Construction and Building Materials xxx (xxxx) 120604

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Construction and Building Materials

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Efficient application of cellulose pulp and paper production wastes to produce
sustainable construction materials
Vsevolod Mymrin a ,⁎ , Cleber L. Pedroso a , Daniela E. Pedroso a , Monica A. Avanci a , Stephanie A.S. Meyer b ,

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Paulo H.B. Rolim a , Marco A. Argenta b , Maria J.J. Ponte b , Alexandre J. Gonçalves a
a
Department of Civil Engineering, Federal Technological University of Paraná, 4900, Heitor Alencar Furtado St. Campus Curitiba, CEP: 81280-340 – Ecoville, Paraná, Brazil
b
Federal Technological University of Paraná, Curitiba, Brazil

ARTICLE INFO ABSTRACT

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Article history: The mechanical and physical properties of the composites developed from dregs, grits, and lime mud of the Kraft
Received 27 December 2019 cellulose and paper production process (55–75%), concrete waste (10–25%) and lime production waste (0–25%),
Received in revised form 20 July 2020 far exceeded the demands of Brazilian standards for bricks, blocks, and road-base construction materials. The
Accepted 13 August 2020
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study of the developed composites structure by XRF, XRD, SEM, EDS, and LAMMA methods demonstrated that
Available online xxx
new mainly amorphous formations were responsible for all attained properties. The industrial application of these
construction materials would introduce excellent efficiency from an economic and environmental points of view.
Keywords © 2020
Cellulose pulp/paper production wastes
Concrete waste
Lime production waste
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Chemical interaction
High mechanical properties
Environment protection
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1. Introduction
The rapidly growing amount of industrial and municipal wastes is
the major cause of atmospheric pollution and the rise in its temperature.
According to S.W. Hawking’s [1] calculations, in 300 years, this will in-
evitably cause the death of our civilization due to the overheating of the
Earth’s atmosphere. The authors of this article consider that the only
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mud [4]. It was produced in Brazil, in 2011, 207 mln. t. of dregs, 224
mln.t of grits, and 172 mln.t of lime mud [5]. Paper and pulp mills gen-
erate 48 tons of waste per 100 tons of pulp produced [6]. Monte [7]
cited other statistics: 300 kg of sludge for each ton of paper. Paper pro-
duction wastes are usually disposed of in landfills in Australia [8] and
North America [9]. Sludge is generally landfilled, ponded, or subjected
to land cultivation.

way to prevent a global ecological catastrophe is the urgent and com-
plete utilization of all types of wastes as raw components for the pro-
duction of environmentally friendly materials. Besides, it is well known
that industrial and municipal wastes contain many toxic substances and
threats to the environment and public health. Fetene et al [2] believe
that “lack of integrated solid waste management practice in fast-growing
cities… is posing a threat to sustainable and green cities development”.
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Pulp and paper production wastes can be used as an organic
pore-forming addition in the quantity of 2.5–5% mixed with raw
brick-clay [10]; to improve soil fertility instead of commercial agricul-
tural limestone [11], in amounts below 1.2 t/ha due to the higher Na
concentration [12]. The addition of these wastes to the concrete en-
hances its strength and durability in aggressive environments [9].
Throughout the concrete production and in the construction process,

The Brazilian Tree Industry (IBÁ 2017) reported [3] that, in 2016,
Brazilian paper and cellulose pulp production was 18.8 million tons,
8.1% higher than in 2015. The most hazardous wastes from the Kraft
process are the three ones from the caustification system: green liquor
clarifier – dregs, lime eraser – grits, and white liquor clarifier – lime
⁎ Corresponding author.
E-mail address: seva6219@gmail.com (V. Mymrin)
as well as during the demolition of structures, a large amount of con-
crete waste is formed [13]. Concrete is the most widely used construc-
tion material in the world, second to water [14]. Annual production
of construction and demolition debris in the European Union was ap-
proximately 860 million tons, i.e., about 35% of Europe’s total wastes
[15]. Annual global concrete production was 6 billion [16]; according
to WBCSD calculations [17], it was much more − 21 billion tons. The
reuse of this concrete in the construction industry can significantly re-
duce the extraction of natural aggregates [18]. The United States was
the leading producer of sand and gravel worldwide in 2019, having pro-
duced 110 million metric tons that year[19].

