安全知识---三氟化氮（NF3）安全操作实践.doc

广州市世源气体有限公司安全知识-三氟化氮(NF3)安全操作实践1. General概述Nitrogen trifluoride (NF3) is a toxic, colorless, odorless, nonflammable, oxidizing compressed gas NF3offers the advantages of relative ease of use at ambient conditions and the ability to act as a fluorinating agent. Because of these factors, it has gained commercial acceptance in a number of applications. The electronics industry uses it in plasma and thermal cleaning applications for its advantages such as high etch rates, high selectivity, carbon-free etching, and minimal residual contamination. NF3 is also used as a fluorine source in high energy chemical lasers, owing to its ease of use relative to fluorine gas. NF3is also used as an intermediate in the production of specialized chemicals.三氟化氮（NF3）是有毒、无色、无嗅、不可燃的氧化性压缩气体。NF3具有在室温条件下相对容易使用和可以用作氟化剂的优点。由于这些因素，它在许多应用中获得了广泛的认可。由于它的优点，如高蚀刻率、高选择性、无碳蚀刻和最小限度的残留污染，电子工业把它用在等离子和热清洁应用中。由于它相对于氟气更容易使用，NF3在高能化学激光器中用作氟源。在特殊化学品的生产中NF3还用作媒介。NF3is available in a variety of grades and at purity levels in excess of 99.999 % due to advanced purification techniques developed by Air Products. Table 1 lists the physical and chemical properties of NF3.NF3有多种等级，由于Air Products发展的先进的净化技术，还有纯度超过的99.999 %的NF3。表1列出了NF3的物理和化学性质。2. Key Considerations关键的考虑Health Effects对健康的影响NF3 is not hazardous by skin contact and is a relatively minor irritant to the eyes and mucous membranes. 皮肤接触NF3是没有危险的。对于眼睛和黏膜，它是一个相对程度较轻的刺激物。Over-exposure to NF3via inhalation induces the conversion of hemoglobin to methemoglobin. The formation of methemoglobin reduces the amount of oxygen available to body tissues. This can lead to chemical cyanosis, headache, dizziness, weakness, confusion, and other manifestations associated with a reduced oxygen supply. Hemolytic anemia, enlargement of the spleen, and pathologic changes in the liver, kidneys, and heart muscle may occur as secondary effects of methemoglobinemia, which is reversible. At the cessation of NF3exposure, methemoglobin reverts back to hemoglobin. While methemoglobinemia clears spontaneously over several hours, hemolytic anemia may take several weeks to resolve.过量吸入NF3会导致血色素转化成高铁血红蛋白。高铁血红蛋白的形成减少了身体组织可以得到的氧的数量。这会导致化学黄萎病、头痛、眩晕、虚弱、昏聩和其它伴随着氧气供应减少的表现。作为高铁血红蛋白症的次要影响，会发生溶血性贫血、脾扩大和肝、肾、心肌的病变，这些影响是不可逆转的。在NF3暴露停止后，高铁血红蛋白转化回血红素。高铁血红蛋白症会在几个小时后自动消失，而溶血性贫血需要几个星期才能解除。Toxicological Properties毒物学性质Inhalation吸入 LC50 = 6,700 ppm (1 hour小时) rat鼠 For all species tested, the immediate effect of acute exposure to high concentrations of NF3 is extensive methemoglobin formation with subsequent hypoxia. This is often followed by hemolytic anemia that can cause liver, kidney, spleen, and sometimes heart effects. Vomiting has also been observed in dogs and monkeys that have inhaled NF3.对于测试的所有物种，急性暴露于高浓度NF3的直接影响是大范围高铁血红蛋白形成和并发的组织缺氧。随后的通常是会导致肝、肾、脾和有时候的心脏病变的溶血性贫血。在已经吸入了NF3的狗和猴子身上还观察到了呕吐。