Materials and Design 51 (2013) 810–818

Contents lists available at SciVerse ScienceDirect

Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Effect of cellulose microcrystalline particles on properties

of cement based composites
Catalina Gómez Hoyos a, Emilien Cristia b, Analía Vázquez a,⇑
a
Polymer and Composite Materials Group, Institute of Engineering in Technology and Science (INTECIN), Engineering Faculty, University of Buenos Aires,
National Research Council (CONICET), Las Heras 2214 (C1127AAR), Buenos Aires, Argentina
b
École Normale Supérieure de Cachan, Département Génie Civil Francia, France

a r t i c l e i n f o a b s t r a c t

Article history: The hydrophilic character and water retention capability of cellulose microcrystalline particles (MCC), are
Received 24 December 2012 useful properties to achieve new developments in cement based materials. This work evaluates the
Accepted 17 April 2013 influence of interactions between MCC, cement particles, hydration products and water; on rheology,
Available online 25 April 2013
hydration kinetic, microstructure and mechanical properties of cement based materials. The effect of
MCC on mechanical properties of cement mortars with 0 wt.% and 3 wt.% of MCC, were evaluated by
Keywords: flexural and compression tests within two curing procedures (i) regular curing: specimens were cured
Cellulose microcrystalline particles
28 days into lime stone solution (pH 13) at room temperature, (ii) accelerated curing: specimens were
Portland cement
Rheology
cured into a lime stone saturated solution for 7 days at room temperature followed by 7 days at 50 °C.
Hydration kinetics Finally they were kept in a dry oven at 60 °C for 48 h. Thermogravimetric analysis was used to character-
Precast pieces ize the effect of curing procedure and MCC addition on hydration degree of cement materials with 0 wt.%
and 3 wt.% of MCC. Results showed that interactions between MCC, cement particles, hydration products
and water, decreased the workability and delayed the hydration reaction. Additionally, results from ther-
mogravimetric analysis showed that, both accelerated curing and MCC addition increased the hydration
degree of cement materials because of increases in temperature during the curing process and because of
MCC releases its water content, contributing to hydration process. From results discussion it was found,
that MCC could be added to increases the hydration degree of based composites; additionally it was
concluded that cement based composites with MCC could be used to elaborate precast pieces.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction tration process. Finally the filter cake is suspended in water and
subjected to a spray drying process, yielding the MCC with a size
Natural fibers are constituted by several cellulose microfibrils, distribution and moisture content according to the conditions of
where cellulose chains are arranged in two types of conformations: the last two stages [6].
an amorphous conformation, characterized by its flexibility; and a The MCC have been widely utilized in the food, cosmetics and
crystalline conformation in which the cellulose chains are disposed medicine industries; as stabilizers for aqueous suspensions, flow
in organized and repetitive arrays to form crystals [1–4]. Micro- controllers and as reinforcement of final product [4,5,7]. However,
crystals of cellulose microfibrils are highly hydrophilic, have high until now there are not known publication that investigate the use
water retention capability and excellent mechanical properties: of cellulose microcrystalline particles in cement based materials.
an elastic modulus of about 150 GPa, superior to glass fibers Developments in cement based materials have shown great pro-
(85 GPa) and aramide fibers (65 GPa) modulus [4,5]. gress for humanity, because their usefulness in infrastructure,
Hydrolyzing the cellulose chains, MCC can be extracted from housing and transport [8]. Portland cement is a combination of
vegetable matter by means of a diluted mineral acid at its boiling minerals specially formulated and processed to react with water
temperature. The hydrolysis process removes most of the amor- by several physical and chemical processes, known as hydration.
phous fraction and destroys the fibrillar morphology of cellulose Water is a substance strongly involved in elaboration of cement
as follows: first vegetable mater is selected and cuted, then is based materials, therefore the hydrophilic character and the water
hydrolyzed converting insoluble hydroxides, oxides and sulfates retention capability of MCC, are interesting properties to consider
of vegetable mater in soluble compound that are removed by a fil- exploring potential applications of MCC in cement material.
This work studies interactions between MCC, products of ce-
⇑ Corresponding author. ment hydration and water. In addition, it was analyzed how those
E-mail address: avazquez@fi.uba.ar (A. Vázquez). interactions modify rheology, hydration reaction and hydration

0261-3069/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.matdes.2013.04.060
 C. Gómez Hoyos et al. / Materials and Design 51 (2013) 810–818 811

Table 1 evaluate the possibility of use MCC to develop new cement based
Mineralogical composition of Portland cement of low alkali 40. composites. Techniques used in this work are not commonly used
Mineral Composition (%) to characterize cement based materials. However its information
MgO 0.7 resulted useful to characterize cement based materials with MCC
SiO2 20.6 and to develop applications for cement based composites with
CaO 63.5 MCC as a building material.
Al2O3 3.9
Fe2O3 4.6
Na2O 0.5 2. Materials
K2O 0.6

2.1. Portland cement

Cement Portland Low Alkali CP40, following Argentinean stan-

dard IRAM 50.000 from Cemento Loma Negra Argentina, with
391 m2/kg of blaine surface was used as received. The general com-
position of this cement is presented in Table 1; this cement was
used to achieve a lower pH on cement materials and reduce the
possibility of cellulose degradation by the alkaline environmental.

