硝基氧化剂的毒理及安全防护

硝基氧化剂作为高能可贮存液体推进剂的组成部分,广泛应用于大型运载火箭和导弹[1].俄罗斯现役洲际导弹SS-18、SS-19,我国长征系列运载火箭都采用硝基氧化剂和肼类燃料作为发动机的能源和工作介质[2-4].为满足靶场试验、作战和训练的需要,军事和航天部门贮存了相当数量的硝基氧化剂,由于硝基氧化剂具有强腐蚀性、强氧化性、易挥发且毒性大的特点,在储存、运输、转注、使用和装备维修中由于违章操作、设备故障、偶然因素或处置不当等原因均会引起不同程度的泄漏,对人员和环境可能会造成伤害或污染.在我国导弹和航天发射试验中,曾发生过多起由于推进剂泄漏引起的人员中毒事故[5].本文介绍硝基氧化剂在贮存、使用中可能的接触途径、对人员的伤害及安全防护.     

皮肤防护材料耐火箭推进剂渗透试验方法的建立及应用

目的：在设计加工渗透容器的基础上，探索皮肤防护材料耐火箭推进剂渗透率测试方法。方法：通过测定密闭容器内火箭推进剂在设定时间内透过试片的质量，计算单位时间、单位面积试片的推进剂介质渗透量。结果：利用渗透容器内推进剂介质质量变化率。建立了皮肤防护材料耐火箭推进剂渗透率测试方法，提出了将渗透率超过100μg／（cm^2·min）作为对推进剂无防护能力的基本判据，提高了材料防护性能测试的可靠性。结论：通过国内外防护材料渗透性能测试比对．初步验证了所建立方法的科学性，该方法可以作为检验材料对推进剂防护性能的基本依据。     

间甲酚的家兔皮肤防护试验

间甲酚对人体危害主要是其对皮肤,粘膜有强烈刺激和腐蚀作用。为了其安全生产,试制几种皮肤防护剂,旨在通过试验,验证其防护效果。1 材料和方法1.1 材料间甲酚原液由燕化公司曙光厂提供,染毒时用花生油配成35%的溶液;家兔为新西兰纯种,由中日友好医院提供;     

五种环氧树脂固化剂的刺激/腐蚀性试验结果及安全防护

目的 定性和半定量评价环氧树脂固化剂对哺乳动物皮肤局部的刺激或腐蚀作用,为皮肤防护提供依据.方法 按照GB/T 21604-2008《化学品 急性皮肤刺激性/腐蚀性试验方法》,对5种常见环氧树脂固化剂进行检测.结果 5种环氧树脂固化剂中,异氰酸酯和酸酐环氧树脂固化剂两种产品皮肤刺激强度为轻刺激性,皮肤刺激反应积分均值分...     

硝酸羟胺防护装具的研制

目的：研制一种包括防护服和防护头罩在内的硝酸羟胺皮肤防护装具，可以在新型推进剂硝酸羟胺贮运、加注等使用过程中对作业人员起到有效防护作用。方法：该防护装具针对硝酸羟胺新型推进剂的特性，利用渗透实验选择涤纶基布涂覆聚氨酯为防护服和头罩主体防护材料，以防雾技术处理的聚碳酸酯（PC）作为头罩眼窗材料。结果：该防护装具经性能测试和现场试用评价，各项技术指标满足相关标准的要求。结论：该防护装具结构设计合理，克服了现有防护服和面具透气性能差、人体负荷大等缺陷，具有轻便、舒适、实用等特点，完善了液体推进剂的防护体系。     

火箭推进剂应急抢险个体防护装备的设计与研究

目的:研制一种用于液体火箭推进剂应急救援的个体防护装备。方法:防护服采取全包覆隔绝式结构,主要材料采用丁基胶或丁基胶涂覆聚乙烯胶布,内部安装温度、压力监测传感器。大眼窗全闭合头罩,内部安装量程为(0~20)×10-6(V/V)、精度为±1%的推进剂毒气监测传感器,内置头戴式有线耳麦和具备有线/无线2种传输方式的通信模块,无线和有线传输距离不小于150 m和1 000 m。采用空气压缩机作为主供气源,出口含油量不大于2 mg/m3,露点1~3℃。长管正压供气,气路安装涡流降温阀。结果:个体防护装备系统防护因数不小于100,呼吸防护因数不小于10 000,推进剂"气-液"防护时间不小于150 min。结论:该防护装备适用于保护操作人员在遂行推进剂突发事件应急抢险任务时免受推进剂伤害,防护性能好,并显著改善人体生理负荷,可满足发射场推进剂安全防护保障的需要。     

