Method has been developed for the determination of traces of arsenic, boron, bismuth, gallium, germanium, phosphorus, lead, antimony, selenium, silicon and tellurium in nickel matrix. Nickel was settled as crystalline nickelperchlorate [Ni(ClO 4 ) 2] on cooling. Matrix removal was 499% and the recoveries of analytes were in the range 92-97%.
Method has been developed for the determination of traces of arsenic, boron, bismuth, gallium, germanium, phosphorus, lead, antimony, selenium, silicon and tellurium in nickel matrix. Nickel was settled as crystalline nickelperchlorate [Ni(ClO 4 ) 2] on cooling. Matrix removal was 499% and the recoveries of analytes were in the range 92-97%.
Method has been developed for the determination of traces of arsenic, boron, bismuth, gallium, germanium, phosphorus, lead, antimony, selenium, silicon and tellurium in nickel matrix. Nickel was settled as crystalline nickelperchlorate [Ni(ClO 4 ) 2] on cooling. Matrix removal was 499% and the recoveries of analytes were in the range 92-97%.
Determination of traces of As, B, Bi, Ga, Ge, P, Pb, Sb, Se, Si and Te
in high-purity nickel using inductively coupled plasma-optical
emission spectrometry (ICP-OES) S. Thangavel, K. Dash, S.M. Dhavile, A.C. Sahayam n National Centre for Compositional Characterization of Materials, Bhabha Atomic Research Centre, ECIL-Post, Hyderabad-500062, India a r t i c l e i n f o Article history: Received 22 May 2014 Received in revised form 7 August 2014 Accepted 8 August 2014 Available online 19 August 2014 Keywords: Nickel Impurities Nickel perchlorate Nickel alloys a b s t r a c t A method has been developed for the determination of traces of arsenic, boron, bismuth, gallium, germanium, phosphorus, lead, antimony, selenium, silicon and tellurium in nickel matrix. The sample was dissolved in HClO 4 (150 1C) and nickel was settled as crystalline nickelperchlorate [Ni(ClO 4 ) 2 ] on cooling. The mixture was ultrasonicated and after the separation of Ni(ClO 4 ) 2 , analytes of interest were determined in the supernatant using ICP-OES. Similarly, it was also found that, after the dissolution of nickel in perchloric acid, when the solution temperature was maintained at 100 1C, long needle like crystals of nickel perchlorate were formed. The crystals were separated from the mixture and trace elements in the supernatant were determined using ICP-OES. In both methods the matrix removal was 499% and the recoveries of analytes were in the range 9297%. The limits of detection for As, B, Bi, Ga, Ge, P, Pb, Sb, Se, Si and Te were found to be 0.18, 0.21, 0.07, 0.06, 0.25, 0.11, 0.09, 0.10, 0.17, 0.20 and 0.07 g g 1 respectively. The procedure was applied for the analysis of a standard reference material nickel oxide (SRM 761, Nickel Oxide No.1, NBS, USA) and the values obtained are in close agreement with the certied values. & 2014 Elsevier B.V. All rights reserved. 1. Introduction Nickel base super alloys, by virtue of their excellent high tempera- ture properties coupled with corrosion resistance, have been widely used in jet engine, gas turbine engine components where high strength at high temperature is needed [1,2]. The quality of nickel- base alloys is highly dependent on the amounts of trace elements present as the presence of trace elements has serious effects on the mechanical and physical properties of these high temperature alloys [3,4]. Among the impurities in nickel base alloys, lowmelting elements such as As, Se, Te, Pb etc. are detrimental to the strength of high temperature alloys even when present at very low concentrations [5]. Therefore it is essential to determine traces of these low melting elements (As, Se, Te and Pb) in nickel matrix. Hydride generation atomic absorption spectrometry (HG-FAAS) and Hydride generation Inductively Coupled Plasma Optical Emis- sion Spectrometry (HG-ICP-OES) are among the most sensitive techniques for the determination of traces of As, Se and Te [6,7]. However, due to the strong interference of nickel in hydride generation process, it is difcult to analyze nickel matrices for low melting elements mentioned above by hydride generation [8,9]. In these techniques, the interference caused by nickel is minimized by masking the interferents [6,10] or by rapid hydride generation followed by fast separation of hydride from the liquid phase [11]. Inductively Coupled Plasma Mass Spectrometry (ICP- MS) is a powerful technique for the trace multi-element analysis. The determination of traces of Te in alloys by ICP-MS suffers from severe non-spectroscopic interference when conventional pneu- matic nebulizer was used for sample introduction. This problem was overcome by applying the vapor generation of Te and its introduction to ICP-MS [12]. Graphite Furnace Atomic Absorption Spectrometry (GFAAS) methods were developed for the determi- nation of selenium, tellurium in nickel after the matrix separation by reductive co-precipitation with palladium using ascorbic acid [13,14]. As per our knowledge, no single method has been reported to date for trace level determination of these impurities (As, Sb, Bi, B, Ga, Ge, Pb, P, Se, Si and Te) in nickel matrix. Herein, a new method has been described for the determina- tion of traces of As, Sb, Bi, B, Ga, Ge, Pb, P, Se, Si and Te in nickel matrix. The sample was dissolved in con.HClO 4 at hot condition and after cooling, the matrix (nickel) was separated from the sample solution either as crystalline precipitate or needle like crystals of Ni(ClO 4 ) 2 . The crystalline precipitate was ultrasonicated Contents lists available at ScienceDirect journal homepage: www.elsevier.com/locate/talanta Talanta http://dx.doi.org/10.1016/j.talanta.2014.08.026 0039-9140/& 2014 Elsevier B.V. All rights reserved. n Corresponding author. Tel.: 91 40 27121365. E-mail address: sahayamac@gmail.com (A.C. Sahayam). Talanta 131 (2015) 505509 to leach out the impurities from crystals and the concentration of trace impurities in the supernatant was measured using ICP-OES. In the second procedure, needle like crystalline Ni(ClO 4 ) 2 was prepared by maintaining the sample solution at 100 1C and the supernatant was analyzed for trace impurities by ICP-OES. 2. Experimental 2.1. Apparatus A Horiba scientic model of ULTIMA-2 Inductively Coupled Plasma-Optical Emission Spectrometer (ICP-OES) was used. The instrumental specications are given in Table 1. A Bandelin model of SONOREX DIGITEC 35 kHz ultrasonic bath with heater (20 80 1C) was used. 2.2. Reagent and standard solutions Suprapur grade HClO 4 (70%,w/v) from Merck, Germany was used. Standard stock solutions of all the elements (1000 mg L 1 ) were obtained from Merck, Germany. Working standard solutions were freshly prepared from these stock solutions as required. 2.3. Procedure 2.3.1. Matrix separation after precipitation of Ni(ClO 4 ) 2 followed by ultrasonication Around 0.5 g of nickel sample was taken in a at bottom quartz test tube of 25 mL capacity, 10 mL suprapur grade HClO 4 (70%,w/v) was added, the tube was covered with watch glass and heated over a hot plate at 150 1C (solution temperature) for 30 min. After the complete dissolution of the sample, the sample solution was allowed to cool to 60 1C. Then the sample solution was sonicated at 50 1C (35 kHz) for 40 min. After ultrasonication, the sample solution was taken out from the ultrasonic bath and cooled to room temperature and was centrifuged between 1000 and 1500 rpm and the supernatant was separated using a micropip- ette. Then the supernatant (3 mL) was diluted to 25 mL and impurities present were measured using ICP-OES. If the concen- tration of impurities is not detectable, pre-concentration of impu- rities can be carried out by evaporating the supernatant on a hot plate (surface temperature of 130 1C) in a fume hood till no more dense fumes came out from the sample solution. Then after cooling it was diluted to 10 mL using mill-Q water and the analytes were measured using ICP-OES. 2.3.2. Matrix separation after the formation of needle like crystals of Ni(ClO 4 ) 2 Around 0.5 g of nickel sample was dissolved in perchloric acid as described above. After complete dissolution of sample, the test tube was removed from the hot plate and temperature of the solution was maintained at 100 1C using