Progress in Organic Coatings 71 (2011) 136146

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Progress in Organic Coatings

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Waterborne polyurethane dispersions obtained with polycarbonate of

hexanediol intended for use as coatings
Vanesa Garca-Pacios a , Vctor Costa b , Manuel Colera b , Jos Miguel Martn-Martnez a,
a
b

Adhesion & Adhesives Laboratory, University of Alicante, 03080 Alicante, Spain

UBE CHEMICAL EUROPE, S.A. Zone El Serrallo, 12100 Grao, Castelln, Spain

a r t i c l e

i n f o

Article history:
Received 10 November 2010
Received in revised form 19 January 2011
Accepted 19 January 2011
Keywords:
Polyurethane coating
Stainless steel
Waterborne polyurethane dispersion
Polycarbonate of hexanediol
NCO/OH ratio

a b s t r a c t
Three waterborne polyurethane dispersions derived from polycarbonate of hexanediol (PCD) with molecular weight of 1000 Da were synthesized by the acetone method and used as coatings for stainless
steel plates. Different hard segments content in the polyurethanes were obtained by varying the isocyanate/macroglycol (NCO/OH) molar ratio. A decrease in the NCO/OH ratio produced an increase in
the mean particle size as well as a decrease in the Brookeld viscosity of the dispersions. Furthermore,
the greater the NCO/OH ratio the higher the urea and urethane hard segment content, the higher the
glass transition temperature value and the higher the elastic modulus of the polyurethane was. On
the other hand, the NCO/OH ratio affected the adhesion of the polyurethanes. The adhesion was evaluated by using three different procedures: T-peel strength tests of exible PVC/waterborne polyurethane
dispersion/exible PVC joints; single lap-shear tests of aluminium/waterborne polyurethane dispersion/aluminium joints and cross-cutter adhesion test of polyurethane coatings on stainless steel pieces.
Finally, several properties of the polyurethane coatings on stainless steel pieces were tested including
Persoz hardness, gloss, chemical resistance and yellowness index.
2011 Elsevier B.V. All rights reserved.

1. Introduction
The emission of organic solvent is severe problem for solventborne polyurethane coatings. It is mandatory to decrease the
level of volatile organic compounds (VOCs) for environmental and
health protection. Polyurethane dispersions (PUDs) have received
increased attention because they are non-toxic, non-ammable
and do not pollute the air. In particular, waterborne polyurethane
has merged as a new chemical technology for ecofriendly adhesive
and coatings.
Aqueous polyurethane dispersion coatings are one of the examples compliant with the removal of COVs as they are expanding
their applications in various elds [1,2]. Polyurethanes have been
used extensively in coating industry and they are currently one
of the growing industrial markets due to their excellent abrasion
resistance, exibility at low temperature, and excellent chemical,
mechanical and physical properties. PUDs are mainly used as exible coatings for textiles and hard coatings for wood and metallic
surfaces.
Waterborne polyurethane dispersion consists in linear thermoplastic polyurethane chains dispersed in water due to the presence

Corresponding author. Tel.: +34 96 5903977; fax: +34 96 5903454.

E-mail address: jm.martin@ua.es (J.M. Martn-Martnez).
0300-9440/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2011.01.006

of ionic groups in the structure (i.e. polyurethane ionomer), which

act as internal emulsier. Typically, an NCO-ended prepolymer
ionomer is rst prepared, which is readily dissolved in acetone.
Afterwards, a chain extender, such as diamine, is added to react
with the terminal NCO groups to increase the molecular weight of
the polymer. For facilitating the dispersion of the polyurethane in
water, the acetone has to be removed to produce phase inversion
and thus obtain the polyurethane dispersion. A major ingredient
of the PUDs is the polyol (i.e. hydroxyl ended oligomer) as it provides their main properties such as exibility, cross-linking ability
or thermosetting potential. Several polyols can be used to manufacture PUDs such as polyesters, polyethers, polycarbonates and
renewable source based polyols [3].
The properties of the PUDs are mainly determined by the
interactions between the hard and soft segments, and by the
interactions between the ionic groups [4]. The hard segments are
mainly produced by reacting the isocyanate and the chain extender and they are polar and impart the mechanical properties to the
polyurethane. On the other hand, the soft segments are mainly due
to the polyol chains and they are non-polar and imparted the exibility to the polyurethane. Recent studies [517] demonstrated that
the ionic group content, segmented structure, molecular weight
of the polyol, the type of chain extender and the hard/soft segments ratio determined the PUDs properties. However, there are
few studies dealing with the synthesis and characterization of
polyurethanes based on polycarbonate polyols [1824].

V. Garca-Pacios et al. / Progress in Organic Coatings 71 (2011) 136146

137

O
OH

OH
n

Fig. 1. Chemical structure of polycarbonate diol.

