Shock-induced energy release behaviors of reactive materials
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摘要: 活性材料是一种具备释能特性的新型材料,其在冲击导致的高压/高温作用下可以发生化学反应,释放大量的化学能,因此在破片、聚能破甲战斗部等军事领域有广泛的应用潜力。为了实现对活性材料释能过程的设计与控制,推进活性材料武器化应用进程,就必须解答活性材料冲击释能行为中所包含的一系列复杂的力-热-化耦合问题。近40年来,对活性材料的冲击释能行为已开展了大量研究,本文在此基础上系统梳理了活性材料的冲击诱发化学反应机理、动力学以及相关效应的研究现状,重点关注活性材料的冲击释能实验表征技术、冲击诱发化学反应理论模型以及考虑力-热-化耦合的冲击压缩数值模拟方法等3方面的研究进展。总结认为,对活性材料冲击释能行为的研究已经具有一定的积淀,但目前对实验中超快化学反应行为的实时诊断研究还缺乏更加丰富、精细、直观的表征与探索,相关理论与数值模拟研究尚未建立能够完整描述活性材料冲击释能行为的力-热-化理论模型,缺乏能够从宏观尺度描述冲击释能行为的有效方法。因此,超快化学反应实验表征技术、宏观角度的力-热-化机理与模型建立及其数值模拟应用以及具备可调性能的活性材料制备新工艺3方面研究内容将是推进活性材料未来军事化应用的重点关注对象。Abstract: Reactive material is a new type of material with energy-releasing characteristics. It can react chemically and release a large amount of chemical energy under the high pressure and high temperature caused by the impact. Therefore, it has a wide range of potential applications in military fields such as fragments and energy-splitting warheads. In order to realize the design and control of the energy release process of reactive material and promote its weaponized application process, it is necessary to solve a series of complicated mechanical-thermal-chemical coupling problems in the impact-induced energy release behaviors of reactive materials. In the past 40 years, domestic and foreign scholars have carried out a lot of research on the impact-induced energy release behavior of reactive materials. Based on this, this paper systematically combs the research status of the impact-induced chemical reaction mechanism, kinetics and related effects of reactive materials, focusing on the research progress in three aspects: the experimental characterization technology of impact-induced energy release of materials, the theoretical model of impact-induced chemical reaction and the numerical simulation method of shock compression considering the mechanical-thermal-chemical coupling effects. Finally, the summaries are carried out and the future research work, challenges and suggestions are proposed. It is concluded that domestic and foreign scholars have accumulated a certain amount of research on the energy release behaviors of reactive materials, but there is still a lack of richer, finer and intuitive characterization and exploration for the real-time diagnosis of ultra-fast chemical reaction behavior in experiments. However, for the related theoretical and numerical simulation studies, the mechanical thermal chemical theoretical model which can fully describe the impact energy release behavior of active materials has not been established, and there is no effective method to describe the impact energy release behaviors from the macro scale. Therefore, the three aspects of research content, ultra-fast chemical reaction experimental characterization technology, macro-level mechanical-thermal-chemical mechanism and model establishment and its numerical simulation application, and preparation of reactive materials with adjustable properties, will be the focus of attention in promoting the future military application of reactive materials.
