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Raman Spectroscopy, a review

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869 (O) 2454-4698 (P), Volume-6, Issue-1, September 2016

Raman Spectroscopy, Review

Paul Rostron, Safa Gaber, Dina Gaber

Abstract— Raman spectroscopy is a branch of vibrational the displacement of the constituent atoms from the
spectroscopy, which allows an easy interpretation and highly equilibrium positions as the result of the molecular vibrations
sensitive structural identification of trace amounts of chemicals [9].
based on their unique vibrational characteristics (fingerprints).
Due to the continuous technical improvement in Raman
spectroscopy, an advanced development of the device was
For many decades Raman spectroscopy had a limited
achieved and more applications have become possible. This application because of very low efficiency of the normal
review is the first one to illustrate most of the main types of Raman scattering and the spectrometer parts were expensive
Raman spectroscopy in a single review. We present the general and not suitable for on-site analysis [8]. Significant
idea of theoretical and instrumental Raman device. The aim of development and enhancement happened to Raman
this review is to highlight potential applications of different spectroscopy structure allow it to overcome those limitations
types, especially the application developed to identify corrosion and change the capabilities of the spectroscopy fundamentally
products. It includes information about various types of where a portable and relatively cheap devices are now
corrosion product and a database presenting some corrosion
available [10]. Raman spectrum can be treated as a fingerprint
products. This review ends with a concluding section summarize
the main points of the review. Raman scattering is a
tool for different compounds [8]. So the obtained spectrum of
spectroscopic tool predicted first theoretically by Smekal in the analyte can be used as qualitative analysis for unknown
1923 and experimentally by Raman and Krishnan in 1928. samples or a mixture of components.
Raman spectroscopy is vibrational technique involve high
energy photons based on the inelastic scattering of radiation in
the visible or near-infrared region of the sample. Most of the II. INSTRUMENT AND SPECTRUM
scattered light (Rayleigh scatter) has the same wavelength as
laser source light. There are two types of light scattering the
elastic and inelastic scattering. The elastic scattering is when the A Raman spectrometer is composed of light source,
photon frequency doesn’t shift or change its wavelength. The monochromator, sample holder and detector. Dispersive
opposite is the inelastic scattering, which is involved in Raman Raman spectroscopy and Fourier transform Raman
spectroscopy. The shift of the frequency can be used to get an spectroscopy (Fig.1) are different in their laser sources and by
information about the molecular chemistry. the method of detection for Raman scattering. Both
techniques showed unique advantages and the method that
Index Terms— Corrosion, corrosion detection, Raman
best suit the sample should be preferred [11]. Several types of
spectroscopy.
lasers can be used as the excitation source, like krypton ion
(530.9 and 647.1 nm), He:Ne (632.8 nm), Nd:YAG (1064 nm
and 532 nm) argon ion (488.0 and 514.5 nm), and diode laser
I. INTRODUCTION
(630 and 780 nm). Use of 1064 nm near-IR (NIR) excitation
Raman spectroscopy is a technique specialized in laser causes a lower fluorescent effect than visible wavelength
measuring the frequency shift of inelastic scattered light from lasers [12].
the sample when the photon from incident light strikes a
molecule and produce a scattered photon [1-5]. The out Raman spectroscopy has the great advantage of remote
coming scattered light can be a photon with a lower frequency sensing when it is associated with optical fibers. The optical
than the original photon and in that case, it is known as stokes fibers are responsible to transport Raman signals by collecting
Raman scattering or with higher frequency and known as the scattered photons. The fiber optic system includes fibers
anti-Stokes Raman scattering [6]. In the latter case, the photon in which the laser excitation is transmitted along one fiber and
will get energy from the bond of the molecule when the bond the scattered radiations are transmitted to the detector along
is initially in the excited vibrational state [7,8]. Generally, different fibers. Raman Spectroscopy has been used in real
Raman is based on measuring the shift in the energy of the time monitoring system to detect illegal drugs, toxic material
outgoing photon. The shift in wavelength of the scattered light in the environment and chemical and biological warfare
depends upon the chemical composition of the molecules agents.
responsible for scattering. The intensity of Raman scattering
is proportional to the magnitude of the change in the There is several commercially available hand held Raman
molecular polarization. According to Raman selection rule, spectrometers reviewed and mentioned by Ashley J., on 2013.
the change in the molecular polarizability will be the result of Some of these spectrometers are, the SciAps ReporteRt
(formerly DeltaNu, Inc.), the Snowy Range Instrument
Paul Rostron, Department of Chemistry, The Petroleum Institute, Abu CBEXt, the Thermo Scientific FirstDefendert (formerly
Dhabi, UAE, +97126075217. Ahura, Inc.) and the B&W TEK NanoRamt [13].
Safa Gaber, Department of Chemistry, The Petroleum Institute, Abu
Dhabi, UAE, +971501107167.
Dina Gaber, Department of Chemistry, The Petroleum Institute, Abu
Dhabi, UAE, +971507200115.

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 Raman Spectroscopy, Review

III. RAMAN TYPES

A. Surface Enhanced Raman Spectroscopy (SERS)

Surface-enhanced Raman spectroscopy (SERS) is one of the
most sensitive devices that allows for highly sensitive
structural detection of low concentration analytes through

Fig. 2: Surface enhanced Raman scattering system.

and 2D Au nano-mushroom arrays [14]. The development in

the metal substrate enables the technique to give faster and
more accurate detection results for chemical and biological
samples [16]. Different concepts have been developed to
enhance the fabrication of SERS substrates using bottom up
and top down approaches. The most important thing to realize
to improve SERS is to provide the industry with more
Fig. 1: Raman instrumentation. sensitive, cheaper components for the structure of the
spectroscopy and simpler fabrication method. In this
the amplification of electromagnetic fields generated by the Perspective a brief review was published in 2014 by Jordan F.
excitation of localized surface plasmons (LSP) of adsorbate Betz describes some of the popular methods for SERS
molecules on the roughened metal surface [14]. The first substrate fabrication and discuss the characteristics of simple
published paper reporting the strong Raman signal from the SERS substrates [20]. Also other fabrication methods for
interface was done in 1974 by Fleischmann and co-workers. SERS substrates have covered by many reviews papers
The authors reported that the high intensity the signal is [21–24].
because of the large number of adsorption sites on the The laser can be designed using gas, dye and solid state as
roughened surface [15]. Jeanmaire and van Duyne [9] and excitation sources for analyte to produce Raman signal [9].
Albrecht and Creighton [4] groups in 1977, proved that the Choosing the best laser source will depend on the wavelength
high intensity of Raman signal is due to the large increase of needed for the absorption band of SERS substrate and the
the Raman cross section of the adsorbed molecules which power to avoid the formation of the interference [25]. Tunable
known as surface enhanced Raman spectroscopy. However, lasers will be more suitable to match the excitation frequency
additional studies proved that SERS has resulted from a of the substrate. The limitation is the complications of the
combination of two effects the electromagnetic effect and a process to prevent Rayleigh-scattered photons from reaching
resonance -like charge transfer effect [9]. the detectors [9].
While the signals obtained by normal Raman scattering is B. Surface enhanced hyper Raman Scattering (HR) scattering
usually weak, SERS can detect very low concentration of the
analytes because of the large increase of the Raman
cross-section of an analyte up to 15 orders of magnitude in Surface enhanced hyper Raman scattering is an inelastic
comparison to normal Raman scattering [8, 16]. Fig. 2 is a sum of frequency scatted from two photons while the normal
sketch that presents the main parts and component of Surface Raman scattering result from single photon. Total surface
enhanced Raman scattering device [4]. enhancement factors of SERS can be estimated to be the order
Colloidal metals and roughened metal electrodes are of 1014. The enhancement can be the result of molecular
SERS-active surfaces [17]. Colloidal metal is easy to be electronic resonance where the molecular transition
prepared and characterized because of its morphology and corresponds to the sum frequency of the incident photons
size. Even though it usually shows a relatively strong activity [26]. A higher surface enhancement for hyper-Raman
for the adsorbed molecules it has poor reproducibility of their scattering can be achieved if both the surface effect and
properties because it is difficult to control its size [17]. The resonance effect are applied together [17]. Most of SEHRS
first recorded SERS spectra was by using a roughened silver experiments were done at 1064 nm excitation using
electrode [18]. Another type of metal surfaces was tested after mode-locked [27-29] Nd:YAG lasers or Q-switched [30,31].
that like gold and copper. All those metal surfaces increased Van Duyne group in 1988 [26], presented the first report of
the intensity of Raman signal up to 104 to 106 fold. In general SEHRS spectra with experiment and theory for the vibrational
silver and gold substrate are the most often used types because assignments. Also, it was found that compressing the pulse to
they are the most air stable materials. Copper on the other few picoseconds can increase SEHRS intensity.
hand is more reactive with air, which will affect the success of SEHRS has also been tested for biologically relevant
SERS [14]. SERS substrates become available in various applications. An early study was performed by the Kneipp
shapes and coating after advance development. As an group where they used SEHRS to record the stretches of the
example, Shell isolated nanoparticle- enhanced Raman bond of biological samples like amide I and III and C-O bond
Spectroscopy [19] in the DNA [32]. Also SEHRS can be used to study the redox

