Progress in Organic Coatings 62 (2008) 393–399

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Progress in Organic Coatings

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Phase morphology and surface properties of moisture cured polyurethane-urea

(MCPU) coatings: Effect of catalysts
S.K. Rath, A.M. Ishack, U.G. Suryavansi, L. Chandrasekhar, M. Patri ∗
Naval Materials Research Laboratory, Shil-Badlapur Road, Addl. Ambernath, Ambernath 421506, Maharashtra, India

a r t i c l e i n f o a b s t r a c t

Article history: Effect of catalysts on curing behaviour, phase morphology and surface properties of a moisture cured
Received 20 November 2007 polyurethane-urea (MCPU) coating has been studied. The prepolymer, prepared by capping hydroxy termi-
Received in revised form 13 February 2008 nated polybutadiene (HTPB) with isophorone diisocyanate (IPDI), was cured with moisture using different
Accepted 19 February 2008
urethane catalysts at 30 ◦ C and relative humidity of 60%. Fourier transform infrared spectroscopy (FTIR)
was used to monitor the curing process. Gel fraction studies through solubility method, show catalyst
Keywords:
induced shortening of induction period for gelation and increase in gel fraction. Effect of catalysts on
Moisture cure
phase morphology of the MCPU was evaluated by X-ray diffraction, small angle X-ray scattering (SAXS)
Polyurethane-urea
Phase morphology
and differential scanning calorimetry (DSC). The results show that the heat of fusion and interdomain
Surface property distance of hard segments are influenced by the choice of catalysts. The effect on surface properties was
evaluated by FTIR-ATR and contact angle goniometry. The type of H-bonding interaction was identified by
deconvolution of the FTIR spectra. The results show that the surface polar group concentrations increase
with increasing efficiency of the catalysts. Consequently there is a clear observation of catalyst induced
surface energy changes of the MCPU.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction phase separation include segmental polarity difference [11], seg-

Moisture cured polyurethane-ureas contain NCO-terminated
polyurethane prepolymer [1], which on curing in the presence
of atmospheric moisture produce highly crosslinked networks.
MCPUs are widely used in the high performance coating appli-
cations as well as reactive hot melt adhesive industries. The
advantages of one component polyurethane-urea systems have
been summarized by Gardner [2]. First of all they can be man-
ufactured as one package system and their application is easier.
Secondly since the reactant is water, the formulations have less VOC
than two component systems. In comparison to two component
polyurethanes, the MCPUs have good adhesion, abrasion resistance,
thermal stability, hardness, chemical and solvent resistance [3]. Fur-
ther these materials adhere well to visibly damp surfaces as they
penetrate into pores and tight crevices, where moisture is present.
In order to obtain adequate modulus and strength development, the
cure of NCO-terminated polyurethane prepolymer with moisture
requires a careful control of processing conditions. The parameters
affecting the cure process are relative humidity, isocyanate content
in the prepolymer and catalyst type [4,5].
Phase morphology of segmented polyurethanes has been stud-
ied extensively by researchers [6–10]. The factors which influence
mental length [12], crystallizability of either segment [13], intra-
and intersegment interactions such as hydrogen bonding [13,14].
overall composition and molecular weight [11]. Extensive phase
mixing of soft and hard segments of PTMG/IPDI based MCPUs and
their effect on surface properties are reported [15]. In compari-
son to segmented polyurethanes, the phase morphology studies
on MCPUs have been relatively scanty.
The behaviour of the MCPUs at the surface and interfaces has
a significant effect on various properties and plays a vital role in
coating applications. The surface composition of multicomponent
MCPUs during cure progress has been studied in detail by many
researchers [16–18]. XPS studies have shown the enrichment in soft
segments on the air-side surface of polyurethanes [19–21].
In the present study, hydroxy terminated polybutadiene capped
with isophorone diisocyanate has been used as the prepolymer
for MCPU formation. Effect of catalysts on curing, thermal proper-
ties, phase morphology and surface properties of MCPU have been
studied.
2. Experimental
2.1. Materials

Isophorone diisocyanate (IPDI) from E-Merck was used as

∗ Corresponding author. Tel.: +91 251 2620401x337; fax: +91 251 2620604. received. Hydroxy terminated polybutadiene (HTPB) (functional-
E-mail address: mrpatri@rediffmail.com (M. Patri). ity 2.4, OH value 50) was purchased from ORION Chem Ltd., India.

