Comprendiendo La Recistencia Del NBRA A Oil PDF

UNDERSTANDING OIL RESISTANCE OF NITRILE RUBBER:
CN GROUP INTERACTIONS AT INTERFACES
A Dissertation
Presented to
The Graduate Faculty of The University of Akron
In Partial Fulfillment
of the Requirements for the Degree
Doctor of Philosophy
Veronique Lachat
December, 2008
UNDERSTANDING OIL RESISTANCE OF NITRILE RUBBER:
CN GROUP INTERACTIONS AT INTERFACES
Veronique Lachat
Dissertation
Approved: Accepted:
_________________________________ _________________________________
Advisor Department Chair
Dr. Ali Dhinojwala Dr. Ali Dhinojwala
_________________________________ _________________________________
Co-Advisor Dean of the College
Dr. Mohsen S. Yeganeh Dr. Stephen Z. D. Cheng
_________________________________ _________________________________
Committee Member Dean of the Graduate School
Dr. Gary R. Hamed Dr. George R. Newkome
_________________________________ _________________________________
Committee Member Date
Dr. Gustavo A. Carri
_________________________________
Committee Member
Dr. Roderic P. Quirk
_________________________________
Committee Member
Dr. Rex D. Ramsier
ii
ABSTRACT
Nitrile rubber (NBR) is copolymer of acrylonitrile and butadiene. It is resistant to
swelling by hydrocarbon oils.1 Swelling and thermal degradation decrease as acrylonitrile
content increases. Infrared-visible Sum Frequency Spectroscopy (SFS) is used in the
present study to probe the molecular origin of oil resistance. SFS is a surface specific
spectroscopic technique and was used to probe an NBR/liquid interface. Oil resistance of
the NBR is reflected in changes in the SFS spectra of NBR at the interface. As reference
materials, two additional polymers polyacrylonitrile (PAN) and polybutadiene (PBD)
were included and analyzed prior to analyzing the nitrile rubber.
SFS analysis of the film revealed a shift of the CN stretching mode at the sapphire/PAN
interface compared to that of PAN bulk when the PAN film was annealed above its glass
transition temperature. This demonstrates how environment affects nitrile dipole-dipole
interaction. The influence of liquid environment on the PAN surface was directly
assessed by comparing the SFS spectra of the PAN/air to that of PAN/heptane and
PAN/water interfaces. This showed a minor effect of the solvent on the nitrile CN
stretching mode of PAN.
iii
The second section was devoted to the analysis of PBD. A positive shift of the
methylene stretching mode of PBD is detected in the SFS spectrum. This indicates that
the polar sapphire surface influences the specific vibrational mode of PBD.
Finally, NBR rubbers with 40% or 20% acrylonitrile content (ACN) were characterized.
In the SFS spectra of NBR (40% and 20 %ACN)/air surfaces, a new vibrational band was
observed at 2050 cm-1, in addition to the CN stretching mode of nitrile rubber at 2233 cm-
1
. This band was not detected in bulk NBR (40% and 20% ACN). Additives in bulk NBR
were determined using High Performance Liquid Chromatography (HPLC). Results
suggested the presence of amines molecules. However, purified NBR also showed the
2050 cm-1 band. There are a limited number of assignments that can be present in this
range. This includes nitrile groups interacting with salts. Probable assignments are
proposed after considering the chemical compounds present in NBR emulsion
polymerization.
The final part of this dissertation is concerned with the interaction between an NBR film
and two solvents: heptane and toluene. No change at the sapphire/NBR interface upon
heptane exposure indicates the stability of the NBR film in contact with heptane. This is
in accord with the oil resistance of NBR to hydrocarbon solvents. Solubilization of the
NBR rubber thin film after toluene exposure is revealed by changes in the SFS spectrum
at the sapphire/NBR interface. This shows that SFS is capable of accurately detecting
molecular changes at polymer/liquid interfaces.
iv
SFS results are consistent with the resistance of NBR to aliphatic solvent and instablity in
aromatic solvents. Quantitative interpretation of the oil resistance will require an
assignment of the 2050 cm-1 absorption band.
v
ACKNOWLEDGMENTS
I would like to thank Dr. Dhinojwala for placing into my hands the most challenging
opportunity I had the luck to live as a PhD student. Accomplishing the experimental part
of this work at ExxonMobil Research and Engineering center represented for me an
extremely valuable exposure to corporate research and environment. The key difference
between industrial and academic research is the time constraint, that is why I would like
to warmfully acknowledge Dr. Mohsen S. Yeganeh for managing the presence of a full-
time student in his lab. His scientific input, professional experience and interest definitely
guided my research. Working in the SFS lab was very enlightening from a technological
point of view and I would like to express my gratitude to Shawn M. Dougal for his
kindness and patience all along my stay. I would like also to thank Bernard Silbernagel
and Paul Stevens without whom this collaboration between the University of Akron and
ExxonMobil would not have been possible.
I would like to thanks Robert Seiple and Critt Ohlemacher for their professionalism and
help. Finally I would like thank my committee members, Dr. Gary R. Hamed, Dr.
Gustavo A. Carri, Dr. Roderic P. Quirk and Dr. Rex D. Ramsier.
vi
I would like to specially thank Valerie Hill and Vicki England Patton for their endless
resources and support. Both of them contributed in countless ways to the elaboration of
this thesis. I also cannot forget Mayela Ramirez, Betul Buehler, Emilie Gautriaud, Gocke
Ugur, Vasav Sahni and Sunny Sethi for their help in editing this thesis. Finally, I would
like to thank our group of students who made of the laboratory a very enjoyable research
environment.
vii
TABLE OF CONTENTS
Page
LIST OF TABLES ........................................................................................................... xii
LIST OF FIGURES ........................................................................................................ xiv
CHAPTER
I. INTRODUCTION ...........................................................................................................1
II. BACKGROUND.............................................................................................................5
2.1 Nitrile Rubber ...................................................................................................5
2.1.1 Polyacrylonitrile..................................................................................5
2.1.2 Polybutadiene......................................................................................8
2.1.3 Nitrile Rubber .....................................................................................9
2.2 Oil Resistance of Nitrile Rubber......................................................................11
2.2.1 Theoretical Approach........................................................................11
2.2.2 Key Experimental Parameter: Acrylonitrile Content........................15
2.2.3 Industrial Approach ..........................................................................16
2.3 Advances in Probing Polymer/Liquid Interactions...........................................17
2.3.1 Experimental Parameter....................................................................18
2.3.2 Linear Partition Model......................................................................20
2.3.3 In-situ Swelling Measurements of Thin Polymer Films ...................21
2.3.4 Polymer Membrane Design ..............................................................24
viii
2.4 Summary...........................................................................................................26
III. PROBING MOLECULAR INTERACTIONS USING SPECTROSCOPY ...............28
3.1 Linear Spectroscopy........................................................................................30
3.1.1 Infrared Spectroscopy .......................................................................32
3.1.2 Raman Spectroscopy.........................................................................34
3.1.3 Non-Linear Effects............................................................................39
3.1.3.1 Hot Band ........................................................................................40
3.1.3.2 Fermi Resonance............................................................................42
3.2 Non-Linear Spectroscopy ...............................................................................42
3.3 Spectroscopy for Probing Interactions............................................................52
3.3.1 Acetonitrile Model Compound ........................................................52
3.3.2 Polyacrylonitrile Model Compound .................................................57
3.3.3 Frequency Shift at Surfaces ..............................................................61
3.4 Messages of This Dissertation .........................................................................62
IV. EXPERIMENTAL.......................................................................................................64
4.1 Polymer Thin Film Preparation ........................................................................64
4.2 NBR Purification ..............................................................................................66
4.3 High Pressure Liquid Chromatography Characterization.................................66
4.4 IR-Visible Sum Frequency Generation Spectroscopy Measurements (SFS) ...67
4.4.1 ExxonMobil Narrow-line SFS Spectrometer......................................67
4.4.2 The University of Akron Broadline SFS Spectrometer ......................70
ix
4.4.3 SFS in Total Internal Reflection (TIR) Geometry ..............................72
4.5 Differential Scanning Calorimetry (DSC) Measurements...............................76
4.6 FTIR Measurements.........................................................................................76
4.7 Raman Spectroscopy Measurements ...............................................................76
4.8 Nuclear magnetic Resonance Measurements...................................................77
4.9 Size Exclusion Chromatographic Measurements ............................................77
4.10 Thin Film Thickness Measurements ..............................................................77
V. RESULTS AND DISCUSSION ...................................................................................79
5.1 Spectroscopic Investigation of Nitrile Groups Interactions in

PAN..................................................................................................................80
5.1.1 SFS Spectra and Peaks Assignments ...................................................80
5.1.2 PAN under Solvent Exposure ..............................................................90
5.1.3 Summary on PAN Investigation ..........................................................94
5.2 Analysis of PBD ..............................................................................................94
5.2.1 Bulk and SFS analysis of PBD .............................................................94
5.2.2 Summary on PBD Investigation ...........................................................99
5.3 Analysis of NBR ..............................................................................................99
5.3.1 Bulk Analysis of NBR ..........................................................................99
5.3.2 SFS Investigation of NBR in the CN Region .....................................103
5.3.3 Summary of the Analysis of Dried NBR at Interface .........................111
5.4 Resistance of NBR to Solvents ......................................................................113
5.4.1 Resistance of NBR Surface to Heptane ..............................................113
x
5.4.2 Resistance of NBR Surface to Toluene ..............................................117
5.4.3 Resistance of NBR Surface to Water..................................................121
5.4.4 Assigning the 2050 cm-1 Vibrational Band .........................................123
5.4.5 Conclusions on Solvent Resistance of NBR...................................... 126
VI. SUMMARY AND CONCLUSIONS ........................................................................128
REFERENCES ................................................................................................................132
APPENDICES .................................................................................................................138
APPENDIX A. PAN AND NBR THERMAL TRANSITIONS .....................139
APPENDIX B.THIN FILMS ELLIPSOMETRY THICKNESS

MEASUREMENTS.........................................................................................141
APPENDIX C. HPLC RUBBER ADDITIVES ANALYSIS..........................144
APPENDIX D. NMR SPECTRA OF NBR.....................................................147
APPENDIX E. SEC OF NBR..........................................................................149
xi
LIST OF TABLES
Table Page
4.1 Solvents used during the HPLC separation ..........................................................67
4.2 Solvent profile used to characterize the methanol extract in Section 5.3.2 ..........67
5.1 Positions of the CN stretching vibration for PAN from Figure 5.2 obtained
by fitting using equation (3.22) ...........................................................................84
5.2 Positions of the CN stretching vibration for PAN from Figure 5.3 obtained
by fitting using equation (3.22).............................................................................87
5.3 PBD vibrational bands observed in Figure 5.10 compared to PBD

vibrational bands observed by Binder...................................................................98
5.4 Observed frequencies (in cm-1) and assignments for Furukawa

alternating copolymers and our NBR. (CN) and (BD) refer to the acrylonitrile
and butadiene units respectively .........................................................................102
5.5 Positions of the CN stretching vibration for NBR (40% ACN) from
Figure 5.13 obtained by fitting using Equation (3.22)........................................104
5.6 Positions of the CN stretching vibration for NBR (40% ACN) and
purified NBR (40% ACN) at the NBR (40% ACN)/air interface
from Figure 5.14 by fitting using Equation (3.22)..............................................108
5.7 Positions of the CN stretching vibration for NBR (40% ACN)

in the different regions probed obtained from Figures 5.13 and 5.15
by fitting using Equation (3.22) ..........................................................................111

in the different regions probed from Figures 5.16 and 5.17 obtained

in the different regions probed from Figure 5.18 obtained
xii
5.10 Vibrational modes absorbing in the (2000-2100 cm-1) region64 .........................124
5.11 Typical recipe for NBR emulsion polymerization5 ............................................125
xiii
LIST OF FIGURES
Figure Page
2.1 PAN chemical structure ...........................................................................................6
2.2 PBD chemical structure ...........................................................................................8
2.3 NBR chemical structure...........................................................................................9
2.4 Schematic representation of the dilution process occurring during

rubber welling ........................................................................................................12
3.1 Ball and spring model for a diatomic molecule .....................................................30
3.2 Schematic representation of the location of the atoms in the nitrile

and CO2 moieties as the molecules vibrate with their corresponding
dipole moment .......................................................................................................34
3.3 Correlation between the vibrational frequency shift and the change in
magnitude of the force constant ............................................................................39
3.4 Energy scheme and corresponding vibrational spectrum

for fundamental and hot transitions .......................................................................41
3.5 A sketch illustrating the production of SHG through crystalline

quartz with vibrational excitation at 694 nm and the corresponding
harmonic at 347 nm ...............................................................................................43
3.6 A sketch illustrating the SFG process through a non-linear material ...................45
3.7 Definition of Euler angle relating the attached molecular axes

frame (abc ) to the laboratory axis system ( xyz ) ....................................................47
3.8 Schematic of an SFS experiment at interface in external reflection.

The two polarization cases S and P have been illustrated for the incident
infrared beam. The directions of the laboratory-fixed coordinate
axes are indicated ...................................................................................................49
xiv
3.9 Acetonitrile chemical structure ..............................................................................52
3.10 PAN chemical structure .........................................................................................57
3.11 Structure of singly-conjugated, pyrolyzed polyacrylonitrile .................................59
3.12 Structure of conjugated, pyrolyzed polyacrylonitrile ...........................................59
4.1 Schematic diagram of the ExxonMobil narrowline SFS spectrometer..................69
4.2 Typical normalized SFS spectrum .........................................................................70
4.3 Schematic diagram of the University of Akron broadline SFS spectrometer........71
4.4 Schematic diagram of the TIR geometry used in SFS experiments ......................73
4.5 Angular dependence of SFS signal at the sapphire/NBR interface

under heptane exposure in SSP polarization for a film of a thickness
of 300 nm. The solid line corresponds to fit modeled by program written
by Li91 ....................................................................................................................74
4.6 Angular dependence of SFS signal at the sapphire/NBR interface

in SSP polymerization for a film of a thickness of 300 nm. Solid line
corresponds to fit modeled by program written by Li91 .........................................75
5.1 FTIR spectrum of bulk PAN in the CN stretching region .....................................81
5.2 (A) FTIR spectrum of PAN bulk, (B) SFS spectrum of PAN in PPP
polarization at the sapphire/PAN interface after PAN annealing at 90 °C
for 8 h followed by a second heating at 120 °C for 4 h and (C) SFS spectrum
of PAN in PPP polarization of PAN at the sapphire/PAN interface after
annealing at 90 °C for 8 h only, in the CN stretching region ............................... 83
5.3 (A) FTIR spectrum of PAN bulk, (B) SFS spectrum of PAN in PPP
polarization at the sapphire/PAN interface after PAN annealing at 90 °C
for 8 h followed by a second heating at 120 °C for 4 h and (C) SFS spectrum
of PAN in PPP polarization at the sapphire/PAN interface after PAN annealing
at 90 °C for 8 h followed by an additional heating at 120 °C for 4 h
on sapphire (temperature-treated at 750 °C for 36 h), in the CN stretching
region .....................................................................................................................86
5.4 (A) SFS spectrum of PAN in PPP polarization at the sapphire/PAN interface
after PAN annealing at 90 °C for 8 h and 120 °C for 4 h with
spin-coating on sapphire (temperature-treated at 750 °C for 36 h)
xv
and (B) SFS spectra of PAN in PPP polarization after PAN annealing
at 90 °C for 8 h and 120 °C for 4 h at sapphire/PAN in the CH
stretching region.....................................................................................................88
5.5 SFS spectrum of PAN in PPP polarization at the PAN/air interface, in the CN
stretching region......................................................................................................90
5.6 SFS spectra of PAN in PPP polarization at (A) PAN/water interface sapphire
in the CN stretching region (2000-2100 cm-1) and (B) PAN/water interface
in the CN stretching region (2100-2300 cm-1). SFS spectra were obtained
with the University of Akron broadline SFS spectrometer.....................................91
5.7 SFS spectra of PAN in PPP polarization (A) at the PAN/air interface
in the CN stretching region (2000-2100 cm-1) and (B) at the PAN/air interface
in the CN stretching region (2100-2300 cm-1). SFS spectra were obtained
with the University of Akron broadline SFS spectrometer.....................................92
5.8 SFS spectra of PAN in PPP polarization (A) at the PAN/heptane interface and
(B) PAN/water interface in the CN stretching region.............................................93
5.9 Raman spectrum of PBD and corresponding fit .....................................................96
5.10 (A) Raman spectrum of bulk PBD, (B) SFS spectrum of PBD in
PPP polarization at the sapphire/PBD interface and (C) SFS spectrum of PBD
in PPP polarization at the PBD/air interface in the CH stretching region.
The data points number was reduced for clear labeling of the spectra...................97
5.11 FTIR spectra of bulk (A) NBR (20% ACN), (B) NBR (30% ACN), and
(C) NBR (40% ACN) in the CN region................................................................100
5.12 FTIR spectra of bulk (A) NBR (20% ACN), (B) NBR (30% ACN), and
(C) NBR (40% ACN) in the CH region................................................................101
5.13 (A) FTIR spectrum of NBR (40% ACN), (B) SFS spectrum of NBR
(40% ACN) in PPP polarization at the sapphire/NBR (40% ACN) interface
and, (C) SFS spectrum in PPP polarization at the NBR (40% ACN)/air interface,
in the CN stretching region. The data points number was reduced for clear
labeling of the spectra ...........................................................................................104
5.14 SFS spectra of NBR (40% ACN) in PPP polarization (A) at the
NBR (40% ACN)/air interface and (B) at the purified NBR (40% ACN)/Air,
in the CN stretching region ...................................................................................108
5.15 (A) FTIR spectrum of NBR (20% ACN), (B) SFS spectrum of
NBR (20% ACN) in PPP polarization at the sapphire/NBR (20% ACN)
xvi
interface and (C) SFS spectrum of NBR (20% ACN) in PPP polarization
at the NBR (20% ACN)/air interface in the CN stretching region.
The data points number was reduced for clear labeling of the spectra.................110
5.16 SFS spectra of NBR (40% ACN) in PPP polarization, (A) at the NBR
(40% ACN)/air interface and (B) at the NBR (40% ACN)/heptane interface
in the CN stretching region ...................................................................................113
5.17 SFS spectra of NBR (40% ACN) in PPP polarization (A) at the sapphire/NBR
(40% ACN) interface before heptane exposure and (B) after 1 h of
heptane exposure in the CN stretching region ......................................................113
NBR (40% ACN)/air interface, (B) at the sapphire/NBR (40% ACN)
interface before toluene exposure, (C) at the sapphire/NBR (40% ACN)
interface after 30 s of toluene exposure and N2 drying, and (D) at the
sapphire/NBR (40% ACN) after 4 additional min of toluene exposure and N2
drying, in the CN stretching region.......................................................................119
5.19 SFS spectra of NBR (40% ACN) in PPP polarization at the

sapphire/NBR (40% ACN) interface (A) before water exposure and (B) after
water exposure, in the CH stretching region.........................................................122
NBR (40% ACN)/air interface and (B) at the NBR (40% ACN)/water
Interface, in CH stretching region.........................................................................122
xvii
CHAPTER I
INTRODUCTION
The first reference to nitrile rubber can be found in a French patent in 1931. Nitrile
rubber (NBR) was commercialized four years later in Germany for its outstanding oil and
fuel resistant properties. The NBR market just began growing in the United States when
WWII broke out in December 1941. Nitrile production became a full-fledged war effort,
along with other synthetic elastomers, due to attacks by U-boats in the Atlantic stopping
shipments of natural rubber to the US. Many of the U.S. synthetic rubber production
plants that exist today were built because of the war effort2. Sixty years later, NBR
production in the U.S. alone represents 130 million pounds3 annually and is often referred
to as the workhorse of automobile rubber products. NBR is the oldest and most widely
used O-ring material in fuel applications4 and it is also used in grease sealings, creamery
equipment5, and textile applications.6 The reason why NBR is used in these applications
is its resistance to swelling when in contact with these liquid environments. The polar CN
group is the key to nitrile rubber’s ability to resist oil penetration.7
1
Early on, industry developed ASTM testing procedures to characterize the oil resistance
of nitrile to “help” predict the lifetime of a rubber piece in a “standard” liquid
environment.2 However, these procedures up to the present day have not been able to
predict the behavior of nitrile in “complex” or non-standard formulated oil. As the
number of chemical compounds increases in the oil, the tests imagined by rubber
designers fail to answer the important question: how will the rubber interact with the oil?
Despite the recent advances in modeling associative solvents8, there still no microscopic
picture of the rubber/oil interactions.
The approaches developed up to today have focused on indirect information like the
effect of the oil on the rubber’s physical and mechanical properties. Furthermore,
understanding the nature of these interactions between the rubber and the oil must
involve direct information regarding the impact of the oil on the rubber molecules
properties. For example, observing the first spectroscopic changes of rubber molecules at
the rubber/oil interface could significantly help in shaping a molecular mechanism of the
oil resistance phenomenon. Such an approach requires a tool capable of probing the
rubber/oil interface and represents a technical challenge as the presence of liquid
prohibits the use of vacuum techniques.
The technique of Sum Frequency Spectroscopy (SFS) is able to probe the polymer/liquid
interface and retrieve molecular information about the microscopic environment at the
interface. Such an interfacial description represents an important step in understanding
2
and controlling phenomena starting at the interface. This technique was used for
investigations in fields including sensor designing, food processing, medical industries9-

