卤代海因的危险特性实验研究

为评价卤代海因的危险特性,通过克南实验、时间压力实验以及固体氧化性实验分别对二氯海因、溴氯海因以及二溴海因的爆炸性和氧化性进行了测试,通过家兔皮肤刺激性/腐蚀性实验对三种卤代海因的刺激性进行了研究,并分别对三种卤代海因的危险性进行了对比分析。结果表明：二氯海因、溴氯海因以及二溴海因都具有氧化性、对家兔皮肤具有严重刺激性、在正常商业包件中可能达到的压力下点火会导致具有爆炸猛烈性的爆燃;溴氯海因以及二溴海因克南实验极限直径均小于1.0mm,在封闭条件下加热不显示效应,二氯海因的克南实验极限直径为2.0mm,在封闭空间加热显示某种效应。三种卤代海因的氧化性和对家兔皮肤的刺激性没有显著区别,但二氯海因较溴氯海因以及二溴海因在封闭空间加热显示的效应更强。     

二氯海因热稳定性研究

为评价二氯海因在储运过程中的热稳定性,采用C80微量热法对二氯海因进行反应放热测试,并计算了该物质在50 L标准包装条件下的自加速分解温度；同时采用克南试验、时间/压力试验对二氯海因在封闭条件下加热和点火的效应进行了研究.结果表明:二氯海因的分解起始温度为202.3℃,分解热为1 168.8 J/g,50 L标准包装下的自加速分解温度为120℃；二氯海因的克南试验极限爆炸直径为2.0mm,在封闭条件下外部加热具有敏感性；时间/压力试验中反应压力从690 kPa升至2 070 kPa,所用时间为260 ms,在封闭条件内部点火时具有爆燃性.     

微波促进无机酸对金属腐蚀速率的研究

为缩短无机酸对金属腐蚀性的检测时间,提高危险性鉴定效率,在联合国《关于危险货物运输的建议书-试验和标准手册》关于化学品对金属腐蚀性检测方法的基础上,以微波辐射装置代替传统的电加热水浴,以20#碳钢和7075-T6铝作为金属试片,研究了不同温度下采用微波法与标准试验方法时稀盐酸和硫酸溶液对金属的腐蚀速率。研究表明,金属的重量损失率随着测试温度的升高而增加,微波法下金属试片的质量损失率显著高于相同腐蚀时间和温度下的标准试验方法。微波法在75℃下40h可与标准试验方法55℃下168h的腐蚀效果进行等效,可以明显提高无机酸对于金属腐蚀性的检测效率。     

碘甲基舒巴坦的安全性和稳定性研究

通过外部和内部加热、热稳定性测试、自加速分解温度(SADT)及固体燃烧速率测试,研究碘甲基舒巴坦的燃爆危险性及安全稳定性。考察分析了该化学品在不同外界环境升温速率、水、酸及碱性条件下的碘甲基舒巴坦稳定性。结果表明:该化学品的燃烧速率为1.3 mm/s,低于2.2 mm/s,不属于易燃固体。该化学品的SADT为55℃,具有自加速分解的危险性,属于自反应物质。在安全稳定性考察中发现,水对碘甲基舒巴坦的稳定性影响不大,而酸碱条件均对其分解具有促进作用,与纯碘甲基舒巴坦相比,使其反应起始放热温度分别降低了24.5和50.0℃,放热量分别增大了57.5和111.5 J/g。     

硝酸异辛酯的热安全性研究

为了研究十六烷值改进剂—硝酸异辛酯(EHN)的热稳定性与热危险性,采用C600微型量热仪测试硝酸异辛酯的热分解特性.利用热分析技术考察温升速率对EHN热分解特性的影响,并利用活化能、TMRad(在绝热条件下最大反应速率到达时间)和自加速分解速率(SADT)方法评价此改进剂的危险性.结果表明,EHN发生分解反应的起始放热温度和最大放热温度均随着温升速率的增加而增大,且四种温升速率的反应机理是一致的.计算得到EHN热分解活化能在143.6-213.6kJ/mol之间.通过绝热条件下TMRad评价得出EHN在常温常压条件下不易发生危险失控,EHN自加速分解温度为98℃＞75℃,即在常温条件下储运是安全的,为储运硝酸异辛酯提供有力的数据支持.     

过硫酸铵胶囊破胶剂的自加速分解温度和自反应过程研究

为评价过硫酸铵胶囊破胶剂在运输中的自反应危险性,按照联合国<关于危险货物运输的建议书--试验与标准手册>中的H.2方法,采用绝热杜瓦量热仪对过硫酸铵胶囊破胶剂进行绝热储存试验,并计算了该物质在3种典型包装下的自加速分解温度.结果表明,分解反应分为2步,其活化能接近,这2步反应实质上是同一反应,即最初反应进行到一定阶段后由于接触面上的反应物消耗和产物积累而停止,而温度升高又引起包覆的聚合物软化,增大了反应物接触面和产物的扩散速度,从而使反应重新开始.研究表明,该物质的包装件不应划入联合国规定的4.1项危险品中的自反应性物质.     