0300-9440/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2008.02.004
394 S.K. Rath et al. / Progress in Organic Coatings 62 (2008) 393–399
Dibutyltin dilaurate (DBTDL) was purchased from Fluka and used as
received. Ferric chloride and triethyl amine (TEA) were purchased
from S.D. Fine Chemicals, India. Trietheyl amine was vacuum dis-
tilled before use.
2.1.1. Synthesis of prepolymer
The prepolymer from IPDI and HTPB was synthesized at 60 ◦ C in
a three-necked R.B. flask equipped with a mechanical stirrer. The
molar ratio of NCO to OH groups was 2:1. The reaction was car-
ried without use of any catalysts under a dry nitrogen blanket until
the desired isocyanate content is obtained. Isocyanate content in
the prepolymer was determined by titration with diethyl amine
[22]. The NCO value was 3.48% compared to the theoretical value
of 3.64%.
2.2. Preparation of films
The prepolymer was mixed with different catalysts (0.05 wt%)
and the films were cast on a Teflon mould. The films were cured with
moisture at 30 ◦ C and 60% RH. The progress of curing was monitored
by monitoring the decay of the isocyanate band by FTIR spectra. The
time for complete cure for various catalysts were found to be 1120 h
(unanalysed), 1080 h (FeCl3 ), 930 h (TEA) and 820 h (DBTDL).
2.3. Characterization techniques
2.3.1. FTIR analysis
FTIR spectra of the samples were recorded using a PerkinElmer
1650 FTIR spectrophotometer with a resolution of 4 cm−1 and 32
scans. Crosslinking for the one component system was followed by
monitoring the disappearance of isocyanate band. In the FTIR anal-
ysis, integrated intensities of the absorbance bands were corrected
for sample thickness differences using the CH2 stretching band near
2980 cm−1 as normalising factor.
For calculating the degree of curing it is assumed that there are
no side reactions [11]. From the isocyanate conversion the degree
of curing was calculated as follows
At − A∞
Isocyanate conversion (p) = 1 −
A0 − A∞
Where A0 is the normalised area of absorption at the initial time,
At is the normalised area of absorption at a certain time during
the cure process, and A∞ is the final normalised area of absorption
at infinite time. For a completely cured system A∞ will be zero,
because no NCO functionality will be available for IR absorption in
such a case.
2.3.2. Determination of sol and gel fraction
The sol and gel fraction of the MCPUs with progress of cure was
evaluated by soxhlet extracting the MCPUs with toluene. The sol
fraction was determined using the following equation
W − W 
1
Sol fraction (%) = × 100
W1
where W is the initial weight and W1 is the weight of the sample
after extraction
Gel fraction (%) = 100 − sol fraction (%)
2.3.3. TGA
The thermal stability of the polymer film with progress of cure
was studied in Nitrogen environment using TA instruments Hi Res
2950 Thermogravimetric Analyser. The measurements were carried
out from 30 to 800 ◦ C at a heating rate of 10 ◦ C/min.
2.3.4. Wide-angle X-ray diffraction
The crystallinity of the MCPUs was evaluated by using Cu K␣ ray
of wavelength 1.54 Å between 10 and 30◦ at 0.2◦ /10 s in a Philips
X-ray diffractometer.
2.3.5. SAXS
Small angle X-ray scattering, SAXS (Ariton Paar, Austria) exper-
iments was performed on moisture cured polymer films using an
X-ray source having wavelength 1.54 Å. The samples were scanned
for 15 min at 25 ◦ C. The scattering patterns were recorded using the
collimation technique. The scattering patterns were integrated to
generate an I(q) versus q curve, where I(q) is the intensity of the
scattered X-rays and q is the scattering vector.
2.3.6. DSC
Calorimetric measurements of the completely cured MCPUs
were carried out using TA instruments DSC Q-100, from −80 ◦ C to
120 ◦ C at a heating rate of 5 ◦ C/min under nitrogen atmosphere. The
instrument was calibrated with Indium standards before measure-
ments.
2.3.7. FTIR-ATR
Attenuated total reflectance (ATR) analysis was carried out in
a Thermocom Nicholet 5700 spectrometer with a horizontal flat
plate ATR accessory. The ATR crystal was diamond with an end-
face angle of 45◦ . The substrate-facing side of the polymer film was
placed against the crystal and clamped into position. Each sam-
ple was scanned 100 times at a resolution of 4 cm−1 and the scans
were signal averaged. In ATR the depth of penetration for a non-
absorbing medium, defined as the distance required for the electric
field amplitude to fall to e−1 of its value at the surface, has been
given by Harrick [23].