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869 (O) 2454-4698 (P), Volume-6, Issue-1, September 2016
reaction on electrode surfaces [33]. The research studies
proved that SEHRS can be used as a potential ultrafast
technique to study the dynamics of complex reaction with
sensitivity higher than the one which can be acquired by
SERS. In addition, SEHRS can be used to study excited states
like what was demonstrated by the Camden group [26].
Appling the unique second-order non linearity multiphoton
plasmonic enhancement and the intrinsic frequency doubling
will give the advantage for SEHRS to be considered as a Fig. 3: Tip enhanced Raman spectroscopy concept.
useful technique [34,35].
C. Tip enhanced Raman Spectroscopy (TERS)
Many research interest require Raman imaging of a small
area within the sample, however conventional Raman
technique can be misleading in some cases due to the masked
signal contribution by the surrounding area signals [1]. Such Fig. 4: Diagram alignmentferent optical alignments setup in
issues encouraged further research on Raman scattering TERS. (a) Bottom illumination (b) side illumination (c)
enhancement. Tip enhanced Raman spectroscopy (TERS) is bottom illumination.
one of the powerful solution that combines between two
techniques; scanning probe microscopy and Raman research deals with point scanning, although it cannot provide
spectroscopy [36]. TERS can provide a topographical and a correlation between the chemical information about Raman
spectral/ chemical information simultaneously using SPM and data and the structural feature of the sample [44,45]. In some
Raman respectively [36,37]. cases, line scanning can also be used especially when the
TERS has similar instrumentation, material requirement sample consists of a multilayer [46].
and enhancement principle as SERS, but by using a metal tip The concept of TERS was first proposed in 1928 by Synge
or metal nanoparticle instead of the metal film [37,38]. The [47]. However, the concept was considered impractical until
TERS technique is based on the fact that a metal tip or a metal the second half of the twentieth century. In 1985, Wessel
nanoparticle is brought into close proximity of nanometer provided the theoretical concept of combing SERS
distance with the sample. An excitation laser beam will enhancement and SPM resolution in TERS measurements
illuminate the tip apex creating an enhanced and confined [48]. As a result, TERS concept is mostly attributed to Wessel.
electric field zone. This localized field will result in enhanced Later on, at 2000 the experimental evidence was reported by
Raman scattered light from the sample located under the tip Stöckle et al [39], Anderson [49] and by Kawata et al. [50].
[39,40]. A diagram of TERS concept can be seen in Fig.3 Tips of TERS are fabricated using two noble metals either
[41]. The mechanism behind TERS ability to enhance the Au or Ag [37,51]. While Ag are preferred in term of higher
electromagnetic field at a tightly focused spot can be field enhancements, Au are more stable. Ag are susceptible to
attributed to surface plasmon resonance and electrostatic degradation due to oxidation [37]. Current area of TERS
lighting rod effect [40]. Further details were discussed in research is working on identifying more reproducible and
other sources [42]. robust tips design and materials.
There are three main scanning probe microscopy modes TERS is a great Raman tool that combines signal
that are used in TERS experiments. The most commonly used enhancement, high sensitivity with excellent spatial resolution
is the Atomic Force Microscopy. The other two SPM modes of few nanometers [14,38]. TERS scattering enhancement
are Shear-Force Microscopy and Scanning Tunneling has been reported to be in the range of 1010 to 1012 [1]. For
Microscopy [37]. instance, about 109 enhancements were obtained
One of the most important requirement for the successful experimentally by Neacsu et al. [8]. The most important
use of TERS is the optical alignments and geometry [37,43]. feature of TERS in comparison with SERS is the quantitative
The illuminating laser should properly focus at the tip apex analysis possibility because of the identical electromagnetic
-sample interface while the scattered Raman should be field enhancement at all points [39]. In addition, TERS
collected efficiently. Several set-up configurations are enhanced the reproducibility issue of SERS techniques [36].
available in recent years, reflecting the flexibility of TERS Another advantage of TERS is its ability to work in the
[18]. As can be seen in Fig.4, the tip can be illuminated in presence of water and humidity [37].
three ways; bottom or back reflection illumination, side TERS is powerful tools in a wide range of fields. It was
illumination and top illumination [41]. The bottom successfully applied in nano-structural investigation of both
illumination works for transparent or very thin film sample. organic and non-organic materials [13]. For example,
While the other two are used also for opaque samples [43]. detection of single-walled carbon nanotubes was reported by
Each of these illumination techniques has its own limitations using TERS [40]. Using such technique of high spectral
and advantages as discussed in the Gibson review [36]. The resolution, it was possible to detect any fluctuation in the
selection is mainly based on the analyzed sample and the SPM spectra due to SWCNT structural changes [52]. CNT are not
modes. the only carbon material investigated by TERS. TERS have
TERS can be divided into two techniques point scanning been successful in providing information about the chemistry
and mapping [36]. The latter is more efficient as it provides and structure of other carbon materials such as carbon
topographic and spectroscopic simultaneously. Most of nanotubes [53] and graphene [46,54].