紫外线防护剂的毒性评价

为确保紫外线防护剂使用安全，并为产品应用提供实验依据，我们对毒性进行了检测，用小白鼠测紫外线防护剂的急性毒性，兔子及豚鼠测其皮肤刺激性、皮肤光毒、皮肤致敏性和眼的刺激性。结果显示紫外线防护剂的ＬＤ５０〉５０００ｍｇ／ｋｇ，多次皮肤刺激试验积分为０，病理检查积分为０．５分，多次眼刺激试验，皮肤光毒试验积分均为０，皮肤致为敏率为０；人体斑贴试验积分０。由此可见，紫外线防护剂为微毒类物质，对动物及人的皮     

放射防护材料和个人防护产品辐射屏蔽性能状况分析

目的 通过对国内送检的放射防护材料和个人防护材料及用品的检测结果进行统计整理,分析我国放射防护材料的辐射屏蔽性能及防护产品质量的现状。方法 整理2008年至2011年我国部分放射防护材料的检测结果,应用统计学软件分析。结果 统计分析得出三种防护材料的比铅当量和主要的几种个人防护用品铅当量的平均值和分布区间。结论 研究统计结果表明,我国的放射防护材料样品的屏蔽性能大部分达到或超过诊断X射线放射防护相关标准的要求。     

紫外线防护剂的毒性评价

为确保紫外线防护剂使用安全，并为产品应用提供实验依据，我们对其毒性进行了检测。用小白鼠测紫外线防护剂的急性毒性，兔子及豚鼠测其皮肤刺激性、皮肤光毒、皮肤致敏性和眼的刺激性。结果显示紫外线防护剂的ＬＤ５０＞５０００ｍｇ／ｋｇ；多次皮肤刺激试验积分为０，病理检查积分为０．５分；多次眼刺激试验，皮肤光毒试验积分均为０；皮肤致敏率为０；人体斑贴试验积分为０。由此可见，紫外线防护剂为微毒类物质，对动物及人的皮肤无刺激性、光毒作用及致敏作用，对动物的眼睛无刺激作用。     

两种新型高能量密度材料对家兔的皮肤刺激

正六硝基六氮杂异伍兹烷(CL-20)为白色结晶,是目前国际上重点研究的新型含能材料之一;3,4-二呋咱基氧化呋咱(DNTF)是一种新型高能量密度材料,可用作低特征信号推进剂的氧化剂,能量与CL-20相当。笔者开展了CL-20、DNTF对家兔皮肤刺激性试验,分别选用健康清洁级成年家兔各4只,雌雄各半,体重约1.5 kg,购自西安交通大学动物中心,动物合格证号:SCXK(陕)2007-001],试验前24 h,将背部脊柱两侧体毛     

A test method for the evaluation of protective glove materials used in agricultural pesticide operations.

The ASTM Standard Test Method for Resistance of Protective Clothing Materials to Permeation by Liquids and Gases (F 739-85) and the recommended permeation cell have been modified to permit the testing of protective clothing materials for permeation by the low volatility, low water solubility active ingredients present in many pesticide formulations. The modification makes use of solid collection medium, a thin (0.02-in. thick) sheet of silicone rubber, to collect permeants. Those compounds permeating the protective material can then be desorbed into an appropriate solvent and analyzed using conventional methods and instruments. A series of permeation tests have been conducted using samples of 10 common, commercially available protective glove materials and the modified cell. Permeation of the active ingredient as well as carrier solvent components of several concentrated pesticide formulations containing low volatility, low water solubility active ingredients and aromatic hydrocarbon carrier solvents has been monitored. The relative breakthrough and the total mass of material permeating the glove materials appears to be strongly related to the concentration of the aromatic carrier solvent present in the formulations studied to date. The collection method was found to be less useful for monitoring the permeation of active ingredients, which have reasonably high water solubilities. The results obtained by using this method with samples of protective glove materials challenged by several concentrated pesticide formulations are described. For these formulations containing xylene boiling range aromatic solvents, gloves made of nitrile rubber, butyl rubber, and Silver Shield were most resistant to permeation; natural rubber and polyethylene glove materials were least resistant.     

