本文關(guān)鍵詞：磁控濺射制備火炮身管材料表面氮化物膜層技術(shù)研究　出處：《沈陽工業(yè)大學(xué)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 火炮身管壽命 磁控濺射 氮化物膜層 抗氧化性 耐腐蝕性

【摘要】：火炮在發(fā)射過程中,身管內(nèi)膛為高溫高壓的火藥氣體工況,同時(shí)彈帶與內(nèi)膛表面存在劇烈的摩擦磨損,另外在海洋等氣候條件下,身管受到劇烈的鹽氣腐蝕作用,因此火炮身管內(nèi)膛表面抗高溫氧化性能、耐磨損性能和耐鹽氣腐蝕性能是衡量其性能的重要指標(biāo)。隨著對火炮射擊遠(yuǎn)程化的要求,更高能量的發(fā)射藥應(yīng)用于火炮系統(tǒng)中,傳統(tǒng)的電鍍鉻已經(jīng)越來越不能滿足炮管內(nèi)膛的工況要求。為了提高火炮身管內(nèi)膛的性能,需要開發(fā)新的膜層制備技術(shù)和膜層材料。本文在綜合分析國內(nèi)外火炮身管延壽技術(shù)的基礎(chǔ)上,從膜層制備來提高火炮身管材料表面性能的角度出發(fā),首次采用磁控濺射技術(shù)在火炮身管材料PCrNi_3Mo鋼表面施鍍CrAlN膜層,并在此基礎(chǔ)上添加稀有金屬V元素來進(jìn)一步改善膜層的綜合性能,通過對所制備膜層硬度與彈性模量、摩擦磨損、抗高溫氧化、耐腐蝕性能的測試與分析,綜合確定了合理的膜層制備工藝,以此為火炮身管延壽技術(shù)提供理論參考。本研究取得了如下的研究成果:(1)工藝參數(shù)對磁控濺射膜層性能的影響:濺射膜層過程中,未施加基體負(fù)偏壓情況下,膜層結(jié)構(gòu)疏松并出現(xiàn)明顯的斑點(diǎn)缺陷,當(dāng)施加50-100V偏壓時(shí),由于濺射粒子能量提高,膜層表面平整致密,繼續(xù)增加負(fù)偏壓至150V時(shí),濺射粒子對膜層表面轟擊作用增強(qiáng)而導(dǎo)致膜層表面損傷,隨著負(fù)偏壓增至200V、300V,表面損傷越發(fā)嚴(yán)重而造成膜層表面質(zhì)量下降,其中施加100V偏壓的膜層具有最佳的表面質(zhì)量;濺射電流在0.1-0.2A范圍內(nèi)變化時(shí),隨著濺射電流的增大,濺射速率增大,同時(shí)由于濺射粒子能量的增加,導(dǎo)致膜層平整致密,力學(xué)性能提高,濺射電流在0.2-0.4A范圍內(nèi)變化時(shí),由于過高的粒子能量轟擊表面使得表面損傷,同時(shí),過高的濺射電流使得Cr粒子能量與數(shù)量增加,未被氮化的Cr以單質(zhì)Cr的形式存在于膜層中,導(dǎo)致膜層力學(xué)性能下降,其中濺射電流為0.2A時(shí)膜層具有最佳的表面質(zhì)量和力學(xué)性能;當(dāng)N_2/Ar3/4時(shí),由于部分Cr原子未被氮化,隨著N_2流量的增加,膜層硬度和彈性模量增大,當(dāng)N_2/Ar流量比達(dá)到1的時(shí)候,Cr原子完全被氮化,膜層硬度和彈性模量達(dá)到最高,當(dāng)繼續(xù)增大N_2/Ar流量比的時(shí)候,膜層的硬度和彈性模量開始略微降低。在負(fù)偏壓100V,濺射電流0.2A,N_2/Ar流量比為1時(shí)濺射的CrN膜層質(zhì)量最佳,其硬度和彈性模量分別為21.38GPa和272.71GPa。(2)CrAlN與CrAlVN膜層的制備與力學(xué)性能:通過控制Al靶功率(50-200W),制備出不同Al含量的CrAlN膜層,所制備膜層表面均為“菜花狀”結(jié)構(gòu),斷口顯示出典型的柱狀晶結(jié)構(gòu)。Al的引入細(xì)化了晶粒,在一定范圍內(nèi)起到了固溶強(qiáng)化的作用,其中Cr0.34Al0.66N膜層具有最佳的硬度與彈性模量,分別為23.91GPa和316.2GPa,其摩擦系數(shù)為0.293;通過控制V靶電流(0.03-0.09A),制備出不同V含量的CrAlVN膜層,稀有金屬V元素的引入使得晶粒細(xì)化越發(fā)明顯,V固溶在CrAlN膜層中導(dǎo)致晶格發(fā)生變化進(jìn)而引起固溶強(qiáng)化,致使膜層表面更加平整而致密,柱狀晶間距減小,結(jié)構(gòu)更加致密。其中Cr0.31Al0.62V0.07N膜層具有最佳的硬度與彈性模量,分別為24.98GPa和336.02GPa,摩擦系數(shù)降低至0.186。(3)炮鋼基體、CrAlN與CrAlVN膜層抗氧化性能:炮鋼在空氣中500℃氧化10小時(shí)后表面形成Fe_3O_4和Fe_2O_3兩種氧化物,600℃、700℃氧化10小時(shí)后表面形成FeO、Fe_3O_4和Fe_2O_3三種氧化物,其中700℃時(shí)表面氧化膜出現(xiàn)大量分層和剝落。CrAlN膜層在750℃、850℃下空氣中氧化20小時(shí)后,表面形成了以Al_2O_3為主的氧化膜,750℃氧化后膜層內(nèi)部除了主要含有fcc結(jié)構(gòu)的CrN外,還有少量的纖維鋅礦結(jié)構(gòu)的w-AlN;850℃氧化后膜層中相結(jié)構(gòu)由CrN、Cr_2N和Cr組成。在950℃下恒溫氧化20小時(shí)后,表面主要形成了以Fe_3O_4和Fe_2O_3為主的氧化物;CrAlVN膜層在750℃、850℃和950℃下空氣中氧化20小時(shí)后,表面形成了以Al_2O_3為主的氧化膜,隨著溫度的提高,其表面V的氧化物按AlVO4→V3O7→VO2轉(zhuǎn)變,膜層中的相一直保持fcc-CrN結(jié)構(gòu)。V的加入抑制了膜層中柱狀晶的長大,使膜層中的晶粒細(xì)化尺寸約為7nm,提高了膜層的抗高溫氧化性能,延緩了基體元素Fe向膜層中的擴(kuò)散,穩(wěn)定了膜層中的相結(jié)構(gòu)。隨著氧化溫度的提高,CrAlN膜層的硬度和彈性模量下降很快;而CrAlVN膜層僅有小幅下降,經(jīng)950℃下恒溫氧化20小時(shí)后,CrAlVN膜層的硬度和彈性模量分別為20.82GPa和314.6GPa,較沉積態(tài)分別僅下降了16.7%和6.4%。(4)炮鋼基體、CrAlN與CrAlVN膜層耐腐蝕性能:PCrNi_3Mo鋼在3.5%NaCl溶液中發(fā)生活性溶解,表面腐蝕產(chǎn)物不具有保護(hù)作用;CrAlN與CrAlVN膜層均提高了PCrNi_3Mo鋼的耐腐蝕性能,并存在鈍化現(xiàn)象。CrAlN和CrAlVN膜層均使PCrNi_3Mo鋼的陰極反應(yīng)得到抑制。CrAlVN膜層表現(xiàn)出更為優(yōu)異的防護(hù)效果,源于其均勻而致密的微觀結(jié)構(gòu)。
