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Novel biochar-concrete composites: Manufacturing, characterization and

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DOI: 10.1016/j.scitotenv.2017.10.319

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 Science of the Total Environment 616–617 (2018) 408–416

Contents lists available at ScienceDirect

Science of the Total Environment

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

Novel biochar-concrete composites: Manufacturing, characterization and

evaluation of the mechanical properties
Ali Akhtar, Ajit K. Sarmah ⁎
Department of Civil and Environmental Engineering, Faculty of Engineering, The University of Auckland, Private bag 92019, Auckland 1142, New Zealand

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Waste derived biochar has potential to

be used as cement replacement.
• Flexural strength improved approxi-
mately 20% with the addition of biochar.
• Water absorption of biochar concrete is
comparable to the control at 0.1% of
total volume.

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

Article history: In this study, biochar, a carbonaceous solid material produced from three different waste sources (poultry litter,
Received 18 August 2017 rice husk and pulp and paper mill sludge) was utilized to replace cement content up to 1% of total volume and the
Received in revised form 30 October 2017 effect of individual biochar mixed with cement on the mechanical properties of concrete was investigated
Accepted 30 October 2017
through different characterization techniques. A total of 168 samples were prepared for mechanical testing of
Available online xxxx
biochar added concrete composites. The results showed that pulp and paper mill sludge biochar at 0.1% replace-
Editor: D. Barcelo ment of total volume resulted in compressive strength close to the control specimen than the rest of the biochar
added composites. However, rice husk biochar at 0.1% slightly improved the splitting tensile strength with pulp
Keywords: and papermill sludge biochar produced comparable values. Biochar significantly improved the flexural strength
Poultry litter of concrete in which poultry litter and rice husk biochar at 0.1% produced optimum results with 20% increment
Rice husk than control specimens. Based on the findings, we conclude that biochar has the potential to improve the con-
Biochar crete properties while replacing the cement in minor fractions in conventional concrete applications.
Concrete © 2017 Elsevier B.V. All rights reserved.
Compressive strength
Flexural strength

1. Introduction Klee (2009), annual concrete production has crossed over 25 billion
tonnes which is N 3.5 t for every person in the world. Even though con-
Concrete is an essential part of any construction project, be it a crete usually has different compositions according to its required use,
multi-storey commercial building or bridges to connect people of two cement in concrete is an essential component along with sand, water
sides and thus it is being produced in huge amounts. According to and gravels (Stolaroff et al., 2005). The main components of cement
are tricalcium silicate (C3S) (50–70%), dicalcium silicate (C2S) (15–
⁎ Corresponding author. 30%), tricalcium aluminate (5–10%) and tetracalcium aluminoferrite
E-mail address: [email protected] (A.K. Sarmah). (5–15%). Other minor components include sodium oxide, potassium

https://doi.org/10.1016/j.scitotenv.2017.10.319
0048-9697/© 2017 Elsevier B.V. All rights reserved.
 A. Akhtar, A.K. Sarmah / Science of the Total Environment 616–617 (2018) 408–416 409

