摘要
为了改善新型高能发射药的力学强度,本论文以硝化棉(NC)、聚叠氮缩水甘油醚(GAP)、硝化甘油(NG)和黑索金(RDX)为主要组分的配方体系为研究对象,通过理论分析,在同等能量和爆温前提下,设计和研究了不同氮量硝化棉、不同叠氮粘合剂,不同混合增塑剂、不同固化剂及不同工艺来提高高分子基体体系分散均匀程度和高分子粘合剂链的柔性,同时研究了包覆RDX改善高分子基体与RDX的界面相容性、加补强剂阻止分子链滑移来增强新型高能发射药的力学性能。研究结果表明：
(1)在相同的能量和爆温前提下,提高NC含氮量,可以减少固体填料RDX的量,增加GAP和增塑剂的量,使高分子基体网络的柔性增加、体系的分散均匀性程度改善、缺陷减少,从而使发射药的抗冲强度(α_κ)增加,而且体系的燃烧性能变化不大。用含氮量13%的NC取代含氮量为12.46%的NC,发射药的α_κ提高了30%。
(2)相对于NG增塑剂,采用DEGN和NG混合增塑剂可以使增塑剂的溶度参数接近NC和GAP、从而在捏合、挤出等制造工序中提高发射药体系的分散均匀程度,使高分子基体可以更加自由舒展,柔性增加,从而提高α_κ
(3)使用枝化GAP取代线性GAP后,尽管体系分散均匀程度变差,但由于B-GAP有较低的玻璃化温度、高分子量、较多的承载力原子,使α_κ得以提高,增幅达25%；当使用B-GAP作叠氮粘合剂时,使用固化剂IPDI取代N100可以防止B-GAP过度交联而变脆,相对于GAP体系,使用IPDI固化B-GAP可使发射药的α_κ提高32%。
(4)使用大分子水性聚氨酯(WPU)包覆固体填料RDX后,可以降低RDX的表面能、改善填料与粘合剂基体的界面性能、阻止NG向RDX渗透,从而使α_κ、抗压强度σ_(max)和压缩率ε_(max)都有明显的提高。
(5)选择将GAP预固化再捏合的固化工艺,虽然由于分子量变大粘度增加造成体系分散均匀程度降低,但保证了GAP有足够的固化程度,而且能自身或与NC形成聚氨基甲酸酯或聚氨酯脲弹性体,对发射药的α_κ有良好的改善,增幅达30%。
To improve the mechanical strength of New high-energy propellant, the formulation system nitrocellulose (NC), glycidyl azide polymer (GAP), nitroglycerine (NG) and RDX as the main component was studied on this proper. Through theoretical analysis, different Nitrated NC,different azide binder, different mix plasticizer, different curing agents and different curing techniques on the premise of same energy and burst temperature was designed and researched to improve the dispersion of polymer matrix system and the flexibility of polymer chain, coated RDX were studied to improve the interface compatibility between polymer matrix and RDX, adding reinforcing agents were also studied to prevent molecular chains from slippaging to enhance the mechanical properties of the new type of high-energy propellant. The results show that:
(1)On the premise of same energy and burst temperature, increasing the nitrogen content of NC can help to reduce the amount of solid filler RDX and increase the amount of GAP and plasticizer to enhance the flexibility of polymer matrix network, improve the dispersion of polymer matrix system and reduce defect, so that the impact strength of the propellant(αk) increase, and the change of the combustion performance was little. With 13% nitrogen NC replacing 12.46% nitrogen NC, theαk of the propellant was increased 30%.
(2) Compared to the NG plasticizer, the solubility parameter of the plasticizer mixed with DEGN and NG was close to the NC and GAP, which can help to improve the dispersion of the propellant, stretch the polymer matrix more freely and increase the flexibility of the polymer to enhance in the kneading, extrusion and other manufacturing processes, so the ak can be increased.
(3)With Branched GAP replacing GAP, the dispersed degree of the system reduced, but B-GAP had a lower glass transition temperature, higher molecular weight,and more atoms for bearing stress, theαk was increased 25%;when using B-GAP for azide binder, the use of curing agent IPDI instead of N100 can prevent excessive cross-linking of B-GAP from being crisp, compared with GAP system, theαk of the B-GAP propellant cured with IPDI can be increased 32%.
(4) Using macromolecule water-based polyurethane (WPU) as the coating agent of solid fillers RDX can help to reduce the surface energy of the RDX, improve the interfacial properties between filler and binder matrix, prevent the penetration of NG to RDX, thus, theαk,the compressive strengthσmax and compressibilityεmax are all significant improved.
(5) Selecting the curing process that kneading the pre-cured GAP, the dispersed degree of the system reduced because the viscosity of the GAP was increased as a result of the larger molecular weight, but the curing level of GAP can be ensured effectively, and GAP or GAP and NC can form polyurethane or polyurethane-urea elastomers, the ak of the propellant can be increase 30%.
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