Two-wavelength mid-IR absorption diagnostic for simultaneous measurement of temperature and hydrocarbon fuel concentration

A two-wavelength mid-IR laser is used for time-resolved absorption-based measurements of temperature and n-heptane concentration in shock-heated gases. The novel difference-frequency-generation laser provides tunable mid-IR light from nonlinear conversion of near-IR light, enabling access to the strong hydrocarbon absorption bands between 3.3 and 3.5 μm associated with the CH stretching vibration. This laser was modified to alternate between two mid-IR wavelengths at 200 kHz, providing 5 μs time resolution for simultaneous monitoring of temperature and concentration in reactive flows and combustion systems. Temperature-dependent absorption spectra of n-heptane are first measured in a cell from 298 to 773 K using an FTIR spectrometer. These spectra are used to select candidate pairs of wavelengths with good sensitivity to temperature and concentration and to provide accurate temperature-dependent absorption cross-sections at the selected wavelengths. Laser absorption measurements of shock-heated n-heptane are then used to extend the cross-section data to 1300 K and to investigate the sensor accuracy and noise characteristics. The temperature and concentration inferred from the measurements are compared to known post-shock conditions, with a 4.5% RMS deviation from the calculated temperature and 1.7% RMS deviation from the calculated concentration. Finally, at high temperatures, the sensor is used to monitor decomposition of n-heptane, illustrating the potential of this diagnostic for hydrocarbon kinetics experiments in shock tubes. This new sensor concept should prove useful for simultaneous, time-resolved temperature and hydrocarbon concentration measurements in a variety of combustion and propulsion applications.     

Infrared absorption in In-doped degenerate Hg1−xCdxTe

The infrared absorption spectra, including absorption edge spectra and below-gap absorption spectra, were investigated both experimentally and theoretically for an In-doped degenerate HgCdTe sample with an electron concentration N_e = 7.0 × 10¹⁷ cm^-3 for wavelengths 7 μm<L<17 μm at the temperatures 77 K <T< 300 K. The possibility of applying free-carrier absorption theory developed for InSb to HgCdTe is discussed. It is concluded that the virtual crystal approximation works fairly well for HgCdTe and that the two-mode Callen effective charge should be used in the calculation of free-carrier absorption coefficients to account for the two-mode character of the optical phonons of HgCdTe. Good agreement between theory and experiment in the below-gap absorption spectra was obtained. The concentration of ionized impurities was found to be N_imp=3.4 × 10¹⁸ cm^-3. A good account of the behaviour of absorption edge in the light of Burstein-Moss effect has also been given.     

Absorption spectra and light penetration depth of normal and pathologically altered human skin

A three-layered skin model (stratum corneum, epidermis, and dermis) and engineering formulas for radiative transfer theory are used to study absorption spectra and light penetration depths of normal and pathologically altered skin. The formulas include small-angle and asymptotic approximations and a layer-addition method. These characteristics are calculated for wavelengths used for low-intensity laser therapy. We examined several pathologies such as vitiligo, edema, erythematosus lupus, and subcutaneous wound, for which the bulk concentrations of melanin and blood vessels or tissue structure (for subcutaneous wound) change compared with normal skin. The penetration depth spectrum is very similar to the inverted blood absorption spectrum. In other words, the depth is minimal at blood absorption maxima. The calculated absorption spectra enable the power and irradiation wavelength providing the required light effect to be selected. Relationships between the penetration depth and the diffuse reflectance coefficient of skin (unambiguously expressed through the absorption coefficient) are analyzed at different wavelengths. This makes it possible to find relationships between the light fields inside and outside the tissue. __________ Translated from Zhurnal Prikladnoi Spektroskopii Vol. 74, No. 3, pp. 387–394, May–June, 2007.     