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含铝炸药在军事领域的广泛应用以及其典型的非理想特性,吸引了大量学者对含铝炸药的爆轰驱动特性和铝粉在爆轰产物中的反应过程开展研究。Miller等[1-3]提出了针对高能非理想炸药和推进剂的反应流模型,该模型将含铝炸药爆轰分为两阶段:理想组分快速爆轰阶段和金属粉末缓慢燃烧阶段,并将该反应流模型应用于二维有限元Lagrangian流体力学代码计算。Frost等[4-5]、Zhang等[6]、Ripley等[7]、Milne等[8]、Cooper等[9]、Massoni等[10]和Kim等[11]应用多相流体动力学模型(computational fluid dynamics,CFD)数值计算了铝粉在炸药中的反应条件。Kim等[12]对含铝炸药反应流进行了实验研究,在JWL++状态方程的基础上,研究了RDX/Al/HTPB(50%/35%/15%)的尺寸效应和爆轰特性。
目前,含铝炸药的研究以实验为主要手段,对含铝炸药的爆轰驱动过程一直缺乏理论指导。本文中针对含铝炸药爆轰产物的非理想膨胀过程,提出局部等熵假设,并建立含铝炸药爆轰产物流动的非线性特征线理论模型,为分析含铝炸药的驱动做功能力以及爆轰产物的非等熵流动规律提供一种全新的方法,为深入理解含铝炸药爆轰产物的膨胀过程提供理论方法。
1. 含铝炸药爆轰产物非线性特征线模型的必要假设
1.1 含铝炸药爆轰反应机理假设
含铝炸药的爆轰机理比较复杂,基于目前的研究普遍认为:微米级以及粒度更大的铝粉在爆轰反应区基本不参加反应,铝粉反应主要发生在爆轰产物膨胀驱动过程中[13]。裴红波等[14]研究了粒径为9.8 μm的RDX/Al在不同铝粉含铝条件下的反应进程,结果显示,10 μs后铝粉的反应度才开始随时间逐渐增大。陈朗等[15]对铝粉粒径为几十纳米到几十微米、铝粉含铝为20%的RDX/Al炸药进行了爆轰驱动研究,发现微米级铝粉的反应主要发生在爆轰反应后期。Kim等[12]设计并研究了混合炸药RDX/Al(65/35)的柱型装药实验(铝粒子直径为微米级),发现大部分铝粒子不参与爆轰反应,反应主要发生于爆轰波阵面后的爆轰产物流动区。
根据文献调研分析以及二次反应理论对含铝炸药爆轰机理的论述,认为对含微米级或微米级以上铝粉的含铝炸药,铝粉在爆轰反应区不发生化学反应或只有极少量铝粉发生反应,因此假设铝粉在炸药爆轰反应区完全不发生化学反应,即铝粉在炸药爆轰反应区表现为惰性。纳米级铝粉活性较高,对于炸药爆轰反应区的影响不可忽略,因此,本文中建立的模型只适用于含有微米级铝粉的含铝炸药。
1.2 铝粉在炸药爆轰产物中的状态假设
(1)含铝炸药爆轰波阵面后的铝粉与爆轰产物以相同的速度运动。
Zhang等[16]假设在冲击波通过铝粒子的过程中,炸药不发生反应,并采用Murnaghan状态方程描述炸药受到冲击的状态,计算结果发现铝粉与爆轰产物的相对速度与炸药密度有关,对于常用的RDX基和HMX基含铝炸药而言,可近似认为铝粉与爆轰产物一起运动。
(2)对于爆轰波阵面后的微米级铝粉,可认为铝粉以气相形式燃烧[17-18]。
1.3 含铝炸药爆轰产物流动的局部等熵假设
铝粉反应对爆轰产物的热力学影响是不可忽略的,铝粉释放能量增加爆轰产物的内能,进而影响爆轰产物的压力、声速等状态参数,因此,经典理想炸药爆轰产物膨胀的等熵流动理论无法科学描述含铝炸药爆轰产物的流动规律。考虑到爆轰产物中铝粉的氧化反应速率相对较慢,一般可持续反应1~3 ms,若将含铝炸药爆轰产物的膨胀过程沿时间轴划分为许多微小的时间域,在每个微小时间域内,爆轰产物中铝粉反应量较少且爆轰产物体积膨胀较小,那么在每个微小时间域内可近似认为爆轰产物膨胀过程是等熵的,据此本文提出了分析含铝炸药爆轰产物流动的局部等熵假设,其主要假设包括以下内容:
