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Construction and Building Materials 102 (2016) 167–174

Contents lists available at ScienceDirect

Construction and Building Materials


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

Thermo-physical properties of nanostructured lightweight fiber


reinforced cementitious composites
H. Shoukry a,⇑, M.F. Kotkata b, S.A. Abo-EL-Enein c, M.S. Morsy a, S.S. Shebl a
a
Housing & Building National Research Center, HBRC, Cairo, Egypt
b
Semiconductors Technology Lab, Faculty of Science, Ain Shams University, Cairo 11566, Egypt
c
Chemistry Department, Faculty of Science, Ain Shams University, Cairo, Egypt

h i g h l i g h t s

 New lightweight cement plaster with unique physical properties is developed.


 A significant enhancement in thermal resistance and solar reflectivity is achieved.
 NMK is very effective for preserving flexural strength of lightweight cement plaster.

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

Article history: Cementitious materials are widely used for cladding of the building envelopes; however, they possess
Received 23 April 2015 low thermal resistivity, low tensile strength and ductility which leading to cracking with time. It would
Received in revised form 12 October 2015 be advantageous to improve thermal resistivity of lightweight cementitious materials whilst keeping
Accepted 28 October 2015
their mechanical performance acceptable/reasonable. This study represents an extension to a work that
Available online 2 November 2015
has investigated the role of nano metakaolin (NMK) in enhancing the flexural strength of fiber reinforced
cementitious composites (FRCC). An optimum composite of NMK – modified FRCC was determined. The
Keywords:
aim of this study is to develop nanostructured lightweight fiber reinforced cementitious surface compos-
Cement
Perlite
ites (NLWFRCC) with improved thermal properties and reasonable mechanical strength. For this purpose;
Natural fiber white Portland cement (WPC) was partially replaced with different amounts of perlite ranging from 10%
Nano metakaolin up to 70% by volume of cement then substituted by 10% nano metakaolin. Natural fibers were added by
Thermal conductivity 2% by mass of binder. The bulk density, thermal conductivity, solar reflectivity, flexural strength, and cap-
Flexural strength illary water absorption were determined in accordance to ASTM standards at 28 days of curing. The
Reflectivity microstructure characteristics of the hardened NLWFRCC were investigated by scanning electron micro-
Capillary absorption scope (SEM). It was found that the density, thermal conductivity and flexural strength decrease with
increasing replacements of cement by perlite, thermal conductivity at 70% perlite is 6.3 times less than
the composite with no perlite (plain). Even at 70% Perlite; the developed NLWRFCC still retaining suffi-
cient strength. Incorporating perlite into WPC, led to a significant enhancement in reflectivity especially
in near infrared region; an increase of about 33% was obtained at 70% perlite.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction efficiency of buildings and can make a significant contribution in


minimizing the building energy consumption for heating and cool-
Building sector is one of the major energy consumers, studies ing and hence in reducing CO2 emissions [2]. The most basic prop-
indicate that buildings in Egypt (residential and commercial sec- erty that used for determining the thermal performance of building
tors) consume about 58% of the total energy use concerning elec- materials is the thermal conductivity, which describes the ability
tricity; therefore, it is necessary that Egypt should devote more of heat to flow across the material under a specific temperature
efforts to reduce energy use in buildings [1]. Thermal characteris- gradient [3]. Therefore, improving the thermal performance of a
tics of the building envelope have a major impact on the energy building envelope will result in minimizing heat transfer through
building skins; this will reduce the amount of cooling energy
required to maintain comfortable indoor air temperature in hot cli-
⇑ Corresponding author. mate, i.e. this will lower the load on the air-conditioning system
E-mail address: [email protected] (H. Shoukry).

http://dx.doi.org/10.1016/j.conbuildmat.2015.10.188
0950-0618/Ó 2015 Elsevier Ltd. All rights reserved.
168 H. Shoukry et al. / Construction and Building Materials 102 (2016) 167–174

which is responsible for a significant portion of a typical building’s Table 2


electricity consumption [4]. Improving the thermal properties of Physical properties of perlite.

