coatings

Article
Impact of Molecular Weight on Anti-Bioadhesion Efficiency of
PDMS-Based Coatings
Mama Aïssata Bangoura 1, * , David Mimeau 2 , Eric Balnois 3 , Karine Réhel 1 , Fabrice Azemar 1
and Isabelle Linossier 1

1 Laboratoire de Biotechnologie et de Chimie Marines (LBCM), EMR CNRS 6076, Université Bretagne Sud,
IUEM, CS7030, 56321 Lorient, France; karine.rehel@univ-ubs.fr (K.R.); fabrice.azemar@univ-ubs.fr (F.A.);
isabelle.linossier@univ-ubs.fr (I.L.)
2 Nautix, Parc d’activités Les 5 Chemins, 56520 Guidel, France; d.mimeau@nautix.com
3 Laboratoire de Biotechnologie et de Chimie Marines (LBCM), EMR CNRS 6076, Université de Bretagne
Occidentale, 29000 Quimper, France; eric.balnois@univ-brest.fr
* Correspondence: mama-aissata.bangoura@univ-ubs.fr

Abstract: Silicone elastomer coatings have shown successful fouling release ability in recent years. To
further enhance the design of silicone coatings, it is necessary to fully understand the mechanisms that
contribute to their performance. The objective of this study was to examine the relationship between
the molecular weight of polydimethylsiloxane (PDMS) and antibioadhesion efficiency. PDMS-based
coatings were prepared via a condensation reaction, with a controlled molecular weight ranging
from 0.8 to 10 kg·mol−1 . To evaluate changes in surface wettability and morphology, contact angle
experiments and atomic force microscopy (AFM) were performed. Finally, the antibioadhesion and
self-cleaning performance of PDMS coatings was carried out during in situ immersion in Lorient
harbor for 12 months. Despite small variations in surface properties depending on the molecular
weight, strong differences in the antibioadhesion performance were observed. According to the
results, the best antibioadhesion efficiency was obtained for coatings with an Mn between 2 and
4 kg·mol−1 after 12 months. This paper provides for the first time the impact of the molecular weight
of PDMS on antibioadhesion efficiency in a real marine environment.

Citation: Bangoura, M.A.; Mimeau,

Keywords: silicone elastomers; anti-bioadhesion; polydimethylsiloxane; fouling release coating;
D.; Balnois, E.; Réhel, K.; Azemar, F.; self-condensation
Linossier, I. Impact of Molecular
Weight on Anti-Bioadhesion Efficiency
of PDMS-Based Coatings. Coatings
2024, 14, 149. https://doi.org/ 1. Introduction
10.3390/coatings14010149 Marine biofouling, the accumulation of marine organisms such as bacteria, algae, and
Academic Editor: Giancarlo Galli
barnacles on immerged surfaces, is a major problem for the naval industry, generating
severe economic and ecological impacts. Biofouling of ship hulls induces increased fuel
Received: 21 December 2023 consumption, an important loss of vessel maneuverability, and expensive maintenance
Revised: 11 January 2024 costs [1–3]. In addition, marine biofouling leads to the introduction of invasive marine
Accepted: 18 January 2024 species in non-native environments through ship transport. Antifouling paints are widely
Published: 21 January 2024 used to control bioadhesion via the use of biocidal molecules. However, these kinds of
coatings are highly regulated to protect marine environments, hence new strategies with a
lower environmental impact are required.
More recent research in the field has seen the emergence of technologies without
Copyright: © 2024 by the authors.
biocides, known as fouling-release coatings (FRC). Silicone elastomer coatings such as
Licensee MDPI, Basel, Switzerland.
This article is an open access article
polydimethylsiloxane (PDMS) have shown successful antibioadhesion properties when
distributed under the terms and
subjected to hydrodynamic forces such as those produced by movement in water. PDMS
conditions of the Creative Commons is one of the most widely used soft polymers due to specific properties: high flexibility,
Attribution (CC BY) license (https:// biocompatibility, elasticity, and high availability. Its antibioadhesion efficiency has been
creativecommons.org/licenses/by/ attributed to three main characteristics: an optimal critical surface energy to minimize
4.0/). adhesion forces [4], a low elastic modulus, and a low roughness to facilitate the detachment

Coatings 2024, 14, 149. https://doi.org/10.3390/coatings14010149 https://www.mdpi.com/journal/coatings

Coatings 2024, 14, 149 2 of 15

of hard foulants such as barnacles [5,6] under shear forces during navigation. Silicone-
based coatings are generally prepared via a hydrosilylation reaction or a condensation
reaction [7]. Hydrosilylation describes the addition reactions between two types of PDMS,
one containing vinyl groups and the other silane groups, in the presence of a platinum-
based catalyst [8]. On the other hand, a silicone crosslinker with many alkoxysilane
groups, and a polysiloxane precursor with silanol end-groups can undergo a condensation
reaction [9].
The first use of crosslinked silicone to prevent the adhesion of barnacles was patented
by Robbart Edward in 1961 [10]. He pointed out that siloxane polymers such as methyl poly-
dimethylsiloxane, methyl phenyl polydimethylsiloxane, and ethyl polydimethylsiloxane
were particularly suitable for silicone coatings. He had already claimed that the efficiency of
silicon resins in preventing the accumulation of marine organisms could be at least related
to the smoothness of the silicone surface. Many studies have reported on the efficiency of
silicone coatings. Truby et al. showed that the incorporation of free polydimethyldiphenyl-
siloxane (PDMDPS) oil in a cured polydimethylsiloxane (PDMS) network decreased the
adhesion of barnacles and certain species of oysters [11]. Wynne et al. carried out a study
to compare the fouling-release performance of filled condensation-cured room-temperature
vulcanizing (RTV) silicone rubber coatings [9,12] with that of an unfilled hydrosilylation
system (with the same molecular weight of PDMS macromonomers). They demonstrated
that all hydrosilylation-cured coatings released barnacles (Balanus eburneus) more readily
than filled RTV. The surface roughness observed for filled RTV may certainly improve the
adhesion of foulants [9]. In addition, Stein et al. have tried to fully understand the effect
of the filler (coating composition) of both condensation-cured and hydrosilylation-cured
silicone coatings on barnacle attachment strength. They showed that barnacle adhesion
increased as the filler loading increased in both systems [13]. They also tried to understand
the relationship between the molecular architecture (crosslinking density) and the adhesion
of barnacles in hydrosilylation-cured systems. They observed no significant effect of the
crosslinking density on the adhesion strength of barnacles, but some change on the failure
mechanism of barnacles were noticed. They have suggested that lower crosslink density
was better for stable (durable) coating. In another study, the influence of the elastic modulus
on the release of the soft foulant alga (Ulva linza) from hydrosilylated PDMS coating has
been investigated. No significant effect of elastic moduli ranging from 0.2 to 9.4 MPa was
observed for the settlement of Ulva sp. zoospores. However, more detachment of sporeling
was observed for the softer materials with lower moduli (0.2 and 0.8 MPa): the sporeling
were readily detached on these coatings [5]. In another study, Gray et al. showed that the
settlement of larvae could be positively correlated with elastic modulus [14].
The literature states that several specific parameters can contribute to the antibioad-
hesion performance of silicone-based coatings. We identified molecular weight as one of
these parameters. To date, few studies have reported the relationship between the network
characteristics of PDMS coatings and their antibioadhesion performances. In particular,
there is a need to examine the impact of molecular weight on efficiency. Most of these
studies were performed on silicone coatings obtained via hydrosilylation. In this work, the
focus was on condensation reactions. The successive mechanism of alkoxysilane hydrolysis
and condensation reactions enable the formation, by aggregation, of a three-dimensional
network at room temperature. The material thus formed presents intermolecular chemical
bonds ensuring the mechanical cohesion of the material. To study the relationship between
chain size and antibioadhesion efficiency, different PDMS-based coatings were prepared via
condensation reaction, with a controlled molecular weight ranging from 0.8 to 10 kg·mol−1 .
In contrast with other methods usually used, the PDMS coatings studied were obtained via
self-condensation without a precursor, in the presence of a catalyst at room temperature.
Indeed, PDMS used in this study were modified using thiol-ene click chemistry to obtain
crosslinkable methoxysilane end groups. In the presence of humidity and a catalyst, a tridi-
mensional network could be formed [15]. The polymeric solutions obtained were applied
on different surfaces to be characterized after curing. The Soxhlet extraction method was
Coatings 2024, 14, x FOR PEER REVIEW 3 of 15

