This document discusses water soluble polymers used in household cleaning products and their benefits and mechanisms of action. It summarizes that polymers can deliver benefits to consumers through faster and easier cleaning, with products that do multiple jobs and use fewer perceived chemicals. The mechanisms include enhanced control of the oil-water interface to improve solubilization and wetting. Polymers can form complexes with surfactant micelles that influence curvature and solubilization. Formulation variables like polymer/surfactant ratios and types can be tuned to optimize these effects.

1. Water Soluble Polymers
in Household Cleaning
Products – Benefits and
Mechanisms
D.R.Scheuing
Clorox
2018 Surfactants in Solution

2. Outline
Intro to Clorox & Cleaning Division
Consumers and customers
Tools used
Literature review
Delivering benefits with different mechanisms
Summary

3. • A leading multinational manufacturer and marketer of consumerand professionalproducts.
• 80%+ of sales generated from No. 1 or No. 2 brands in their categories.
What Is Clorox?
3

4. Company Overview – FY 2016
Sales by Segment and Category
4
* For additional information visit: annualreport.thecloroxcompany.com

5. Corporate Responsibility at Clorox
5
* For additional information visit: annualreport.thecloroxcompany.com

6. Cleaning is a means to an end – and – “Clean” matters – but -
Not about convincing people to “clean more”
Clorox believes clean is more than getting rid of dirt and germs.
Sure, it’s about wiping away what came before, but it’s also about celebrating what
happens after.
Clean is just the beginning.
What comes nextis everything.
https://www.youtube.com/watch?time_continue=73&v=9lVngvANQUE
Read more at https://www.clorox.com/our-purpose/why-clean-matters/

7. Consumers want cleaners that …
They perceive as a good value because –
They deliver real benefits
Fit with their lifestyle (cleaning “on the go” – rarely a major “event”)
They trust - based on their full experience with the product

8. http://corporate.walmart.com/global-responsibility/environment-
sustainability/sustainability-index-leaders-shop
And our customersdemand profitableproductsthat meet their needs – including
sustainability, safety and public perception

9. First thought – polymers for rheology control (thickening)
Benefit - Cling to surfaces – toilet bowl cleaners & gels, shower
cleaners.
Enhance contact time (bleaching, antimicrobial efficacy)
Keep surfaces cleaner longer
Benefit – Controlledsmooth pouring - dilutables,laundry
additives
Design rheology together with package – prevent splashing,
glugging, etc.
This talk =
Other benefits and mechanisms to deliver them

10. Polymer – micelle complexes in cleaners can deliver benefits to
consumersand customers
Consumers -
Faster cleaning of hard surfaces
Easier cleaningof surfaces – less scrubbing in “tough jobs”
Safer cleaning – less “chemicalsin my home” or ingredientsthat I understand
More sustainable ingredients
Customers–
“Safer” ingredients (per their own definitions or NGO or government regulation)
Products that help them meet their declared sustainabilitygoals
Successful products in their categories that growthe category
“Share wars” between Brands limit profits
Customer requirementsapply to the cleaningformulationsand the packages !!!

11. Tools used - products with polymer/micelle complexes
Classicalphysicalexaminations = phase behavior
Dynamic Light Scattering
Fit Exponential Decay Function
tDq2

Monodisperse particles
Decay rate Diffusion
coefficient
Gaussian Distribution of Diffusion Coefficients – Use
“Cumulants Method” to Fit Decay
Z – average Diffusion
Coefficient
Polydispersity Index
(PDI)
Sessile and sliding drop contact angle
Fourier Transform Infrared Spectroscopy
ATR (Attenuated TotalReflectance sampling optics)

12. IRE
(Ge)Air
Sampling depth, dp= 736
nm at 1650 cm-1
dp = l/2p (sin2 q - n21
2 )1/2
Refractive index = n2 = 1.5
Refractive index = n1=
4.0
q
n21=n2/n1
Attenuated Total Reflection (ATR) optics key to analysis of surfaces –
including the IRE surface with adsorbed layers
Ref 1

13. Evanescent wave probes x,y,z dimensions at
interface Transmissionexperiments do not !
ATR optics + polarized light = probe anisotropyof
adsorbed surfactant layers
Commercially available ATR optical rigs enable easier experiments
Solution/Formulation
Ref 2
Ge surface –
solutioninterface

14. Briefliteratureintroductionand review

15. Mixed Micelle-Polymer Binding
• Binding requires a “critical” charge on the micelle, scrit
– Sharp change, like a phase boundary
– Similarto polyelectrolyteadsorptionon a charged surface
– s ~ mole fraction anionicsurfactant = Y = [ionic surfactant]/[ionic surfactant
+nonionicsurfactant]
– q is the charge per polymer repeat unit (distance between charges)
– k is Debye-Huckel parameterof solution(nm-1), depends on salt concentration(I1/2).
– b varies with polymer flexibility,micelle shape (spheres near 1.4, rods near 2.0)
– Isothermal form – Temp dependence includes hydration,micelle effects (6-9)
scrit ~ q-1 kb
Ref 3 - 6

16. Coacervates have high MW and low/no charge
Soluble complexes can be net cationic or anionic
High micelle charge (Y) widens coacervate
Complex
Charge
Wider coacervate
region at higher Y
Ref 3
Lower
charge on
micelles
Higher charge on
micelles
r = DADMAC/SDS in bulk
Of the complexes
Triton X100/SDS/pDADMAC

