a p p l i c at i o n N o t e ICP-Optical Emission Spectroscopy Author Chady Stephan PerkinElmer, Inc. Woodbridge, Ontario, Canada ICP-OES Analysis of FeCr Alloys Prepared by Sodium Peroxide Fusion Introduction Ferroalloys, alloys of iron with sufficient amounts of one or more other elements present (V, Mo, Cr, etc.), are important as a source of various metallic elements in the production of all types of steels. They usually have low melting points and can be incorporated readily into molten steel where they provide a certain chemical composition with specified properties.1 The ferrochrome alloy is produced by electric arc melting of the mineral chromite (FeCr2O4). It is largely used for the production of stainless steels. Increasing the amount of chromium content in the steel allows for increased corrosion and oxidation resistance. Other alloying elements, such as nickel (Ni) or molybdenum (Mo), aid in making the steel more passive and increasing its stainless properties.2 The presence of unwanted impurities in the metal and slag may alter reaction temperatures and cause undesirable reactions of their own.1 The chemical analysis of the chromite ore and its final products are mandatory to assess the quality of the chromite ore and to optimize the grade of stainless steel production. Analysis of waste products is also needed to optimize recovery of chromium and other additives.2 Chromite does not dissolve well in aqua regia or nitric acid, the typical acids used for digestion of samples for atomic spectroscopy.1 The traditional method for the dissolution of chromite and ferrochrome is time consuming and includes the use of hydrofluoric (HF) and perchloric (HClO4) acids. Sodium peroxide fusions offer an alternative to working with these high risk acids. Fusions are also less time consuming, providing a safer and more efficient method to obtain full dissolution of ferrochrome samples.3 In this work, we describe the performance of the Optima™ 8300 inductively coupled plasma-optical emission spectrometer (ICP-OES) in analyzing ferrochrome samples prepared by sodium peroxide fusion. The revolutionary radio frequency (RF) generator in the Optima 8300 spectrometer features flat induction plates that replace the traditional helical load coil. The Flat Plate™ plasma induction plate technology delivers a low-flow operating system that does not require coil cooling and is capable of operating at a plasma argon flow as low as 8 L/min. Several key parameters were evaluated for this particular application: accuracy and precision by measuring the recovery and the relative standard deviation of three standard reference materials (SRMs), stability by plotting the recovery of continuing calibration verification (CCV) samples versus time for more than 12 hours, and method detection limits (MDLs) calculated as three times the standard deviation of the measured concentrations of 10 fused matrix blank replicates. Experimental Conditions Instrumentation All samples were analyzed for elemental content using the PerkinElmer® Optima 8300 ICP-OES (Figure 1) with a singleslot one-piece torch (Part No. N0780130). A SeaSpray™ nebulizer (Part No. N0775345) and baffled cyclonic spray chamber (Part No. N0776053) were used for their known ability to handle samples with high levels of dissolved solids. Instrumental parameters used for the analysis are listed in Table 1. The wavelengths and viewing mode are listed in Table 2 (Page 3). By combining a segmented-array charge coupled device (SCD) detector and an Echelle optical system, the Optima 8300 ICP-OES can measure all the wavelengths simultaneously. Its wavelength flexibility allows the end users to easily add new elements or wavelengths as their program changes. The Flat Plate technology generates a unique transversely symmetrical plasma that exhibits an extremely flat bottom which caps off the sample and prevents it from escaping around the outside (Figure 2). The symmetry and stability of the Flat Plate plasma, in conjunction with the new torch geometry, allows for a high level of stability and precision. 2 Figure 1. Optima 8300 spectrometer – the most economical ICP-OES, capable of running at a plasma flow rate as low as 8 L/min. Figure 2. Low-flow operation with Flat Plate plasma induction plate technology. Another benefit of using the Optima 8300 ICP-OES for fusion samples includes a 40 MHz free-running solid state RF generator. It is capable of handling the high power required to generate a robust plasma which is essential for precise analysis of complex matrices such as fusion samples. Table 1. Instrumental operating conditions. Parameter Value Instrument Optima 8300 ICP-OES Nebulizer SeaSpray Spray Chamber Baffled cyclonic Torch Single slot quartz torch Injector 2.0 mm alumina Power (W) 1500 Plasma Gas (L/min) 10 Aux Gas (L/min) 0.3 Neb Gas (L/min) 0.65 Sample Uptake Rate (mL/min) 1.5 Sample Tubing Samples and standards (Black/Black) Internal standard (Green/Orange) Internal Standard 5 ppm yttrium + 10 ppm cesium (as an ionization buffer) Table 2. Wavelength and viewing mode for the elemental analysis of dissolved ferrochrome samples. Analyte Wavelength Viewing Mode Al394.401 Axial Ca317.933 Radial Co228.616 Axial Cr206.158 Axial Cu327.393 Axial Fe239.562 Axial K 766.490Radial Mg279.077 Radial Mn257.610 Axial Mo202.031 Axial