Invited talk presented at the 2008 New Horizons Conference of the Consumer Specialty Products Association. Addresses aspects of the modification of household surfaces - chemical type, performance, and characterization.

1. NEW HORIZONS 2008
Consumer Acceptable Surface
Modification and Hard Surface
Cleaners
Hydrophilic or Hydrophobic ?
David R. Scheuing
Mona M. Knock
Colloid and Interface Science Group
Clorox Technical Center

2. Consumers Want Cleaning Products
that  Are efficacious
 Are convenient to use, saving time and effort – Wipes
 Are pleasant to use – Orange
 Preserve or enhance household surfaces, garments
 Fall within definite price ranges
Therefore
Innovative Surfactants, Polymers, Additives and
Formulations Will Continue to Appear !
981 US patents issued in “Home Cleaning” in 2003
(All US universities =3181, IBM=3457)

3. Hard Surface Cleaning with RTU Products =
Complex Kinetics
 Spraying/wiping occurs within seconds – No washing bath
 Applicator chemistry – Polymer and surfactant loss onto paper
towels, etc.
 Wiping is high shear environment (>1000 s-1)
 Soils are spatially heterogeneous
 High energy surfaces = glass, porcelain,tiles,aluminum
 Lower energy = appliance/plumbing coatings,PVC
flooring,poly(styrene) and related ABS plastics
 Evaporation of cleaner = evolution of a wide range of
surfactant/oil/water phases

4. Surface Modification Technology Can Deliver
New Consumer Benefits
 “Stays Cleaner, Longer” = delay formation of soap scum,
hard water spots on sink, shower.
 “Easier Next Time Cleaning” = faster, less effort
 Delivery from a familiar cleaner format
 Trigger sprayer, toilet cleaner liquid, disposable Wipe
 Or a novel format –
 Disposable head/nonwoven with a tool
 Reasonable pricing

5. Hydrophilic Surface Modification = Approach #1
To Deliver New Benefits
 Adsorb very thin (<100 nm) layers of hydrophilic polymers
during cleaning process
 Polymers that incorporate significant amounts of water
molecules in equilibrium with ambient air  Yield a disordered surface that is Gel-like
Hydrophilic Layers Can Deliver Both –
Hydrophilic Layers Can Deliver Both –
Soil resistance = poor wetting of household surfaces by
Soil resistance = poor wetting of household surfaces by
greases = lower adhesion energy
greases = lower adhesion energy
Soil release = easier cleaning
Soil release = easier cleaning

6. Deliver Soil Resistance with Hydrophilic
Polymers
γ LA cos θ= (γ SA – γ SL) Young – Dupre’
cos θ= (γ SA – γ SL) / γ LA
cos θ = 0 (at θ =90º)
γ LA = liquid oil/air tension (can measure !)
γ SA = solid/air tension γ SL = solid/liquid tension
γ LA of oil is fixed ! To prevent good wetting of the surface with oil, need to
decrease the difference term
“Polar” polymers raise γ SL- surface “resists” non-polar oil !
“Polar” polymer increases θ, decreasing adhesion
Liquid
Oil
Air
Solid
Air
Liquid
θ Oil
Solid

7. Improve Soil Release with Polymer/Water
Layers
 Reduce Work of Adhesion Under water –
∆ Wa = γ SO – γ OW – γ SW
 SO = solid/oil OW=oil/water SW=solid/water tensions
γ OW is fixed and large (40 mN/m)
 If γ SW small or vanishes, the energy change is driven by
how large γ SO gets !
 Oil release spontaneous at ∆ Wa = 0 !
Adsorbed polymer layers swollen with liquid water (“gels”)
affect both “controlled” tensions.
Water only “displacement” of oil possible.

