International Conference on “Cement – Based Materials Tailored for a Sustainable Future”

7-8 May 2020 – Istanbul / TURKEY

Sorptivity and mechanical properties of micro-fibrillated

cellulose reinforced cementitious composites

O.Öztürk1, M. Stefanidou2
1
Department of Civil Engineering, Konya Technical University, Konya, Turkey
2
Department of Civil Engineering, Aristotle University, Thessaloniki, Greece

Abstract
Recently, natural reinforcements in construction materials are of growing interest since environmental issues have
become a significant criterion in construction technology. Compared to traditional reinforcement elements such as
synthetic fibers, the use of natural fibers can reduce the material cost and improve engineering properties as well
as preserving nature and sustaining a low carbon footprint. Also, natural fibers have other advantages over
synthetic fibers such as lower density, better rheological behavior, improved mechanical properties, modulus of
rupture, renewability, availability, low cost, low environmental impact related to their production, having no
toxicity and easy for processing. By mechanical refining or purification of natural fibers, nano/micro-fibrillated
cellulose (MFC) which is one of the promising nature-based reinforcement can be produced for the utilization in
cement-based materials. This paper underpins the enhancement of engineering properties of strain-hardening
cementitious composites by using bio-based fibers. Accordingly, MFC and synthetic fibers were used in hybrid
system in the cementitious composites. Transport properties of specimens were addressed by conducting sorptivity
tests while mechanical characterization was made based on compressive and flexural tests. Microstructure analysis
(SEM) was also performed to verify the findings. Results exhibit that addition of 1% MFC by volume of mixture
increased the mechanical properties and induced reduced sorptivity coefficients. The findings advocate that MFC
supports lower connected porous structure and tortuosity of the pore network. Further studies on the dispersion
method, long-term durability and preventing the mineralization of cellulosic fibers can be exacerbated with the
aforesaid findings to compete with synthetic fibers in cement-based materials.

Keywords: Micro-fibriliated cellulose (MFC); transport properties, mechanical properties, cementitious

composites

1 Introduction
Cement production is annually around the order of 4 billion tons (Andrew, 2019) and responsible for 8% of total
amount of anthropogenic CO2 emission (Andrew, 2019). Therefore, industries based on cement production require
durable and sustainable cement-based materials. To achieve the relevant improvements, there has been a wide
range of efforts such as using supplementary cementitious materials (SCMs) (Ridi et al., 2011), chemical
admixtures (Öztürk et al. 2020), and fiber reinforcement (Pacheco-Torgal and Jalali, 2011; ACI Committee, 2009).
Among fiber reinforcements, natural fibers are of growing interest to tailor cement-based materials in terms of
different properties such as internal curing (Mezencevova et al., 2011), controlling shrinkage cracks (Betterman,
1995), rheology modifying admixture (UPM, 2012) and using for restorations (Rosato et al., 2017). Micro-
fibrillated cellulose (MFC) fibers are one of the members of natural fibers and seem to have utilization area as a
reinforcement agent to compete with traditional reinforcing fibers. For example, recent studies show that specially-
handled natural fibers (MFC) possess significant potential to alter hydration mechanisms and improve mechanical
properties (Kesikidou and Stefanidou, 2019). These purified cellulose fibers are also environmentally friendly, fast
renewable and low-cost as they are extracted from abundant resources. It has been reported by the researchers that
MFCs are able to modify cracking characteristic of cementitious mortars and can be a promoter of different
structural and non-structural attribute (Fu et al, 2017). For example, Snoeck et al. (2015) stated that treated natural
fibers were able to provide additional multiple microcracks resulting in improved durability (Snoeck et al., 2015).

1
International Conference on “Cement – Based Materials Tailored for a Sustainable Future”
7-8 May 2020 – Istanbul / TURKEY

On the other hand, long-term durability of cellulose reinforced cementitious composites is still questioned due to
degradation of natural fibers in the presence of high alkali compounds. Therefore, it is worth noting that natural
fibers may not be solely an assurance for the pre-targeted cracking behavior of cementitious composites at long
ages and can be regarded to use in hybrid form with the reduced amount of traditional fibers.