Ni231.604 Axial P178.221Axial S 181.975Axial Si251.611 Axial Ti334.940 Axial V290.880Axial Zn206.200 Axial Table 3. FeCr alloy (SRM 64c) recovery – all values are in mg/kg; dashed lines indicate no certified value was provided by the manufacture. Analyte Certified Measured Recovery (%) Al --- 658 --- Ca --- 295 --- Co 510 520 102 Cr 680000 655000 96.3 Cu 50 < MDL --- Fe 249800 260000 104 K --- 4.20 --- Mg --- 23120 --- Mn 1600 1650 103 Mo --- 165 --- Ni 4300 4050 94.2 P 200 191 95.6 S 670 731 109 Si 12200 11450 93.9 Ti 200 205 102 V 1500 1587 106 Zn --- < MDL --- Sample Preparation All samples were prepared by sodium peroxide fusion. In a zirconium crucible, precisely 0.2 g of finely ground sample was fused with 3 g of sodium peroxide (Na2O2) and 0.5 g of sodium carbonate (Na2CO3). The fused mixture was poured into a beaker containing 250 mL of a 20% acid mixture of 1:1 hydrochloric (HCl) and nitric (HNO3) acids. Table 4. Cr ore (SARM 8) recovery – all values are in mg/kg. Analyte Certified Al Measured Recovery (%) 5590053250 95.3 Ca 18581875 101 Co ---265 --Cr 335050345000 103 PerkinElmer NIST Traceable Quality Control Standards for ICP were used as the stock standards for preparing working standards. A four-point calibration curve was used for each measured element. Cu ---103 --- Results Mn 17401820 105 ® Accuracy and Precision The method accuracy was monitored by measuring the recovery of two different SRMs: a high-carbon ferrochromium (FeCr) alloy (SRM 64c) (Table 3) and chromium ore South African Reference Material 8 (SARM 8) (Table 4). The method precision was monitored by measuring the variation of a FeCr slag SRM (SARM 77) analyzed 55 times over a period of 12 hours (Table 5 – Page 4). Both SRMs showed excellent recoveries for all analyzed elements (± 10%). Fe 141300145600 103 K ---182 --Mg 8859094110 106 Mo ---105 --Ni ---1460 --P S Si ---17.3 --341359 105 2010019510 97.1 Ti 14401390 96.5 V 780821 105 Zn --- < DL --- 3 Table 5. Analysis of FeCr slag (SARM 77) over 12 hours (n=55) – all values are in mg/kg. Average Analyte Certified Measured SD RSD (%) Recovery (%) Al 145540 149800 1283 0.86 103 Ca 26015 24440 319 1.3 93.9 Co --- 79.4 1.9 2.4 --- Cr 85530 93370 442 0.47 109 Cu --- 125 8.6 6.9 --- Fe 53100 52210 2049 3.9 98.3 K --- 1060 14 1.3 --- Mg 138640 143800 1200 0.83 104 Mn --- 1474 24 1.6 --- Mo --- 73.1 6.0 8.2 --- Ni --- 303 16 5.1 --- P --- < MDL --- --- --- S --- 2736 95 3.5 --- Si 125410 128000 2008 1.6 102 Ti --- 3201 22 0.69 --- V --- 536 6.5 1.2 --- Zn --- < MDL --- --- --- Method Detection Limits The method detection limits (MDLs) were calculated based on ten replicate measurements of the matrix blank. The MDL was calculated by multiplying the standard deviation of the ten replicate measurements by three (Table 6). The low-flow plasma was able to achieve MDLs less than or within a reasonable range of the traditional plasma flow rate. This would suggest that the lower Ar flow and hence lower cost of ownership can be achieved without sacrificing performance. Table 6. Method detection limits for low argon plasma gas flow. All values are in the calibration units of mg/L. Analyte MDL Al 0.0055 Ca (Radial) 0.045 Co 0.0015 Cr 0.0034 Cu 0.0019 Fe 0.018 K (Radial) 0.17 Mg (Radial) 0.037 Mn 0.0010 Mo 0.0019 Ni 0.0022 Stability P 0.017 The instrument stability was assessed by plotting the recovery of SARM 77 as a CCV versus time for more than 12 hours (Figure 3). There was little change in concentration (< 4%) for all elements measured. The excellent instrument stability allows laboratories to confidently run samples without the need for time consuming recalibration or optimization. S 0.0036 Si 0.029 Ti 0.0008 V 0.0015 Zn 0.0012 Conclusions Figure 3. Instrument stability showing the % recovery of CCV (FeCr slag) over time. R = radial viewing. 4 The Optima 8300 spectrometer demonstrated its ability to run heavy matrix samples using 44% less argon than typical ICP-OES systems while maintaining superior performance. By incorporating Flat Plate™ technology, a robust matrixtolerant plasma was generated and fusion samples were run successfully with only 10 L/min argon plasma gas flow. The Optima 8300 system maintained remarkable accuracy and precision throughout the 12-hour testing period, demonstrating excellent calibration stability. The method detection limits, when analyzing at a low plasma argon flow, were comparable to higher traditional argon flow ICP-OES systems. References 1.The New Encylopædia Britannica: Micropedia Ready Reference. 15th ed., Vol. 3-4, Chicago: Enclyopædia Britannica, 1998. s.v. “Ferrochromium”. 2.Davis, J.R., ed. Metals Handbook Desk Edition. 2nd ed., Materials Park, OH: ASM International, 1998. s.v. “Ferroalloy”. 3.Pitre, Janice, Melanie Bedard, and Aaron Hineman. ”Dissolution Made Easy Using Peroxide Fusions for ICP-OES Analyses for Chromite Ores, Ferrochromes and Chromium Slags.” http://www.claisse.com/claisse_ highlights_details.php?no=63. PerkinElmer, Inc. 940 Winter Street Waltham, MA 02451 USA P: (800) 762-4000 or (+1) 203-925-4602 www.perkinelmer.com For a complete listing of our global offices, visit www.perkinelmer.com/ContactUs Copyright ©2011, PerkinElmer, Inc. All rights reserved. PerkinElmer® is a registered trademark of PerkinElmer, Inc. All other trademarks are the property of their respective owners. 009935_01