身管材料的高温氧化行为

doi:10.12382/bgxb.2022.0901

摘要/Abstract

摘要：

随着对火力打击要求的提高、大威力火炮的发展、身管材料的高温氧化日益严重,严重影响武器性能的发挥,甚至导致武器报废。但目前对身管材料的抗氧化性能研究较少。针对3种身管材料PCrNi3MoVA钢、30SiMn2MoVA钢和MPS700钢,研究其在600℃空气条件下的抗氧化性能和氧化机理。通过扫描电子显微镜、能谱和X射线衍射仪分析了氧化层的截面形貌和物相,分析其氧化动力学行为。研究结果表明:随着氧化时间增加,3种钢的氧化膜厚度逐渐增厚,厚度增加率逐渐降低,3种身管钢的氧化动力学曲线都符合氧化膜抛物线生长动力学规律;在600℃高温下,PCrNi3MoVA钢中的内氧化层形成了具有网络结构的粘附层,该网络结构主要由富含Ni和Cr的尖晶石氧化物组成,而该粘附层并不能成为防止氧化的屏障;30SiMn2MoVA钢氧化层的内层为Si氧化物的多孔聚集区,结构较为松散,氧化物剥落较为严重;MPS700钢的内氧化层形成了富含Cr的保护性氧化层,有效的阻碍了氧化的继续进行;同时,Mo稳定了氧化膜,间接提高了抗氧化性;综合对比,由于Cr、Mo等合金元素的综合作用,在高温工况下MPS700钢比PCrNi3MoVA钢和30SiMn2MoVA钢能够更好地形成致密的氧化层,从而可降低基体的高温氧化和磨损程度,更有适用于制备长寿命、高可靠性身管材料。

关键词: 身管材料, 高温氧化, 氧化层, 合金元素

Abstract:

With the increase in firepower strike requirements and the development of high-powered artillery, the high-temperature oxidation of barrel materials is becoming more and more serious, which seriously affects the performance of weapon and even leads to the scrapping of weapon.However, there is little research on the anti-oxidation performance of barrel materials at present.In this paper, the oxidation resistances and oxidation mechanisms of three barrel materials, i.e.,PCrNi3MoVA steel. 30SiMn2MoVA steel and MPS700 steel, at 600℃ in airare investigated. The cross-sectional morphology and phases of the oxide layers are analyzed by scanning electron microscopy, energy spectroscopy and X-ray diffractometry. The oxidation kinetics of three barrrel materials were analyzed. The results show that the oxide film thicknesses of the three steels gradually thicken and the rate of increaseinthickness gradually decreaseswith the increase in oxidation time. The oxidation kinetics curves of the three barrel materials are consistent with the parabolic growth kinetics law of oxide film. At 600℃, the internal oxide layer of PCrNi3MoVA steel forms an adhesive layer of a network structure consisting mainlyof Ni and Cr-richspinel oxides but theadhesive layerdoes not act as a barrier against oxidation.The inner layer of oxide layer of 30SiMn2MoVA steel is a porous aggregation zone of Si element oxide with a loose structure and relatively serious oxide flaking.The internal oxide layer of MPS700 steel forms a protective Cr-rich oxide layer that effectively prevents further oxidation. At the same time, Mo element stabilises the passivation film and indirectly improves oxidation resistance. Compared with PCrNi3MoVA steel and 30SiMn2MoVA steel, MPS700 steel can better form a dense oxidized layer under high temperature condition, so as to reduce the high temperature oxidation and wear degree of the matrix under high temperature conditions. MPS700 steel is more suitable for the preparation of long life and high reliability barrel.

Key words: barrel material, high-temperature oxidation, oxide layer, alloying element

中图分类号:

TG14

张程, 张玉琦, 温相丽, 白鹏鹏, 孟永钢, 马丽然, 田煜. 身管材料的高温氧化行为[J]. 兵工学报, 2024, 45(4): 1354-1362.