Strain-hardening cementitious composites (SHCCs) having distinct crack characteristics are introduced to
construction industry a few decades ago (Li, 1998). As implied with the name of these composites, the SHCCs can
bear excessive tensile loadings presenting many multiple microcracks. Based on the micromechanical design
criteria, matrix of the material and fibers are engineered through interface interaction. However, these composites
include synthetic fibers which is the most expensive ingredient and comprises petroleum-based resources.
Therefore, certain natural fibers can be a low-cost and sustainable solution to cover pre-targeted engineering
properties of such composites through hybrid utilization. Moreover, natural fibers can be an alternative promoter
of different multifunctional properties of SHCCs with their unique multiple microcracking behaviors. Prior to
developing these properties, the effect of natural fibers on the hardened properties of cementitious mortars should
be extensively understood. To do this, an experimental program was performed by using MFC in the SHCCs
matrix. The mechanical (compressive and flexural strength) properties of MFC and control specimens were
evaluated and investigated with microstructural findings. As the penetrability of cement-based composites can be
explained with permeability, diffusion and sorption properties, durability properties are closely related to these
performances. For the MFC-based materials, sorptivity properties can be more influential on the durability as
natural fibers are prone to water uptake at further ages especially for the circumstances where they are undergone
partially or fully wet/dry conditions. Therefore, sorptivity performance of MFC-bearing mixtures was also
evaluated and compared with control specimens.

2 Materials and Methods

2.1 Materials
The cement used in the study was an ordinary Portland cement (PC) similar to ASTM Type I. In addition, F-class
fly ash (FA) was incorporated into mixtures as a substitution of PC. PC cement and F-class fly ash had specific
gravity of 3.06 and 2.10, respectively. The physical and chemical compositions of FA and PC are given in Table
1. Polycarboxylate-based high range water reducing admixture (HRWRA) was also used to achieve appropriate
workability in the mixtures.

Table 1. Chemical and physical properties of cementitious materials

Chemical Composition (%) PC FA
SiO2 20.80 60.8
Al2O3 5.55 21.7
Fe2O3 3.35 5.48
MgO 2.49 1.71
CaO 61.40 3.48
Na2O 0.19 0.74
K2O 0.77 1.95
Loss on ignition 2.20
Physical Properties
Specific gravity 3.06 2.1
Blaine fineness (m2/kg) 325 290

Silica sand having maximum aggregate size of 1.0 mm, water absorption capacity of 0.3% and specific gravity of
2.65 was used in mixtures in accordance with the micromechanical design of SHCCs (Sahmaran et al., 2009).
When aggregate size increases more than the fiber spacing, balling of fibers is probable in the matrix. Accordingly,
homogenous distribution of fibers and strain-hardening behavior becomes challenging. The particle size
distribution of fine silica sand was given in Table 2.

Table 2. Particle size distribution of fine silica sand

Sieve +1000 μm 710-1000 μm 500-710 μm 355-500 μm 250-355 μm 180-250 μm 0-180 μm
Passing (%) 0-1 1-8 7-25 10-35 25-45 5-30 0-7

To investigate the MFCs in high performance cementitious composites, mixtures were reinforced with polyamid
fibers (PA) and MFCs in a hybrid use. PA fibers had a length of 6 mm, diameter of 550 μm, specific gravity of

2
International Conference on “Cement – Based Materials Tailored for a Sustainable Future”
7-8 May 2020 – Istanbul / TURKEY

1.14 and tensile strength of 900 MPa. MFC having 9-11 μm particle length and 155 m2/g specific surface area was
used in the mixtures and given in Figure 1 together with PA fibers.

a) b)
Figure 1. PA fibers (a); and MFC fibers (b)

2.2 Proportioning and Production of Mixtures

In the preparation of mixtures, a common strain-hardening cementitious composite design namely Engineered
Cementitious Composites (M45-ECC) was considered although fiber type was preferred PA instead of PVA to
compete with additional MFC costs. The water to cementitious materials (W/CM) ratio and fly ash to Portland
cement ratio (FA/PC) of mixtures were constant at 0.27 and 1.2 by mass, respectively. PA fibers were incorporated
at 2% as reference and 1% of PA was replaced with 1% MFC by volume of total mixture. Given varying
particle/length sizes of PA and MFC fibers, it was not possible to keep HRWRA amounts constant for four
mixtures. Therefore, to evaluate consistency of different mixtures, mini-slump tests were conducted and the
amount of HRWRA was taken into consideration based on similar flow deformation levels of around 20 cm. The
mixture design is reported in Table 3.

