Journal of Cleaner Production 220 (2019) 87e98

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Journal of Cleaner Production

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

Use of lignin biopolymer from industrial waste as bitumen extender

for asphalt mixtures

rez a, Ana María Rodríguez Pasandín a, *, Jorge Carvalho Pais b,

rez Pe
Ignacio Pe
Paulo Antonio Alves Pereira b
a ~ a, E. T. S. I. Caminos, Canales y Puertos, Campus de Elvin
Universidade da Corun ~ a s/n, 15071, A Corun
~ a, Spain
b
Universidade do Minho, Escola de Engenharia, 4800-058, Guimara ~es, Portugal

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

Article history: Liquid waste containing lignin, a biopolymer of vegetable origin, is generated from the production of
Received 21 June 2018 wood hardboards. Because polymers improve the performance of asphalt mixtures, this work studies the
Received in revised form possibility of using this industrial waste as a bitumen extender in the production of asphalt mixtures.
4 February 2019
Thus, asphalt mixtures with 0% (control), 5%, 10%, 20%, and 40% of industrial waste were produced. The
Accepted 8 February 2019
Available online 18 February 2019
bitumeneaggregate adhesion, moisture damage resistance, resilient modulus, permanent deformation
resistance, and thermal susceptibility of such mixtures were analysed. Asphalt mixtures with 20% of
industrial waste showed the best moisture damage resistance. As the percentage of industrial waste
Keywords:
Lignin
increased, the thermal susceptibility of the mixture also increased. In this regard, at 5
C, the resilient
Biopolymer modulus of the mixture made with 20% of industrial waste was 19.08% lower than that of the control
Industrial waste mixture. Moreover, at 30
C, the resilient modulus of the mixture made with 20% of industrial waste was
Asphalt mixture 10.48% higher than that of the control mixture. Therefore, it can be stated that it is appropriate to use this
Bitumen extender industrial waste containing lignin as a bitumen extender. It can be used in asphalt mixtures for road
pavement, mainly by substituting 20% of the bitumen by this liquid waste. It reduces the consumption of
bitumen and improves the performance of asphalt mixtures, contributing to the purpose of sustainable
construction. The industrial waste was not subjected to any transformation process, thus facilitating its
use. The reduction in the use of bitumen in asphalt mixtures by adding this industrial waste contributes
to the goals of sustainable development and cleaner production of asphalt mixtures.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction A particular kind of polymers, are the biopolymers. Biopolymers,

also known as ‘green polymers’ (Hern
andez et al., 2014), are organic
Polymers are widely used as bitumen modifiers as it has been polymers synthesized by microorganisms, plants, trees, and other
demonstrated that they can improve the performance of asphalt biological organisms (Chang et al., 2016). Furthermore, the poly-
mixtures. Thus, asphalt mixtures made with polymer-modified mers chemically synthesised from vegetable oils, resins, sugars, and
bitumen have better rutting performance at high temperatures, other biological sources could be included in this definition
higher fatigue resistance, and higher cracking resistance at low tem- (Herna
ndez et al., 2014). Biopolymers are produced from renewable
peratures as a consequence of a noticeable reduction in their thermal resources (Chang et al., 2016), which makes them environmentally

ndez
susceptibility (Ait-Kadi et al., 1996; Brovelli et al., 2015; Herna friendly. Moreover, biopolymers are harmless and can easily be
et al., 2014). In addition, environmental benefits are associated with found in nature (Hataf et al., 2018). In fact, biopolymers can be
the use of modified bitumens owing to the increase in their lifecycle obtained from several available raw materials (Chang et al., 2016).
(Brovelli et al., 2013, 2014; Vila-Cortavitarte et al., 2018). Lignin is the second most abundant biopolymer on Earth after
cellulose (Boerjan et al., 2003), and it is present in all vascular
plants (Cha
vez-Sifontes and Domine, 2013) binding the fibres in
wood (Boerjan et al., 2003). Part of the vegetal biomass containing
* Corresponding author.
E-mail addresses: iperez@udc.es (I.P. Pe
rez), arodriguezpa@udc.es, ana. lignin can be considered as a waste material, which is mainly ob-
rodriguez.pasandin@udc.es (A.M. Rodríguez Pasandín), jpais@civil.unminho.pt tained from the wood, paper, and biofuel industries (Batista et al.,
(J.C. Pais), ppereira@civil.uminho.pt (P.A. Alves Pereira).

