Journal of Polymer Research (2021) 28:104

https://doi.org/10.1007/s10965-021-02461-w

ORIGINAL PAPER

Evaluation of a rapid and long‑effective pickling method for iron rust

removal on metallic surfaces using carboxylic acid‑based polymers
Antonio Guerra‑Contreras1,2 · Abygail Camacho‑Ramírez2,3 · Miguel Olvera‑Sosa2,3 · Raúl González‑García2,3 ·
Gabriela Palestino2,3 

Received: 25 August 2020 / Accepted: 18 February 2021

© The Polymer Society, Taipei 2021

Abstract
This paper reports an alternative pickling method for rust removal on metallic surfaces using poly(acrylic acid) and
poly(acrylic acid-co-itaconic acid). Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance
(NMR), thermogravimetry (TGA), static light scattering (SLS), and scanning electron microscopy (SEM) were performed
to determine polymer and copolymers formation, thermal properties, molecular weights, and the morphological analysis
of polymers, respectively. Through an experimental design, polymers’ response was determined in terms of the synthesis
parameters. It was observed that both the initiator and the monomers’ molar ratio significantly affect the value of the polymers’
molecular weight. In contrast, for the rust removal, only the initiator had influence. The rust removal process was carried out
by the carboxylic acid groups’ adhesion properties, which interacted with the oxidized plates’ polar hydroxyl groups. This
method provides an effective and environmentally friendly way to rust removal on metallic surfaces compared with traditional.

Keywords  Radical Polymerization · Poly(acrylic acid) · Pickling Polymers · Adhesiveness · Rust Removal

Introduction actively enduring corrosive agents such as moisture, acids,

The high cost of corrosion affects numerous industries,
domestic applications, and public sectors worldwide and
highlights the need for improving corrosion measure
methods. In the oil, gas, and chemical industries alone,
corrosion is one of the most challenging tasks [1]. Carbon
steel (CS) is used as the preferred construction material
across various applications, including structural components,
industrial pipes, and kitchen appliances [2, 3]. In the early-
stage, most metallic materials, including carbon steel,
* Gabriela Palestino
palestinogabriela@uaslp.mx
1
Departamento de Química, División de Ciencias Naturales
y Exactas, Universidad de Guanajuato, Campus Guanajuato,
Col. Noria Alta s/n, 36050 Guanajuato, Gto, México
2 as hydrochloric acid (HCl) should be avoided since there is an
Laboratorio de Biopolímeros y Nanoestructuras, Facultad
de Ciencias Químicas, Universidad Autónoma de San Luis
Potosí, Av. Dr. Manuel Nava No. 6, 78210 San Luis Potosí,
México
3
Sección de Biotecnología, Centro de Investigación en
Ciencias de la Salud y Biomedicina, Universidad Autónoma
de San Luis Potosí, Avenida Sierra Leona 550, Lomas
Segunda Sección, C.P. 78210 San Luis Potosí, Mexico
bases, salts, oils, and contaminants. However, over time,
these corrosive agents attack the material’s surface and cause
corrosion, resulting in damage to the entire material [4].
Therefore, to eliminate the metal corrosion and restore
CS surface quality, a cleaning process is often required.
Nowadays, the strategies for rust removal have been
diversified and include chemical and mechanical methods,
and sometimes a combination of both. Among the most used
are sandblasting, shot blasting, manual polishing, and pickling
acid [5]. In a large-scale plant, the pickling acid method is
generally the primary option. It is commonly-adopted for its
flexibilities and adaptabilities in continuous production to
clean work-pieces with complex shapes and structures [6].
A routine industrial pickling process typically uses an acid
mixture containing 8–20 vol% nitric acid ­(HNO3) and 0.5–5
vol% hydrofluoric acid (HF). Chloride-containing agents such
obvious risk of pitting corrosion [7, 8].
Although pickling acid is the most used corrosion
removal method, it has certain drawbacks from electrolytic
treatment. One is related to applying repeated cycles over
time, which might decrease mechanical properties and
induce hydrogen formation. This last can be incorporated

