碳氧杂质对93W-5Ni-2Fe高密度钨合金冲击性能的影响

采用真空液相烧结制备了不同碳氧杂质含量的93W-5Ni-2Fe合金试样,研究了碳氧杂质含量对合金冲击性能的影响。结果表明,压坯在真空高温烧结过程中,原料中自身含有的碳具有较强的脱氧能力,通过碳氧平衡反应可减少合金中碳氧含量。碳氧杂质含量较高时,合金中存在较大尺寸的碳氧非金属夹杂物,合金的冲击性能较差。降低碳氧杂质含量可减小或避免碳氧夹杂物的生成,有利于提高钨合金的冲击性能。     

碳氧含量对93W-5Ni-2Fe钨合金冲击性能的影响

采用真空液相烧结制备了不同碳氧杂质含量的93W-5Ni-2Fe合金试样,研究了碳氧杂质含量对合金冲击性能的影响。结果表明,压坯在真空高温烧结过程中,原料中自身含有的碳具有较强的脱氧能力,通过碳氧平衡反应可减少合金中碳氧含量。碳氧杂质含量较高时,合金中存在较大尺寸的碳氧非金属夹杂物,合金的冲击性能较差。降低碳氧杂质含量可减小或避免碳氧夹杂物的生成,有利于提高钨合金的冲击性能。     

真空自耗电弧熔炼TZM合金

前言Mo-0.5Ti-0.08Zr-(0.02～0.03)C,常称 TZM 合金。通过真空自耗电弧熔炼的 TZM 合金,借助在自耗熔烁过程中的特性,能获得较高质量的铸锭。本文通过实际生产情况,对 TZM 合金的真空自耗电弧熔炼工艺,包括电极制备、水冷效果、稳弧搅拌和熔炼功率等参数问题作一探讨,以供科研及生产人员的参考。一、电极制备(一)原料1.钼条:采用垂熔烧结钼条。     

Influences of Contents and Reaction of Carbon and Oxygen on Microstructure and Mechanical Properties of Sintered 93W-4.6Ni-1.9Fe-0.5Co Alloys

采用具有不同碳氧含量的初始粉末,利用真空液相烧结制备93W-4.6Ni-1.9Fe-0.5Co合金试样,研究碳氧含量的变化及其平衡反应对合金力学性能与组织的影响。结果表明,压坯在真空高温烧结过程中,原料自身含有的碳具有较强的脱氧能力,通过碳氧反应可减少合金中的氧、碳含量,阻止氧化物、碳化物夹杂的生成,在钨颗粒与粘接相之间形成牢固的界面。当合金总氧含量低于500μg/g时,合金的力学性能显著提高。     

熔盐电解制备低成本Ti12LC钛合金的研究

采用熔盐电解法由混合氧化物成功制备出了低成本Ti12LC合金,并对脱氧过程机理进行分析。结果显示:脱氧反应过程首先生成CaTiO3、低价氧化物Ti6O、Ti2O和Ca2Al2O5;其次随脱氧时间的进行钛的低价氧化物含量逐步增加,再其次出现金属钼,最后生成Ti12LC合金相。由于MoO2的理论电压低于TiO2、Al2O3,因此钼优先还原,且钼在-Ti中能固溶,所以最终钼是以固溶体形式存在于钛中,而Fe2O3虽然理论分解电位更低,但由于含量低,而没有检测到铁的单质还原。通过对电解产物表面的背散射电子像分析,发现电解制备出的产物其形貌和Ti12LC合金的组织相似。     

碳氧含量及其反应对93W-4.6Ni-1.9Fe-0.5Co合金力学性能与组织的影响(英文)

采用具有不同碳氧含量的初始粉末,利用真空液相烧结制备93W-4.6Ni-1.9Fe-0.5Co合金试样,研究碳氧含量的变化及其平衡反应对合金力学性能与组织的影响。结果表明,压坯在真空高温烧结过程中,原料自身含有的碳具有较强的脱氧能力,通过碳氧反应可减少合金中的氧、碳含量,阻止氧化物、碳化物夹杂的生成,在钨颗粒与粘接相之间形成牢固的界面。当合金总氧含量低于500μg/g时,合金的力学性能显著提高。     

