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Bacterial exopolysaccharides for corrosion

resistance on low carbon steel

Article in Journal of Applied Polymer Science · March 2017

DOI: 10.1002/app.45032

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Bacterial exopolysaccharides for corrosion resistance on low carbon
steel
Victoria L. Finkenstadt,1 Claudiu B. Bucur,* Gregory L. Co  ,2 Kervin O. Evans2
^ te
1
Plant Polymer Research, National Center for Agricultural Utilization Research, Agricultural Research Service, United States
Department of Agriculture, Peoria IL 61604
2
Renewable Product Technology Research, National Center for Agricultural Utilization Research, Agricultural Research Service,
United States Department of Agriculture, Peoria IL 61604
*Present address: Environment, Analysis, and Future Battery, Toyota Motor Engineering & Manufacturing North America, Inc., Ann
Arbor, MI 48105
Correspondence to: V. L. Finkenstadt (E - mail: victoria.finkenstadt@ars.usda.gov)

ABSTRACT: Corrosion is a global issue that affects safety and economics. There is an increasing demand for bio-based polymers for
industrial applications and production of polymers by micro-organisms is especially attractive. This work reports on the electrochem-
ical and physical properties of exopolysaccharides produced from lactic acid bacteria and their suitability as anti-corrosive coatings.
Bacterial exopolysaccharide coatings protected low carbon steel from corrosion by reducing ionic diffusion rates and maintaining a
relatively passive metal-coating interface. The data suggest the kinetics of film deposition are fast (<5 min) and there is little excess
(loosely bound) material when hydrated. Measurements show thin (50 nm) coatings that when exposed to water exhibit self-repairing
phenomenon. The corrosion protection offered by the coatings is reported as the corrosion rate calculated from the corrosion current
obtained by electrochemical impedance and polarization spectroscopy. V C 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45032.

KEYWORDS: bacterial exopolymers; corrosion; EIS

Received 30 September 2016; accepted 17 February 2017

DOI: 10.1002/app.45032

INTRODUCTION
Corrosion is a global issue that affects safety and economics. It
affects almost every industry in an economy from electronics1
to healthcare,2 energy,3 and infrastructure,4 and it causes exorbi-
tant losses. 5 Corrosion can be defined as the disintegration of a
material into its constituent atoms due to chemical reactions
with its surroundings6 otherwise known as rusting.7 Corrosion
inhibition technology ranges from a metallurgical approach8 to
a chemical modification of the substrate and to specialized pro-
tective coatings and paints.9,10 Plating, painting, and the appli-
cation of enamel are the most common anti-corrosion
treatments.11 They are effective by providing a physical barrier
(coating) between the damaging environment and the structural
material. Coatings start failing rapidly if scratched or damaged
because a corrosion process called “pitting” occurs at very high
rates in small cracks or paint defects.12
Thin polymer films are the subject of intensive study as cheap
and efficient alternatives to traditional anti-corrosive coating
technology.13 They are easy to tailor to the specific needs of an
application, have varying diffusive and hydrophobic properties
and are easily applied, usually by spraying or dipping in solu-
tions. Polymer thin films also provide more esoteric capabilities
such as “healing” inflicted deformations (scratches) and a tight
interaction with the substrate which minimizes collection of
water or dust at the substrate/film interface.14,15 They also often
need only be applied in thin layers (and so less quantity needs
to be used) which adds to their profitability appeal. Covering
the substrate protects it from corrosion through reducing diffu-
sion rates of ions and maintaining a relatively hydrophobic
environment at the substrate/coating interface. Two major
shortcomings of corrosion inhibitive paints are incomplete pro-
tection16 especially when damaged and weak adherence to the
substrate.17 Coatings often experience rapid and complete

Additional Supporting Information may be found in the online version of this article.
Disclaimer: Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and
does not imply recommendation or endorsement by the U.S. Department of Agriculture. USDA is an equal opportunity provider and employer.