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 104   Page 2 of 13
into the material, causing the metallic piece’s fragility [9].
Thus, to overcome the issues related to pickling acid (mainly
those associated with the production of toxic vapors and
environmental contamination), green methods such that
based on iron-oxidizing and iron-reducing bacteria have
been developed with promising results [10].
The laser beam has also been proposed as a not polluting
method to remove paint, rust, and grease from surfaces [11,
12]. The advantage is that laser cleaning does not need any
abrasive or chemical media. However, the laser type and
optimal parameters should be selected according to the
application. In this regard, Narayanan et al. [13] performed
experiments on rusted and pure mild steel samples to
determine the laser parameters’ effect in the de-rusting
process. They found that for laser rust cleaning, a range
of parameters on which cleaning satisfaction exists. For
instance, with low speed and a high number of scans, the
surface gets damaged, which seems to be a combined effect
of corrosion and deformation. Although laser cleaning is
considered a promising technique to remove rust, it has the
disadvantage that a long time laser exposition can strongly
affect many metal parts’ surface properties.
In the same framework, our group recently reported a
new environmentally friendly method that uses poly(acrylic
acid-co-itaconic acid) hydrogel partially neutralized with
sodium hydroxide for rust removal [14]. In this work,
we demonstrate that hydrogel is a suitable material for
eliminating rust grown on carbon steel and metallic
copper plates. The pH of the hydrogel swelling was found
critical for rust removal capability. Acidic pH was more
effective than basic pH in both CS and copper surfaces. The
maximum iron rust removal was 269 mg g−1 of the hydrogel,
equivalent to 0.106 g cm−2 of the metal surface. This value
was almost four times greater than the reported in similar
work (0.028 g cm−2 of the metal surface) [10].
Therefore, based on our previous method’s promising
results and with the idea of fulfilling the industrial
requirements that request an easy-to-application rust removal
product capable of adapting to different surface geometries
and large surface areas. We propose in this work a rapid
and long-effective polymeric system based on poly(acrylic
acid) (PAA) and poly(acrylic acid-co-itaconic acid) (PAA-
co-IA). The polymers were not crosslinked to preserve the
adhesive properties of carboxylic acid groups (COOH). In
this way, the polymeric film was allowed to interact with the
rusted surfaces through cohesive forces providing an easy-
environmentally friendly way to eliminate corrosion from
metallic surfaces.
The synthesis of both polymers was conducted by
free radical polymerization. The copolymer properties
as a function of monomers ratio (AA:IA) and initiator
concentration were determined and discussed. It was
established the ability of polymeric films to remove surface
13
Journal of Polymer Research (2021) 28:104
rust from carbon steel plates. Through an experimental design
with response surface statistical analysis, it was determined
the influence of the synthesis parameters on rust removal
capacity and the average molecular weight of polymers.
Experimental
Materials
Acrylic acid (Fluka) and itaconic acid (Sigma-Aldrich)
analytical pure grade were used as monomers. 2,2′-Azobis(2-
methylpropionamidine) dihydrochloride (Sigma-Aldrich)
was used as an initiator. All reagents were used as received
without further purification. Deionized water was used as the
solvent. The HPLC-grade toluene and HPLC-grade water
used in the molecular weight calculations were purchased
from Karal (Mexico) and were sonicated 20 min before use
to remove bubbles.
Design of experiments (DOE)
Design of experiments (DOE) and a contour plots analysis
were performed to understand better the synthesis
parameter’s impact on the PAA and PAA-co-IA polymers’
physicochemical and morphological properties. These
powerful tools help identify those factors that significantly
affect the synthesis, the polymer’s removal capabilities,
and the determination of the optimal levels of each of these
variables [15–17]. Polymer removal capacity and the average
molecular weight ­(MW) of the synthesized polymers were
evaluated using a central composite design centered on
face “CCF”. The factors were varied together, allowing the
elaboration of contour plots using MINITAB® 16 software.
The studied parameters were: % initiator (% I) and the
monomer ratio (AA:IA). The used model was defined in
Eq. 1 as follow:
yPMw = b0 + b1 𝛼 + b2 𝛽 + b3 𝛼 2 + b4 𝛽 2 + b5 𝛼𝛽 (1)
where bn are linear regression coefficients, α and β are
independent variables (shown in Table 1). The coefficient of
determination R2 was used to estimate the fit quality of the
model. The interaction parameters of the model were evaluated
using an analysis of variance (ANOVA) by mean P-value
Table 1  Experimental values and coded levels of independent vari-
ables
Variables Coded Levels
% Initiator α 0.2 0.4 0.6
Monomer ratio β 0.8 0.9 1.0
(AA:IA)
Journal of Polymer Research (2021) 28:104 Page 3 of 13  104

(P < 0.05) for two responses: 1) mg of iron oxide removed/g
of polymer and 2) the average molecular weight values.
Synthesis of PAA and PAA‑co‑IA
The synthesis of both polymers was performed via free
radical polymerization. For PAA, 8  g of acrylic acid
(109.6 mmol) were dissolved in 25 mL of deionized water
and placed in a 50  mL round bottom two-necked flask
equipped with a thermometer. The solution was vigorously
stirred and heated at 60ºC; after reaching the temperature,
the initiator, previously dissolved in 5  mL of deionized
water, was added. The concentration of the initiator was varied
from 0.2 wt% to 0.6 wt% concerning the monomers. The
progress of the reaction was monitored by FTIR based on
the disappearance of the C = C band (1680 cm−1). At the
end of the reaction, the polymer was recovered by adding
deionized water to the flask to dissolve the reaction product.
Subsequently, it was centrifuged at 5000 RPM for 20 min
using a 10 kDa millipore membrane to remove the initiator
and the excess residual monomer. Finally, the polymer
was dried at 50 °C for 24 h in a conventional oven. For
the synthesis of the copolymer (PAA-co-IA), the same
procedure described above was followed. Acrylic acid/
itaconic acid (AA/IA) ratio in the copolymers ranged from
100:0 to 80:20, respectively. Table 2 shows the amounts of
% of initiator, acrylic acid, itaconic acid, and reaction time
for each monomer ratio.
Iron rust formation
drops of NaCl (5% w/w). This procedure was repeated each
24 h for the steel during a month. During treatment, the
samples were maintained in a home-made acrylic chamber.
Water vapor was introduced periodically into the chamber
to maintain an atmosphere with constant relative humidity.
This process helped promote rust growth and simulate
the humid environment necessary to generate atmospheric
corrosion conditions.
Removal of metal rust
The oxides removal was carried out in a series of steps.
First, the polymer film was cut and then weighed on an
analytical balance. After that, the PAA film was immersed
in deionized water (pH = 6.5) for 5 s to produce superficial
carboxylate anions (­COO−). Subsequently, the oxidized
plate was wholly covered with the polymer film and allowed
to contact for a drying time of 3 h. Finally, the polymeric
dry film was pulled off from the plate. The amount of metal
oxide removed was determined by gravimetric methods,
according to Eq. 2. Figure 1 shows the removal process for
a plate with iron oxide.
( )
mgofrustremoved Wcp − Wtp
= (2)
gofpolymerapplied Wp
where Wcp is the weight (mg) of the corrode plate, Wtp is the
weight (mg) of the treated plate after polymer peel off, and
Wp is the weight (g) of the polymer before being applied.