17. Coacervate region, fixed [polymer] - Triton X-100/SDS micelles with
pDADMAC. Nothing stoichiometric about coacervate formation !
Y=mole
fraction
anionicin
micelle
r = cationic/anionic
charge ratio
Ref 3

18. Coacervate Formation – cartoon summary
I – No complexes, micelle charge too low
II – Add ionic surfactant, initial binding of micelles
III- More ionic surfactant - Net charge of complexes near 0, coacervate formed
IV – Still more ionic surfactant – Charge reversed complexes are soluble
V – Most ionic surfactant – tight binding of surfactant = precipitate due to loss
of counterions and hydration
Ref 7
Increasing Ionic Surfactant = Increasing “Y”

19. Effect of salt – cartoon summary for system nonionic/SDS –
pDADMAC cationic polyelectrolyte
I – High salt – no complexes
II – Net positive charge complexes
III – Neutral charge coacervate
IV – Net negativecomplex
Salt “screens” polymer – micelle interactions.
Can both “enhance” and “suppress” coacervate formation – depends on micelle
composition = “Y”
More Salt
Ref 7
Less Salt

20. Nonionic/anionic micelles can exhibit a cloud point (coacervate)
Polymer – micelle complexes show temperature –dependent sizes
Tϕ
Ref 8

21. Polydispersenonionic= wider temperature range and larger coacervate yield –
Evidence for micellar heterogeneity as large complexes aggregate and coacervate
C12EO8 (less
polydisperse)
TX-100
(polydisperse)
System = SDS/Nonionicwith polyDADMAC
Adsorbed layersshow evidence of disproportionation.
Polydisperse
nonionic
Polydisperse
micelles
Polydisperse
complexes
Coacervation temp
range
Splittinginto 2 sizes -
Driven by energy of
coacervation?
Or
Neutral complexes require
disproportionation of micelle
compositions –
Some complexes need “above
average” # of SDS molecules?
Ref 8

22. Benefits –
Faster, easier cleaning
One product does multiple jobs
Less “chemicals” in my home (lower actives cleaners)
Enhancedexperience – fragrance delivery or “fragrance free”
Mechanisms –
Enhancedcontrolof the oil – water interface to drive solubilization
Lower total surfactant levels for equivalentsolubilizationandwetting kinetics
Improved wetting & spreading on hydrophilicand hydrophobichard surfaces

23. “Water Soluble”
Surfactant
cmc in water < cmc in oil
“Oil Soluble”
Surfactant
cmc in oil < cmc in water
“Equal” Waterand Oil Solubility
cmc in water = cmc in oil
H < 0H=0H >0
Decreasing Curvature
Increasing Surfactant Hydrophobicity by -
Increasing T (nonionics)
Changing ratio of hydrophilic and hydrophobic surfactants
Increasing [Electrolyte]
Curvature of oil-water interface – a way to think about optimizing oil
solubility

24. Poly(electrolyte) – ionic micelle/microemulsion interactios – use polymers
(polyelectrolytes) as counterions to enhance oil solubilization ?
+
Add poly(acrylic acid) salt ++
+
+
+
++
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
++
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
OR
Polymeric
Counterion
Coacervate
Quat
Cl-
+ Na+
Amine
Oxide
_ Acrylic
Acid
Monomer
Limonene

25. PEs on the oil-water interface are key – How much control of
spontaneouscurvature?
+
Cl-
Na+
Acrylic
Acid
Monomer
Limonene
+
_
+
Quat Amine
Oxide
Quat – Quat Repulsions –
Screened by AO and Cl-
ions
+
+ +
+Add
Electrolyte or
water-
miscible
alcohol
+
+
+
+
_
+ +
+
+
+ +
Or - Add Na(poly acrylate)
NaPAA – on water side
only. Polymer flexibility,
spacing between
charges,total [salt]
affectquat spacing,
curvature of interface
and oil solubilization
“Flexibility” of
oil – water
interface has to
be “just right”

26. Co-polymer PEs on the oil-water interface – Is a combination of hydrophobic
and electrostatic interactions useful?
+
Cl-
Na+
Acrylic
Acid
Monomer
Limonene
+
_
+
Quat Amine
Oxide
Quat – Quat Repulsions –
Screened by AO and Cl- ions
+
+
+
+
_
+
+
+
+
Add a commercial,
polydisperse co-polymer
+
+
+
+
+
+
+
+
Styrene
Monomer
Or
Styrene mostly on
water side
Styrene mostly
on oil side
50 – 50 styrene –
acrylic acid

27. Model System To Improve Upon is Already Efficient
Model System =
Didecyl dimethyl ammonium
chloride
Dodecyl dimethyl amine oxide
MEA (pH adjust @ 0.1%)
Na carbonate (50 mM)
Oil = Limonene
Solubilizes 0.3 wt% limonene with [total surfactant] = 1.27%
Or = oil wt/surf wt = 0.236
Include MEA = 0.219
Natural solvent & model fragrance. Low water solubility (13 mg/L) vs. use levels @ 0.1 – 0.3%
(1000 - 3000 mg/L, 77-230x sol. limit)

28. Formulation Levers - Summary
“Y” = [quat] / ([quat+nonionic]
Or
“Y” = [anionic surf] / ([anionic+nonionic]
“Y” sets the net charge on the micelles – high Y gives highly charged micelles &
strong interaction with polymeric counterion. Below a critical Y, no complexes.
Range = 0.0 to 1.0 – calculate on molar (preferred) or weight basis
P/Q = Equivalents of Anionic
polymer charge/Equivalents of
Quat charge
P/Dnet = Equivalents of Cationic polymer
charge/Equivalents of anionic surfactant
charge.
Dnet = net charge on anionic/nonionic micelle
Surfactant type and concentration – inherent curvature
Oil (fragrance, solvent) – type, concentration (EACN)
Polymer type and Molecular weight
Electrolyte level – screening of polymer-micelle interactions
And -