dp =
2 0.5
2n1 (sin  − (n1 /n2 ) )
Where n1 is the refractive index of the sample and n2 is the refrac-
tive index of the ATR element. Micebella and Harrick [24] has shown
that sampling depth for polymeric materials is about three times dp .
2.4. Surface energy analysis through goniometry
The surface free energies of polymer samples were deter-
mined by contact angle goniometer using a Kruss G10 goniometry
interfaced to image capture software. The surface energy system
measures and averages contact angles of various liquids and cal-
culates the surface energy. Advancing ( A ) contact angles were
measured for droplets (2–10 ␮L) of double distilled water and
diidomethane using the movable protractor scale of the goniome-
ter. The spatial size probed (in the plane of the surface) was 1–2 mm
in diameter. The images of three droplet liquids of each test liquid
are taken by a CCD camera and the contact angles were determined
using automated image analysis.
3. Results and discussion
3.1. Cure behaviour of MCPUs
Hydroxy terminated polybutadiene with a functionality of 2.4
has been used for prepolymer synthesis. Hence during the cure
process a three dimensional network is formed without the aid of
an external crosslinker. The evidence of a crosslinked network is
apparent from the evaluation of the gel fraction by extraction of
the MCPUs with toluene. Fig. 1 shows the effect of catalysts on cure
time dependant gel fractions of the MCPU. From the results it is seen
 S.K. Rath et al. / Progress in Organic Coatings 62 (2008) 393–399
Fig. 1. Dependence of gel fraction on curing time of MCPU cured with various cat-
alysts.
that the induction period for gel formation is longer for uncatalysed
MCPU. With introduction of catalysts the induction period for gela-
tion decreases and the gel fraction content increases. However, in
a crosslinked network, still some unreacted functional groups exist
at the end of the curing process, some chains with low molecular
weight are entrained in the network and rendered inactive [25].
The possibility of entrainment of unreacted chains decreases with
the efficiency of the catalyst, hence the lower sol fraction.
The curing reaction of moisture cured polyurethane-ureas
(MCPUs) involves a series of polyaddition reactions which depends
upon the curing conditions. Water vapour from the atmosphere
diffuses into the MCPU, and the nucleophilic attack of water on
NCO-terminated prepolymer results in an irreversible reaction,
which produces carbamic acid. The carbamic acid is unstable at
room temperature and decomposes into CO2 and a primary amine.
The primary amine is reactive with the NCO-terminated prepoly-
mer and produces urea. The cure progress was monitored by FTIR,
monitoring the disappearance of the –NCO peak. Fig. 2 illustrates
Fig. 2. FTIR spectra of HTPB/IPDI, showing the decay of NCO group at a cure time of
760 h (film thickness 0.15 mm).
395
the FTIR spectrum (corresponding to the isocyanate band) of the
MCPUs after 760 h of cure time. From the figure it is seen that the
intensity of unreacted isocyanate peak is of the order: no cata-
lyst > FeCl3 > triethyl amine > DBTDL. At this cure time the DBTDL
catalysed system has approached 92% completion of the cure,
whereas without catalyst only 33% completion of cure has been
accomplished. Complete curing of uncatalysed prepolymer took
place in 1120 h, whereas the DBTDL catalysed system cured in 820 h.
From the FTIR results, it is clear that use of catalysts hastens the
cure process and DBTDL is found to be the most efficient catalyst
followed by triethylamine and ferric chloride.
Now we discuss the gel fraction and curing process results
vis à vis the reactivity of IPDI towards various catalysts. Among
diisocyanates, IPDI possesses a primary aliphatic and a secondary
cylcoaliphatic isocyanate group leading to four isomers from cis