The procedure for the growth of iron oxide was reported

in our previous work [14]. Briefly, plates of carbon steel
and copper with dimensions of 1 × 1  cm were used to
grow a controlled layer of rust. In the first step, natural
contaminants were eliminated from the surface plates
using water sandpaper (No. 320). Then, the oxide layer was
controlled grown by wetting the metallic surface with a few

Table 2  Amounts used for the synthesis of PAA and PAA-co-IA

Monomer ratio AA IA %I Initiator t
(AA:IA) (mmol) (mmol) (mmol) (min)

80:20 87.4 18.2 0.2 0.064 30

0.4 0.128 30
0.6 0.192 30
90:10 98.4 9.1 0.2 0.061 30
0.4 0.122 15
0.6 0.183 15
100:0 109.6 0.0 0.2 0.058 5
0.4 0.116 3 Fig. 1  Removal process of iron oxide grown on a carbon steel sur-
0.6 0.174 2 face: (a) rusty plate, (b) application of the polymeric film, (c) rust
removal by pulling off and (d) clean plate after the pickling process

13
 104   Page 4 of 13
Characterization
To confirm the formation of the polymer and copolymers,
Fourier transform infrared spectroscopy (FTIR) and
nuclear magnetic resonance (NMR) were used. A Cary 660
spectrometer, coupled with an attenuated total reflectance
(ATR) accessory, was used for FTIR analysis. All the FTIR
spectra were obtained at room temperature with a resolution
of 4 cm−1 and 64 scans. The NMR spectra were acquired
on a 500 MHz Bruker Avance III HD spectrometer and
using ­D2O as the solvent. The experimental parameters
were: D1 = 1 s, NS = 36. The thermal stability of the PAA
and PAA-co-IA was determined by using a TA Instrument
Q500 TGA. The samples were placed in an aluminum
pan and heated from 30 to 500°C with a heating rate of
10°Cmin−1. During heating, the nitrogen flow rate was kept
at 20 ­mLmin−1. A Zetasizer Nano-ZS Malvern Instruments
was used to calculate the average molecular weight (­ Mw)
and second virial coefficient (­ A2) of PAA and PAA-co-IA.
The Static Light Scattering (SLS) analysis was conducted
using a He–Ne laser with a wavelength λ = 632.8 nm. The
light was detected at an angle of 173º and a temperature
of 25ºC in automatic duration mode. The cuvette was
cleaned meticulously with deionized water and force-dried
using compressed air between measurements. The values
were calculated as a function of the concentration: at low
concentrations, ­Mw for a specific volume was determined
from the KC∕R(𝜃) as a function of Sin2 (𝜃∕2) (Debye Plot).
The intersection with the y-axis yields the ­Mw, while the
­A2 value was obtained from the same plot by limiting
the projection angle to zero [18, 19]. The morphological
analysis and the elemental composition of the polymers
before and after the rust removal process were carried out
in a Quanta FEG 250 scanning electron microscope coupled
Fig. 2  Polymerization mechanism for PAA-co-IA via free radicals using 2,2′-Azobis(2-methylpropionamidine) dihydrochloride as initiator
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Journal of Polymer Research (2021) 28:104
with an elemental analysis accessory (SEM/EDS) operated
at voltages of 20–25 kV, magnifications of 50, 100, 250 and
500X were acquired. Finally, crystalline phases analysis of
oxides grown on the plates was determined in a Bruker D8
Advance da Vinci X-ray diffractometer (XRD) using Cu Kα
radiation (λ = 1.5406 Å).
Results and discussion
Copolymer formation (PAA‑co‑IA)
The polymerization of acrylic acid and itaconic acid via
free radical is an efficient method to obtain polymers and
copolymers [20]. It is well known that the reaction is carried
out by adding a catalyst that generates a homolytic breaking
in the presence of temperature, attacking the double bonds
present in the monomers. At the end of the reaction, the
increase of viscosity in the solution indicates the polymer
formation, decreasing the stirring rate. The yield of the
reactions ranges from 90–94%. Figure  2 describes the
reaction mechanism for PAA-co-IA.
Physicochemical characterization of PAA
and PAA‑co‑IA
Fourier transform infrared (FTIR) analysis
In order to confirm the formation of poly(acrylic acid) (PAA)
and poly(acrylic acid-co-itaconic acid) (PAA-co-IA), an
FTIR study was carried out. FTIR spectra of PAA (Fig. 3b),
PAA-co-IA (Fig.  3d), as well as acrylic acid (AA) and
itaconic acid (IA) monomers (Fig. 3a, c, respectively), were
recorded to have appropriate references. The polymerization
Journal of Polymer Research (2021) 28:104 Page 5 of 13  104
Fig. 3  Fourier transform
infrared spectra of (a) acrylic
acid (AA),(b) Poly(acrylic acid)
(PAA),(c) itaconic acid (IA) and
(d) Poly(acrylic acid-co-itaconic
acid) (PAA-co-IA) in a molar
ratio of 80:20 (AA:IA)
reaction of AA and IA was followed by analyzing
the changes in the fingerprint zone (700–1000  cm −1)
attributed to the alkene substitution patterns [21, 22] and
in the characteristic band at 1620 cm−1 associated with the
unsaturated hydrocarbon chain (C = C).
As expected, the FTIR spectra of PAA and PAA-co-IA
are characterized by relatively broad and conformationally
sensitive backbone modes and hydrogen-bonded COOH
modes. It can be seen that PAA and PAA-co-IA Fourier
transform infrared spectra show quite similar features. It
was observed for both polymers an important sharp band
at 1710  cm −1 assigned to carbonyl group vibrations of
the carboxylic acid groups (R-COOH). Besides, wide and
low-intensity stretching bands characteristic of OH and
