Construction and Building Materials 50 (2014) 184–189

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Construction and Building Materials

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

Manufacture of a construction material using the physicochemical

properties of ash and sludge wastes from MDF board production
V. Mymrin a,⇑, S.A.S. Meyer b, K.P. Alekseev c, U. Pawlowsky b, L.H. Fernandes a, C.B. Scremim a, R.E. Catai a
a
Federal Technological University of Parana, St. Deputado Heitor de Alencar Furtado, 4900, Campus, Curitiba, CEP 81280-340 Ecoville, Parana, Brazil
b
Federal University of Parana, St. Coronel Francisco dos Santos Heraclitus, No. 210, Block 5, Campus Polytechnic, CEP 81530-000 Curitiba, Parana, Brazil
c
Moscow State University, Vorobievy Gory, Moscow, Russia

h i g h l i g h t s

 New material from ash and sludge of MDF fabrication and lime production wastes.
 Resistance 8.37 MPa on the 90-th day of hydration and very high water resistance.
 Established by XRD, SEM and EDS methods the processes of hydration and hardening.
 Utilization of industrial wastes have high economical and environment efficiency.

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

Article history: The need to reduce and recycle industrial wastes is increasing apace due to the rising cost of water and of
Received 15 July 2013 effluent disposal, and the need for compliance with environmental legislation. The purpose of this work
Received in revised form 11 September 2013 was to study the use of sludge derived from the physicochemical treatment involved in the MDF board
Accepted 13 September 2013
production process, and to take advantage of the physicochemical properties of ash, sludge and lime pro-
Available online 15 October 2013
duction wastes for the manufacture of a new product with improved characteristics for use in civil con-
struction. To this end, samples were prepared with different combinations of the aforementioned wastes
Keywords:
and their mechanical, chemical and mineralogical properties were tested and analyzed to obtain a
Industrial waste
Recycling
product with optimal characteristics and mechanical strength. The results indicate that a waste content
MDF industry of 30–45% in weight provides good levels of mechanical strength, making these products suitable for
Construction materials application as construction materials. Moreover, the use of these industrial wastes is economically attrac-
tive in view of their low cost, and highly beneficial to the environment because it eliminates or at least
reduces their incorrect disposal.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction serves of raw materials – if not in an entire country, at least in

The purpose of reusing or recycling solid wastes is to make full
use of raw materials and minimize the problem of pollution and of
their treatment [1]. The incorrect treatment of industrial solid
wastes contributes markedly to worsen environmental problems,
particularly in large urban centers, by potentially polluting the
air, soil, and especially surface and groundwater. Therefore, the re-
use of industrial solid wastes and sub products as construction
materials has been studied by various researchers in recent years
[2]. According to Prim et al. [2], this line of research is motivated
by three reasons: (1) concerns about the depletion of natural re-
⇑ Corresponding author. Tel.: +55 41 32794547.
E-mail addresses: seva6219@gmail.com (V. Mymrin), teffymeyer@hotmail.com
(S.A.S. Meyer), ale-kitill@yandex.ru (K.P. Alekseev), pawl@terra.com.br
(U. Pawlowsky), luisahelena@utfpr.edu.br (L.H. Fernandes), cristoferscremim@
hotmail.com (C.B. Scremim), catai@utfpr.edu.br (R.E. Catai).
some specific regions; (2) concerns about conservation of the envi-
ronment, which is increasingly impacted by discarded solid
wastes; and (3) in countries where raw materials are scanty, the
need to compensate for the economic imbalance resulting from
the high price of fossil moil by recycling solid wastes.
It is known that the wood sector of Brazilian industry is one of
the most productive in the world, coming to be among the most
advanced in the manufacture of reconstituted wood panels. The
industrial sector of Medium Density Fiberboard (MDF) has shown
strong growth in the world and in particular in Brazil. A special
production of MDF in 2012 was 3.6 million m3 in Brazil [3]. The
factory studied has an MDF production near 30,000 m3/month with
a generation of wastewater 600 m3/day with accumulation of
physicochemical sludge 4680 tons/year. The burning of the wood
chips coming to 8400 tons/year also produce ashes [4] used in this
research as raw component.

