Thermal Analysis (DMA, Stress-Strain, MDSC, TGA) Studies of Marine Coatings

Shyam Malliprakash1, 2, Ameya Khot1, 2, Ninad Dixit1, 2,

Ted Provder1 And John Texter1, 2
1
Coatings Research Institute and 2School of Engineering Technology
Eastern Michigan University, Ypsilanti, MI 48197, USA
E-mail address: [email protected]

ABSTRACT:
Marine top coats based upon Polydimethylsiloxane (PDMS) polymers and epoxy
based primer coating have been characterized by DMA, Stress-Strain analysis, TGA and
MDSC. Degree of cure of the epoxy coating by DMA has been determined by the Time-
Temperature Superposition method. Stress-Strain mechanical properties have been
determined for PDMS and Epoxy coatings. DMA analysis of PDMS coatings show that the
storage and loss moduli are inversely and directly proportional to film thickness for data
obtained from the thin film and shear sandwich clamp, respectively. These results are
important for the determination and application of an optimal thickness fouling release
coating. Also, DMA-WLF analysis of the PDMS coatings are compared with dielectric
spectra.

INTRODUCTION:
Bio-Fouling by the adherence of microorganisms on boat hulls is a major nuisance
for the shipping industries. The bio-fouling can cause corrosion and a decrease in
hydrodynamic transport efficiency and resulting in increased fuel consumption. To avoid
these problems anti-fouling coatings and fouling-release coatings have been used. However
leaching of anti-fouling coatings based on cuprous oxide or tin based compound causes
many environmental hazards.
The US- Navy desires to use only fouling release coatings. The service life of the
coating depends on the hardness-flexibility balance of the coating as a function of exposure
time to seawater and to hydrodynamic flow. The Hardness-flexibility balance and
erodibility of the coating will be directly affected by the mechanical properties of the
coating.
In this study, the thermal and mechanical properties of the top coat poly(dimethyl
siloxane) (PDMS) and epoxy based primer are characterized by Dynamic Mechanical
Analysis, Differential Scanning Calorimetry and by Thermo Gravimetric Analysis. The
Dynamic and ultimate mechanical properties, Glass Transition Temperature (Tg), Degree
of Cure of the coating and the film formation behavior are studied.

EXPERIMENTAL:
Thermal analyses were conducted with a TA Instruments (New Castle, Delaware)
Model Q800 Dynamical Mechanical Analyzer (DMA), TA Instruments Q2000 Differential
Scanning Calorimeter (DSC) and a TA Instruments Q500 Thermogravimetric Analyzer
(TGA). DMA studies were done at various temperatures, using liquid nitrogen as a coolant
and were generally done at 1 Hz with thin film, and shear sandwich clamps.
 Thin films ranging in thickness from 0.18 mm to 3.6 mm were obtained by casting
in molds machined into a Teflon block. A cutter just under 13 mm in diameter was used to
machine, at constant depth, rectangular molds about 31 mm long (plus the semicircular
ends).
The materials used for curing studies and for properties determination are
commercially available and were obtained from marine coatings supply sources. The
fouling release top coat paint was a three part formulation with 28% by weight VOC, and is
denoted as PDMS 1, PDMS 2 and PDMS 3. Each coating has different catalyst systems
and pigments. The Epoxy based primer is a two part formulation and with 55% by weight
VOC.

RESULTS AND DISCUSSION:

DSC Results:
MDSC profiles were obtained for the PDMS 1,2 and 3 samples. We could clearly
see a sharp crystalline like transition at ~ -50˚C which is believed to be ordering of the
PDMS polymer chains and corresponds to the β transition seen in the loss peak centered at
-55˚C obtained by the thin film clamp. The Tg α-transition is clearly seen at ~ -120˚C and
corresponds to the α transition seen in loss peak centered at -120˚C obtained by the thin
film clamp and the shear clamp. The MDSC data obtained on sample PDMS 1, PDMS 2
and PDMS 3 is shown in Figure 1 where the total heat flow, reversing and non-reversing
heat flow curves are displayed.

Figure 1: MDSC analysis of PDMS1, PDMS 2 and PDMS 3 showing α and β transition at -120˚C and
- 50˚C respectively.
DMA Result:
The liquid coating formulation were prepared at room temperature and coated on
Teflon sheet or cast on Teflon block and cured at 50˚C/ 80% RH for 24 hours before
measurements were made. The results for sample PDMS 1, 2 and 3 are shown in Figure 2-4
(left) for the storage and loss modulus using the thin film clamp at 1 Hz and (right) for the
storage and loss modulus using the shear clamp at 1 Hz.
For PDMS 1 and PDMS 2 in Figure 2 and Figure 3, the magnitude of the storage
modulus and loss modulus dramatically increases as sample thickness increases from
0.25mm to 1.87mm for the thin film clamp. Similarly, for shear sandwich clamp the
corresponding storage and loss modulus dramatically increases as sample thickness
decreases from 3.45mm to 0.22mm.

