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Correlation Between Hydration of Cement and Durability of Natural Fiber-Reinforced Cement Composites PDF
Correlation Between Hydration of Cement and Durability of Natural Fiber-Reinforced Cement Composites PDF
Corrosion Science
journal homepage: www.elsevier.com/locate/corsci
a r t i c l e i n f o a b s t r a c t
Article history: The influence of cement hydration on the durability of natural fiber-reinforced cementcomposites and
Received 15 June 2015 the deterioration of the embedded natural fibers were investigated by incorporating four supplementary
Received in revised form 13 January 2016 cementitious materials (SCMs). Cement hydration was presented to be a crucial factor in understanding
Accepted 21 January 2016
natural fiber degradation behavior. The results indicated that the incorporation of SCMs slowed down
Available online 24 January 2016
both mineralization and alkaline hydrolysis of fiber cell walls by promoting the hydration of cement.
This is attributed to the reduced alkalinity of pore solution and calcium hydroxide content. Degrada-
Keywords:
tion of natural fiber was significantly mitigated and the durability of cement composites was improved
A. Concrete
B. SEM
consequently.
B. X-ray diffraction © 2016 Published by Elsevier Ltd.
C. Alkaline corrosion
C. Inclusion
http://dx.doi.org/10.1016/j.corsci.2016.01.020
0010-938X/© 2016 Published by Elsevier Ltd.
2 J. Wei et al. / Corrosion Science 106 (2016) 1–15
Fig. 1. Particle size distributions of cement and the SCMs: (a) relative frequency of particles in dependence of the diameter (noncumulative), and (b) volume of the particles
smaller than a certain diameter (cumulative).
Fig. 2. The microstructure of RHA (a) and sisal fiber surface (b).
Fig. 3. The process of casting sisal fiber-reinforced mortar beams (a) pave long aligned sisal fiber layer and (b) mortar layer.
Three 200 mm × 50 mm × 12 mm beams for four-point flexural The duration and frequency of vibration were established accord-
test were cast for each testing point. Two layers of long aligned ing to American Society for Testing Material (ASTM) C192 [25]. The
sisal fiber with a total volume fraction of 2% were used to rein- specimens were demolded after 1 day and immersed in Ca(OH)2 -
force cement mortar beams. As shown in Fig. 3a, a mortar layer saturated water at 23 ± 2 ◦ C for 28 days prior to accelerated aging
of 2 mm thickness was placed at the bottom of the mold then a treatment.
layer of sisal fiber (1% volume fraction) was carefully laid. A sec- Three 30 mm × 30 mm × 300 mm prismatic samples for each
ond layer of mortar of approximately 3–4 mm thickness was then testing point were prepared for fiber pull-out tests. Sisal fibers were
spreaded followed by the second layer of sisal fiber. The fabric was vertically embedded in the matrix with an embedment length of
fully saturated with paste by a roller and for each specimen, the 30 mm. The samples were demolded after 24 h. Five specimens per
final layer was cement mortar (Fig. 3b). A vibration table was used data point were tested after 1, 7 and 28 days of curing at 23 ◦ C with
to consolidate the mortar beams after filling each layer of mortar. a relative humidity of 50%.
4 J. Wei et al. / Corrosion Science 106 (2016) 1–15
2.3. Accelerated aging condition where f(x) is the frequency distribution of the variable x, and m is
the Weibull modulus, which indicates the scatter degree of testing
The durability of sisal fiber reinforced cement based compos- data.
ites was determined by the degradation of mechanical properties The failure probability P can be calculated as cumulative distri-
of specimens subjected up to 50 cycles of wetting and drying, which bution function by defining the variable x as / 0 and integrating
can accelerate the deterioration of both sisal fiber and the cement both sides of Eq. (3):
matrix. For the drying and wetting cycles, the specimens were m
submerged in sealed tap water at 70 ◦ C and then oven dried in a P = 1 − exp − (4)
circulating air environment at 70 ◦ C alternately. In order to deter- 0
mine the duration of each cycle, the development of mass change as where is the measured failure stress of each fiber and 0 is a
a function of immersing or drying time was investigated. Increase normalizing parameter, which can be defined as a characteristic
and decrease of specimen mass subjected to wetting and drying strength of each group.
cycles were measured every 10 min for the first 2 h, every 1 h subse- By taking logarithm of both sides twice, it yields:
quently and every 3 (for wetting) or 4 (for drying) hours after 12 h. 1
Samples were considered at equilibrium when the mass change lnln = mln − mln0 (5)
was less than 2% over 3 consecutive measurements. 1−P
The Weibull modulus and characteristic strength can be deter-
2.4. Flexural properties of natural fiber-reinforced cement mortar mined by plotting the straight line fitting ln vs. lnln ((1 − P)−1 ).