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 Raman Spectroscopy, Review

Another area of interest in using TERS is bio-organic intrinsic vibrational bond of the sample with three
compound investigation, including nucleic acid, DNA and dimensional resolutions. Since CARs is a four wave mixing
RNA identification [40,55]. Additionally, TERS are powerful process, the signal has a quadratic dependence on the incident
tools in cell analysis, lipids and single virus particle radiation (nonlinear), unlike the spontaneous Raman signal
[18,36,55]. TERS ability to give a spatial resolution of 1nm2, which has a linear dependence on the incident field intensity
give it the possibility to analyze single biological molecules [66]. Fig. 5 indicates the diagram of CARS energy levels [64].
[37]. A reliable spectra of single RNA strand was reported
using TERS [56]. It can be considered as a successful initial
step toward a direct sequencing of single biomolecule.
Another example, is the Raman spectra of shell components
of a single bacteria as reported by Popp and coworkers [57].
Many ongoing researches are focusing on using TERS as a
reliable and reproducible technique for biological samples.
Extensive reviews on this topic and other applications such as
catalysis and polymer blends are available in the literature
[37,40,55]. Naresh Kumar has recently produced a nice
review about TERS wide range applications and principle
[55].
Some issues need to be addressed in TERS before it
Fig. 5: Diagram of the coherent anti-Stokes Raman scattering
becomes a common robust technique. First, TERS
(CARS) process [64].
measurement and practice are still complex and challenging
in real life [8,36]. Therefore, only a limited number of TERS
The signal can be collected into two directions using two
application can be found. Further work on Tip fabrication is
different geometries for excitation and detection. In the case
required mainly in term of its stability and commercial
of forward detected CARS (F-CARS) the signal is strong, but
availability. Currently tip metal coating such as gold and
in some cases the signal can be masked by the non-resonant
silver metal coating are easy to be worn off [37]. Also, the
background signal from scatterers and solvent. Therefore,
metal used are not stable and strong enough to withstand
epi-detected CARS (E-CARS) are considered as a solution to
harsh conditions. Many ongoing research is focusing on
overcome the non-resonant background from the solvent and
finding new materials. For example, alloys are one of the
improve overall sensitivity [62]. The E-CARS make imaging
promising material to increase the lifetime of tips [37].
possible for new samples by introducing phase mismatching
Among the different ongoing research, improving TERS
and detecting the signal in the background direction.
probe stability and reproducibility received the highest
Simultaneous use of E-CARS and F-CARS allow revealing
priority [58,59]. Also, a lot of TERS research is trying to
various features in the studied sample. There are different
study the sample at better controlled environments like using
other approaches to suppress the non-resonant background
stainless steel chamber that can be filled with the desired gas
signal such as polarization coherent anti-Stokes Raman
or evacuated in case of vacuum condition [60].
scattering (P-CARS) microscopy, frequency-modulation
D. Coherent anti-Stokes Raman Spectroscopy (CARS) CARS and heterodyne CARS [66,67]. In 2009, a new
Coherent anti-stoke Raman scattering spectroscopy known approach was reported using a single-shot interferometric
as CARS is a nonlinear Raman technique that used to enhance [68]. Time-resolved CARS microscopy (T-CARS) is another
the Raman signal [61]. As the name indicated, it uses coherent approach to improve signal to noise ratio based on using the
laser beams to generate a signal with frequency higher than Raman free induction decay of molecular vibrations [69].
the excitation frequency, therefore it is considered as Among the developments in CARS study, nanosecond,
anti-stoke frequency technique. The initial idea of CARS is picosecond and femtosecond laser-based CARS techniques
contributed to P.D. Maker and R.W. Terhune who described were used and reviewed extensively by many groups [67,70].
it as a three wave mixing process [4]. However, the first There are two types of CARS, single and multiplex
CARS construction is assigned to Duncan et al in 1982 [62]. frequency CARS [64,69]. While the first one concern
Later on, in 1999 CARS have witnessed a major improvement individual vibrational resonance, the latter covers a broad
by replacing the visible dye laser source with near infrared range of vibrational resonance. As a result, multiplex CARS
laser beams [63]. are slower, but provide more spectral information than single
The main principle of this technique is based on using frequency CARS. Single frequency CARS record the
multiple excitation laser sources [64]. It involves pump response from each location of the sample at the specified
coherent monochromatic field at frequency of ωp, and stoke frequency, therefore it is used in qualitative analysis to save
excitation field at frequency of ωS, overlapping spatially and time, while multiplex frequency is preferred in quantitative
temporally. When the incident light is focused on the sample approaches [64]. With respect to the quantitative use of
at small focal volume and probed by a third laser beam, a CARS. Several methods have been developed by researchers
strong anti-stoke Raman signal is created at blue shifted to gain quantitative information from CARS. These methods
frequency away from fluorescence effects and in the face include experimental as well as mathematical approach, but
matching direction [4,61,65]. A strong signal is created with generally can be classified into two groups, phase extraction
frequency of ωas = 2 ωp – ωS, when the difference in the and separation of the resonant and non-resonant responses.
frequency of the incident light, Δω = ωp – ωS, is tuned to the An extensive review and comparison of these methods
Raman active molecular vibration of the sample Ωvib [61]. advantages and limitations was provided by James and his
Hence, CARS are able to provide information about the group [64,71].

