Comparison of burn rate and thermal decomposition of AP as oxidizer and PVC and HTPB as fuel binder based composite solid propellants

In the present investigation an effort has been made to understand the thermal decomposition and burn rate characteristics of AP as oxidizer and PVC and HTPB as fuel binder in composite solid propellant. The burning rate study has been carried out at ambient and different pressures of 2.068 Mpa, 4.760 Mpa,6.895 Mpa. The mechanism of thermal decomposition of each composition have also been determined by NETZSCH simultaneous thermal analyser, comprising differential scanning calorimeter(DSC) and thermo-gravimetric analyser(TGA). An effort has been made to study the burn rate and decomposition of fuel binder and oxidizer in presence of Fe_2O_3 and also their overall impact on combustion of propellant.

Effects of phase change material(PCM)-based nanocomposite additives on thermal decomposition and burning characteristic of high energy propellants containing RDX

A kind of phase change material(PCM)-based nanocomposite was prepared and added into high energy propellants containing RDX as additives to investigate its effect on thermal decomposition and burning characteristic of high energy propellants.The effect of PCM-based nanocomposites on thermal decomposition of high energy propellants is investigated by TG/DSC-FTIR-MS technology.Due to the delayed protection effect(PCM-based nanocomposites can absorb lots of heat at the range of certain temperature when it undergoes structure change or phase transitions)of PCM-based nanocomposites under the thermal decomposition condition,the thermal stability of high energy propellants modified with PCMbased nanocomposites is improved.At the same time,the concentration of N2,NO2,H2O and CO_(2)is increased during thermal decomposition of high energy propellants whereas NO and CO is decreased.The burning gaseous products and burning characteristic of high energy propellants are studied by the combination of closed bomb test and Fourier transform infrared spectrum.The main burning gaseous products are N2,CO_(2),CO,H2O,CH4,etc.After the high energy propellant modified with PCM-based nanocomposites,the concentration of CH4is increased while CO,CO_(2) and H2O is decreased under the high-pressure burning condition.The progressivity factor of high energy propellants is increased by22.2%compared with the control sample while the maximum pressure is merely decreased 1.25%after the addition of the PCM-based nanocomposite,thus PCM-based nanocomposites can be used to adjust the burning process and improve the burning progressivity of high energy propellants.This study is expected to boost the practical application of PCM-based nanocomposite to the propellant formulation and effectively control the burning characteristic of high energy propellants.

Cu–Co–O nano-catalysts as a burn rate modifier for composite solid propellants

Nano-catalysts containing copper–cobalt oxides(Cu–Co–O) have been synthesized by the citric acid(CA) complexing method. Copper(II) nitrate and Cobalt(II) nitrate were employed in different molar ratios as the starting reactants to prepare three types of nano-catalysts. Well crystalline nano-catalysts were produced after a period of 3 hours by the calcination of CA–Cu–Co–O precursors at 550 °C. The phase morphologies and crystal composition of synthesized nano-catalysts were examined using Scanning Electron Microscope(SEM), Energy Dispersive Spectroscopy(EDS) and Fourier Transform Infrared Spectroscopy(FTIR) methods. The particle size of nano-catalysts was observed in the range of 90 nm–200 nm. The prepared nano-catalysts were used to formulate propellant samples of various compositions which showed high reactivity toward the combustion of HTPB/AP-based composite solid propellants. The catalytic effects on the decomposition of propellant samples were found to be significant at higher temperatures. The combustion characteristics of composite solid propellants were significantly improved by the incorporation of nano-catalysts. Out of the three catalysts studied in the present work, Cu Co-I was found to be the better catalyst in regard to thermal decomposition and burning nature of composite solid propellants. The improved performance of composite solid propellant can be attributed to the high crystallinity, low agglomeration and lowering the decomposition temperature of oxidizer by the addition of Cu Co-I nano-catalyst.

