Showing posts with label Hiromichi Hoshina. Show all posts
Showing posts with label Hiromichi Hoshina. Show all posts

Monday, November 4, 2019

Abstract-Exploring the Dynamics of Bound Water in Nylon Polymers with Terahertz Spectroscopy



 Hiromichi Hoshina,  Takuro Kanemura, Chiko Otani, Michael Ruggiero

https://chemrxiv.org/articles/Exploring_the_Dynamics_of_Bound_Water_in_Nylon_Polymers_with_Terahertz_Spectroscopy/10007027

Terahertz (THz) spectroscopy was used to observe adsorbed water structure and dynamics within polymer films, ultimately providing a strong rationale for the observed rates of water desorption. The THz absorption spectra of nylon-6 films undergoes drastic changes during the hydration and drying process. Additionally, the structural change from g to a crystals, induced by the hydration, was observed by the characteristic band of a-nylon-6 at 6.5 THz. Importantly, the THz spectra of adsorbed water, as well as deuterated water, within in the nylon films were observed by the continuous measurement of a-nylon during dehydration. The differential spectra clearly show three absorption bands of water molecules named Peak I, II and III, which behaved differently between the H2O and D2O materials. The spectra were assigned using a combination of ab initio molecular dynamics simulations and solid-state density functional theory calculations, and were compared to previous spectral assignments of bulk water. The results show that the inclusion of H2O and D2O into polymer films results in a distinct set of spectral features that, while similar in frequencies to the dynamics of bulk water, represent significantly different motions owing to the unique chemical environment within the material. These results highlight the significant utility of using THz spectroscopy to study the hydration dynamics and spectral signature of bound water in this important class of materials.

Monday, November 19, 2018

Abstract-Isothermal crystallization of poly(glycolic acid) studied by terahertz and infrared spectroscopy and SAXS/WAXD simultaneous measurements


Fumita Nishimura, Hiromichi Hoshina, Yukihiro Ozaki & Harumi Sato



https://www.nature.com/articles/s41428-018-0150-7

Isothermal crystallization of poly(glycolic acid) (PGA) has been studied using terahertz (THz) and infrared (IR) spectroscopy and simultaneous small-angle X-ray scattering (SAXS)/wide-angle X-ray diffraction (WAXD) measurements. Changes in the intermolecular interactions in PGA during the isothermal crystallization were monitored using THz spectroscopy, which is an efficient technique for analyzing the higher-order structure of polymers. In the THz spectra, the temporal difference in the intensity observed in the isothermal crystallization is due to the difference in the vibrational origins of two bands at 192 and 65 cm−1. The band at 192 cm−1 primarily originates from the intramolecular vibrational mode (twisting of the local structure of the PGA molecular chain). Furthermore, the band at 65 cm−1 exists due to the intermolecular vibration mode (C = O···H-C hydrogen bonds between polymer chains). In addition, these THz bands appeared after the appearance of the SAXS and WAXD peaks. When a lamellar structure is formed and the molecular chains are oriented, the THz band originating from the intermolecular vibration is observed. It is highly possible that the intermolecular vibration appearing in the THz spectra requires the molecular chains to be oriented.

Sunday, June 24, 2018

Abstract-Structure and dynamics of bound water in poly(ethylene-vinylalcohol) copolymers studied by terahertz spectroscopy




Hiromichi Hoshina, Yoh Iwasaki, Eriko Kometani, Makoto Okamoto, Chiko Otani,

https://www.sciencedirect.com/science/article/pii/S0032386118305135



Poly (ethylene-vinylalcohol) copolymer (EVOH) films under different humidity conditions were studied by THz absorption spectroscopy to obtain information about the bound water. An intermolecular stretching mode of bound water was observed at around 6 THz, similar to that in liquid water; and the very weak libration mode indicates that this water is frozen. By generalized two-dimensional correlation spectroscopy (2DCOS) and perturbation-correlation 2D moving window (PCMW2D) correlation spectroscopy, the bound water was categorized into three types: frozen with amorphous structure (I), liquid-like with librational motion (II), and nearest neighboring water with weaker hydrogen bonding network (III). The strongly inhomogeneous intermolecular stretching band of water I shows that the frozen bound water is amorphous. The frequency shift of this band in water III indicates a weaker hydrogen bonding network around the ethylene group. Changes in the films' oxygen permeability are discussed and correlated with the dynamics of bound water.

