Thixotropy, Flocculation and

Laser Spectroscopy

Jae Hong Kim, Associate Professor, UNIST, Korea

Hong Jae Yim, Assistant Professor, KNU, Korea
Surendra P. Shah, Professor Emeritus, Northwestern Univ., IL

ACI Spring 2016 Convention

Milwaukee, WI
April 19, 2016
CONTENTS

Introduction

Experimental design

Effect of time on flocculation

Effect of binding materials

Conclusions
Introduction (1)
Freshly mixed concrete is a granular materials, and its microstructure
is composed of the cement suspension at a micrometer scale.
Flocculation and agglomeration of cement particles is supposed to
govern the change in the rheological properties and the evolution of
solidifying microstructure.

Cement
Sand

Gravel

Cement suspension Sand in paste Gravel in mortar

Jae Hong Kim (jaekim@unist.ac.kr)

Introduction (2)
Cause and effect of flocculation
Colloidal interaction
Percolation How to measure
the flocculation?
Shear thinning
Thixotropy

Jae Hong Kim (jaekim@unist.ac.kr)

Typical setup for a diluted sample
Laser diffraction technology measures the particle size distribution.
(1) Our cement paste sample should be diluted in alcoholic solution
(2) Use an overhead stirrer for the particles to move at the focus

Diagram from Particle Sizing Systems, Inc. Jae Hong Kim (jaekim@unist.ac.kr)
 In-situ particle size measurement
Laser backscattering technology
allows to measure the floc size
distribution in an intact cement
paste sample.

Rotating
Optics Focusing
Lens

Fiber 1 min 2 min 3 min

Volume Fraction (%)

Fiber-Optic 18
12
Coupler
Coupling
Lens Sapphire
6

Window
0

0 10 20 30 40 50
Particle size (μm)

Diagram from Sequip GmbH Jae Hong Kim (jaekim@unist.ac.kr)

Flocculation stability at a shearing
Floc size in cement suspension depends on the intensity of shearing
Measurement on a neat cement paste of which w/cm=0.45
The median size at 150 s-1 or 1 s-1 was 120 um or 160 um, respectively

Diluted in In-situ measurement on

alcohol the cementitious paste

18 μm 120 μm 160 μm
Median (D50)
1
135 313

Jae Hong Kim (jaekim@unist.ac.kr)

Laser backscattering-rheometer
The experimental setup was proposed to
control the applied rate of shear strain
The laser backscattering probe was
assembled in the parallel-plates geometry

Yim, Kim, and Shah (2013), Cem Concr Res 53, 36-43 Jae Hong Kim (jaekim@unist.ac.kr)
Size distribution at rest
Do we expect that the particle size increases over time?
(1) The cement particles follow a lognormal curve.
(2) Large-sized particles unevenly increases over time.
(3) But it is hard to say the size distribution increases (moves right).

0.1

Larger flocs evolve w/cm=0.4

Probability Density Function

0.08

0.06 0 min
5 min
10 min
0.04 15 min

0.02

0
0 50 100 150 200 250 300 350 400
Particle Size (um)

Jae Hong Kim (jaekim@unist.ac.kr)

 Size distribution at 10 s-1 or 100 s-1
0.06
• The mean of the size
Both mean and standard deviation
distribution increase by
Probability Density Function

0.05
increase at low shearing (10 s-1)
0.04
flocculation.
0 min
0.03
5 min • Flocculation gradually
develops, which causes
10 min
15 min
0.02
to increase the
0.01 standard deviation.
0
0 50 100 150 200 250 300 350 400
Particle Size (um)

0.05

Both mean and standard deviation • On the contrary, high

shearing breaks the
Probability Density Function

0.04
decrease at high shearing (100 s-1)
flocs in a moment.
0.03 0 min
5 min
Deflocculation is
10 min instantaneous, and
the particles get mono-
0.02 15 min

0.01
sized. As a result, the
standard deviation of
0 particle sizes decreases.
0 50 100 150 200 250 300 350 400
Particle Size (um)

Jae Hong Kim (jaekim@unist.ac.kr)

Change in the packing density    
[ ]M

 1  
 c  M 
Krieger-Dougherty equation
Increasing the packing density gives the decrease of the viscosity
Compressible packing model by de Larrard
1
 i 1 
   