Pesticide glove permeation analysis: comparison of the ASTM F739 test method with an automated flow-through reverse-phase liquid chromatography procedure

The results of two methods of analysis for measuring glove permeability to pesticides are reported. The standard ASTM F739-85 testing procedure was used to determine breakthrough times and permeation rates for four protective glove materials for two commercially available pesticide formulations. The same glove materials and pesticides then were tested using an in-house developed automated in-vitro diffusion analysis (AIDA) procedure. The ASTM and AIDA procedures both demonstrated no detectable breakthrough of Sevin 50W or 2,4-D Amine 96% for nitrile butyl rubber and polyvinyl chloride gloves. Although no breakthrough of Sevin 50W or 2,4-D Amine 96 was detected for natural rubber or neoprene gloves following the ASTM procedure, permeation was observed in 2 of 3 replicate tests for both rubber and neoprene gloves when using the AIDA method. The observed discrepancy may have been caused by a longer sampling duration for the AIDA method (16 hr) than the ASTM procedure (8 hr). Advantages of the AIDA procedure are discussed.     

Selection and testing of a glove combination for use with the U.S. Coast Guard's chemical response suit

A study was sponsored by the U.S. Coast Guard to select a glove system for its chemical response suit that could meet or exceed the chemical resistance performance of the suit's base material. Three different protective glove combinations were evaluated for their permeation resistance to 28 chemicals. The glove combinations were based on three materials--Viton, butyl rubber, and Silvershield. The test chemicals were selected for one of two reasons. First, no single glove material could be identified to be resistant against the chemical of interest, or second, no permeation test data were available for judging glove material performance for the specific chemical. As can be expected, the permeation resistance of the glove combinations greatly exceeded that of the single glove material components. The butyl rubber/Silvershield glove combination was found to provide permeation resistance greater than 1 hr for all but one of the chemicals tested.     

Glove permeation by semiconductor processing mixtures containing glycol-ether derivatives.

Results of permeation tests of several glove materials challenged with semiconductor processing formulations containing glycolether derivatives are described. Commercial glove samples of nitrile rubber (Edmont), natural rubber (Edmont and Baxter), butyl rubber (North), PVC Baxter), a natural rubber/neoprene/nitrile blend (Pioneer), and a natural rubber/neoprene blend (Playtex) were tested according to the ASTM F739-85 permeation test method (open-loop configuration). The liquid formulations examined included a positive photoresist thinner containing 2-ethoxyethyl acetate (2-EEA), n-butyl acetate, and xylene; a positive photoresist containing 2-EEA, n-butyl acetate, xylene, polymer resins, and photoactive compounds; a negative photoresist containing 2-methoxyethanol (2-ME), xylene, and cyclized poly(isoprene); and pure 2-methoxyethyl acetate (2-MEA), which is the solvent used in a commercial electron-beam resist. With the exception of the negative photoresist, butyl rubber provided the highest level of protection against the solvent mixtures tested, with no breakthrough observed after 4 hr of continuous exposure at 25 degrees C. Nitrile rubber provided the highest level of protection against the negative photoresist and reasonably good protection against initial exposure to the other solvent mixtures. Gloves consisting of natural rubber or natural rubber blends provided less protection against the mixtures than either nitrile or butyl rubber. For most of the glove samples, permeation of the glycol-ether derivatives contained in the mixtures was faster than that predicted from the permeation of the pure solvents. Increasing the exposure temperature from 25 to 37 degrees C did not significantly affect the performance of the butyl rubber glove. For the other gloves, however, exposures at 37 degrees C resulted in decreases in breakthrough times of 25-75% and increases in steady-state permeation rates of 80-457% relative to values obtained at 25 degrees C. Repeated exposure of nitrile rubber samples resulted in shorter breakthrough times for all mixture components. In fact, exposure for as little as one-half of the nominal breakthrough time followed by air drying overnight resulted in measurable quantities of one or more of the component solvents at the inner surface of the gloves at the beginning of the next exposure. This effect was not observed with the butyl rubber samples. With the exception of the negative photoresist, heating previously exposed nitrile rubber samples at 70 degrees C for 20 hr prior to retesting reduced or eliminated the effects of residual solvents, permitting reuse of the gloves. The use of thin PVC or natural rubber gloves adjacent to the nitrile gloves provided moderate increases in permeation resistance.(ABSTRACT TRUNCATED AT 400 WORDS)     

