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Fabrication of Nano-Structured Duplex and Ferritic Stainless Steel by Planetary Milling Followed by Consolidation

机译:行星铣削然后固结制备纳米结构双相和铁素体不锈钢

摘要

The use of stainless steel has been increased extensively in various fields from past few decades. Now a day stainless steels are in great demand due to good corrosion resistance, high toughness, low thermal expansion, high energy absorption, good weldability, high strength, high thermal conductivity, creep resistance, wear resistance, higher yield strength and excellent high temperature oxidation resistance properties. The stainless steels are mainly used in refrigeration cabinets, bench work, cold water tanks, chemical and food processing, water treatment plant, street furniture, electrical cabinets, chemical, oil, petrochemical, marine, nuclear power, paper and pulp industries. Properties of the materials improve tremendously when bring down their size to nano level. Hence, we synthesized nano structured duplex and ferritic stainless steel by high energy planetary milling. Nano-structured duplex and ferritic stainless steel powders were prepared by milling of elemental Fe, Cr and Ni powder in pulverisette planetary mill for 40 hours and then consolidated by conventional pressureless sintering. Activation energy for formation of duplex and ferritic stainless steel were calculated by Kissinger method using differential scanning calorimetry and was found to be 159.24 and 90.17 KJ/mol respectively. Both duplex and ferritic stainless steel powders were consolidated at 1000, 1200 and 1400C in argon atmosphere to study microstructure, density and hardness. In duplex stainless steel, 90% of maximum sintered density and 550HV of Vickers microhardness were achieved at 1400C sintered temperature. Similarly, 92% sintered density and 263HV microhardness were achieved for ferritic stainless steel sintered at 1400C.The nano-structured duplex and ferritic stainless steel powders were also prepared by milling elemental powders in a specially designed dual-drive planetary mill (DDPM) for 10 hours. The progress of milling and phase transition of stainless steel have been studied by means of x-ray diffraction. The crystallite size and the lattice strain of the duplex stainless steel after 10 hours milling are 9nm and 5.59x10-3 respectively. Similarly, the crystallite size and the lattice strain of the ferritic stainless steel after 10 hours milling are 8nm and 9.05x10-3 respectively. Annealing of milled powder at 750C promotes ferritic to austenitic transformation in both argon and nitrogen atmosphere as limited transformation takes place after milling. However, nitrogen favours the transformation to a greater extent than argon. Lattice parameters calculated from both high resolution transmission electron micrographs (HRTEM) and Nelson-Riley method match with duplex and ferritic stainless steel. It has been found that initially particles are flattened and finally become almost spherical of size around 10-15 micrometer in both cases.The effect of process controlling agent (PCA) such as stearic acid (SA), effect of ball to powder weight ratio (BPR 6:1and 12:1), milling speed (64 and 75% critical speed) and dry and wet milling were studied during planetary milling of elemental Fe–18Cr–13Ni (duplex) and Fe–17Cr–1Ni (ferritic) powders for 10h in a dual drive planetary mill (DDPM). We have found