Infra Red (IR) lamp (IR lamp was kept by the side with respect to sample solution). After the appearance of needle like crystals, the sample solution was kept at this temperature for around 30 min. Then the IR lamp was switched off and allowed the solution to cool to room temperature (25 1C). The sample solution was carefully transferred into a clean 25 mL quartz beaker using a micropipette. Then the separated sample solution (3 mL) was diluted to 25 mL and measured for the impurities using ICP-OES. To reduce the dilution factor, the separated sample solution could be diluted to 10 mL after the evaporation of excess HClO 4 as described in the above procedure. 3. Result and discussion 3.1. Role of HClO 4 on dissolution and separation of nickel Nickel/nickel oxide reacts with con. HClO 4 (70%,w/v) at 150 1C (solution temperature) forming intense green color Ni (ClO 4 ) 2 solution. When this solution is allowed to cool 499% of nickel is settled as crystalline form of Ni(ClO 4 ) 2 . This unique property of Ni(ClO 4 ) 2 is utilized to separate the matrix for its trace element analysis. Due to high solubility of Ni(ClO 4 ) 2 in water, after the crystallization, any dilution of HClO 4 with water leads to redissolution of the matrix and decrease in matrix separation. Therefore, sample dissolution and matrix separation were carried out using concentrated HClO 4 . The effective matrix separation was not affected when the concentration of HClO 4 is maintained 495% (v/v). Any increased dilution of HClO 4 drastically increases the dissolution of Ni(ClO 4 ) 2 and leads to complete dissolution when the concentration of HClO 4 is o50% (v/v). However, the matrix separation (99%) was independent of the amount of HClO 4 (70%, w/v) used for the sample dissolution. 3.2. Ultrasonic extraction of analytes Preliminary experiments were carried out for the separation of Ni as Ni(ClO 4 ) 2 precipitate and the recovery of analytes in the supernatant was found to be only 2030%. Lower recovery of analytes could be due to the occlusion of the analytes during the formation of bulky molecule of Ni(ClO 4 ) 2 (5 times the weight of nickel) precipitate. Therefore, after the precipitation of crystalline form of Ni(ClO 4 ) 2 , ultrasonication was carried out to leach out the analytes from Ni(ClO 4 ) 2 precipitate. Even after the ultrasonication, the recovery of analytes was in the range of 80%. Increase in the temperature of the sample solution and ultrasonication bath lead to further improvement in recovery of analytes. However, it also leads to increase in the dissolution of Ni(ClO 4 ) 2 which resulted in poor matrix separation. Therefore these two parameters are required to be optimized. After the separation of nickel, a high concentration of HClO 4 remains in the sample solution requiring large dilution prior to the determination of impurities using ICP- OES which lead to poor limit of detection (LOD). Hence, to obviate large dilution, excess HClO 4 from sample solution needed to be evaporated. Due to hazardous nature of HClO4, it is very essential to optimize its amount to as minimum as possible. 3.3. Optimization of ultrasonic extraction of analytes Based on the recovery of arsenic, ultrasonic extraction was optimized for each parameter, i.e., amount of HClO 4 , temperature of the sample solution/ sonication bath and time duration of ultrasonica- tion. To study the effect of amount of HClO 4 on matrix removal and analyte recovery, after the dissolution of sample, ultrasonication was carried out at a solution temperature of 60 1C and ultrasonic bath temperature of 50 1C for 30 min. The amount of HClO 4 was increased from 5 mL onwards (minimum 5 mL of HClO 4 is required for the dissolution of 0.5 g of nickel) in steps of 2 mL and when it was Table 1 Operating conditions of ICP-OES. Power 1.1 kW Wavelengths (nm) Se (196.090), As (197.198), Sb (206.833), Ge (209.426), P (213.618), Te (214.281), Pb (220.353), Bi (223.061), B (249.772), Si (251.611) and Ga (294.364) Plasma gas ow rate 12.1 l min 1 Nebulizer gas ow rate 0.83 l min 1 , concentrique nebulizer Auxiliary gas ow rate 0.52 l min 1 Solution uptake rate 2.0 