oxide and gypsum which are b 5% (Mindess and Young, 1981). It can be the potential to produce the concrete of adjacent strength to steel rein-
observed that tricalcium and dicalcium silicates are the major compo- forced concrete after proper processing of the bamboo. However, the
nents of cement which are also responsible for so called hydration prod- raw inclusion of biomass leads to challenges significantly affecting the
ucts, calcium hydroxide (Ca(OH)2) and calcium silicate hydrate durability properties (Kriker et al., 2008). Date palm fiber was found
(C\\S\\H) gel (Barron, 2010). to be effective for thermal insulation but reduced the compressive
strength and increased the water absorption as the content increases
2ðCaOÞ3 ðSiO2 Þ þ 7H2 O→ðCaOÞ3 ðSiO2 Þ2 4ðH2 OÞ þ 3 CaðOHÞ2 ð1Þ (Benmansour et al., 2014).
Organic waste is being produced in vast quantity throughout the
Carbon dioxide (CO2) production has been a great debate in the cur- world in the form of municipal waste, industry waste, and agricultural
rent scenario where it is contributing as a greenhouse gas and causing a waste etc. This type of wastes cannot be recycled like its counterpart
major threat to the environment. One of many man-made sources of glass and plastic. That is why a number of alternatives have been devel-
CO2 production; cement industry has a significant role in producing oped besides landfilling to decompose this type of waste to reduce the
CO2 through production, processing and preparation phase adding ap- size efficiently and produce useful by products which can be utilized
proximately 7% of total world's production of CO2 (Oh et al., 2014). for different purposes. One of the recently recognized techniques is py-
The major part contributing towards the CO2 emission is the heating rolysis to convert organic waste into biochar. Biochar is a porous carbo-
of limestone during calcination process. Cement contribution in con- naceous solid material produced through thermochemical conversion
crete is merely 20% of total volume but it is responsible for approximate- of biomass in the absence of oxygen at a temperature ranging from
ly 90% of the total emission of CO2 (Yang et al., 2015) with one tonne of 450 to 550 °C (Lehmann and Joseph, 2010; Shackley et al., 2011). Bio-
cement production causing0.95 t of CO2 (Ludwig and Zhang, 2015). This char has found its ways into various applications, though predominantly
makes cement the most studied material to understand the proper- used for soil improvement in agricultural lands as soil amendment (Zhu
ties and possibly replacing it with other materials called as supple- et al., 2017). A number of studies have been conducted to include this
mentary cementitious materials. The number of materials by-product in other applications and researchers around the world
introduced successfully in concrete to partially replace the cement have obtained positive results e.g., as a bio modifier in asphalt cement
in recent years include fly ash and pumice powder (Kabay et al., (Zhao et al., 2014), horticultural applications (Vaughn et al., 2017) and
2015), silica fume (Zhang et al., 2016), ground granulated blast fur- waste water treatment application (Lee et al., 2016). For instance,
nace slag (Divsholi et al., 2014), waste glass (Aliabdo et al., 2016). study by Zhao et al. (2014) showed that biochar can be an effective as-
For example, Aliabdo et al. (2016) found that glass powder exhibited phalt binder as compared to commercially available carbon binders con-
pozzolanic properties and 15% replacement of cement with glass taining high surface area. Biochar improved the rutting resistance under
powder enhanced the compressive strength and 10% showed opti- high surface temperature and showed no modification in fatigue crack-
mum replacement for splitting tensile strength for targeted 33 MPa ing resistance of the asphalt, which however, decreased with the addi-
concrete. Babu and Neeraja (2017) studied the effects of hen eggs tion of commercially available active carbon.
shell inclusion in concrete and mortar with fly ash as partial replace- To date, however, there has not been a single study conducted to in-
ment of cement and recommended that the dosage of hen shell at vestigate the biochar's use in concrete making and its potential for car-
0.25% and fly ash at 55% not only improved strength performance bon storage. Therefore, the overarching aim of this work is to study the
but was also found to be cost effective. Elsewhere, Vegas et al. effect of three different types of biochar as an additive in concrete on its
(2006) reported that paper mill sludge after calcination at 700 °C strength properties and determine the optimal usage in conventional
for 2 h produced optimal pozzolanic properties. This calcined prod- concrete applications.
uct showed slightly higher compressive strength at the age of
28 days with 10% replacement of cement content in cement paste
2. Materials and methods
showing the potential to utilize the waste sludge in partial cement
replacement.
Ordinary Portland cement (OPC) was obtained from Golden Bay Ce-
Different waste materials are being added to concrete to improve its
ment, Auckland; while washmix sand, gravels, tap water and three
properties and also to reduce the impact of greenhouse gases. Spiesz
types of biochar: poultry litter (PL) biochar, rice husk (RH) biochar
et al. (2016) suggested the use of waste glass with fly ash and ground
and pulp and paper mill sludge (PP) biochar were other materials that
granulated blast furnace slag to reduce the effect of Alkali-silica reaction
were employed in this study. Gravels were of standard 10 mm size se-
(ASR) and also recommended the use of washed glass to remove other
lected to minimize the uncertainty in strength caused by size and
impurities associated with glass for better strength and durability prop-
shape of gravels. PL biochar was produced at 450 °C using slow pyrolysis
erties. Torres et al. (2017) incorporated fine and coarse foundry waste in
(residence time of 20 min), while PP sludge biochar was produced at
concrete and found that fine foundry waste at 30% replacement pro-
500 °C using high temperature gasifier, while RH biochar was produced
duced optimum strength (compressive, splitting tensile and flexural)
by Oliver Enterprises Philippines at 500 °C using a slow pyrolysis pro-
properties rather than a mixture of coarse and fine foundry waste.
cess (residence time of 20 min). Chemical composition of OPC and bio-
Ling and Nor (2006) have reported the use of waste tyres in concrete
char was determined by X-ray fluorescence (XRF) spectrometry and
paving blocks and found that paving blocks containing rubber found
inductively coupled plasma mass spectrometry (ICP-MS) analysis re-
to improve the skid resistance, however, reducing the compressive
spectively. Other characterization techniques used for biochar is de-
strength. Similarly, Modarres et al. (2016) used the coal waste ash and
scribed below.
coal waste powder in concrete pavements at different percentages of
cement replacements from 5 to 20% and 5% of replacement of coal
waste powder and ash improved the compressive strength and tough- 2.1. X-ray fluorescence (XRF) spectrometry
ness of pavements.
There has been a growing trend in the utilization of agricultural The chemical composition of cement and concrete samples is deter-
waste in concrete as well for several reasons. Primarily, one of which mined by X-ray Fluorescence (XRF) spectrometry. The manufacturer of
is to minimize the burning of waste on fields to eradicate the handling Portland cement was Golden bay cement. PANalytical Axios 1kW X-Ray
costs. Secondary reason explains the importance in strength improve- Fluorescence spectrometer was employed for this test. The equipment
ment where many waste sources like bamboo can produce overall works on the principle of wavelength dispersive X-ray fluorescence
good properties with the sustainable availability of the material (van spectrometry with high resolution. The chemical composition of cement
der Lugt et al., 2006). Agarwal et al. (2014) reported that bamboo has is given in Table 1.
410 A. Akhtar, A.K. Sarmah / Science of the Total Environment 616–617 (2018) 408–416