11
and in biotechnology, more precisely with catalysis, and biosensor disease diagnosis.12-
14
Insight on polymer/liquid interactions would not only shred light on a problem related to
the rubber industry problem but would also contribute to other sciences that pursue
similar goals such as membranes science,15 coatings fabrication,16 and polymer implant
design.17
The approach proposed within the framework of this dissertation is to probe the surface
of nitrile rubber using SFS and collect molecular information, such as solvent-induced
shift on the NBR absorption bands to understand the impact of the liquid environment on
the molecular properties of rubber. Therefore, the old industrial phenomenon of NBR’s
oil resistance will be reinvestigated.
This dissertation is articulated in 6 chapters. The second chapter describes the
experimental tools available to characterize the oil resistant properties of the elastomer
focusing on two main areas. The first area is the industrial approach, which essentially
focuses on the mechanical properties of the swollen rubber. The second area describes the
advances in fields where the polymer/liquid interaction characterization is the prime
concern. Chapter 3 sets the foundation of non-linear spectroscopy methods and illustrates
3
the spectroscopic manifestations of the interaction between the nitrile groups and the
environment. Chapter 4 describes the details of the Sum Frequency Spectroscopy
technique and how it will be used in this research. Chapter 5 presents the experimental
results and Chapter 6 emphasizes the main conclusions of this investigation.
4
CHAPTER II
BACKGROUND
2.1 Nitrile Rubber
Nitrile rubber (NBR), a copolymer of acrylonitrile and butadiene monomer, will have
properties intermediate between those of PAN and PBD. This is why a brief background
about these two homopolymers that make up NBR is an appropriate starting point for this
section.
2.1.1 Polyacrylonitrile.
Polyacrylonitrile (PAN) is a commercially important polymer18 and widely used as a
fiber. PAN fibers are used in protective clothing,19 biomedical materials20 and
nanosensors.21 PAN is produced by a reaction of acrylonitrile monomer with a free
radical or an anionic initiator. The polymerization can be carried out in bulk, emulsion,
suspension, slurry or solution.21 The growing acrylonitrile polymer chain occurs in a
head-to-tail fashion, attaching to every alternate carbon atom a compact and highly polar
nitrile unit.
5
Figure 2.1. PAN Chemical structure.
This polar nitrile side group is a very small moiety and yet exerts a major influence on
the electrical, mechanical, thermal and barrier properties of PAN. Calculation of the
strength of the nitrile-nitrile dipole interaction in low molecular weight compound
demonstrated that electrostatic forces are large and control molecular arrangements.22 If
parallel intramolecular nitrile groups induce repulsion, anti-parallel intermolecular dipole
moment causes attraction between polymer chains. Also, the intramolecular dipole
interactions are responsible for both stiffness and high extension properties of PAN
molecules. The backbone of PAN molecule is stiff and rotation around successive bonds
is possible only in a cooperative manner. Pitsyn and Sharonov23 elaborated a model
where the rotation of every other bond correlated with its predecessor is required before
any concerted motion of nitrile side groups could occur. PAN morphology and
crystallinity does not resemble that of any other polymer.21 PAN has a low degree of
crystallinity (paracrystallinity) and a high melting point.24 Analytical techniques such as
X-ray diffraction fail to provide information about PAN crystallinity. However, electron
diffraction, showed two-dimensional order.25 The scientific community tends to agree on
a heterogeneous structure for PAN, constituted of three phases: amorphous, quasi-
crystalline and crystalline phases.21 Furthermore, the existence of two thermal transitions
6
around 100 °C and 150 °C is also recognized.18, 21 the first transition at 80-100 °C is
attributed to the glass transition and the second transition around 140 °C is attributed to
the loosening of dipole-dipole interactions.18, 26, 27

Okajima et al.28attributed both
transitions to two amorphous phases having a different degree of order; the highest order
phase contributing to the highest transition relaxation. However, other authors such as
Minami29 envisioned the lowest temperature transition originating from molecular motion
in the paracrystalline phase. Some authors reported three thermal transitions.30
The nitrile-nitrile interactions in PAN are strong to the extent that only a limited number
of solvents can dissolve the polymer chains. At a molecular level, the solvent has to form
a hydrogen bond with a strength higher or at least comparable to those forces holding
polyacrylonitrile chains together.
Furthermore, PAN has the capability of interacting with specific surrounding molecules
via two sites. The lone pair orbital of the nitrogen atom is readily inclined to hydrogen
bonding with molecules such as water, and Bronsted and Lewis acids.31 Also, the π -
orbital electrons of the triple bond can interact with transition metal ions. These two
interactions give two distinct infrared spectroscopic manifestations, which will be
discussed later in Chapter 3.
7
2.1.2 Polybutadiene
Polybutadiene (PBD) is made by the polymerization of butadiene monomer. The
reactivity of butadiene monomer is characteristic of the chemistry of conjuguated
unsaturated double bonds. The polymer microstructure is characterized by the disposition
of the double bonds present in the polymer chains. Butadiene polymerizes by addition of
a monomer butadiene unit on an allyl radical resonance structure. The three possible
structures are vinyl-1,2, cis-1,4 and trans-1,4
Figure 2.2. PBD chemical structure.
The 1,4 addition process leads to the formation of either cis-1,4 (Z) or trans-1,4 (E)
groups. In its final form, the polymer consists of one of these forms or is a mixture of all
of them depending on the polymer recipe and polymerization conditions.32
PBD is a non-polar rubber whose chains are attracted to one another via dispersion
forces. It is essentially a rubbery material whose susceptibility to oxidation is high
because of the presence of double bonds.
8
2.1.3 Nitrile Rubber
When butadiene is copolymerized with acrylonitrile, a completely new set of
macroscopic properties appears for the poly(acrylonitrile-co-butadiene) or nitrile rubber
(NBR) as it is commonly referred to in the industry. From a synthesis point of view,
acrylonitrile and butadiene are polymerized using standard free radical emulsion
polymerization techniques. A typical recipe for NBR includes the monomers of
acrylonitrile and butadiene, the emulsifier or soap, stearic acid, t-dodecylmercaptan and
potassium chloride, sodium pyrophosphate, ferrous peroxide and of course, water.1 The
copolymerization reactivity ratios are rB= 0.4, rAN =0.04 (at 50 °C)5. The product of rB.rAN
is close to 0 and this indicates an alternate copolymerization (a-b-a-b-a-b).
-a-
-b-
Figure 2.3. NBR chemical structure.
9
Emulsion polymerization is done using a batch process where 40% acrylonitrile in the
original reaction charge corresponds to the 40% ACN in the final polymer composition.
This allows formation of an azeotrope copolymer. The major consequence is that the
copolymer has a constant composition over the entire polymerization process. If the
composition of monomer is either below or above 35-40% ACN, the acrylonitrile
copolymer composition will, respectively, decrease or increase with increasing
conversion. Composition drift could be responsible for butadiene-rich chains which could
turn into a specific point of entry for the oil.
Many macroscopic properties of NBR directly depend on this acrylonitrile content. For
example, the tensile strength, abrasion resistance, hardness, and heat resistance increases
as the acrylonitrile content (ACN) increases.2 Certainly, the most famous feature of nitrile
rubber that increases with the ACN content is its remarkable resistance to oil.
Many polar rubbers such as polysulfide, the first solvent resistant polymer ever
synthesized, also exhibit oil resistance.33 The superior solvent resistance of polysulfide
rubber is explained by the presence of sulfur (highly polar atoms) in the polymer
backbone. The role and importance of the polarity of sulfur is demonstrated by the fact
that the solvent resistance increases with the content of sulfur atoms. Other important
polar rubbers are the acrylic elastomers (ASTM designation ACM) and epichorohydrine
(EPI), a polar polymer containing a chorine atom on every other methyl group.
10
2.2 Oil Resistance of Nitrile Rubber.
The following sections describe the various approaches attempted to characterize
polymer-solvent interactions and model elastomer swells in liquid environments.
2.2.1 Theoretical Approach
From a thermodynamic point of view, the Gibbs free energy balance in a swollen
elastomer is controlled by enthalpy, entropy, and elastic retraction energy. Gee and
Treloar34-42 thoroughly investigated the interaction between rubber and liquid. Later on,
Treloar43 used this information to shape an entire chapter in his book dedicated to the
swelling phenomenon of rubber. It is a well known fact that aromatic oils cause rubber
swelling. This is why the rubber/benzene system was chosen to represent the main issues
related to the swelling of rubber in a solvent.
Rubber swelling is entropically driven and is not a consequence of an attractive force
between the rubber molecule and the solvent, since ∆H m > 0 . This behavior differs from
that of water-swelling of a substance that typically shows ∆H m < 0 , characteristic of an
enthalpic-driven swelling. The swelling of the rubber molecule is therefore a reflection of
the tendency of the rubber molecule to mix with oil by thermal motion in the same exact
manner as a gas or common liquids. Interestingly though, the swelling of rubber by
chloroform is enthalpically driven.
11
Rubber swelling corresponds to a equilibrium between a pure phase (liquid) and a mixed
phase (swollen rubber). A dilution of the pure liquid into the rubber and a stretching of
the chains of the rubber network must be accounted for to understand the thermodynamic
equilibrium of rubber in a swelling agent.
Two phases: Solvent in Swollen Rubber
One phase: Pure Solvent

(Benzene) ~ ~
~
~ ~ ~
~~
~ ~
DILUTION PHENOMENON
Figure 2.4.Schematic representation of the dilution process occurring during rubber

swelling.
Mathematically this means:
∆G = ∆G1 + ∆Gel (2.1)
∆G1 stands for the change in Gibbs free energy of the system due to the transfer of 1 mol
of liquid from the liquid phase to the mixed phase, also called the Gibbs free energy of
dilution. ∆Gel corresponds to the change in Free Enthalpy (per mole of liquid absorbed)
resulting from the elastic expansion of the network.
12
The statistical treatment of swelling determines ∆G and ∆S by counting the number of
the configurations available versus the composition of the system and capture the
behavior of the mixture during the dilution process. Many textbooks explain the
calculation, the final result of which is expressed as:
[
∆G1 = RT ln (1 − v2 ) + v2 + χv22 ] (2.1)
where v2 is the volume fraction of polymer in the mixture, and χ is the Flory-Huggins
energy parameter.44 Equation (2.1) is known as the Flory-Huggins equation. Equation
(2.1) only describes the dilution of the liquid into the rubber.
The stretching affects the Free Enthalpy variation of the system via the dependence of the
work, W , on the number of liquid molecules, n1 , swelling the rubber network. Since
n1 influences the stretching ratio corresponding to the rubber isotropic expansion such as
3ρRT  − 3 
2
1 1
v2 = and that = 1 + n1V1 , it is easy to show that if W = λ − 1 and
λ3 v2 2 M c  

∆S = −
2 Nk
(
1 2 2 2
l1 + l2 + l3 − 3 ) (2.2)
∂W ρV1 3
1
then, ∆Gel = = v2 (2.3)