https://doi.org/10.1016/j.jclepro.2019.02.082
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
88 I.P. P
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2018) or even from agricultural processes (Ch
avez-Sifontes and rich corn stover waste. It is interesting to note, that the worsening
Domine, 2013). Depending on the biomass source and because of effect of lignin at low temperature found by Williams and
the industrial process used to obtain wood hardboards, paper, etc., McCready (2008) is not in accordance with the result obtained by
various types of lignin with different properties can be obtained. Batista et al. (2018). As said above, several types of lignin can be
According to the industrial process used, the most common kinds of obtained depending on the biomass source and on the industrial
lignin are the sulphite, kraft, and soda lignin, followed by the process. For this reason, the effects of the lignin on the asphalt
organosolv lignin (Cha
vez-Sifontes and Domine, 2013). The high performance could lead to apparently contradictory findings.
abundance of lignin, its cementitious nature, and the fact that lignin In 2010, a trial bike path was constructed in Iowa replacing 3% of
and asphalt have some similar chemical compounds, the carbon- its bitumen by this bioasphalt. The bike path showed adequate
rings (aromatics) (Herna
ndez et al., 2014), make this biopolymer performance (Bourzac, 2015). In 2015 (Gosselink, 2016; Wageningen
particularly interesting for manufacturing asphalt mixtures. University and Research, 2015), the first test section worldwide was
The problem associated with the real overexploitation and made using bioasphalt from lignin in Zeeland (the Netherlands). The
limited crude oil resources (Sun et al., 2017) can be mitigated by the lignin was chemically transformed using fast pyrolysis. The bio-
use of lignin as a partial substitute of bitumen. Additionally, the use asphalt was made by using 50% of lignin. The trial section, 70 m in
of lignin in bitumen is beneficial for the reduction of CO2 emissions length, was made with low temperature bioasphalt. After two years,
(van Vliet et al., 2016), because it does not generate any additional the performance of the road was adequate. Following the same
CO2. Thus, the use of lignin in the manufacture of asphalt mixtures research line, a bicycle path was constructed in 2017 using eight
can contribute to the goals of sustainable construction and cleaner types of lignin.
production. Other biopolymers were used in the bitumen industry, such as
Some attempts to use lignin in the production of asphalt mix- xantan gum (Tu et al., 2016a), welan gum (Tu et al., 2016b), and
tures have been reported. The first was conducted by the Federal starch (Al-Hadidy et al., 2011), but their characteristics make them
Highway Administration (FHWA). FHWA carried out a study in less suitable than lignin for road pavement applications.
which the possibility of using wood lignin as a substitute for
bitumen and as a bitumen extender in hot and cold asphalt mix- 2. Aims and scope
tures was analysed (Terrel, 1980). As a result, the wood lignin
showed promising results as an extender, but not as a bitumen In the present study, industrial waste containing a vegetal lignin
substitute. Nevertheless, this study also concluded that, at that biopolymer was used for partial substitution of the bitumen in
moment, the use of lignin as bitumen extender was not economi- asphalt mixtures. This industrial waste from the manufacture of
cally feasible. wood hardboards was used without any transformation, i.e., it was
Afterwards, other researches continue deepening on the anal- mixed directly with conventional bitumen. Different percentages of
ysis of the effects of lignin as bitumen extender or as a bitumen bitumen substitution by industrial waste were tested, namely, 0%
modifier. Sundstrom et al. (1983) stated that asphalt mixtures made (control mix), 5%, 10%, 20%, and 40% by bitumen weight. These
with 30% of lignin by weight of bitumen reached the maximum percentages were chosen in order to cover a wide range of
Marshal stability at 6% of binder content. Pan (2012) stated that percentages.
lignin could be used as antioxidant for bitumen. However, the The obtained binder (bitumen þ industrial waste) was used to
lignin temperature must be controlled to avoid lignin aging. Xu produce AC 22 base G asphalt mixtures and produce laboratory
et al. (2017) demonstrated that lignin-modified bitumen im- specimens for testing. The volumetric and mechanical properties of
proves the rutting performance at high temperatures and aging the specimens (indirect tensile strength, water sensitivity, resilient
resistance of asphalt mixtures. On the contrary, their fatigue life modulus, thermal susceptibility, and permanent deformation
could be reduced. Xie et al. (2017) also demonstrated that Kraft resistance) were analysed.
lignin could be used as bitumen modifier, leading to asphalt mix- This work analyses the use of this waste as a partial substitute
tures with better performance at high temperature. Boomika et al. for bitumen, as a bitumen extender, for application in asphalt
(2017) used plastic and lignin as partial bitumen substitutes. The mixtures, and the improvement in performance of these asphalt
authors stated that the use of 15% of lignin and 20% of plastic mixtures is also studied. Moreover, the research contributes to the
produced efficient results. Batista et al. (2018) stated that lignin purposes of sustainable construction and cleaner production, as
modified bitumen significantly improves the thermal cracking industrial waste rich in raw materials was utilised, without the
resistance of asphalt mixtures at temperatures as low as 12
C. need for subsequent transformations or production of leftover
Finally, in another research conducted by The Netherlands Or- waste materials.
ganization for Applied Scientific Research (TNO) (Bourzac, 2015;
Slaghek et al., 2017; van Vliet et al., 2016), some chemical modifi- 3. Materials and methods
cations were made to lignin. As a result, a more hydrophobic lignin
was achieved. This modified lignin was blended with bitumen (up The material and methods used in this investigation are
to 25% by weight of bitumen). The obtained bitumen presented described below.
high resistance to climatic conditions with greater service life.
Nevertheless, this bitumen was more expensive than conventional 3.1. Aggregates
bitumen.
It is interesting to note that most researchers did not use directly A local contractor supplied the aggregates used in this work for
lignin waste in bitumen modification for road applications because the manufacture of asphalt mixtures. The material is hornfels from
the untreated lignin does not mix with bitumen (Bourzac, 2015; a Galician quarry (Spain) (Fig. 1). It was expected that these ag-
Herna
ndez et al., 2014). gregates presented a poor water resistance because of its miner-
In addition, some trial stretches were constructed. Williams and alogical composition, which is rich in silica (62.30% of SiO2)
McCready (2008) used four lignin-containing co-products as (Pasandín and Pe
rez, 2015). The main properties of the aggregates
bitumen antioxidant, obtaining an improvement of the high tem- were analysed according to the Spanish General Technical Specifi-
perature properties and a worsening of the low temperature cations for Roads, also known as PG-3 (MFOM, 2015). As can be
properties of the bitumen. The bioasphalt was derived from lignin- observed in Table 1, the sand equivalent (SE) complied with the PG-
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Table 2
Main properties of the industrial waste containing lignin.