The failure probability P is actually a provability index:
The durability of sisal fiber-reinforced cement mortar was eval- R
P= (6)
uated by means of flexural properties of the beams after accelerated N+1
aging. Three identical beam specimens with a span of 150 mm were where R is the number of fibers broken at stress R , and N is the
bended on an Instron 5984 34k Universal Testing Machine with a total number of sisal fibers that have been tested (here N = 20).
crosshead rate of 0.2 mm/min. The displacements at midspan were The interfacial bonding properties between fiber and cement
determined using linear variable differential transformers (LVDTs). matrices were determined by means of fiber pull-out tests, which
According to ASTM C 1185 [26], two indices, post-cracking strength were carried out using the same micro-force device for fiber tensile
( p ) and post-cracking toughness (Ip ) were selected to evaluate testing with a loading rate of 0.2 mm/min. It is well known that the
the durability of sisal fiber-reinforced cement mortars. The post- typical force-displacement curve of fiber pull-out test consists of
cracking strength was determined using the equation: four stages: (i) in the linear region of the typical force-displacement
Fmax L curve (when the load is lower than the maximum load Fd of linear
p = (1) region), the interface remains intact and the linear curve is gen-
bh2
erated by the elastic deformation of the fiber, (ii) when the load
where L is the span of specimens (150 mm), b and h are the width becomes higher than Fd but lower than the maximum pull-out load
and thickness of specimens, respectively. For the beams subjected (Fmax ), the fiber begins to debond from the matrix through interfa-
to a larger number of wetting and drying cycles, and in absence cial crack propagation in the interfacial zone [29,30], (iii) after the
of post-cracking toughening, the peak strength will be equal to peak load value Fmax , the whole embedded length fully debonds
the first crack strength. Post-cracking toughness is defined as the from the matrix through unstable crack propagation, and (iv) the
amount of energy absorption after an initial crack, which is calcu- last stage indicates the failure of interfacial zone and the fiber is
lated as the area under a load-deflection curve after first cracking pulled out without resistance. Here, the interfacial bond strength
up to specified deflection criterion. In this study, the test was termi- depending on the pull-out behavior of the fibers from the matrix
nated when deflection reaches 16.5 mm. For the aged sample, the was determined by the maximum pull-out load Fmax , as following:
maximum deflection was less than 16.5 mm. The test was ended
Fmax
when the load drop to 1/5 of its maximum load. The post-cracking = (7)
2dLf
toughness was determined using the equation:
16.5or0.2εT
where Fmax is the maximum pull-out load, 2dLf is the contact
Ip = Fdε (2) area between the fiber and cement matrix, d is the radius of interfa-
ε0 cial zone (equals to the radius of fiber) and Lf = 30 mm is the length
of interfacial zone or embedment length of the fiber. The pull-out
where F is load and ε is deflection in bending test. ε0 and εT are energy, which indicates energy absorption needs to be dissipated
deflections at first cracking and maximum load, respectively. to pull out a fiber from the matrix, which was calculated as the area
under a load-deflection curve up to specified deflection criterion.
2.5. Uniaxial tensile behavior of embedded fiber and interfacial Here the test was terminated up to a pullout distance of 2 mm. The
bonding property pull-out energy Epull was determined using Eq. (8):
2
In accordance to ASTM D 3822 [27], the uniaxial tensile proper- Epull = Fdx (8)
ties of single raw and immersed fibers, which were separated out 0
from cement pastes after aging as described in the author’s previ- where F is pull-out load and x is the pullout distance of fiber from
ous work [28], were determined using a micro-force Instron 5948 the cement matrix.
testing system with a gauge length of 20 mm and a loading rate of
0.2 mm/min. Twenty single fibers were tested for each group and 2.6. Hydration heat
the scattered data of the tensile tests were analysed using Weibull
distribution model. Probability function of this double-parameter The heat flow of the hydration of cement and blended pastes
distribution is given by: was determined using TAM Air iso-thermal calorimeter at 25 ◦ C. In
accordance to ASTM C305, pastes with a water to binder ratio of
f (x) = m (x)m−1 exp −xm (3) 0.5 were mixed by hand with a spatula for 1 min at a temperature
J. Wei et al. / Corrosion Science 106 (2016) 1–15 5
of 23 ± 2 ◦ C. 5 g of paste was cast in glass cylinders using a plastic ing to the amorphous fraction, which is taken at a 2 angle between
dropper within 2 min after initial contact of cement and water. Then 18◦ and 19◦ where the intensity is a minimum [37–39].