∂n1 Mc
which gives:
 ρV 1 
∆G = RT ln (1 − v2 ) + v2 + χv22 + 1 v2 3  (2.4)
 Mc 
with the corresponding swelling equilibrium:
13
ρV1
ln (1 − v2 ) + v2 + χv22 +
1
v2 3 = 0 (2.5)
Mc
If instead of Equation (2.2) the following expression is used:
{
∆Sel = − 1 Nk l12 + l22 + l32 − 3 − ln l12l22l32
2
( )} (2.6)
then Equation (2.4) becomes:
ρV1  v 
∆G = ln (1 − v2 ) + v2 + χv22 +
1
 v2 3 − 2  (2.7)
Mc  2
which is also known as Flory-Rehner equation.
Predictive models for the rubber swelling emerged with the concept of the solubility
parameter (SP). The SP model is based on several important assumptions. First, moderate
swelling-power liquids must be used so that ∆S is not modified by the crosslinking
density. This was experimentally established as similar ∆S were obtained for solvents of
low swelling power. Furthermore, ∆S is the same in all solvents, which makes the
interaction between rubber and liquid entirely governed by ∆H . Essentially, then, the
model predicts the solubility of an elastomer in liquid environment via the determination
of ∆H and its connection to the physical properties of the rubber and the liquid.
Hildebrand and Scott defined the heat of vaporation as the cohesive energy density (c.e.d)
and it’s square root as the SP,
1
 ∆H − RT  2
δ =  (2.8)
 V 
14
Equation (2.8) stipulates that the heat of vaporization, ∆H − RT , is the energy needed to
maintain the liquid state. This equation is valid only for vapor following the ideal gas
law. For non-polar materials then, the maximum swelling is predicted when the rubber
and liquid have a solubility parameter close in magnitude which defines the “force-
matching” concept underlying SP ideas.
45
In order to predict the swelling of polar liquids, Hansen modified Hildebrand’s theory
by considering the driving forces controlling interactions namely, dispersion forces,
hydrogen bonds, and dipole moment interactions and further decomposed the SP into
three contributions:
δ 2 = δ D2 + δ P2 + δ H2 (2.8)
2.2.2 Key Experimental Parameter: the Acrylonitrile Content
Salomon7 initiated the characterization of the solvent resistance of polar rubbers such as
NBR by immersing elastomeric pieces in various solvents until the swelling equilibrium
was reached. The swelling equilibria of a series of copolymers from acrylonitrile with
three different comonomers (butadiene, isoprene, and dimethylbutadiene) was
investigated. Historically, the extent of the swelling was expressed using “weight
fraction” which represents the increase in weight after rubber plates were immersed in
various liquids at 25 °C for a specific amount of time (see Figure 1 of reference7). The
three copolymers were immersed separately in pentane, hexane, heptane, cyclohexane
and benzene. The major conclusion from his work was that for the three copolymers the
15
extent of the swelling decreased with the amount of acrylonitrile; the least swelling
corresponded to copolymers containing 30 to 40 % ACN. This study pointed to the polar
unit of NBR as a major parameter governing the oil resistance of NBR.
2.2.3 Industrial Approach
The definition the oil resistance of a rubber is, as a matter of fact, related to the “ability of
the vulcanized product to retain its original physical properties, such as modulus, tensile
strength, abrasion resistance, dimensions”.32 A 20% change in volume due to oil
absorption can cause a reduction up to 60% in properties such as hardness, stiffness and
strength.46
The industrial approach uses mainly the extent of swelling at thermodynamic equilibrium
and the effects of swelling on stress-strain isotherms to predict the oil resistance
performance of rubber pieces. The swelling measurements were seen as accurate to
predict the serviceability of commercial rubbers. Rubber designers evaluated then the
effect of liquids on vulcanizates by studying at the changes in thickness as explained in
ASTM D471.
Tests for tensile strength, percent elongation at break, hardness, and percent volume
swelling are performed after a specified immersion time period at a specified temperature
in the characterization of oil-resistant rubbers as described in ASTM D5964. In the case
16
of engine oil formulations, the lack of compatibility with certain elastomers used for seals
in automotive engines is tested using ASTM D7216.
Only a few academic studies have devoted attention to the mechanical properties of
swelled rubber. Magryta et al.47 et al. showed that there are observable changes in the loss
angle values of the swelled samples compared with those of non-swelled, making
mechanical characterization of swollen rubber a sensitive characterization tool.
Furthermore, the mechanical properties such as tensile strength, elongation at break,
moduli, and Shore A hardness of swollen CR and NBR vulcanizates are lower than the
non-swollen vulcanizates.
The effect of liquids on the dynamic properties of carbon black filled natural rubber has
been investigated by Busfield at al.48 They used a free oscillating technique to assess the
dynamic storage and loss moduli of carbon black filled natural rubber. The researchers
actually probed how the fillers resist liquid exposure. They evidenced a significant
decrease in the storage and loss moduli of swollen filled rubber compared to the one of
non-swollen filled rubber. They attributed this to a combined effect of swelling of the
rubber matrix and a reduction of the volume fraction of the fillers.
2.3 Advances in Probing Polymer/Liquid Interactions
Alternative methods to predict the swelling behavior of elastomers in solvent involves
activity coefficients and polarity indices and are developed in the next section.
17
2.3.1 Experimental Parameters
Predicting the oil resistance phenomenon comes down to predict the swelling power of a
liquid. The solubility parameter model, presented earlier, has important limitations when
the study of a polar liquid is concerned. In some case, experimental anomalies were
observed for polymers such as nitrile rubber that appeared to have two solubility
parameters.8 Furthermore, the SP concept is unable to correlate accurately the interaction
between two liquids characterized by a negative excess heat of mixing like in the case of
gasoline-ethanol mixture. Also, the SP model relies on the hypothesis that ∆S does not
depend on the swelling and that is not always true. Furthermore, it is reasonable to expect
that the energy needed to vaporize a liquid to be much larger than that needed to mix a
liquid.
Finally, even the modified Hansen SP, when valid, requires treatment of a large number
of data in the case of a multi-component solution. The amount of data needed to define
the system comprises 3 constants for the rubber and 3 additional constants for each of the
solvent parts of the mixture.
Pre-determining the rubber swelling behavior in polar and non-polar solvent requires
correlating swelling measurement data to rubber and solvent parameters or to an
interaction parameter between rubber and solvent. Starmer49, 50 reduced the information
contained in a swelling measurement of a rubber/polymer pair to one single value A. The
swelling behavior is determined by plotting the swelling extent (in % volumic ratio)
18
versus the %ACN content in the copolymer, like Salomon7 did. The curve was fitted to a
Gaussian function that passes through a maximum noted A, A being the ACN content at
the maximum swelling. For example, NBR/isooctane, the swelling curve has maximum
swelling with a fictitious copolymer having a negative ACN. In the case of
NBR/aromatics, A 20-25 %ACN and finally in the case of NBR/methanol, A 40% ACN.
Starmer investigated the correlation between A and parameters describing the properties
of the rubber and the solvent. There are five potential parameters available to describe the
polarity of a liquid, the dielectric constant ε , the miscibility parameter M, the molar
transition energy ET(30), and the polarity index.49-52 The dielectric constant is, like the
solubility parameter, entirely related to the properties of the material. The miscibility
parameter (M) separates the solvents into 31 classes and predicts the solubility of pairs
according to the miscibility difference number. The molar transition energy, ET(30), is an
empirical parameter measuring the polarity of a solvent based on a solvent-dependent
process called solvatochromism. The effect of the solvent on the position and absorption
intensity of UV-Vis absorption band of a dye dispersed in the medium under analysis is
monitored. ET(30) is defined as the molar transition energy for the solvatochromic band
of the dye in the solvent. The last parameter is the polarity parameter measured from
liquid chromatography. These three last parameters are based on the interaction between
the liquid and one or other materials. Starmer examined the correlation between,
respectively, the dielectric constant, the miscibility parameter, ET (30) and the polarity
indices with the A value. The correlation between the dielectric constant and A, if it
exists, is weak. Acceptable correlation was observed for the miscibility parameter and
ET(30) if the case of alcohol was left out. The highest correlation was observed for the
19
polarity indices. Finally Starmer, like Gee37 did using the solubility parameter, offers an
experimental mean of deducing the polarity indices of a polymer from that of the liquid
which swells that polymer more than any other. Using such a parameter to predict the oil
resistance of nitrile rubber is not successful yet as the reverse approach is used in the
sense that it is the swelling of the rubber that determines the polarity index of the
polymer. Note that, according to Starmer approach, the location of the maximum of the
swelling curve, only characterizes the swelling, which leaves out another parameter, the
extent of the swelling.
2.3.2 Linear Partition Model
The linear partition model was developed to predict the swelling behavior in a mixed
associative solvent.8 In the case of an elastomer swelling in an ideal mixture, the
observed swelling is directly determined by the solvent composition and the swelling
behavior of the rubber in the pure solvent part of the mixture. An example of a nearly
ideal solution is a gasoline mixture formed by oil and methyl tertiary-butyl ether
(MTBE).8 MTBE is a Lewis base that will interact with acidic protons. The other
constituent of this specific gasoline mixture does not contain any acidic hydrogen making
this oil a “non-associative” oil. If MTBE does not interact with any other chemical in the
solution, it does present affinity toward the polar moiety of poly(vinylidene fluoride-co-
hexafluoropropylene) (FKM-66). FKM-66, specifically, contains chlorine atoms and,
consequently, acidic hydrogens. The component that will essentially be absorbed by the
polymer is MTBE rather than the rest of the oil.
20
Now, the swelling behavior of an elastomer by a non-ideal solution is accounted for by
multiplying the partition coefficient by the volume-fraction based activities for each
solvent. Methanol is an example of a non-ideal solution as the molecule forms tetramers
at room temperature, thought to be more aggressive toward FKM-66 than its non-
associated form. The partition coefficient model assumes that the tendency of a chemical
to swell a rubber is characterized by its activity in solution such that the partition
coefficient must be multiplied by the activity of solvent in solution.
vm , e = ∑ ai , s vi0, s (2.9)
i
with, ν i0,e the partition coefficient and ai , s the activity of the solvent. Despite the fact that
prior knowledge of the chemical composition of the elastomer is not needed, the model
requires thermodynamic data for each component.
2.3.3 In-situ Swelling Measurements of Thin Polymer Films
The thin film approach involves thickness uptake measurements of polymeric thin film
using, for example, X-ray reflectivity. Singh and Mukherjee53 looked at the dynamic
behavior of a spin-coated polyacrylamide thin film on a silicon substrate. The film was
exposed to water vapor at a saturated vapor pressure. The mass uptake was measured by
gravimetry (microbalance) measurement and the thickness uptake by X-ray reflectivity.
Working with a thin film supported onto a substrate is delicate due to a possible
interaction between the substrate and the polymer. The outcome of such a system is
21
unpredictable. In the work by Singh, it was proven that the diffusion coefficient of water
is not dependent on the thickness of the film which means that the substrate does not
modify the diffusion process. Also, their data showed that there was a time window
during which the entire film of polyacrylamide was exposed to water before the film
begins to swell. According to the present data, the time window was roughly on the order
of 20 minutes. That time window is a useful time frame that can be used to probe the
interactions between polymer and solvent before the macroscopic changes, such as
swelling, occur and complicate the system.
The second example concerns the in-situ measurement of thickness uptake of polymeric
thin film using ellipsometry. Overall, the investigators were interested in determining the
role of the interface in the anomalous swelling of various polymers in supercritical CO2
(Sc-CO2). The conclusion on the influence of the interface in the swelling behavior of
these polymers was based on the direct comparison between the known swelling behavior
of the bulk polymer to that of the thin film swelling behavior. Li et al. 54 investigated the
swelling of poly(ethylene oxide) (PEO) and polystyrene (PS). Because of a low cohesive
energy density, CO2 was thought to be in excess at the polymer/CO2 interface causing an
anomalous swelling of the polymer. Li and coworkers carried out in-situ swelling
measurements of a polymer using an ellipsometer apparatus. Each pressure point of CO2
was correlated to a measurement of thickness. By plotting the % of swelling versus the
pressure of CO2 or what they called swelling isotherm for different polymers, they finally
showed that the interface alone cannot account for the excess of CO2 adsorption at the
polymer interface. The investigation of the role of the interface in the polymer/solvent
22
interaction is therefore possible when in-situ swelling measurement of thin polymeric
films is undertaken.
The last example is related to the use of a Quartz micro-balance coupled with a heat
sensor to in-situ record the mass uptake of a thin polyether urethane elastomer film
(roughly 1 µm thick) exposed to ethanol vapor with heat changes. Smith and Shirazi55 et
al. simultaneously monitored the heat flow and mass/unit area change versus the
composition of the gas and thus were able to record a direct measurement of the
thermodynamic quantities that characterize the interaction between polymer and solvent
vapor. The reliability of these measurements over those obtained from inverse gas
chromatography resides in knowing when the equilibration between organic gas and the
polymer occurs so that reliable enthalpic changes for gas-surface interactions are
determined. Furthermore, the device design would be especially appropriate for analyzing
surface specific phenomenon such as catalyst poisoning.
In-situ swelling measurements of thin polymeric films start with a time window during
which the system under analysis evolves toward its equilibrium. This time frame is
experimentally observable for the first time is a unique opportunity to probe the influence
of the interface in polymer/liquid interactions.
23
2.3.4 Polymer Membrane Design
Membrane science is interested in developing methods to control and quantify the flux of
specific molecules through polymer matrices. The interaction between polymer and
solvent is the basis of membrane science where the appropriate chemical function of a
polymer (forming the membrane) is able to selectively separate out one component in a
mixture containing many. Such a phenomenon is called selection by a permselective
membrane. Permselective membrane separation is an attractive alternative to distillation
when the temperature-based difference between the components to separate is small. For
example, the distillation of benzene/hexane is difficult because their boiling points are
only separated by 0.6 °C. So instead of distilling the benzene/hexane mixture, it is
preferable to force the mixture through a polymeric membrane and have the polymer act
as a third phase to separate the two constituents. The goal will be to find a polymer with
a great affinity toward one component so that it has a high selectivity. For instance, the
removal of an organic solvent from aqueous solution will require an oranophilic
membrane while a hydrophilic membrane will be selected for a dehydration of an organic
solvent.
56
For example, Yamaguchi et al. filled the pores of a HDPE film with poly(methyl
methacrylate) and due to the presence of this polymer in the membrane, benzene over
cyclohexane was able to permeate through it. Koops et al.57 studied permeation of solute
in ethanol and n-hexane through cellulose acetate and concluded that solute-membrane-
solvent interactions are important for mass transport.
24
Membrane/solvent interactions were revealed by directly comparing the performance of
two membranes: poly(ethylene oxide)-b-poly(dimethyl siloxane)-b-poly(ethylene oxide)
(PEO-PDMS-PEO) membrane and hydrophobic poly(dimethyl siloxane) (PDMS)
membrane in contact with a common solvent such as ethanol or isopropanol.58 A ternary
interaction was determined by keeping two parameters constant and changing the third
one. So to analyze polymer-solvent-solute interactions, they needed three sets of data to
permute the variable. First, they kept the solute and membrane as a constant and changed
the solvent. Second, they kept the membrane and the solvent as a constant and changed
the solute and so on. By comparing the performance of not one, but two membranes with
the same solvent, the conclusion was that membrane-solute interactions are possible. For
example, they compared the flux of ethanol, isopropanol, methyl ethyl ketone, toluene
and hexane on first PEO-PDMS-PEO/PAN and second PAN/PDMS. PAN was used as a
support. The authors intended to compare the properties of hydrophobic PDMS and
hydrophilic PEO-PDMS-PEO. They kept the membrane and the solute as a constant and
changed the solvent as they analyzed the PAN/PDMS membrane and compared the
transport of oil/hexane to that of oil/toluene. Then, they correlated the variables together.
They connected the permeability to the nature of the membrane. They effectively noticed
that for the hydrophilic membrane, PEO-PDMS-PEO, the flux of the polar solvents
(ethanol, MEK) was higher while in the case of the hydrophobic PDMS membrane the
flux of non-polar solvents (hexane, toluene) was higher. Stamatialis et al.58revealed that
the flux of oil/toluene mixtures depends on the concentration of toluene in the oil
(triglyceride or ester). Oil (triglycerides or ester) slows the diffusion of the mixture. The
higher coupling of oil/toluene than that of the oil/hexane may be due to the higher
25
viscosity of oil/toluene. Higher coupling implies higher solvent dragging. Another
example is the ion pairing of tetraoctylammonium bromide, TOABr, in toluene
solution.58 The nature of the composition is pivotal for the transport of (TOABr)/toluene
through polyimide. It means that ion pairing of TOABr in solvent (toluene) leads to the
observation of an anomalous behavior.
A recent study59 of polyelectrolyte ultra filtration membrane based on poly(acrylonitrile-
b-2-dimethylamino ethyl methacrylate) (PAN-DMAEMA) copolymer revealed an
enriched surface of PDMAEMA. The spontaneous migration of membrane casting
solution bulk to membrane surface is due to the incompatibility between hydrophobic
PAN and hydrophilic PDMAEMA. Furthermore, immersion of the membrane in basic
(pH = 8) solution alters the surface composition.
60
Garcia et al. observed that when polysulfone membranes were directly exposed to
heptane after water cleaning, hexane flux is blocked. But if the membranes were
pretreated by earlier exposures to solvent of decreasing polarity, the flux was recovered.
Surface compositional segregations and surface pretreatment can have a decisive
influence on the behavior of a piece of polymer in contact with liquids.
2.4 Summary
The chief parameter, pointed out in the early 50s, makes the nitrile content, ACN, the
prime parameter controlling the oil resistance of NBR. The ACN leading to the maximum
26
swelling depends on the chemical nature of the oil or fuel with which the rubber is in
contact. Characterization of the mechanical properties of swollen rubbers remains the
first means of assessing the NBR oil resistance performance by industrial rubber
engineers despite inaccurate predictions in the case of complex oil formulations.
Recently, the linear partition model was able to predict the swelling behavior of mixed
associative solvents by applying the concept of solvent activity to the partition coefficient
of an elastomer-solvent pair. Such model concentrates on the solvent composition and the
nature of the interactions in the solvent. Certain fields of research motivated by the
common interest of understanding polymer/liquid interaction developed in-situ
characterization techniques of polymeric thin films while others pointed out the
importance of the interface in controlling the flux of specific molecules through polymer
matrices. However, molecular information is still missing.
A new approach is needed to understand the mechanism of oil resistance. Along with an
industrial need, the oil resistance mechanism is a very fundamental problem with many
questions remaining unanswered.
27
CHAPTER III
PROBING MOLECULAR INTERACTIONS USING SPECTROSCOPY
In Chapter 2, the limitation of the thermodynamic approach to predict the rubber/liquid
interactions was reviewed. It was also shown that the oil resistance of nitrile rubber
depends on the amounts of nitrile groups present in NBR, pointing out the nitrile dipole
interactions as the most probable cause of the oil resistance phenomenon. The prevailing
polar nature of NBR directly correlates with the nitrile-nitrile dipole interactions in NBR
bulk. The purpose of this chapter is to demonstrate that these nitrile-nitrile interactions
give rise to spectroscopic manifestations that could be used to investigate the origin of the
oil resistance phenomenon by connecting specific vibrational manifestations to the
amount of nitrile in the rubber.
In addition, according to the framework of this project, the study of the environmental
perturbation on these specific vibrations is also meaningful. This perturbation is related to
the liquid environment to which the rubber is exposed. The C≡N bond possesses 21%
ionic character61, 62 due to its large dipole moment (3.5 D).63 Thus, the dielectric constant
of the surrounding medium plays an important role in the prediction of the strength of the
intermolecular interactions between nitrile groups.
28
It is the objective of this chapter to connect the spectroscopic characteristics of nitrile
rubber to the nitrile content and the nature of the environment. Molecular vibration,
infrared and Raman spectroscopy, as well as Sum Frequency Spectroscopy (SFS) will be
used in the characterization of the samples. Specific attention is given to establishing the
suitability of SFS to investigate the oil resistance of nitrile rubber since it is the main
technique used in this investigation. SFS is a non-linear spectroscopic technique which
has two powerful features: surface selectivity and molecular orientation detection. The
mathematical equations leading to this unique set of characteristics are presented and
spectroscopic observations of nitrile associations in two CN-bearing compounds,
acetonitrile and polyacrylonitrile, are reviewed.
The preliminary hypothesis of this work was that the participation of polar groups in
dipole-dipole interactions is reflected in the parameters of the bands, which correspond to
the vibrations of the polar fragments of the molecules. The main interest, then, was in
how this affected the molecular bond properties. For this reason, understanding the
parameters controlling the vibrational behavior of molecules is fundamental to this
research. Therefore, the beginning of this chapter will be devoted to spectroscopy as a
tool for chemical identification.
The basics of infrared and Raman spectroscopy needed to understand Sum Frequency
Spectroscopy are exposed in the next section; a complete theoretical background can be
found elsewhere.64
29
3.1 Linear Spectroscopy
A molecule with n number of atoms, rotates, translates and vibrates with a total of 3n
degrees of motional freedom. The molecular vibrational modes (3n-6) are characterized
by the periodic motions involving changes in bond lengths and bond angles. For now, the
case of a diatomic molecule is considered. When treated as a harmonic oscillator, the
diatomic vibration behaves as an oscillating spring characterized by a force constant, k ,
that connects two heavy masses, m1 and m2 , as shown in Figure 3.1.
j l0
k F
x
m1 m2
Figure 3.1. Ball and spring model for a diatomic molecule
The force F applied to the spring that oscillates around its equilibrium position, l0 , at a
distance , x , is given by Hooke’s law:
F = −kx (3.1)
where F , k and x stand for the force acting on the spring, the force constant and the
displacement from the equilibrium position, respectively. Applying Newton’s law of the
equation of motion to the isolated spring system becomes:
d 2 (x )
u = − k .x (3.2)
dt 2
30
1 1 1
where u is the reduced mass such that = + , with m1 and m2 shown on Figure
u m1 m2
3.1
Solving Equation (3.2) leads to the following expression:
1 k
ν= (3.3)
2π u
where ν is the frequency of vibration of the diatomic bond. If units of mass are used and
the force constants are expressed in N/m, the frequency of vibration of a diatomic
molecule is given by:
 1 1 
ν / cm −1 = 1303 k  +  (3.4)
 m1 m2 
The force constant (k) corresponding to spring's stiffness in the ball and spring model
relates directly to the strength of the covalent bond linking m1 and m2. and. According
Equation (3.3), a C=N double bond is approximately twice as strong as a C-N single
bond, and the C≡N triple bond is similarly stronger than the double bond. The infrared
stretching frequencies of these groups vary in the same order, ranging from 1100 cm-1 for
C-N, to 1660 cm-1 for C=N, to 2220 cm-1 for C≡N. Intrinsically, the strength of a bond
depends on the bonding nature of the molecular orbital. The wave function describing a
bonding molecular orbital correspond to a situation where the electron are in between the
atom creating a covalent bond. The bond order is equal to the number of bonding
electrons minus the number of antibonding electrons, divided by 2.
Furthermore, a direct correlation exists between the force constant, the bond length and
hybridization state of the atom.65 This directly means that if the electronic population of a
31
molecule changes upon solvation or interaction, the vibrational frequency is shifted.
Equation (3.3) states that, an increase in the force constant, k , (or a decrease in the bond
length) contributes to an increase in the vibrational frequency, while a decrease in force
constant, k , (or an increase in bond length) yields to a decrease in the vibrational
frequency,ν . In others words a vibrational frequency shift can be either positive or
negative.
Finally, the energy levels corresponding to the vibrations of a molecule are quantized and
determined by solving the Schrodinger equation:66
 1
Evib =  n + hν (3.5)
 2
where n is the vibrational quantum number,ν is the classical vibrational frequency of
the oscillator and h is the Planck constant.
3.1.1. Infrared Spectroscopy
The determination of this vibrational frequency is achieved when a change in the
vibrational energy of the molecular oscillator is induced by an external photon having a
frequency matching that of the fundamental frequency of the molecule. If the mechanism
of that transfer of energy involves a change in the dipole moment in addition to matching
the frequency of the normal coordinates, then absorption of light in the infrared region
occurs such as:
32
 1  1
where ∆E = (n + 1) +  hν m −  n + hν m = hν m
 2  2
(3.6)
∆E is the increase in vibrational energy of the molecule and ν m is the vibrational
frequency of the molecule.
To illustrate infrared absorption, the polar CN moiety is considered. A strong dipole
moment exists in the CN moiety due to the difference in electronegativity between the
carbon and nitrogen atoms. Around the electronegative nitrogen atom, there will be a
slight excess of negative charges. Opposite to this situation, the carbon atoms will have a
slight excess of positive charges. Exaggeration of this situation allows picturing the
positive and negative poles that constitute the carbon and nitrogen atoms, respectively, as
a dipole. By definition the dipole moment (usually of magnitude of 10-30 C.m) points
toward the most negative atom as shown on Figure 3.2. As the CN bond stretches and
contracts during vibration, the charge distribution changes along with the distance
between the carbon and nitrogen atoms. That is, the dipole moment of the CN bond
changes while the bond is vibrating. This is the specific mechanism which allows infrared
absorption to occur. The CN vibration (around 2250 cm-1) is therefore said to be an
infrared active vibration. Also displayed on Figure 3.2 is the case of CO2. As the oxygen
atoms move away from the carbon atom during the symmetric stretching mode at (1337
cm-1), the changes in the dipole moments continuously cancel each other out. Thus, the
dipole moment does not change during vibration making the CO symmetric stretch of
33
CO2 molecule infrared inactive. The CO asymmetric stretching mode (at 2349 cm-1),
though, is infrared active.
C N
δ+ δ-
O C O
δ- δ+ δ-
p p
Figure 3.2. Schematic representation of the location of the atoms in the nitrile moiety and
CO2 as the molecules vibrate with their corresponding dipole moment.
3.1.2 Raman Spectroscopy
Infrared and Raman spectroscopy differ in the mechanism of transferring energy between
light and matter. For a given vibration the intensity of the Raman band will be different
from the intensity of the infrared band despite the fact that the vibration mode will
theoretically occur at the same wavenumber. When a molecule is placed in an electric
field, electrons will move in the opposite direction of the field gradient while the protons
will move in the same direction as the field gradient. The spatial separation between
34
electrons and protons is small but sufficient to create an induced dipole moment in the
molecule. E is the external electric field applied to the molecule producing an induced
dipole moment proportional to the polarizability of the molecule. By definition
=α (3.7)
where µ is the dipole moment of the molecule and α is the polarizability of the molecule.
Such that, if an oscillating field is applied where
= E0 sin 2πν t (3.8)
the magnitude of the dipole moment will follow as
= αE0 sin 2πν t (3.9)
The magnitude of the dipole moment is proportional to the deformability of the electrons
or the ease with which they move away from the positive nuclei, in other words to the
deformability of the electron cloud. This property, conventionally called the atom’s
polarizibility, is directly proportional to the volume and the shape of the molecule which
may or may not change during the vibration of the molecule. It will also depend on the
geometry of the molecule. In this case, the simplest way to account for it is to expand the
polarizability according to the normal coordinate, Q, as the following:
∂α
α = α0 + Q + ... (3.10)
∂Q
35
In this equation Q is the normal coordinate rigidly fixed to the molecule and ∂α is the
∂Q
rate of polarizability change as the molecule vibrates. Internal coordinates measure the
change in shape of a molecule as compared to its equilibrium shape.
Since the normal coordinate is attached to the vibrating atoms, we can assume that:
Q = Q0 sin 2πν v t (3.11)
and by plugging this into Equation (3.10) it is easy to eventually demonstrate that
∂α
α = α0 + Q0 sin 2πν v t (3.12)
∂Q
and
∂α
µ = α 0 E0 sin 2πν t + Q 0 E0 (sin 2πν vt )(sin 2πν t ) (3.13)
∂Q
Finally, after reorganization:
∂α
µ = α 0 E0 sin 2πν t + Q 0 E0 [cos 2π (ν − ν v )t − cos 2π (ν + ν v )t ] (3.14)
∂Q
This last equation stipulates that the induced dipole moment, µ, varies with three
component frequencies v , ν − ν v , ν + ν v , which are responsible for Rayleigh, Stokes
and anti-Stokes scattering, respectively. The intensity of the Stokes and anti-Stokes lines
are both directly related to the variation of the induced dipole moment or variation in
polarizability. The intensity of the Rayleigh scattering is related to the polarizability of
the molecule.
36
Experimentally, the sample is illuminated with light and the scattered light is analyzed.
The first term of Equation (3.14) corresponds to the major part of the scattering. The
photon and molecule are colliding elastically leaving the rotational and vibrational energy
of the molecule unchanged. Scattered photons match in energy and frequency with those
of the incident light. In the ground vibrational state, when a molecule absorbs a photon,
the energy of the molecule increases as the molecule reaches a higher level of energy for
a very short period of time. As the molecule relaxes, the excess of energy just gained is
released in the form of a photon having an energy corresponding to hν i , which is
Rayleigh scattering. If the rotational and vibrational energies of a molecule are changed
during an inelastic collision with a photon then,
hν i − hν s = ∆E m = hν m (3.15)
where ν i is the frequency of the incident photon and ν s is the frequency of the scattered
photon. If the molecule gains energy then ν s is smaller than ν i and this is known as the
Stokes line of the Raman spectrum. If the molecule loses energy then ν s is larger than ν i
and is called the Anti-Stokes line of the Raman spectrum. The Boltzmann distribution
function implies that higher levels of energy are less populated. This means that the
intensity of the Stokes line is greater than that of the anti Stokes lines at room
temperature. The main point is that if the vibration causes no change in the polarizability,
then the intensity of the band associated with this vibration would be null and the band
would be said to be Raman inactive. The polarizability would be in the most general case
a 3x3 tensor or matrix.
37
The magnitude of polarizability, expressed in volume unit, is related to the volume of the
loose electron cloud. Large scatterers will be typically large polarizable molecules and
delocalized systems such as rings, double and triple bonds. The polarizablity tensor is
often represented using a so-called polarizability ellipsoid. The construction of the
ellipsoid starts by drawing vector in specific directions having length proportional to
1 .The end of the vectors forms a 3D surface whose distance from the electric center
αi
of the molecules is proportional to where α i is related to the symmetric real
polarizability tensor.
Thus, the CN stretch vibrational band, in addition to being infrared active, will also be
Raman active. For the same reason the CO symmetric stretch of the CO2 molecule is
Raman active and the asymmetric CO stretching mode is Raman inactive.
Whether linear infrared or Raman is employed to probe molecular vibration, the approach
is the same, vibrational frequency unravels molecular identity and a vibrational frequency
shift indicates interaction with specific molecules. A positive shift delocalizes toward a
higher frequency as shown in Figure 3.3. It is also know as “hypsochromic” shift, from
Greco hupsos, “height, elevation” or “blue” shift. A negative shift corresponds to a
decrease in the vibrational frequency, also called “bathochromic”, from Greco root
“depth” or “red” shift. A shift in vibrational frequency of a mode indicates a change in
the characteristic of the bond. Therefore changes in the electronic population of a
38
molecule upon specific interactions such as hydrogen bonding or during solvation
process are indicated by a spectroscopic vibrational shift.
Red shift Blue shift

k decreases k increases
2.0
1.5 k k
Abs (a.u.)
1.0
0.5
0.0
-1
Wavenumber (cm )
Figure 3.3. Correlation between the vibrational frequency shift and the change in force
constant magnitude.
3.1.3 Non-Linear Effect
Molecules will fail to respond harmonically by coupling of harmonic modes. In most
cases it will lead only to the appearance of spectroscopic manifestations such as hot band
and Fermi resonance.
From a general point of view, anharmonicity creates new levels of energy such as
combination, difference and overtone. Overtones occur as a necessity to accommodate
the dependence of the dipole moment on the intensity of the electric field. As the motion
of the molecules slightly diverts from harmonicity, the dipole moment of the vibrating
molecule will not only oscillate at the fundamental frequency, but at the double, triple
39
and so on of the fundamental frequency. Along with overtones, combinations and
differences bands are also possible. Theoretically, peaks at the sum or difference of the
fundamental frequency exist. However, they will be very weak and contribute only in a
minor proportion to the spectral features of a molecule. In other cases though, the impact
of anharmonicity is sufficient to be experimentally observable, through phenomena such
as vibrational hot band,64 Fermi resonance,67 and the vibrational Stark effect.68-70
Since the results of this project will be compared to those of acetonitrile, it is important to
understand two of the three effects previously cited, namely the Fermi resonance and the
hot bands. The following sections will be dedicated to explaining these two effects.
3.1.3.1 Hot Band
The term “hot” band was most likely created by Herzberg and Ottawa in the 1930's.71 A
hot band is a transition involving two excited states from ν 2←1 and ν 3← 2 . As molecules
are in thermal equilibrium, the population of each level contain a Boltzmann correction
such that
Ei
−
ni e kT
= E0 i (3.16)
n0 e − kT
where ni and n0 are the number of molecules in the ith and 0 levels. (Ei-E0) is the energy
difference between the levels, k is the Boltzmann constant and T is the absolute
temperature (Kelvin scale). The intensity of the hot band is very low compared to the
fundamental transition because it occurs from two excited levels with populations
40
decreasing as it obeys the Boltzmann distribution. Figure 3.4 (A) shows a transition from
an excited level ν i = 1 to ν i = 2 . Such a transition is possible at room temperature only if
the energy of the mode is lower or close to RT ≈ 209 cm −1 . If this is not the case, most
molecules will be found in the ground level. A second type of hot band can be expected at
room temperature when low energy vibrational modes excited at room temperature
couple with a high energy vibrational mode like it is shown in Figure 3.4 (B). A recent
example of a hot band transition can be found in the literature.72
A Energy scheme and vibration spectrum corresponding to vibration i:
Vibration i
Fundamental
νi=2 Cold band
νi=1
Hot Band
Frequency
Ground State
νi= νCN
B Energy scheme and vibration spectrum corresponding to vibration i coupled with j
Fundamental
νi=2 Cold band
νi=1
Hot Band
Frequency
Ground State
νi= νCN
ν 2 lower energy mode excited at room
temperature
Figure 3.4. Energy scheme and corresponding vibrational spectrum for fundamental and
hot transition.
41
3.1.3.2 Fermi Resonance
Fermi resonance arises when a combination band (or an overtone) resulting from
anharmonicity lies sufficiently close to the fundamental band. Thus, instead of observing
only one fundamental band, two bands involving the fundamental and the combination
are observed. The intensification of the combination band is to such an extent that a
second band is observable. In the event that the combination (or overtone band) is not
sufficiently close to the fundamental band, the Fermi resonance will not exist (See Figure
1.14).64 Molecules exhibiting Fermi resonance are aldehydes, CO2, and acetonitrile.
3.2 Non-Linear Spectroscopy
The following section highlights the salient features of SFS spectroscopy; further details
can be found in the work of Hirose73-75 and Shen.76, 77 Non-linear spectroscopy involves
physical processes of light mixing where the frequency of an input beam is converted into
another one. Historically, the first experimental observation of light conversion was
reported by Franken et al.78 using a ruby pulsed laser. A monochromatic light (694 nm)
was focused onto to a piece of crystalline quartz and an output at 347 nm was detected.
The experiment is conceptually illustrated in Figure 3.5. Two incident photons were
converted into one emerging photon with exactly twice the energy or half the wavelength.
42
Second Harmonic Generation using Quartz:
γ 2xγ
Input laser beam Output light
E k Ek
B Quartz B
Non-linear material
Photon
Figure 3.5. A sketch illustrating the production of SHG through crystalline quartz with
vibrational excitation at 694 nm and the corresponding harmonic at 347 nm.
This doubling of the input beam frequency was called Second Harmonic Generation
(SHG). Note here, that this non-linear effect occurs in the bulk medium of crystalline
quartz.
This interaction between light and matter arises when molecules are impinged by
extremely intense electric fields such as those produced by pulsed laser.
Under laser exposure the polarization of a material is given by:
= α0 +β +γM + ... (3.17)
where is the polarization vector, is the electric field vector, and α 0 , β and γ are
the first, second and third order electric hyperpolarizability tensors of the molecule,
respectively. This expression is also known as the electric dipole approximation where
quadrupoles are neglected.
43
In Equation (3.17), α 0 is the linear polarization of the molecule, self-sufficient when
the electric field applied is low. The incorporation of higher order terms captures the
non-linearity of the induced polarization of the molecule. The first non-linear term is
( )
accounted by the

