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Energy Sources, Part A: Recovery, Utilization, and

Environmental Effects

ISSN: 1556-7036 (Print) 1556-7230 (Online) Journal homepage: https://www.tandfonline.com/loi/ueso20

A review of the effect of biodiesel on the corrosion

behavior of metals/alloys in diesel engines

Anh Tuan Hoang, Meisam Tabatabaei & Mortaza Aghbashlo

To cite this article: Anh Tuan Hoang, Meisam Tabatabaei & Mortaza Aghbashlo (2019):
A review of the effect of biodiesel on the corrosion behavior of metals/alloys in diesel
engines, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, DOI:

To link to this article: https://doi.org/10.1080/15567036.2019.1623346

Published online: 29 May 2019.

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A review of the effect of biodiesel on the corrosion behavior of

metals/alloys in diesel engines
Anh Tuan Hoang , Meisam Tabatabaeic,d,e,f, and Mortaza Aghbashloe
Faculty of Mechanical Engineering, Ho Chi Minh city University of Transport, Ho Chi Minh city, Vietnam;
Engineering Institute, Ho Chi Minh city University of Technology (HUTECH), Ho Chi Minh city, Vietnam; cFaculty of
Plantation and Agrotechnology, Universiti Teknologi MARA, Shah Alam, Selangor, Malaysia; dMicrobial
Biotechnology Department, Agricultural Biotechnology Research Institute of Iran (ABRII), Agricultural Research,
Extension, and Education Organization (AREEO), Karaj, Iran; eDepartment of Mechanical Engineering of Agricultural
Machinery, Faculty of Agricultural Engineering and Technology, College of Agriculture and Natural Resources,
University of Tehran, Karaj, Iran; fBiofuel Research Team (BRTeam), Karaj, Iran


Biodiesel is the most promising bio-based alternative to the large quantity Received 29 October 2018
of fossil diesel fuel used in the transportation sectors. However, its corrosive Revised 12 April 2019
behavior when in contact with the diesel engine and fuel system compo- Accepted 21 April 2019
nents is of serious concern. The present work comprehensively reviews the
impacts of biodiesel on the corrosion behavior of metal-based parts in Biodiesel; corrosiveness;
diesel engines such as copper and copper-based alloys, aluminum and diesel engine metals/alloys;
aluminum-based alloys, cast iron, carbon steel, and stainless steel. The corrosion mechanism; static
corrosion mechanisms of the mentioned metals in biodiesel are also pre- immersion test; corrosion
sented and discussed in detail. Methods applied to study the corrosion inhibitor
phenomenon and its level are also presented. The reasons leading to the
higher corrosiveness of biodiesel vs. diesel fuel, including its higher hygro-
scopicity, higher electrical conductivity, higher polarity, higher solvency, the
presence of water and oxygen in biodiesel promoting microbial growth,
and finally, its auto-oxidation resulting in the generation of corrosive
agents, i.e., monocarboxylic acids, are also detailed. Finally, the use of
corrosion inhibitors in biodiesel to enhance metals/alloys resistance to
corrosion is reviewed. Future research needs to further expand biodiesel
utilization worldwide are also envisioned.

Air pollution is an extremely serious problem which has mainly originated from the exhaust
emissions of fossil-fuel-driven internal combustion engines (ICE) used in the transportation sector
(Aghbashlo et al. 2018c, 2016; Hajjari et al. 2017; Hoang 2018a; Khalife et al. 2017b). This problem is
expected to intensify given the 40% increase in fossil-fuel demands anticipated by the year 2030,
equaling to 16.8 billion tons of oil equivalent per year (Xia 2016; Yan et al. 2014). In order to solve
the above-mentioned problem, two strategies related to ICE have been presented: (1) improving
engine technologies to achieve higher engine thermal efficiencies (Hoang 2018b) and (2) the
application of biofuels (Demirbas 2017; Hoang 2019; Khalife et al. 2017a).
Among various biofuels, biodiesel as a replacement for fossil diesel has attracted a great deal of
attention (Aghbashlo et al. 2017d; Hosseinzadeh-Bandbafha et al. 2018; Takase et al. 2018). In spite
of its advantages, however, biodiesel/bio-based fuel application has also been associated with
a number of challenges such as corrosion and tribocorrosion phenomena on one hand, and low

CONTACT Anh Tuan Hoang anhtuanhoang1980@gmail.com Faculty of Mechanical Engineering, Ho Chi Minh city
University of Transport, Ho Chi Minh city, Vietnam
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ueso.
© 2019 Taylor & Francis Group, LLC

stability of the fuel when it is exposed to metals of the mechanical parts and fuel supply system on
the other hand (Al-Dawody and Bhatti 2013; Fazal, Haseeb, and Masjuki 2010; Pantoja et al. 2013).
According to the Nernst equation, most metal elements tend to release ions into electrolytic
solutions such as acid, base, saline, etc. Nonetheless, the mass of metal matters degraded or the
extent of corrosion differs and varies depending on the extent of abrasion and oxidation potential, as
well as on different operating and prevailing conditions related to fuel properties. Generally, the
presence of metals in fuel is considered as the consequence of corrosion, and it can result in abrasion
(Singh, Korstad, and Sharma 2012). Due to these reasons, the biggest obstacle faced by the
manufacturers is the failure of the mechanical parts of engines fueled with biodiesel. These parts
including the static components of the fuel system (such as fuel tank, filter, fuel supply pumps,
injector, fuel line) as well as the other engine components (such as exhaust system and cylinder liner)
are thought to be prone to corrosion (Hoang and Pham 2019a) or deposit formation (Hoang and Le
2019; Hoang, Le, and Pham 2019a). Some moving components such as piston crown, piston rings,
valve, plunger, connecting rod also suffer from corrosion (Haseeb et al. 2011; Hoang and Pham
2019b). The components of diesel engines and fuel system along with as-used materials for their
fabrication are shown in Figure 1.
Although biodiesel properties are generally similar to those of commercial diesel fuel (Aghbashlo
et al. 2017d, 2015), and therefore, it is rated as a realistic alternative fuel, the issues concerning its
corrosion aspects when used in diesel engines need to be thoroughly investigated. For instance, the
absence of sulfur in biodiesel is considered as an important advantage leading to reduced corrosion
in fuel containers (Hoang et al. 2019b). However, one of the frequently used catalysts in biodiesel
production is sulfuric acid, which could impart corrosive characteristic to the resultant biodiesel fuel
(Aysu and Esim 2016; Su and Guo 2014). To overcome this issue, the application of solid acid
catalysts is suggested as they could be easily separated from biodiesel upon the completion of the
transesterification process (Shalaby, Elmelawy, and Hassan 2018).
High purity of biodiesel is also of significant importance. In fact, impurities resulting from the
transesterification reaction including glycerol, fatty acids, alcohol, and catalysts could lead to
adversely affect diesel engines through deposit formation, corrosion, and fuel system failure (Shan

