomodified Polysiloxane 4–9 40 Low 40 CFR 180. By using BREAK-THRU® wetting agents grapes are uniformly wetted 9 . TAE-15: tallow amine ethoxylate with 15 mole EO. compatibilizers and even as solvents. a universal solution to foaming issues does not exist. ates. e. For example. while maintaining the efficiency and low dose rates typical of silicone oils. emulsifiers.15 % 13 – 1 Since individual formulations contain different active ingredients. glyphosate IPA salt formulation was prepared with 10 % v/v TAE-151 and different concentrations of BREAK-THRU® AF 9903. dispersants. BREAK-THRU® AF antifoam agents are very robust in their performance and are used in a variety of formulations. Please contact us to discuss your specific application. available from Evonik as VARONIC® T-215** Defoaming of a 360 g/l a.1 wt% BREAK-THRU® AF-9903 Trisiloxane * Alkylpolyglycoside = APG 10 APG* Laurylethersulfate ** Registered trademark by Evonik APG control without antifoam . solvents and surfactants. glyphosate IPA SL formulations often contain tallow amine ethoxyl- Benefits of BREAK-THRU® Antifoams: • Tailored to overcome incompatibility.Antifoams In agrochemical formulations. Many of them tend to concentrate at interfaces often generating and stabilizing foam. e. and 50 ml were added to a 100 ml graduated cylinder. different surface active chemistries are used as wetting agents. While silicone oils are excellent defoamers. Evonik has a line of defoamer/ antifoam products with the BREAK-THRU® AF designation. each formulation was then diluted 1 : 50.0165 % 48 1 0. they are notoriously immiscible in water-based systems. but can also occur during field application where it is especially burdensome to end users. Foaming can occur during manufacturing and packaging.05 % 25 – 0. After mixing the components. (ml) Control 60 50 0. These silicone products are modified with other organic groups and are tailor-made to overcome incompatibility. Following vigorous shaking for 15 s. A 360 g/l a. To overcome this obstacle. while maintaining the efficiency • Variety of different chemistries to fulfill different application requirements Foam control with 0. glyphosate formulation Concentration of BREAK-THRU® AF-9903 Initial Foam Height (ml) Foam Height after 90 sec. which cause foam when agitating the spray solution. the foam height was recorded. causes less cloudiness than AF 9903 in SL formulations BREAK-THRU® AF-9902 OMS 100/Compound 500– 1000 40 CFR 180. salt tolerant.Properties of selected antifoams Concentration/Form Viscosity (mPas) EPA FIFRA status Special properties OMS* 100/EC** 600 40 CFR 180. suitable for granule preparation Product Chemical base BREAK-THRU® AF-5503 *OMS = Organomodified siloxane **EC = self-emulsifying concentrate 11 .910 For water based formulations. not self-emulsifying. for glyphosate BREAK-THRU® AF-9906 Silicone oil 100/Compound 200– 600 40 CFR 180. suitable for oil based formulations BREAK-THRU® AF-9903 OMS 100/EC 500– 1500 40 CFR 180. g.910 Antifoam concentrate without emulsifier for nonaqueous or solvent based systems (e.910 For water based formulations.910 Antifoam for in-can formulations. g. ODs) BREAK-THRU® AF-9908 Silicone oil/OMS 40/Emulsion 300 Not listed Increased stability towards temperature and shear. salt tolerant e. electrostatical stabilisation 50 % SC not listed BREAK-THRU® EM TD 6 POE (6) isotridecyl ether OD pending EPA approval ® 12 100 % . Benefits of Dispersing Agents: • Enhanced wetting of solid particles and increased stability of formulations • Reduced milling time • Improved dispersion in water Chemical description Concentration Formulation suitability EPA FIFRA status BREAK-THRU® DA 646 Modified polyether 100 % EC. Dispersing agents interact with the surface of the particles and prevent the formation of agglomerates. SC not listed BREAK-THRU® DA 652 Fatty acid derivative 100 % OD not listed BREAK-THRU® DA 655 Polyether phosphate. Without BREAK-THRU® DA 655 With BREAK-THRU® DA 655 Dispersing agents have amphiphilic structures which need to be insoluble in the solvent.Dispersing Agents Dispersing agents are surfactants which enhance the incorporation of solids into liquids and are used in suspension concentrates and more recently in oil dispersions. sterical stabilisation 40 % SC not listed BREAK-THRU DA 752 W Aqueous based organically modified polymer. Properties of selected dispersing agents Product Some examples for the incorporation of BREAK-THRU® dispersing agents (DA series) in SCs and ODs are given in the section “formulation activities”. They must possess anchoring groups capable of being strongly absorbed onto the particle surface. electrostatical stabilisation 100 % OD not listed BREAK-THRU® DA 675 Aqueous based organically modified polymer. 