原位红外光谱法研究HMX炸药的热分解过程

原位红外光谱法是一种新兴的动态研究方法.该方法具有原位实时监控和红外光谱精确分析物质化学结构的优点,能够实时跟踪材料在不同温度下的化学变化,测定材料的微观结构与温度的关系.文章采用原位红外光谱研究了炸药1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷(HMX)在5℃·min-1升温条件下的热分解过程.研究结果表明:HMX在205℃发生C-N键和N-N键的断裂,随着温度的升高,C-N键的断裂速率远高于N-N键的断裂速率,表明C-N键的断裂是HMX的主要断键方式,在C-N键的断裂中伴随着N-N键的断裂.同时环的张力增大,表明断键的HMX产生分子内重新结合.检测到HMX的分解所释放出的CO2,N2O,CO,NO,HCHO,HONO,NO2和HCN等八种气体.根据HMX分解中凝聚相结构的变化和气相产物,推出HMX的分解机理:HMX产生C-N键的断裂,会释放出HCHO和N2O以及HONO和HCN;N-N键的断裂会释放出NO2.     

Structural Characterization and Thermal Properties of 1-Amino-1-ethylamino-2,2-dinitroethylene

1,1-二氨基-2,2-二硝基乙烯(FOX-7)和乙胺水溶液在92 oC下反应合成出了一种新型含能材料1-氨基-1-乙氨基-2,2-二硝基乙烯(AEFOX-7). 利用理论计算方法研究了AEFOX-7的分子结构、红外吸收和核磁共振化学位移. 用DSC和TG/DTG研究了AEFOX-7的热行为. 其热行为可分为一个熔化过程和一个紧接的剧烈放热分解过程. 热分解反应的放热焓、表观活化能和指前因子分别为：374.88,169.7 kJ/mol和1019.24 s^-1, 热爆炸的临界温度 是145.2 oC. 采用微量热法和理论计算方法研究了AEFOX-7的比热容,298.15 K时为214.50 J/(mol K).     

原位漫反射红外光谱研究升温速率对HMX炸药热分解过程的影响

原位红外光谱法是一种新兴的动态研究方法。该方法具有原位实时监控和红外光谱精确分析物质化学结构的优点,能够实时跟踪材料在不同温度下的化学变化,测定材料的微观结构与温度的关系。采用原位漫反射红外光谱研究了炸药1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷(HMX)分别在每min 5, 10, 20和40 ℃四种不同升温速率下的热分解行为。研究结果表明：在5 ℃·min-1升温速率下,断裂的HMX环发生分子内结合,在10, 20和40 ℃·min-1升温速率下,断裂的HMX发生分子间成环,形成稳定的八元环结构。随着温度的升高,C—N键的断裂数率远高于N—N键的断裂速率。随着升温速率的增加,C—N键的起始分解温度增加,表明增加升温速率会引起HMX分解的滞后。检测到HMX的分解所释放出CO₂, N₂O, CO, NO, HCHO, HONO, NO₂和HCN共八种气体,升温速率的变化未改变HMX的分解机理。     

聚偏氯乙烯热解动力学研究

聚偏氯乙烯的热不稳定性被用作制备含碳材料的前驱体。本工作利用红外光谱在线检测功能，原位测定了聚偏氯乙烯热分解动力学过程的红外谱图，分析并计算了聚偏氯乙烯分子链中C-H和C-C1键断裂的反应活化能，得到了聚偏氯乙烯分解过程的动力学特性。     

1,1-二氨基-2,2-二硝基乙烯晶体热膨胀各向异性的模拟研究

对新型钝感高能炸药组分1,1-二氨基-2,2-二硝基乙烯（FOX-7）,考察并选择了适用的分子力场和超晶胞初始构型,通过303K-378K温度范围在NPT系综下的分子动力学模拟（MD）,得到常压下各温度的FOX-7晶体平衡构型,发现随温度升高晶体内分子的取向和堆积方式不变;通过线性拟合求算出线膨胀系数,发现αb明显较大而αc与αa接近但不相等;接着采用密度泛函理论(DFT)方法随各向棱长膨胀的能量变化进行了模拟计算,发现得到的能量变化成各向异性并与各向热膨胀系数相关,从而建立FOX-7晶体特定分子堆积模式与热膨胀各向异性的关联。     