29. Polyacrylic acid homopolymer (sodium salt, MW = 65K)
Small effect at P/Q = 0.001
No polymer total surfactant concentrations, wt% total surfactant concentrations, wt%
BTC 1010 wt%0.05 0.1 0.15 BTC1010 0.2 0.3 0.4 0.5
AmmonyxLO wt% AmmonyxLO wt%
0 0.050 0.100 0.150 0.000 0.200 0.300 0.400 0.500
0.108108 0.158 0.208 0.258 0.108 0.308 0.408 0.508 0.608
0.218919 0.269 0.319 0.369 0.219 0.419 0.519 0.619 0.719
0.327027 0.377 0.427 0.477 0.327 0.527 0.627 0.727 0.827
0.435135 0.485 0.535 0.585 0.435 0.635 0.735 0.835 0.935
0.545946 0.596 0.646 0.696 0.546 0.746 0.846 0.946 1.046
0.654054 0.704 0.754 0.804 0.654 0.854 0.954 1.054 1.154
0.764865 0.815 0.865 0.915 0.765 0.965 1.065 1.165 1.265
0.872973 0.923 0.973 1.023 0.873 1.073 1.173 1.273 1.373
0.981081 1.031 1.081 1.131 0.981 1.181 1.281 1.381 1.481
1.091892 1.142 1.192 1.242 1.092 1.292 1.392 1.492 1.592
1.2 1.250 1.300 1.350 1.200 1.400 1.500 1.600 1.700
0.53% Na2CO3 buffer
total surfactant concentration, wt%
P/Q=0.001 BTC 1010 wt%0.2 0.3 0.4 0.5
AmmonyxLO wt%
0.000 0.200 0.300 0.400 0.500
0.108 0.308 0.408 0.508 0.608
0.219 0.419 0.519 0.619 0.719
0.327 0.527 0.627 0.727 0.827
0.435 0.635 0.735 0.835 0.935
0.546 0.746 0.846 0.946 1.046
0.654 0.854 0.954 1.054 1.154
0.765 0.965 1.065 1.165 1.265
0.873 1.073 1.173 1.273 1.373
0.981 1.181 1.281 1.381 1.481
1.092 1.292 1.392 1.492 1.592
1.200 1.400 1.500 1.600 1.700
Clear
Excess oil
[AmineOxide]
[Quat]
[total surf]
[AmineOxide]
[AmineOxide]
No Polymer
P/Q=0.001
50 mM buffer

30. P/Q =0.005 triggers coacervation but also improves oil
solubilization
Clear
Excess oil
total surfactant concentration, wt%
P/Q=0.001 BTC 1010 wt%0.2 0.3 0.4 0.5
AmmonyxLO wt%
0.000 0.200 0.300 0.400 0.500
0.108 0.308 0.408 0.508 0.608
0.219 0.419 0.519 0.619 0.719
0.327 0.527 0.627 0.727 0.827
0.435 0.635 0.735 0.835 0.935
0.546 0.746 0.846 0.946 1.046
0.654 0.854 0.954 1.054 1.154
0.765 0.965 1.065 1.165 1.265
0.873 1.073 1.173 1.273 1.373
0.981 1.181 1.281 1.381 1.481
1.092 1.292 1.392 1.492 1.592
1.200 1.400 1.500 1.600 1.700
P/Q=0.005 total surfactant concentration, wt% CB total surfactant concentration wt%
BTC 1010 wt% 0.05 0.1 0.15 0.2 0.2 0.3 0.4 0.5
ES AmmonyxLO wt% AmmonyxLO wt%
0.000 0.05 0.1 0.15 0.2 0 0.200 0.300 0.400 0.500
0.108 0.158 0.208 0.258 0.308 0.108 0.308 0.408 0.508 0.608
0.219 0.269 0.319 0.369 0.419 0.219 0.419 0.519 0.619 0.719
0.327 0.377 0.427 0.477 0.527 0.327 0.527 0.627 0.727 0.827
0.435 0.485 0.535 0.585 0.635 0.435 0.635 0.735 0.835 0.935
0.546 0.596 0.646 0.696 0.746 0.546 0.746 0.846 0.946 1.046
0.654 0.704 0.754 0.804 0.854 0.654 0.854 0.954 1.054 1.154
0.765 0.815 0.865 0.915 0.965 0.765 0.965 1.065 1.165 1.265
0.873 0.923 0.973 1.023 1.073 0.873 1.073 1.173 1.273 1.373
0.981 1.031 1.081 1.131 1.181 0.981 1.181 1.281 1.381 1.481
1.092 1.142 1.192 1.242 1.292 1.092 1.292 1.392 1.492 1.592
1.200 1.250 1.300 1.350 1.400 1.2 1.400 1.500 1.600 1.700
Coacervate
[AmineOxide]
[AmineOxide]
[Quat]
P/Q=0.001
P/Q=0.005
[Quat]
P/Q=0.005 total surfactant concentration, wt% CB total surfactant concentration wt%
BTC 1010 wt% 0.05 0.1 0.15 0.2 0.2 0.3 0.4 0.5
ES AmmonyxLO wt% AmmonyxLO wt%
0.000 0.05 0.1 0.15 0.2 0 0.200 0.300 0.400 0.500
0.108 0.158 0.208 0.258 0.308 0.108 0.308 0.408 0.508 0.608
0.219 0.269 0.319 0.369 0.419 0.219 0.419 0.519 0.619 0.719
0.327 0.377 0.427 0.477 0.527 0.327 0.527 0.627 0.727 0.827
0.435 0.485 0.535 0.585 0.635 0.435 0.635 0.735 0.835 0.935
0.546 0.596 0.646 0.696 0.746 0.546 0.746 0.846 0.946 1.046
0.654 0.704 0.754 0.804 0.854 0.654 0.854 0.954 1.054 1.154
0.765 0.815 0.865 0.915 0.965 0.765 0.965 1.065 1.165 1.265
0.873 0.923 0.973 1.023 1.073 0.873 1.073 1.173 1.273 1.373
0.981 1.031 1.081 1.131 1.181 0.981 1.181 1.281 1.381 1.481
1.092 1.142 1.192 1.242 1.292 1.092 1.292 1.392 1.492 1.592
1.200 1.250 1.300 1.350 1.400 1.2 1.400 1.500 1.600 1.700
[total surf]
50 mM buffer