the sealed samples were placed in the calorimeter, which records The Cr.I. (ˇ), which indicates the embedded fiber’s crystallinity
the hydration heat flow of the sample up to 45 h. degree [35], was evaluated by using the following equation
[37,40–42]:
2.7. Thermal analysis I002 − Iam
ˇ= (13)
I002
Cement hydration products and sisal fiber components were
determined by means of thermogravimetric analysis (TGA) and
3. Results and discussion
derivative thermogravimetry (DTG) using a TA Instruments Q50
Thermogravimetric Analyzer and a PerkinElmer Pyris1 Thermo
3.1. Determination of aggressive condition
Gravimetric Analyzer, respectively. For the TGA investiagtion of
cement, the ground hardened cement powder was heated at a heat-
The mass changes of mortar beams (for flexural test) reinforced
ing rate of 10 ◦ C/min from room temperature to 150 ◦ C and then
with natural fiber in the first wetting and drying cycle as functions
15 ◦ C/min to 800 ◦ C in N2 -atmosphere. The measured content of
of immersion and drying times are shown in Fig. 4. The compari-
Ca(OH)2 (CCH ) is expressed as percentage of the dry sample weight
son between Fig. 4a and b indicates that the weight change is more
at 500 ◦ C as follows [31,32]:
sensitive to water immersion than drying environments and that
W400 − W500 MCa(OH)2 W400 − W500 the amount of water absorbed at equilibrium is less than that loss
CCH = × = × 4.1 (9)
W500 MH2 O W500 in drying process, which may be caused by the hysteresis between
water absorption and desorption and can be explained by the ink-
where WT is the dry sample weight at the temperature T (◦ C). bottle effect in capillary pores [43]. Due to large particle size (as
The bound water content (Cbw ) was determined as the differ- shown in Fig. 1) and specific porous structure (Fig. 2a), the incor-
ence between the mass measurements at 105 ◦ C and 800 ◦ C and poration of 20 wt.% RHA leads to a dramatic increase of free water
corrected for the ignition losses of the unhydrated cement powder in the capillary pores and, thus, an evident increase of weight loss
and the substitution cementitious materials [31–33]: in drying stage. Similar effect can also be noticed in FA30, which
W105 − W800 yields a severer mass change than that of neat PC mortar. Owing
Cbw = − (fc × ILuc + fSCM × ILSCM ) (10) to their fine particle size and high pozzolanic activity, the partial
W800
replacements of cement by MK and SF make the cement matrix
where fc , fSCM are the mass fractions of cement (PC) and SCM in denser than neat PC. As a result, less weight losses were observed
the dry mix, respectively; ILuc and ILSCM are the ignition losses of in SF10 and MK30. According to the longest required period of time
unhydrated cement and SCM, respectively. (25 h for drying (MK30) and 15 h for wetting (SF20)) to reach mass
The degree of hydration (DOH) () for the cement pastes was equilibrium, the accelerated aging condition for all samples were
calculated using the following formula: determined to test their durability all at same age. A duration of 42 h
Cbw(t) was selected for each wetting and drying cycle: 15 h immersion in
= × 100% (11) tap water at 70 ◦ C and 25 h drying in an oven at 70 ◦ C, with 1 h air
Cbw(∞)
drying under 23 ◦ C and 10% humidity between each half-cycle.
where Cbw(t) is the bound water content of cement paste at time
t normalized to the fraction of cement in a paste; Cbw(∞) is the non- 3.2. Kinetics of cement hydration
evaporable water corresponding to full hydration of 1 g cement
(0.23 g [34]). For the TGA investigation of sisal fiber, the ground The development of normalized specific heat flow and released
sisal powder samples of 25 mg were placed in an alumina crucible heat of hydration of neat PC and the blends at early age (up to
and tests were carried out in a N2 atmosphere with a heating rate of 40 h) are shown in Fig. 5. Each curve represents the average of two
10 ◦ C/min from room temperature to 600 ◦ C. The DTG curves, which measurements, the error of which is less than 0.2 mW/g. From the
are the derivative of TGA curves with respect to the temperature, curves, it can be seen that the heat flow of each blend is almost the
were employed to read the exact boundaries for the temperature same in the first hydration stage: pre-induction period. Both the
intervals. neat PC and cement blends show a strong heat evolution generated
by the quick conversion of aluminate phases in the first minutes.
2.8. X-ray diffraction analysis The main differences occur during the following three hydration
stages: induction, acceleration and deceleration periods. The cur-
The crystallinity fraction of the embedded natural fibers after 30 tate induction period indicates that the incorporations of SF, FA
wetting and drying cycles was analyzed by X-ray diffraction (XRD) and MK effectively accelerated the hydration process of cement.
carried out on ground powders with an X2 Scintag X-Ray diffrac- The induction period for all groups starts after 0.5 h of hydration.
tometer in a –2 configuration using CuK␣ source ( = 1.54 Å) at The acceleration periods of the neat PC and MK30 begins after
−40 kV and 35 mA. The samples were scanned in step mode with a 2 h, however in the SF10 and FA30 this period starts 0.75 h ear-
step size of 0.02◦ (2) in the angular range of 5–25◦ . Two indexes lier, which means the formation rate of C–S–H was accelerated.
were calculated from the X-ray diffraction spectra of sisal fibers However, RHA20 presented a longer induction period than neat
embedded in the cement matrices after aging: the percentage of PC: the acceleration periods begins after 4.5 h of hyradation and its
crystallinities using the peak height method [35] (%Cr) and crys- first heat flow peak does appear until 15 h. This may be due to its
tallinity index (Cr.I.). The Segal empirical %Cr (˛) was calculated large particle size and surper water absoprtion, which significantly
using the following equation [36]: arrest the cement hydration at early age (first 6 h) and the release
of which will provide additional water for the unhydrated cement
I002
˛= × 100% (12) and enhence cement hydration at a later stage.
I002 + Iam
There are two peaks (shoulders) on the PC curve, namely a
where I002 is the maximum intensity of diffraction of the (0 0 2) silicate and an aluminate peak, due to the silicate reaction, and tri-
lattice peak at 2 = 22.5◦ , Iam is the intensity of diffraction contribut- calcium aluminate reactions to form ettringite and subsequently
6 J. Wei et al. / Corrosion Science 106 (2016) 1–15
Fig. 4. Mass change of natural fiber-reinforced mortar beams in the drying (a) and wetting (b) stage.