Table 1 Table 2
Chemical composition of Ordinary Portland Cement (wt%). Distribution of inorganic fractions in biochar (mg/g).

Composition Cement (%) Sample Si Ca K Cr Fe Zn As Zr Pb

CaO 65.63 PL 29.3 33.3 43.5 0.009 5.32 0.79 0.002 0.007 0.0095
SiO2 21.04 PP 15.9 49.21 2.4 0.01 3.09 0.00 0.0014 0.06 0.012
S 3.81 RH 246.7 4.58 12.04 0.002 0.321 0.00 0.0006 0.00 0.004
Al2O3 3.932
PL = Poultry litter biochar.
Fe2O3 2.59
PP = Pulp and papermill biochar.
MgO 0.885
RH = Rice husk biochar.
Sr 0.73
K2O 0.49
TiO2 0.305 than all of the samples, however, RH showed highest silicon concentra-
Na2O 0.24 tion with least amount of calcium. Elemental analysis was done four
Ba 0.2
P2O5 0.148
times for each of the biochar sample and average values reported in
LOI⁎ 3.1 Table 3.
⁎ LOI = loss on ignition.
2.4. Mix design and specimen preparation

2.2. Thermogravimetric analysis (TGA) Different mix ratios were designed to determine the effect of biochar
in normal strength concrete. Biochar was added in the percentage of
Thermogravimetric analysis for the biochar samples was performed 0.1–1% of total volume of concrete (Table 4). Water to binder ratio
in the presence of Argon as a purge gas at the flow rate of 100 ml/min. was kept at 0.32 considering cement and biochar as a binder. There
TG-50 instrument was utilized for thermal analysis of the biochar with was no superplasticizeror water reducer used during the preparation
platinum crucible and weight of the samples was maintained between of mixes. Materials were mixed in a stationary mixer, having attached
7.0 and 8.5 mg. Balance and temperature of the equipment maintained dedicated blades for mixing. Materials were first dry mixed for 2 min
for 10 min before the start of the experiment and heating rate was kept and then added water to continue mixing for 2 min. All the samples
at 20 °C/min for all the samples. The thermogravimetric analysis (TGA) were prepared and cured according to ASTM C192/C192M (2016). Cy-
curves are shown in Fig. 1. PP biochar showed highest weight loss ap- lindrical samples (100 mm × 200 mm) were casted and then cured in
proximately N55% and RH showed the lowest weight loss b15% up to the moist environment for 7, 14 and 28 days to measure the mechanical
800 °C. RH showed the highest weight loss in the form of moisture properties.
whereas single stage degradation observed between 300 and 600 °C
for PP and PL.
2.5. Water absorption