Coatings 2024, 14, 149 humidity and a catalyst, a tridimensional network could be formed [15]. The polymeric 3 of 15
solutions obtained were applied on different surfaces to be characterized after curing. The
Soxhlet extraction method was employed to study crosslinking efficiency. The key prop-
erties for fouling
employed to studyrelease such as surface
crosslinking roughness
efficiency. The keyand elastic modulus
properties were
for fouling studied
release with
such as
atomic force
surface microscopy
roughness (AFM),
and elastic and surface
modulus energywith
were studied wasatomic
calculated
forceusing contact(AFM),
microscopy angle
and surface energy
measurements. was calculated
Finally, the influence using contact angle
of molecular measurements.
weight Finally, the influence
on the antibioadhesion of PDMS
of molecular
coatings weight on the
was investigated antibioadhesion
during the immersionof PDMS coatings
of samples in thewas investigated
Atlantic during
Ocean (Lorient
the immersion
harbor) in staticofconditions
samples in forthe
12Atlantic
months. Ocean (Lorient harbor) in static conditions for
12 months.
2. Materials and Methods
2. Materials and Methods
2.1. Materials
2.1. Materials
Three vinyl-terminated polydimethylsiloxanes (Mn: 800 g·mol−−11, PDMS-V0.8K; Mn:
Three −1vinyl-terminated polydimethylsiloxanes (Mn: 800 g·mol , PDMS-V0.8K; Mn:
6000 g·mol , PDMS-V6K; Mn: 9400 g·mol−1, PDMS-V10K) were acquired from Gelest Inc.
6000 g·mol−1 , PDMS-V6K; Mn: 9400 g·mol−1 , PDMS-V10K) were acquired from Gelest
(Morrisville, NC, USA). Polydimethylsiloxane and bis(3-aminopropyl)-terminated (Mn:
Inc. (Morrisville, NC, USA). Polydimethylsiloxane and bis(3-aminopropyl)-terminated
2500 g·mol−1, PDMS-N2.5K) were purchased from Sigma Aldrich® (Taufkirchen, Ger-
(Mn: 2500 g·mol−1 , PDMS-N2.5K) were purchased from Sigma Aldrich® (Taufkirchen,
many). Linear, trimethoxysilane-terminated polydimethylsiloxane (Mn: 4010 g·mol−1
Germany). Linear, trimethoxysilane-terminated polydimethylsiloxane (Mn: 4010 g·mol−1
PDMS-TMS4K) was kindly offered by our industrial partner. The zinc complex catalyst
PDMS-TMS4K) was kindly offered by our industrial partner. The zinc complex catalyst
was purchased from King Industries Inc. (Norwalk, CT, USA). The 2,2-dimethoxy-2-phe-
was purchased from King Industries Inc. (Norwalk, CT, USA). The 2,2-dimethoxy-2-
nylacetophenone (>99%
phenylacetophenone (>99%DMPA)
DMPA) was purchased
was purchasedfrom
fromThermo
ThermoFisher
FisherScientific
Scientific(Waltham,
(Waltham,
MA, USA). The N,N′-dicyclohexylcarbodiimide
′ (>98% DCC),
MA, USA). The N,N -dicyclohexylcarbodiimide (>98% DCC), 4-dimethylaminopyridine4-dimethylaminopyridine
(>99% DMAP),
(>99% DMAP), (3-mercaptopropyl)-trimethoxysilane
(3-mercaptopropyl)-trimethoxysilane (>96% (>96% HS-TMS),
HS-TMS), and 4-pentenoic
and 4-pentenoic
acid were
acid werepurchased
purchasedfrom fromTCITCI Chemicals
Chemicals (Zwijndrecht,
(Zwijndrecht, Belgium).
Belgium). Chloroform,
Chloroform, hexane,
hexane, ace-
acetonitrile, toluene, and glass microscope slides (76 × 26 × 1 mm) were
tonitrile, toluene, and glass microscope slides (76 mm × 26 mm × 1 mm) were purchased purchased from
VWRVWR
from International (Radnor,
International PE, USA).
(Radnor, Deuterated
PE, USA). chloroform
Deuterated chloroform (CDCl 3) for Eurositop 1H
(CDCl 3 ) for Eurositop
1NMR
H NMR analysis waswas
analysis acquired from
acquired (Hadfield,
from UK).
(Hadfield, All All
UK). products
products were used
were as received.
used as received.