8. Delivery of Polymers from Cleaners –
Challenges
 Bulk sacrificial films not of interest – poor aesthetics
 Polymer must compete with surfactants for surface
sites
 Polymer must not interfere with detergency
 Ideal polymer or mix of polymers will modify glass
and plastic surfaces
 Polymer adsorption onto emulsified oils, particulate
soils, or applicator is a waste
 Price/performance always an issue

9. Fourier Transform Infrared Spectroscopy Can
Guide Polymer Selection and Formulation
 Attenuated Total Reflectance (ATR) optical rig
 Characterize monolayers, sub-monolayers of surfactants, polymers
– adsorbed directly on internal reflection element (IRE)
 In thin film case (<200 nm) Absorbance ~ layer thickness
 Substrate for adsorption = Ge surface (model polar surface) = the
IRE ! (500 mm2)
 Adsorption time controlled, 5 min typical
 Remove solution, rinse with water
 (2.5 ml/rinse)

10. Internal Reflection Optics Key To Analysis of Surfaces – Including the
IRE Surface Itself !
IRE
(Ge)
Air
Refractive index = n1=
4.0
θ
Refractive index = n2 = 1.5
n21=n2/n1
Sampling depth, dp= 736
nm at 1650 cm-1
dp = λ/2π (sin2 θ − n21 2 )1/2

11. Multiple Reflections Aid Sensitivity with
Versatile Horizontal IRE
Ge surface can also
bear thin film of a
plastic polymer, i.e.,
polystyrene
Trough on Horizon rig
Classical multiple IRE
50 mm

12. Commercial Optics & Chamber Control
Atmosphere Over Adsorbed Layers
Trough – 2.5 ml capacity
Dry Nitrogen/Air
Input

13. Examples of Copolymers for Hydrophilic
Surface Modification
Dimethylacrylamide co - acrylic acid
DMA – AA
Tristyryl phenol ethoxylate ester of
methacrylic acid co - acrylic (or
methacrylic) acid
“Bigfoot” types
Y
X
O
O
O
OH
O
25
Monitor Amide & Acid Groups in
Spectra of Adsorbed Layers
Monitor EO & Acid Groups in
Spectra of Adsorbed Layers
And – Intense H-O-H stretching and bending bands in
And – Intense H-O-H stretching and bending bands in
FT-IR spectra = Water Uptake Monitoring
FT-IR spectra = Water Uptake Monitoring

14. DMA co AA stds on Ge from MeOH
Amide
CH3-N
Linear (Amide)
0.14
0.035
ATR spectra
resemble
transmission
spectra when film
thickness << dp.
0.1
0.08
0.03
0.025
0.02
0.06
0.015
0.04
0.01
0.02
0.005
0
0
0
5
10
micrograms applied to IRE
15
Absorbance CH3-N
Absorbance AMide I
0.12

15. DMA-AA Copolymer Takes Up Water from
Atmosphere At All Layer Thicknesses
DMA co-AA films on Ge IRE - calibration with cast films
.12
13.3 ug, approx 35 nm thickness - ambient air
Absorbance
.1
13.3 ug - under nitrogen purge
.08
.06
0.133 ug stds, approx 0.35 nm
thickness, purge and ambient air
.04
H-O-H
.02
0
4000
3500
3000
2500
Wavenumber (cm-1)
2000
1500
1000

16. Shifts in Amide I Consistent with Hydration in Air
– Leverage Literature on Proteins for Details
DMA co-AA films on Ge IRE - calibration with cast films
Amide I and H-O-H deform.
Not to same scale
Absorbance
.1
CH3-N
.05
13 ug - 35 nm "thick" film under nitrogen purge
COOH
0
-.05
0.133 ug - 0.35 nm "thin" film under purge
Thick film - ambient air
-.1
Thin film ambient air
1700
1600
1500
1400
1300
Wavenumber (cm-1)
1200
1100
1000
900

17. Reversible Water Uptake - Blanks vs. minimum DMA
2
co-AA 0.035 ug/cm (0.35 nm thickness)
Amide +Water
H-O-H
0.003
0.0025
Absorbance
0.002
0.0015
0.001
0.0005
0
-0.0005
Purge
blank
In air blank In air blank
immed
5 min
#2 Purge
#2 Purge
blank
blank 5 min
0.035