精炼及破空对镍基合金中氧氮含量的影响

采用真空感应法熔炼镍基合金,测定了精炼后合金的氧、氮含量,并观察合金中的夹杂情况.研究了精炼、破空处理对合金中氧、氮含量及夹杂的影响.结果表明:真空感应熔炼镍基高温合金在精炼的初始阶段,氧的脱除速率较大,主要通过氧与碳的还原反应生成CO气体进行;精炼后期氧元素的脱除速率有所降低.合金中氮元素的排除主要依赖高温和高真空作用,氮元素排除速率受CO的生成和排出影响.合金中的氧、氮含量与合金中的夹杂含量相关,精炼期间合金中Al2O3夹杂与高温液态金属中的氧元素之间存在动态平衡,随精炼时间延长合金中Al2O3夹杂分解,合金中夹杂含量及氧、氮含量均降低.     

超细钼粉生产中最佳工艺的选择

钼基难熔合金在苛刻要求的航空工业和能量转换系统中的应用具有显著优势。则要求钼粉粒度较细,并且严格控制粉末粒度分布,在中等烧结温度下制备钼合金才能取得好的性能。比如在0.6TM~0.7TM烧结材料时,平均粉末粒度不应大于5m(商业钼粉的平均粉末粒度约为50m)。钼粉还原分两个阶段,即从MoO3至MoO2,以及从MoO2还原为钼粉。这两步都是放热反应,很易造成粉末颗粒长大或者细粉末团聚成大颗粒。此文研究的目的是探索从氧化钼还原成为细钼粉过程中的内在机理。 实验所用原料是高纯三氧化钼(99.98%),MoO3在氢气气氛下经两步工艺还原成钼…     

真空碳热还原制备Mg-Li合金热力学分析

提出了真空碳热还原制备Mg-Li合金的新思路,并对还原反应进行了热力学分析,研究了还原反应的反应式、吉布斯自由能及临界还原温度。结果表明:真空碳热还原制备Mg-Li合金具备热力学可行性,且其吉布斯自由能随真空度和反应温度的升高而降低;相同真空度下,该反应的临界反应温度低于真空碳热还原制备金属Mg、金属Li的临界温度,反应更容易进行;当真空度为10 Pa,Li_2O的相对比例为0.1时,真空碳热还原制备Mg-Li合金的临界反应温度为1345 K;在常规皮江法(真空硅热还原法)制镁的反应条件下,不论反应物料中Mg O、Li_2O相对比例为多少,真空碳热还原制备Mg-Li合金均具有热力学可行性。     

钼钨基难熔金属与铜和石墨相接的钎焊特征

最近,法国JL.Boutes等人在第十二届国际普兰西会议上发表文章,论述了钼、钨基难熔金属与铜和石墨相接的钎焊特征。研究使用的钼和钨基难熔金属和合金为:烧结态、锻造态钼;Z6;TZM;Mo-5Re;Mo-41Re;烧结态、锻造态钨;W-5Re;W-26Re。难熔金属试验用板的厚度为7毫米。铜和石墨板的厚度为5毫米。     

A novel approach to boriding of TZM by spark plasma sintering method

Boriding can be candidate method to increase mechanical properties and oxidation resistance of molybdenum based alloys. Rapid oxidation of TZM at elevated temperature and low wear resistance are considered to be main drawbacks for possible applications. In this study molybdenum boride layer was formed on the surface of TZM by spark plasma sintering (SPS) method. Pre-mixed TZM was used as a raw material in powder form. Both sintering and boriding process were performed in a single step at constant temperature of 1420 °C in various pressures (40–60 MPa) and holding times (5–15 min) under vacuum. The effects of molybdenum boride layer on density, hardness and oxidation behavior were investigated. Thickness, microstructure and hardness of Mo-B based protective layer showed a variety with different process parameters. The boride layer thickness was reached to approximately 200 μm by increasing pressure and holding time. Formation of this layer provided a decrease in mass loss about 73.4% during oxidation test at 1000 °C for 60 min. The maximum surface hardness value was obtained as 21.4 GPa while hardness of base metal was 2.3 GPa.     