Two-wavelength mid-IR diagnostic for temperature and n-dodecane concentration in an aerosol shock tube

A two-wavelength, mid-IR optical absorption diagnostic is developed for simultaneous temperature and n-dodecane vapor concentration measurements in an aerosol-laden shock tube. FTIR absorption spectra for the temperature range 323 to 773 K are used to select the two wavelengths (3409.0 and 3432.4 nm). Shock-heated mixtures of n-dodecane vapor in argon are then used to extend absorption cross section data at these wavelengths to 1322 K. The sensor is used to validate a model of the post-evaporation temperature and pressure of shock-heated fuel aerosol, which can ultimately be used for the study of the chemistry of low-vapor-pressure compounds and fuel blends. The signal-to-noise ratio of the temperature and concentration are ～20 and ～30, respectively, illustrating the sensitivity of this diagnostic. The good agreement between model and measurement provide confidence in the use of this aerosol shock tube to provide well-known thermodynamic conditions. At high temperatures, pseudo-first-order decomposition rates are extracted from time-resolved concentration measurements, and data from vapor and aerosol shocks are found to be in good agreement. Notably, the n-dodecane concentration measurements exhibit slower decomposition than predicted by models using two published reaction mechanisms, illustrating the need for further kinetic studies of this hydrocarbon. These results demonstrate the potential of multi-wavelength mid-IR laser sensors for hydrocarbon measurements in environments with time-varying temperature and concentration.     

Tunable mid-IR laser absorption sensor for time-resolved hydrocarbon fuel measurements

A wavelength-tunable mid-infrared (mid-IR) laser is used to make time-resolved absorption measurements of methyl-cyclohexane (MCH) and n-dodecane vapor concentration, demonstrating the use of this novel laser source for sensing hydrocarbon fuels. Two sensitive and species-specific diagnostic strategies are investigated: (1) direct absorption at a fixed wavelength, and (2) dual-wavelength differential absorption with two rapidly-alternating wavelengths. The tunable laser light is produced using difference frequency generation by combining two near-infrared diode lasers in a periodically poled lithium niobate crystal, providing a continuous-wave (cw), room temperature mid-IR source with the low intensity noise, and rapid wavelength tunability typical of telecommunications diode lasers. Direct absorption measurements of MCH with a wavelength of 3413.7 nm demonstrate fast time response (1 μs) and low noise in cell (300-675 K) and shock tube (650-1450 K) experiments. The detection limits of MCH range from 0.5 ppm-m at 300 K to 11 ppm-m at 1440 K (pressure = 101 kPa). Next, time-division multiplexing is used to alternately generate two mid-IR wavelengths at 20 kHz, enabling the use of dual-wavelength differential absorption to eliminate interference absorption. Measurements of MCH concentration are first made in a cell, with varying amounts of n-heptane interference absorption. Accurate values of MCH concentration are obtained for n-heptane/MCH ratios as high as 15, demonstrating the utility of this sensor for species-specific hydrocarbon detection in systems with interfering absorption. Finally, time-resolved n-dodecane vapor concentration measurements are made in a shock-heated evaporating aerosol. The dual-wavelength differential absorption diagnostic is sensitive only to the vapor concentration, rejecting droplet extinction. These measurements illustrate the power of the differential absorption strategy for sensitive vapor-phase detection in the presence of particle scattering. The tunability of this new source will allow these concepts to be extended to other hydrocarbon fuels.     

Isosbestic points in absorption spectra of isooctane, <Emphasis Type="Italic">n</Emphasis>-heptane,toluene, and benzene binary mixtures

Experimental absorption spectra of several pure hydrocarbons such as isooctane, n-heptane, toluene, and benzene and their binary mixtures are compared in the 1090–1240 nm and 1620–1820 nm wavelength regions, in which the second and first overtones, respectively, of vibrational frequencies of molecular groups CH, CH₂, and CH₃ are located. It is shown that in all cases there exist narrow isosbestic areas for binary mixtures specific for each of them. These areas can serve as individual characteristics of binary hydrocarbon mixtures, making qualitative analysis possible without recording the entire spectrum. Optimal wavelengths for quantitative analysis of the hydrocarbon mixture composition are determined for which the dependence between the absorption coefficient and the component concentration is approximately linear.     