18. 2
DMA co-AA 3.57 ug/cm on Ge (35.7 nm thickness) - Reversible
Water Uptake
Amide + Water
H-O-H
Purge
2
#2 In
air 5
min
0.16
0.14
Absorbance
0.12
0.1
0.08
0.06
0.04
0.02
0
Purge
In air In air 5
1
immed
min
#2 In
air
immed
Purge
3
#3 In
air
immed
#3 In
air 5
min

19. DMA co-AA on Ge - Water Uptake at 5 min in Air Effect of Polymer weight - ug/cm 2
H-O-H
0.14
Water uptake increases
with amount of polymer
present. None of these
layers are visible to the
eye !
0.12
Absorbance
0.1
0.08
0.06
0.04
0.02
0
0, blank
0.035
3.57
14.24
49.06

20. Performance of Hydrophilic Polymer
Layers – FT-IR Also Useful
 Example – Bathroom Cleaning Formulations
 Resistance to build-up of soap scum desired
 Track soap scum formation via several FT-IR protocols
• Multiple Exposure
• Kinetic Exposure

21. Interactions of Hydrophilic Polymer
Layers with Soaps
 Sodium laurate = model soap

Phase behavior known – “soluble” at ambient temperature
• CMC = 20mM, pH > 8.5, T>23 C
• Forms crystal structures, adsorbed layers, etc. similar
to longer chain analogs
 C14,C16,C18 saturated acids
• Similar phase behavior, solubility, but at higher
temperatures = less convenient
 Oleate (cis 9,11 octadecenoate) soluble at ambient T

22. Use 1mM NaLaurate exposure to distinguish performance of
different polymers
 Multiple Exposure Protocol –
 Deliver an adsorbed polymer layer or product.
 Expose to NaLaurate 5 min, then vacuum off solution
 Dry under purge 1 min. Record spectrum
 Do four successive exposures.
 Then start rinse study. One “rinse” = fill trough with water, then vacuum off.
 Kinetic Exposure Protocol
 Deliver adsorbed polymer layer
 Fill trough with 1mM NaLaurate. Record spectrum every 2 minutes for 12
minutes
 Vacuum off NaL, record spectrum
 Fill trough with water. Record spectrum every 2 minutes during “desorption”

23. .8
Solid Na Laurate reference - 20 ul of 100mM solution dried on Ge IRE
COO - asymm
Absorbance
.6
CH2 str. asymm, symm
.4
.2
0
4000
3500
3000
2500
Wavenumber (cm-1)
2000
1500
1000

24. Solid Na Laurate reference - 20 ul of 100mM solution dried on Ge IRE
COO - asymmetric str
.7
.6
Absorbance
.5
.4
.3
CH2-C=O
CH2 def
COO- symm str
.2
CH2 wagging
.1
1600
1500
1400
1300
Wavenumber (cm-1)
1200
1100
1000

25. Net Scum Adsorption Depends on
Exposure/Rinse Protocol
Ge IRE Exposed to 1 mM NaLaurate - "Soap Scum" Buildup Test
Run 2 no rinse
Absorbance
.15
Run 2 12x water rinse
.1
Run 2 24x water rinse
.05
Run 1 no rinse
Run 1 12x water rinse
Run 1 24x water rinse
0
4000
3500
3000
2500
Wavenumber (cm-1)
2000
1500
1000

26. Crystalline Lauric Acid Adsorbs from Dilute
Solutions
Ge IRE Exposed to 1 mM NaLaurate - "Soap Scum" Buildup Test
.1
COO- asymm
Absorbance
.08
COOH
.06
no rinse
Na Laurate dried reference from 100 mM solution "bulk film"
.04
12x rinse
.02
Lauric acid adsorbed from 1 mM NaLaurate solution pH 8.5
CH2 def
C-OH acid
24x rinse
0
1800
1700
1600
1500
1400
1300
Wavenumber (cm-1)
1200
1100
1000
900

27. Lauric Acid Adsorbs, Then Crystallizes on
Surface – Kinetic Run Spectra, Under Water
1mM NaLaurate pH 7.8 Adsorbing on Ge
All to same scale
Liquid Water subtracted (0-12 min)
Final - dry
.08
12 min
Absorbance
10 min
.06
.04
8 min
6 min
4 min
2 min
0 min
.02
Wavenumber (cm-1)
3000
2950
2900
2850