Thermal stability assessment of anti-explosive ammonium nitrate

The explosivity experiment of anti-explosive ammonium nitrate (AEAN) shows that the explosive characteristic of AEAN is eliminated. The adiabatic decompositions of ammonium nitrate and AEAN were investigated with an accelerating rate calorimeter (ARC). The curves of thermal decomposition temperature and pressure versus time, self-heating rate and pressure versus temperature for two systems were obtained. The kinetic parameters such as apparent activation energy and pre-exponential factor were calculated. The safety of AEAN was analyzed. It was indicated that AEAN has a higher thermal stability than AN. At the same time, it can be shown that the elimination of its explosive characteristic is due to the improvement on the thermal stability of AEAN.

不同粒径黑火药点火过程中与纤维素壳体材料的热相互作用

为了研究点火装置中纤维素外壳对不同粒径黑火药固相反应放热特性、反应气相产物、点火燃烧特性等方面的影响,制备系列黑火药/纤维素复合物样品,并采用扫描电子显微镜表征其微观结构和形貌。通过同步热分析仪和傅里叶变换红外光谱仪联用,研究纤维素对黑火药热反应性能的影响。用氧弹量热仪测量各样品的爆热,利用综合燃烧诊断系统(高速相机和高速红外热像仪)获得黑火药及其纤维素复合物燃速与火焰温度分布。研究结果表明:纤维素会降低黑火药放热量,当纤维素含量为33.33%时,两种黑火药的总放热量分别降低了66.4%和58.5%;纤维素并未改变黑火药热解路径;黑火药的主要气相产物分别为H_(2)O、CO_(2)和NO_(2),与纤维素复合后除浓度变化外,气相产物种类保持不变;纤维素仅影响黑火药能量释放过程,但对不同粒径黑火药的能量释放影响的差别较小,与纤维素复合后能量释放变化仅相差3.1%。实验研究发现,小粒径黑火药及其纤维素复合物燃烧更剧烈,火焰面积更大、燃温更高;纤维素对黑火药的燃烧起消极作用,主要是降低黑火药的燃速和火焰辐射强度,火焰温度分别降低273.7℃和299.4℃;黑火药及其纤维素复合物的凝聚相产物形貌表明纤维素一定程度上促进了黑火药凝相产物团聚,即纤维素会降低其燃烧效率。

含能燃速抑制剂的制备及其对AP分解的负催化效应

燃速抑制剂作为固体推进剂的核心功能组分,在降低固体推进剂高压燃速方面起关键作用。精准设计具有降速效应的季铵与醛基结构,获得高氮三氨基胍乙二醛二维共聚物(Triaminoguaniding Glyoxal two dimensional Copolymer,TAGP)含能配体,并与碱土金属离子K^(+)、Ba^(2+)和Ca^(2+)发生络合反应,制备系列新型含能燃速抑制剂(TAGP-M)。采用粉末衍射、X射线光电子能谱、扫描电镜/能谱和差示扫描量热/热重联用等技术分析其形貌、结构和热稳定性,并研究这些含能燃速抑制剂对高氯酸铵(Ammonium Perchlorate,AP)热分解的负催化作用。研究结果表明:TAGP-K对AP转晶抑制最为显著,使AP的转晶吸热峰温提高5.9℃、低温分解峰峰温升高28.7℃;添加10 wt%的TAGP-K,可使AP的最大热分解速率降低58%;TAGP-Ca燃速抑制剂可使AP的释能效应集中在高温分解过程,AP/TAGP-Ca混合体系的放热量比纯AP提高50%以上;TAGP-Ca和TAGP-Ba燃速抑制剂在抑制含AP分解的同时提高了其释能效率;TAGP-M燃速抑制剂在分解过程中释放NH_(3)并与AP分解产物HClO_(4)结合,形成更难分解的M(ClO_(4)^(-))n;通过碱土离子与ClO_(4)^(-)离子强静电作用,抑制后者分解产生氧化性气氛,进而抑制AP高温放热反应过程。