Table 3. Proportions of the four SHCC mixtures.

Mixture ID. PC1 FA1 Sand1 Water1 SP1 PA2 MFC W/CM3
SHCC/Ref. 566 679 456 332 5.9 %2 - 0.27
SHCC/MFC 566 679 456 332 6.5 %1 %1 0.27
1 3 2 3
in kg/m ; by volume ; ratio by mass

During the production of SHCC/Ref. mixtures, PC, FA and sand were mixed together in a conventional mortar
mixer at 100 rpm for two minutes. Then total water and half of the SP were slowly added into the dry blend.
Mixing was performed for a minute at 100 rpm followed by an additional two minutes at 200 rpm. The PA fibers
were then gradually incorporated into mixing for a minute and mixing was continued for further three minutes.
During the production of SHCC/MFC mixtures, similar procedure was followed for the PC, FA and sand. MFCs
were additionally added to ongoing mixture as MFCs having micro-scale fibers should be uniformly dispersed into
cementitious matrix. Accordingly, MFC fibers were separately mixed with the half of mixing water in a separate
mechanical homogenizer with 900 rpm. After mixing procedure is followed for the PC, FA and sand, suspension
of MFC fibers were gradually added to ongoing mixture. After inclusion of PA fibers, the total mixture was
additionally continued for two minutes at 200 rpm. The produced mixtures were poured into cubic (with the
dimension of 50 mm3) and prismatic oiled molds by 40×40×160 mm3. After 24 hours of curing at 50±5% RH,
23±2 oC, specimens were taken from molds and placed into plastic bags isolated from the outside environment to
complete their further curing ages (6 and 27 days) at 95±5% RH and 23±2 o C.

2.3. Experiments
Compressive strength tests were conducted based on ASTM 109 (ASTM C109, 2020) by using six different cubic
specimens from each mixture. On the other hand, flexural tests were applied by using three different prism
specimens with the loading rate of 0.05 kN/mm and flexural strength values were averaged for 7- and 28-day old
specimens. Two supports were 15 mm far from each edge of the specimen (Figure 2.a). The sorptivity experiments
(Figure 2) were performed by using three separate specimens from each mixture having silicon coated edges in
conformity with the procedures given in ASTM C 1585 (ASTM C 1585, 2020). After isolation in plastics bags for

3
International Conference on “Cement – Based Materials Tailored for a Sustainable Future”
7-8 May 2020 – Istanbul / TURKEY

7 days, specimens were immersed in water by 3-5 mm of bottom edges for the tests at 7 and 28 days (Figure 2.b).
Prior to sorptivity testing, specimens were dried at 50±2 oC until the weights of specimens were stabilized with
the accuracy of 0.01 g. Changes in the mass during the capillary suction of specimens were recorded at 1, 2, 3, 4,
6, 8, 12 ,16, 20, 25, 36, 49, 64, 81, 120 and 360 minutes of time intervals. The rate of absorption (mm) was
evaluated by averaging three specimens using the change of mass (g) divided by the cross section area of tested
surface (40×160 mm2) and the density of water. Results were then was graphed versus square root of time (min1/2).

Figure 2. Three-point bending tests (a); and MFC fibers (b)

Figure

3 Results and Discussions

3.1 Mechanical Properties
The averaged compressive strength values given in Fig. 3 indicate that the role of MFC on compressive strength
varies according to curing age. For example, compressive strength of SCHH/MFC mixture was found to be 22.8
MPa and 45.0 MPa at 7 and 28 days, respectively. On the other hand, SCHH/Ref. mixture had 18.8 MPa and 42.2
MPa at 7 and 28 days, respectively. Findings indicate that the mixture of SHCC/MFC showed 21% and 7% higher
compressive strength than SHCC/Ref. at 7 and 28 days. A more significant improvement of MFC on compressive
strength is obtained at 7 days. This behavior can be explained by the fostering effect of MFC on the hydration
degree of matrix at early ages (Hisseine et al., 2019). This effect may have been stabilized during further curing
ages as hydration reactions were assumed to be matured. The increased compressive strength in the presence of
MFC may be also correlated with the effect of micro-scale cellulose having hydrophilic and hygroscopic properties
(Cao, 2015). The hydrophilic and hygroscopic properties of MFC with 9-11μm particle length may have
additionally provided dispatching of mixing water to the unhydrated cementitious particles.