C 2017 Wiley Periodicals, Inc.

V

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Table I. Designations (Strain) for Lactic Acid Bacteria Capable of Producing Dextran-Like Exopolysaccharides
NRRL #
B-1254
B-1127
B-1501, B-1498, B-1355, B-742
B-1145
B-1202, B-1203, B-1205, B-1207, B-1208, B-1211, B-1212,
B-1213, B-1216, B-1290, B-1382, B-1384, B-1390, B-
1395, B-1417, B-1422, B-1499, B-1525, B-1527
a
Available from the USDA ARS Northern Region Research Lab (NRRL) Culture Collection.
b
All strains are lactic acid bacteria endemic to the environment. Recent taxonomy has not been completed (Cote and Leathers, 2005).
failure when scratched due to accelerated pitting and undercoat
corrosion. Improving the interfacial bond strength and mini-
mizing coating defects due to scratching while maintaining the
hydrophobic and diffusion inhibition properties of a film
enhance its anti-corrosion properties and applicability. A good
review of polymers and bio-based polymers for corrosion inhi-
bition is available.18
There is an increasing demand for bio-based polymers for
industrial applications and production of polymers by microor-
ganisms is especially attractive. Many microorganisms produce
biofilms composed of proteins, fatty acids, and carbohydrates.
Carbohydrate polymers excreted by microbes (exopolysacchar-
ides) have been commercialized.19 Examples of commercially
available microbial exopolysaccharides are xanthan produced
from Xanthamonas spp; cellulose from Acetobacter spp; and dex-
tran from Leuconostoc mesenteroides. Recently, some Chryseobac-
terium and Klebsiella species endemic to the Middle East
environment have been shown to have anti-corrosive proper-
ties.20 Lactobacillus delbrueckii and L. rueteri both produce exo-
polysaccharides that were shown to inhibit corrosion of metal
substrates submerged in electrolyte solutions.21,22 In addition,
sulfur-reducing bacteria (SRB) exopolysaccharides were shown
to have anti-corrosive properties.23 The SRB exopolysaccharides
are structurally similar to the exopolysaccharides excreted from
the lactic acid bacteria, L. mesenteroides. There are many strains
of L. mesenteroides that produce biofilms composed of exopoly-
saccharides. Their molecular weights vary but they have a pre-
dominant structural feature of a(1!6)-linked D-glucose
(generically known as dextrans) with some degree of branching
of a(1!3) linkages.24,25 In previous work, two strains of Leuco-
nostoc mesenteroides as well as xanthan, pullulan, and phospho-
mannan with similar chemical structures to the dextrans were
evaluated.26
This work uses electrochemical methods based on experiments
developed to characterize biofilms that are suspect in microbial
induced corrosion of metal surfaces27 and reports the electro-
chemical and physical properties of 29 strains or fractions of
lactic acid bacteria that produce dextran-like exopolysaccharides
