Construction and Building Materials 114 (2016) 625–637

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Construction and Building Materials

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

The potential use of chitosan as a biopolymer additive for enhanced

mechanical properties and water resistance of earthen construction
Rafael Aguilar a,⇑, Javier Nakamatsu b, Eduardo Ramírez a, Mariela Elgegren b, Jorge Ayarza b, Suyeon Kim c,
Miguel A. Pando d, Luis Ortega-San-Martin b
a
Department of Engineering, Civil Engineering Division, Pontificia Universidad Católica del Perú PUCP, Av. Universitaria 1801, San Miguel, Lima 32, Peru
b
Department of Science, Chemistry Division, Pontificia Universidad Católica del Perú PUCP, Av. Universitaria 1801, San Miguel, Lima 32, Peru
c
Department of Engineering, Pontificia Universidad Católica del Perú PUCP, Av. Universitaria 1801, San Miguel, Lima 32, Peru
d
Department of Civil and Environmental Engineering, University of North Carolina at Charlotte, 9201 University City Blvd., Charlotte, NC 28223-0001, USA

h i g h l i g h t s

Chitosan successfully improved the engineering behavior of earthen construction.

Coating with 0.5% chitosan solution protected earthen materials from water erosion.

Earthen material with 1%–3% chitosan admixture had high water erosion resistance.

Samples with 3% chitosan admixture showed improved mechanical properties.

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

Article history: The study investigates the feasibility of using chitosan biopolymer as an admixture, or as an external
Received 24 January 2016 coating, for earthen constructions to improve their resistance in two components: water induced degra-
Received in revised form 30 March 2016 dation and key mechanical properties. The resistance to water induced degradation was evaluated in
Accepted 30 March 2016
terms of contact angle and drip erosion tests, while the influence on mechanical properties was measured
through compressive, tensile and three-point bending tests. The results indicate that the use of low con-
centrations of chitosan can improve significantly the performance in the two components and therefore
Keywords:
was found to be a promising treatment for new or existing construction.
Material modification
Earthen construction
Ó 2016 Elsevier Ltd. All rights reserved.
Chitosan biopolymer
Water induced degradation
Mechanical strength

1. Introduction economic considerations, include low ecological impact due to

reduced greenhouse gas emissions during construction [2] as well
Earth has been used as a construction material since ancient as facilities with good thermal and acoustic behavior [5].
times to build houses, archaeological, and historical monuments Different techniques have been reported for earthen construc-
over the world. It is estimated that approximately 30% of the world tion primarily depending on the region of the world where it is
population live in unreinforced earthen houses located principally used. According to [1], earthen construction techniques can be
in developing countries primarily due to economic considerations divided into three main groups: structure, monolithic and brick-
[1]. In recent years the use of earthen construction has seen an work. Rammed earth walls (monolithic) and adobe masonry
increase in popularity as an eco-friendly sustainable architectural (brickwork) are the most widespread methods. As an example, in
approach. Its ability to be recycled indefinitely and aesthetic ben- Peru, 34% of the houses are built with these two techniques [6].
efits have resulted in increased popularity of earth architecture Unfortunately earthen buildings can have some disadvantages.
with many museums, embassies, and other building types made From a mechanical perspective, they are usually heavy, brittle,
of earth [2–4]. Additional benefits of building with earth, beyond and present low tensile resistance which makes them especially
vulnerable to seismic events [7]. For example, as shown in Fig. 1a,
after the 2003 earthquake of Bam, Iran, historical earthen buildings
⇑ Corresponding author. were severely damaged [8]. Another negative aspect to consider
E-mail address: raguilar@pucp.pe (R. Aguilar).

http://dx.doi.org/10.1016/j.conbuildmat.2016.03.218
0950-0618/Ó 2016 Elsevier Ltd. All rights reserved.
626 R. Aguilar et al. / Construction and Building Materials 114 (2016) 625–637