2-氨基-2,3-二甲基丁酰胺氧化合成热危险性研究

为研究2-氨基-23,-二甲基丁酰胺氧化合成的热危险性,采用差示扫描量热仪(DSC)测试2-氨基-2,3-二甲基丁腈和2-氨基-2,3-二甲基丁酰胺的热分解情况,采用反应量热仪(RC1)研究反应温度、双氧水滴加速度和氢氧化钠用量对反应的影响。研究结果显示,2-氨基-2,3-二甲基丁腈吸热热分解温度为149.5℃2,-氨基-2,3-二甲基丁酰胺表现为吸热和放热2段分解过程,吸热和放热分解温度分别为234.4℃和456℃。反应放热速率主要为加料控制,但是,存在一定的热累积。热失控体系最高温度(MTSR)低于2-氨基-23,-二甲基丁腈和2-氨基-23,-二甲基丁酰胺的分解温度,高于体系沸腾温度,在热失控的条件下,反应体系容易导致冲料危险;在优惠的工艺条件范围内,提高反应温度,延长滴加时间,可降低反应的MTSR,提高热转化率和反应安全性。     

重结晶LLM-105的热危险性分析

为了研究重结晶前后LLM-105在敞开体系、绝热体系中的热分解特性,采用溶剂-非溶剂法制备了形状规则、缺陷更少的重结晶LLM-105。以差示扫描量热仪研究了LLM-105的非等温热分解行为,利用Friedman法得到了非等温热分解动力学参数及TD24。采用加速量热仪研究了LLM-105的绝热分解行为,计算了绝热分解动力学参数及SADT。结果表明,重结晶LLM-105的非等温热分解起始温度(升温速率为10℃/min)、绝热起始分解温度、绝热最大升温速率分别为353.12℃、277.19℃、77.39℃/min,未重结晶LLM-105的相应参数值分别为341.62℃、273.77℃、136.62℃/min。重结晶LLM-105的非等温热分解起始温度、绝热起始分解温度更高,绝热最大升温速率更小。结晶品质是LLM-105的热分解特性、热危险性的重要影响因素。重结晶LLM-105具有更好的热稳定性,绝热分解反应更温和。     

过氧化氢异丙苯热稳定性与热安全性研究

为研究过氧化氢异丙苯(CHP)的热稳定性和热安全性,利用C80微量量热仪对CHP在空气中的热分解进行试验研究。利用热分析技术研究CHP的热分解,得到了升温速率对CHP热分解的影响,CHP热分解的活化能,绝热条件下最大反应速率到达时间Tmrad和不同包装下的自加速分解温度。结果表明:随着升温速率的增加,CHP的起始放热温度和最大放热温度随之升高;CHP热分解的活化能范围为52～91 kJ/mol;Tmrad为1,8,24,50和100 h时对应的起始温度分别为118.08,75.41,55.83,44.83和34.52℃;CHP的储罐内径越大,其对应的自加速分解温度越低。     

过氧化二异丙苯的热稳定性及安全性研究

为了分析过氧化二异丙苯(Dicumyl Peroxide,DCP)的热稳定性和热安全性,利用C80微量量热仪对DCP在空气中的热分解及稳定性能进行试验研究,得到了升温速率对DCP热分解的影响规律,运用AKTS高级热动力学软件计算得到DCP热分解的活化能及指前因子、绝热条件下最大反应速率到达时间TMRad和不同包装下的自加速分解温度。结果表明:随升温速率增加,DCP的起始放热温度和最大放热温度升高;并由Friedman法得到不同转化率下活化能E和指前因子A的关系,计算得到DCP热分解的活化能范围为50~130 kJ/mol;TMRad为1 h、8 h、24 h、50 h和100 h时对应的起始温度分别为105.33℃、84.38℃、74.38℃、68℃和62℃;DCP的储罐内径越大,其对应的自加速分解温度越低。在生产、制造、储存、运输等过程中,应防止因温度变化而引发DCP的自分解放热爆炸事故。     

The “Mini Closed Pressure Vessel Test (MCPVT)” as a screening or classification test for explosive properties of organic peroxides

Tests according to the UN Recommendations on the Transport of Dangerous Goods for the determination of explosive properties of organic peroxides have been compared with screening criteria for explosivity based on measurements in a closed mini-autoclave (MCPVT). It will be shown that an additional screening test may be helpful but the information obtained from the UN tests are more important to characterise the specific properties of a substance under different conditions.     

Comparison of calculated data for the flammability and the oxidation potential according to ISO 10156 with experimentally determined values

The classification of flammable gas mixtures is based on either testing or calculation methods proposed by the revised international standard ISO 10156. This standard is used for classification of physical hazards in Chapters 2.2 and 2.4 of the UN Globally Harmonized System of Classification and Labelling of Chemicals (GHS) and in the UN Recommendations on Transport of Dangerous Goods (TDG). The test methods of flammability and oxidizing potential in this standard were developed by BAM. Earlier versions of this standard are not based on triangular diagrams and on the reference combustible substance “ethane”. The old material characteristics, especially in case of oxidizing potential, are based mostly on practical experience without any quantifiable test results. First time it is possible to compare experimental results from the CHEMSAFE database with the newly developed calculation method. In this paper the basic principles of the calculation methods are presented and the methods are validated by examples. A comparison of experimental flammability data with classification results gained by the calculation methods of ISO 10156 is demonstrated.     

