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Surface Interactions between

“small” particles

You need to know

Determine when small particles will

coagulate or deposit (stability)
What is small?
Inertial and viscous forces are not relevant for small particles

When can the DLVO theory be used? Why

do we care about the secondary
minimum?
Apply surface interaction theory to
environmental engineering problems

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Fine aerosols <2.7 µm Coarse aerosols >2.7 µm

Sedimentation

Surface forces (chapter 6) can stabilize suspensions and hinder sedimentation

Polydisperse suspensions 3

Interaction of small charged

particles
3.1 Introduction
3.3 Acquisition of Surface Charge
3.4 Particle size, shape
3.5 Double layer theory (take notes)
DLVO application (take notes)
Paper presentation

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Select the statement that makes the

most sense to you (Q1)

A. Most micro and nano-sized particles can settle

by sedimentation
B. Surface charge of particles can control particle
aggregation
C. It is NOT possible to manipulate surface
charge of particle
D. Things always attract each other
E. Things always repel each other

Examples of relevance of particle

interactions

Conditions for two surfaces to stick to

each other according to the DLVO theory
Environmental implication of secondary
minimum deposition
Conditions for which DLVO theory does
not work for water treatment or transport in
subsurface

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Aerosols
Less reflection

20um

2 mm

Contributes to It prevents coallescence

greenhouse effect and formation of rain droplets

Select the statement Estuarine Deposition

that makes the most
sense to you (Q2)
A. Water is clearer in the
river compared to the sea.
B. Higher salinity in the sea
allow particles to sink
C. Particles in river water
sink because of low
salinity
D. I have no idea
E. Salinity does not control
clarity of water in river and
sea http://openlearn.open.ac.uk/rss/file.php/stdfeed/2457/formats/T210_1_rss.xml

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Lower salinity

Select the statement that makes the most

sense to you (Q3)
A. Small particles have small surface
area A
B. Small particles have large surface
area A
C. Large particles have large surface
Total volume of a solid= 1 cm3 area A
D. Size does not matter.

N=Number of particles in 1 cm
A1=Surface area/particle

A=A1*N [m2]

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Stabilization of colloids in the

environment
A few words about nanotechnology
Cosmetics, paints, coatings, CNTs, semiconductor industry, NPs for
catalysis, etc…
Release of NPs in the environment can have serious
implications, e.g. concerns regarding health
No sedimentation by inertial and viscous forces
Important to determine when small particles aggregate
or stick to surfaces
Why are colloids stable?
Surface charge stabilizes small particles
How can surface charge be created
In aerosols: by transfer
In aquasols: by adsorption, (de)protonation, differential loss of ions

Differential loss of ions from the

crystal lattice

If a crystal of Agl is placed in water, it starts to dissolve

If equal amounts of Ag+ and l- ions were to dissolve, the surface would be uncharged
In fact Ag+ ions dissolve preferentially leaving a negatively charged surface

http://www.silver-colloids.com/Tutorials/Intro/pcs22.html

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Adsorption of charged species

(ions, and ionic surfactants, polymers)

RSO3-

RSO3-

http://www.silver-colloids.com/Tutorials/Intro/pcs22.html

Ionization of Surface Groups

pH influence

http://www.silver-colloids.com/Tutorials/Intro/pcs22.html

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MS2 capsid
Bacterial virus

Red= glutamic and aspartic acid

(pKa=4, anionic)
Ionizable aminoacids Orange=lysine (pKa=7.6 and 10.8, cationic)

lysine (pKa=7.6 and 10.8, cationic)

Because of the ionizable groups on

the surface (Q4)
A. Surface charge does not depend on pH
B. Surface charge depends on pH

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Isoelectric point
The zeta potential of particles suspended in solution can be measured

40 Isoelectric point
is the pH
Rotavirus

Zeta Potential (mV)

20
MS2 condition, at
0 which there is
no net surface
-20
charge
-40
2 4 6 8 10
pH

MS2 bacteriophage
Rotavirus

At isoelectric point, (Q5)

A. Aggregation of particles is minimum;

B. Aggregation of particles is the same as
at other pH
C. Aggregation of particles is maximum
D. None of these is correct
E. I have no idea

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Surface is charged because of (Q6)

A. Presence of ionizable groups at the

surface
B. Defects in the crystal lattice
C. Adsorption of charged species
D. All of the above
E. None of the above
Methods to measure surface charge of hydrosols and aerosols are available

Electrical Double Layer

Stern Layer is another name for Double Layer Debye length is the distance over which significant charge separation can occur

OHP - Outer Hemlholtz Plane Proper Definition given in later slides

H2O

Diffuse layer

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Electrical double layer

Zeta Potential - the potential difference existing between the surface of a solid
particle immersed in a conducting liquid (e.g., water) and the bulk of the liquid.