the existing building envelope can be considered as one of the Color White
most reasonable solutions in order to reduce the building energy Refractive index 1.5
consumption. The use of lightweight cementitious plastering can Free moisture, Max. 0.50%
Specific gravity 0.12
enhance the building envelope thermal resistivity. The uses of Grain size 0–5 mm
lightweight aggregate in the production of lightweight cementi- Specific heat 837 J/kg k
tious surface materials can reduce the thermal conductivity and Thermal conductivity at (24 °C) 0.04–0.06 W/m K
minimizing energy consumption in building [5]. The lightweight
aggregate can be classified into organic and inorganic cellular
materials. Examples of organic cellular materials include expanded Table 3
polystyrene foam (EPS), extruded polystyrene foam (XPS) and Physical properties of linen fiber.
polyurethane foam. The inorganic cellular materials are produced Color Yellowish
from natural and artificial such as expanded perlite, expanded clay, Length 18–30 in
vermiculite, ceramic microsphere, and glass hollow sphere [6]. Specific gravity 1.3
Tensile strength (tenacity) 5.5–6.5 gm/den
These materials are characterized by high porosity and contain
high volume of voids so their density and thermal conductivity
are very low [7,8]. While cement pastes and mortars are the most
The fiber thickness is less than 200 lm. The natural fiber has a cellular structure and
widely used for plastering, they are brittle, suffer from cracks and
its surface is very rough with large wrinkles and longitudinal grooves. The fiber is
low tensile strength, and exhibit low tensile strains prior to failure not solid; it is porous, like a honeycomb structure. It has a low mass density, yet
[9]. In order to overcome these weaknesses, fibers are incorporated it has a high degree of strength and stiffness. It has lower density because linen fiber
into cementitious matrix, and the use of this microfiber reinforce- has lots of long tubular running the length of the fiber on the inside.
ment leads to the improvement of mechanical properties of
2.2. Samples preparation
cement based materials [10]. This microfiber inclusion will help
to delay the development of micro-cracks but it will not help to Table 4 illustrates the mix design of NLWFRCC. WPC was partially replaced by
stop or terminate their initiation [11]. The addition of nano parti- different amounts of perlite ranging from 10% up to 70% (by volume) and then sub-
cles has been shown to improve the resistance to crack initiation stituted by constant amount of 10 wt% NMK for all mixes. The natural fiber was first
of cement based materials [12]. Nano-particles are very reactive cut into 2 cm length; fibers were added by 2 wt% of nano metakaolin cement binder
(90% WPC + 10% NMK) since it is the optimum ratio as concluded from our previous
because of their ultrafine size and large surface area and have par-
study [10]. The dry WPC, perlite and short fibers were mixed at a speed of 50 rpm
ticular potential in improving cement and concrete properties [13]. using electric mixer for 2 min for complete homogeneity. The NMK particles were
The changes in mechanical and micro-structural properties of first dispersed in the mixing water using ultrasonic bath for 15 min to assure good
cement mortar due to the effect of nano-clay have been considered dispersion and to avoid agglomeration. In this case, the mixture is now ready for