Exposure of rats to 100 ppm NF3 by inhalation for 7 hours per day, 5 days per week for 19 weeks resulted in mild to moderate pathological changes in the liver and kidneys. No other effects were noted. These chronic exposures failed to produce any measurable changes in the general appearance, appearance of teeth, activity, growth, mortality, blood, serum chemistry, or fluorine content of the teeth and bones of the rats tested.老鼠通过吸入暴露在100 ppm NF3 中连续19周，每周5天，每天7小时，导致了肝和肾的轻微到中度的病变。没有注意到其它影响。这些长时间的暴露没有在被测试老鼠的总体外观、牙齿外观、活动性、生长、死亡率、血液、血清化学性质或牙齿和骨骼的氟含量方面产生任何可测量的变化。NF3 has been found to be weakly mutagenic in bacterial cells and non-mutagenic in animal cells and whole animal test systems.已经发现，在细菌细胞内NF3是轻微的诱导有机质突变的物质，而在动物细胞和整个动物测试系统内NF3不会诱导有机质突变。Exposure Levels暴露水平The National Academy of SciencesNational Research Council, Committee of Toxicology, has recommended an Emergency Exposure Limit (EEL) for NF3 of 22,500 ppm. This is based upon actual measurements which indicate that exposure of up to 30,000 ppm x min did not cause any negative health effects in laboratory animals, while anemia did occur at exposures of 120,000 ppm x min. 国家科学院国家研究理事会毒物学委员会已经推荐的NF3紧急暴露极限(EEL)为22,500 ppm。这是基于实际测量的。该测量显示，大到30,000 ppm x min的暴露不会在实验室动物身上导致对健康的负面影响，而当暴露达到120,000 ppm x min时确实发生了贫血。The EEL is a concentration that is believed not to result in a period of disability or interfere with the performance of tasks. While exposure at these levels may produce injury, the injury would be reversible. The EEL represents a cumulative exposure limit taking into account both the time of exposure and the concentration at which the exposure occurs. Any combination of time of exposure and concentration that is less than the recommended level of 22,500 ppm x min is acceptable. Table 2 illustrates acceptable exposure times for varying concentrations of NF3 in air at the EEL of 22,500 ppm x min. EEL是这样一个浓度，在此浓度下不会导致一段时间的无力或妨碍完成任务。虽然在这种水平的暴露可能导致伤害，但伤害是可逆的。EEL代表了一个既考虑了暴露时间又考虑了暴露发生时的浓度的累积的暴露极限。任何小于22,500 ppm x min的推荐水平的暴露时间和浓度的组合都是可以接受的。表2说明了在22,500 ppm x min的EEL下，对于空气中不同的NF3浓度可以接受的暴露时间。The TLV-TWA (10 ppm or 29 mg/m3ACGIH,1997) for NF3 was set by the American Conference of Governmental Industrial Hygienists at one-tenth the test level of the previously cited 19-week study under Toxicological Properties. 美国政府工业卫生学者会议把NF3的TLV-TWA (10 ppm或29 mg/m3ACGIH,1997)设定为前面在“毒物学性质”下引用的19周研究的测试水平的十分之一。Tables 3, 4 and 5 provide detailed information on the TLV-TWA, Immediately Dangerous to Life and Health (IDLH) concentrations, and Acute Toxicity, LC50 levels for common gases used in wafer fabrication.表3、4和5提供了用于晶片制造的常用气体的关于TLV-TWA水平、立即危及生命和健康的浓度水平、剧毒LC50水平的详细资料。Table 1 Physical and Chemical Properties表1 物理和化学性质(NF3 is a colorless gas. Trace quantities of impurities can impart a musty or pungent odor to the gas.)NF3是无色气体。痕量的杂质会使气体带有一种霉味或刺激性气味。