Shock tube/laser absorption studies of the decomposition of methyl formate

Reaction rate coefficients for the major high-temperature methyl formate (MF, CH₃OCHO) decomposition pathways, MF → CH₃OH + CO (1), MF → CH₂O + CH₂O (2), and MF → CH₄ + CO₂ (3), were directly measured in a shock tube using laser absorption of CO (4.6 μm), CH₂O (306 nm) and CH₄ (3.4 μm). Experimental conditions ranged from 1202 to 1607 K and 1.36 to 1.72 atm, with mixtures varying in initial fuel concentration from 0.1% to 3% MF diluted in argon. The decomposition rate coefficients were determined by monitoring the formation rate of each target species immediately behind the reflected shock waves and modeling the species time-histories with a detailed kinetic mechanism [12]. The three measured rate coefficients can be well-described using two-parameter Arrhenius expressions over the temperature range in the present study: k₁ = 1.1 × 10¹³ exp(?29556/T, K) s^?1, k₂ = 2.6 × 10¹² exp(?32052/T, K) s^?1, and k₃ = 4.4 × 10¹¹ exp(?29 078/T, K) s^?1, all thought to be near their high-pressure limits. Uncertainties in the k₁, k₂ and k₃ measurements were estimated to be ±25%, ±35%, and ±40%, respectively. We believe that these are the first direct high-temperature rate measurements for MF decomposition and all are in excellent agreement with the Dooley et al. [12] mechanism. In addition, by also monitoring methanol (CH₃OH) and MF concentration histories using a tunable CO₂ gas laser operating at 9.67 and 9.23 μm, respectively, all the major oxygen-carrying molecules were quantitatively detected in the reaction system. An oxygen balance analysis during MF decomposition shows that the multi-wavelength laser absorption strategy used in this study was able to track more than 97% of the initial oxygen atoms in the fuel.     

IR-induced features of AgGaGeS4 crystalline semiconductors

Complex investigations of the photoconductivity and photoinduced absorption together with the piezoelectric features were performed for the AgGaGeS₄ semiconducting single crystals under the influence of 3.5 μs CO₂ (80 mJ) pulsed laser emitting at 10.6 μm. These crystals are transparent in the wide spectral range 0.4–17 μm, which allows operating due to their properties in the spectral range covering the excitation of the phonons and electron subsystem. The piezoelectric properties show substantial increment during illumination by microsecond CO₂ laser and irreversible relaxation after swathing off the laser excitation. The temperature dependent studies of absorption and photoconductivity confirm the main role of intrinsic defects forming the tails of electronic states below the bottom of conduction band gap. Principal role of IR-induced electron–phonon interactions in the observed changes of the piezoelectricity is demonstrated.     

A near-infrared acetylene detection system based on a 1.534 μm tunable diode laser and a miniature gas chamber

A near-infrared (NIR) dual-channel differential acetylene (C₂H₂) detection system was experimentally demonstrated based on tunable diode laser absorption spectroscopy (TDLAS) technique and wavelength modulation spectroscopy (WMS) technique. A distributed feedback (DFB) laser modulated by a self-developed driver around 1.534 μm is used as light source. A miniature gas chamber with 15 cm path length is adopted as absorption pool, and an orthogonal lock-in amplifier is developed to extract the second harmonic (2f) signal. Sufficient standard C₂H₂ samples with different concentrations were prepared, and detailed measurements were carried out to study the detection performance. A good linear relationship is observed between the amplitude of the 2f signal and C₂H₂ concentration within the range of 200–10,000 ppm, and the relative measurement error is less than 5% within the whole range. A long-term monitoring lasting for 20 h on a 1000 ppm C₂H₂ sample was carried out, and the maximum concentration fluctuation is less than 2%. Due to the capability of using long-distance and low-loss optical fiber, the gas-cell can be placed in the filed for remote monitoring, which enables the system to have good prospects in industrial field.     