8 200
a 180 b
7 PC
MK30
160
Normalized heat flow (mW/g)
RHA20
6
SF10
Released heat (J/g)
140
FA30
5
120
4 100
80
3
PC
60 MK30
2 RHA20
40 SF10
1 FA30
20
0 0
0 5 10 15 20 25 30 35 40 45 0 5 10 15 20 25 30 35 40
Time (h) Time (h)
Fig. 5. Specific normalized heat flow (a) and released heat (b) with a w/b ratio of 0.5 at 25 ◦ C.
conversion into monosulfate, respectively. The two peaks, with and PC. This may correlate to the high armorphous silicate content
maximum heat flows of 2.3 mW/g and 2.0 mW/g, were observed and the release of water from the specific porous structure of RHA,
after 9.7 h and 16.5 h of hydration. There are at least three contribu- which can enhance cement hydration significantly at a later stage.
tions of SCMs to the hydration heat of Portland cement: providing Owing to high pozzolanic activity, the incorporation of 10 wt.% SF
extra space for the hydration products, enhanced nucleation, and enhanced the silicate reaction most considerably, with a maximum
the reaction between SCMs and clinkers of cement [44]. The heat heat flow of 3.3 mW/g after 7.5 h of hydration. The incorporation of
flow peaks in Fig. 5a demonstrates that among the SCMs in this 30 wt.% FA leads to an earlier acceleration period and a maximum
study, MK shows the most remarkable impact on cement hydration heat flow of 2.5 mW/g. In the subsequent deceleration period, FA30,
at early age. Compared with its contribution to silicate reaction, The FA10 and MK30 present a similar heat flow development, which
effect of MK on the aluminate reaction was much more significant: decreases significantly faster than the rest groups and transfers to
with the addition of MK, the second peak occurred much earlier diffusional period after 25 h.
and became much narrower and higher (the maximum second heat Fig. 5b shows the normalizad cumulative released heat up to
flow: 7.22 mW/g for MK30 and 1.98 mW/g for PC). Because of the 40 h of hydration. The improvement in both silicate and aluminate
low tricalcium aluminate (C3 A) amount in PC, the second shoulder reactions cause a high hydration heat release at early hydration
peak was lower than the silicate peak for neat PC, but the oppo- time. It can be seen that SF10 releases more hydration heat than
site held for PC-MK blends. Corresponding to the second formation neat PC before 22.5 h, and then PC releases the maximum heat
of ettringite, besides the nucleation role, the aluminates originat- among the groups. Due to the dramatic second heat flow peak as
ing from MK also possibly participate in the reaction at this stage shown in Fig. 5a, the release heat of MK30 presents a rapid growth
[24]. The fact that this “shoulder” can be found in RHA20 as well, after 9.5 h of hydration and then gently increases and become lower
but both of its two peaks appeared with an evident delay as ana- than that of neat PC after 19 h. Although the acceleration period
lyzed above. It can be noted that the second heat flow of RHA20 appeared later, RHA20 presents a similar normalizad released heat
maximum reaches 2.9 mW/g, which is higher than that of FA30 as MK30 after 40 h of hydration. Among all the blends, due to the
J. Wei et al. / Corrosion Science 106 (2016) 1–15 7
lower pozzolanic activity and quick end of both the acceleration According to the bound water content normalized to dry cement
and deceleration period, FA30 releases a lowest hydration heat after fraction, the degree of cement hydration of each blend was calcu-
1 day. lated to evaluate the efficiency of these SCMs in enhancing cement
hydration. By replacing 30 wt.% cement, MK30 shows the highest
3.3. Effect of SCMs on cement hydration products cement DOH among all pastes, which is 28.70% higher than that of
neat PC. This may be attributed to the high initial pozzolanic reac-
It is well known that, by incorporating SCMs, cement hydra- tivity of MK owing to its Al2 O3 phases, which are involved in the
tion can be effectively enhanced owing to pozzolanic reactions formation of gehlenite (C2 ASH8 ) and a small amount of crystalline
[24,31,45,46]. When materials rich in amorphous silica (pozzolans) C4 AH13 phase [50]. Therefore the amount of calcium suffered a sig-
are added to the Portland cement, they react with the Ca(OH)2 , lib- nificant reduction and thus the induction period of cement paste
erated during the formation of C–S–H by the hydration of C3 S and was shortened. Moreover, the incorporation of MK provides more
ˇC2 S, thereby generating an extra production of C–S–H with higher siliceous surface for early precipitation of hydration products of
Si/Ca ratio [47]. As a result, the alkalinity of cement paste is reduced cement (mainly C–S–H), which also results in a short induction
and a high early-age strength can be obtained. TGA investigation of period [51]. With same mechanism, silica fume, which has a high
cement blends containing the SCMs was performed after 28 days of silicate content and large surface area, also shows a high efficiency
hydration to determine their influence on cement hydration prod- factor in enhancing cement hydration. It can be seen that, after 28
ucts. The Ca(OH)2 and bound water contents of neat PC and the days, the degree of cement hydration in SF10 is 21.02% higher than
blends are shown in Fig. 6. that of neat PC and is slightly lower than that of MK30. By replacing
From Fig. 6a, it can be noted that the amount of Ca(OH)2 is 20 wt.% and 30 wt.% cement by RHA and FA, the degree of cement
very sensitive to SCM’s incorporation in cement. After 28 days hydration was improved by 16.69% and 9.22%, respectively. It can
of hydration, neat cement yielded a Ca(OH)2 content of 23.19%. be noted that the efficiencies of these two ashes, RHA and FA, is
By partially replacing cement with SCMs, the Ca(OH)2 content of lower than those of MK and SF in cement hydration modification.