https://doi.org/10.1016/j.conbuildmat.2020.120604
0950-0618/© 2020.
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Such an impressive scale of nature’s destruction compels the search
for substitutes for these materials. CO2 emissions in Portland cement
production are up to 8% of total
pollution [20] (Oliver et al., 2012) because, for the production of
one ton of Portland cement, about 1 ton of carbon dioxide is released
[21]. More carbon dioxide is set free in the processes of extracting, pro-
where RW is the uniaxial compressive strength after 24 h in water, and
RD is the uniaxial compressive strength after 24 h in outdoor storage.
Water absorption (WA) tests were performed on samples, on the 28th
day, in accordance with the NBR 9778 2 [32], which uses the following
equation:
(2)

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cessing, and moving natural construction raw materials, warming up the
atmosphere, and causing a greenhouse effect [22]. The same situation where MSAT is the mass of the saturated specimen after 24 h in the wa-
occurs with almost all types of industrial and municipal wastes and their ter, and MD is the mass of the specimen after oven drying at 100 °C for

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gases. 24 h.
There are many studies on the problem of recycling concrete waste
for various purposes. Among them, Tam et al. [23] used concrete wastes 2.3. Raw materials
for base and sub-base of roads; Pasandín and Pérez [24] applied them to
asphalt; Arabani and Azarhoosh [25] used mixes of asphalt and ferrous The industrial wastes, used as raw materials herein, were collected
slag. from companies located near the city of Curitiba, capital of the state
Lime production waste (LPW) is a carbonate raw material mixed of Paraná, Brazil, were used. The Berneck Company pulp mills supplied
with some impurities (mainly sand and clay) burned at insufficiently low

temperature; it can also be a calcined lime transformed into carbonates
due to storage with the access to moisture and air [26]. Usually, it is
used for the neutralization of acidic soils or the cement industry [27].
Mymrin and Correa [28] used LPW as an alkaline concrete waste acti-
vator. Stroeven et al. [29] mixed LPW and low-quality Portland cement
for the production of cement composite with high bonding properties,
obtaining a new high-performance material. Al-Sayed [30] applied LPW
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the paper and cellulose production wastes (CPW): green liquor clari-
fier (dregs), lime eraser (grits), and white liquor clarifier (mud of lime).
Small local plants provided concrete (CW) and lime production wastes
(LPW). To use of all three wastes of paper and cellulose production,
a mixture was prepared at the local Berneck plant, in proportion to
their production − 34.33% dregs, 37.12% grits and 28.55% lime sludge,
named “cellulose production waste” (CPW).

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to increase the resistance strength of concrete pavements. Do et al. [31] 3. Results
investigated the use of lime residue as filler in asphalt paving mixtures.
The objectives of this study were 1. To develop new composites ex- 3.1. Raw materials characterization
clusively from industrial wastes with maximum content of three types
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of paper production sludges (dregs. grits, and lime mud) in composites The detailed characterization of all the studied raw materials
with concrete and lime production wastes; 2. To investigate the inter- through their granulometric, chemical and mineralogical compositions,
action processes of the original components to form a new composite and morphological microstructure made it possible to choose 1. the most
structure; 3. To adapt existing technologies to manufacture the devel- promising combinations of components and their percentage ratios to
oped materials at laboratory and pilot levels; 4. To study the environ- obtain maximum values of mechanical and physical properties and 2. to
mental efficiency of using the developed composites to solve ecological
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determine the influence of each component on the structure formation

problems from cellulose pulp and paper production industry. processes of the developed materials.