31. P/Q = 0.01 further extends coacervation and improves oil
solubilization
P/Q=0.01 total surfactant concentration, wt%
BTC 1010 wt% 0.05 0.1 0.15 0.2
AmmonyxLO wt%
0.000 0.05 0.1 0.15 0.2
0.108 0.158 0.208 0.258 0.308
0.219 0.269 0.319 0.369 0.419
0.327 0.377 0.427 0.477 0.527
0.435 0.485 0.535 0.585 0.635
0.546 0.596 0.646 0.696 0.746
0.654 0.704 0.754 0.804 0.854
0.765 0.815 0.865 0.915 0.965
0.873 0.923 0.973 1.023 1.073
0.981 1.031 1.081 1.131 1.181
1.092 1.142 1.192 1.242 1.292
1.200 1.250 1.300 1.350 1.400
Clear
Excess oil
Coacervate
[AmineOxide]
[AmineOxide]
[Quat]P/Q=0.01
P/Q=0.005
[Quat]
P/Q=0.005 total surfactant concentration, wt% CB total surfactant concentration wt%
BTC 1010 wt% 0.05 0.1 0.15 0.2 0.2 0.3 0.4 0.5
ES AmmonyxLO wt% AmmonyxLO wt%
0.000 0.05 0.1 0.15 0.2 0 0.200 0.300 0.400 0.500
0.108 0.158 0.208 0.258 0.308 0.108 0.308 0.408 0.508 0.608
0.219 0.269 0.319 0.369 0.419 0.219 0.419 0.519 0.619 0.719
0.327 0.377 0.427 0.477 0.527 0.327 0.527 0.627 0.727 0.827
0.435 0.485 0.535 0.585 0.635 0.435 0.635 0.735 0.835 0.935
0.546 0.596 0.646 0.696 0.746 0.546 0.746 0.846 0.946 1.046
0.654 0.704 0.754 0.804 0.854 0.654 0.854 0.954 1.054 1.154
0.765 0.815 0.865 0.915 0.965 0.765 0.965 1.065 1.165 1.265
0.873 0.923 0.973 1.023 1.073 0.873 1.073 1.173 1.273 1.373
0.981 1.031 1.081 1.131 1.181 0.981 1.181 1.281 1.381 1.481
1.092 1.142 1.192 1.242 1.292 1.092 1.292 1.392 1.492 1.592
1.200 1.250 1.300 1.350 1.400 1.2 1.400 1.500 1.600 1.700
P/Q=0.005 total surfactant concentration, wt% CB total surfactant concentration wt%
BTC 1010 wt% 0.05 0.1 0.15 0.2 0.2 0.3 0.4 0.5
ES AmmonyxLO wt% AmmonyxLO wt%
0.000 0.05 0.1 0.15 0.2 0 0.200 0.300 0.400 0.500
0.108 0.158 0.208 0.258 0.308 0.108 0.308 0.408 0.508 0.608
0.219 0.269 0.319 0.369 0.419 0.219 0.419 0.519 0.619 0.719
0.327 0.377 0.427 0.477 0.527 0.327 0.527 0.627 0.727 0.827
0.435 0.485 0.535 0.585 0.635 0.435 0.635 0.735 0.835 0.935
0.546 0.596 0.646 0.696 0.746 0.546 0.746 0.846 0.946 1.046
0.654 0.704 0.754 0.804 0.854 0.654 0.854 0.954 1.054 1.154
0.765 0.815 0.865 0.915 0.965 0.765 0.965 1.065 1.165 1.265
0.873 0.923 0.973 1.023 1.073 0.873 1.073 1.173 1.273 1.373
0.981 1.031 1.081 1.131 1.181 0.981 1.181 1.281 1.381 1.481
1.092 1.142 1.192 1.242 1.292 1.092 1.292 1.392 1.492 1.592
1.200 1.250 1.300 1.350 1.400 1.2 1.400 1.500 1.600 1.700
[total surf]