when dealing with this material is its hydrophilic and porous nat- and mineral composites have been successfully used for the pro-
ure making buildings vulnerable to erosion and severe degradation tection of earthen construction materials against rainfall erosion.
upon water exposure [9]. As shown in Fig. 1b, rising damp and rain The focus of this paper is on the use of the biopolymer chitosan
penetration can severely affect the exposed structural elements to enhance mechanical and water durability properties of earthen
reducing their strength and affecting the structural stability [10]. materials. A review of the literature on modification of earthen
Finally, it has also been reported that earthen buildings can be sus- construction using biopolymers revealed some preliminary appli-
ceptible to extensive cracking, due to drying and desiccation, cations using a few types of biopolymers but not chitosan. For
which not only affects the structural performance of the earthen example [18] used alginate for modifying the mechanical behavior
building but also provides an attractive habitat for insects and fun- of fiber treated adobe blocks and the results showed that its addi-
gus that can pose a serious health risk to the inhabitants since they tion can improve the flexural and compressive strength of the final
may transmit diseases. For example, millions of human deaths has product. Another biopolymer reported in the literature for the
been reported in Central and South America due to the Chagas dis- improvement of water resistance of earthen construction materials
ease transmitted by Triatomine bugs that are often found inside is the cactus mucilage, which according to several studies [19–21]
cracks in adobe walls as shown in Fig. 1c [11]. has positive effects on the water protection and conservation of
The improvement of the mechanical properties of earthen con- earthen constructions.
structions has been the subject of study by many research groups The research presented in this paper investigated the use of chi-
using various approaches. Several studies have focused their atten- tosan for the modification and improvement of earthen construc-
tion on improving the mechanical properties of earthen construc- tion materials such as rammed earth and adobe blocks. Chitosan
tions using additives applied during material fabrication. For is a biopolymer composed of 2-amino-2-deoxy-D-glucose and 2-
example, notable increases in the compressive strength of adobe acetamido-2-deoxy-D-glucose units linked through b-(1 ? 4)
blocks (more than 80%) were reported when two types of poly- bonds and it is derived from alkaline deacetylation of chitin, one
meric agents (cationic amine and emulsified asphalt) were added of the most abundant natural polysaccharides. The chemical struc-
as solutions during the mixture process [12]. This same study ture of chitosan is shown in Fig. 2. Due to its high percentage of
reported a reduction of the levels of water absorption of the treated nitrogen (around 6.89%), chitosan is of commercial interest com-
adobe blocks from 80% (percentage by weight) to 10%. Other pared to synthetically substituted cellulose (1.25%) [22]. Another
authors recommended the use of emulsified asphalt for the stabi- attractive feature of chitosan is its low cost as it usually is obtained
lization of soil in earthen construction with high silt content from discarded crab and shrimp wastes processed from canning
[13]. Another popular approach to improve mechanical properties industries or from crustacean shells obtained from the food indus-
of earthen constructions has involved the inclusion of synthetic or try [22]. Chitosan has attracted attention as a material and poten-
natural fibers. Quagliarini et al. [14] successfully showed how the tial additive due to its proven advantageous properties such as
inclusion of fibers may contribute to control the plastic behavior biodegradability, antibacterial activity, non-toxicity and high
of earthen blocks and to prevent cracking due to shrinkage in the charge density [23]. Due to its polymeric and chemical nature it
drying process. Aymerich et al. [15] also reported the benefit of has been used for surface modification of materials such as textiles,
increased capacity for energy absorption when wool fibers were films and others, transferring its functionalities and properties
added to earthen materials. The use of polymeric fibers for the fab- [24–26].
rication of compressed earth blocks also evidenced positive influ- For this work different solutions of chitosan biopolymer were
ence in the increment of the compressive and flexural strength used either as an additive introduced during the fabrication pro-
up to 22.5% and 22%, respectively [16]. The same study reported cess of new earthen specimens or as an external coating applied
that the addition of these fibers also allowed reaching considerable to existing earthen materials. The effect of chitosan biopolymer
levels of deformation compared to unreinforced specimens. treatment on earthen materials focused on evaluating: i) suscepti-
The literature review also revealed several studies that have bility to water induced degradation, and ii) mechanical properties.
explored solutions to improve the durability of earthen materials The susceptibility to water induced degradation was evaluated in
to water degradation. Most of the studies report the use of stabiliz- terms of sessile drop contact angle measurements and drip erosion
ers for enhancing the durability of these types of materials. As tests. The influence of chitosan biopolymer treatments on the
summarized by [17], different types of additives such as lime, poz- mechanical properties of earthen materials was measured through
zolan, cement, biopolymers (e.g., tuna cactus mucilage, nopal and an experimental program designed to assess the compressive, ten-
agave cactuses; linseed and cooking oils; seaweeds fibers, etc.), sile and flexural behavior of the treated and untreated earthen

Fig. 1. Typical problems of earthen houses: (a) earthen structure after the 2003 Bam earthquake [8]; (b) adobe wall eroded by water (http://emeraldcut.blogspot.pe/2015/10/
nevada-fort-churchill-state-park.html); and (c) Triatomine bug living in an earthen wall and carrying the parasite that causes Chagas disease (http://archivo.elsalvador.com/).
 R. Aguilar et al. / Construction and Building Materials 114 (2016) 625–637 627

Jimenez Delgado and Guerrero [30] after reviewing a wide range of adobe bricks
around the world suggested that most base soils used for the adobe fabrication fell
within the range of the grain size distributions shown as a shaded grey area in
Fig. 3. It can be seen that the base soil used in this study is slightly outside the range
of gradation curves reported by Jimenez Delgado and Guerrero [30], however this is
not a concern as this range is not a requirement but rather the range that corre-
sponds to the database of adobe projects they compiled in that study.
The Atterberg plastic and liquid limits of the base soil were found to be 17% and
33%, respectively. These limits correspond to a low plastic clay. Based on the grada-
tion curve and Atterberg limits the base soil was therefore classified as low plastic
Fig. 2. Chitosan chemical structure. clay (CL) as per the Unified Soil Classification System [28].