CO modes were observed at 3020 and 1160–1240 cm−1,
respectively [22, 23] coupled with an OH in-plane bending
mode. Moreover, the asymmetric stretching band of
methylene ­(CH2) groups was observed at 2927 cm−1, while
twisting vibration mode, corresponding to the polymer’s
backbone where all the methylene groups oscillate in phase,
was found at ~800 cm−1. The absence of the infrared band at
1620 cm−1, which corresponds to the monomers’ CH = CH2
bond, in Figs.  3b, d corroborates PAA and PAA-co-IA  monomer conversion (%) =
formation.
Nuclear magnetic resonance (NMR)
NMR analysis was carried out to corroborate the addition
of itaconic acid (IA) in the copolymers. Figure 4a–c shows
the 1H-NMR spectra, before purification and using 0.2%
of initiator, for PAA, PAA-co-IA 90:10, and PAA-co-IA
80:20. The methylene ­(CH2) and methine (CH) protons
of the poly(acrylic acid) (PAA) backbone show signals
at 1.4–2.1 (1) and 2.2–2.9 (2) ppm, respectively. The
OH signal of carboxylic acid groups can be seen at 4.35
(3) ppm (Fig. 4a). These chemical shifts are consistent
with those reported in the literature for poly(acrylic acid)
[24–26]. Figure 4b shows the spectrum of the PAA-co-IA
90:10 copolymer corresponding to 10% of IA. It can be
seen that the spectrum shows the same signals as PAA,
and additionally, it shows a new signal at 2.21 (4) ppm
that is assigned to methylene (­ CH2) of itaconic acid. When
20% of IA is added (Fig. 4c), it can be seen that the signal
corresponding to the methylene ­(CH2) of itaconic acid is
shifted upfield slightly at 2.19 (4) ppm. These 1H-NMR
chemical shifts give clear evidence of the formation of the
copolymers.
Also, monomer conversions from the spectra in Fig. 4
were determined, which corresponds to the products before
purification. The degree of total monomer conversion was
calculated using Eq. 3 by comparing the relative intensities
of the methylene (­ CH2) and methine (CH) protons of the
polymer and copolymer backbones and the vinyl protons
(CH = CH2) at 5.8–6.5 ppm, which occur due to unreacted
monomer.
ICH 2 + ICH
x100 (3)
ICH=CH 2 + ICH 2 + ICH
where ­I CH2, ­I CH, and I­CH=CH2 are the integrals under
the ­C H 2, CH, and CH = CH 2 peaks, respectively. The
values obtained for PAA, PAA-co-IA 90:10, PAA-co-IA
80:20 were 96, 96, and 89%, respectively. The monomer
conversion was found to decrease with increasing itaconic
acid concentration. This may be due to the steric hindrance
of the two carboxylic acid groups in the IA, which causes a
slower diffusion rate of monomers and hence a decrease in
monomer conversion.
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 104   Page 6 of 13
Fig. 4  1H-NMR spectra in ­D2O before purification of (a) PAA, (b) PAA-co-IA 90:10, and (c) PAA-co-IA 80:20
Thermogravimetric analysis (TGA)
The derivative thermogravimetry (DTG) was performed
to confirm the PAA-co-IA formation and determine the
polymers’ thermal stability. The DTG results of PAA and
PAA-co-IA at different molar ratios are shown in Fig. 5.
It is well known that PAA shows three degradation steps.
The first stage is related to dehydration reaction above
150°C or ~170°C, due to intramolecular reaction between
two carboxyl groups to form anhydride ring. The second
step consists of the anhydride ring’s decarboxylation at
250–350°C, observed at 270°C in Fig.  5a. Finally, the
third stage occurs above 350°C, which corresponds to
the polymeric hydrocarbon chain degradation. This last
degradation temperature was identified at 400°C in Fig. 5a.
These findings are consistent with the data described in the
literature for PAA [27–29].
Figure  5b shows the PAA-co-IA copolymer at 90:10
molar ratio. It can be seen that the presence of 10% of IA
in the PAA induces a new decomposition temperature at
230ºC, which agrees with the signature of pure IA that we
previously reported [14], confirming the formation of the
copolymer. Finally, Fig. 5c shows the DTG with 20% of
IA grafted to PAA. In the thermogram, a high amount of
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Journal of Polymer Research (2021) 28:104
mass lost at 240°C and a slight shift from 410 to 412°C is
observed, which is consistent due to the excess of itaconic
acid compared to Fig. 5b. The presence of IA resulted in
the decrease of thermal stability in both copolymers, and
the mass loss was more significant when added a higher
amount of IA [30]. These results provide clear evidence of
the copolymer formation and seem to impact the degradation
and stability of PAA-co-IA substantially.
Mw and ­A2 of PAA and PAA‑co‑IA
The intensity of scattered light that a particle produces is
proportional to the weight-average molecular weight and
the concentration of the particle [19]. The zetasizer Nano
ZS measure the intensity of scattered light ( KC∕R(𝜃) ) of
various concentrations ( C  ) of sample at one angle; this is
compared with the scattering produced from a standard. The
graphical representation of this is called a Debye plot and
allows for the determination of both the absolute molecular
weight ­(MW) and second virial coefficient (­ A2) [18]. The
physicochemical characterization using the Static Light
Scattering (SLS) technique was carried out to determine the
­MW and A ­ 2 of PAA and PAA-co-IA. The average scattering
intensity for different concentrations of PAA and PAA-co-IA
Journal of Polymer Research (2021) 28:104 Page 7 of 13  104