cement paste experienced a considerable reduction. The smallest Owing to higher silicate amount and the specific porous structure,
Ca(OH)2 content (5.63%) and Ca(OH)2 content normalized to the RHA enhanced cement hydration more significantly than FA.
amount of Portland cement (7.67) were achieved by MK30 and
SF10, respectively. Due to the high content of Al2 O3 , MK has a 3.4. Interfacial bonding properties
higher pozzolanic activity than SF at early stages, which leads to
a fast Ca(OH)2 consumption. It is also important to note that SF has The flexural properties of fiber-reinforced composites depend
a higher portlandite consumption ability than MK at later hydra- on several factors, such as fiber strength, fiber modulus, properties
tion processes, because of its higher SiO2 content. By considering of the matrix, and interfacial bonding properties. Under tension,
the cement replacement level, silica fume is more effective in con- natural fiber reinforced cement composites fail by a combination
suming Ca(OH)2 than other SCMs. Owing to the high content of of fiber fracture and pull-out [52,53], and the fiber pull-out is the
amorphous silicate, RHA also showed an effective role in reduc- principal mechanism of failure [54]. In this study, effects of SCM
ing Ca(OH)2 . By replacing 20 wt.% cement with RHA, the blend incorporation on interfacial bonding properties between natural
yields a Ca(OH)2 content of 10.34% and a normalized Ca(OH)2 fiber and cement matrices were investigated by means of single
content of 12.93, which are 55.41% and 44.24% lower than those fiber pull-out testing. Fig. 7 shows the bond strength and pull-out
of neat cement, respectively. With a 30% corporation of FA, the energy after 1, 7 and 28 days. It can be noticed that both bond
Ca(OH)2 content decreased by 37.04%, however, by considering the strength and energy are very sensitive to curing age, and natu-
high cement substitution level, the normalized Ca(OH)2 content of ral fiber-reinforced neat PC yields the worst values. Among all the
cement only decreased by 10.05%. composites, MK30 shows the best interfacial properties, especially
The amount of ‘bound’ water present in the hardened Portland at early age. This may be attributed to the high content of Al2 O3 in
cement paste depends on the phase composition of the original MK, which could consume Ca(OH)2 more effectively and the cement
cement, on the degree of hydration and also on the way in which matrix become dense at early age. By replacing 30 wt.% cement with
the term ‘bound water’ has been defined [48]. Bound water includes metakaolin, the 1-day, 7-day and 28-day bond strength is improved
contributions from all the hydration products, such as Ca(OH)2 , by 156.25%, 102.49%, and 43.40%, respectively. Similar trends can
C–S–H, ettringite, and monocarbonate, which are all water rich also be found in pull-out energy. Although there is only 10 wt.%
products of cement hydration. Fig. 6b shows the influences of cement replacement by SF, SF10 yields a comparable bond strength
SCM incorporations on bound water content and degree of cement and pull-out energy as MK30 after 7 days. The 28-day bond strength
hydration after 28 days. The bound water contents of MK30, RHA20 and pull-out energy increased by 26.42% and 50.79%, respectively,
and FA30 are 8.81%, 6.56%, and 23.45% lower than that of neat PC. in the presence of 10 wt.% SF. By incorporating 30 wt.% fly ash, the
This may be attributed to two causes: (i) the stabilization of water 28-day bond strength was only improved by 11.32%. Although the
rich hydration products, i.e. ettringite and monocarbonate [31], modifying effect of RHA is not comparable with metakaolin and
and (ii) the lower cement fractions in these blends due to cement silica fume, it leads to an enhancement in improving the bond-
replacement. It can be seen that the contents of bound water in ing behavior of natural fiber in a cement matrix, which is more
cement blends are lower than that in the neat PC, but are greater if considerable than that of fly ash.
they are referred to the Portland cement fraction. This is believed It can be noticed that cement substitution results in an increase
to relate to the fact that pozzolanic reaction is a water-intake pro- of interfacial bonding properties between natural fiber and cement
cess other than from Ca(OH)2 [49], so more water can be fixed. In matrices. By reducing Ca(OH)2 , ettringite and forming more C–S–H,
addition, in cement blends, the hydration of PC can be enhanced mainly porosity and thickness of the transition zone [55,56] adja-
substantially and an increased amount of water rich hydration cent to the fibers were reduced and more cement products adhered
products with better stabilization is thus obtained. The comparison on the fiber’s surface, thereby the bonding strength was improved
between neat PC and SF10 demonstrates the slightly higher content and the fibers’ slipping needed more energy. It is anticipated that
of bound water in the SF-blend after 28 days of hydration, and thus the initial flexural properties of natural fiber-reinforced cement
a higher normalized bound water content. Among all the pastes, mortar, before exposed to accelerated aging, will be improved sig-
MK30 and neat PC show the highest and the lowest normalized nificantly owing to the improved interfacial bonding properties.
bound water contents, respectively. In addition, by incorporating these SCMs, the durability of sisal
8 J. Wei et al. / Corrosion Science 106 (2016) 1–15
25 100 100
Bound water
a b Degree of hydration
Ca(OH)2 content 90 90
15 60 60
50 50
10 40 40
30 30
5 20 20
10 10
0 0 0
PC MK30 RHA20 SF10 FA30 PC MK30 RHA20 SF10 FA30
Fig. 6. The effects of SCMs on cement hydration: (a) original and normalized Ca(OH)2 contents, and (b) degree of hydration determined by means of normalized bound water
contents.