and trans conformation [26]. An unequal reactivity between the
primary and secondary NCO groups is usually reported. Depend-
ing on the reaction conditions of temperature and catalyst type,
the reactivity difference ratio between the secondary and the pri-
mary isocyanates is reported to be in the range 0.2:1–12:1 [26].
Lamölder et al. [27] showed that catalyst nature had a dramatic
effect on the selectivity of IPDI in the urethane reaction. Further
Burel et al. [26] studied the effect of catalyst concentration and
temperature on kinetics of urethane reactions. They found that the
selectivity decreases and tends towards a plateau as DBTDL con-
tent increases. In the present study the catalyst concentration has
been fixed for all the compositions. Moreover, the curing process
leads to formation of urea functional groups instead of urethanes.
Based on the observations of Burel et al. [26] we presume that in
the capping reaction the primary aliphatic isocyanates of IPDI are
involved (in absence of any catalyst) owing to their higher reactiv-
ity compared to secondary isocyanate functional group. Thus, the
secondary cycloaliphatic isocyanates are expected to participate in
urea formation. The longer curing times observed for the uncatal-
ysed system provide evidence to our presumption. Moreover, since
the curing process was carried out at room temperature and same
concentration of catalyst (0.05 wt%) for all the systems, selectivity
of the isocyanates is not expected to be altered.
It must be noted that the composition of the MCPUs is same,
except for the nature of catalysts. The hard and soft segment
concentration of the completely cured MCPUs were calculated as
follows.
MOH + Miso + Mce
Hard segment concentration (%) = × 100
Mtotal
where MOH is the molecular mass of hydroxyl group of polyol, i.e.
HTPB, Miso is the molecular mass of isocyanate compound used, i.e.
IPDI, Mce is the molecular mass of chain extender, i.e. water, Mtotal
is the total molecular mass. The calculations were carried out based
on the 2:1 molar ratio of IPDI/HTPB used in the capping reaction and
accordingly the amount of water required for complete curing.
Soft segment concentration (%)
= 100 − hard segment concentration (%)
3.2. TGA
The weight loss versus temperature plot of the MCPU cured
by using different catalysts is shown in Fig. 3. The tests were car-
ried out after a cure time of 760 h which corresponds to different
degree of cure with different catalysts. From the figure it is seen
that the DBTDL catalysed MCPU shows slightly higher thermal sta-
bility compared to other systems. Enhancement of thermal stability
could be attributed to the progress of cure for the samples. Further
396 S.K. Rath et al. / Progress in Organic Coatings 62 (2008) 393–399
Fig. 3. TGA thermogram of moisture cured polyurethane-ureas catalysed with dif-
ferent catalysts at a cure time of 760 h.
it is seen that the degradation pattern of the MCPU for all the cat-
alysts is similar, with a two-step decomposition profile. The initial
decomposition temperature is 285 ◦ C for the DBTDL catalysed sys-
tem at the given cure time. The other systems differ only marginally
in the order TEA > FeCl3 > uncatalysed reflecting the cure progress.
This result is in line with our FTIR results of DBTDL being the most
efficient catalyst in the cure process followed by TEA, FeCl3 .
3.3. Morphology studies
3.3.1. Wide-angle X-ray diffraction (WAXD)
It has been previously reported [28,29] that polyureas exhibit
crystallinity. In this study, the crystallinity of the MCPUs was
examined by WAXD. Fig. 4 shows the diffraction patterns of the
MCPUs. From the figure it is seen that the diffraction patterns in
all cases exhibit a dominant amorphous halo indicating absence of
crystalinity. These results are in agreement with previous studies
that shown that polyureas containing nonsymmetrical structure