and their suitability as anti-corrosive coating*.
*Finkenstadt, V. L., Cote, G. L., & Willett, J. L. (2015). U.S. Patent No.
9,034,436. Washington, DC: U.S. Patent and Trademark Office.
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Organisma
Lactobacillus satsumensis
Lactobacillus brevis
Leuconostoc citreum
Leuconostoc mesenteroides subspecies dextranicum
Leuconostoc mesenteroidesb
EXPERIMENTAL
Exopolysaccharide Preparation
Lactic acid bacteria capable of producing dextran-like exopoly-
saccharides, such as L. mesenteroides, were obtained from the
ARS Northern Region Research Lab (NRRL) Culture Collection†
(Table I). They were grown as previously described with the
cell-free culture fluids used to produce dextrans from sucrose.28
The glucans were precipitated from cultures with ethanol.29 The
bacterial strains in their native state synthesize two glucans,
referred to as fraction L (Less soluble, precipitated at 38% etha-
nol) and fraction S (Soluble, precipitated at 46% ethanol). L
means less soluble in EtOH-water mixtures, S means more solu-
ble in the mixtures. This is the convention introduced by Jeanes
et al. (1954) and is in common usage. Fraction L is predomi-
nantly a(1!6)-linked D-glucose, with approximately 3–4%
branching through a(1!3)-linkages. Fraction S, better known
as alternan, consists of an alternating sequence of a(1!3) and
a(1!6)-linked D-glucopyranosyl units with approximately 11%
branching.30 Both are high-molecular weight (> 106 g/mol),
water-soluble D-glucans. Low carbon stainless steel (R-35, Q-
Panel) substrates were sonicated in hexane then rinsed with a
50–50 ethanol/methanol mixture and dried before being
sprayed. The sprayer was a Norgen compressor valve attached
to the air spout in the laboratory wall connected to a Badger
Air Brush set, model 350. The air pressure was maintained at
20 psi with a compressor gauge. Films were applied with a dou-
ble pass of the air brush over vertically suspended samples by
hand, from a distance of 12 in. The exopolysaccharide was dis-
persed in deionized, nanopure water with a concentration of
100 mg/L.
Electrochemistry
Electrochemical experiments were conducted on a Parstat model
2273 potentiostat (Princeton Applied Research Instrumentation)
equipped with a three electrode corrosion cell (Gamry PTC1).
The working electrode was a coupon of SAE 1010 stainless steel
(Q Panel Products) on top of which a 50 mL open glass tube
was sealed with a rubber gasket. The electrolyte solution [5%
(w/v) NaCl] was poured into the cell from the top. A graphite
†
NRRL Culture Collection, located in the National Center for Agricultural
Utilization Research in Peoria, Illinois, can be accessed at: http://nrrl.ncaur.
usda.gov/ (Last accessed: January 31, 2017)
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Table II. Electrochemical Values for 29 Exopolysaccharides EPS Coating Characterization