Polycarbonate diol (PCD) (Fig. 1) has been extensively used

to manufacture biocompatible biomaterials with high mechanical properties. The use of polycarbonate diols, as compared to
polyester and polyether polyols, imparts better hydrolysis resistance, improved ageing and oil resistance, and increases the
weathering and fungi resistance of the polyurethanes [13,25]. On
the other hand, the polyurethanes synthesized with PCDs show several advantages with respect to those obtained with polyether or
polyester polyol, such as excellent hydrolytic stability, better elastomeric properties, higher mechanical properties and improved
resistance at low temperature.
Little effort has been paid on synthesizing and characterizing
waterborne polyurethane dispersions derived from polycarbonate
diols. To the best of our knowledge, there are two studies only
[13,25] which consider the synthesis and characterization of aqueous polyurethane dispersions derived from polycarbonate diols but
the use of PUDs as coatings has not been studied. However, there
are some papers on PUDs coatings manufactured with other polyols
[26,27]. Therefore, in this study the preparation and characterization of PUDs based on polycarbonate of hexanediol and different
NCO/OH ratios to produce polyurethane coatings have been carried
out. Several properties of the polyurethane coatings were studied
such as the drying time, thickness, Persoz hardness, gloss, yellowness index and chemical resistance.
2. Experimental
2.1. Materials
The aqueous polyurethane dispersions were prepared by the
acetone process consisting in the reaction of an isocyanate, a
polyol, an internal emulsier and a chain extender. Polycarbonate
of hexanediol (Mw = 1011 Da) (supplied by UBE Chemical Europe,
Castelln, Spain) was used as polyol, and it was melted at 70 C for
8 h before use.
The diisocyanate used was isophorone diisocyanate (IPDI,
98 wt% purity) (mixture of cis/trans isomers) (supplied by
Aldrich, Barcelona, Spain) which is liquid at room temperature.
Diethyleneglycol (DEG, 99 wt% purity) and dimethylolpropionic
acid (DMPA, 98 wt% purity) (both supplied by Aldrich, Barcelona,
Spain) were used as short diol and internal emulsier, respectively,
without further purication. Triethylamine (TEA, 99 wt% purity)
was used as neutralization agent, and monohydrated hydrazine
(HZ, 99 wt% purity) (both supplied by Fluka, Madrid, Spain) was
used as chain extender. Deionised water was used as dispersing
phase, and high purity acetone (99.5 wt% purity) was also used.
2.2. Synthesis of the waterborne polyurethane dispersions
Three aqueous polyurethane dispersions with different hard to
soft segments molar ratios (NCO/OH = 1.3, 1.5 and 1.7) were prepared by the acetone process. The DEG content was set to 0.5 wt%
and that of DMPA to 5 wt% (both with respect to the prepolymer).
The nomenclature of the waterborne polyurethane dispersions
consists in the capital letters PU followed by the NCO/OH ratio.
The polyol, IPDI, DEG and DMPA were added to a glass jacketed reactor equipped with a mechanical stirrer to obtain the
prepolymer. The reaction was carried out at 80 C under nitrogen

atmosphere. When the amount of residual NCO groups reached

the desired value (it was obtained by n-dibutylamine titration),
the prepolymer was dissolved in acetone at 4555 C by continuous stirring at 450 rpm until complete dissolution and then
triethylamine (TEA) aqueous solution was added to neutralize
the carboxylic acid moieties of the DMPA. Afterwards, the chain
extender (hidrazine) was added to complete the reaction with the
unreacted NCO groups. Then, water was added and the mixture was
stirred at 900 rpm. Finally, the residual acetone was removed in a
rota vapour unit at 50 C and 300 mbar for 60 min.
2.3. Preparation of the polyurethane lms
Some properties of the polyurethanes were measured in solid
lms that were prepared by placing about 100 cm3 of polyurethane
dispersion in a Teon mould and allowing slow evaporation of the
water at room temperature for 72 h. Afterwards, the remaining
water in the polyurethane was removed by heating at 40 C for 8 h.
Polyurethane lms were about 0.70.9 mm thick.
2.4. Preparation of the polyurethane coatings
Waterborne polyurethane dispersions were applied on stainless steel plates 304 by means of a metering rod of 200 m. The
polyurethane coatings were obtained by drying at room temperature for 72 h.
2.5. Experimental techniques
2.5.1. Characterization of the waterborne polyurethane
dispersions (PUDs)
2.5.1.1. pH measurement. About 25 ml PUD was placed in a beaker.
The pH values of the polyurethane aqueous dispersions were measured at 25 C in a pH meter using a silver reference electrode model
HI 8418 (Oakton Instruments, Vernon Hills, USA). The pH was calculated as the average of three experimental determinations.
2.5.1.2. Particle size. The mean particle size and the particle size
distribution of the PUDs were measured in Coulter LS230 system
(Beckman Coulter, Miami, FL, USA), provided with laser diffraction and polarised light detectors. A small amount of aqueous
polyurethane dispersion was added to a deionised water tank.
The statistical model used to obtain the particle size distribution
assumes that the particles are polystyrene.
2.5.1.3. Brookeld viscosity. The viscosities of the PUDs were
measured in Brookeld viscometer LVDV-I-Prime (Brookeld
Engineering Laboratories, Stoughton, MA, USA). About 50 ml waterborne polyurethane dispersion was placed in a beaker and the
measurements were carried out at 25 C by using the spindle no.
61 and the stirring speed of 100 rpm. The Brookeld viscosity was
calculated as the average of three experimental determinations.
2.5.1.4. Solids content. The solids content of the PUDs were
obtained by difference in weight before and after water evaporation. About 1 g PUD was placed on an aluminium container and the
water was evaporated at 105 C in an oven until constant weight