are amorphous and that introduction of chemical crosslinks in
polyurethanes disrupts the crystallinity [30]. From the gel frac-
tion studies it is already evident that the MCPUs are crosslinked,
Fig. 4. Wide-angle X-ray diffraction of moisture cured polyurethane-ureas catalysed
with different catalysts.
Fig. 5. SAXS plot (I vs. q) of moisture cured polyurethane-ureas catalysed with
different catalysts.
although the extent varies with nature of catalysts. Hence it is likely
that this same situation is produced in the MCPU synthesized in this
study.
3.3.2. SAXS
The polybutadiene based polyurethane networks are reported to
exhibit a pronounced two-phase structure [31,32] As follows from
Fig. 5 an interference maximum is observed in the scattering vec-
tor range 0.7–1 nm−1 for all the curves (SAXS experiments were
performed only on uncatalysed, DBTDL and TEA catalysed MCPUs).
This type of SAXS curve could be attributed to a two-phase struc-
ture. In the MCPU system, first phase, the soft one, is formed by
the butadiene component of the network, while the urea and ure-
thane form hard segments, the second phase. This structure model
of the moisture cured polyurethenae-ureas is quite similar to the
ones studied by others for polybutadiene based networks [31].
In the tracking of morphological changes, one of the key exper-
imentally determined parameters is the interdomain spacing from
SAXS. The interdomain distance (L) defined as the average distance
between two hard domains can be obtained from the SAXS intensity
profiles by the application of Bragg’s equation: L = 2/qmax , where
qmax is defined as the first-order scattering maximum. The interdo-
main values obtained from the SAXS plots are presented in Table 1.
From the results it is seen that catalysts affect the interdomain dis-
tance. It is well established that the interdomain distance depends
on the hard and soft segment composition of a phase separated
material. The hard segment concentration of the present MCPU is
20.1%. On investigating a series of polyurethane elastomers with
varied hard segment concentration, Abouzhar et al. [33] proposed
Table 1
Effect of catalysts on the interdomain distance and enthalpy of fusion of MCPU
Catalyst Interdomain distance (nm) Enthalpy of fusion (J/gm)
None 8.3 0.246
FeCl3 – 0.203
TEA 8.6 0.051
*
DBTDL 8.5
*
A base line shift is observed instead of an endotherm.
 S.K. Rath et al. / Progress in Organic Coatings 62 (2008) 393–399
Fig. 6. DSC thermogram of fully cured poly urethane-ureas cured with different
catalysts.
an interconnected hard segment morphology at relatively higher
hard segment concentration (>25 wt%). They suggested that ran-
domly dispersed micro domains existed in the polyol matrix when
the hard segment concentration is less then 25 wt%. We cannot
therefore conclusively comment on the effect of catalysts on distri-
bution of hard segments from the present data at a hard segment
concentration of less then 25 wt%, as the results do not show any
particular trend of interdomain distance with introduction of cat-
alysts. However, DSC results give additional information regarding
the hard segments, which is discussed later.
3.3.3. DSC
Fig. 6 shows the DSC thermogram of HTPB and the fully cured
MCPU cured with various catalysts. From the figure it is seen that
HTPB has a sub-room temperature transition at −26.2 ◦ C, which cor-
responds to the glass transition temperature. The MCPU show two
transitions for all the catalysts. The low temperature transition cor-
responds to the soft segment, the polybutadiene segment, whereas
the high temperature transition at 53–55 ◦ C corresponds to the
hard segment, i.e. transition associated with breakdown of hydro-
gen bonding between hard segments of urethane/urea groups. Two
transitions clearly suggest that the MCPUs are phase separated
