Construction and Building Materials 51 (2014) 97–105

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Construction and Building Materials

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Properties of a lightweight cement composite with an ecological organic

filler
Michał Bołtryk, Edyta Pawluczuk ⇑
Faculty of Civil and Environmental Engineering, Bialystok University of Technology, Wiejska 45E, Bialystok 15-351, Poland

h i g h l i g h t s

 Two-stage technology of organic filler mineralisation is determined.

 Appropriate consolidation method of mixture is established.
 Chemisorption abilities of cement composite and of organic filler are determined.
 Microstructure of cement composite with reed and sawdust is examined.

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

Article history: This study aimed to establish the properties of lightweight cement composites with organic fillers, such
Received 3 August 2013 as common reed and conifer sawdust. The reed Phragmites australis is a notably common plant in Poland
Received in revised form 12 October 2013 that grows on waterlogged lands, and sawdust is a waste product that appears during the mechanical
Accepted 31 October 2013
processing of wood.
Available online 21 November 2013
The first step was to determine the influence of the mineralisation on the water absorbability of the
organic filler. Next, the influences of the superplasticiser (SP) content and the method of mixture consol-
Keywords:
idation on cement composite properties, such as the compressive strength, the water absorbability, the
Common reed
Sawdust
density and the porosity structure, were established. The chemisorption abilities of the cement composite
Lightweight cement composite and of the organic filler were also determined.
Mineralisation Ó 2013 Elsevier Ltd. All rights reserved.
CO2 carbonation

1. Introduction analysed. In this research, the common reed Phragmites australis

and conifer sawdust were used as the filler. The common reed is
Economic development, the increase in the environmental the most popular plant that is grown on waterlogged lands in
awareness of societies and ecological reasons require the construc- Poland and in many other countries. This reed is a valuable plant,
tion industry to apply recyclable [1,2] and renewable materials finding application in the building construction as a material with
within a human life period [3–6]. Due to the decreasing deposits high thermal insulation properties. The reed has also ecological
of natural aggregates that are used as basic building materials, as advantages. During its period of growth, the reed absorbs CO2 from
well as environmental reasons, the use of waste materials, such air and builds the gas into the structure of its tissues. The reed is
as sawdust and shavings [7–12], and organic materials, such as also cultivated in sewage treatment plants as a recycler of chemical
hemp and straw, is becoming justified in concrete technology pollutions. The young plants are used as a feed, and the rhizomes of
[13–15]. In Poland, as well as in the rest of Europe, these types of the reed are used in health care. The composition of reed grass is
building materials are not applicable on the mass scale. The use approximately 10.8% mineral compounds, mainly silica. The grass
of these materials is hampered by the habit of using ordinary also contains sugars, wax and saponins. Reed grass has high fire
cement concrete with mineral aggregates, as well as by a lack of and frost resistances, high pH and high salinity. Because of all these
research into the properties of cement composites with plant fillers. properties, the reed has been applied in building construction for
For many years, authors have used tree waste and plant fillers many years in the form of insulating boards, under-plaster mats
in lightweight concrete [16–19]. In this paper, the influence of or roofs covering. There have been made attempts to use this reed
organic filler mineralisation on cement composite properties was in reed-concrete structural elements [20,21].
Frothing agents in the reed, such as wax and saponins, cause
technical problems in the process of mixture consolidation and
⇑ Corresponding author. Tel.: +48 696945904. specimen formation. The authors therefore examined the selection
E-mail address: [email protected] (E. Pawluczuk). of the mixture consolidation method.