910 BREAK-THRU® EM TD 6 POE-(6)-Isotridecyl Ether 11. Rely on our long-standing experience and know-how and save valuable time. sunflower or rapeseed oil) without any foam. This surfactant also reduces the surface tension of oils (e. The required HLB value can be adjusted by selected blending.4 it creates emulsion spontaneity in ECs and EWs.Emulsifiers Our product range includes primary and secondary emulsifiers that are based on renewable resources like ethoxylated or non-ethoxylated glycerol fatty acid esters. Therefore BREAK-THRU® emulsifiers can also be used as dispersants. for excellent emulsification Benefits of glycerol fatty acid esters: • Excellent emulsifying and stabilizing properties • Excellent solubility in vegetable and synthetic oils • Derived from renewable resources • No skin irritation. With an HLB-value of 8. No phytoxicity was exhibited in wheat and maize field trials. BREAK-THRU® emulsifiers (BREAK-THRU® EM series) are non-ionic. dose rate 10 % 40 CFR 180.g. benign tox classification Properties of selected* liquid emulsifiers Product Chemical base HLB Recommended oil EPA FIFRA status BREAK-THRU® EM V 20 POE-(20)-Glyceryl Oleoricinolate 8. hydrophilic and lipophilic organic surfactants used in the preparation of both oil-in-water and water-in-oil emulsions.910 BREAK-THRU® EM 0 7 PEG-(7)-Oleate 10 Paraffinic oil.4 Mineral oil. toxicological and dermatological behavior. sorbitan esters. recommended in combination (5:1) with co-emulsifier Tegin OV. preferred 1:1 mixture with TEGO® SMO 80 V (20 %) Pending EPA approval * In order to obtain the whole emulsifier portfolio brochure. However. To emulsify a specific oil. In herbicide field trials this product showed higher biological efficacy than methylated rapeseed oil. total dose 15 % 40 CFR 180. BREAK-THRU® EM. During screening of various emulsifiers with a pyrethroid EC formulation it demonstrated superior performance (see publication Poffenberger et. various fatty acid polyglycol esters and lauryl polyglycol ethers. al ISAA 2007). Our regional technical service group will assist you in finding the right formulation. even at lower dose rate. solubilizers and wetting agents. emulsifiers with precisely adjusted HLB values are needed. our focus is on the more environmentally friendly glycerol fatty acid esters. BREAK-THRU® EM V 20 is one of our vegetable-based nonionic emulsifiers with excellent ecological. please contact our regional technical groups 13 . By balancing the hydrophilic and lipophilic parts the properties of a surfactant can be adjusted to the needs of different applications.4 Vegetable oil. the green curve the end of the lumifuge cycle. Various examples of ongoing activities with different liquid formulation types are described on the next pages.11 μm). Berlin. www. The red curve describes the beginning. Preparation of the formulation Grinding was accomplished with all of the ingredients except the thickener with a corrugated teflon rotor blade for 2 hrs at 625 rpm using glass beads. South Africa. one can estimate that this formulation will form a clear top layer under normal storage conditions at a rate of 1. proceedings ISAA 2004. GmbH.5 Xanthan gum. A clear phase developed on the surface of the formulation containing the TSP (see Diagram 1 a). Formulation stability was evaluated using a LUMiFuge® 116 (L. The top of the sample is at 95 mm. Results showed a significant improvement of the BREAK-THRU® DA 646 containing formulation over the other formulations at the intermediate dosage level (see Fleute-Schlachter et al. Creating a stable. While both dispersing agents produce Guideline recipe of the SC formulation Component wt% Sulfur (Mesh 100) 25. For us the aim is to give you the ability to differentiate your formulation in the market place by offering superior agrochemical products. the bottom at 113. Germany. The efficacy of both formulations and a commercial sulfur SC formulation were tested in a greenhouse environment on powdery mildew colonized on barley (see Diagram 2). such as BREAK-THRU® S 240 at 1-8 wt%. In the following example. an SC formulation (see recipe below) containing sulfur and BREAK-THRU® DA 646 as the dispersing aid was compared with a formulation containing ethoxylated tristyrylphenol phosphate (TSP). Sedimentation is observed for the TSP containing formulation between 110 and 113 mm.U. ISBN 1-920-01716-X). effective and environmentally friendly formulation requires the use of surfactants.6 Tego® Antifoam MR 2021 0. the physical stability of the formulation favored the use of BREAK-THRU® DA 646. Suspension Concentrate Formulation Suspension concentrate (SC) formulations have gained popularity as a means of delivering water insoluble actives in a liquid formulation without need for solvents. a commonly used dispersing agent.M.3 BREAK-THRU S 240 0–8.0 Monoethylene glycol (antifreeze) 2.2 mm per month. 