Photovoltaic properties of black silicon microstructured by femtosecond pulsed laser

Prototype devices based on black silicon have been fabricated by microstructuring 250 μm thick multicrystalline n doped silicon wafers using femtosecond pulsed laser in ambient gas of SF₆ to measure its photovoltaic properties. The enhanced optical absorption of black silicon extends across the visible region and all the black silicons prepared in this work exhibit enhanced optical absorption close to 90% from 300 nm to 800 nm. The highest open-circuit voltage (V_oc) and short-circuit current (I_sc) under the illumination of He–Ne continuous laser at 632.8 nm were measured to be 53.3 mV and 0.11 mA, respectively at a maximum power conversion efficiency of 1.44%. Upon excitation with He–Ne continuous laser at 632.8 nm, external quantum efficiency (EQE) of black silicon as high as 112.9% has also been observed. Development of black silicon for photovoltaic purposes could open up a new perspective in achieving high efficient silicon-based solar cell by means of the enhanced optical absorption in the visible region. The current–voltage characteristic and photo responsivity of these prototype devices fabricated with microstructured silicon were also investigated.     

Tunable fiber laser based photoacoustic gas sensor for early fire detection

A photoacoustic gas sensor using a near-infrared tunable fiber laser and based on wavelength modulation spectroscopy technique is developed. This sensor is capable of quasi-simultaneous quantification of water vapour, acetylene, carbon dioxide, and carbon monoxide (H₂O, C₂H₂, CO and CO₂) concentrations in the fire emulator. The feasibility of using this sensor as an early fire detector was demonstrated. The fire warning gases from smoldering paper were measured. The peak concentrations of gases from smoldering paper were 20,300 ppm H₂O, 2.1 ppm C₂H₂, 756 ppm CO, and 1612 ppm CO₂ after 400 s.     

Continuous measurements of stable carbon isotopes in CO2 with a near-IR laser absorption spectrometer

A near-IR laser absorption spectrometer using a technique of wavelength modulation spectroscopy is used to measure stable carbon isotope ratios of ambient CO₂ (δ¹³C) via the absorption lines ¹²CO₂ R(17) (2ν₁ + ν¹₂ − ν¹₂ + ν₃) at 4978.205 cm⁻¹ and ¹³CO₂ P(16) (ν₁ + 2ν₂ + ν₃) at 4978.023 cm⁻¹. The isotope ratios are measured with a reproducibility of 0.02‰ (1σ) in a 130-s integration time over a 12-h period. The humidity effect on δ¹³C values has been evaluated in laboratory experiments. The δ¹³C values of CO₂ in ambient air were measured continuously over 8 days and agreed well with those from isotope ratio mass spectrometry of canister samples. The spectrometer is thus capable of real-time, in situ measurements of stable carbon isotope ratios of CO₂ under ambient conditions.     

Development of an efficient coherent optical source at 6.04 μm

Efficiency as high as 26% is obtained for generation of mid-infrared radiation at 6.04 μm by frequency doubling of ammonia laser emission at 12.08 μm in a 15 mm long type-I cut AgGaSe₂ crystal. The NH₃ laser used for this work is optically pumped by a commercial TEA CO₂ laser operating on 9.22 μm and produces pulsed output of ∼210 mJ with a duration of ∼200 ns at 12.08 μm. The generated radiation at 6.04 μm is separated out from the residual radiation at 12.08 μm by exploiting the principle of polarization dependent diffraction of reflection grating.     

Investigation on Tm3+-doped silicate glass for 1.8 μm emission

A Tm³⁺-doped silicate glass (SiO₂–CaO–Na₂O–K₂O) with good thermal stability is prepared by the melt-quenching method. Intense 1.8 μm emission is obtained when pumped by an 808 nm laser diode. Based on the measured absorption spectra, radiative properties are predicted using Judd–Ofelt theory and Judd–Ofelt parameters Ω_λ (λ=2, 4, 6), as well as absorption and emission cross-sections are calculated and analyzed. The difference between the measured Tm³⁺:³F₄ lifetime and the calculated lifetime is also discussed. The emission property together with good thermal property indicates that Tm³⁺-doped silicate glass is a potential kind of laser glass for efficient 2 μm laser.     

Structural and luminescence properties of Nd3+-doped PbO–B2O3–TiO2–AlF3 glass for 1.07 μm laser applications