Figure 1. Materials used for the fabrication of different mechanical parts in diesel engines.

et al. 2018). It should be noted that exposure to biodiesel, and the presence of dissolved oxygen can
increase the corrosive behavior of the fuel resulting in corrosion of the metallic elements of the
mechanical parts (Hoang and Pham 2018; Zuleta et al. 2012). Therefore, it is important to apply
corrosion inhibitors to enhance diesel engine endurance when using biodiesel as an alternative fuel
(Singh, Korstad, and Sharma 2012). In a comprehensive review, Haseeb et al. (2011) elaborated on
the effects of biodiesel on the durability of the materials contained in diesel engine components and
fuel system (Figure 1). Those materials include metals or alloys (such as carbon steel (CS), stainless
steel (SS), copper/copper-based alloy, aluminum/aluminum-based alloy, cast iron), as well as non-
metal materials (such as elastomer, plastics, rubber, ceramic fiber). It has been shown that there is
a strong relationship between the impurities found in biodiesel as well as the products of biodiesel
deterioration with corrosiveness through oxidation (Jakeria, Fazal, and Haseeb 2014).

Biodiesel production and impacts on fuel corrosive behavior

Biodiesel is the product of transesterification reaction between triglycerides (vegetable oils/animal
fats) and alkanol (methanol or ethanol) (Aghbashlo et al. 2018b, 2017c, 2018d, 2018e). Hence,
biodiesel is basically an oxygenated fuel containing mono-alkyl esters of long-chain fatty acids (C14‒
C24) (Aghbashlo, Tabatabaei, and Hosseinpour 2018a; Hosseinpour et al. 2016). In fact, the
efficiency of transesterification reaction cannot reach 100% in practice. Nevertheless, biodiesel
fuels meeting the minimum amount of 96.5% ester content meet the requirements of the interna-
tional standards such as EN 14214 (Aghbashlo et al. 2019). Different catalysts including homo-
geneous alkaline or acid catalysts have been used to enhance the reaction efficiency and to achieve
higher yields (Table 1).
As shown in Table 1, there is a certain amount of impurities in biodiesel regardless of the catalyst
used. These impurities include unused catalysts, monoglycerides, diglycerides or triglycerides, free
fatty acids, water, etc. Among these impurities, catalyst residues especially acid catalysts can be
aggressively intensifying the corrosion of various materials. It can also be seen from Table 1 that
alkaline catalysts result in higher reaction efficiency than their acid counterparts. Among the

Table 1. A summary of the catalysts employed for biodiesel production from various feedstocks and the resultant yields.
Catalyst type Feedstock Yield (%) Reference
NaOH Waste oil 95.6 Singhasiri and Tantemsapya (2016a)
Beef tallow 96.3 Banković-Ilić et al. (2014)
Safflower oil 93.4 Aksoy (2016)
Coconut oil 91 Tupufia et al. (2013)
KOH Waste oil 90 Abubakar et al. (2016)
Soybean oil 94.5 Wang et al. (2016)
Soybean oil 93.2 Moradi et al. (2013)
Mahua oil 98 Joshi and Negi (2017)
Waste cooking oil 99.31 Aghbashlo et al. (2017a, Aghbashlo et al. 2017b)
H2SO4/KOH Jatropha curcas oil 90‒95 Patil and Deng (2009)
Dimethyl carbonate (DMC) Soybean oil 99 Celante, Schenkel, and de Castilhos (2018)
H2SO4 Algae 98.3 Salam, Velasquez-Orta, and Harvey (2016)
CaO Waste oil 94.7 Singhasiri and Tantemsapya (2016b)
Palm oil 97 Roschat et al. (2016)
Ostrich-eggshell-based-CaO Cooking oil 94‒96 Tan et al. (2015)
CaSO4/Fe2O3-SiO2 Jatropha curcas oil 94 Teo et al. (2019)
CaO/SBA-14 Sunflower oil 95 Chew and Bhatia (2008)
Ca-Al-CO3 Euphorbiaceae curcas oil 99 Eskandari et al. (2017)
Ca(OCH3)2/AC Jatropha oil 98.65 Teo et al. (2018)
NaOCH3 Cotton oil 96.5 Rashid, Anwar, and Knothe (2009)
Cannabis sativa oil 86 Rashid et al. (2016)
NaOH/sepiolite Canola oil 80.93 Aslan, Aka, and Karaoglu (2019)
Others Waste cooking oil 97 Thirugnanasambandham et al. (2017)
Eucalyptus oil 95.7 Khan et al. (2017)

alarming issues associated with biodiesel utilization, total acid number (TAN) is considered as the
primary cause of degradation of the exposed metal surfaces (Fazal, Haseeb, and Masjuki 2014a).
Thus, using alkaline catalysts could be regarded as more suitable for biodiesel production, as alkaline
catalysts are attributed with reduced TAN of biodiesel and consequently, a lower affinity for metal
surface corrosion. This further highlights the strong effects of the choice of catalyst type on biodiesel
corrosive behavior.