10 % solution 1.8 Water to 100 ® 14 similar particle sizes (d50 of 3. It is believed that the improved efficacy can be attributed to the lower static and dynamic surface tension imparted by the BREAK-THRU® DA 646 which was confirmed in the laboratory. From the movement of the phase boundary.de) – a device which can measure transmission profiles during centrifugation.5 mm.1 Dispersing agent 1. The glass beads were filtered off and the thickener was added at the end of the milling. The sedimentation speed of the BREAK-THRU® DA 646 containing formulation was reduced by a factor of fifteen (see Diagram 1b).Formulation Activities We at Evonik decided to develop prototype formulations to provide guidance to the user with respect to product selection. .lum-gmbh. To further enhance the biological efficacy it is recommended to incorporate a trisiloxane based wetting agent. 0 60.0 12.Diagram 1: Stability of a formulation tested in the LUMiFuge b) with BREAK-THRU® DA 646 120.0 60.0 108.0 84.0 72.0 108.0 36.0 120.0 96.0 48.0 84.0 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 95 Position [mm] 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 Position [mm] Diagram 2: Number of powdery mildew pustules per leaf segment of barley Control 31 mg S/l 500 mg S/l 2000 mg S/l 168 a* – – – Formulation with BREAK-THRU DA 646 – 147 b 1d 0d Formulation with TSP – 145 b 30 c 0d Commercial formulation WG 80 % – 164 ab 38 c 20 cd Treatment Untreated ® *All mean values with the same letter are statistically not different at P=0.0 0.0 12.0 72.0 36.0 Transmission [%] Transmission [%] a) with TSP 24.0 0.0 95 96 97 98 99 24.05 15 .0 48.0 96. 0 Thickener 4. Typically sulfonylurea actives are formulated as water dispersable granules (WDG) because they are sensitive to hydrolysis. Liquid formulations are more convenient as this kind of formulation type incorporates an effective adjuvant which can increase and broaden weed control. Tank-mix adjuvants are recom- 16 mended for these formulations as the up-take of the active ingredient is slow.Oil Dispersion Formulation Regulatory pressure and the chemistry of certain modern active ingredients have given rise to Oil Dispersion (OD) formulations.5 Oil component 61. Guideline recipe of a 40 g/l OD sulfonylurea formulation The goal of this particular example was to create a sulfonylurea formulation with improved stability and biological performance compared to commercial standards. We at Evonik addressed this challenge and have tested various additives for oil dispersing systems.5 BREAK-THRU EM Emulsifier mix 20 BREAK-THRU OE Oil enhancer 5.0 .0 BREAK-THRU DA Dispersing agent 5. Component wt% Active 4. OD formulations represent a significant challenge for pesticide formulations and require unique dispersing agents and emulsifiers. Evonik has developed an OD formulation which delivers on both counts. After this time the thickener is added and an additional 1.5 g ai/ha 10 g ai/ha Commercial standard 60 74 Evonik formulation 1 81 90 Evonik formulation 2 62 100 * Note that suboptimal a. The biological efficacy of the Evonik formulation was evaluated in the glass house as well as in the field and showed better results than a commercial standard. The temperature should not exceed 20 °C during grinding. The physical stability was analyzed according to the CIPAC accelerated storage test at 54°C judging the sedimentation behavior. Results Our efforts resulted in a sulfonylurea formulation with 40 g/l load.5 hrs of milling should be done in order to create very small particles (d50 < 5 μm).5 g ai/ha./ha. rates were chosen to differentiate the formulations. The 30 DAT assessment data are shown below. which is easy to handle due to its low viscosity (28 mPas). Biological efficacy of different formulations against Poa pratense 30 DAT [%]* 2.5 ml of formulation per ha. 10 and 2.i. corresponding to 250 or 62. therefore cooling is necessary.Emulsification behavior of the Evonik formulation (left) compared to a commercial standard (right) Preparation of the formulation Grinding was accomplished with all of the ingredients except the thickener with 3 cylindrical rotating blades for 1 hour at 1000 rpm using glass beads. In addition. The spray volume was equivalent to 200 l/ha.i. The chemical stability of the formulation was analyzed by HPLC (modified CIPAC method 709). see picture above. In the glass house two slightly different Evonik OD formulations were compared to a commercial standard to control Poa pratense. Normal field rates would be 40 g a. the emulsification behavior was also improved. Within the testing two different dose rates have been used. 17 . For each formulation 3 pots have been used as replications. and plant wetting.2 Safener 2.Emulsifiable Concentrate Formulation Emulsifiable concentrate (EC) formulations are popular formulations for oil soluble active ingredients. clear Stable. The goal of this particular example was to create a clodinafop formulation with similar stability and performance to a commercially available 80 g/l standard. the formulation matched the commercial standard in terms of efficacy when tested against black grass (Alepecurus myosuroides) in winter wheat.5 l/ha in 300 l/ha spray volume Emulsion stability (CIPAC 342 ppm) Homogeneous. clear Emulsion stability (24 h at 4 °C) Homogeneous. stable 15 DAT 28 DAT Evonik Formulation 72 77 Commercial Standard 65 75 . 18 Guideline recipe of an 80 g/l EC clodinafop formulation Component wt% Clodinafop active 8. but without a nonylphenol ethoxylate.7 BREAK-THRU EM blend 20. Overall.0 ® ® Biological efficacy [%] * Formulation Properties Evonik Formulation Commercial Standard Formulation stability (24 h at -18 °C) Liquid. stable Homogeneous. clear Turbid. A proper surfactant system is necessary in EC formulations to ensure spray tank stability. In addition.1 Mineral Oil 64. stable Homogeneous.0 BREAK-THRU OE product 5. rapid emulsification. stable *Test conducted at 0. the Evonik formulation showed improved stability at low temperatures (see table formulation properties). gel Formulation stability (14 d at 54 °C) Stable. Once the microemulsion is poured into water droplet sizes below 100 nm are formed and the resulting formulation is called a nanoemulsion. unweighted The stability of emulsifiable concentrates (EC) and the corresponding tank mixtures can be a challenge.4 0. Until now. Benefits of Evonik’s microemulsion technology at a glance: • Simple manufacturing at room temperature • Obtained microemulsions and their dilutions have an unlimited shelf life • Small droplet size creates superior biological performance • Phase separation is reversible. the shelf life is unlimited. Because microemulsions (ME) are thermodynamically stable.8 EC 0. Such a technology provides another option for formulating an active. Equipment.PSQ Microemulsion Technology from Evonik The manufacturing of PSQ based microemulsions is limited to water insoluble actives and requires only simple stirring.000 * analysed by dynamic light scattering with a Malvern HPPS 3. The very small particle size distributions (see chart on right hand side) which are derived. middle: Microemulsion diluted to 0. Malvern Instruments Ltd.0 Size distribution. the addition of more water will stabilize the PSQ derived nanoemulsions even further. Although it sounds surprising. dilutions were about 1:1000 Example recipe of a microemulsion concentrate based on permethrin Component wt% Paraffinic oil 41–31 Water 5–10 Evonik emulsifier package 33 Permethrin 21 Wetting agent 0–5 left: Microemulsion.g. Based on an Evonik patented microemulsion technology – phase shift by quenching (PSQ) – production of clear and transparent MEs at room temperature is possible.6 ME 0. microemulsions with particle sizes this small were only achievable by the use of high shear or high energy demand and required specialized mixing equipment. Guideline recipes (such as the one described for permethrin) for various actives are available from Evonik. for wood protection where a small particle size is required for good penetration. The surfactants necessary to create such a microemulsion are offered by Evonik as a package. microemulsions are freeze-thaw stable Particle size distribution of a permethrin ME and an EC 1. This is in contrast to the phase inversion temperature method which requires heating and cooling. right: Nanoemulsion (diluted microemulsion 1:1000 with water) 19 .000 10.2 0 1 10 Hydrodynamic radius [nm] 100 1. 