= . The anisotropy of condensed matter requires expanding
β as a 3x3x3 tensor. It is easy to show that:

( )

= βE0 cos(νt )cos(νt ) = 1 β E02 (1 + cos 2νt ) (3.18)
2
The electric field, , is defined as E = E0 cosνt with an oscillating frequencyν . The first

term of Equation (3.18) represents a static electric field and the second term corresponds
to a dipole oscillating at double the frequency and emits light at 2ν or SHG.
A direct correlation of SHG is the Sum Frequency Generation (SFG) where, two intense
beams of frequency ν 1 and ν 2 excite a material and induce a polarization which oscillates
at the sum of the two incoming frequencies as shown in Figure 3.6.
44
E
k γ1
Ek
B γ3 =γ1+ γ2
E k
γ2 Non-linear material
Figure 3.6. A sketch illustrating the SFG process through non-linear material.
The mathematical expression for the molecular hyperpolarizability tensor, as a function
of the two input frequencies when none of the two input frequencies is resonating with an
electronic transition of the molecule, is:76
 ∂α lm   ∂µ n 
   
Q
 ∂Q q  ∂Q q
β (ν =∑
q =1 (ν 2 − ν q + iΓq )
2 , lmn ) . (3.19)
where (l , m,.n ) is the Cartesian frame attached to the molecule associated with the set of
 ∂α 
axes (a, b, c ) , c is the axis of highest symmetry of the molecule,  lm  is the lm
 ∂Q q
 ∂µ 
component of the Raman tensor and  n  is the n component of the transition dipole
 ∂Q q
moment. ν q and Γq are, respectively, the frequency and width of the resonance, q. The
microscopic description of the SFS tensor, represented by Equation (3.19), stipulates that
45
an SFS active mode is, by definition, an Raman and infrared active mode; if not, the
hyperpolarizability tensor elements vanish according to the specific point group of the
molecules. For example, the -C≡N moiety introduced to illustrate the Raman and infrared
activity of the CN stretching is an SFS active vibrational mode. The hyperpolarizability
tensor, therefore, comprises molecular information about the chemical structure of the
molecule under light excitation.
A direct analogue of Equation (3.19) exists at a macroscopic level. When an oscillating
field is applied to condensed matter, a dipole proportional to the applied electric field is
induced such as:
= χ (1) + χ (2 ) + χ (3 ) M
+ ... (3.20)
where χ (1) , χ (2 ) and χ (3 ) are the first, second, and third order susceptibility tensors of the
medium, respectively. Equation (3.20) is an analogue of Equation (3.19) that relates the
polarization (dipole per unit volume) of molecules to the applied electric field. The
dimension of the susceptibility tensor, χ (2 ) , matches that of the hyperpolarizability tensor
and is a 3x3x3 tensor. A correspondence between the microscopic hypolarizability and
the macroscopic susceptibility tensor can be obtained by projecting the β lmn, q into the
laboratory axes ( xyz ) from the attached molecular axes (abc ) using the Euler angles. The
Euler transformation coefficients are functions of ψ , θ , and φ and are represented in
Figure 3.7. The original notation from Hirose73 is modified for the Euler angle, χ , and is
referred to,ψ , instead. The coordinate transformation includes three rotations, a first
46
rotation of the N axis of an angle φ around the c axis and a second of an angle ψ around
the z axes. The third rotation is that of the c axis around z axis of an angle θ .
z
c
θ
Φ
N
ψ b
y x
a
Figure 3.7. Definition of Euler angle relating the attached molecular axis frame (abc ) to
the laboratory axis system ( xyz ) .
The expression of β lmn in the laboratory axis corresponds to
β ijk (ν 2 , Ω ) = ∑U ijk ,lmn (Ω )β lmn (ν 2 ) (3.20)

l , m , n = a ,b , c
where Ω is the Ω = Euler angle (ψ ,θ , φ ) and U ijk :lmn is the 27x27 Hirose projection
coefficient. The contribution of all molecules, providing their β ijk s is non-zero, adds up
to an extent that depends on the number N and the molecule orientation. A probability
distribution function ( f (Ω)) accounts for the orientation of each molecule, and is
mathematically expressed as
Aijk ,q = N  ∫ ∑ U ijk:lmn (Ωβ lmn ,q ) f (Ω )dΩ

 
(3.21)
 lmn =abc 
47
where Aijk , q is the resonant component of the susceptibility
Q
Aijk , q
χ ijk (ν 2 ) = χ NR eiφ + ∑ (3.22)
ij ijk k
q =1 ν ir − ν q + iΓq
and where φ (not related to Euler angle) is the possible phase between the non-resonant
(wavelength independent) term and the resonant term(s).
By probing the susceptibility tensor, the symmetry of the local arrangement is captured
because the symmetry of the molecules is embedded into the macroscopic response of the
material to an electric field (also known as Neumann principle). This principle applies to
many other physical properties such as elastic deformation, the piezo-electric effect, the
magnetic effect, and pyroelectricity. The symmetry of a material affects the
susceptibility tensor by reducing certain terms of the tensor to zero. The number of
vanishing terms will strictly depend on the level of symmetry of the local molecular
arrangement observed. For a centro-symmetric medium χ (2 ) = − χ (2 ) = 0 .
The main conclusion is that media such as bulk polymer that shows inversion symmetry
cannot produce any second order effect. The interface, though, by definition, is a non-
centrosymmetric medium and will exhibit a non-linear effect. For that reason, SFS is a
surface selective tool.
In an SFS experiment, from the laboratory axis point of view, two incoming beams
overlap on a sample and generate surface polarization which gives rise to SF signal in the
48
reflected and transmitted directions. θ i (ν 1 ) and θi (ν 2 ) are the angle of incidence of the
beamsν 1 andν 2 , respectively. The angles of reflection and refraction are θ r (ν 1 ) , θ r (ν 2 ) ,
θt (ν 1 ) , and θt (ν 2 ) respectively. The direction of the SFS beam propagating in medium 1
and 2 is given by θ r and θt as shown in Figure 3.8.
The excitation source and the refractive index of the medium characterizing the material
at the interface (see Figure 3.10) are related via the following equation73
θi (ν 1 ) = θ r (ν 1 ) , θi (ν 2 ) = θ (ν 2 ) (3.23)
The directions of the reflected and transmitted beam in media 1 and 2 are given by the
following relationships
ν 1n1 (ν 1 )sin θ r (ν 1 ) + ν 2 n1 (ν 1 )sin θ r (ν 2 ) = ν SF n1 sin θ r , (3.24)
ν 1n2 (ν 1 )sin θt (ν 1 ) + ν 2 n2 (ν 2 )sin θt (ν 2 ) = ν SF n2 sin θ t (3.25)
γSFS,r
γ1,i γ1,r
Ep θi (γ1) θr (γ1)
γ2,i θi (γ2)
ES θr (γ2) Linear medium
γ 2,r
(air,oil…)
n1 Non-Linear medium : interface
n2
γ1,t Linear medium:

polymer bulk
z γSFS,t
y γ2,t
x
Out of page
Figure 3.8. Schematic of an SFS experiment at an interface in external reflection. All the
light beams lay in the plane of incidence (xz). The two polarization cases, S and P, have
been illustrated for the incident infrared beam. The directions of the laboratory–fixed
coordinate axes are indicated.
49
In the laboratory axes for the polymer interface, it is assumed that SFS active groups at
the surface are isotropically distributed in φ andψ . In other words, χ(2) must be
rotationally invariant around the z axis. Only seven combinations of i, j , k out of 27 are
non-vanishing; χ XXZ = χYYZ , χ XZX = χYZY , χ ZXX = χ ZYY , χ ZZZ need to be determined.
These susceptibility tensor elements are experimentally determined by setting-up the
polarization of the SFS experiment. Three polarizers convert, respectively, the SFS,
visible and infrared beam to a single polarization state: S or P. It is a convention to report
the polarization state of the three beams precisely in this order of decreasing frequency. S
polarization corresponds to an electromagnetic wave having its electric field
perpendicular to the plane of incidence (x-z, see Figure 3.7) and a P polarization signifies
a polarized electric field parallel to the plane of incidence (y-axis). The polarization of
the excitation and SF beams allows probing the component of an effective susceptibility
χ (2 ) whose expression depends on the polarization of the beam. The correspondence

eff
between the χ (eff2 ) and the elements of the susceptibility tensor is as following:
χ eff( 2 ), SSP = L YY (ν 3 )L YY (ν 1 )L ZZ (ν 2 )sin θ 2r χ YYZ (3.26)
χ eff(2 ), SPS = LYY (ν 3 )LYY (ν 1 )sin θ1r LZZ (ν 2 )χYZY (3.27)
The L pre-factor is the Fresnel optical coefficient associated with the incoming beams; it
relates the intensity of the input field with that at the interface. The Fresnel factor is
related to the SF beam intensity to the non-linear source polarization of the interface.
50
(2 )
Finally the relation between χ eff and the intensity of the beam at ν 3 is:
(2 )
I1 (ν 1 )I 2 (ν 2 )
2
I (ν 3 =ν 1 +ν 2 ) ∝ χ eff (3.28)
It has been shown before that the tilt angle ( θ ) of a moiety at the interface can be
experimentally determined. As this study concentrates on the detection of the nitrile
moiety, a calculation of the angular dependency of the SF signal enhancement of the
nitrile CN stretching mode is provided. The CN belongs to C∞v symmetry group. As a
usual convention, the (a, b, c ) axes are attached to the molecule in such a way that the c
axis coincides the rotation axis of the molecule.
The CN Aijk ,q related to this study expands as a function of the tilt angle θ of the c axis
from the surface normal (z axis). The calculation is carried out by first identifying the
non-zero β abc from the symmetry of the molecules. Each β abc is transformed
into β ijk using the Hirose76 Table and finally expressed as:
cosθ cosθ − cos3 θ

AYYZ ,CN = N CN (β aac + β bbc ) + (− β aac − β bbc + 2 β ccc ) (3.29)
2 4
cosθ − cos3 θ
AYZY ,CN = N CN (2 β ccc − β aac − β bbc ) (3.30)
4
where cosθ and cos3 θ represent the average of cosθ and cos3 θ over all the
orientations of the molecules at the surface.
51
3.3. Spectroscopy for Probing Interactions
Nitrile associations that present spectroscopic manifestations have been observed in two
nitrile-bearing compounds: acetonitrile and polyacrylonitrile. In addition, acetonitrile and
polyacrylonitrile are extremely sensitive to their environment and “micro-environment”.
Multiple examples will be shown where nitrile side groups of acetonitrile form specific
interactions with certain molecules in the environment. In each case the spectroscopic
proof of the interaction will be presented.
3.3.1 Acetonitrile Model Compound
In the family of nitrile bearing compounds, acetonitrile is the simplest molecule. It is
constituted of a methyl group (CH3) and a nitrile group (-C≡N) as shown in Figure 3.9.
Acetonitrile has been extensively analyzed using infrared and Raman spectroscopy
because it offers the advantage of low spectral interferences in the region where the most
characteristic feature, the C≡N stretching mode, is detected.
Figure 3.9. Acetonitrile chemical structure.
From different points of views, acetonitrile is a molecule with singular physical and
spectral properties. For example, the boiling point of acetonitrile is 82 °C compared to
that of hydrogen-bonded methanol which is 64.7 °C. This observation led to the
hypothesis that dimers and higher order aggregates exist in acetonitrile solution.
52
Temperature- dependent studies of acetonitrile mixtures could not confirm the existence
of dimers.31 Furthermore, from a spectroscopic point of view, when mixed with water,
acetonitrile forms a hydrogen bond with the water molecule, which is associated with a
positive shift of the nitrile stretch band. This shift is unusual compared to the carbonyl
analogue which is indicated by a negative shift of the carbonyl stretch vibration.
Furthermore, acetonitrile is also well known to exhibit a Fermi resonance in the (2000-
2300 cm-1) spectral region31, 79, 80.
Studies have concentrated on acetonitrile behavior as a solvent such as the one carried by
Nyquist.79 Nyquist studied mixtures of acetonitrile with a series of solvents having
different Guttmann acceptance numbers (AN). AN is a number measuring the acidity of
the solvent. Nyquist observed frequency shifts of the nitrile stretching band of acetonitrile
in various solvent mixtures. For acetonitrile, the bulk CN stretch occurs at 2253 cm-1.
He first noted a positive shift of the CN stretching band compared to that of neat
acetonitrile in almost all of the mixtures. Acetonitrile was found to exhibit a positive
shift upon hydrogen bonding or coordination with a Lewis acid with a magnitude
correlating to the AN number of the solvent. The range of nitrile frequencies of the
acetonitrile was from 2253 cm-1 to 2257 cm-1 as the solvent AN number ranged from 0
with hexane to 41 with methyl alcohol. One exception, though, was found in the mixture
of acetonitrile/dimethylsulfoxide (DMSO) that showed a negative shift. For a mixture of
benzonitrile with most solvents, Nyquist noted a negative shift. As he tested different
compositions of mixtures, it was observed that in the 10% benzonitrile/hexane mixture
the CN stretch was more red- shifted (2231 cm-1) than that of the 1% benzonitrile/hexane
53
mixture (2233 cm-1). Nyquist thought that the dipole interactions between benzonitrile
molecules were more important in the 10% solution. Thus, it was directly responsible for
the red shift of the C≡N stretching mode. This set of experiments shows that
hypsochromic and bathochromic shifts of the C≡N stretching mode of acetonitrile are
possible.
This unusual occurrence is predicted on the basis of the following reason. There are two
sites, thus two orbitals, available for interaction in the C≡N triple bond. The first one is
the lone pair orbital of the nitrogen and the second one is one of the π -orbitals of the
triple bond in C≡N. If interaction occurs via the lone pair orbital of the nitrogen atoms, a
blue shift of the C≡N stretch vibration will be observed. Interaction between nitrile and a
molecule can occur via a dative (or coordinate covalent) bond, which is donated from the
lone pair orbital to the acceptor orbital of another molecule. The lone pair electron orbital
has a non-bonding character in nature since it is, in essence, neither bonding nor anti-
bonding. Upon interaction or chemical reaction, the orbital changes; that is, the amount of
bonding/anti-bonding character of the orbital changes. If the anti-bonding character of the
lone pair orbital increases, then the bond length of CN will increase. If the anti-bonding
character decreases, then the bond length of CN will decrease. Thus, the important
concept is the reaction of the anti-bonding character of the lone pair orbital to an
interaction. If the anti-bonding character of the lone pair orbital decreases, the CN bond
length will decrease and a blue shift will be observed. The main reason for blue shift is an
electronic effect which, in turn, changes the bond length.
54
If the interaction occurs via a π -orbital, then a negative shift of the nitrile CN stretch is
observed. Another way to understand this is by correlating this concept to the case of
olefin and acetylene molecules that coordinate with the π-orbitals leading to a lowering of
the bond order of C=C and C≡C vibrational stretching modes. It is the lowering of the
bond order of the nitrile CN stretching during an interaction via one of the π-orbitals that
explain a bathochromic shift of the CN stretch.
Intrinsically, the nitrile bond can interact via two different sites. Each interaction type has
a specific shift direction allowing a straightforward identification. The specific character
of the nitrile bond has been modeled in a recent simulation correlating the relative
orientation of a water molecule interacting with acetonitrile, shown in Figure 1 by Doo-
Sik Ahn and Sungyul Lee.81
Furthermore, complementary studies investigated how the acidity of the surrounding
medium affected the nitrile C≡N stretching band of acetonitrile. In those studies,
acetonitrile behaved as a spectroscopic molecular probe where the monitoring of the C≡N
stretching band provided information about some physical properties of the environment.
Among the most successful molecular probes are pyridine and acetonitrile.80 Pyridine
was frequently used as a probe for IR detection of acid sites on oxides and mixed
oxides.80 Unfortunately, its strong basicity limits its applications because of its inability
to distinguish surface acidic sites. Acetonitrile, due to its small size and moderate
basicity, became an attractive molecule to probe acidic environments.80 In this case, the
55
mechanism for the detection of acidic sites is the sensitivity of the CN stretching
vibration to the electron withdrawing power of the metal ion to which the nitrile is
associated. The acidity strength distribution will be directly reflected in the wavenumber
shift of this band.
80
Knoezinger et al. compared the IR spectrum for the adsorption of acetonitrile on δ-
Al2O3 with the IR spectrum of liquid acetonitrile. The experiment consisted of adsorbing
acetonitrile onto alumina disks by increasing the pressure. At low pressure, the OH
stretching bands of the surface hydroxyl groups did not undergo significant changes. The
strongest modification came from the C≡N spectral region, where two blue shifted bands
occurred at 2300 and 2328 cm-1. The perturbation of the C≡N region with the
consistency of the OH region led to the conclusion that the adsorption of acetonitrile was
made between the Al3+ ions on the surface, leaving any hydroxyl sites out of the
interactions. Interestingly, at higher pressure the 2253 cm-1 band increased and the OH
region was perturbed, which means that, at this particular pressure, the coordination
between acetonitrile and the alumina surface changed and involved the hydroxyl groups.
This raised a second unusual experimental observation as multiple peaks in the C≡N
region were observed despite the existence of one unique vibrational mode.
Assigning the IR spectrum of acetonitrile can be challenging, like in the case related to
the red-shifted shoulder of the C≡N fundamental band observed by Rowlen and Harris31.
While studying an acetonitrile/water mixture, Rowlen and Harris realized that the low
56
frequency band was actually a convolution of two bands. They named the low frequency
component as νII and the high frequency component as νIII (see Figure 1 from ref31).
The low frequency shoulder, νIII , was attributed to self-associated acetonitrile molecules
and the high frequency band, νII, was attributed to the non-associated acetonitrile
molecules. The respective locations of these two bands were explained by the fact that, in
an associated state, the dipole moments of the acetonitrile aggregates were lower and a
partial cancellation of the dipole charges lowered the strength of the bond which, in turn,
red shifted the CN band with respect to the free nitrile band. Fini and Mirone 82 rejected
this model based on their assertion that dimerization was the origin of the assignment of
the low frequency shoulder. This shoulder was eventually called “secondary” structure.
They proposed that the red-shifted feature, according to ν2 , is a hot band. By definition, a
hot band appears in the spectrum as the temperature increases and is unaffected by
dilution. This debate is still open and reflects a delicate assignment situation.
3.3.2 Polyacrylonitrile Model Compound:
Figure 3.10. PAN chemical structure.
The chemical structure of polyacrylonitrile is presented in Figure 3.11. The interaction
between the nitrile groups of acetonitrile was shown to be sensitive to the dipole
57
concentration and their degree of association, while the interaction between the nitrile
groups of polyacrylonitrile mainly depends on the temperature. Hence, the spectroscopic
behavior of polyacrylonitrile was investigated as a function of temperature,
demonstrating spectroscopic manifestations of the nitrile groups during complexation and
cyclization. The study of the mechanism of thermal degradation is motivated by the
carbon-product fabrication as polyacrylonitrile is a superior precursor for carbon black.
The case of polyacrylonitrile is slightly more complex than that of acetonitrile because a
chemical change can induce a shift of the spectra, which can complicate the spectra
assignment process.
Andreeva and Burkova83investigated the physical changes occurring before the chemical
degradation of polyacrylonitrile. They showed (see Figure 1 from ref83) that the
intermolecular interaction of the CN group is revealed when the CN stretching vibrational
frequency changes in intensity and position during heating. They recorded the in situ
position and intensity of the nitrile stretching vibrational mode during a continuous cyclic
thermal treatment.
The C≡N stretching vibrational mode shifted from 2242 cm-1 to 2236 cm-1 during the first
phase of the heating from 0 to 90 °C. Above 100 °C, the location of the band stabilized
and the intensity started to decrease. This sequence of spectral events reversed as the
temperature was decreased.
58
Two chemical changes occur in PAN as it is heated up. First, a polymerization of the
C≡N side groups occurs at 200 °C, consuming the C≡N bonds and producing conjugated
C=N double bonds and C=C double bonds.84 IR spectroscopy shows the disappearance of
the 2242 cm-1 band and the appearance of a band in the range 1400-1600 cm-1. This has
been called a polymerization of C≡N because, in the parallel direction to the backbone of
the polymer, C≡N groups react with each other leading to a conjugated polymer. Figure
3.11 shows how the C=N bonds are formed.
Figure 3.11. Structure of singly-conjugated pyrolyzed polyacrylonitrile.
At this point, the carbon polymer backbone is untouched, and CH2 is still present. Real
degradative loss starts at 265 °C and reaches 34% at 435 °C, where the nitrogen content
begins to decrease. The second step involves the aromatization of the polymer chains.
occurring in the temperature range from 265 °C to 423 °C. This reaction results in a
double conjugated polymer structure, as shown in figure 3.12.
Figure 3.12. Structure of conjugated pyrolyzed polyacrylonitrile.
59
Pyrolyzed polyacrylonitrile (PPAN) on aluminium led to a conjugation reaction occurring
at a lower temperature than that of the bulk PAN (400 °C).85 On aluminium, the
disappearance of CH2 methylene stretching mode indicated the formation of a conjugated
backbone. This experimental observation coupled with the appearance of a peak at 800
cm-1 confirms the creation of a conjugated polymer chain at 300 °C. Interestingly, the
conjugation reaction occurred first at 200°C even though there was still a C≡N signal in
the IR spectrum. This confirms the presence of unreacted CN. The C≡N signal also
shows features at a downward shifted peak at 2227 cm-1, indicating an interaction
between aluminium atoms and the nitrile groups. The authors concluded that the
reduction in the required temperature of the conjuguated backbone formation was a
consequence of the nitrile/aluminium interaction. For the case of the copper/PAN, a
conjugation reaction occurred. The C≡N moiety did not react but complexed with copper
atoms. Interestingly, a split in the vibrational frequency occurred, and two C≡N were
observed due to the diffusion of copper atoms into PAN at 200 °C. The authors observed
a split of the C≡N groups. The low component contribution arose from side-on
coordination between the nitrile groups with copper atoms and the high component is
attributed to end-on complexation between side nitrile groups and copper atoms18.
PAN interacted with water under specific conditions of temperature and pressure to allow
melt spinning of PAN fibers at 180 °C under 40-70 atm.18 This experimental observation
was confirmed by the fact that finely divided PAN powder formed a single phase with
water at that pressure. As reported, the CN stretching band at 2234 cm-1 disappeared and
a new band at 2050 cm-1 appeared. Such a large bathochromic shift18 was not expected
60
and was described as a certain type of hydration. Furthermore, such an interaction was
reversible; the band would shift back to 2234 cm-1 upon cooling of the PAN.
3.3.3 Frequency Shifts at Surfaces
Many recent studies were conducted to investigate the molecular structure of liquids at
the surface of a polymer along with the interactions between a surface polymer molecule
and a solvent. Some of these involved the detection of a vibrational shift only at the
surface. Li et al. 17 investigated the surface of poly(2-methoxyethyl acrylate) (PMEA).
Their studies focused on the interaction of water molecules with the carbonyl function of
PMEA. The carbonyl function has the ability to hydrogen bond with a hydrogen donor
solvent, such as water or ethanol, resulting in a red shift of the carbonyl stretch. To
distinguish the carbonyl at the surface of PMEA, they used SFS on a PMEA thin film in
water. The water structure at the surface of PMEA was unclear and expected to be
related to the blood biocompatibility of PMEA. The SFS spectrum clearly showed a red
shifted carbonyl at the surface of PMEA while bulk characterization of the carbonyl
groups using infrared absorption reflection showed only a bulk carbonyl at a vibrational
frequency typical of a free carbonyl.
Loch et al.86 investigated the interfacial structure between poly(ethylene terephtalate)
(PET) and 3-aminopropyltrimethoxysilane. The classical red shift of the carbonyl
stretching was observed using SFS. They presented this as proof of hydrogen bonding of
the silane group and ester carbonyl of PET.
61
The mixture acetonitrile/water was studied by Zhang and coworkers.87 The CN stretching
vibration of acetonitrile at the interface (acetonitrile/water) mixture/air was monitored
using SFS. They observed that below a certain bulk composition (XCH3CN=0.07), the CN
stretch vibration frequency at the air/mixture interface was higher than that of the bulk by
14 cm-1. At a bulk concentration higher than 0.07 mole fraction, molecules at the surface
vibrate at a frequency that was close to that of pure acetonitrile. They concluded that a
nitrile at the surface experiences two different environments: one below the bulk molar
fraction of 0.07 where the CN vibrational frequency is characteristic of a CN hydrogen
bonded to water, and a second one above the bulk molar fraction of 0.07 ,where
acetonitrile no longer hydrogen bonds with water. The transition between both was sharp.
Therefore, above a bulk concentration of 0.07 mole fraction, the acetonitrile molecules at
the interface had spectral and structural properties approaching that of the pure
acetonitrile. It is noteworthy to mention that acetonitrile is miscible in water and yet an
abrupt transition occurred at the surface leading to a surface segregation in favor of
acetonitrile molecules. This implied that the surface of acetonitrile could not be predicted
based exclusively on bulk properties.
3.4 Messages of This Thesis
The goal of this research was to use SFS to analyze the surface of PAN, PBD and NBR
(40% and 20% ACN) in the nitrile stretching region of the spectrum. The surfaces of
these three polymers were analyzed in the dried state and under liquid exposure. As
previous research showed spectroscopic manifestations of interactions between nitrile
groups and water, it was therefore the first liquid to be tested at the PAN and NBR
62
surface. Furthermore, in order to investigate the NBR oil resistance, the PAN and NBR
surfaces were characterized under heptane exposure. The last solvent to be included in
the study was toluene, a known aggressive swelling agent for rubber.
The objective of this approach was to develop an understanding of how rubber/oil
interaction at a molecular scale affects the oil resistance of NBR. The overall solvation
process of NBR would therefore be captured by microscopic interactions rather than
individual physical data. It was of interest to investigate how polar association, or dipole
interaction, affects the relationship between the oil resistance of a specific nitrile rubber
and its molecular capability to associate. Thus, an old problem was investigated using a
new tool to correlate the oil resistance of a polymer to simple properties of its molecules
with direct spectroscopic evidence. To understand the nature of the vibrational
perturbation of solvent on the CN stretch of the nitrile at the surface of nitrile rubber, the
scope of the investigation covered the behavior of the CN stretching vibration in rubber
of varying CN composition from 40% to 20% ACN in various environments, such as air,
water, heptane and toluene. Since the copolymer was relatively complex, this
investigation started by analyzing the homopolymers PAN and PBD. The investigation of
PAN provided an opportunity to focus on polar associations of PAN and formed the basis
for the NBR analysis.
63
CHAPTER IV
EXPERIMENTAL
This section describes the sample preparation procedures and the various experimental
techniques that were employed in this work.
4.1 Polymer Thin Film Preparation
All solvents used were HPLC grade. Reagent grade dimethylsulfoxide (DMSO), heptane,
toluene and methyl ethyl ketone (MEK) were purchased from Aldrich Chemical
Corporation and used as received. Water was distilled and deionized using a MilliQ
system (18 MΩ). Unstabilized THF was ordered from Aldrich (grade CHROMASOLV
Plus). All solvents were used as received; unstabilized THF was used no longer than a
week after the bottle was opened. All substrates were cleaned as followed: rinsed with
ethanol and heptane, blown dry in flowing nitrogen, and cleaned in an air-plasma oven
before being used.
Polyacrylonitrile (PAN) (MN = 22,600 /MW=86,200g/mol) was purchased from Aldrich
Chemical Corporation, and used as received. Thin films (500 nm) were prepared by spin
coating of a 4 wt % solution PAN in DMSO on sapphire prism at 2400 rpm for 15
64
seconds. The solution was left overnight for homogenization. After coating, the film was
annealed at 90-120 °C for 8 to 12 hours.
Polybutadiene (PB) was ordered from Polymer Scientific (CAS unavailable) and used as
received. Thin films (800 nm) were prepared by spin-coating of a 4 wt% PB in
unstabilized THF solution on sapphire prism at 2400 rpm for 15 seconds. The solution
was left to rest overnight. After coating the film was annealed at room temperature for 4
hours.
NBR (40% ACN) (MN = 113,000 /MW=344,000g/mol) was purchased from Polymer
Scientific (CAS # 532) and used as received. Thin films (250 nm) were prepared by spin
coating a 4 wt% solution of NBR (40% ACN) in unstabilized THF on a sapphire prism at
2400 rpm for 15 seconds. The film was then annealed at room temperature in vacuum for
4 hours.
NBR (30% ACN) (MN = 125,000 /MW=453,000g/mol) was purchased from Polymer
Scientific (CAS # 529) and used as received. Thin films (250 nm) were prepared by spin
coating a 4 wt% solution of NBR (40% ACN) in unstabilized THF on a sapphire prism at
2400 rpm for 15 seconds. The film was then annealed at room temperature in vacuum for
4 hours.
65
NBR (20% ACN) (MN = 128,200 /MW=460,800g/mol) was purchased from Lanxess
(CAS # 1846-F) and used as received. Thin films were prepared by spin coating a 4 wt%
solution of NBR (20% ACN) in MEK on a sapphire prism at 2400 rpm for 15 seconds.
The film was the annealed at room temperature in vacuum for 4 hours.
4.2 NBR Purification
The following procedure describes the purification of NBR (40% ACN) analyzed in
Section 5.3.2. A solution of NBR 4 wt% in unstabilized THF was prepared. A beaker was
filled with 700 mL of methanol and the NBR/unstabilized THF solution was slowly
transferred drop by drop into the stirring solution of methanol using a Pastor pipette.
When the transfer was completed, the stirring was stopped and the solution was allowed
to rest for 20 minutes. The precipitated NBR was taken from the methanol solution and
placed in a vacuum oven overnight for drying.
4.3 High Pressure Liquid Chromatography Characterization
Solid pieces of NBR of (1/5 inches)3 were extracted overnight into methanol solution to
remove possible additives. HPLC separation was achieved using a Varian HPLC system
(USA), consisting of a Varian PROSTAR pump module, Rheodyne injector and a Varian
PROSTAR diode array detector and a C 18 column manufactured by Phenomenex. Data
acquisition was accomplished using Galaxie software. The chromatographic eluent used
to separate the low molecular weight compounds extracted in the methanol solution is
summarized in Table 4.1 and 4.2:
66
Table 4.1. Solvent used during the HPLC separation
75% Water-25%
Solvent A
Acetonitrile
Solvent B 100% Acetonitrile
Table 4.2. Solvent profile used to characterize the methanol extract in Section 5.3.2
Flow rate
At Solvent composition
(mL/min)
0 1.5 A=75% B=25%
2 11 A=75% B=25%
30 11 A=0% B=100%
38 11 A=0% B=100%
38.8 2 A=0% B=100%
43.5 2 A=0% B=100%
44 1.5 A=75% B=25%
46 1.5 A=75% B=25%
4.4 IR-Visible Sum Frequency Generation Spectroscopy (SFS) Measurement.
All the SFS spectra presented in the work were acquired using either one the two
spectrometers described in the next two sections.
4.4.1 ExxonMobil Narrow-Line SFS Spectrometer
The SFS apparatus is based on a laser system that uses a visible pulse at (532 nm; 3mJ)
overlapped with a tunable pulse (3-10 µm;1-2 mJ); both have a duration of 7 ns and a
repetition rate at 10 Hz.

