發(fā)布時(shí)間：2018-03-21 03:47

  本文選題：四氫化硅　切入點(diǎn)：職業(yè)接觸限值　出處：《華中科技大學(xué)》2012年碩士論文　論文類(lèi)型：學(xué)位論文

【摘要】：四氫化硅是一種常見(jiàn)的工業(yè)原料，是提供硅組分的重要?dú)怏w源，可用于制造高純度單晶硅、多晶硅、異質(zhì)硅、微晶硅、非晶硅、氮化硅、氧化硅等各種硅化物。四氫化硅在過(guò)渡溫度17K（熱力學(xué)溫度單位）和極高的壓力下（96和120GPa）可作為超導(dǎo)體使用[1]。由于四氫化硅的高純度和能實(shí)現(xiàn)精細(xì)控制，，已經(jīng)成為許多其他硅源無(wú)法取代的重要特種氣體[2-3]。四氫化硅目前在電子工業(yè)、能源工業(yè)、玻璃工業(yè)、化學(xué)工業(yè)及高科技領(lǐng)域等多個(gè)行業(yè)中均被大量使用[4]。既往研究顯示四氫化硅的主要毒性是刺激作用，有研究顯示它可對(duì)皮膚、眼睛和呼吸道產(chǎn)生強(qiáng)烈刺激作用，造成對(duì)作業(yè)人員的健康危害[5-6]，但是，目前我國(guó)尚未制定工作場(chǎng)所空氣中四氫化硅的職業(yè)接觸限值和檢測(cè)方法。為保護(hù)工人健康和預(yù)防職業(yè)危害，制訂工作場(chǎng)所空氣中四氫化硅的職業(yè)接觸限值十分重要。本研究在查閱相關(guān)文獻(xiàn)的基礎(chǔ)上，進(jìn)行了工作場(chǎng)所空氣中四氫化硅的職業(yè)接觸限值的探討和檢測(cè)方法的研究。本研究主要包括兩部分： 第一部分：工作場(chǎng)所空氣中四氫化硅的職業(yè)接觸限值的探討 目前，世界上有美國(guó)、加拿大、澳大利亞、日本等近20個(gè)國(guó)家制定了工作場(chǎng)所空氣中四氫化硅的職業(yè)接觸限值。其中將近三分之二的國(guó)家將工作場(chǎng)所空氣中四氫化硅的8小時(shí)時(shí)間加權(quán)平均容許濃度定為(PC-TWA)為7mg/m~3；其余的國(guó)家將工作場(chǎng)所空氣中四氫化硅的8小時(shí)時(shí)間加權(quán)平均容許濃度定為(PC-TWA)為0.7mg/m~3。通過(guò)查閱文獻(xiàn)，結(jié)合四氫化硅的化學(xué)特性、毒性實(shí)驗(yàn)資料、人群流行病學(xué)資料，以及企業(yè)生產(chǎn)過(guò)程中四氫化硅實(shí)際水平測(cè)定，建議我國(guó)工作場(chǎng)所空氣中的四氫化硅時(shí)間加權(quán)平均容許溶度(PC-TWA)為7mg/m~3。 第二部分：工作場(chǎng)所空氣中四氫化硅檢測(cè)方法的研究 目前國(guó)內(nèi)外檢測(cè)四氫化硅的方法主要有原子吸收分光光度計(jì)法、氣相色譜法、紫外分光光度法、直讀儀法。這幾種方法實(shí)施起來(lái)均有一定的局限性，我國(guó)尚未制定測(cè)定四氫化硅的標(biāo)準(zhǔn)方法，本研究在仔細(xì)分析相關(guān)測(cè)定方法的基礎(chǔ)上，進(jìn)行了分光光度計(jì)法測(cè)定四氫化硅含量的研究。 本方法原理為：用堿性樹(shù)脂基球形活性炭管采集空氣中的四氫化硅，經(jīng)熱水解吸，轉(zhuǎn)化為偏硅酸鈉，在酸性溶液中，偏硅酸鈉轉(zhuǎn)化為偏硅酸，并與鉬酸銨反應(yīng)，生成硅鉬雜多酸，再用1，2，4-氨基萘酚磺酸溶液將硅鉬雜多酸還原為硅鉬藍(lán)，在680nm波長(zhǎng)下測(cè)量吸光度，進(jìn)行定量。 本方法的主要測(cè)定步驟為：用堿性樹(shù)脂基球形活性炭管采集空氣中的四氫化硅，將活性炭取出并用熱水解吸，吸取適量的解吸液于15mL聚乙烯管中，用水稀釋。加入鹽酸溶液和鉬酸銨溶液，充分搖勻，于水浴中放置10min，加入草酸溶液，充分搖勻，放置2min～15min，加入1，2，4-氨基萘酚磺酸溶液，充分搖勻。5min后，于分光光度計(jì)上680nm波長(zhǎng)處，以試劑空白作參比測(cè)定吸光度。 本方法的平均采樣效率為97.53%，平均解吸效率為94.94%，穿透容量＞0.84mg/300mg，檢出限為0.054μg/mL，定量下限為0.18μg/mL，最低檢測(cè)濃度為1.2mg/m~3（以采樣3.0L計(jì)算），隨著堿性樹(shù)脂基球形活性炭放置時(shí)間的延長(zhǎng)，四氫化硅的轉(zhuǎn)換率逐漸降低，采過(guò)的樣品在室溫下密封保存后一周下降率10%。 本方法經(jīng)武漢市職業(yè)病防治院、華中科技大學(xué)同濟(jì)醫(yī)學(xué)院和武漢市職業(yè)病醫(yī)院三家單位驗(yàn)證，同時(shí)也在現(xiàn)場(chǎng)進(jìn)行了驗(yàn)證，表明該測(cè)定方法重復(fù)性好、簡(jiǎn)單可行、結(jié)果準(zhǔn)確、可用于現(xiàn)場(chǎng)檢測(cè)。 結(jié)論: 通過(guò)工作場(chǎng)所空氣中四氫化硅職業(yè)接觸限值和檢測(cè)方法研究，得出以下主要結(jié)論： 1、建議我國(guó)工作場(chǎng)所空氣中的四氫化硅時(shí)間加權(quán)平均容許溶度(PC-TWA)為7mg/m~3。 2、測(cè)定方法中，四氫化硅采樣用活性炭浸漬氫氧化鈉真空干燥后最好在一天內(nèi)使用，或者將活性炭在真空狀態(tài)下保存�，F(xiàn)場(chǎng)采集樣品密封保存在室溫下至少可保存一周。 3、用分光光度計(jì)檢測(cè)四氫化硅含量的方法其各項(xiàng)指標(biāo)均達(dá)到《作業(yè)場(chǎng)所空氣中毒物檢測(cè)方法的研制規(guī)范》（GBZ159-2004）的要求，適用于作業(yè)場(chǎng)所空氣中四氫化硅的測(cè)定。