2.2. Sand

Cement mortars with 0 wt.% and 3 wt.% of MCC were elaborated

using standardized sand supplied by MPA Stuttgart University in
accordance with EN standard 196-7 [13].

2.3. Cellulose microcrystalline particles (MCC)

The cellulose microcrystalline particles provided by Sigma

Aldrich were saturated for 2 days in water. Fig. 1 shows the field
Fig. 1. FE-SEM images of cellulose microcrystalline particles used to elaborate
emission scanning electronic microscopy images of MCC used in
cement materials. this work. Sigma Aldrich reported that MCC have the size distribu-
tion shown in Table 2.
The following methodology was applied to estimate the amount
of water absorbed by MCC and replace it to elaborate the fresh ce-
degree. Until now are known few investigations on the subject of
ment mix: a proportion of 0.5 g of MCC were mixed with 3 ml of
cement based materials with micro and cellulose nanofibers; their
water and left standing for 3 days at 25 °C, to promote saturation.
results usually are focused on the mechanical properties of cement
After 3 days the saturated solution, was separated into two phases
based materials without study the interactions between micro and
by centrifugation at 3000 rpm during 25 min. Following several
nanocellulose fibers and cement particles and without determine
tests, it was found that 0.5 g of MCC absorbed about 1.05 ml of
how those interactions changes the properties of cement based
water, which corresponds to 100% of its own volume and 230% of
composites. Mohamed et al. [9] studied the effect of microcellulose
its own mass. The MCC bulk density was calculated by a volumetric
addition to a self-compacting concrete mix. They found that micro-
method. It occurs that 0.5 g of MCC occupied a volume of 1.09 ml,
cellulose fibers addition (21 wt/v.%) increased compression and
therefore MCC have a bulk density of 0.459 g/ml.
flexural resistance after 7 of curing. Moreover, Peters [10] deter-
mined that adding 3 wt.% of a mixture of micro and cellulose
nanofibers to a reactive powder concrete with high compressive 3. Methods
strength, increased their impact strength by 53%. Additionally,
Claramunt et al. [11] elaborated cement mortars with nanofibrillar 3.1. Cement pastes elaboration
cellulose to studied its mechanical properties; they concluded that
addition of 3 wt.% of nanofibrilar cellulose increased significantly The composition of cements pastes with 0 wt.% and 3 wt.% of
flexural properties after 28 days of curing. The work of Nilsson MCC are presented in Table 3; cement pastes were named by its
and Sargenius [12], is the most recent publication on this filed; MCC content. A Hobart planetary mixer (Model N-50) was used
they developed Portland cement mortars with 0.11, 0.22 and to mix both cement pastes, following a procedure very similar to
0.33 wt.% of recycled cellulose microfibers from the paper indus- described in the EN standard 196-7 [13]. In case of cement paste
try; in order to characterize changes in workability of fresh mix- with 3 wt.% of MCC, first saturated MCC mixture was added to
ture, and changes in mechanical properties, autogeneous Portland cement, and then the remaining water was added. The
shrinkage by drying and capillary absorption properties of cement mixer was set at the low speed setting for 30 s and then paused
mortars in hardened state. They concluded that, cellulose microfi- for 90 s. A paddle was used to scrape the sides of the mixing bowl
bers addition modifies the rheology; decreases the mechanical during the first 30 s of pause. After the pause, the mixer was set at
properties and has no effect on drying shrinkage properties. How- the high speed setting for 60 s.
ever they found that cellulose microfibers addition had a positive Cement pastes were prepared using 3 wt.% of MCC, based on re-
effect on the water absorption: increases strongly absorption resis- sults reported by Peters et al. [14]. They found that 3 wt.% of micro-
tance because cellulose microfibers modify the pore structure of cellulose provided the greatest increment in mechanical
cement mortars. properties. Higher additions of microcellulose decreased the work-
The aim of this work is investigate the effects of MCC on prop- ability of the fresh material increasing the super-plasticizer
erties of cement based materials in fresh and hardened state, to requirements.
812 C. Gómez Hoyos et al. / Materials and Design 51 (2013) 810–818

Table 2 3.4. Density determination for cement pastes (PUV)

Mass proportions used to elaborate cements pastes.