Water absorption and volume of permeable voids of the samples

2.3. Inductively coupled plasma mass spectrometry (ICP-MS) and elemen-
were measured according to ASTM C642 (2013). The samples of dimen-
tal analysis
sions 75 × 75 × 250 mm were prepared for these tests and conducted
the experiment after 28 days of moist curing of the specimen.
The Ca and Si concentration with other inorganic fractions in bio-
mass samples were measured using Agilent 7700 ICP-MS instrument
in He mode to reduce polyatomic interferences. The samples were 2.6. Compressive strength
digested with 69% HNO3 and 35% H2O2 and then later digested in the
Ethos-Up microwave at 200 °C for 20 min. The resultant product then Cylindrical concrete specimens (100 mm × 200 mm) were tested for
later diluted with pure water and final weight was obtained. Calibration compressive strength according to ASTM C39 (2016). The samples were
standards were prepared by weight in matrix matched solution from capped before compressive strength test according to ASTM C617/
1000 ppm single element standards. The inorganic fractions in biochar C617M−12 (2012). Three specimens were tested for each of the mix
presented in Table 2 in mg/g. It can be seen that the highest amount design after 7, 14 and 28 days of moist curing.
of calcium existed in PP biochar containing the least amount of silicon
2.7. Splitting tensile and flexural strength

Splitting tensile strength of cylindrical specimens of size (100 mm

× 200 mm) were measured according to ASTM C496/C496M (2011).
The samples were tested similarly after 7, 14 and 28 days of curing.
Beam specimen of size (100 × 100 × 500) mm were prepared to mea-
sure the flexural strength of concrete composites. Tests were conducted
according to ASTM C78/C78M (2016) standards. All the tests were con-
ducted after 28 days of moist curing.

Table 3
Elemental analysis of biochar showing the carbon, hydrogen, nitrogen and oxygen concen-
tration (%).

Element PL RH PP

C 19.03 36.06 30.0

H 1.37 0.63 0.49
N 1.68 0.47 1.53
S b0.3 b0.3 0.18
O⁎ 77.63 49.23 68.5
Fig. 1. TGA curves for pulp and papermill sludge (PP), poultry litter (PL), and rice husk
(RH) biochar. ⁎ calculated by the difference from C, H, N and S.
 A. Akhtar, A.K. Sarmah / Science of the Total Environment 616–617 (2018) 408–416 411

Table 4
Mix design of concrete for various biochar proportions in kg/m3.

Samples Cement Sand Gravels PL biochar PP biochar RH biochar w/b

Control 345 915 1122 – – – 0.32

PL0.1 342 915 1122 0.69 – – 0.32
PL0.25 339 915 1122 1.73 – – 0.32
PL0.5 334 915 1122 3.45 – – 0.32
PL0.75 328 915 1122 5.18 – – 0.32
PL1 323 915 1122 6.9 – – 0.32
PP0.1 342 915 1122 – 0.69 – 0.32
PP0.5 334 915 1122 – 3.45 – 0.32
PP1 323 915 1122 – 6.9 – 0.32
RH0.1 342 915 1122 – – 0.69 0.32
RH0.25 339 915 1122 – – 1.73 0.32
RH0.5 334 915 1122 – – 3.45 0.32
RH0.75 328 915 1122 – – 5.18 0.32
RH1 323 915 1122 – – 6.9 0.32

(w/b = water to binder ratio).

PL = Poultry litter biochar.
Fig. 2. Compressive strength of biochar-concrete composites after 7, 14 and 28 days of
PP = Pulp and papermill biochar.
curing.
RH = Rice husk biochar.