[Abstract]:The gun during the firing process, bore propellant gas for high temperature and high pressure conditions, and projectile severe friction and wear with the inner surface, also in the ocean climate conditions, tube corrosion by salt gas dramatically, so the gun barrel bore surface oxidation resistance, abrasion resistance the performance of corrosion resistance and salt gas is an important indicator to measure the performance of firing distance. With the requirements of higher energy propellant used in gun system, traditional chromium plating has been increasingly unable to meet the requirements of artillery bore condition. In order to improve the performance of the gun bore. Need to develop a new film preparation technology and coating materials. Based on the comprehensive analysis of domestic and foreign gun barrel life extension technology, from the angle of film preparation to improve the surface properties of gun barrel of the magnetron sputtering technology In the gun tube material PCrNi_3Mo steel surface plating CrAlN coating, comprehensive performance and on the basis of adding rare metal elements V to further improve the film, the film hardness and elastic modulus, friction and wear, high temperature oxidation resistance, corrosion resistance test and comprehensive analysis, to determine a reasonable coating system the preparation process, so as to provide theoretical reference for gun tube life extension technology. The research results are obtained as follows: (1) the influence of technological parameters on the film properties of magnetron sputtering: sputtering coating process, without substrate bias conditions applied, film structure and loose spots appeared obvious defects, when applying the 50-100V bias when the particle energy is increased due to sputtering, coating surface smooth and dense, continue to increase the negative bias to 150V, sputtering particles on the film surface bombardment increased film surface damage, with a negative bias to 200V, 300V, surface damage caused by more serious decline in the quality of coating surface, the coating surface quality by applying the 100V bias is the best; the sputtering current varies in the range of 0.1-0.2A, with the increase of sputtering current, the sputtering rate increases due to the increase of sputtering energy of particles, resulting in film is compact and smooth, improve mechanical properties, sputtering the current changes in the range of 0.2-0.4A, because of the high energy particle bombardment surface makes the damage, at the same time, the increase of Cr sputtering current high energy and particle number has not been nitrided Cr exists in the form of elemental Cr in the film, resulting in a decline in mechanical properties of film, wherein the sputtering current of 0.2A film with surface quality and the best mechanical properties; when N_2/Ar3/4, the Cr atoms are not nitride, with the increase of N_2 flow rate, increasing the hardness and elastic modulus, when the flow of N_2/Ar The amount is more than 1 when the Cr atom is completely nitride, film hardness and elastic modulus reached the highest when continues to increase when N_2/Ar flow ratio, hardness and elastic modulus of the film began to decreased slightly. In the negative bias voltage of 100V, sputtering current of 0.2A, the flux ratio of N_2/Ar is 1 when the sputtering CrN film quality is best, its hardness and the elastic modulus were 21.38GPa and 272.71GPa. (2) preparation and mechanical properties of CrAlN and CrAlVN film: by controlling the power of the Al target (50-200W), were prepared with