Zeta
Particle negatively charged potential

Stern layer Slipping plane: ions do not feel

attraction/repulsion to the
charged particle

At neutral pH, hematite nanoparticles are

positively charged. Select the statement that
makes the most sense to you (Q7)
A. In 1 mM NaCl solution with unadjusted pH,
hematite nanoparticles are negatively charged
B. In 1 mM NaHCO3, hematite nanoparticles are
negatively charged
C. In 0.5 mM NaHCO3, hematite nanoparticles
are positively charged
D. In 0.1 mM NaHCO3, hematite nanoparticles
are positively charged
E. I have no idea

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hematite
20
nanoparticles
Zeta Potential (mV)
0

-20

1mM 1mM 0.5 mM 0.1 mM

NaCl NaHCO3 NaHCO3 NaHCO3

In 1 mM NaHCO3, hematite
nanoparticles are negatively charged,
because (Q8)
A. Hematite surface contains ionizable
groups
B. Defect is present in the hematite crystal
lattice
C. HCO3- adsorb onto hematite surface

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Debye-Hückel Model for the Double

Layer
Zeta y x ∼ y 0 exp ( -k x )
potential
Stern layer
Diffuse layer

-80
Surface potential
-70

-60 Stern potential

at the Stern plane

potential [mV]
-50

-40
Zeta potential
-30
Stern Slipping at the slipping /shear
plane plane -20 plane
-10

0
0 20 40 60
distance from particle surface
[nm]

Zeta potential
Debye-Hückel Model
for the Double Layer

Y = Y 0 exp(-k x)
Y = electric field potential
Y 0 = electric field potential at the surface (x = 0) Stern layer Slipping
plane
Assumption: the potential is low |zieY |<< kT
e 2 å zi2ni¥
k2 = i
ee 0kT
1/ k = double layer thickness or Debye length

Smaller Debye length means thinner double layer

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Debye length
The Debye length (1/κ) represents the
distance from the colloid surface at which the
potential has decayed to 37% of the surface
potential
e åz n Characteristic length of DL,
2 2
i i¥
k = 2 i commonly assumed as the
ee 0kT thickness of the DL
e = proton charge
k = Boltzmann constant
e 0 = permittivity in vacuum
e = relative permittivity in water
zi =ion valence
ni¥ = ionic number concentration of bulk solution

Debye length depends on ionic

strength
-1/2
k -1 (nm) = 0.307 ´ éë I ùû

120.00
Debye length (nm)

100.00
80.00
60.00
40.00
20.00
0.00
0.001 0.01 0.1 1
Ionic Strength (M)

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Consider 1 mM of each of the following

salts: NaCl, CaCl2, and AlCl3. Place the
salts in order of increasing ionic
strength at the same salt concentration
(Q9)?

A. AlCl3; NaCl; CaCl2; 1

B. NaCl; CaCl2; AlCl3 I =
2 i
z 2
åC
i i
C. CaCl2; NaCl; AlCl3
D. CaCl2; AlCl3; NaCl;
E. They have the same ionic strength

Consider particles in either 1mM NaCl

solution or 1 mM CaCl2 solution. In which
solution, particles have smaller Debye
length (Q10)?

-1/ 2
k -1 = 3.04 ´ 10 -10 I

A. CaCl2 solution
B. NaCl solution

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Important: origin of the double layer

repulsion!

Double layer interaction between

two charged surfaces (excel file)
80
70 1mM

60 3mM
Interaction energy [kT]

1
50 10mM

40 30mM

30 60mM
20 120mM
2
10
0
0 5 10 15 20
separation distance h [nm]

pee 0 a1a2 (y 01
2 2 é
+ y 02 ) ê 2y 01y 02 æ 1+ exp ( -k h) ö ù
VEDL (kT ) = ln ç ÷ + ln (1- exp(-2k h)) ú
(a1 + a2 )kT ê (y 01 + y 02 ) ç 1- exp ( -k h) ÷
2 2 ú
è êë ø úû
a1;a2 = particle size
y 01;y 02 = surface potential (e.g. zeta potential) Similar example: Aggregation and Deposition
Kinetics of Fullerene (C60) Nanoparticles
h=separation distance Kai Loon Chen and Menachem Elimelech
Langmuir, 2006, 22 (26), pp 10994–11001

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Consider two particles with same size and same

surface potential (value and sign). Select the statement
that makes the most sense to you (Q11).

