Development of High-

Performance Cement Composite

Using Cellulose Nanocrystals

ACI SPRING 2016

PRESENTED BY TENGFEI FU
APRIL 18TH, 2016
Collaborators:
Tengfei Fu, Prannoy Suraneni, Jason Weiss, Oregon State University

Yizheng Cao, Jeff Youngblood, Pablo Zavattieri, Purdue University

Robert Moon, Forest Products Laboratory

Undergraduate Researcher:

Celena Gerken, Oregon State University

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What is Cellulose Nanocrystal (CNC)?
Rod like nanoparticles (typically
50~500nm in length and 3~5 nm in
width)
Produced from micro cellulose by acid
hydrolysis process
Usually from trees and plants, can also
from algae and bacteria
Mostly (~100%) cellulose
Highly crystalline (54% ~ 88%) TEM Image of CNCs
extracted from wood
Moon, R. J., et al. (2011). "Cellulose
nanomaterials review: structure, properties and
nanocomposites." Chem. Soc. Rev. 40: 54.

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What is Cellulose Nanocrystal (CNC)?
Some unique physical and mechanical properties:
High aspect ratio (>50)
High elastic modulus ( 110~220 GPa)
High tensile strength ( 7.5~7.7 GPa)
Low density ( ~ 1.6 S.G.)
High surface area (up to BET 600 m2/g)

Some benefits
Renewability
Sustainability
low toxicity
potentially low cost

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Why cement and concrete?
Concrete is most widely used materials
15 billion tons are used annually
Do more with less
small amount of addition of CNCs to increase concrete performance
Nano materials have shown remarkable opportunity to potentially tailor
variety of concrete properties:
Higher strength
Manipulate setting
Faster strength gain
Lower cost
Last longer

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Where do the CNCs go in cement paste?
Steric Stabilization
The hypothesis is that the CNCs are
attracted to the cement particle surfaces

They cover the surface and this can lead

to a retarding effect

The initial reaction is slowed, however,

hydration reaction is increased at later
age

Yizheng Cao. Nano-modification for high

performance cement composites with
cellulose nanocrystals and carbon
nanotubes." Ph.D. Dissertation, Purdue
University, 2014
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Where do the CNCs go in cement paste?
Short Circuit Diffusion
What appears to happen is that the
CNCs attach to the surface of the
cement and provide physical or
chemically optimal channels where
the C-S-H can preferentially grow

It allows more hydration to take

place at later ages (like preferential
straw/path allowing diffusion)

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Cao et al. The influence of cellulose
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nanocrystal additions on the performance
of cement paste." CCC, 56, 2015
Objectives
How does CNCs interact with cement particles?
Will CNCs works with different cement systems?
Which is the most efficient system?

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Materials
Type V cement
Type I/II cement
Three CNCs
CNC1
CNC2
CNC3

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Materials Preparing Cement Paste
For Type I/II cement system, w/c = 0.40
For Type V cement system, w/c = 0.36
CNCs were added as 0.2% (volume) of cement
CNC1 were also added at higher dosages ( 0.5%, 1.0%, 1.5% 2.0%)
All CNCs were premixed with mixing water for 45 to 60 mins before mixing
using magnetic stirrer to achieve better dispersion.
A vacuum mixer was used to minimize entrapped air.

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Isothermal Calorimeter Type I/II Cement

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Isothermal Calorimeter Type V Cement

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Isothermal Calorimeter
Heat release CNC1 different dosage
Type V Type I/II

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Isothermal Calorimeter Total Heat Release

CNC2 CNC3 CNC1 CNC1 CNC1 CNC1 CNC1

Mix Control
0.2% 0.2% 0.2% 0.5% 1.0% 1.5% 2.0%
237 260 272 255 258 269 280 n/a
7 Day Heat
Type V (J/g cement) Diff: 23 35 17 21 31 43 n/a

308 320 322 319 319 320 322 328

7 Day Heat
Type I/II (J/g cement) Diff: 12 14 11 11 12 14 20

Type V Type I/II

C3S 62% 53%
C2S 12% 18%
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C3A 0 7%
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C4AF 13% 11%
Isothermal Calorimeter V.S. TGA
For Type V cement
system, CH increase
correlates well with
heat release of
difference dosage
For Type I/II system,
the correlation is
weak, suggesting
possibly other phases
are affecting heat
release
For Type I/II CH
content decreased for
CNC1 0.2%

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Isothermal Calorimeter - Summary
All CNCs increase DOH for both Type I/II and Type V cement system
Much more increase in Type V (10-15%) than Type I/II (4-6%)
High dosage of CNCs tends to retard reason more in the early age, but
increase overall heat release in the later age
Aluminate phase (C3A) might affect effectiveness of CNCs
Evidence points to that C3A might hinder the interaction between
CNCs with calcium silicate phases
More work is on the way to blended synthesized C3A phase with Type
V cement
Might provide insight into how to use CNCs efficiently with day to day
Type I/II cement

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B3B Flexural Strength
Ball-on-three-ball
biaxial stress state
For this study, 2 disk
(50 mm diameter)
with 2.5 mm thickness
was used

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B3B Flexural Strength Repeatability Type V Cement

Mix CNC1 0.2% CNC1 0.2% Repeat

3 Day (Mpa) 11.81 11.63

Std Dev. (Mpa) 0.691 0.517
COV 5.8% 4.5%

Mix CNC1 0.2% CNC1 0.2% Repeat

7 Day (MPa) 16.57 16.12
Std Dev. (Mpa) 0.719 0.828
COV 4.3% 5.1%

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B3B Flexural Strength Different CNCs Type V Cement

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B3B Flexural Strength Different dosages Type V Cement

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B3B Flexural StrengthDifferent dosages Type I/II Cement

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B3B vs Heat Release

CNC1 @ different dosage, Type V Cement

B3B strength correlates

well with DOH for UM
below critical dosage
(~1.0%)
High dosage (1.5%) further
High dosage (1.5%) increases DOH, however,
CNCs agglomerates and
serves as defects
Better dispersion could be
a solution.
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Summary
CNCs effectively increase degree of hydration in portlant cement system
For Type V cement system, 10-15% at 7 day
For Type I/II cement system, 4-6% at 7 day
Cement composite with CNCs had higher early age strength (3 day) in the
Type V cement system.
Dispersion is the key
Some CNCs are more efficient than others
Further research is needed to understand how different cement
composition affect CNC effectiveness
Aluminate phase (C3A) seems to be the key

Questions? Comment? Contact:

Jason Weiss: Jason.Weiss@oregonstate.edu
Tengfei Fu: Tengfei.fu@oregonstate.edu
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