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 Strength–Different 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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