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.10.065
98 M. Bołtryk, E. Pawluczuk / Construction and Building Materials 51 (2014) 97–105

Because a lightweight cement composite with an organic filler 2.1.5. Chemical agents
is a porous material, a high probability exists that the composite For the mineralisation of the reed and the sawdust, two type of chemical agents,
aluminium sulphate Al2(SO4)3 and hydrated lime Ca(OH)2 (9% and 18% in propor-
has chemisorption properties connected with its carbonation. A tion to the mass of the organic filler respectively) were used. These agents were
significant amount of the calcium hydroxide in the lightweight ce- selected based on the analogy of mineralisation technology for wood shavings
ment composite with the organic filler reacts with the atmospheric [16–18]. Mineralisation by the Al2(SO4)3 solution prevents the organic filler against
carbon dioxide and, as a result, the calcium carbonate is formed the dissolution of compound sugars and reduces the hygroscopicity and water
absorption of the filler. In its hydrated form, aluminium sulphate should have an
[22–24]. In addition, hydrated calcium silicate (CSH), un-hydrated
acidic reaction (pH = 3–5). The presence of hydrated lime increases the effective-
tri-calcium silicate (C3S) and bi-calcium silicate (C2S) also consume ness of the aluminium sulphate action, neutralises the acidic reaction of the agent,
carbon dioxide [25–29]. During the carbonation process of calcium and improves the mixture’s workability.
silicate, in addition to the precipitation of the CaCO3 content, a sil-
ica gel forms. This gel accumulates in pores that are larger than 2.2. Organic filler mineralisation process
100 nm, which facilitates further carbonation. This phenomenon
has a great ecological significance. It is possible that cement hydra- Reed and sawdust constitute essential compositions of the lightweight cement–
organic composite and contain many organic compounds such as polyoses, starch,
tion products in composites with organic fillers absorb not only
cellulose, hemicellulose, pentosans or pectins, which may decompose in acids or
carbon dioxide but also other greenhouse gases. alkaline environments into monosaccharides – saccharose, glucose and xylose.
This study objected to establish the properties of lightweight These monosaccharides retard hydration of the cement, especially in the initial
cement composites with an organic fillers such as common reed period, due to the significant diffusion resistances. Another harmful result of the
adsorption layers is the loss of the ability of the cement grains to coagulate. Tri-
and conifer sawdust, to identify the possibilities of the improve-
calcium silicate (3CaOSiO2) as the main cement component increases the early
ment of its quality and to determine the ways of using it in the compressive strength of the cement composite but is also the most susceptible to
building construction. the harmful influence of carbohydrates. Therefore, carbohydrates are purposefully
eliminated from the reed (especially from its surface layers) and are bound into
compounds neutral to cement hydration. Mineralisation allows the organic filler
2. Materials and experimental methods
to resist decay, increases durability and decreases such properties as water absorp-
tion, susceptibility to volume changes and shrinkage. Mineralisation also results in
2.1. Materials
better adhesion of the filler to cement paste and decreases the composite’s initial
setting time and hardening [19].
2.1.1. Cement
At the Bialystok University of Technology, the following mineralisation process
Portland cements CEM I 32.5R and CEM I 52.5R specified in the Polish standard
was developed [16,18]: 9% aluminium sulphate Al2(SO4)3 and 18% hydrated lime
PN-EN 197–1 (Cement – Part 1: Composition, specifications and conformity criteria for
Ca(OH)2 in proportion to the mass of the organic filler are dissolved in mixing water
common cements) were used. The cements’ physical properties and chemical
divided into two equal parts. First, the organic filler is mixed with Al2(SO4)3 for
compositions are listed in Table 1.
3 min to a homogeneous saturation. After waiting 15 min, Ca(OH)2 is added, and
all components are mixed again for 1 min.
2.1.2. Organic filler
In laboratory tests, conifer sawdust and common reed were applied as the 2.3. Preparation of specimens
organic filler (Fig. 1).
Reed particles was cut in the winter period and, after drying, was cut into To apply the mixture composition onto 1 m3 of area, the two-stage covering
5–20 mm long pieces. Next, the straw was sieved to obtain two different fraction method by Paszkowski was used [18]. The mixture compositions for each experi-
of reed: 2–10 mm and 10–20 mm. The reed should not be mouldy and should not ment are given in Tables 3 and 4. After mineralisation of the organic filler (p.
have a dark colour. Conifer sawdust was delivered from the nearby sawmill and 2.2.), cement was added and mixed for 3 min to obtain a homogeneous mass. The
sieved to obtain a dust size range of 0–2 mm. Both the reed and the sawdust were consistency of the mixture should be S2 (slump 50–90 mm). Next, the cement com-
stored in laboratory air-dry conditions. The main physical properties, such as the posite mix was cast into 10  10  10 cm moulds and compacted manually into
bulk density, the skeletal density, the water absorption (WA) and the humidity three equal layers using a 1.8 kg metal. Every layer was compacted by 15 blows
(H), of the organic filler are given in Table 2. of the compactor falling freely from a height of approximately 10 cm onto the mix-
ture surface. The specimens were demoulded after 1 day and were then placed on
2.1.3. Resin the wooden grid where they cured in air-dry conditions at 50–60% RH and at a tem-
The Ceresit CT17 resin consisted of a styrene–acrylic copolymer, additions and perature of 20 ± 2 °C until the specimens were 28 days old. This process allowed for
water. This resin is a substance for surface strengthening all water absorbability regular drying of the specimens. For the CO2 carbonation test (p. 3.3.) the upper
bases. The range of concentration of resin used in experiment was 0–22.5% in surface of the specimens, after demoulding, was smoothed by a 0.5–1.0 cm layer
relation to the mass of the organic filler. of the cement mortar with a cement-to-sand ratio of 1:1 to imitate outside plaster.