Investigation the effect of B4C addition on properties of TZM alloy prepared by spark plasma sintering

TZM alloy is one of the most important molybdenum (Mo) based alloy which has a nominal composition containing 0.5–0.8 wt.% titanium (Ti), 0.08–0.1 wt.% zirconium (Zr) and 0.016–0.02 wt.% carbon (C). It is a possible candidate for high temperature applications in a variety of industries. However, the rapid oxidation of TZM alloys at high temperature in air is considered to be one of the drawback. In this study, TZM alloys with additions of 0–5 wt.% B₄C were prepared by spark plasma sintering (SPS) at 1420 °C utilizing 40 MPa pressure for 5 min under vacuum. The effects of B₄C addition on oxidation, densification behavior, microstructure, and mechanical properties were investigated. The TZM alloy with 5 wt.% B₄C have exhibited an approximately 66% reduction in mass loss under normal atmospheric conditions in oxidation tests made at 1000 °C for 60 min. And an increase from 1.9 GPa to 7.8 GPa has been determined in hardness of the alloy.     

Carburization of high temperature PM-materials

Carburization of powder metallurgically processed materials for high temperature use is interesting for several reasons: Production of carbide powders e.g. for hard metals, formation of carbide layers on bulk materials to improve corrosion and/or wear resistance and degradation of material properties like strength and ductility by metal-carbon reactions. Molybdenum, TZM (Mo-0.5Ti-0.07Zr-0.05C) and tungsten are finding wide application as construction material in high temperature furnaces which are operated under high vacuum or inert/protective gas conditions. If grafite is used in the same system reactions of the refractory metal components with carbon containing species have to be considered. Therefore a variety of examinations was performed on the carburization characteristics of molybdenum and tungsten (and alloys), especially at temperatures above 1200°C where carburization rates become technically relevant. High temperature oxidation resistant alloys like steels or Ni- and Co-based superalloys can withstand severe carburization as long as their surfaces are covered with tight, protective chromia scales. In case of porous or cracked scales or conditions where chromia is not stable anymore a front of carburization proceeds through the materials – frequently along the grain boundaries. The PM-materials Ducropur (pure chromium) and PM 2000 (Fe-19Cr-5.5Al-0.5Ti-0.5Y₂O₃) show distinctly lower carburization rates: Ducropur forms tight chromium carbide layers, whereas PM 2000 is nearly unaffected up to 1100°C because of its tight and stable alumina scale.     

La-TZM合金板材制备及其氧化行为

采用粉末冶金法,在TZM合金的基础上,固-液掺杂稀土元素La,且以有机碳源硬脂酸替代传统的石墨粉引入C元素,经混料、压制成形、高温烧结、热轧、温轧、冷轧等工艺制备La-TZM合金板材。将La-TZM合金板材分别在300、450、600、800、1000℃进行高温氧化实验,通过质量损失率、差热分析等实验方法研究其氧化行为。研究表明:La-TZM合金板材的抗拉强度为1361.74 MPa,伸长率为8.81%,较传统的TZM合金均有显著提高。La-TZM合金板材纤维组织细长,组织致密;第二相细小且分布均匀。其细小的氧化镧及第二相颗粒钉扎在晶界,生成的氧化物会在基体表面形成致密氧化物覆盖层,可以有效地阻碍氧向基体的侵入,表面不易氧化,从而使TZM合金的抗氧化性能提高,扩展了TZM合金的使用温度范围。     