2.2. PDMS Functionalization

2.2.1. PDMS-NH22 Functionalization
Functionalization via
via Steglich
Steglich Esterification: PDMS-V2.5K
PDMS-V2.5K
Vinyl-terminated polydimethylsiloxane as
Vinyl-terminated polydimethylsiloxane as PDMS-V2.5K
PDMS-V2.5K was was prepared via Steglich
esterification using N,N ′ -dicyclohexylcarbodiimide as a coupling agent, as previously
esterification using N,N′-dicyclohexylcarbodiimide as a coupling agent, as previously de-
described
scribed by by Gillet
Gillet et [15].
et al. al. [15]. PDMS-NH
PDMS-NH 2 (1
2 (1 g, g, 1 equiv),
1 equiv), pentenoic
pentenoic acid g,
acid (0.12 (0.12 g, 4 equiv),
4 equiv), N,N′-
N,N ′ -dicyclohexylcarbodiimide (0.38 g, 6 equiv), and 4-dimethylaminopyridine (0.11 g,
dicyclohexylcarbodiimide (0.38 g, 6 equiv), and 4-dimethylaminopyridine (0.11 g, 3 equiv)
3were
equiv) were dissolved
dissolved in anhydrousin anhydrous toluene1).
toluene (Figure (Figure 1). Nitrogen
Nitrogen was bubbledwas bubbled into the
into the solution
solution forThe
30 min. The mixture
reactionwas
mixture was ◦
for 30 min. reaction stirred at stirred
135 °C at
for135
6hC for 6reflux.
under h under Thereflux. The
resulting
resulting product was cooled to room temperature and filtered to remove
product was cooled to room temperature and filtered to remove solid byproduct. The sol- solid byproduct.
The
vent solvent
was then was then removed
removed under reduced
under reduced pressure.pressure.
The coloredTheoilcolored oil was
obtained obtained was
dissolved
dissolved in hexane and washed 5 times with 50:50 acetonitrile/methanol.
in hexane and washed 5 times with 50:50 acetonitrile/methanol. The hexane phase The hexane
con-
phase
tainingcontaining the product
the product was evaporated
was evaporated under vacuum
under vacuum to yieldto ayield a yellow
yellow oil. 1 H-NMR
oil. 1H-NMR was
was
usedused to characterize
to characterize the final
the final product.
product.

Syntheticpathway
Figure 1. Synthetic pathwayofofmodification
modificationofofpolymers
polymers with
with crosslinkable
crosslinkable groups.
groups. (a) (a) Steglich
Steglich es-
terification to to
esterification obtain vinyl-terminated
obtain PDMS
vinyl-terminated PDMS(PDMS-V-MW).
(PDMS-V-MW). (b) (b)
Thiol-ene coupling
Thiol-ene to obtain
coupling tri-
to obtain
methoxysilane-terminated PDMS
trimethoxysilane-terminated PDMS(PDMS-TMS-MW).
(PDMS-TMS-MW).

2.2.2. PDMS-V-MW Functionalization

2.2.2. PDMS-V-MW Functionalization via
via Thiol-Ene
Thiol-Ene Reaction:
Reaction: PDMS-TMS-MW
PDMS-TMS-MW
The crosslinkable PDMS-TMS were synthetized via thiol-ene reaction between
The crosslinkable PDMS-TMS were synthetized via thiol-ene reaction between (3-
(3-
mercaptopropyl)-trimethoxysilane
mercaptopropyl)-trimethoxysilane (HS-TMS)
(HS-TMS) and
and vinyl-terminated polydimethylsiloxane
vinyl-terminated polydimethylsiloxane
(PDMS-V) (Figure 1). The PDMS-V, the HS-TMS (1:2.2 molar ratio), and a catalytic amount
of 2,2-dimethoxy-2-phenylacetophenone were dissolved in chloroform. The thiol-ene
reaction occurred at room temperature under UV at 365 nm for 1 h. The crude polymer was
Coatings 2024, 14, 149 4 of 15

purified by solvent extraction with hexane/acetonitrile. After purification the products

were analyzed using 1 H NMR.

2.3. Coating Preparation

To evaluate the impact of PDMS molecular weight onantibioadhesion and physico-
chemical properties, the coating solutions were applied to glass or PVC slides. The hy-
drophobic silicone-based coatings were obtained via self-condensation of trimethoxysilane-
terminated polydimethylsiloxane with various molecular weights. The crosslinkable PDMS-
TMS and the zinc catalyst (2.5 wt%) were dissolved in chloroform (1:1 wt). The mixture
was homogenized for 5 min with a lab shaker. The preparation in liquid state was applied
immediately after mixing onto a glass slide and a PVC surface by drop deposition. Glass
substrates were used only for surface characterizations during laboratory assays, and PVC
plates for marine field tests, because PVC surfaces are more suitable for our primers. The
coatings were cured at room temperature for 5 days, then dried under vacuum at 50 ◦ C
for 48 h. Transparent coatings were named as follows: PDMS-0.8K (800 g·mol−1 ), PDMS-
2.5K (2500 g·mol−1 ), PDMS-4K (4010 g·mol−1 ), PDMS-6K (6000 g·mol−1 ), and PDMS-10K
(9400 g·mol−1 ). The final film thickness measured via an Elcometer 456 (Elcometer®, La
Chappelle Saint Mesmin, France), was approximately 200 µm.

2.4. Characterization
2.4.1. Proton Nuclear Magnetic Resonance Spectroscopy
The 1 H NMR spectra of the modified polymers were recorded at room temperature
on a Brucker (Billerica, MA, USA) 500 MHz spectrometer using deuterated chloroform
(CDCl3 ) as the standard. Peak shifts were calibrated from residual solvent peaks. The
1 H NMR of Steglich esterification was monitored via the following peak shift δ (ppm):

apparition of allyl protons peak at 6–5 ppm (m, 2 H, CH2 -CH=CH2 ) and 5–4 ppm (m, 4 H,
CH2 -CH=CH2 ), and the shift of the proton close to amide function, 3 ppm (m, 4 H, CH2 -
NH-CO-CH2 ). The 1 H NMR of thiol-ene coupling was distinguished by the decrease in
allyl protons peaks and the apparition of trimethoxy groups at 3.5 ppm (s, 9 H, Si-(OCH3 )3 ).

2.4.2. Gel Permeation Chromatography

GPC chromatograms were measured using an Agilent Technologies (Santa Clara, CA,
USA) 1200 Infinity II chromatography containing an isocratic pump, a column oven at 35
◦ C and a RID detector equipped with a Varian 410 autosampler. Two Viscoteck T2000 and

T3000 series columns (org GPC/SEC 300 × 8 mm) and a guard column (Org Guard, 10 ×
4.6 mm) from Malvern (Malvern Panalytical, Palaiseau, France) were used. Polystyrene
standards (PolyCAL UCS-PS) from Malvern were used for the molecular weight calibration
curve. The samples were dissolved in HiPerSolv CHROMANORM® HPLC grade THF
(VWR International, Radnor, PE, USA) and filtered through 0.45 µm PTFE syringe filters.
The filtrate was then analyzed at a flow rate of 1 mL·min−1 . Data were collected and
analyzed using Cirrus Software (version 2.0) from Aligent technologies.