基于头峰的多步分解反应过程热失控特征参数计算方法研究

目前微通道反应器在含能材料合成领域广泛应用,极大提高了合成过程的安全性,但是仍然需要关注物料的热稳定性。绝热条件下最大反应速率到达时间(TMR_(ad))与TMR_(ad)为24 h所对应的引发温度(T_(D24))是两个表征危险化学品及含能材料热分解危险性的重要特征参数,这两个参数的传统计算方法为单步N级法和数值计算法,存在分析过程费时费力的缺点。为此,根据差示扫描量热仪动态升温测试曲线,提出了基于头峰(即多峰曲线分峰后的第一个峰)的热分解失控特征参数计算方法,采用穷举法比较了该方法与模型计算法的T_(D24)偏差,进行了数值模拟验证,并基于文献实验计算了1,8-二硝基蒽醌、改性硝基胍(M-NQ)、1,5-二硝基蒽醌和3,4-二硝基呋咱基氧化呋咱(DNTF)4种物质的热失控特征参数。数值模拟结果表明,对于两步和三步连续反应,T_(D24)的最大偏差百分比分别为2.88%和6.9%,最大偏差为6.41℃;对于三步连续反应,T_(D24)最大偏差为5.39℃。结果表明,4种含能材料的T_(D24)计算偏差分别为-4.55,0.71,3.16℃和-0.84℃,与模型计算法得到的T_(D24)相比,偏差百分比的绝对值均小于2%,证实了T_(D24)计算方法的有效性,计算T_(D24)时偏差较小,计算简便,能够较为准确地获得其热分解失控特征参数。

山竹皮吸附剂对铜离子的吸附行为及其燃烧特性研究

以山竹果皮渣为原料,经过异丙醇脱色、碱性试剂活化制备出吸附材料,用于吸附溶液中的铜离子。实验结果表明,pH值升高有利于山竹皮吸附剂吸附铜离子,最大吸附容量达1.5 molCu^(2+)/kg,且30 min内可达到吸附平衡。负载铜离子数量对吸附剂燃烧热分解的特征温度有显著影响,铜离子浓度低于2 mmol/L时,负载的铜离子数量增加,其开始热分解以及剧烈燃烧分解的温度点显著降低;铜离子浓度高于2 mmol/L后,其热分解温度特征值不再发生明显变化。铜离子在燃烧过程中扮演催化剂的作用,能有效促进燃烧反应。

酚醛环氧乳液的制备及其漆膜耐热和燃烧性能研究

为了开发具有高耐热性的酚醛环氧基成膜物,满足防火涂料耐热性能的要求。以相反转技术制备了酚醛环氧乳液,利用正交实验极差分析法,探讨了乳化剂种类、乳化剂用量及助溶剂用量对乳液性能的影响,并通过DSC、TG、微型量热分析(MCC)对其固化漆膜的耐热和防火性能进行研究。结果表明:采用6%由羟基与环氧基物质的量比为1∶1时合成的乳化剂、6%助溶剂制备的酚醛环氧乳液,粒径最小为900 nm,分布均一且稳定性好。酚醛环氧乳液制备的漆膜的玻璃化转变温度为98.78℃,800℃时残炭率为17.7%,均显著高于由普通双酚A型环氧乳液对应漆膜的。且酚醛环氧漆膜在燃烧时的热释放速率低于普通双酚A型环氧乳液对应漆膜的,可应用于防火涂料。

Ballistic Testing and Thermal Behavior of Cast Double-base Propellant Containing BuNENA

Preparation of cast double-propellant grains depends on the ability of nitrocellulose powder to swell and coalesce into a coherent mass when treated with a suitable solvent.The cast double-base process has been developed into a highly versatile technique for manufacturing solid rocket charges.Propellants manufactured by this process provide a wide range of energies and burning rates.Successful preparation of cast double-base propellant grains has been performed using compatible casting liquid with the casting powder.BuNENA was used as an energetic plasticizer for manufacturing of casting powder.Burning rate measurements have been performed using closed bomb SV-2to investigate the burning behavior along a wide range of operating pressure.Plateau burning had been detected in pressure range(50-70)×105 Pa for the composition included BuNENA.DTA and TGA thermal analysis were conducted to evaluate the thermal behavior of the prepared cast double-base propellants.Results from DTA were used to calculate the apparent activation energy.