Figure 3. Compressive strength of mixtures at 7 and 28 days

The flexural strength of SHCC/Ref. and SHCC/MFC mixtures were given in Figure 4. Average of SHCC/Ref.
mixture was around 4.45 MPa and 8.96 MPa at 7 and 28 days, respectively. On the other hand, flexural strength
of SHCC/MFC mixture was found to be 5.70 MPa and 12.20 MPa at 7 and 28 days, respectively. In contrast to
compressive strength, the role of MFC on the flexural parameters was more influential in each curing age. For
example, SHCC/MFC mixture had 28% and 36% higher flexural strength than control mixture. The reason can be
ascribed to the fibrillated dimensions of MFCs. Under flexural loadings, fiber-like behavior of MFC at microscale
may have improved the crack bridging mechanism of SHCC/MFC having 1% PA fibers in comparison with the
SHCC/Ref having 2% PA fibers. It is worth noting that higher length of fibers was reported to be more influential
on the crack-bridging mechanism especially at larger crack widths (Fu et al., 2017). However, higher volume of
PA fibers having 6mm length in SHCC/Ref. was more unfavorable compared to lesser amount of PA fibers (1%)
with the presence of MFC (9-11μm particle length). As SHCCs had only a few cracks after fracture due to 3-point

4
International Conference on “Cement – Based Materials Tailored for a Sustainable Future”
7-8 May 2020 – Istanbul / TURKEY

test configuration where stress is concentrated at certain mid-point, the crack delaying or/and bridging ability of
MFC can be more understood. Nevertheless, this finding necessitates additional research based on fiber type (such
as PVA) and test configurations where SHCCs provide multiple microcracks especially under 4-point bending.

Figure 4. Flexural strength of mixtures at 7 and 28 days

Although 7 days-old specimens were not expected to undergo higher pozzolanic reactions due to slow pozzolanic
reaction of F-class fly ash in both mixtures, SHCC/MFC specimens had higher chemical bond between PA and
MFC fibers. During scanning electron microscope (SEM) observations, higher hydration products on the surface
of PA fibers were obtained although unhydrated F-class fly ash particles are abundant in the matrix at 7 days
(Figure 5.a). This may also indicate that more hydration was likely to have occurred in the presence of MFC fibers
which facilities the dispatch of mixing water to anhydrous cement grains. The improved matrix-fiber interaction
through natural fibers that results in higher flexural strength (herein 28%) was also reported in the literature
(Ajouguim, 2020). In addition, MFC fibers provided resistance to crack propagation of the matrix. For example,
Figure 5.b shows the crack arresting ability of MFCs under flexural loadings although it was not possible for some
entangled MFCs at certain widths. Also, Figure 5.b shows the well-dispersed MFCs covered with dense hydration
products in the matrix (near crack path). This may also be an indicator of the higher mechanical strength for MFC-
bearing specimens both under compressive and flexural loadings.

Although higher compressive and flexural strength values were achieved using MFC fibers, improved flexural
strength of MFC-bearing specimens was more pronounced compared to improvement of compressive strength.
The reason can be related to the fact that existence of the MFC fibers may not have contributed to the improvement
of load-bearing capacity under compressive tests unlike in flexural strength due to lower shear modules of
individual MFC fibers. Nevertheless, the inclusion of MFC did not exhibit negative effect on compressive strength.
As fibrillated cellulose fibers easily induce stress concentrations in the presence of non-uniform dispersion (Fu et
al., 2017), it can be noted well-dispersed MFC through the use of 1% by volume of total mixture can be achieved
based on the mechanical findings and Figure 5.b. However, further research is required to evaluate the optimum
MFC ratio parametrically in SHCCs mortars.