0.9 22
a b
0.8 20
1d
18 1d
0.7 7d
Pull-out energy (N·mm)
28d 7d
Bond strength (MPa)
16
0.6 28d
14
0.5 12
0.4 10
8
0.3
6
0.2
4
0.1 2
0.0 0
PC MK30 RHA20 SF10 FA30 PC MK30 RHA20 SF10 FA30
Fig. 7. Interfacial bonding properties between natural fiber and cementitious matrices: (a) bond strength (MPa) and (b) pull-out energy (N mm).
fiber-cement composites will also be improved attributing to the A significant increase in durability for natural fiber-reinforced
reduction of Ca(OH)2 content and alkalinity in the cement matrices. cement composites was achieved by incorporating SCMs. As wet-
ting and drying cycles proceeded, natural fiber-reinforced PC
yielded the most dramatic decrease of flexural properties: after
3.5. Durability of natural fiber-reinforced mortar
50 wetting and drying cycles, strength and toughness decreased
by 85.58% and 99.18%, respectively. This means, among the five
Owing to crack bridging and stress transfer between fiber and
groups, natural fiber-reinforced neat PC has the worst durability,
the cement matrix, mortar beams reinforced with long aligned nat-
which may be caused by the severe degradation of natural fibers in
ural fibers yielded remarkable post-cracking flexural behavior. Sole
PC. By replacing 30 wt.% cement with MK, the flexural properties
big-scale crack was replaced by multiple fine cracks, consequently
of sisal fiber-reinforced mortar did not experience evident decline
more energy was consumed and the brittle failure of cement mortar
after the first 5 and 15 cycles. The high Al2 O3 content in MK results
was prevented. This makes it more reasonable here to determine
in an enhanced cement hydration and Ca(OH)2 consumption at
the durability of natural fiber-reinforced cement composites by
early age, consequently the degradation of natural fiber in MK30
means of flexural properties after exposed to accelerated aging. The
can be mitigated more effectively than other groups. After 50 wet-
durability of natural fiber-reinforced mortar, after each aging stage,
ting and drying cycles, the flexural strength and toughness of MK30
determined by post-cracking flexural strength and toughness, are
decreased by 33.48% and 37.44%, respectively. For SF, after 5 cycles,
presented in Fig. 8a and b, respectively. From Fig. 8, it can be noticed
the decrease of flexural behavior is slightly more dramatic than that
that, after 28 days of curing, MK30, RHA20 and SF10 show sim-
of MK30. This indicates that silicate is not as effective as aluminate
ilar initial post-cracking strength, which are 35.73%, 32.97% and
in enhancing cement hydration at early age, and the natural fibers
34.73% higher than that of natural fiber-reinforced neat PC mortar,
suffered certain degree of deterioration before Ca(OH)2 was con-
respectively. The incorporation of 30 wt.% FA leads to an increase of
sumed. The final strength and toughness of SF10 were 52.57% and
flexural strength by 14.56%, which is not as considerable as those of
57.66% lower than its initial values. Although RHA20 can lead to a
MK, RHA and SF. Similar trends can be found in flexural toughness,
significant increase of initial properties, its strength and toughness
in which MK30 and SF10 yielded the best values among the groups.
J. Wei et al. / Corrosion Science 106 (2016) 1–15 9
14
0 Cycle 0 Cycle
Post-cracking flexural strength (MPa) a 5 Cyles
7 b 5 Cyles
12 15 cycles 15 Cycles
8
4
6
3
4
2
2 1
0 0
PC MK30 RHA20 SF10 FA30 PC MK30 RHA20 SF10 FA30
Fig. 8. Durability of natural fiber-reinforced cement mortar by means of four-point flexural properties, (a) post-cracking flexural strength, and (b) post-cracking flexural
toughness.
Fig. 9. Tensile properties of single natural fibers: (a) Weibull plots and (b) tensile strength.
experienced an evident decrease after exposed to wetting and dry- ing data for natural fibers and the Weibull modulus can be clearly
ing cycles. This may be caused by the remarkable water penetration observed from the fitting lines and their slopes. The raw natural
in RHA20 samples attributed to RHA’s porous structure. More pore fiber and the embedded fiber in PC yield similar Weibull modu-
solution, which plays an important role in alkaline hydrolysis and lus, however, they show the highest and lowest tensile strength,
cell walls mineralization, was produced, especially in the transition respectively, among the groups. This indicates that the data of a
zone between natural fiber and the cement matrix. Similar phe- single fiber tensile test are concentrated when the tensile strength
nomenon was observed in FA30: after 50 wetting and drying cycles, is high or low, and apparently scattered for strengths in between.