2.1.4. Superplasticiser (SP) 2.4. Experimental methods

An Addiment FM6 superplasticiser, which significantly reduced the amount of
water, was applied. In our examinations, the SP improved the mixture’s workability 2.4.1. Water absorption test of the organic filler
and facilitated the consolidation of the specimens at the constant contents of The water absorption test of the organic filler was conducted according to the
cement and water. In the cement composite the superplasticiser content changed standard EN 1097-6 (Tests for mechanical and physical properties of aggregates.
from 0% to 4% in relation to the cement mass. Determination of particle density and water absorption). For the test reed samples
fraction 2–10 mm (500 g) were used and were dried at a temperature of 70 ± 5 °C
to a constant mass. After the mineralisation process, all specimens were dried again
Table 1 at the same temperature, weighed and then saturated with water at a temperature
The physical properties and chemical compositions of the cements. of 20 ± 2 °C. Because the organic filler is lighter than water, the filler was put into
nets and properly ballasted. Before each weighing, water present at the surface of
Parameter CEM I 32.5R CEM I 52.5R
reed particles was removed with an absorbing cloth. A constant mass of the filler
Chemical composition (%) was obtained after 2 days of saturation.
SO3 2.87 3.4
Cl 0.06 0.03
Na2O 0.81 0.9 2.4.2. Water absorption test of the cement composite
Insol. 1.28 0.4 The water absorption test of the cement composite was conducted on
Ign. Loss 1.84 3.1 10  10  10 cm cubic specimens according to the Polish standard PN-88/B-
06250 (Ordinary concrete). The specimens were saturated with water until full
Compressive strength (MPa) saturation and were then dried to a constant mass.
2 days 25.6 36.9
28 days 49.0 58.0
Initial setting time (min) 165 179 2.4.3. Compressive strength test
Final setting time (min) 225 217 The compressive strength test was conducted on 10  10  10 cm cubic
Specific surface (cm2/g) 3500 4120 specimens in accordance with EN 12390-3 (Testing hardened concrete – Part 3:
Compressive strength of test specimens).
 M. Bołtryk, E. Pawluczuk / Construction and Building Materials 51 (2014) 97–105 99

Fig. 1. Sawdust (on left) and common reed (on right) used as organic filler.

