Composite material obtained by powder metallurgy with applications in the automotive industry

C. Pascu, Ș. Gheorghe, C. Nicolicescu, D. Tărâţă
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The initial powder mixture consists in TiH2 powder particles that have been combined with some metallic powders (Al, Mn, Sn, Zr) for improving the final mechanic-chemicals and functional properties for using in the automotive industry. As a result it was studied the physical-mechanical properties after sintering, the influence of the sintering temperature and time on the microstructural changes of the composite material based on titanium. Introduction Titanium alloys have multiple applications in diverse fields such as industrial and medical fields [1-4]. This is due to their excellent performances such as: low density, good corrosion resistance, non-magnetic properties, high specific strength, high chemical stability, resistant to high temperatures, etc. [5, 6]. The basic advantages of titanium alloys in terms of the automotive industry are the high strength to density, their low density, the outstanding corrosion resistance [7, 8]. In the automotive field, one of the greatest applications of titanium-based materials is for components of the internal combustion engine area that equip the vehicle (pistons, valves, connecting rod, crank caps, bolts, etc.) [9, 10]. Also, for modern jet turbine engines titanium alloys usually represent approximately 30% of the used materials, especially in the forward zone of the engine [11]. However, compared to other traditional materials, the major impediment represents the high cost of titanium [12]. Another disadvantage of titanium for applications in the automotive industry is its low tribological properties because of poor plastic shearing resistance and work hardening ability [13, 14]. Using inexpensive alloying elements (such as Sn, Mn, Fe, Cr, etc.) instead of expensive alloying metals (V, Nb, Mo, Zr, etc.) to improve the strengthen alloys is one of the methods to reduce the cost of manufacturing titanium alloys [15]. Due to the properties they possess, by alloying Ti with small amounts of aluminium percentage a Ti-Al (γ Ti-Al) alloy is obtained with excellent mechanical properties and corrosion resistance at Powder Metallurgy and Advanced Materials – RoPM&AM 2017 Materials Research Forum LLC Materials Research Proceedings 8 (2018) 200-211 doi: http://dx.doi.org/10.21741/9781945291999-23 201 temperatures above 700°C, which allows the replacement for traditional Ni based superalloy for turbine engine components [16]. Due to the very good wear behaviour of tin, by adding small amounts of Sn percentage based Ti-alloys are obtained, such as Ti-5Al-2.5Sn which is a medium-strength all alpha alloy, used for gas turbine engine and other applications that request oxidation resistance, good weld fabric ability and intermediate strength at temperatures up to 4800 °C [17]. Manganese is a metal that has Fe-like properties, being a good substitute for it, and improves wear resistance giving plasticity and good alloy elasticity, so adding small percentages of Mn to a Ti-based alloy gives remarkable properties [18, 19]. According to Wang [20], a novel near-α titanium alloy Ti-6.0Al-4.5Cr-1.5Mn was designed and prepared by the water-cooled copper crucible and present better mechanical strength compared other Ti-alloys which has been presented, but worse elongation because of the presence of Cr2Ti phase which may cause alloy's poor plasticity. Carbon has Van der Waals bonds and has good wear behaviour, so, according to [21] the incorporation of a small amount of Al and C into the