Property Value

pH 3.2
Densitity at 75
C (kg/m3) 1155
Viscosity at 80
C (mPa$s) 14
Total solids (g/L) 444
Volatile solids (g/L) 385
Sulphates (mg/g) 8
Aluminium (Al) (mg/L) 8197
Calcium (Ca) (mg/L) 4600
Magnesium (Mg) (mg/L) 5500
Sodium (Na) (mg/L) 4725
Silicon (mg/g) <3
Vanadium (mg/kg) <0.5
Chlorine (mg/kg) 6500
Fig. 1. Fraction 4/8 mm of the hornfels used in this work.

Table 1 According to the supplier, the industrial waste had 43.69% of dry
Aggregate characterization. Traffic category T00 refers to AADHT (Annual Average matter. This means that 100e43.69 ¼ 56.31% was water. The main
Daily Heavy Traffic)4000. components of this dry matter were 41.46% of sugar (mainly xylose,
Property Standard Hornfels PG-3 Specifications glucose, galactose, rhamnose, arabinose, and mannose), 23.39% of
lignin (16.29% of insoluble Klason lignin and 7.10% of soluble lignin),
T00-T1 T3-T2 T4
13.3% of pectin, 11.8% of polyphenols, 9.05% of mineral matter, and
SE (%) EN 933-8 (AENOR, 2012a) 61 50 50 50 other compounds that appeared in low percentages.
LA abrasion (%) EN 1097-2 (AENOR, 2010a) 14.1 25 30 e
In this work, the industrial waste was added to the hot bitumen
Traffic category T0 refers to 4000 > AADHT 2000. (170
C) in percentages of 0% (control), 5%, 10%, 20%, and 40% by
Traffic category T1 refers to 2000 > AADHT 800.
bitumen weight and manually blended for 10 min. Furthermore, a
Traffic category T2 refers to 800 > AADHT 200.
Traffic category T3 refers to 200 > AADHT 50. percentage of 60% of industrial waste was added to determine the
Traffic category T4 refers to AADHT<50. volumetric properties. Table 3 includes the penetration and the
softening point of the extended bitumen, that is, the bitumen with
5%, 10%, 20%, 40% and 60% of industrial waste. As can be seen in
3 for all the traffic categories, as well as the Los Angeles (LA) Table 3, in general, as the industrial waste percentage grows, the
abrasion coefficient. penetration and the softening point also grow. The water content of
the industrial waste seems to be mainly responsible for this per-
3.2. Bitumen formance. The water is less dense than the bitumen and its specific
heat is higher than that of the bitumen.
A B50/70 penetration grade bitumen was chosen to prepare the
asphalt mixtures. The bitumen had a penetration of 66  0.1 mm at 3.4. Asphalt mixture
25
C and with a moving load of 0.98 N acting for 5 s. The softening
point was of 48
C. These tests were conducted following EN-1426 For this research, the AC 22 base G asphalt mixture for road
(AENOR, 2007a) and EN-1427 (AENOR, 2007b) respectively. pavement base course was chosen. The aggregate gradation limits
given by the PG-3 (MFOM, 2015) and the selected aggregate
3.3. Industrial waste containing lignin grading curve are shown in Fig. 3.

The industrial waste used as bitumen extender is a 100% natural 3.5. Volumetric properties
product. It is a concentrate of wood extracts, mainly from euca-
lyptus, from the manufacture of hard fibres boards. As shown in For the volumetric characterization of the asphalt mixtures, the
Fig. 2, the industrial waste is a liquid with a faint odour of caramel. air voids (Va) were determined following EN 12697-8 (AENOR,
Its main properties are listed in Table 2. 2003) by using the following equation:

rm  rb
Va ¼  100 (1)
rm

where rb ¼ bulk specific density and rm ¼ maximum specific

density.
The bulk specific density by saturated surface dry (SSD) was

Table 3
Penetration and softening point of the extended bitumen.