67
The laser set-up is shown in Figure 4.1. The frequency of pulsed Nd:YAG laser (solid
state laser) is doubled using a non-linear crystal. The output at 532 nm pumps the
molecules of organic dye (LDS-698 or DCM) that absorbs energy of the source and re-
radiates the energy as a laser radiation. A grating selects one wavelength (tunable laser
dye) and sends it to the Raman cell or Multi-pass high pressure H2 cell, for IR conversion
using a third order stimulated Raman process. For most molecules, the Raman mode with
the greater gain has a frequency resulting in a shift less than the tuning range of the dye
laser except for molecules such as H2 molecules with a vibrational mode corresponding
to 4122 cm-1. The stimulated Raman emission is used to down shift the frequency of the
input by an amount equal to the Raman mode of the H2 molecule; the input frequency for
one process acts as the input of the next one. The IR pulses exiting the Raman cell are
guided to the sample and are overlapped with the remaining fraction of the visible green.
The sapphire coated with sample is used in total internal reflection (TIR) geometry which
is described in section 4.4.3. Three polarizers set the polarization to S or P orientation of
the SFS, Green and infrared beams, respectively. The SFS signal intensity is amplified
using a pre-amplifier and detected using a photon multiplier (model PS 325 from
Stanford Research System) after which the infrared intensity is recorded using an infrared
meter (Rj-7200 Energy meter). This spectrometer has a narrow-resolution
(bandwitdth ≈ 0.2 cm-1) also labeled “narrowline.”
68
Figure 4.1. Schematic diagram of the ExxonMobil narrowline SFS spectrometer.88
Most of the SFS spectra obtained in this study were acquired by scanning the tunable
laser dye in two regions (2000-2300 cm-1) and (2800-3200 cm-1) at intervals of 1 to 2
wavenumber(s). Each data point corresponds to an average of 20 to 50 SFS signal pulses.
For each spectrum, the background noise from the environment was measured while
blocking the infrared beam and this value was subtracted from the SFS signal intensity.
Finally to account for the intensity and shape of the IR source, the SFS spectra were
normalized to the profile of the infrared intensity. A typical SFS spectrum corresponds to
the SFS intensity plotted as a function of the IR wavenumber as shown in Figure 4.2.
69
Further analysis of the SFS spectrum was achieved by fitting the experimental data using
Igor Pro software fitting procedures.
1.0
SFG Int. (a.u.)

0.8
(A)
0.6
0.4
0.2
2850 2900 2950 3000 3050 3100

-1
I.R. wavenumber (cm )
Figure 4.2. Typical normalized SFS spectrum.
The solid lines are fit to the data using Equation 3.22. The detected resonances
correspond to the CH and CH2 groups at the surface of polyacrylonitrile at the
sapphire/PAN interface. The neon atomic absorption lines are used for dye calibration
by observing the opto-galvanic effect of a neon hollow cathode lamp as a
function of the dye laser frequency. A small part of the dye laser beam
is incident between the cathode and the anode. When the dye laser
frequency is tuned, the impedance of the discharge increases or
decreases when resonance occurs. The dye laser frequency controller
read out is monitored and adjusted to match the observed the peaks of the observe neon
atomic lines.89
4.4.2 The University of Akron Broadline SFS Spectrometer
The laser set up is shown in Figure 4.3. A pulsed (femtosecond) Ti-Sapphire red (800
nm) laser (Tsunami, Spectra-Physics, Inc) and a continuous-wave, solid-state green (532
70
nm) laser (Millenia V, Spectra-Physics, Inc.) drive a regenerative amplifier (Spitfire,
Spectra-Physics, Inc). The spitfire produces an output of picosecond-long pulses at a
repetition rate of 1 kHz. A part of the output is directed into the optical parametric
amplifier (OPA)-(OPA-800, Spectra-Physics, Inc) which produces the tunable IR beam.
The IR and visible beam are taken out of the OPA through different paths to be spatially
and temporally overlapped at the sample. The overlap in space is achieved using a
dichroic mirror to transmit only the infrared beam. As the red beam takes a shorter path
through the OPA, the overlap in time is achieved using a delay stage.
Figure 4.3. Schematic diagram of the University of Akron SFS broadline spectrometer.90
71
The sum frequency spectroscopy phenomenon explained in the second section of Chapter
3 is produced as the sample is guided through filter to reduce noise and is detected and
amplified using a photomultiplier tube and photon counter (SR400, Stanford research
Systems, Inc). At the same time, the IR intensity for each SFS measurement at the sample
is recorded. These outputs are recorded simultaneously, the SFS intensity is normalized
to account for the fluctuation in IR intensity while scanning.
This spectrometer has a lower resolution as the IR pulse energy as a function of
wavenumber is described by a Gaussian function of standard deviation 8.7 cm-1, also
labeled “broadline”.
4.4.3 SFS in Total Internal Reflection (TIR) Geometry
SFS has been used in TIR geometry on all experiments present in this work and is
presented in Figure 4.4. The polymer coated sapphire is mounted in a cell immobilized on
a rotating stage (not shown) allowing to tilt the normal of the sapphire interface with
respect to the incident visible and infrared beams. The visible and infrared beams strike
the sapphire prism (interface A) and with angle φ A,i are refracted before reaching the
interface B with an angle φB,i where the sum frequency beam is generated without
attenuation by the sapphire.
72
Medium (n4)
C
Polymer (n3)
B
Prism Sapphire (n2)
SFG Φ
B,3
ΦB,2
D ΦB,1 A
n1(air)
νSFG ΦA,i
νvis
νIR
PMT
Figure 4.4. Schematic diagram of the TIR geometry used in SFS experiments.
The incident visible and IR beams enter the prism at interface A with an angle, φ A,i ,with
respect to the normal at the interface and strikes interface B at an angle, φB,i ,which is the
angle for the total internal reflection to take place. The refractive indices of the media are
as indicated.
The intensity of the SFS signal detected at the sapphire/polymer interface depends on the
incident angle of the IR and visible beams and the refractive indices of the media forming
the interface and can be computerized as shown in Figures 4.5 and 4.6.
73
SFS Intensity (a.u.)
Angle of Incidence ( φ A,i )

Figure 4.5. Angular dependence of SFS signal at the sapphire/NBR interface under
heptane exposure in SSP polarization for a film of a thickness of 300 nm. Solid line
corresponds to fit modeled by a program written by Li.91
The refractive indices values used to simulate the SFS enhancement from the
sapphire/NBR interface as a function of φ A,i are that of the sapphire and NBR, n=1.7 and
n=1.52,95 respectively. Similarly, the NBR/oil interface, interface C in Figure 4.4, can be
probed by choosing the proper angle that satisfies the total internal geometry at the
polymer/heptane interface. The angle dependence of the SFS signal at the C interface is
presented on Figure 4.6. The refractive indices values used to simulate Figure 4.6 are that
of the NBR and heptane and are n=1.52 and n=1.38, respectively.
74
SFS Intensity (a.u.)
Angle of Incidence ( φ A,i )
Figure 4.6. Angular dependence of SFS signal at the NBR/heptane interface in SSP
polymerization for a film of a thickness of 300 nm. Solid line corresponds to fit modeled
by a program written by Li91.
These angles were first estimated by modeling the SFS intensity enhancement from the
interface in question (Figure 4.6) and were further optimized experimentally by
determining the angle giving the maximum SFS signal. Sapphire/PAN, sapphire/PB and
sapphire/NBR were selectively probed by using an angle of φ A,i ≈ 1°, and the PAN/air,
PB/air and NBR/air interfaces were investigated using φ A,i ≈ 40°. The PAN/water,
PAN/heptane, NBR/water and NBR/heptane interfaces were characterized at an angle of
φ A,i ≈ 10° as the refractive indices of water and heptane are, respectively n=1.33 and
1.38.
To study the polymer/liquid interface a stainless steel flow cell was used. For
reproducibility purposes the cell was disassembled and cleaned prior to each experiment
75
by rinsing with ethanol and heptane. It was then placed in oven at 250 °C for 15 minutes,
cooled to room temperature, and plasma treated for one minute. The coated prism was
clamped onto the cell and a Teflon spacer was used to ensure adequate sealing between
the prism and the cell.
4.5 Differential Scanning Calorimetry (DSC) Measurements
DSC on a TA DSC Q 1000 was performed on polymers at heating and cooling rates of 10
°C/min.
4.6 FTIR Measurements
FTIR spectra were obtained using a Digital Excalibur Spectrometer (FTS 3000). The
data are acquired with a resolution of 4 cm-1. Solution-casted films of the polymer sample
on KBr disks were used to obtain absorbance spectra in the transmission mode.
4.7 Raman Spectroscopy Measurements
Raman spectra were obtained using a Renishaw System 1000 Raman Microscope with a
514.5 nm Ar ion laser. A calibration using crystalline silica allows determining a
resolution for the Raman experiment at approximately 6 cm-1.
76
4.8 Nuclear magnetic Resonance (NMR) Measurements
NMR spectra were obtained using a Varian 500 MHz spectrometer. Solution of NBR in
deuterochloroform were prepared with tetramethylsilane as the internal reference. NMR
spectra were placed in Appendix D.
4.9 Size Exclusion Chromatographic (SEC) Measurements.
Size Exclusion Chromatographic (SEC) analyses were carried out using an Multi Angle
Laser Light Scattering instrument equipped with three Waters HR Styragel columns with
THF as eluent at a flow rate of 1 mL/min at 35°C; the detector system combined a Wyatt
Dawn Eos laser light scattering (MALLS) detector and differential refractometer
concentration detector (Waters 410). SEC chromatograms were placed in Appendix E.
4.10 Thin Film Thickness Measurements.
Thickness measurements were performed with a J.A. Woollam spectroscopic
ellipsometer. Ellipsometer data were acquired in reflection mode on sapphire coated
prism at an angle of incidence of 45°. Ellipsometry measures the change in polarization
state of light reflected from the surface of a thin polymer film.92 The experimental data
are expressed as psi (ψ) and delta (∆ ) such that:
Rp
ρ= = tan (ψ )ei∆ (4.1)
Rs
~ ~
where ρ is the ratio of the Fresnel coefficients, R p and Rs , for p and s polarized light.
77
The reflected surface parameter such as thickness is related to the measured data through
a system of non–linear and non-invertible sets of equations. The Cauchy layer model was
used to model the influence of the polymer film thickness on the measured (ψ) and (∆ )
and fit experimental data. The geometry of the spin-coated polymer film on sapphire
substrate was modeled with a first layer, layer “0”, of infinite thickness corresponding to
the sapphire substrate and layer”1” a function based Cauchy layer related to the polymer,
that follows Equation (4.2):
n(λ ) = An +
Bn Cn
+ (4.2)
λ2
λ4
For the thickness calculation, experimental data were fitted to refractive indices of n=1.52
for PAN, PB and NBR.93
78
CHAPTER V
RESULTS AND DISCUSSION
The ACN content of NBR rubber is the main parameter controlling the oil resistance of
NBR. This chapter contains the results of bulk and interfacial spectroscopic
characteristics of PAN, PBD and NBR polymers. Spectroscopic shifts are of primary
importance in extracting information about the polar nitrile interactions. The
spectroscopic methods described in Chapter 3 were used to interrogate the polar
associations in bulk NBR and at the NBR surface.
Within the NBR polymer, interactions can occur between two nitrile groups but also
between the nitrile side groups and the olefinic segments of butadiene which together
create a more complex system to study. To break down this complexity, the stronger of
the two, the nitrile-nitrile interactions are set as the reference point. The best reference
material to carry out this study would be a polymer where interactions between nitrile
groups dominate. That material would be the homopolymer PAN. The spectral
vibrational characteristics of PAN will be investigated in the CN (2000-2300 cm-1) and in
the CH region (2800-3200 cm-1).
79
The results and discussion section is articulated in four sections. First, PAN was
analyzed, and then secondly, the bulk and surface character of homopolymer PB were
investigated. The analysis of these two homopolymers created the basis of the
investigation presented in the third section: bulk and surface characterization of NBR.
In the fourth and final section, the nitrile rubber surface was exposed to aliphatic,
aromatic, and polar solvents. Surface changes were analyzed using the set of SFS data
showing the first spectroscopic manifestations of the surface of nitrile rubber in a solvent
environment. The commercially available NBR rubber samples used in this research
differed in ACN content from 40% ACN to 20% ACN.
5.1 Spectroscopic Investigation of Nitrile Interactions in PAN.
An extended view of the PAN physical and spectroscopic features was given in Chapter
2. A DSC of PAN, placed in Appendix A on Figure A-1, confirms the detection of two
thermal transitions below 160 °C. A first transition detected at 100 °C referred to as the
glass transition and a second one at 150 °C, attributed to the nitrile loosening of the
dipole-dipole interaction.26, 27 The focus narrows down to the vibrational characteristics
of the nitrile side group of PAN in the infrared region.
5.1.1 SFS spectra and peaks assignments.
First, the details of the CN functional group vibration in the bulk PAN will be
characterized and compared with the literature data on the location, width and intensity of
the CN band. Since PAN has never been analyzed using Sum Frequency Spectroscopy
80
(SFS), previously established infrared and Raman assignments will be used to attribute
the peaks corresponding to the interfacial nitrile moiety. The point of entry of this
investigation is to acquire a classical FTIR spectrum of PAN to determine the features,
mainly the location, of the CN stretching vibrational band. Due to its highly polar nature,
the CN stretching mode should give rise to an intense transition and the CN stretch mode
should be readily detected. Step one is to analyze bulk PAN using an FTIR spectrometer.
0.210
0.205
Abs.(a.u)
0.200
0.195
0.190
0.185
0.180
2100 2150 2200 2250 2300
-1
Figure 5.1. FTIR spectrum of bulk PAN in the CN stretching region.
The CN stretching vibration mode is detected at 2242 cm-1. Earlier experiments reported
a CN stretching mode between 2238 cm-1 94 to 2243 cm-1,95 a range in agreement with the
FTIR result of a absorption band of bulk PAN at 2242 cm-1. This value will be used as
the spectroscopic reference.
The primary interest of this research project is to characterize what happens to the
polymer molecules in contact with liquid. A real life example for this research would be
81
to know what happens to polymer chains on the surface of an O-ring rubber piece
immersed in a solvent.
To know the characteristics of the interfacial PAN molecules, and more precisely, the
interfacial nitrile group, we performed SFS on PAN spin-coated thin films. The result is
presented in Figure 5.2 (B) where we probed the interface between the PAN film and the
sapphire prism. To the infrared spectrum in Figure 5.2(A), we compare the SFS spectrum
of the PAN/sapphire interface, shown in Figure 5.2(B), which covers the same region
from 2100 to 2300 cm-1. It is clear from that SFS spectrum that the CN stretch of PAN is
not located at 2242 cm-1 as expected but at 2254 cm-1.
The CN resonance frequency of PAN at the sapphire/PAN interface is positioned at 2254
cm-1 which is 12 cm-1 blue-shifted with respect to the CN stretching mode of the bulk
PAN. The bulk spectroscopic data at 2242 cm-1 falls in the range reported by various
works18, 95
. However the difference of 12 wavenumbers between the vibrational
frequency of PAN at the sapphire/PAN interface cannot be explained by experimental
errors as the resolutions of the FTIR spectrometer and the SFS spectrometer used are
below 4 and 1 cm-1 respectively. Therefore, the shift existing between the nitrile
stretching mode of PAN bulk and sapphire/PAN molecule represents a potentially
significant shift which requires investigation because for an unknown reason the nitrile
groups in the bulk of PAN do not vibrate at the same frequency as those at the
sapphire/PAN interface. The significance of CN frequency shift has been extensively
investigated and explained as the following. The shifting of the CN stretching vibrational
82
79, 80
band has been observed with acetonitrile and more recently PAN.18, 83 Positive and
negative shifts are possible for both acetonitrile and polyacrylonitrile and it is a diagnosis
of the interactions of nitrile with surrounding molecules.
0.210
SFG Signal Int.(a.u.) Abs. (a.u)
0.200
(A)
0.190
0.180
10
8
6
4
(B)
2
20
15
10
(C)
5
2100 2150 2200 2250 2300