Dynamic contact angle measurements were conducted with a
EPS Rct (X) Cd (mF) Etafel (-V) icorr (lA) c.r. (mpy) Cahn Dynamic Contact Angle Analyzer, model DCA-312 con-
nected to a Pentium III computer. The film substrate was a
B-1254c 650 23.11 0.669 10.26 0.315
microscope slide cover glass, clipped to the instrument’s forceps.
B-1355 526 22.26 0.719 11.12 0.366
The advancing and receding angles are determined using a goni-
B-1498L 521 22.19 0.75 11.56 0.393 ometer to observe a small drop of water placed on a
B-1254L 505 21.02 0.763 11.85 0.395 exopolysaccharide-coated glass slide. Measurements were con-
B-1501 504 20.11 0.768 12.01 0.399 ducted in deionized water. The contact angle is determined by
B-1213 503 19.46 0.761 12.2 0.402 drawing a tangent at the contact where the liquid and the solid
B-1203 467 18.66 0.767 12.24 0.403 intersect. Three interacting forces of interfacial tension (gas, liq-
B-1208 465 18.36 0.772 14.76 0.486 uid, and solid) determine the shape of the drop and the magni-
tude of the contact angle. Higher contact angle means less
B-1254b 464 18.34 0.775 15.9 0.523
wettability and greater hydrophobicity.
B-1417 452 18.08 0.781 16.95 0.545
B-1290 436 17.69 0.784 17.49 0.576 A quartz crystal microbalance (QCM) is a piezoelectric microbal-
B-1212 434 17.29 0.789 18.83 0.619
ance used to measure mass per unit area by measuring the change
in the resonating frequency of a quartz crystal using its piezoelectric
B-742 427 17.18 0.792 18.01 0.593
properties.31 In addition, a dissipation value can also be recorded
B-1422 413 17.11 0.795 18.97 0.615
and used to quantify the damping of the system which can be used
B-1207 412 16.45 0.798 19.13 0.629 to determine the sample’s viscoelastic properties.32 The Q-Sense
B-1384 403 16.36 0.799 22.49 0.631 D300 Quartz Crystal Microbalance (QCM) system with an axial
B-1395 401 16.22 0.81 22.86 0.632 flow sample chamber (Q-Sense, Inc., Glen Burnie, MD) was used to
B-1382 378 16.03 0.812 23.46 0.649 evaluate polysaccharide film formation.33 Samples were gravity-fed
B-1390 373 15.36 0.819 24.01 0.678 into the crystal chamber. Flow rate was reduced to minimize
B-1216 369 15.2 0.821 24.15 0.694
incomplete mixing. The system was allowed to equilibrate in the
buffer for at least 10 min before addition of polymer solution to
B-1527 365 15.18 0.828 24.89 0.708
reduce drift. All experiments were conducted at 23 8C. Frequency
B-1254a 359 14.6 0.831 25.08 0.715
(and dissipation) shifts were recorded for all four frequencies (the
B-1211 354 14.57 0.835 25.67 0.768 fundamental frequency of 5 MHz and the 3rd, 5rd and 7th over-
B-1499 352 14.01 0.832 25.98 0.779 tones at 15, 25, and 35 MHz, respectively). Data were recorded
B-1145m 351 13.06 0.841 26.07 0.812 using Q-Soft 301 software version 1.6.16 and analyzed using Q-
B-1202 349 12.59 0.849 26.59 0.851 Tools software version 2.0.6.79 (software was supplied with Q-
