4.

Concentrated Aqueous Emulsions

(EW)
Concentrated aqueous emulsion (EW) formulations are stable emulsions of an insoluble liquid in a continuous
water phase. The insoluble liquid can be either a liquid active ingredient or a solid active ingredient dissolved in
a solvent.

They can be considered as a safer and more environmentally friendly alternative to emulsifiable concentrates
(EC). In an EW the continuous phase is water (as opposed to an organic solvent for ECs) which offers the
benefit of lower phytotoxicity, no flashpoint concern, ease of handling, and a lower environmental impact.
EW formulations are physically stabilised by specifically identified polymeric surfactants incorporated at an
appropriate level. The emulsion has already been established in the formulation and is only diluted further in
the spray mixture.

Benefits Limitations
 Low solvent  Achieving long term stability can be an issue
 Low phytotoxicity  Active ingredient solubility in solvent
 No flashpoint concern  Stability upon dilution
 Easy to handle  Unsuitable for hydrolytically unstable actives
 Lower environmental impact

Components of an EW
A concentrated aqueous emulsion contains the following components:

1. Active ingredient – provides functionality

2. Oil/solvent – to dissolve any solid active ingredients, to improve biological activity
3. Emulsifiers – to stabilise the concentrated emulsion and emulsify upon dilution in water
4. Rheology modifier – to provide structure to the formulation
5. Anti-freeze – to prevent the formulation from freezing
6. Biocide – to prevent the presence of any unwanted bacteria in the formulation
7. Anti-foam – to prevent the formulation from entraining air during manufacture and transport
8. Water – continuous phase

1. Active Ingredient (AI)

The active ingredient can either be a liquid, or a solid dissolved in a water-immiscible solvent. The active
ingredient must be completely soluble in the oil over the range of temperatures the formulation will incur. The
active ingredient must have minimum water solubility under all conditions.

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If the active ingredient is not a liquid under all storage conditions then crystals of the active ingredient could
form. The presence of crystallised active ingredient will reduce the physical stability of the formulation, impact
application through spray nozzle blockage, and lead to possible reductions in the eventual efficacy of the
application.

If an active ingredient demonstrates increased solubility at elevated temperatures then the solution may
become supersaturated. When the temperature decreases the supersaturated solution might start to form an
oily sediment which would be difficult to re-suspend.

2. Oil/Solvent
Certain solvents are subject to governmental restrictions and this should be considered when a solvent/oil is
selected. Solvents should be chosen with the following performance considerations:

 The active ingredient must remain in solution over the range of temperatures the formulation will incur
 The flashpoint of a solvent is an important consideration, a low flashpoint can endanger the end user
 Odour will not affect formulation performance, but it should be considered
 Solvents which are used across a large variety of industries usually have a lower cost associated with
them
 The solvent should be polar enough to give good solvency power, but a solvent that is too polar or slightly
water soluble could lead to crystallisation problems

3. Emulsifiers
Emulsion performance is primarily dictated by the nature of the surfactants selected and their collective effect
on how they arrange themselves at the oil/water interface. Due to the differences between EC and EW
formulations, it is not necessary for emulsifiers to aid the spontaneous formation of an emulsion as this forms
during the manufacture of the concentrate. It is therefore important that emulsifiers chosen are able to impart
long term stability to the formulation in its concentrate form and maintain this emulsion upon dilution.

Under ideal conditions, the chemical nature of the surfactants along with their overall concentration, relative
ratios, and partitioning properties will govern how quickly the emulsion forms and how stable it will be when
formed. In actual fact, emulsification performance is also affected by many external factors including the
electrolytes present, water hardness, dilution rate, temperature, and the presence of other formulations in the
spray mixture.

The common instability factors experienced in EW formulations are explored further in the appendix of this
toolbox.

In order to form a concentrated emulsion with long term stability under many conditions, it is recommended that
high performance polymeric emulsifiers are used during EW developments. It is recommended that
combinations of low and high HLB polymeric surfactants are used to obtain a concentrated aqueous emulsion
with excellent colloidal stability. This surfactant combination ensures that the formulation maintains colloidal
stability over a range of application temperatures.