mL min 1 S. Thangavel et al. / Talanta 131 (2015) 505509 506 10 mL or higher the recovery of analyte (As) was more than 92% (Fig. 1). From this gure, it can be seen that no signicant increase in the separation of matrix was observed by further increasing the amount of acid. Hence, 10 mL of acid was used for further studies. The effect of temperature of the sample solution and the temperature of the ultrasonication bath on matrix separation and recovery of analytes are given in Figs. 2 and 3 respectively. For these studies, after the dissolution (0.5 g of sample in 10 mL of HClO 4 ) the sample solution was cooled to various temperatures (10025 1C) and kept inside the ultrasonication bath maintained at a temperature between 25 and 80 1C. When the temperature of ultrasonic bath and sample solution were between 25 and 60 1C matrix separation was 99%. However, when these temperatures were between 50 and 60 1C, the recovery of analytes was found to be more than 93%. Therefore optimized temperature of between 50 and 60 1C was employed in subsequent studies. At optimized temperatures, the required time duration of ultrasonic bath was also studied and the results are shown in Fig. 4. It can be seen from this gure that optimized time duration was 40 min to achieve near quantitative recovery of all the analytes. 3.4. Preparation of needle like crystals of Ni(ClO 4 ) 2 In our preliminary experiments after the dissolution of nickel, when the sample solution was allowed to cool, during transition of temperature formation of needle like crystals was observed occasionally. When these crystals were formed, the recovery of analytes was in the range of 9296%, thus obviating the need for ultrasonic extraction. However, it was very difcult to achieve reproducible preparation of long needle like crystals. From repeated experiments, it has been observed that the following parameters namely heating apparatus, the crystallization tempera- ture and dimension of the container (where crystallization is carried out) were crucial for the formation of long needle like crystals. As in the case of ultrasonic extraction, even in this matrix separation method, no signicant variation in the separation of matrix (499%) was observed with the amount of HClO 4 used for the dissolution sample. 3.5. Optimization of crystallization Preliminary experiments were carried out for the formation of needle like crystals by maintaining the temperature of the sample solution using a hot plate. On hot plate it is very difcult to maintain the temperature of solution and hence it was found to be very intricate to produce needle like crystals. After the dissolution of sample at 150 1C, when the temperature of the hot plate was decreased nickel perchlorate was precipitated in crystalline form and is completely dissolved when the temperature was increased. Therefore, crystallization was attempted by maintaining the tem- perature of the sample solution using IR lamp. In this case also, it was stringent to develop needle like crystals when IR lamp was kept above or below the sample solution. When the IR lamp was kept in horizontal position (by the side) with respect to sample solution, long needle like crystals were formed that were not settled down as precipitate (Fig. 5). The distance between IR lamp and test tube was also optimized. In our laboratory atmosphere the optimized distance was found to be 10 cm. When the Fig. 1. Effect of amount of con.HClO 4 on 0.5 g of sample on matrix (A)/analyte (B) separation (No. of replicates (n)3). Fig. 2. Effect of temperature of ultrasonication bath/sample solution on separation of matrix (n3). Fig. 3. Effect of temperature of ultrasonication bath/sample solution on recovery of analyte (n3). Fig. 4. Effect of time duration of ultrasonic bath (50 1C) on matrix/analyte separation. A-matrix separation; B-analyte recovery (n3). S. Thangavel et al. / Talanta 131 (2015) 505509 507 temperature of the sample solution was 4120 1C, Ni(ClO 4 ) 2 remained in the solution form. As soon as the temperature was decreased below 115 1C, needle like crystals started to form and did not settle down as precipitate