0. are specifically useful for non-crop applications e.1.5 wt % active. AEROSIL® fumed silica creates a three dimensional network giving viscoelastic properties to the liquid formulation and thus avoiding the sedimentation of solid particles. the hydrophobic AEROSIL® grades AEROSIL® R 974 and AEROSIL® R 972 are both beneficial. combine a moderate shear viscosity with a sufficient yield point. The use of AEROSIL® fumed silica supports these functionalities as a rheology modifier and anti-settling additive.5% AEROSIL® 200 4.5 2 3 Tenside Concentration [mmol/l] . The more hydrophobic AEROSIL® R 972 achieves the highest yield point at a given viscosity. Yield Point using 2.5 3. the use of the hydrophilic AEROSIL® 200 leads to a distinct yield point at a low concentration. the silica envelops the active ingredient and prevents reagglomeration. At a given surfactant concentration the yield point increases with lower pHvalues. As an efficient stabilizer AEROSIL® products prevent the agglomeration of active ingredients helping to ensure that they are evenly distributed and show a long-term stability.5 2.0 0. This can be achieved by adjusting suitable viscoelastic properties. Based on the selected AEROSIL® grades.5 1.0 2. The proper choice of AEROSIL® fumed silica combines an excellent anti-settling effect with a low shear viscosity. AEROSIL® fumed silica establishes a yield point and prevents settling of active ingredients. At a given pH-value. OD Formulations Mineral and natural oils containing active ingredients are easy to stabilize using hydrophilic or hydrophobic AEROSIL® products. The performance of AEROSIL® fumed silica in liquid formulations is based on two mechanisms.5 1. Hydrophobic AEROSIL® types in particular.0 Yield Point [Pa] 3.5–3 2–2. In addition. Suspension Concentrates To demonstrate the influence of some of the above mentioned parameters the figure shows how the yield point of a waterbased AEROSIL® 200 suspension depends on the pre-adjusted pH-value and the surfactant concentration (sorbitan mono-oleate). there is an optimum surfactant concentration leading to the maximum yield point. Oil Dispersions. These properties provide excellent suspension stabilization and pourability.5 2.Rheology Modifiers In SC and OD formulations there is a general need to protect dispersed. The figure shows the strong shear thinning effect of different AEROSIL® 200 concentrations in soybean oil.5 4 6 pH-value 20 8 6 5 4 3.5–2 1–1. If one defines a certain viscosity as the maximum that is acceptable.5 0. insoluble active ingredient particles against sedimentation.5–1 0–0. First. this is at the expense of a relatively high viscosity. Second. The hydrophobic AEROSIL® grades AEROSIL® R 974 and AEROSIL® R 972 lead to a lower viscosity at a given yield point than the hydrophilic AEROSIL® 200.5–4 3–3. their viscosity has to be low enough to make sure packages can easily be emptied without residue.0 1. However. 4 0.1 0 Viscosity at a shear rate of 1/s (mPas) 0 AEROSIL® R972 1000 2000 AEROSIL® R974 3000 4000 5000 6000 AEROSIL® 200 Liquid Formulations: OD (AEROSIL® 200 in Soybean Oil) Shear thinning behavior of AEROSIL® 200 at different concentrations viscosity [mPas] 18000 16000 14000 12000 10000 8000 6000 4000 2000 0 shear rate (1/s) 1 5 wt.3 0.2 0.% AEROSIL® 200 10 wt.5 0.% AEROSIL® 200 21 .% AEROSIL® 200 10 100 1000 7 wt. Viscosity) Model formulation based on vegetable oil derivative Yield Point [Pa] 0.6 0.Liquid Formulations: OD (Yield Point vs.% AEROSIL® 200 9 wt. as the silica must stay suspended from the moment of dispersing the formulation until it is sprayed onto the field.Carrier. Granules (GR) Hydrophobic silica on the surface of granulates or dusts enables the formulator to increase stability in humid environments or to delay (“slow release”) the diffusion of the active ingredient. In formulations which need to be dispersed in water before use. if non-milled silica types would be used. large particle size silica can be advantageous. anti-caking and milling aids and as carriers for liquid active ingredients. Hydrophilic SIPERNAT® 2200 is an ideal carrier for liquid or low melting actives to be converted to granules. As a positive side effect. free-flowing and do not tend to cake on storage. Wettable Powder formulations treated with SIPERNAT® or AEROSIL® products are dry. particles which are too big may also block the spray nozzles. 