B-1127 347 12.12 0.856 26.84 0.875 Sense system). Silicon dioxide crystals purchased from Q-Sense
B-1525 345 12.06 0.859 27.68 0.912
were cleaned by first rinsing in water followed by an ethanol rinse
and drying under a gentle nitrogen stream. The crystals were next
B-1205 343 11.77 0.868 28.57 0.951
placed into an UV/Ozone chamber (Bioforce Nanosciences, Ames,
H2O spray 294 10.59 0.871 29.32 0.965
IA) for 10 min. The crystals were submerged in 2–4% (v/v) sodium
Bare 289 9.114 0.872 30.14 0.992 dodecyl sulfate in nanopure water for 30 min to remove any biolog-
Rct is the diffusion limited charge transfer resistance, Cd is the diffusion ical contaminants followed by rinses with water and then ethanol,
capacitance across the film, Etafel is the corrosion potential as recorded drying with a nitrogen stream, and a final cycle in the UV/Ozone
from Tafel plots, icorr is the corrosion current, and c.r is the corrosion cleaner just prior to use. Experiments show the areal mass of the
rate. The first exopolysaccharides on the list (B-1254c) is the most effi-
cient corrosion inhibitor
film deposited on the quartz/stainless steel substrate.
Atomic Force Microscopy (AFM) imaging was conducted using
counter and saturated calomel electrodes were also inserted a multimode system equipped with a Nanoscope IV controller,
through a sealed cover. The working electrode area was E-scanner, and heater (Veeco, Inc., Santa Barbara, CA). A fluid
14.0 cm2. The cell was brought to a steady corrosion state after cell with a silicon o-ring was utilized to reduce evaporation. Sil-
24 h. The electrochemical impedance (EIS) experiment scanned icon nitride cantilevers with a nominal spring constant of 0.06
65 mV about the open circuit (corrosion) potential of the cell N/m were used. Cantilevers were cleaned by soaking in ethanol
with frequencies between 100 kHz and 10 mHz. A primer for for 15 min, allowed to air dry and exposed to UV/ozone for 10
the electrochemical experiments is available in Supporting min just prior to use. All images were taken in tapping mode,
Information. Polarization data were obtained by scanning 6250 using a minimum force to eliminate any artifacts created by the
mV around the open circuit potential. Scan rate was 0.166 mV/s, tip (minimum force was accomplished by maintaining the low-
the EW was calculated to be 27.925 g and the density of the cor- est drive amplitude and lowest set point amplitude possible
roding species was 7.8 g/mL. Working electrode area was without losing contact with the surface). Scan speed was set to
14.0 cm2. The change in resistance was used to evaluate the pro- 1–2.5 Hz. Si wafers (CDN Systems) were cut to size with a dia-
tective properties of 29 water-dispersible dextran-like exopoly- mond scribe prior to imaging. AFM scans over 20 lm wide
saccharides that were sprayed onto the metal substrate. scratches made in films deposited indicate that the