2.8. Fourier transform infrared (ATR-FTIR) spectroscopy strength development with pore structure refinement (Poon et al.,
2001). However, poultry litter (PL) biochar reduced the strength signif-
ATR- FTIR analysis was performed to characterize the concrete and icantly at 7 days of testing at all mix ratios as compared to the control
determine the variation in surface functional groups in each of the samples. The difference in compressive strength between control and
mix design. The samples were prepared through the ring mill machine biochar concrete decreased after 14 days of testing and showed compa-
to consider the homogeneity of the samples and converted to powder rable values for RH and PP biochar at 0.1%. There was a decrease in
form. The spectra were observed and analysed in the range of strength shown at 0.09 MPa for PP0.1 and 0.36 MPa for RH0.1. On the
700 cm−1 to 4000 cm−1 wave numbers at a scan rate of 64 with a spec- other hand, at 0.1% PL and 0.5% PL and PP addition of biochar showed
tral resolution of 4 cm−1. strength N 26 MPa after 14 days, exhibited 3.5 MPa reduction on average
according to Control specimens. Toutanji et al. (2004) found that fly ash
2.9. X-ray diffraction (XRD) spectrometry reduced the strength up to 50% at 30% addition at the age of 14 days
which might be due to slow cementitious reactivity in early phase of de-
In order to determine the phase identification for a variety of crystal- velopment as compared to Portland cement and other supplementary
line phases of hardened concrete samples, XRD analysis was done using materials.
Bruker D2 phaser instrument. Concrete samples were first dried for 24 h There was a significant change in strength properties observed after
to remove any moisture and then grind with the help of ring mill ma- 28 days where control samples were of high compressive strength than
chine to convert into a fine powder. Spectra were collected at a range the rest of the samples. The closest values were given by PP0.1 and
angle (2θ) 10°–50° with a step size of 0.02 at 0.1 s per step. X-ray gen- RH0.1 with a decrease in 3 MPa, however, the reduction of strength
erator was set to 30 kV voltage and current at 10 mA. existed within 10%. It is noteworthy that at 0.25% RH and PL samples ex-
hibited consistently the least values throughout the testing, making the
0.25% the least suitable ratio of biochar for compressive strength to uti-
2.10. Microscopic analysis lize in concrete applications. This change in strength pattern showed the
filler effect of biochar which is creating the dense structure in the early
To gauge an understanding of the surface morphological characteris- age development whereas it is prohibiting the production of (Calcium
tics of the specimen, scanning electron microscopy was conducted at silicate hydrate) C\\S\\H due to higher volume occupation and show-
20 kV accelerating voltage and 0.08 Torr pressure with the help of in- ing slightly slower contribution towards pozzolanic activity after
strument FEI Quanta 200F SEM. Samples were taken out of the tested 7 days. Long term curing of the biochar is required, like fly ash, to fully
specimen for compressive strength test in the form of the cube by dia- understand the strength development as compared to control samples.
mond saw and then later oven dried for 24 h at 100 °C to remove any
moisture. The samples were then mounted into an epoxy resin and 3.2. Splitting tensile strength
then ground and polished as shown in Fig. 8. After preliminary prepara-
tion samples were coated with platinum to ensure good conductivity. The results of the splitting tensile strength of the samples were plot-
ted in Fig. 3 after 7, 14 and 28 days of curing. The error bars are showing
3. Results and discussion the variation of the values from the average values for each of the mix
design. It can be observed that after 7 days, PP0.1 significantly improved
3.1. Compressive strength the strength than the control samples, showing N12% increment. On av-
erage, 6 out of 13 samples showed higher strength including PP0.1,
The results for Compressive strength of the cylindrical samples in PP0.5, PP1, RH0.1, RH0.5, and RH1. Furthermore, PL0.75 and PL0.1 also
three intervals after 7, 14 and 28 days of curing are presented in Fig. 2. produced comparable strength as compared to the control samples.
The error bars are showing the variation in the values from average However, there was a sudden shift of strength observed at the age of
values. At 0.1% addition of biochar, both Pulp and paper mill sludge 14 days where control samples exhibited higher values for splitting ten-
(PP) and rice husk (RH) biochars markedly increased the strength sile strength on average than all of the samples. Both RH0.1 and PL0.75
than control after 7 days of curing. On average, there was 10% increase showed comparable average strength with the approximate decrease of
in compressive strength for PP biochar and 6% for RH biochar. PP0.5 5%.
was also found to be in comparable range at the age of 7 days. This The increase in strength values observed at RH0.1 according to the
might be due to higher pozzolanic activity in the early stages of the control samples whereas PP0.1 and RH0.5 showed comparable values
412 A. Akhtar, A.K. Sarmah / Science of the Total Environment 616–617 (2018) 408–416

2014), thus the lower macro pores will increase the strength. Biochar
appeared to reduce the size of the pores and tend to increase the bend-
ing strength. Generally, PL biochar was found to be of higher strength
than the RH for most of the mix ratios which were of lower strength
for compressive and splitting tensile, suggesting the pores irregularity
in the structure. This led to abnormal distribution of the load in the
structure which ultimately leads to earlier fracture in static loads.
A careful examination of load-displacement curves showed that
RH0.1 have achieved a higher displacement under fracture load as com-
pared to rest of the specimen, prohibiting the sudden failure of the con-
crete (Figure S1). This implies the higher resistance to fracture at the
peak loads according to the control specimen. However, this phenome-
non does not exist in other specimen of similar strength. The increment
in pulp and paper mill biochar did not provide better strength perfor-
mance than RH and PL biochar. The displacement fluctuation was nearly
Fig. 3. Splitting tensile strength of biochar-concrete composites after 7, 14, and 28 days of
curing. similar to the control in approximately all specimen with 0.5 mm of dis-
placement was consistent.