22 Wettable Powder (WP) and Water Dispersible Granules (WG) SIPERNAT® speciality silica provides three main functionalities to Wettable Powder and Water Dispersible Granule formulations: • Highly efficient absorption of liquid actives: Solid formulations containing up to 75 % of liquid active ingredient can easily be prepared using suitable SIPERNAT® grades. . The granular shape of the absorbate is already predesigned with the silica. SIPERNAT® 2200 is able to absorb 190 ml liquid / 100 g silica still providing a dry and free flowing formulation. finely ground SIPERNAT® speciality silica or AEROSIL® fumed silica have to be chosen. No additional granulation step is necessary. the suspensability of the WP and WG at the point of use is much improved with the use of SIPERNAT® and AEROSIL® products. will not create dust and reduce direct skin contact which facilitates their handling. • Free flow additive/anti-caking additive: 1 – 3 % of SIPERNAT® speciality or AEROSIL® fumed silica added to powder or granule formulations enhance the flowability greatly and avoid caking during storage. • Milling aid: Adding up to 10 % of SIPERNAT® speciality silica facilitates the milling of low melting ingredients. Those grades can be used as carrier for liquid or low melting actives providing both a free flowing as well a non-caking absorbate. Such carried actives are easy to be applied directly to the soil. In granules for direct application in the field. Besides. Flow and Anti-Caking Agents SIPERNAT® speciality silica and AEROSIL® fumed silica are used in solid formulations as flow. 960 Hydrophobic precipitated silica.960 Hydrophobic fumed silica. AEROSIL® OX 50 AEROSIL® 200 AEROSIL® 300 AEROSIL® R 202 AEROSIL®R 812 S AEROSIL® R 972 AEROSIL® R 974 Carrier and Flow Agents Recommendations Product EPA FIFRA Status Use Description 180.950 Mixture of fumed silica and fumed aluminium oxide used in water based SC formulations. SIPERNAT® 50 180. which are directly applied to the field. Especially recommended in OD formulations for viscosity control.950 Micro-granular hydrophilic silica can be used as carrier for granules.950 Hydrophilic precipitated silica and hydrophilic fumed silica (see table above) provide good properties as flow aid and anti caking agent in WP and WG formulations.950 Hydrophilic precipitated silica can be used as carrier in WP and WG formulations 180.910 + 180. can slow down the penetration of moisture for applications in seed coatings SIPERNAT® 22 (1) SIPERNAT® 50(1) SIPERNAT® 22 S SIPERNAT® 50 S SIPERNAT® 320 SIPERNAT® 350 SIPERNAT® 22 S SIPERNAT® 50 S SIPERNAT® 350 SIPERNAT® 22 (1) Grinding of the whole formulation is necessary with these products 23 .950 Hydrophilic fumed silica which can be used as anti-settling agent/rheology modifier in SC and OD formulations. 180. AEROSIL® COK 84 180. SIPERNAT® D 17 180.950 Hydrophilic precipitated silica especially appropriate as grinding aid in WP and WG formulations SIPERNAT® 2200 180.Rheology Modifier Recommendations Product EPA FIFRA Status Use Description AEROSIL® 380 180. Randolph Rd. including with regard to existing third party intellectual property rights. 914 E.www.O. nor does it imply that similar products could not be used.-Nr. Reference to trade names used by other companies is neither a recommendation. Chundong Road Xinzhuang Industry Park Shanghai.com/break-thru For more detailed information or to obtain a brochure which addresses a specific area of interest. However. This information and all further technical advice is based on our present knowledge and experience. no warranty. P. We reserve the right to make any changes according to technological progress or further developments.: 07-13 Phone +86 21 6119-1125 fax +86 21 6119-1406 01/2013 Phone +49 201 173-2665 fax +49 201 173-1990 . please visit our website. VA 23860 USA Phone +1 804 541-8658 fax +1 804 541-2783 Inv. 201108 PR China Evonik Goldschmidt Corp. Performance of the product described herein should be verified by testing. The customer is not released from the obligation to conduct careful inspection and testing of incoming goods.evonik. Ltd. whether express or implied. it implies no liability or other legal responsibility on our part. 55. especially patent rights. In particular. which should be carried out only by qualified experts in the sole responsibility of a customer. Box 1299 Hopewell. (April 2008) Europe | Middle East | Africa Asia | Pacific The Americas Evonik Industries AG Goldschmidtstraße 100 45127 Essen Germany Evonik Degussa Specialty Chemicals Co. or guarantee of product properties in the legal sense is intended or implied.
Report "Brochure Additives for Pesticide Formulationsl"