Material 0 wt.% 3 wt.% The test of mass per unit weight or density determination was
Cement BA 1 1 carried out on cement pastes with 0 wt.% and 3 wt.% of MCC in
Water 0.45 0.45 fresh state; results were used in calculus of yield critical stress val-
MCC (wt.%) by weight of cement BA None 0.03 ues. This test was performed following ASTM: C-138.

3.5. Monitoring early hydration reaction for cement pastes, from

Table 3 adiabatic temperature data over time
Mass proportions used to elaborate cements mortars.

Material M 0 wt.% M 3 wt.%

In order to study the hydration kinetics on cement pastes with
0 wt.% and 3 wt.% of MCC, a semi adiabatic box of
Cement BA 1 1
Sand/cement 2.7 2.7
150 mm  150 mm  150 mm was fabricated using Styrofoam
Water/cement 0.45 0.45 sheets of 15 mm thick and expanded polyurethane foam to fill
CMF (wt.%) by weight of cement BA None 0.03 the voids between the box and the specimen. The fresh cement
paste specimen was placed at the middle of the box. The scheme
of the semi-adiabatic box and the measure system used are shown
3.2. Cement mortars elaboration in Fig. 3. The semi adiabatic box was placed in a temperature con-
trolled room at 25 °C and the temperature was measured with a
The composition of Portland cement mortars with 0 wt.% and Test Electrical Electronic Corp data-logging using a K thermocouple.
3 wt.% of MCC are presented in Table 3; cement mortars were The temperature of the system increases as the hydration reaction
named by the letter M followed by the MCC content. A Hobart plan- proceeds, therefore the rate of hydration reaction can be repre-
etary mixer (Model N-50) was used to mix both cement mortars in sented as the slope of the curve temperature vs. hydration time
a procedure very similar to described in the EN 196 standard. In [22]. However, this system is not completely adiabatic and is nec-
case of cement paste with 3 wt.% of MCC, first saturated MCC mix- essary an energy balance to calculate the global heat transference
ture was added to Portland cement, and then the remaining water coefficient (U), and correct the adiabatic temperature. Eq. (1)
was added. The mixer was set at the low speed setting for 30 s. shows the energy balance on the semi adiabatic box:
After 30 s of mixing, the sand was added steadily during the next dT exp da  
30 s, after that the mixer was set at high speed for 30 s; then the q  Cp ¼ ðDHÞ  q  U T exp  T 0 ð1Þ
dt dt
mixer was paused for 90 s. A paddle was used to scrape the sides
With U is the global transfer heat coefficient per unit mass, Texp is
of the mixing bowl during the first 30 s of pause. After the pause,
measured temperature, T0 is room temperature, Cp is specific heat,
the mixer was set at the high speed setting for 60 s. In order to
t is time and a is hydration degree, DH is hydration heat and q is
compare mechanical properties prismatic specimens were manu-
the density.
factured (40 mm  40 mm  160 mm).
Integrating Eq. (1) when ddta ! 0, leads to:
Two different curing procedures were evaluated in both cement
   
mortars and cement pastes [14]: ln T exp  T 0 ¼ ln T exp 1  T 0  U 0 ðt  t1 Þ ð2Þ
where (Texp1, t1) are the particular set of values at the beginning of
3.2.1. Regular curing the integration and U 0 ¼ qUC p is assumed to be constant.
After 24 h specimens were unmolded and just placed into a Eq. (3) shows the relationship between experimental and adia-
lime stone saturated solution for 28 days at room temperature. batic temperatures:
dT ad dT exp  
¼ þ U 0 T exp  T 0 ð3Þ
3.2.2. Accelerated curing dt dt
After 24 h specimens were unmolded and placed into a lime
where Texp is the experimental temperature and Tad is the adiabatic
stone saturated solution for 7 days. Then the specimens were
temperature.
maintained for 7 days more into a lime stone saturated solution
Finally integrating Eq. (3), leads to expression used to calculate
at 50 °C. Finally they were kept in a dry oven at 60 °C for 48 h.
the adiabatic temperature:
Z t
3.3. Slump test for cement pastes T ad ¼ T exp þ U 0 ðT exp  T 0 Þdt ð4Þ
0