Industrial waste (%) Penetration (0.1 mm) Softening point (ºC)

5 79 51.5
10 108 52.3
20 97 54.8
40 136 56.2
60 168 56.5
Fig. 2. Industrial waste containing lignin used in this work.
90 I.P. P
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Fig. 3. Aggregate gradation curve and standard limits.

determined on cylindrical Marshall specimens compacted with 75 remains coated with bitumen is visually estimated by two opera-
blows per face according to EN 12697-6 (AENOR, 2012c) and the tors. For each case, three samples were analysed.
maximum specific density was determined on loose asphalt mix- There are no requirements on the percentage of aggregate sur-
tures following EN 12697-5 (AENOR, 2010b). According to the PG-3, face that should be coated with bitumen after the rotation periods.
the minimum bitumen content of the AC 22 base G is 3.9%. Per- Therefore, this test is useful for comparison between mixtures
centages of 3.9%, 4.1%, 4.3%, and 4.5% of binder were used in this produced with different proportions of industrial waste. Particu-
work. larly, this test is used to analyse the affinity between bitumen and
aggregate, strength of the adhesion, and stripping resistance
3.6. Bitumen and aggregate adhesion (Solaimanian et al., 2003).

Two qualitative tests, namely the boiling water test and the 3.7. Moisture damage resistance
rolling bottle test were carried out to analyse whether the incor-
poration of industrial waste containing lignin improves the adhe- To evaluate the water sensitivity of the asphalt mixtures made
sion between the aggregate and the binder. Both tests were with 0%, 5%, 10%, 20%, and 40% of industrial waste as bitumen
conducted on loose asphalt mixtures. extender, the indirect tensile test was conducted as specified in EN
12697-12 (AENOR, 2009). This standard indicates that eight cylin-
3.6.1. Boiling water test drical specimens, compacted with 50 blows per face in the Marshall
The boiling water test was carried out in accordance with ASTM hammer, must be tested for each binder content.
D 3625-96 (ASTM, 2005). In this test, a sample of loose asphalt Four samples constitute the ‘dry set’, while the other four
mixture is introduced in boiling water for 10 min. Afterwards, the constitute the ‘wet set’. The samples of the ‘dry set’ remains at room
bitumen that remains in the water is removed using a towel. Then, temperature, while the samples of the ‘wet set’ are saturated in a
the asphalt mixture is removed from the water and dried. The water bath for 3 days at 40
C. Then, both sets are left for a mini-
percentage of the aggregate surface that continues coated is visu- mum of 2 h at 15
C with the ‘dry set’ in air and the ‘wet set’ in
ally estimated. For each case, one sample was analysed. water. After this period of time, the tensile strength ratio (TSR) is
It is not easy to establish a criterion that indicates the suitability determined as follows:
of asphalt mixtures in terms of moisture damage resistance
(Solaimanian et al., 2003). In the case of the boiling water test, ITSW
TSR ¼  100 (2)
Kennedy et al. (1984) indicated that based on the correlation be- ITSD
tween tests conducted on the laboratory and field performance,
asphalt mixtures that retained less than 70% of the bitumen on the where TSR ¼ the tensile strength ratio (%), ITSW ¼ the average ten-
aggregate surface are moisture susceptible. Kim and Coree (2005) sile strength of the ‘wet set’ (MPa), and ITSD ¼ the average tensile
indicated that this percentage must be 95%. In any case, results strength of the ‘dry set’ (MPa).
over this percentage cannot guarantee a good field performance The PG-3 (MFOM, 2015) requires a TSR80% to accept an AC 22
owing to other factors contributing to moisture damage resistance base G in terms of moisture damage resistance.
(Solaimanian et al., 2003). Thus, this test is useful for initial
screening of the asphalt mixtures (Brown et al., 2001) and for 3.8. Resilient modulus and thermal susceptibility
identifying problematic materials (Jorgensen, 2002).
The resilient modulus of the asphalt mixtures was calculated
3.6.2. Rolling bottle method following the Annex C of EN 12697-26 (AENOR, 2012d). In this test,
The rolling bottle test was carried out in accordance with the EN compressive repeated haversine loads are applied in a vertical
12697-11 (AENOR, 2012b) standard. In this test, a sample of loose diametral plane of cylindrical specimens compacted with 75 blows
asphalt mixture is introduced into a bottle containing distilled per face with the Marshall hammer. The repetition period of the
water and allowed to rotate for 6 h and for 24 h. At the end of these impulse is 3 ± 0.1 s and the rise time is 124 ± 4 ms. The maximum
two rotation periods, the percentage of aggregate surface that load must lead to a maximum horizontal strain of 0.005% of the
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specimen diameter. In this test, 10 conditioning pulse cycles are 4.1. Bitumen foaming
followed by 5 load pulse cycles. Then, the resilient modulus is
determined as follows: It is interesting to note that when industrial waste was blended
with bitumen, some foaming occurred owing to the sudden
F  ðn þ 0:27Þ warming of the water included in this waste. As the industrial
MR ¼ (3)
zh waste percentage was increasing, the foaming was more pro-
nounced in such a way that for 40% and 60% of industrial waste, it
where MR ¼ resilient modulus (MPa), F ¼ maximum applied load
was difficult to operate the blend owing to the high foam forma-
(N), z ¼ horizontal deformation (mm), h ¼ sample thickness (mm),
tion. This fact can be observed in Fig. 4, which shows 20% of in-
and n ¼ Poisson's ratio (assuming a Poisson's ratio of 0.35 for the
dustrial waste blended with bitumen. At the beginning (Fig. 4a), the