32. P/Q=0.01 total surfactant concentration, wt%
BTC 1010 wt% 0.05 0.1 0.15 0.2
AmmonyxLO wt%
0.000 0.05 0.1 0.15 0.2
0.108 0.158 0.208 0.258 0.308
0.219 0.269 0.319 0.369 0.419
0.327 0.377 0.427 0.477 0.527
0.435 0.485 0.535 0.585 0.635
0.546 0.596 0.646 0.696 0.746
0.654 0.704 0.754 0.804 0.854
0.765 0.815 0.865 0.915 0.965
0.873 0.923 0.973 1.023 1.073
0.981 1.031 1.081 1.131 1.181
1.092 1.142 1.192 1.242 1.292
1.200 1.250 1.300 1.350 1.400
No polymer total surfactant concentrations, wt% total surfactant concentrations, wt%
BTC 1010 wt%0.05 0.1 0.15 BTC1010 0.2 0.3 0.4 0.5
AmmonyxLO wt% AmmonyxLO wt%
0 0.050 0.100 0.150 0.000 0.200 0.300 0.400 0.500
0.108108 0.158 0.208 0.258 0.108 0.308 0.408 0.508 0.608
0.218919 0.269 0.319 0.369 0.219 0.419 0.519 0.619 0.719
0.327027 0.377 0.427 0.477 0.327 0.527 0.627 0.727 0.827
0.435135 0.485 0.535 0.585 0.435 0.635 0.735 0.835 0.935
0.545946 0.596 0.646 0.696 0.546 0.746 0.846 0.946 1.046
0.654054 0.704 0.754 0.804 0.654 0.854 0.954 1.054 1.154
0.764865 0.815 0.865 0.915 0.765 0.965 1.065 1.165 1.265
0.872973 0.923 0.973 1.023 0.873 1.073 1.173 1.273 1.373
0.981081 1.031 1.081 1.131 0.981 1.181 1.281 1.381 1.481
1.091892 1.142 1.192 1.242 1.092 1.292 1.392 1.492 1.592
1.2 1.250 1.300 1.350 1.200 1.400 1.500 1.600 1.700
Clear
Excess oil
Coacervate
PAA homopolymer – boosts oil solubilization – but coacervateregion is large – strong
polymer-micelle interactions
0.3% limonene (fixed)
Dialkyl dimethyl quat
and C12 amine oxide
total surfactant concentrations, wt% total surfactant concentrations, wt%
BTC 1010 wt%0.05 0.1 0.15 BTC1010 0.2 0.3 0.4 0.5
AmmonyxLO wt% AmmonyxLO wt%
0 0.050 0.100 0.150 0.000 0.200 0.300 0.400 0.500
0.108108 0.158 0.208 0.258 0.108 0.308 0.408 0.508 0.608
0.218919 0.269 0.319 0.369 0.219 0.419 0.519 0.619 0.719
0.327027 0.377 0.427 0.477 0.327 0.527 0.627 0.727 0.827
0.435135 0.485 0.535 0.585 0.435 0.635 0.735 0.835 0.935
0.545946 0.596 0.646 0.696 0.546 0.746 0.846 0.946 1.046
0.654054 0.704 0.754 0.804 0.654 0.854 0.954 1.054 1.154
0.764865 0.815 0.865 0.915 0.765 0.965 1.065 1.165 1.265
0.872973 0.923 0.973 1.023 0.873 1.073 1.173 1.273 1.373
0.981081 1.031 1.081 1.131 0.981 1.181 1.281 1.381 1.481
1.091892 1.142 1.192 1.242 1.092 1.292 1.392 1.492 1.592
1.2 1.250 1.300 1.350 1.200 1.400 1.500 1.600 1.700
P/Q=0.01
No
Polymer [Quat]
[AmineOxide][AmineOxide]
[total surf]
50 mM buffer

33. PAA boosts oil solubilization only at low actives. Inversion (oil
rejection) found at high P/Q.
P/Q=0.01 total surfactant concentration, wt%
BTC 1010 wt% 0.05 0.1 0.15 0.2
AmmonyxLO wt%
0.000 0.05 0.1 0.15 0.2
0.108 0.158 0.208 0.258 0.308
0.219 0.269 0.319 0.369 0.419
0.327 0.377 0.427 0.477 0.527
0.435 0.485 0.535 0.585 0.635
0.546 0.596 0.646 0.696 0.746
0.654 0.704 0.754 0.804 0.854
0.765 0.815 0.865 0.915 0.965
0.873 0.923 0.973 1.023 1.073
0.981 1.031 1.081 1.131 1.181
1.092 1.142 1.192 1.242 1.292
1.200 1.250 1.300 1.350 1.400
P/Q=10 total surfactant concentration, wt%
BTC 1010 0.05 0.1 0.15 0.2
AmmonyxLO wt%
0.000 0.05 0.1 0.15 0.2
0.108 0.158 0.208 0.258 0.308
0.219 0.269 0.319 0.369 0.419
0.327 0.377 0.427 0.477 0.527
0.435 0.485 0.535 0.585 0.635
0.546 0.596 0.646 0.696 0.746
0.654 0.704 0.754 0.804 0.854
0.765 0.815 0.865 0.915 0.965
0.873 0.923 0.973 1.023 1.073
0.981 1.031 1.081 1.131 1.181
1.092 1.142 1.192 1.242 1.292
1.200 1.250 1.300 1.350 1.400
Clear
Excess oil
Coacervate
Inverted
Oil solubilization boosting appears only at
• P/Q << 1
• Low quat concentrations
Extensive coacervation
Phase inversion at P/Q > 1
[Quat]
[AmineOxide]
P/Q=10
P/Q=0.01 0.05% quat 0.1% quat

