Liquid encapsulated-melt zone processing of GaAs

A liquid encapsulated melt Bone process has been developed for single crystal growth of GaAs. Single crystals of 40 mm long have been grown with this technique. To avoid unwanted nucleation events and maintain a constant crystal diameter, from top to bottom growth using a short zone with a convex zone surface was found to give the best results. An arsenic overpressure was used to in conjunction with a B2O3 encapsulant in order to suppress arsenic dissociation from the melt and maintain the stoichiometry of the crystal.

Properties of GaAs single crystals grown by molecular beam epitaxy at low temperatures

Properties of GaAs single crystals grown at low temperatures by molecular beam epitaxy (LTMBE GaAs) have been studied. The results shaw that excessive arsenic atoms of about 10(20) cm(-3) exist in LTMBE GaAs in the form of arsenic interstitial couples, and cause the dilation in lattice parameter of LTMBE GaAs, The arsenic interstitial couples will be decomposed, and the excessive arsenic atoms will precipitate during the annealing above 300 degrees C. Arsenic precipitates accumulate in the junctions of epilayers with the increase in the temperature of annealing. The depletion regions caused by arsenic precipitates overlap each other in LTMBE GaAs, taking on the character of high resistivity, and the effects of backgating or sidegating are effectively restrained.

Aggregation and precipitation in high dose as ion implanted Ge0.5Si0.5 alloy

Thermally stimulated redistribution and precipitation of excess arsenic in Ge0.5Si0.5 alloy has been studied by X-ray photoelectron spectroscopy (XPS), cross sectional transmission electron microscopy (XTEM) and X-ray energy disperse spectrometry (EDS). Samples were prepared by the implantation of 6 X 10(6) As+ cm(-2) and 100 keV with subsequent thermal processing at 800 degrees C and 1000 degrees C for 1 h. The XPS depth profiles from the implanted samples before and after the thermal annealing indicate that there is marked redistribution of the elements in heavily arsenic-implanted Ge0.5Si0.5 alloys during the annealing, including: (1) diffusion of As from the implanted region to the surface; (2) aggregation of Ge in the vicinity of the surface. A high density of precipitates was observed near the surface which were by XTEM and EDS identified as an arsenide. It is suggested that most of the implanted As in Ge0.5Si0.5 alloy exists in the form of GeAs.

Dislocations and precipitates in semi-insulating gallium arsenide revealed by ultrasonic Abrahams-Buiocchi etching

The dislocations and precipitates in SI-GaAs single crystals are revealed by ultrasonic-aided Abrahams-Buiocchi etching (USAB), and the etch pits are observed and measured by metalloscope and scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectrometer (EDS), respectively. The size of etch pit revealed by USAB etching is about 1 order of magnitude smaller than that revealed by molten KOH. The amount of arsenic atoms in the dislocation-dense zone is about 1% larger than that in an adjacent dislocation-free zone measured by EDS attached to SEM, which indicates that the excess arsenic atoms adjacent to the dislocation-dense zone are attracted to the dislocations and precipitate there due to the deformation energy.

Structural and optical changes in GaAs/InAs/GaAs structure induced by thermal annealing

Self-organized InAs quantum; dots sheets are grown on GaAs(100) substrate and tapped by 80nm GaAs layer with molecular beam epitaxy. Samples were annealed and characterized with Raman spectra, transmission electron microscopy (TEM) and photolumincscence (PL). The Raman spectra indicates arsenic clusters in the GaAs capping layer. The TEM analysis revealed the relaxation of strain in some InAs islands with the introduction of the network of 90 dislocations. In addition, the structural changes also lead to the changes of the PL spectra from me InAs islands. Their correlation was discussed, Our results suggest:est that annealing may be used to intentionally modify me properties of self-organized InAs islands on GaAs.