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V. Garca-Pacios et al. / Progress in Organic Coatings 71 (2011) 136146

was reached. The solids content was calculated as the average of

three experimental determinations.
2.5.1.5. Transmission electron microscopy (TEM). A Jeol TEM-2010
(Tokyo, Japan) instrument was used to analyse the morphology of
the polyurethane particles in the PUDs; an acceleration voltage of
100 kV was used. To obtain the TEM micrographs of the PUDs, they
were diluted in water and the solutions placed on a copper grid.
2.5.2. Characterization of the polyurethane lms
2.5.2.1. Infrared spectroscopy (ATR-IR spectroscopy). The ATR-IR
spectra of the polyurethane lms were obtained in Bruker Tensor
27 spectrometer (Bruker Optik GMbH, Ettlingen, Germany), provided with Fourier transform analysis (FTIR). Measurements were
carried out in the attenuated total reectance mode by using a ZnSe
prism. An incidence angle of the IR radiation of 45 was used, and
100 scans were averaged with a resolution of 4 cm1 .
2.5.2.2. Differential scanning calorimetry (DSC). DSC experiments
were carried out in TA DSC Q100 V6.2. instrument (TA Instruments,
New Castle, DE, USA). Aluminium pans containing 1015 mg of
sample were heated from 70 C to 200 C under nitrogen atmosphere (ow rate: 50 ml/min). The heating rate was 10 C/min. The
rst heating run was carried out to remove the thermal history
of the samples. From the second heating run, the glass transition
temperature (Tg) of the polyurethanes was obtained.
2.5.2.3. Thermal gravimetric analysis (TGA). TGA experiments were
carried out in TGSD TA thermal balance model 851e/1600/LF
(TA Instruments, New Castle, DE, USA). Polyurethane samples
(1015 mg) were heated under nitrogen (ow rate: 100 ml/min)
from room temperature up to 800 C by using a heating rate of
10 C/min.
2.5.2.4. Shore A hardness. The hardness of the polyurethane lms
was measured according the ASTM D2240 standard in Shore A
Durotech BS550 durometer (Durometers, Northampton, UK). The
Shore A hardness scale ranges between 0 and 100, the higher the
Shore A hardness value, the harder the material is. The Shore A
hardness was calculated as the average of ve experimental determinations.
2.5.2.5. Plateplate rheology. The rheological properties of the
polyurethane lms were determined in shear stress-controlled
Bohlin CS50 rheometer (Optilas Ibrica S.A., Madrid, Spain) using
parallel plates (upper plate diameter = 20 mm); the gap selected
was 0.4 mm. Experiments were performed in the region of linear viscoelasticity by melting the polyurethane lm at 200 C and
cooling down to 30 C at a cooling rate of 5 C/min.
2.5.2.6. Laser confocal microscopy. A Leica TCS SP2 microscope
(Heidelberg, Germany) was used to analyse the particle size of
the PUDs and the segmented structure of the polyurethane lms.
The PUD was placed on glass microscope slide (dimensions of
76 mm 26 mm) and then covered by a small glass cover slide. The
sample was drying at room temperature for 72 h followed by heating at 40 C for 8 h to allow the complete removal of water before
analysis. The polyurethane lms without heating were placed on
glass microscope slide (dimensions of 76 mm 26 mm) and then
covered by a small glass cover slide.
2.5.3. Adhesion properties
2.5.3.1. T-peel strength measurements. Adhesive strength (under
peeling stresses) of the waterborne polyurethane dispersions
was obtained from T-peel tests of solvent-wiped plasticized PVC/polyurethane adhesive/solvent wiped plasticized