as found from SAXS studies. Very recently Daniel Da-Silva et al.
[34] showed the evidence of phase separation in moisture cured
polyurethane-ureas by means of modulated differential scanning
calorimetry. Through irreversible heat flow measurements, they
found the location of the broad endotherms in the range 60–100 ◦ C.
In the present study we observe mild endotherms (through con-
vention DSC measurement) attributable to the lower hard segment
content of the MCPUs. The enthalpy of fusion of the hard segments
is given in Table 1. From the results it is seen that the uncatalysed
MCPU has the highest H value, suggesting bigger hard domain
sizes. The H value decreases with catalysts. Interestingly enough,
with increase in catalytic activity of the catalysts, the enthalpy of
fusion decreases. This provides evidence to our speculation that
rapid aggregation behaviour decreases the hard domain size. The
DSC results by Kwei [35] on segmented polyurethanes showed that
the phase separation of soft and hard segments was relatively faster
while the ordering of hard segments took a longer time. Further Li
et al. [36] argued that hard segment mobility and system viscos-
ity are the main controlling factors for the phase behaviour of the
polyurethanes. The same reasoning holds well for the present study.
Further the observation of domain formation could be attributed
to the large difference in the reactivity of the cycloaliphatic sec-
397
Fig. 7. FTIR-ATR spectra of the air-side surface of fully cured polyurethane-ureas
catalysed with different catalysts.
ondary isocyanate and the primary aliphatic isocyanates. As already
mentioned in the discussion on curing studies, the less reactive
secondary isocyanates are involved in the urea formation, which
contributes to the ordered domain formation. The slower reactiv-
ity of the secondary isocyanates provides ample time for formation
of ordered domains of ordered urea hydrogen bonds involving the
urea functional groups as discussed in the FTIR-ATR analysis. With
catalysts the system viscosity builds up and hence the hard segment
mobility is hindered. Thus, the ordering of hard segments would be
incomplete even in otherwise fully cured MCPU.
3.4. Surface properties
3.4.1. FTIR-ATR
Fig. 7 shows the FTIR-ATR spectra (for the polar urethane and
urea groups) of the fully cured MCPU cured with different catalysts.
A spectral range from 1600 to 1750 cm−1 was chosen to emphasize
the carbonyl region which contributes to the polarity of the surface.
The sampling depth for the ATR analysis at various wave numbers
in the carbonyl region was found to be 3–3.7 ␮m. The refractive
index of the MCPU was found to be 1.5156 from Abbe refractome-
ter and does not change with nature of the curing catalysts. Hence
the sampling depths in the analysis did not vary with the nature of
the catalyst. From the spectra a complex band envelope is observed
in this region of urea and urethane carbonyls in different environ-
ments. Hence to identify the underlying component bands in the
C O zone deconvolution of the peaks were performed. The spec-
tra of MCPU (uncatalysed) were chosen for display to identify the
component bands. Fig. 8 shows the deconvoluted spectra of the
uncatalysed MCPU. The band assignments of the C O zone is illus-
trated in Table 2. The degree of phase separation was evaluated by
the area analysis of the free and bonded urea and urethane peaks.
Table 2
Infrared stretching band assignments of the carbonyl group in the MCPUs as seen
from the deconvoluted FTIR-ATR spectra
Functional group Wavenumber (cm−1 ) Band assignment
(C O) urethane 1740–1730 Free urethane
1730–1725 H-bonded urethane
(C O) urea 1700–1690 Free urea
1690–1650 Monodentate urea (less ordered
H-bonded urea)
1650–1640 Bidentate urea (ordered urea
H-bonded urea)
398 S.K. Rath et al. / Progress in Organic Coatings 62 (2008) 393–399