3.1.1. Particles size distribution and physical properties of the raw materials
2. Methods and raw materials The most coarse-grained material among the five wastes used (Table
1) was the concrete waste with 85.02 wt% of particle size between 4.00
2.1. Methods and 0.25 mm; grits followed it with 48.56% and lime production waste
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To achieve the proposed goals, the authors employed the available
methods to carry out the research, reported below.
All raw materials were characterized by granulometric composition
by analysis of particle size distribution by laser diffraction on an LA-950
Horiba analyzer. Mineral composition by X-ray diffraction (XRD) on
a Philips PW 1830. Morphological structure by scanning electron mi-
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with 25.47% particles of the same size. The thinnest material was the
lime mud, which had 81.24 wt% particle size ≤ 0.20 mm, followed by
dregs with 66.85 wt% of the same size.
Table 1
Particles size distribution of the raw materials.

croscopy (SEM) on a Jeol JSM-6360 LV. Sieve

The developed composites were characterized by axial compressive (mm) Particles size content. wt. %
strength on an EMIC universal testing machine, water absorption (WA)
on the Instrutherm BD-200, and linear shrinkage on Mitutoyo caliper. Lime Concrete Lime Production
Dregs Grits Mud waste Wastes
Mineral composition by X-ray diffraction (XRD) on a Philips PW 1830.
Morphological structure by scanning electron microscopy (SEM) on a 4 – 20.23 – 35.34 1.17
Jeol JSM-6360 LV. Micro chemical composition of new formations were
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2 0.30 13.10 – 24.36 2.68

analyzed by energy dispersive spectroscopy (EDS) on a Jeol JSM-5410 0.5 0.20 6.70 – 17.21 9.37
LV and by atomic absorption analysis (AAS) on a Perkin Elmer 4100 0.25 2.60 8.43 – 8.11 14.25
0.053 0.07 9.83 0.05 3.01 21.52
spectrometer. Isotopes composition by laser micro-mass analyzer on a
0.043 5.33 5.74 1.22 4.18 26.35
LAMMA-1,000. 0.036 8.04 5.38 4.04 4.93 14.74
0.028 16.59 3.86 13.45 1.17 3.20
2.2. Calculations 0.020 21.13 5.62 25.70 0.34 3.58
0.010 28.26 4.86 33.29 0.56 2.19
0.006 7.76 5.58 8.91 0.48 0.74
The coefficient of water resistance (CWR) was calculated, on the 28th 0.003 4.78 6.88 4.32 0.22 0.18
day, using equation [32]: 0.001 3.61 2.14 4.59 0.06 0.05
>0.001 1.31 1.65 4.43 0.03 0.16
(1) Total 99.98 100.00 100.00 100.00 100.00
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The dregs' moisture content was 59.15 wt%, and the specific mass,
defined by the Chapman Specific Gravity Flask Method, was 1.370 kg
/ m3, showing the lowest pH = 10.15 due to the lower content of al-
kaline elements (Table 2). The grits' moisture content was much lower
− 17.56%, but their apparent specific mass was significantly higher −
2.083 kg / m3, with pH = 10.95. The lime mud's humidity was 19.30%,
According to the Brazilian standard [34], construction lime with calci-
nation loss (C.L.) superior to 12% should only be named as lime pro-
duction waste due to the high amount of crude carbonate CO2 leftovers
as a result of low temperature during calcination. Dregs presented the
maximum C.L. value (46.0%), followed by lime mud (43.1%), and grits
(37.1%). Concrete waste exhibited the lowest C.L. value (13.8%) due to

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and the apparent specific mass was the highest − 2.320 kg / m3, with the minimum CaO content (23.0%) and, correspondingly, lower carbon-
pH = 11.04, probably due to the higher CaO content = 54.5% (Table ates content. The CaO, MgO, and C.L. ratio results indicated the com-
2). plete carbonization of CaO and MgO and, therefore, the complete loss of