28. 1mM NaLaurate pH 7.8 Adsorbing on Ge
All to same scale
Liquid Water subtracted (0-12 min)
Final - dry
12 min
10 min
Absorbance
.04
8 min
6 min
.02
4 min
2 min
0 min
0
-.02
1700
1600
1500
1400
Wavenumber (cm-1)
1300
1200
1100

29. Adsorbed Species Depends on pH
Ge Exposed to 1mM NaLaurate Effect of pH
Dried Layers in Air
Not to same scale
pH 6.5
.1
pH 7.8
pH 8.8
Absorbance
.08
.06
pH 9.8
.04
.02
0
2980
2960
2940
2920
2900
2880
Wavenumber (cm-1)
2860
2840
2820

30. Laurate Adsorbs Only from high pH
Monomeric Solutions
Ge Exposed to 1mM NaLaurate Effect of pH
Dried Layers in Air
Not to same scale
pH 6.5
pH 7.8
.06
pH 8.8
Absorbance
.04
pH 9.8
.02
0
-.02
Wavenumber (cm-1)
1700
1600
1500
1400
1300
1200
1100
1000
900

31. Exposure to 1 mM NaLaurate indicates  Lauric acid is adsorbed, not soap, at bulk conc. < cmc and “low” pH
 Consistent with early FT-IR studies of sodium laurate on Ge *
 Net amount of acid adsorbed depends on number of rinses between
exposures
 Real world soiling of surfaces with fatty acids and soaps begins at very
low concentrations during rinsing of basins, showers, and wiping of
countertops.
Soap scum starts with a hydrophobic layer that is too thin to
Soap scum starts with a hydrophobic layer that is too thin to
see.
see.
A mono-layer is all you need to change the nature of the
A mono-layer is all you need to change the nature of the
surface.
surface.
* Takenaka,T. Higashiyama,T. J.Phys.Chem. 1974,78,9

32. Significant Differences Between Anionic and
Amphoteric Polymers in Scum Prevention
Ge Surface with Polymers Exposed to 1 mM NaLaurate
Rinsing of Lauric Acid as Evaluated by CH2 Band
Control
Control 2
DMA:AA
Amphoteric Copolymer
Absorbance, CH2 Lauric Acid
0.3
0.25
0.2
0.15
0.1
0.05
0
Run
1
Run
2
Run
3
Run 12x
4
rinse
24x
36x
48x
60x
72x
84x
96x

33. Kinetic Protocol Probes Resistance of DMA
-AA and Others to Lauric Acid Adsorption
Polymers on Ge (0.5%, 5 min ads time) Exposed
to 1mM NaLaurate
No polymer
Polymer Mix A
DMA-AA
Polymer B
Polymer C
Absorbance, CH2 lauric acid
0.12
0.1
0.08
0.06
No Polymer
0.04
DMA-AA
0.02
0
0
2
4
6
time, mins
8
10
12

34. Polystyrene Surfaces Rendered Hydrophilic via
Adsorbed Layers of “Bigfoot” co – AA Polymers
.007
C-O-C, EO groups
all to same scale
.006
Under Water, Cycles 1,2,3
ps
ps
Absorbance
.005
C=O, ester,acid
.004
.003
ps
.002
Under purge, Cycles 1,2,3
.001
0
1800
1700
1600
1500
1400
1300
1200
1100
1000
Wavenumber (cm-1)
Copolymer layer is unchanged after 40x rinses/3 water immersions. Band
shifts show EO chains are not crystalline and readily hydrate !