Fig. 5  Thermogravimetric
analysis of (a) Poly(acrylic
acid) (PAA), (b) Poly(acrylic
acid-co-itaconic acid) (PAA-co-
IA) in a molar ratio of 90:10
(AA:IA) and (c) PAA-co-IA in
a molar ratio of 80:20 (AA:IA)

in deionized water (0.3 g cm−3 to 3.5 g cm−3) was recorded.
Based on the data in Table 3, it can be seen that for PAA,
the molecular weight decreases when the amount of initiator
increases; this is because a greater number of active centers
are generated, which interact rapidly with the monomers
giving short chains during the grown step. On the other
hand, for PAA-co-IA with molar ratios of 90:10 and 80:20
(AA:IA) there is no tendency with the amount of initiator in
the reaction; however, it can be observed that when adding
a higher amount of itaconic acid, the molecular weight
decreases, this is due to steric hindrance of the carboxylic
groups in the itaconic acid which play an essential role during
the synthesis. The polymer–solvent interactions characterized
by ­A2 indicate that deionized water is a good solvent for
these polymers. Hara and Nakajima [31] reported a value of
weights of PAA (from 1.3 × 105 to 56 × 105 ­gmol−1) using
1,4-dioxane as solvent [32]. The ­A2 value is critical to the
determination of solubility. It is important to highlight that
the ­A2 values for PAA and PAA-co-IA obtained in deionized
water have not been previously reported.
Figure  6 shows the Debye plot of PAA with 0.2%
I. The squares represent the experimental points for
each concentration analyzed in this figure, while the
line represents the automatic linear fit using Malvern
Instruments Software. The M ­ W was determined from the
intercept at zero concentration, i.e., KC∕R(𝜃) = 1/MW (for
c → 0), and the ­A2 was determined from the gradient of
the Debye plot. For this sample, the values obtained for
­MW and A ­ 2 were 77.22 ± 0.27 kDa and 1.11 ± 0.13 (× 10–2)
­cm molg−2, respectively.
3

­A2 = 1.3 × 10–3 ­molcm3g−2 for PAA solutions in 0.1 M NaCl

indicating that NaCl is a good solvent. Wohlfarth reported
­A2 values of 1.0–7.0 × 10–3 ­molcm3g−2 for several molecular

Table 3  SLS measured experimental values of PAA and PAA-co-

IA. The linear regression gives the fit error to different concentration
data. Triplicate measurements were performed to check repeatability

Monomer ratio %I MW A2 × 102

(AA:IA) (kDa) (cm3molg−2)