含不同质量分数三价铁离子乳胶基质的绝热分解研究

为研究绝热条件下Fe^(3+)对乳胶基质的热稳定性和热危险性的影响,采用加速量热仪研究了含不同质量分数Fe^(3+)的乳胶基质的绝热分解行为,计算了绝热分解动力学参数和TSAD。结果表明,绝热条件下,Fe^(3+)会促进乳胶基质的热分解,使其起始分解温度降低,绝热温升和放热量提高,释放更多的气体产物,这种促进效果随着Fe^(3+)质量分数提高会有所减弱,Fe^(3+)质量分数为0.04%时,乳胶基质的起始分解温度降低了34.65℃,放热量提高了44.74%。加入Fe^(3+)后,乳胶基质达到最高放热温度所需时间更短,Fe3+质量分数为0.08%时反应最快,但Fe3+质量分数达到0.10%时,乳胶基质内部结构被严重破坏,到达最高放热温度所需时间增加。通过比较选取不同反应级数时所作回归直线的拟合优度,得到4种样品绝热分解反应的反应级数为2,含Fe^(3+)乳胶基质的活化能和TSAD都有一定程度降低,热危险性更高,在Fe^(3+)处于低含量时更明显,Fe^(3+)质量分数为0.04%时,乳胶基质的活化能降低了44.61%,TSAD降低了60.61℃。

缓慢加热条件下壳装PBX炸药响应特性研究

为了研究弹药在热刺激作用下的响应规律,进行了壳装PBX炸药慢速烤燃试验,获得了1 K/min升温速率下壳体内部的压力-时间曲线,壳体内部压力变化过程表现为炸药热分解产气段、点火燃烧段和壳体破裂段3个阶段。提出了一种模拟计算慢速烤燃时壳装PBX炸药发生低等级响应过程的理论方法,首先计算炸药点火前的温度场分布,引入热分解系数k描述炸药热分解消耗的程度,在此基础上建立改进的内弹道方程组,模拟计算了因炸药点火燃烧导致壳体内部压力快速上升的行为,理论值和试验值吻合良好,随后应用LS-DYNA软件模拟了壳体在内部压力作用下的破裂行为。计算了1.0~10.0 K/min之间6种不同升温速率条件下炸药点火后的压力-时间曲线,当升温速率为1.0 K/min时,炸药点火后压力增长速率明显高于其他工况。

铅铜催化剂在低铝HTPE推进剂中的应用研究

研究了柠檬酸铅(PbCi)、2,4-二羟基苯甲酸铜(β-Cu)及其与炭黑(CB)的复合物对低铝HTPE推进剂主要组分、燃烧性能、工艺性能及力学性能的影响。结果表明,PbCi、β-Cu对低铝HTPE推进剂燃速表现出不同的催化效果。PbCi对5~11 MPa的燃速影响不明显,但能够提高11~19 MPa的燃速;β-Cu可有效提高5~19 MPa下的燃速。复合催化剂PbCi/CB对推进剂9~19 MPa下的燃速具有抑制作用,复合催化剂β-Cu/CB对燃速的影响与相同含量β-Cu相当。PbCi、β-Cu及其与CB的复合催化剂均能降低5~11 MPa的压强指数,提高11~19 MPa的压强指数。低铝HTPE推进剂药浆工艺性能不受PbCi、β-Cu及其CB复合催化剂的影响;PbCi可有效提高低铝HTPE在-40℃下的延伸率;β-Cu使推进剂20℃及50℃下的抗拉强度和延伸率大幅降低。

