煤中汞,砷,硒赋存形态的研究

本文利用连续化学浸提法对三种典型煤进行连续浸提,根据不同形态的溶解度,将煤中的汞,砷,硒分为可交换态,硫化物形态,有机物结合态及残渣态四种形态。结果表明不同的煤有不同的形态分布特征。但总体来看,汞主要以硫化物形态和残渣态存在。砷主要以硫化物形态存在。硒赋存在硫化物,有机物及残渣态中。     

氢化物发生-液体阴极辉光放电发射光谱对海水中硒、砷、汞的高灵敏定量检测

通过将氢化物发生装置与液体阴极辉光放电发射光谱仪相耦合,建立了一种定量检测海水中痕量硒、砷、汞的方法。实验对氢化物发生的载酸种类和浓度、还原剂浓度以及液体阴极辉光放电装置的放电电压、电解质种类和流速等工作条件进行了优化,确定了联用仪器定量分析硒、砷、汞的最佳工作条件:氢化物发生载酸为5%的HCl,还原剂为1.5%的NaBH_4,液体阴极辉光放电装置的放电电压为1060V,电解质溶液为pH 1的HCl,电解液流速为2.2 mL·min~(-1)。分别选取204.0, 228.8和253.7 nm作为硒、砷、汞的分析谱线,在上述最佳工作条件下对硒、砷、汞的系列混合标准溶液进行测定,硒、砷、汞的质量浓度在2～100μg·L~(-1)范围内与其发射强度呈线性关系,线性相关系数分别为0.999 2, 0.999 4和0.998 5,其检出限分别达到0.54, 0.92和1.91μg·L~(-1),浓度为0.1 mg·L~(-1)的硒、砷、汞的信号值相对标准偏差均小于3%。与单一的液体阴极辉光放电发射光谱相比,硒、砷、汞的检出限分别降低了3个、 4个、 2个数量级。选取国家土壤标准物质GBW07405对联用仪器检测结果的准确度进行了验证,其检测值与参考值一致;将该方法应用于中国黄海沿岸实际海水样品中痕量硒、砷、汞的定量分析,分析结果与电感耦合等离子体质谱法一致,用标准加入法测得其加标回收率在94.9%～105.3%之间。氢化物发生-液体阴极辉光放电发射光谱能够实现快速、准确地对海水中痕量硒、砷、汞的高灵敏在线定量检测。     

水浴消解-原子荧光光谱法测定土壤和沉积物中砷、汞、硒、锑和铋

建立了王水水浴消解-原子荧光光谱法测定土壤和沉积物中砷、汞、硒、锑和铋。将试样置于50 mL具塞玻璃比色管中,加入10 mL王水(1+1),于沸水浴中消解2 h,取出冷却后,超纯水定容,摇匀后取上清液待测。相比于微波消解的昂贵设备和低安全(高温高压)性,水浴消解法具有设备简单、易操作、重复性高等优点;同时由于实际样品中汞、硒和铋的含量都比较低,水浴消解后的试样能直接上机测定,可以大大地简化操作过程。重点研究了硼氢化钾浓度对检测灵敏度的影响,结果表明,相同仪器条件下,对于砷、硒、锑和铋元素,高的硼氢化钾浓度能在一定程度上提高其荧光强度;而对于汞而言,低的硼氢化钾浓度反而能增加其荧光强度,当采用0.1%硼氢化钾作为还原剂时,汞可以获得较好的检测灵敏度。通过比较不同预还原剂对测定结果的影响,验证了该方法测定样品中硒的可靠性,数据表明,该方法消解所用的盐酸量足够将Se(Ⅵ)还原成Se(Ⅳ),不仅不需要额外添加盐酸或硫脲,向样品中添加硫脲反而会使测定结果偏低很多。仪器最佳条件下,采用王水水浴消解-原子荧光光谱法测定土壤或沉积物中砷、汞、硒、锑和铋的方法检出限分别为0.008, 0.002, 0.002, 0.005和0.003 mg·kg~(-1)(取样量为0.500 0 g,定容体积为50 mL),测定下限分别为0.032, 0.008, 0.008, 0.020和0.012 mg·kg~(-1)。该方法用于测定土壤/沉积物标准样品中砷、汞、硒、锑和铋的相对误差范围分别为-3.3%～4.5%,-3.9%～15%,-20%～-7.8%,-13%～3.4%和2.2%～7.0%;该方法用于测定实际样品,相对标准偏差范围为1.3%～11%。采用水浴消解原子荧光光谱法测定土壤和沉积物中砷、汞、硒、锑和铋,具有操作简便、无需转移容器、普及性强、检出限低、精密度和准确度好等优点,分析结果满足环境监测要求。     