有机酸对砷在针铁矿表面吸附影响研究

砷（As）在自然环境下的迁移转化受到矿物质尤其是铁氧化物吸附过程的制约,大量溶解性有机酸影响了砷的吸附过程。 柠檬酸(CA)和As(Ⅴ)不同加入顺序实验表明CA抑制As(Ⅴ)吸附与其促进针铁矿溶解有关。当CA首先加入时，吸附体系溶解铁浓度为~0.3mmol/L，As(Ⅴ)吸附量随初始浓度增加在0.004~0.10mmol/g针铁矿之间；As(Ⅴ)先加入体系，溶解铁浓度为~0.16mmol/L，As(Ⅴ)吸附量在0.007~0.12mmol/g针铁矿之间。为进一步考察有机酸溶解作用对As(Ⅴ)吸附影响，本研究比较了在柠檬酸(1.0 mM)、草酸(1.5 mM)和乙酸(3.0 mM)与As(Ⅴ)共存条件下砷吸附变化和针铁矿溶解状况，结合三种有机酸引起针铁矿表面等质子状态点迁移结果认为：草酸促进针铁矿溶解趋势强于柠檬酸，而抑制砷吸附程度低于柠檬酸，可归因于小分子量有机酸抑制砷吸附是竞争表面位与溶解作用协同作用的结果。 在酸性区域，CA和As(Ⅴ)共存导致二者在针铁矿表面吸附量分别下降28%和29%左右，这与二者在针铁矿表面发生竞争吸附作用有关。在碱性区域，As(Ⅴ)吸附不受CA存在的影响；CA则随加入顺序不同存在明显差异：As(Ⅴ)先于CA加入的体系，CA严重下降达75%左右，而当CA先加入时，As(Ⅴ)的后续加入导致CA吸附少量升高。As(Ⅴ)对CA在碱性区域的影响与二者随pH变化吸附模式不同有关。 本研究采用平衡透析的方式研究了砷在腐殖酸和针铁矿之间的迁移转化问题。结果显示腐殖酸的存在影响了砷向针铁矿表面的迁移，且对As（Ⅴ）的影响比As（Ⅲ）更显著。在酸性区域，腐殖酸导致As（Ⅴ）在针铁矿表面分配系数降低最高可达70%左右；对As（Ⅲ）而言，腐殖酸在弱酸性、中性和弱碱性区域表现出最大抑制效应，As（Ⅲ）分配系数的降低在10%左右。

微生物还原对砷迁移性影响的机理研究

本研究从沈阳冶炼厂旧址采集土壤样品，从中富集厌氧的砷还原菌，并以其为接种微生物，在厌氧条件下考察微生物的作用对砷的还原及迁移的影响，从分子角度探索地下水和土壤体系中砷污染的机理，同时对工业上含砷废渣的长期稳定性进行探讨。 实验在以L-半胱氨酸作为还原剂创造的严格厌氧条件下接种微生物进行培养时，可以观察到As(V)的快速还原并向固体的转移，利用XRD和SEM-EDS技术对固体的分析表明该沉淀为AsS，指出了在周围环境中如果存在足够的含硫化合物时，微生物能够通过形成硫化砷的形式将砷固定下来。 本研究考察了工业上常见的含砷废渣（As:Fe摩尔比为1:8的含砷氢氧化铁）在微生物作用下的长期稳定性，结果表明在厌氧条件下微生物对砷和铁的还原速度都很快，在39天内就将~53%的As(V)还原为As(III)，在一天之内就能将约8.82 mg/L的As(III)释放出来，因此可以得出如果含砷废渣处理不当，就会在长期堆放过程中造成对环境甚至于地下水系统的污染。 本研究进一步采用不同比例（Al:Fe = 1:0, 1:1, 0:1）的铁铝氢氧化物为吸附剂，以As:(Fe+Al)摩尔比为1:100的比例在该介质上吸附砷并进行厌氧培养，考察微生物对吸附于这些载体上的As(V)的还原和迁移作用，结果指出微生物对砷的还原是砷向环境中释放的主要原因，砷的还原发生在铁还原之前，铁的还原和溶解并没有引起砷的迁移量的增加，因此铁的还原性溶解不是砷释放的主要原因；相反，由于氢氧化铝对As(III)几乎不吸附，因此，当铝被引入该体系时，可以观察到As(III)的释放明显增加。该实验结果表明在自然环境中，砷的释放主要是由于微生物对砷的释放以及铝氧化物对As(III)无吸附能力所导致的。

铁砷共沉淀物长期稳定性研究

有色金属的冶炼过程中会产生大量砷含量很高的酸性废水，其任意排放会造成严重的环境砷污染，必须对其进行除砷处理达标后才能向环境排放。目前，铁砷共沉淀法是一种被广泛应用且较为经济的废水除砷技术，然而由此产生的大量含砷工业废渣中砷的化学形态尚不清楚，其稳定性也较差，容易造成严重的二次砷污染。因此，弄清铁砷共沉淀法产生的工业废渣中砷的化学形态，通过技术改造增强其长期稳定性，探索砷稳定性变化的分子机制具有重要的理论和现实意义。 本文对硫酸盐体系铁砷共沉淀法处理含砷废水所产生的废渣在长期稳定堆放过程中的稳定性及其影响因素进行了系统深入的研究。实验结果表明： （1）铁砷共沉淀物的稳定性受体系的最终pH值影响很大，随体系pH升高，含砷共沉淀物稳定性明显下降。溶液呈弱酸性时(pH 4或5)，含砷共沉淀物的稳定性较好，溶液呈弱碱性时(pH 8或9)，含砷共沉淀物的稳定性较差。 （2）碱类型影响含砷共沉淀物的稳定性，使用CaO中和酸性铁砷溶液显著提高了共沉淀的稳定性。在含砷溶液中添加钙离子也具有明显提高含砷共沉淀物稳定性的作用。 （3）Fe(III)/As(V)比影响铁砷共沉淀物稳定性，Fe(III)/As(V)越大，所形成共沉淀物越稳定。在铁砷酸性溶液的中和过程中，在pH=4时停留一段时间能够明显提高共沉淀物的稳定性，这种特性对于优化工业共沉淀法除砷工艺从而提高共沉淀含砷废渣稳定性具有重要意义。 （4）腐殖酸的加入最终削弱了铁砷共沉淀物中砷的稳定性。 （5）与Fe(III)-As(V)体系相比，Fe(III)-As(III)共沉淀体系中，共沉淀物在弱碱性区稳定性较好，在弱酸性区稳定性较差。在Fe(III)-As(III)-As(V)体系中，使用NaOH作为碱时，在弱碱性区稳定较好，而在弱酸性区稳定性较差。使用CaO作为中和碱在弱碱性区提高了共沉淀体系的稳定性，而在弱酸性区则降低了共沉淀体系的稳定性。

