Shaumik Ray

Terahertz Spectroscopy and Solid-State Density Functional Theory Calculations of Cyanobenzaldehyde Isomers

Spectral signatures in the terahertz (THz) frequency region are mainly due to bulk vibrations of the molecules. These resonances are highly sensitive to the relative position of atoms in a molecule as well as the crystal packing arrangement. To understand the variation of THz resonances, THz spectra (2-10 THz) of three structural isomers: 2-, 3-, and 4-cyanobenzaldehyde have been studied. THz spectra obtained from Fourier transform infrared (FTIR) spectrometry of these isomers show that the resonances are distinctly different especially below 5 THz. For understanding the intermolecular interactions due to hydrogen bonds, four molecule cluster simulations of each of the isomers have been carried out using the B3LYP density functional with the 6-31G(d,p) basis set in Gaussian09 software and the compliance constants are obtained. However, to understand the exact reason behind the observed resonances, simulation of each isomer considering the full crystal structure is essential. The crystal structure of each isomer has been determined using X-ray diffraction (XRD) analysis for carrying out crystal structure simulations. Density functional theory (DFT) simulations using CRYSTAL14 software, utilizing the hybrid density functional B3LYP, have been carried out to understand the vibrational modes. The bond lengths and bond angles from the optimized structures are compared with the XRD results in terms of root-mean-square-deviation (RMSD) values. Very low RMSD values confirm the overall accuracy of the results. The simulations are able to predict most of the spectral features exhibited by the isomers. The results show that low frequency modes (<3 THz) are mediated through hydrogen bonds and are dominated by intermolecular vibrations.

Non-destructive evaluation of GFRP-wood sandwich structure composite using terahertz imaging

Engineering of novel structures with high strength to weight ratio for applications in aerospace, renewable energy and naval industries has resulted in an increased popularity of sandwich structured composites. A sandwich-structured composite is fabricated by bonding a thick lightweight core between two stiff, thin skins such as Glass Fiber Reinforced Plastic (GFRP). Balsawood is a type of homogeneous core which is widely used for renewable energy structures, such as wind turbine blades. In this paper, a GFRP-balsawood sandwich structure is evaluated non-destructively for internal defects such as holes, using a CW Terahertz system in transmission mode. Internal defects will give rise to differential THz transmission and hence can be identified using THz imaging. The imaging studies are carried out with a central frequency of 0.35 THz and the sample is raster scanned using 2-D translational stages controlled by high precision stepper motors in x-y directions to obtain the THz image. The image acquired using CW THz system clearly identifies the defects in the GFRP-balsawood composite structure with good contrast demonstrating the potential of THz imaging for non-destructive testing of sandwich composite structures.

Terahertz Spectroscopy of Concrete for Evaluating the Critical Hydration Level

Concrete, a mixture of cement, coarse aggregate, sand and filler material (if any), is widely used in the construction industry. Cement, mainly composed of Tricalcium Silicate (C3S) and Dicalcium Silicate (C2S) reacts readily with water, a process known as hydration. The hydration process forms a solid material known as hardened cement paste which is mainly composed of Calcium Silicate Hydrate (C-S-H), Calcium Hydroxide and Calcium Carbonate. To quantify the critical hydration level, an accurate and fast technique is highly desired. However, in conventional XRD technique, the peaks of the constituents of anhydrated and hydrated cement cannot be resolved properly, where as Mid-infrared (MIR) spectroscopy has low penetration depth and hence cannot be used to determine the hydration level of thicker concrete samples easily. Further, MIR spectroscopy cannot be used to effectively track the formation of Calcium Hydroxide, a key by-product during the hydration process. This paper describes a promising approach to quantify the hydration dynamics of cement using Terahertz (THz) spectroscopy. This technique has been employed to track the time dependent reaction mechanism of the key constituents of cement that react with water and form the products in the hydrated cement, viz., C-S-H, Calcium Hydroxide and Calcium Carbonate. This study helps in providing an improved understanding on the hydration kinetics of cement and also to optimise the physio-mechanical characteristics of concrete.

Understanding the effect of nanosilica incorporation on dicalcium silicate hydration using terahertz spectroscopy

Ordinary Portland Cement (OPC) primarily constitutes Tricalcium Silicate (C3S) and Dicalcium Silicate (C2S) making up 60–70 % and 20–30 % of the cement matrix respectively. During cement hydration, C3S starts to react faster contributing to early stage strength in comparison to C2S, which reacts slowly and is responsible for long term strength development of concrete. C2S is manufactured at lower temperatures compared to C3S, resulting in lesser emission of carbon dioxide as compared to C3S. Moreover, C2S produces less Ca(OH)2 than C3S, which is an undesirable hydration product. Thus, incorporation of greater percentages of C2S in cement matrix will be highly beneficial, provided it’s early stage reactivity can be increased. One of the key methods to increase reactivity of C2S is incorporating nanosilica which accelerates the hydration along with the formation of greater amount of calcium silicate hydrate (C-S-H) which is responsible for the strength development of concrete. Hence, understanding the acceleration in hydration dynamics of the nanosilica incorporated β-C2S can help in optimizing the percentages of C3S and C2S in cement. In this study, Terahertz spectroscopy has been employed to track the acceleration of hydration of C2S due to the addition of nanosilica. Results show early stage reduction in peak height of the resonance around 520 cm-1 in nanosilica incorporated sample which indicates faster hydration of C2S during hydration. Furthermore, early stage formation of a prominent resonance around 453 cm-1 for the nanosilica incorporated C2S sample implies formation of C-S-H like structures confirming the accelerated hydration rate.