[Abstract]:Four hydrogenated silicon is a common industrial raw materials, is to provide an important source of gas silicon components, can be used in the manufacture of high purity silicon, polycrystalline silicon, silicon heterojunction, microcrystalline silicon, amorphous silicon, silicon nitride, silicon oxide and other silicide. Four hydrogenated silicon in the transition temperature of 17K (thermodynamic temperature units) and high pressure (96 and 120GPa) can be used assuperconductor four [1]. due to the high purity silicon hydride and can achieve precise control, has become many other silicon sources can not replace important special gas hydrogenation of [2-3]. four silicon currently in the electronics industry, energy industry, glass industry, chemical industry and many industries such as high-tech fields are used extensively by the [4]. previous studies showed that the main toxicity of four hydrogenated silicon is stimulated, studies have shown it to the skin, eyes and respiratory tract have a strong stimulating effect, causing health hazards to workers [5-6], but. China has not yet formulated before the occupation exposure to workplace air four hydrogenated silicon limits and testing methods. In order to protect the health of workers and the prevention of occupation hazards, occupation contact four hydrogenated silicon made in the air of workplace limits is very important. This study on the basis of literature review, the research value and detection method the occupation exposure in the air of workplace four hydrogenated silicon limit. This study mainly includes two parts:
The first part: Discussion on the occupational exposure limit of four hydrogenated silicon in the air of the workplace
At present, the United States, Canada, Australia and the world, nearly 20 countries such as Japan made contact in the air of workplace occupation four hydrogenated silicon limits. The 8 hour time weighted nearly 2/3 countries will work four silicon in workplace air average concentration is 7mg/m~3 (PC-TWA) for 8 hours; the rest of the country will be weighted four hydrogenated silicon in workplace air as the average concentration (PC-TWA) of 0.7mg/m~3. through the literature, combined with the chemical properties of four hydrogenated silicon, toxicity data, epidemiological data, determination of four hydrogenated silicon actual level and the enterprise production process, suggestions for China's workplace four silicon time the air in the weighted average allowable (PC-TWA) 7mg/m~3. solubility
The second part: Study on the method of detecting four hydrogenated silicon in the air of the workplace
At present the four detection methods are mainly silicon hydride atomic absorption spectrophotometry, gas chromatography, UV spectrophotometry, direct reading instrument method. These methods implement have certain limitations, our country has not yet developed the standard method for the determination of four hydrogenated silicon, the basic research in the related careful analysis method, studied the spectrophotometric determination of silicon content of four hydrogenation meter.
