Additives for
Pesticide 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.
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,
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, 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. For us the aim
is to give you the ability to differentiate
your formulation in the market place by
offering superior agrochemical products.
The effects of our products are not limited
to enhancing and safeguarding biological
efficacy. We also offer unique antifoams
with superior compatibility allowing crystal clear formulations or novel additive
systems such as our patented thermody-
namically stable microemulsions. With a
decreasing number of new actives specifically in the crop protection area, and a
growing generic market, it is our goal to
provide solutions to meeting the competitive demands of the pesticide industry.
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. In this way, we offer a novel
package of products and expertise. Various examples of guideline formulations
are given in the end of this document.
While this brochure is designed to give an
overview of our current agro activities,
we are continuing to add new products
and develop new guideline formulations.
Contact your representative for the latest
information.
Oil Enhancers
Many pesticides exhibit limited water solubility, so mineral and vegetable oils often serve as the
carriers to deliver these actives to plants or pests. When incorporated into oil-containing formulations such as ECs, EWs or ODs, 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. With the improved performance of these
oil-based pesticide formulations, it is possible to increase pesticide performance and reduce the
amount of spray oil, thereby reducing cost, phytotoxicity risk and environmental concerns. As
oil types and compositions vary globally, the BREAK-THRU OE oil spreaders are designed for
a broad spectrum of formulation types. All three BREAK-THRU OE products are approved for
use under 40 CFR 180.910 and generate only little or no foam.
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 0.55 wt%
of the oil. It must be added as a component of the oil phase and not post added
to the finished formulations. On a hydrophobic surface, this product increases the
spreading of seed oil droplets by 300 to
500 percent after 30 minutes.
25 wt% of the oil phase. On a hydrophobic surface, this product at 5 wt% enhances methylated seed oil to improve spreading five fold. Since BREAK-THRU
OE 441 is also soluble in water it can be
used in SC, SL, EW and SE formulations.
Accelerated studies at pH 49 refute the
concerns of hydrolytic instability for this
robust product.
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
0.55 wt% of the oil phase. Field studies
with BREAK-THRU OE 444 on several
fruits confirm that it leads to improved foliar coverage and efficacy with fungicides
and insecticides. Addition of only 0.5 wt%
to a mineral oil or paraffinic oil results in
spreading up to a five fold increase after
thirty minutes.
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, methylated rape seed oil
Soluble
Soluble
Soluble
Vegetable Oil e.g. rapeseed oil, soya oil
Soluble
Dispersible
Dispersible
Mineral Oil
Insoluble
Soluble
Soluble
Paraffinic Oil
Insoluble
Insoluble
Soluble
Solvesso 150*
Soluble
Soluble
Soluble
Others: Butanol, NMP, Cyclohexanone
Soluble
Soluble
Soluble (only in butanol)
* Registered trademark of Exxon Mobil
Wetting Agents
Trisiloxane based Wetting Agents
While all wetting agents have the ability
to decrease surface tension, silicone wetting agents stand out in their ability to do
so at concentrations between 0.02 to 0.15
wt%. Some of them also cause super
spreading of the spray solutions whereas
others designed solely to reduce surface
tension behave as penetrants. For highperformance applications, our organomodified siloxanes are perfectly suited to
meet varying requirements.
Owing to their ultra low static surface
tensions, trisiloxane surfactants can provide superior spray coverage and are
unique among surfactants in their ability
to impart phenomenal spreading characteristics to formulations. These products
can also be instrumental in enabling stomatal flooding and cuticular penetration.
These surfactants can decrease the spray
volume required for a particular pesticide
application, allow for better targeting,
and increase pesticide up-take.
Example of a trisiloxane based
Super Spreader
The results of field trials on grapes in Italy
with the super spreader BREAK-THRU
S 240, used as tank-mix adjuvant, are
shown in Diagram 1. Despite a lower
amount of pesticide, 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.