2.4.3. Soxhlet Extraction

To determine the efficiency of the crosslinking, the number of uncrosslinking materials
in the coating was determined via Soxhlet extraction. The film was removed from the glass
slides and extracted with chloroform in a Soxhlet device for 24 h at 90 ◦ C under reflux. The
weight loss was then calculated and corresponded to the difference between the extracted
and unextracted weight divided by the unextracted weight, as follows:

W0 − Wex
Weight loss(%) =
W0
Coatings 2024, 14, 149 5 of 15

2.5. Surface Characterization

Coatings were observed using a Scanning Electron Microscope JEOL—IT500 HR
SED (Secondary Electron Detector) (Tokyo, Japan). Samples were metallized with gold
to obtain a conductive material. Each sample was scanned, and a screenshot of the most
representative global topography was taken (magnification 2000×). For all investigations,
the beam energy was 10 kV.
Static contact angle measurement was performed using a Digidrop GBX (Dublin, Ire-
land) system at room temperature (20 ◦ C). Three replicates of deionized water, formamide,
and methylene iodide contact angles were measured for each sample. For each replicate
three coated surfaces were analyzed. The static contact angle (θ) was measured at five
different locations for each coated surface with a 3 µL droplet after 3 s of stabilization. The
indicated values were an average measured on different coated surfaces. Surface energy for
each sample was calculated via the Owens−Wendt method [16] using the average of the
static contact angle measurement. Both the dispersive and polar components were assessed
(γ S = γSD + γSP ). Measurements were performed on PDMS samples after curing.
Atomic force microscopy (AFM) was used to study the surface topography of the
coatings. A Multimode 8 AFM instrument equipped with a NanoScope V controller (Bruker,
Santa Barbara, CA, USA) was used. Images were recorded using the Scanasyst® mode and
the Peak Force Quantitative Nanomechanical Mode (PFQNM® ). Topographical images
were recorded on a sample area of 1 µm × 1 µm in the ScanAsyst under ambient conditions
using a ScanAsyst-Air cantilever (resonance frequency of 70 KHz, spring constant of
~0.4 N·m−1 and tip radius of 10 nm) at a scan rate velocity below 2 µm·s−1 . Topographic
images were analyzed using NanoScope Analysis software version 1.8. For each coated
surface, images were recorded at varying locations. PFQNM was used for determining the
nanomechanical properties of the different samples. The piezo in PFQNM was oscillating
vertically at a frequency of 2 KHz and an amplitude of 150 nm. With a constant force that
was maintained by the peak force feedback loop, a force–distance curve was recorded at
each pixel while the piezo scanned the samples beneath the tip (scan velocity 2 mm·s−1 ).
The thermal tuning approach for the ScanAsyst tip (spring constant of 0.34 N·m−1 ) was
used to calibrate the cantilever’s spring constant. The linear portion of an average of
10 forced resistance curves generated by ramping the tips onto a Sapphire surface was used
to calculate their deflection sensitivity. The tip radius was calibrated using the relative
technique based on reference samples (PFQNM SPM kit 12 M, Bruker), with a PDMS
standard of 2.5 MPa for the ScanAsyst tip. The peak force setpoints for the PDMS surfaces
were commonly set at 20 pN based on these calibration standards. All measurements were
made in natural lighting. Real-time analysis of the force curves from each contact between
the tip and the sample produced a nanomechanical map in addition to a topographical
image. The modulus was calculated according to the Derjaguin–Muller–Toporov (DMT)
model (i.e., a Hertz model including the effect of adhesion without any change in the contact
area) [17]. All AFM data analysis and image processing were made using NanoScope
software version 1.8.

2.6. Marine Field Test

The samples were coated on PVC plates (12 cm × 6 cm) first covered by a primer
and a tie-coat, both supplied by our industrial partner, to ensure good adhesion of the
coatings to the panels during immersion. The samples were dried at room temperature for
10 days before immersion. The coatings were immersed vertically in the Atlantic Ocean
near Lorient. In order to study the influence of solar irradiation on the development of
organisms, the samples were coated on both sides of the PVC surface: one exposed to
radiation from sunlight, the other to shade. The antibioadhesion efficiency was evaluated
in static conditions over 12 months from June 2022 to July 2023. The samples were removed
from the water once a week and photographed before being re-immersed. The pictures of
different coatings were compared to evaluate their antibioadhesion efficiency.
 crosslinkable PDMS were then characterized using 1H-NMR and GPC to evaluate the
structure and the molecular weight.
The dry product of PDMS-V2.5K was analyzed using 1H NMR. The shift of the proton
H4 assigned to the proton close to amide group from 2.7 ppm to 3.4 ppm confirmed the
Coatings 2024, 14, 149 transformation of the amine group into an amide group (Figure 2), thus the formation of
6 of 15
symmetric vinyl-terminated PDMS. The yield calculated from its relative intensity was close
to 90%. The presence of a vinyl peak at 5.0–5.25 ppm and 5.7–6.0 ppm on the 1H NMR spec-
tra,
3. corresponding
Results to H8 and H9, showed the success of the Steglich modification.
and Discussion
The vinyl-terminated
3.1. Modification of PDMS Polymers polymers (PDMS-V0.8K, PDMS-V2.5K, PDMS-V6K, and
PDMS-V10K) were analyzed using 1H NMR after thiol-ene reaction. The 1H NMR spectra
The preparation of PDMS with crosslinking groups was achieved using thiol-ene click
showed a decrease in vinyl proton peaks. In addition, the apparition of methoxy after
chemistry to attach the trimethoxysilane group to the PDMS vinyl-end group. For the
purification confirmed
amine-terminated PDMS the(PDMS-N2.5K),
coupling between the group
the end vinyl group andmodified
was first the thiolvia
trimethox-
Steglich
ysilane group, thus the formation of symmetric trimethoxysilane-terminated
esterification. This reaction allowed the formation of an amide (Figure 1). The modified PDMS (Fig-
ure 2). The yield calculated from the proton relative intensities of
crosslinkable PDMS were then characterized using 1 H-NMR and GPC to evaluate the the trimethoxysilane
group was
structure >90%.
and The molecular
the molecular weight and polydispersity of modified PDMS after thiol-
weight.
ene were
The dry product of PDMS-V2.5K 1).
measured via GPC (Table wasThe molecular
analyzed weights
using 1 H NMR. calculated
The shiftvia GPC
of the were
proton
different from the values obtained using 1H NMR. This could be explained by the use of
H4 assigned to the proton close to amide group from 2.7 ppm to 3.4 ppm confirmed the
polystyrene standards
transformation to calculate
of the amine molecular
group into an amideweight.
group Also, the 2),
(Figure observed
thus thepolydispersity
formation of
values suggested a heterogeneity of the samples in terms of
symmetric vinyl-terminated PDMS. The yield calculated from its relative size. This couldintensity
be attributed
was
to thetoreactivity
close 90%. Theof trimethoxysilane
presence functions,
of a vinyl peak which
at 5.0–5.25 are and
ppm sensitive toppm
5.7–6.0 moisture.
on theThey may
1 H NMR
start to react
spectra, during GPC
corresponding analysis,
to H leading to an increase in macromolecule chain size.
8 and H9, showed the success of the Steglich modification.