that all these mill parameters have great influence in tuning the final particle morphology, size and phase evolution during milling. It was found that addition of PCA, a BPR of 12:1, dry milling and 75% critical speed is more effective in reducing particle size and formation of duplex and ferritic stainless steel after 10h milling of elemental powder compositions than their counterparts. Yittria free and yittria dispersed duplex and ferritic stainless steels were fabricated by both conventional sintering and spark plasma sintering (SPS) methods. The effect of sintering temperature, sintering atmosphere and addition of Y2O3 nanoparticles on phase transformation, microstructure, mechanical properties were evaluated during conventional sintering. Non-lubricated sliding wear properties of conventional and spark plasma sintered stainless steel samples against a diamond indenter were compared successfully at 10 and 20N wear loads. Spark plasma sintered stainless steel samples show maximum wear resistance compared to conventionally sintered stainless steel. The present study also involves the comparison of wear behaviour of yittria dispersed and yittria free stainless steel sintered conventionally at 1000°C in argon and nitrogen atmospheres. The wear mechanism of all the stainless steel samples were studied by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and found to be abrasive and oxidation wear. Qualitative analysis of wear track and wear debris confirm the presence of oxygen during wear. Wear debris of less harder ferritic stainless steel samples are found to be flakes and harder duplex is spherical. The microstructure and corrosion properties of spark plasma sintered yittria dispersed and yittria free duplex and ferritic stainless samples were studied. Spark plasma sintering (SPS) was carried out at 1000°C by applying 50MPa pressure with holding time of 5minutes. The SPS duplex, ferritic and yittria dispersed duplex and ferritic stainless steel samples were characterized by field emission scanning electron microscopy (FESEM) and XRD. Linear sweep voltammetry (LSV) tests were employed to evaluate corrosion resistance of the samples. Corrosion studies were carried out in 0.5, 1 and 2M concentration of NaCl and H2SO4 solutions at different quiet time of 2, 4, 6, 8 and 10 seconds. Yittria dispersed stainless steel samples show more resistance to corrosion than yittria free stainless steel samples. It was observed that as concentration of NaCl and H2SO4 increases from 0.5M to 2M the corrosion resistance decreases due to the availability of more Cl¯ and SO4¯ ions at higher concentration. Maximum pitting potential (EP) at 0.5M NaCl (almost equal to NaCl present in sea water) of yittria dispersed duplex and ferritic stainless steel samples are 1.45V and 0.64V respectively. Similarly, yittria free duplex and ferritic stainless steel samples show 0.63V and 0.57V respectively. EP value of yittria dispersed duplex and ferritic stainless steel samples at 0.5M H2SO4 are 0.30V and 0.23V respectively. Similarly, yittria free duplex and ferritic stainless steel samples show EP value of 0.18V and 0.14V respectively at 0.5M H2SO4. Corroded samples were then characterized by FESEM and optical microscopy to confirm the presence of corrosion region.Carbon paste electrode was modified with yittria free and yittria dispersed duplex stainless steel respectively to study their electrocatalytic