TiAlVSiCN will improve the hardness, wear and erosion resistance, and, also, lower production cost. Also, due to similar properties of Zr with those of Ti, in the last years, Ti-Zr alloys with zirconium contents ranging from 10 to 40 wt% have been investigated by melting process and were reported characteristics as excellent corrosion resistance with obvious applications in the automotive industry [22]. Another way of reducing the cost price in making alloys based on Ti is the use of Powder Metallurgy (PM) techniques [23, 24]. Accordingly to [25] a Ti-6Al-2Sn-4Zr-2Mo alloy produced by arc melting and powder metallurgy processes presents excellent mechanical properties and high resistance, in sections exposed to high temperatures. Toyota uses sintered titanium alloys Ti-6Al4V/TiB and Ti-Al-Zr-Sn-Nb-Mo-Si/TiB in the intake and exhaust engine valves, respectively, are used from Toyota for own cars [26]. Among the PM method that appears to offer the greatest opportunity for real cost reductions it is considered that Two-Steps (TSS) and Multiple-steps (MSS) Sintering Techniques allow to obtain different compositions and microstructures of Ti products [27] for automotive components. Conventional methods used for obtaining titanium alloys require special conditions of controlled atmosphere which result in a high cost of obtaining these alloys [28]. For this reason, in the last decade, many studies have focused for the producing of Ti-alloys by Powder Metallurgy using TiH2 powder [29-34]. According to [35] a Ti-6Al-2Sn-4Zr-2Mo alloy was obtained by Powder Metallurgy using titanium hydride powders. This alloy based on TiH2 powders proved an improvement of the mechanical properties and high corrosion resistance on high temperatures. For this study, was proposed to obtain a titanium hydride alloy by adding small percentages of Al, Sn, Mn, Zr and C in order to improve the mechanical and tribological properties of this alloy, and further processing to be achieved by compacting and sintering, using the TSS and MSS techniques. Experimental Procedures Materials For this research, titanium hydride (TiH2) produced by Chemetall GmbH, has been used as initial material. The following chemical elements are present in TiH2 composition: Titanium (min 95%), Hydrogen (min. 3.8%), Al (max.0.15%), Si (max.015%), Nitrogen (max.0.3%), Fe, Ni, Cl, Mg, C, Ni (all the last component are under 0.1%). In order to improve the mechanical and tribological characteristics in the initial powder were introduced by mixing for 60 min the following Powder Metallurgy and Advanced Materials – RoPM&AM 2017 Materials Research Forum LLC Materials Research Proceedings 8 (2018) 200-211 doi: http://dx.doi.org/10.21741/9781945291999-23 202 components: Mn powder, Sn powder, Alumix 321, 8% powder, Zr powder, and graphite powder. The mixing and homogenization of the mixture was carried out in a ball mill Planetary Mono Mill PULVERISETTE 6 classic line from Fritsch with ball: powders ratio 1:1, 250 ml grinding bowl, argon atmosphere, balls material stainless steel – 1.3541 ISO/EN/DIN codeX47Cr14, B50, rotational speed of main disk of 200 rpm. The weight ratio between the components is: 80%wt. TiH2, 8%wt., Mn, 3%wt. Sn, 2%wt. Zr, 6%wt. Alumix321, and 1%wt. C. Particle size distributions, Fig. 1, was studied by dynamic laser scattering (DLS) using a 90Plus particle size analyser, Brookhaven Instruments Corporation, USA, equipped with 35 mW solid state laser, having 660 nm wavelength. The temperature was 25°C and the scattering angle was 90°. The dilution of the powders was made in water and the solution was subjected to ultrasonic treatment for 5 minutes