Stoppage tests like slump test are commonly used in civil engi-
neering because are cheaper and could be developed on-site con- 3.6. Thermogravimetric analysis (TGA)
struction work. They consist in measuring the shape of a fresh
material deposit after flow occurred. This kind of tests are based With the aim of study the effect of MCC addition and curing
on the fact that if shear stress in tested sample is smaller than yield procedure on hydration degree, cement pastes with 0 wt.% and
stress, flow does not occurs [15–19]. 3 wt.% of MCC were subjected to a thermogravimetric analysis be-
The slump test was developed using a mini-cone test. It is a tween 25 and 800 °C at 10 °C/min under N2; in a thermogravimet-
smaller version of the Abrams cone for concrete; its dimensions rical analyzer (Shimadzu TGA-50).
are shown in Fig. 2a and b shows the final shape of a cement paste
tested. Mini slump test was conducted on cement pastes with 3.7. Mechanical test for cement mortars
0 wt.% and 3 wt.% of MCC. This test was realized following the
ASTM: C-143. The mini-cone was supported on a flat glass; Three point and compression tests were performed in a Baldwin
once its entire volume was filled the mini-cone was lifted to allow universal machine for cement mortars with 0 wt.% and 3 wt.% of
the cement paste to flow. When the fresh cement past reached the MCC. Those tests were carried out in accordance to EN standard
equilibrium the slump was measured. 196-1 [20].
 C. Gómez Hoyos et al. / Materials and Design 51 (2013) 810–818 813

Fig. 2. Images form mini-slump test for cement paste. (a) Sketch of the cone used in mini-slump test. (b) Images of the slump test for cement paste with 3 wt.% of MCC.

Fig. 3. Scheme of semiadiabatic box developed to measure the adiabatic temperature of cement pastes during the early hydration reaction.

3.8. Microstructure analysis Additionally, the MCC are saturated with water and therefore,
products of cement hydration growing close to them and use some
The microstructure of all cement materials was analyzed using of its water content for its formation. The size of CSH crystals and
a Zeiss Supra 40 Field emission scanning electron microscope (FE- porosity of cement materials depends on cement composition and
SEM) operated at 3 kV. especially on water cement ratio (w/c) [8,21]. If the proper w/c is
used, the CSH crystals reaches lengths between 6 and 8 lm, like
3.9. Energy dispersive X-ray spectrometer (EDX) the CSH crystals observed Fig. 4a and b. As mentioned in materials
and method section, MCC used in this work have the size distribu-
Energy dispersive X-ray spectrometer (EDX) attached to the FE- tion shown in Table 2. Therefore the MCC are around 4 times big-
SEM operated at 20 kV was used for identifying the MCC in cement ger than the CSH crystals, with size distribution near to air voids
materials. size. The air voids, are voids intentionally incorporated into freshly
mixed cement to protect the cement material from freezing and
thaw processes [8,21].
4. Results and discussions
Size distribution and composition are the most important dif-
ference between MCC and cellulose pulp commonly used to elabo-
4.1. Microstructure analysis of cement bases materials with MCC
rate cement based composites [22–24]. Fibers of cellulose pulp
have lengths between 0.8 and 1.5 mm [25,23], additionally hemi-
To understand the results of this research, first it is necessary
cellulose and lignin in low concentrations are still present in cellu-
understand the interactions between MCC, hydration products, ce-
lose pulp, making them more susceptible to degradation in alkaline
ment particles and water. Fig. 4a–c shows the FE-SEM images of
environmental [26]. Micrometrical sizes of MCC make them more
three different MCC surrounded by calcium silicates hydrated crys-
reactive than cellulose pulp, therefore MCC interact with hydration
tals (CSH). The MCC have highly hydrophilic character and highly
products more closely than cellulose pulp.
water retention capacity, therefore they could link closely with
the CSH as can be observed in Fig. 4b and c. The ability of interac-
tion between the MCC and the hydration products as the CSH or 4.2. Mini-slump test for cement pastes
calcium hydroxide (CH) is because MCC are constituted by several
bonded chains of cellulose with three hydroxyl groups per anhy- The method proposed by Roussel et al. [16], was used to calcu-
droglucose unit [1]. Those free –OH groups gives to MCC the ability late the yield stress from slump test. The surface tension effects
to interact through hydrogen bonds with other compounds con- were neglected because they are smaller than yield stress conse-
taining hydrogen atoms in its structure like CSH and CH [1]. quences. Roussel et al. [16], proposed this model for a finite volume
Agglomeration of MCC in cement materials was not observed in of fluid that is released on a horizontal plate, following the next
microstructure analysis because affinity between MCC and hydra- three assumptions: (i) the initial shape of the fluid is conical; (ii)
tion products favored the dispersion of MCC in cement matrix. there is not angular velocity and (iii) the characteristic length of
814 C. Gómez Hoyos et al. / Materials and Design 51 (2013) 810–818

Fig. 4. FE-SEM image of cement based materials with 3 wt.% of MCC. (a) cement mortar with 3 wt.% of MCC. (b) cement paste with 3 wt.% of MCC. (c) FE-SEM image of cement
paste with 3 wt.% of MCC.