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.09.016
 V. Mymrin et al. / Construction and Building Materials 50 (2014) 184–189 185

Table 1 In the scientific literature we found no one study that could

Compositions of the samples.
Proportions (wt.%)
Compositions Sludge Ash
1 45 45
2 40 45
3 35 50
4 30 55
5 40 40
6 35 45
7 30 50
Skodras et al. [5] offered co-firing of MDF production wastes in
mixes with coal as a promising option for the thermal recycling to
achieve the use of the waste, as well as conservation of fossil fuel
resources and minimization of waste disposal and reduction of
impacts on health. But Brazilian law prohibits the burning of all
types of physicochemical sludge to prevent environment pollu-
tion [6].
Ochoa de Alda and Torrea [7] studied chemical and microbio-
logical stability of waste sludge of MDF fabrication for brick pro-
duction. A revision of the scientific literature about toxicity of
sludge indicated that these solid wastes are not toxic in general,
although this must be clearly specified for each application. They
came to conclusions that the drying of the sludge is one of the most
critical factors that determine sludge upgrading.
Wood waste ash can be utilized as a partial cement replacement
material in the production of structural grade concrete and mortar
[8], for brick production in mixtures with limestone [9]. SIDDIQUE
[10] added sawdust and wood shaving till 30% by weight of cement
with insignificant decreasing of the strengths and increasing of the
water absorption.
Udoeyo et al. [11] investigated the physical properties and
chemical properties of the concrete produced by replacing 5–25%
by weight of ordinary Portland cement with wood ash at the ages
of 3, 7, 28, 56 and 90 days. The results showed that ash is a good
pozzolan. The compressive strength of concrete with ash was low-
er at early stages but improves significantly up to 90 days.
According to [12,13], reusing industrial and municipal solid
wastes for the production of construction materials is an option
that has been studied by numerous researchers worldwide. How-
ever, for this purpose it is important to possess mechanical proper-
ties of new materials that comply with the standards of national
and international legislation, such as the levels of uniaxial com-
pressive strength established by the national technical standards
[14–16]. The purpose of this work was to study combinations of
sludge from the physicochemical treatment of wastewater and
ash generated by the incineration of biomass at an MDF (Medium
Density Fiberboard) plant, using waste of lime production [17] as
binder, for the formation of a value-added construction material
that meets Brazilian standards.
serve as a prototype of the present research. The problem of
excessive humidity [7] was achieved in this study by using of dry
LPW wood burning ash mainly as water absorption component.
10
15
15 2. Materials and methods
15
20 This experimental research was performed in three steps: physicochemical
20 characterization of the raw materials (sludge, biomass wood ash and lime wastes);
20 preparation and study of the best specimens containing different proportions of the
wastes; and characterization and evaluation of mechanical, chemical and mineral-
ogical properties of the new construction material.
The sludge and ash were supplied by an MDF plant located in the region of
Araucaria (Paraná state, Brazil); the lime production wastes (LPW) used as binding
material was obtained from a factory in Paraná (Brazil). Sampling was performed
according to the Brazilian standard [16], and served as a representative sample.
The raw materials and final products were characterized by X-ray fluorescence
(XRF), Philps/Panalytical, model PW 2400, X-ray diffraction (XRD) Philips, model
PW 1830, scanning electron microscopy (SEM) FEI, model Quanta 200 LV, energy
dispersive spectroscopy (EDS) of Oxford (Penta FETPrecison), model X-ACT, Laser
Micro-Mass Analysis, model LAMMA-1000, Laser Diffraction Particle Size
Distribution Analyzer, model LA-950 – HORIBA, three-point flexural strength (FS)
by EMIC universal testing machine, water absorption (WA), linear shrinkage (LS),
marc Mitutoyo, caliper and apparent density (AD), to determine the chemical and
mineralogical compositions and the new structures of the composites.
Test specimens (TSs) were prepared with different proportions of the wastes
(Table 1). The 20  20 mm TPs were hand mixed and then compacted under a pres-
sure of 5 MPa, without preliminary drying and without Portland cement. They were
then tested at the ages of 3, 7, 14, 28, 60 and 90 days.
The specimens were subjected to several tests to determine their uniaxial com-
pressive strength, water resistance, water absorption and dilatometry.
3. Results and discussion
3.1. Characterization of the raw materials
The chemical composition of the sludge determined by XRF pre-
sented mainly Al2O3 – 10.2%, CaO – 3.7%, P2O5 – 0.9% and SiO2 –
0.8%, a moisture content of 73.47% and loss on ignition of 82.55%,
probably due to the high content of organic matter. The mineralog-
ical composition of the sludge revealed by XRD showed three
phases: Nitratine (NaNO3), Kamacite (Mg3Al6(Si,Al,B)5O21(OH))
and Aragonite (CaCO3).
The XRF analysis of the ash from burning biomass indicated the
presence of SiO2 – 53.0%, Al2O3 – 12.8%, Fe2O3 – 5.7% and CaO –
2.5%, a moisture content of 9.37% and loss on ignition of 20.18%,
due to the high content of poorly burned wood. The mineralogical
composition of the ash analyzed by XRD showed the presence of
Quartz (SiO2) and Halite (NaCl).
The lime production waste (LPW) is a poorly burned lime that
was used as a binder of the mixtures in these experiments. Accord-
ing to the Brazilian standard [17], one of the chemical require-
ments for the application of lime as a binder in construction
materials is that it must present a minimum content of 88% of
total nonvolatile oxides (CaO + MgO). This standard establishes