1
Figure 2. 1 H NMR spectra of PDMS polymers
Figure 2. polymers after modification
modification and purification.
purification. (Black) amine-
terminated
terminatedPDMS.
PDMS.(Blue) vinyl-terminated
(Blue) vinyl-terminatedPDMS
PDMSafterafter
Steglich esterification.
Steglich (Red) trimethoxysilane-
esterification. (Red) trimethox-
ysilane-terminated PDMS after thiol-ene
terminated PDMS after thiol-ene reaction. reaction.

The vinyl-terminated polymers (PDMS-V0.8K, PDMS-V2.5K, PDMS-V6K, and PDMS-

V10K) were analyzed using 1 H NMR after thiol-ene reaction. The 1 H NMR spectra showed
a decrease in vinyl proton peaks. In addition, the apparition of methoxy after purification
confirmed the coupling between the vinyl group and the thiol trimethoxysilane group,
thus the formation of symmetric trimethoxysilane-terminated PDMS (Figure 2). The yield
calculated from the proton relative intensities of the trimethoxysilane group was >90%. The
molecular weight and polydispersity of modified PDMS after thiol-ene were measured via
GPC (Table 1). The molecular weights calculated via GPC were different from the values
obtained using 1 H NMR. This could be explained by the use of polystyrene standards
to calculate molecular weight. Also, the observed polydispersity values suggested a
heterogeneity of the samples in terms of size. This could be attributed to the reactivity of
trimethoxysilane functions, which are sensitive to moisture. They may start to react during
GPC analysis, leading to an increase in macromolecule chain size.
Coatings 2024, 14, 149 7 of 15

Table 1. Characterization of modified polymers.

Theoretical Molar Molar Masses by 1 H

Commercial Modified Molar Masses by SEC
Masses NMR ÐM
Polymers Polymers (g·mol−1 ) b
g·mol−1 (g·mol−1 ) a
PDMS-V0.8K 800 PDMS-TMS0.8K 858 1341 1.83
PDMS-N2.5K 2500 PDMS-TMS2.5K 2775 4404 2.18
PDMS-TMS4K 4010 - 3774 4775 2.06
PDMS-V6K 6000 PDMS-TMS6K 5164 7173 3.14
PDMS-V10K 9400 PDMS-TMS10K 9021 11,720 2.78
a Calculated with relative intensities of peak of PDMS at 0.04 ppm. b In THF as eluent and with polystyrene
standard.

3.2. Preparation of PDMS Coating

The trimethoxysilane-terminated PDMS (PDMS-TMS0.8K, PDMS-TMS2.5K, PDMS-
TMS4K, PDMS-TMS6K and PDMS-TMS10K) were solubilized in chloroform with the
catalyst, and homogenized with a vortex for 5 min to ensure good homogenization. The
proportions of catalyst and solvent were kept consistent. After the curing process, the
coatings obtained were colorless, with a smooth surface and good adhesion on a glass
surface. All formulations had good film-forming properties except for the lowest molar
mass, PDMS-0.8K, which showed cracks; the coating was too brittle and cracked during
the curing stage.
To demonstrate the complete crosslinking of PDMS films, a Soxhlet extraction test was
carried out on each sample. The quantitative residue of uncrosslinking chains was evaluated
via mass loss calculations after Soxhlet extraction. Figure 3 shows the weight loss of each
coating according to molecular weight. The calculated weight loss was less than 4 wt%
for all formulations, which showed an excellent crosslinking efficiency. Similar results
were observed by Drebezghova et al. for PDMS-based coatings cured via a hydrosilylation
reaction [18]. PDMS-2.5K showed a higher mass loss compared to the other coatings. The
PDMS-2.5K polymer was obtained after a two-synthesis step which reduced the overall
yield compared with other polymers that were obtained in one step. The higher ratio of
PDMS macromolecules without a TMS end-group could explain the higher mass loss during
Soxhlet analysis. In another study, where a sol-gel reaction occurred between a silanol
and a triethoxysilane, lower weight loss was observed (≈1 wt%) [19]. In such a network,
triethoxysilane-terminated PDMS was used as a crosslinker which allowed easier and
more significant crosslinking compared to self-condensation, leading to fewer free chains.
Moreover, uncrosslinked chains were not the only materials that could be released from the
films; the catalyst was soluble in chloroform and could be extracted. It was most important
to show there were no significant free polymer chains in the network system, because
their presence could impact surface properties such as contact angle, atomic composition,
AFM Young’s modulus, and bacterial retention, as shown in Drebezghova et al’s recent
study [18].

3.3. Surface Properties of PDMS Coatings

After the curing process, the surface of PDMS coatings were investigated via SEM,
contact angle measurements, and AFM. Scanning electron microscopy was employed to
assess the surface morphology of the PDMS coatings on the micrometer scale. Images
obtained via SEM for all coatings were similar and showed PDMS elastomer surface
morphology as seen in supplementary data (Figure S1). SEM images showed homogeneous
surfaces with no aggregates. These results were in agreement with the literature. Gillet
et al. observed the same result for PDMS coatings obtained via a condensation process [15].
The different PDMS polymers showed similar SEM morphologies, suggesting that at this
scale, the distance between crosslinking nodes, hence the molecular weight, did not affect
the morphology of the PDMS network.
 important to show there were no significant free polymer chains in th
because their presence could impact surface properties such as contact
position, AFM Young’s modulus, and bacterial retention, as shown in D
Coatings 2024, 14, 149 8 of 15
recent study [18].

Figure 3. Observed weight loss after Soxhlet extractions of PDMS-based coatings.