应用负载型纳米铁去除饮用水中砷的研究

砷是毒性最强的元素之一，水体中砷的污染己经引起人们广泛的关注。我国的新疆、内蒙、山西和台湾等省和地区地下水砷含量严重超标。全球共有5,000多万人遭受高砷饮用水的威胁，其中中国有1,500多万，是饮用水砷污染最严重的国家之一。WHO推荐饮用水砷的最高允许浓度从原来的50 µg•L-1已降至10 µg•L-1。更为严格的砷卫生标准的颁布，对作为饮用水源的地下水中的砷去除工艺提出了更高的要求。吸附法除砷比膜法、混凝法和离子交换法更安全、简便，是砷去除工艺中最有效的方法之一。 首先，本研究通过优化制备条件（包括炭种类的选择、炭的粒径大小、还原剂的浓度及滴定速率、反应温度、铁盐的种类及浓度、分散剂的比例及浓度），制备了负载型纳米铁。考虑到砷的去除效率、工程应用的可行性以及经济性，最优的制备条件如下：选用粒径为20~40目煤质炭，在室温、一定的分散剂比例及浓度，0.2 M KBH4滴速为20 d•min-1时所制备的Fe/炭为82.0 mg•g-1；纳米铁在活性炭孔内呈针状，其直径为30~500 nm，长度为1,000~2,000 nm。绝大多数的铁都负载到活性炭内部，这在处理水时铁不流失很重要。 其次，利用制备的负载型纳米铁作吸附载体，进行了饮用水中As(Ⅴ)的吸附去除实验。研究了该吸附剂对As(Ⅴ)的吸附等温线、动力学以及影响动力学的各种因素（包括As(Ⅴ)的不同初始浓度、吸附剂用量、pH值、共存离子和不同温度）、pH值、共存离子等环境条件对As(Ⅴ)去除的影响；以及吸附剂的再生及再生后的吸附效率等。研究发现在前12 h内吸附较快，72 h时达到了平衡。用Langmuir 吸附等温式估算出As(Ⅴ)的吸附量为12.0 mg•g-1。该吸附剂在pH 6.5， (25±2)℃， As(Ⅴ)初始浓度为2 mg•L-1，吸附剂用量为1.0 g•L-1时，As(Ⅴ)的去除率为75.2%；当把吸附剂的用量增加到1.5 g•L-1时，As(Ⅴ)的去除率可达99.9%以上。吸附剂可以用0.1M的NaOH浸泡12 h后即可再生，再生效率较高。常见的阴离子中PO43-、SiO32-对As(Ⅲ)的去除抑制较大，而SO42-、CO32-、C2O42-等离子对砷的去除影响较小。Fe2+对As(Ⅲ)的吸附抑制作用较大而其它阳离子影响不大。吸附剂可用0.1 M NaOH 有效再生，并且具有良好的机械性能。实验室初步实验数据表明，该吸附剂对饮用水除砷具有较好的应用前景。 第三，利用实验室制备的负载型纳米铁对饮用水中As(Ⅲ)的吸附去除也进行了研究。考察了吸附等温线、动力学以及影响动力学的各种因素、pH值、共存离子等环境条件对As(Ⅲ)去除的影响；以及吸附剂的再生及再生后的吸附效率等。研究发现，该吸附剂在pH 6.5， (25±2)℃， As(Ⅲ)初始浓度为2 mg•L-1，吸附剂用量为1.0 g•L-1时， 对As(Ⅲ)的去除率为99.8%；其吸附容量为1.996mg•g-1。吸附过程中部分As(Ⅲ)被氧化。与As(Ⅴ)的吸附相比，该吸附剂对As(Ⅲ)的效率比较高-而常见的其它除砷吸附剂如载铁纤维棉等，对As(Ⅴ)的效率比As(Ⅲ)高，为有效去除As(Ⅲ)，常常需要专门加上氧化这一过程。 最后，利用负载型纳米铁对饮用水中As(Ⅲ) 的氧化性能进行考察，发现该吸附剂不但能够有效吸附去除饮用水中的砷，而且还能把As(Ⅲ)有效地氧化为As(Ⅴ)。经过对吸附剂的构成组分分析发现，活性炭表面因富含多种官能团而对三价砷的氧化作用最大；其次是纳米铁也能把As(Ⅲ)氧化为As(Ⅴ)。