different temperatures according to EN 12697-26 (AENOR, 2012d).
bitumen showed its usual appearance, but after a few seconds
The thermal susceptibility may be defined as the resistance of
(Fig. 4b), foaming led to bubble formation inside the bitumen,
the binder to change its resilient modulus and viscosity with
which was clearly noticeable in its surface. Moreover, a high vol-
temperature (Cong et al., 2012). The lower temperature depen-
ume expansion of the bitumen was produced when foaming
dence the asphalt mixture has, the less thermal susceptible the
occurred. The arrows included in Fig. 4 show this increase in
binder is (Cong et al., 2012). The test was conducted at different
volume.
service temperatures with the purpose of analysing the influence of
the industrial waste on the thermal susceptibility of the mixtures.
4.2. Crystallised particles
In order to avoid problems of non-linearity, the temperatures were
chosen below 40
C. Particularly, the samples were tested at tem-
It must be said that some crystallized particles were appreciated
peratures of 2
C, 10
C, 20
C, and 30
C. Furthermore, the mixtures
at first sight when 40% and 60% of industrial waste were used.
were tested after an initial curing time of 14e42 days (as stated in
These crystallised particles (Fig. 5) were detected with the naked
the standard) and before a period of 6 months with the aim of
eye, after the blending was completed and the foaming process was
analysing the effect of ageing time in the thermal susceptibility.
ended. Nevertheless, when 20% or less waste was used, the crys-
tallised particles were not appreciated. Probably, when higher
3.9. Permanent deformation resistance amounts of waste were used, some coalescence tend to occur,
leading to these crystallised particles, and thus, to a heterogeneous
A repeated load axial test without confinement was conducted structure of the binder.
in order to evaluate the resistance to permanent deformation. The
Cooper NU 14 tester machine was used to conduct this test. The 4.3. Volumetric properties
British Standard DD 226:1996 (BSi, 1996) describes this test as
follows: each cylindrical Marshall specimen must be held at 30
C Fig. 6 shows the air void content (Va) versus the binder content
in a climate chamber for a minimum of 4 h, and then preloaded for of the asphalt mixtures, for each industrial waste percentage. This
600 ± 6 s at 10 kPa of axial stress with the load platens. After this figure also shows the Va limits required by the PG-3.
time, each specimen is subjected to 1800 load cycles. In order to Two one way analysis of variance (ANOVA) were conducted to
simulate loading in the field, square repeated load pulses were determine the effect of the industrial waste percentage (0%, 5%, 10%,
selected. The width pulse and the rest period were of 1 s, while the 20%, 40% and 60%) and the bitumen content (3.9%, 4.1%, 4.3% and
stress level was of 100 ± 2 kPa. 4.5%) on the Va. The waste percentage (p ¼ 0.039 < 0.05) and the
The axial permanent strain was calculated as follows: bitumen content (p ¼ 0.004 < 0.05) are statistically significant at
the 95% confidence level. That is, both bitumen content and in-
Dh
εd ðn;TÞ ¼  100 (4) dustrial waste percentage influence the air voids content.
h0 Fig. 6 shows that mixtures made with 40% of industrial waste
generally presented a Va higher than that of mixtures made with
where εd(n, T) ¼ the axial permanent strain (%) after n load appli-
lower waste percentages. This trend is even clearer when analysing
cations at temperature T in
C, Dh ¼ the axial permanent defor-
the asphalt mixtures made with 60% of industrial waste. In this
mation (mm), and h0 ¼ the initial distance between the two load
case, Va was much higher than the one obtained for mixtures with
platens (mm).
0%e40% of waste. In this regard, it must be taken into account that
A group of specimens was tested just after it was manufactured,
higher waste percentages introduced higher water content in the
whereas the other group of specimens was tested after a period of 6
mixture. Some polar components in asphalt could form intermo-
months with the aim of analysing the effect of ageing time in the
lecular forces with water molecules, so that part of the water
permanent deformation resistance.
molecules were remained in asphalt, leading to higher air voids
content.
3.10. Statistical analysis In addition, when a very high amount of industrial waste was
used, the compaction was more difficult, probably due the crys-
Analyses of variance (ANOVA) were conducted in order to tallized particles. This could also explain the irregular performance
analyse the statistical significance of the results. As is well known, of mixtures made with bitumen blended with 60% of industrial
ANOVA is a statistical model that compares the mean group of waste.
various samples and allow us to know if the differences between The results presented in Fig. 6 also show that the Va decreased as
each other are significant. IBM SPSS Statistics 24 was used in all the binder content increased, but mixtures made with 60% of in-
cases to perform the statistical analyses. dustrial waste showed an irregular behaviour. Probably, the crys-
tallized particles introduced in the mixture were mainly
4. Results and discussion responsible for this performance.
As observed in Fig. 6, mixtures made with 0% (control mixture),
The results obtained in the investigation detailed in this article 5%, 10%, 20%, and 40% of industrial waste containing lignin
are described and analysed below. biopolymer and with 4.30% and 4.50% of binder content complied
92 I.P. P
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Fig. 4. Bitumen with 20% of industrial waste: a) at the beginning of the mixing process and b) after 5 s of the beginning of the mixing process.