by many researchers [10,14,15]. The inclusion of nano-clay to addition into cement to make the fresh blended cement pastes.
The blended cement pastes were prepared using the standard water of consis-
cement and mortar enhances the compressive and flexural tency in order to maintain a constant degree of workability between different sam-
strength and resulted in quite dense, compact and uniform ples. Three groups of NLWFRCC were casted for tests, the first group was cast as
microstructure [14,15]. This study aimed at developing nanostruc- bars 4  4  16 cm3 for flexural strength, the second group was casted as cubes
tured lightweight fiber reinforced cementitious surface composites 5  5  5 cm3 for density and capillary water absorption tests and the third group
was cast as disks (5 cm Dia & 2 cm height) for thermal conductivity and solar reflec-
(NLWFRCC) with high thermal resistivity, enhanced solar reflectiv-
tivity tests. The samples of fresh pastes were kept in molds for 24 h, and then de-
ity and reasonable flexural strength for energy efficient building molded and allowed to cure under water for 27 days.
envelope applications.
2.3. Testing
2. Experimental procedure
2.3.1. Bulk density
The average bulk density of three cubic samples with dimensions of
2.1. Materials
5  5  5 cm3 was determined in oven-dry condition according to ASTM 6426-82
[16].
The materials used in this investigation were white Portland cement (WPC)
(type I), nano kaolin clay (NK), lightweight aggregate (perlite) and natural fiber
(linen). Nano kaolin was supplied by Middle East Mining Investments Company 2.3.2. Thermal conductivity
(MEMCO), Egypt; the perlite was supplied by the Egyptian company for manufac- Thermal conductivity test was performed using FOX 50 thermal conductivity
turing perlite & vermiculite (E.C.P.V) and linen fiber was supplied by United For analyzer in accordance with ASTM C 518 [17]. Since moisture content affects the
Export Co., Egypt. thermal conductivity, all the specimens were tested in oven-dry condition.
Nano metakaolin (NMK) was obtained by thermal activation (calcination) of NK
at 750 °C for 2 h. The oxide compositions of WPC, NMK and perlite were determined 2.3.3. Capillary water absorption
by X-ray fluorescence analysis (XRF) as shown in Table 1. The physical properties of Fig. 2 shows the experimental set up of capillary water absorption test. In this
perlite and linen fiber are introduced in Tables 2 and 3 respectively. The SEM micro- test the specimens were dried in oven at about 105 °C until a constant mass was
graphs of NMK, perlite and fiber are presented in Fig. 1. obtained. The sides of the specimen were coated with paraffin to achieve unidirec-
NMK has plate like structure and characterized by large length to thickness tional flow. The specimens were exposed to water on one face by placing it on
aspect ratio; it is especially favorable in matrix reinforcement, and the platelet slightly raised seat (about 5 mm) on a pan filled with water. The water on the
thickness is only 1–20 nm, although its dimensions in length and width can be mea- pan was maintained about 5 mm above the base of the specimen during the test.
sured in hundreds of nanometers, with a majority of platelets in 200–500 nm range The mass of the specimen was measured at regular 30 min interval up to 2.5 h to
after purification [10]. The perlite has a cellular like structure with micro air voids. get the little absorption variation of water. The capillary absorption coefficient (k)