Table 2
Changes of uniaxial compressive strength during materials hydration and curing.

N Compositions (wt (%)) Resistance (MPa) after days of curing

Sludge Ash LPW 3 7 14 28 60 90
1 45 45 10 5.09 ± 0.54 4.25 ± 0.29 5.50 ± 0.44 5.32 ± 0.72 5.17 ± 0.38 5.25 ± 0.43
2 40 45 15 3.90 ± 0.60 4.17 ± 0.98 5.26 ± 1.06 5.40 ± 0.65 6.08 ± 1.10 5.87 ± 0.15
3 35 50 15 2.20 ± 0.40 2.97 ± 0.28 3.05 ± 0.43 3.70 ± 0.89 3.66 ± 0.58 3.09 ± 0.05
4 30 55 15 1.95 ± 0.16 2.93 ± 0.46 3.38 ± 0.32 3.48 ± 0.59 3.35 ± 0.32 3.42 ± 0.13
5 40 40 20 5.25 ± 0.89 6.13 ± 0.72 7.18 ± 0.44 6.96 ± 0.97 7.95 ± 1.67 8.37 ± 2.14
6 35 45 20 3.75 ± 0.28 4.86 ± 0.48 5.62 ± 0.40 5.10 ± 1.42 6.14 ± 0.65 6.04 ± 0.93
7 30 50 20 1.62 ± 0.35 2.30 ± 0.52 3.02 ± 0.56 3.13 ± 0.57 3.55 ± 0.45 3.87 ± 0.55

Note: In accordance to national norms NBR 7171 (1992) uniaxial resistance of ceramics blocs must be as following: Class 15 = 1.5 < 2.5 MPa, Class 25 = 2.5 < 4.5 MPa. In
accordance to NBR 7170 (1983) uniaxial resistance of solid bricks must be: Class A < 2.5 MPa; Class B 2.5 < 4.0 MPa; Class C > 4.0 MPa.
186 V. Mymrin et al. / Construction and Building Materials 50 (2014) 184–189

maximum carbon dioxide (CO2) content of 6% for special quicklime
and of 12% for ordinary lime. The LPW used in this study showed a
content of 23.6% of CO2, characterizing it as lime production waste.
The X-ray diffractograms showed strong peaks corresponding to
Calcite (CaCO3), Brucite (Mg(OH)2), Portlandite (Ca(OH)2), and
Quartz (SiO2). Also highly visible is the considerable distance be-
tween the curves in the diffractograms and the zero line of the
graphs – a characteristic of the high content of amorphous
materials.
An analysis by SEM and EDS indicated that the sludge has a ten-
dency to form agglomerates. The SEM analysis of the ash revealed a
wide particle size distribution, indicative of the high porosity of the
material due to the absence of chemical bonds among the compo-
nents, characterizing a non-homogeneous material. The SEM anal-
ysis of the LPW indicated very smooth uniform surfaces, without
elevations, with a large network of irregular pores. Most of the par-
ticles presented spherical cloud-like shapes, which is typical of
amorphous substances.
3.2. Characterization of mechanical properties of the developed
materials
The analysis of changes in the uniaxial compressive strength of
the TPs (Table 2) revealed that the compressive strength of the
compositions increased gradually. This indicates that the chemical
interaction among the components increases over time, reducing
the volume of voids. According to the Brazilian technical standard
[14], the uniaxial resistance strength of backed bricks is classified
as follows: Class A < 2.5 MPa; Class B from 2.5 to 4.0 MPa; and
Class C > 4.0 MPa. Uniaxial resistance of ceramics blocks must be:

Fig. 1. XRD changes of the composition 5 during structure formation.