The principle is: four silicon hydrogenation collected in air using alkaline resin based spherical activated carbon tube, hot water, into sodium metasilicate, in acidic solution, sodium metasilicate into silicic acid, and reacted with ammonium molybdate to form silicon molybdenum heteropoly acid, then 1,2,4- amino naphthalene phenol sulfonic acid solution silicon molybdenum heteropoly acid reduction of silicon molybdenum blue, quantitative measurement of the absorbance at the wavelength of 680nm.
The main steps of the method for the determination of silicon hydride: four collected in air using alkaline resin based spherical activated carbon tube, remove activated carbon and water desorption, the appropriate amount of desorption in 15mL polyethylene pipe, diluted with water. Add hydrochloric acid solution and ammonium molybdate solution, fully shaken, placed in water bath 10min the addition of oxalic acid solution, shake well, place the 2min ~ 15min, adding 1,2,4- amino naphthol sulfonic acid solution, shake well after.5min, spectrophotometer at the wavelength of 680nm, to determine the absorbance of reagent blank as reference.
The method of the average sampling efficiency was 97.53%, the average desorption efficiency was 94.94%, the penetration capacity of more than 0.84mg/300mg, the detection limit is 0.054 g/mL, the lower limit of quantification was 0.18 g/mL, the minimum detectable concentration was 1.2mg/m~3 (3.0L, by sampling calculation) with the extension of basic resin based spherical activated carbon placed time, conversion of four hydrogenated silicon the rate decreased gradually, decreased rate of 10%. extraction samples were sealed and stored at room temperature after a week
The method was verified by three units of Tongji Medical College, Wuhan Tongji Medical College and Wuhan occupational disease hospital. Meanwhile, it was also verified at the scene. The results showed that the method is repeatable, simple, feasible and accurate, and it can be used for field detection.
Conclusion:
Through the study of the occupational exposure limit and detection method of four hydrogenated silicon in the air of the workplace, the following main conclusions are drawn:
1, it is suggested that the time weighted average permissible solubility (PC-TWA) of the four hydrogenated silicon in the air of the workplace of our country is 7mg/m~3.
2, in the determination method, four hydrogenated silicon sample was impregnated with activated carbon and sodium hydroxide. After vacuum drying, it was best to use in a day or save the activated carbon in vacuum. The field samples were sealed and kept at room temperature for at least one week.
3, using spectrophotometer to detect the content of four hydrogenated silicon, all of the indicators meet the requirements of < < specification for detection of toxic substances in workplace air > > (GBZ159-2004), which is suitable for the determination of four hydrogenated silicon in the air of workplace.

【學(xué)位授予單位】：華中科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2012
【分類(lèi)號(hào)】：R134.4

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