a) SHCC/MFC-7-day old

5
International Conference on “Cement – Based Materials Tailored for a Sustainable Future”
7-8 May 2020 – Istanbul / TURKEY

b) SHCC/MFC-28-day old
Figure 5. SEM images of SHCC/MFC mixture

3.2 Transport Properties

Figures 6-7 show the cumulative absorption rate vs. square root of time (mm/min1/2) for 7- and 28-day old different
SHCC mixtures. Each curve represents the average curve obtained from the three specimens tested per SHCC
mixture. As depicted in the results, both mixtures underwent rapid reduction of capillary suction values during
tests from 7 days to 28 days, as expected. For example, cumulative sorptivity rates of 7- and 28-day-old SHCC/Ref.
specimens were found to be (0.0840 to 0.0934 mm.min1/2 [11.2%]) and (0.0842 to 0.0874 mm.min1/2 [3.8%]),
respectively. Similarly, SHCC/MFC specimens had capillary suction values of (0.0814 to 0.0894 mm.min1/2
[9.8%]) and (0.0816 to 0.0839 mm.min1/2 [%2.8]) at 7 and 28 days, respectively. Although both mixtures had lower
values of sorptivity index from 7 days to 28 days due to continued hydration reactions, higher reduction was more
pronounced for the SHCC/MFC specimens at both curing ages. As capillary suction degree is generally explained
with the size, distribution and tortuosity of pores in cement-based materials (Alyousef et al., 2015), the role of
MFC can be also attributed to reduced pore size and creating more disconnected pore interwork through promoter
of hydration reactions. However, it is known that the loss of durability of cellulose modified cement-based
composites is challenging due to degradation of cellulose fibers in longer period in the presence of high-alkali
environment (Fu et al., 2017). For example, (Mohr et al., 2005) stated that cellulose fibers had fiber embrittlement
due to portlandite compounds which is abundant in cement-based system. Accordingly, most of solutions
concentrate on the protection strategies of cellulose-based fibers from alkali environment or using high volume of
pozzolanic materials to reduce portlandite in the matrix. Although further research is needed, typical SHCCs
matrices (Li, 1998) having 60% of fly ash by weight of total cementitious materials would be promising to compete
with these problems.

Figure 6. 7-day-old sorptivity index of SHCC/Ref. and SHCC/MFC

6
International Conference on “Cement – Based Materials Tailored for a Sustainable Future”
7-8 May 2020 – Istanbul / TURKEY

Figure 7. 28-day-old sorptivity index of SHCC/Ref. and SHCC/MFC

4 Conclusions
This work studied basic engineering properties (compressive and flexural strength) of MFC-modified strain
hardening cementitious composite mixtures. Transport properties of SHCC/MFC and SHCC/Ref. mixtures were
also evaluated through sorptivity measurements. Based on mechanical, microstructural and transport properties,
the study reached the following conclusions:

 The compressive strength of both mixtures was able to exhibit more than 40 MPa which is appropriate to
use at 28 days. However, progress of compressive strength varied between 7 and 28 days for the mixtures
developed with MFC and reference SHCCs mixtures. MFC-bearing mixtures were more favoring compared
to reference mixtures although increment of compressive strength was more pronounced at 7 days.
 Improvement in the flexural strength of SHCC/MFC was clearer than compressive strength at each curing
age. The study advocates that the role of MFC was more influential on flexural parameters in comparison
with results under compressive loadings. This was mainly attributed to individual physical and mechanical
properties of MFC fibers and behavior in the cementitious matrix.
 The sorptivity index evaluated for SHCC/MFC and SHCC/Ref was promising in terms of transport
properties. However, SHCC/MFC mixtures had slightly lower capillary suction forces than SHCC/Ref.
mixtures. Nevertheless, the behavior of MFC should be also addressed in terms of mechanical,
microstructural and durability properties at longer curing ages.
 The microstructure analysis showed that incorporating MFC fibers presented higher density due to the
role of different in dimensions and function fibres. The fibres combination seemed to form a net at different
scales, improving the mechanical and physical properties of the composites.