M  min i 1   1  i  bij 1  1  j  i y j   1  aij 1  j  i y j 
n

 
i
j 1 j i 1

Jae Hong Kim (jaekim@unist.ac.kr)

 Effect of binder materials
Cement paste, ground granulated blast-furnace slag, and their blend
were tested, where their solid volume fraction is fixed: ϕ=0.42.
(1) At a low rate, the cement and slag pastes have an identical size
distribution. So does the slag-cement paste.
(2) At a high rate, deflocculation in the cement paste is intenser. The
slag-cement paste follows the intense deflocculation.
0.015 0.015
BS40-PC60
Measured

Probability Density Function

Probability Density Function

BS40-PC60
Measured
Calculated
Estimated
Calculated
Estimated
PC
Cement
PC
Cement
0.01 0.01 BS
Slag
BS
Slag
At a high rate
At a low rate

0.005 0.005

0 0
0 200 400 600 0 200 400 600
Particle Size (um) Particle Size (um)

Jae Hong Kim (jaekim@unist.ac.kr)

Microstructure of the suspension (1)
A diluting layer (thickness, b) covers the flocs (diameter, d), which is
supposed to dilute the maximum packed state
d
The diagonal of a diluted FCC becomes 2(b+d) b
d

Its unit volume, 𝑉 = 2 2 𝑏 + 𝑑 3

1 𝜋𝑑3 𝜋 𝑑 3
Its solid volume fraction, 𝜙 = ×4=
𝑉 6 3 2 𝑏+𝑑

The diluting thickness, 𝑏Τ𝑑 = −1 + 0.905𝜙 −1Τ3 Diluting

layer Agglomerates
For the example of the cement, 𝜙=0.42 and d=160 um,
The diluting layer is given by b/d=0.208
The mean separation is then b=33 um
𝟐 𝒃+𝒅

Van der Waals attraction, when b <<10 µm

(Soua et al, Colloids Surfaces A 274 (2006) 1–10)
Face centered cubic (𝜙𝑚=0.74)
DLVO interparticle potential, when b/d<<0.25
(Yang et al., Adv Cem Based Mater 5 (1997) 1–7) Jae Hong Kim (jaekim@unist.ac.kr)
Microstructure of the suspension (2)
The pulverized cement particles get flocculated and the flocculated
particles construct a volume-spanning gel network in cement paste.
The particle interaction on such a high separation is thought to be a
capillary pressure of the gel network, rather than colloidal forces.

3 3
Microstructural stability ∆𝑉 𝑉2 − 𝑉1
= =
𝑑2
−1 ∆𝑝 =
1
1−
𝑑2
of a suspension 𝑉 𝑉1 𝑑1 𝛽 𝑑1

Sample Cement Slag Blend

paste paste paste
Particles 18 um 18 um 18 um
Flocs at 1 s-1 161 um 169 um 160 um
Flocs at 150 s-1 111 um 144 um 109 um
Capillary pressure 1.46 GPa 0.83 GPa 1.49 GPa
Viscosity at 1 s-1 2.60 Pa·s 0.85 Pa·s 1.68 Pa·s
Jae Hong Kim (jaekim@unist.ac.kr)
Conclusions
In-situ floc size measurement
• An experimental setup was proposed to monitor the flocculation at a controlled
shear rate: Laser backscattering probe was coupled with a rheometer.
• The floc sizes in a cement paste decrease with a higher rate of shear strain.
Effect of time on flocculation: Change in the packing density
• At a low shear rate (10 s-1 ), gradual flocculation was observed: Both mean and
standard deviation increase over time.
• High rate of shearing (100 s-1) reduces the dimension of the cement flocs, and
the deflocculation is instantaneous – also decrease in the standard deviation.
• The size distribution determines the change in the packing density and
consequently addresses the viscosity change over time.
Effect of binding materials: Capillary pressure stabilizes the floc-gel network
• Cement paste shows larger difference in floc size according to the rate of shear
strain: intenser flocculation than ground granulated blast-furnace slag.
• Higher pressure is needed for self-stability of the cement paste, which causes
to increase its viscosity.
Jae Hong Kim (jaekim@unist.ac.kr)