at the age of 28 days making RH0.1 as the most suitable for splitting ten-
sile strength. However, PP0.1 and RH0.5 values were within 2% of the 3.4. Water absorption
control sample, implying a reasonable replacement of cement content
for splitting tensile strength. This can be seen that biochar affects this The water absorption pattern with the addition of biochar is shown
property in a different manner than compressive strength and can con- in Fig. 5 for conventional concrete. It is clear that PL0.25 and PP0.5 re-
tribute positively to improve the strength at the later stages of the de- duced the water absorption in concrete than control specimen, where-
velopment. Moreover, PL0.25 and RH0.25 showed a similar pattern in as, PL0.1, RH0.1, PL0.75, RH1, and PP1 showed comparable absorption
splitting tensile strength as that of compressive strength, being consis- within 0.5% increment to the control specimens (Fig. 6). The rest of
tently less than the rest of the samples which can be concluded for specimen showed considerably higher absorption. Poultry litter biochar
their least suitability in concrete applications. on average produced higher water absorption except PL0.25 where
PL0.1 and PL0.75 showed comparable values to the control sample,
3.3. Flexural strength however, rice husk biochar showed contrast behaviour where RH0.25
produced the highest water absorption in concrete. RH0.1 and RH1
The average results are presented in Fig. 4 which shows the overall showed comparable values according to the control specimens.
picture at the age of 28 days of testing whereas displacement-load Pulp and paper mill biochar was found to be in similar range to the
curves are shown in Supplementary file Fig. S.1. It can be observed control specimen for PP0.5 and PP1 which shows the potential to pro-
that there is a striking contrast between the compressive and flexural duce concrete of comparable absorption in the concrete at higher re-
strengths of the biochar concrete samples where most of the samples placement ratios. The nearest void values were observed by RH0.1,
showed higher strength than control samples. For instance, PL0.1, RH0.5 and RH1 with RH0.25 giving the highest permeable voids in
RH0.1, and RH1 produced N20% increase in strength than control, biochar-concrete composites. It is important to note that RH0.25 pro-
whereas, rest of the samples except PL0.75 showed N 5% increase in duced consistently lowest strength values for compressive and splitting
strength. This may be attributed to the available flexibility due to bio- tensile strength. An explanation for this could be that this decreased
char in concrete which acts as a link between biochar particles and hy- value in strength may be attributed to the increasing permeable voids
drated cement to avoid earlier fracture. The flexural strength is affected and water absorption inside the concrete to prohibit the creation of
by the macro pores in the cross-sectional area of the plane (Snoeck et al., dense structure. Similar finding was also reported by Bozkurt and
Yazicioglu (2010) where silica fume created the dense structure by fill-
ing the pores inside the concrete, however, fly ash contained the rela-
PP1 tively larger particle size was unable to fill the pores efficiently,
PP0.5 resulting into lower strength and higher capillary pores.
PP0.1
RH1
RH0.75
RH0.5
RH0.25
RH0.1
PL1
PL0.75
PL0.5
PL0.25
PL0.1
Control

0 1 2 3 4 5
Flexural Strength (MPa)

Fig. 5. Water absorption and volume of permeable voids in concrete after 28 days of
Fig. 4. Flexural strength of biochar-concrete composites at 28 days of curing. curing.
 A. Akhtar, A.K. Sarmah / Science of the Total Environment 616–617 (2018) 408–416 413

calcium silicate hydrate (C\\S\\H) phases (Fig. 7). Peaks obtained for
Control, PL0.1, PP0.1, RH0.1, and RH0.5 showed at the similar 2θ posi-
tions, however, with different intensities. For instance, RH0.1 showed
a higher peak at 26.6° for SiO2 than rest of the samples including a con-
trol which might be due to the high percentage of silicon presence in RH
biochar, which agrees with the data obtained in ICP-MS analysis.
Highest peak for C3S/C2S was obtained at 27.8° by control sample and
RH0.1 which also translated to higher splitting tensile strength. Similar-
ly, calcium hydroxide peak at 50.1° was also highest in control and
RH0.1 samples while PL0.1 showed the least hydrated calcium in its
structure. These observations led us to conclude that PL inhibits the
growth of calcium hydroxide than other biochars in concrete structures
which in turn reduces the C\\S\\H to lower the strength performance.
The increasing concentration of biochar slightly shifts the peaks of C3S
and C2S which can be observed in RH0.5 with significantly higher
peak than others.