Concrete waste (CW) showed a specific mass of 2.280 kg / m3 and
a moisture content of 7.43%, with pH = 10.34. Lime production waste
exhibited a density of 2.211 kg / m3, moisture content of 12.44%, and
the highest pH among the raw materials = 11.47, most likely due to the
maximum amount of non-hydrated lime in it (Fig. 2-E).
3.1.2. Chemical composition of the raw materials
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the binding properties of all raw materials used in this study, except for
LPW, since the CO2 contained in dolomite is 23.9% and in calcite 44.0%.
3.1.3. Mineral composition of the raw materials
The X-ray diffractogram patterns (Fig. 2) showed that calcite
(CaCO3) was the only mineral detected in lime mud. In all other raw
materials under study, calcite was the main mineral found, followed by
dolomite CaMg (CO3)2. Small SiO2 quartz peaks are visible in the XRD

The main chemical element of pulp production wastes was CaO
(Table 2), which ranged from 37.4% in dregs to 54.5% in lime mud.
Even the lime production waste (LPW) contained a smaller amount
of lime mud (51.6%) because it was produced from dolomite CaMg
(CO3)2 and, consequently, it had the highest amount of MgO (29.0%).
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of dregs, grits, and LPW, but in concrete waste, it was the highest peak.
In the XRD of grits and LPW, the presence of a small amount of port-
landite Ca (OH)2 was detected and, in concrete waste, the presence of
albite NaAlSi3O8. All raw materials exhibited an equally small level of
mineral crystallinity with a peak intensity scale of 3.000 to 4.000 counts
per second (cps), except for lime construction waste (1.000 cps).

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Table 2 3.1.4. Morphological microstructure of the raw materials
Contents of the main elements (oxides) in the chemical composition of the raw materials
used in this study (by XRF method).
SEM photomicrograph analysis (Fig. 3) of the raw materials at the
same 5,000-fold magnification indicated a broad particle size distribu-
Oxides Dregs Grits Lime Mud CW LPW tion of different shapes ranging from 1 to 50 µm. The pores between
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them also are exceptionally different in size and configurations.
CaO 37.4 50.8 54.5 23.0 51.6
MgO 5.1 0.3 0.5 3.4 29.0
Many particles had cloud-like shapes, typical of amorphous materi-
Na2O 4.5 4.5 0.7 1.1 – als. Lime mud (Fig. 3-C) stood out among the other wastes, with many
Fe2O3 0.5 0.4 0.1 2.2 0.2 cubic-shaped crystal particles, characteristic of calcite, which coincided
SO3 1.6 1.7 0.2 0.4 with the XRD analysis results (Fig. 1-C).
P2O5 0.2 0.5 0.2 0.3 <0.1
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MnO 0.7 – – <0.1 <0.1