 V. Mymrin et al. / Construction and Building Materials 50 (2014) 184–189 187

Table 3
Changes of mineralogical composition of the samples 5, Table 2, after curing days.

Dry mixture 3 Dais 14 Dais 60 Dais

Quartzo–SiO2 Quartzo–SiO2 Quartzo–SiO2 Quartzo–SiO2
Portlandite– Portlandite–Ca(OH)2 Portlandite–Ca(OH)2 Portlandite–Ca(OH)2
Ca(OH)2
Periclase–MgO Periclase–MgO Periclase–MgO Periclase–MgO
Calcite–CaCO3 Calcite–CaCO3 Calcite–CaCO3 Calcite–CaCO3
Grafite–C Grafite–C Grafite–C Grafite–C
a
Kornerupine– Kornerupine–Mg3Al6(Si,Al,B) Kornerupine–Mg3Al6(Si0.8,Al0.2)5O21(OH) e
Mg3Al6(Si,Al,B)5O21(OH) 5O21(OH) Fe4Mg10Al25(Si,B)18O86
a
Tobermorite–(CaO)xSiO2.H2O Tobermorite–(CaO)xSiO2.H2O Tobermorite–(CaO)xSiO2.H2O
a
New formations crystalline with the lapse of time.

+4

+1
+2
+3
Area 1
Area 2

(A) x 5.000 - 3 days (B) x 5.000 - 3 days (C) x 4.000 - 60 days

Fig. 2. EDS micrographs of composition 5, Table 1 during the curing.

Class 15 = 1.5 < 2.5 MPa, Class 25 = 2.5 < 4.5 MPa [15].
The best properties were exhibited by composition 5, which
consistently showed the highest compressive strength, reaching
8.37 MPa after 90 days. Composition 5 was therefore chosen for
the analysis of the physicochemical processes involved in the for-
mation of structures, using the XRD, SEM, EDS and LAMMA
techniques.
A comparison of the data in Table 1 against the requirements
established in the standards [14,15] indicates that the
compressive strengths of the newly materials comply with the
aforementioned standards, often even exceeding their maximum
limits.
The dilatometry results showed a variation of 0.93–2.35% di-
rectly proportional to the increase in ash content. The lowest
LPW content presented the smallest dilation, and composition 5
showed a dilation of 1.40%.
The coefficient of water resistance (CW) was determined based
on the ratio:
C W ¼ RSAT =RD ð1Þ
where of RSAT – the uniaxial compressive strength of test specimens
saturated after total immersion in water for 24 h,
RD – the uniaxial compressive strength of the specimens oven-
dried at 100 °C for 24 h.
Water resistance values after 60 days were 2.24–4.76 MPa, with
Cw of 0.60–0.82. The water resistance values obtained after 90 days
were 2.41–5.22 MPa, with Cw values of 0.62–0.85.
Thus, the aging of the materials and increase of values of sludge
content responded positively in terms of water resistance.
Water absorption (WA) tests were performed with specimens
cured for 28 days, in accordance with the Brazilian standard [18],
which uses the following equation:
W A ¼ ½ðMSAT  M D Þ=M D   100 ð2Þ
where MSAT is the mass of the saturated specimen after 24 h of
immersion in water and MD is the mass of the specimen oven-dried
at 100 °C for 24 h.

Fig. 3. LAMMA – laser micro-mass analysis of new formations of composition 5 at the 60th curing day.
188 V. Mymrin et al. / Construction and Building Materials 50 (2014) 184–189

Table 4
Results of EDS analyses of composition 5 at the 60-th curing day, SEM micro image, Fig. 2, areas 1–2 and points 1–4.