Effect of pressure on the intensity of absorption bands in the IR spectra of compacted polyethylene powde

The investigation of the IR spectra of compacted reactor powders of ultra-high-molecular-weight polyethylene showed that the intensities of the absorption bands depend on the compaction pressure; namely, they decrease with increasing pressure. It is found that the ultimate pressure above which the absorption band intensity ceases to decrease depends on the spectral position of the band; the shorter the wavelength, the higher the ultimate pressure. This pressure is 5–10 MPa for bands in the long-wavelength spectral region (the band at 720 cm^?1) and 100 MPa for the short-wavelength region (the band at 5875 cm^?1). It is assumed that this phenomenon is related to a change in the size of pores d with pressing. Beams with wavelengths λ < d will undergo multiple diffuse reflections and reach a photodetector that is weaker than beams with λ > d. With increasing pressure, the size of pores decreases and the boundary between the two regions of the spectra shifts to short wavelengths.     

Wavelength Dependant Quenching of 2,5-Diphenyloxazole Fluorescence by Nucleotides

The quenching of 2,5-diphenyloxazole (PPO) fluorescence by nucleotides has been investigated by electronic absorption and steady state fluorescence spectra. Five purine nucleotides AMP, ADP, ATP, GMP and dGMP, one pyrimidine nucleotide UMP and one dinucleotide NAD have been employed in the present study. Electronic absorption studies indicate that there is no ground state complexation between the nucleotides and PPO. The quenching of PPO fluorescence was investigated at two different wavelengths. When excited at 304 nm, the λ _max of PPO, the fluorescence spectra of PPO is quenched following Stern–Volmer kinetics. The quenching ability of nucleotides are in the order NAD > AMP > ADP > GMP > dGMP > UMP. The K _SV and k _q values obtained indicate that AMP is a better quencher of PPO fluorescence than GMP, which is contrary to commonly observed pattern. The quenching is found to be dynamic in nature. However, when excited at 260 nm, the absorption maximum of the nucleotides, the fluorescence intensity of PPO is reduced with increase in the concentration of the nucleotide. This is attributed to the primary inner filter effect arising due to the absorption of the incident radiation by the nucleotides. Thus the inner filter effect phenomenon can be employed to assay the non-fluorescent molecules by fluorimetry.     

Analysis of aromatic constituents in multicomponent hydrocarbon mixtures by infrared spectroscopy using multiple linear regression

Absorption spectra of multicomponent hydrocarbon mixtures based on n-heptane and isooctane with addition of benzene (up to 1%) and toluene and o-xylene (up to 20%) were investigated experimentally in the region of the first overtones of the hydrocarbon groups (λ = 1620–1780 nm). It was shown that their concentrations could be determined separately by using a multiple linear regression method. The optimum result was obtained by including four wavelengths at 1671, 1680, 1685, and 1695 nm, which took into account absorption of CH groups in benzene, toluene, and o-xylene and CH₃ groups, respectively.     

Optical study of Ce ion in gamma-irradiated binary barium-borate glasses

Absorption spectra measurements of cerium-doped binary system from barium-borate glasses have been measured. The effects of dopant concentration of CeO₂ and Al₂O₃ in the concentration range 0.54-2.9 and 4.8-9.2 mol%, respectively, and exposed to different irradiation doses have been measured in the range 1-7 eV and the result have been interpreted in terms of structural concepts. The radiation-induced broad band at 2.25-1.88 eV in the base glass is observed to be suppressed by the presence of cerium due to the transformation of Ce⁴⁺ to Ce³⁺. The released electrons are then used to annihilate positive holes responsible for this band. The resolution of the observed absorption spectra show two to seven induced bands depending on the glass composition. Absorption spectra of the irradiated binary glass system are found to be controlled by the cerium concentration. From the absorption edge studies, the values of optical band gap E_opt and Urbach energy ΔE have been evaluated. The oxidoreduction (redox) reaction Ce³⁺/Ce⁴⁺ is assumed to be related to the glass basicity and the possible complex-ion formation. The oxygen ion activity (O²⁻) is believed to be related to the basicity and to the possible oxygen ion formation in the glass melt, and the redox equilibrium is shifted toward the reduced state.     

Bound exciton in CuGaS2

In CuGaS₂ crystals absorption and luminescence spectra at the temperature 9 K at excitation by different wavelengths of Ar laser are investigated. A series of lines available in luminescence and absorption spectra is found. Another series of lines is found only in absorption spectra. The found series of lines of absorption and luminescence are determined by excitons bound on neutral acceptor. A model of electron transitions between the energy levels of the exciton bound on neutral acceptor is proposed.     

