A Review on the Impact Dynamic Behaviors of Metals with Heterogeneous Structures

ZHANG Zihan; MA Yan; YUAN Fuping

doi:10.11858/gywlxb.20200662

Volume 35 Issue 4

Aug 2021

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Chinese Journal of High Pressure Physics > 2021 > 35(4): 040105.

XIA Yu, CHENG Yangfan, HU Fangfang, WANG Rui, ZHU Shoujun, SHEN Zhaowu. Inhibition Characteristics of Typical Solid Explosion Suppressors on Acetylene-Air Explosion[J]. Chinese Journal of High Pressure Physics, 2022, 36(6): 065201. doi: 10.11858/gywlxb.20220580

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ZHANG Zihan, MA Yan, YUAN Fuping. A Review on the Impact Dynamic Behaviors of Metals with Heterogeneous Structures[J]. Chinese Journal of High Pressure Physics, 2021, 35(4): 040105. doi: 10.11858/gywlxb.20200662

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A Review on the Impact Dynamic Behaviors of Metals with Heterogeneous Structures

doi: 10.11858/gywlxb.20200662

ZHANG Zihan^{1, 2
,},
MA Yan^{1, 2,*
,
,},
YUAN Fuping^{1, 2}

1.
State Key Laboratory of Nonlinear Mechanics, Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190, China
2.
School of Engineering Science, University of Chinese Academy of Sciences, Beijing 100049, China

Received Date: 29 Dec 2020
Rev Recd Date: 06 Feb 2021

Abstract

Abstract

The ductility/toughness of the high strength materials is usually inadequate, while high strength metals and alloys with good ductility/toughness can be obtained by designing the heterogeneous structures. Thus, the quasi-static and dynamic behaviors of the metals and alloys with heterogeneous structures have attracted extensive research interests in the areas of mechanics of materials and impact dynamics. The present paper reviewed the progress in the aspect of the dynamic properties and the corresponding microstructural mechanisms of several heterogeneous structures, such as gradient structures, dual-phase structures, multi-modal grain structures. For example, the metals with heterogeneous structures show better dynamic shear toughness and impact toughness than those with homogeneous structures. The initiation and propagation of adiabatic shear bands in the heterogeneous structures are totally different from those in homogeneous structures, due to the inhomogeneous microstructures. The interfaces and the soft domains in the heterogeneous structures can suppress the initiation and propagation of adiabatic shear bands, delaying the failure of materials. The superior dynamic properties can be achieved in the heterogeneous structures due to the extra strain hardening induced by the inhomogeneous deformation.
- heterostructured metals,
- dynamic impact,
- toughness,
- adiabatic shear band,
- dynamic recrystallization

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乙炔是一种无色无味的可燃气体，广泛应用于金属焊接、切割等，同时也是化工生产中合成橡胶、芳烃和高聚物等的重要原材料^[1-3]。乙炔在空气中的爆炸极限为2.5%～80%^[4]，具有很高的爆炸风险和破坏性。在乙炔的生产、运输和储存等环节，由于气体泄漏、通风和回火等原因，极易引发爆炸^[5]。近年来，由乙炔引发的爆炸事故频发，例如：2018年，张家口盛华化工有限公司附近发生燃爆事故^[6]，装载乙炔的货车被爆燃的氯乙烯引爆，造成24人死亡、22人受伤；2018年，印度科钦造船厂因工人焊接导致乙炔泄漏引发爆炸事故，造成5人死亡、13人受伤。乙炔爆炸事故发展迅速、爆炸危险性大，给人们的生命和财产安全带来了巨大的威胁。因此，研究乙炔气体的抑爆技术对于保障安全生产具有重要的意义。