PVC joints. The PVC test samples used had dimensions of

30 mm 150 mm 5 mm. Before applying the PUD, the PVC
surface was methyl ethyl ketone wiped allowing the solvent
to evaporate for 30 min under open air. Then, 0.450.92 g PUD
solution was applied by brush to each PVC strip to be joined. After
water evaporation (it took about 1 h 30 min) the adhesive lm
was heated suddenly at 80 C for 10 s under infrared radiation
(reactivation process). The PVC strips were immediately placed in
contact and a pressure of 0.8 MPa was applied for 10 s to achieve
a suitable joint. The T-peel strength was measured 72 h after joint
formation in Instron 4411 universal testing machine (Instron Limited, Barcelona, Spain) by using a cross-head speed of 100 mm/min.
The values obtained were the average of three replicates.
2.5.3.2. Single lap-shear test. The adhesive strength (under shear
stresses) of the waterborne polyurethane dispersions was evaluated from single lap-shear tests of aluminium/waterborne
polyurethane dispersion/aluminium joint. Aluminium 5754 test
samples of dimensions of 30 mm 150 mm 1.7 mm were used.
Before applying the PUD, the aluminium surface was methyl ethyl
ketone wiped allowing the solvent to evaporate for 30 min under
open air. Then, 0.30 g PUD solution was applied by means of a spatula on an area of 30 mm2 30 mm2 of one of the aluminium pieces
to be joined. The aluminium strips were immediately placed in contact and a static weight of 700 g was applied for 72 h to achieve
a suitable joint. The shear strength was measured 72 h after joint
formation in Instron 8516 universal testing machine (Instron, Buckinghamshire, England) by using a cross-head speed of 10.2 m/min.
The values obtained were the average of three replicates.
2.5.3.3. Cross-cutter adhesion. This test was used to measure the
adhesion of the polyurethane coatings according to ISO 2409:2007
standard. The cross cutter adhesion was measured in a multi blade
cutting device 0302001 (Sheen Instruments Ltd, Surrey, England)
and an adhesive tape are needed for the test. The polyurethane
coating on stainless steel was maintained at 23 C and 50% relative
humidity for 24 h before test. The values obtained were the average
of three replicates.
2.5.4. Polyurethane coating properties
2.5.4.1. Drying time. The drying time was measured as the time
necessary to leave a trace by an indenter on a lm of PUD. The
waterborne polyurethane dispersions were applied on a glass slide
of 25 mm 700 mm. 0.30 g PUD was applied on the glass slide
by means of a spatula. The drying time was measured according
to ASTM D5895-03 standard in BK Drying Time Recorder DT-BK3
(Shean Instruments, Kingston, UK). One indenter was passing at a
given constant rate on the top of the wet PUD lm; once, the PUD
is dried, the indenter does not produce any trace on top and this
provide the drying time.
2.5.4.2. Thickness. The thickness of the polyurethane coating on
stainless steel plates was measured according to ISO 2808:2007
standard in Neurtek Positector 6000 instrument (Neurtek, Eibar,
Spain). The measurements were carried out at 23 C and 50% relative humidity. The values obtained were the average of twenty
replicates.
2.5.4.3. Persoz
hardness. The
Persoz
hardness
of
the
polyurethane coatings on stainless steel pieces (dimensions
of 60 mm 50 mm 2 mm) was measured according to ISO
1522:2006 standard in 707 Konig (707 KP) instrument (Shean
Instruments, Kingston, England). The Persoz hardness was obtained
as the number of oscillations of the pendulum until it stops, i.e. the
lower the number of oscillations, the greater the coating hardness
is. The values obtained were the average of three replicates.

V. Garca-Pacios et al. / Progress in Organic Coatings 71 (2011) 136146

139

Fig. 2. Particle size distributions of the polyurethane dispersions with different NCO/OH ratios.

2.5.4.4. Gloss. The gloss of the polyurethane coatings on stainless

steel pieces (dimensions of 60 mm 50 mm 2 mm) was measured
according to ISO 2813:1994 standard in a Micro-TRI-Gloss instrument (BYK Gardner GmbH, Geretsried, Germany). Gloss is measured by directing a constant intensity light beam at a xed angle
(60 ) on the coating surface and measuring the amount of reected
light. The values obtained were the average of three replicates.
2.5.4.5. Yellowness index. The yellowness index of the
polyurethane coatings on stainless steel pieces (dimensions
of 60 mm 50 mm 2 mm) was measurement according to ASTM
D1925-70 standard in a Minolta CR410 Colorimeter (Ramsey,
USA). The polyurethane coating was always maintained into a
black box to avoid light interference in the measurements. The
values obtained were the average of three replicates.
2.5.4.6. Chemical resistance against ethanol. The chemical resistance of the polyurethane coatings on stainless steel pieces
(dimensions of 60 mm 50 mm 2 mm) against ethanol were
obtained according to the ISO 4210:1979 modied standard. The
test consists in applying a cotton fully embedded in ethanol on
the polyurethane coating surface and maintaining it for different
times (10 s10 min). The deterioration of the coating was analysed
according to scale of 1 (full removal of the coating) to 5 (intact
coating).
3. Results and discussion
3.1. Characterization of the waterborne polyurethane dispersions
Fig. 2 shows the particle size distributions of the aqueous
polyurethane dispersions with different NCO/OH ratios. The par-