2.2.2. X-ray fluorescence tests on the base soil

material samples. The following sections describe the experimen- The X-ray fluorescence testing (XRF) of the base soil was carried out using a por-
tal study and results. table X-ray fluorescence spectrometer model Bruker Tracer III-SD which was
equipped with a rhodium tube under vacuum mode at 40 kV and 10.3 mA to delimit
the main elements. XRF tests were performed on a small soil sample that was first
2. Materials manually ground with an agate mortar and then pelletized. Pellets were produced
using a 13 mm die under a uniaxial load of 10 tons sustained for 5 min to obtain
2.1. Chitosan biopolymer dense samples. The resulting XRF spectrum is shown in Fig. 4(a). The XRF results
provide evidence of the presence of Al, Si, P, S, K, Ca, Ti, V, Mn, Fe, Ni, Cu, Zn, Rb,
The chitosan biopolymer used in this study was purchased from Sigma-Aldrich Sr, Pb. The most abundant elements are Fe, Ca, Sr, Ti and Si. Small quantities of
Corporation. Chitosan has low solubility and is a high viscosity substance. The Ni, Mn, P and Cu were detected below the levels where exact amount can be quan-
molecular weight of the chitosan, measured by means of a capillary viscometry, tified and thus were labeled as present as trace elements. Due to the equipment
was 1370 kDa. The chitosan used in this study had a degree of deacetylation of parameters, the presence of the following elements, typically present in most soils,
65%, therefore still has remaining 35% of non-free amino groups in its structure pro- cannot be discarded (light elements): H, C, N, O, F, Na and Mg.
voking low levels of solubility and high levels of viscosity when dissolved in a 1% of
acetic acid solution [27]. For this experimental study, several concentrations of an
aqueous acidic chitosan solution were used for the treatment of the earthen mate- 2.2.3. X-ray powder diffraction tests on the base soil
rials. The different concentrations of the chitosan admixtures were prepared in all The X-ray powder diffraction test (XRPD) was performed on the ground, dry
cases by dissolving a predetermined mass of chitosan in a 1% (volume to volume) base soil using a Bruker D8 XRD device. XRPD data was collected for phase angles
acetic acid solution. The concentrations of chitosan used in this study ranged from (2h) ranging between 5° and 80°, with a 0.02° step and an integration time of 4 s.
0.5% to 3% mass to volume, which correspond to a range of 5–30 mg of chitosan per The identification of the different crystalline phases was carried out using the X’Pert
liter of the 1% acetic acid solution. The two main solutions investigated are termed High Score 2.0 software from Philips Analytical with the PDF-2 database. Only the
Solutions A and B which corresponded to concentrations of chitosan of 0.5% and 3% elements previously detected using XRF and all light elements not detected by the
of chitosan in the 1% acetic acid solution, respectively. instrument (H to Mg) were used for the identification. The XRPD pattern together
with the identification of the main peaks are shown in Fig. 4(b).
Table 1 summarizes the main minerals detected with the XRPD test and also
2.2. Base soil used for fabrication of earthen materials
compares the results (wt%) with values reported in the literature similar adobe
materials from other regions of the world. Mineral quantification was carried out
Soils used for earthen construction can have a high variability in terms of par-
by the Rietveld method using GSAS software [31] and the EXPGUI interface [32].
ticle size gradation, chemical composition, mineralogy, and others [30]. To a great
The base soil seems to be a granitoid in which the main phases are quartz, an
extent, the soil characteristics and properties will depend on the available local soil
albite/anorthite mixture (feldspar) and muscovite (mica). It also contains a small
sources of the area where the earthen materials are fabricated. For the present
portion of an amphibole and chlorite minerals (clinochlore and vermiculite, a
study the base soil was selected to represent a typical Peruvian coastal region soil
degraded chlorite). Minor phases such as calcite and orthoclase were also identified.
that is commonly used for fabrication of adobe bricks for building earthen houses in
Due to the complex mixture present and the preferred orientations found in some
the rural areas near Lima. The following subsections describe in more detail the
minerals, mass percentages should be considered as approximate. Muscovite, for
base soil used in this study.
example, might be overestimated due to its strong (0 0 1) preferred orientation.

2.2.1. Gradation and index properties of the base soil

The base soil was a dark brown, low plastic silty clay with sand and some traces 3. Experimental program
of fine gravel. The grain size distribution curve of the base soil was obtained by
means of sieve analysis coupled with hydrometer testing carried out in general
The experimental program involved investigating the influence
accordance with ASTM D2487 [28]. The gradation curve for the base soil is shown
in Fig. 3. As shown in this gradation curve the base soil has 1% by weight of gravel that the use of a chitosan biopolymer had on earthen materials in
sizes, 20% of sand content, 43% of silt sizes, and 36% of clay content based on soil the following two aspects: i) susceptibility to water induced degra-
particle size ranges recommended in ASTM Standard D422 [29]. Typically adobe dation, and ii) mechanical properties. The chitosan biopolymer
construction uses base soils with different proportions of sand, silt and clay that
solutions were applied in two different manners. One as an admix-
can vary widely based on local experience and available soil sources. For example
ture that was added during the fabrication of the earthen material
samples and the second mode of application was as an external
coating that was applied to the outside surface of an existing
earthen material sample. The following subsections describe the
test procedures used for the assessment of these two components.
Results and discussions are presented in Section 4.

3.1. Evaluation of susceptibility to water induced degradation

As mentioned earlier, earthen-based construction materials are

hydrophilic and porous, thus present low durability when exposed
to water. For example [37] reported significant erosion of adobe
walls when exposed to rainfall. Permeability issues need also to
be addressed because water penetration and moisture entrapped
inside may adversely affect the aesthetic, biological, and structural
performance of earthen buildings, e.g., efflorescence, mildew, and
freeze/thaw damage [38]. The susceptibility to water induced
Fig. 3. Grain size distribution of base soil. degradation was quantified in this study using two indicators,
628 R. Aguilar et al. / Construction and Building Materials 114 (2016) 625–637

140 Ca

120
Si
Al S K
100 P
Ti
V Mn

80

60 1 5 - keV -
Fe
40 Ca
Si
Al S K Ti
V Mn Ni Zn Rb Sr
20 P

0
5 10 15
- keV -

(a)

(b)
Fig. 4. Chemical and mineralogical analyses of base soil: (a) X-ray Fluorescence spectrum and (b) X-ray powder diffraction pattern.

Table 1
Mineral composition of some soils used for adobe building blocks compared to base soil analyzed in this study.