Change in permeation parameters and the decontamination efficacy of three chemical protective gloves after repeated exposures to solvents and thermal decontaminations

BACKGROUND: Chemical protective clothing (CPC) and gloves, which provide adequate protection, are usually too expensive to be considered disposable. Repeated use of CPC without effective decontamination may result in secondary exposure and injury. However, decontamination may change the physical and/or chemical properties of the barrier material, causing variations in breakthrough time (BT) and steady-state permeation rate (SSPR). METHODS: Glove materials including neoprene, Guardian butyl rubber, and nitrile synthetic rubber were selected for this study. Toluene and acetone were chosen as the challenge chemicals. Permeation was measured in a closed loop system using a 2.5 cm permeation cell and a MIRAN infrared analyzer (Foxboro, MA). Following the permeation test, the samples were thermally decontaminated. After each exposure/decontamination cycle, BT and SSPR were measured. A total of 260 permeation tests were conducted. Permeation test results were collected on each material/chemical combination for up to 10 exposure/decontamination cycles. RESULTS: On average, changes in BT and SSPR in comparison with respect to new swatches were 11.5% and 13.7% after seven exposure/decontamination cycles. The percentages increased to 26.6% and 15.9% after 10 exposure/decontamination cycles, respectively. For at least seven cycles, the BT mean for four out of five material/chemical combinations tested (neoprene/acetone, neoprene/toluene, nitrile/acetone, and nitrile/toluene) was not significantly different from the original value of the BT for each corresponding swatch. Similarly, the SSPR mean for each of the five material/chemical combinations after at least five cycles was not significantly different from those for new swatches. The BT mean for the butyl/toluene combination, however, was significantly different from the new swatches even after the first exposure/decontamination. The SSPR mean was significantly different after five cycles compared to the new swatches. CONCLUSIONS: Except for the butyl/toluene combination, thermal decontamination was an effective method in removing the solvents from the matrix of selected glove materials. Multiple reuses of some chemical protective gloves could be safe if effective decontamination methods are used and the glove materials do not have significant degradation.     

Permeation of multifunctional acrylates through selected protective glove materials.

In support of the Premanufacture Notification (PMN) program of the Environmental Protection Agency's Office of Toxic Substances, the resistance of three glove materials to permeation by multifunctional acrylate compounds was evaluated through a program for the Office of Research and Development. Several recent PMN submissions relate to multifunctional acrylates and essentially no permeation data are available for this class of compounds. To better understand permeation behavior, tests were conducted with trimethylolpropane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDDA), and two mixtures of HDDA with 2-ethylhexyl acrylate (EHA). Because of the low vapor pressure and low water solubility of these compounds, the tests were conducted by using ASTM Method F739-85 with a silicone rubber sheeting material as the collection medium. Tests were performed at 20 degrees C with butyl, natural, and nitrile rubber glove materials. None of the acrylate compounds nor mixtures was found to permeate the butyl or nitrile rubber under the test conditions. Permeation through the natural rubber was observed in tests with pure HDDA, a 50% HDDA/50% EHA mixture, and a 25% HDDA/75% EHA mixture. TMPTA permeation through the natural rubber was also detected, but only in one of the triplicate tests after the 360-480 min sampling interval. For pure HDDA, the breakthrough detection time was 30-60 min and the steady-state permeation rate was 0.92 micrograms/cm2-min. For the HDDA/EHA mixtures, permeation of both mixture components was detected during the same sampling interval in each test. The breakthrough detection time was 30-60 min for the 50/50 mixture and from 15-30 to 30-60 min for the 25/75 mixture.(ABSTRACT TRUNCATED AT 250 WORDS)     