For a better observation of the network morphology of PDMS-based coatings, atomic

force microscopy (AFM) was performed in a dry state in ambient conditions in air, to assess
surface topography and roughness. The smoothness of an antibioadhesion coating seems
to be an important parameter to avoid bioadhesion: many studies report that a decrease in
surface roughness can be related to a reduction in bacterial adhesion [20,21]. The surface
topography of coatings at different molecular weights were examined at nanometric scale
(0.25 µm2 ) (Figure 4), and analysis of image sections enabled the determination of the
roughness mean square (RMS). The RMS values of the coatings are represented in Figure 5.
PDMS surfaces showed a very smooth surface with low RMS values around 2 nm to 6
nm. All PDMS coatings exhibit a typical mesh-like network structure as described by
Drebezghova et al. [22]. The low roughness of the coatings was not surprising according
to the literature [22,23]. The RMS values of the films were between 1 and 6 nm, with a
slight increase of the RMS when increasing molecular weight of the PDMS, indicating the
molecular weight could impact the surface roughness of coatings. The coating with the
higher molecular weight, PDMS-10K, presented domains with higher RMS values com-
pared to PDMS-2.5K, for example. To the best of our knowledge, there is no study reported
in the literature regarding the correlation between the molecular weight of polymers and
the RMS values of crosslinked PDMS. In our study, further experiments to interpret this
variation, such as precise control of the crosslinking rate of the film, were necessary. We
could nonetheless hypothesize that the structural organization of the polymer chain at the
surface of the film may be modified by the length of the polymer, between crosslinked
points, to generate local z variation in the film surface topography.
Surface elasticity of coatings can be measured using a contact mechanics model (the
hertz model) using AFM. Young’s moduli of PDMS coatings were found to be around
0.3–3.2 MPa. Variation depending on the chain size of the different polymers was observed.
PDMS-0.8K with the lowest molecular weight seems to have a higher value of elastic
modulus (3.20 ± 0.01 MPa) compared to other coatings. PDMS-2.5K (0.58 ± 0.01 MPa),
PDMS-4K (1.64 ± 0.08 MPa), PDMS-6K (0.44 ± 0.03 MPa) and PDMS-10K (0.34 ± 0.11 MPa)
appear to be in the same range. Therefore, the molecular weight seems to affect elastic
moduli, which is only relevant for coatings with significantly different chain sizes. For
example, PDMS-0.8K has an elastic modulus nine times higher than that of PDMS-10K.
However, these values were in good accordance with previous studies, as elastic moduli
for fouling release coatings are typically ranged between 0.2 and 9 MPa [3,23–25]. In
their recent study, similar results were observed by Sun et al. [26]. They observed that
when the crosslinking density of the polymeric network of PDMS decreases, Young’s
 ing to the literature [22,23]. The RMS values of the films were between 1 and 6 nm, with a
slight increase of the RMS when increasing molecular weight of the PDMS, indicating the
molecular weight could impact the surface roughness of coatings. The coating with the
higher molecular weight, PDMS-10K, presented domains with higher RMS values com-
Coatings 2024, 14, 149
pared to PDMS-2.5K, for example. To the best of our knowledge, there is no9 study of 15
re-
ported in the literature regarding the correlation between the molecular weight of poly-
mers and the
modulus RMS values
consequently of crosslinked
decreases from 8.90 PDMS. In our
to 2.99 MPa. study,
It was further
assumed thatexperiments
the lower the to in-
terpret this variation, such as precise control of the crosslinking rate of the
molecular weight of PDMS, the smaller the network size [27]. It appears that when film, were nec-
a higher
essary. We could
molecular weightnonetheless hypothesize
was used, the that the
distance between the structural
crosslinkingorganization of the
point increased, polymer
leading
chain at the
to lower surface
Young’s of the compared
modulus film may tobethe
modified
PDMS-0.8Kby (3.20
the length
± 0.01 of theand
MPa) polymer,
PDMS-10K between
(0.34 ± 0.11 MPa).
crosslinked points, to generate local z variation in the film surface topography.

Coatings 2024, 14, x FOR PEER REVIEW 9 of 15

Figure
Figure4.4.Representative
RepresentativeAFM
AFMheight images
height (0.5(0.5
images µmµm× 0.5×µm) showing
0.5 µm) topography
showing of PDMS
topography coat-
of PDMS
ing of PDMS-0.8K, PDMS-2.5K, PDMS-4K, PDMS-6K and PDMS-10K.
coating of PDMS-0.8K, PDMS-2.5K, PDMS-4K, PDMS-6K and PDMS-10K.

Figure 5. RMS values of PDMS-based coating obtained via AFM.

Figure 5. RMS values of PDMS-based coating obtained via AFM.
Contact angle measurement was used to examine the wetting properties and surface
Surfacedepending
free energy elasticity of
oncoatings can beweight
the molecular measured using aThe
of PDMS. contact mechanics
contact angle wasmodel (the
measured
hertz model) using AFM. Young’s moduli of PDMS coatings were found to be around 0.3–
in static conditions. Figure 6a shows the results of contact angle measurements for three
3.2 MPa. Variation depending on the chain size of the different polymers was observed.
PDMS-0.8K with the lowest molecular weight seems to have a higher value of elastic mod-
ulus (3.20 ± 0.01 MPa) compared to other coatings. PDMS-2.5K (0.58 ± 0.01 MPa), PDMS-
4K (1.64 ± 0.08 MPa), PDMS-6K (0.44 ± 0.03 MPa) and PDMS-10K (0.34 ± 0.11 MPa) appear
to be in the same range. Therefore, the molecular weight seems to affect elastic moduli,
Coatings 2024, 14, 149 10 of 15

solvents. Unsurprisingly, all PDMS coatings showed a hydrophobic character, with high
contact angle values comparable to what is found in the literature (θwater ≥ 100◦ ). PDMS-
2.5K was slightly more hydrophobic than other PDMS-based coatings (θwater = 108◦ ). There
was no change in hydrophobicity as function of molecular weight of the PDMS coatings.
Figure 6b illustrates the surface energy (SE) calculated from the water contact angle (WCA),
Coatings 2024, 14, x FOR PEER REVIEW 10 of 15
methylene iodide (MICA), and formamide (FCA) values using the Owen–Wendt method.
Surface energies of the PDMS coatings were between 18 and 23 mN/m. Gevaux et al. found
similar values for the surface energy of PDMS coatings (γs ≈ 18 mN/m) [28]. Lower surface
energy
18 mN/m) was[28].
observed
Lowerfor the PDMS-0.8K
surface energy was coating withfor
observed lowthemolecular
PDMS-0.8K weight. Despite
coating with this,
low
there was no
molecular correlation
weight. Despitebetween surface
this, there was energy and molecular
no correlation betweenweight.
surfaceThis implies
energy and that
mo-
there
lecularisweight.
no chemical changethat
This implies at the surface
there is no of the coating
chemical change depending on the
at the surface sizecoating
of the of the
macromolecules at this scale.
depending on the size of the macromolecules at this scale.

Figure 6.
Figure 6. Contact
Contactangle
anglemeasurement
measurementwith
withdifferent
differentsolvents
solvents(a)(a) and
and surface
surface energy
energy calculation
calculation (b)(b)
of
of PDMS-based coatings.
PDMS-based coatings.