Saturday, January 27, 2018

Abstract-Three different kinds of weak C-H⋯O=C inter- and intramolecular interactions in poly(ε-caprolactone) studied by using terahertz spectroscopy, infrared spectroscopy and quantum chemical calculations



Chihiro Funaki, Shigeki Yamamoto, Hiromichi Hoshina, Yukihiro,Ozaki, Harumi Sato




https://www.sciencedirect.com/science/article/pii/S0032386118300260

The long range structure of poly(ε-caprolactone) (PCL) has been studied by terahertz (THz) spectroscopy, infrared (IR) spectroscopy and quantum chemical calculations (QCCs). Natural bond orbital (NBO) analysis and the calculation of the interatomic distances between C-H and O=C groups in PCL crystalline indicate that the PCL chain has three kinds of weak intermolecular interactions between the CH2 and C=O groups. In the IR spectra, significant changes due to the influence of hydrogen bondings were observed in the CH2 and C=O stretching vibration regions. The results of QCCs performed by using the Cartesian Coordinate Tensor Transfer (CCT) method to assign the THz spectra of PCL suggest that the peaks at 47 and 67 cm−1 reflect the atomic motions of the C=O + CH2 moiety derived from the weak C-H⋯O=C hydrogen bondings. THz spectroscopy allows us to observe the intermolecular hydrogen bondings of the polymer separately, since hydrogen bondings with different strengths yield different peaks in a THz spectrum. The results of THz and IR spectral analysis, and QCCs all indicate that PCL forms three kinds of weak intermolecular C-H⋯O=C hydrogen bondings between the CH2 and C=O groups. This may be one of the causes for the low melting temperature but high crystallinity of PCL. There are about six interactions in PCL and about sixteen interactions in polyglycolic acid (PGA), within the lamellar thickness. Therefore, it is suggested that the difference in the number of intermolecular interactions within the lamellar thickness leads to the difference in melting points between the two polymers.

Sunday, January 7, 2018

Abstract-Terahertz Imaging of the Distribution of Crystallinity and Crystalline Orientation in a Poly(ɛ-caprolactone) Film



Chihiro Funaki, Takuya Toyouchi, Hiromichi Hoshina, Yukihiro Ozaki, Harumi Sato,

https://www.osapublishing.org/as/abstract.cfm?uri=as-71-7-1537&origin=search


The distribution of crystallinity and the crystalline orientation of a poly(ɛ-caprolactone) (PCL) film have been studied using terahertz (THz) imaging. Terahertz images were developed by using the intensity ratio of the two spectral peaks at 1.42 and 2.03 THz that are assigned to the crystalline modes parallel and perpendicular to the c-axis (I/I||) of the PCL film. The obtained THz images show that the distribution of crystallinity and crystalline orientation vary considerably between the different regions in the PCL film, even though this inhomogeneity is not visible in the corresponding optical image. Our results clearly illustrate that THz imaging is a promising technique to characterize the physical properties of semi-crystalline polymers.
© 2017 The Author(s)

Saturday, October 17, 2015

Abstract-THz generation from optical rectification tilted-pulse-front pumping scheme with laser pulse focused to a line


Hai-Wei DuHiromichi HoshinaChiko Otani
RIKEN Ctr. for Advanced Photonics (Japan)
Proc. SPIE 9671, AOPC 2015: Advances in Laser Technology and Applications, 96710M (October 15, 2015); doi:10.1117/12.2199229




In this study, we investigate THz pulses generated from optical rectification with tilted-pulse-front pumping scheme in which the laser beam is focused to a line in a stoichiometric lithium niobate (sLN) crystal. A cylindrical lens and a common lens are used to focus the pump laser beam to a line. The power law of THz pulse generation and the redshift induced from the sLN crystal are measured. The spectral shapes of the laser pulse are changed by inserting a filter into the pump laser beam, causing the THz radiation to change. The filter is a metal wire with 2 mm diameter. Experimental results show that this method can change the generated THz time waveforms but not their spectra. Such method offers a simple means to change and manipulate THz field generated from optical rectification with tiled-pulse-front pumping scheme.
 © (2015) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

Saturday, July 19, 2014

Abstract-Kinetics of Polymorphic Transitions of Cyclohexanol Investigated by Terahertz Absorption Spectroscopy


RIKEN519-1399 Aramaki-Aoba, Aoba-ku, Sendai, Miyagi 980-0845Japan
Cryst. Growth Des., Article ASAP
DOI: 10.1021/cg500706f
Publication Date (Web): July 18, 2014

http://pubs.acs.org/doi/abs/10.1021/cg500706f


Abstract Image
The phase behaviors and kinetics of the polymorphic transitions of cyclohexanol, C6H11OH, were investigated by terahertz absorption spectroscopy over the temperature range of 150–330 K. A new phase was found, labeled phase I′, which is more stable than the previously observed phase I but less stable than phase III′. The kinetics of the irreversible transitions from phase I to I′, phase I to III′, and phase III′ to III were analyzed using Avrami’s theory. The transition geometries of the first two transitions were found to be one-dimensional, while the latter was two-dimensional. The transitions from phase I to III and phase III to II were revealed to occur through two-step processes. The mechanism of these irreversible transitions is discussed in relation to the formation and dissociation of hydrogen bonds between the hydroxyl groups as well as the steric restriction effects of the cyclohexyl ring.


Thursday, December 30, 2010

Terahertz performs noninvasive mail inspection

 My note: I just saw this somewhat dated story on the Yahoo MB. It's notable, as it provides concrete evidence of another THz  application we will see in the near future.