国内外学者在可燃气体抑爆方面做了大量的研究工作，常用的抑爆剂包括气体抑爆剂、液体抑爆剂和固体抑爆剂。Wang等^[7]运用氮气和二氧化碳稀释烃类燃料，发现惰性气体的加入能够抑制燃料的爆炸强度，且二氧化碳的抑制效果优于氮气。Luo等^[8]研究了气-固抑爆剂（二氧化碳-ABC粉末）对瓦斯气体爆炸的影响，实验结果表明，ABC粉末与二氧化碳存在协同增效，可以降低瓦斯的爆炸威力。Wang等^[9]运用实验与数值模拟相结合的方法，研究了超细水雾对气体爆炸的抑制机理，结果表明，超细水雾对火焰温度、火焰传播速度和最大爆炸压力均有显著的衰减作用。Wen等^[10]研究了惰性纳米粉末颗粒对甲烷-空气爆炸的抑制作用，发现氢氧化铝（Al(OH)₃）、碳酸氢钠（NaHCO₃）和二氧化硅（SiO₂）都可以用于抑制火焰的传播和超压，并且金属氢氧化物比二氧化硅的抑制效果更好。丁超等^[11]基于100 L的爆炸容器探究了超细ABC粉末对瓦斯爆炸的影响，结果表明，抑制爆炸所需的超细ABC粉体存在确定的临界量，且抑爆效果与抑爆装置的触发时间有关。国内外有关乙炔爆炸特性的研究较少，而涉及抑爆效果的研究则更少。在乙炔的爆炸特性方面：宋诗祥^[12]利用20 L球形爆炸装置研究了水分子在乙炔-碳化钙气-固两相爆炸中的作用，揭示了其爆炸反应机制；郭璐等^[3]探究了杂质对乙炔气体分解爆炸的影响，发现氮气对乙炔爆炸分解有抑制作用，而氧气、硫化氢、铁锈对其具有促进作用。Mizutani等^[13]利用1 L密闭容器研究了乙炔的分解爆炸特性，结果表明，最大分解爆燃压力和压力上升速率随着容器温度的降低而升高。在乙炔的抑爆特性方面：王犇等^[14]采用20 L球形爆炸测试系统研究了氮气对乙炔分解爆炸特性的影响，结果显示，乙炔的爆炸抑制作用随着氮气体积分数的增加而逐渐增大；Kopylov等^[15]研究了丙烷、甲烷和18%С₃Н₆-40%С₃Н₈-42%С₄Н₁₀混合物对乙炔-空气混合气体燃烧的影响，发现当乙炔的体积分数在2%～8%范围内时，丙烷和18%С₃Н₆-40%С₃Н₈-42%С₄Н₁₀混合物对乙炔的燃烧具有较强的抑制作用，并且随着混合物中乙炔含量的增加，抑制作用减弱。目前，有关乙炔抑爆研究主要集中在气体和液体抑爆剂方面，而固体抑爆剂对乙炔的抑爆特性研究很少。

SiO₂、Al(OH)₃和NaHCO₃^[16-19]是典型的固体抑爆剂。本研究采用20 L球形爆炸测试系统，研究3种固体抑爆剂对乙炔-空气（当量比 $\varphi$ =1）预混气体的抑爆效果，通过爆炸特性参数（最大爆炸压力p_ex、最大爆炸压力上升速率(dp/dt)_ex）分析固体抑爆剂对乙炔的抑爆效果，结合乙炔气体爆炸机理，阐明固体抑爆剂的抑爆机理，为乙炔工业生产、储运和使用过程中乙炔意外爆炸防治提供理论指导。

1. 实验装置与材料

1.1 实验装置

本实验采用的20 L球形爆炸测试系统如图1所示。该系统主要由爆炸容器、点火系统、喷粉系统、配气系统、数据采集系统和控制系统组成。爆炸容器为球形，体积为20 L；点火系统由导线和点火电极构成；喷粉系统由气固两相阀、储粉罐（600 mL）、压力表和压缩气体构成；数据采集系统由压力传感器和计算机构成；控制系统由导线和控制器构成。首先，在储粉罐中装入固体抑爆剂粉体，用真空泵将爆炸容器抽至真空，采用分压法向其中通入乙炔气体；然后，将高压空气通入储粉罐，当储粉罐前的电接点式压力表达到2.0 MPa后，开启气固两相阀，将固体抑爆剂粉体喷入爆炸容器中，此时爆炸容器内部达到常压，固体抑爆剂粉体弥散形成粉尘云；最后，采用控制系统点火，由压力传感器（美国Dytran）采集数据，并传输至计算机，经计算机软件初步处理得到压力时程曲线，存储图像和数据。实验中，乙炔与空气的当量比 $\varphi$ =1，每种工况下重复3次以上实验。