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Figure 1. Corrosion resistance and corrosion rate for 29 EPS coatings on low carbon steel. All standard deviations were less than 5% of the total value.
[Color figure can be viewed at wileyonlinelibrary.com]
polysaccharide polymers build a coating approximately 50–
500 nm thick depenidng on the number of layers applied by
spraying.
ATR measurements were performed with a Varian 3100 FT-IR
Excalibur Series fitted with a horizontal ATR heated plate from
PIKE Technologies with a 458 germanium (Ge) crystal. The
crystal was cleaned using 50:50 v/v ethanol/H2O with sonication
for 20 min and cleaned in a UV/Ozone chamber (Bioforce
Nanosciences, Ames, IA) for 10 min. The crystal was then
washed with 18 MX deionized water and dried with a stream of
nitrogen. Polysaccharide film deposition was carried out by cast-
ing a polymer solutions (100 mg/L) by letting it evaporate on
top of the Ge crystal.
RESULTS AND DISCUSSION
Corrosion Inhibition
Electrochemical impedance measures the ability of a circuit (in
this case, the solution-coating-metal system) to resist the flow
Figure 2. EIS spectra (Nyquist) for the top 4 EPS coatings. The bare
uncoated metal is represented by *, B-1254 L coating by D, B-1498 L by
‡, B-1355 by 䊊 and B-1254c by w.
WWW.MATERIALSVIEWS.COM 45032 (4 of 7)
of electrical current with a dependency on frequency and was
used to evaluate corrosion potential.34 See Supporting Informa-
tion for detailed information regarding interpretation of EIS
data. Impedance spectra taken shortly after exposure to the elec-
trolyte solution gave irregular results which we compensated for
this by allowing the coated substrate to hydrate for 24 h in
order to reach equilibrium. According to Fickian diffusion, the
overall density of ion flow in a system is the sum of ion diffu-
sion and ion conductivity.35 Conductive paths through the EPS
coating were undeveloped at the initial stage of exposure. The
only means for ion transport in the coatings is diffusion due to
difference in chemical potentials within the system. The diffu-
sion of ions and water through the coating (from the electrolyte
solution to the metal substrate) reduce the coating resistance
(commonly called, “pore resistance,” but represented here by
the charge-transfer resistance, “Rct,” of the coating and coating-
metal interface). Once the film is hydrated enough such that
Figure 3. Polarization spectra (Tafel) for the best four inhibiting exopoly-
saccharides. Better corrosion inhibition is denoted here by a shift in the
inflection point (Ecorr) toward less negative potentials (to the right). Leg-
end: Metal substrate (‡); B-1254 L (D); B-1498 L (w); B-1355 (䊊) and
B-1254c (x).
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45032
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Table III. Dynamic Contact Advancing and Receding Angles for Exopoly- have an obvious demarcation between coating and coating-
saccharides Exhibiting Good Corrosion Resistance metal impedance response conventionally shown by a division
between high frequency and low frequency data points.38 Better
Advancing Receding corrosion inhibition could be due to phenomena such as film
EPS contact angle contact angle formation kinetics, diffusion dynamics through the coating,
none 46.96 42.12 adsorption of the EPS coating to the metal surface and/or chela-
tion at the metal surface. Polarization curves (Tafel plots) can
B-1213 49.98 41.10
determine corrosion rate and the mechanism of the reaction
B-1501 54.68 42.17
(anodic, cathodic, or both). Figure 3 shows that both the anodic
B-1254L 76.97 44.21 and cathodic reactions are reduced by the EPS coating. Unpro-
B-1498L 77.90 67.54 tected bare metal (blank) shows steeper slopes and occur at
B-1254c 79.97 42.94 higher currents than its coated counterparts. Also, the EPS coat-
B-1355 83.06 67.85 ing tends to shift the open corrosion potential toward less nega-
tive values. These factors suggest that the exoplysaccharides act
predominantly as anodic-type corrosion inhibitors. Exopolysac-
conductive paths are formed, Rct is the sum of water diffusion
charide coatings inhibit corrosion by (1) forming a protective
and ion conduction through the coating.36,37 The anti-corrosive
barrier between the metal substrate and the corrosive environ-
behavior of the EPS is related to coating structure, adherence to
ment (salt solution) and slowing down the diffusion of corrod-
the substrate and the diffusion rate(s) of the corrosive species
ing species through the coating; and (2) adhering to the surface
once hydrated.
and reacting with the metal surface to create a passive layer
Table II tabulates several important parameters obtained from thus blocking the corroding species from the surface.18
impedance and polarization experiments: corrosion rate (c.r.),
The surface of the EPS coating is hydrophilic as determined by
corrosion current (icorr), corrosion potential (Etafel), diffusion
dynamic contact angles that are less than 908 shown in Table
capacitance (Cd), and charge transfer resistance (Rct). Larger
III. We chose the top six EPS coatings. In dynamic contact
values of the Cd and Rct indicate slower processes leading to
angle measurements, larger angles correspond to more
less corrosion and smaller corrosion rates (c.r.). The exopolysac-
charides are arranged in order of their corrosion rate which is
inversely correlated to polarization resistance (Figure 1). Experi-
mental Nyquist plots for the best four performing polysacchar-
ides films (Figure 2) give Rct values based on extrapolated
intercepts. The higher the radius of the semicircle, the higher
the Rct value and the better protection the coating provides.
The solution (NaCl) resistance was found to be approximately
3.6X in all cases. Inspection of bode phase angle plots (from
which the Nyquist plot in Figure 2 is derived) suggest the exis-
tence of a dominant maxima and hence a single dominant con-
stant. The coating contribution is evident in terms of an
increase in overall impedance. Also, the Nyquist plot does not