As polymeric surfactants require more time to occupy the oil/water interface than conventional monomeric
surfactants, special attention must be given to emulsification processing conditions.

Polymeric surfactants have many benefits over conventional monomeric surfactants as they:

 Offer excellent stability over a wide temperature range

 Are less sensitive to electrolytes
 Are low foaming
 Can tolerate highly loaded phases
 Are effective at low concentrations

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4. Rheology Modifier
If an EW is not properly structured, the formulation can break down resulting in the oil phase either creaming to
the surface or settling to the bottom depending on the relative density. This leads to reduced shelf life stability
and poor performance in the field. To overcome this issue, the viscosity of a formulation can be increased to
improve stability by acting as a barrier to sedimentation and creaming. Viscosity can be altered by adding a
rheology modifier.

Concentrated aqueous emulsions mainly use polymeric rheology modifiers such as xanthan gum to prevent
emulsion creaming and sedimentation. Polysaccharide thickeners are high molecular weight polymers which
build viscosity within the continuous phase through controlled incompatibility with water.

Polymeric rheology modifiers are used at a relatively small % w/w concentration in the formulation. Their water
dispersibility is however adversely affected by the presence of high electrolyte (fertilizer) solutions and this can
cause compatibility issues.

An aqueous formulation that uses polymeric rheology modifiers as the suspension system will demonstrate
variable viscosity upon storage as a function of temperature - as temperature increases, viscosity decreases.
This may result in formulation pourability issues at reduced temperatures and oil separation issues upon
extended storage at elevated temperatures.

5. Anti-freeze
Concentrated aqueous emulsions may change rheological properties upon freezing and subsequent thawing.
Physical deterioration of the concentrated aqueous emulsion is first and foremost a function of formulation
active ingredient concentration - the higher the concentration, the greater the susceptibility of the formulation to
failure after freeze/thaw cycling.

There are two ways to address freeze/thaw stability issues:

1. Product labelling (‘Do not store below 0˚C’)

2. Addition of freeze/thaw stabilisers

6. Biocide
If polysaccharides (xanthan gum) are used as rheology modifiers, a perfect medium for bacterial growth will
have been created. This could cause the formulation to smell unpleasant and turn black but more importantly,
might affect the structure of the rheology modifier. In addition, some bacteria might actually degrade the active
ingredient and if the colonies are large enough, they might block the inline screens found in the spraying
applicator.

Bactericides are therefore added at low concentrations to prevent the formation of bacteria colonies. A
bacterial inhibitor’s governmental status as an inert usually depends on its concentration; too high a
concentration and it will no longer count as an inert.

7. Anti-foam
Foam may form when a concentrated aqueous emulsion is subjected to high shear. Foam may adversely
affect the efficiency of processing equipment and the bulk density of the formulation during packaging.
Therefore, foam control agents are incorporated into the formulation.

8. Water
Water composition and quality may impact formulation performance either upon production or upon extended
storage. The presence of dissolved salts may adversely affect surfactant partitioning.

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How to Develop an EW Formulation

General formulation recipe:

Component % w/w
Active ingredient 5-50
Oil/solvent 0-30
Emulsifiers 5-10
Rheology modifier 0.1-0.5
Anti-freeze 5-10
Anti-foam 0.2
Biocide 0.1
Water To 100

Method:
1. If the active ingredient is solid, identify a suitable solvent system for your formulation.
2. Select a suitable surfactant package for the system. Product recommendations from Croda are
highlighted in this chapter.
3. Mix the anti-freeze and rheology modifier. Then add the water, preservative and anti-foam. Stir until
homogenous (continuous water phase).
4. Combine the emulsifiers and active ingredient/oil until homogenous (oil dispersed phase).
5. Add the oil phase to the water phase with low shear and then apply high shear mixing at 10,000rpm
to fully homogenise.