Table 2 was measured at 5 points (di,j) on each side of the specimen; next, the specimens
The physical properties of the organic filler. were weighed. An average carbonation depth was calculated for each side and for
all specimens. The results from the side of the sample with the mortar layer were
Organic filler qbulk (kg/m3) qskeletal (kg/m3) WA (%) H (%) not taken into account (p. 2.3.).
Sawdust 0–2 mm 137.3 299.0 283 7.75
Reed 2–10 mm 71.0 257.5 231 7.90 2.4.5.2. CO2 carbonation in the organic filler. To examine the susceptibility of the or-
Reed 10–20 mm 67.3 270.0 228 7.15 ganic filler to CO2 action, the sawdust and reed were weighed out in amounts equal
to the filler needed to form 3 cubic specimens (10  10  10 cm). The carbonation
test was conducted both for non-mineralised fillers and for fillers that were minera-
lised by an Al2(SO4)3 and Ca(OH)2 solution (p. 2.2.). The organic fillers were
2.4.4. Apparent density test subjected to CO2 action in the 5.1% concentration for 2 days. After removal from
The density test was conducted on 10  1010 cm cubic specimens in the chamber, the specimens were weighed and sprayed with a phenolphthalein
accordance with EN 12390-7 (Testing hardened concrete – Part 7: Density of hardened solution.
concrete). The specimens were dried at a temperature of 70 ± 5 °C for 72 h to obtain
a constant mass and were weighed with an accuracy of 1 g. The specimens were
2.4.6. Mercury intrusion porosimetry (MIP)
next measured in three dimensions in the middle of each side length to calculate
For the porosity structure examinations, the Autopore 9229 computer-aided
the specimens’ volumes.
measuring unit was used. The range of the measured pore sizes was 3–360,000 nm.

2.4.5. CO2 carbonation test 2.4.7. Scanning electron microscopy (SEM)

2.4.5.1. CO2 carbonation in the cement composite. Carbonation is one of the chemical For the structural examinations, the Hitachi S-3000N QUEST scanning electron
methods of CO2 sequestration. It is a safe, ecological method of long-term CO2 stor- microscope with EDX analysis unit was used. The research was performed on
age. The carbonation test was conducted on 10  10  10 cm cubic specimens (24 specimens that had cured for approximately 1 year.
specimens) according to EN 13295 (Products and systems for the protection and repair
of concrete structures. Test methods. Determination of resistance to carbonation) and to
EN 14630 (Products and systems for the protection and repair of concrete structures.
3. Test results and discussion
Test methods. Determination of carbonation depth in hardened concrete by the phenol-
phthalein method). The cement composite mixture composition is given in Table 4. 3.1. Influence of mineralisation of organic filler on its water absorption
After 28 days of curing in air-dry conditions, the specimens were weighed and were
broken in half. The fresh broken surfaces were cleaned of dust and loose particles
Lightweight cement composites with organic fillers are particu-
and were then gently moistened with distilled water so that the liquid did not flow
down the surface. This technique prepared the surfaces that were sprayed with a 1% larly characterised by high water absorption. Evaporating water
phenolphthalein solution. The specimens were divided in two parts. The first part results in large pores, which weaken most of technical properties
(12 specimens) were control specimens that remained in the air-dry conditions un- that are essential to the later material work. Therefore, an
til the moment of the test, and the 12 remaining specimens were put into the CO2 experiment studying the influence of mineralisation on the reduc-
chamber. The specimens in the carbonation chamber were subjecting to CO2 action
with an approximate concentration of 5% for 56 days. Every 14 days, 3 specimens
tion of the water absorption of the organic filler was conducted
were taken out of the chamber and, along with 3 control specimens, were chosen (Table 5). Ten series of samples of the 2–10 mm reed were
to examine the susceptibility of the specimens to CO2 action. The carbonation depth prepared. The results of reed water absorption are given in Table 5.

Table 3
Mix proportions of the cement composites.

Composition No. CEM I 32.5R (kg) Quartz sand (kg) Water (dm3) SP (%) Organic filler (kg)
Sawdust 0–2 mm Reed 2–10 mm Reed 10–20 mm
1 0
2 1
3 400 300 439.6 2 84.6 44.0 45.4
4 3
5 4

Table 4
Mix proportions of the cement composite.