till the temperature of the sample solution remained above 90 1C. As described earlier, settling down of crystals as precipitate leads to poor recovery of analytes. Therefore, to keep the Ni(ClO 4 ) 2 as needle like crystals, optimized temperature of the solution was found to be 100710 1C. If this temperature was maintained for 30 min, 499% of 0.5 g of nickel was formed as long needle crystals of Ni (ClO 4 ) 2 . The IR lamp was switched off to bring the solution to room temperature. After reaching room temperature, the sample solu- tion needs to be separated from the crystals within one hour. Otherwise, the needle like crystals starts to settle as precipitate, which leads to lower recovery of analytes. It was observed that the dimensions of container also play an important role in the formation of needle like crystals. Since the volume of HClO 4 optimized is 10 mL for the dissolution of 0.5 g of sample, diameter of the tube should be as low as possible. Therefore at bottom quartz test tubes with different diameters were taken for crystal formation. If the vessel is very narrow the crystals started to form from the wall of the vessel in horizontal direction and hence complete crystal growth could not taken place. The crystals formed on the wall of the tube fell down and settled as precipitate. The optimized diameter of the tube was found to be between 2 and 3 cm. 3.6. Recovery of other elements In both matrix separation methods (crystallization and ultra- sonication), since most of the transition elements such as Fe, Al, Cu, Mn etc. form perchlorates, these elements will co-precipitate with Ni(ClO 4 ) 2 resulting in poor recovery (o30%). However, after the matrix separation in the form of needle like crystals, poorer recovery of B, Ga, Ge, Pb and Si was observed (Table 2). It could be due to the adsorption of perchlorates of B, Ga, Ge and Pb on Ni (ClO 4 ) 2 resulting in poorer recovery for these analytes. Silicon is prone to hydrolysis on treatment with concentrated acids (except HF). In this method since crystallization was carried out in concentrated HClO 4 medium, silicon might be hydrolyzed and Fig. 5. Ni(ClO 4 ) 2 in solution form (A) and needle like crystalline form (B). Table 2 Recovery study and limit of detection. Element After evaporation of HClO 4 Without evaporation of HClO 4 Limit of Detection (g g 1 ) After crystallization After ultrasonication After crystallization After ultrasonication As 95 94 94 96 0.18 B 46 28 42 93 0.21 Bi 94 96 97 95 0.07 Ga 45 95 42 99 0.06 Ge 45 22 46 92 0.25 P 95 97 96 99 0.11 Pb 42 94 48 97 0.09 Se 94 95 93 94 0.17 Sb 38 36 95 96 0.10 Si 32 40 32 96 0.20 Te 94 94 97 96 0.07 S. Thangavel et al. / Talanta 131 (2015) 505509 508 adsorbed on Ni(ClO 4 ) 2 . However, matrix separation followed by ultrasonication, improved recoveries of these analytes to 492%. It could be due to the fact that ultrasonication was carried out at 50 1C and at this condition these analytes are quantitatively leached out from Ni(ClO 4 ) 2 precipitate. After the separation of matrix, when excess HClO 4 is evaporated on hot plate, poor recovery was found out for B, Ge and Sb. It could be due to the loss of these analytes on evaporation of HClO 4 . 3.7. Sample analysis, limit of detection (LOD) and recovery To validate the developed method, this procedure was applied to a standard reference material of Nickel oxide (Standard Sample 671, Nickel Oxide, No.1, National Bureau of Standards, Washington) and the results are in close agreement with certied values (Table 3). The limit of detection (LOD), given as three times the variation on repeated measurements of blank (n6) for all the analytes in solid sample is given in Table 2 and it was calculated based on the dilution factor of 0.5 g of sample made upto 10 mL whereas for B, Ge and Sb it was calculated based on the dilution factor of 0.5 g made upto 25 mL as loss of these analytes was observed on evaporation of HClO 4 . 4. Conclusion This new sample digestion and matrix separation approach is simple and all the critical elements in nickel matrix could be determined. 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