煤粉锅炉燃烧产物中汞,砷分布特征研究

对某300 MW燃煤电厂锅炉进行煤、渣、飞灰取样后,测定煤和燃烧产物中汞和砷的含量,研究了电除尘四个电场飞灰中汞与砷的分布特点。结果表明飞灰中砷的浓度随着粒度的降低而升高。在底渣中含量较低。通过飞灰粒度与砷浓度的拟合,初步得出砷的富集并不是只由物理凝结造成的,也有外部表面反应(或孔扩散)控制的过程。汞在电除尘1,2,3电场中是预料中的随着粒度的减小浓度增加。但在四电场中汞的浓度又降低了。通过分析得出飞灰含碳量也是影响汞吸附量的重要因素。     

煤中多元素同时分析的湿法消化法及其利用

采用高压消化罐法消化样品,采用正交试验设计实验方案,用ICP-AES测定了原煤、飞灰和底灰中的铝、钾、钙、镁、锰、锌、铜、钛、钡、硒、锶、铈、锡、铬、砷、铊16种元素的含量,方法回收率在93.5%-109.3%之间,相对标准偏差均小于2.31%.方法简单,快速,准确性好,实现了多元素同时测定.测量结果表明,煤燃烧后的底灰、飞灰中微量金属元素普遍得到了富集,底灰、飞灰中的常量元素基本在土壤标准的正常范围,而有毒微量元素As、Cr超标.     

煤燃烧过程中灰层的扩散阻力及其微观结构的研究

煤的灰层扩散系数对煤粒的燃烧有较大的影响。因此,本文用实验的方法测定了三种煤的灰层扩散系数。研究还发现,不同的颗粒直径、不同的煤种以及不同的灰层厚度、煤的灰层扩散系数均不同。最后,从其微观结构得到了合理的解释。     

原子荧光光谱法测定环境水中砷、硒和汞

原子荧光光谱法测定环境水中砷、硒和汞,试验了标准系列的配制方法;硼氢化钾浓度、盐酸酸度对测定的影响;优化了仪器条件。砷、硒和汞检出限分别为0.51μg/L、0.53μg/L、0.065μg/L,相对标准偏差(n=11)分别为1.51%、2.36%、1.63%,加标回收率分别为90.0%-105.0%、92.0%-97%、90.0%-97.5%。     

湿消解-原子荧光法测定煤中硒和砷

煤中微量元素砷、硒的含量与环境安全和居民健康密切相关,快速准确测定煤中砷、硒含量具有重要的理论和实践意义。现有中国国标(GB/T 16415—2008, GB/T 3058—1996)测定煤中总砷、总硒含量为干法分析法,该方法具有操作步骤复杂,误差大的缺陷。为了准确、快速测定煤中总砷、总硒的含量,克服干法分析方法的缺陷,在长期摸索的基础上,借鉴土壤中砷、硒的测试方法,建立了电热板混酸消解-氢化物发生-原子荧光测定煤中总砷、总硒的方法,即湿法分析方法。方法：准确称取0.05～0.10 g煤样(100目),转移入100 mL玻璃烧杯中,加入10 mL硝酸、2 mL高氯酸,加盖玻璃表面皿,于通风橱中静置过夜。次日,在电热板(180 ℃)上加热消解至白色浓烟冒出,液体透明,残余样品呈白色或者灰白色。取下冷却后,加入6 mol·L-1盐酸溶液3 mL,再次放在电热板上加热消解。当再次有白色浓烟开始冒出时,取下冷却后,加入1 mL浓盐酸。少量亚沸水冲洗烧杯和表面皿内壁,将消解液转移入25 mL试管,亚沸水定容至刻度线,摇匀待测硒;取3 mL消解液,转移入15 mL试管,加入1 mL浓盐酸,1 mL硫脲+抗坏血酸还原剂,亚沸水定容至刻度线,摇匀待测砷;用原子荧光法测定消解液中砷、硒含量。用该方法对煤成分分析标准物质(GBW11115, GBW11117)中砷、硒含量进行测定,测得砷回收率在99.7%～100.3%之间,相对标准偏差范围为5.6%～6.0%;硒相对标准偏差范围为11.1%～13.5%;对应砷和硒的检测限分别为0.05和0.01 μg·L-1。该方法可以准确测定煤中砷、硒含量,且较国标干法分析方法具有操作步骤少、准确性高等优点。     