CEM I 52.5R (kg) Water (dm3) Organic filler (kg) Chemical agents (kg)
Sawdust 0–2 mm Reed 2–10 mm Reed 10–20 mm Al2(SO4)3 Ca(OH)2
382 356 58.7 58.7 13.1 22.9 23.5
100 M. Bołtryk, E. Pawluczuk / Construction and Building Materials 51 (2014) 97–105

There are significant differences between the water absorption Table 6

of the organic filler depending on the method of mineralisation Compressive strength of the cement composite with the organic filler.

way (Table 5). The water absorption of samples without the Composition No. SP (%) Compressive strength (MPa)
mineralisation was the highest (300.8%); however, after full miner- Consolidation method
alisation and the addition of 4.5% resin, the water absorption Manual Balance press Vibro-pressing
decreased approximately fourfold (to 81.6%). For technical 1 0 4.22 3.27 3.90
purposes, full mineralisation without the addition of resin is 2 1 4.10 3.21 2.87
completely satisfactory (164.6%). 3 2 4.09 2.91 2.39
4 3 3.41 2.86 1.74
5 4 3.09 2.21 0.78
3.2. Influence of consolidation method and superplasticiser content on
cement composite properties
However, the superplasticiser caused a decrease of the composite
In the next step, the influences of the mixture consolidation
density for all analysed consolidation methods. The density de-
method and of the superplasticiser content on the cement compos-
creased the most, by 11%, when 2% of the SP was added and by
ite properties were established. Quartz sand (0–2 mm in particle
13% for a 4% content of SP when the vibro-pressing method was
size), which improved the homogeneity and strength properties
used. Similar density in the range of 0.72–1.10 kg/dm3 for light-
of the lightweight cement composite with the organic filler, was
weight composites with hemp fibres was presented in other study
also used. Additionally, full mineralisation was applied every time.
[31].
The laboratory specimens were prepared using three types of con-
solidation methods as follows:
3.2.3. Water absorption test results
In Table 8 the results of the water absorption test for each con-
– Manual consolidation.
solidation method and SP content are presented.
– Consolidation with a balance press.
As seen from Table 8, the water absorption of the samples
– Vibro-pressing.
formed by the manual method decreased from 46.1% to 41.1%
when the superplasticiser content changed from 0% to 2%. At a
In all mixtures, the amounts of cement, water, quartz sand and
higher SP content (4%), the water absorption increased to 50.1%.
organic filler in 1 m3 were constant (Table 4).
The high water absorption (up to 26.3% by mass) of the cement
composite with the vegetable filler was confirmed in other study,
3.2.1. Compressive strength test results where 12% (by mass) of commercial sisal was used [32].
The compressive strength test results for each consolidation When the vibro-pressing consolidation method was used, the
method and superplasticiser content are presented in Table 6. water absorption of the composite was the highest and increased
The results presented in Table 6 indicate that the use of the with the superplasticiser content. These results show that the max-
manual compacting method lead to the highest compressive imum superplasticiser content for lightweight cement composites
strength of the cement composite with the organic filler with organic fillers cannot be higher than 2% relative to the cement
(4.22 MPa with 0% superplasticiser content). However, for the vi- mass. The superplasticiser in the amount of 4% can caused air
bro-pressing method, the compressive strength was the lowest. A entrainment of the mixture and can therefore weaken the physi-
4% c.m. increase of the superplasticiser content resulted in a grad- cal–mechanical properties of the hardened composite. A manual
ual decrease of compressive strength up to 27%, 32% and 80% for method using the standard 1.8 kg laboratory compactor was the
the manual, press balance and vibro-pressing compacting meth- most favourable method of lightweight cement composite consol-
ods, respectively. The compressive strength of the tested cement idation. In practice, this method will allow this material to be ap-
composite with organic filler without SP content changed from plied in individual building construction conditions without the
3.27 to 4.22 MPa. Reported in other studies compressive strength use of complicated consolidation devices.
values for hemp composites was generally lower and varied from
1.06 to 1.7 MPa depending on the chemical treatment and from 3.2.4. Mercury intrusion porosimetry
0.02 to 1.22 MPa depending on the mixture respectively [15,30]. The total porosity of the cement composite with the organic filler
was established for the favourable consolidation method of mixture
3.2.2. Apparent density test results – manual compacting. The physical properties of the specimens with
The test results of the apparent densities of the composite spec- different superplasticiser contents (apparent density, density and
imens in air-dry conditions for each consolidation method and porosity) described by using mercury intrusion porosimetry (MIP)
superplasticiser (SP) content are presented in Table 7. and helium porosimetry (HP) are presented in Table 9.
The results given in Table 7 show that the composite density for The MIP results of the tested specimens are given in Table 10:
the three consolidation methods when 0% superplasticiser (SP) was
added is comparable. The highest density was obtained with the – Total porosity (cm3/g), pt(skeleton).
manual consolidation method (0.925 kg/dm3); the lowest density – Total pore area under the acceptance a model of cylindrical
was obtained with the vibro-pressing method (0.896 kg/dm3). pores (m2/g), Stotal.

