二氧化氯母体材料安全性研究

On the safety of base materials of solid chlorine dioxide preparation

为研究二氧化氯母体材料（氯酸钠、亚氯酸钠，分别用0#和1#表示）的安全性能，采用摩擦和撞击感度仪、电火花感度仪和差式扫描量热仪（DifferentialScanningCalorimetry，DSC），对二者的机械感度、静电感度及热安全性能进行了对比研究，并研究了掺杂对母体材料机械感度和静电感度的影响。结果表明，未掺杂的样品机械安全性较高，爆炸危险性较低。掺杂树脂、木粉、油脂后，0#样品特性落高对数值分别为1．64．2、1．688、1．758，爆炸概率分别为0．72、0、0．64；1#样品特性落高对数值分别为1．427、1．354、1．447，爆炸概率分别为0．92、0、0．88。可知掺杂后二者均有爆炸危险，机械感度提升。当木粉与0#／1样试样掺杂比例分别为1：10、1：5、1：2时，随木粉掺杂量增加，0#样品特性落高对数值由1．758降至1．715，爆炸概率由0．．64上升至0．8；1#样品特性落高对数值由1．447增至1．522，爆炸概率由0．88上升至1。据此可知，随木粉与试样掺杂比例由1：10增至1：2，0#样品撞击感度趋于增加，1#样品撞击感度趋于减小，二者的摩擦感度呈上升趋势。且1帮较0撑样品对撞击、摩擦作用更敏感。两样品及掺杂3种掺杂物后样品均对静电作用不敏感；在0—300℃温升范围内，0#样品无放热峰，仅有1个吸热峰；1#样品出现两个放热峰，初始放热温度分别为167．00℃、207．21℃，焓变分别为519．7956J／g、301．5258J／g。这说明1#样品易发生热积聚，引起热爆炸；而0#样品在此温升范围内，相对较安全，热安全性能较高。

The paper is aimed at introducing our study of safety be- havio~ of the base materials （sodium chlorate, sodium chlorite, marked as 0 # and 1 # respectively） intended to be applied for chlo- rine dioxide preparation in hoping to reduce and even to avoid hazards and risks in their production. As is known, the base materials as those above mentioned are characterized by their mechanical sensitivi- ty, electrostatic sensitivity and thermal safety sensitivity when they were experimented or transported due to friction and impact, or other mechanical interactions. Coming from such particular reasons, we have put our stress on the sensitivity influences given by such devices as sensitivity instruments, the electric sparks and differential scanning calorimeters （DSC） as well as the influence of doping on mechanical sensitivity and electrostatic sensitivity. Experimental results we have gained from our systematic testing and measurements can be shown as follows ： the two samples without doping were found of higher mechan- ical safety performance and lower explosion risks. When doping with resin, oil or wood powder, the logarithmic of characteristic height of 0 # samples were found to be 1.642, 1.688, 1.758 respectively and the exploding probability of 0 # samples tend to 0.72, O, 0.64, re- spectively. In comparison, the logarithmic of characteristic heights of 1 # samples were found to be 1.427, 1.354, 1.447 respectively and the exploding probability of 1 # samples--0.92, 0, 0.88 respective- ly. Thus, it can be said that both of them are prone to the explosion hazards and their mechanical sensitivities also tend to rise after dop- ing. When the doping ratios of wood powder and 0 #/1 # samples were 1 ： 10, 1：5, 1：2, with the increase of doping rate of wood pow- der, the logarithmic of characteristic height of 0 # samples tend to lower from 1.758 to 1.715 whereas their explosion probability tends to increase from 0.64 to 0.8, The logarithmic of the characteristic height of 1 # samples tends to rise from 1.447 to 1.522 and their ex- plosion likeliness tends to go up from 0.88 to 1. And, accordingly, with the increase of the doping ratio of wood powder （ rising from I ： 10 to 1： 2）, the impact sensitivity of 0 # samples tends to rise whereas that of samples 1 # tends to decrease, though the friction sensitivity of both can be found elevated. Moreover, the sodium chlo- rite has also been found more sensitive to the impact and friction than those of sodium chlorate. The two samples and their doping mixture with three dopants were not sensitive to the static electricity. For ex- ample, within the temperature range of 0 300 ℃, no exothermic peaks cropped up with 0 # samples, except for the only endothermic peak. There were two exothermic peaks cropped up in 1 # samples, with the initial exothermal temperatures of samples l # being 167 ℃ and 207.21 qE, and their enthalpy changes of samples 1 # being 519.795 6 J/g and 301.525 8 J/g. Therefore, sodium chlorite can be said more prone to accumulate the temperature, and likely to lead to heat explosion. On the other hand, within the same temperature range, sodium chlorate tends to be comparatively safer and behave higher thermostatically safer.