K2O 0.7 0.6 – 1.8 <0.1
3.2. Mechanical and physical properties of the developed composites
SiO2 2.8 3.5 0.3 47.8 1.5
Al2O3 0.5 0.6 0.4 6.2 0.1 3.2.1. Test samples preparing
C.L. 46.0 37.1 43.1 13.8 17.5 Test samples (TSs) preparation included weighing of the raw mate-
Total 100.0 100.0 100.0 100.0 100.0
rials to previously selected proportions (Table 3), homogenization of
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Fig. 1. Photos of the raw materials: A – mixture of drags, B – grits, C – lime sludge, D – Lime production waste and E – Concrete waste.
4 V. Mymrin et al. / Construction and Building Materials xxx (xxxx) 120604
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Fig. 2. Diffractogram patterns of the raw materials under study.
the dry mixes, hydration with an experimentally determined amount of
water, compacting into cylindrical molds under 10 MPa pressure to pro-
duce TSs with dimensions of 20 × 20 mm. The manufactured TSs were
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stored outdoors and tested at 3, 7, 14, 28, 60, 90, 180, and 365 hy-
dration days. Studies were carried out on 8 compositions, and the total
number of TSs in five replications reached 350 samples. All three wastes
(dregs, grits, and lime mud) were produced at the pulp and paper mill in
the same batch. Therefore, the variations in the contents of each residue
in the studied compositions were also quite small (Table 3).
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3.2.2. Axial strength of the test materials
The axial strength showed (Table 3) its dependence on LPW con-
tent. So, the axial strength of the test samples (TSs) of composite 1 (zero
LPW content) increased from 0.69 MPa on the 3rd day to 3.55 MPa on
the 365th day. This fact indicates the presence of residual binder prop-
erties in concrete waste [28]. Replacing 10% of concrete waste with an
equal quantity of LPW (composite 2), increased these values to 0.93 and
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5.83 MPa. Consecutive increases in LPW content rather than other com-
ponents of the initial mixes led to an expansion in TSs strength.
Thus, the substitution of 5% of dregs (composite 3) with LPW en-
larged these values up to 1.09 – 7.52 MPa; the subsequent replacement
of grits and mud of lime with an increase in concrete waste content of
up to 20% (composite 4) impelled the resistance to 1.81 – 8.55 MPa.
However, reducing concrete waste by 10% (composite 5) led to a drop
in resistance to 1.76 – 7.68 MPa. Along with the resistance of compos-
ite 1 (without LPW) and composite 6 (concrete waste 15%), this reveals
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the clearly visible existence of bonding properties of concrete waste.
Composite 7, with maximum LPW content (25%), showed maximum re-
sistance at all TSs hydration ages (4.81–9.61 MPa). The replacement of
5% mud of lime with dregs (composites 8 versus 7), keeping the contents
of the other components constant, led to a decrease in resistance up to
4.01–8.22 MPa at all TSs ages due to the higher CaO content (54.5%) in
lime mud compared to dregs (37.4%). Composites 4 and 7, which differ
only in dreg and LPW contents, confirmed the role of lime production
waste as the main bonding substance of these CaO abundant mixtures.
3.2.3. Expansion and shrinkage of TSs during hydration and cure
Analysis of the results in Table 4 showed the expansion of the TSs
diameter of all composites up to 28 days, followed by their shrinkage in
the next stages until the 365th day of cure. Composite 1 (with zero con-
tent of LPW) presented the lowest shrinkage values at all TSs ages, and
unlike the others, the slow shrinkage began after 60 days. All processes
seem to manifest considerably weaker in composite 1 than in other com-
posites in Table 3, probably due to the absence of the most chemically
active component – LPW.
The incorporation of 10 – 20% LPW (composites 2 – 6) led to a faster
expansion of the TSs until the 28th cure day, with a more intense TSs
shrinkage from the 60th to the 365th day of hydration and cure. The
difference between the maximum TSs expansion (28th day) and 365-day
shrinkage values of all composite exceeded 1%. Compositions 7 and 8,
with maximum LPW content (25%), presented the maximum expansion
magnitudes at 28 days (2.57 and 2.50%, correspondingly), with slower
shrinkage until 365 days (up to 2.00 and 1.96%).
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Fig. 3. SEM photos of the raw materials under study: A – dregs, B – grits, C –lime mud, D – concrete waste (CW) and E – lime production waste (LPW).
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Table 3
Changes in axial strength of the test samples during cure.
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N° Composites, wt. %
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Dregs Grits Mud lime Conc. waste LPW 3 7 14 28 60 90 180 365