ticle size of the PUDs increases slightly for an NCO/OH ratio lower
than 1.5 and the particle size distribution becomes narrower. This
trend can be ascribed to the increase in the prepolymer viscosity
produces by decreasing the NCO/OH ratio during the PUD synthesis,
that inhibits the fragmentation of the polymer into smaller particles during the dispersion in water [7]. Therefore, the NCO/OH
ratio determines the particle size of the PUD. On the other hand,
the TEM micrographs of the PUDs (Fig. 3) reveal that the dispersion
with NCO/OH ratio of 1.3 shows a smaller and homogeneous particle size and by increasing the NCO/OH ratio the particle size of the
dispersion increases and the particle crowding is favoured.
In general, the most average particle size of the PUD depends
on the specic application to which is intended. Thus, the PUDs
of relatively larger particles are preferred in surface coatings for
rapid drying whereas the PUDs of smaller particle sizes are desirable when deep penetration of the dispersion into a substrate is
essential [29]. The relatively wide range of particle size from 73 nm
diameter for PU1.5 dispersion to 128 nm diameter for PU1.7 dispersion suggests that the PUDs prepared in this study are promising
for application as coatings.
The aqueous polyurethane dispersions have pH values between
7.8 and 8.2 (Table 1), which are into the range of stability of the
commercial typical polyurethane dispersions. The Brookeld viscosity and pH of the aqueous polyurethane dispersions increases
as the NCO/OH increases (Table 1).
Table 1
Some properties of the waterborne polyurethane dispersions.
Polyurethane

pH

Solids content (wt%)

 (mPa s)

PU1.3
PU1.5
PU1.7

7.8
8.0
8.2

38.4 0.2
39.0 0.2
38.5 0.1

18.1
26.7
174.0

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V. Garca-Pacios et al. / Progress in Organic Coatings 71 (2011) 136146

Fig. 3. TEM micrographs of the polyurethane dispersions with different NCO/OH ratios.

3.2. Characterization of the polyurethane lms

The chemistry of the polyurethane lms was analysed by ATR-IR
spectroscopy. The assignment of the most characteristic IR bands
in the polyurethanes is given in Table 2. The most relevant IR bands
correspond to NH stretching at 3338 cm1 , CN stretching and NH
stretching at 1531 cm1 , CH stretching at 2938 and 2855 cm1 ,
and C O stretching due to urea (17001648 cm1 ) and urethane
(17391717 cm1 ) groups (Fig. 4). On the other hand, the ATR-IR

Table 2
Assignment of the main IR bands in the ATR-IR spectra of the polyurethanes with
different NCO/OH ratios.
Wavenumber (cm1 )

Assignment

Groups assignment

3338
2938, 2855
2270
1740
17391717
17001648
1640
1531
14751450
14501400
1242
1162, 955
1035

st NH (bonded)
st (asym) CH y st (sym) CH
st N C O
st C O
st C O
st C O
st C O
st CN y st NH
CH2
st (sym) COO
st (asym) NCOO y st COC
st COC
st (sym) NCOO

Urethane
Polyol
Urethane (free)
Urethane (free)
Urethane (bonded)
Urea (free)
Urea (bonded)
Urea
Polyol
Polyol
Urethane and polyol
Polyol
Urethane

st , stretching; , bending; sym, symmetric; asym, asymmetric.

spectra show the characteristic CO and NCOO stretching (1242

and 1035 cm1 ), and COC stretching (1162 and 955 cm1 ) bands
of the polyol.
The ATR-IR spectra of the polyurethanes with different NCO/OH
ratios are quite similar (Fig. 4), and only some differences in the relative intensities of several bands can be distinguished. The increase
in the NCO/OH ratio increases the intensity of the bonded NH
stretching band at 3338 cm1 , because of the increase in the hard
segment content in the polyurethane. Furthermore, as urea groups
are created during chain extension of the prepolymer, the increase
in the NCO/OH ratio increases the intensity of the stretching bands
of both free and bonded ordered urea groups (17001648 cm1 )
to a greater extent than for urethane groups (17401717 cm1 )
[6,7,17]. On the other hand, the increase in the NCO/OH ratio
also increases the relative intensity of the NCOO stretching
band at 1034 cm1 of urethane group and the CN stretching and
NH bending at 1531 cm1 of urea group, because of the increase
in the hard segment content (urethane and urea groups) in the
polyurethanes.
The thermal stability of the polycarbonate of hexanediol (Fig. 5)
and of the polyurethanes (Fig. 6) was determined by TGA. The TGA
thermogram of the polycarbonate of hexanediol shows the main
degradation at 368 C and other less important at 263 C. On the
other hand, the polyurethanes show several different degradations.
Between 55 and 110 C and 120180 C the removal of residual
water in the polyurethanes is produced, the amount of residual
water is more important by increasing the NCO/OH ratio. The degra-

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141

0.30
0.28
0.26
0.24
0.22

1739
1717
1699

Absorbance (a.u) (u.a)

0.20
0.18
0.16
0.14
0.12
0.10

1648
PU1.7

0.08
0.06
0.04

PU1.5
PU1.3

0.02
0.00
-0.02
1800

Wavenumber (cm-1)

1600

Fig. 4. Region of 18001600 cm1 in the ATR-IR spectra of the polyurethanes with different NCO/OH ratios.