Corrosion mechanism of metals in biodiesel

Ferrous and non-ferrous metals are two common material types used in engine fabrication. Metals
and alloys including iron and iron-based alloys (CS and SS), aluminum and aluminum-based alloys,
as well as copper and copper-based alloys are more or less prone to corrosion in biodiesel. Fujita and
Mizuno (2007) classified the corrosion phenomenon of metals contained in the mechanical parts of
the engine into three categories including perforation, cosmetic, and edge corrosion. However, the
corrosion phenomenon based on perforation mechanism is the most prevalent type. In addition to
these, galvanic corrosion type was also mentioned by Prieto, Sorichetti, and Romano (2008) and
Squissato et al. (2018). This corrosion phenomenon is due to the fact that biodiesel is more
conductive compared with fossil diesel. This is ascribed to the presence of oxygen in biodiesel and
the electronegativity of oxygen. Therefore, the electrolytic dissociation of acid, water or esters
contained in biodiesel into radicals or ion groups containing oxygen acts as the primary factor in
the enhancement of biodiesel corrosiveness. In addition, it should also be noted that the accumula-
tion of aerobic and anaerobic microorganisms is also considered as the main cause increasing
biodiesel acidity further contributing to the mentioned phenomenon (Sazzad et al. 2016).
Presently, there are not any reports precisely explaining the corrosiveness mechanism of metals in
biodiesel. On the corrosion mechanism of copper, a study by Fazal, Haseeb, and Masjuki (2010)
showed the occurrence of pitting corrosion phenomenon of copper when exposed to biodiesel at
80ºC. Being more problematic to predict, pitting corrosion is generally regarded as more damaging
compared with uniform corrosion. The presence of oxygen in biodiesel reportedly resulted in the
formation of Cu2O which is unstable and it therefore swiftly turns into CuO (Zuleta et al. 2012).
Nevertheless, following prolonged exposure to biodiesel and by the gradual disappearance of the Cu2
O layer (located between CuO and metallic copper), CuO is reduced by metallic Cu resulting the
formation of CuCO3 (Fazal, Haseeb, and Masjuki 2013). The presence of dissolved oxygen, moisture,
CO2, and RCOO− in biodiesel could further increase the corrosion rate of copper in biodiesel (Fazal,
Haseeb, and Masjuki 2013). These could, in fact, lead to the formation of carbonate and hydroxyl-
based copper compounds (CuCO3, Cu(OH)2.CuCO3, Cu(OH)2). The corrosion mechanism of
metals is presented in the following reactions (Eqs. 1‒6) and the complex MxOyHzCm, Mx+, M2
(CO3)2y/x, M(OH)m represent the corrosion products (Zuleta et al. 2012).
Acid : RCOOH ! RCOO þHþ (1)

Metals : 2xM þ yO2 ! 2Mx Oy (2)

Mx Oy þ 2yHþ ! xMxþ þ yH2 O (3)

2Mx Oy þ yCO2 ! xM2 ðCO3 Þ2y=x (4)

4M þ mO2 þ 2mH2 O ! 4MðOHÞm (5)

Mx Oy þ 4MðOHÞm þ xM2 ðCO3 Þ2y=x þ Hþ þ O2 þ CO2 þ H2 O ! Mx Oy Hz Cm (6)
According to Gil and Leygraf (2007), the presence of a thin aqueous layer (1 μg/cm ) was the 2

prerequisite to forming the hydroxyl bonds for copper oxide. Fazal, Haseeb, and Masjuki (2013)
investigated the relationship between different compounds produced due to copper exposure to

biodiesel and the time of static immersion test (SIT). They reported that following the first 200 h of
exposure, small amounts of compounds such as Cu2O, CuO, Cu(OH)2, CuCO3 were formed. By
further increasing the exposure time to 300 h, there was an increase in the quantity of CuCO3
measured. While, after 2880 h of copper surface exposure to biodiesel and shown by X-ray
diffraction (XRD) analysis, the quantity of the CuCO3 formed was too high completely hiding the
peaks associated with metallic copper while small quantities of other corrosion compounds, i.e.,
CuO, Cu2O, and CuCO3.Cu(OH)2 could still be detected. Other copper-based compounds may also
be generated by further oxidation of the above-mentioned oxides (Eqs. 7‒13) (Cursaru et al. 2014).
2CuþO2 ! 2CuO (7)

4CuþO2 ! 2Cu2 O (8)

2Cu2 OþO2 ! 4CuO (9)

2Cu2 O þ 4CO2 þO2 ! 4CuCO3 (10)

CuO þ CO2 ! CuCO3 (11)

2CuþO2 þ2H2 O ! 2CuðOHÞ2 (12)

2CuþO2 þ2H2 O ! 2CuðOHÞ2 :CuOþH2 O ! CuðOHÞ2 (13)
The main cause of copper carbonate formation is thought to be the generation of RCOO• radicals
through esters decomposition (Eqs. 14‒16)
RCOOR1 ! RCOO þR1  (14)

2RCOO þCu ! CuCO3 þR  R þ CO (15)

2CuðOHÞ2 þCO2 ! CuðOHÞ2 :CuCO3 þH2 O (16)
Iron is the main component in steel, and therefore, steel is also prone to corrosion when exposed
to biodiesel. XRD analysis has confirmed the formation of corrosion products, i.e., Fe(OH)3, Fe2O2
CO3, and Fe2O3 in response to the presence of oxygen and water in biodiesel (Fazal, Haseeb, and
Masjuki 2011a). Fe2O2CO3 is produced through the chemical reaction between H2CO3 and
FeO(OH), whereas FeO(OH) itself is generated through the redox reaction between Fe, O2, and
H2O (Fazal, Haseeb, and Masjuki 2011a). The absorption of CO2, O2, and H2O from air into
biodiesel could also lead to the formation of some corrosive compounds for steel, such as H2CO3.
The chemical reactions describing the corrosion mechanism of iron-based alloys are presented in
Eqs. 17‒21 (Cursaru et al. 2014):
4Fe þ 3O2 ! 2Fe2 O3 (17)

2FeþO2 þ2H2 O ! 2FeðOHÞ2 (18)

4FeðOHÞ2 þO2 ! 2Fe2 O3 :H2 O þ 2H2 O (19)

RCOOR1 ! RCOO þR1  (20)

2RCOO þFe ! FeCO3 þR  R þ CO (21)
Alkaline residues in biodiesel such those of KOH and NaOH used as a catalyst during transester-
ification are considered as the main cause of aluminum or aluminum-based alloys corrosion (Díaz-
Ballote et al. 2009). However, the corrosive effect of biodiesel on aluminum is insignificant in
comparison with on steel and copper (Cursaru et al. 2014). Figure 2 presents the morphological
changes of metals in response to corrosion by biodiesel.