Melting Point熔点 340.2F (206.8C)Boiling Point沸点 200.2F (129C)Critical Temperature临界温度 38.5F (39.3C)Critical Pressure临界压力 44.02 atm (4.46 MPa)Liquid Density液体密度 (atm at Boiling Point在沸点) 97.13 lb/ft3(1554 kg/m3)Gas Density气体密度 (atm, 70F) 0.184 lb/ft3(2.95 kg/m3)Heat of Vaporization at Normal Boiling Point正常沸点时的蒸发热 2.77 kcal/mol (11.60 kj/mol)Heat of Fusion熔解热 0.095 kcal/mol (0.40 kj/mol)Specific Gravity比重 (70F, air空气=1) 2.503Specific Volume比容 (70F, atm) 5.43 ft3/lb (0.339 m3/kg)Standard Enthalpy of Formation at 0 K 0 K时的生成标准焓 28.43 kcal/mol (119.03 kj/mol)Standard Enthalpy of Formation at 298 K 298K时的生成标准焓 29.80 kcal/mol (124.77 kj/mol)Standard Entropy at 298 K 298 K时的标准熵 62.2 cal/mol-K (260.5 j/mol-K)Gibbs Free Energy of Formation at 298 K 298 K时的吉布斯生成自由能 21.4 kcal/mol (89.6 kj/mol)Heat Capacity at 298 K at Constant Pressure 298 K时的恒压热容 12.79 cal/mol-K (53.54 j/mol-K)Molecular Weight分子量 71.002Geometry几何形状 Pyramidal金字塔形N-F Bond Length N-F键长 1.37 AngstromsN-F Bond Angle N-F键角 103 DegreesMean Bond Energy 平均键能 66.4 kcal/mol (278.0 kj/mol)Dipole Moment 偶极矩 .234 DSolubility (slightly soluble in water)溶解性（微溶于水） 1.43 x 10-5mole fraction at 1 atm/22CTable 2. Acceptable Exposure Times for Varying Concentrations of NF3in Air (EEL=22,500 ppm x min)表2 对于空气中不同的NF3浓度，可以接受的暴露时间(EEL=22,500 ppm x min)Time of Exposure (min) 暴露时间（分钟）Concentration (ppm)浓度1 22,50010 2,25030 75060 375Source: “Recommendation for Revised Emergency Exposure Limits for Spills of NF3,” NAS/NRC Committeeon Toxicology, 1974. 来源：“关于修改的NF3逸出紧急暴露极限的建议”，NAS/NRC毒物学委员会，1974年。Reactivity反应活性Reactivity is similar to that of oxygen at room temperature. NF3 is relatively inert at ambient temperature and pressure conditions and exhibits little, if any, reactivity. However, at higher temperatures (>300C), NF3 will dissociate into reactive fluorine species that react with most materials. These reactive species can lead to uncontrolled reactions with polymers and certain metals, liberating heat and causing further dissociation of NF3. As temperatures increase above 400C, the reactivity of NF3 becomes more like that of fluorine. Therefore, avoid conditions and/or mechanisms that could lead to the inadvertent heating of NF3.反应活性与室温下的氧相似。在常温常压下NF3是相对不活泼的，显示出很低，如果说有的话，的反应活性。但是，在更高的温度(>300C)时，NF3将分解成活泼的能同大多数物质反应的氟。这些活泼的氟会导致无法的控制的同聚合体和特定金属的反应，释放出热量，导致NF3的进一步分解。当温度上升到400C以上时，NF3的反应活性变得更象氟。因此，要避免可能导致无意中对NF3加热的条件和/或机制。For example, one such mechanismadiabatic compressionoccurs when high-pressureNF3 is introduced rapidly into a low-pressure dead-end space. The resulting rise in gas temperature may be sufficient to cause the dissociation of NF3.例如，当把高压引入一个低压的密闭空间时，一种这样的机制绝热压缩就会发生。所导致的气体温度的上升可能足以导致NF3的分解。NF3 is often used in concert with other gases such as silane in the processing of semiconductors. Related information regarding reactivity involves Air Products flammability testing of NF3/Silane (SiH4) mixtures, which yielded consistent results with those reported at the Chemical Technology Research Lab in Tokyo, Japan in 1990. The lower and upper flammability limits (LFL and UFL) for SiH4 in NF3 are 0.66% and 95.3%, respectively. In other words, in a binary blend of SiH4 and NF3, concentrations