35. Scum Resistance of Polymers on
Polystyrene/Ge Screened Via FT-IR
Polymers on Polystyrene Exposed to 1mM
NaLaurate
Bigfoot copolymer run1
Bigfoot run2
Polymer B
No polymer
Absorbance, CH2 Lauric acid
0.12
0.1
0.08
0.06
0.04
0.02
0
0
2
4
6
Time (min)
8
10
12

36. Macroscopic Perfomance – Black Acrylic Exposed to Bar
Soap & Hard Water – 5 Cycles
Untreated
Treated
Original Product Contact Time = 90 seconds, Then First Soap Exposure

37. Macroscopic Perfomance – Black Acrylic Exposed to
Bar Soap & Hard Water – 10 Cycles
Untreated
Treated

38. Macroscopic Perfomance – Black Acrylic Exposed to Bar
Soap & Hard Water – 15 Cycles
Untreated
Treated

39. Summary – Hydrophilic Approach
 Adsorbed monolayers of hydrophilic polymers can modify surfaces to
deliver consumer benefits - “Easier Cleaning” and “Stays Cleaner,
Longer”
 Uptake of atmospheric water into adsorbed layers is reversible and
essential to performance
 Control of the interactions of soluble soaps with surfaces needed in
bathroom applications
 Soap – surface interactions can be engineered with appropriate
polymers
 FT-IR is routinely used in evaluation of –
 Amounts of polymer adsorbed and water uptake
 Interaction of the polymer with oils, soaps, etc.

40. Approach #2 – Hydrophobic/Oleophobic
Modification
 Oleophobic = Deliver Adsorbed Layers of Anionic
Fluorosurfactant/Cationic Polymer Complexes
 Most useful = Reduced adhesion of oily soils
 Hydrophobic = Ordinary Anionic Surfactant/Cationic
Polymer Complexes
 Formulate in a RTU cleaner format
 Surfactant system = Mixed Nonionic/Anionic micelles
 Cationic polymer – Example DADMAC

41. Stepping Back a Moment - -
 Does everyone agree on what hydrophobic means ??

42. Surface Modification for Soil-Repellancy:
Defining Success
 High Contact Angle: Oil, Water
 Slide-off (roll-off, low hysteresis): Oil, Water
γL
γS
θ
γSL
air
solid
Young’s equation: γS = γSL + γL cos θ

43. Contact Angles and Sliding Droplets –
Common Truisms
θ
θ
smaller
Common
advancing / receding
contact angle
measurement
larger
better
wettability
worse
better
adhesiveness
worse
larger
Not always true!
contact angle
surface free energy
smaller

44. Drop Shape Analysis
 Equilibrium sessile drop contact angles obtained with Krüss
DSA-10L with tilting table feature
Test fluids
•Ultrapure H2O
•Anhydrous C16
For non-pinned
drops:
•Sliding angle, α
•θA and θR
γ
(A)
cing
van
L ad
γ
(R)
ding
e
L rec
θR
θA
α
air
solid

45. Hysteresis – the basics
Hysteresis: ∆θ = θA – θR for liquid on surface
 Liquid-solid adhesive bond
created during spreading
 Homogeneous smooth surface
may exhibit less hysteresis
 Recession of contact line can
break adhesive bond.
 θR > 0: liquid debonds from
solid; adhesive failure.
 θR ≈ 0: liquid – solid
adhesion > cohesive
strength of liquid; drop
ruptures and leaves a trail
= sheeting
mg sin α
θr
θa
α
mg cos α
mg

46. More on Hysteresis
 Hysteresis is particularly detrimental to hydrophobic surfaces.
 For minimum surface tilt of α, a droplet of surface tension γLV
with mass, m, and width, w, will spontaneously move:
m g (sin α) / w = γLV (cos θR – cos θA)
 Difference between θA & θR (hysteresis) is more important to
hydrophobicity than the absolute values of the contact angles!
Only water molecules on 3-phase
Only water molecules on 3-phase
contact line must move for drop to
contact line must move for drop to
move.
move.
DROP
TOP
VIEW

47. Hydrophobicity and Hysteresis
Pinned drops with any θ not very
useful !
Sliding drops are ideal to deliver
real consumer benefits !
Control of the composition and
uniformity of the adsorbed layers is
critical !