the post-cracking strength and toughness decreased by 84.03% and The raw fibers, without any degradation, show a tensile strength
95.80%, respectively. Although RHA and FA modified samples show of 605.5 MPa. The tensile strength of the natural fiber embedded in
obvious property decline subjected to accelerated aging, they still the neat PC matrix decreased by 35.07% and 86.19% after 5 and 30
lead to an increase in durability of cement composites reinforced wetting and drying cycles, respectively. The dramatic reduction of
with natural fiber. The final flexural strength of RHA20 and FA30 strength demonstrates that natural fiber experienced a sever degra-
is 165.04% and 26.83% higher, respectively, than that of natural dation in the alkaline environment of pure cement matrix. A result
fiber-reinforced neat PC. of interest can be noticed that, after 5 wetting and dying cycles,
the fiber embedded in MK30 yields a higher tensile strength than
3.6. Degradation of the embedded natural fibers the raw natural fiber. This may be attributed to the slight removal
of amorphous components (i.e. lignin and hemicellulose) and the
3.6.1. Tensile behavior rearrangement of cellulose microfibrils in the mild alkaline matrix
The uniaxial tensile behavior of raw and embedded sisal fibers in of MK30, which could improve the mechanical behavior of natural
the five different cement matrices, after 5 and 30 wetting and dry- fibers [57,58]. From, Fig. 9b, it can be seen that the replacement of
ing cycles, were investigated. The Weibull plots of testing results 30 wt.% cement by MK is the most effective way to mitigate natural
are shown in Fig. 9a, from which the scatter natural of tensile test- fiber degradation: after 30 wetting and drying cycles, the tensile
10 J. Wei et al. / Corrosion Science 106 (2016) 1–15
Fig. 11. TGA and DTG curves of the raw and embedded natural fibers in cement matrices after 30 wetting and drying cycles.
Fig. 12. XRD analysis of the raw and embedded natural fibers after 30 wetting and drying cycles: (a) XRD pattern, (b) %Cr. and Cr.I.
−
1, 2, 4: cellulose crystallographic plane (1 1 0), (1 1 0) and (0 0 2); 3: Ca(OH)2 ; 5: ettringite; 6: Calcite; 7: C–S–H, C–A–S–H.
ural fiber and the cement matrix is better in MK30 than other tion, the fiber embedded in RHA20 yields higher indices than those
matrices, which agrees well with the results shown Fig. 7. embedded in MK30 and SF10. By replacing the same amount of
Fig. 12b shows the Segal empirical percentage of crystallinity cement, the fiber embedded in FA30 shows %Cr. of 86.70% and Cr.I.
(%Cr.) and crystallinity index (Cr.I.), which were calculated to quan- of 0.85, which are 2.46% and 4.49% higher than those of fiber in
tify the fiber’s crystalline properties. Raw natural fiber show the MK30, but are 1.20% and 1.24% lower than those of fiber embedded
lowest %Cr. and Cr.I. among all groups, and these two indices of fiber in neat PC, respectively.
increased by 12.98% and 20.31%, respectively, after 30 cycles in PC.
Although the embedded fiber’s %Cr. and Cr.I. are 8.94% and 13.70% 3.6.4. Microstructure analysis
higher than those of raw natural fiber, MK30 shows the best effect The microstructure of natural fibers (Fig. 13) were analyzed on
in mitigating natural fiber crystallization. Compared with natural the fracture surfaces of fiber reinforced cement mortar samples
fibers embedded in neat PC, the fiber’s %Cr. and Cr.I. decreased by after 30 wetting and drying cycles to visually evaluate the influ-
3.02% and 3.77%, respectively, by replacing 10 wt.% cement with SF. ence of SCMs on fiber degradation. Due to the alkaline hydrolysis
Due to lower Ca(OH)2 consumption and degree of cement hydra- of lignin and hemicellulose, the natural fiber’s surface was fully
12 J. Wei et al. / Corrosion Science 106 (2016) 1–15
Fig. 13. SEM micrographs of the natural fibers on fracture surface of fiber-reinforced cement mortar after 30 wetting and drying cycles: (a) and (b) PC, (c) MK30, (d) RHA20,
(e) SF10 and (f) FA30.
decomposed and all the cellulose micro-fibrils are stripped from smaller than those in other groups, this may be attributed to lower
each other. The space of lumen was saturated with the cement autogenous shrinkage of the MK modified cement and less dry-
hydration products, which provides evidence for cell wall min- ing shrinkage of natural fiber in the low alkaline environment. In
eralization. As a result, fibers become more brittle and lose their FA30, after 30 wetting and drying cycles, the degradation degree
reinforcement capacity in cement based materials. Attributed to of natural fiber is worse than that in RHA20. The surface of fiber
the reduction of the amount of Ca(OH)2 and alkalinity depression has been completely broken and more than half of the cellulose
in the MK modified cement matrix, the fibers still retain their initial fibrils were stripped. Compared with the degraded fiber in neat
morphology with a good integrity, except for several cracks on their PC, the stripped fibrils are still clinging together and less hydration
cross section. In addition, due to the retention of lignin and hemi- products are found in between. SEM micrographs of the embed-
cellulose, which act as protective layers for cellulose micro-fibrils, ded natural fiber clearly demonstrate the degradation degree of
no cellulose chain stripping and cement products precipitation was the fiber and agree well with the results in TGA and XRD analysis,
detected in natural fibers. The fiber embedded in RHA20 experi- as well as the durability of fiber-reinforced cement composites.