3.7. Concrete microscopic analysis

Microscopic analysis was performed for biochar concrete compos-

ites and is shown in Figs. 9 and 10. A visual examination of images sug-
gests that rice husk biochar integrated into the structure through the
filling of its pores with concrete (Fig. 10). However, further increase in
the concentration of biochar led to increased number of unfilled pores
in concrete which ultimately increased water absorption. This phenom-
enon yields low strength due to a less compact structure which needs to
be investigated to improve the properties of concrete with the addition
of biochar. Biochar's filler effect is more dominant than its pozzolanic ef-
Fig. 6. ATR-FT-IR spectra of biochar-concrete composites.
fect, showing the capability to produce compact structures with a little
contribution towards chemical enhancement. This agrees with the ob-
3.5. ATR-FTIR spectroscopy tained results where biochar is significantly helpful to achieve higher
strength at the age of 7 days. Tricalcium silicate is being shown as a
FTIR spectra are being shown in Fig. 6 for concrete samples with granular structure changing to calcium hydroxide filling up the voids
added biochar obtained from rice husk, poultry litter, and pulp and in concrete in Fig. 10(b). Biochar addition may require significantly
paper mill sludge against reference concrete (Control) containing no more time to reduce the strength difference as compared to the conven-
biochar. Various peaks were observed at 781 cm− 1, 980 cm− 1, tional concrete due to less C\\S\\H production in the early phase devel-
2364 cm− 1, 2316 cm− 1, and abrupt peaks in the range of 1463– opment. Hence long-term evaluation is necessary to understand the
1716 cm−1, and 3564–3900 cm−1. The major peaks at 781 cm−1 and behaviour of biochar in concrete applications.
980 cm− 1 were assigned to the C\\O band (Chollet and Horgnies,
2011) and Si\\O band to confirm the presence of calcium silicate hy- 4. Economic analysis
drate (C\\S\\H) gel (Chollet and Horgnies, 2011; Alghamri et al.,
2016). Two minor peaks also observed at 2364 and 2316 cm−1 repre- Despite of growing interest and research in biochar production and
sented the sulphate presence in the samples (Nasrazadani et al., its suitability in different applications, commercial availability of biochar
2015). The 1400–1500 cm− 1 range contained the CO3 band and has not been standardized yet. There have been number of studies that
3564–3900 cm− 1 range represented \\OH band (Nasrazadani et al., focused on the economic analysis of various biochars produced using
2015). The minor weak bands are due to the presence of biochar in different types of feedstocks, for instance from eucalypt plantations
the samples where it combines with calcite and portlandite between (Wrobel-Tobiszewska et al., 2015), agricultural residue and yard
the ranges of 1463–1716 cm−1 and 3564–3900 cm−1 respectively.
It can be postulated from the obtained results that the strength perfor-
mance was likely to be due to the calcium silicate hydrate (C\\S\\H) for-
mation which was also in agreement with acquired test results. PP0.1
samples have shown similar high absorbance peak at approximately
980 cm−1 as that of the control specimen while other specimens PL0.1
and RH0.1 showed the least absorbance peak. Additionally, PL and RH
also exhibited the minor peaks in the range of 1463–1716 cm−1 and
3564–3900 cm−1 which were absent in the control specimen. Further-
more, PP biochar produced a highest C\\S\\H band with least minor
peaks in the spectra than both other biochar concrete composites con-
cluding its higher integration into concrete structure than other biochars
under the studied period during the development of concrete.

3.6. X-ray diffraction (XRD) analysis

XRD analysis showed that all the spectra showed silica and calcium
hydroxide with dicalcium and tricalcium silicate phases (C2S/C3S) and Fig. 7. Phase identification of concrete by XRD at different percentages of biochar.
414 A. Akhtar, A.K. Sarmah / Science of the Total Environment 616–617 (2018) 408–416

Fig. 8. Polished and mounted specimen of concrete in epoxy resin.