Example of a trisiloxane based
Super Penetrant
Improved penetration of a pesticide is not
necessarily the result of super spreading, it
can also be caused by the reduction in surface tension of the spray mixture and is
critical for enhanced active ingredient uptake. In the case of the non-spreading trisiloxane surfactant, BREAK-THRU S 233,
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.
e.g. BREAK-THRU S 240, even though
both products decrease the surface tension
of the spray mixture down to 21 mN/m.
The speed of uptake was analysed with
radiolabeled glyphosate (see Diagram 2).
Bean leaves were washed at different time
intervals to quantify the rate of uptake (Ref.
Weed Science 2007, 55, p. 406-411). Used
with glyphosate, BREAK-THRU S 233 can
enhance the speed and volume of uptake,
improving rainfastness and efficacy. This
class of super penetrants, such as BREAKTHRU S 233, is most suitable for actives
with systemic action.
Diagram 1: Increased efficacy with BREAK-THRU S 240
with reduced spray volumes
Spray volume 500 l/ha
Efficacy against grape
powdery mildew (%)
Ortiva
0.75 l/ha
Ortiva
0.5 l/ha
250 l/ha
Ortiva
0.5 l/ha
Ortiva
0.5 l/ha
90
85
80
b*
75
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
90
80
70
60
50
40
30
20
10
b*
a
+ 0.1 % BREAK-THRU S 240
+ 0.1 % BREAK-THRU S 233
* All values with the same letter are statistically not different at P = 0.05
pH stable Polysiloxane based Spreaders
Due to their extended siloxane backbone,
the silicone character of BREAK-THRU
OE 441 and BREAK-THRU S 243 is pronounced. The mode of action of these
products is similar to that of penetrants.
These products display solubility in either
oil or water. The reduction in surface tension of these products is not so dramatic as
for trisiloxanes, but polysiloxanes have a
great impact on the properties of oils (see
oil enhancer section). 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.
Benefits of Wetting Agents:
In the table below, the stability towards
hydrolysis was analysed by monitoring the Safeguarding the performance
of pesticides
static surface tension (mN/m).
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 3050 %
agent. Details are available upon request.
Greater or equal up-take of pesticide
Specifically for SL formulations somein less time, 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
@ 0.1 %
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
49
40
Low
40 CFR
180.910
BREAK-THRU S 200
Organomodified
Trisiloxane
58
22
High
40 CFR
180.910
BREAK-THRU S 233
Organomodified
Trisiloxane
58
23
High
40 CFR
180.910
BREAK-THRU S 240
Organomodified
Trisiloxane
58
22
High
40 CFR
180.910
BREAK-THRU S 243
Organomodified
Polysiloxane
49
47
High
40 CFR
180.910
BREAK-THRU S 279
Organomodified
Trisiloxane
58
21
High
40 CFR
180.910
with a solubilizer or amphoteric surfactant
is advantageous. For more detailed
recommendations please contact us.
By using BREAK-THRU wetting agents
grapes are uniformly wetted
Antifoams
In agrochemical formulations, different surface active chemistries are used as wetting agents,
emulsifiers, dispersants, compatibilizers and even as solvents. Many of them tend to concentrate
at interfaces often generating and stabilizing foam. Foaming can occur during manufacturing
and packaging, but can also occur during field application where it is especially burdensome
to end users.
While silicone oils are excellent defoamers, they are notoriously immiscible in
water-based systems. To overcome this
obstacle, Evonik has a line of defoamer/
antifoam products with the BREAK-THRU AF designation. These silicone products are modified with other organic
groups and are tailor-made to overcome
incompatibility, while maintaining the
efficiency and low dose rates typical of
silicone oils.
ates, which cause foam when agitating
the spray solution. A 360 g/l a. e. glyphosate IPA salt formulation was prepared
with 10 % v/v TAE-151 and different concentrations of BREAK-THRU AF 9903.
After mixing the components, each formulation was then diluted 1 : 50, and 50
ml were added to a 100 ml graduated
cylinder. Following vigorous shaking for
15 s, the foam height was recorded.