Trivalent neodymium doped multi-component lead borate titanate aluminumfluoride (LBTAFNd) glasses were prepared and characterized as a function of Nd³⁺ ions concentration through optical absorption, NIR luminescence and decay measurements. The intensity (Ω_2,4,6) and other radiative parameters were determined within the frame work of Judd–Ofelt theory. The intensities of absorption bands were expressed in terms of experimental oscillator strengths. Reasonably small root mean square deviation of ±0.384×10^?6 obtained between the experimental and calculated oscillator strengths indicates the validity of intensity parameters. Upon 805 nm laser excitation, the NIR emissions at 0.92 μm (⁴F_3/2→⁴I_9/2), 1.07 μm (⁴F_3/2→⁴I_11/2) and 1.35 μm (⁴F_3/2→⁴I_13/2) were observed. The spectroscopic quality factor has been determined from the Ω₄ and Ω₆ intensity parameters as well as the intensities of emission bands centered at 1.07 and 1.35 μm. The decay curves of the ⁴F_3/2 excited state were recorded by monitoring the emission and excitation wavelengths at 1.07 μm and 805 nm, respectively. The decay curves exhibit single exponential behavior for all the glasses. The laser characteristic parameters of ⁴F_3/2→⁴I_11/2 (1.07 μm) transition were determined and compared with other reported glasses.     

Experiment research on ellipsoidal structure methane using the absorption characteristics of 3.31 μm mid-infrared spectroscopy

The intensity distribution of absorption spectroscopy of methane mid-infrared fundamental absorption bands, near-infrared combination band of v₂ + 2v₃ and overtone band of 2v₃ were discussed in details in this paper. Quantitative data showed that the absorption intensities of fundamental bands are twice larger than overtone bands, and three times larger than combination bands. Based on the methane 3.31 μm (v₃) fundamental absorption bands and differential signal disposal method, a rotational ellipsoidal light structure was designed using ordinary light source and detector to improve gas detection sensitivity. The experimental results of concentration detection showed that the precision of concentration measurement can reach 3% and detection sensitivity is 50 ppm. Meanwhile, experiment was performed to investigate the influence of temperature on mid-infrared absorption performance of methane and the experience curve of 3.31 μm (v₃) fundamental absorption signal depending on temperature and its rate of change was drawn.     

Multi-species time-history measurements during high-temperature acetone and 2-butanone pyrolysis

High-temperature acetone and 2-butanone pyrolysis studies were conducted behind reflected shock waves using five species time-history measurements (ketone, CO, CH₃, CH₄ and C₂H₄). Experimental conditions covered temperatures of 1100–1600 K at 1.6 atm, for mixtures of 0.25–1.5% ketone in argon. During acetone pyrolysis, the CO concentration time-history was found to be strongly sensitive to the acetone dissociation rate constant k₁ (CH₃COCH₃ → CH₃ + CH₃CO), and this could be directly determined from the CO time-histories, yielding k₁(1.6 atm) = 2.46 × 10¹⁴ exp(?69.3 [kcal/mol]/RT) s^?1 with an uncertainty of ±25%. This rate constant is in good agreement with previous shock tube studies from Sato and Hidaka (2000) [3] and Saxena et al. (2009) [4] (within 30%) at temperatures above 1450 K, but is at least three times faster than the evaluation from Sato and Hidaka at temperatures below 1250 K. Using this revised k₁ value with the recent mechanism of Pichon et al. (2009) [5], the simulated profiles during acetone pyrolysis show excellent agreement with all five species time-history measurements. Similarly, the overall 2-butanone decomposition rate constant k_tot was inferred from measured 2-butanone time-histories, yielding k_tot(1.5 atm) = 6.08 × 10¹³ exp(?63.1 [kcal/mol]/RT) s^?1 with an uncertainty of ±35%. This rate constant is approximately 30% faster than that proposed by Serinyel et al. (2010) [11] at 1119 K, and approximately 100% faster at 1412 K. Using the measured 2-butanone and CO time-histories and an O-atom balance analysis, a missing removal pathway for methyl ketene was identified. The rate constant for the decomposition of methyl ketene was assumed to be the same as the value for the ketene decomposition reaction. Using the revised k_tot value and adding the methyl ketene decomposition reaction to the Serinyel et al. mechanism, the simulated profiles during 2-butanone pyrolysis show good agreement with the measurements for all five species.     

Effect of Li2CO3 addition on the structural,optical, ferroelectric,and electric-field-induced strain of lead-free BNKT-based ceramics

In this work, we reported the effect of Li₂CO₃ addition on the structural, optical, ferroelectric properties and electric-field-induced strain of Bi_0.5(Na,K)_0.5TiO₃ (BNKT) solid solution with CaZrO₃ ceramics. Both rhombohedral and tetragonal structures were distorted after adding Lithium (Li). The band gap values decreased from 2.91 to 2.69 eV for 5 mol% Li-addition. The maximum polarization and remanent polarization decreased from 49.66 μC/cm² to 27.11 μC/cm² and from 22.93 μC/cm² to 5.35 μC/cm² for un-doped and 5 mol% Li- addition BNKT ceramics, respectively. The maximum S_max/E_max value was 567 pm/V at 2 mol% Li₂CO₃ access. We expected this work will help to understand the role of A-site dopant in lead-free ferroelectric BNKT materials.     