-1
Figure 5.2. (A) FTIR spectrum of PAN bulk, (B) SFS spectrum of PAN in PPP
polarization at the sapphire/PAN interface after PAN annealing at 90 °C for 8 h followed
by a second heating at 120 °C for 4 h and (C) SFS spectrum of PAN in PPP polarization
at the sapphire/PAN interface after PAN annealing at 90 ºC for 8 h only, in the CN
region.
The CN side groups have an intriguing capability to interact via either the lone pair
orbital of the nitrogen “end-on” leading to an hypsochromic (positive or blue) shift of the
83
CN stretching vibrational frequency or to interact via a “side-on” coordination leading to
a bathochromic (negative or red) shift of the CN stretching vibrational frequency.16
Table 5.1: Positions of the CN stretching vibration for PAN from Figure 5.2 obtained by
fitting using Equation (3.22).
PAN/sapphire PAN/sapphire
a interface interface
PAN (bulk)
PAN annealed at PAN annealed at
90 °C and 120 °C b 90 °C only b
Appears in 5.2(A) 5.2 (B) 5.2 (C)

Peak position
2242 2254 2236
(cm-1)
a
The error limit for peak location is ± 2 cm-1.
b
The error limit for peak location is ± 0.5 cm-1.
Based on previous studies, it is reasonable to believe that the observed frequency shift of
CN at the sapphire/PAN interface is due to an interaction between the sapphire substrate
and the polymer via its CN groups. Moreover, Andreeva and Burkova 83 observed a shift
of the nitrile groups stretching mode of PAN as the temperature was raised from 0 to 90
°C for thin PAN films. They eventually connected the shift to the density of the polymer
and more precisely the distance and relative orientation of the dipole-dipole interaction of
nitrile groups of PAN.
Therefore, the present surface study of PAN investigation started with the observation of
this experimental shift. It raises two questions: first, why is there a positive 12 cm-1 shift
of the CN stretch of PAN; and second, why such a shift is observed especially at the
interface? What is so special about the environment that these nitrile groups experience
84
against the sapphire surface? Moreover, is there an experimental parameter controlling
this shift?
The first parameter questioned was the temperature at which the polymer was annealed as
mentioned before by Andreeva and Burkova.83 Within the framework of this study, the
thermal history of the PAN thin film includes a heating to 90 ºC in a vacuum oven for 8
hours followed by cooling to room temperature followed by a second heating to 120 ºC
for 4 hours. The resultant vibration peak position of CN stretch at the sapphire interface is
2254 cm-1 as shown on Figure 5.2 (B). To further investigate the nature of the sapphire-
PAN interaction, the experiment was repeated with a sample annealed for 8 hours at 90
ºC only.
As depicted in Figure 5.2(B) and 5.2(C) when the PAN film was annealed at 90 °C for 8
hours only, the SFG spectrum exhibits a CN resonance feature at 2236 cm-1 with no
positive shift with respect to the same resonance feature in bulk PAN. This result could
indicate that the interaction between nitrile groups and sapphire is activated by
temperature, and more specifically, by heating the PAN polymer above its Tg (100 ºC).
To explain this annealing effect, the chemical structure of the sapphire surface can be
decomposed into two types of sites or environments that can interact with the polymer:
first, it can react with residual hydroxyl groups or H bonding sites; and second, it could
coordinate with unsaturated aluminum cation sites.96 To understand the spatial origin of
the interaction between PAN and the sapphire surface, the surface OH groups were
markedly reduced by heating the sapphire at 750 ºC for 36 hours. The effectiveness of the
85
heat treatment in reducing the hydroxyl number density at the sapphire surface was
previously demonstrated using SFG spectroscopy.97 Following this specific sapphire heat
treatment, the sapphire surface was coated with PAN using the same spin coating
conditions.
The SFS spectrum in the CN region of the PAN/heated sapphire interface is displayed in
Figure 5.3(C). For the PAN/heated sapphire interface, the fitting reveals a CN resonance
feature of PAN at 2237 cm-1 which is significantly lower than the CN stretching vibration
for PAN at the PAN/sapphire interface at 2254 cm-1. The positions of the nitrile CN
stretch of PAN presented in Figure 5.3 are gathered in Table 5.2.
0.210
Abs. (a.u)
0.200
(A)
0.190
0.180
10
8
SFG Signal Int.(a.u.)
6
4 (B)
2
6
2
(C)
2100 2150 2200 2250 2300

-1
Figure 5.3. (A) FTIR spectrum of PAN bulk, (B) SFS spectra of PAN in PPP polarization
at the sapphire/PAN interface after PAN annealing at 90 °C for 8 h followed by a second
heating at 120°C for 4 h and (C) SFS spectra of PAN in PPP polarization at the
sapphire/PAN interface after PAN annealing at 90 ºC for 8 h followed by an additional
heating at 120°C for 4 h with spin-coating on sapphire (temperature treated at 750 °C
for 36 h), in the CN stretching region.
86
Table 5.2: Positions of the CN stretching vibration for PAN from Figure 5.3 obtained by
fitting using Equation 3.22.
PAN/sapphire
PAN/sapphire
interface 90 °C
interface 90 °C and
PAN (bulk) a and 120 °C
120 °C
non heated
heated sapphireb
sapphireb
Appears in 5.3 (A) 5.3(B) 5.3(C)
Peak position
2242 2254 2237
(cm-1)
a
b
In addition to a marked change in the resonance frequency of the CN vibrational mode
upon heat treatment of the substrate, a notable change in vibration mode of the CH and
CH2 groups was also observed. Figure 5.4 (A) shows the SFS spectrum of the PAN/
heated sapphire interface in the 2800-3000 cm-1 range. Three resonant features at 2870,
2940 and 2950 cm-1 were observed for the PAN/heated sapphire interface in contrast to
the SFS spectrum of the PAN/ sapphire interface, shown in Figure 5.4 (B) where no
resonance structure was detectable. The resonance structures at 2870 and 2950 cm-1 were
assigned to the methylene stretching modes and the 2930 cm-1 resonance was due a
stretching mode of the CH group.94
To investigate the significance of these spectroscopic changes, first the data analysis was
focused on the absence of a 12 cm-1 positive shift of the CN stretching vibration when the
sapphire was heated.
87
0.5
1.0
S F G Int. (a.u.)
0.4
S F G Int. (a.u.)
0.8
(A) 0.3 (B)
0.6
0.2
0.4
0.1
0.2
0.0
2800 2850 2900 2950 3000 3050 3100

2850 2900 2950 3000 3050 3100
-1 -1
I.R. wavenumber (cm ) I.R. Wavenumber (cm )
Figure 5.4. (A) SFS spectrum of PAN in PPP polarization at the sapphire/PAN interface
after PAN annealing at 90 °C for 8 h and 120 °C for 4 h with spin-coating on sapphire
(temperature-treated at 750 °C for 36 h) and (B) SFS spectrum of PAN in PPP
polarization after PAN annealing at 90 °C for 8 h and 120 °C for 4 h at sapphire/PAN
interface, in the CH stretching region.
This demonstrates that when hydroxyl species are depleted from the sapphire surface, the
resonance feature of the interfacial CN stretching vibrational band at the sapphire
interface is very close to the vibrational frequency of PAN bulk. In other words, the main
interaction between the sapphire surface and the polymer is due to OH-CN interaction
and can be significantly reduced by decreasing the number of the surface hydroxyl
groups. Heating PAN chains above 100 ºC (Tg) would allow conformational
rearrangement: CN side groups along the chains reorient in a specific direction to interact
with the surface sapphire OH. Whether the disappearance of CH2 peaks and CH in
spectrum 5.4 (B) is due to a simple reorientation or a true chemical reaction is at this
point unclear. The direct correlation between the presence of the OH species with the
shift of the CN stretching vibrational features strongly suggests the existence of an
interaction between the OH and the CN groups of PAN at the interface. It is interesting
to note that this effect occurs at a temperature below the temperature assigned to the
88
loosening of the nitrile-nitrile dipole interaction in PAN bulk which tends to show that
either the thermal transition associated to the nitrile dissociation is lower at the surface
compared to that of the bulk (150 °C) or that the interactions between sapphire OH and
nitrile groups favor the reorientation of interfacial PAN chains at 120 °C.
From the first section it is shown that PAN interacts via its nitrile groups with
surrounding molecules at high temperature, this interaction weakens the nitrile dipole-
dipole coupling and is indicated by a significant frequency shift of the CN stretching
vibration. This experimental finding correlates with the results reported by Goodman and
Suwyn98 where the authors observed interaction of PAN with water at 140 ºC under
pressure. They further noted a corresponding negative shift of the Raman CN stretching
vibration. The interaction between PAN fibers at high temperature correlates with the
interaction we observed for a PAN film on a sapphire prism above 120 °C.
An unexpected shift of the CN stretch at the sapphire interface confirms the high
temperature sensitivity of CN stretch and reveals the importance and specificity of the
interface as a role in understanding macroscopic properties. Do those results hold for the
nitrile on the opposite interface of the film where the nitrile side groups protrude at the air
interface?
The angle of incidence of the visible and IR beam was changed by rotating the sapphire
prism to probe the PAN/air interface; the spectrum is displayed in Figure 5.5. A double
peak was fitted to the experimental SFS data. Up to this point only one resonance feature
89
was observed in the 2100-2300 cm-1 range but observing multiple peaks is a common
experimental fact and is attributed to the interacting capability of the CN moiety with its
environment.SFG Intensity (a.u.)
20
15
10
2100 2150 2200 2250 2300

-1
I.R. Wavenumber (cm )
Figure 5.5. SFS spectra of PAN in PPP polarization at the PAN/air interface in the CN
stretching region.
Fitting reveals two resonant features at 2238 cm-1 (positive) and 2242 cm-1 (negative).
Despite the fact that there is only one CN vibrational stretching mode, multiple peaks are
commonly observed in the 2100-2245 cm-1 range for CN bearing compounds.18, 80 Each
peak corresponds to a specific CN state. This tends to indicate that two different types of
nitrile groups populate the PAN surface.
5.1.2 Polyacrylonitrile under Solvent Exposure
The PAN bulk, the PAN/air and sapphire/PAN interfaces were characterized using FTIR
and SFS analysis, respectively. Unlike NBR, PAN is resistant to a wide range of solvents
such as water, aliphatic and aromatics hydrocarbons. The next step of this research was to
90
expose the PAN surface to a variety of specific solvents. Heptane and water, two solvents
with two different polarities, were used. Heptane is an aliphatic hydrocarbon, non-polar
and non-hydrogen-bonding solvent used to simulate the oil that comes into contact with
rubber O-rings. Water is a highly polar material with hydrogen bonding properties, and
from documented works, water has an important influence on polar association of nitrile
bearing compounds. Water is the first liquid that was used in this study.
The interaction between PAN and water is known to be very strong at high temperatures
causing the PAN to dissolve. Although water cannot dissolve PAN at room temperature,
the existence of the PAN/water interaction at the polymer/water interface is an important
issue that will be discussed below. The SFS spectra of the PAN/water interface are
displayed in Figures 5.6 (A) and (B).

SFG Intensity (a.u.)
20
20
15
15
10
10
(A)
5
(B)
5
0
2000 2020 2040 2060 2080 2100
2100 2150 2200 2250 2300
-1 -1
I.R. Wavenumber (cm ) I.R. Wavenumber (cm )
Figure 5.6. SFS spectra of PAN in PPP polarization at (A) PAN/water interface in the CN
stretching region (2000-2100 cm-1) and (B) at PAN/water interface in the CN stretching
region (2100-2300 cm-1). SFS spectra were obtained with the University of Akron
Broadline SFS spectrometer.
Upon water injection, the binodal surface population of CN becomes uniform [spectrum
on Figure 5.6 (B)] and only one CN vibrational band is observed at 2237 cm-1 which
corresponds to a red shift of 1 and 5 cm-1, respectively, for the two original bands at 2238
91
and 2242 cm-1. By changing from two peaks to one peak, the data now shows that CN
groups experience only one unique environment which could be reasonably in the
outermost layer of the PAN film in contact with water molecules. Since Henrici-Olive
and Olive18, commented on the observation made by Goodman98 about an extraordinary
200 cm-1 negative shift in the vibrational CN stretch upon interaction between PAN and
water molecules, it seemed necessary to probe that range for the PAN/water interface and
that spectrum is shown on Figure 5.6 (A). It is clear that at the interface between PAN
and water molecules no such feature is detected. Most likely, the nitrile-nitrile
interactions are too strong at room temperature to allow any interaction with water
molecules. A comparative spectrum of the PAN/air interface in the exact same range is
included in Figures 5.7 (A) and (B).
80 80
70 70
60
60
50
50 (B)
40 (A) 40
30
30
20
20
10
2200 2220 2240 2260 2280 2300

2000 2020 2040 2060 2080 2100
-1
-1 I.R. Wavenumber (cm )
Figure 5.7. SFS spectra of PAN in PPP polarization at (A) PAN /air interface in the CN
stretching region (2000-2100 cm-1) and (B) at the PAN/air interface in the CN stretching
region (2100-2300 cm-1). SFS spectra were obtained with the University of Akron
Broadline SFS spectrometer.
The purpose of this investigation was to study the PAN/heptane interface and this is
treated in the following section. Interestingly, upon heptane injection a similar spectrum
92
is collected at the PAN/heptane interface (Figure 5.8) where only one vibrational band is
detected at 2238 cm-1.

50
40
30
20 (A)
10
15
10
(B)
5
2100 2150 2200 2250 2300

-1
Figure 5.8. SFS spectra of PAN in PPP polarization (A) at the PAN/heptane interface and
(B) at the PAN/water in the CN stretching region.
The similarity of PAN/water and PAN/heptane interfaces could demonstrate that a small
amount of water is present in the heptane, in a sufficient amount to alter the
compositional environment of the PAN/heptane interface. If we further compare both
interfaces with PAN bulk it appears that PAN surface properties are not significantly
changed upon water or heptane exposure. From a bulk point of view, these results
certainly correlate the solvent resistance of PAN toward solvent in general; from a
surface point of view, the data directly indicate that even at the surface of PAN, the nitrile
dipole interactions are stronger than nitrile-heptane or nitrile-water interactions.
93
5.1.3 Summary on PAN Investigation.
In conclusion, the CN groups of PAN are able to interact with the surface hydroxyl
groups of a sapphire substrate at high temperatures producing a blue shift with respect to
bulk PAN in the CN vibrational mode. The interaction between PAN and the sapphire
surface can be markedly decreased when the surface hydroxyl groups of sapphire are
reduced. This chemical modification of the buried interface affects the molecular
arrangement at the PAN film surface. It was also demonstrated that PAN does not
strongly interact with heptane or water at room temperature.
5.2. Analysis of PBD.
The analysis of PBD is as important as the analysis of PAN. If the acrylonitrile unit is the
chemical unit bringing the oil resistance property to the NBR chain, the butadiene
monomer is the unit sensitive to the oil. If the penetration of the oil is due to a specific
interaction between the butadiene comonomer and aliphatic hydrocarbon, then there
should be spectroscopic changes in the vibration mode of PBD CH stretch.
5.2.1 Bulk and Surface Analysis of PBD
It is well known that emulsion homopolymer PBD have three structures 1,4-trans, 1,4-cis
and 1,2-vinyl. The relative amount of cis, trans, and vinyl varies according to the method
of preparation and the temperature of polymerization.
94
Some regions of the infrared spectrum, especially the bending region, led to
straightforward determination of the relative amount of cis, trans, and vinyl. Morero99
developed a method that accurately quantifies the level and type of double bonds using
specific bands in the 700-900 cm-1. For example, 724 cm-1 was attributed to 1,4-trans
microstructure, 911 cm-1 was ascribed to 1,2-vinyl microstructure and 967 cm-1 arose
from 1,4-cis microstructure. Comparing the relative intensity of these three peaks allows
the determination of the relative content of the different types of double bonds in a
specific PB polymer. PBD is, for that reason, a sophisticated case to analyze by
spectroscopy. The bending region is unfortunately inaccessible to SFS experiments.
Therefore the analysis concentrated on the CH stretch region.
First, the bulk vibrational features of PBD were analyzed, and the Raman spectrum of
PBD is presented in Figure 5.9. Four resonance features contribute to the Raman
spectrum of bulk PBD at 2840 cm-1, 2900 cm-1 and 3000 cm-1 and 3060 cm-1. These
bands were compared to the PBD IR data obtained from Binder100. Binder, attributed
2840, 2900, 3000, and 3060 cm-1 respectively to the symmetric CH stretches of CH2,
asymmetric CH stretch of CH2, CH stretch of cis-CH=CH and CH stretch of CH2=CH
vinyl side group.
95
Raman Count. (a.u.)
5000
4000
3000
2000
1000
2800 2900 3000 3100 3200

-1
Wavenumber (cm )
Figure 5.9: Raman spectrum of PBD and corresponding fit.
These assignments were close to what was observed in the SFS spectra and will therefore
be the same assignment of peaks in this research, (according to Binder’s assignments).
The SFS spectrum at the sapphire/PBD interface is displayed in Figure 5.10 (B) and
compared to the SFS spectrum of the PBD/air interface on trace C and to the Raman
spectrum of bulk PBD on trace A.
96
Abs. (a.u.) (A)
1.2
0.8
(B)
SFG Int. (a.u.)
0.4
1.6
1.2
0.8
0.4
(C)
2800 2900 3000 -1 3100 3200

Wavenumber (cm )
Figure 5.10. (A) Raman spectrum of PBD, (B) SFS spectrum of PBD in PPP polarization
at the sapphire/PBD interface and (C) SFS spectrum of PBD in PPP polarization at the
PBD/air interface in the CH stretching region. The number of data points was reduced for
clear labeling of the spectra.
It is clear from Figure 5.10 that spectra (A) and (B) do not overlap perfectly; comparison
reveals a positive shift of the 2840 cm-1 band arising from CH stretch of CH2 to 2860 cm-1
at the sapphire interface compared to that of the bulk PBD [Figure 5.10 (A)].The location
and assignment for the methylene and C-H groups of PBD bulk and surface in the CH
region are gathered in Table 5.3.
97
Table 5.3. PBD vibrational bands observed in Figure 5.10 compare to PBD vibrational
bands observed by Binder100.
Polybutadiene (PBD) bands in the C-H region
Fig. Fig. Fig. 5.10
Binder101 Assignment
5.10(A)a 5.10(B)b (C)b
PB bulk sapphire/PB PB/air Bulk
3070 3077 CH (CH2=CH) stretching
3010 3016 3007 3012 CH (cis-CH=CH) stretching
2910 2910 2907 2900 Asym methylene stretching
2843 2863 2849 2840 Sym. methylene stretching
a
b
This shift of the methylene stretch of PBD reveals the effect of a polar environment, the
sapphire, on the vibrational properties of PBD. This dependence of the vibrational band
of BD units on the polarity of the environment is an interesting correlation that is worth
being checked later in the case of the nitrile rubber. The correlation will be slightly
different and involves the influence of the polar acrylonitrile groups on the vibrational
properties of butadiene units. This will be presented in the next section; for now, the
attention remains on PBD spectral features displayed on from Figure 5.10. Apart from
the positive shift of the methylene stretching mode of PBD at the sapphire interface, all
the other features of PBD at the sapphire interface appear to closely match those of the
bulk in term of their positions. The last spectrum, on Figure 5.10 (C), is the SFS spectrum
of PBD at the interface between the PBD and air. The location of the peaks of PBD at the
air surface matches those of the bulk PBD. Note that PBD bulk and PBD/air interface are
both weakly polar media, which tend to demonstrate that the polarity of surrounding
environment does affect the vibrational features of PBD. Finally, the peak at 3060 cm-1
present in the bulk was not found in either PBD/air or sapphire/PBD interfacial spectra.
98
5.2.2 Summary on PBD Investigation.
As a conclusion, the analysis of PBD revealed a very interesting modification when PBD
was exposed to a polar environment at room temperature. This shift was a rare
occurrence, at least for hydrocarbon molecules. This should be kept in mind when
analyzing a copolymer that combines a polar unit, acrylonitrile, and a weakly polar unit,
butadiene.
5.3 Analysis of NBR
Three commercial grades of NBR were provided with a content of acrylonitrile ranging
from 40 to 20% ACN. NBR respectively containing 40%, 30% and 20% of ACN are
industrially known as “high,” “medium” and “low” acrylonitrile content nitrile rubber,
respectively.
5.3.1 Bulk Analysis of NBR
The bulk and surface spectroscopic features are presented in the first part of this section.
The bulk spectroscopic features of the NBR are also discussed for ACN ranging from
20% to 40% of acrylonitrile units.
The effect of the ACN on the nitrile stretching band is now investigated. Figure 5.11
shows the FTIR spectra of three copolymers containing 20%, 30% and 40% ACN in the
nitrile stretching region 2220 to 2280 cm-1.
99
2237 cm-1
(A)
I.R. Abs.(a.u.)
(B)
(C)
2200 2220 2240 2260 2280
-1
Figure 5.11. FTIR spectra of bulk (A) NBR (20% ACN), (B) NBR (30% ACN), (C) NBR
(40% ACN) in the CN stretching region.
To identify the peak positions, the FTIR spectra were fitted to a Gaussian function and
the results are tabulated in Table 5.4. The results indicate that the nitrile CN stretching
band is at 2237 cm-1 for the three copolymers, demonstrating that the nitrile CN
stretching mode is independent of the ACN content. In other words, the vibrational
frequencies of the CN triple bond are independent of the increasing polarity of the
system.
In contrast with the nitrile band, the methylene resonance feature showed sensitivity to
the amount of the ACN in nitrile rubber. Figure 5.11 shows the FTIR spectra of NBR
containing 20%, 30%, and 40% ACN. The spectra were acquired in the region of 2800 to
3200 cm-1. It is observed that the location of the methylene band varies with acrylonitrile
content. Higher ACN content causes a shift to higher frequency. This shift in frequency
is related to the increase of the polarity of the medium. We should note that Furukawa et
al.101 detected the symmetric stretching of methylene at 2850 cm-1 and attributed it to the
100
butadiene and acrylonitrile units of NBR. The locations and assignments of the observed
peaks in Figure 5.12 are gathered in Table 5.4.
-1
2920 cm-1
2844 cm
(A)
2923 cm-1
I.R. Abs.(a.u.)
2848 cm-1
(B)
2928 cm-1
2852 cm-1
(C)
2800 2900 3000 -1