34. Low MW (6 – 8 K) Styrene/Acrylic acid (1:1) copolymers – 0.1% fixed polymer concentration
Vary limonene level with Y = 0.09 (quat/quat+amine oxide)
Without polymer – minimum surfactant needed = 1.27% to solubilize 0.3% limonene
Total Surfactant+ NEMO polymer , wt%
Limonene, wt% 0 0.05 0.1 0.2 0.3
P/Q, moles 0.1 0.1 0.1 0.1 0.1
8.57 0.28 0.28 0.28 0.28 0.28
4.24 0.464 0.464 0.464 0.464 0.464
2.84 0.644 0.644 0.644 0.644 0.644
2.12 0.828 0.828 0.828 0.828 0.828
1.70 1.008 1.008 1.008 1.008 1.008
1.41 1.192 1.192 1.192 1.192 1.192
1.21 1.372 1.372 1.372 1.372 1.372
1.06 1.556 1.556 1.556 1.556 1.556
0.94 1.736 1.736 1.736 1.736 1.736
0.85 1.92 1.92 1.92 1.92 1.92
0.77 2.1 2.1 2.1 2.1 2.1
Total Surfactant + Alco 747 polymer, wt%
Limonene, wt% 0 0.05 0.1 0.2 0.3
P/Q, moles 0.1 0.1 0.1 0.1 0.1
7.62 0.28 0.28 0.28 0.28 0.28
3.77 0.464 0.464 0.464 0.464 0.464
2.52 0.644 0.644 0.644 0.644 0.644
1.88 0.828 0.828 0.828 0.828 0.828
1.51 1.008 1.008 1.008 1.008 1.008
1.26 1.192 1.192 1.192 1.192 1.192
1.08 1.372 1.372 1.372 1.372 1.372
0.94 1.556 1.556 1.556 1.556 1.556
0.84 1.736 1.736 1.736 1.736 1.736
0.75 1.92 1.92 1.92 1.92 1.92
0.69 2.1 2.1 2.1 2.1 2.1
Wt% Limonene Wt% Limonene
[totalsurfactant]
Minimumrequired
Normalizedtotal
actives
Clear Excess oil Coacervate
Solubilization boosting increaseswith
oil level !
Polymer A Polymer B
Commercial polymers need
careful evaluation

35. Benefits –
Less “chemicals” in my home (lower actives cleaners)
No harsh residues
No streaks – better shine
One product does multiplejobs
Good on glass/cooktop/microwave/stainlesssteel
Mechanisms –
Lower total surfactant levels for equivalentsolubilization, wetting kinetics
Improved wetting & spreading on hydrophilic and hydrophobic hard surfaces
Surface tension reduction by complexes at low actives
Reduced need for co-solvents (glycol ethers, alcohols)

36. Polymer-Surfactant Complexes “Force” Micelle Formation!
C16TAB= cationic surf., Polymer = PAMPS
= anionic copolymerof acrylamide (neutral)
and AMPS (anionic sulfonate)(Ref 1)
CTAB only
CTAB + 114
ppm Polymer
Synergistic interaction lowers tension
below cmc of surfactant.
“cac” = complexes
appear in bulk soln.
Normal cmc
Polymer
“saturated” with
complexes
Ref 9

37. Very dilute systems – other important factors
Complexes form at air-water interface “first” (at lowest concentration)
Equilibration times are long - depend on measurementtechnique used
Details of surface tension plots depend on
Flexible polymers exchange counterions for surfactant
Charge density of polymer chain
Length of surfactant tails
Large distance between charges, short surfactant tails decrease binding
Complexes at air-water interface can show complex rheology (gels)
Tune with polymer rigidity, surfactant type, and [salt]
Formulation wetting/spreading rates and foam stability affected
Ref 10-13

38. Thin foam film containing “surface gels”
Drainage time = hours
100 um thick
area
Surface “gel”
aggregate
System = Poly(styrene sulfonate) 500 ppm, C12TAB 2 mM
Ref 11

39. • CMC of quat reduced (1/21) by 50 mM
Na2CO3 electrolyte
• CMC of quat in electrolyte reduced
further (1/150) by pAA
Avg. SFT vs Concentration
Concentration [mg/l]
Avg.SFT[mN/m]
0.01 0.05 0.1 0.5 1 5 10 50 100 500 1000
20
25
30
35
40
45
50
55
CMC of
quat alone
CMC with
carbonate
CMC with PAA
& carbonate
 CAC of quat/PAA lower than
quat/carbonate
 CMC reduced to only 1 mg/L quat,
0.8 mg/L pAA
 Results consistent with literature.
Poly(acrylic acid) – cationicmicelle interactions
Polydisperse polymer and quat – need to confirmperformance of commercial
materials
PAA – MW =65 K Quat = didecyl dimethyl
ammonium chloride

40. 0
5
10
15
20
25
30
35
40
ContactAngle/Degrees
Glass
PVC
Polymer B
P/Q = 0.05
Polymer B
P/Q = 0.05
Y=0.1
Polymer B
P/Q = 2.0
Micelle system = 0.3% limonene, Quat/Amine oxide Y=0.09
No glycol ether cosolvents
No
polymer
Polymer A
P/Q = 0.05
Polymer A
P/Q=2.0
Glass Cleaner
No solvents
Poor cleaning
“Natural” HSC
with alcohol
Brand X
Low glycol
ether level
Brand Y
High glycol
ether level
Exceeds current US
EPA limits on volatile
solvents
15°
25°
35°
Copolymer (A or B) – micelle complexes improve wetting of hydrophobic
surfaces = modern hard surface cleanerswith low volatiles