1 25 25 25 25 0 0.69 1.71 1.67 2.00 2.14 2.31 3.02 3.55

2 25 25 25 15 10 0.93 0.96 1.24 2.30 4.86 5.07 5.65 5.83
3 20 25 25 15 15 1.09 1.72 1.97 2.34 3.17 5.74 6.03 7.52
4 20 20 20 20 20 1.81 2.68 3.06 3.75 4.47 6.59 7.91 8.55
5 20 25 25 10 20 1.76 2.53 2.96 2.98 3.50 6.51 6.80 7.68
6 20 20 25 15 20 2.78 3.19 3.12 3.35 3.56 6.13 6.47 7.95
7 15 20 20 20 25 4.81 4.93 5.43 5.97 6.86 7.45 8.75 9.61
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8 20 20 15 20 25 4.01 4.15 4.35 4.75 5.70 7.27 7.80 8.22

3.2.4. Water absorption (WA)
Water absorption (WA) values depend on the open porosity of the
TSs. Therefore, a reduction in all WA values over a period from 28 to
90 days (Table 5), calculated using Equation (2), indicates a decrease
in the open porosity of materials due to the synthesis of new forma-
tions. Composition 1, in which there was no LPW as the main cementi
tious material, exhibited the highest WA values. Such a small number
of new formations led to lower TSs strength at all hydration ages of the
initial mixtures (Table 3). Composition 7, with maximum LPW content
(25%), presented the lowest WA value (8.2%) due to the synthesis of
a more substantial amount of new formations in the pore spaces, thus
strengthening the entire volume of the TSs at all ages (Table 3).
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Table 4
Changes in the linear expansion and shrinkage coefficients of the test samples during hydration and cure.
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N° Compositions, wt. % Coefficient of linear expansion. %

Dregs Grits Mud lime CW LPW 3 7 14 28 60 90 180 365

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1 25 25 25 25 0 1.45 1.53 1.62 1.70 1.81 1.76 1.73 1.62
2 25 25 25 15 10 1.65 1.88 2.05 2.22 2.09 1.98 1.75 1.10
3 20 25 25 15 15 1.71 1.98 2.15 2.32 2.19 2.08 1.65 1.27

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4 20 20 20 20 20 1.75 1.98 2.15 2.32 2.19 2.08 1.85 1.15
5 20 25 25 10 20 1.80 2.03 2.20 2.37 2.24 2.13 1.90 1.30
6 20 20 25 15 20 1.83 2.08 2.25 2.42 2.29 2.18 1.95 1.30
7 15 20 20 20 25 1.96 2.18 2.45 2.57 2.49 2.38 2.14 2.00
8 20 20 15 20 25 1.94 2.18 2.35 2.50 2.45 2.26 2.09 1.96

Table 5 ites 7 and 8 (both with 25% LPW content) had the highest CWR, 0.82

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Changes in water absorption coefficient (WA, wt. %) during 28 and 90 days of cure.
and 0.81 after 28 days and 0.80 and 0.87 after 90 days.
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According to the demands of [31] standards, after 90 days of water
N° Composites, wt. % saturation, 1st class building materials should have resistance between
4 and 6 MPa, and 2nd class materials between 2 and 4 MPa. Therefore,
Dregs Grits Mud lime CW LPW WA (%) after (days)
composite 2 met the requirements for second class materials and com-
28 90 positions 3–8 – for first class.

1 25 25 25 25 0 21.8 18.0 3.3. Physicochemical processes of structure formation of the developed

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2 25 25 25 15 10 11.5 9.2
composites
3 20 25 25 15 15 12.4 11.2
4 20 20 20 20 20 10.3 8.3
5 20 25 25 10 20 13.5 12.1 The studies of the physicochemical processes of structure formation
of the developed composites were performed through the analysis of the
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6 20 20 25 15 20 13.3 12.4
7 15 20 20 20 25 9.6 8.2
changes in their mineral composition by the X-ray phase composition
8 20 20 15 20 25 10.2 9.0
method (XRD), the morphology of the new formations by electron mi-
croscopy (SEM), their micro chemical composition (EDS), and their iso-
topic compositions by laser micro-mass analysis (LAMMA).