富勒烯灰对聚乙二醇热分解和红外光谱的影响

采用热分析和原位升温红外光谱实验研究了富勒烯灰(FS)对聚乙二醇(PEG)的影响。热分析结果显示,FS使得PEG的起始热分解温度和最大失重速率处的温度都明显推后。红外光谱结果证实,FS和PEG之间并没有生成新的化学键,FS也没有改变PEG分解产物的组成。通过对PEG和PEG+10%FS的凝聚相和气相升温红外光谱的检测,发现FS对PEG的凝聚相红外光谱影响并不明显,但却使得PEG分解放出气相产物的温度显著升高,说明FS对PEG热分解的抑制作用主要是通过对PEG气相产物的吸附和脱附来进行的。少量FS的加入即可显著抑制PEG的分解,使PEG的分解趋向高温。     

聚偏二氯乙烯热解过程的原位红外光谱

聚偏二氯乙烯是一种热不稳定性的高分子材料，可作为制备含碳材料的前驱体。以红外光谱在线检测功能实现了聚偏二氯乙烯热分解过程的原位分析，通过谱图分析了聚偏二氯乙烯分解过程的机理和温度效应。     

[Co(Gly)2(DABT)]·2H2O配合物的红外光谱及热稳定性的研究

研究了标题配合物的红外光谱和热稳定性.红外光谱分析结果表明,配位的2,2'-二氨基-4,4'-联噻唑的噻唑环和氨基上的两个氮的异构化交换引起的骨架振动由1342cm-1红移至1298cm-1.热分析结果表明,配合物在135℃附近先失去两个结晶水,在314℃附近甘氨酸羧基中C-O(配位)键断裂,配合物失去两个甘氨酸阴离子部分,配合物的剩余部分则在320℃以后继续以缓慢的速率进行放热分解.     

氢催化的二硝酰胺铵热分解的从头算分子动力学研究（英文）

本文采用从头算分子动力学方法研究了一种著名的高能氧化剂二硝酰胺铵(ADN)在高温下(2000和3000 K)的热分解行为.在ADN的单分子分解中,发现了与温度有关的两种不同的引发分解机理,即分子内氢转移和N-NO_2键断裂.这两种机理在2000 K时存在竞争关系,但是在3000 K时后者是主要的分解机理.而在ADN的多分子分解中,观察到了四种受温度控制的引发分解反应.除了上述两种外,还有分子间氢转移和N-H键直接断裂.在2000 K时,N-NO_2键断裂发生的概率与其它3种相当,但是在3000 K时N-H键断裂是主要的分解通道.在引发分解发生后,发现升温可以加快反应速率,但是不会改变重要的反应特征.在氢的催化下,ADN通过简单、快速和直接的化学断裂分解为小分子,这个过程中并没有形成任何可能阻碍分解的较大中间体.在2000和3000 K时的主要分解产物相同,分别是NH_3、NO_2、NO、N_2O、N_2、H_2O和HNO_2.     

聚氨酯的FTIR光谱与热分析研究

采用原位傅里叶变换红外光谱法,研究了聚酯型聚氨酯和聚醚型聚氨酯在空气气氛中从室温到400 ℃之间的热解反应,实时考察了其在不同温度条件下分解残留物的基团特性。利用热分析技术考察了它们在不同气氛下从室温到700 ℃之间的热解反应。探讨了在有氧条件下的热解反应机理。结果表明聚酯型聚氨酯在空气中存在硬段和软段先后分解的两个阶段,而聚醚型聚氨酯则是硬段与软段同时分解。热分解结果也显示,硬段相同的聚氨酯,聚酯型聚氨酯的起始失重温度高于聚醚型聚氨酯,显示聚酯型的热稳定性强于聚醚型。同时聚氨酯在空气中的起始失重温度比在氮气中提前,说明氧气的存在能促进聚氨酯主链上C—C和C—O键的断裂。     