Table 1
Chemical composition of starting raw materials (mass%).

Oxide (%) SiO2 Al2O3 Fe2O3 CaO MgO SO3 L.O.I. Na2O K2O TIO2 P2O5
WPC 20.65 3.96 0.18 68.30 0.58 2.69 3.49 0.12 0.02 – –
NMK 53.33 32.43 0.18 0.32 0.03 0.039 13.47 0.14 0.04 – –
Perlite 74.69 9.91 0.58 2.19 0.01 0.04 1.48 5.76 4.56 0.14 0.03
H. Shoukry et al. / Construction and Building Materials 102 (2016) 167–174 169

a b internal c

Surface

Fig. 1. SEM micrographs of (a) NMK, (b) natural fiber and (c) perlite.

3. Results and discussion


Table 4
Mix design of NLWFRCC (mass expressed per 1 m3). 3.1. Bulk density and thermal conductivity
Mix code Perlite (%) Constituents (kg)
NCBa Perlite Water Fiber
Fig. 3 shows the variations in bulk density and thermal conduc-
tivity of the developed NLWFRCC as a function of the amount of
M0 0 1277 0 455 25.5
perlite. It can be seen that, the density decreases with increasing
M1 10 1150 6.13 461 23
M2 20 1022 12.26 473 20.44 the amount of perlite in the composite. The density was varied
M3 30 894.25 18.39 475 17.88 between 1585 kg/m3 and 575 kg/m3. The significant reduction in
M4 40 766 24.52 477.5 15.33 density is due to the presence of large number of open pores and
M5 50 638.7 30.66 480 12.77
air voids in the structure as a result of the porous nature of perlite;
M6 60 511 36.79 481.3 10.22
M7 70 383 42.93 483.1 7.66
this will be shown from SEM micrographs.
The thermal conductivity of NLWFRCC decreases with decreas-
a
Nano clay cement binder (90% WPC + 10% NMK). ing the density. The thermal conductivity (TC) was decreased from
0.76 W/m K for the plain composite to 0.12 W/m K when the
p replacement ratio of perlite reached 70% i.e. the thermal conductiv-
was calculated by using formula: k = W/(A t) where, W = amount of water
absorbed in g, A = cross sectional area in (cm2) in contact with water and t = time ity at 70% perlite is about 6.3 times less than that of the composite
in seconds [18]. with no perlite. The reduction rates of TC values for every mix at
28 days of curing are presented in Fig. 4, the maximum reduction
2.3.4. Flexural strength in TC was 84.2% for 70% replacement of perlite. The expanded per-
The flexural strength test was performed on 4  4  16 cm3 bars using 600 kN lite led to a great reduction of TC of mixtures as a result of its por-
machine (DARTEC) in accordance with ASTM C348-08 [19]. Three samples per batch
ous structure which resulted in the creation of high amount of
were tested, and the average strength was reported.
pores in the structure. The air contained in the pores contributes
significantly to the poor conduction properties of the material.
2.3.5. Reflectivity
The pozzolanic activity of perlite leads to the consumption of cal-
Reflectivity measurements were performed using double-beam spectropho-
tometer equipped with integrating sphere (Schimadzu UV 3600), considering both cium hydroxide (CH) crystals and the creation of an additional cal-
specular and diffuse radiation according to ASTM E 903-96 [20]. The reflectivity was cium silicate hydrates (CSH) gels. Due to the amorphous and
determined at wavelength intervals of 1 nm from 230 to 2500 nm, which is the porous nature of CSH, it consequently contributes to lowering ther-
solar spectrum range with the highest concentration of solar energy according to
mal conductivity [22].
ASTM G 173-03 [21].
Porosity is one of the factors affecting the thermal conductivity
of cement and concrete structures and enclosed pores reduce the
2.3.6. Scanning electron microscopy (SEM)
conductivity due to low thermal conductivity of air [23]. Reducing
The scanning electron microscope (JSM 6360) was used for identification of the
changes occurred in the microstructure. the thermal conductivity increases the thermal resistance (R value)
provided by the lightweight cementitious composite, significantly
2.3.7. Thermogravimetric analysis (TGA) contributing to a reduction in heating and cooling loads for resi-
The phase composition analysis of NLWFRCC was studied by using (Schimadzu dential and commercial buildings.
TGA-50) thermal analyzer. Inert atmosphere with N2 flow of 30 mL/min, heating As the core of the natural fibers is porous and air is entrapped,
rate 10 °C/min, analysis range 30–600 °C. the natural fibers have low thermal conductivity; so, make a signif-
icant contribution to the insulating effect/poor conduction of fiber
reinforced cement composites. These may be the reasons for the
Test cube
higher thermal insulation characteristics of the developed
NLWFRCC samples. Hence; these materials may be considered as
building components to reduce heat transfer in air conditioned
Paraffin
buildings in order to decrease energy consumption.

Seat 3.2. Flexural strength


Water
Fig. 5 shows the variations in flexural strength of NLWFRCC as a
function of the amount of perlite at 28 days of curing. Evidently,
Fig. 2. Experimental set up of capillary water absorption test. the flexural strength decreases slowly with increasing the amount
170 H. Shoukry et al. / Construction and Building Materials 102 (2016) 167–174

1800 0.8
1600 0.7

Thermal conductivity, W/m.K


Density Thermal conductivity
1400 0.6
1200

Bulk density, Kg/m3


0.5
1000
R² = 0.9974 0.4
800
0.3
600
400
R² = 0.9981 0.2

200 0.1

0 0
0 10 20 30 40 50 60 70 80
Perlite ratio, %

Fig. 3. Variations in bulk density and thermal conductivity of NLWFRCC as a function of the perlite replacement ratios.