Brazilian standards [33] [35] establishes as average values of wa-

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3.3.1. Changes in the mineral composition during hydration and cure

ter absorption in sealing concrete blocks a maximum of 10% for normal
aggregates and 16% for light aggregates. Therefore, compositions 2, 4,
7, and 8 were in accordance with the required standard for the sealing
concrete blocks parameter on the 90th day of cure, and compositions 3,
5, and 6 almost met this demand, but so far only corresponded to the
light aggregate parameter.
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XRD pattern of composite 7 on the 3rd hydration day (Fig. 4-A)
showed all minerals that appeared in the XRD of the raw materials (Fig.
2), in addition to brucite Mg (OH)2. After 365 hydration days, brucite
and portlandite Ca (OH)2 were transformed in carbonates, which led to
a noticeable increase in the intensity of both main peaks at 2Θ° = 29.5°
and almost all other calcite peaks.

The intensities of microcline K(AlSi3O8) and quartz SiO2 peaks, as

3.2.5. Coefficient of water resistance of the test samples (CWR)
The coefficients of water resistance (CWR) of the TSs (Table 6) were
calculated using Eq. (1), according to the standard [31]. TSs of compo-
sition 1 (without LPW content) collapsed in water, but the addition of
10% of LPW in composite 2 was enough to increase CWR values to 0.51
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well as the overall X-ray background of the diffractogram pattern, re-
mained without clearly visible changes in the alkaline environment of
the materials. All this suggests that the strengthening of the material
during its hydration occurred due to the synthesis of new mainly car-
bonate formations, particularly calcite. The inevitability of this process

after 28 days of outdoor hardening and to 0.69 after 90 days. A subse- is confirmed by the high predominance of CaO in the chemical composi-
quent increase in the amount of LPW to 15% in composition 3 led to a tions of almost all initial components except concrete waste (Table 2).
growth in CWR to 0.72 after 28 days, and 0.74 after 90 days. Compos

Table 6
Water resistance (WR) of the test samples on the 28th and 90th days of cure.
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N° Compositions, wt. % 28th day 90th day

Dregs Grits Mudlime CW LPW Dry Water satur. CWR Dry Water satur. CWR

1 25 25 25 25 0 2.00 0 0 2.31 0 0
2 25 25 25 15 10 2.30 1.17 0.51 5.07 3.93 0.69
3 20 25 25 15 15 2.34 1.68 0.72 5.74 4.25 0.74
4 20 20 20 20 20 3.75 2.74 0.73 6.59 5.00 0.76
5 20 25 25 10 20 2.98 2.26 0.76 6.51 5.08 0.78
6 20 20 25 15 20 3.35 2.61 0.78 6.13 4.90 0.80
7 15 20 20 20 25 5.97 4.90 0.82 7.45 6.71 0.90
8 20 20 15 20 25 4.75 3.85 0.81 7.27 6.32 0.87
 V. Mymrin et al. / Construction and Building Materials xxx (xxxx) 120604 7

D Fig. 4. XRD patterns of composite 7 on the: A − 3rd day, B – 365th of cure.
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3.3.2. Changes in the morphological structure during hydration and cure
The morphological structure before hydration and cure (Fig. 5-A),
magnified 3.000 times, was presented by a random mixture of parti-
cles of various shapes and sizes, with a large number of pores between
them, also of various configurations and sizes. Most particles have no
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cal interaction between these solutions with the synthesis of new
sol–gel-like formations of different chemical compositions. A small num-
ber of pores and thin cracks are still visible with an increase of 3.000
times in the dense monolithic field of new formations. Such integrity
and density of the new formations might explain the samples' axial

bonds between them, but some are aggregated, which is typical at the
micro level for dry and ground sludge from pulp and paper production
wastes (dregs, grits, and lime mud) and concrete waste. Poorly fired lime
production waste also contained aggregated particles. Nevertheless, the
initial dry mixture of these materials was a loose mixture of particles
that had no connection to each other and, therefore, had no mechanical
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strength of 9.1 MPa (Table 3).
3.3.3. Chemical composition of new formations by EDS and LAMMA
methods
The chemical composition of the new formations that strengthened
the developed composites was studied by energy dispersive spectroscopy