other hand, the polyurethanes show two glass transition temperatures due to the soft segments (Fig. 7b) indicating the existence of
two different structures due to interactions between the hydrocarbon chains (Tg1 ) and between the carbonate moieties (Tg2 ) in the
polyol. The Tg1 value in the polyurethanes decreases as the NCO/OH
ratio decreases (Table 3) indicating a higher degree of phase separation. The value of Tg2 of the polyurethanes does not change with
the NCO/OH ratio. Furthermore, the increase in the NCO/OH ratio
decreases the rst melting temperature (Tm1 ) of the polyurethanes
while the second melting temperature (Tm2 ) increases. Therefore,
the thermal stability of the polyurethanes increases by increasing
the NCO/OH ratio.
The mechanical properties of the polyurethanes were indirectly measured throughout the values of the Shore A hardness.
Fig. 8 shows the variations of the Shore A hardness as a function of the NCO/OH ratio in the polyurethanes. An increase in the
hardness (i.e. in the mechanical properties) is produced as the
NCO/OH ratio increases due to higher hard segments content in
the polyurethanes.
The morphology of the polyurethanes was examined with laser
confocal microscopy. Because of the different molecular weight
of the hard and soft segments in the polyurethanes, the differences in brightness in the micrographs may allow to distinguish
between both of them. Depending on the NCO/OH ratio, different
extents of degree of phase separation can be distinguished in the
polyurethanes (Fig. 9). Thus, the polyurethane with NCO/OH ratio
of 1.3 shows a dark micrograph that corresponds to the soft segments, i.e. the structure is mainly dominated by the soft segments.
By increasing the NCO/OH ratio to 1.5 and 1.7 both soft (dark region)
and hard (bright region) can be distinguished in the polyurethanes.
The higher the NCO/OH ratio, the more abundant and larger the
hard segments are. These structures in PU1.5 and PU1.7 with unique
periodicity and phase connectivity show the two-phase domains
which formation was ascribed elsewhere [29] to spinodal decomposition of the polymeric chains in the polyurethane.
The rheological properties of the polyurethanes were determined by plateplate rheometry experiments. Fig. 10a shows as

Fig. 5. TGA thermogram of the polycarbonate of hexanediol.

dation in the polyurethanes at 266271 C is characteristic of the

polyol. Because diol and diamine were used in the synthesis of the
polyurethanes, two kind of hard segments are formed, i.e. urethane
and urea. The degradation of the urethane and urea hard segments
can be distinguished in the TGA thermograms at around 310 C and
330 C, respectively. It has been established [28] that the urethane
bond has lower thermal resistance than the urea bond and thus the
rst decomposition process at around 310 C in the polyurethanes
should correspond to the beginning of the degradation of urethane
hard segment and the second one (330 C) to the urea hard segments. The decomposition of the soft segments (mainly composed
of polyol) is produced at around 350 C. By increasing the NCO/OH
ratio the hard segment content in the polyurethanes increases
(Fig. 6).
The inuence of the NCO/OH ratio on the thermal properties
of the polyurethanes was also studied by differential scanning
calorimetry (DSC). The DSC thermogram of the polycarbonate of
hexanediol (Fig. 7a) shows two glass transitions at low temperature and three melting peaks, the main is located at 43 C. On the

Table 3
Some parameters obtained from the DSC thermograms of the polyurethanes with different NCO/OH ratios. Second heating run.
Polyurethane

Tg1 SS ( C)

Tg2 SS ( C)

PU1.3
PU1.5
PU1.7

10
3
7

38
37
38

Melting temperature 1 ( C)
200
165

Melting enthalpy 1 (J/g)

Melting temperature 2 ( C)

Melting enthalpy 2 (J/g)

3.7
3.2

139
147

7.7
8.1

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V. Garca-Pacios et al. / Progress in Organic Coatings 71 (2011) 136146

Fig. 7. DSC thermograms of (a) the polycarbonate of hexanediol, and (b) the
polyurethanes with different NCO/OH ratios. Second heating run.

3.3. Adhesion properties

The adhesion properties of the polyurethanes with different NCO/OH ratios were determined under different mechanical
stresses by means of different tests. The adhesion under
peel stresses was obtained from T-peel tests of plasticized
PVC/waterborne polyurethane dispersion/plasticized PVC joints.
According to Fig. 11, the increase in the NCO/OH ratio in the
polyurethane produces an increase in adhesive strength, except for

Fig. 6. TGA thermograms of the polyurethanes with different NCO/OH ratios.

typical example the variation of the storage (G ) and the loss (G )
moduli as a function of the temperature of the polyurethane with
NCO/OH ratio of 1.5. Both moduli of the polyurethane decrease
as the temperature increases, and a cross-over between the storage and loss modulus is produced. At temperature lower than that
of the cross-over, the polyurethane is mainly elastic, and at temperature higher than that of the cross-over, the viscous regime is
dominant. Fig. 10b shows the variation of the storage modulus (G )
as a function of the temperature for the polyurethanes with different NCO/OH ratios. An increase in the NCO/OH ratio produces an
increase in the storage modulus (G ), due to higher hard segment
content and lower degree of phase separation in the polyurethane.
Similarly, the cross-over between the moduli shifts toward higher
temperature and modulus as the NCO/OH increases (Table 4) due
to the increase in the hard segments content in the polyurethanes.

Fig. 8. Variation of the Shore A hardness of the polyurethanes as a function of the

NCO/OH ratio.