Table 5
Experiment and test results of reed water absorption.

Composition No. 1 2 3 4 5 6 7 8 9
Resin* (%) 0 9 18 0 4.5 9 13.5 18 22.5
Full mineralisation** (Yes/No) No No No Yes Yes Yes Yes Yes Yes
Water absorption (%) 300.8 284.9 239.2 164.6 81.6 105.6 118.7 126.1 128.1
*
Relative to the mass of the organic filler.
**
Full mineralisation by using 9% aluminium sulphate and 18% hydrated lime relative to the mass of the organic filler.
 M. Bołtryk, E. Pawluczuk / Construction and Building Materials 51 (2014) 97–105 101

– Median pore diameter by volume (lm), /vol . increased by 21% compared to the reference specimens. The
– Median pore diameter by area (lm), /area . growths of the total pore area and the median pore diameter by
– Average pore diameter (lm), /subst . volume and by area were also the result of superplasticiser appli-
cation. The 4% SP content also caused the fivefold increase in the
The total porosity of the composite is in the ranges of 45–48% average pore diameter than that of the specimens without SP
(mercury intrusion porosimetry) and 50–58% (helium porosime- (Table 10). The pore distribution in the tested specimens is
try). It is comparable to porosity of lightweight concrete presented presented in Table 11.
by other researchers [33]. However, the presence of the superplas- Applying the superplasticiser in the examined cement compos-
ticiser caused an increase of the porosity of the lightweight cement ite with the organic filler changed the porosity structure of this
composite with the organic filler (Table 9). The porosity of the material. An increase of the SP content caused a decrease of the
specimens containing 2% SP was 14% higher than that of the gel pore (3–10 nm) content from 2.3% to 0.0% as well as a decrease
reference specimens (without SP); for a 4% SP content, the porosity of the macropore (<1000 nm) content, which is a particularly
adverse phenomenon from the point of view of composite durabil-
ity. However, the presence of superplasticiser caused an increase of
Table 7 the macropore (>1000 nm) and large pore (>50,000 nm) content
Apparent density of the cement composite with the organic filler. (Table 11). These pores in lightweight cement composites are fully
saturated with free mix water. The greatest increase in the pores
Composition No. SP (%) Apparent density qp (kg/dm3)
Consolidation method content was observed in the 10,000–300,000 nm pore size range
when 4% SP was added; it is therefore possible to imagine that
Manual Balance press Vibro-pressing
applying the superplasticiser in the alkali environment caused air
1 0 0.925 0.881 0.896
entraining the mixture. The disadvantageous pore structure char-
2 1 0.916 0.894 0.842
3 2 0.908 0.851 0.797
acteristics of the composite modified by the superplasticiser ex-
4 3 0.874 0.835 0.789 plains the very high water absorption and the decreases in the
5 4 0.877 0.815 0.779 compressive strength and in the apparent density. Figs. 2–5 illus-
trate the porosity characteristics of the cement composite with
and without the SP with the manual consolidation method.
The presented results indicate that the presence of the super-
Table 8
Water absorption of the cement composite with the organic filler.
plasticiser in the cement composites with the organic filler causes
the increase in the total porosity of the cements. A disadvanta-
Composition No. SP (%) Water absorption (%) geous composite structure was clear obtained by moving the
Consolidation method
porosity towards large pores (>10,000 nm). Therefore, a 2% super-
Manual Balance press Vibro-pressing plasticiser content in the cement composite with the organic filler
1 0 46.1 44.7 44.3 is the upper limit.
2 1 44.3 42.0 46.3
3 2 41.1 47.3 52.9
4 3 44.9 47.9 55.3 3.2.5. Scanning electron microscopy (SEM)
5 4 50.1 51.2 63.7 Specimen fractures were observed under SEM to show an image
of the microstructure of the cement composite with reed and saw-
dust (Figs. 6 and 7).
In case of the lightweight cement composite, the structure of
Table 9
Physical properties of the cement composite specimens.
the cement paste is quite homogeneous, and the mechanical per-
meation of the paste into the organic filler is observed (Fig. 6).
SP (%) Apparent density (kg/dm3) Density (kg/dm3) Porosity (%) However, for an insufficient consolidation of the cement paste,
MIP 0 1.112 2.039 45.41 cracks are possible in the contact zone (Fig. 7). The results of
2 1.037 2.002 48.16 EDX analysis show that the dominant peaks in the organic filler
4 0.985 1.922 48.62
area are carbon, oxygen and calcium; therefore, calcium carbonate
HP 0 – 2.105 50.48 was likely formed (Fig. 8a). In the cement paste area, calcium, oxy-
2 – 2.100 53.61
gen and silica, that is, products of the cement hydration, such as
4 – 2.100 58.06
CSH gel and calcium hydroxide, dominate (Fig. 8b).