Figure 2. Optical photographs showing the morphological changes of the surfaces of copper (Cu), aluminum (Al), and stainless
steel (SS) in response to diesel and palm oil biodiesel at 80°C for, A: 1600 h (500× magnification) (Ahmmad et al. (2018); With
Permission from Taylors & Francis. Copyright© 2019. License Number: 4557690863385) and B: 1200 h (100× magnification) (Fazal,
Haseeb, and Masjuki (2010); With Permission from Elsevier. Copyright© 2019. License Number: 4557790846725).

As shown in Figure 2, the surfaces of the metal coupons after exposure to biodiesel were more
corroded compared with diesel fuel. Moreover, copper was more prone to corrosion in response to
biodiesel exposure than aluminum and steel. This could be ascribed to the high conductivity of copper
or copper-base alloys compared with iron and iron-based alloys (steel or stainless steel) as well as
aluminum and aluminum-based alloys (Román et al. 2018). A higher corrosion rate of copper and
copper-based alloys in biodiesel compared with those of the other metals has also been demonstrated
through the determination of Open Circuit Potential (OCP) (Rocabruno-Valdés et al. 2018).

Effect of biodiesel on corrosion behavior of metals

The corrosion of metals exposed to biodiesel and their resultant degradation are difficult questions
to answer given the long time required to test the matters related to corrosiveness, degradation, the
durability of mechanical parts in response to the utilization of biodiesel-based fuel. It should be
noted that many parts of diesel engines and fuel system require high precision and should be
corrosion-resistant. Any types of corrosion-related damages could dramatically increase the rate of
fuel oxidation as well. Oxidized biodiesel containing moisture could also result in microbial
contamination. In a study, Sazzad et al. (2016) showed the accelerated oxidation and/or hygroscopic
nature of biodiesel led to damages in the automotive components. The ease of water absorption and
microbial contamination of biodiesel in comparison with fossil diesel have been previously reported
(Tomić et al. 2019; Yang et al. 2018). These, in turn, allow the electrochemical corrosion processes to
take place easily.
To measure the corrosiveness level of biodiesel, ASTM D130 is used. Accordingly, a copper strip
is immersed in biodiesel at a specific temperature and for a certain period of time. Subsequently, it is
removed and washed to observe and evaluate the color of the copper strip (Fazal et al. 2018b).
Another standard, i.e., ASTM D93, is also used to test the corrosiveness to copper (Singh, Korstad,
and Sharma 2012).
As presented in Figure 1, most engine parts and fuel system components are made from metals
and alloys based on aluminum, copper, iron, and stainless steel, and elaborated earlier, these
materials are prone to corrosion. In small diesel engines, aluminum/aluminum-based alloys are
used in piston components, cylinder heads, engine blocks, while copper and its alloys are used in fuel

pump components and injector components. Stainless steel is used in fuel filter, valve bodies, and
pump rings. To evaluate and test the corrosion of these metals/alloys, the observation of changes in
biodiesel color can be the simplest method while other methods including SIT at various tempera-
ture conditions should also be considered. The flowchart of the experimental procedure based on
SIT is shown in Figure 3. At the end of the SIT, corrosion behavior of metals exposed to biodiesel is
tested through the evaluation of the corrosion rate (CR; mpy – millimeter per year). CR is usually
calculated by Eq. 22 (Thangavelu, Ahmed, and Ani 2016):

CR ¼ 534W=ðD  T  AÞ (22)
where W is the mean weight loss (mg); D stands for the density of metal (g/cm3); T denotes the
exposure time (h), and A is the exposed surface area (in2).
In addition to the methods described above, conventional and modern equipment could also be
employed to analyze the microstructure changes of the surface of the metals. In a study, Sgroi et al.
(2005) looked into the corrosive behavior of biodiesel in a diesel engine with a focus on injector and
burner filter components. High chrome stainless steel was used to fabricate the injector, while copper
and copper-based alloys were used in the burner filter components. They claimed that the copper
content found in biodiesel fuel increased from 0.1 to 21 ppm after 2 h of the test. Corrosion
including the pitting was observed on the bronze filter after 10 h of using preheated biodiesel
(70ºC). However, no corrosion signs were found on the injector.
Fazal, Haseeb, and Masjuki (2011a) examined the corrosion properties of mild steel after being
immersed into different fuels including B0 (100% diesel fuel), B50 (50% palm biodiesel and 50%
diesel fuel), B100 (100% palm biodiesel) at various temperatures, i.e., room temperature, 50ºC, and
80ºC during 1200 h. Tsuchiya et al. (2006) conducted an investigation into the corrosion of steel in
B5 at 80ºC for 500 h and detected some acids such as formic, acetic, propionic, and caproic acids
causing pitting corrosion. Norouzi et al. (2014) also studied the corrosive behavior of blends of ultra-
low sulfur diesel (ULSD) and rapeseed-based biodiesel for Al and Cu at 80°C for 600 h as well as at
room temperature for 5760 h. In a different study, Jin et al. (2015) examined the impacts of
temperatures and exposure time on the corrosion of mild steel in biodiesel. Based on the results
of these studies, the corrosiveness of biodiesel to the above-mentioned metals and alloys (iron,
copper, steel, and aluminum) was generally increased in response to the increase in temperature and

Figure 3. Flowchart of the experimental procedure used to investigate biodiesel corrosiveness to copper based on SIT (Fazal et al.
(2018b); With Permission from Elsevier. Copyright© 2019. License Number: 4557581062097).