strength.
The morphological structure of the hydrated and compacted initial
mix after 365 days was transformed into a rather monolete monolith
material (Fig. 5-B) due to the chemical dissolution of the particles’ sur-
faces in a highly alkaline medium of hydrated materials and the chemi
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(EDS) (Fig. 5-B and Table 7) and laser micro-mass analyses (LAMMA)
(Fig. 6).
Laser micro-mass analyses results confirmed the high level of hetero-
geneity found in composite 7 at points 2, 3, and 4 (Fig. 4), since the
graphics of each point displayed various sets of isotopes with different
isotopes weight and isotopes peaks intensities (quantitative content).

Fig. 5. SEM micrographs of composite 7 of the initial dry mix (A) and on the 365th day of hydration and cure (B).
8 V. Mymrin et al. / Construction and Building Materials xxx (xxxx) 120604

Table 7
Micro chemical composition of the composite 7 at 365th day of cure.
Expand

Points Na Mg Al Si K Ca Fe Total

1 8.89 15.79 7.66 12.87 2.15 46.23 3.41 100.00

2 4.33 20.28 8.07 12.28 1.23 52.32 1.49 100.00

F
3 1.26 13.68 12.97 1.86 0.73 61.20 8.30 100.00
4 8.17 5.06 19.00 15.58 6.23 34.36 11.60 100.00
5 11.00 9.19 0.00 7.08 9.11 57.24 6.38 100.00

OO
6 3.60 15.88 11.03 8.96 0.00 49.19 11.34 100.00

PR
D
TE
Fig. 6. Isotopic composition of the new formations at three nearest points of composite 7 on the 365th day of hydration (by LAMMA method).

4. Conclusions Declaration of Competing Interest

1. This study demonstrated the possibility of applying the three pri- The authors declare that they have no known competing financial in-
EC

mary wastes from pulp and paper production wastes – green liquor clar- terests or personal relationships that could have appeared to influence
ifier (dregs), lime eraser (grits), and white liquor clarifier (lime mud) as the work reported in this paper.
principal components to produce different types of construction materi-
als – bricks, blocs, road and airfields bases – with excellent mechanical
and physical properties. Thus, the axial compressive strength of the de- Acknowledgements
veloped materials reached 4.81 MPa in 3-day age samples, 5.97 MPa in
The authors express their gratitude to the Berneck Company, Cu-
RR

28 days, 8.75 MPa in 180 days, and 9.61 MPa in 365 days. The devel-
oped composites showed very high values of water resistance and low ritiba, Brazil, for providing three types of their pulp and cellulose pro-
linear expansion. duction wastes: green liquor clarifier (dregs), lime eraser (grits), and
2. These properties were achieved due to the alkaline corrosion of white liquor clarifier (lime mud).
the solid surfaces of the initial components and the chemical inter-
action of sol solutions with their transformation into gel of heteroge- References
neous chemical composition. These rather long processes caused in-
CO

[1] HawkingS.W. 2018 http://www.independent.co.uk/news/

creased strength of the materials and transition of the composites into a
stone-like state.
3. Industrial application of the developed materials should be very
profitable, making it very economically attractive due to the use of in-
dustrial wastes only rather than relatively expensive traditional natural
raw construction materials such as clay, sand, gravel, crushed stone, as
well as the sharp drop in transportation costs due to the delivery of
UN
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4. The developed composites are also immensely appealing from an
environmental point of view, as they consist of five types of industrial
wastes that pollute industrially developed and densely populated re-
gions of the world and dramatically worsen the quality of life of the
populations in these areas and they simultaneously allow to decline the
irreversible destruction of nature by quarries of traditional construction
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