Azodicarboxylates: Explosive properties and DSC measurements

A large number of azodicarboxylates and their derivatives are produced and used in the chemical industries. The versatile applications of these azodicarboxylates in research institutes and in the chemical industries for chemical synthesis arouse additional hazards. The intent of this paper is to obtain first knowledge about the structure–response relationship regarding the explosive properties and the thermal hazards of different versatile used azodicarboxylates. The substances are examined with the differential scanning calorimetry (DSC). Furthermore, different laboratory test methods, based on the UN Recommendations on the Transport of Dangerous Goods, are applied to determine the explosive properties of the mentioned substances. On the basis of the obtained results, the known influence of the nitrogen content within the molecule regarding their thermal behaviour could be confirmed. The measured heat of decomposition appeared to be proportional to the nitrogen content within the group of the aliphatic and the aromatic azodicarboxylates. To emphasize this dependency, further investigations should be done. The long term objective of this research is to develop structure–response relationships of the explosive properties and the thermal hazards originating from azodicarboxylates.     

CEQAT-DGHS interlaboratory tests for chemical safety: Validation of laboratory test methods by determining the measurement uncertainty and probability of incorrect classification including so-called “Shark profiles”

Laboratory test results are of vital importance for correctly classifying and labelling chemicals as “hazardous” as defined in the UN Globally Harmonized System (GHS)/EC CLP Regulation or as “dangerous goods” as defined in the UN Recommendations on the Transport of Dangerous Goods. Interlaboratory tests play a decisive role in assessing the reliability of laboratory test results. Interlaboratory tests performed over the last 10 years have examined different laboratory test methods. After analysing the results of these interlaboratory tests, the following conclusions can be drawn:1There is a need for improvement and validation for all laboratory test methods examined.2To avoid any discrepancy concerning the classification and labelling of chemicals, the use of validated laboratory test methods should be state of the art, with the results accompanied by the measurement uncertainty and (if applicable) the probability of incorrect classification.This paper addresses the probability of correct/incorrect classification (for example, as dangerous goods) on the basis of the measurement deviation obtained from interlaboratory tests performed by the Centre for quality assurance for testing of dangerous goods and hazardous substances (CEQAT-DGHS) to validate laboratory test methods. This paper outlines typical results (e.g. so-called “Shark profiles” – the probability of incorrect classification as a function of the true value estimated from interlaboratory test data) as well as general conclusions and steps to be taken to guarantee that laboratory test results are fit for purpose and of high quality.     

Validation of the UN test method N.5

Many substances react with water in such a way that flammable gases are formed. For transport issues this reaction may possess a considerable hazard especially if the cargo is wetted by rain or by water from other sources. In the UN Recommendations on the Transport of Dangerous Goods these kinds of problems are addressed. The UN test N.5 “Test method for substances which in contact with water emit flammable gases” corresponds to this hazard. Classification according to the test method is done by measurement of the gas evolution rate of the flammable gas by any suitable procedure. At BAM a gravimetric approach is used to measure the gas evolution rate. In this paper we present the evaluation of the apparatus by means of an absolute calibration routine utilizing a reaction where a known amount of gas is produced as well as the evaluation of important parameters influencing the gas evolution rate using different substances. It can be shown that the apparatus is capable of measuring absolute gas volumes as low as 6 mL with an acceptable error of about 17% as determined from the reaction of Mg with demineralized water.     

氯丙烯直接环氧化工艺反应物料危险性研究

为了保证利用双氧水氧化氯丙烯直接环氧化制备环氧氯丙烷新工艺的安全开发，针对此工艺涉及的混合危险物料，利用C80量热仪对混合物料热稳定性进行了测试，获得了混合物料热扫描曲线；利用AKTS软件处理得到了混合物料热特性参数和分解动力学数据，在此基础上结合HYSIS软件进行了预防气相燃爆方面的安全分析。结果表明:混合物料初始pH值为8左右，其pH值随放置时间延长而降低；混合物料TD24值为21.3℃，混合物料发生失控的可能性等级为高；混合物料中双氧水分解受温度影响较大，在30℃和60℃下，混合物料分别经过1.3 h和0.8 h就会分解释放出达到氧含量报警值的氧气。     

Effect of urea on detonation characteristics and thermal stability of ammonium nitrate

A study has examined the effect of urea on the thermal stability and detonation characteristics of ammonium nitrate (AN). The thermal decomposition temperature and surface morphology of samples were investigated by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). For further research on the thermal sensitivity and shock sensitivity of the samples, the Koenen test and UN gap test were conducted. The results indicate that urea can substantially increase the thermal stability of AN (the greatest exothermic peak is increased by more than 100 °C) and reduce the thermal sensitivity of AN. However, AN-50wt. % urea mixtures can still produce a steady detonation in the UN gap test. Urea cannot reduce the ability to propagate a detonation. Possible explanations for these results are discussed.