53 www.erpublication.org
 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869 (O) 2454-4698 (P), Volume-6, Issue-1, September 2016
CARS is an anticipated alternative to spontaneous Raman E. Stimulated Raman Scattering (SRS)
spectroscopy. It offers high sensitivity, chemical specificity in SRS is another nonlinear process stands for simulated
addition to excellent spatial and spectral resolution Raman Spectroscopy [80]. It was discovered by accident in
[61,66,72]. Due to the coherent nature of Raman 1962 when Woodbury and Ng observed an increase in
spectroscopy, a strong signal is generated with a sensitivity of radiation intensity without knowing its source [81]. Later on,
around 5 orders of magnitude more than spontaneous Raman Eckhardt attributed this increase to two photon process and
[63]. Accordingly, CARS require lower excitation power than simulated Raman scattering [82]. He proved that through his
conventional Raman and hence CARS can be noninvasive and experiments. On the other hand, theoretical description was
tolerable by sensitive biological samples [4,73]. Another provided by Healthwarth [82]. A short time after this early
advantage is the fact that CARS can help in monitoring discovery, a lot of experiments conducted and SRS was used
dynamic biological process due to the fast speed imaging that in the analysis of atomic and molecular gases, liquids and
approach video rate speed. Conor L. Evans combined the solids [83]. The basic principle of this coherent phenomena is
CARS with video rate microscopy and investigated the based on the incident of two photons (pump and stoke) like
possibility of in-vivo chemical imaging of lipid-rich tissue CARS principle [84]. The two laser beams coincide on the
[74]. The results were promising as image were obtained at sample. When the frequency difference matches the
high speed and with high contrast. Moreover, the nonlinear molecular vibration frequency of a bond in the target
excitation of CARS and the signal generated only at the focal molecule, this will induce simulated excitation in the
spot gives CARS its intrinsic three dimensional sectioning vibrational transition. Consequently, this will result in stoke
capability [67]. Among the advantages, CARS signal is blue field amplification where the intensity of the stoke
shifted which means that the signal will be insensitive to experiences a gain and pump- field attenuation where the
fluorescence interference [4,67]. Overall, due to the pump intensity experiences a loss known as stimulated Raman
enormous properties of CARS which range from fast speed to gain (SRG) and stimulated Raman loss (SRL), respectively
depth penetration abilities, CARS are involved in many [84,85]. It should be mentioned that SRS are not identical to
applications and research in recent years. CARS are receiving CARS. Although both are coherent phenomena that based on
special attention from biological researchers due to its two incident photons. The SRS does not have a signal at
structural specificity and no labeling requirement [74,75]. It is frequencies other than the excitation wavelength [84].
used in many live cell or organism studies, including liver, Another difference is that SRS has a linear dependence on
skin and brain tissue imaging as well as lipid metabolism concentration and the resulting spectra match with
[73,76]. Also, it aids in understanding cancer classification spontaneous Raman spectroscopy, making interpretation
and mechanisms [74]. Among the important biological use of much easier than CARS [85]. Also, the SRL and SRG only
CARS is studying drug delivery and distribution [75]. CARS occur if the frequency difference matches a molecular
does not only contribute to animal and human study, but also resonance. As a result, unlike CARS, stimulated Raman
plants. CARS were used to study the distribution of lignin spectroscopy does not have a non-resonant background
within the wall of individual cell of corn Stover [74]. A (background-free) [86]. However, SRS signal is less intense
published review of the recent advances in linear and than CARS signal [84].
nonlinear Raman spectroscopy, reported the use of CARS in Simulated Raman spectroscopy as a coherent Raman
the measurements of temperatures and relative species technique, allows an enhanced real time imaging, overcome
concentrations in gas phase [70]. the low signal intensity of spontaneous Raman spectroscopy
and improve signal to noise ratio [83]. Additionally, the
Although, CARS are mostly known to be used in biological photon flux is directed collinearly with the probe laser, that
and medical application, there are other fields where CARS means that SRS are not sensitive to the background
have shown promising results such as material science [77], fluorescence, since only a small fraction of this fluorescence
catalysis [78] and kinetic reactions [79]. In recently published is emitted collinearly with the probe [87].
review by Iwan W. Schie, some examples about the results of SRS is an attractive imaging tool in the analysis of several
combining CARS with other techniques such as second vibrational bonds. This analysis has aided in the accurate
harmonic generation (SHG) or two-photon excited determination of several bond lengths such as C-F bonds [88].
fluorescence (TPEF) were reported [75]. It has been indicated Its capability has been shown mostly in biological application
that such combination can give further insight to the material such as distribution and uptake of drugs, lipid storage in living
under study. cells and skin tissue analysis [84-86]. As an example,
quantification of lipid components such as cholesteryl ester
There are still some drawbacks that should be solved. One and triacylglycerol has been demonstrated by Fu and
of the main limitation is the non-zero background nature [77]. co-worker using SRS imaging [89]. SRS has also been used in
This is mainly due to the sample and solvent, electronic combination with multivariate curve resolution (MCR) to
origins which contribute to the third order susceptibility, analyze and map a fatty liver tissue [85]. SRS can also be used
hence limiting CARS ideal sensitivity. Although studying in agrochemical and plant study. As an example, Mansfield et
dynamic system is possible by CARS, it is still affected by al. demonstrated the usefulness of using SRS in the analysis of
laser instabilities and signal fluctuations in the small time the components of plant cell wall [90].
scale [67]. Similar to stimulated Raman spectroscopy, Continuous research and strategies aimed at enhancing
ongoing research is trying to simplify CARS in order to SRS. For example, in the initial stage of SRS discovery.
permit its commercialization in the near future [93]. Also, an Narrow-bandwidth dye lasers were used to provide the probe.
active area of research is trying to extend the penetration Later on, it was replaced by broadband Ti: sapphire lasers
depth mainly through adaptive optics [74]. [87]. Among the developments, in 2007, the first femtosecond

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 Raman Spectroscopy, Review

stimulated Raman spectroscopy was reported by Ploetz et al about the molecular composition. Also, it's been used for
[91]. Stimulated Raman spectroscopy has been discovered biological tissues because the optical sectioning avoids the
long time ago, however, their powerful potential in imaging need for any sample preparation and give high spatial
has attracted a lot of recent research interests. Generally, most resolution images [4,99].
research is focused on improving pulse generation, involving In-situ chemical imaging of plant cell wall is possible using
SRS in more application and scaling down the complexity of confocal imaging, also it can directly visualize the variation in
the system. Several examples of recently published cell wall polymer composition. In addition, the technique also
application of SRS can be found in the annual review of enables detection of changes in orientation of the cellulose
Laurence A. Nafie [92]. molecules. [100]. Confocal Raman microscopy has been
found to be very effective to obtain information about the
F. Resonance Raman Spectroscopy (RRS)
molecular composition in relation to skin architecture and can
Resonance Raman spectroscopy is an instrument which be used in different application of skin research [4]. Eugenii
measure the shift in the frequency of the photon when the U. Donev team’s presented the first attempted to measure the
energy of photons from the incident light is approximately structural changes of the nanoparticle vanadium dioxide with
similar to the energy needed for electronic transition [4]. The confocal Raman microscopy. Raman scattering could identify
resonance excitation can increase the oscillation charge the lattice configuration and provide a direct way to obtain a
displacement of electrons. As a result, it will increase the statical information about the distribution of nucleation sites
induced dipole moment, which will directly enhance the [101]. Raman confocal microscopy was used to identify and
efficiency of Raman scattering [6]. The enhancement factor of quantify glycation end product accumulation in ocular tissues.
resonance Raman scattering comparing with normal Raman Tracking pathogenic can be useful to diagnose information
can be high as 108 [6]. It is important to note that fluorescence about a range of diseases such as cataract formation and
is more likely to interfere with resonance Raman more than diabetic retinopathy [102].
non- resonance scattering. Confocal microscopy is a useful technique to analyze local
Fluorescence is one of the challenges that limit the corrosion of metal and can be helpful in understanding
applicability of Raman technique. It was found that using UV corrosion mechanisms [103]. In general, this type of the
resonance Raman spectroscopy for characterization of Raman microscope has proven to be a useful analytical
catalyst reactions and synthesis can eliminate the fluorescence technique. It showed a set of advantages such as high spatial
effect. Most of the catalyst showed fluorescence spectra resolution, clear image quality in addition the sample need no
within the visible region so shifting the excitation laser to the preparation [98].
UV region (λ <300 nm) will help to avoid interferences. Also,
it can enhance the sensitivity of the technique to be used in H. Raman imaging microscopy
many material sciences and biological fields [93,94]. Raman imaging is a technique found first in 1975 by
Resonance Raman spectroscopy can be used to study the Delhaye and Dhamelincourt [104] and it is capable to
structure of hemi protein and the function of human body cell generate a detailed chemical image of the Raman spectrum
[95]. It can help to determine the shapes of potential surfaces [105]. In general, Raman imaging is a combination of Raman
or molecular geometries in excited states [96]. Also, it can be spectroscopy and digital imaging technique [105]. The direct
used for various analyses of biological samples like pigment Raman imaging is a function of Raman intensity and spatial
and enzymes [4]. In addition, it can be used to study food coordinates and the color images are based on material
protein structure [5]. In recent years, resonance Raman molecular composition, phase, structure and crystalline [106].
spectroscopy has been used as a technique to get vibrational As an example of serial imaging approaches are point and
spectra for specific sites in macromolecular systems [97]. line Raman mapping. The difference between the two
examples is the laser involve in scanning proses. Point
G. Confocal Raman microscopy
imaging is involving a spot laser or a raster scanning in x and
The first confocal Raman microscopy was invented by y dimensions and produce a spectrum with two spatial
Marvin Minsky in 1955 [98]. The probe head in Confocal dimensions. In the line mapping approach, the laser line will
Raman Microscopy work on focusing laser light on the scan either in x or y axis [106].
sample through the microscope objective. And the pinhole The technique is widely used in different application that
will refocus the backscattered Raman signal which makes it cover a range of science, such as material science, medicine,
behave as spatial filter. After that the signal will be collected polymer, artwork and semiconductors. It can be used to
on charge coupled device camera (detector) to produce a identify the drugs and toxic materials in forensic science and
spectrum [4]. to analyze or understand the relationship between molecular
Depth profiling with confocal Raman microscopy can be structure of the sample and its functions in biomedical [106].
applied in two ways. The first approach uses plotting of It was proven that an endoscopic Raman probe can
intensity of a specific band as a function of the distance from demonstrate a good ability to provide a rapids and direct
the sample surface. This way can provide information about image based on Raman technique which can be used in
the composition and structure of gradients of the sample. The clinical research and routine endoscopic inspection [107].
second way is to acquire a pure spectrum of buried structures Furthermore, this technique can be used to study the drug
and used for identification determinations. [99]. distribution in living cells like cancer cells. [108,109]. Also
Confocal Raman microscopy is known as ―optical Raman imaging can be used to study plants organs like seeds
sectioning‖ and as non-invasive technique. It can provide an and leaves [110]. Raman imaging techniques can be classified
optical section of tissues without mechanical cutting or to either direct or serial or what is known as raster imaging
physical dissection. Many authors have used confocal Raman techniques. The direct imaging approach at a given
to study the layered system to obtain detailed information wavenumber is where all spatial points in the Raman image