Table 4 erned by diffusion and occurs slowly therefore it could be ne-

Results from PUV and mini-slump test. glected [21]. After calculate U0 for every test, the experimental
Specimen q (kg/m3) Diameter (m) s0 (Pa) temperatures were corrected using Eq. (4). Fig. 5b shows the
0 wt.% 1805 ± 1.3 0.17 ± 4.8E-4 0.55 ± 0.01 curves of adiabatic temperature vs. time, for cement pastes with
3 wt.% 1766 ± 5.1 0.14 ± 4.9E-4 1.43 ± 0.02 0 wt.% and 3 wt.% of MCC. The addition of 3 wt.% of MCC delayed
the hydration reaction; additionally cement paste with 3 wt.% of
MCC reached a maximum adiabatic temperature 5 °C lower than
cement paste with 0 wt.% of MCC (Table 5). Polysaccharides are
the contact surface is larger than the characteristic length of the
admixtures commonly used in construction industry to modify
fluid depth. They deducted Eq. (5) and we used it to calculate the
the water retention ability of the cement materials [27], with the
yield stress of cement pastes.
secondary effect of delaying the hydration reaction because:
225  qgV 2
s0 ¼ ð5Þ (1) Absorption of polysaccharides in the surface of anhydrous
128  p2 R5
particles of cement and CH crystals, forming a water-resis-
where q is the density of the tested sample, g is the gravitational tant film on cement particles that is hydrolyzed with time
constant, V is the tested sample volume and R is the slump [28–32].
measured. (2) Formation of complexes between ions of CH solution and the
Results from mini slump test are presented in Table 4. The addi- polysaccharides, increasing solubility of CH and decreasing
tion of 3 wt.% of MCC decreased the slump of cement past in 3 cm. its rate of formation [28–32].
Cement paste in fresh state is constituted by a large number of (3) Formation of insoluble derivatives by the interaction
small suspended particles interacting via colloidal forces, like between the polysaccharide and the pore water solution or
Van der Waals, electrostatic repulsion, steric hindrance and hydro- alkaline solution, these derivatives are precipitated around
gen bonding, and some bigger particles that interact via direct con- anhydrous cement particles forming a protective layer that
tact like friction or collisions and the yield stress (s0) is the stress prevents water ingress [28–32].
necessary to break those interactions and separate the particles
[15–19]. As mentioned above the free –OH groups in MCC gives Additionally, Pourchez et al. [29] studied the delay produced by
them the ability of interact through hydrogen bonds with hydra- different cellulose ethers in hydration reaction of cement pastes,
tion products, cement particles and water through hydrogen the molecular structure and specially the degree of substitution
bonds; increasing s0 by 2.6 times respect to cement paste with of cellulose ether influence significantly the delay of this reaction;
0 wt.% of MCC. because greater number of hydroxyl groups in cellulose molecule,
The increment in s0 generated by MCC addittion, increases the generates a larger number of interactions between cellulose mole-
energy costs in construction, because it will be necessary higher cules, cement particles and cement hydration products, increasing
compaction energy and higher pump power to transport concrete the delay in hydration reaction.
from one side to another. However cement materials with high The heat generated by the hydration of cement increases the
s0 values are useful to elaborate precast pieces; during processing temperature of concrete. During normal concrete construction that
of these pieces is necessary that material retains the shape of the heat is dissipated into the environment therefore the temperature
mold, and does not flow easily outside it to be able to remove of structure decrease rapidly. However in massive structures such
the formwork rapidly. Additionally cement materials with high as dams, mat foundations, or any element more than about a meter
s0 values are also useful to elaborate rigid pavements in which is or yard thick, the heat cannot be readily released. These tempera-
required that mixture keeps its shape in fresh state. ture rises cause expansion while the concrete is hardening. If the
temperature rise is significantly high and the concrete undergoes
4.3. Monitoring early hydration reaction of cement paste, using data in non uniform or rapid cooling, stresses because of thermal contrac-
adiabatic temperature time tion in conjunction with structural restraint can result in cracking
[8]. Therefore the reduction in adiabatic temperature generated by
Fig. 5a shows the experimental temperature curves of cement MCC addition will be useful where larges masses of concrete are
paste with 0 wt.% and 3 wt.% of MCC. The U0 values presented in Ta- used. Since a reduction of 6 °C in maximal adiabatic temperature
ble 5, were calculated for every test using the curve data far apart implies a significantly reduction in the heat generated by hydra-
from the curve plateau because at this time the reaction is gov- tion reaction.
 C. Gómez Hoyos et al. / Materials and Design 51 (2013) 810–818 815

Fig. 5. Temperature curves during the hydration reaction. (a) Experimental temperature. (b) Adiabatic temperature.