of silane greater than or equal to 0.66% and less than or equal to 95.3%, form an explosive mixture. Dilution with nitrogen (N2) provides a three-component flammability limit of 2.0% SiH4/2.5% NF3/95.5% N2. Although the LFL for SiH4 increases to 2.0% with the addition of N2, the large range of flammability still exists. To achieve safe operating conditions in a system using SiH4 and NF3, dilution with N2 is required to remain outside the flammability limits. Table 6 indicates the magnitude of the flammability range of SiH4 and H2 blends of NF3, O2 and air, respectively. NF3经常同其它气体，如硅烷一起用于半导体的处理。关于反应活性的相关资料包括Air Products的NF3/硅烷(SiH4)混合物的可燃性测试。该测试得到的结果同1990年日本东京的化学技术研究实验室报道的结果相一致。在NF3中的硅烷的可燃下限和上限分别是0.66%和95.3%。换句话说，在硅烷和NF3的二元混合物中，硅烷的浓度大于或等于0.66%和小于或等于95.3%，都会形成爆炸性混合物。用氮(N2) 稀释后的三组分的可燃极限为2.0% SiH4/2.5% NF3/95.5% N2。尽管随着氮的加入，硅烷的LFL增加到2.0% ，可燃范围仍然很大。为了在使用SiH4和NF3的系统里得到安全的操作条件，要求用氮稀释，使之保持在可燃极限以外。表6说明了SiH4和H2分别在NF3、O2和空气中的混合物的可燃范围的大小。Environmental Impact对环境的影响NF3 can be manufactured, used, and disposed of in a safe and environmentally responsible manner. NF3 poses a minimal environmental hazard due to its non-reactivity and insolubility in water under normal conditions可以通过一种安全的对环境负责的方式来制造、使用和处理NF3。由于它的不活泼性和正常状态下在水中的不溶解性，NF3几乎不会造成环境危害。Air Products has sponsored research at the Massachusetts Institute of Technology to study the reactivity of NF3 in the atmosphere. Also, Air Products continues to conduct and/or support the analysis of emissions from semi-conductor manufacturing production tools.Air Products已经在麻省理工学院赞助了在空气中NF3的的反应活性的研究。Air Products还一直进行和/或支持来自半导体工业生产工具的辐射的分析。NF3 has negligible impact on ozone depletion. The photolysis of NF3 in the stratosphere yields a fluorine radical that reacts fairly rapidly to form hydrogen fluoride (HF). The stability of HF results in an ozone-depleting potential of the fluorine radical that is approximately three orders of magnitude less than that of the chlorine radical. NF3 has a relatively short atmospheric lifetime (740 years) and dissociates more readily than C2F6 and CF4.HF ultimately diffuses down to the troposphere where it is removed by wet deposition. NF3对于臭氧损耗几乎没有影响。在同温层里NF3的光解作用氟原子团，氟原子团相当迅速地发生反应，生成氟化氢(HF)。HF的稳定性导致了氟原子团的臭氧损耗的可能。氟原子团大约比氯原子团小三个数量级。NF3具有相对短的大气寿命（740年），比C2F6和CF4.更容易分解。HF最终扩散到大气中，在大气中它通过湿沉积被除去。Due to the low solubility of NF3 in water (1.43x 10-5 mole fraction at 1 atm partial pressure of NF3 and 22C) and its non-reactivity with water under normal conditions, the environmental hazards of an NF3 leak at sea, or in coastal waters during shipment, are minimal. Any large release of NF3 would dissipate before significant concentrations of gas could build up in water.由于NF3在水中的低溶解性（在22C和NF3的分压为1 atm时为1.43x 10-5）和通常条件下它同水不反应，在运输过程中，在海洋或海岸的NF3泄露的环境危害是最小的。在有意义的气体浓度在水中能够积累起来之前，任何大量释放的NF3都已经弥散了。