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869 (O) 2454-4698 (P), Volume-6, Issue-1, September 2016
are determined simultaneously from a single measurement of also influence the environment [114]. Although the
globally illuminated sample. While, the raster imaging is development in the industry lead to use multi-phase
where numerous spectra are recorded to construct the entire transportation of oil and gas, which increase the tendency for
Raman image at specific wavenumber [106]. the risk of corrosion, many other factors can affect the
severity and the type of the occurred corrosion [116].
IV. RAMAN VS FT-IR Many factors can influence the corrosion layer formation,
Raman and IR spectroscopy are similar but not identical severity, and properties [114]. Corrosion is mainly affected
techniques. It is true that both are types of vibrational by the air and water content or both of them. Also, many
spectroscopy, which deals with same vibrational energy levels environmental parameters can influence the corrosion
of the material [111]. However, each one of these techniques formation. Most of those parameters related to the chemistry
is based on different ways of interacting with the studied of the water, the change of the temperature or pH, CO2 partial
object and the results are ruled by different principles. pressure, pollution and the presence of H2S, oxygen, and
Generally, Raman scattering depends on the polarization organic acids and the flow type and velocity. High CO2 partial
change, while IR spectroscopy mainly depends on dipole pressure, water chemistry and low pH can increase the
moments change. Also, it was found that Raman spectroscopy severity of the corrosion [115].
can identify different components in sample mixtures much A. Corrosion types
easier than IR spectroscopy due to Raman narrower Corrosion can damage the material and cause a defect or
bandwidth [112]. IR signal is produced upon IR light fault in the industrial system. A simple representation in Fig. 6
absorption. Since this technique uses long wavelength explains the interaction and the definition of faults, defects
excitation, the corresponding spatial resolution is low [61]. and failures [117].
The spatial resolution of IR was reported to be in the range of There are many types of corrosion which can happen to the
2.5-25 μm [64]. Another issue with IR is related to water metals. The following lines will explain each type of
absorption [64,77]. The strong water absorption hinders IR corrosion and method for prevention and control [117].
use in bio-imaging, archeology and other studies that contain Uniform corrosion: The exposed parts of a metal surface to
water or moisture in its studied structure. Such problems were the acids, Aerated fresh water or salt water corrode uniformly
avoided in Raman spectroscopy. This alternative technique leading to weakening the metal layers and then damage those
can use an excitation laser source that works in the visible or parts. Industrial gases can increase the corrosion rate of the
near IR spectral range [64]. Also, Raman cross section metal as an example of those gases Sulfur dioxide, Carbon
scattering is lower than IR absorption. Consequently, Raman dioxide and Nitrogen oxides [118].
is not affected by the presence of air, water or glass and has a Galvanic Corrosion: Galvanic type is a corrosion which
wider, extending applicability range [37,112]. occurs when two dissimilar metals are in contact and
electrochemical series is formed. It requires the presence of
V. CORROSION electrolyte, metallic path in addition to the anodic and
According to DIN EN ISO 8044, corrosion is defined as: cathodic materials. The severity of this corrosion can be
―Physical interaction between a metal and its environment affected by the distance between the active and noble metal,
which results in changes of the metal’s properties and which temperature and the oxygen concentration. It's important to
may lead to significant functional impairment of the metal, the select the structural material and consider an inhibitor to
environment or the technical system of which they form a consume cathodic depolarizers. Also, it will be better to avoid
part.‖ [113]. thread joints and build anodic materials to be easily
There are two types of corrosion reaction: replaceable to reduce the cost of the replacement process
Electrochemical corrosion is the corrosion that includes [113].
reaction between anodic and cathodic parts. Chemical Pitting: is a corrosion that occurs when the protective film
corrosion: reaction of the metal with environment, excluding or the coasting of the materials break down. The exposed, tiny
electrochemical reactions. pits start to react with the environment and a localized
Corrosion is a spontaneous and exothermic process can corrosion form. The depth of the petting usually exceeds its
lead to wear and damage the structure of many industries diameter. [113]. The exposed metal gives up electrons easily,
[113]. The word corrosion is not specified for iron it is used but the actual mechanisms of pitting are not clear. [115]. In
for all materials and even some time nonmaterial things like general, the tendency of pitting can be affected by the
the soul that wear out or damaged because of its instability temperature and carbon dioxide partial
toward a change of air component or flow of waters [114].
In 2013 it was reported that in oil and gas production
industry the total annual cost of corrosion is estimated to be
US$1, 372 billion divided as follows, around $589 million for
pipeline and facilities costs, $463 million annually for
downhole tubing costs, and $320 million for corrosion
management and control costs [115]. In the oil and gas
industry, it is important to use the most effective and sensitive
detection, and control management methods to reduce the
annual cost of corrosion. Corrosion not only affect the
economics of the industries, but also it can affect the safety of
Fig. 6: Interrelation among defects, failures and faults
the worker and the resident life, cause a health hazard by the
Pressure [117].
release of some toxic compound from storage tanks which can