exposure time. The correlations between the increasing corrosion degree of metals/alloys corrosion
and temperature as well as exposure time as reported by different studies are illustrated in Figure 4.
In an interesting study, Fazal, Haseeb, and Masjuki (2010) studied the effects of palm oil-based biodiesel
and neat diesel on the corrosion behavior of various engine metal/alloy materials, i.e., copper (99.99% of
purity), aluminum (99% of commercial purity), 316 stainless steel (18% of chromium, 11% of nickel, 2% of
manganese, 1% of silica and 0.08% of carbon) when immersed in fuel samples at temperature 80ºC with
a stirring speed of 250 rpm by a magnetic stirrer. They observed corrosion for copper and aluminum, but
stainless steel seemed not prone to corrosion. More specifically, after 1200 h of test time, the corrosion rate of
the samples immersed in B100 was 0.586 mpy for copper, 0.202 mpy for aluminum, and only 0.015 mpy for
stainless steel. These corrosion rates were much lower for B0 standing at 0.3 mpy for copper, 0.15 mpy for
aluminum, and 0.015 mpy for carbon steel. Moreover, results on surface morphology showed a higher
pitting corrosion of copper and aluminum strips in biodiesel (corresponding to 80% and 18%, respectively)
in comparison with their pitting corrosion values in neat diesel (54% and 10%, respectively), while no
morphological changes were observed on the surface of stainless steel in response to exposure to biodiesel.
On the other hand, substantial changes were recorded in some biodiesel properties such as density and
viscosity as a result of exposure to all the metals investigated (Figure 5(a)) (Fazal, Haseeb, and Masjuki 2010).
Similar results were also reported recently by Ahmmad et al. (2018) (Figure 5(b)).
Hu et al. (2012) also evaluated the corrosion properties of metals, including copper, mild
carbon steel, stainless steel, and aluminum, in biodiesel compared with neat diesel. After being

Figure 4. The relationship between temperature, exposure time, and biodiesel percentage with corrosion rate as reported by
different studies. (a) Corrosion rate of mild steel after exposure to B0, B50 and B100 for 1200 h at different temperatures (Fazal,
Haseeb, and Masjuki (2011a); With Permission from Elsevier. Copyright© 2019. License Number: 4557671426510); (b) & (c)
Corrosion rate of aluminum (Al), copper (Cu), and mild carbon steel (MCS) at room temperature and 60ºC, respectively (Cursaru
et al. (2014); With Permission from Elsevier. Copyright© 2019. License Number: 4557670497949); (d) Variations in corrosion rates of
brass in response to exposure to different percentages of waste sunflower oil biodiesel (Samuel and Gulum (2018); With
Permission from Taylors & Francis. Copyright© 2019. License Number: 4557671070717).

Figure 5. Changes in the density of neat diesel and biodiesel in response to the exposure to different metals, i.e., aluminum (Al),
copper (Cu), and stainless steel (SS). (a) Fazal, Haseeb, and Masjuki (2010); With Permission from Elsevier. Copyright© 2019. License
Number: 4557790846725, and (b) Ahmmad et al. (2018); With Permission from Taylors & Francis. Copyright© 2019. License
Number: 4557690863385.

immersed for 60 h at 43ºC, the corrosion rates recorded in biodiesel were higher than in diesel.
In addition, the copper and mild carbon steel corrosion rates were also significantly higher than
those of aluminum and stainless steel. Similar copper corrosion properties were also claimed by
Geller et al. (2010) and Aquino et al. (2012), indicating that copper and copper-based alloys
(brass) were significantly more prone to pitting corrosion as revealed by the weight loss
experiment. Haseeb et al. (2010a) looked into the effects of palm oil biodiesel on the corrosion
of copper and leaded bronze under two different experimental conditions, i.e., 1) room tem-
perature for B0, B50, and B100 for 2640 h, and 2) at 60°C for B0, B100 and B100 (oxidized) for
840 h. They argued that under the first test conditions, the rates of corrosion level for copper
and bronze in B100 were 0.042 mpy and 0.018 mpy, respectively. While under the second test
conditions, oxidized-B100 led to higher rates of copper and bronze corrosion (0.053 mpy and
0.023 mpy, respectively). The higher corrosion resistance level of bronze compared to copper
could be ascribed to the presence of tin (Sn) (Nguyen et al. 2018).
In another study by Kaul et al. (2007), the effects of different biodiesels produced from feedstocks on the
corrosion behavior of a diesel engine piston fabricated from aluminum alloys were tested using SIT at
different temperatures (ranging from 15 to 40°C). They claimed that the corrosion of piston liner and piston
metal occurred after being immersed in different biodiesels (including Jatropha curcus biodiesel (S1),
kanarja biodiesel (S2), mahua biodiesel (S3), salvadora biodiesel (S4)). The weight loss of piston liner due
to corrosion by S1, S2, S3, and S4 were 3.6 mg, 0.3 mg, 0.3 mg, and 6.1 mg, corresponding to the corrosion
rates of 0.0117 mpy, 0.0058 mpy, 0.0058 mpy, and 0.0136 mpy, respectively, in comparison with 0.0058 mpy
of diesel fuel. Moreover, S4 led to the highest weight loss of piston metal (i.e., 2.1 mg) against 0.2 mg by S1
and 0.1 mg by S2 and S3. They attributed this finding to the higher TAN of S4 intensifying the rate of
corrosion (Kaul et al. 2007). Sorate and Bhale (2013) presented similar results on the weight loss of engine
metal parts including top ring, compression ring, scrap ring, and oil ring after being exposed to biodiesel in
comparison with fossil diesel. The corrosion rates of other metals and alloys such as cast iron, leaded bronze,
phosphorous bronze, galvanized steel, and magnesium when immersed in biodiesel have also been
investigated previously (Chandran et al. 2018; Chew et al. 2013; Fazal et al. 2016, 2018a).
Using electrochemical impedance spectroscopy (EIS), it was shown that steel had a higher resistance
to corrosion compared to copper and copper alloys owing to its carbon content (0.2 to 2.1 wt.%) and
the high corrosion resistance of carbon (Rocabruno-Valdés et al. 2018; Román et al. 2018).
The source of oil feedstock used to produce biodiesel could also affect its corrosive properties.
Table 2 tabulates a summary of the corrosion rate (mpy) of different metals including mild steel,
copper, and aluminum in biodiesels produced from different oil feedstocks.