Table 5 observed that the MCC are constituted by carbon and are sur-
Global heat transference coefficient and maximal adiabatic temperature. rounded by cement hydration products principally constituted by
Sample U 0 ¼ qUC p (min1) Tad max (K) calcium and silicon. As mentioned above, MCC were saturated be-
fore cement material elaboration. When MCC absorbed water they
0 wt.% 0.0025 341
3 wt.% 0.0019 323
swell; the reverse process of water absorption and swelling is the
water removal and shrinkage of MCC [1]. The FE-SEM images pre-
sented in Fig. 6a and d show that there are voids between the ce-
ment matrix and the MCC because; they shrinkage after release the
water retained within their structure.
4.4. Effect of MCC and curing procedure on hydration degree of cement
On the other hand, Fig. 7a and b shows the TGA and DTGA anal-
pastes
yses for cement pastes with 3 wt.% of MCC cured by both proce-
dures standard and accelerated; in Fig. 7b are observed three
The chemical structure of cellulose increases its volume signif-
peaks related with three thermodegradation processes: (i) The first
icantly to retain large quantities of water and as its structure re-
peak is observed below 200 °C and is associated with evaporation
leases water, returns to its initial volume. It was necessary use
of free water and water presented on CSH surface [8,21,33]. (ii)
EDX analysis to localize the MCC in cement materials. Fig. 6a–d
The second degradation process associated to the peak at 450 °C
shows the FE SEM and EDX images of cement mortar, it could be
is attributed to CH dehydration shown in Reaction (6). (iii) The last

Fig. 6. FE SEM and EDX images for cement materials with 3 wt.% of MCC. (a) FE-SEM imagen of the interface between a MCC and cement paste. (b) Location of the carbon
atoms in FE-SEM image. (c) Location of the calcium atoms in FE-SEM image. (d) FE-SEM imagen of the interface between a MCC and cement mostar. (e) Location of the carbon
atoms in FE-SEM image. (f) Location of the calcium atoms in FE-SEM image.
816 C. Gómez Hoyos et al. / Materials and Design 51 (2013) 810–818

Fig. 7. Effect of curing method on hydration degree of Portland cement pastes. Thermogravimetric analyses of cement paste with 3 wt.% of MCC cured by different curing
processes. (a) TGA and (b) differential TGA (DTGA).

Fig. 8. Effect of MCC content on hydration degree of Portland cement pastes. Thermogravimetric analyses of cement paste with 0 wt.% and 3 wt.% of MCC. (a) TGA and (b)
differential TGA (DTGA).

thermodegradation process, occurs around 700 °C is attributed to CaðOHÞ2ðSÞ ! CaOðSÞ þ H2 OðgÞ ð6Þ
decomposition of calcium carbonate shown in Reaction (7)
[8,21,33]: CaCO3ðSÞ ! CaOðSÞ þ CO2ðgÞ ð7Þ
 C. Gómez Hoyos et al. / Materials and Design 51 (2013) 810–818 817

Fig. 9. Stress strain typical curves of mortar from compression test (a) mortar with 0 wt.% of MCC and (b) mortar with 3 wt.% of MCC.

Table 6
Compression modulus (E) and flexural strength (r) from stress–strain curves for cement mortars.

Specimen E (GPa) E (GPa) r (MPa) r (MPa)

Standard curing Accelerated curing Standard curing Accelerated curing
M 0 p/p% 52 ± 1.9 55 ± 3.4 9.5 ± 0.3 11 ± 0.8
M 3 p/p% 45 ± 0.4 51 ± 1.9 7 ± 0.4 10 ± 0.3

The intensity of those three peaks is directly related with the hydration process progresses; the MCC releases its water to
degree of hydration reached by the material [8,21,33]. As can be increasing the hydration degree, like was evidenced by the volume
observed in Fig. 7b peaks corresponding to water evaporation change observed in FE-SEM images shown in Fig. 7.
and CH dehydration of cement paste cured by accelerated process
increased its intensity respect to cement paste cured by standard 4.5. Mechanical tests for cement mortars
process, because of increment in temperature during the curing
procedure. Additionally Fig. 8a and b shows the TGA and DTGA Fig. 9a–d shows the stress strain curves for compression and
analyses for cement pastes with 0 wt.% and 3 wt.% of MCC both flexural tests for cement mortars with 0 wt.% and 3 wt.% of MCC.
cured by accelerated process. It could be observed that peaks cor- A summarize of results obtained from mechanical tests is presented
responding to water evaporation and CH dehydration incremented in Table 6. Flexural strength and compressive modulus were deter-
significantly their intensity in cement paste with 3 wt.% of MCC re- mined according to EN standard 196-1 [20]. Table 6 compares the
spect to cement paste with 0 wt.% of MCC. Therefore cement paste compression modulus and the flexural strength of cement mortars
with 3 wt.% of MCC cured by accelerated process, reached higher with 0 wt.% and 3 wt.% of MCC under two conditions of curing. The
degree of hydration than cement paste with 0 wt.% of MCC cured addition of cellulose microfibrils decreased the modulus and flex-
by accelerated process. This is because as mentioned above, the ural strength for cement mortar cured by standard curing. However
MCC has a substantial capacity for water retention and as the cement mortars cured by accelerate curing process increased their
818 C. Gómez Hoyos et al. / Materials and Design 51 (2013) 810–818