Figure 5. QCM determination of coating deposition (B-1254c). (A) There

Figure 4. ATR-FTIR spectra during the hydration of an exopolysaccharide
coating (B-1254c). The water peak around 3300 cm-1 is monitored for an
increase and shown in the inset. Peaks from 1450 to 900 cm21 pertain to
the polymer. The EPS film fully hydrates in less than 5 min, after which
the area of the water peak ceases to increase.
is little change in adsorbed mass upon subsequent polymer solution and
water rinses suggesting a homogeneous, well adsorbed film weighing
720 ng/cm2. (B) The quartz response during film deposition (air, water,
exopolysaccharide solution, and then drying under nitrogen). The 0 point
on the y-axis represents the behavior of the sample in a water medium.

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Figure 6. AFM images of an exopolysaccharides coating (B1254c) (left) and its subsequent healing upon a 30 s exposure to water (right). Profilometry is
displayed below the AFM image. [Color figure can be viewed at wileyonlinelibrary.com]
hydrophobic surfaces. The receding angle is lower than the
advancing angle because the EPS coating absorbs water and the
coating swells. We explored the EPS coating hydration phenom-
enon using ATR-FTIR.
Coating Evaluation
Exopolysaccharide solutions were cast out of aqueous solutions
onto the ATR crystal and the resulting film was allowed to take
up water and dry in monitored sequences.39 Figure 4 shows the
hydration of a 60 nm thick representative sample of an EPS
coating (B-1254c). We observed a change in the water peak area
present at 3300 cm21 corresponding to hydration/dehydration
of the film. The data suggest that most exopolysaccharide films
fully hydrate in less than 5 min.
QCM experiments show that approximately 720 ng/cm2 is being
deposited (Figure 5). The areal mass difference related to the
coating deposition occurs in a repeatable fashion [Figure 5(A)].
Subsequent addition of exopolysaccharide solution does not add
extra polymer to the thin coating. This experiment suggests the
formation of a coating which adheres well to the metal substrate
and does not peel off during successive rinses. The film reaches
its maximum thickness after approximately 10 min. The data
suggest the kinetics of film deposition are fast (<5 min) and
there is little excess (loosely bound) material coming off during
rinses in water. Figure 5(B) shows film deposition from a poly-
mer solution and subsequent rinsing and drying. It shows a
similar areal mass for the coating [lower right corner of Figure
5(B)]. Future experiments will explore viscoelastic properties of
the coatings and data regarding the adhesive forces in the
coating-metal system.
WWW.MATERIALSVIEWS.COM
AFM is routinely used to construct images with nanometer res-
olution by rastering a small tip mounted on a cantilever across
the sample surface. The samples were imaged in tapping mode.
AFM imaging of exopolysaccharide films on surrogate Si wafers
show an overall thickness of 45–65 nm by measuring the depth
of a scratch in the coating (Figure 6). Interestingly, after the dry
coating was exposed to water for 30 s, the exopolysaccharides
coating “healed” the scratch. The cross-sectional view of the
scratched surface shows 400 nm tall residual ridges on either
side of the scratch formed displaced material. The AFM image
shows the scratch being filled in. The original edges are still vis-
ible but the polymer film slides in toward the center of the
scratch where it meets. Hydration-dehydration experiments
show that the EPS coatings absorb water without causing the
coating to delaminate from the metal surface, and can allow the
excess material along the scratches to flow and then adhere to
the metal surface. Further studies will be conducted on the
coating structure and the diffusion parameters of ionic species.
CONCLUSIONS
Bio-based polymers, produced from lactic acid bacteria in a
commercially available process, have shown to inhibit corrosion
on low carbon steel substrates. Extensive electrochemical analy-
ses showed that the exopolysaccharide, purified from cell-free
cultures, adhered strongly to the metal substrate, provided
active resistance to corrosive environments, and displayed limit-
ed self-healing after scratching. The coating is applied through
commercial spray technology with a controlled thickness of 50–
500 nm. Hydration phenomenon, ion diffusion, and viscoelastic
45032 (6 of 7) J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45032
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properties of the exopolysaccharide coatings will be investigated
in the future.
ACKNOWLEDGMENTS
This work was funded in part by CSREES-USDA Critical Agricul-
tural Materials Program. The Midwest Area of the Agricultural
Research Service (USDA) funded a summer undergraduate fellow-
ship for Eru Kyeyune-Nyombi to support Project 3620–41000-
157–03, “Agricultural Polymers for Prevention of Corrosion on
Metals.” The authors thank Richard Haig for technical support.
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J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.45032
SUPPORTING INFORMATION

Bacterial exopolysaccharides for corrosion resistance on low carbon steel

Victoria L. Finkenstadt1*, Claudiu Bucur**, Gregory L. Côté 2, and Kervin O. Evans2

1
Plant Polymer Research
2
Renewable Product Technology Research

National Center for Agricultural Utilization Research, Agricultural Research Service, United
States Department of Agriculture, 1815 North University Street, Peoria, IL 61604

*corresponding author: victoria.finkenstadt@ars.usda.gov, tel: 309-681-6469

**Current address: Environment, Analysis, and Future Battery, Toyota Motor Engineering &
Manufacturing North America, Inc., 1555 Woodridge Avenue, Ann Arbor, MI 48105;
claudiu.bucur@tema.toyota.com

Electrochemical Experimental

The AC current and voltage signal through the resistor (corrosive solution) do not need to

be in phase with each other. EIS is measured experimentally by applying a small AC excitation

signal (5 mV in our experiments) to the electrochemical cell and measuring the current response.

