Chemical reactions are the most important phenomena in chemistry. However, chemical reactions at buried solid/solid interfaces are very difficult to study in situ. In this research, the chemical reaction between two solid polymer materials, a nylon film and a maleic anhydride (MAH) grafted poly(ethylene-octene) (MAHgEO) sample, was directly analyzed at the buried nylon/MAHgEO interface at the molecular level in real time and in situ, using surface and interface sensitive sum-frequency generation (SFG) vibrational spectroscopy. Disappearance of nylon signals indicated a chemical reaction between amine and hydrolyzed amide groups of nylon and MAH groups on the MAHgEO at the buried interface. The appearance of SFG signals from reaction products was also observed at the buried nylon/MAHgEO interface. The mechanism of the observed interfacial reaction was further analyzed. Temperature-dependent SFG experiments were performed to measure the activation energy of the interfacial reaction, enabling a comparison with that reported for the bulk materials. The interfacial chemical reaction between nylon and MAHgEO greatly improved the adhesion of these dissimilar materials. The detailed analysis of a chemical reaction between two polymers at the polymer/polymer buried interface underscores the utility of SFG as a powerful analytical tool to build understanding of buried interfaces and to accelerate the design of interfacial structures with desired properties.
Nylon and maleic anhydride (MAH)-grafted polyolefin-based thin co-extruded multilayer films are widely used in packaging applications encountered in daily life. The molecular structure of the nylon/MAH-grafted polyolefin buried interface and molecular bonding between these two chemically dissimilar layers are thought to play an important role in achieving packaging structures with good adhesion. Here, the molecular bonds present at a nylon/maleic anhydride (MAH)grafted polyethylene buried interface were systematically examined in situ for the first time using sum frequency generation (SFG) vibrational spectroscopy. The carbonyl stretching frequency region of the SFG spectra of a nylon/MAH-grafted polyethylene buried interface showed the presence of hydrolyzed MAH groups grafted to the polyethylene chain and very low levels of unreacted MAH enriched at the buried interface. The ability of SFG to detect these molecular species at the buried interface yields important understanding of the interfacial molecular structure and provides the basis for subsequent in situ studies of the bonding reaction between the grafted MAH and nylon directly at the interface. This understanding may guide the design of multilayer films with improved properties such as enhanced adhesion between polymer layers. The approach used in this study is general and is applicable to study the molecular characteristics of other buried interfaces of significance, such as buried interfaces involving polymers in solar cells, polymer semiconductors, and batteries. Nylon impact modification is another area of interest where the interaction between the MAH-grafted elastomer and the continuous phase of nylon is important.
Modulating terahertz (THz) waves actively and smartly through an external field is highly desired in the development of THz spectroscopic devices. Here, we demonstrate an active and smart electro-optic THz modulator based on a strongly correlated electron oxide vanadium dioxide (VO2). With milliampere current excitation on the VO2 thin film, the transmission, reflection, absorption, and phase of THz waves can be modulated efficiently. In particular, the antireflection condition can be actively achieved and the modulation depth reaches 99.9%, accompanied by a 180° phase switching. Repeated and current scanning experiments confirm the high stability and multibit modulation of this electro-optic modulation. Most strikingly, by utilizing a feedback loop of “THz-electro-THz” geometry, a smart electro-optic THz control is realized. For instance, the antireflection condition can be stabilized precisely no matter what the initial condition is and how the external environment changes. The proposed electro-optic THz modulation method, taking advantage of strongly correlated electron material, opens up avenues for the realization of THz smart devices.
Birefringence, which modulates the polarization of electromagnetic wave, has been commercially developed and widely used in modern photonics. Fostered by high-frequency signal processing and communications, feasible birefringence technologies operating in gigahertz (GHz) range are highly desired. Here, a coherent phonon-induced GHz optical birefringence and its manipulation in SrTiO 3 (STO) crystals are demonsrated. With ultrafast laser pumping, the coherent acoustic phonons with low damping are created in the transducer/STO structures. A series of transducer layers are examined and the optimized one with relatively high photon-phonon conversion efficiency, i.e., semiconducting LaRhO 3 film, is obtained. The most intriguing finding here is that, by virtue of high sensitivity to strain perturbation of STO, GHz optical birefringence can be induced by the coherent acoustic phonons and the birefringent amplitudes possess crystal orientation dependence. Optical manipulation of both coherent phonons and its induced GHz birefringence by double pump technique are also realized. These findings reveal an alternative mechanism of ultrafast optical birefringence control, and offer prospects for applications in high-frequency acoustic-optics devices.
Using metals as signal magnified substrates, surface plasmon-enhanced sum frequency generation (SFG) vibrational spectroscopy is a promising technique to probe weak molecular-level signals at surfaces and interfaces. In this study, the vibrational signals of the n-alkane monolayer on the gold (Au) and silica substrates are investigated using the broadband femtosecond SFG. The enhancement factors are discovered to be up to ∼1076 and ∼31 for the methyl symmetric and asymmetric stretching (ss and as) modes of the monolayer, respectively. By systematically analyzing the second-order nonlinear susceptibility tensor components (χ ijk s), the Fresnel coefficients (F ijk s), and the surface plasmon resonance (SPR) effect, we find that the interplay between F ijk and χ ijk terms and the SPR effect dominate the SFG signal enhancement. Our study reveals that the relative contributions of different influencing factors (i.e., Fresnel coefficients and SPR) to the SFG signal enhancement provide an approach to interpreting enhanced SFG vibrational signals detected from probe molecules on distinct substrates and may finally guide the design of the experimental methodology to improve the detection sensitivity and signal-to-noise ratio.
Finding appropriate materials to shape the terahertz (THz) wave is highly desired due to the increasing development of practical devices and application systems. In this work, the THz phase shifts of four typical oxide crystals, i.e., NdGaO 3 (NGO), quartz, (LaAlO 3 ) 0.3 (Sr 2 AlTaO 6 ) 0.35 , and sapphire, have been investigated by using THz time-domain spectroscopy. It is interesting to find that the NGO crystal is the only one that shows a distinct phase shift. The phase shift (Δφ) of a ∼500 μmthick NGO crystal is almost linearly dependent on the THz frequency and it reaches as large as ∼94°at 1.5 THz with a temperature variation from 100 to 400 K. Moreover, the THz phase shift of NGO possesses crystal anisotropy and Δφ(100) > Δφ(001) > Δφ(110). In addition, the effects of both electric field and laser illumination on the THz phase shift in the NGO crystal have also been explored. It is found that the electric field (∼260 V/ cm) has negligible effect, while the laser illumination can efficiently cause a noticeable THz shift and Δφ ∼ 78°with good manipulation stability can be achieved with 20 J/cm 2 light fluence. These findings suggest that NGO crystals are an appropriate candidate for THz phase modulator and their sensitivity and stability are expected to have a great technological impact and offer prospects for their applications in THz optics.
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