90

80

70
TC - reduction ratio, %

60

50

40

30

20

10

M0 M1 M2 M3 M4 M5 M6 M7

Mix code
Fig. 4. Reduction rates of thermal conductivity (TC) for all designed mixes.

of perlite. The flexural strength was decreased from 5.2 MPa for the reduces the gap between fiber and cement matrix and increase
plain composite to 2.9 MPa when the replacement ratio of perlite the bonding of fiber with the cement matrix; i.e. improving the
reached 70%; i.e. the flexural strength at 70% perlite (M7) is about interfacial zone. In addition, the high active silica content of perlite
55% of the flexural strength of the reference plain composite (M0). participates in the pozzolanic reaction, reducing CH crystals and
Even at 70% Perlite; the flexural strength 2.9 MPa might satisfies increasing the amount of CSH in the cement paste that is in turn
prescribed structural requirements. As compared with flexural increase the adhesion between perlite and cement paste.
strength of the reference sample (without fibers and without
NMK) which is 1.75 MPa [10]; it can be shown that NMK and fibers 3.3. Capillary water absorption
are very effective for covering the loss in flexural strength which is
caused due to the increase of amount of perlite. Fibers act as Fig. 6 shows the capillary absorption coefficient (k) of NLWFRCC
bridges between cement hydration products and cause internal as a function of perlite percentages at 28 days of curing. Generally,
matrix reinforcement; furthermore, the short fibers provide resis- the water absorption increases with increasing perlite ratio; this is
tance to crack propagation and retains load transfer during tension due to the large number of pores or voids which have been created
or flexure [10]. The pozzolanic reactivity of NMK with the free lime in the structure. The perlite aggregates possess cellular structure
(CH) which liberates during cement hydration resulted in the pro- and their inner cavities are able to accommodate large amounts
duction of additional amounts of CSH which is the strength respon- of water. Furthermore, the fibers themselves absorb some quantity
sible phase with a strong hydraulic character [10,13,14]. Due to its of water due to its micro-porous structure. The high water absorp-
ultrafine size, NMK particles fill the voids between cement grains tion and sorptivity could be a problem in terms of durability;
and reduce the capillary pores of internal matrix; furthermore they therefore, when applying these lightweight composites for build-
consume the CH crystals that accumulated about fiber surface, ing cladding it is recommended to be used with water proof paints.
H. Shoukry et al. / Construction and Building Materials 102 (2016) 167–174 171

Flexural strength, Mpa


4

0
0 10 20 30 40 50 60 70

Perlite ratio, %
Fig. 5. Flexural strength of NLWFRCC as a function of perlite percentages at 28 days of curing.

12
Capillary absorption coefficient, K

10

8
mg.cm-2.sec-1/2

R²= 0.9739

0
0 10 20 30 40 50 60 70
Perlite percentage, %

Fig. 6. Capillary absorption coefficient of NLWFRCC as a function of perlite percentages at 28 days of curing.