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 Raman Spectroscopy, Review

Schmitt and coworkers studied the effects of temperature, Cl– (3)

concentration, the nature of anions and cations on pitting Sweet corrosion is affected by many environmental
corrosion. [116]. The severity of pitting corrosion can be parameters. Chemistry of the water, pH of solution,
control be selecting the best resistant material and controlling temperature [115], CO2 partial pressure and presence of H2S
the chemistry of fluid [118]. [119] and the chemistry of metal of alloy [115]. Situ pH — pH
Crevice corrosion: Crevice is a highly localized corrosion of the solution can influence the precipitation and dissolution
process start with an oxygen concentration reduction followed of iron and effect the corrosion rates [116]. The effect of H2S
by a reduction in the pH of the system and an increase in the — H2S can either increase rate of CO2 corrosion by affecting
concentration of chloride ions. The process usually happened the pH or decrease it by forming sulfide scale as a protective
under the deposits, in the voids or gaps between metals and in layer. The presence of organic acids influences the sweet
the dead ends which make it difficult to be noticed or corrosion because it reduces the protectiveness of the films. In
detected. Corrosion occurs rapidly and lead to the breakdown addition to environmental parameter, several physical
of the passive film as a result of high oxygen demand. To parameters can affect the rate and the severity of CO2
prevent crevice corrosion or reduce it using welds instead of Corrosion. Theses physical parameter includes wax [116],
bolts is required. Also, avoiding sharp corners and using crude oil [120] and fluid dynamics which is part of the oil and
sealant and blast resistant materials can help in the controlling gas industry [116].
process [118]. Microbial Corrosion: is the degradation of materials as the
De-alloying: This is the type of corrosion which affect the result of the presence of fungi, molds and bacteria or their
alloy materials when the combination of its component have a by-products. It can attack the material itself of the coating
large difference in its activity. It depends on flow rate and the layers by acid by-products, sulfur, hydrogen sulfide or
concentration of oxygen. The problem with detection this type ammonia [118].
of corrosion is that it doesn’t change the metal appearance,
may be it will result in small differences in the volume, but if a B. Corrosion detection methods
cross section from the alloy is studied it will reveal the change Predication models are developed for oil and gas industry
in its color [118]. to predict CO2 corrosion in its pipelines. These models are
Environmental Cracking: either based on empirical correlations with laboratory results
Hydrogen damage: (Hydrogen-Induced Cracking (HIC) of field data or based on mechanistic modeling of different
and Hydrogen Embrittlement (HE)): Hydrogen can damage process of CO2 corrosion. The main problem with those
metal by different mechanisms. Hydrogen ion adsorbs onto predication models is that it can predict low corrosion rate
the metal and then form a neutral hydrogen atom which while the actual situation is very high in the field. Also, it can
combine with H radical and form hydrogen gas (H2). The give false information that the corrosion rate is very high
small size hydrogen ions and gas particle will migrate to while it is not the case and affect the production process
defect parts and damage metal, cause blistering or cracks in [121]. The corrosion inspection and monitoring is very
the presence of tensile stresses, especially in the high hardness important to give accurate information about the situation.
area of the metal [113]. As a result of hydrogen induced Non- destructive evaluation techniques are the most favorable
cracking and damage a sudden loss in the strength of the method for industry to get critical information about the
structure will happen. To avoid or reduce this type of system. Many inspection techniques were used for corrosion
corrosion it’s important to use hydrogen free material or evaluation like the visual inspection, electromagnetic,
remove hydrogen in the metal by backing [118]. thermographic inspection and ultrasonic system. [117].
(H2S) Sulfide Stress Corrosion Cracking: It was found that Visual inspection requires human staff to enter the pipeline
the presence of hydrogen sulfide (H2S) can be one of the looking for evidence of corrosion [122]. Ultrasound
reasons to initiate the corrosion process specially in oil and evaluation is done using a beam of sound waves. The sound
gas industry. The formation of hydrogen sulfide can be by wave is reflected as a result of the change of the density of the
product of the industrial process or from microbial action. material. One of the limitation of this technique, it requires an
[115]. H2S reacts with Iron to form Iron Sulfides and accesses and complete cleaning of the pipe before inspection
Hydrogen. [122]. Some industries usually run the inspection for
CO2 Corrosion: sweet corrosion is the most dominant corrosion using CCTV (closed-circuit TV) cameras. The
form of corrosion that face the oil and gas industry [115]. The technique is lacking the visibility in the interior of pipes and
first case of sweet corrosion was recorded in U.S. oil and gas the image is poor in quality because of the difficult lighting
industry in 1940s in gas wells located in Texas. [116]. The conditions inside the pipes [123]. A physical sensor based on
mechanism of CO2 corrosion is complex and need further reflectance theory and experimental data is more accurate
work [116]. In general, dry CO2 is noncorrosive to steels and than CCTV. The sensor intensity can be extracted to give a
alloys so first CO2 dissolve in water to promote an map image for the internal side of the pipe in addition to the
electrochemical reaction and form carbonic acid [115, 116]. ability to sense the defect parts [123]. Now a days using
Iron carbonate can be formed on the steel surface and then Raman Technology for corrosion inspection can save time
when it precipitates it can act as a protective layer. The and money for oil and gas industry.
protective layer can be destroyed as a result of environmental
condition and the presence of H2S and a localized corrosion VI. APPLICATION OF RAMAN IN CORROSION
can take place as (1) (2) and (3). [116]
Numerous techniques have been employed to measure and
(1) study the corrosion of the steel surface like X-ray
(2) Photoelectron spectroscopy (XPS) [124], secondary ion mass
spectrometry (SIMS) [125], atomic force microscopy [126],

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869 (O) 2454-4698 (P), Volume-6, Issue-1, September 2016
and Raman spectroscopy [127]. Most of the available corrosion products formed in the presence of chlorine and
corrosion detection techniques require extensive sample sulfate [11]. Earlier studies by Reguer and coworkers [140]
preparation methods, it also can’t be used in aqueous investigated the Chloride containing corrosion products. Nie
condition [128]. This is the advantage of using Raman and coworkers [138] worked on the corrosion of carbon steel
spectroscopy for the characterization of corrosion where no in seashore saltysoils with different water content. Earlier
extensive sample preparation is needed and it can be study by S. Savoye et al. Reported the nature of corrosion
employed under aqueous conditions. Raman spectroscopy products formed in the presence of carbonate and oxygen
also offers the advantage of identifying hydrogen bonds, using Raman spectroscopy [137].
which is difficult with standard characterization methods such Delphin Neff with co-workers have devoted a lot of their
as XPS (X-Ray photoelectron spectroscopy) [128]. research work to the analysis of corrosion products using
Generally, Raman spectroscopy is widely used in unknown Raman spectroscopy [132,141-143]. Most of their studies
identification and characterization because it depends on the were performed on archaeological iron artifact samples. An
intrinsic vibrational modes in the studied material. Therefore, interesting work published by Judith Monneir from the same
Raman is considered as an extraordinary finger printing tool group [144]. The work introduced a technique for extracting
that provides a large number of information applicable for quantitative parameters from the Raman hyperspectral map
condensed, gas phase and even non-crystalline metals using LADIR-CAT software. This approach was established
[112,129]. specifically for the iron corrosion study. The results obtained
A nice example of Raman efficiency in corrosion study was from De Faria et al. [145] investigation showed that
done by De Faria et al [130]. The corrosion products of steel increasing the laser power can cause a change in the corrosion
were identified using a Raman spectrometer with laser light at spectra were a hematite characteristic bands show up in the
532nm and at low powers from 0.025 to 0.25mw and laser spectra of the most of
light at 633nm at higher power between 2.5 and 25 Mw. The
corrosion products found to be iron oxy hydroxides, goethite
and lepidocrocite. Also, it was found that some corrosion
product will give higher and sharper peaks when the laser
powers increased to 0.25 and 0.5 mW such as goethite [130].
Many studies have indicated that corrosion products are
usually composed of several iron oxide layers [131-135].
Among corrosion products discussed previously, rust
products in carbon and weathering steel have received a wide
attention due to their widespread and severe effects on
pipeline, instruments and ancient artifact lifetime. Rust forms Fig. 7: Raman imaging results indicating a comparison
thick layers over time and its composition can differ between qualitative and semi-quantitative results from
depending on the environment condition such as atmospheric, spectral decomposition
aerated or anoxic soils surroundings [136]. Also, the type of
materials and other factors like the presence of chloride ions,
pH and temperature can lead to different compositions [137].
For example, Xin Zhang identified the outer layers which is in
contact with the environment is composed of lepidocrocite
(ɤ-FeOOH), while goethite (α-FeOOH) or magnetite (Fe3O4)
can form in the inner parts according to the corrosion
conditions [11]. On the other hand, a study by Xianhai Nie has
indicated α-FeOOH formation in the inner layer of carbon
steel, while the outer layer consists mainly of Fe2O3 and Fe3O4
under salty soil environmental [138]. Generally, it is believed
that α-FeOOH is the initial corrosion product in steel which
can transfer to other form according to the conditions [138].
Here will focus on some literature studies on iron
corrosion, including different oxides and hydroxides using
Raman spectroscopy techniques. A nice recent study by
Ludovic Bellot- Gurlet has reported the investigation of iron
Fig. 8: Raman spectra of some iron corrosion products
corrosion products under different environments [136]. In
obtained at 532 nm and power <100 µW
addition, a quantitative phase proportion was studied as can
be seen in Fig. 7. Similarly, in 2015 Toshiaki Ohtsuka
monitored the rust layer formation on weathering steels under
the oxides and oxyhydroxides studied in his work. The laser
alternating environment of wet and dry conditions for a long
power is a very important parameter which affects the
time (144 hours) and under the presence of sodium chloride
obtained spectrum significantly. El Mendili et al. [146] found
deposits to represent the coastal environment [139]. Initially,
that the vibration modes attributed to the hematite become
lepidocrocite and magnetite were identified. Later on, other
stronger with increasing the laser power and the thermal
phases were identified, such as akaganeite in the presence of
treatment. Singh et al [147] on the other hand, found that the
NaCl, which is known to reduce the rust protection property.
noise in the Raman spectrum increased when the laser power
Several groups have performed research on the effect of
become less than 1.5m W. It is important to differentiate if
different conditions. As an example Xin Zhang studied the