TAE-15: tallow amine ethoxylate with
15 mole EO, available from Evonik as
VARONIC T-215**
Defoaming of a 360 g/l a. e.
glyphosate formulation
Concentration of
BREAK-THRU
AF-9903
Initial
Foam
Height
(ml)
Foam
Height
after 90
sec. (ml)
Control
60
50
0.0165 %
48
0.05 %
25
0.15 %
13
Since individual formulations contain different active ingredients, solvents and
surfactants, a universal solution to foaming issues does not exist. 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.
For example, glyphosate IPA SL formulations often contain tallow amine ethoxyl-
Benefits of BREAK-THRU Antifoams:
Tailored to overcome incompatibility,
while maintaining the efficiency
Variety of different chemistries to fulfill
different application requirements
Foam control with 0.1 wt% BREAK-THRU AF-9903
Trisiloxane
* Alkylpolyglycoside = APG
10
APG*
Laurylethersulfate
** Registered trademark by Evonik
APG control
without
antifoam
Properties of selected antifoams
Concentration/Form
Viscosity
(mPas)
EPA FIFRA
status
Special properties
OMS*
100/EC**
600
40 CFR
180.910
For water based formulations, salt tolerant; causes
less cloudiness than AF 9903 in SL formulations
BREAK-THRU AF-9902
OMS
100/Compound
500
1000
40 CFR
180.910
Antifoam for in-can formulations; not self-emulsifying; suitable for oil based formulations
BREAK-THRU AF-9903
OMS
100/EC
500
1500
40 CFR
180.910
For water based formulations, salt tolerant e. g.
for glyphosate
BREAK-THRU AF-9906
Silicone
oil
100/Compound
200
600
40 CFR
180.910
Antifoam concentrate without emulsifier for nonaqueous or solvent based systems (e. g. ODs)
BREAK-THRU AF-9908
Silicone
oil/OMS
40/Emulsion
300
Not listed
Increased stability towards temperature and shear;
suitable for granule preparation
Product
Chemical
base
BREAK-THRU AF-5503
*OMS = Organomodified siloxane
**EC = self-emulsifying concentrate
11
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. Dispersing agents interact
with the surface of the particles and prevent the formation of agglomerates.
Without BREAK-THRU DA 655
With BREAK-THRU DA 655
Dispersing agents have amphiphilic
structures which need to be insoluble
in the solvent. They must possess anchoring groups capable of being strongly
absorbed onto the particle surface.
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.
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, SC
not listed
BREAK-THRU DA 652
Fatty acid derivative
100 %
OD
not listed
BREAK-THRU DA 655
Polyether phosphate,
electrostatical stabilisation
100 %
OD
not listed
BREAK-THRU DA 675
Aqueous based organically modified polymer;
sterical stabilisation
40 %
SC
not listed
BREAK-THRU DA 752 W
Aqueous based organically modified polymer;
electrostatical stabilisation
50 %
SC
not listed
BREAK-THRU EM TD 6
POE (6)
isotridecyl ether
OD
pending
EPA
approval
12
100 %
Emulsifiers
Our product range includes primary and secondary emulsifiers that are based on renewable
resources like ethoxylated or non-ethoxylated glycerol fatty acid esters, sorbitan esters, various
fatty acid polyglycol esters and lauryl polyglycol ethers. However, our focus is on the more
environmentally friendly glycerol fatty acid esters.
BREAK-THRU emulsifiers (BREAK-THRU
EM series) are non-ionic, hydrophilic and
lipophilic organic surfactants used in the
preparation of both oil-in-water and water-in-oil emulsions. By balancing the hydrophilic and lipophilic parts the properties of a surfactant can be adjusted to the
needs of different applications. Therefore
BREAK-THRU emulsifiers can also be
used as dispersants, solubilizers and wetting agents.
To emulsify a specific oil, emulsifiers with
precisely adjusted HLB values are needed.
The required HLB value can be adjusted
by selected blending. Our regional
technical service group will assist you in
finding the right formulation. Rely on our
long-standing experience and know-how
and save valuable time.