Maru et al. (2009) immersed strips of structural carbon steel (CS) in biodiesels produced from two
different oil feedstocks, i.e., soybean oil, sunflower oil, and diesel fuel for 115 d. Using Fourier Transform
Infra-Red (FT-IR) and Raman spectra analysis, they revealed the formation of secondary products origi-
nated from fuel degradation while soybean oil biodiesel was found to have caused more aging than
sunflower oil biodiesel. These results were in line with those of the study conducted by Hu et al. (2012).
In another study, ASTM 1045 mild steel was immersed in palm oil biodiesel (Jin et al. 2015). The results of
the FT-IR analysis performed after 120 d showed the presence of the main corrosion products on the sample
immersed in biodiesel, namely α-FeOOH (1372.27 cm−1), β-FeOOH (881.84 cm−1), δ-FeOOH
(465.62 cm−1, 1196.93 cm−1, 1436.81 cm−1), and Fe2O2CO3 (609.17 cm−1). While the corrosion products
detected on the sample immersed in fossil diesel were primarily α-FeOOH (1372.81 cm−1), γ-FeOOH
(1022.00 cm−1), δ-FeOOH (11196.81 cm−1) and Fe2O2CO3 (609.23 cm−1). These results confirmed the
presence of compounds such as FeO, Fe2O3, FeO(OH), FeCO3, Fe2O2CO3 on the surface of the biodiesel-
immersed sample while the last two compounds were absent on the surface of fossil diesel-immersed

Table 2. Corrosion rate and weight loss of metals and alloys in biodiesels produced from different oil feedstocks.
Experimental conditions Corrosion rate
Temperature Duration Copper/copper-
Biodiesel type (ºC) (h) Steel/steel-based alloy based alloy Aluminum Reference
Palm oil RT 2640 - i) 0.042 mpy for - Haseeb et al. (2010a)
biodiesel copper
ii) 0.018 mpy for
leaded bronze
60 2640 - i) 0.053 mpy for -
ii) 0.023 mpy for
leaded bronze
RT 1200 0.052 mpy - - Fazal, Haseeb, and
80 0.059 mpy - Masjuki (2011a)
RT 2880 - i) 0.329 mpy for 0.173 mpy Fazal, Haseeb, and
copper, Masjuki (2012)
ii) 0.209 mpy for
RT 1440 - - 0.123 mpy Chew et al. (2013)
RT 480 0.05254425 mpy 0.450684356 mpy - Fazal, Jakeria, and
960 0.068770638 mpy 0.942552815 mpy - Haseeb (2014b)
1440 0.06946705 mpy 0.910573506 mpy -
RT 1200 3.45 µmpy - - Fazal et al. (2016)
RT 1440 1.8 µmpy 23 µmpy - Fazal et al. (2017)
RT 600 - 6.6 µmpy - Fazal et al. (2018b)
1200 - 9.8 µmpy -
100 540 i) 0.000188 mmpy for 0.000929 mmpy 0.000244 Chandran et al. (2018)
stainless steel mmpy
ii) 0.000625 mmpy for
galvanized steel
Sunflower oil RT 3000 0.170124 mpy 0.323615 mpy 0.162201 Cursaru et al. (2014)
biodiesel mpy
60 0.336845 mpy 0.640758 mpy 0.316292
RT 960 - 0.4 mpy - Samuel and Gulum
Rapeseed oil 43 1440 i) 0.01819 mpy for mild 0.02334 mpy 0.00324 Hu et al. (2012)
biodiesel steel, mpy
ii) 0.00087 mpy for
stainless steel,
80 600 - 0.92 mpy 0.35 mpy Norouzi et al. (2012)
Jatropha oil 80 1600 0.000406 mmpy 0.011 mmpy 0.000762 Ahmmad et al. (2018)
biodiesel mmpy
RT: Room temperature.

Along with microscopic analysis such as Scanning Electron Microscopy (SEM), Energy Dispersive
X-Ray Spectroscopy (EDS) could also be used to investigate the corrosion morphology of the metal
surface. Hu et al. (2012) employed EDS analysis and reported on the corrosion level of different
metals/alloys in biodiesel and fossil diesel (Figure 6). They demonstrated the following order: copper
or copper-based alloys>aluminum>mild carbon steel>stainless steel. A similar analysis using SEM/
EDS can be found in other published reports (Fazal et al. 2016, 2018b; Jin et al. 2015).
It should be noted that the corrosion process may be an electrochemical process due to the small amount
of water contained in biodiesel. Therefore, electrochemical methods are also thought to be good since they
could provide the results within a short time. Polarization and EIS are usually used to determine the
corrosion resistance of metals to biodiesel (Kamiński and Kurzydłowski 2008). In a study, Díaz-Ballote et al.
(2009) used different electrochemical techniques, including open circuit potential (Eocp) measurement, EIS,
and anodic polarization measurement to investigate corrosion behavior of aluminum in biodiesel. The
results showed a decrease in aluminum surface activity due to a layer of corrosion products formed,
resulting in a negative Eocp value of below −600 mV. Such finding and those reported in similar studies
indicate that electrochemical techniques might be used to determine the biodiesel corrosiveness to metals
quantitatively (Fazal et al. 2018a; Santana, De, Meira, and Tentardini 2015; Yan, Sun, and Meng 2018; Zuleta
et al. 2012). Atomic Force Microscopy (AFM) has also been used to investigate changes in surface roughness
of metals after exposure to biodiesel (Fazal et al. 2016, 2018b).
XRD analysis is another relabel technique to monitor the corrosion behavior of metals in response to
biodiesel exposure. As shown in Figure 7, before immersion in biodiesel, base metals such as Al, Cu, and Fe
were found and degradation products such as AlO(OH), CuO, Cu(OH)2, Fe2O3, FeO(OH) and FeCO3 were

Figure 6. EDS spectra before and after corrosion at 43ºC for two months. (A) Copper, (B) Mild carbon steel, (C) Aluminum, and (D)
Stainless steel (a: before corrosion, b: biodiesel, and c: diesel). Hu et al. (2012); With Permission from Elsevier. Copyright© 2019.
License Number: 4558160184416.

seldom detected. However, after being immersed in biodiesel, comparatively higher concentrations of the
compounds originated from Cu corrosion such as CuO, Cu(OH)2, CuCO3.Cu(OH)2, or from Fe corrosion
such as FeO could be seen (Cursaru et al. 2014). Moreover, by increasing the temperature throughout the
corrosion experiment, a higher frequency of peaks associated with corrosion products, i.e., AlO(OH), CuO,
CuCO3.Cu(OH), Fe2O3, FeO(OH), FeCO3 were observed in the XRD patterns, confirming increased
corrosion rates (Cursaru et al. 2014). Similar XRD results on the corrosion level of metals and alloys
when exposed to biodiesel could be found in the published literature (Fazal et al. 2018b; Rocabruno-Valdés
et al. 2018).