3100 3200
Figure 5.12. FTIR spectra of bulk (A) NBR (20% ACN) (B) bulk NBR (30% ACN) and
(C) NBR (40% ACN) in the CH region.
As discussed in the previous sections, the methylene vibrational frequency at the
PBD surface was positively shifted with respect to the bulk. This shift was attributed to
the interaction of the polymer with the polar sapphire surface. A comparative analysis can
be made in the case of NBR. That is, the polarity of the bulk increases with the increasing
ACN content, causing the same positive shift as previously observed at surface of the
PBD. It was emphasized that the primary effect on PBD is a surface phenomenon
because only the PBD chains at the sapphire surface exhibit the frequency shift in the
101
methylene symmetric stretch. However, in the NBR bulk, it is the content of ACN units
in NBR that affects the methylene symmetric stretch.
Table 5.4. Observed frequencies (in cm-1) and assignments for Furukawa et al101
alternating copolymers and our NBR. (ACN) and (BD) respectively designate the
acrylonitrile and butadiene units.
Copolyacrylonitrile (ACN)-co- butadiene (BD)
C-H 40% 30% 20%
Infrared Assignments102
region ACNa ACNa ACNa
2852 2848 2844 Methylene sym stretching (CN) and (BD)
2928 2923 2920 Methylene antis. and CH stretching (CN)
2991 2990 2991 (2980,combination) BD
3009
3027 3028 3029 CH (BD) stretching
3077 3076 3074 CH (CH2=CH) stretching
C≡N
2237 2237 2237 Nitrile stretching (CN)
region
a
On one hand, from the previous section, NBR bulk analysis showed that the nitrile stretch
was independent of ACN of NBR. This is in contrast with the interfacial nitrile stretch of
PAN that was sensitive to the polarity of the environment on the vibration of the nitrile
groups (to OH groups – after heating). The fact that the nitrile stretch of NBR is
insensitive to the polarity of the bulk does not preclude a possible dependence of the
nitrile stretch of NBR at the NBR interfaces.
The hypothesis states that the oil resistance is driven by the capability of NBR to interact
with the environment. For example, NBR molecules are expected to interact with heptane
molecules differently than with toluene molecules. Analyzing the nitrile stretch at the
102
sapphire and air interfaces is the next logical step of the investigation. The goal of this
experiment was, first, to obtain a direct comparison between the nitrile spectroscopic
feature of NBR bulk and that of the surface to reveal any spectroscopic differences
related to the environmental impact on the interfacial nitrile. Second, a set of SFS spectra
was gathered at the air and sapphire interface which became the reliable starting point for
later analysis on polymer/liquid interface.
5.3.2 SFS Investigation of NBR in the CN Region
The attention is now concentrated on the spectroscopic features of NBR at the sapphire
interface. The SFS spectra of NBR (40% ACN) was acquired at the sapphire/NBR and
NBR/air interface and compared to the FTIR bulk of NBR (40% ACN). Figure 5.13 trace
(A) shows the FTIR spectrum of NBR in the (2000-2300 cm-1 range). This spectrum was
described earlier in Section 5.3.1 which showed a vibrational band detected at 2237 cm-1
and was assigned to the nitrile stretch of NBR (40% ACN).
Figure 5.13 also compares the SFS spectrum of NBR (40% ACN) at the sapphire
interface on trace(B). The first feature is recognized at 2233 cm-1 and is assigned to the
nitrile stretch of NBR. This feature red-shifted 4 cm-1 compared to that of the bulk. For
the same reasons advanced in the section concerning PAN, a 4 cm-1 shift between the CN
stretching band at the sapphire/NBR interface and that of the NBR bulk can be attributed
to the instrumental differences.
103
Abs. (a.u.) (A)
1.6
1.2
0.8
0.4
(B)
0.0
60
40
20 (C)
0
2000 2050 2100 2150 2200 2250 2300cmÐ1
-1
Figure 5.13. (A) FTIR spectrum of NBR (40% ACN), (B) SFS spectrum of NBR (40%
ACN) in PPP polarization at the sapphire/NBR (40% ACN) interface and (C) SFS
spectrum of NBR (40% ACN) in PPP polarization at the NBR (40% ACN)/air interface.
The data points number was reduced for clear labeling of the spectra.
It is clear from trace (B) that in addition to the nitrile stretch at 2233 cm-1 there are two
peaks of weaker intensity detected in the lower frequency region (2000-2100 cm-1). For
clarity, the spectroscopic features of these bands are summarized in Table 5.5.
Table 5.5. Positions of the CN stretching vibration for NBR (40%ACN) from Figure 5.13
obtained by fitting using Equation(3.22).
Region Nitrile stretching position (cm-1) NBR(40%
probed ACN)
Bulk 2237
Sapphire/NBR 2039 2054 2233
NBR/air 2060
a
The error limit for peak location is ± 0.5 cm .
-1
The SFS results concerning the sapphire/NBR interface are therefore partially understood
to be one band at 2233 cm-1 and assigned to the nitrile stretch of NBR. The two peaks
104
observed in the low frequency region of the spectrum are attributed to a specific
vibrational mode.
The SFS analysis of NBR (40% ACN) carried out on the NBR/air interface remains to be
probed. Figure 5.13 shows the SFS spectrum, trace (C), for the NBR (40% ACN)/air
interface. The first major observation in the SFS spectrum of the NBR/air interface is the
absence of any feature in the (2200-2300 cm-1) region. If the nitrile stretch of NBR is
detected at the sapphire interface, it is nowhere to be found at the NBR/air interface as no
SFS signal is detected between 2200 and 2300 cm-1. The second major difference
between the spectral features of sapphire/NBR and NBR/air interface is an intense band
around 2050 cm-1. Figure 5.13, therefore, shows that in the nitrile region, the spectral
profile of NBR bulk differs from that of the sapphire/NBR interface; this also
distinguishes it from that of the NBR/air interface. The two SFS spectra are, however,
related as the additional unassigned vibrational bands are observed in both cases in the
low frequency side of the (2000-2300 cm-1) region.
Two peaks are observable in the (2000-2100 cm-1) region at the sapphire/NBR interface
compared to one at the NBR/air interface. But also the intensity of the 2050 cm-1 peak at
the NBR/air interface is higher than that of features present in the (2000-2100 cm-1)
region at the sapphire/NBR interface. A direct comparison of the number of peaks is not
meaningful due to the difference in width between the features at both interfaces. For
example, if the SFS spectrum of the NBR /air interface had only one narrow feature in
105
the (2000-2100 cm-1) region, a comparison of the peak number would be meaningful. The
difference in intensity between the features at the NBR/air interface and sapphire/NBR
interface is more interesting and shows that a specific molecule may be present at the
NBR/air interface. For the assignment of the 2050 cm-1 band, two possibilities have to be
considered. The first hypothesis stipulates that this band is due to a molecule interacting
with the nitrile CN side groups of NBR. There are a several assignments reported for the
nitrile bands at 2050 cm-1; one of them was presented by Goodman and Suwyn.98 More
precisely, it concerns a nitrile stretching mode of PAN interacting with water at high
pressure and high temperature. Another possibility is an interaction of the nitrile moiety
with a metal complex, such as Ni(O)CO(dialkylcyanamid),18 which led to an
experimental bathochromic shift ∆ν CN = −200 cm-1. The second hypothesis states that
the 2050 cm-1 is due to the presence of a molecule that has a vibrational mode of its own
at this location. There are dosen of vibrational modes known to have an assignment in
this region. Low molecular weight compounds such as azides, isocyanides, cyanide ions,
and interestingly, water molecules64 have a vibrational band in the 2100 cm-1 region.
Also, it is possible that the peak between 2030 and 2050 cm-1 could be due to specific
molecules added to the NBR during normal polymerization. Antioxidants are
systematically added by the rubber companies to prevent the rubber from degradation via
oxidation. These are the first molecules on the list of polymerization ingredients to
account for.
The necessity of finding an assignment for these bands provided the motivation to carry
out a purification of nitrile rubber. The hypothesis chosen to be tested first is the presence
106
of additives in the rubber contributing to an intense vibrational band in the 2050 cm-1
region. The intention was to compare an SFS spectrum of both sapphire and air interface
of a purified and non-purified NBR. If the SFS spectrum of the purified NBR shows, at
the NBR/air interface, a disappearance of the 2050 cm-1 band and an appearance of the
2233 cm-1, a conclusive assignment of the 2050 cm-1 will be achieved. Here, SFS alone
cannot provide an assignment. It is necessary to involve a complementary
characterization analysis that will positively identify additives, if any. HPLC analysis of
the purification extract was selected as the complementary analysis. The conclusion will
be based on coupling the SFS spectrum with an identification of the additive via
UV/visible detection.
The purification of NBR employed the overnight extraction method using methanol as
the solvent that removed the low molecular weight components in NBR. An HPLC
analysis along with UV/visible analysis of the extract separated and detected the
molecules present in the methanol solution. The UV visible spectrum of the extract
revealed a close match between the molecule present in NBR and an amine antioxidant
(Chromatogram and UV-Visible spectrum were placed in appendix C).
The SFS spectra of non-purified and purified NBR are presented in Figure 5.14.
107
0.5
SFG Int.(a.u.)
0.4
0.3
0.2
0.1 (A)
0.0
1.2
0.8
0.4 (B)
0.0
2000 2050 2100 2150 2200 2250 2300

-1
Figure 5.14. SFS spectra of NBR (40% ACN) in PPP polarization (A) at the NBR (40%
ACN)/air interface and (B) at the purified NBR (40% ACN)/air interface, in the CN
stretching region.
A direct comparison of purified NBR/air and NBR/air interfacial spectra from 2000 to
2340 cm-1 refutes the hypothesis of an amine being the contributor at the 2050 cm-1
features. Furthermore, the absence of detection of a peak at 2233 cm-1 at the
purified/NBR interface and the persistence of the 2050 cm-1 confirms this fact.
Table 5.6. Positions of the CN stretching vibration for NBR (40% ACN) and purified
NBR (40% ACN) at the NBR (40% ACN)/air interface.
Region probed Nitrile stretching position (cm-1)

NBR (40% ACN)/air 2061
NBR (40% ACN)
2077
purified/air
a
The error limit for peak position is ± 0.5 cm-1.
According to the fitting results, a shift exists between these two bands located in the
(2000-2100 cm-1) region. The reason behind this is uncertain and at this stage of the study
108
the presence of the 2050 cm-1 band in the purified sample was the primary source of
interest.
From this experiment, it was determined that the 2050 cm-1 band was not that of an
amine. The possibility of an additive molecule, in this case an amine, contributing to the
2050 cm-1 band in the NBR spectrum, was ruled out. The purification method using
methanol will typically wash out aromatics and polar molecules such as phenols and
amines, but there is still a possibility for specific molecules to remain trapped in the NBR
matrix after extraction.
To further characterize the nature of this band, attention was given to an NBR’s different
acrylonitrile nitrile content. The next experiment was designed to identify an
experimental parameter that can modify the spectroscopic features in the (2000-2100 cm-
1
) wavenumber region. Figure 5.15 shows the SFS spectrum of NBR (20% ACN) at the
sapphire and air interfaces, along with that of the bulk.
109
0.40
Abs.(a.u)
0.36
0.32
(A)
0.28
0.24
1.2
SFG Int. (a.u.)
0.8
0.4
(B)
0.0
25
20
15
10 (C)
5
0
2000 2050 2100 2150 2200 2250 2300

-1
Figure 5.15. (A) FTIR spectrum of NBR (20% ACN), (B) SFS spectrum of NBR (20%
ACN) in PPP polarization at the sapphire/NBR (20% ACN) interface and (C) SFS
spectrum of NBR (20% ACN) in PPP polarization at the NBR (20% ACN)/air interface
in the CN stretching region. The data points number was reduced for a clear labeling of
the spectra.
Trace (A) corresponds to the FTIR spectrum of NBR (20% ACN). Trace (B) relates to
the sapphire/NBR (20% ACN) interface and strongly resembles that of NBR (20%
ACN)/air interface except for its narrower width. As far as the NBR/air spectrum is
concerned, there were no major difference between NBR (40% ACN) and NBR (20%
ACN). Trace (B) then, shows an SFS spectrum of the sapphire/NBR (20% ACN)
interface where no nitrile CN stretch band was found in the range of (2200-2300 cm-1).
The major point is that the known assignment at 2233 cm-1 attributed to the nitrile stretch
of NBR is absent from the SFS spectrum of NBR (20% ACN) at the sapphire interface.
110
Table 5.7. Positions of the CN stretching vibration for NBR (40% ACN) in the different
regions probed from Figure 5.13 and 5.15 obtained by fitting using Equation (3.22).
Region probeda Location (Widthb)cm-1
NBR (20%ACN)/Air 2059(6)
NBR (40%ACN)/Air 2059(6)
Sapphire/NBR
(20%ACN) 2057(3)
Sapphire/NBR 2039/2024(2/1)-
(40%ACN) 2233(5)
a
The error limit for peak position is ± 0.5 cm .
-1
b
The width of the vibrational band is defined as Γq in Equation 3.22.
The set of SFS data on NBR (20% ACN) demonstrates the effect of the ACN on the
NBR/sapphire spectrum in an unexpected manner. Instead of influencing the 2050 cm-1
vibrational bands, it affected the nitrile features in the (2200-2300 cm-1) range. The
NBR/air spectra were independent of the ACN content.
5.3.3 Summary of the Analysis of Dried NBR at Interfaces
The NBR’s fundamental vibration stretch was detected at 2233 cm-1 at the sapphire/NBR
interface and was absent from the SFS spectrum of NBR at the NBR/air interface.
Furthermore, the investigation of the NBR revealed a series of bands and a band located
in the (2000-2100 cm-1) range on the SFS spectra of the sapphire/NBR and NBR/air
interfaces respectively.
The first step in elucidating the origin of these bands at 2050 cm-1 comprised a
purification step (as mentioned earlier) to determine if the assignment of the 2050 cm-1
111
band to determine if the band could be attributed to additives (i.e. an amine) present at the
rubber interface. The purification showed that the 2050 cm-1 band persisted after the
purification and that furthermore the intensity between the bands in the SFS spectra of
NBR (40% ACN)/air and purified NBR (40% ACN)/air are similar. This experiment
ruled out the additive as the contributor of the 2050 cm-1 band.
The following study was devoted to the influence of the ACN on the SFS spectra of two
NBRs with 40% and 20% ACN which revealed an effect shown in the SFS spectra at the
sapphire/NBR interface. As the content in acrylonitrile decreases, only the vibrational
feature at 2050 cm-1 is present at both interfaces.
If the hypothesis of an assignment of the band in the low frequency region is an
interaction between a nitrile functional group and a specific molecule it is probably
possible to affect this interaction by altering the dielectric constant of the medium and the
ideal interface to carry on the experiment is the NBR/air interface where the 2050 cm-1
features are the strongest.
The following experiments were designed for a twofold reason: to observe first the
spectroscopic changes in the 2233 cm-1 vibrational band of nitrile rubber and correlate the
nature of the environment to the nitrile stretching mode. Second, the observation of the
behavior of the 2050 cm-1 band in various environments should help in the assignment of
this peak.
112
5.4 Resistance of NBR to Solvents
This section presents the SFS experiments on sapphire/NBR (40% ACN) and NBR (40%
ACN)/solvent interfaces. Experimentally, the air molecules against the NBR thin film are
replaced by solvent molecules, while the spectroscopic feature of the nitrile rubber film
are recorded.
5.4.1 Resistance of NBR Surface to Heptane
The features of the SFS spectrum of NBR/heptane interface are compared first to the
NBR/air interface to quantify the impact of the solvent on the NBR thin film. Figure 5.16
shows trace (A), the NBR/air interface, and trace (B), the NBR/heptane interface, for
comparison purposes. The fitting for both traces is reported in Table 5.8.
60
40
20 (A)
0
20
15
10
5 (B)
0
2000 2050 2100 2150 2200 2250 2300

-1
Figure 5.16. SFS spectra of NBR (40% ACN) in PPP polarization: (A) at the NBR (40%
ACN)/air interface and (B) at the NBR (40% ACN)/heptane interface in the CN
stretching region.
113
At a first glance, the two spectra at the NBR (40% ACN)/air and NBR (40%
ACN)/heptane interfaces reported in Figure 5.16 look similar. The dominant feature of
these spectra is the vibrational band in the (2000-2100 cm-1) region. The intensity and the
width of this feature change upon heptane injection as it slightly red-shifts (5 cm-1) and
decreases in intensity. At a secondary level, it is noticeable to point out the appearance of
a band at around 2233 cm-1 upon heptane exposure. A possible explanation would be that
the solvent molecules replace molecules present at the interface, revealing a peak around
2233 cm-1. If this explanation is correct, the 2050 cm-1 band would disappear upon
heptane injection and it is clear that this band at 2050 cm-1 still dominates the SFS
spectrum at the NBR (40% ACN)/heptane interface.
If the 2050 cm-1 feature would be attributed to independent molecules at the NBR (40%
ACN)/air interface that are soluble in heptane, then these molecules would be washed out
upon heptane exposure and the 2050 cm-1 vibrational band would disappear from the SFS
spectrum. Furthermore, the hypothesis of the presence of molecules at the NBR (40%
ACN)/air interface interacting with the nitrile groups of NBR seems to be credited by the
slight shift of the 2050 cm-1 feature upon heptane exposure. The molecular picture
describing the NBR/heptane interface would involve specific molecules interacting
strongly with the nitrile groups of NBR. The interaction between these molecules and the
NBR nitrile moieties is indicated by a large shift of the CN stretching mode, and is only
slightly modified by the heptane injection.
114
If heptane is not a good solvent for NBR, the heptane molecules should stay at the
interface rather than solubilize the thin film and reach out to the sapphire interface. This
point can be investigated further by probing the spectroscopic feature of NBR at the
sapphire/NBR interface to see if any observable changes are picked up as well. The
sapphire/NBR SFS spectrum was collected one hour after the injection of heptane.
Figure 5.17 presents a comparison between the SFS spectra at the sapphire/NBR (40%
ACN) in the dried state before the injection of heptane and the corresponding SFS
spectrum at the sapphire/NBR (40% ACN) after one hour of exposure to heptane.
1.6
1.2
0.8
(A)
0.4
0.0
1.5
1.0
0.5 (B)
0.0
2000 2050 2100 2150 2200 2250 2300

-1
Figure 5.17. SFS spectra of NBR (40% ACN) in PPP polarization at the sapphire/NBR
(40% ACN) interface: (A) before heptane exposure and (B) after 1 h of heptane exposure
in the CN stretching region.
Contrary to the previous case of the NBR (40% ACN)/heptane interface, the SFS
spectrum of the interface sapphire/NBR in the dried state is almost identical to that of the
115
sapphire/NBR after one hour of exposure to heptane. The peak position, relative intensity
between the peaks, and the width of the peaks are similar. None of the two spectral
regions pointed out so far have changed. The 2233 cm-1 band assigned to the nitrile CN
stretch of nitrile rubber dominates both SFS spectrum before and after the heptane
injection. The weak bands in the (2000-2100 cm-1) region persist as well.
Table 5.8: Positions of the CN stretching vibration for NBR (40% ACN) in the different
regions probed from Figure 5.16 and 5.17 obtained by fitting using Equation(3.22).
Region probed Locationa(width) cm-1
NBR (40% ACN)/air 2059(6)
NBR (40% ACN)/heptane 2055(5)

Sapphire/NBR (40% ACN) 2039(2) 2054(2) 2234(5)
Sapphire/NBR (40% ACN) under heptane
2039(2) 2053(2) 2234(5)
exposure
a
The first comment that deserves credit concerns the feasibility of such an experiment.
Investigation of polymer/liquid interface is certainly not new, but it is challenging. When
investigating a polymer for the first time, it is best to first find a spectral region free of
interference or with a limited number of bands. Therefore, the first conclusion based on
the set of SFS data related to the NBR (40% ACN)/heptane interface and sapphire/NBR
(40% ACN) interface under heptane exposure is that SFS can be used to monitor the
behavior of a polymeric thin film under liquid exposure.
116
The next step of the investigation is to extract scientific information from this set of four
spectra. The obvious first remark interpreted from Figures 5.16 and 5.17 is that heptane
molecules weakly interact with the NBR surface and do not diffuse. According to
Salomon102 and Starmer50 NBR swelling curves, a low interaction exists between the
NBR and heptane. This is confirmed by the stability over time of the spectra for the
sapphire/NBR interface.
This study was designed to seek interaction information via spectroscopic manifestations.
To obtain information on the interaction of rubber with solvent, it is better to study a
highly interactive system to capture spectroscopic manifestations such as NBR/toluene. 7,