100:0 0.2 77.2 ± 0.3 1.1 ± 0.1

0.4 35.9 ± 10.7 2.1 ± 0.8
0.6 32.3 ± 8.6 0.8 ± 0.3
90:10 0.2 48.3 ± 19.3 1.5 ± 0.4
0.4 41.9 ± 7.8 3.9 ± 0.3
0.6 43.8 ± 18.3 2.5 ± 0.5
80:20 0.2 13.7 ± 0.9 2.6 ± 0.2
0.4 17.7 ± 2.4 2.1 ± 0.2
0.6 16.6 ± 4.1 4.2 ± 0.9 Fig. 6  Debye plot of PAA with 0.2% I. The squares represent the
experimental points and the line represents the automatic linear fit

13
 104   Page 8 of 13
X‑ray diffraction analysis (XRD) of grown iron oxide
A wide-angle X-ray scattering (WAXS) analysis was
conducted to determine the crystalline phases of rust on
carbon steel plates (diffractograms not shown here). We
previously reported [14] the crystalline phases found in
the grown iron rust and compare them with the appropriate
crystallographic cards. The following characteristic peaks
were found: Akaganeite-Q ­(Fe3+O(OH)) with the principal
crystalline planes (110), (200), (310) (211), (301) and (521),
Lepidocrocite (FeO(OH)) with the planes (020), (021), (130)
and (002), Goethite (­ Fe3+O(OH)) with the planes (110),
(111) and (221), and halite (NaCl) with the planes (200) and
(220). These results indicate that several crystalline phases
are produced during the corrosion process. It is important
to point out that the identified phases corresponded to iron
oxyhydroxides instead of iron oxides. The halite phase’s
presence is attributed to the remaining electrolyte solution
used during the corrosion process, which agrees with the
elemental analysis performed by EDS.
Evaluation of the iron oxide removal
Morphological analysis
The iron oxide morphology and thickness before and after
the removal process were investigated using SEM/EDX
analysis. Figure 7a shows the side view of the iron plate with
the rusting process. The plate’s bottom was intentionally
Fig. 7  SEM micrographs of (a) rusty iron plate 1 (δ =  ~ 371 µm), (b) EDX of sanded plate of carbon steel, (c) iron rusty EDX, (d) plate after
removal process using PAA, (e) rusty iron plate 2 (δ =  ~ 191 µm) and (f) plate after removal process using PAA-co-IA
13
Journal of Polymer Research (2021) 28:104
sanded to quantify the thickness of oxide grown on its
surface; it can be observed a detachment of this oxide.
It is important to note that because the oxidation growth
process was carried out in an acrylic chamber simulating
atmospheric corrosion conditions, the thickness does not
grow uniformly, obtaining an average value of δ =  ~ 371 μm.
Furthermore, a change in morphology was observed,
indicating greater porosity and surface area. Figure  7b
shows the EDX of the sanded plate and corresponds to
carbon steel. In contrast, Fig. 7c shows the EDX spectrum
of grown oxide, which confirms the existence of Fe and O
signals indicating the formation of iron oxide on the surface
due to the corrosion process. Cl and Na signals come from
saline water used in this process, which agrees with the XRD
analysis of grown iron oxide.
On the other hand, Fig. 7d shows the iron plate’s side
view after the removal process using PAA. It can be seen
that the thickness of grown oxide diminished from ~371 μm
to ~33 μm, and the carbon steel surface become smooth.
Similarly, Figs.  7e, f show the thickness of iron oxide
before and after the removal process, respectively, using
PAA-co-IA. In this case, the thickness only diminished
from ~191 μm to ~110 μm. Thus, it can be concluded that
the addition of itaconic acid has an important effect on the
removal process by decreasing the amount of oxide removed.
Additionally, SEM micrographs of PAA before and after
the removal process were obtained. Figure 8a shows the
surface polymer before the rusting process. It can be seen the
irregularities caused by airdrops coming from the synthesis.
Journal of Polymer Research (2021) 28:104 Page 9 of 13  104

Fig. 8  The surface of PAA: (a) before and (b) after the iron removal process

Once the process was carried out, a high amount of iron
oxide adhering to the surface of the polymer was observed
(Fig. 8b). This micrograph provides clear evidence of the
PAA for the ability to remove large amounts of iron oxides.
Analysis of the design of experiments (DOE)
Analysis of variance  The results of the analysis of variance
(ANOVA) for the two studied responses (Mw and Fe rust
removal) are shown in Table 4. It is important to notice that
the coefficients are displayed encoded.
Table 4 shows that for both Mw and Fe rust removal, the
constant probability is ~0, which means that the two models
are statistically significant (at a significance level of 0.05)
[14]. In other words, this indicates that % Initiator (α)
and monomer ratio (β) are associated with the responses’
changes. The determination coefficient (R2) for the M ­ W
response variable shows that 86.11% of the change in this
Table 4  Linear regression coefficients and “P” probability of the
quadratic model
variable is explained by the adjusted regression model,
which is considered a suitable fit compared to other models
reported in the literature [33, 34]. However, for the rust
removal process, the R2 value decreases to 36.11%. Although
this value is low, it does not mean that the process was
unsuccessful. The most significant evidence is the SEM
micrographs showing how the oxides’ thickness is decreased
on the metal surface once carried out the removal process.
In this context, the weak value of R2 indicates a lower
model fit that can be attributed to the lack of experimental
reproducibility on some variables (e.g., reaction time and
synthesis temperature, curing time, the polymer’s thickness,
adhesion strength, and so on.), which could influence the
removal process. And they were not considered as possible
factors in the response. Nevertheless, it is important to
remind that the R2 values do not usually present higher
values [14] and depend more on the research area.
Contour plot analysis  Two contour plots were obtained
to analyze the effect of the factors studied in the model.
Figure 9a corresponds to AA:IA, %I vs M ­ W. It can be seen