Main mineral Mineral amount (wt %)

Reference
[33] [34] [35] [36]a This study
Phyllosilicates Muscovite-illite (K1xNax)(Al1xyMgxFey)2(Si3Al) 15(2) – 14 – 32(3)
O10(OH)2
Kaolinite (Al2Si2O5(OH)4) – 30 45 X –
Clinochlore/vermiculite ((Mg,Fe,Al)6(Si, – – – – 4(2)/2(1)
Al)4O10(OH)8)/(Mg,Fe+2,Fe+3)3[(Si,Al)4O10](OH)24H2O
Fe-rich magnesiohornblende (Ca2(Mg,Fe+2)4Al(Si7Al) – – – – 1.0(1)
O22(OH)2)
Talc (CaSO42H2O) 6(1) – – – –
Tectosilicates Quartz (SiO2) 13(3) 65 23 X 32(2)
c
Feldspars Potassium (Microcline) 6(1) (2) – – –
(Sanidine) 24(3) – – –
(Orthoclase) – – – – 5(1)
Plagioclase (Albite) – – – – 21(4)
(anorthite) – – – –
Non silicate minerals Brushite (CaHPO42H2O) 11(1) – – – –
Indigirite (Mg2Al2(CO3)4(OH)215H2O) 4(1) – – – –
Calcite (CaCO3) 6.3(6) – 4 – 3(1)
Goethite (FeO(OH)) – 2 7 X –
Gibbsite (Al(OH)3) – – – X –
b
Magnetite (Fe3O4) – – – –

Notes:
[ ] Numbers in brackets indicate references.
a
Amounts were not quantified in the original paper (X denotes presence of mineral).
b
Soil sample slightly magnetic so magnetite presumed to exist but not detected in the XRPD test.
c
Data given as ‘‘potassium feldspar”, without specifying the exact mineral.

namely the water contact angle and performance of samples in contact angle in this test method is defined as the angle formed
drip erosion tests. by the liquid from the sessile drop and the surface of the material
(see Fig. 5a). Materials with contact angles less than 90° are consid-
3.1.1. Contact angle and drip erosion tests ered to have high wettability, while contact angles above 90° cor-
The wettability of porous materials is often assessed using respond to materials with low wettability [39]. For this study, the
contact angles measured using the sessile drop method [39]. The contact angle was measured from digital photographs taken with
 R. Aguilar et al. / Construction and Building Materials 114 (2016) 625–637 629

Fig. 5. Assessment of water induced degradation: (a) contact angle test; and (b) drip erosion test (the needle position is only referential for illustration purposes; the height in
all tests was of 1 m).

Surface coating

(a) (b)
Fig. 6. Preparation of specimens for water induced degradation tests: (a) hand mixing process; and (b) cylindrical specimen with surface coating of chitosan biopolymer.

appropriate light contrast immediately after a 10 lL drop of dis- solution). The higher amount of liquid in the earthen sample mix-
tilled water was deposited on top of the earth surface using a tures that used chitosan solution was found to be necessary to
micro-syringe. achieve a similar consistency and workability to the control sam-
The second test used to assess the susceptibility to water ples that only used water. This was attributed to the high levels
induced degradation was the drip erosion test. These tests were of viscosity of the aqueous acidic chitosan solutions. The earthen
carried out in general accordance with recommendations from sample preparation involved thorough hand mixing of the base soil
the AENOR Spanish standard [40] and the Australian standard and water, or the base soil and aqueous chitosan solution, using a
described in [41]. This test entails placing a sample on a surface metal trowel for a period of about five minutes until a homoge-
inclined at an angle of 27° with respect to the horizontal. The spec- neous mixture was achieved (Fig. 6a). The earthen mixture was
imen is then subjected to water drops released from a point exactly then placed inside a cylindrical mold and air cured for a period
1 m above the center of the test specimen. The drops are released of about 7 days in a controlled environment at a 60% relative
at a rate of 50 mL per minute. A photo of the test is shown in Fig. 5 humidity and a temperature of 20 °C. The cylindrical earthen spec-
(b). In this test, the time elapsed was measured up to a maximum imens used for the erosion tests had a diameter of 55 mm and a
exposure time of 10 min or until the test specimen reached a state height of 10 mm (Fig. 6b).
of significant erosional damage, whichever occurred earlier. The samples with chitosan biopolymer solutions involved pri-
marily two concentrations: i) Solution A prepared at a concentra-
3.1.2. Sample preparation and water induced degradation assessment tion 0.5% mass to volume ratio of chitosan to 1% acetic acid
test program solution; and ii) Solution B corresponding to a concentration of
The base soil, described earlier, was first sieved using the sieve 3% mass to volume ratio of chitosan to 1% acetic acid solution.
No. 4 (opening = 4.75 mm) to remove any gravel size particles. The However, after a first round of tests, two additional solutions with
earthen material samples were then prepared manually by mixing concentrations of 1% (Solution C⁄) and 2% (Solution D⁄) were added
the base soil with either water or with chitosan biopolymer solu- to the test program to determine the minimum concentration of
tions. The samples prepared with water used a base soil to water biopolymer to provide an effective protection to the specimens.
ratio of about 4:1 by weight (i.e., 20% of the total sample weight The test matrix of the water induced degradation component of
was water). This ratio is based on local practice to ensure adequate this study is shown in Table 2.
workability. The earthen samples prepared using chitosan solu- The contact angle and erosion tests were carried out on earthen
tions as the liquid during mixture preparation used a base soil to samples treated with chitosan in two different ways. The first one
chitosan solution ratio by weight of about 3:1 (i.e., about 25% of consisted on applying the biopolymer as a surface coating that was
the total weight of the sample corresponded to the chitosan applied by briefly dipping one face of the untreated earthen
630 R. Aguilar et al. / Construction and Building Materials 114 (2016) 625–637

Table 2
Test matrix for the water induced degradation experimental component.