behaviour in detecting folic acid. We determined optimum concentration of both the modifiers which show maximum anodic peak current in determining the folic acid. Electro catalytic properties of analyte were investigated at 2, 4, 6, 8, 10 and 12mg concentrations of modifier. Among all, 8mg yittria dispersed duplex stainless steel modified carbon paste electrode showed maximum current sensitivity than 4mg yittria free duplex stainless steel modified carbon paste electrode in 2mM folic acid concentration and 0.2M phosphate buffer solution of pH 7.2 at scan rate of 100mVs-1. We reported the effect of scan rate, concentration of folic acid and pH effect on oxidation peak of folic acid in both the modified carbon electrodes. Plot of all the above effects shows linear relationship and their electrode reactions were adsorption controlled. We successfully fabricated reliable, stable and fast response electrochemical sensor to detect folic acid.
机译:在过去的几十年中,不锈钢的使用在各个领域得到了广泛的增加。现在,由于良好的耐腐蚀性,高韧性,低热膨胀性,高能量吸收性,良好的可焊接性,高强度,高导热性,耐蠕变性,耐磨性,较高的屈服强度和出色的高温氧化性,如今对不锈钢的需求量很大。抗性。不锈钢主要用于制冷柜,工作台,冷水箱,化学和食品加工,水处理厂,街道家具,电气柜,化工,石油,石化,船舶,核电,造纸和纸浆工业。当将其尺寸减小到纳米级时,材料的性能会大大提高。因此,我们通过高能行星铣削合成了纳米结构的双相和铁素体不锈钢。纳米结构的双相和铁素体不锈钢粉末是通过在粉状行星式磨机中研磨元素Fe,Cr和Ni粉末40小时,然后通过常规无压烧结进行固结而制备的。用差示扫描量热法通过基辛格法计算形成双相和铁素体不锈钢的活化能,分别为159.24和90.17 KJ / mol。将双相和铁素体不锈钢粉末在氩气中分别于1000、1200和1400°C固结,以研究组织,密度和硬度。在双相不锈钢中,在1400C的烧结温度下可获得90%的最大烧结密度和550HV的维氏显微硬度。同样,在1400°C烧结的铁素体不锈钢中,烧结密度达到92%,显微硬度达到263HV。纳米级双相和铁素体不锈钢粉末也通过在特殊设计的双驱动行星式磨机(DDPM)中研磨单质粉末而制得持续10个小时。通过X射线衍射研究了不锈钢的研磨和相变过程。研磨10小时后的双相不锈钢的微晶尺寸和晶格应变分别为9nm和5.59x10-3。类似地,经过10小时研磨后,铁素体不锈钢的微晶尺寸和晶格应变分别为8nm和9.05x10-3。研磨后的粉末在750°C退火可促进在氩气和氮气气氛中铁素体向奥氏体的转变,因为在研磨后会发生有限的转变。但是,氮比氩更有利于转化。根据高分辨率透射电子显微照片(HRTEM)和Nelson-Riley方法计算出的晶格参数与双相和铁素体不锈钢相匹配。已经发现,在两种情况下,最初的颗粒都是扁平的,最终变成几乎球形,尺寸约为10-15微米。过程控制剂(PCA)的作用,例如硬脂酸(SA),球对粉末重量比的影响( BPR 6:1和12:1),行星状Fe–18Cr–13Ni(双相)和Fe–17Cr–1Ni(铁素体)粉末的行星式铣削过程中,研究了铣削速度(64和75%临界速度)以及干磨和湿磨。在双驱动行星式磨机(DDPM)中运行10小时。我们发现,所有这些磨粉参数在调整磨粉过程中的最终颗粒形态,尺寸和相变方面都具有很大的影响。已发现,添加PCA,12:1的BPR,干法研磨和75%的临界速度比元素粉末组合物在研磨10小时后能更有效地减小粒径和减少双相和铁素体不锈钢的形成。通过常规烧结和火花等离子烧结(SPS)方法制造无氧化钇和分散有氧化钇的双相和铁素体不锈钢。在常规烧结过程中,评估了烧结温度,烧结气氛和添加Y2O3纳米颗粒对相变,微观结构和力学性能的影响。在10和20N的磨损载荷下,成功比较了常规和火花等离子烧结不锈钢样品相对于金刚石压头的非润滑滑动磨损性能。与传统的烧结不锈钢相比,火花等离子烧结的不锈钢样品具有最大的耐磨性。本研究还涉及比较在常规氩气和氮气气氛中于1000°C烧结的分散氧化钇和无氧化钇的不锈钢的磨损行为。通过扫描电子显微镜(SEM)研究了所有不锈钢样品的磨损机理。,能量色散光谱(EDS),发现具有磨蚀性和氧化性磨损。对磨损痕迹和磨损碎屑的定性分析确认了磨损期间氧气的存在。较硬的铁素体不锈钢样品的磨损碎片被发现为薄片,而较硬的双相不锈钢为球形。研究了火花等离子体烧结氧化钇分散体和无氧化钇的双相和铁素体不锈钢样品的显微组织和腐蚀性能。通过施加50MPa的压力在1000℃下进行火花等离子体烧结(SPS),保持时间为5分钟。通过场发射扫描电子显微镜(FESEM)和XRD对SPS双相,铁素体和氧化钇分散的双相和铁素体不锈钢样品进行了表征。线性扫描伏安法(LSV)测试用于评估样品的耐腐蚀性。在浓度为0.5、1和2M的NaCl和H2SO4溶液中,在2、4、6、8和10秒的不同静默时间下进行腐蚀研究。分散有氧化钇的不锈钢样品比无氧化钇的不锈钢样品显示出更高的耐腐蚀性。可以看到,随着NaCl和H2SO4的浓度从0.5M增加到2M,由于在更高的浓度下可获得更多的Cl'和SO4'离子,因此耐腐蚀性降低。氧化钇分散双相不锈钢和铁素体不锈钢样品在0.5M NaCl(几乎等于海水中存在的NaCl)下的最大点蚀电位(EP)分别为1.45V和0.64V。同样,无氧化钇的双相不锈钢和铁素体不锈钢样品分别显示0.63V和0.57V。氧化钇分散的双相不锈钢和铁素体不锈钢样品在0.5M H2SO4下的EP值分别为0.30V和0.23V。同样,无氧化钇的双相和铁素体不锈钢样品在0.5M H2SO4下的EP值分别为0.18V和0.14V。然后用FESEM和光学显微镜对腐蚀样品进行表征,以确认腐蚀区域的存在。分别用无氧化钇和分散有氧化钇的双相不锈钢修饰碳糊电极,以研究其在检测叶酸中的电催化行为。我们确定了两种改性剂的最佳浓度,这些浓度在确定叶酸时显示出最大的阳极峰值电流。在2、4、6、8、10和12mg的改性剂浓度下研究了分析物的电催化性能。其中,在100mVs-1的扫描速度下,在2mM叶酸浓度和0.2M pH 7.2的磷酸盐缓冲溶液中,8mg氧化钇分散的双相不锈钢修饰碳糊电极显示出比4mg氧化钇分散的双相不锈钢修饰碳糊电极最大的电流敏感性。我们报道了扫描速度,叶酸浓度和pH值对两个修饰碳电极中叶酸氧化峰的影响。所有上述作用的曲线图显示线性关系,并且它们的电极反应受到吸附控制。我们成功地制造出可靠,稳定和快速响应的电化​​学传感器来检测叶酸。

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    Shashanka R;

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