Fig. 6. Air void content versus bitumen content for different percentages of industrial
waste.
Fig. 5. Detail of the crystallized particles than remain in the binder for bitumen
blended with 60% of industrial waste.

4.4. Bitumen and aggregate adhesion

with the PG-3 for all the heavy traffic categories. Mixtures made Fig. 7 shows the percentage of aggregate surface that remained
with 0%, 5%, and 10% of industrial waste and binder content of 4.10% coated after 24 h of rolling time in the rolling bottle test and after
complied with the PG-3 for T1 to T4 heavy traffic categories. The 24 h of drying time in the boiling water test. Fig. 7 shows that all
same occurred with mixtures made with 20% of industrial waste tested mixtures led to boiling water test results over 70%, which is
and 3.90% and 4.10% of binder content. Mixtures made with 60% of the minimum required by some researchers to accept the material.
industrial waste did not comply with the PG-3 for any of the heavy However, only the mixtures made with 10%e40% of industrial
traffic categories. waste led to boiling water test results over 95%, which is the
The irregular behaviour of the mixtures made with 60% of in- minimum required by other researchers.
dustrial waste, together with the large Va and the difficulty in using Boiling water test results show that, in general, for industrial
the binder made with bitumen and 60% of waste, caused these waste percentages of 0%e20%, as the industrial waste percentage
mixtures to be discarded. increased, the percentage of aggregate surface that remained
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waste containing lignin biopolymer as extender improved the af-

finity between bitumen and aggregate when using percentages up
to 20%. As said before, higher waste percentages (40%) led to the
formation of crystallised particles, which negatively affect the af-
finity between aggregates and binder. At lower percentages (5%e
20%), the effect of the lignin included in the industrial waste and
the foaming effect of the water led to better affinity between the
aggregates and the binder. Particularly, it is possible that the foam
formation as a consequence of the industrial waste water evapo-
ration improved the aggregateebinder mixing, thus improving the
aggregateebitumen adhesion.
Nevertheless, the water sensitivity of the mixture is conditioned
by factors different from the bindereaggregate affinity. In this re-
gard, it was necessary to analyse the water resistance of the asphalt
mixtures on compacted specimens, as described in the following
Fig. 7. Bitumen-aggregate adhesion results after 24 h. section.

coated with the binder also increased. The result of the rolling 4.5. Moisture damage resistance
bottle test did not follow this trend, due to the low values achieved
for 10% of industrial waste. Nevertheless, both tests showed that Fig. 8 shows the TSR versus the binder content for mixtures
the best binder coating always occurred for mixtures with 20% of made with 0%, 5%, 10%, 20%, and 40% of industrial waste containing
industrial waste. Also, both test showed that for industrial waste lignin. As can be seen, for 3.9% of bitumen content, only 20% of
percentages of 40%, the binder coating was lower than that of 20%. industrial waste was analysed. For the other industrial waste per-
Two one way analysis of variance (ANOVA) were conducted to centages (0%, 5%, 10% and 40%), the air voids content obtained using
determine the effect of the industrial waste percentage (0%, 5%, 10%, 3.9% of bitumen content were out of the range of compliance with
20% and 40%) on the adhesion for both tests (Rolling Bottle Test and the PG-3, as was showed in Fig. 6.
Boiling Water Test). As was expected, for the boiling water test the Fig. 8 shows that there did not exist any relationship between
ANOVA analysis indicated that the industrial waste percentage the industrial waste percentage or the bitumen content and the
is statistically significant at the 95% confidence level TSR. Two one way analysis of variance (ANOVA) were conducted to
(p ¼ 0.000 < 0.05). As was also expected, for the rolling bottle test determine the effect of the industrial waste percentage (0%, 5%, 10%,
the industrial waste percentage is not statistically significant at the 20% and 40%) and the bitumen content (3.9%, 4.1%, 4.3% and 4.5%)
95% confidence level (p ¼ 0.282 > 0.05). In only percentages of 0%, on the TSR. The waste percentage (p ¼ 0.142 > 0.05) and the
5% and 20% of industrial waste were used, also this last test would bitumen content (p ¼ 0.292 > 0.05) were not statistically significant
indicate that the waste percentage is statistically significant at the at the 95% confidence level. These statistical results were expected
95% confidence level (p ¼ 0.000 < 0.05). These results could be because, as said before, no trend was found between these two
explained by the greater complexity in the realization of this test factors and the TSR.
that can give rise to greater dispersions. Nevertheless, Fig. 8 shows that for mixtures made with 0% of
Therefore, in general, it can be stated that the use of industrial industrial waste (control mixture), only 4.5% of binder content