Test type Sample type Description N° of specimens

Contact angle Control sample Mixture proportion 4:1 (earth/water) 1
Surface coating Solution concentration: Solution A, Solution B, Solution C⁄, Solution D⁄ 3 for each solution
Admixture Solution concentration: Solution A Mixture proportion 3:1 (earth/solution) 1
Admixture Solution concentration: Solution B, Solution C⁄ and Solution 3 for each solution
D⁄ Mixture proportion 3:1 (earth/solution)
Drip erosion Control sample Mixture proportion 4:1 (earth/water) 1
Surface coating Solution concentration: Solution A, Solution B, Solution C⁄, Solution D⁄ 3 for each solution
Admixture Solution concentration: Solution A, Solution B, Solution C⁄ and Solution 3 for each solution
D⁄ Mixture proportion 3:1 (earth/solution)

Notes: Mixture proportions correspond to dry base soil to liquid ratios by weight.
Solution A: 0.5% mass to volume ratio of chitosan to 1% acetic acid solution.
Solution B: 3% mass to volume ratio of chitosan to 1% acetic acid solution.
Solution C⁄: 1% mass to volume ratio of chitosan to 1% acetic acid solution.
Solution D⁄: 2% mass to volume ratio of chitosan to 1% acetic acid solution.

specimen into the corresponding chitosan solution to completely Displacements for all mechanical tests were recorded using a cali-
wet its surface. The increase of sample weight after this procedure brated Linear Variable Differential Transducer (LVDT).
was minimum and estimated to be between 0.5% and 1%. The other
technique consisted in preparing the earthen material by mixing 3.2.2. Sample preparation and mechanical behavior assessment test
the dry base soil and the corresponding chitosan solution. In both program
the contact angle and drip erosion tests, untreated control samples Samples for mechanical testing were prepared using a proce-
were included to properly assess the influence of the chitosan dure similar to the one used for fabricating the specimens for the
biopolymer treatment. erosion tests. The dry base soil was first sieved through a sieve
No. 4 (opening of 4.75 mm) to remove any fine gravel sizes. All
samples were manually mixed with a metal trowel for about five
3.2. Evaluation of influence on mechanical behavior minutes, using either water or chitosan solution, until a homoge-
neous mixture was obtained and then placed in one of the different
3.2.1. Mechanical behavior testing formworks shown in Fig. 8. Samples prepared with water repre-
The influence of the chitosan additives on the mechanical prop- sented the control reference for the samples prepared with chi-
erties of earthen specimens was evaluated through compression, tosan as the admixture. The dry base soil to liquid proportions
split, and three point bending tests. Schematic drawings of these were the same as described before, i.e., about 4:1 by weight for
three mechanical tests are shown in Fig. 7. All mechanical tests the control samples prepared with water and about 3:1 by weight
were carried out as displacement controlled with a constant for the samples prepared using the chitosan solution as the liquid
displacement rate of 1.27 mm per minute. For the uniaxial com- during mixture preparation. For compression and split tests, cylin-
pression tests, a fine sand layer was placed on both ends of the drical specimens of 34 mm diameter and 71 mm of height were
cylindrical specimens to help reduce friction end effects and to fabricated (Fig. 8a). The three-point bending tests involved pris-
minimize stress concentrations as per suggestions made by [42]. matic beam samples with a cross section of 42 mm by 44 mm

Load Ring

LVDT Earthen
specimen

(b)
Earth specimen

Additional piece for

three point bending

Compression
load frame
Simple supports

(a) (c)
Fig. 7. Setup details for the mechanical characterization tests: (a) compression test; (b) split test; and (c) three point bending test.
 R. Aguilar et al. / Construction and Building Materials 114 (2016) 625–637 631

Fig. 8. Preparation of earthen specimens: (a) cylindrical specimens and formwork; (b) placing mixture in the formwork; and (c) prismatic specimens.

Table 3
Test matrix for the mechanical behavior assessment.

Sample type Description Performed tests N° of specimens

Control sample Mixture proportion 4:1 (earth/water) Compression 8
Split 6
Bending 8
Admixture Solution concentration: Solution B Mixture proportion 3:1 (earth/solution) Compression 10
Split 6
Bending 4

Notes: Mixture proportion measured by weight.