Mw (R2 = 86.11%) Fe rust removal Table 5  Values of oxide removed using PAA and PAA-co-IA. The
(R2 = 36.11%) testing were performed in duplicate to check repeatability
Coefficient Probability Coefficient Probability Monomer ratio %I Oxide removed
(AA:IA) (mg Fe-Ox/g Pol)
Constant 39.411 0.000* 1017.13 0.000*
α -7.8670 0.012• -151.21 0.047• 100:0 0.2 1294.5
β 17.917 0.000* 14.210 0.839 0.4 1079.2
α2 7.9330 0.112 -33.340 0.783 0.6 725.7
β2 -11.367 0.030• 5.3300 0.965 90:10 0.2 1061.0
αβ -11.137 0.005• -110.93 0.210 0.4 1132.3
0.6 847.5
Units of Fe rust removal: mg Fe-Ox/g Pol = milligrams of removed
80:20 0.2 1116.3
iron oxide/gram of polymer
0.4 906.6
* P < 0.001 highly significant variable that affects the response
0.6 991.3
• P < 0.05 significant variable that affects the response

13
 104   Page 10 of 13
that by using a low percentage of the initiator (0.2%) and
an AA:IA ratio of 100:0, polymers with molecular weights
above 70 kDa are obtained. On the other hand, as the number
of itaconic acid groups increases, the molecular weight
decreased considerably to 48 kDa and 14 kDa for the AA:IA
ratios of 90:10 and 80:20, respectively. These behaviors are
also observed in the ­MW model’s negative and positive signs
(Table 4). The positive sign of the monomer ratio coefficient
shows an increase in the molecular weight when increasing
AA ratio. On the other hand, the negative regression
coefficient of the %I demonstrates a decrement in the ­MW
at increasing the initiator. This decrease in M
­ W during the
copolymer formation was attributed to the carboxyl groups
belonging to IA. The volume occupied by the molecules is
large; thus, it is generated a steric hindrance that prevents
the chain from growing, favoring the termination stage and
the consequent decrease in polymer molecular weight [35].
Figure 9b corresponds to AA:IA, %I vs. mg Fe-Ox/g Pol.
The highest value of iron oxide removal (1295 mg g−1 of
the PAA which is equivalent to 0.510 g cm−2 of the metal
surface) was reached at 100:0 AA:IA monomer ratio and
0.2%I. This value is eighteen times greater than the reported
in previous studies [10] (0.028 g cm−2 of the metal surface)
and almost five times greater than that obtained in our
recently published work [14] (0.106  g  cm−2 of the metal
surface). Besides, it can be seen that for PAA, the amount of
oxide removed increases as the concentration of the initiator
decreases (Table 5). This behavior agrees with the M
­ W study (Fig. 9a),
which indicates that the polymer rust removal capability is
more significant by increasing the PAA’s molecular weight.
On the other hand, there is no significant difference in rust
removal values when using both PAA or PAA-co-IA with
0.4%I red arrow in Fig. 9b. This finding suggests that, in
this case, the steric hindrance of the carboxylic groups does
not play a substantial role in the removal process.
Fig. 9  Plots of response contour
analysis. (a) Mw of PAA:IA
copolymer and (b) Fe rust
removal response, as a function
of initiator and monomers ratio
13
Journal of Polymer Research (2021) 28:104
Finally, it is important to note that the monomers ratio,
initiator percentage, and the carboxylic groups’ number are
essential factors to maximize the iron oxide removal on the
metal surface (mg Fe-Ox./g Pol) and ­MW.
Adhesion rust removal process
Once the oxide growth on the metal plate was completed,
the rust removal process by adhesion was carried out. It
is well known that acrylic-based systems are essential
due to resistance to oxidation, transparency, thermal
stability, and anti-aging against solar irradiation [36–38].
Besides, materials based on acrylic polymers also exhibit
outstanding intrinsic adhesive properties superior to most
of the other polymers [36, 39]. These adhesive properties
are attributed to the carboxylic acid groups present in the
polymer structure known to be pH-responsive. The apparent
pKa value of poly(acrylic acid) is 5.8 [40–42]. When
pH < pKa, the carboxylic acid in PAA is not dissociated.
When pH > pKa, the groups are deprotonated to create
negatively charged (­ COO−) groups. In this regard, both
PAA functionalities are used in our approach to providing
molecular adhesion capabilities [43].
Before explaining the rust removal interaction process,
it is important to discuss the air passivation layer’s nature
on the iron substrate. The oxidized metal substrates were
prepared by water vapor humidification that was periodically
introduced into the acrylic chamber to maintain an
atmosphere with constant relative humidity. Thus, thin layers
of oxidative products are formed, which act to protect from
further corrosive attack. Castle and Watts have shown that
passivated iron’s surface is predominantly FeOOH in nature
[44]. This finding is in agreement with our results obtained
by XRD analysis, where the identified phases of oxide were
mainly iron oxyhydroxides: Akaganeite-Q ­(Fe3+O(OH)),
lepidocrocite (FeO(OH)), and goethite ­(Fe3+O(OH)).
Journal of Polymer Research (2021) 28:104 Page 11 of 13  104
Fig. 10  Rust removal process:
(a) Type I: Interfacial acid–base
interaction mechanism by car-
boxylate formation, (b) Type II:
Hydrogen bonding mechanism,
(c) Type III: Salt-bridge inter-
molecular reaction mechanism
by free ferrous ions
On the other hand, the rust removal interfacial interaction
between the poly(acrylic acid) and the iron oxide layers is
due to the following two mechanisms: Type I consists of
a strong ionic interaction associated with charge transfer
bonding mechanisms that predominate over weaker dipole
interactions [45]. Thus, this mechanism is carried out in
the initial stage of contact once the PAA film has been
introduced into the water and subsequently deposited on
the oxidized plate’s surface. It can be seen in Fig.  10a,
acid–base surface interactions occurring between the
carboxylate anions ­(COO −) in the PAA and the polar
hydroxyl (OH) groups on hydrated oxide surface sites
are strongly chemisorbed to the iron oxidized plate. This
rust removal mechanism is responsible for significantly
enhancing the adhesion properties [44, 45].
The type II mechanism (Fig. 10b) occurs simultaneously
with Type I. It is carried out by forming hydrogen bonding
between the carboxylic acid (COOH) groups that do not
dissociate during the PAA film’s wetting process and the
hydroxyl (OH) groups on the iron oxide plate surface. A
plausible explanation for this mechanism was given by
Leadley et  al., who mention that the hydrogen bonding
between the carbonyl oxygen and the oxide requires acidic
hydroxide species [46]. As the natural oxide becomes
basic, the chance of any surface hydroxides being acidic
would become less, and thus the Type I mechanism would
be expected to predominate.
In addition to the above two mechanisms, there is an
alternative hypothetical type III mechanism (Fig.  10c)
proposed by Sugama et al. [45]. The salt-bridge formation
caused by the ionic bond between the F ­ e3+ ions, which are
present in the crystalline phases of iron oxide (confirmed by
XRD), and the ­COO− anions from the PAA. It is important
to note that very few ­Fe3+ tricarboxylate salt bridges are
formed between rust plate and PAA. This is mainly due
to steric effects. The carboxylic acid groups are closely
attached or directly attached to the polymer backbone. Lack
of polymer mobility after hardening plays a significant role
in preventing ­Fe3+ tricarboxylate salt-bridge formation.
Nevertheless, there is no doubt that when the reactive
surface oxide layer chemically interacts with the dissociated
COOH groups to form metal–oxygen polymer interfacial
complex bonds, the yielded ionic bonds contribute
particularly to an increase in adhesion.
Conclusions
It was demonstrated that PAA films are suitable material
for eliminating iron rust grown on metallic surfaces. The
addition of itaconic acid during the synthesis origins a steric
hindrance in the polymer chain, which causes a significant
decrease of M­ W. The experimental design established that
the reaction parameters, such as % initiator and monomers
ratio, directly affect the molecular weight. At the same
time, for the removal of the oxide, only the % initiator had
influence. The determination coefficient (R2) for the ­MW
response variable shows a suitable fit compared to other
models reported in the literature. However, for the Fe rust
removal response, the R2 value significantly decreases. This
is mainly due to the reaction time and synthesis temperature,
curing time, the polymer’s thickness, adhesion strength, and
so on, which were not considered in the model and might
influence the response. Remarkably, PAA film’s capability
for Fe rust removal was eighteen times greater than similar
studies and almost five times more than our previous
published work. The primary rust removal mechanism is
13
 104   Page 12 of 13
carried out by acid–base surface interactions between the
functional carboxylic acid groups and the oxidized plate’s
polar hydroxyl groups. This mechanism is responsible for
the significant enhancement of the adhesion properties.
This rapid and effective process presented the advantage
of not polluting the environment and is user-friendly. In
case of interest, the metallic phases can be recovered by the
polymer’s simple dissolution in water.
Acknowledgments  The authors wish to thank Eng. Fernando
Rodríguez Juárez and B.S. Chem. Claudia Hernández Galván for the
SEM and XRD analyzes, respectively, at the Institute of Metallurgy-
UASLP. Many thanks to Chem. Daniel Ruiz Plaza and the National
Laboratory for Characterization of Physicochemical Properties and
Molecular Structure UG-UAA-CONACyT for the facilities granted
during the NMR analysis. A. Camacho-Ramírez wishes to thank Prof.
Gabriela Palestino for the scholarship awarded through the project
DSA/103.5/15/11048 supported by the Functional Materials Network–
PRODEP. A special acknowledgment to Q.F.B. Elena Monreal García
for the fruitful scientific discussions we had at the beginning of this
study and for her honest friendship.
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