图 1 20 L球形爆炸测试系统示意图

Figure 1. Schematic diagram of the 20 L spherical explosion test system

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1.2 实验材料

本实验采用的乙炔气体由安徽合肥恒隆电气有限公司提供，纯度为99.9%；空气由安徽合肥恒隆电气有限公司提供，氧气和氮气的体积分数分别为20.98%和79.02%。考虑到粒子的表面积会影响吸热效果^[20]，为此本研究统一选用微米级抑爆剂粉体。微米级SiO₂、Al(OH)₃和NaHCO₃均由国药集团化学试剂有限公司提供，其粒径分布如图2所示。可见，SiO₂、Al(OH)₃和NaHCO₃粉体的粒径分布接近，平均粒径D₅₀分别为13.0、10.4和11.5 μm。

图 2 固体抑爆剂粉体的粒径分布

Figure 2. Particle size distribution of solid explosion suppressors

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2. 实验和模拟结果

乙炔-空气爆炸的主要反应式为^[21]

$\rm{{C_2}{H_2}+2.5\left( {{O_2}+3.76{N_2}} \right) \to 2C{O_2}+{H_2}O+9.4{N_2}}$

(1)

采用乙炔与空气的当量比 $\varphi$ =1的乙炔-空气预混气体进行爆炸实验

$\varphi {\text{ = }}{n}/{{{n_{{\text{st}}}}}}$

(2)

式中：n为实验中乙炔与空气的物质的量之比；n_st为理论上乙炔完全反应时乙炔与空气的物质的量之比^[5]。图3为20 L球形爆炸容器内 $\varphi=1$ 时乙炔-空气预混气体的爆炸压力时程曲线（未加入固体抑爆剂的实验结果，即对照组），其最大压力p_ex为0.68 MPa，最大压力上升速率(dp/dt)_ex为203.09 MPa/s。

图 3 乙炔-空气爆炸压力时程曲线（

$\varphi$ =1）

Figure 3. Explosion pressure-time curve of C₂H₂-air (

$\varphi$ =1)

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2.1 SiO₂对乙炔-空气预混气体爆炸特性的影响

SiO₂的化学性质稳定，熔点高达(1723±5) ℃，沸点高达2230 ℃，是一种常用的耐火材料和固体抑爆剂。微米级SiO₂因表面效应特性，在催化、扩散、光吸收、热阻和自由基捕捉能力等方面具有广泛的应用^[22]。图4给出了在不同粉体浓度的SiO₂作用下乙炔-空气爆炸压力时程曲线，除100和300 g/m³粉体浓度外，高浓度的SiO₂对乙炔-空气爆炸压力起到了抑制作用。图5为不同SiO₂粉体浓度对乙炔-空气预混气体的爆炸特征参数的影响。当SiO₂粉体浓度小于300 g/m³时，加入SiO₂粉体能够快速吸收燃烧产生的水分，使燃烧反应加速，此时SiO₂粉体表现出对乙炔爆炸参数的促进作用^[23]；当SiO₂粉体浓度超过300 g/m³时，SiO₂粒子的吸热作用和吸收活性自由基作用增强，远高于SiO₂粒子吸收水分的影响，从而导致p_ex和(dp/dt)_ex均随着SiO₂粉体浓度的增大而不断下降。

图 4 不同SiO₂粉体浓度下乙炔-空气爆炸压力时程曲线

Figure 4. Explosion pressure-time curves of C₂H₂-air at different concentrations of SiO₂

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图 5 SiO₂对乙炔-空气爆炸特性的影响

Figure 5. Effect of SiO₂ on explosion characteristics of C₂H₂-air

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2.2 Al(OH)₃对乙炔-空气预混气体爆炸特性的影响

Al(OH)₃是一种两性氧化物，熔点为300 ℃，受热易分解，在378.7 ℃出现热分解吸热峰^[24]，具有无毒、阻燃和不产生二次污染的优点，被广泛用于阻燃剂^[25-26]。图6显示了在不同Al(OH)₃粉体浓度下乙炔-空气的爆炸压力时程曲线。可见，Al(OH)₃粉体对乙炔-空气的爆炸压力起到抑制作用。图7显示了不同Al(OH)₃粉体浓度下乙炔-空气预混气体的爆炸特征参数。随着Al(OH)₃粉体浓度的增加，p_ex和(dp/dt)_ex均呈下降趋势。当Al(OH)₃的粉体浓度小于300 g/m³时，p_ex和(dp/dt)_ex下降缓慢，说明Al(OH)₃粉体量较少时，对乙炔爆炸特性的影响较小；当Al(OH)₃粉体浓度大于300 g/m³时，随着Al(OH)₃粉体浓度的增加，p_ex和(dp/dt)_ex的下降速率加快。