waste (Joseph et al., 2010) and from poultry waste (Huang et al., 2015).
Huang et al. (2015) reported that biochar production cost from poultry
litter waste is around 218 £/t (297US$/t) without considering the elec-
tricity and heat as a product. If electricity and heat is sold and gate fee is
introduced then this amount reduced to 65 £/t (88US$/t). Moreover, the
electricity generation cost will also be compatible with the fossil fuel
based generation. Shackley et al. (2011) have done comprehensive re-
view combining different studies related to economic cost of biochar
production from feedstock availability to biochar application into the
fields. Three different pyrolysis units were assumed in the study includ-
ing small, medium and large-scale pyrolysis units according to the feed- Fig. 9. SEM images of control concrete(a) overview of structure (b) visualizing the
stock consumption 2000, 16,000 and 185,000 odt (oven dry tonne) per microstructure.
year respectively. The cost of production, transport and field application
of biochar has been estimated to be between 222 and 584 US$ per content, assuming all the other factors were constant. It is conceivable
tonne. that if biochar is produced in a large-scale unit, this could potentially
Different values of cost production from small, medium and large contain overall net zero cost for the production, while there is possibility
scale are being shown in Table 5. Biochar cost largely depends on feed- of profit being generated through the sales of electricity and power gen-
stock type and scale of the production. As it can be observed from the eration. However, this area of research using biochar in concrete making
Table that biochar production from straw costs around 313,399 and is in its infancy and more research needs to be undertaken to under-
181 $/t for small, medium and large-scale production respectively. La- stand its full potential and economic viability.
bour and plant costs are significantly lower in large scale production
unit which makes this unit profitable for many of the feedstocks
(Table 5). 5. Conclusion
Medium scale production unit of biochar was considered for the
present study to extract the biochar costs for utilization in concrete pro- We have demonstrated through this study that biochar prepared
duction and the results have been compared for the total concrete pro- from waste biomass can be used to improve the flexural strength and
duction per m3. Cost of biochar application to the field was included in splitting tensile strength of conventional concrete at certain mix de-
the Table 5, however, during the calculations, this cost was not consid- signs, however, reduced the compressive strength. Pulp and paper
ered. Prices for each of the materials were derived from Orkney aggre- mill sludge and rice husk biochar at 0.1% of total volume were found
gates and costs of the biochar were estimated from Shackley et al. to be the most suitable replacement binder with respect to mechanical
(2011). All the prices converted from GBP to USD per tonne to keep strength in concrete. Poultry litter and pulp and paper mill sludge bio-
the results consistent. The results presented in Table 6 suggest that char improved the water absorption in concrete, while poultry litter
when biochar was added to concrete, it showed slight decrease in over- and rice husk biochar exhibited water absorption equivalent to control
all price of concrete production due to minor replacement with cement specimens. Biochar can be potentially a suitable material where early
 A. Akhtar, A.K. Sarmah / Science of the Total Environment 616–617 (2018) 408–416 415

Table 6
Cost of concrete production according to UK market in USD/m3 for studied mix design.

Specimen Cement Sand Gravels Biochar ⁎Price/m3 Delivery rate/h

Control 85.04 45.36 18.78 ¯ 149.18 67

PL-0.1 84.30 45.36 18.78 0.04 148.48
PL-0.25 83.56 45.36 18.78 0.09 147.79
PL-0.5 82.33 45.36 18.78 0.18 146.65
PL-0.75 80.85 45.36 18.78 0.27 145.26
PL-1 79.62 45.36 18.78 0.36 144.12
RH-0.1 84.30 45.36 18.78 0.27 148.71
RH-0.25 83.56 45.36 18.78 0.68 148.38
RH-0.5 82.33 45.36 18.78 1.35 147.82
RH-0.75 80.85 45.36 18.78 2.03 147.02
RH-1 79.62 45.36 18.78 2.71 146.46
PP-0.1 84.30 45.36 18.78 0.04 148.48
PP-0.5 82.33 45.36 18.78 0.18 146.65
PP-1 79.62 45.36 18.78 0.36 144.11
⁎ Price does not include the delivery costs of each of the material, instead given in the
last column as it varies with distance and weight.

of long term influence of biochar in its strength development and de-

tailed durability studies can be considered where biochar might have
the potential to reduce shrinkage and carbonation resistance. Further
research will bring closer to the sustainable concrete solutions where
waste derived materials can be viewed as an optimal solution for the re-
duction of CO2 in concrete production and a carbon storage solution.

Acknowledgement

The doctoral scholarship awarded to the first author by The Univer-

sity of Auckland is gratefully acknowledged and the authors wish to
thank Stuart Morrow, the mass spectrometry centre, Auckland Science
Analytical Services, The University of Auckland, New Zealand, for assis-
tance in ICP-MS analysis. Authors also would like to thank Dr. Lukas Van
Zwieten, Department of Primary industries for providing rice husk and
pulp and papermill sludge biochar and Sumaraj, Department of civil
and environmental engineering, The University of Auckland, for help
in the elemental analysis of biochars.

Appendix A. Supplementary data

Supplementary data to this article can be found online at https://doi.

org/10.1016/j.scitotenv.2017.10.319.

Fig. 10. SEM images of concrete with rice husk biochar (a) biochar incorporation into
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