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 Raman Spectroscopy, Review

hematite peaks produced from laser irradiation (http://rdrs.uaic.ro/minerals/hematite.html) is another

transformation or is it a component of corrosion products. extensive source for a large mineral and pigments database.
Several other papers have been reported on the The site not only offer Raman spectra, but also give
investigation of different iron oxides with Raman information about the crystal structure and sample image. The
spectroscopy and provide a large number of spectra that can other interesting database is reviewed by Peter Vandenabeele
be used as reference material [148-152]. An example of and his team [164]. Another method for comparing spectral
representative Raman spectra of the most common phases of database are provided by HORIBA Scientific. It offers an
iron corrosion products can be seen in Fig. 8 [136]. extensive database searching package covering over 1500
Unlike pure iron, very little investigation has been done on spectra in different materials not only minerals. It is provided
the characterization and identification of corrosion products with advance features allowing correlation between the
in other materials such as AISI-4340 steel or Tin [128]. P. spectral peaks and the expected responsible functional group
Eckold et al [153] used confocal ―Horiba Lab ARAMIS‖ [165].
Raman microscope to detect Sn3O2(OH)2−xClx phases as
intermediates in tin corrosion. The Raman spectra were Table 1: Raman fingerprint of main corrosion products [159]
processed using Origin 8.0 and Lab Spec version 5.25.15 Characteristic
Compound Formula
software. wavenumber
The developed corrosion cell is consisting of a glass Wustite FeO 655
chamber equipped with specimen holder and sapphire Hematite Fe2O3/ corundum 1320,290,220
window and then implemented within the Raman Magnetite Fe3O4/ spinel 670
Maghemite ɤFe2O3x H6/spinel 670-720,~1400
Spectrometer. Ashley C. Stowe [154] showed that Raman
Ferrihydrite Fe5HO8, 9H2O 710-~1380
spectroscopy is an effective complementary method to detect
Goethite αFeOOH 390
lithium hydride corrosion since Li2O vibrations are Raman
Lepidocrocite ɤFeOOH 250-1300
active. Also found that using UV laser wavelengths to excite Akaganeite β FeOOH (Cl) 310,390,720
the sample will solve the fluorescence interferences while Ferooxyhyte ɤFeOH 680,~1350
allowing all of the spectral features from LiH, LiOH, and Li2O Hydroxychloride β Fe2 (OH) 3Cl 160,423
to be observed. Thiago S. Puglieri and his coworker [155] Green rust 430-510
investigated the effect of relative humidity (RH) and Iron chloride FeCl2 610
formaldehyde (H2CO) concentration on Pb corrosion. Raman Zinc chloride ZnCl2 80,248
images for the study were obtained using laser line from Zinc Oxide ZnO 100,540-580
He-Ne and diode laser respectively, and the laser power was Zinc hydroxide Zn (OH)2 470
below 1.5 mW to avoid degradation [155]. In situ Raman Zinc carbonate ZnCO3 1095,370
spectroscopy was also used to study the hydrothermal White rust 3Zn (OH)2 2ZnCO3 1050,385
corrosion of a zirconium- niobium alloy at temperatures 4Zn (OH)2 ZnCl2
White rust 910,3455-3486
ranging from 22 to 407⁰C [156]. Spectra of the synthesized (OH)4. H2O
Zn (OH)4
uranium compounds U (VI) were recorded to make the White rust 955,208,292
Cl2SO4.5H2O
Raman spectral library to use it to investigate the unidentified ZnSO4.3Zn (OH) 2.
materials on the corroded samples [157]. Copper corrosion White rust 961,1007,463
3H2O
was studied by R. L. Frost [158]. He reported and identified Zinc phosphate ZnPO4 996
the different copper minerals identified by their characteristic Zinc phosphate Zn3 (PO4)2H2O 1055,1150
Raman spectra. Other corrosion products were studied by Manganese oxide MnO2 ~600
other groups such as Mg, Zn and Cr oxides as indicated in Nickel oxide NiO ~510
Table 1 [159]. Chromium oxide Cr2O3 351,551,609
Chromium CrOOH (Cr2O3, n
485
VII. RAMAN DATABASE hydroxide H2O)
Raman identification is based on comparing the unknown Machinawite FeS ~280-300
Greigite Fe3S4 ~350-360
spectra, which is characteristic to the material structure and
bonds, with reference known materials [112]. As a result, the
availability of such references is important to facilitate the Although, noteworthy improvements have been made in
analysis of materials. In addition, it offers a quicker way to the construction of the database reference library. Further
identify the material and hence extend the use of Raman work is needed to unify and provide a full spectra database
techniques in a wide range of application. The need for that allow comparisons between the results obtained in
establishing a spectral database for different material inspired different laboratories. It should be noted Raman spectra
the work of many research groups [160-163]. comparison can be tricky and should be handled carefully.
Beside the different publications, nowadays there are Difference in laser source wavelength, crystal orientation,
digital, searchable libraries that offer an easy access to a wide different calibration method can lead to some difference
range of materials including pigments, resin and minerals between the compared spectra. In addition, the different data
[164]. For example, RRUFF project website reporting method can lead to apparent spectral differences
(http://rruff.info/) offers a wide range of good quality spectra [136,164].
of different minerals. Handbook of Minerals Raman Spectra
(http://www.ens-lyon.fr/LST/Raman/index.php), is another VIII. CONCLUSION
nice online, spectral database, but have limited number of Raman spectroscopy is a well-known powerful analytical tool
spectra. Romanian Database of Raman Spectroscopy-website that become increasingly important in recent years. The main