Fig. 8. TSR vs binder content for mixtures with 0%, 5%, 10%, 20%, and 40% of industrial waste.
94 I.P. P
erez et al. / Journal of Cleaner Production 220 (2019) 87e98

achieved the minimum TSR of 80%, required by the PG-3 for AC 22 Fig. 9 shows the indirect tensile strength of the dry and wet sets
base G. Thus, the optimum binder content for the control mixture for mixtures made with 0%, 5%, 10%, 20%, and 40% of industrial
was 4.5%. This binder content led to mixtures that could be used in waste containing lignin. This figure clearly shows that mixtures
all heavy traffic categories, as said in section 4.3. For mixtures made made with 20% of industrial waste presented dry (Fig. 8a) and wet
with 5%, 10%, and 40% of industrial waste, none of the tested binder (Fig. 8b) indirect tensile strengths higher than the control mixture,
contents led to mixtures with adequate water sensitivity. for all the tested binder contents.
The mixture made with 20% of industrial waste achieved the It is possible to observe that mixtures made with 20% of in-
minimum TSR with 4.1% of binder content. Thus, the optimum dustrial waste at their optimum bitumen content (4.1%) displayed
binder content for this mixture was 4.1%. This bitumen percentage higher dry indirect tensile strength than the control mixture at its
led to mixtures that could be used in heavy traffic categories T1 to optimum bitumen content (4.5%). Regarding the wet indirect ten-
T4, as said in section 4.3. It means that using a 20% of industrial sile strength, for mixtures made with 20% of industrial waste it was
waste as bitumen extender requires less bitumen content than the slightly lower, but very similar. Thus, there was not a loss of indirect
control mixture to achieve an adequate water resistance. Never- tensile strength when using 20% of industrial waste at the optimum
theless, the mixtures should be used for heavy traffic categories T1 bitumen content.
to T4 (medium and low traffic roads). Four one way analysis of variance (ANOVA) were conducted to
There are two mechanisms that justify that the mixture man- determine the effect of the industrial waste percentage (0%, 5%, 10%,
ufactured with 20% of industrial waste presented higher moisture 20% and 40%) and the bitumen content (3.9%, 4.1%, 4.3% and 4.5%)
damage resistance than the control mixture. Firstly, the lignin is a on the ITSD and the ITSW. The waste percentage (p ¼ 0.142 > 0.05)
biopolymer than could aid to improve the properties of the binder, and the bitumen content (p ¼ 0.292 > 0.05) were not statistically
in this case, the bitumen-aggregate adhesion. Secondly, the foam- significant at the 95% confidence level. These statistical results were
ing that took place when the bitumen was blended with the in- expected because no trend was found between these two factors
dustrial waste, could also affect the results due to it led to a better and the ITSD or the ITSR.
coating of the aggregates by the bitumen and, as a consequence, to These results allow to state that the percentage of 20% of in-
a better moisture damage resistance. Thus, despite as can be seen in dustrial waste as bitumen extender seemed to be the most
section 4.3 mixtures made with 20% of industrial waste at 4.1% of adequate for the production of asphalt mixtures. Industrial waste
bitumen displayed higher air voids content (6.5%) than the control percentages of 10% or less seemed not to have enough lignin to
mixture at 4.5% of bitumen content (5.2%), the two aforementioned appreciate its effect on the asphalt mixtures. In contrast, industrial
mechanisms were clearly prevalent. waste percentages of 40% or more introduced heterogeneities in

Fig. 9. Indirect tensile strength versus binder content for mixtures made with 0%, 5%, 10%, 20%, and 40% of industrial waste: a) ‘dry set’ and b) ‘wet set’.
 I.P. P
erez et al. / Journal of Cleaner Production 220 (2019) 87e98 95

the asphalt mixtures owing to the formation of crystallised parti- mixture made with 20% of industrial waste was 10.48% higher than
cles that negatively affect the performance of the asphalt mixtures. that of the control mixture. Thus, the thermal susceptibility of the
Thus, 20% was the optimum amount of industrial waste containing mixtures made with 20% of industrial waste was lower than that of
lignin biopolymer to be used as bitumen extender. It improves the the control mixture. Low thermal susceptibility controls permanent
affinity between the aggregate and the binder and reduces bitumen deformation at high temperatures and avoids fracture at low
consumption in terms of water sensitivity for low and medium temperatures (Zapie
n-Castillo et al., 2016). Thus, the performance
traffic roads. The lignin content of the industrial waste and the of the asphalt mixture made with 20% of industrial waste was
foaming effect of the water included in this waste, seemed to be higher, leading to higher fatigue resistance at low temperatures and
mainly responsible for this performance. higher resistance to permanent deformation at high temperatures.
Fig. 10b also confirms this conclusion. Asphalt mixtures made
with 20% of industrial waste containing lignin led to lower thermal
4.6. Resilient modulus and thermal susceptibility susceptibility. Nevertheless, it must be taken into account that after
six months of curing time the resilient moduli were higher owing to
Fig. 10 shows the resilient modulus for an AC 22 base G made the ageing of the mixture. Furthermore, the thermal susceptibility
without industrial waste at its optimum bitumen content (4.5%) of mixtures made with 20% of industrial waste was not as low as
and for an AC 22 base G made with 20% of industrial waste, also at that at the initial moment. That is, the differences between the
its optimum bitumen content (4.1%). The resilient modulus was control mixture and the mixture made with 20% of industrial waste
obtained at 2
C, 10
C, 20
C, and 30
C. Fig. 10 clearly shows that as were less pronounced as time elapses.
the temperature increases, the resilient modulus decreases owing
to the thermoplastic nature of the binder.
In Fig. 10a, the differences between the control mixture and that 4.7. Resistance to the permanent deformation
with 20% of industrial waste can be appreciated. Clearly, at low
temperatures (5
C), the resilient modulus of the control mixture Fig. 11 shows the axial permanent deformation vs. the number
was higher (19.08%) than that of the mixture made with 20% of of load cycles for an AC 22 base G for the control mixture at its
industrial waste. The opposite occurred at the highest tempera- optimum bitumen content (4.5%) and for an AC 22 base G made
tures. As can be seen in Fig. 10, at 30
C the resilient modulus of the with 20% of industrial waste at its optimum bitumen content (4.1%).