48. Both Fluorosurfactants Soluble @ 1% in Water – AT-1002
Has Fewer, More Hydrophobic Tines than PF 156
 Polyfox PF-156A from Omnova
 Polyfox AT-1002 (experimental)
Thomas, R.R., et. al, Langmuir, 2002, 18, 5933-5938
C-F stretching yields
intense IR
absorbance
Cationic Polymer
= pDADMAC

49. pDADMAC Binding To Micelles Depends on
Micelle Charge and Electrolyte
Mixed Nonionic/Ionic micelles interacting with a
Polyelectrolyte (opposite charge)
Micelle Charge Defined by “Y”
Y = [Ionic]
[Ionic] + [Nonionic]
A “critical charge” (σ crit) required for polymermicelle binding !!
σcrit ~ κb / q
κ= Debye-Huckel parameter, (nm )
-1
+
+
+
+
+
+
+
+
q = polymer charge spacing
b varies with micelle shape, polymer type
NH4+
Cl-
Mixed Anionic
Fluoro /
Surfonic micelle
Anionic
Fluorinated
Oxetane
+
+
+
+
+
+ +
+
+ +
+
+
+
+
+
+ +
+
+ +
+
+
+ +
+ +
+
Nonionic

50. Binding of micelles required to form
coacervate and precipitate
 Precipitate = polymer/surfactant phase, solid, no water
 Coacervate = polymer/surfactant – rich phase, with water
 Critical MW/size & near neutral overall charge
 Intrapolymer complexes yield interpolymer complexes
 Complexes reject some water, settle (“bottom” phase)
 Coacervation depends on
 Micelle Charge (“Y”)
 Polymer MW
 Screening” of charges by electrolyte (Debye length)

51. Critical [Polymer] Needed To Form Large
Complexes for Coacervation
System = p(DADMAC) / Triton X100 / SDS
Coacervate Formed at >
0.01% DADMAC, Aggregates
> 45 nm radius
Complexes But No Coacervates
– Aggregates Too Small !
Intrapolymer Complexes Only

52. Phase Behavior Variables = [DADMAC] &
Ratio of Anionic/Cationic groups = R
 Systems Made on 20 ml Scale – Rapid/Easy Mixing
 Nonionic = Surfonic L12-8, Constant @ 2 wt% (39 mM)
 Poly(DADMAC) Level Varied  @ Low = 0.3 mM (50 ppm)
 @ High = 3.0 mM (500 ppm)
 Anionic Fluoro-oxetane Varied  Cover R= Anionic/Cationic Equivalents – 0.04 to 8.0
 At low [DADMAC] = [Oxetane] = 0.001 to 0.25 %
 At high [DADMAC] = [Oxetane] = 0.01 to 2.2%

53. Surface Compositions Assessed With FT-IR
How Does Modification of Surfaces (within 5 minutes)
Depend on Location in Phase Boundary Diagram ?

54. Poly(DADMAC) Adsorbed on Ge – Adequate
Detection Limit < 0.5 mg/m2
Detection Limit (CH3-N+) < 0.3 mAU
Dried
Reference,
Not to
same scale
Dried, Rinsed
Freely Adsorbed
from 3 mM Solution

55. Intense Bands Available for Detection of
Fluorinated Oxetanes in Adsorbed Layers
Bands due to Coupled C-F, S-O, C-O-C stretching
C4F9 oxetane
C2F5 oxetane
SDS, hydrated
S-O Asymm.
Stretch
S-O Symm.
Stretch

56. PF156 (C2F5 chains) Systems Yield
Coacervates but No Precipitates
PF 156/Surfonic Interactions
with 3.0 mM DADMAC
clr
PF 156/Surfonic Interactions
with 3.0 mM DADMAC
2, clr+coacervate
clr
0.5
0.4
0.4
NaCl, M
0.6
0.5
NaCl, M
0.6
2, clr+coacervate
0.3
Net Cationic
Complexes
Net Anionic
Complexes
1
4
0.3
0.2
0.2
0.1
0.1
0
0
0
0.05
0.1
0.15
0.2
0.25
Y, Mole Fraction Anionic in Micelle
0.3
0
2
3
5
6
7
R= Anionic/Cationic Equivalents
8