Fig. 8. Representative deconvoluted FTIR-ATR spectra of unctalyzed MCPU.

Table 3
Fraction of free and bonded, urea and urethane carbonyl from deconvoluted FTIR-ATR spectra

Sample A (urea C OH-bonded)/At A (urea C O free)/At A (urethane C O H-bonded)/At A (urethane C O free)/At

Uncatalysed 0.46 0.54 0.39 0.61

FeCl3 0.42 0.58 0.36 0.64
TEA 0.39 0.61 0.33 0.67
DBTDL 0.34 0.66 0.29 0.71

At is the total area encompassing the carbonyl peak.

From the results in Table 3, it is seen that the bonded urethane and Table 4
Effect of catalysts on the surface energy of MCPU
urea fractions decrease with increasing catalytic activity. That is the
free carbonyl fraction for both urea and urethanes increase. Since Catalyst Surface energy Disperse Polar
the unsatisfied bonding potential of the free carbonyl is larger com- (, mJ/m2 ) component ( d , component ( p ,
mJ/m2 ) mJ/m2 )
pared to bonded ones, it can be concluded that the free energy of the
surface increases with increasing catalytic activity of the catalysts. None 34.6 ± 0.58 32.2 ± 0.32 2.4 ± 0.09
FeCl3 37 ± 0.69 34.1 ± 0.38 2.9 ± 0.14
TEA 38.9 ± 0.73 35.3 ± 0.39 3.7 ± 0.19
3.4.2. Surface energy DBTDL 40.4 ± 0.79 35.8 ± 0.42 4.6 ± 0.22
Surface energies were evaluated using the surface tension-
component theory. According to this approach, the surface tension
of a phase could be divided up into independent components such
as London dispersions contribution  d and polar contribution  p ,
as represented below. The variation of surface energy of the MCPUs with different
catalysts is shown in Table 4. It must be noted that because of
 = d + p the observed variation in surface roughness between samples,
the reported values do not represent the true surface energy of
For a drop of liquid at equilibrium with a solid surface, the
the materials and are presented for reasons of comparison only.
liquid–solid contact angle () is given by the following equation
From the results it is seen that the surface energy of the unac-
talyzed MCPU is 34.6 ± 0.58 mJ/m2 with a polar component of
L (1 + cos ) 1/2 p 1/2 1/2 2.4 ± 0.09 mJ/m2 . It is observed that with introduction of cata-
= (SP ) (L Ld ) + (Sd )
1/2 lysts the surface energy increases. Further with increasing catalytic
2(Ld )
activity the surface energy of the MCPUs increase. The polar com-
Where  L is the surface tension of the liquid and subscript S = solid ponent contribution to the surface energy is also found to follow
p
and L = liquid. ␥L , Ld , L can be found in literature [37]. In this study the same trend. With introduction of catalysts the viscosity of the
diiodomethane and water were used as the probing liquids. For MCPUs increases, thus the diffusion of the hard segments towards
p
water  L = 72.8 mJ/m2 , L = 51.0 mJ/m2 and Ld = 21.8 mJ/m2 . For the bulk away from the air interface is hindered. This in turn causes
p
diidomethane  L = 50.76 mJ/m2 , L = 0 mJ/m2 , Ld = 50.76 mJ/m2 localization of the polar segments compared to unanalysed MCPUs.
◦
at 20 C. Hence by measuring the contact angle for two well char- This trend is supported by the findings from FTIR-ATR analysis that
p
acterized liquids two equations with two unknowns, i.e. Sd and S the fraction of free carbonyl content with increasing catalytic activ-
p ity as observed in FTIR-ATR.
are generated. The surface energy S = Sd + S can be obtained.
 S.K. Rath et al. / Progress in Organic Coatings 62 (2008) 393–399 399

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