(1)假设铝粉在爆轰反应区内不发生化学反应,即铝粉在炸药爆轰反应区表现为惰性;
(2)考虑到铝粉反应速率相对较慢,假设铝粉反应对爆轰产物的影响具有一定的弛豫效应,也就是说铝粉反应释放的能量需要一段时间后才会对爆轰产物参数(包括当地声速、压强和产物密度)产生影响;
(3)将含铝炸药爆轰产物的膨胀过程沿时间轴分割为有限微小时间域(本文中的计算以0.2 μs为一个微时间域),在每个微时间域内,铝粉反应释放的能量没有立刻对周围爆轰产物状态参数产生影响,因此,可认为任意微时间域内铝粉的反应度不变,爆轰产物可近似为等熵膨胀;
(4)铝粉反应对爆轰产物状态参数的影响体现在相邻下一微时间域的初始时刻,即相邻两个微时间域的交界处,爆轰产物的压强、密度和声速将产生变化,交界处产物粒子速度不变(内能的微小变化不影响粒子速度),在任一微时间域内,爆轰产物遵循等熵流动规律,但微时间域间的熵不同。
以爆轰产物任意一条特征线为例,说明铝粉反应释放能量对爆轰产物流动规律的影响,特征线示意图如图1所示。
当铝粉在爆轰产物中发生反应时,由于受到铝粉反应放热的影响,沿特征线的爆轰产物状态参数将不再是常数,爆轰产物的熵也不再是固定值。在微时间域1内(0~t1),铝粉没有开始反应或反应还没有对爆轰产物参数产生影响,在绝热膨胀条件下,此时间域内爆轰产物的熵S1恒定不变,特征线为直线,沿特征线的爆轰产物状态参数压强p1、密度ρ1、声速c1等同样恒定不变(经典等熵膨胀理论),也就是说铝粉不反应或不作用时,非等熵模型与等熵模型是等价的;受铝粉反应释放能量的影响,在t1时刻(两个微时间域的交界时刻),产物状态参数变为p2、ρ2、c2,依据局部等熵假设,在微时间域2内(t1~t2),产物状态参数变为p2、ρ2、c2沿特征线维持不变,但受到铝粉反应影响,熵值变为S2且特征线斜率也发生变化,表明爆轰产物流动规律发生变化。依据局部等熵假设,可分析出其他微时间域的特征线变化。
含铝炸药爆轰产物流动的局部等熵假设是在经典等熵特征线理论的基础上提出的,为了能够科学地理论分析铝粉二次反应对爆轰产物流动的影响规律,将炸药置于无限长刚性圆管中,忽略了侧向稀疏作用的影响,且忽略了炸药对外部环境的热效应(炸药爆轰驱动过程极其迅速,在有效驱动时间内对外部环境的热效应很小)。因此,含铝炸药非线性特性线模型适用于强约束条件下,混合微米级铝粉的含铝炸药爆轰产物的流动规律分析及金属板有效驱动段(金属板从开始运动后的6~8 μs达到最大速度,这段驱动时间称为有效驱动段)的运动规律分析。
2. 含铝炸药爆轰驱动的非线性特征线模型
2.1 含铝炸药爆轰产物状态方程
假设含铝炸药处于无限长刚性圆管中,炸药两侧为真空,因此爆轰产物流动可视为一维流动。上一节必要假设中提到在C-J面后铝粉与爆轰产物以相同的速度运动,忽略了铝粉与理想组分的相互作用,因此,含铝炸药爆轰产物中的理想组分的状态方程可以表示为:
pe=wbρRT (1) 式中:
pe 为含铝炸药爆轰产物压力,wb 为含铝炸药中炸药组分的初始质量分数,ρ 为含铝炸药爆轰产物密度,R 为气体常数,T 为含铝炸药爆轰产物温度。铝粉的燃烧状态近似表现为气相燃烧,且铝粉均匀分布于爆轰产物中,因此,铝粉燃烧对压力的贡献可表示为[12]:
pAl=waλAlρRT1−nAn (2) 式中:
pAl 为铝粉燃烧对压力的贡献,λAl 为已经反应了的铝粉的质量分数,wa 为含铝炸药中铝粉的初始质量分数,n 为单位体积的物质的量,An 为经验系数且是一个常数。本文计算中nAn 取值0.75。应用标准混合准则,含铝炸药爆轰产物的状态方程可表示为:
ptotal=pe+pAl=(wb+waλAl1−nAn)ρRT = A(λAl)ρRT (3) 式中:
A(λAl) = (wb+waλAl1−nAn) 。通过热力学变换,可以得到微时间域
i 内含铝炸药爆轰产物的等熵方程:ptotalργi=[(wb+waλAli1−nAn)⋅CiR]γi (4) 式中:
Ci 为常数,λAli 为时间域i 内的铝粉反应度,下标i 表示第i 时间域。2.2 含铝炸药爆轰产物的非线性特征线模型
忽略爆轰产物流动过程中的热传递,因此,爆轰产物平面绝热运动的流体动力学方程组为:
{∂ρ∂t+u∂ρ∂x+ρ∂u∂x=0∂u∂t+u∂u∂x+1ρ∂p∂x=0∂S∂t+u∂S∂x=0 (5) 对流场状态参数全微分,得到:
dp=(∂p∂ρ)Sdρ+(∂p∂S)ρdS (6) 经变换并联立方程组(5)第1式,得到:
dpdt−(∂p∂E)ρ(TdSdt)+ρc2∂u∂x=0 (7) 引入系数
λ ,联立方程组(5)第2式和式(7),得到:λ[∂u∂t+(u+ρc2λ)∂u∂x]+[∂p∂t+(u+λρ)∂p∂x]−(∂p∂E)ρ(TdSdt)=0 (8) 令
λ=±ρc ,得到:±ρc[∂u∂t+(u±c)∂u∂x]+[∂p∂t+(u±c)∂p∂x]−(∂p∂E)ρ(TdSdt)=0 (9) 当
dxdt=u±c 时,方程(9)可变为:{dxdt=u±cdpdt±ρc(dudt)−(∂p∂E)ρ(TdSdt)=0 (10) 根据含铝炸药爆轰产物的局部等熵假设,在每个小时间域内,爆轰产物的流动规律可近似认为是等熵流动。因此,对于微时间域
i ,方程组(10)可表示为:{dxdt=ui±cidui±1ρicidpi = 0 (11) 对方程组(11)第2式求积分,得到:
ui±∫dpρc=ui±∫cdρρ (12) 根据爆轰产物的等熵方程(4),声速
c2i=γi[(wb+waλAli1−nAn)CiR]γiργi−1i ,于是可以得到:∫cidρiρi=∫2γi−1dci=2γi−1ci (13) 由此可以得到爆轰产物的特征线方程:
{dxdt=ui±ciui±2γi−1ci=constant (14) 式中:
ui 和ci 分别表示微时间域i 内爆轰产物的粒子速度和当地声速,由于在微时间域i 内产物流动是局部等熵的,因此,沿特征线ui 和ci 的值保持不变。2.3 含铝炸药爆轰驱动金属板的非线性特征线计算
假设长为L的含铝炸药和质量为M的金属平板置于无限长刚性圆管中,炸药两侧为真空环境。采用一侧端面引爆炸药,炸药对金属平板驱动的特征线图如图2所示。
设含铝炸药引爆时刻为0时刻,金属板后爆轰产物的流动方程可表示为:
{x=(ui+ci)t+Fix=(ui−ci)t+F′i (15) 式中:
Fi 为与铝粉反应度相关的特征线参数,F′i 为与铝粉反应度和金属板运动相关的特征线参数。根据经典力学牛顿第二定律可知:
Mdvdt=Arpm (16) 式中:
M 为金属板的质量,v 为金属板的速度,Ar 为金属板的横截面面积,pm 为金属板内表面处爆轰产物的压强。基于局部等熵假设,在微时间域i 内,可以得到如下关系:pmpi=(cmci)γ (17) 式中:
pm 和cm 分别为紧挨金属板内表面处爆轰产物的压强和当地声速,pi 为微时间域i 内右传波到达金属板内表面前爆轰产物的初始压强。将式(17)代入式(16),得到:dvdt=ArpiMcγicγm (18) 爆轰产物中的每一道右传波都以各自的
u+c 速度传播,并且在微时间域内沿特征线传播速度保持不变。当右传波追赶上运动的金属板时,右传波将发生反射,在此瞬间,爆轰产物的粒子速度立即由ui 降低为金属板壁面的速度um ,声速也立即由ci 变为金属板后产物的声速cm ,从而得到:ui+ci=um+cm (19) 对方程组(15)中的第1式对时间