Raman Spectra of Porphyrins

The spectroscopy of porphyrins has been developing rapidly during the last two decades, this class of compounds being of great biological importance and possessing a number of significant properties. Different spectroscopic techniques, viz., electronic spectroscopy including fine-structure quasiline spectra (Shpolsky effect), infrared spectroscopy, luminescence, flash photolysis, ESR and NMR spectroscopy etc., have been applied to the study of these molecules (see reference ¹ for a review). However until recently there were no publications on Raman spectra of porphyrins and related compounds although it is evident that a complete analysis of molecular vibrations is impossible without knowing the Raman frequencies, especially for centrosymmetrical molecules. We have obtained Raman spectra of two porphin derivatives, viz., copper and nickel octamethylporphin ² which seems to be, together with data on hemoglobin and cytochrome^3-5 and on chlorophylls ⁶, the first observation of Raman spectra of porphyrins. In this paper Raman spectra of several metalloporphyrins are presented including metal complexes of porphin, octamethylporphin, etioporphyrin I, meso-tetraphenylporphin and tetrabenzporphin. For some of them Shpolsky spectra have been obtained and a juxtaposition is made of the two kinds of spectral data concerning the frequencies of molecular no- modss. Also some data of infrared spectra are presented.     

IR CHARACTERISTICS AND CATALYTIC ACTIVITIES OF CU-CO-AL HYDROTALCITES

Series of Co-Al and Co-Cu-Al hydrotalcites were synthesized, thermally activated and characterized. The correlation between the hydrotalcite composition and their IR spectra were discussed along with the results of X-ray diffraction analyses. The specific surface areas of hydrotalcites and their catalytic activities for nitrous oxide decomposition upon calcination were studied. As Co was partially replaced by Cu. the catalytic activity was improved by 10% under the same reaction conditions (Co/Cu/Al = 2.7/0.3/1). A spinel Cu_xCo_3-xO₄ was formed in calcined hydrotalcites.     

IR signature estimation of an object or a target by taking into account atmospheric effects

In this study, a reference infrared (IR) image of an object or a target was analyzed, and the IR signature was calculated. Background and atmospheric effects were decomposed so that the calculation errors were minimized. Depending on the reference IR image, the IR signature at any distance and any angle was estimated while considering atmospheric effects. Calculated results were obtained from IR images taken from the same distance and angle, and were compared with the estimated results. The comparison of the measured and calculated signatures demonstrated the accuracy of the proposed method of estimation.     

Frequency modulated infrared imaging for thermal characterization of nanomaterials

The paper presents frequency modulated thermal wave imaging (FMTWI) as a fast and efficient non-contact technique for in-plane thermal characterization of thin plate nanomaterials. A novel excitation signal in the form of an up-chirp is applied and the thermal response is monitored using an infrared (IR) thermography based temperature sensing system. The in-plane thermal diffusivity of any sample can be measured using the multiple phase information extracted from a single run of the experiment. This feature provides a time efficient approach for thermal measurements using infrared thermography techniques. The theoretical background and experimental details of the technique are discussed, with practical measurement of thermal diffusivity of an empty anodic alumina (AAO) template in direction perpendicular to the nanochannel axis, in support.     

Thermal imaging during infrared final cooking of semi-processed cylindrical meat product

The temperature measurements during the infrared cooking of the semi-cooked cylindrical minced beef product (koefte) were taken by both contact (thermocouples) and non-contact (thermal imaging) techniques. The meat product was semi-cooked till its core temperature reached up to 75 °C by ohmic heating applied at 15.26 V/cm voltage gradient. Then, infrared cooking was applied as a final cooking method at different combinations of heat fluxes (3.7, 5.7 and 8.5 kW/m²), applied distances (10.5, 13.5 and 16.5 cm) and applied durations (4, 8 and 12 min). The average surface temperature increased as the heat flux and the applied duration increased but the applied distance decreased. The temperature distribution of the surface during infrared cooking was determined successfully by non-contact measurements. The temperature homogeneity varied between 0.77 and 0.86. The process condition of 8.5 kW/m² for 8 min resulted in core temperature greater than 75 °C, which was essential for safe production of ready-to-eat (RTE) meat products. Thermal imaging was much more convenient method for minimizing the point measurement mistakes and determining temperature distribution images more clear and visual.     