Figure 7. XRD pattern of (a) aluminum (Al), (b) copper (Cu), and (c) mild carbon steel (MCS) after immersion in diesel fuel (B0) and
(d) aluminum (Al), (e) copper (Cu), and (f) mild carbon steel (MCS) after immersion in biodiesel (B100) at 60ºC for 3000 h. Cursaru
et al. (2014). With Permission from Elsevier. Copyright© 2019. License Number: 4557670497949.

Overall, the reasons leading to the higher corrosiveness of biodiesel vs. diesel fuel could be
summarized as higher Hygroscopicity in nature, higher electrical conductivity, higher polarity,
higher solvency in comparison with diesel fuel, the presence of water and oxygen in biodiesel
promoting microbial growth, and finally, the auto-oxidation of biodiesel resulting in the generation
of monocarboxylic acids further intensifying the corrosion process (Figure 8).
Regarding the corrosion process in fuel containers, an experimental study conducted by
Boonyongmaneerat et al. (2011) highlighted the role of high TANs of biodiesel in corroding
steel-based containers, resulting in the formation of sediments and deposits on engine parts
(injectors and pumps) as well as pressure drops through the filter. They suggested to protect
metal surfaces exposed to biodiesel using electrodepositing. Accordingly, they used nickel
tungsten (NiW)-based alloys in their study. However, only after 2 months, in comparison with
the initial biodiesel sample, both the acid value and the water content of biodiesel increased by
0.3 mg KOH/g and 1100 ppm, respectively, indicating the occurrence of corrosion. More
favorable results were obtained in a different study by Amaya, Piamba, and Olaya (2018) who
utilized Niobium carbide (NbC) coating as an alloy layer for corrosion protection from biodiesel.
The obtained results indicated that the NbC coating was a viable alternative to reduce the
corrosive impacts of biodiesel for gray cast iron.

Application of corrosion inhibitors to protect metals exposed to biodiesel

As elaborated earlier, corrosion could cause serious damages to the different engine and fuel system
compartments. These damages could on one hand, significantly jeopardize the shelf life of these
compartments while on the other hand, could substantially deteriorate their performance over time.
Therefore, it is vital to lessen the corrosive properties of biodiesel through different approaches
including the application of corrosion inhibitors. Amino-amines, oxyalkylated amines, diamines,
primary amines, dodecyl benzene sulfonic acids, imidazolines, naphthenic acid, phosphate esters are
among the most popular corrosion inhibitors used (Jakeria, Fazal, and Haseeb 2015). It should be
noted that different corrosion inhibitors may be recommended for biodiesel compared with fossil
diesel due to some differences in the physicochemical properties of these fuels (Deyab 2016a).

Unfavorable environment:
Intrinsic attributes of biodiesel:
• High temperature
• Higher hygroscopicity • Exposure to ambient air
• Higher electrical conductivity • Exposure to light
• Higher polarity Higher
• Higher solvency Corrosiveness
of Biodiesel
Biodiesel composition-related vs. Diesel

• High oxygen content Promoting

Corrosion figures:
• Presence of water microbial growth Fazal et al. (2016). With
Permission from Elsevier.
Copyright© 2019. License
• Auto-oxidation Generation of Number: 4558250517194.
corrosive agents

Figure 8. Factors affecting the higher corrosiveness of biodiesel vs. diesel.


Nonetheless, it should be noted that corrosion inhibitors are only capable of extending the initiation
phase of corrosion (or in a better word, delaying the aggressive phase) and cannot prevent corrosion
in full (Ashraful et al. 2014). Generally, the working mechanism of the inhibitors is to form a stable
metallic oxide layer, which is difficult to dissolve when the metal surface is exposed to biodiesel.
Some corrosion inhibitions such as isoxazolidine-based derivatives, pyridoxal hydrochloric, and
pyridoxol hydrochloride were found efficient for iron and steel in acidic media (Haseeb et al. 2010b)
while benzimidazole-2-tione and benzoxazole-2-tione were found suitable for aluminum in acidic
media (Bereket, Pınarbaşı, and Öğretir 2004). Other corrosion inhibitions such as polyisobutylene-
based succinimide derivative (SID) and irganor NPA have been shown inhibitive of corrosion in
rapeseed oil and palm oil biodiesels (Hancsók et al. 2008). Given the negative correlation between
oxidation stability and corrosion, antioxidants could also serve as corrosion inhibitors. Accordingly,
tert-butyl-hydroquinone (TBHQ) was successfully used to control copper corrosion in an SIT
experiment by Almeida et al. (2011). They argued that after 50 h, the presence of TBHQ resulted
in a decrease in copper concentration in biodiesel (1.16 µg/g) vs. without TBHQ (3.62 µg/g). They
attributed the favorable results obtained to the formation of a protective film layer on the copper
surface in the presence of the corrosion inhibitor.
Amine-based corrosion inhibitors, i.e., ethylenediamine (EDA), n-butylamine (nBA), and tert-
butylamine (TBA) were also investigated for the cast iron-based parts of a diesel engine by Fazal,
Haseeb, and Masjuki (2011b). After a 50-d SIT, the corrosion rate of grey cast iron (composition (wt.%):
3% carbon, 1.84% silica, 0.098% phosphorus, 0.089% sulfur and iron) was analyzed, and the inhibition
efficiencies of the additives used were found to be EDA > TBA > nBA. In a different study, Fazal et al.
(2016) explored the corrosion rates of cast iron (CI) and low carbon steel (LCS) in B100 at room
temperature with (250 ppm) and without a number of additives. The achieved results indicated that tert-
butylamine (TBA) inhibitor could reduce the corrosion rates of CI and LCS by 1.8 µm/y and 3.15 µm/y,
respectively, compared to the TBA-free biodiesel sample. Moreover, they also claimed more significant
reductions in corrosion rates of CI and LCS in response to the application of other additives such as
benzotriazole (BTA), butylated-hydroxy-toluene (BHT), and Pyrogallol (PY) (Fazal et al. 2016). In a more
recent investigation, the effectiveness of TBA and butylated hydroxyanisole (BHA) on copper was
evaluated by Fazal et al. (2018b). They found TBA as a highly effective corrosion inhibitor for copper.
The formation of nitrogen-based compounds (Cu(NO3)2.3H2O) on the copper surface when exposed to
biodiesel was highlighted as the main reason decreasing the corrosion rate (Fazal et al. 2018b). Similarly, the
formation of a layer of Fe(NO3)3.9H2O on the surface of cast iron (CI) and low carbon steel (LCS) when
biodiesel was doped with TBA was claimed to have increased the resistance of the mentioned metals/alloys
to biodiesel-caused corrosion (Fazal et al. 2016). Therefore, it could be concluded that amine-based
corrosion inhibitors are capable of creating an effective barrier on the metal surfaces, preventing their
exposure to biodiesel and/or oxidation products and consequently, increasing their corrosion resistance.
A summary of the results of different studies investigating the efficiency of various corrosion inhibitors in
biodiesel is tabulated in Table 3.