典型污染海湾河口沉积物中砷的形态分布研究

锦州湾是我国较大的浅水海湾之一，该湾西南五里河沿岸汇集数家工厂排污直接人海， 形成该湾口处的最大污染源。其西南部潮滩地段已成为我国海域污染最严重的区域之一。 本文对葫芦岛3条河流、五里河口和锦州湾水体、沉积物中As的含量、分布、形态及行为进行了系统研究。结果表明，葫芦岛的连山河和五里河未受到明显的As污染，沉积物总As含量一般低于10 mg•kg-1，河水As含量一般低于10 μg•L-1，茨山河下游紧邻葫芦岛锌厂，受到了严重的As污染，沉积物As含量达75.2 mg•kg-1。五里河口区As污染非常严重，锌厂在该区排污口处沉积物As含量高达3176.1 mg•kg-1，超过国家沉积物As标准158倍。受锌厂排污的影响锦州湾As污染也很严重，沉积物中As最高含量达到569.5 mg•kg-1。沉积物和孔隙水As含量在剖面上具有相似的变化趋势，表明孔隙水As含量主要受沉积物As含量影响。锦州湾沉积物中As主要以可交换态存在，残渣态次之，盐酸提取态最少，表明锦州湾沉积物中As的活性很强，有大量的可交换态As随时会进入上覆水体，是重要的As释放源，沉积物中大量As的释放可能会对葫芦岛和锦州湾地区生态系统造成严重的威胁。 以盐度和酸碱度作为环境影响因子进行的释放模拟实验，结果显示：不同盐度条件下，沉积物中的As均在48h左右达到最大释放量。此时，盐度为0‰的水体中As的释放量最大，而其他两种盐度的水体中As的释放量较小且二者相差不大。另外，在室温条件下，随着pH值的升高，沉积物中As的释放量逐渐增加。 通过对不同形态的单一含砷矿物的As提取效果研究得出：对于分级提取方法中吸附态砷的最佳提取条件应为1M KH2PO4 (pH5) 24h, 无定型铁氧化物上结合的砷0.2M oxalic/oxalate (pH3)避光 6h, 硫化亚铁上结合的砷，0.2M oxalic/oxalate (pH3)避光 1h。

Adsorption of arsenite and arsenate on amorphous iron hydroxide

Adsorption isotherms in solutions with ionic strengths of 0.01 at 25°C were measured over the arsenite and arsenate concentration range 10−7−10−3 M and the pH range 4–10. At low concentrations, these isotherms obeyed equations of the Langmuir type. At higher concentrations the adsorption isotherms were linear, indicating the existence of more than one type of surface site on the amorphous iron hydroxide adsorbent. Removal of arsenite and arsenate by amorphous iron hydroxide throughout the concentration range were determined as a function of pH. By careful selection of the relative concentration of arsenic and amorphous iron hydroxide and pH, removals on the order of 92% can be achieved.

Coal-burning roasted corn and chili as the cause of dental fluorosis for children in southwestern China

To find the pathologic cause of the children's dental fluorosis in southwestern China, diet structure before the age of 6 and prevalence rate of dental fluorosis (DF) of 405 children were investigated, and the fluorine and arsenic content of several materials were determined. The prevalence rate of DF of children living on roasted corn before the age of 6 is 100% with nearly 95% having the mild to severe DF; while that of children living on non-roasted corn or rice is less than 5% with all having very mild DF. The average fluorine and arsenic concentration are 20.26 mg/kg and 0.249 mg/kg in roasted corn, which are about 16 times and 35 times more than in non-roasted corn, respectively. The average fluorine concentration is 78 mg/kg in coal, 1116 mg/kg in binder clay and 313 mg/kg in briquette (coal mixed with clay). The average arsenic concentration of coal is 5.83 mg/kg, the binder clay is 20.94 mg/kg, with 8.52 mg/kg in the briquette. Living on roasted corn and chili is the main pathologic cause of endemic fluorosis in southwestern China. The main source of fluorine and arsenic pollution of roasted corn and chill is the briquette of coal and binder clay. (C) 2010 Elsevier B.V. All rights reserved.