ZHANG Cheng, ZHANG Yuqi, WEN Xiangli, BAI Pengpeng, MENG Yonggang, MA Liran, TIAN Yu. High-temperature Oxidation Behavior of Barrel Materials[J]. Acta Armamentarii, 2024, 45(4): 1354-1362.

图/表 13

表1 实验钢的名义成分

Table 1 Chemical composition of the teststeels %

钢号	C	Si	Mn	Cr	Ni	Mo	V	W	P	S	Fe
PCrNi3MoVA	0.38	0.24	0.40	1.40	3.10	0.41	0.16		<0.015	<0.015	余量
30SiMn2MoVA	0.29	0.40	1.75		0.25	0.50	0.21		<0.015	<0.015	余量
MPS700	0.23	0.02	0.05	2.79	1.10	2.33	0.25	0.60	<0.015	<0.015	余量

图1 3种钢的热处理工艺

Fig.1 Heat treatment process of three steels

图2 实验材料在600℃氧化条件下的增重率

Fig.2 Weight gain rates of test materials under 600℃ oxidation

表2 氧化动力学方程

Table 2 Oxidation kinetic equation

材料	氧化动力学方程	相关系数
PCrNi3MoVA钢	Δm²=0.90242t	0.98012
30SiMn2MoVA钢	Δm²=0.54339t	0.97683
MPS700钢	Δm²=0.39628t	0.98259

表3 实验材料不同氧化时间的平均质量变化

Table 3 Average mass change of test materials at different oxidation times

材料	氧化时间/h	平均质量/(mg·cm^-2)
	1	1.2
PCrNi3MoVA钢	3	1.8
	7	2.43
	10	2.91
	1	0.6
30SiMn2MoVA钢	3	1.32
	7	1.76
	10	2.51
	1	0.72
MPS700钢	3	1.24
	7	1.57
	10	1.96

图3 试样经600℃氧化10h后氧化层的XRD图谱

Fig.3 XRD patterns of the samples oxidized for 10h at 600℃

表4 实验钢氧化10h的氧化层平均厚度

Table 4 Average thickness of oxide layer ofteststeel oxidized for 10h

材料	氧化层平均厚度/μm
PCrNi3MoVA钢	20.71
30SiMn2MoVA钢	16.32
MPS700钢	13.64

图4 PCrNi3MoVA钢高温氧化后氧化层横截面的SEM-EDS面扫

Fig.4 SEM-EDS surface scanning of cross section of oxide layer of PCrNi3MoVA steel after high temperature oxidation

图5 30SiMn2MoVA钢高温氧化后氧化层横截面的SEM-EDS面扫

Fig.5 SEM-EDS surface scanning of cross section of oxide layer of 30SiMn2MoVA steel after high temperature oxidation

图6 MPS700钢高温氧化后氧化层横截面的SEM-EDS面扫

Fig.6 SEM-EDS surface scanning of cross section of oxide layer of MPS700 steel after high temperature oxidation

表5 实验钢中各元素在600℃下的氧化反应

Table 5 Oxidation reactions of the elements in the test steels at 600℃

元素	反应式	ΔG/(kJ·mol^-1)
Fe	4/3 Fe+O₂(g)=2/3 Fe₂O₃	-393.846
Ni	2Ni+O₂(g)=2NiO	-319.296
Cr	4/3 Cr+O₂(g)=2/3Cr₂O₃	-602.199
Si	Si+O₂(g)=SiO₂	-752.543
Mn	2Mn+O₂(g)=2MnO	-641.350
Mo	2/3Mo+O₂(g)=2/3MoO₃	-349.097
	NiO+Fe₂O₃=NiFe₂O₄	-23.569
	NiO+Cr₂O₃=NiCr₂O₄	-6.635

图7 氧化物产生的自由能与温度之间的关系

Fig.7 Relationship between the free energy produced by the oxide and the temperature

图8 3种材料在600℃下的氧化机制示意图

Fig.8 Schematic diagrams of oxidation mechanisms of three materials at 600℃

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