压力对煤粒燃烬时间影响的研究

一、前言近年来国内外均在发展煤的加压燃烧技术。但是加压条件下煤的燃烧特性可供参考的数据很少,国内还是一片空白。本文介绍了一种加压燃烧炉的研制、调试和实验方法;测定了不同压力下煤粒燃烧过程中的温度变化曲线(T-t);得到了压力对煤的燃烬时间的影响规律;用煤粒表面扩散燃烧模型计算了不同压力下煤粒的燃烬时间,计算结果与实验结果符合得很好。     

土壤中汞与砷分析的热分解浸提前处理方法探讨

采用热分解浸提法处理土壤,以氢化物-原子荧光光谱法测定汞和砷的含量。研究了浸提时间、水浴温度、共存元素对测定结果的影响,对比测定国家级土壤标准物质以及考核样品中汞和砷的含量,其结果与土壤标准物质推荐值相吻合,回收率94.23%—102.73%。用该方法测试了耕地土壤样品中汞和砷的含量,结果表明,该方法简便、快速、准确,适用于实验室常规分析。     

Tuneable photoluminescence,raman spectroscopy and electrical properties of GaAs doping superlattices

Optical properties of three GaAs doping superlattices (SLs) were studied by low and high temperature photoluminescence (PL) as well as inelastic light scattering. A new optically active transition has been observed at 1.48 eV and the high temperature behaviour of the main e–(Zn)h band has been studied. Electrical properties were monitored by current-voltage, resistivity and Hall measurements. This showed a strong variation of carrier concentration in the p-layers associated with mixed electron–hole conduction. The influence of α-particle irradiation on the superlattice structures was also investigated.     

Structural,elastic, electronic,and thermodynamic properties of MgAgSb investigated by density functional theory

The structural, elastic, electronic, and thermodynamic properties of thermoelectric material Mg Ag Sb in γ, β, α phases are studied with first-principles calculations based on density functional theory. The optimized lattice constants accord well with the experimental data. According to the calculated total energy of the three phases, the phase transition order is determined from α to γ phase with cooling, which is in agreement with the experimental result. The physical properties such as elastic constants, bulk modulus, shear modulus, Young's modulus, Poisson's ratio, and anisotropy factor are also discussed and analyzed, which indicates that the three structures are mechanically stable and each has a ductile feature. The Debye temperature is deduced from the elastic properties. The total density of states(TDOS) and partial density of states(PDOS) of the three phases are investigated. The TDOS results show that the γ phase is most stable with a pseudogap near the Fermi level, and the PDOS analysis indicates that the conduction band of the three phases is composed mostly of Mg-3s,Ag-4d, and Sb-5p. In addition, the changes of the free energy, entropy, specific heat, thermal expansion of γ-MgAgSb with temperature are obtained successfully. The obtained results above are important parameters for further experimental and theoretical tuning of doped MgAgSb as a thermoelectric material at high temperature.     