References
ACI Committee 544 State-of-the-art report on fiber reinforced concrete. Farmingon Hills, MI: American Concrete
Insititue; 1996. (reapproved 2009).
Alyousef, A., Lachemi, M., Yıldırım, G., Şahmaran, M. (2015). Effect of Self-Healing on the Different Transport
Properties of Cementitious Composites. Journal of Advanced Concrete Technology, Vol. 1 3 pp.112-123.
Ajouguim, S., Stefanidou, M., Abdelouahdi, K., Waqif, M., Saâdi, L. (2020). Influence of treated bio-fibers on the
mechanical and physical properties of cement mortars. European Journal of Environmental and Civil
Engineering, DOI: 10.1080/19648189.2020.1782773
Andrew, R.M. (2019). Global CO2 emissions from cement production. 1928–2018. Earth System Science Data,
Vol. 11, pp. 1675–1710.
Andrew, R.M. (2018). Global CO2 emissions from cement production. Earth System Science Data, Vol. 10, pp.
195-217.

7
International Conference on “Cement – Based Materials Tailored for a Sustainable Future”
7-8 May 2020 – Istanbul / TURKEY

ASTM C109 / C109M-20b, Standard Test Method for Compressive Strength of Hydraulic Cement Mortars (Using
2-in. or [50 mm] Cube Specimens), ASTM International, West Conshohocken, PA, 2020, www.astm.org
ASTM C1585-20, Standard Test Method for Measurement of Rate of Absorption of Water by Hydraulic-Cement
Concretes, ASTM International, West Conshohocken, PA, 2020, www.astm.org.
Betterman, L.R., Ouyang, C., Shah, S.P. (1995). Fiber-matrix interaction in microfiber-reinforced mortar.
Advances in Cement Based Material, Vol. 2:2 pp. 53–61.
Cao, Y., Zavaterri, P., Youngblood, J., Moon, R., Weiss, J. (2015). The influence of cellulose nanocrystal additions
on the performance of cement paste. Cement and Concrete Composites, Vol. 56 pp. 73-83.
Fu, T., Moon, R. J. Zavattieri,P. Youngblood, J., Weiss W.J. (2017). Cellulose nanomaterials as additives for
cementitious materials, Cellulose-Reinforced Nanofibre Composites, pp.455-482.
Hisseine, O.A, Wilson, W., Sorelli, L., Tolnai, B., Tagnit-Hamou, A. (2019). Nanocellulose for improved
concrete performance: A macro-to-micro investigation for disclosing the effects of cellulose filaments on
strength of cement systems, Construction and Building Materials Vol. 206, pp. 84-96.
Kesikidou, F. and Stefanidou M. (2019). Natural fiber-reinforced mortars. Journal of Building Engineering, Vol.
25, pp. 100786.
Li, V. C. (1998). ECC-Tailored composites through micromechanical modeling. Fiber reinforced concrete: present
and the future conference. Montreal: CSCE Press, pp. 64-97.
Mezencevova, A., Garas, V., Nanko, H., Kurtis, K.E. (2011) Influence of thermomechanical pulp fiber
compositions on internal curing of cementitious materials. Journal of Materials Civil Engineering Vol. 24, 8
pp. 970–5.
Mohr, B., Nanko, H., Kurtis, K. (2005). Durability of kraft pulp fiber–cement composites to wet/dry cycling.
Cement Concrete Composites Vol. 27:4 pp. 435–48.
Öztürk, O., Yıldırım, G., Keskin, U.S., Siad. H., Şahmaran M. (2020). Nano-tailored multi-functional cementitious
composites. Composites: Part B, Vol. 182 pp.107670.
Pacheco-Torgal, F. and Jalali, S. (2011). Cementitious building materials reinforced with vegetable fibres: a
review. Construction Building Materials. Vol. 25:2 pp. 575–81
Ridi, F., Fratini, E., Baglioni, P. (2011). Cement: a two thousand year old nano-colloid. Journal of Colloid
Interface Science, 357:2 pp. 255–64.
Snoeck D., Smetryns, P.A., Belie, N. (2015). Improved multiple cracking and autogenous healing in cementitious
materials by means of chemically-treated natural fibres, Biosystems Engineering, Vol.139, pp. 87-99.
Şahmaran, M,, Lachemi, M., Khandaker, M.A., Hossain, Ranade R, Li V.C. (2009). Influence of Aggregate Type
and Size on Ductility and Mechanical Properties of Engineered Cementitious Composites, ACI Materials
Journal, 106:308-316.
UPM-Kymmene corporation, (2012). UPM Biofibrils. A New Generation Admixture for Concrete Application,
Helsinki, Finland, www.upm.com.