41. Acrylic acid/starchgraft copolymer - complexes with micelles also can deliver good
wetting of hydrophobicsurfaces – no cosolvents
“Filling” micelles with limonene improves wetting even more
Micelle system = Quat/Amine oxide Y=0.09 - No glycol ether cosolvents
No
polymer
P/Q=4.0
P/Q=1.0
P/Q=0.576
P/Q=0.576
0.3%
limonene
Glass Cleaner
No solvents
Poor cleaning
“Natural” HSC
with alcohol
Brand X
Low glycol
ether level
Brand Y
High glycol
ether level
15°
25°
35°

42. Benefits –
Faster, easier cleaning for quick “clean as you go” jobs
Longer lasting clean – especially from “bigger jobs”
Surfaces look better or newer with less effort
Surfaces fight “germs”
Mechanisms –
Reduced adhesion of oily soils via surface modificationfrom layers< 100 nm thick
Polymer-surfactant complexes which are rapidlyadsorbed during cleaning
Non-equilibriumlayers create more uniform surfaces – sliding water or oil drops
Polymer – quat adsorbed layersincorporateenough water to be bacteriostaticor bactericidal

43. Surfactants adsorb onto & modify solid surfaces – but will
also desorb !
Adsorption increases up to
cmc – then is constant.
All adsorbed layers in
equilibrium with surfactant
in solution –
Surface modification is
loose & dynamic.
Dilution of system will
rinse surfactant off
surface!
Ref. 14

44. Adsorption is maximized near the coacervate phase boundary
Polymer/micelle complexes yield low charge density, thick
layers
Micelles “solubilize” polymer segments = More loops and tails
= more flexible chains at surface
Surfactant monomer - micelle exchange remains fast
Anionic - DADMAC – surface becomes hydrophobic =
significant tail exposure
Adsorbed layers of complexes almost never at equilibrium
+
+
+
+
+
+++
+
+
+
+
+
+
+
+
+
+ +
+
+
+
+
+
+
+
+ +
+
+
+ +
+
+
+
+
Mixed anionic /nonionic
micelle
Anonic
surf
Na+
Cl-
Nonionic
- - - - - -- - - -+ +
+
+
+
+
++
+ ++ +
+
+
+
+
+
++
Significant
Lateral
Interactions of
Surfactants
20 – 200 nm
Ref 15-17

45. Reduce spreading and adhesion of oily soils on household surfaces via
hydrophilic surface modification
45
cos q = (g SG – g SL) / g LG
g LG cos q = (g SG – g SL)
cos q = 0 (at q =90)
Minimize this difference
Decrease oil spreading on the surface
Water – swollen adsorbed polymer-surfactant monolayers can deliver
this benefit.

46. Not all household surfaces are horizontal !
To “staycleaner” – drops of hard water or liquid oils should slide off surfaces.
Adsorbed layers should be uniform – to minimize contact angle hysteresis.
Krüss DSA-10L (tilting table feature) can determine
sessile contact angles and sliding angles
Test fluids
•Ultrapure H2O
•Anhydrous C16
For non-pinned drops:
•Sliding angle, α
•θA and θR
α
q = qA – qRRecession of contact line can break adhesive
bond.
qR > 0: liquid debonds from solid;
adhesive failure
qR  0: liquid– solid adhesion > cohesive
strength of liquid;
drop ruptures - leaves undesirable trail

47. Hydrophobicity and Hysteresis
Pinned drops with any q not very
useful
Sliding drops are ideal to deliver real
consumer benefits
Control of the composition and
uniformity of the adsorbed layers is
critical
This is the most “hydrophobic”surface !
Ref 18

48. 1. Add 1 ml solution – polymer/micelle complexes
2. Fix adsorption time
3. Vacuum off solution while adding pure water to rinse
4. Control total rinse volume (20 – 40 ml)
5. Obtain spectrum of adsorbed layer - in ambient atmosphere
or under dry nitrogen purge
o Total absorbance depends on layer thickness and area fraction
covered
o Can be quantitative – calibrate with wet solutions or dried layers
o Interpret spectra with appropriate standards of raw materials used
o Surface of ATR crystal can be modified with nanoparticles or thin
polymer layers prior to adsorption experiment
Nitrogen purge box
FT-IR (ATR) gives adsorbed layer compositions and interactions between
polymer and surfactants

49. Polydisperse pDADMAC and polydisperse C12EO8 with SDS –
a model system with industrial materials
pDADMAC(300-500K)
Mixed micelles = SDS/C12EO8 - total surfactant concentration = 40 mM
Moderate electrolyte = 0.1 M NaCl – pH about 7
Ge IRE exposed to solution for 5 minutes
Extensive water rinses
What adsorbs? Dependence of adsorption on Y

50. Max.
Adsorption
near
coacervate
phase !
~ Micelle Charge
Adsorption increases near coacervate boundary
Commercial polydisperse polymer and nonionic can be used.