BREAK-THRU EM V 20 is one of our
vegetable-based nonionic emulsifiers
with excellent ecological, toxicological
and dermatological behavior. This surfactant also reduces the surface tension of
oils (e.g. sunflower or rapeseed oil) without any foam. With an HLB-value of 8,4
it creates emulsion spontaneity in ECs
and EWs. During screening of various
emulsifiers with a pyrethroid EC formulation it demonstrated superior performance (see publication Poffenberger et.
al ISAA 2007). In herbicide field trials
this product showed higher biological efficacy than methylated rapeseed oil, even
at lower dose rate. No phytoxicity was
exhibited in wheat and maize field trials.
BREAK-THRU EM,
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, 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
8.4
Vegetable oil, recommended in combination (5:1)
with co-emulsifier Tegin OV, total dose 15 %
40 CFR 180.910
BREAK-THRU EM 0 7
PEG-(7)-Oleate
10
Paraffinic oil, dose rate 10 %
40 CFR 180.910
BREAK-THRU EM TD 6
POE-(6)-Isotridecyl
Ether
11,4
Mineral oil, preferred 1:1 mixture with
TEGO SMO 80 V (20 %)
Pending
EPA approval
* In order to obtain the whole emulsifier portfolio brochure, please contact our regional technical groups
13
Formulation Activities
We at Evonik decided to develop prototype formulations to provide guidance to the user with
respect to product selection. 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
ongoing activities with different liquid formulation types are described on the next pages.
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.
Creating a stable, effective and environmentally friendly formulation requires the
use of surfactants. 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), a commonly used dispersing agent.
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. The glass
beads were filtered off and the thickener
was added at the end of the milling.
While both dispersing agents produce
Guideline recipe of the SC formulation
Component
wt%
Sulfur (Mesh 100)
25.1
Dispersing agent
1.6
Tego Antifoam MR 2021
0.3
BREAK-THRU S 240
08.0
Monoethylene glycol (antifreeze)
2.5
Xanthan gum, 10 % solution
1.8
Water
to 100
14
similar particle sizes (d50 of 3.11 m), the
physical stability of the formulation favored the use of BREAK-THRU DA 646.
Formulation stability was evaluated using
a LUMiFuge 116 (L.U.M. GmbH, Berlin,
Germany; www.lum-gmbh.de) a device which can measure transmission
profiles during centrifugation. A clear
phase developed on the surface of the
formulation containing the TSP (see Diagram 1 a). The red curve describes the
beginning, the green curve the end of
the lumifuge cycle. Sedimentation is observed for the TSP containing formulation between 110 and 113 mm. The top of
the sample is at 95 mm, the bottom at
113.5 mm. From the movement of the
phase boundary, one can estimate that
this formulation will form a clear top layer under normal storage conditions at a
rate of 1.2 mm per month. The sedimentation speed of the BREAK-THRU DA
646 containing formulation was reduced
by a factor of fifteen (see Diagram 1b).
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). 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. proceedings ISAA 2004, South Africa, ISBN
1-920-01716-X). 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.
To further enhance the biological efficacy
it is recommended to incorporate a trisiloxane based wetting agent, such as
BREAK-THRU S 240 at 1-8 wt%.
Diagram 1: Stability of a formulation tested in the LUMiFuge
b) with BREAK-THRU DA 646
120,0
120,0
108,0
108,0
96,0
96,0
84,0
84,0
72,0
72,0
60,0
60,0
48,0
48,0
36,0
36,0
Transmission [%]
Transmission [%]
a) with TSP
24,0
12,0
0,0
95
96
97
98
99
24,0
12,0
0,0
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=0.05
15
Oil Dispersion Formulation
Regulatory pressure and the chemistry of
certain modern active ingredients have
given rise to Oil Dispersion (OD) formulations. OD formulations represent a significant challenge for pesticide formulations and require unique dispersing agents
and emulsifiers. We at Evonik addressed
this challenge and have tested various additives for oil dispersing systems.