Cd(Ⅲ)、Co(Ⅲ)、Cu(Ⅲ)与异烟酸的配合物合成与性质

以异烟酸为配体合成了Cd(Ⅱ)、Co(Ⅱ)、Cu(Ⅱ)3种配合物,用X-射线单晶衍射研究了其结构,3种配合物具有类似的六配位结构,由于Jahn-Teller效应使Cu(Ⅱ)的配合物的结构为一伸长的八面体;3个配合物的配位原子均为4个水分子的氧原子和两个异烟酸根的氮原子,羧基仅参与形成氢键。对配合物的热稳定性进行了研究,并对Cd(Ⅱ)配合物非等温热分解动力学方程和动力学参数进行了拟合,结果表明动力学补偿效应方程与数据拟合方法无关。     

Glass formation and properties of GeTe4-Ga2Te3-AgX (X = I/Br/Cl) far infrared transmitting chalcohalide glasses

A new family of Tellurium-based glasses GeTe₄-Ga₂Te₃-AgX (X = I/Br/Cl) has been investigated and the glass-forming region was determined. Properties measurements include XRD, DTA, vis-NIR, and IR transmission spectra. The amorphous nature of the glasses has been proved by X-ray diffraction. Among the three systems, the GeTe₄-Ga₂Te₃-AgI glass system shows superior glass-forming ability and thermal stability. The maximum value of ΔT (= T_x − T_g) lies at about 110 °C for the glass composition 60GeTe₄-2-20Ga₂Te₃-20AgI, while for 60GeTe₄-20Ga₂Te₃-20AgBr and 60GeTe₄-20Ga₂Te₃-20AgCl, the ΔT values are both only 88 °C. Most of the studied glasses have a wide optical transmission window from 1.8 to 25 μm.     

Development and integration of near atmospheric N2 ambient sputtered Au thin film for enhanced infrared absorption

The exceedingly fragile nature of thermally grown Au-black coating makes handling and patterning a critical issue. Infrared absorption characteristics of near atmospheric, N₂ ambient DC sputtered Au thin films are studied for this purpose. The thin Au films are sputtered at different chamber pressures in Ar and N₂/Ar gas ambient from 4.5 to 8.0 mbar and optimized for enhanced infrared absorption. The absorber film sputtered in N₂/Ar ambient at 8.0 mbar chamber pressure offers significant absorption of medium to long wave infrared radiations. The micro-patterning of sputtered Au thin film is carried out by using conventional photolithography and metal lift off methods on a prefabricated µ-infrared detector array on Si (1 0 0) substrate. The steady state temperature response of sputtered film has been examined using nondestructive thermal imaging method under external heating of the detector array.     

The epoxy-siloxane/Al composite coatings with low infrared emissivity for high temperature applications

Low infrared emissivity coatings with good thermal resistance were prepared by using epoxy-siloxane and aluminum as adhesive and pigment, respectively. The influence of chemical composition, surface texture, roughness and thickness on the infrared emissivity was systematically investigated. The detailed results of experimental investigation indicate that the cured composite coatings could possess low emissivity value. Due to reducing infrared absorption and forming uniform and compact char construction, the infrared emissivity decreases obviously. Both the surface roughness and thickness have a critical value, respectively. Too large roughness or thickness would not contribute to the decrease of the emissivity. Moreover, the composite coatings were tested for thermal stability in air to explore the effect of high-temperature environment on the emissivity. The results indicate that the composite coatings, still possessing low emissivity after the test, exhibit favorable thermal ageing and thermal shock resistance.