脱氢枞酸基D-A型分子的合成、空间构型及光谱性能

对三苯胺进行溴代和C-N偶联反应合成4-萘基三苯胺(a),对脱氢枞酸进行酯化、溴代、硝化、还原和C-N偶联反应合成13-[N,N-(4-萘基苯基)-苯基]胺基-脱异丙基脱氢枞酸甲酯(b)及13-[N,N-双(4-萘基苯基)]胺基-脱异丙基脱氢枞酸甲酯(c)两个化合物,通过1H MNR,13C MNR及MS对化合物的结构进行表征。为了研究化合物结构与光谱性能之间的关系,首先利用Gaussian 09程序采用密度泛函DFT/B3LYP方法,对三个化合物的空间构型进行全优化,得到它们的键长、键角和二面角,对比发现脱氢枞酸骨架和萘环的引入会影响化合物的共平面性,而萘环的引入会增大化合物的共轭程度。光谱性能方面,研究了三种化合物在甲醇、二氧六环、四氢呋喃、二氯甲烷和环己烷这5种极性逐渐减小的溶剂中的荧光发射光谱和紫外吸收光谱。结果表明,在荧光光谱中,化合物a,b和c在不同极性溶剂中最大荧光发射波长均有不同程度位移,在甲醇中最大,在环己烷中最小,但是位移并非随着极性的增大而只发生红移,在二氯甲烷、四氢呋喃和二氧六环3种极性依次增大的溶剂中,a,b,c的荧光发射波长均随着溶剂极性的增大而发生较大程度的蓝移;在同一溶剂中,化合物b和c相对于a的荧光发射波长依次发生红移,c的红移程度与b差距不大。紫外吸收光谱中,三个化合物在不同极性溶剂中的最大吸收波长也有差异,在200～250 nm区间,三个化合物均在二氯甲烷中有较大位移,在300～350 nm区间,在甲醇中位移较大,而在250～300 nm区间,最大吸收波长差别不大;在同一溶剂中,它们在300～350 nm区间的最大吸收波长差别较大,化合物c较a红移26 nm。结合结构优化所得数据可以证明,化合物的共轭程度对荧光发射光谱和紫外吸收光谱均有影响,而共平面性对荧光发射光谱影响较大。化合物a,b和c在不同极性溶剂中荧光发射光谱和紫外吸收光谱的较大变化,表明它们有明显的溶致变色行为,具有作为分子探针探测外部环境极性大小的潜能。     

Estimation of lunar titanium content: Based on absorption features of Chang’E-1 interference imaging spectrometer (ⅡM)

Two linear regression models based on absorption features extracted from CE-1 IIM image data are presented to discuss the relationship between absorption features and titanium content. We computed five absorption parameters (Full Wave at Half Maximum (FWHM), absorption position, absorption area, absorption depth and absorption asymmetry) of the spectra collected at Apollo 17 landing sites to build two regression models, one with FWHM and the other without FWHM due to the low relation coefficient between FWHM and Ti content. Finally Ti content measured from Apollo 17 samples and Apollo 16 samples was used to test the accuracy. The results show that the predicted values of the model with FWHM have many singular values and the result of model without FWHM is more stable. The two models are relatively accurate for high-Ti districts, while seem inexact and disable for low-Ti districts.     

Atomic absorption spectra induced by NaRb in sodium-rubidium vapour

Six atomic spectral lines induced by NaRb molecules in the absorption spectrum of sodium-rubidium vapour have been observed in the wavelength range 611–641 nm. For sodium-rubidium vapour, the laser induced fluorescence spectra at laser wavelengths 616.04 and 615.81 nm and the excitation spectra at sodiumD-lines with the laser scanning in the range 613.9–616.9 nm have also been measured. The possible mechanisms for the appearance of these absorption lines are discussed.     