modulus and flexural strength, because of an increment in hydra- References

tion degree of cement materials, as consequence of water releasing
that favored the creation of new hydration products. [1] Fengel D, Wegener G. Wood—chemistry, ultrastructure, reactions. 1st
ed. Berlin: Wiley; 1984. p. 613.
The implementation of a thermal curing process increased sig- [2] Bledzki AK, Gassan J. Composites reinforced with cellulose based fibres. Carbon
nificantly the hydration degree of cement paste with MCC; and im- 1999;24:221–74.
proved the mechanical behavior of cement mortars with MCC. The [3] Abe H, Ryo F. Review – the orientation of cellulose microfibrils in the cell walls
of tracheids in conifers. A model based on observations by field emission-
change in hydration degree and in mechanical properties with cur- scanning electron microscopy. IAWA J 2005;26(2):161–74.
ing procedure also represents an advantage in the development of [4] Azubuike CP, Esiaba J. Investigation into some physico-technical and tableting
precast pieces. Since processing of precast pieces requires a special properties of low-crystallinity powdered cellulose prepared from corn
residues. J Pharm Res Opin 2012;8:94–8.
curing procedure that allows the piece obtains a determined
[5] Azizi Samir MAS, Alloin F, Dufresne A. Review of recent research into cellulosic
mechanical properties, related to their degree of cure. whiskers, their properties and their application in nanocomposite field.
Biomacromolecules 2005;6(2):612–26.
5. Conclusions [6] Reier GE, Shangraw R. Microcrystalline cellulose in tableting. J Pharm Sci
1966;55(5):510–4.
[7] Majeed K, Jawaid M, Hassan A, Abu Bakar A, Abdul Khalil HPS, Salema AA, et al.
This works evaluated the effect of addition 3 wt.% of MCC on Potential materials for food packaging from nanoclay/natural fibres filled
properties of cement based materials. The system MCC cement hybrid composites. Mater Des 2013;46:391–410.
[8] Zongjin L. Advanced concrete technology. 1st ed. Hoboken; 2011.
and water is highly compatible because hydrophilic character [9] Mohamed MAS, Ghorbel E, Wardeh G. Valorization of micro-cellulose fibers in
and water retention capability of MCC; additionally hydroxyl self-compacting concrete. Constr Build Mater 2010;24(12):2473–80.
groups of cellulose give to MCC the capacity of interact with hydra- [10] Peters SJ. Fracture toughness investigations of micro and nano cellulose fiber
reinforced ultra high performance concrete. University of Maine; 2009.
tion products, cement particles and water. It was observed good
[11] Claramunt J, Ardanuy M, Arevalo R, Pares F, Tolêdo Filho RD. Mechanical
dispersion of MCC on cement matrix. Additionally because of its performance of ductile cement mortar composites reinforced with
micrometrical sizes MCC interact with hydration products more nanofibrillated cellulose. In: 2nd international RILEM conference. Strain
strongly than cellulose pulps commonly used in others hardening cementitious, composites; 2011. p. 131–8.
[12] Nilsson J, Sargenius P. Effect of microfibrillar cellulose on concrete equivalent
investigations. mortar fresh and hardened properties. Swedish Cement and Concrete Research
Results from slump tests showed that because of hydrophilic Institute; 2011.
nature and presence of hydroxyl groups on its surface, the MCC [13] EN 196-7. Methods of testing cement – Part 7: Methods of taking and
preparing samples of cement; 2007.
interact with cement particles, hydration products and water; [14] Peters SJ, Rushing TS, Landis EN, Cummins TK. Nanocellulose and
increasing s0 of cement paste by 2.6 times respect to cement paste microcellulose fibers for concrete.pdf. Trans Res Rec: J Trans Res Board
with 0 wt.% of MCC. 2010;2142:25–8.
[15] Roussel N. Steady and transient flow behaviour of fresh cement pastes. Cem
Adiabatic temperature measurement in time showed that the Concr Res 2005;35(9):1656–64.
ability of interaction between the MCC, hydration products, cement [16] Roussel N, Stefani C, Leroy R. From mini-cone test to Abrams cone test:
particles and water, promoted solubilization of calcium hydroxide measurement of cement-based materials yield stress using slump tests. Cem
Concr Res 2005;35(5):817–22.
and the formation of a waterproofing barrier on the anhydrous