Fig. 10. Resilient modulus at different temperatures: a) initial modulus and b) modulus after a curing time of six months.
96 I.P. P
erez et al. / Journal of Cleaner Production 220 (2019) 87e98

Fig. 11. Repeated load axial test results.

The permanent deformation resistance was obtained at 30
C. This The energy consumption (Q) was calculated as follows (Song et al.,
figure includes the results of the initial permanent deformation and 2018):
the results for mixtures cured during 6 months at room tempera-
ture. Because no specifications have been included in the PG-3 for Q ¼ ðmb  cb þ m1  c1 þ m2  c2 Þ  DT (5)
repeated load axial test results, this test is useful for comparison. Were mb, m1 and m2 are the masses (kg) of the bitumen, the
Fig. 11 clearly shows that the mixture made with 20% of in- hornfels and the industrial waste respectively; cb, c1 and c2 are the
dustrial waste presented lower permanent deformation than the specific heat capacities (J/(kg$ºC)) of the bitumen, the hornfels and
control mixture (0%) at an initial moment. These results were the industrial waste respectively. The specific heat capacity varies
coherent with those showed in Fig. 10. In this way, at the initial depending on the temperature of the material. In this regard, the
moment, the stiffness at 30
C was higher for mixtures made with specific heat capacities values were selected to leave the calcula-
20% of industrial waste than that for the control mixture. According tions on the security side. For the bitumen, cb ¼ 2.089 J/(kg$ºC) was
to this, the deformation will be lower in the stiffer mixture (20% of chosen (Song et al., 2018); for the hornfels, c1 ¼ 1.052 J/(kg$ºC)
industrial waste). Also, the higher bitumen content of the control (Martin et al., 2018) was assumed; and for the industrial waste,
mixture could contribute to this performance. c2 ¼ 2.692 J/(kg$ºC) was also assumed (Zanotti et al., 2016). DT is the
Nevertheless, the differences between mixtures made with 0% increase of temperature from the room temperature (20
C), to the
and 20% of industrial waste were not noticeable when 6 months of mixing temperature (170
C).
curing time have passed. Again, the results were coherent with Table 5 shows the energy consumption per ton of mixture. As
those showed in Fig. 10, because after 6 months of curing time the can be seen, the energy consumption is similar in both cases: the
stiffness at 30
C was similar for both mixtures. mixture made at the optimum lignin content consumes slightly
lower energy (0.0025%).
5. Cost-effectiveness analysis
6. Conclusions
A cost-effectiveness analysis was conducted. In this analysis, the
control mixture and the mixture that showed the optimum lignin When the industrial waste containing lignin biopolymer was
content (20%) according to the results showed in section 4, were
compared. Both mixtures were analysed at their optimum bitumen
content: 4.5% for the control mixture and 4.1% for the mixture made Table 5
with 20% of industrial waste. As is shown in Table 4, the cost of Energy consumption per ton of bituminous mixture (kJ).

manufacture the mixture made with 20% of industrial waste was Control mixture Mixture at the optimum lignin content
16.5% lower than that of the control mixture. (0% lignin and 4.5% of bitumen) (20% of lignin and 4.1% of bitumen content)
In addition to the analysis of the costs of the raw materials, it is
164,800 164,796
necessary to quantify the energy consumption of both mixtures.

Table 4
Cost-effective analysis.

Component Cost (V/t) Cost per ton of bituminous mixture (V)

Control mixture Mixture at the optimum lignin content

(0% lignin and 4.5% of bitumen) (20% of lignin and 4.1% of bitumen content)

Bitumen (B50/70) 386.00 17.37 13.19

Aggregate (hornfels) 8.21 7.84 7.87
Industrial waste 0.00 0.00 0.00
Total 25.21 21.06
 I.P. P
erez et al. / Journal of Cleaner Production 220 (2019) 87e98 97

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