Table 10
MIP test results.

SP (%) Total porosity pt(skeleton) (cm3/g) Stotal (m2/g) /vol (lm) /area (lm) /subst (lm)

MIP 0 0.4082 6.7945 0.9361 0.0148 0.0825

2 0.4643 7.8190 1.6303 0.0510 0.2012
4 0.4932 9.8385 3.0402 0.0757 0.4183

Table 11
Pore distribution in the specimens.

Composition No. Total porosity, pt(skeleton) (cm3/g) Pores by size (%)

3/10 (nm) 10/50 50/100 100/1000 1000/10,000 10,000/50,000 50,000/300,000
SP_0 0.4082 2.3 10.8 13.3 24.5 19.7 17.4 12.2
SP_2 0.4643 0.1 7.2 10.8 25.1 25.3 20.7 10.7
SP_4 0.4932 0.0 4.2 7.8 17.9 25.7 29.4 15.1
102 M. Bołtryk, E. Pawluczuk / Construction and Building Materials 51 (2014) 97–105

0.60 35%
SP_0% SP_2% SP_4%
30%
0.50

Content of pores, %
25%
0.40
20%
V, cm3/g

0.30 15%

10%
0.20
5%
0.10 SP_0% SP_2% SP_4% 0%
10 50 100 1,000 10,000 50,000 300,000
0.00 Pore diameter, nm
1 10 100 1,000 10,000 100,000
Pore diameter, nm Fig. 5. Porosity structure of the cement composite with and without the SP with the
manual consolidation method.
Fig. 2. Cumulative pore volume in the cement composite with and without the SP
with the manual consolidation method.

120%

100%

80%
V, %

60%

40%

20% SP_0% SP_2% SP_4%

0%
1 10 100 1,000 10,000 100,000
Pore diameter, nm

Fig. 3. Pore distribution in the cement composite with and without the SP with the
manual consolidation method (total porosity = 100%).

Fig. 6. Transition zone between the cement paste and the developed surface of the
reed straw. Magnification 1000.
0.30
SP_0% SP_2% SP_4%
0.25

0.20
1dV/dlogD

0.15

0.10

0.05

0.00
1 10 100 1,000 10,000 100,000
Pore diameter, nm

Fig. 4. Differential pore distribution in the cement composite with and without the
SP with the manual consolidation method.

3.3. CO2 carbonation

Fig. 7. Transition zone between the cement paste and the reed straw. Magnification
3.3.1. CO2 carbonation in the cement composite 1000.
The physical–mechanical properties of the specimens are pre-
sented in Table 12.
The average masses of the control specimens and of the speci- in addition, these samples had higher masses than the control sam-
mens stored in the CO2 chamber for 14, 28, 42 and 56 days are pre- ples remained in laboratory conditions. The result was due to the
sented in Table 13. carbonation process; carbon dioxide (CO2) reacts with the calcium
The results presented in Table 13 indicate that the control spec- hydroxide (Ca(OH)2) to produce calcium carbonate (CaCO3) and
imens have lower masses at the test moment than after 28 days of water according to the following reaction:
curing. However, the masses of the specimens stored in the CO2
CaðOHÞ2 þ CO2 ! CaCO3 þ H2 O:
chamber were higher after removal from the chamber than before;
 M. Bołtryk, E. Pawluczuk / Construction and Building Materials 51 (2014) 97–105 103

Table 13
Specimens mass (control and exposure to CO2).