Proton transfer in water–hydroxyl mixed overlayers on Pt(1 1 1): Combined approach of laser desorption and spatially-resolved X-ray photoelectron spectroscopy

Proton transfer in water–hydroxyl mixed overlayers on a Pt(1 1 1) surface was studied by a combination of laser induced thermal desorption (LITD) method and spatially-resolved X-ray photoelectron spectroscopy (micro-XPS). The modulated pattern OH + H₂O/H₂O/OH + H₂O was initially prepared by the LITD method; vacant area with a 400 μm width was first formed in the mixed OH + H₂O overlayer by irradiation of focused laser pulses, and followed by refilling the vacant area with pure H₂O. Spatial distribution changes of OH and H₂O were measured as a function of time with the micro-XPS technique, which indicated that H₂O molecules in the central region flow into the OH + H₂O region. From quantitative analyses using a diffusion equation, we found that the proton transfer in the mixed overlayer consists of at least two pathways: direct proton transfer from H₂O to OH in the nearest site and the proton transfer to the next-nearest site via H₃O⁺ formation. The time scale of first and second path was estimated to be 5.2 ± 0.9 ns and 48 ± 12 ns at 140 K, respectively. In the presence of water capping layer, however, the rate of proton transfer is reduced by an order of magnitude, which would be explained by peripatetic behavior of proton into H₂O capping layer.     

Derivation and solution of multifrequency radiation diffusion equations for homogeneous refractive lossy media

Starting from the radiation transport equation for homogeneous, refractive lossy media, we derive the corresponding time-dependent multifrequency diffusion equations. Zeroth and first moments of the transport equation couple the energy density, flux and pressure tensor. The system is closed by neglecting the temporal derivative of the flux and replacing the pressure tensor by its diagonal analogue. The radiation equations are coupled to a diffusion equation for the matter temperature. We are interested in modeling heating and cooling of silica (SiO₂), at possibly rapid rates. Hence, in contrast to related work, we retain the temporal derivative of the radiation field. We derive boundary conditions at a planar air–silica interface taking account of reflectivities obtained from the Fresnel relations that include absorption. The spectral dimension is discretized into a finite number of intervals leading to a system of multigroup diffusion equations. Three simulations are presented. One models cooling of a silica slab, initially at 2500 K, for 10 s. The other two are 1D and 2D simulations of irradiating silica with a CO₂ laser, λ = 10.59 μm. In 2D, a laser beam (Gaussian profile, r₀ = 0.5 mm for 1/e decay) shines on a disk (radius = 0.4, thickness = 0.4 cm).     

Positive influence of Tm3+ on effective Er3+: 3 μm emission in fluoride glass under 980 nm excitation

Er³⁺ and Tm³⁺ singly doped and codoped new fluoride glasses were prepared by traditional melt-quenching method. Efficient 3 μm emission was obtained under 980 nm laser excitation. It is worthy to notice that one of the two ions can be the sensitizer to the other one by depressing the Er³⁺: 1.5 μm emission through the energy transfer process from Er³⁺:⁴I_13/2 level to Tm³⁺:³F₄ level. On the basis of measured absorption spectra, the Judd-Ofelt intensity parameters and radiation emission probability were calculated to evaluate the spectroscopic properties. Additionally, the micro-parameters together with the phonon assistance of Er³⁺:⁴I_13/2 → Tm³⁺:³F₄ and Er³⁺:⁴I_11/2 → Tm³⁺:³H₅ processes were quantitatively analyzed by using Dexter model. The theoretical micro-parameters results meet well with the experiments which indicates that Er³⁺/Tm³⁺ codoped fluoride glass is a potential kind laser glass for 3 μm laser.     

Monitoring of laser heating temperature in laser spectroscopic measurements

During laser spectroscopic measurement, a part of laser energy will be converted into heat in the processes of excitation and light emission. Temperature monitoring can help to evaluate such nonradiative process. Upconversion luminescence of phosphor Y₂O₃:Er,Yb under laser excitation at 980 nm was investigated in this work. Point temperature of the phosphor was monitored using the fluorescent intensity ratio (FIR) technology. Laser induced temperature rising was identified by comparison with a theoretically ideal temperature calibration function: lnR = 3.1738–1167/T. The monitored temperature of laser heating rises monotonically with increasing laser power. Circumstances around heating point will modify the calibration function, but the linear slope of lnR ~ 1/T is constant.     