图 6 不同Al(OH)₃粉体浓度下乙炔-空气爆炸压力时程曲线

Figure 6. Explosion pressure-time curves of C₂H₂-air at different concentrations of Al(OH)₃

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图 7 Al(OH)₃对乙炔-空气爆炸特性的影响

Figure 7. Effect of Al(OH)₃ on explosion characteristics of C₂H₂-air

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2.3 NaHCO₃对乙炔-空气预混气体爆炸特性的影响

NaHCO₃的化学性质不稳定，分解温度在110～140 ℃^[27]之间，易分解生成惰性物质，因此具有良好的灭火作用，是BC类干粉灭火剂的主要填充材料^[28]。图8显示了不同NaHCO₃粉体浓度下乙炔-空气爆炸压力时程曲线。可以看出，NaHCO₃对乙炔-空气的爆炸压力起到抑制作用。图9显示了不同NaHCO₃粉体浓度下乙炔-空气预混气体的爆炸特征参数变化情况。随着NaHCO₃粉体浓度的增加，p_ex和(dp/dt)_ex均呈不断下降的趋势。这是因为在乙炔-空气爆炸火焰传播过程中，NaHCO₃粉体能够使前锋面的火焰出现局部熄灭，由于微米级粒子的比表面积高，因此分解反应速率快，与无NaHCO₃粉体的对照组相比，p_ex和(dp/dt)_ex下降明显，抑制火焰发展的效果好。随着粉体浓度的增加，爆炸容器内参与抑制作用的粉体颗粒数目增多，对乙炔-空气爆炸的抑制作用增强，p_ex和(dp/dt)_ex逐渐下降。

图 8 不同NaHCO₃粉体浓度下乙炔-空气爆炸压力时程曲线

Figure 8. Explosion pressure-time curves of C₂H₂-air at different concentrations of NaHCO₃

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图 9 NaHCO₃对乙炔-气体爆炸特性的影响

Figure 9. Effect of NaHCO₃ on explosion characteristics C₂H₂-air

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2.4 爆炸压力敏感性分析

为了进一步研究固体抑爆剂的影响机制，选取与实验相同当量的乙炔-空气预混气体，对影响爆炸压力的主要反应进行敏感性分析，进而探究固体抑爆剂对乙炔爆炸的抑爆机理。设初始温度为1400 K，初始压力为0.1 MPa，时间为5 ms，影响爆炸压力的主要反应见表1。图10给出了当量比为1的乙炔-空气预混气体爆炸压力的敏感性分析结果。

表 1 影响爆炸压力的主要反应

Table 1. Main reactions affecting explosion pressure

No.	Reaction	No.	Reaction
R1	H+O₂↔O+OH	R158	C₂H₂+O↔HCCO+H
R39	HCO+M↔CO+H+M	R161	C₂H₂+OH↔C₂H+H₂O
R41	HCO+O₂↔CO+HO₂	R166	C₂H₂+C₂H↔C₄H₂+H
R141	C₂H+O₂↔HCO+CO	R194	C₂H₃+O₂↔CH₂CHO+O
R155	C₂H₃(+M) ↔C₂H₂+H(+M)	R195	C₂H₃+O₂↔HCO+CH₂O

下载: 导出CSV

| 显示表格

图 10 爆炸压力敏感性分析

Figure 10. Sensitivity analysis of explosion pressure

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从图10可以看出：R1、R39、R158、R161、R166和R194反应促进爆炸压力，R41、R141、R155和R195反应抑制爆炸压力，其中R1反应占主导地位。加入固体抑爆剂时，固体抑爆剂会与其中的关键自由基结合，从而影响爆炸特征参数。