Thickness measurement of tablet coating using continuous-wave terahertz reflection spectroscopy

THz rays have higher penetration depth compared to infrared rays and hence can be effectively used to measure tablet coating thickness. In addition, THz wavelength (1 mm - 0.1 mm) provides an optimal depth resolution for the thickness measurement. This method can be non-invasive and hence ideal for inline quality monitoring. Tablet coating thickness is one of the major parameters of interest in Process Analytical Technology (PAT). In this paper, a reflection mode Continuous Wave (CW) Terahertz (THz) system has been employed to measure the tablet coating thickness. A frequency scan of the sample has been carried out from 0.1 THz to 1.1 THz and the reflection coefficient of the sample is inverse fourier transformed to obtain the tablet thickness. The calculated thickness has also been validated using the optical microscope. Results show that the thickness can be measured with considerable accuracy.

Enhancement of water retention in UV-exposed fuel-cell proton exchange membranes studied using terahertz spectroscopy

Proton Exchange Membrane (PEM) fuel cells are increasingly gaining importance as a clean energy source. PEMs need to possess high proton conductivity and should be chemically and mechanically stable in the fuel cell environment. Proton conductivity of PEM in fuel cells is directly proportional to water content in the membrane. Among the various PEMs available, Nafion has high proton conductivity even with low water content compared to SPEEK (Sulfonated Poly(ether ether ketone)) but is also expensive. SPEEK membranes and it’s composites have better mechanical properties and have comparatively higher thermal stability. Operating the fuel cell at higher temperatures and at the same time maintaining the water content of the membrane is always a great challenge. In this paper, to increase water retention capacity, Nafion, SPEEK and it’s composite (SPEEK PSSA-CNT) membranes are exposed to Ultra-Violet (UV) radiation for varied times. Terahertz Spectroscopy, in both pulsed and CW mode has been used as an efficient tool to quantify the water retention of the membrane. Results using Terahertz spectroscopy show that even though the initial water absorption capacity of Nafion membranes is more, SPEEK membranes and it’s composites show considerable improvement in the water retention capacity upon high intensity UV irradiation.

Enhancing the low frequency THz resonances (< 1 THz) of organic molecules via electronegative atom substitution

Terahertz (THz) technology is an active area of research with various applications in non-intrusive imaging and spectroscopy. Very few organic molecules have significant resonances below 1 THz. Understanding the origin of low frequency THz modes in these molecules and their absence in other molecules could be extremely important in design and engineering molecules with low frequency THz resonances. These engineered molecules can be used as THz tags for anti-counterfeiting applications. Studies show that low frequency THz resonances are commonly observed in molecules having higher molecular mass and weak intermolecular hydrogen bonds. In this paper, we have explored the possibility of enhancing the strength of THz resonances below 1 THz through electronegative atom substitution. Adding an electronegative atom helps in achieving higher hydrogen bond strength to enhance the resonances below 1 THz. Here acetanilide has been used as a model system. THz-Time Domain Spectroscopy (THz-TDS) results show that acetanilide has a small peak observed below 1 THz. Acetanilide can be converted to 2-fluoroacetanilide by adding an electronegative atom, fluorine, which doesn’t have any prominent peak below 1 THz. However, by optimally choosing the position of the electronegative atom as in 4-fluoroacetanilide, a significant THz resonance at 0.86 THz is observed. The origin of low frequency resonances can be understood by carrying out Density Functional Theory (DFT) simulations of full crystal structure. These studies show that adding an electronegative atom to the organic molecules at an optimized position can result in significantly enhanced resonances below 1 THz.

Hydration kinetics of cement composites with varying water-cement ratio using terahertz spectroscopy

Cement is mixed with water in an optimum ratio to form concrete with desirable mechanical strength and durability. The ability to track the consumption of major cement constituents, viz., Tri- and Dicalcium Silicates (C3S, C2S) reacting with water along with the formation of key hydration products, viz., Calcium-Silicate-Hydrate (C-S-H) which gives the overall strength to the concrete and Calcium Hydroxide (Ca(OH)2), a hydration product which reduces the strength and durability, using an efficient technique is highly desirable. Optimizing the amount of water to be mixed with cement is one of the main parameters which determine the strength of concrete. In this work, THz spectroscopy has been employed to track the variation in hydration kinetics for concrete samples with different water-cement ratios, viz., 0.3, 0.4, 0.5 and 0.6. Results show that for the sample with water-cement ratio of 0.3, significant amount of the C3S and C2S remain unreacted even after the initial hydration period of 28 days while for the cement with water-cement ratio of 0.6, most of the constituents get consumed during this stage. Analysis of the formation of Ca(OH)2 has been done which shows that the concrete sample with water-cement ratio of 0.6 produces the highest amount of Ca(OH)2 due to higher consumption of C3S/C2S in presence of excess water which is not desirable. Samples with water-cement ratio of 0.4 and 0.5 show more controlled reaction during the hydration which can imply formation of an optimized level of desired hydration products resulting in a more mechanically strong and durable concrete.

Terahertz Resonances of Di(pyridin-2-yl)amine: A Detailed Experimental and Computational study

Terahertz spectra of synthesized organic molecule di(pyridine-2-yl)amine have been studied and vibrational modes are explained using Density Functional Theory simulations.Crystal structure simulation confirms that lower terahertz resonances originate due to intermolecular hydrogen bond vibrations.