Specimens Specimens age Mass (kg)

(days)
After 28 days At the test
cured moment
Control 28 1.046 1.046
42 1.066 1.064
56 1.047 1.038
70 0.984 0.982
84 1.081 1.077
Exposure to 42 (14)* 1.156 1.176
CO2 56 (28)* 1.081 1.124
70 (42)* 1.044 1.115
84 (56)* 1.063 1.152
*
The time of exposure to CO2 is presented in brackets.

Table 14
Carbonation depth for the specimens (control and exposure to CO2).

Specimens Specimens age (days) Carbonation depth (mm)

d1 d2 d3 daverage
Control ... ... ... ... ...
84 0.0 0.0 0.0 0.0
*
Exposure to CO2 42 (14) 0.0 0.0 0.0 0.0
56 (28)* 3.6 3.5 2.7 3.2
70 (42)* 11.4 11.5 10.5 11.1
84 (56)* 18.1 16.1 18.5 17.6
*
The time of exposure to CO2 is presented in brackets.

Table 15
Mass of the non-mineralised and mineralised organic fillers.

Organic filler Fraction and filler Mass (g)

mass
Before putting in After removing
CO2 chamber from CO2 chamber
Non-mineralised sawdust 0–2 mm 391 403
(176 g)
reed 2–10 mm
Fig. 8. EDX analysis of (a) the organic filler area and (b) the cement paste area. (176 g)
reed 10–20 mm
(39 g)
Mineralised sawdust 0–2 mm 818 1563
Table 12
(176 g)
Properties of the specimens.
reed 2–10 mm
2 days 7 days 14 days 21 days 28 days (176 g)
reed 10–20 mm
Compressive strength, MPa after:
(39 g)
1.51 2.21 4.66 4.77 4.85
Humidity in air-dry conditions, % after:
35.5 17.7 13.6 11.6 10.8
The carbonation depths for all control specimens were equal
Water absorption, % mass zero, so only selected results for specimens remained in laboratory
50.19 conditions for 84 days were presented in Table 14. Under the effect
Density, kg/dm3 of a phenolphthalein solution, the entire examined surface of the
0.85 specimens after 28 days of curing in laboratory conditions and
after the first 10 days of storage in the CO2 chamber changed to a
pink colour. This reaction was because the cement composite with
the organic filler had a high-alkali reaction (pH > 9.5); however,
This phenomenon was also reported in other studies where the this reaction did not necessarily indicate the lack of carbonation.
effect of carbonation on the durability of cement composites rein- After a longer period of storing the specimens in the CO2 chamber
forced with sisal pulps was determined [34,35]. As the result of the (28, 42 and 56 days), the effects of this phenomenon started being
carbonated curing the improvement of mechanical strength, de- visible in the form of colourless areas at the edges of the
crease in water absorption, lower porosity and densification of specimens.
the matrix by the formation of new hydration products were The initial fast absorption of the CO2 by the composite could be
observed. due to the composite’s low humidity. The carbon dioxide could
The carbonation depths for the control specimens and those quickly enter the pores that were filled with air where a certain
that were stored in the CO2 chamber were obtained from three amount of humidity that enabled the further carbonation process
sides and are given in Table 14. was produced.
104 M. Bołtryk, E. Pawluczuk / Construction and Building Materials 51 (2014) 97–105

The increase of the specimens’ humidity was indicated by the Acknowledgment

growth of the relative humidity in the chamber and by the increase
in the specimens’ masses. When the humidity in the chamber was The study was performed under the Research Project Number S/
approximately 92%, insignificant changes in the temperature and WBiIŚ/1/13.
in the specimens’ humidity were observed, and the absorption of
carbon dioxide was much slower. A significant increase of the car-
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