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 International Journal of Engineering and Technical Research (IJETR)
ISSN: 2321-0869 (O) 2454-4698 (P), Volume-6, Issue-1, September 2016
aim of this review is to present a comprehensive yet simple analytical chemistry potential. analytica chimica acta, 606(2),
119-134.
overview of Raman spectroscopy. After discussing the main
[4] Das, R. S., Agrawal, Y. K. (2011). Raman spectroscopy: recent
Raman principle, instrumentation as well as its history and advancements, techniques and applications. Vibrational Spectroscopy,
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[6] Asher, S. A. (1993). UV resonance Raman spectroscopy for analytical,
scattering (CARS), Tip enhanced Raman scattering (TERS), physical, and biophysical chemistry. Analytical chemistry, 65(4),
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overcoming its limitation through different approaches. In 603(10), 1328-1334.
[8] Kudelski, A. (2008). Analytical applications of Raman spectroscopy.
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possible by CARS. Using TERS, quantitative approach and Surface-enhanced Raman spectroscopy. Analytical Chemistry, 77(17),
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through sub-diffraction imaging. SERS improved Raman Rapid detection of an anthrax biomarker by surface-enhanced Raman
sensitivity by several orders of magnitude involving a spectroscopy. Journal of the American Chemical Society, 127(12),
substrate material. Many other properties such as 4484-4489.
reproducibility and selectivity has been improved through the [11] Zhang, X., Xiao, K., Dong, C., Wu, J., Li, X., Huang, Y. (2011). In situ
Raman spectroscopy study of corrosion products on the surface of
different techniques opening new application opportunities carbon steel in solution containing Cl− and. Engineering Failure
for Raman spectroscopy. The basic, advantages and Analysis, 18(8), 1981-1989.
limitations of each type of Raman subsets were highlighted. [12] Ferraro, J. R. (2003). Introductory raman spectroscopy. Academic
Nice examples on the applications of each type have been press.
[13] Driscoll, A. J., Harpster, M. H., Johnson, P. A. (2013). The
given. The wide range of application field ranging from development of surface-enhanced Raman scattering as a detection
biology and medical application to forensic and archeology, modality for portable in vitro diagnostics: progress and challenges.
demonstrated the great potential of Raman technique that will Physical Chemistry Chemical Physics, 15(47), 20415-20433.
continually increase in the future. Raman imaging and [14] Sharma, B., Frontiera, R. R., Henry, A. I., Ringe, E., Van Duyne, R. P.
(2012). SERS: materials, applications, and the future. Materials today,
confocal Raman spectroscopy has been also discussed. In this
15(1), 16-25.
work, we focused in the second part of this review on [15] Schatz, G. C. (2001). Electrodynamics of nonspherical noble metal
providing a detailed investigation highlighting the importance nanoparticles and nanoparticle aggregates. Journal of Molecular
and the state of the art of Raman application in corrosion Structure: THEOCHEM, 573(1), 73-80.
study. After a brief summary about corrosion type, causes and [16] Zeisel, D., Deckert, V., Zenobi, R., Vo-Dinh, T. (1998). Near-field
surface-enhanced Raman spectroscopy of dye molecules adsorbed on
effects. We demonstrated a lot of great publications related to silver island films. chemical Physics letters, 283(5), 381-385.
Raman spectroscopy and corrosion. However, we found that [17] Li, W. H., Li, X. Y., Yu, N. T. (1999). Surface-enhanced resonance
most of these works are based on spontaneous Raman hyper-Raman scattering and surface-enhanced resonance Raman
spectroscopy. We believe that further involvement of advance scattering of dyes adsorbed on silver electrode and silver colloid: a
comparison study. Chemical physics letters, 312(1), 28-36.
Raman techniques in corrosion study can provide a great [18] Cialla, D., März, A., Böhme, R., Theil, F., Weber, K., Schmitt, M.,
contribution to corrosion field study. Especially, with the Popp, J. (2012). Surface-enhanced Raman spectroscopy (SERS):
latest developments of charge-coupled device (CCD) chips, progress and trends. Analytical and bioanalytical chemistry, 403(1),
filter technologies and analysis software which makes 27-54.
[19] Li, J. F., Huang, Y. F., Ding, Y., Yang, Z. L., Li, S. B., Zhou, X. S.,
portable Raman instruments and even real time video Wang, Z. L. (2010). Shell-isolated nanoparticle-enhanced Raman
possible. Generally, from this review, it is clear that despite spectroscopy. nature, 464(7287), 392-395.
the fact that all these techniques can still have some [20] Betz, J. F., Wei, W. Y., Cheng, Y., White, I. M.,Rubloff, G. W. (2014).
limitations, especially in regard to the system complexity and Simple SERS substrates: powerful, portable, and full of potential.
Physical Chemistry Chemical Physics, 16(6), 2224-2239.
fluorescence interferences, the continuous research interest in [21] Love, S. A., Marquis, B. J., Haynes, C. L. (2008). Recent advances in
Raman techniques can ensure its successful improvements nanomaterial plasmonics: fundamental studies and applications. Appl
and importance in the near future. Spectrosc, 62(12), 346A-362A.
[22] Lin, X. M., Cui, Y., Xu, Y. H., Ren, B., Tian, Z. Q. (2009).
Surface-enhanced Raman spectroscopy: substrate-related issues.
ACKNOWLEDGEMENTS Analytical and bioanalytical chemistry, 394(7), 1729-1745.
This work was supported by Abu Dhabi National Oil [23] Brown, R. J., Milton, M. J. (2008). Nanostructures and nanostructured
Company (ADNOC) Gas Sub Committee (GSC), Abu Dhabi, substrates for surface—enhanced Raman scattering (SERS). Journal of
Raman Spectroscopy, 39(10), 1313-1326.
UAE project Number 14703 with the work carried out at the [24] Banholzer, M. J., Millstone, J. E., Qin, L., Mirkin, C. A. (2008).
Petroleum Institute, Abu Dhabi, UAE. The authors thank the Rationally designed nanostructures for surface-enhanced Raman
GSC for their support. We also appreciate Nannan Li’s spectroscopy. Chemical Society Reviews, 37(5), 885-897.
assistance with the manuscript. [25] Halvorson, R. A., Vikesland, P. J. (2010). Surface-enhanced Raman
spectroscopy (SERS) for environmental analyses. Environmental
science & technology, 44(20), 7749-7755.
[26] Gruenke, N. L., Cardinal, M. F., McAnally, M. O., Frontiera, R. R.,
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especially on corroded metals and coloured glass. Spectrochimica Acta
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an/SO-TN02_- _Searching_spectral_databases_with_LabSpec_6.pdf

Dr Paul Rostron is professor of Chemistry and

Corrosion at the Petroleum Institute, ADNOC’s University and Research
Center. He has taught courses, both undergraduate and post graduate in
Chemistry and in Corrosion for more than 20 Years, as well as conducting
masterclasses in corrosion globally. Current research topics include the
synthesis of novel corrosion inhibitors, mitigation of biofouling,
atmospheric corrosion mapping, and is building a flow – loop for corrosion
in pipeline studies. Currently he is a member of the Board of Directors for
NACE UAE section, and was recently chairman of the section as well as a
member of the Institute of Corrosion and Chartered Chemist of the Royal
Society of Chemistry.

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