Telltale spectra can identify illicit drugs hidden in packages.
24 February 2009, SPIE Newsroom. DOI: 10.1117/2.1200902.1505
 Detecting hazardous materials and illicit drugs inside posted mail is necessary because of security concerns and to deter drug trafficking. In Japan, confidentiality of private mail is guaranteed by law, and only noninvasive inspection methods are permitted. Detection (sniffer) dogs and x-ray imaging have been used, but x-rays cannot identify suspect materials and dogs are only useful if drug vapors leak from a package.
Systems using terahertz (THz) radiation have recently been demonstrated as quick and reliable mail-inspection devices.1–4 Like radio waves, THz radiation is not significantly scattered by soft materials such as paper, wood, and plastics, and creates clear images of hidden objects. In addition, many materials exhibit unique THz-absorption spectra—fingerprint spectra—which can be used to identify the contents of suspicious packages.
A prototype apparatus has been built to inspect all mail handled in Japanese international post offices (around 100,000 items per day). However, the THz spectrometer takes too long to examine every package. Therefore, to achieve complete inspection, the process has been divided into two stages. The first involves rapid screening using x-rays and THz waves, and the second identifies the suspicious substances selected in the first stage. The initial screening stage uses x-rays to exclude envelopes containing only paper. Images revealing shadows are then scanned and measured at 0.54THz. A diagram of the THz system is shown in Figure 1.

Figure 1. (top) THz rapid-screening system. A Schottky diode is characterized by a very low forward-voltage drop. (bottom) THz-scattering signal intensity of sucrose powder of different particle sizes. The Mie-scattering extinction curves are for nonabsorbing (solid line) and partially absorbing spheres (dashed line). The data point labeled ‘envelope’ illustrates the extinction for a paper-only envelope.
According to Mie scattering theory,5 which describes electromagnetic-radiation scattering by spherical particles, THz waves are intensely scattered when the particle size is comparable to the wavelength. Our experiment confirms that powders with particle sizes greater than 100μm result in a significantly stronger scattering signal than empty envelopes. Therefore, the rapid-screening system flags envelopes showing strong THz-wave scattering as suspicious mail.
Substance identification is achieved with a THz time-domain spectrometer (based on time-resolved Fourier-transform spectroscopy) using femtosecond laser pulses. The absorption spectra are obtained from 0.1 to 3THz with a frequency resolution of 0.03THz and a measurement time of two minutes. Figure 2 shows typical spectra of (a) empty envelopes and (b) folders containing methamphetamine hydrochloride powder. The empty envelopes show weak absorption and almost no spectral features, while those containing methamphetamine hydrochloride show strong absorption and fingerprint peaks at 1.2, 1.6, and 1.8THz. The spectral baselines in Figure 2(b) increase gradually with frequency due to the powder's scattering properties, and reach the detection limit at 2.4THz.


Figure 2. (a) THz absorption spectra of different kinds of empty envelopes. (b) THz absorption spectra of methamphetamine hydrochloride (HCl) with a particle size of 170μm and (c) first derivative. (d) First derivative of the database spectrum of methamphetamine HCl. Dashed lines show the frequency range used for calculating the correlation coefficients.
To identify controlled substances, we assembled a THz-spectrum database of widely used chemicals and drugs. Most of these show clear fingerprint spectra at 0.5–3THz, with different peaks, positions, and line shapes for each chemical. Any match between the spectra of suspicious envelopes and the database is evaluated using the correlation between their first derivatives, which removes the baseline slope and clarifies the spectral features: see Figures 2(c) and (d). The appropriate frequency range over which to calculate the correlation coefficients depends on the powder's particle size and the condition of the package. The range is determined on the basis of the spectrum's absorption intensity. A list of possible materials is displayed based on the correlation coefficient.
Procedures for spectral analysis and database retrieval are executed automatically and no special knowledge is necessary to operate the system. The prototype is now installed in Japanese post offices, and our current research focuses on evaluating the system's performance and its limits.

Hiromichi Hoshina, Yoshiakim Sasaki, Aya Hayashi, Chiko Otani
Terahertz Sensing and Imaging Laboratory
RIKEN
Sendai, Japan
Hiromichi Hoshina received his PhD from Kyoto University in 2003. His current research focuses on developing spectroscopic applications using THz waves.
Yoshiaki Sasaki received his PhD from Yamagata University in 2004. His current research interests include the detection of scattered THz waves from powders, THz imaging, and THz heterodyne detection.
Aya Hayashi received her MSc from Meiji University in 2002. Her research is in bioimaging of cancer and DNA using THz waves.
Chiko Otani received his PhD in astronomy from the University of Tokyo in 1995 and is now head of the Terahertz Sensing and Imaging Laboratory. His research interests include superconducting THz detectors and their applications.
Koko Kawase
Optical Quantum Engineering Group
Nagoya University
Nagoya, Japan
Kodo Kawase received his PhD in electronic engineering from Tohoku University in 1996. A professor in the Graduate School of Engineering (since 2005), he has been involved in research on THz-wave generation using nonlinear optics since 1992.