3.4. Marine Field Test

The evaluation of the antibioadhesion and self-cleaning performances of PDMS coat-
ings was carried
carried using
usingin insitu
situexperiments.
experiments.Coated Coated PVC-panels
PVC-panels were
wereimmersed
immersed in the At-
in the
lantic Ocean
Atlantic Ocean in in
static conditions
static conditions forfor
12 12
months.
months. It isItimportant to note
is important thatthat
to note theythey
were im-
were
mersed at at
immersed thethebeginning
beginningofofthe thesummer
summerseason,
season,whichwhichisisthethe harshest
harshest season
season for fouling
development. In temperate climates, seasonality has a significant impact on the coloniza-
tion and success of biofouling communities;
communities; less less fouling
fouling develops
develops in the winter
winter as a result
of the
the lower
lower seawater
seawater temperature
temperature and and solar
solar radiation
radiation intensity
intensity [29,30].
[29,30]. Higher
Higher fouling
fouling
pressure
pressure results
results from
from rising
rising nutrient
nutrient levels
levels and
and seawater
seawater temperature from spring to late
summer. In this present work, the impact impact of of solar
solar radiation
radiation on on the
the fouling
fouling communities
communities
was
was also evaluated by observing the proliferation of macrofouling on different different immerged
surfaces.
surfaces. Two faces of coated surfaces were observed: observed: one face exposed to the sun and the
other
other not. The antibioadhesion efficiency
efficiency of the coatings was assessed by comparison with
an uncoated PVC surface, as
an uncoated PVC surface, as a control.a control.
Firstly,
Firstly, the
the images
images were
were observed
observed after
after 55 months
months of of immersion.
immersion. TheThe different
different images
images
in
in Figure
Figure 77 show
show the the antibioadhesion
antibioadhesion efficiency
efficiency depending
depending on on the
the PDMS
PDMS molecular
molecular weight
weight
and
and solar radiation after 5 months. As expected, the control surfaces were quickly fouled
solar radiation after 5 months. As expected, the control surfaces were quickly fouled
by
by macroorganisms,
macroorganisms, indicating
indicating the the suitability
suitability of of the
the chosen
chosen immersion
immersion site.site. Different
Different
types
types of
of marine
marine fouling
fouling adhered
adhered depending
depending on on the
the solar
solar radiation.
radiation. Surfaces
Surfaces exposed
exposed toto
solar
solar radiation were mostly covered by brown slime and algae. However, with no
radiation were mostly covered by brown slime and algae. However, with no solar
solar
radiation
radiation surfaces
surfaces werewere mainly
mainly colonized
colonized by by other
other hardhard fouling
fouling organisms:
organisms: barnacles,
barnacles,
sponges, or bryozoans. After five months in seawater, all samples were colonized, but
covered less than the control. The best antibioadhesion efficiency for panels under solar
exposition was observed for PDMS-2.5K and PDMS-4K. For panels immersed in the ab-
sence of solar exposition the PDMS-2.5K did not exhibit the same AF efficiency. The self-
cleaning properties of PDMS-6K were observed after three months, as organisms were
Coatings 2024, 14, 149 11 of 15

sponges, or bryozoans. After five months in seawater, all samples were colonized, but
covered less than the control. The best antibioadhesion efficiency for panels under solar
exposition was observed for PDMS-2.5K and PDMS-4K. For panels immersed in the absence
of solar exposition the PDMS-2.5K did not exhibit the same AF efficiency. The self-cleaning
properties of PDMS-6K were observed after three months, as organisms were removed
during immersion without any intervention, indicating their weaker adhesion to the surface.
The same property was observed for PDMS-4K. An image of this phenomenon can be
seen in the supplementary data (Figure S2). The efficiency of fouling release coatings
is estimated by the strength of adhesion of settled fouling organisms [4,5,31]. Hence,
PDMS-4K and PDMS-6K seemed to display a fouling release efficiency because of their
self-cleaning capacity.
The antibioadhesion efficiency of all PDMS-based coatings after 12 months can be
seen in Figure 8. After 12 months of immersion, the PDMS-6K sample started to lose its
antibioadhesion efficiency while the PDMS-2.5K and PDMS-4K coatings still exhibited the
best efficiency under solar radiation, being only covered by a brown film of algae. The
PDMS samples with the highest molecular weight, PDMS-6K and PDMS-10K, exhibited
less antibioadhesion efficiency. The poor performance of the lowest molecular weight,
PDMS-0.8K, could be attributed to its poor film-forming properties. The coating exhibited
cracks before immersion which created heterogeneity on the surface and anchor points
for the biofouling. In the absence of solar exposition, all the surfaces were completely
covered after 12 months of immersion, with no significant difference between the PDMS
surfaces (Figure 8). However, the biovolume of fouling settled on surface was found to
be greatly lower after 12 months compared to 5 months. These results showed that in
terms of efficiency, two groups of molecular weight could be distinguished, with better
efficiency for lower molecular weight. It is difficult here to make a correlation between
surface energy and the settlement. Different reviews reported that lower surface energy
contributed to decreased bacterial settlement. In the present case, no significant change was
observed for PDMS coatings in terms of surface energy measurement, and the observed
surface energy values were consistent with the minimum range defined by Baier [4] for
best fouling release properties. Despite that, differences in antibioadhesion efficiency have
been observed. It’s also known that surface roughness plays an important role in the
adhesion process: lower surface roughness can reduce bacterial adhesion [20]. However,
this observation remains controversial, as in certain studies the opposite result has been
observed. In fact, Liu et al. studied the adhesion of Escherichia coli (Gram-negative)
and Staphylococcus aureus (Gram-positIve) on nanostructured PDMS surfaces, and found
that increasing the nanoscale roughness on PDMS surfaces alone can inhibit bacterial
adhesion and growth for both bacteria [32]. In a recent review on the effect of surface
structure on bacterial adhesion [33], Yang et al. plotted the adhesion of cells as a function
of the roughness parameters (RMS or Ra) for various substrates. Above a critical Ra
value, estimated to be approximately 6 nm, their plot demonstrated a generally positive
correlation between the number of cells adsorbed on the surface and the roughness, while
a negative, or no correlation, is noted below the Ra value. They concluded that microscale
roughness generally encourages bacterial adhesion and nanoscale roughness provides the
best antibioadhesion efficiency [33].
In our work, we can see that our films have a nanometer size RMS (1–6 nm), even
if a small variation in nanoscale roughness with the molecular weight can be observed.
The nanometer RMS of our films (below the critical Ra value defined by Yang et al. [33])
is thus likely to have no impact on the adhesion of micro or macroorganisms, and this
parameter is probably not determinant in our experiments, as revealed by the bioadhesion
test in a real marine environment. Indeed, low long-term efficiency was observed for the
PDMS-6K and PDMS-10K coatings, which presented high roughness at the nanoscale as
compared with the PDMS-2.5K and PDMS-4K (low surface roughness), which showed
better efficiency. It appears that the RMS parameter alone cannot explain this difference,
 Coatings 2024, 14, x FOR PEER REVIEW 11
Coatings 2024, 14, 149 12 of 15

coatings is estimated by the strength of adhesion of settled fouling organisms [4,5

but that otherHence,
parameters should
PDMS-4K andbe PDMS-6K
considered,seemed
such astothe mechanical
display properties,
a fouling release or more becau
efficiency
local organizational parameters such as
their self-cleaning capacity. the glass temperature Tg or chain end.