A. Smaller Debye length means less attraction

between these two particles
B. Smaller Debye length means more attraction
between these two particles
C. Smaller Debye length means less repulsion
between these two particles
D. Higher Debye length means less repulsion
between these two particles
E. I have no idea

Van der Waals interactions –

usually attractive forces
10
8
Interaction Energy (kT)

6
4
2
0
-2 0 5 10 15 20
-4
-6
-8
-10
Separation distance h (nm)

Aa
Vvdw (J ) = -
12h(1+14h / l )
A: Hamaker constant; l :dielectric constant Similar example: Aggregation and
Deposition Kinetics of Fullerene (C60)
Nanoparticles
Kai Loon Chen and Menachem Elimelech
Langmuir, 2006, 22 (26), pp 10994–11001

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DLVO interactions V DLVO

= VVDW +VEDL
70
1mM
60 Energy barrier
3mM

Interaction energy [kT]

50
10mM
40
30mM
30
60mM
20 120mM
10

-10
0 5 10 15 20
separation distance [nm]
Secondary minimum
Energy barrier decreases with ionic strength
Reversible attachment at secondary minimum
Aggregation and Deposition Kinetics of Fullerene (C60) Nanoparticles
Kai Loon Chen and Menachem Elimelech
Langmuir, 2006, 22 (26), pp 10994–11001

Secondary Minimum – Greater distances between particles but attraction causes flocculation. Particles form weak
attractions but are easily redispersed. Reversible

DLVO theory
Increase ionic strength by adding salt allow
particles to aggregate because of double layer
compression
DLVO consider only CHARGE SCREENING that
reduces the Debye length
Prediction of aggregation between particles and
deposition of particles onto surfaces
DLVO DOES NOT consider ion specific effects,
charge regulation, bridging etc…
There are non-DLVO interaction forces!

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Atomic Force Microscopy (AFM) to

measure interaction forces

Sharp tip

Colloidal probe,
it can be coated with molecules of interest

Ionization of polar aminoacids

Aspartic Acid: pKa 3.86 Glutamic Acid: pKa 4.07

VP4

Lysine: pKa 10.53 VP7

VP8

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Rotavirus Interaction with silica

Force-distance curve between rotavirus and
silica sphere upon separation
0.4 + Silica is
3 mM Na
negatively charged
Adhesion Force (nN)

0.2
0.0
-0.2 1 mM
2+
Mg
-0.4 2+
1 mM Ca
-0.6
-0.8 pH=7.0
0 20 40 60 80
Distance (nm) Ion specific effects!
Attraction (Aggregation)

Attachment Kinetics of MS2 on NOM

(~adsorption kinetics on NOM)
Ion specific effects also affects adsorption kinetics!

1
Attachment Efficiency ( )

MS2
CaCl2

0.1

MgCl2
0.01 pH=7.0
0.0 0.2 0.4 0.6 0.8 1.0
Cation Concentrations (mM)

Pham, et al., Journal of Colloids and Interface Science, 2010

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Attachment Kinetics of MS2 on

NOM
) 0
Ca2+ > Mg2+ > Na+
10
Ion specificity
Attachment Efficiency (

2+
Ca
-1
10 Na+ screens the charge
Mg
2+ Na
+
which reduces double layer
10
-2 thickness and energy
barrier
detection limit
-3
Mg2+ adsorbs onto the
10
1 10 100 surface and it neutralizes
Ionic Strength (mM) the surface charge
Ca2+ form bonds with both
MS2 and NOM surface
(ion-bridging)
Yuan et al., 2008 and Pham et al., 2009

Consider particle deposition onto a surface in

either NaCl or CaCl2 solution at the same IONIC
STRENGTH. What does the DLVO theory predict
(Q12)?

A. Same deposition for both solutions

B. Faster deposition in NaCl solution
C. Faster deposition in CaCl2 solution
D. No prediction
E. I have no idea

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Ca2+ in solution

Ca2+ in solution

Mg2+ in solution
COO-

Mg2+ in solution
COO-

-
-

COO-

COO-
-

-
carboxylate group of NOM

Na+ only screens the charge to reduce double layer thickness;

Mg2+ adsorbs on the surface and it neutralizes the charge
Ca2+ form bonds with both MS2 and NOM surface
Why? Still subject of research – perhaps related to the much
stronger hydration shell of Mg2+