液体钾、钠及其合金NaK的密度

我们用膨胀计方法,在温度0—300℃的范围内,测定了液体金属钠、钾以及它们的合金NaK三种样品的密度。所用金属的纯度约在三个九以上,结果表明,所测液体金属及其合金的密度可作为温度的线性函数来表示,但NaK合金的(d,t)直线在接近冰点地方偏离直线上翘。     

D6A、921和45钢的动态破坏与低压冲击特性

 通过对称碰撞研究了D6A、921和45钢的动态损伤与破坏行为。利用自由面速度的双波结构，结合材料在常压下的弹性纵波声速，确定了三种钢的低压Hugoniot关系，同时给出了三种钢的弹性Hugoniot屈服极限以及层裂强度。但是发现，屈服极限和层裂强度的材料分散性明显，在其影响下，层裂强度对加载幅度以及应变率的依赖性得不到体现，从而在其不确定度范围内，可将层裂强度看成一个常数。提出了一个唯象的损伤演化方程，在此基础上，对实验结果进行了部分数值模拟，数值模拟给出的层裂强度远大于近似解析模型的计算结果，两者之间的差异有待进一步研究。     

银、银-铝合金及其内氧化银-铝合金的内耗峯

用频率约为1周/秒的扭摆,测量了99.99％和99.95％两种纯银以及99.99％纯银分别加入0.01％、0.02％、0.05％、0.15％、0.5％铝和99.95％纯银加入0.5％铝的六种合金的内耗。并且,还比较了三种合金的多晶和其中一种合金的单晶在内氧化前和后,以及经过不同时间的内氧化处理后的内耗变化。实验的结果表明:(1)99.99％纯银试样在空气中测量,升温过程中在130℃左右出现一个内耗峯,从高温作降温测量这个峯不再明显地出现。(2)99.95％纯银试样和99.99％纯银加有少量铝的三种合金试样,在空气中作升温测量,都出现两个明显的内耗峯。低温峯出现在130℃到260℃的范围内,高温峯出现在380℃到430℃的范围内。这两种内耗峯的高度和巅值温度都随杂质含量的多少而改变。从高温作降温测量,高温峯可以重复出现,而低温峯就不再出现。加入合金元素一方面会引起一个新的高温峯,另一方面它又起着抑制低温峯出现的作用。当铝含量超过0.05％(即0.2原子％)时,就只出现一个高温峯。实验的结果指出,低温峯和氧在银中存在时的状态有关,可能是由于晶界上Ag₂O的变化导致晶界结构状态和空位的平衡浓度的改变而引起的。高温峯可能是由于富集在晶界或亚晶界处的合金元素,在一定温度的交变应力下向晶粒内扩散和反扩散所引起的。(3)经过内氧化处理后的合金试样,其内耗巅值是随处理时间的增加而减小。这种内耗的变化也是由于晶界处的铝和氧原子的平衡浓度和界面结构状态受到改变引起的。     

Dynamics and burning limits of near-limit hot,warm, and cool diffusion flames of dimethyl ether at elevated pressures

The near-limit diffusion flame regimes and extinction limits of dimethyl ether at elevated pressures and temperatures are examined numerically in the counterflow geometry with and without radiation at different oxygen concentrations. It is found that there are three different flame regimes—hot flame, warm flame, and cool flame—which exist, respectively, at high, intermediate, and low temperatures. Furthermore, they are governed by three distinct chain-branching reaction pathways. The results demonstrate that the warm flame has a double reaction zone structure and plays a critical role in the transition between cool and hot flames. It is also shown that the cool flame can be formed in several different ways: by either radiative extinction or stretch extinction of a hot flame or by stretch extinction of a warm flame. A warm flame can also be formed by radiative extinction of a hot flame or ignition of a cool flame. A general €-shaped flammability diagram showing the burning limits of all three flame regimes at different oxygen mole fractions is obtained. The results show that thermal radiation, reactant concentration, temperature, and pressure all have significant impacts on the flammable regions of the three flame regimes. Increases in oxidizer temperature, oxygen concentration, and pressure shift the cool flame regime to higher stretch rates and cause the warm flame to have two extinction limits. At elevated temperatures, it is found that there is a direct transition between the hot flame and warm flame at low stretch rates. The results also show that, unlike the hot flame, the cool flame structure cannot be scaled by using pressure-weighted stretch rates due to the its significant reactant leakage and strong dependence of reactivity on pressure. The present results advance the understanding of near-limit flame dynamics and provide guidance for experimental observation of different flame regimes.     