Figure 2: Loss and Storage Moduli for PDMS 1 fouling release cast thickness series of samples measured
by Thin film clamp (Left) and Shear clamp (Right) in DMA. The illustrated curves are for thicknesses (left)
0.25mm, 0.59mm, 0.65mm, 1.42mm and 1.87mm and (right) 0.22mm, 0.7mm, 1.5mm, 2.2mm and
3.45mm.
Figure 3: Loss and Storage Moduli for PDMS 2 fouling release cast thickness series of samples measured
by Thin film clamp (Left) and Shear clamp (Right) in DMA. The illustrated curves are for thicknesses (left)
0.28mm, 0.35mm, 0.53mm, 1.41mm and 1.97mm and (right) 0.76mm, 1.00mm, 1.5mm, 1.75mm and
3.00mm.

In the case of PDMS 3 shown in Figure 4 which does not contain pigment, an
opposite result for both the thin film clamp and the shear sandwich clamp is obtained. The
storage and loss modulus dramatically increases as the thickness of the sample decreases
from 0.28mm to 0.91mm for thin film clamp. In the case of Shear sandwich clamp, the loss
and storage modulus decreases as sample thickness decreases from 0.18mm to 0.77mm.

Figure 4: Loss and Storage Moduli for PDMS 3 fouling release cast thickness series of samples measured
by Thin film clamp (Left) and Shear clamp (Right) in DMA. The illustrated curves are for thicknesses (left)
0.28mm, 0.31mm, 0.54mm and 0.91mm and (right) 0.18mm, 0.38mm and 0.77mm
 For the epoxy coating series the castings (on the Teflon block) were cured for a
week at room temperature at room temperature and then heated at 50°C for several hours.
The epoxy results, for the storage modulus were obtained using a single cantilever clamp at
1 Hz. The magnitude of the storage modulus dramatically decreases as sample thickness
increases to several mm. Similarly, the corresponding loss modulus decreases with
increasing thickness, and further that the α (Tg) transition steadily shifts to lower
temperature by 10˚C to 30˚Cwith thickness increasing from 0.2mm to 3.6mm.

Stress-Strain Analysis:

Figure 5: Stress-Strain curves for Epoxy, PDMS 1, PDMS 2 and PDMS 3 fouling release cast samples, all
measured using a thin film clamp in DMA at 25˚C.

Stress-Strain curves are illustrated in Figure 5 for the epoxy primer sample and the
fouling release poly(dimethylsiloxane) topcoat samples PDMS 1 , PDMS 2 and PDMS 3.
The epoxy primer sample, filled with PTFE particles, exhibits a very high elastic modulus
(2) . The highest levels are of the order of 2.5-2.7 GPa. The strain % is also low which is on
the order of 1.005- 1.01%. This low strain at failure is indicative of a high crosslink density
brittle material.
The behavior illustrated in Figure 5 for the PDMS based coating is markedly
different. The elastic modulus of 1-5 MPa is in the range commonly encountered in
siloxane rubbers(7). The elasticity (strain at break) is a hundred- fold greater than that of
the epoxy, but markedly less than that obtained for PDMS in the absence of fillers.
However, it is believed that such a low modulus value is conducive to fouling release
behavior.
WLF Analysis:

Figure 6: Multi frequency curve (left) for Epoxy primer and the resulting master curve (right), it is
measured using single cantilever clamp in DMA at a temperature range from -50˚ to 180˚C for a frequency
range from 0.01Hz to 100Hz.

The DMA data from the cured epoxy sample was subjected to WLF analysis which
is shown in Figure 6. This WLF analysis is useful for comparing viscoelastic properties of
various coating formulations.

FUTURE WORK:
WLF analysis will be applied to PDMS samples and results are compared to Di-
electric spectroscopy results. Cure kinetics of epoxy sample will be studied with TTS
method of Neag and Prime (6)

CONCLUSION:
Methods to characterize fouling release coatings by stress-strain and dynamic
mechanical analysis techniques have been developed and applied to some commercial
fouling release coatings. The stress-strain studies yielded elastic (Young’s) moduli in
conformity with values reported for similar materials. The polydimethylsiloxane
formulation is much more rubbery than the epoxy primer. The effect of fillers on epoxy
elasticity has a dramatic effect on decreasing the strain at failure.
The three of the PDMS topcoats exhibited an inverse dependence of storage modulus
with coating thickness on the thin film clamp, while it showed a direct dependence of the
storage modulus on thickness on the shear sandwich clamp. The epoxy based primer
exhibited an inverse dependence of storage modulus with coating thickness on the single
cantilever clamp. The dependence on thickness has significant ramification for service life
and durability of the coatings.

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