Solution B: 3% chitosan dissolved in 1% acetic acid.
Only Solution B added as admixture was evaluated based on contact angle and drip erosion tests results presented in Section 4.

and a length of 125 mm (Fig. 8b and 8c). For mechanical testing all
specimens were air cured for a period of about 14 days in environ-
mental conditions. Given that mechanical properties of earthen
materials are heavily influenced by sample moisture content [10]
the actual curing duration for each sample was such that a residual
gravimetric moisture content of approximately 4% was obtained.
The actual moisture content of all specimens was measured imme-
diately after testing by drying tested samples in an oven for 24 h at
110 °C and as shown later the sample moisture contents were very
uniform and close to the target value of 4%. Additionally the den-
sity of all test specimens was documented by carefully recording
the mass and dimensions of each sample at the time of testing.
The mechanical evaluation test program involved comparison
of test results obtained from untreated (control) samples with cor- Fig. 9. Contact angle tests results in coated specimens.
responding results obtained from specimens prepared using the
base soil mixed with Solution B of the chitosan biopolymer which
corresponded to a concentration of 3% mass to volume ratio of chi- particles and the more polar functional groups of the thin polymer
tosan to 1% acetic acid solution. The test matrix of the mechanical layer, this leaves the less polar groups on the surface. In other
testing program is shown in Table 3. words, the lower contact angles measured when a higher concen-
tration is used, is due to the thicker film on the surface of the spec-
4. Results and discussion imen, which leaves the superficial polymer chains less attached
and with more freedom to move and attract water with their polar
4.1. Assessment of water induced degradation groups. Additionally a thinner polymer film (Solution A) will pro-
duce a rougher surface which yield increased contact angles in
4.1.1. Contact angle measurement results similar fashion to the lotus effect. However, both of these hypothe-
Contact angle measurement results on surface treated samples, ses should be corroborated with further studies. Nevertheless,
employing Chitosan Solutions A and B, are shown in Fig. 9. Speci- these results demonstrate that the surface treatment using even
mens coated with Solution A yielded contact angles of 94° ± 9° very low chitosan concentration can have a positive impact on
which corresponds to a hydrophobic or water repellent condition. increasing the contact angle to values close to 90°. These results
For Solution B, the contact angle results were 85° ± 5°. Both solu- are in agreement with other references that show that chitosan
tions resulted in surface treatments which are moderately water films and the modified materials (e.g., fabrics) with chitosan gener-
repellent based on contact angle values near 90°. However it is ally shows high contact angles and thus are highly hydrophobic
important to point out that tests using the higher concentration depending on the degree of deacetylation and crystallinity of chi-
solution (i.e., Solution B) resulted in slightly lower contact angles. tosan [43–46]. Tests on untreated control earthen samples showed
This reduction of the contact angle could be attributed to the dif- that measurement of the contact angle was not possible given the
ferences of film thickness for both solutions. The coating film thick- highly hydrophilic condition. In other words, for most control sam-
ness was greater for the higher concentration solution. Since the ples the water drop was immediately absorbed by the sample
surface coating involves a strong attachment between the soil impeding measurement of the contact angle. This is as expected
632 R. Aguilar et al. / Construction and Building Materials 114 (2016) 625–637

4.1.2. Drip erosion test results

The results of the drip erosion tests on untreated control
earthen samples were as expected given the well documented poor
water resistance of untreated earthen materials. Fig. 11 shows
photos of an untreated sample after 1, 3 and 5 min of exposure
to water dripping. The photos show substantial erosion even after
only one minute of water dripping. After five minutes of exposure
the specimen was almost completely disintegrated.
The first set of drip erosion tests was carried out on earthen
material samples treated with chitosan biopolymer applied exter-
nally as a coating. Fig. 12 shows photos of drip test results for
coated specimens with Solutions A and B. Both of these surface
treatment levels passed the 10 min time limit of this test suggest-
Fig. 10. Contact angle tests results for earthen materials prepared with chitosan ing a good resistance to water induced erosion. These results sug-
biopolymer as an admixture.
gest that even a very small concentrations of chitosan coating of
0.5% (Solution A) would be enough to protect the earthen samples
as untreated earthen materials are porous and with a high water by making its surface more hydrophobic and more resistant to
absorption rate [12]. water induced erosion. The effectiveness of chitosan for providing
The above results corresponded to tests on earthen specimens water protection can be explained because this biopolymer forms a
with surface coating of chitosan. The second set of contact angle hydrophobic barrier keeping soil particles bound and preventing
tests involved testing earthen material samples where the prepara- them from breaking apart which is due to the strong dipole-
tion involved mixing the base soil directly with the chitosan dipole hydrogen bonding and ionic intra and inter molecular inter-
biopolymer. Fig. 10 summarizes the results obtained for this type actions of the polymer chains.
of sample treatment. As shown in this figure, no contact angles The second set of drip erosion tests was carried out on earthen
were measurable for the untreated control samples and for the samples prepared using the chitosan solution as an admixture. The
samples prepared with Solution A (0.5% solution) of the chitosan drip erosion test results for specimens prepared with chitosan
biopolymer. This was due to the fast infiltration rate of the water biopolymer in the earthen mixture are shown in Fig. 13. The
sessile drop. Contact angle measurements were only possible for earthen samples prepared with the lowest concentration level of
earthen samples prepared with Solution B of the chitosan biopoly- chitosan (Solution A at 0.5%) showed significant erosion after
mer (3% solution) which has the higher chitosan concentration. 5 min of water dripping. It should be noted, however, that the ero-
Fig. 10 also includes contact angle results for samples prepared sion was different from what was observed in the control sample,
with two intermediate concentrations of chitosan of 1% and 2% as in this case the erosion observed to be localized and affected
which are labeled in this figure as Solutions C⁄ and D⁄, respectively. only the immediate area around the contact point where the water
Of the four chitosan concentration levels evaluated, only the sam- drops impacted the sample (see left photo in Fig. 13). In contrast,
ples prepared with the highest concentration, i.e., prepared with the drip erosion tests results for the specimen prepared with the
Solution B at 3% chitosan, permitted measurement of contact highest concentration level of chitosan (Solution B at 3%) resisted
angles. The contact angles recorded for samples prepared with the full test duration of 10 min thus denoting a good water erosion
Solution B ranged within 65° ± 10° which show some water resis- resistance. An additional test with an intermediate solution of 1%
tance but still correspond to a hydrophilic condition. These contact of chitosan (Solution C⁄) was carried out and the results showed
angle measurements suggest that earthen material prepared with a that the 1% concentration level was also able to resist the full
soil similar to the base soil used in this study would require mix- 10 min of water dripping. Therefore for earthen materials prepared
ture with a chitosan solution concentration of at least 3% in order by mixing the base soil and chitosan biopolymer solutions of at
to start recording contact angle values approaching 90° which is least 1% concentration (Solution C⁄ and Solution B) is required to
the minimum required for a hydrophobic behavior. Based on these reach the 10 min exposure time requirement of the drip erosion
contact angle results the test matrix for the mechanical tests, pre- test. However, based on the contact angle measurements on
sented in Subsection 3.2.2, involved only earthen material speci- earthen samples prepared with chitosan biopolymer as an admix-
mens prepared with Solution B of the chitosan biopolymer (3% ture, a 3% concentration (Solution B) was required in order to mea-
solution). sure contact angles. Based on the combined observations from the