V. Garca-Pacios et al. / Progress in Organic Coatings 71 (2011) 136146

143

Fig. 9. Laser confocal micrographs of the polyurethanes with different NCO/OH ratios.

the joint produced with the polyurethane with NCO/OH ratio of

1.7. The locus of failure of the joints was assessed by visual observation. Depending on the NCO/OH ratio in the polyurethane, two
types of locus of failure were found in the peeled surfaces after peel
tests. The joints produced with the polyurethanes with NCO/OH
ratio of 1.3 and 1.5 show a mixed failure (adhesion + cohesive
failure in the adhesive), whereas the joint produced with the
polyurethane with NCO/OH ratio of 1.7 shows a cohesive failure
in the adhesive. Because of the increase in the in hard segment
content and in the mechanical properties of the polyurethane by
increasing the NCO/OH ratio, a decrease in peel strength value can
be expected in the joint made with PU1.7 polyurethane as the
failure of the joint will be produced in the weakest part of the
joint, i.e. the polyurethane. Therefore, it can be anticipated that the
polyurethane with higher NCO/OH ratio should have the lowest
peel strength value.

Table 4
Variation of temperature and modulus at the cross-over between the storage and
loss modulus in the polyurethanes with different NCO/OH ratios. Plateplate rheology experiments.
Polyurethane

Tcrosss over ( C)

Gcross-over (Pa)

PU1.3
PU1.5
PU1.7

76
84
88

2.8 105
2.9 105
7.1 105

The adhesive strength of the waterborne polyurethane dispersions under shear stresses was evaluated from single lap-shear tests
of aluminium/waterborne polyurethane dispersion/aluminium
joints. Fig. 12 shows an increase in the shear strength by increasing the NCO/OH ratio of the polyurethane, the maximum value is
obtained in the joint produced with the polyurethane with NCO/OH
ratio of 1.5. A cohesive failure in the adhesive was always obtained.
The trends obtained in peel strength and shear strength as a function of the NCO/OH ratio in the polyurethane are opposite because
the increase in the hard segments content in the polyurethane
should favour the adhesion under shear stresses and at the same
time decrease it under peel stresses.
The adhesion of the polyurethane coatings on stainless steel was
evaluated by cross-cutter adhesion tests. Table 5 shows the code for
assessment of the damaged coating surface, i.e. the adhesion of the
coating to the substrate, according to ISO 2409:2007 standard. The
values obtained for the polyurethane coatings with different NCO
ratios range between 0 and 1, indicating excellent adhesion of all
polyurethane coatings to stainless steel plate.
3.4. Coating properties
Several properties (additional to adhesion) of the polyurethane
coatings with different NCO/OH ratios on stainless steel plates were
measured.
The drying time of the polyurethane dispersions applied as coatings on stainless steel plates varies with the NCO/OH ratio. Whereas

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V. Garca-Pacios et al. / Progress in Organic Coatings 71 (2011) 136146

Fig. 12. Variation of the single lap-shear strength values of aluminium/waterborne

polyurethane dispersion/aluminium joints as a function of the NCO/OH ratio. Values obtained 72 h after joint formation. Locus of failure: CA: cohesive failure in the
adhesive.

Fig. 10. (a) Variation of the storage (G ) and loss (G ) modulus of PU1.5 as a function
of temperature. (b) Variation of the storage (G ) modulus of the polyurethanes as a
function of temperature.

the waterborne polyurethane dispersion with NCO/OH ratio of 1.5

has a drying time larger than 2 h, the polyurethane dispersions
with NCO/OH ratios of 1.3 and 1.7 have a drying time lower than
2 h, likely due to the higher mean particle size. In general, the
waterborne polyurethane dispersions of relative larger particles are
preferred in surface coatings for their rapid drying [29].
The thickness of the polyurethane coatings on stainless steel
also varies by increasing the NCO/OH ratio. The thickness of the
polyurethane coatings with NCO/OH ratios of 1.3, 1.5 and 1.7
applied on stainless steel plates are 35, 43 and 49 m, respectively. An increase in the NCO/OH ratio produces an increase in
the thickness of the coating on stainless steel.
Fig. 13 shows the variation of the Persoz hardness of the
polyurethane coatings on stainless steel as a function of the
NCO/OH ratio for different cure times. The Persoz hardness of the
coatings increases as the NCO/OH ratio of the polyurethane coating increases because of the increase in the hard segments content.
Furthermore, the Persoz hardness values of the coatings increase by
increasing the cure time, indicating that the coatings needs more

Table 5
Adhesion scale obtained by cross-cutter measurements (ISO 2409:2007 standard).

Fig. 11. Variation of the T-peel strength values of plasticized PVC/waterborne

polyurethane dispersion/plasticized PVC joints as a function of the NCO/OH ratio.
Values obtained 72 h after joint formation. Locus of failure: M: mixed failure (adhesion + cohesive failure in the adhesive); CA: cohesive failure in the adhesive.