Conclusions and future prospects

Concerns over the unfavorable biodiesel properties in particular corrosiveness to (especially metal)
diesel engine and fuel system compartments have limited commercial utilization of neat biodiesel
fuel. Therefore, understanding and prevention of corrosion of mechanical parts of diesel engines
when exposed to biodiesel is a major challenge to scientists, engineers, and manufactures. The higher
corrosion rates of metals in biodiesel in comparison with fossil diesel were comprehensively
discussed herein while the underlying mechanisms were also presented. The factors affecting the
corrosion level were also elaborated. Based on the results of various investigations, metals and alloys
generally used in the fabrication of diesel engine and fuel systems such as copper, aluminum, and
steel could be easily corroded by biodiesel. Pitting corrosion is the most common type of corrosion
for nonferrous metals and alloys and carbon steel, while stainless steel seems to be immune to this

Table 3. Efficiency of some corrosion inhibitors.

Chemical Concentration efficiency
Corrosion inhibitor formula (ppm) Metal (%) References
Tert-butylamine (TBA) C4H11N 100 Cast iron 49.41 Fazal, Haseeb, and Masjuki
250 Cast iron 86.54 Fazal et al. (2016)
Low carbon 86.71
500 Copper 65.77 Fazal et al. (2018a)
Leaded bronze 61.43
Phosphorus 86.28
Ethylenediamine (EDA) C2H8N2 100 Cast iron 31.38 Fazal, Haseeb, and Masjuki
n-Butylamine (nBA) C3H11N 100 Cast iron 12.06 (2011b)
Butylated hydroxytoluene C15H24O 150 Carbon steel 94.40 Deyab (2016b)
(BHT) 500 Copper 45.51 Fazal et al. (2018a)
Leaded bronze 52.42
Phosphorus 27.74
500 Copper 73.00 Fazal et al. (2017)
Mild steel 39.00
Pyrogallol (PY) C10H12O5 500 Copper 61.86 Fazal et al. (2018a)
Leaded bronze 62.19
Phosphorus 48.18
Copper 92.00 Fazal et al. (2017)
Mild steel 33.00
Propyl gallate (PG) C6H6O3 500 Copper 23.89 Fazal et al. (2018a)
Leaded bronze 38.57
Phosphorus 26.64
400 Carbon steel 83.00 Santana, De, Meira, and
Tentardini (2015)
Benzotriazole (BTA) C6H5N3 500 Copper 69.12 Fazal et al. (2018a)
Leaded bronze 58.57
Phosphorus 94.78
Butylated hydroxyanisole C11H16O2 100 Copper BHA < TBA Fazal et al. (2018a)
Tert-butyl-hydroquinone C10H14O2 500 Carbon steel High (Fernandes et al. (2013)
(TBHQ) Galvanised High
Rosemary leaves - 100‒500 Aluminium 62.70–95.70 Deyab (2016a)
T. cordifolia - 500‒2000 Copper 97.00 Amgain et al. (2018)
Aluminium 79.00
β-Carotene C40H56 400 Carbon steel 62.00 Santana, De, Meira, and
Stearic acid C18H36O2 400 Carbon steel 75.00 Tentardini (2015)

type of corrosion. Among different metals, copper is the most prone to corrosion by biodiesel
followed by aluminum and carbon steel.
Various strategies could be employed to lessen the corrosiveness of biodiesel to metals/alloys used
in diesel engines and fuel systems. Those include (1) development of novel alloys coated by layers
resistant to biodiesel and (2) doping biodiesel with corrosion inhibitors. Gray cast iron with niobium
carbide coating showing resistance to the corrosive impacts of biodiesel is an example of the first
strategy. Corrosion inhibitors added to biodiesel are in fact capable of delaying the aggressive phase
of biodiesel corrosion and not completely stopping the corrosion phenomenon. Among various
inhibitors investigated, amine-based corrosion inhibitors and in particular TBA, are the most
capable by creating an effective barrier on the metal surfaces, preventing their exposure to biodiesel
and/or oxidation products and consequently increasing their corrosion resistance. Nevertheless, it
should be noted that most of the studies involving the application of corrosion inhibitors were

carried out for limited durations only and thus, it is necessary to carry out further tests with longer
periods of time to get a more in-depth understanding on the impacts of these additives on biodiesel
corrosiveness in the long-run. Moreover, more efforts should be devoted to the development of
novel alloys/alloy coatings of high resistance to various blends of biodiesel and in particular to neat

Anh Tuan Hoang http://orcid.org/0000-0002-1767-8040

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