1 minute 3 minutes 5 minutes

Fig. 11. Drip erosion test results for an untreated earthen specimen at different times of water drop exposure.
 R. Aguilar et al. / Construction and Building Materials 114 (2016) 625–637 633

Solution A - 0.5% Solution B - 3%

(results after 10 minutes) (results after 10 minutes)

Fig. 12. Drip erosion test results of earthen specimens coated with chitosan solutions.

Solution A - 0.5% Solution C* - 1% Solution B - 3%

(results after 5 minutes) (results after 10 minutes) (results after 10 minutes)

Fig. 13. Drip erosion test results for earthen materials prepared with chitosan biopolymer as an admixture.

contact angle measurements and the drip erosion tests it was the untreated control condition, was 65% and 80% for the split,
decided that only earthen materials prepared with Solution B of and three-point bending tests, respectively. The stress-strain
the chitosan biopolymer as an admixture was adequate to yield curves (for uniaxial compression tests) presented in Fig. 14 also
reasonable improvements in water resistance. Therefore the show increased values of the initial slope of these curves for the
mechanical test program only involved tests on treated samples treated samples compared to the untreated samples. This would
with Solution B. suggest that the chitosan treatment results in some stiffening
effects of the treated earthen material. However, the most impor-
4.2. Assessment of influence on mechanical behavior tant improvement of the mechanical properties is in term of the
strength (or peak values) of the different tests considered. This is
The results of all three types of mechanical tests, for treated and consistent with [47] who reported that higher values of stiffness
untreated earthen specimens, are presented in Fig. 14. This figure are correlated to higher strength in adobe bricks.
also shows photos of the typical failure modes observed in each The increment of strength, and to a lesser extent on stiffness, is
of the tests. As mentioned earlier, mechanical properties were difficult to explain. The addition of the chitosan biopolymer admix-
measured only for the admixture type treatment (no coating treat- ture would result in a strong attachment between the polymer
ment) and for samples treated with Solution B (3% concentration) chains and the clay particles of the base soil, thus leading to an
which was found to be the concentration level that provided both increment of the compressive strength. The addition of the poly-
hydrophobicity and resistance to water erosion in the water mer may also change the net air void space in the sample in a sim-
induced tests presented in the previous section. ilar fashion as observed in bitumen treated soils [1]. The improved
Fig. 14 shows that treated earthen samples had substantial strength may also be related to the modification of the drying or
strength gains for all three mechanical test types compared to curing process of the soil caused by the addition of the biopolymer.
the untreated control samples. Uniaxial compression test results Earthen materials are sun or air-dried during curing, and not baked
showed strength gains of the treated samples of up to 170% with as in the case of conventional bricks, thus during curing they are
respect to control samples. On average the uniaxial compression susceptible to shrinkage and contraction which will often cause
strength increase was 85%. Similarly, the split and three-point- hairline internal and external micro-fissures [3,14]. Thus the sec-
bending tests, showed a maximum strength increase of the treated ond explanation for the observed improved mechanical properties
versus untreated conditions of 250% and 175%, respectively. The of the chitosan-treated earthen material samples is the improved
average levels of strength increase, of the treated with respect to volume stability which resulted in reduced shrinkage and
634 R. Aguilar et al. / Construction and Building Materials 114 (2016) 625–637

Non-treated samples Treated samples Faillure modes

Compression 5 5

4 4

Stress (MPa)
Stress (MPa) 3 3

2 2

1 1

0 0
0 0.01 0.02 0.03 0.04 0.05 0 0.01 0.02 0.03 0.04 0.05
Strain (mm/mm) Strain (mm/mm)

1.2 1.2

1.0 1.0
Split

0.8
Stress (MPa)

0.8
Stress (Mpa)
0.6 0.6

0.4 0.4
0.2 0.2
0.0 0.0
0 0.2 0.4 0.6 0.8 0 0.2 0.4 0.6 0.8
Displacement (mm) Displacement (mm)

2.5 2.5
Three point bending

2.0 2.0
Flexural stress (MPa)

Flexural stress (MPa)

1.5 1.5

1.0 1.0

0.5 0.5

0.0 0.0
0 0.3 0.6 0.9 1.2 1.5 0 0.30.60.91.21.5
Displacement (mm) Displacement (mm)

Fig. 14. Summary of the results of the mechanical tests in treated and non-treated specimens.