不同白云石掺量的高镁磷尾矿热处理动力学研究

为了给高镁磷尾矿煅烧提供动力学理论指导,以白云石矿粉和低品位高镁磷矿粉为原料,通过调整二者的掺量,模拟不同矿产区的高镁磷尾矿,对其进行热重-差示扫描量热法(TG-DSC)测试,利用Flynn-Wall-Ozawa法、Kissinger法、Satava-Sestak法分别对白云石非等温热分解进行计算分析,结果表明:相同白云石掺量的高镁磷尾矿煅烧时,升温速率越快,白云石热分解的起始温度和结束温度越高,白云石热分解的驱动力越大,分解速率越快;磷尾矿中白云石热分解遵循三维扩散机理,活化能为106.48 kJ/mol,指前因子为9.46×10^(5);基于研究成果,建立了磷尾矿热分解动力学模型,为悬浮煅烧高镁磷尾矿提供了理论基础。

相转移催化作用下大豆油的环氧化反应的安全特性研究

针对在自制相转移催化剂([(C18H37)2(CH3)2N]3{PO4[W(O)(O2)2]4})作用下大豆油(SBO)的环氧化反应过程的热危险性进行了研究。首先,通过DSC研究了双氧水在本体系中的热力学及稳定特性,结果表明该催化剂能够提升H2O2的热稳定性,强化其氧化能力。其次,采用原位红外技术监测了SBO环氧化反应的全过程,通过建立环氧化反应动力学进一步研究潜在的危害性。动力学的决定系数(0.9886~0.9974)表明SBO环氧化反应为一级反应。计算得到的SBO环氧化反应的表观活化能为15.43 kJ/mol,表明该反应体系对温度敏感,易受到温度变化的影响。另外,ΔG(31.38~32.50 kJ/mol)和ΔH(12.67 kJ/mol)为正值以及ΔS(-56.18 kJ/mol)为负值,表明使用催化剂的SBO环氧化反应是遵循非自发的、吸热的过程。因此,研究结果表明低温反应和间歇进料的方式能够最有效地降低其热失控风险。

浅谈煤的挥发分测定中应注意的问题

针对挥发分这项在煤质特性和加工利用研究中起重要作用的指标、在煤质分析检测中体现操作者水平高低的规范性试验项目,本文根据煤质分析检测实践经验和国家标准要求,总结了挥发分测定试验中应注意的若干细节,对仪器设备的要求、采制样的规范、称量时应注意的问题、特殊煤种采取的必要措施分别予以阐述,针对加热时坩埚的摆放技巧、灼烧后坩埚的冷却处理、加热时间、加热速度等关键环节分别通过大量的试验数据来说明如何获得可靠准确的测试结果,并探讨了操作时的规范性,以使挥发分测定结果更准确。

聚乳酸熔体流动速率测试方法研究

分别采用标准法、半模口法和外推法测试了聚乳酸(PLA)的熔体流动速率(MFR),研究了3种方法用于测试PLA MFR的可行性。结果表明:采用标准法测试PLA的MFR时,切样操作困难,多次加样所得测试结果的相对误差较大;采用半模口法测试PLA的MFR时,切样操作方便,但测试结果的相对误差偏大;采用外推法测试PLA的MFR时,克服了PLA极易热降解的特性,熔体流速适中,切样操作方便,表现出很好的可重复性,此时,PLA的MFR为5.0 g/10 min。

覆铜板半固化环氧树脂热分解行为

采用热重分析(TG)以不同的升温速率(5、10、15、20、30℃/min)分别在氮气气氛和空气气氛下对覆铜板中双氰胺固化环氧树脂热分解行为进行了研究,讨论不同升温速率以及不同气氛下双氰胺固化双酚A环氧树脂的热分解行为的变化。研究发现环氧树脂的TG曲线随升温速率的提高移向高温区,说明热分解温度随升温速率的增加而上升。DTA曲线的峰顶随着升温速率的增加移向高温段,说明受热分解所需达到的温度更高。氮气气氛下环氧树脂只有一个阶段的受热分解且其分解放热量较小,而空气气氛下环氧树脂则分两个阶段进行且其分解放热量高,主要集中在第二阶段放热,说明环氧树脂在空气气氛下与空气中的成分发生了复杂的热分解反应。