[17] Philippe C, Sébastien P, Christope A. Rheological interpretation of deposits of
particles of cement. Those interactions delayed the hydration yiel stress fluids. J Non Newton Fluid Mech 1996;66:55–70.
reaction and decreased the maximum adiabatic temperature. [18] Banfill PFG. Rheology of fresh cement and concrete. Rheology Reviews London,
The British Society of Reology; 2006. p. 61–130.
Thermogravimetric analysis showed that both accelerated cur-
[19] Mokhtar M, Hassan A, Rahmat AR, Abd Samat S. Characterization and
ing procedure and MCC addition, increased the hydration degree treatments of pineapple leaf fibre thermoplastic composite for construction
of cement pastes. Accelerated curing increased the hydration de- application. Universiti Teknologi Malaysia; 2007.
gree because of increment in temperature during cure process [20] EN 196-1. Methods of testing cement – Part 1: Determination of Strength;
2006.
and MCC addition increased the degree of hydration because [21] Ramachandran VS. Concrete science. In: Beaudoin JJ, editor. Handbook of
MCC released its water content in cement mortar and favored analytical techniques in concrete science and technology. Principles,
the creation of more hydration products. techniques, and applications, 1st ed., Otawa; 2000. p. 1–55.
[22] Chun YM, Tarun N. Repulping fibrous residuals from pulp and paper mills for
Addition of MCC decreased the mechanical properties of cement recycling in concrete. TAPPI J 2004;3(12):7–10.
mortar cured by standard process; however cement mortar with [23] Tonoli GHD, Savastano Jr H, Fuente E, Negro C, Blanco A, Rocco Lahr FA.
3 wt.% of MCC cured in accelerated way reached mechanical prop- Eucalyptus pulp fibres as alternative reinforcement to engineered cement-
based composites. Ind Crops Prod 2010;31(2):225–32.
erties close to mechanical properties of cement mortar without [24] Balwaik SA, Raut SP. Utilization of waste paper pulp by partial replacement of
MCC. This is because both accelerated curing and MCC addition in- cement in concrete. J Eng Res Appl 2011;1(2):300–9.
creased the hydration degree of cement materials, increasing the [25] Coutts RSP, Ni Y. Autoclaved bamboo pulp fibre reinforced cement. Cem Concr
Compos 1995;17(2):99–106.
presence of hydration products that provide resistance and modu-
[26] Masoodi R, El-Hajjar RF, Pillai KM, Sabo R. Mechanical characterization of
lus like CSH. cellulose nanofiber and bio-based epoxy composite. Mater Des
Increment registered in s0 by MCC addition as well as increment 2012;36:570–6.
[27] Phong NT, Gabr MH, Okubo K, Chuong B, Fujii T. Enhancement of mechanical
registered in hydration degree and improvements reached in
properties of carbon fabric/epoxy composites using micro/nano-sized bamboo
mechanical properties by implementation of an accelerated curing fibrils. Mater Des 2013;47:624–32.
procedure and addition of MCC; are important characteristics to [28] Pourchez J, Grosseau P, Ruot B. Changes in C3S hydration in the presence of
consider cement based composites with MCC as a potential mate- cellulose ethers. Cem Concr Res 2010;40(2):179–88.
[29] Pourchez J, Govin A, Grosseau P, Guyonnet R, Guilhot B, Ruot B. Alkaline
rial to develop precast pieces. Additionally results from early stability of cellulose ethers and impact of their degradation products on
hydration reaction showed that in case of massive structures cement hydration. Cem Concr Res 2006;36(7):1252–6.
MCC could be added to a cement matrix to reduce cracking caused [30] Peschard A, Govin A, Pourchez J, Fredon E, Bertrand L, Maximilien S, et al. Effect
of polysaccharides on the hydration of cement suspension. J Eur Ceram Soc
by the stresses because of thermal contraction and the structural 2006;26(8):1439–45.
restraint. [31] Peschard A, Govin A, Grosseau P, Guilhot B, Guyonnet R. Effect of
polysaccharides on the hydration of cement paste at early ages. Cem Concr
Res 2004;34(11):2153–8.
Acknowledgements [32] Khan B, Baradan B. The effect of sugar on setting-time of various types of
cements. Quart Sci Vision 2002;8(1):71–8.
The authors acknowledged to CONICET and to the agency of sci- [33] Hover KC. The influence of water on the performance of concrete. Constr Build
Mater 2011;25(7):3003–13.
entific and technological promotion (ANPCyT) from the ministry of
science and technology.