Age, days Areas and points C O Mg Al Si K Ca Fe Total

3 Area 1 46.76 25.98 9.20 1.79 1.03 0.32 13.96 0.97 100
3 Point 1 9.85 37.97 7.60 0.71 0.35 0.22 42.65 0.66 100
3 Point 2 25.30 15.86 5.69 2.25 1.82 0.70 44.62 3.75 100
60 Area 2 46.24 14.69 14.93 2.66 3.96 0.74 15.24 1.54 100
60 Point 3 47.29 22.29 19.90 1.56 – 0.23 8.18 0.56 100
60 Point 4 43.43 26.01 11.83 2.08 – 0.38 15.2 1.07 100

The Wa of most of the mixtures increased with increasing ash 4. Conclusions

content, varying from 0.77 to 1.61 after 60 days of curing, and from
0.86 to 1.65 after 90 days of curing.
3.3. Physic-chemical processes of the developed materials’ structure
formation
Changing of the mineralogical compositions and structures of
the material, of chemical compositions of new formations,
responsible for mechanical properties during the TSs hydration
and hardening, was performed using X-ray diffraction (XRD),
scanning electron microscopy (SEM), energy dispersive spectros-
copy (EDS) and Laser Micro-Mass Analysis (LAMMA). For this
purpose were studied samples of composition 5 (Table 1) with
the maximum amount of binder component (LPW) at different
stages of curing.
Summarized results of the interpretation of the X-ray diffracto-
grams (Fig. 1) of samples of composition 5 shown in Table 1.
The data in Table 3 indicate that, in terms of hydration and cur-
ing time, the diffractograms show minerals of crystalline modifica-
tions of Kornerupine – Mg3Al6(Si0.8,Al0.2)5O21(OH) and
Fe4Mg10Al25(Si,B)18O86 and Tobermorite – (CaO)SiO2H2O, and an
increase in the intensity of the peaks corresponding to Calcite –
CaCO3. In addition, there is a conspicuous growth in the content
of amorphous materials, which is clearly visible in a comparison
of the XRD patterns of the initial dry material and the material
after 60 days of curing.
The SEM results indicate that on day 3 there were still pieces of
ash structure. In Fig. 2C, recorded on day 6, the structures appear to
be relatively monolithic, indicating that the material gains strength
and the particles react and interlink over time. This statement is
supported by the fact that there are few and only small cracks.
A chemical microanalysis by EDS was performed of areas
marked 1 and 2 in the micrographs shown in Fig. 3A, B and C at
3 and 60 days of age. The results of this analysis are described in
Table 4.
Comparing the chemical compositions of Areas 1 and 2 by EDS
confirms the considerable difference in the Mg, Al and Si con-
tents, which is typical of amorphous substances of new forma-
tions. In the chemical comparison of the different points in
these areas, the difference in content of practically all the
elements is much greater. This information confirms the high
content of amorphous materials, which is consistent with the
XRD findings.
The results of Laser micro-mass analysis by ‘‘LAMMA-1000’’
(Fig. 3) are similar to results of EDS analysis. All the spectra ob-
tained for the chemical compositions of all the nearest points of
new formations at the 60th curing day show quite dissimilar com-
binations of isotopes and its quantities (intensity of LAMMA picks).
New materials can be used as solid or holed bricks or blocks. It
is possible to affirm, based on the considerable world technical lit-
erature and on the experience of one of the authors [12], that
materials developed in this work at the end of their service life
can be successfully recycled as valuable components of new
materials.
The industrial wastes used in this study (sludge and biomass
ash from MDF production, and lime production waste) can be used
as main raw materials for the production of new construction
materials, without firing and without addition of Portland cement.
The materials developed in this study have the following mechan-
ical properties: high uniaxial compressive strength (up to
8.37 MPa), water resistance coefficient (0.60–0.82 in 60 days, and
0.62–0.85 in 90 days), water absorption (0.77–1.61% in 60 days,
and 0.86–1.65% in 90 days), and dilation (0.93–2.35% on day 90).
These characteristics meet the requirements of the Brazilian tech-
nical standards for solid or hollow brick type construction materi-
als. These high values of mechanical properties are attributed to
the formation of new structures resulting from the dissolution of
aluminosilicates from the raw materials in a moist alkaline envi-
ronment and the alkali silicates resulting from their mixture, and
especially the growth of carbonaceous mainly amorphous and
partly crystalline structures. The materials developed in this study
are economically attractive due to the low cost of these industrial
wastes. However, the greatest advantage of using these wastes is
environmental, because it means a reduction in the extraction of
natural raw materials and because the use of these industrial
wastes precludes their contaminating the environment through
incorrect disposal.
Acknowledgements
The Laboratory of Mineralogy and Rocks (LAMIR), the Labora-
tory of Environmental Technology (LTA), both at the Federal Uni-
versity of Paraná (UFPR) and filial of BOSCH, Curitiba, Brazil.
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