different Al content CrAlN films, prepared by coating on the surface are the "cauliflower" structure, the fracture showed a columnar structure of typical.Al the introduction of the grain refinement in a certain range of the solution strengthening the role of the Cr0.34Al0.66N film has the best hardness and elastic modulus, respectively 23.91GPa and 316.2GPa, the friction coefficient is 0.293; through the control of V target current (0.03-0.09A ), were prepared with different V content CrAlVN film, introducing rare metal element V makes the grain refinement is more and more obvious, V solid solution crystal lattice changes caused by the solid solution strengthening in CrAlN film, the film surface more smooth and dense, columnar crystal spacing decreases, the structure is more compact. The film has a hardness of Cr0.31Al0.62V0.07N with the optimal elastic modulus, respectively 24.98GPa and 336.02GPa, the friction coefficient is reduced to 0.186. (3) gun steel matrix, the oxidation resistance of CrAlN and CrAlVN film: gun steel in the air oxidation of 500 DEG C after 10 hours of Fe_3O_4 and Fe_2O_3 formed on the surface of two kinds of oxides formed on the surface of FeO, 600 C, 700 C 10 hours after oxidation. Fe_3O_4 and Fe_2O_3 three kinds of oxides, the oxide film on the surface of 700 DEG C, the emergence of a large number of delamination and spalling of.CrAlN film at 750 C, 850 C in air oxidation after 20 hours, formed on the surface of oxide based on Al_2O_3 Film, 750 DEG C after oxidation film inside in addition to the main structure of CrN containing FCC, and a small amount of wurtzite w-AlN; 850 DEG C after oxidation film phase structure by CrN, Cr_2N and Cr. In 950 c oxidation after 20 hours, the surface mainly formed by Fe_3O_4 and Fe_2O_3 based oxides CrAlVN film; at 750 degrees, 850 degrees and 950 degrees in air oxidation after 20 hours, formed on the surface of Al_2O_3 film, with the increase of temperature, the surface oxide of V by AlVO4 - V3O7 - VO2 transformation in the coating phase has been kept restrained the growth of columnar crystal film fcc-CrN the structure of.V, the film grain refinement size is about 7Nm, improves the oxidation resistance of the coatings, delaying the diffusion matrix elements Fe to film in the stable phase structure in the films. With the increasing oxidation temperature, hardness and elastic film layer CrAlN Modulus decreased rapidly; while the CrAlVN film only slightly decreased, the isothermal oxidation under 950 DEG C for 20 hours, the hardness and elastic modulus of CrAlVN film were 20.82GPa and 314.6GPa, were deposited respectively decreased by only 16.7% and 6.4%. (4) gun steel substrate, the corrosion resistance of CrAlN and CrAlVN film: PCrNi_3Mo steel hair life is dissolved in 3.5%NaCl solution, the corrosion product has no protective effect; CrAlN and CrAlVN film improves the corrosion resistance of PCrNi_3Mo steel, and the presence of.CrAlN and CrAlVN film passivation of the cathode reaction of PCrNi_3Mo steel to inhibit.CrAlVN film exhibits more excellent protective effect, due to its uniform dense microstructure.

【學(xué)位授予單位】：沈陽工業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TJ304;TG174.4

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