50
In the following section, a duplicate investigation was conducted, this time on the NBR
(40% ACN)/toluene system.
5.4.2. Resistance of NBR Surface to Toluene
This experiment uses the same procedures as described earlier but now exposing an NBR
film to toluene. Toluene is a good swelling agent of NBR; therefore, the characterization
of the NBR (40% ACN)/toluene interface would lead to information on how NBR
interacts specifically with toluene or on the impact of toluene solvent molecules of NBR
up to an extent where the 2050 cm-1 band could significantly change. However, the
interface NBR/toluene cannot be directly probed as the refractive index of toluene is
higher than that of the NBR. In such a case, the requirement for total internal geometry
cannot be satisfied and the reflected SFS signal is weaker. Instead, an alternate
117
experiment was designed where the sapphire interface would be monitored after
successive exposure to toluene. Figure 5.18 presents the results of the experiment. Trace
(A) is the SFS spectrum of the NBR (40% ACN)/air interface, trace (B) is the SFS
spectrum of the sapphire/NBR interface in the dried state, trace (C) represents the
sapphire/NBR (40% ACN) interface after the NBR film was exposed during 30 s to
toluene. And finally, trace (D) corresponds to the spectroscopic profile of the
sapphire/NBR (40% ACN) after a second toluene exposure this time for 4 minutes.
The SFS spectra of the NBR (40% ACN)/air on trace (A) and sapphire/NBR (40% ACN)
on trace (B) in the dried state were analyzed first. These spectra look almost identical to
that obtained in the previous section. The band at 2233 cm-1 was attributed to the nitrile
stretch of NBR. After the acquisition of the first SFS spectrum at the sapphire/NBR
interface, the NBR spin-coated prism was exposed to toluene for 30s and nitrogen-dried
for 2 minutes, then placed under moderate nitrogen flow for a second SFS analysis. The
corresponding SFS spectrum is displayed on trace (C) of Figure 5.18. The 2233 cm-1
band still dominates the spectrum while a small contribution appeared in the lower
frequency range of the spectrum at 2050 cm-1.
118
25
20
15
10
5 (A)
50
SFG Int. (a.u.)
4
3
2
1
(B)
0
2.5
2.0
1.5
1.0 (C)
0.5
0.0
3.0
2.0
1.0 (D)
0.0
2000 2050 2100 2150 2200 2250 2300

-1
Wavenumber (cm )
ACN)/air interface, (B) at the sapphire/NBR (40% ACN) interface before toluene
exposure, (C) at the sapphire/NBR (40% ACN) interface after 30 s of toluene exposure
and N2 drying and (D) at the sapphire/NBR (40% ACN) interface after 4 additional
minutes of toluene exposure and N2 drying, in the CN stretching region.
It seems that the toluene exposure produced some spectroscopic changes at the
sapphire/NBR interface. To further confirm this trend, the NBR spin-coated prism was
exposed to toluene for 4 minutes and nitrogen dried for 2 minutes. It was then placed
under moderate nitrogen flow for a second SFS analysis. A third SFS spectrum of the
sapphire/NBR (40% ACN) interface was acquired and is represented by trace (D) on
Figure 5.18. Evident changes are observed at the sapphire/NBR interface. After the
second toluene exposure, a band as intense as the band assigned to the nitrile is detected
119
at 2050 cm-1. The sapphire/NBR interface closely resembles the NBR/air interface in the
dried state with an intense band at 2233 cm-1. It is surprising that the 2233 cm-1 band is
not changing as the 2050 cm-1 band continues to increase. Speculation was that this 2050
cm-1 band would continue to increase and that the 2233 cm-1 band would at some point
decrease as the film will start to dissolve at the sapphire/NBR interface. This data set
strongly suggests that toluene etched the NBR film because specific spectroscopic
features initially present at the NBR/air interface were transmitted to the sapphire/NBR
interface.
The appearance of the 2050 cm-1 band on the spectroscopic profile of the SFS spectra at
the sapphire/NBR interface could also be due to a significant decrease of the NBR film
thickness during the toluene exposure. It is clear that the band is present at the NBR(40%
ACN)/air interface, and could be detected at the sapphire/NBR(40% ACN) interface if
the thickness decreases. Also, it means that the 2050 cm-1 peak cannot be due to an
independent molecule that is soluble in toluene because it is still detected after two
exposures to toluene.
Table 5.9. Positions of the CN stretching vibration for NBR (40% ACN) in the different
regions probed from Figure 5.18 obtained by fitting using Equation (3.22).
Region probed Positiona(width) cm-1

Sapphire/air 2059(7)
Sapphire/NBR (40% CAN) (dried) 2233(5)
Sapphire/NBR (40% ACN) (after first toluene
2055(3) 2233(4)
exposure)
Sapphire/NBR (40% ACN) (after second toluene
2054(5) 2233(5)
exposure)
a
120
Spectroscopic analysis of the NBR/toluene system reveals different behavior at the
sapphire surface than that of the NBR/heptane system. From a spectroscopic viewpoint,
the changes in the SFS spectrum at the sapphire interface upon toluene exposure shows
that the toluene molecules reach the sapphire interface. It is important to note that this
effect is either a real perturbation of the sapphire interface caused by solvent molecules or
it is the direct effect of a decrease in the NBR film thickness.
5.4.3 Resistance of NBR Surface to Water
As observed in the first part of the previous section, there are several hypothetical
molecules capable of inducing a significant shift of the nitrile stretch. But out of all of
them, the one that has the highest probability to cause a spectroscopic shift is water.
This final section will study on the behavior of NBR in contact with water.
Chapter 3 explained how the nitrile moiety is capable of interacting with water.
Acetonitrile and polyacrylonitrile both interact with water with a positive shift of 3 cm-1
at room temperature and a 200 cm-1 negative shift at high temperature and under pressure,
respectively. Because the fact that the observation was made on PAN and not nitrile
rubber and because the interaction between nitrile groups in NBR is weaker than that in
PAN, it is possible that another interaction between interfacial nitrile of NBR and water
takes place at room temperature and atmospheric pressure.
121
A comparison between the NBR (40% ACN)/air interface and NBR (40% ACN)/water
interface is presented in Figure 5.19. Various motivations drove this project over time,
and when these data were recorded, special attention was given to the C-H region of
NBR. That is why the spectra were acquired in the (2800-3200 cm-1) region. An
immediate loss of the SFS signal was recorded at the sapphire/NBR (40% ACN) interface
presented in Figure 5.19. The same response is observed at the sapphire/NBR (40%
ACN) interface, as shown in Figure 5.20.

SFG intensity (a.u.)
(A)
(B)
2800 2900 3000 3100 3200

-1
Figure 5.19. SFS spectra of NBR (40% ACN) in PPP polarization at the sapphire/NBR
(40% ACN) interface (A) before water exposure and (B) after water exposure, in the CH
stretching region.
(A)
SFG intensity (a.u.)
(B)
2800 2900 3000 3100 3200

-1
ACN)/ air interface and (B) NBR (40% ACN)/water interface, in the CH stretching
region.
122
The loss of SFS signal led to a non-conclusive experimental result with respect to
assigning the band at 2050 cm-1 to nitrile/water interaction. However, losing the SFS
signal itself carries potential information. As explained in the first section of Chapter 3,
this technique is sensitive to the symmetry of the molecular arrangement at the interface.
One could infer a complete disorganization of the NBR interface due to the high polarity
of the water solvent inducing a loss of SFS signal.
Therefore water, a very polar medium, significantly affects the NBR surface while it does
almost nothing to the PAN surface. The role of the nitrile groups could be easily
investigated by probing NBR/water interface with ACN content intermediate between
100 and 40% ACN.
5.4.4 Assigning the 2050 cm-1Band.
There are around 25 vibrational modes in the (1900-2300 cm-1) region. The assignments
for these vibrational bands include stretching of triple bonds or out-of-phase stretching of
cumulated double bonds stretching vibrations.64 Out of these 25 vibrational modes, only
eight appear in the (2000-2100 cm-1) region (see Table 5.10)
Several possibilities can explain the detection of a band at 2050 cm-1 at the NBR/air
surface. A residual chemical present at the NBR surface having a vibrational frequency of
its own at this location, a by-product of a chemical reaction between the nitrile groups of
123
nitrile rubber or a chemical species that interacts with the nitrile group of NBR inducing a
negative spectroscopic shift of the nitrile stretch vibration.
Table 5.10. Vibrational modes absorbing in the (2000-2100 cm-1) region.64
Triple bonds and cumulated double bonds vibrations in the (2000-2100
2050-2150 cm-1 Isothiocyanate
2000-2050 cm-1 Ketene imines
2012-2132 cm-1 Diazo compound
2080-2170 cm-1 Organic azid
2070-2200 cm-1 Cyanide Ions
2100 cm-1 Ferri-cyanide
2020-2090 cm-1 Thiocyanate ions
Metal (CO) 1900-2170 cm-1
To decrease the number of potential assignments for the 2050 cm-1 band, a typical recipe
of NBR is presented in Table 5.1121 and will serve to assess the probability of the each
assignment.
124
Table 5.11 Typical recipe for NBR emulsion polymerization5
Typical recipe for butadiene-acrylonitrile copolymerization
Butadiene 75
Acrylonitrile 25
Soap 4.5
Stearic acid 0.6
t-dodecyl mercaptan (thiol) 0.5 R-SH

Potassium chloride 0.3
Sodium 0.35
Ferrous sulfate 0.1
Hydrogen peroxide 0.02
Water 180
A comparison between Table 5.10 and Table 5.11 reveals several common points. First,
the presence of salt such as potassium chloride, sodium pyrophosphate and ferrous sulfate
gives credit to a possible interaction between the nitrile groups of NBR and specific
molecules. It also indicates that there is a possibility of finding cyanide ion in complex.
For example, cyanide ion sodium and potassium salts absorb at 2080-2070 cm-1 and ferri
cyanide ion absorbs near 2100 cm-1.64
Also, a small amount of mercaptan(thiol) could hypothetically react with nitrile groups of
nitrile rubber and form thiocyanate ions. As Table 5.10 shows, inorganic thiocyanate ions
absorb strongly at 2020-2090 cm-1.

125
The second hypothesis is that the amine detected by HPLC could react and forms diazo
compounds. Therefore, the next question is, whether further reactions could take place in
the NBR, knowing that some amine and acidic molecules (stearic acid) are present in the
formulations. In other words, what is needed to carry a diazotization? Alkane amine can
be N-nitrosated and the resulting species rearrange to form diazonium ions. These ions
are unstable unless stabilized by a resonance structure.103 The experimental conditions for
the N-nitrosation involve nitrous acid as a reactant which is very unlikely to be found in
NBR.
The next hypothesis concerns the possibility of obtaining organic acid by-products.
Organic azides are typically synthesized by transforming a haloalkane by reacting an
azide ion, N 3− . These azides would have to be present in the emulsion recipe, which is
unlikely, according to Table 5.11.
The most probable assignment for the 2050 cm-1 vibrational band is either an interaction
with residual salt used during the NBR emulsion polymerization or that of a nitrile
complex. It is unclear at this point why the 2050 cm-1 band is only detected at the
NBR/air interface.
5.4.5 Conclusions on Solvent Resistance of NBR.
The response of the NBR thin film surface to heptane, toluene and water exposure was
analyzed using SFS. From a diffusion point of view it is clear that the NBR/heptane case
126
differs from that of the NBR/toluene. The SFS signal at the sapphire/NBR interfaces
under heptane exposure was effectively stable over time while that corresponding to the
sapphire/NBR under toluene exposure shows observable changes. It is not possible at this
time to discriminate between an interference effect due to the sensitivity of SFS that is
directly related to the film thickness or to a real spectroscopic manifestation resulting
from the penetration of toluene through the NBR film.
The uncertainty about the assignment of the 2050 cm-1 does not affect the conclusion on
NBR thin film stability in various solvent because two SFS spectra of NBR interface are
compared before and after solvent exposure. But it for now impedes any conclusion on
the spectroscopic impact of the solvent on NBR surface as it is still unclear if the film
went through a major change due the possible presence of chemical interacting at the
NBR surface.
The spectroscopic investigation of NBR surface under liquid exposure demonstrated the
ability of SFS to distinguish two systems such as NBR/heptane and NBR/toluene. As a
conclusion, the SFS experiment allows accurate tracking of the diffusion of the solvent
molecules to the sapphire interface. Summary and further conclusions are placed in the
next and final chapter of this dissertation.
127
CHAPTER VI
SUMMARY AND CONCLUSIONS
The main goal of this work was to determine, using SFS spectroscopy, a molecular
mechanism that explains the resistance of nitrile rubber (NBR) to hydrocarbon liquids.
The ACN content of nitrile rubber was varied and it was hypothesized that the CN stretch
of NBR would depend on the environment. The nitrile rubber/air interface was probed
and compared to an NBR/liquid interface.
First, bulk and surface bulk characterization of PAN, PBD and NBR (40 % and 20%
ACN) was carried out using FTIR, Raman and SF spectroscopies. Next, the solvent
resistances of PAN and NBR were determined.
The effect of the hydroxyl groups present at the sapphire/PAN interface on the CN
stretching of PAN was determined on the SFS sapphire/PAN spectrum. The strong
dipole-dipole interactions in PAN were disrupted at high temperature so that the nitrile
groups of PAN can now interact with the environment. The effect of the hydroxyls at the
sapphire interface on the nitrile stretching frequency was demonstrated.
128
Analysis of PBD revealed a very interesting response when PBD was exposed to a polar
environment at room temperature. The SFS spectrum of PBD at the sapphire/PBD
interface exhibits, at room temperature, a positive shift of the methylene stretch compared
to that of bulk PBD. The sapphire shifts the PBD methylene stretch vibration.
The investigation of the surface of NBR with 40% and 20% ACN demonstrated a new
2050 cm-1 band at the NBR/air interface, even though this band is not present in NBR
bulk. The CN stretch of NBR, at 2233 cm-1, was detected only at the sapphire/NBR (40%
ACN) interface. The band found at 2050 cm-1 did not seem to be due to additives in the
rubber since SFS results of purified NBR were very close to those of non-purified NBR.
Molecules such as salts that complex with the nitrile groups of NBR to induce a shift of
the nitrile stretching mode from 2230 to 2050 cm-1 is the most probable cause.
The second part of the studies involved exposing NBR to various solvents, heptane,
toluene and water. The sapphire/NBR and NBR/liquid interfaces were analyzed.
Comparison between the SFS spectra of sapphire/NBR interface before and after solvent
exposure was done. No changes were detected at the sapphire/NBR interface after one
hour of heptane exposure.
But specific spectral feature appeared at the sapphire/NBR interface after exposure to
toluene.
129
The appearance of a band at 2050 cm-1 for the sapphire/NBR interface may be due to
toluene molecules as they reach the sapphire interface or to mixing of the SFS signals
between the NBR/air and sapphire/NBR interfaces, as a consequence of a significant
decrease in NBR film thickness.
Finally, the SFS spectra of NBR/water interface under water exposure show a loss of
signal detection. This differs from the case of PAN where an SFS spectrum at PAN/water
interface gave an SFS signal.
The hypothesis that the 2050 cm-1 band is due to salts remaining from emulsion
polymerization could be further checked by looking for this band in other acrylonitrile
polymers synthesized using similar salts.
For the sapphire/NBR interface after toluene exposure, dissolution of the film prevents a
conclusion. Originally, since the amount of acrylonitrile was the primary parameter to
consider, crosslinked NBR samples were not studied to avoid the complex situation,
where two parameters, the crosslinked density and the NBR acrylonitrile content, would
be analyzed simultaneously. However, the use of crosslinked samples may help in further
characterizing the sapphire/NBR interface under toluene exposure. A monitoring of the
nitrile CN stretch in the 2200-2300 cm-1 region of both the SFS spectra of the
sapphire/NBR in, heptane and toluene exposure may show whether or not oil resistance
phenomenon is a surface-related phenomenon.
130
It would also be important to use a series of solvents in the SFS studies. A comparative
study of toluene and cyclohexane would be helpful in revealing the exact impact of the
aromatic ring. Finally, the use of halogenated compounds would be very interesting since
the rubber/Cl system has a negative change in enthalpy upon mixing.
131
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137
APPENDICES
138
APPENDIX A
PAN AND NBR THERMAL TRANSITIONS
Differential Scanning Calorimetry (DSC) was performed on PAN at a heating rate of 10
°C/min. Two transitions are detected at 102 °C and 150 °C.
Figure A-1: DSC thermogram of PAN carried at a heating rate of 10 °C/min.
139
Figure A-2: DSC thermogram of NBR carried at a heating rate of 10 °C/min.
140
APPENDIX B
THIN FILMS ELLIPSOMETRY THICKNESS MEASUREMENTS
Fitting results of ellipsometer data performed on PAN, NBR and PBD spin-coated films
using Cauchy layer model are presented in Figures B-1,B-2 and B-3.
Generated and Experimental

15 30.0
12
27.0
8
Ψ in degrees
∆ in degrees
Model Fit 24.0

Exp ∆-E 75°
5 Model Fit
Exp Ψ -E 75°
21.0
1
18.0
-3
-6 15.0
200 400 600 800 1000
Wavelength (nm)
Figure B-1: Fitting of the measured (dotted lines) and computed values of Ψ and ∆ for the
measurement on the PAN film spin-coated on a sapphire prism.
141
35 32
25 26
Ψ in degrees
∆ in degrees
Model Fit
15 Exp ∆-E 75°
19
Model Fit
Exp Ψ-E 75°
5 13
-5 6
-15 0
200 400 600 800 1000
Wavelength (nm)
measurement on the NBR film spin-coated on a sapphire prism.

15 35.1
12 28.1
8
Ψ in degrees
∆ in degrees
21.1
5
14.0
1
Model Fit
Exp ∆ -E 75° 7.0
-3
Model Fit
Exp Ψ -E 75°
-6 0.0
200 400 600 800 1000
Wavelength (nm)
measurement on the PPB film spin-coated on a sapphire prism.
142
Table B-1, shows the values of An, Bn and Cn in the Cauchy layer model for each of the
measurements and corresponding film thicknesses.
Table B-1: Fitted Cauchy parameters and polymer thin films thicknesses
Polymer Thickness
Cauchy parameters
sample (nm)
An Bn Cn
PAN 1.51 0.0051 0 435 + 1
−
NBR 1.5 0.0087 0 226 + 1
−
PB 1.53 0.0018 0 824 + 2
−
143
APPENDIX C
HPLC RUBBER ADDITIVES ANALYSIS
The chromatogram of methanol extraction solution is presented in Figure C-1.
Figure C-1: Chromatogram of NBR extract.
Additives identification was carried out by scanning UV-Visible detection (spectrum
presented in Figure C-2). It is clear that the UV-Vis corresponding to the additive is not
that of BHT (Figure C-3). Comparison with spectra of reference substances led to the
hypothesis of an amine type of additive.
144
Figure C-2: Chemical structure of possible amine type molecule and corresponding UV
spectrum.
145
Figure C-3: Chemical structure of Butyl Hydroxylated Toluene (BHT) molecule and
corresponding UV spectrum.
146
APPENDIX D
NMR SPECTRA OF NBR
Olefinic protons of BD units appeared at δ =5.3-5.7 ppm. The relative intensity of the
higher field peak (low chemical shift) increases with an increase in the BD units in the
NBR, the higher peak field is assigned to the BD-BD-BD sequence and the lower field
peak is assigned to the AN-BD-AN sequence.
The methylene protons of the BD units in NBR appeared at δ =2.1-2.3.
Figure D-1. 500 MHz-NMR spectrum of NBR (20% ACN).
147
148
APPENDIX-E
SIZE EXCLUSION CHROMATOGRAPHIC MEASUREMENTS OF NBR
Figure E-1: Chromatogram of NBR (20% ACN)
149
150

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UNDERSTANDING OIL RESISTANCE OF NITRILE RUBBER:

CN GROUP INTERACTIONS AT INTERFACES

The Graduate Faculty of The University of Akron

of the Requirements for the Degree

CN GROUP INTERACTIONS AT INTERFACES

Nitrile rubber (NBR) is copolymer of acrylonitrile and butadiene. It is resistant to

swelling by hydrocarbon oils.1 Swelling and thermal degradation decrease as acrylonitrile

content increases. Infrared-visible Sum Frequency Spectroscopy (SFS) is used in the

materials, two additional polymers polyacrylonitrile (PAN) and polybutadiene (PBD)

were included and analyzed prior to analyzing the nitrile rubber.

transition temperature. This demonstrates how environment affects nitrile dipole-dipole

stretching mode of PAN.

were determined using High Performance Liquid Chromatography (HPLC). Results

proposed after considering the chemical compounds present in NBR emulsion

molecular changes at polymer/liquid interfaces.

aromatic solvents. Quantitative interpretation of the oil resistance will require an

assignment of the 2050 cm-1 absorption band.

of this work at ExxonMobil Research and Engineering center represented for me an

ExxonMobil would not have been possible.

Gustavo A. Carri, Dr. Roderic P. Quirk and Dr. Rex D. Ramsier.

LIST OF TABLES ........................................................................................................... xii

LIST OF FIGURES ........................................................................................................ xiv

2.1 Nitrile Rubber ...................................................................................................5

2.1.3 Nitrile Rubber .....................................................................................9

2.2 Oil Resistance of Nitrile Rubber......................................................................11

2.2.1 Theoretical Approach........................................................................11

2.2.2 Key Experimental Parameter: Acrylonitrile Content........................15

2.2.3 Industrial Approach ..........................................................................16

2.3 Advances in Probing Polymer/Liquid Interactions...........................................17

2.3.1 Experimental Parameter....................................................................18

2.3.2 Linear Partition Model......................................................................20

2.3.3 In-situ Swelling Measurements of Thin Polymer Films ...................21

2.3.4 Polymer Membrane Design ..............................................................24

III. PROBING MOLECULAR INTERACTIONS USING SPECTROSCOPY ...............28

3.1 Linear Spectroscopy........................................................................................30

3.1.1 Infrared Spectroscopy .......................................................................32

3.1.2 Raman Spectroscopy.........................................................................34

3.1.3 Non-Linear Effects............................................................................39

3.1.3.1 Hot Band ........................................................................................40

3.1.3.2 Fermi Resonance............................................................................42

3.2 Non-Linear Spectroscopy ...............................................................................42

3.3 Spectroscopy for Probing Interactions............................................................52

3.3.1 Acetonitrile Model Compound ........................................................52

3.3.2 Polyacrylonitrile Model Compound .................................................57

3.3.3 Frequency Shift at Surfaces ..............................................................61

3.4 Messages of This Dissertation .........................................................................62

4.1 Polymer Thin Film Preparation ........................................................................64

4.2 NBR Purification ..............................................................................................66

4.3 High Pressure Liquid Chromatography Characterization.................................66

4.4 IR-Visible Sum Frequency Generation Spectroscopy Measurements (SFS) ...67

4.4.1 ExxonMobil Narrow-line SFS Spectrometer......................................67

4.4.2 The University of Akron Broadline SFS Spectrometer ......................70

4.5 Differential Scanning Calorimetry (DSC) Measurements...............................76

4.6 FTIR Measurements.........................................................................................76

4.7 Raman Spectroscopy Measurements ...............................................................76

4.8 Nuclear magnetic Resonance Measurements...................................................77

4.9 Size Exclusion Chromatographic Measurements ............................................77

4.10 Thin Film Thickness Measurements ..............................................................77

V. RESULTS AND DISCUSSION ...................................................................................79

5.1 Spectroscopic Investigation of Nitrile Groups Interactions in

5.1.1 SFS Spectra and Peaks Assignments ...................................................80

5.1.2 PAN under Solvent Exposure ..............................................................90

5.1.3 Summary on PAN Investigation ..........................................................94