Fig. 15. Strength results from mechanical tests.

contraction during the air-dried curing process. This improved vol- careful measurement of dimensions. The periodic sample examina-
ume stability resulted in treated specimens with less micro- tions during the curing process revealed higher levels of contrac-
fissures and thus higher mechanical properties. In the present tion for the untreated control samples compared to the treated
study, all samples were subjected to periodic examination during specimens. The results of this analysis showed that the untreated
curing which involved tracking the residual moisture content and specimens presented an average volumetric reduction of 10.5%
 R. Aguilar et al. / Construction and Building Materials 114 (2016) 625–637 635

from fabrication to testing time while the chitosan-treated speci- content was close to 4%. This resulted in sample curing periods
mens had only an average volume reduction of 8.7%. This observed ranging from 7 and 14 days, with an average curing period of
decreased volume contraction for the treated samples likely 8 days for the control samples and 10 days for the treated samples.
resulted in a reduction of micro-cracking in the cured samples, as This strategy was implemented because it is well known that sam-
reported by [14], and thus offers an additional explanation for ple moisture content can have an important influence on the
the higher values of strength and stiffness measured in the treated mechanical properties of earthen materials. For example, Bui
samples. However these two factors need to be further investi- et al. [10] reported large reductions of compressive strength, rang-
gated using techniques such as detailed SEM microscopy, and care- ing between 5 and 20%, for samples that had a water content incre-
ful sample volume change measurements during curing under ment as small as 2%. The measured moisture contents for all the
controlled conditions. specimens just before testing are presented in Fig. 16a. As shown,
Fig. 15 presents the statistical comparison of the mechanical registered values for water content range from 4% to 6% with an
tests results. The bar charts show the average strength obtained overall average of 4.6% for the control samples and 5.0% for the
for each test type and for both types of specimens (control versus samples prepared with Solution B as an admixture. Looking at each
treated). All test types show the increase in strength discussed mechanical test type, the difference between average moisture
above, but also show the coefficient of variation measured for each content computed for untreated control samples and treated sam-
set of tests. For example the results of uniaxial compression tests ples was found to be +1, +1.5, and 1.3 percentage points for the
yielded coefficients of variations of 12.4% and 16% for the untreated compression, split and the three-point bending tests, respectively.
and treated samples, respectively. These values of the coefficient of Although there were small differences in sample moisture contents
variation are considered reasonable given the inherent variability between the control and treated samples, these were less than 1.5
associated with earthen materials. For example in references percentage points and for the compression and split tests the trea-
[47,48], which involved samples retrieved from historical con- ted samples had higher moisture contents than the corresponding
structions, reported coefficients of variations ranging from 10.8 controls. Therefore the moisture effects, if anything, would result
to 47%. Additionally [49], reported coefficients of variations from in lower mechanical properties for the treated samples compared
2.6 to 27.5% for fabricated adobe bricks. The results from the split to the control given their higher moisture contents. From the mois-
tests yield coefficients of variations with a range between 23.1% ture content monitoring it is a clear that the observed positive
and 24.2% which are within the range of 10–73% reported by effect of the chitosan solution as admixture (Solution B) on increas-
[47,48]. Finally, the coefficients of variation obtained from the ing the mechanical properties of earthen specimens is not associ-
three point bending tests for the admixture and control specimens ated to moisture content variations, i.e. possible drier conditions
were 1.7–19%, respectively. In [47] coefficients of variation of the treated specimens. This is based on the moisture content
between 24% and 51% were reported for three point bending tests measurements which showed that in general treated specimens
which is slightly above the 19% obtained from control samples. were at similar, or slightly higher moisture content compared to
This is somewhat expected as this study involved samples fabri- the control samples.
cated under more controlled conditions compared to [47] which The sample homogeneity was also assessed based on sample
involved field samples of diverse ages and conditions. The low dry density following suggestions by Adorni et al. [33]. The dry
coefficient of variation from the treated (admixture) samples evi- density (dd) was calculated in terms of the bulk density (d) and
dence less variability in flexural strength which might be also the moisture content (x) as shown in Eq. (1).
due to the controlled fabrication process. However, it should be
pointed out that only four samples were tested and that further dd ¼ d=ðx þ 1Þ ð1Þ
investigation is needed to confirm this finding. Dry density values for untreated (control) and treated samples
As mentioned in the previous section the sample moisture con- for the three different test procedures are summarized in Fig. 16b.
tent was carefully monitored during curing in an attempt to min- This figure shows dry density values were reasonably similar in all
imize the influence of this variable in the mechanical test results. the tests thus confirming samples were prepared in a uniform fash-
This was achieved by allowing some flexibility of the sample curing ion that achieved consistent dry density values. The differences in
duration such that samples were only tested when their moisture the average dry density values measured for the three test types

Fig. 16. Physical conditions of specimens after testing: (a) moisture content; and (b) dry density.
636 R. Aguilar et al. / Construction and Building Materials 114 (2016) 625–637

were 10%, 5%, and 15% for the compression, split and three point within which this work was developed. Aitor Larrañaga (SGIker,
bending tests, respectively. These values are considered small UPV/EHU, Spain) is acknowledged for his help with XRPD data
and within typical variability for handmade earthen construction analysis and critical comments on the adobe composition. The
materials. These results further confirms that Solution B as an authors would finally like to thank the fellowship funding for post-
admixture in the preparation of earthen samples has very good graduate studies for the third author by CONCYTEC, PERU.
potential as evidenced by a real positive effect in increasing the
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