Ho:LaF3 single crystal as potential material for 2 μm and 2.9 μm lasers

Optical properties of a Ho-doped LaF₃ single crystal have been detailed investigated as a promising material for 2 μm and 2.9 μm lasers for the first time. Judd–Ofelt theory was applied to analyze the absorption spectrum to determine the J–O intensity parameters Ω_t(t=2,4,6), based on which the emission probabilities, branching ratio and radiative lifetime for the as-grown crystal were all calculated. The stimulated emission cross-sections of the ⁵I₇ → ⁵I₈ and ⁵I₆ → ⁵I₇ transitions were obtained by using the Fuchtbauer–Ladenburg method. The gain cross-section for 2 μm emission becomes positive once the population inversion level reaches 30%. The Ho:LaF₃ crystal shows long fluorescence lifetime of ⁵I₇ manifold (25.81 ms) as well as ⁵I₆ manifold (10.37 ms) compared with other Ho³⁺-doped crystals. It can be proposed that the Ho:LaF₃ crystal may be a promising material for 2 μm and 2.9 μm laser applications.     

High-pressure measurements of CO2 absorption near 2.7 μm: Line mixing and finite duration collision effects

Room-temperature, high-pressure (1–30 atm) measurements of CO₂ absorption are carried out near 2.7 μm to study line mixing and finite duration collision effects on transitions in the ν₁+ν₃ and 2ν₂+ν₃ vibrational bands. Two distributed feedback diode lasers are used to measure CO₂ transitions near 3631–3635 cm^?1 and 3644–3646 cm^?1, and an FTIR spectrometer covers the entire ν₁+ν₃ and 2ν₂+ν₃ bands from 3500 to 3800 cm^?1. The experiments are carried out in CO₂–air and CO₂–Ar mixtures to observe the non-ideal effects under the influence of different perturbers. Measurements are compared with simulations using the Voigt line shape to analyze the deviation from the Lorentzian behavior with increasing gas density, and show significant deviation from this model at high gas densities. Line shape models using empirical corrections or dynamically based scaling laws are evaluated by comparison to the measured high-density spectra. Although none of the models is able to predict the measured spectra accurately, the line mixing model of Niro et al. [24] does an overall good job but overestimates the band centers by about 4–9%. In light of these observations, challenges of developing a CO₂ sensor for high-pressure combustion applications are discussed.     

Damage/ablation morphology of laser conditioned sapphire under 1064 nm laser irradiation

The damage/ablation morphologies and laser induced damage threshold (LIDT) of three different sapphire samples: original, 1064 nm laser conditioned and 10.6 μm CO₂ laser polished substrates are investigated with ns pulses laser irradiation. The results indicate that the damage resistance capability cannot be enhanced by 1064 nm laser conditioning or CO₂ laser polishing. The damage/ablation morphology of 1064 nm-laser conditioned samples is same as that of the original sapphire. But it is different from the damage/ablation morphology of the CO₂ laser polished sapphire. The “gentle and strong” ablation phases are observed in this work and several phenomena are observed in the two ablation phases. Ripple is observed in the “gentle” ablation processes, while convex spots and raised rims are observed in the “strong” ablation processes. Meanwhile, stripe damage and pin-points are observed in the CO₂ laser conditioned sapphire after ns laser irradiation. The formation mechanisms of the phenomena are also discussed for the explanation of related damage/ablation morphology. The results may be helpful for the damage/ablation investigation of sapphire in high power laser systems.     

CO2 pressure broadening and shift coefficients for the 1–0 band of HCl and DCl

CO₂ broadened spectra of the 1–0 band of H³⁵Cl and H³⁷Cl, observed near 2886 cm^?1, and the 1–0 band of D³⁵Cl and D³⁷Cl, located near 2089 cm^?1, have been recorded at room temperature and five total pressures between 150 and 700 Torr, using a Bruker IFS125HR Fourier transform spectrometer. Spectra of pure HCl were also recorded. CO₂ broadening and shift coefficients of HCl and DCl have been measured using multi-spectrum non-linear least squares fitting of Voigt profiles. The analysis of the 1–0 band of DCl was complicated by the presence of overlapping CO₂ bands, which were included in the treatment as absorption coefficients calculated taking line-mixing effects into account.