A portable chemical protective clothing test method: application at a chemical plant

The National Institute for Occupational Safety and Health (NIOSH), in cooperation with Monsanto Chemical Company, conducted an on-site evaluation of chemical protective clothing at Monsanto's Nitro, West Virginia plant. The Monsanto plant manufactures additives for the rubber industry including antioxidants, pre-vulcanization inhibitors, accelerators, etc. This survey evaluated six raw materials that have a potential for skin absorption: aniline, cyclohexylamine, diisopropylamine, tertiary butylamine, morpholine and carbon disulfide. Five generic glove materials were tested against these chemicals: nitrile, neoprene, polyvinylchloride, natural latex and natural rubber. The NIOSH chemical permeation portable test system was used to generate breakthrough time data. The results were compared to permeation data reported in the literature that were obtained by using the ASTM F739-85 test method. The test data demonstrated that aniline has too low a vapor pressure for reliable analysis on the portable direct reading detectors used. The chemical permeation test system, however, provided comparable, reliable permeation data for the other tested chemicals. Monsanto has used this data to better select chemical protection clothing for its intended use.     

Permeation resistance of glove materials to agricultural pesticides.

The toxicities of many agricultural pesticides require that hand protection be used by persons who mix, load, and apply these products, as specified on the label and material safety data sheet. Selection of gloves for formulations that contain organic solvents is particularly problematic because a solvent that permeates the glove can carry with it the active ingredient of the pesticide formulation. With a test method that measures the simultaneous permeation of the carrier solvent(s) and active ingredient(s), in particular those active ingredients that have low solubility in water and low volatility, over 100 permeation tests (in triplicate) with approximately 20 pesticide formulations were conducted with 13 different glove materials. These results are summarized and generalizations are presented within the perspective of the large base of permeation data for neat chemicals and another large permeation study with pesticides. Key among the findings is that the carrier solvent generally permeates first and at a much higher rate than the active ingredient. Furthermore, the permeation behavior of formulations containing solvents generally mirrored that of neat carrier solvents alone. Thus, insight into the selection of the most appropriate glove material for a given pesticide formulation can be gained from permeation data for neat chemicals. For the types of solvents that may be present in pesticide formulations, preferred materials include nitrile rubber, butyl rubber, and plastic film laminates. Natural rubber and polyvinyl chloride materials generally are not recommended.     

Evaluation of glove material resistance to ethylene glycol dimethyl ether permeation

Some glycol ethers have been reported to cause adverse reproductive effects in exposed male and female workers, and skin absorption has been determined to be an important route of entry of this class of chemicals. Because ethylene glycol dimethyl ether (EGDME) is a possible component of lithium-based primary battery electrolyte systems, a study was undertaken to determine the resistance of various commercially available gloves to permeation of this liquid. The gloves were tested by the ASTM Method F-739-81, and butyl rubber was found to be the most effective barrier to permeation. Further studies determined that the butyl gloves could be reused if they were reconditioned overnight in a vacuum oven at 50 degrees C. When a mixture of ethylene glycol dimethyl ether (30% v/v) and propylene carbonate (70% v/v) was tested, the results indicated that the propylene carbonate retards the permeation of the glycol ether by a factor of 10. This is believed to be caused by the propylene carbonate coating the surface of the butyl membrane to reduce the sorption of EGDME.     

The permeation of multi-component liquids through new and pre-exposed glove materials

The permeation of specimens from 13 commercially available gloves by 20 single- and multi-component solutions was measured. Of the 8 basic glove materials, the butyl rubber and polyvinyl alcohol specimens exhibited the longest breakthrough times over the widest range of chemicals and chemical combinations.