Typically sulfonylurea actives are formulated as water dispersable granules
(WDG) because they are sensitive to hydrolysis. Tank-mix adjuvants are recom-
16
mended for these formulations as the
up-take of the active ingredient is slow.
Liquid formulations are more convenient
as this kind of formulation type incorporates an effective adjuvant which can increase and broaden weed control. Evonik
has developed an OD formulation which
delivers on both counts.
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.
Component
wt%
Active
4.5
Oil component
61.5
BREAK-THRU EM Emulsifier mix
20
BREAK-THRU OE Oil enhancer
5.0
BREAK-THRU DA Dispersing agent
5.0
Thickener
4.0
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. The temperature should not exceed 20 C during
grinding, therefore cooling is necessary.
After this time the thickener is added and
an additional 1.5 hrs of milling should be
done in order to create very small particles (d50 < 5 m).
Results
Our efforts resulted in a sulfonylurea formulation with 40 g/l load, which is easy
to handle due to its low viscosity (28
mPas). The chemical stability of the formulation was analyzed by HPLC (modified CIPAC method 709). The physical
stability was analyzed according to the
CIPAC accelerated storage test at 54C
judging the sedimentation behavior.
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. In
addition, the emulsification behavior was
also improved, see picture above.
In the glass house two slightly different
Evonik OD formulations were compared
to a commercial standard to control Poa
pratense. For each formulation 3 pots
have been used as replications. The spray
volume was equivalent to 200 l/ha.
Within the testing two different dose rates
have been used, 10 and 2.5 g ai/ha, corresponding to 250 or 62.5 ml of formulation per ha. The 30 DAT assessment data
are shown below.
Biological efficacy of different formulations against Poa pratense 30 DAT [%]*
2.5 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.i. rates were chosen to differentiate
the formulations. Normal field rates would be 40 g a.i./ha.
17
Emulsifiable Concentrate Formulation
Emulsifiable concentrate (EC) formulations are popular formulations for oil
soluble active ingredients. A proper surfactant system is necessary in EC formulations to ensure spray tank stability, rapid
emulsification, and plant wetting.
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, but
without a nonylphenol ethoxylate.
Overall, the formulation matched the
commercial standard in terms of efficacy
when tested against black grass (Alepecurus myosuroides) in winter wheat. In
addition, the Evonik formulation showed
improved stability at low temperatures
(see table formulation properties).
18
Guideline recipe of an 80 g/l EC
clodinafop formulation
Component
wt%
Clodinafop active
8.2
Safener
2.1
Mineral Oil
64.7
BREAK-THRU EM blend
20.0
BREAK-THRU OE product
5.0
Biological efficacy [%] *
Formulation Properties
Evonik
Formulation
Commercial
Standard
Formulation stability
(24 h at -18 C)
Liquid,
clear
Turbid,
gel
Formulation stability
(14 d at 54 C)
Stable,
clear
Stable,
clear
Emulsion stability
(24 h at 4 C)
Homogeneous,
stable
Homogeneous,
stable
*Test conducted at 0.5 l/ha in 300 l/ha spray volume
Emulsion stability
(CIPAC 342 ppm)
Homogeneous,
stable
Homogeneous,
stable
15 DAT
28 DAT
Evonik Formulation
72
77
Commercial Standard
65
75
PSQ Microemulsion Technology from Evonik
The manufacturing of PSQ based microemulsions is limited to water insoluble
actives and requires only simple stirring.
Such a technology provides another option for formulating an active. Once the
microemulsion is poured into water droplet sizes below 100 nm are formed and
the resulting formulation is called a nanoemulsion.
Although it sounds surprising, the addition of more water will stabilize the PSQ
derived nanoemulsions even further.
Until now, microemulsions with particle
sizes this small were only achievable by
the use of high shear or high energy demand and required specialized mixing
equipment. The very small particle size
distributions (see chart on right hand
side) which are derived, are specifically
useful for non-crop applications e.g. for
wood protection where a small particle
size is required for good penetration.
Guideline recipes (such as the one described for permethrin) for various actives
are available from Evonik. The surfactants
necessary to create such a microemulsion
are offered by Evonik as a package.