Testing Requirements
The following test parameters are typically performed on this type of formulation:

Test parameter Test method* Comments

Appearance: physical state, colour n/a Any changes should be noted, if separation is
observed the ease of re-homogenisation should be
noted
pH MT 75.3
MT 191
MT 31.1
Viscosity MT 192
Emulsifiability MT 36.3
Re-emulsifiability
Emulsion stability
Persistent foam MT47.3
Flash point n/a
*Reference: Dobrat, W. and Martijn, A. (eds.) (1994) CIPAC Handbook. Volume F edn. Collaborative
International Pesticides Analytical Council Ltd.

Product Recommendations
 High HLB non-ionic surfactants
o Atlas™ G-5002L – liquid polymeric surfactant providing good long term stability
o Atlas G-5004 LD – high purity liquid polymeric surfactant ideal for use with sensitive a.i.
o Tween™ 22 – low-mid polarity oils
o Tween 23 – mid polarity oils
o Tween 24 – mid-high polarity oils

 Low HLB non-ionic surfactants

o Atlox™ 4916 – novel star architecture gives enhanced emulsion stability
o Atlox 4914 - polymeric surfactant providing good long term stability

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  Rheology modifier
o Atlox Rheostrux™ 300A - liquid emulsion polymer with optimised performance in acidic
conditions

Additional high performance emulsifiers available from Croda include the range of phosphate esters. These
surfactants come with the added benefit of maintaining high performance in strong electrolyte solutions.
Phosphate esters are anionic materials so do not exhibit a HLB, however a similar preference should be shown
when choosing suitable products from the range in that pairings should be selected where one surfactant
shows good solubility in the aqueous phase whilst the other is strongly soluble in the oil phase. Good initial
candidates for developments are Multitrope™ 1214 and Crodafos™ C10/5A respectively.

Troubleshooting and Formulation Advice

This section outlines some common problems or issues that you may encounter when formulating an EW and
gives advice about how to overcome these.

Problem: Crystallisation of active

Solution: If the solvent is too polar, or has slight water solubility the active ingredient can migrate from the oil
phase to the water phase leading to crystal growth and active precipitation. Trial a solvent which has no
solubility in water.

Problem: Formulation experiences creaming or separation

Solution: Increase the level of rheology modifier to slow down coalescence, or trial a different emulsification
system that better matches the HLB of the formulation. A reduced / slower rate of addition of one phase (oil
phase) into the other (water) will reduce the droplet size of the emulsion.

Example Formulation
This concentrated aqueous emulsion formulation containing neem oil in water that offers long term stability by
the use of polymeric surfactants Atlas G-5002L and Atlox 4916.

Neem Oil EW CCG057

Product Function g/L % w/w

Neem Oil Active ingredient 390.1 40.0

Atlox™ 49161 Low HLB emulsifier 19.5 2.00

Water Continuous phase 432.9 44.3

Atlas™ G-5002L1 High HLB emulsifier 48.9 5.0

Antifoam Antifoam 1.9 0.2

Propylene glycol Antifreeze 48.9 5.0

Xanthan gum (2% aqueous solution) Rheology modifier 34.2 3.5

Suppliers: 1. Croda

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Other Resources
For additional information on concentrated aqueous emulsion visit www.crodacropcare.com to access our
Product Finder and Formulation Search. The information in this document has been developed by our
dedicated Crop Care team to illustrate how to initiate the development of an EW formulation. We hope this
information is useful to you but we’d also love to talk to you if it does not meet all of your needs. Contact your
Croda representative or email Cropcare@croda.com

Non-warranty
The information in this publication is believed to be accurate and is given in good faith, but no representation or warranty as to its completeness or accuracy is
made. Suggestions for uses or applications are only opinions. Users are responsible for determining the suitability of these products for their own particular
purpose. No representation or warranty, expressed or implied, is made with respect to information or products including, without limitation, warranties of
merchantability, fitness for a particular purpose, non-infringement of any third party patent or other intellectual property rights including, without limit, copyright,
trademark and designs. Any trademarks identified herein are trademarks of the Croda group of companies.
©2017 Croda Europe Ltd.

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