Figure 7. Macrofouling
Figure 7. development
Macrofoulingobserved on PDMS-based
development observed oncoatings × 3 cm). (4 cm × 3 cm).
(4 cm coatings
PDMS-based

The antibioadhesion efficiency of all PDMS-based coatings after 12 months ca

seen in Figure 8. After 12 months of immersion, the PDMS-6K sample started to los
 ness parameters (RMS or Ra) for various substrates. Above a critical Ra value, estimated
to be approximately 6 nm, their plot demonstrated a generally positive correlation be-
tween the number of cells adsorbed on the surface and the roughness, while a negative,
or no correlation, is noted below the Ra value. They concluded that microscale roughness
Coatings 2024, 14, 149 generally encourages bacterial adhesion and nanoscale roughness provides the best13anti-
of 15
bioadhesion efficiency [33].

Figure
Figure8.
8.Marine
Marinefield
fieldtest
testof
ofPDMS-based
PDMS-basedcoatings
coatingsafter
after12
12months
months in
in Lorient
Lorient Bay
Bay (5
(5 cm
cm ××55cm).
cm).

In our work,
Stiffness waswe can see
found to bethat our films
another have a nanometer
parameter size RMS
which can affect (1–6 nm),
bacterial even in
adhesion if
adifferent
small variation in nanoscale roughness with the molecular weight can be observed.
studies [24,34], even if it is less well understood. Song et al. reported that a The
Young’s modulus
nanometer RMS ofofourPDMS
filmscoatings
(below theranging between
critical 0.1defined
Ra value and 2.6 by
MPa notetonly
Yang affected
al. [33]) the
is thus
attachment
likely to haveofno
bacteria,
impact but alsoadhesion
on the the morphology
of micro and antibiotic susceptibility
or macroorganisms, and this of attached
parameter
iscells [24]. More
probably biofilm growth
not determinant wasexperiments,
in our observed onasa revealed
soft PDMS bysurface (0.1 MPa)test
the bioadhesion thaninona
a stiff
real PDMSenvironment.
marine (2.6 MPa). Similar
Indeed,results were reported
low long-term by Valentin
efficiency Escherichia
et al. onfor
was observed the PDMS- coli
adhesion under dynamic condition [34]. It should be noted that the coatings obtained
in these previous studies were prepared in the presence of precursors. The PDMS-based
coatings prepared in this work were obtained via a self-condensation process, by varying
the molecular weight and some network properties. Our hypothesis is that in PDMS
coatings with higher molecular weight, the network is less dense due to the long distance
between crosslinking nodes compared to a network with a short chain. For example, this
spacing between meshes could change the mechanical properties. However, the preliminary
studies on PDMS surfaces prepared here showed surface stiffness between 0.3 and 3.2 MPa,
with no correlation with the molecular weight. Another property impacted by chain size is
the chain mobility between cross-linking nodes and the associated free volume. Indeed, in a
network of long chains, there is more free volume which could lead to different interactions
with organisms.
Finally hydrodynamic forces and shear stress may be responsible of the release of
organisms when it concerns a fouling release coating [31]. In these conditions, the smoother
the surface, the easier it is to release the organisms [35]. In our study, except for sample
PDMS-0.8K, the samples with lower surface roughness showed better antibioadhesion
activity than the samples with higher nanoscale surface roughness. Nevertheless, further
studies are needed to understand the network structure related to the molecular weight. It
is important to note that due to the complexity of the marine environment, other parameters
may be relevant during the adhesion process.

4. Conclusions
In this work, we investigated the impact of the molecular weight of PDMS on the
antibioadhesion efficiency of corresponding coatings. By varying the molecular weight,
we prepared five PDMS-based coatings via a condensation process. Soxhlet extraction
results confirmed that the PDMS networks were well crosslinked and showed there was
no significant free polymer chains. Homogenous PDMS coatings were obtained and
all PDMS-based coatings showed a low surface energy, low elastic modulus and low
surface roughness, making them suitable for marine applications. From contact angle
measurement, no correlation between the molecular weight and the surface energy was
observed. Moreover, changes in surface roughness were observed via AFM, with the
RMS increasing with the molecular weight due to the growth of network free volume.
Overall, PDMS-based surfaces showed good antibioadhesion activity and self-cleaning
Coatings 2024, 14, 149 14 of 15

abilities compared to the control after 12 months. The best antibioadhesion efficiency was
obtained for coatings with an Mn between 2 and 4 kg·mol−1 . This result is explained by
the chain mobility in the network. In situ immersion results showed that in the presence
or absence of solar radiation, different communities of organisms adhere on the surface,
leading to differences in antibioadhesion performance. This work provides evidence that
some network properties, depending on the size of the polymer chains, contribute to
antibioadhesion and self-cleaning efficiencies. However, further characterization is needed
to focus on the crosslinking density, the chain mobility, and the network structure of
PDMS-based coatings.

Supplementary Materials: The following supporting information can be downloaded at

https://www.mdpi.com/article/10.3390/coatings14010149/s1, Figure S1: SEM images of PDMS-
based coating as function of molar masses: (a) P PDMS-0.8K, (b) PDMS-2.5K, (c) PDMS-4K, (d)
PDMS-6K, (e) PDMS-10K; Figure S2: Attachment of macrofouling on sample PDMS-6K over time
with no solar radiation.
Author Contributions: Conceptualization, M.A.B. and F.A.; methodology, M.A.B., E.B. and F.A.;
investigation, M.A.B.; writing—original draft, M.A.B.; review & editing, F.A. and K.R.; resources,
M.A.B. and F.A.; funding acquisition, K.R. and I.L.; project administration, F.A. and I.L. Supervision,
D.M. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by Agence Nationale de la Recherche grant number
15-LCV4-0006.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data are contained within the article and supplementary materials.
Acknowledgments: We sincerely thank our industrial partner for the kind gift of some materials.
The authors want also to acknowledge Anthony Magueresse for help with SEM images.
Conflicts of Interest: The authors declare no conflict of interest.

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