Code Description

Damaged surface

No modication

Light loosening of coating (<5%)

Light loosening of the borders of the coating (510%)

Partial loosening of the coating (1535%)

Strong loosening of the coating (3565%)

Strong loosening of the coating (>65%)

V. Garca-Pacios et al. / Progress in Organic Coatings 71 (2011) 136146

Fig. 13. Variation of the Persoz hardness of polyurethane coatings on stainless steel
plates as a function of the NCO/OH ratio at different cure times (72, 96 and 144 h).

than 72 h to fully cross-link, i.e. to obtain a stable structure. This

is in agreement with previous nding [28] that concluded that
an increase in the hard segments content increased the extent of
crosslinking of the polyurethanes.
The gloss of the polyurethane coatings on stainless steel also
depends on the NCO/OH ratio. According to Fig. 14, the gloss of the
polyurethanes decreases by increasing the NCO/OH ratio, particularly for the NCO/OH ratio of 1.7. However, the gloss of the coatings
on stainless steel does not change by increasing the curing time.
Fig. 15 shows the variation of the yellowness index of the
polyurethane coatings on stainless steel. The yellowness index
of the coatings slightly increases as the NCO/OH ratio increases,
except for the coating produced with the polyurethane with
NCO/OH ratio of 1.7. This can be associated to its higher thickness
with respect to the other coatings.
Finally, the chemical resistance against ethanol of the
polyurethane coatings on stainless steel plates were tested for different times of contact of ethanol with the polyurethane coating
surface. Table 6 shows the code for assessment of the chemical
resistance of coatings on substrates according to UNE-EN 12720
standard. Fig. 16 shows that for short time (10 s) of ethanol in
contact with the polyurethane coating surface, the chemical resis-

Fig. 14. Variation of the gloss (60 ) of polyurethane coatings on stainless steel plates
as a function of the NCO/OH ratio at different cure times (72, 96 and 144 h).

145

Fig. 15. Variation of the yellowness index of polyurethane coatings on stainless steel
plates as a function of the NCO/OH ratio.
Table 6
Code of resistance against ethanol of coatings on substrates (UNE-EN 12720
standard).
Code

Extent of damaged surface

5
4
3
2
1

No modication
Change in gloss or color
Light damage of the coating
Strong damage of the coating
Removal of the coating

tance ranges between 4 and 5 (i.e. good chemical resistance) and

decreases by increasing the NCO/OH ratio in the polyurethane. By
increasing the time of ethanol in contact with the polyurethane
coatings different behaviours are obtained. Thus, the chemical
resistance of the polyurethane coating with lower NCO/OH ratio
decreases by increasing the time in contact with ethanol, although
a value higher than 3 (i.e. light damage of the coating) is obtained. A
slight decrease in chemical resistance is found in the polyurethane
coating with NCO/OH ratio of 1.5, and no change is produced in
the polyurethane coating with NCO/OH ratio of 1.7. Thus, after
10 min of ethanol in contact with the polyurethane coatings, the

Fig. 16. Variation of the chemical resistance against ethanol of polyurethane coatings on stainless steel plates as a function of the NCO/OH ratio. Values obtained at
different time of ethanol in contact with the coatings (10 s, 2 and 10 min).

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V. Garca-Pacios et al. / Progress in Organic Coatings 71 (2011) 136146

chemical resistance increases by increasing the NCO/OH ratio. This

trend can be explained by the increase in hard segment content and
the coating thickness of the polyurethane when the NCO/OH ratio
increases.
4. Conclusions
The increase in the NCO/OH ratio (or the increase in the hard
segment content) decreased the mean particle size, increased the
polydispersity and increased the Brookeld viscosity of the waterborne polyurethane dispersions. On the other hand, the increase in
the NCO/OH ratio favoured the crowding of the polymer particles,
facilitating their collapse and therefore beginning of the crosslinking.
The increase in the NCO/OH ratio increased the glass transition temperature of the polyurethanes. Because of the increase in
hard segments, the elastic modulus of the polyurethanes increased
by increasing the NCO/OH ratio, as well as the temperature and
modulus at the cross-over between the storage and loss modulus increased. In general, by increasing the NCO/OH ratio the
adhesion properties of the polyurethanes decreased under peel
stresses and increased under shear stresses. On the other hand, the
adhesion of the polyurethane coatings to stainless steel was very
good.
The thickness of the polyurethane coatings on stainless steel
plates increased by increasing the NCO/OH ratio. The Persoz hardness of the coatings increased by increasing the hard segments in
the polyurethane, i.e. by increasing the NCO/OH ratio, whereas both
the gloss and the yellowness index of the coatings decreased by
increasing the NCO/OH ratio. Very good chemical resistance against
ethanol of the polyurethane coating with NCO/OH ratio of 1.7 on
stainless steel plates was obtained and for long time in contact
with ethanol the chemical resistance of the coatings increased by
increasing the NCO/OH ratio.
Acknowledgements
Financial support by UBE CHEMICAL EUROPE Corporation
is acknowledged. Contact person: Dr. Manuel Colera (e-mail:
m.colera@ube.es).

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