Abatement消除Air Products will assist customers in determining and implementing appropriate methods to control and monitor NF3 emissions. The method and degree of control, and regulatory compliance, is the ultimate responsibility of the end user. If your facility implements an abatement policy, please contact your Air Products representative for specific recommendations.在决定和实施合适的方法来控制和监测NF3的扩散方面，Air Products会帮助用户。控制的方法与程度和与法规的一致性是终端用户的根本责任。如果你的设备要实施一项消除策略，请同Air Products的代表联系，寻求具体的建议。3. Maintaining User Safety维护用户的安全Material Release 材料释放If a leak develops in a customer system, close the cylinder valve and vent residual product, and purge the lines with inert gas before attempting repairs. Use appropriate protective equipment (SCBA).如果在用户的系统里发生了泄露，关闭阀门并排出残余产品。在试图修理之前，用惰性气体净化管道。使用合适的防护装备（SCBA）。Leaks occurring at the cylinder valves pressure relief device, diaphragms, or valve to the cylinder connection cannot be repaired.发生在钢瓶阀门的减压装置、横膈膜或阀门到钢瓶的接头处的泄露不能维修。Attempts to repair these leaks may result in catastrophic failure of the package.试图修理这些泄露会导致包装的灾难性故障。If such a leak develops, or the cylinder valve cannot be closed, immediately contact the Air Products Emergency Response System at these numbers:如果发生了这样的泄露，或者钢瓶阀门无法关闭，立刻同Air Products的紧急反应系统联系：Continental U.S., Canada & Puerto Rico美国大陆、加拿大和波多黎各:(800) 523-9374Other Locations其它地方: (610) 481-7711Fire Control起火控制NF3 cylinder valves are equipped with pressure relief devices consisting of a frangible rupture disc backed by a fusible alloy. This allows the cylinder contents to be released, preventing cylinder failure under fire conditions. The disc is designed to burst at 3400psig and the alloy will melt at 74C. Both conditions must be met before the pressure release device will vent. Although NF3 is non-flammable, it will vigorously support combustion. Do not use HALON 1301, dry ammonium phosphate, or bicarbonate on NF3 fires because they produce toxic by-products. NF3钢瓶配备有由易碎破裂盘及其后的易熔合金组成的减压装置。在起火的情况下，它允许钢瓶内容物被释放出来，防止钢瓶发生故障。破裂盘设计得在3400psig的压力下破裂，合金在74C时熔化。在减压装置排气之前，两个条件都要被满足。尽管NF3是不可燃的，它会有力地支持燃烧。不要在同NF3有关的火焰上使用HALON 1301、干磷酸铵或重碳酸盐，因为它们产生有毒副产品。Use carbon dioxide (CO2) extinguishers to extinguish small fires. Use large amounts of water to extinguish fires covering a large area. Although NF3 is not water soluble, many of the toxic by-products such as HF are water soluble. The best extinguishing method requires large amounts of liquid nitrogen (LIN) to provide a non-reactive environment and act as a heat sink.使用二氧化碳(CO2)灭火器来熄灭小火。使用大量的水来熄灭覆盖面积很大的火焰。尽管NF3不溶于水，许多的有毒副产品，如HF是可溶于水的。最好的灭火方法是用大量的液氮(LIN)来提供一个不反应的环境，同时作为热接收器。First Aid Treatment急救处理An individual exhibiting symptoms of acute NF3 poisoning from concentrations in excess of 6,000 ppm should be removed from the contaminated area as quickly as possible. Then oxygen therapy should be started at once by trained personnel, and a physician should be notified immediately. 应该把表现出超过6,000 ppm浓度的剧烈的NF3中毒症状的人员尽快从污染区域转移走。接着由经过训练的人员立刻开始进行氧气治疗，并且应该立刻通知医生。Observe these follow-up first-aid measures:遵守下列急救措施：Continue therapy for up to six hours.继续治疗6个小时以上。Individual should rest unde