to avoid flocculation of the particles. Fig. 1. Particle size distribution of the mixture. Fig. 2. SEM image of the mixture. In Fig. 2 a SEM image of the mixture is shown. The mixture presents a bimodal particle size distribution, having particles with dimensions between (188-294 nm) respectively (1110-1730 nm). The highest number of particles (28% from the total number) have the dimension equal to 225 nm. The percent of the particles with higher size is lower than 1.5%. The mean hydrodynamic diameter is 291 nm. In Table 1 sub-micron dimensions and percentages of the powder particles accordingly with the grain-size distribution presented in Fig. 1 are shown. Methods and Techniques The homogenized mixture has been pressed by unilateral cold compaction at 600MPa compaction pressure, as cylindrical specimens with 12,05 mm diameter. An A009 electromechanicalcomputerized testing machine 100 kN equipped with TCSoft2004Plus software was used for unilateral cold compaction. The green density of each part has been determined as has been presented in a previous study [27]. The next step was the sintering of the green compacts. They have used four different sintering regimes using Powder Metallurgy techniques as following: V1 regime, using classical sintering at 1050 °C for 90 min dwell time; Two-steps sintering (TSS) regime, V2, at 1050 °C with dwell time of 15 min and, then, at 1000 °C for 75 min; TSS regime, V3, where the sintering was done at 1050 °C for 15 min and at 950 °C, for 75 min, Fig. 3; Powder Metallurgy and Advanced Materials – RoPM&AM 2017 Materials Research Forum LLC Materials Research Proceedings 8 (2018) 200-211 doi: http://dx.doi.org/10.21741/9781945291999-23 203 Multiple-steps sintering (MSS), V4, in three steps at 1050 °C for 15 min dwell time, 1000 °C for 20 min dwell time and 900 °C for 55 min dwell time, Fig. 4. Table 1. Grain-size distribution and percentages of the powder particles Dimension [nm] Particle size distribution [%] 189 11.8% 206 23.6% 225 28% 246 19.6% 269 9.2% 294 1.9% 1110 1.1% 1213 0.8% 1326 2% 1448 1.4% 1583 0.3% 1729 0.3% Fig. 3. TSS cycle for 1050 °C and 950 °C. Fig. 4. MSS cycle at 1050 /1000/ 900 °C. Powder Metallurgy and Advanced Materials – RoPM&AM 2017 Materials Research Forum LLC Materials Research Proceedings 8 (201","PeriodicalId":20390,"journal":{"name":"Powder Metallurgy and Advanced Materials","volume":"4 1","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2018-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"1","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Powder Metallurgy and Advanced Materials","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.21741/9781945291999-23","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 1

Abstract

Because of their great properties titanium and titanium alloys have been used in automotive industry, biomedical applications, aerospace industry, computer components, emerging applications, architecture of buildings, etc. In the last decade there has been revived interest in the utilization of the Powder Metallurgy (PM) route as a low-cost way for obtaining components from this alloys. This research presents the experimental results concerning the processing of Ti based alloy by Two-Steps Sintering and Multiple-Steps Sintering, techniques belonging to PM technology. The initial powder mixture consists in TiH2 powder particles that have been combined with some metallic powders (Al, Mn, Sn, Zr) for improving the final mechanic-chemicals and functional properties for using in the automotive industry. As a result it was studied the physical-mechanical properties after sintering, the influence of the