Adsorption of charged species (ions

and ionic surfactant)

http://www4.ncsu.edu/~hubbe/Defnitns/DefnitnGIFs/Slide9.GIF

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What happens when you add increasing amount of

Al3+ or Fe3+ to a colloid dispersion in water (Q13)?
The colloids are slightly negatively charged and
the solution is turbid …

A. Turbidity decreases
B. Turbidity increases
C. Turbidity increases and then decreases
D. Turbidity decreases and then increases
E. Turbidity decreases, then increases, then
decreases

Virus in 10 mM NaCl

10 M NaCl Interaction Energy Profiles

10.00
8.00
6.00
Interaction Energy (kT)

4.00
2.00
0.00
-2.00 0 5 10 15 20
-4.00 V VDW (kT)

-6.00 V EDL (kT)

-8.00 Vtotal (kT)
-10.00
Separation distance (nm)

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Virus in 50 mM NaCl
50 mM NaCl Interaction Energy Profiles

10.00
8.00
6.00
Interaction Energy (kT)

4.00
2.00
0.00
-2.00 0 5 10 15 20
-4.00 V VDW (kT)

-6.00 V EDL (kT)

-8.00 Vtotal (kT)
-10.00
Separation distance (nm)

Virus in 75 mM NaCl

75 mM NaCl Interaction Energy Profiles

10.00
8.00
6.00
Interaction Energy (kT)

4.00
2.00
0.00
-2.00 0 5 10 15 20
-4.00 V VDW (kT)
Secondary minimum V EDL (kT)
-6.00
-8.00 Vtotal (kT)
-10.00
Separation distance (nm)

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Virus in 140 mM CaCl2

140 mM CaCl2 Interaction Energy Profiles

10.00

8.00
6.00
Interaction Energy (kT)

4.00
2.00
0.00
-2.00 0 5 10 15 20

-4.00 Secondary minimum V VDW (kT)

-6.00 V EDL (kT)
Vtotal (kT)
-8.00
-10.00
Separation distance (nm)

What do you expect to happen?

(Q14)
75 mM NaCl Interaction Energy Profiles

A. Virus aggregate in
10.00
8.00
6.00
Interaction Energy (kT)

solution of 75 mM
4.00
2.00
0.00

NaCl and 140 mM

-2.00 0 5 10 15 20
-4.00 V VDW (kT)
-6.00 V EDL (kT)
-8.00 Vtotal (kT)

CaCl2. -10.00
Separation distance (nm)

B. Virus do not
aggregate in both 10.00
140 mM CaCl2 Interaction Energy Profiles

solutions
8.00
6.00
Interaction Energy (kT)

4.00
2.00
0.00
-2.00 0 5 10 15 20

-4.00 V VDW (kT)

-6.00 V EDL (kT)
Vtotal (kT)
-8.00
-10.00
Separation distance (nm)

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AFM to measure Debye length

Fit of the DLVO equation to force curve

Bad prediction for the virus… why?

15
Debye Length (nm)

10 virus-silica

silica -
5
PC membrane

predicted PC membrane (-)

0
1 10 100
Ionic Strength (mM)
Non-DLVO forces (additional repulsion)

Why does the Debye length not

change with ionic strength?
20
virus-virus
Debye Length (nm)

virus-silica
10

silica -
PC membrane
predicted
0
1 10 100
Ionic Strength (mM)

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Non-DLVO forces
Virus can be considered as soft
particle, which is covered with an
ion-penetrable surface layer of
macromolecules.
This soft layer cannot be
compressed completely to allow
Ohshima, H. Colloid Polym. Sci. 2007, viral particles to aggregate

Rotavirus MS2 bacteriophage

Interaction Force Can Be

Described by empiric models
Interaction Force (nN)

1mM NaCl
0.4

0.2

0.0
0 5 10 15 20 25 30 35 40
Na+
Na+
Separation Distance (nm)
Na+ Na+

Na+ Na+
Na+
silica surface

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The extraordinary stability of virus

suspension (Q15)

A. allows better removal of virus

B. prevents common water treatment
technologies to remove virus
C. prevents virus to spread
D. none of the above
E. I have no idea

Electrophoresis and zeta potential

Zeta potential measurement
• Potential at the slipping plane (shear plane)
• Can be determined from electrophoretic mobility
(measured)
ee 0z
ue = for k a > 1 and z £ 50mV
m
ue = electrophoretic mobility
e 0 = permittivity in vacuum
e = relative permittivity in water
k = Debye length
a = particle radius
z = zeta potential

http://www.malvern.com/labeng/technolo
gy/images/zeta_potential_schematic.png

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