Reactivity of nano-particles in cementitious

systems
Marné ◊
Helbing , YonathanGv [ □
Reches , Dr. Florence Sanchez□
◊Department of Engineering, University of Tennessee-Martin, Martin, TN 38237
]
□Department of Civil and Environmental Engineering, Vanderbilt University, Nashville, TN 37235

INTRODUCTION AGGLOMERATION OF NP’S CONCLUSIONS

Background:
Nano-particles (NP’s) have been added to cement products
to improve mechanical and durability properties[1]. This
contribution has been attributed to the NP’s high surface
area to volume ratio[1]. However, previous studies have yet
to define the specific chemical reaction between NP’s and
cementitious systems.
Objectives:
Methods:
 Dispersion of nano-anatase-TiO2 by probe sonicator for  NP’s and fly ash reacted pozzolanically as observed by
40 minutes (steady state for particle size) mass gain; steady state has yet to be achieved.
 Solution chemistry modified by salts (Ca(OH)2, NaOH,  Nano-TiO2 largely agglomerated even in deionized water.
KOH, KCl, and K2SO4)  Ions found in cement porewater caused further
 Particle size (i.e. agglomerate size) and zeta potential (ZP agglomeration by a combination of balancing surface
i.e. charge near surface) measured by dynamic light charge and screening charges through the solution.
scattering. Agglomeration was observed at significantly lower
Results and Discussion: OH - concentrations than in cement porewater.
-OH -OH
-OH

 Characterize intrinsic and catalytic reactivity of NP’s in

-OH
-OH
-OH -OH

cement-based systems -OH

FUTURE STUDIES
 Distinguish the effect of cement chemistry on the 1. 2. OH 3. OH 4. - -
-OH  Analyze nano-TiO2/cement pastes with SEM/EDS
agglomeration of nano-TiO2 1. Mostly positive sites near outer surface of NP  Examine the NP’s/cement pastes using DSC-TGA
2. OH- attach to positive sites of NP; ZP decreases  Evaluate the effects of the various NP’s on the hydration
3. OH- cover the positive sites; ZP is ~0 mV; charge
NP’S REACTIVITY balancing
of cement
 Study the effects of polycarboxylates utilized as ligands
Methods: 4. Higher concentration of ions between NP’s; charge
 Reaction of solid phases with dissolved Ca(OH)2 for the screening
formation of new binding phases (i.e. pozzolanic reaction) Zeta potential of various salt solutions - ACKNOWLEDGEMENTS
[2]
60
OH salts reach ~0
in the cement system , monitored by sample mass change. 40
mV (point of zero
 NP’s (nano- SiO2, TiO2, α-Al2O3, γ-Al2O3, α-Fe2O3, γ- Research was made possible in part through
Zeta Potential (mV)

20
KCl electrostatic the Vanderbilt Institute of Nanoscale Science
Fe2O3, bentonite and halloysite) immersed in Ca(OH)2, to K2SO4
0
repulsion). KCl and
study the pozzolanic reactivity of NP’s alone.
KOH
-20 NaOH
and Engineering (VINSE),Vanderbilt
K2SO4 remain
 Fly ash (FA) containing NP’s immersed in Ca(OH)2, to -40
Ca(OH)2
University Civil and Environmental Lab with
positive.
study effect of NP’s on pozzolanic reaction of FA. -60
1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00
a special thanks to Prof. Florence Sanchez,
Normality (mol anion/L)
Z average particle size of salt solutions with anion OH Ph.D. and Yonathan Reches, MS. This work was
Results and Discussion:
800.0 Two points of
supported by the National Science Foundation Research
700.0
agglomeration due
600.0
Experience for Undergraduates, Grant DMR-1263182 and
to surface charge
Z average (nm)

500.0 KOH
Halloysite appeared to DOE NEUP DE-NE0000734.
400.0
NaOH balancing (~10-4
be the most 300.0

200.0
Ca(OH)2
mol/L) and charge
pozzolanically reactive. 100.0
screening (~10-2 REFERENCES
0.0
1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00
mol/L).
F. Sanchez and K. Sobolev, “Nanotechnology in concrete-A
Normality (mol OH/L)

800
Z average particle size of salt solutions with cation K [1]
review,” Construction and Building Materials, vol. 24, pp. 2060-
700

600
Agglomeration for 2071, 2010.
SiO2 appeared to be Cl- and SO42- anions
Z average (nm)

500 KCl

the most catalytic for

400
K2SO4 occurs only for [2] F. Massazza, “Pozzolana and Pozzolanic Cements, “Lea’s
300

the hydration of FA. 200

KOH
charge screening. Chemistry of Cement and Concrete,” edi. 4, pp.471-635, 1998.
100

0
1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00 SEM background image provided by Yonathan Reches
Normality (mol anion/L)