sintering temperature and time on the microstructural changes of the composite material based on titanium. Introduction Titanium alloys have multiple applications in diverse fields such as industrial and medical fields [1-4]. This is due to their excellent performances such as: low density, good corrosion resistance, non-magnetic properties, high specific strength, high chemical stability, resistant to high temperatures, etc. [5, 6]. The basic advantages of titanium alloys in terms of the automotive industry are the high strength to density, their low density, the outstanding corrosion resistance [7, 8]. In the automotive field, one of the greatest applications of titanium-based materials is for components of the internal combustion engine area that equip the vehicle (pistons, valves, connecting rod, crank caps, bolts, etc.) [9, 10]. Also, for modern jet turbine engines titanium alloys usually represent approximately 30% of the used materials, especially in the forward zone of the engine [11]. However, compared to other traditional materials, the major impediment represents the high cost of titanium [12]. Another disadvantage of titanium for applications in the automotive industry is its low tribological properties because of poor plastic shearing resistance and work hardening ability [13, 14]. Using inexpensive alloying elements (such as Sn, Mn, Fe, Cr, etc.) instead of expensive alloying metals (V, Nb, Mo, Zr, etc.) to improve the strengthen alloys is one of the methods to reduce the cost of manufacturing titanium alloys [15]. Due to the properties they possess, by alloying Ti with small amounts of aluminium percentage a Ti-Al (γ Ti-Al) alloy is obtained with excellent mechanical properties and corrosion resistance at Powder Metallurgy and Advanced Materials – RoPM&AM 2017 Materials Research Forum LLC Materials Research Proceedings 8 (2018) 200-211 doi: http://dx.doi.org/10.21741/9781945291999-23 201 temperatures above 700°C, which allows the replacement for traditional Ni based superalloy for turbine engine components [16]. Due to the very good wear behaviour of tin, by adding small amounts of Sn percentage based Ti-alloys are obtained, such as Ti-5Al-2.5Sn which is a medium-strength all alpha alloy, used for gas turbine engine and other applications that request oxidation resistance, good weld fabric ability and intermediate strength at temperatures up to 4800 °C [17]. Manganese is a metal that has Fe-like properties, being a good substitute for it, and improves wear resistance giving plasticity and good alloy elasticity, so adding small percentages of Mn to a Ti-based alloy gives remarkable properties [18, 19]. According to Wang [20], a novel near-α titanium alloy Ti-6.0Al-4.5Cr-1.5Mn was designed and prepared by the water-cooled copper crucible and present better mechanical strength compared other Ti-alloys which has been presented, but worse elongation because of the presence of Cr2Ti phase which may cause alloy's poor plasticity. Carbon has Van der Waals bonds and has good wear behaviour, so, according to [21] the incorporation of a small amount of Al and C into the TiAlVSiCN will improve the hardness, wear and erosion resistance, and, also, lower production cost. Also, due to similar properties of Zr with those of Ti, in the last years, Ti-Zr alloys with zirconium contents ranging from 10 to 40 wt% have been investigated by melting process and were reported characteristics as excellent corrosion resistance with obvious applications in the automotive industry [22]. Another way of reducing the cost price in making alloys based on Ti is the use of Powder Metallurgy (PM) techniques [23, 