51. 0
.0005
.001
.0015
.002
.0025
.003
Absorbance
1500 1400 1300 1200 1100 1000
Wavenumber (cm-1)
asymm. S-O
symm. S-OSDS micelles
Y=Adsorbed Layers 0.294
0.257
0.222
0.170
0.119
0.069
"LBL"
pDADMAC
SDS and pDADMACadsorb from complexes over wide range of Y.
C12EO8 not present in adsorbed layers.
Extreme micellar disproportionation in adsorbed layers !
Ref 20,21

52. 0
.02
.04
.06
.08
.1
.12
.14
Absorbance
3050 3000 2950 2900 2850
Wavenumber (cm-1)
Y= 0.294, clear
0.330, coacervate
0.406, coacervate
0.501, ppt.
Solid SDS
pDADMAC
SDS micelles
CH2 asymm
CH2 symm.
Adsorbed Layers
Adsorbed Layers
Width and wavenumber of CH2 stretching bands indicate -
SDS “tails” in adsorbed layers are disordered, similar to micelles.
Adsorbed polymer-micelle complexes are not precipitates.
Ref 20,21

53. Acrylic acid-starch copolymer complexes with amine oxide/quat/limonene micelles deliver
adsorbed quat/polymer layers.
More adsorption@ P/Q <1.0, even with oil and carbonate buffer in the system.
P/Q = [anionic charges on polymer] / [cationic charges from quat]

54. Water uptake
correlated with
presence of
adsorbed starch
groups. Quat on
a surface
without water
“beading”.
Hydrophilic surface modificationeven with adsorbed quat can be done with
hydrophilicpolymer selection.
Bacteriostaticand reduced oily soil adhesiondelivered with “invisiblelayers”

55. Deliver both hydrophobic and oleophobic surfaces.
Use anionic “bola –fluorosurfactants” (oxetane derivatives) in mixed micelles with
C12EO8 complexed with pDADMAC
C-F stretching yields
intense IR absorbance
Cationic Polymer =
pDADMAC
*Polyfox PF-156A from Omnova Corp.
Micelles = 40mM C12EO8 (2%) + added fluorosurfactant(0-15mM)
Check effects of [NaCl] , Y and R=equivalentsanionicsurfactant/pDADMAC
These fluorosurfactantsform mixed micelles – unlike perfluorinated types !
*
Ref 22, 23

56. Intense Bands Available for Detection of Fluorinated Oxetanes in
Adsorbed Layers
S-O Asymm.
Stretch
SDS, hydrated
S-O Symm.
Stretch
C2F5 -
oxetane
C4F9 -
oxetane
C-F stretch

57. C4F9 systems show collision of precipitate and coacervate regions.
How does R affect surface modification ?
Approach coacervate
phase boundary at
different [NaCl]
= 2 phase dispersions
with coacervate or
precipitate

58. C4F9/C12EO8 complexes with 3.0 mM DADMAC – adsorption increasesnear coacervate
boundary for net cationic complexes @ R < 1
High [Salt] or 2-Phase systems reduceadsorption
Adsorption time = 5
minutes exposure of
Ge IRE.
Then Rinsed 50x
with water (50ml)

59. At Low [DADMAC], coacervate region reduced. How does adsorption
change with R?

60. C4F9/C12EO8 complexes with 0.3 mM pDADMAC= maximum adsorption near
coacervate boundaries.
High [NaCl], Net anionic complexes inhibit adsorption
0
0.002
0.004
0.006
0.008
0.01
Absorbance
DADMAC CH3-N C-F 1236 C-F 1136Equal Fluorosurfactant
Adsorption @ 0.1xconc vs.
3 mM systems.
Lower actives, lower $$

61. C12EO8 is not detected in adsorbed layers.
Example of extreme disproportionation at surface.
ReferenceSpectrum
C12EO8 Dried on Ge
CH2 Stretching
of Methylenes
in Tail
CH2 Stretching
of CH2-O
C-O-C
Stretching
C-F, S-O
Stretching
CH3-N+
Adsorbed
Layer, R=0.94
Adsorbed
Layer, R=1.70
Adsorbed Layer Spectra – C4F9/C12EO8 sytems @ 0.3 mM pDADMAC
Not to same scale

62. Glass made oleophobic vs. hexadecane is possible via adsorbed C4F9 pDADMAC
complexes. Sliding drops with low hysteresis found with intermediate contact
angles!
C4F9 mM C4F9 mM
0.3 mM pDADMAC 3.0 mM pDADMAC
= sliding
drops
Contact Angle of
Hexadecane on solid
Teflon (PTFE) = 68 °

63. 0.3 mM
pDADMAC
3.0 mM pDADMAC
C4F9 mM C4F9 mM
= sliding
drops
Hydrophobicity (together with oleophobicity) with sliding water drops requires
higher C4F9 levels ! Presence of anionic ion pairs in layers vs. orientation of C4F9
groups ?

64. Summary
Easier, faster cleaning - with lasting clean appearance of surfaces
Better results on floors, etc. with less residues
Versatile products that do more jobs
Products that are safer and/or more sustainable and can fight germs
Polymer – micelle complexes deliver benefitsconsumers want
We can use these mechanismsof action for polymer-micelle complexes
Control of the curvature of oil-water interface – for enhanced oil solubilization at lower actives
Enhanced air-water activity of surfactants – drive betting wetting of surfaces by formulations
without common alcohol or glycol ether solvents
Rapid, non-equilibrium adsorption of polymers and charged surfactants from mixed
ionic/nonionic micellar systems
Reduction of the adhesion of oils on surfaces via water-swollenadsorbed layers
Reduction of oil and water adhesion on surfaces via adsorbed polymer-fluorosurfactant complexes

65. With a little help from my friends
Dr. Erika Szekeres
Dr. M. Knock

66. Thank You - -
SIS organizers
Clorox
You – the audience and
consumer !

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