Depth distributions of light action spectra for skin chromophores

Light action spectra over wavelengths of 300–1000 nm are calculated for components of the human cutaneous covering: melanin, basal (bloodless) tissue, and blood oxy- and deoxyhemoglobin. The transformation of the spectra with depth in biological tissue results from two factors. The first is the wavelength dependence of the absorption coefficient corresponding to a particular skin chromophore and the second is the spectral selectivity of the radiation flux in biological tissue. This factor is related to the optical properties of all chromophores. A significant change is found to take place in the spectral distribution of absorbed radiant power with increasing depth. The action spectrum of light for the molecular oxygen contained in all components of biological tissue is also studied in the 625–645 nm range. The spectra are found to change with both the volume fraction of blood vessels and the degree of oxygenation of the blood. These results are useful for analyzing processes associated with optical absorption that are possible mechanisms for the interaction of light with biological tissues: photodissociation of oxyhemoglobin and the light-oxygen effect.     

On the angular dependence of gaps in 1-D Si/SiO2 periodic structures

A multilayer of silicon and silicon dioxide was used to study the angular dependence of reflectance maxima originating from interference and bulk optical properties. Silicon dioxide has a lattice resonance in the infrared causing an interval of high reflectance for wavelengths around 9 μm. The multilayer was designed such that the interference maxima do not overlap/interact with the material related reflectance maximum. In this way the different angular behavior for the two types of reflectance maxima can be studied simultaneously. Experimental and calculated reflectance spectra for s- and p-polarized light for angles of incidence between 0° and 90° collected for every 5° are presented. The reflectance features caused by interference generally move to shorter wavelengths with increasing angle of incidence, and the materials related peak is widened for (s-polarized light) and excitation of the longitudinal modes was observed for p-polarized light.     

基于同步荧光光谱法的鸭肉中西维因残留含量检测研究

为了快速测定鸭肉中西维因残留含量,提出应用同步荧光光谱法检测鸭肉中西维因残留含量,同时运用遗传算法-支持向量回归(GA-SVR)建立了鸭肉中西维因残留含量的回归预测模型。首先,通过荧光分光光度计分别采集了西维因水解物和含有西维因的鸭肉的三维同步荧光光谱图,经过分析确定了最佳波长差Δλ都为140 nm;其次,分析了鸭肉中西维因的浓度猝灭现象;最后采用GA进行同步荧光光谱的优化和选择,根据交互验证均方根误差(RMSECV)选择出了21个特征波长,并分别用全波长和21个特征波长作为SVR回归预测模型的输入特征变量,发现通过GA选择的特征波长可以得到更好的预测效果,并且其预测集的相关系数(R2)达到0.976 4,均方根误差(RMSECP)为12.232 2。试验结果表明利用同步荧光技术结合GA-SVR方法能有效、快速的检测鸭肉中西维因残留含量。     

利用2DCOS进行多组分混合气体傅里叶变换红外光谱分析中同分异构体谱峰的辨别

在利用傅里叶变换红外光谱进行混合气体定量分析中,针对烃类尤其是同分异构体等构成的混合气体其谱图特征相似、吸收峰严重交叠,不易进行特征吸收成分的判别和特征变量选择的问题,为增强谱峰分辨力,采用广义二维相关光谱和傅里叶变化红外光谱对烃类混合气体分析中同分异构体进行辨别,以异丁烷和正丁烷的红外光谱及受浓度扰动组成的光谱组为例进行二维相关红外光谱分析。通过观察全波段和主吸收峰波段单组分气体的傅里叶变换红外光谱,可知其谱图相似,吸收峰严重交叠,如果混合在一起,将基本无法辨别何种分子结构及成分。通过广义二维相关光谱的变换,其二维相关光谱的同步谱和异步谱可以清晰地辨别出异丁烷和正丁烷的特征吸收峰及其各自强度,实验结果可知,异丁烷在2 893,2 954和2 977 cm-1,正丁烷在2 895和2 965 cm-1具有强的吸收特征谱线。分析结果初步验证了二维红外相关光谱在多组分混合气体傅里叶变换红外光谱定量分析中谱分辨率增强方面的应用。     

Spectroscopic control of the properties of organic substances and materials by the property-absorption coefficient correlations

We suggest the determination of some physicochemical properties of organic substances by the spectra of absorption in the UV and visible regions. Correlation equations are obtained which give the optimal correlation between the absorption coefficients at the analytical wavelengths or the integral intensity and the physicochemical properties. Ufa Technological Institute of Service, 145 Chernyshevskii St., Ufa, 450014, Bashkortostan. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 438–440, May–June, 1998.