Benefits of Evoniks 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;
microemulsions are freeze-thaw stable
Particle size distribution
of a permethrin ME and an EC
1,0
Size distribution, unweighted
The stability of emulsifiable concentrates
(EC) and the corresponding tank mixtures
can be a challenge. Because microemulsions (ME) are thermodynamically stable,
the shelf life is unlimited. Based on an
Evonik patented microemulsion technology phase shift by quenching (PSQ)
production of clear and transparent MEs
at room temperature is possible. This is
in contrast to the phase inversion temperature method which requires heating
and cooling.
0,8
EC
0,6
ME
0,4
0,2
0
1
10
Hydrodynamic radius [nm]
100
1.000
10.000
* analysed by dynamic light scattering with a Malvern HPPS
3.1, Malvern Instruments Ltd. Equipment; dilutions were
about 1:1000
Example recipe of a microemulsion
concentrate based on permethrin
Component
wt%
Paraffinic oil
4131
Water
510
Evonik emulsifier package
33
Permethrin
21
Wetting agent
05
left: Microemulsion,
middle: Microemulsion diluted to 0.5 wt % active,
right: Nanoemulsion (diluted microemulsion 1:1000 with water)
19
Rheology Modifiers
In SC and OD formulations there is a general need to protect dispersed, insoluble active ingredient particles against sedimentation. This can be achieved by adjusting suitable viscoelastic
properties. In addition, their viscosity has to be low enough to make sure packages can easily be
emptied without residue.
The use of AEROSIL fumed silica supports these functionalities as a rheology
modifier and anti-settling additive. 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.
The performance of AEROSIL fumed
silica in liquid formulations is based on
two mechanisms. First, the silica envelops
the active ingredient and prevents reagglomeration. Second, AEROSIL fumed
silica creates a three dimensional network
giving viscoelastic properties to the liquid
formulation and thus avoiding the sedimentation of solid particles. The proper
choice of AEROSIL fumed silica combines an excellent anti-settling effect with
a low shear viscosity.
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). At a given surfactant concentration
the yield point increases with lower pHvalues. At a given pH-value, there is an
optimum surfactant concentration leading
to the maximum yield point.
Oil Dispersions, OD Formulations
Mineral and natural oils containing active
ingredients are easy to stabilize using hydrophilic or hydrophobic AEROSIL products. The figure shows the strong shear
thinning effect of different AEROSIL 200
concentrations in soybean oil. AEROSIL
fumed silica establishes a yield point and
prevents settling of active ingredients.
Hydrophobic AEROSIL types in particular, combine a moderate shear viscosity
with a sufficient yield point. These properties provide excellent suspension stabilization and pourability. 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.
Based on the selected AEROSIL grades,
the use of the hydrophilic AEROSIL 200
leads to a distinct yield point at a low concentration. However, this is at the expense of a relatively high viscosity. If one
defines a certain viscosity as the maximum that is acceptable, the hydrophobic
AEROSIL grades AEROSIL R 974 and
AEROSIL R 972 are both beneficial. The
more hydrophobic AEROSIL R 972
achieves the highest yield point at a given
viscosity.
Yield Point using 2.5% AEROSIL 200
4,0
Yield Point [Pa]
3,5
3,0
2,5
2,0
1,5
1,0
0,5
4
6
pH-value
20
3,54
33,5
2,53
22,5
1,52
11,5
0,51
00,5
2
3
Tenside Concentration [mmol/l]
Liquid Formulations: OD (Yield Point vs. Viscosity)
Model formulation based on vegetable oil derivative
Yield Point [Pa]
0,6
0,5
0,4
0,3
0,2
0,1
0
Viscosity at a
shear rate of
1/s (mPas)
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.% AEROSIL 200
9 wt.% AEROSIL 200
10
100
1000
7 wt.% AEROSIL 200
10 wt.% AEROSIL 200
21
Carrier, Flow and Anti-Caking Agents
SIPERNAT speciality silica and AEROSIL fumed silica are used in solid formulations as flow,
anti-caking and milling aids and as carriers for liquid active ingredients.