24]. Accordingly to [25] a Ti-6Al-2Sn-4Zr-2Mo alloy produced by arc melting and powder metallurgy processes presents excellent mechanical properties and high resistance, in sections exposed to high temperatures. Toyota uses sintered titanium alloys Ti-6Al4V/TiB and Ti-Al-Zr-Sn-Nb-Mo-Si/TiB in the intake and exhaust engine valves, respectively, are used from Toyota for own cars [26]. Among the PM method that appears to offer the greatest opportunity for real cost reductions it is considered that Two-Steps (TSS) and Multiple-steps (MSS) Sintering Techniques allow to obtain different compositions and microstructures of Ti products [27] for automotive components. Conventional methods used for obtaining titanium alloys require special conditions of controlled atmosphere which result in a high cost of obtaining these alloys [28]. For this reason, in the last decade, many studies have focused for the producing of Ti-alloys by Powder Metallurgy using TiH2 powder [29-34]. According to [35] a Ti-6Al-2Sn-4Zr-2Mo alloy was obtained by Powder Metallurgy using titanium hydride powders. This alloy based on TiH2 powders proved an improvement of the mechanical properties and high corrosion resistance on high temperatures. For this study, was proposed to obtain a titanium hydride alloy by adding small percentages of Al, Sn, Mn, Zr and C in order to improve the mechanical and tribological properties of this alloy, and further processing to be achieved by compacting and sintering, using the TSS and MSS techniques. Experimental Procedures Materials For this research, titanium hydride (TiH2) produced by Chemetall GmbH, has been used as initial material. The following chemical elements are present in TiH2 composition: Titanium (min 95%), Hydrogen (min. 3.8%), Al (max.0.15%), Si (max.015%), Nitrogen (max.0.3%), Fe, Ni, Cl, Mg, C, Ni (all the last component are under 0.1%). In order to improve the mechanical and tribological characteristics in the initial powder were introduced by mixing for 60 min the following Powder Metallurgy and Advanced Materials – RoPM&AM 2017 Materials Research Forum LLC Materials Research Proceedings 8 (2018) 200-211 doi: http://dx.doi.org/10.21741/9781945291999-23 202 components: Mn powder, Sn powder, Alumix 321, 8% powder, Zr powder, and graphite powder. The mixing and homogenization of the mixture was carried out in a ball mill Planetary Mono Mill PULVERISETTE 6 classic line from Fritsch with ball: powders ratio 1:1, 250 ml grinding bowl, argon atmosphere, balls material stainless steel – 1.3541 ISO/EN/DIN codeX47Cr14, B50, rotational speed of main disk of 200 rpm. The weight ratio between the components is: 80%wt. TiH2, 8%wt., Mn, 3%wt. Sn, 2%wt. Zr, 6%wt. Alumix321, and 1%wt. C. Particle size distributions, Fig. 1, was studied by dynamic laser scattering (DLS) using a 90Plus particle size analyser, Brookhaven Instruments Corporation, USA, equipped with 35 mW solid state laser, having 660 nm wavelength. The temperature was 25°C and the scattering angle was 90°. The dilution of the powders was made in water and the solution was subjected to ultrasonic treatment for 5 minutes to avoid flocculation of the particles. Fig. 1. Particle size distribution of the mixture. Fig. 2. SEM image of the mixture. In Fig. 2 a SEM image of the mixture is shown. The mixture presents a bimodal particle size distribution, having particles with dimensions between (188-294 nm) respectively (1110-1730 nm). The highest number of particles (28% from the total number) have the dimension equal to 225 nm. The percent of the particles with higher size is lower than 1.5%. The mean hydrodynamic diameter is 291 nm. In Table 1 