Studies on sacrificial and carbon deoxidation of niobium

The nature and extent of oxygen removal from Nb–C–O alloys on heating to 2273 K under 2 mPa vacuum has been investigated. Correlations have been given relating the vapour pressure ratios of CO, NbO(v) and NbO₂(v) to the residual oxygen and carbon contents in niobium and the temperature of treatment. Experimental results of treating Nb pellets with initial oxygen content of 1.09 wt% and added carbon corresponding to C/O ratios of 0–1.10 in a thermogravimetry unit up to 2273 K under 2 mPa have been explained on the basis of the relevant vapour pressure ratios. The deoxidation of Nb–C–O begins at 1650 K and proceeds in three distinct steps consisting of both sacrificial deoxidation and carbon deoxidation. The first step is sacrificial deoxidation due to formation of NbO₂(v), the second step is carbon deoxidation, and the final step is sacrificial deoxidation by NbO(v) vaporization. The extent of deoxidation in each of these steps depends on C/O ratio of the charge.     

掺镧方式对La-TZM合金性能的影响

采用粉末冶金法在TZM合金的基础上,分别进行固-固掺杂稀土La2O3,固-液掺杂La(NO3)3,经烧结、热轧、温轧、冷轧后得到不同掺杂方式的La-TZM合金板材。用SEM观察粉末形貌、烧结坯组织及板材断口形貌,用粒度分布、EDS分别对合金粉末粒度及合金成分进行分析。结果表明:固-液掺杂La(NO3)3比固-固掺杂稀土La2O3的La-TZM合金板材第二相分布更为均匀、细小;晶粒尺寸较小;且固-液掺杂La(NO3)3合金的抗拉强度比固-固掺杂稀土La2O3也有显著提高,使其提高了10.9%。     

碳纳米管铜基复合材料的制备

利用CVD法制备多壁碳纳米管，并对其进行亲水化表面处理。在存在表面活性剂的情况下，利用共沉积法制备碳纳米管一超细铜粉复合粉体。复合粉体经还原后，采用冷压烧结、六面顶热压、真空热压烧结和真空热压后热轧4种不同工艺成型。利用SEM和XRD比较了这几种工艺成型的复合材料结构和被氧化的情况。结果表明，采用真空热压后热轧工艺制备的碳纳米管铜基复合材料的致密度较高且能有效地防止被氧化。     

Ni-Ti 钎料高温钎焊TZM晶间渗入行为研究

采用SEM,EDS,XRD和力学试验机等分析测试方法,研究了Ni-Ti钎料对TZM合金钎缝组织和性能的影响。结果表明：Ni-Ti钎料可实现TZM的高温真空钎焊连接。Ni-13.7Ti/TZM界面区,母材中的Mo与钎料中的Ni形成MoNi相,是钎料与TZM形成冶金结合的主要原因。TZM/Ni-44Ti/TZM界面区Ni-44Ti钎料中的Ti与Mo反应,Mo-Ti固溶体,使钎料和TZM形成冶金结合。Ni-44Ti钎料钎焊TZM合金产生严重晶间渗入现象。降低钎料中Ti的含量,晶间渗入和母材溶蚀现象大幅减弱;TZM/Ni-13.7Ti/TZM钎焊接头剪切强度193MPa,TZM/Ni-44Ti/TZM钎焊接头剪切强度167MPa,晶间渗入使钎缝强度降低,降低钎料中的Ti含量,钎焊接头强度提高。     

Suppression of carbon monoxide formation in oxide-coated TZM molybdenum X-ray rotating anodes

Higher performance designs for rotating anode X-ray tubes have increased the average rotating anode temperature from below 1100 °C to well above 1300 °C. This temperature increase has accelerated the formation of carbon monoxide by reaction of carbon from the alloy substrate with oxygen from the emissive coating. The dominant carbon source is thought to be Mo₂C grain boundary precipitates in the TZM molybdenum alloy substrate. The dominant oxygen source is thought to be TiO in the emissive coating. Placement of a monocarbide-forming reactive layer between the alloy substrate and the emissive coating has been demonstrated to lower the thermodynamic activity of the carbon source and dramatically reduce the rate of formation of carbon monoxide.