Wettable Powder formulations treated
with SIPERNAT or AEROSIL products
are dry, free-flowing and do not tend to
cake on storage. In formulations which
need to be dispersed in water before use,
finely ground SIPERNAT speciality silica
or AEROSIL fumed silica have to be chosen, as the silica must stay suspended
from the moment of dispersing the formulation until it is sprayed onto the field.
Besides, if non-milled silica types would
be used, particles which are too big may
also block the spray nozzles. In granules
for direct application in the field, large
particle size silica can be advantageous.
Those grades can be used as carrier for
liquid or low melting actives providing
both a free flowing as well a non-caking
absorbate. The granular shape of the absorbate is already predesigned with the
silica. No additional granulation step is
necessary.
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.
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.
As a positive side effect, the suspensability of the WP and WG at the point
of use is much improved with the use of
SIPERNAT and AEROSIL products.
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. Hydrophilic
SIPERNAT 2200 is an ideal carrier for
liquid or low melting actives to be converted to granules. Such carried actives
are easy to be applied directly to the soil,
will not create dust and reduce direct skin
contact which facilitates their handling.
SIPERNAT 2200 is able to absorb 190 ml
liquid / 100 g silica still providing a dry
and free flowing formulation.
Rheology Modifier Recommendations
Product
EPA FIFRA Status
Use Description
AEROSIL 380
180.950
Hydrophilic fumed silica which can be used as anti-settling
agent/rheology modifier in SC and OD formulations.
AEROSIL COK 84
180.910 + 180.950
Mixture of fumed silica and fumed aluminium oxide used in water
based SC formulations.
180.960
Hydrophobic fumed silica. Especially recommended in OD
formulations for viscosity control.
AEROSIL OX 50
AEROSIL 200
AEROSIL 300
AEROSIL R 202
AEROSILR 812 S
AEROSIL R 972
AEROSIL R 974
Carrier and Flow Agents Recommendations
Product
EPA FIFRA Status
Use Description
180.950
Hydrophilic precipitated silica can be used as carrier in WP and
WG formulations
180.950
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.
SIPERNAT 50
180.950
Hydrophilic precipitated silica especially appropriate as grinding
aid in WP and WG formulations
SIPERNAT 2200
180.950
Micro-granular hydrophilic silica can be used as carrier for
granules, which are directly applied to the field.
SIPERNAT D 17
180.960
Hydrophobic precipitated silica, 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
www.evonik.com/break-thru
For more detailed information or to obtain a brochure
which addresses a specific area of interest, please visit
our website.
This information and all further technical advice is
based on our present knowledge and experience.
However, it implies no liability or other legal responsibility on our part, including with regard to existing
third party intellectual property rights, especially patent rights. In particular, no warranty, whether express
or implied, or guarantee of product properties in the
legal sense is intended or implied.
We reserve the right to make any changes according
to technological progress or further developments.
The customer is not released from the obligation to
conduct careful inspection and testing of incoming
goods. Performance of the product described herein
should be verified by testing, which should be carried
out only by qualified experts in the sole responsibility
of a customer. Reference to trade names used by other companies is neither a recommendation, nor does it
imply that similar products could not be used.
(April 2008)
Europe | Middle East | Africa
Asia | Pacific
The Americas
Evonik Industries AG
Goldschmidtstrae 100
45127 Essen
Germany
Evonik Degussa
Specialty Chemicals Co, Ltd.
55, Chundong Road
Xinzhuang Industry Park
Shanghai, 201108
PR China
Evonik Goldschmidt Corp.
914 E. Randolph Rd.
P.O. Box 1299
Hopewell, VA 23860
USA
Phone +1 804 541-8658
fax +1 804 541-2783
Inv.-Nr.: 07-13
Phone +86 21 6119-1125
fax +86 21 6119-1406
01/2013
Phone +49 201 173-2665
fax +49 201 173-1990