过渡金属Fe，Co，Ni居里点附近热电势的实验研究

测量了纯金属Fe，Co，Ni的热电势发现，在居里点附近热电势随温度的变化关系曲线均呈现先凹后凸的反常现象.由曲线的转折处可确定三个居里温度，即铁磁态居里点T_f，居里点T_C和顺磁居里点θ_p.由曲线可见，金属由铁磁态到顺磁态的相转变，存在一定温度间隔的转变过程，居里温度是这一过程的中间温度.分析曲线表明，温度在T_f与T_C范围有空穴参与导电，说明磁性负载者是d带中的空穴.对于温度在T_C与θ_p范围可能存在短程有序进行了讨论. 关键词： Fe Co Ni 热电势 居里温度     

Temperature dependence of the 1H chemical shift of tetramethylsilane in chloroform, methanol, and dimethylsulfoxide

The chemical shift of tetramethylsilane (TMS) is usually taken to be zero. However, it does vary slightly with temperature, having obvious implications for studies of temperature effects on chemical shifts. In this work, we measure the variation in the chemical shift of TMS with temperature in three solvents, CDCl3, CD3OD, and DMSO-d6, relative to the resonant frequency of 3He gas, which can be reasonably assumed to be temperature independent. In all three solvents, the average temperature coefficient over a wide temperature range is about -6 x 10(-4) ppm/degrees C, a factor of five smaller than that previously reported in the literature. Data are included for 3He resonance frequencies over a temperature range of -110 to +180 degrees C, along with new measurements of volume magnetic susceptibilities of the three solvents and estimates of their temperature dependence. A novel method is used to provide temperature measurement via 2H resonances of methanol and ethylene glycol samples, which can concurrently be used for field/frequency locking.     

Molecular dynamics study on the effects of stamp shape, adhesive energy, and temperature on the nanoimprint lithography process

Molecular dynamics simulations of nanoimprint lithography (NIL) were performed to investigate the effects of three critical process parameters in NIL: stamp shape, adhesive energy between the stamp and polymer film, and imprint temperature. The proposed simulation model of the NIL process consists of an amorphous SiO₂ stamp with a line pattern, an amorphous poly(methylmethacrylate) film, and a Si substrate under the periodic boundary condition in the horizontal direction to simulate a real NIL process imprinting periodical line patterns. The behavior of polymer deformation and the effects of adhesion on pattern transfer were investigated by observing the deformation process, calculating the imprint and separation forces, and analyzing the density and stress distribution inside the polymer film. In addition, their dependency on the process parameters is also discussed with reference to the changes in pattern shape, adhesive energy between the stamp and polymer atoms, and imprint temperature of the polymer film. During the imprint process, the rectangular pattern shows inferior cavity filling and higher stress concentration compared to trapezoidal and triangular patterns because it requires much larger flow and deformation of the polymer film. Low imprint temperature also produces high stress concentration and large imprint force due to the lower fluidity of polymer film. In the separation process, the rectangular pattern generates the largest separation force and causes the most serious defects of the transferred pattern and even the polymer film, while the triangular pattern shows the most satisfactory pattern transfer. In addition, the adhesive energy between the stamp and the polymer film also strongly influences the adhesion between the stamp and the polymer film. Low adhesive energy reduces the separation force of the stamp and transferred pattern defects, and therefore enhances the quality of pattern transfer.     

具有三自旋相互作用XX模型纠缠特性研究

利用Concurrence判据,研究了具有三自旋相互作用的XX模型的纠缠特性;分别在铁磁和反铁磁模型中研究了三自旋相互作用J_2和温度T对两自旋纠缠度的影响.结果表明,三自旋相互作用J_2提高系统的两体纠缠度,但是提高程度会因最近邻自旋间发生铁磁、反铁磁相互作用而有所差异;并且J_2影响两自旋系统纠缠消失的临界温度T_C,T_C会随J_2的增大而减小.系统温度T影响两体纠缠度,随着温度的降低,纠缠度会得到提高.此外,分别在系统本征态和基态中研究了两自旋的纠缠度,求出了系统发生量子相变的量子临界点.