t 求导得到:dxdt=(um+cm)+(dumdt+dcmdt)t (20) 由于金属板内表面处的产物速度
um 与金属板运动的速度v 相等,并且dxdt=v=um ,因此将式(18)代入式(20),得到:dcmdt+cmt+ψcγm=0 (21) 式中:
ψ=ArpiMcγi 。考虑到炸药处于无限长刚性圆管中,可认为爆轰产物在短时间内始终处于高压状态,因此有γ≈3 。应用第2节中提到的参数变换法求解微分方程(21),得到:1+2ψc2mtc2mt2=ϑ1 = constant (22) 在微时间域1,即
0∼t1 时间段内,金属板后的爆轰产物的初始状态参数为:{p1=pH=14ρ0D2Alc1=cH=34DAl (23) 其边界条件为:
{t=LDAlum=0cm=DAl (24) 式中:
ρ0 为含铝炸药的初始密度,pH 和cH 为爆轰波阵面上产物的压力和声速,L 为炸药的长度,DAl 为含铝炸药的爆速。将边界条件(24)代入式(22),得到:ϑ1=1+ηL2 = constant (25) 式中:
η=3227mM ,其中m 为炸药质量,m=ArLρ0 。将式(25)代入式(22),得到:
cm=Ltξ1 (26) 式中:
ξ1=[1+η(1−LDAlt)]−0.5 。将式(26)代入式(18),并积分得到:
v=DAl(1+2(ξ1−1)ηξ1−Lξ1DAlt) (27) 式(27)表示在微时间域1内含铝炸药对质量为M的金属板的驱动规律。
基于局部等熵假设,结合以上方法,可以得到任意微时间域
i 内,爆轰产物对金属板的驱动速度如下:{v−v(ti−1)=(Lξi(ti−1)ti−1+2DAlη1ξi(ti−1)−Lξit−2DAlηξi)ξi=(L2ϑi−ηLDAlt)−0.5ϑi=1+ηc2m(ti−1)ti−1LDAlc2m(ti−1)t2i−1=constant (28) 式中:
ti - 1 表示微时间域i 的起始时刻,v(ti−1) 表示微时间域i 的起始时刻金属板的速度。3. 含铝炸药爆轰产物非线性特征线模型的实验验证
3.1 含铝炸药驱动金属板的实验结果
选择RDX基含铝炸药作为驱动炸药,炸药中铝粉的平均直径为5、50 μm两种,分别驱动厚0.5、1 mm的紫铜板。炸药参数如表1所示。
表 1 实验所用的炸药参数和铜板尺寸Table 1. Parameters of the explosive and size of the copper plate编号 炸药 铝粉(或LiF)质量分数/% 炸药密度/(g·cm−3) 铝粉直径/μm 金属板尺寸/mm×mm 1 RDX/Al/黏结剂 20 1.82 5 ∅50×1 2 RDX/Al/黏结剂 20 1.82 50 ∅50×1 3 RDX/LiF/黏结剂 20 1.80 − ∅50×1 4 RDX/Al/黏结剂 20 1.82 5 ∅50×0.5 5 RDX/Al/黏结剂 20 1.82 50 ∅50×0.5 6 RDX/LiF/黏结剂 20 1.80 − ∅50×0.5 注:炸药尺寸为∅50 mm×50 mm,黏结剂含量占炸药总量的5%。 实验布置示意图如图3所示。
3.2 实验条件下铝粉的反应度变化规律
在同等实验条件下,以含铝炸药驱动金属板的动能减去含LiF炸药驱动金属板的动能,就得到了铝粉反应释放能量对金属板所做的有用功:
ΔE(t)=12M[v2Al(t)−v2LiF(t)] (29) 式中:
vAl 和vLiF 分别表示含铝炸药和含LiF炸药驱动金属板的运动速度。设平板驱动实验的效率为
ϖ ,铝粉的氧化反应热为QAl ,铝粉的反应度为λ(t) ,据此可得到:ΔE(t) = ϖQAlmwaλ(t) (30) 式中:
m 表示含铝炸药的质量,wa 表示含铝炸药中铝粉的质量分数。将式(29)代入式(30),得到:
ϖQAlmwaλ(t) = 12M[v2Al(t)−v2LiF(t)] (31) 通过计算化学生成焓得到
QAl =20.126 kJ/g,炸药驱动金属板的实验效率ϖ 取为0.18[19],据此可计算出铝粉的反应度变化,计算得到的反应度变化规律如图6~7所示:3.3 非线性特征线理论计算结果与实验结果对比
基于含铝炸药爆轰产物的非等熵流动模型,应用非线性特征线计算方法计算5、50 μm含铝炸药对0.5、1 mm金属板的驱动过程,含铝炸药参数见表2。
表 2 含铝炸药和含LiF炸药的参数Table 2. Parameters of the aluminized explosives and the LIF explosive炸药组成 铝粉质量分数/% 铝粉直径/μm 炸药密度/(g·cm−3) 炸药爆速/(km·s−1) RDX/Al 20 5 1.8 8.223 RDX/Al 20 50 1.8 8.223 RDX/LiF − − 1.8 8.223 含铝炸药和含LiF炸药驱动0.5、1 mm厚金属板的实验和计算结果对比如图8~9所示。
从图8中的对比结果可以看出,非线性特征线模型的计算结果与实验结果保持了较好的一致性。在6.3~8 μs的驱动时间段内,计算结果稍大于实验测试结果,8 μs后计算结果与实验结果一致性较高。需要指出的是,此结果仅针对爆轰波到达金属后的6 μs的时间内,由于强约束壳体膨胀破裂的时间约为6 μs,在此时间段内爆轰产物受稀疏波的影响较小,因此理论结果与实验结果较一致,而当强约束壳体破裂时,产物开始泄露稀疏波将对驱动将产生很大影响,计算结果将高于实验测试结果。
图9为5 μm含铝炸药、50 μm含铝炸药和含LiF炸药对1 mm厚金属板的实验和计算结果。计算结果较好地体现了铝粉反应对炸药做功能力的贡献以及铝粉粒度不同对炸药做功能力的影响,但由于受到1 mm金属板内应力波的影响,驱动加速段实验测试结果波动较大。但总体而言,非线性特征线模型能够较好地体现铝粉后期反应对做功能力的贡献,且前期驱动结果与强约束条件下的驱动金属板实验结果保持了较好的一致性。
4. 结 论
主要对微米级铝粉含铝炸药爆轰产物的非等熵膨胀规律进行了理论分析,目标是建立一种理论分析模型,描述包含铝粉氧化反应的爆轰产物流动规律,理论研究铝粉反应对炸药做功能力的贡献,为理论分析含铝炸药爆轰产物的流动规律提供一种方法。
针对微米级铝粉含铝炸药爆轰产物的非理想特性,在经典理想炸药爆轰产物等熵流动理论的基础上,通过科学分析和计算,得到如下结论:
(1)根据微米级铝粉含铝炸药的二次反应特性,提出含铝炸药爆轰产物膨胀过程的局部等熵假设,应用特征线方法能够科学构建含铝炸药爆轰产物的准解析模型;
(2)基于理想炸药爆轰产物的近似状态方程和铝粉反应对压力的贡献方程,能够得到含铝炸药爆轰产物状态方程;
(3)基于局部等熵假设和含铝炸药爆轰产物状态方程,应用非线性特征线方法计算了含铝炸药爆轰产物的流动规律,并推导出含铝炸药爆轰驱动的非线性特征线方程组,分析了含铝炸药爆轰驱动金属板和金属板后产物的非等熵膨胀过程,非线性特征线模型能够定性分析微米级铝粉在爆轰产物膨胀区的二次反应特性;
(4)设计了5、50 μm含铝炸药和含LiF炸药在强约束条件下驱动0.5、1 mm厚金属板实验,通过激光位移干涉仪测试金属板运动的速度历程,通过实验结果间接计算了铝粉在爆轰产物中的反应度,结合含铝炸药爆轰产物的非等熵流动模型,理论计算了不同炸药驱动金属板的速度历程,对比实验结果,理论方法能够很好的描述铝粉二次反应对炸药做功能力的贡献,且与实验结果能够保持较好的一致性,验证了非等熵流动模型对于微米级铝粉含铝炸药的正确性。
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