Given that the cell’s response is pseudo-linear, the current response will be a sinusoid at the

same frequency but shifted in phase.

Expressing the impedance Z analogously to Ohm’s Law gives

Et
Z= , (S1)
It

where Et is the AC excitation signal as a function of time, as follows

Et = E0 sin(ωt ) (S2)

with E0 the amplitude of signal, ω=2πf, or the radial frequency with units of radians/second and f

is frequency in Hz.
 E
Zω = = Z 0 exp( jφ ) = Z 0 (cos φ + j sin φ ) (S3)
I

Plotting the real part of equation (3) on the x-axis and the imaginary part on the y-axis

displays a Nyquist plot. In this plot the impedance is a vector of length Z from the origin to any

data point. The angle between this vector and the x-axis represents the phase angle φ. When this

data is fitted to a circuit, the first x-axis intercept corresponds to the resistance of the solution

(RΩ) and the second x-axis intercept corresponds to the film resistance (Rp) associated with the

corrosion inhibiting film covering the metal substrate 40.

Two important parameters often used in characterizing the corrosion protection offered

by a film are the corrosion rate and the corrosion current (icorr) 41. The corrosion current can be

calculated with the aid of a Tafel plot and the polarization resistance Rp obtained from the

Nyquist diagram. Plotting a modified Tafel plot with the x-axis in terms of I (not log i) can also

∆η
obtain Rp as the slope of the line ( = R p by definition). Rp can thus be calculated with
∆i

certainty with two independent methods.

In our cell, the anode undergoes uniform corrosion at the open circuit. The open circuit

potential is controlled by the equilibrium between two different electrochemical reactions, one of

which generates the cathodic current and the other the anodic current. The open circuit potential

translates into the equilibrium between the two. It is a mixed potential and the value of the

current for either of the reactions is known as the corrosion current.

The cell potential relates to the current as follows

2.303( E − Eoc ) −2.303( E − Eoc )

βa βc
I = I corr (e −e ) (S4)
 where I is the measured current in amps, Icorr is the corrosion current in amps, Eoc is the open

circuit potential in volts, βa is the anodic Beta coefficient in volts/decade, βc is the cathodic Beta

coefficient in volts/decade. The Beta coefficients can be obtained from the slopes of the linear

portions of the two adjoining lines in the Tafel plot.

Rearranging equation (4) gives

βa βc 1
I corr = ⋅ (S5)
2.303( β a + β c ) R p

∆η
where Rp is from the linear polarization plot.
∆i

The corrosion current can be related directly to the corrosion rate (c.r) through the

following equation

0.13 ⋅ I corr ⋅ EW
c.r (mpy ) = (S6)
d

where EW is the equivalent weight of the corroding species (g) and d is the density of the

corroding species (g/cm3). Corrosion rate is expressed as milli-inches per year (mpy).

Tafel plots give numerical insight into the corrosion potential (which, given enough time

for steady state conditions to be met will equal the open circuit potential). In a corroding system,

two co-existing electrochemical reactions are present

M + + e− ↔ M (S7)

Z + + e− ↔ Z (S8)

where M is the corroding metal and Z is usually a species in solution or a second metal present;

in this case, the graphite electrode in our cell 42. The corrosion potential is the potential at which

the rate of oxidation of M is equal to the rate of reduction of Z+. Here “rate” and “current” can

be used interchangeably since they are directly proportional according to equation 5.

40. K’Owino, I. O.; Sadik, O. A. Electroanalysis. 2005, 17, 2101.

41. Allongue, P.; Blonkowski, S.; Souteyrand, E. Electrochim. Acta. 1992, 37, 781.
42. Posner, R.; Giza, G.; Vlasak, R.; Grundmeier, G. Electrochim. Acta. 2009, 54, 4837.

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