57. AT 1002 (C4F9) Systems Show Collision of Precipitate
and Coacervate Regions. How does R Affect Surface
Modification ?
AT 1002/Surfonic
Interactions with 3.0 mM
DADMAC
clr
2, clr+ppt
AT 1002/Surfonic
Interactions with 3.0 mM
DADMAC
2, clr+ coacervate
2, coacervate+ppt
clr
2, clr+ppt
0.4
NaCl, M
0.5
0.4
2, coacervate+ppt
0.6
0.5
NaCl, M
0.6
2, clr+ coacervate
0.3
0.3
0.2
0.2
0.1
0.1
0
0
0
0.1
0.2
Y, Mole Fraction Anionic
0
1
2
3
4
5
6
7
R=Anionic/Cationic Equivalents
8

58. AT 1002/ 3.0 mM DADMAC – Adsorption Increases Near
Coacervate Boundary For Net Cationic Complexes @ R
< 1, High [Salt], 2-Phase Systems Reduce Adsorption
DADMAC CH3-N
0.008
0.006
0.004
0.002
=0
R .19
=0 3
R .37 0 M
=1 6
.9 0 Na
9 M C
R 70 N l
=4
a
.0 M Cl
R R= 0 Na
=0 8. M C
R .19 0 0 Na l
=0 5 M C
R .39 0 .1 Na l
=0 2 M C
.5 0 . N l
1
R 82 M aC
R =4. 0 .1 Na l
=0 0 M C
R .09 0.1 Na l
=0 9 M C
. 0
N l
R 217 .5 M aC
=
R 0.4 0 .5 Na l
=0 2 M C
.9 0
l
R 89 .5 M NaC
=7 0
.9 .5 Na l
4 M C
0. N l
5
M aC
Na l
C
l
0
R
No Drying Step !
C-F @ 1130
0.01
Absorbance
Adsorption conditions
= 5 minutes’
exposure of Ge IRE,
Then Rinsed 50x with
water
C-F @ 1236

59. At Low [DADMAC], Coacervate Region Reduced. How
Does Adsorption Change with R?
AT 1002/Surfonic Interactions
with 0.3 mM DADMAC
clr
2, clr + coacervate
AT 1002/Surfonic Interactions
with 0.3 mM DADMAC
2, clr+ppt
clr
0.6
1
2
2, clr+ppt
0.6
0.5
0.5
0.4
0.4
NaCl, M
NaCl, M
2, clr + coacervate
0.3
0.2
0.3
0.2
0.1
0.1
0
0
0.01
0.02
0.03
Y, Mole Fraction Anionic
0
0
3
4
5
6
Equivalents, Anionic/Cationic
7
8

60. AT1002 at Low [DADMAC] = Maximum Adsorption Near
Boundaries, But High [Salt], Net Anionic Complexes
Inhibit Adsorption
DADMAC CH3-N
C-F 1236
C-F 1136
0.01
0.008
0.006
0.004
0.002
0
R
=0
.
R 40
=0 0
.9 M
N
R 8,
= 7 0 aC
R .86 M N l
=0
a
0
R .40 M Cl
=0 0
N
.9 .1 aC
l
R 4, M
=1 0. N
.7 1 M aC
l
R 0
=0 0. N
.4 1 M aC
R
l
=0 0 0
N
.9 .5 aC
R 8, 0 M N l
=1
.8 .5 M aC
l
6
0. Na
5
M Cl
N
aC
l
Absorbance
Equal
Fluorosurfactant
Adsorption at 1/10
the Level - $$

61. Surfonic L12-8 is Absent From Adsorbed
Layers
Not to same scale
C-F, S-O
Stretching
Adsorbed Layer Spectra – AT 1002/Surfonic
@ low DADMAC
CH2 Stretching
of CH2-O
Adsorbed
Layer, R=1.70
CH3-N+
Adsorbed
Layer, R=0.94
CH2 Stretching
of Methylenes
in Tail
Reference Spectrum
Surfonic L12-8 Dried on
Ge
C-O-C
Stretching