3. 分析与讨论

图11为3种固体抑爆剂对乙炔-空气预混气体的抑爆特性对比。3种固体抑爆剂中，从p_ex和(dp/dt)_ex的减小程度上看，SiO₂粉体对乙炔-空气预混气体爆炸的抑制效果弱于Al(OH)₃粉体，NaHCO₃粉体对乙炔-空气爆炸的抑制效果最好。乙炔-空气预混气体爆炸是一种剧烈的自由基氧化链式反应，在反应过程中会生成O、H、OH和HCO等高活性自由基^[22]。虽然微米级SiO₂粒子（固相）不与乙炔-空气爆炸火焰反应，但是由于其具有很高的比表面积，粒子很容易接触和吸收燃烧反应热，从而直接降低燃烧反应强度，影响反应的传热，进而降低爆炸火焰速度和压力波^[17]。当SiO₂粉体浓度大于300 g/m³时，随着粉体浓度的增加，能够吸收更多的自由基，对乙炔爆炸的抑制效果更好。

图 11 3种固体抑爆剂的抑爆特性对比

Figure 11. Explosion inhibition characteristics of three solid explosion suppressors

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Al(OH)₃在乙炔-空气爆炸过程中既充当吸热介质，又发生分解反应^[18]，即

$\rm{2Al(OH)_3 \to Al_2O_3+3H_2O}$

(3)

Al(OH)₃分解生成Al₂O₃（固相）和H₂O（气-液二相），产生吸热冷却效应。H₂O汽化吸热，导致爆炸容器内的温度下降，生成的水蒸气降低了乙炔分子与氧分子的碰撞概率。同时，Al(OH)₃中的自由基OH能够消耗乙炔-空气链式反应中的关键自由基O，抑制反应R158（C₂H₂+O↔HCCO+H）的进行，使得爆炸压力降低。Al(OH)₃的吸热冷却效应和分解生成的H₂O汽化吸热使得Al(OH)₃的抑爆效果略优于SiO₂，表现出更低的p_ex和(dp/dt)_ex。

NaHCO₃的性质不稳定，NaHCO₃晶体在熔化过程中可吸收热量，并且在乙炔-空气预混气体爆炸过程中发生分解反应^[18]，即

$\rm{2NaHCO_3 \to Na_2CO_3+CO_2+H_2O}$

(4)

分解反应的产物为惰性CO₂气体（气相）和H₂O（气-液二相），是气体爆炸中的惰性物质。其中：分解生成的Na₂CO₃（固相）使燃烧反应的传热受到阻碍；H₂O汽化能够吸收大量的热量，影响乙炔粒子之间的传热。同时，生成的CO₂气体作为一种惰性物质能够稀释乙炔和氧气的体积分数，阻碍火焰的发展，产生气体惰化。此外，NaHCO₃中的HCO消耗乙炔-空气爆炸链式反应中的关键自由基O和OH^[18]，由敏感性分析可知，R158和R161反应对爆炸压力起促进作用，加入NaHCO₃使关键自由基被结合，参与反应的自由基减少，爆炸压力的促进作用减弱。同时，NaHCO₃中的HCO参与R41反应，R41反应对爆炸压力起抑制作用，爆炸压力的抑制作用增强，发生化学抑制。晶体熔化吸热、反应吸热、惰性物质和化学抑制的耦合作用使得爆炸容器内的温度和乙炔气体的体积分数降低，从而抑制乙炔-空气的爆炸反应，p_ex和(dp/dt)_ex的降幅最大。因此，NaHCO₃粉体的抑制爆炸效果优于SiO₂和Al(OH)₃粉体。

4. 结　论

(1) 当SiO₂粉体浓度低于300 g/m³时，SiO₂粉体对乙炔-空气预混气体的爆炸参数具有促进作用，当SiO₂粉体浓度超过300 g/m³时，乙炔-空气预混气体的爆炸参数随着SiO₂粉体浓度的增加而显著降低。

(2) SiO₂粉体对乙炔-空气预混气体爆炸的抑制效果弱于Al(OH)₃粉体，NaHCO₃粉体对乙炔-空气爆炸的抑制效果最好。

(3) NaHCO₃在乙炔-空气预混气体的爆炸过程中兼具气、固、液三相抑爆特点，通过晶体熔化吸热、反应吸热、惰性物质和化学抑制的多种耦合作用，使其表现出最佳的抑爆效果。

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