sub-micron dimensions and percentages of the powder particles accordingly with the grain-size distribution presented in Fig. 1 are shown. Methods and Techniques The homogenized mixture has been pressed by unilateral cold compaction at 600MPa compaction pressure, as cylindrical specimens with 12,05 mm diameter. An A009 electromechanicalcomputerized testing machine 100 kN equipped with TCSoft2004Plus software was used for unilateral cold compaction. The green density of each part has been determined as has been presented in a previous study [27]. The next step was the sintering of the green compacts. They have used four different sintering regimes using Powder Metallurgy techniques as following: V1 regime, using classical sintering at 1050 °C for 90 min dwell time; Two-steps sintering (TSS) regime, V2, at 1050 °C with dwell time of 15 min and, then, at 1000 °C for 75 min; TSS regime, V3, where the sintering was done at 1050 °C for 15 min and at 950 °C, for 75 min, Fig. 3; Powder Metallurgy and Advanced Materials – RoPM&AM 2017 Materials Research Forum LLC Materials Research Proceedings 8 (2018) 200-211 doi: http://dx.doi.org/10.21741/9781945291999-23 203 Multiple-steps sintering (MSS), V4, in three steps at 1050 °C for 15 min dwell time, 1000 °C for 20 min dwell time and 900 °C for 55 min dwell time, Fig. 4. Table 1. Grain-size distribution and percentages of the powder particles Dimension [nm] Particle size distribution [%] 189 11.8% 206 23.6% 225 28% 246 19.6% 269 9.2% 294 1.9% 1110 1.1% 1213 0.8% 1326 2% 1448 1.4% 1583 0.3% 1729 0.3% Fig. 3. TSS cycle for 1050 °C and 950 °C. Fig. 4. MSS cycle at 1050 /1000/ 900 °C. Powder Metallurgy and Advanced Materials – RoPM&AM 2017 Materials Research Forum LLC Materials Research Proceedings 8 (201
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粉末冶金获得的复合材料在汽车工业中的应用
在PM方法中,似乎提供了最大的机会来降低实际成本,人们认为两步(TSS)和多步(MSS)烧结技术允许获得不同成分和显微结构的Ti产品用于汽车零部件[27]。传统的获得钛合金的方法需要特殊的可控气氛条件,这导致获得这些合金的成本很高[28]。因此,在过去的十年中,许多研究都集中在使用TiH2粉末进行粉末冶金制备ti合金[29-34]。根据[35],用氢化钛粉末进行粉末冶金制备了Ti-6Al-2Sn-4Zr-2Mo合金。以TiH2粉末为基体制备的合金具有较好的力学性能和较高的耐高温腐蚀性能。本研究提出通过添加少量Al、Sn、Mn、Zr和C来改善该合金的力学和摩擦学性能,并采用TSS和MSS技术,通过压实和烧结来实现进一步的加工。本研究采用Chemetall公司生产的氢化钛(TiH2)作为初始材料。TiH2成分中存在以下化学元素:钛(最小95%),氢(最小3.8%),Al(最大0.15%),Si(最大015%),氮(最大0.3%),Fe, Ni, Cl, Mg, C, Ni(最后一个成分都在0.1%以下)。为了改善初始粉末的机械和摩擦学特性,通过混合60分钟引入以下粉末冶金和先进材料- RoPM&AM 2017材料研究论坛LLC材料研究进展8 (2018)200-211 doi: http://dx.doi.org/10.21741/9781945291999-23 202成分:Mn粉末,Sn粉末,Alumix 321, 8%粉末,Zr粉末和石墨粉末。混合料的混合和均质在Fritsch公司的经典球磨机中进行,球:粉比1:1,250 ml研磨碗,氩气,球材料不锈钢- 1.3541 ISO/EN/DIN codeX47Cr14, B50,主盘转速200转/分。各组分之间的重量比为:80%wt。wt TiH2, 8%。, Mn, 3%wt。锡、wt 2%。锆、wt 6%。Alumix321,和1%wt。C.粒径分布如图1所示,采用动态激光散射(DLS)技术,采用美国布鲁克海文仪器公司的90Plus粒径分析仪,配备35mw固体激光器,波长为660 nm。温度为25℃,散射角为90°。将粉末在水中稀释,并对溶液进行超声波处理5分钟,以避免颗粒絮凝。图1所示。混合料的粒度分布。图2所示。混合物的SEM图像。图2显示了混合物的SEM图像。混合物的粒径呈双峰分布,粒径分别在(188 ~ 294 nm) (1110 ~ 1730 nm)之间。最高数量的粒子(占总数的28%)的尺寸等于225纳米。粒径较大的颗粒所占比例小于1.5%。平均水动力直径为291 nm。表1给出了与图1所示粒度分布相对应的亚微米尺寸和粉末颗粒百分比。方法与技术将均匀化后的混合料在600MPa压实压力下单侧冷压实,制成直径为12.05 mm的圆柱形试样。采用一台100 kN的A009机电微机试验机,安装TCSoft2004Plus软件进行单侧冷压试验。每个部分的绿色密度已根据先前的研究[27]确定。下一步是绿色粉饼的烧结。他们使用粉末冶金技术使用了四种不同的烧结制度如下:V1制度,在1050°C下使用经典烧结,停留时间为90分钟;两步烧结(TSS)制度,V2,在1050℃下停留时间为15分钟,然后在1000℃下停留75分钟;TSS状态,V3,在1050°C下烧结15分钟,在950°C下烧结75分钟,图3;粉末冶金和先进材料- RoPM&AM 2017材料研究论坛有限责任公司材料研究进展8 (2018)200-211 doi: http://dx.doi.org/10.21741/9781945291999-23 203多步烧结(MSS), V4,在1050°C, 15分钟的停留时间,1000°C, 20分钟的停留时间和900°C, 55分钟的停留时间,图4。表1。粒度分布及粉末颗粒百分比尺寸[nm]粒度分布[%]189 11.8% 206 23.6% 225 28% 246 19.6% 269 9.2% 294 1.9% 1110 1.1% 1213 0.8% 1326 2% 1448 1.4% 1583 0.3% 1729 0.3%TSS循环为1050°C和950°C。图4所示。MSS循环在1050 /1000/ 900°C。
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