3.4. Thermo-gravimetric analysis (TGA) composite (M0) contains 4.52% CH. The partial replacement of WPC
by 70% (by volume) perlite led to decreasing CH content to 1.19%;
Fig. 7 shows the TGA thermograms for the plain composite (M0) i.e. the amount of CH in the composite (M7) is 26% of its content
and the composite incorporating 70% perlite (M7) at 28 days of in the plain M0 composite. Because of, 70% of the volume of the
hydration; the results are also plotted as derivative thermogravi- M7 composite is perlite. So; the amount of hydration products in
metric (DTG) curves in order to identify the detected phases. Cal- M7 must equal to 30% of its content in M0, however, the decrease
cium silicate hydrate (C–S–H) can be seen at 76–89 °C, while, of CH down to 26% might be attributed to the pozzolanic activity
calcium hydroxide Ca(OH)2 was detected at 448–478 °C [24]. From of perlite.
the DTG results, it can be seen that the intensity of both C–S–H and
CH hydration products decreased with increasing perlite content
thus agreeing with the decrease in the flexural strength when per- 3.5. Reflectivity
lite was used to replace part of white Portland cement. The amount
of CH can be calculated from the TGA curves using the following Solar energy, when absorbed by exterior surfaces, can transfer
equation: through to the interior of a building, raising the internal tempera-
ture. An increase in temperature can make the interior more
MWCH
CHð%Þ ¼ WLCH ð%Þ  uncomfortable and place heavy loads on air-conditioning systems.
MWH
This, in turn, can lead to a rise in associated energy consumption,
where WLCH corresponds to the mass loss attributable to CH carbon dioxide and greenhouse gas emissions. Increasing reflectiv-
decomposition and MWCH and MWH are the molecular weights of ity of cementitious exterior cladding materials is of great impor-
CH (74.01 g/mol) and water (18 g/mol), respectively [25]. The plain tance for energy efficient buildings.
172 H. Shoukry et al. / Construction and Building Materials 102 (2016) 167–174

M0 M7

Temperature, °C

Fig. 7. TGA and DTG of plain composite (M0) and the composite incorporating 70% perlite (M7) at 28 days of curing.

Fig. 8 shows the reflectivity of the developed NLWFRCC samples 3.6. Microstructure characteristics
as a function of wavelength. Generally, the reflectivity increases
with increasing the perlite replacement ratio over the whole range Fig. 9 shows the SEM micrographs of NLWFRCC with different
of wavelengths. The enhancement of reflectivity is significant espe- ratios of perlite at 28 days of curing. Freshly fractured samples
cially in the near infrared region. An enhancement of about 33% were used for SEM examination.
was obtained for the composite with 70% perlite. The increase in As clear, natural fibers and perlite particles are embedded in the
reflectivity of NLWFRCC is attributed to the great reflectance of cement matrix. The images demonstrated the good dispersion and
the perlite particles which have distributed through the structure. adhesion/bonding in cement paste. Significantly, the degree of
The perlite particles are characterized by high reflectance due to micro-porosity increased with increasing the perlite replacement
their brilliant white color. ratio. Also as the amount of perlite increases, more water is
Increasing the reflectivity of building skins results in reduced required to achieve the standard consistency than plain cement.
absorbed solar radiation and reduced surface temperatures, which Increasing the water content in any cement mixture will conse-
allow reduction of conduction heat transfer to the building interior. quently increases the degree of porosity in the hardened cement,
This will decrease the solar heat gain and reduces the thermal which in turn contributes to a further reduction in thermal conduc-
loads inside buildings which are helpful for the thermal comfort tivity. Fiber pullout and fiber rupture are also clear in SEM micro-
of occupants and result in energy savings. High reflectivity of graphs; fiber pullout can dissipate energy during the flexure
building skins is always good in summer and has little negative process leading to increasing the flexural strength. These are the
effect in winter, because of the reduced sunshine periods. mechanisms, by which the fiber reinforced nanostructured

Pure Perlite M0 M1 M3 M5 M7
100

90

80

70
Reflectivity, %

60

50

40

30

20

10

0
230 730 1230 1730 2230
Wavelength, nm
Fig. 8. Reflectivity of NLWFRCC as a function of wavelength.
H. Shoukry et al. / Construction and Building Materials 102 (2016) 167–174 173

a b
Perlite

Cement paste
Fiber

c d

Fig. 9. SEM micrographs of NLWFRCC with different perlite ratios: (a) 0%, (b) 10%, (c) 30%, (d) 50% and (e) 70%.

perlite-cementitious surface composites achieved their acceptable/ 3. Even at 70% perlite, the flexural strength of NLWFRCC is 2.9 MPa
reasonable flexural strength. which is a significant value.
4. Perlite particles have increased the reflectivity of NLWFRCC by
about 33% as compared with composite with no perlite.
4. Conclusion 5. The developed NLWFRCC is useful for energy efficient building
envelope
Based on the experimental results of this study it can be con-
cluded that:
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