enced a slight severer degradation of non-cellulose components
than that in MK30. It can be seen that the surface of the fiber has
been partial corroded and the cement hydration products have pre- 3.7. Correlation between durability and cement hydration
cipitated on the fiber periphery. The open lumens also indicate the
deterioration of armorphous components and provide additional From the discussion above, hydration of cement and durabil-
space for cement hydration products migration. A better structure ity of natural fiber-reinforced cement composites, as well as the
of natural fiber was detected in SF10. Although a small part of fiber degradation of embedded natural fibers have been investigated
suffered cellulose miro-fibrils stripping, the remaining portion of separately. The incorporations of SCMs not only enhanced the
the fiber is still in good integrity. In addition to the fiber, the strip- hydration of cement but also play important roles in mitigating
ping space between fiber and the cement matrix in MK30 is much natural fiber’s deterioration owing to their pozzolanic activity in
the cement matrix. It is believed, the reduction of Ca(OH)2 and the
J. Wei et al. / Corrosion Science 106 (2016) 1–15 13
Fig. 14. Correlations between degree of hydration, Ca(OH)2 content and durability of natural fiber-reinforced cement composites: (a) post-cracking flexural strength and (b)
flexural toughness.
Fig. 15. Correlations between cement hydration and degradation of embedded natural fibers: (a) effect of degree of hydration on fiber tensile behavior (b) effect of Ca(OH)2
content on fiber’s crystalline indices.
improvement of DOH are the root causes for the increased dura- tar is more sensitive to DOH and Ca(OH)2 content than flexural
bility. Here, the correlations between durability of composites and strength, especially at higher DOH. When DOH is less than 80%,
hydration of cement, and the correlation between degradation of the effect of DOH on post-cracking flexural toughness (at both 30
natural fiber and cement hydration products, are analyzed. and 50 cycles) is neglectable. However, when the DOH of cement
Fig. 14 a and b shows the effects of cement hydration on becomes higher than 80%, the flexural toughness becomes very
post-cracking flexural strength and the toughness of natural fiber- sensitive to DOH. Again, this can be explained by the variation of
reinforced cement mortar after 30 and 50 cycles, respectively. It can Ca(OH)2 content: with increasing DOH, the reduction of Ca(OH)2
be noticed that the flexural strength of the composites increases content becomes dramatic and its effect on the degradation of nat-
with increasing DOH of the cement matrix, which means the nat- ural fiber decreases.
ural fiber-reinforced cement composites with full hydration can The effects of DOH and Ca(OH)2 content on the embedded fiber’s
obtain improved durability. The correlation between Ca(OH)2 con- tensile behavior and crystalline properties after 30 wetting and dry-
tent and flexural strength may be used to explain this phenomenon. ing cycles are shown in Fig. 15a and b, respectively. The durability
The incorporations of SCMs not only enhanced the hydration of of natural fiber-reinforced cement composites is affected by sev-
cement, but also reduced the Ca(OH)2 content in the cement matrix. eral factors, such as durability of the cement matrix, interfacial
It is well known that Ca(OH)2 is the main reason for the fiber degra- bonding properties and fiber degradation. The incorporations of
dation [59], including mineralization and alkaline hydrolysis. From SCMs not only improved the initial flexural behavior of compos-
Fig. 14a and b, it can be found that, in this study, the higher the ites but also lead to improved interfacial properties between fiber
DOH in the cement matrix the lower Ca(OH)2 content that can be and cement matrices. It is evident that the decreased durability of
detected, thus the better durability obtained. From Fig. 14b, it can modified cement composites is caused by the degradation of nat-
be seen that the toughness of natural fiber-reinforced cement mor- ural fiber. From Fig. 15a, the correlation between DOH and tensile
14 J. Wei et al. / Corrosion Science 106 (2016) 1–15
properties of the embedded natural fibers can be determined: with systematically study the effect of cement hydration on natural
DOH increasing, the depression of tensile strength decreased and fiber durability. In this regard, subsequently, the effects of chem-
the fibers’ toughness increased. The curves in Fig. 15b indicate that ical admixtures, thermal treatment and pre-carbonation on the
both %Cr. and Cr.I. decrease with decreasing Ca(OH)2 content in hydration of cement matrix and the degradation behavior of the
the cement matrix. The deterioration of non-cellulose components embedded natural fibers will be investigated.
and the amorphous regions of cellulose chains may be the reasons
for the increased %Cr. and Cr.I., and they are also important causes
for the increased embrittlement of the embedded natural fiber, in Acknowledgements
addition to fiber cell wall mineralization.
The authors would like to express their sincere thanks to
the Erbilgin Family, for their consistent financial support for the
4. Conclusions author’s doctorate research through the Erbilgin Family fellowship
at Columbia University. The authors also wish to acknowledge Mr.
At an early age (first 1.5 d), the incorporation of SCMs lead to a Hagh Mckee from Bast Fibers LLC, Creskill, New Jersey, for his supply
promoted cement hydration reaction and lower total cumulative of sisal fiber.
released heat. Owing to the pozzolanic avidity and seeding effect
of SCMs, silicate reaction and tricalcium aluminate reactions were
enhanced. References
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