62. Oil Repellancy with Sliding Drops is Possible via AT1002 Complexes, but not with Largest Contact Angle !
Contact Angle of Hexadecane in degrees
70
60
50
C16 Theta 0 M NaCl
C16 Theta 0.1 M NaCl
C16 Theta 0.5 M NaCl
C16 Theta(A) 0 M NaCl
C16 Theta(R) 0 M NaCl
C16 Theta(A) 0.1 M NaCl
C16 Theta(R) 0.1 M NaCl
C16 Theta(A) 0.5 M NaCl
C16 Theta(R) 0.5 M NaCl
40
30
20
10
0
0.3 mM pDADMAC
0.0
0.5
3 mM pDADMAC
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
[PF1002] in mM

63. Water Repellancy Possible with PF AT-1002
Complexes, But Many Drops are Pinned !
100
0.3 mM pDADMAC
3 mM pDADMAC
Contact Angle of Water in degrees
90
80
70
W
W
W
W
W
W
W
W
W
60
50
40
30
Theta 0 M NaCl
Theta 0.1 M NaCl
Theta 0.5 M NaCl
Theta(A) 0 M NaCl
Theta(R) 0 M NaCl
Theta(A) 0.1 M NaCl
Theta(R) 0.1 M NaCl
Theta(A) 0.5 M NaCl
Theta(R) 0.5 M NaCl
20
10
0
0.0
0.5
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
[PF1002] in mM

64. Proximity to Coacervate Drives Adsorption –
Factors
+
++
+
+
+
+
PE with bound micelles yield low charge density, thick
layers.
+
+
+ + +
+
+
+ + +
+ +
+
+
+
+ +
+
+
+
+ +
+ +
+
+
++
+
Micelles solubilize PE segments = More loops and tails
of PE = More flexible PE chains
Surf. Monomer - micelle exchange remains fast
Oxetane - DADMAC – Surface becomes hydrophobic =
Significant tail exposure
Adsorbed Layers of PEs Almost Never at Equilibrium
Significant
Lateral
Interactions of
Surfactants
++ ++ +
++
+ +
+
+
+ ++ ++ ++ + - - - - - - - - -
Nonionic
Anionic
surf
Na+
Mixed anionic /nonionic
micelle
Cl-

65. Conclusions – Hydrophobic Approach
 Complete drop slide-off demonstrates water- and/or oilrepellancy
 High contact angles (~ 90°) do not necessarily confer
repellancy
 Higher complex concentrations produce repellancy at
short adsorption times (5 minutes)
 Salt concentrations > 0.1 M NaCl are detrimental to
repellancy
 PF AT-1002 complexes at 3 mM pDADMAC and 0 – 0.1
M NaCl are able to achieve both water- and oilrepellancy

66. Conclusions – Hydrophobic Approach
 Control of Complex Size & Composition Critical
 Adsorption Kinetics Important (5 minutes or Hours?)
 Understanding structures formed important – cost$
 Oleophobic Modification Performance Correlates With
Fluorosurfactant Adsorption !
 AT 1002 (C4F9 groups) Far Superior
 Best performers are Compositions Near Coacervate Boundary
 FT-IR Useful for Monitoring Composition of Adsorbed Layers

67. Final Thoughts
 Hydrophilic Approach May Be Easier
 Depends on Anticipated Soil Types – Beware Soaps !
 Hydrophobic/Oleophobic Modification Possible !
 Understanding of Coacervate Boundaries Helps !
 Adjust Compositions to Avoid Pinning Oil & Water Drops
 Assess Performance via Drop Hysterisis
 “Targeted” Use of Expensive Materials
 Consumer-perceivable benefits from invisible (thin) layers !
 RTU Cleaning Formulations Possible – One Step
 Industrial/Professional Products Possible
 Labor Reduction in Janitorial Products – but Familiar Formats
 Aesthetic Improvements of Surfaces Encountered By Public

68. Thanks !
 Clorox Management
 Consumer Specialty Products Association
 Mona Knock
You – The Audience &
Consumer !!!