1、 Reference number ISO 17054:2010(E) ISO 2010INTERNATIONAL STANDARD ISO 17054 First edition 2010-02-15 Routine method for analysis of high alloy steel by X-ray fluorescence spectrometry (XRF) by using a near-by technique Mthode de routine pour lanalyse des aciers fortement allis par spectromtrie de f
2、luorescence de rayons X (FRX) laide dune mthode de correction ISO 17054:2010(E) PDF disclaimer This PDF file may contain embedded typefaces. In accordance with Adobes licensing policy, this file may be printed or viewed but shall not be edited unless the typefaces which are embedded are licensed to
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7、ISO 2010 All rights reservediiiForeword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body intere
8、sted in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical
9、Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees is to prepare International Standards. Draft International Standards adopted by the tec
10、hnical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO
11、 shall not be held responsible for identifying any or all such patent rights. ISO 17054 was prepared by the European Committee for Standardization (CEN) (as EN 10315:2006) and was adopted by Technical Committee ISO/TC 17, Steel, Subcommittee SC 1, Methods of determination of chemical composition. IS
12、O 17054:2010(E) ISO 2010 All rights reservediv EN 10315:2006 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative references 4 3 Principle5 4 Reagents.5 5 Apparatus .6 6 Safety precautions.7 7 Sampling.7 8 Final sample preparation 7 9 Procedure .7 10 Calibration 8 11 Standardization9 12 Statistical P
13、rocess Control (SPC) parameters9 13 ”Near by technique” method10 14 Test report 10 Annex A (normative) Precision 12 Annex B (normative) Graphical representation of precision data.17 Bibliography 28 ISO 17054:2010(E) ISO 2010 All rights reservedvEN 10315:2006 (E) 3 Foreword This document (EN 10315:20
14、06) has been prepared by Technical Committee ECISS/TC 20 “Methods of chemical analysis of ferrous products”, the secretariat of which is held by SIS. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest b
15、y December 2006, and conflicting national standards shall be withdrawn at the latest by December 2006. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Rep
16、ublic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. ISO 17054:2010(E) ISO 2010 All rights reserved1EN 1031
17、5:2006 (E) 4 1 Scope This European Standard specifies a procedure on how to improve the performance of a routine XRF method, already in use for analysis of high alloy steels, by using a ”near by technique”. The ”near by technique” requires at least one target sample (preferable a CRM) of a similar c
18、omposition as the unknown sample. The method is applicable to elements within the concentration ranges according to Table 1: Table 1 Concentration ranges Element Concentration range, % (m/m) aSi 0,05 to 1,5 Mn 0,05 to 5,0 P 0,005 to 0,035 Cr 10 to 25 Ni 0,1 to 30 Mo 0,1 to 6,5 Cu 0,02 to 1,5 Co 0,01
19、5 to 0,30 V 0,015 to 0,15 Ti 0,015 to 0,50 Nb 0,05 to 1,0 aThe concentration ranges specified, represents those ranges studied during the precision test. The procedure has the potential to be used outside those ranges but it needs to be validated by each laboratory in every case. The method is appli
20、cable to analysis of either chill-cast or wrought samples having a diameter of at least 25 mm and with a carbon concentration of less than 0,3 % (see NOTE). Other elements should have a concentration below 0,2 %. NOTE High carbon concentrations, in combination with high Mo and Cr concentrations, cou
21、ld have undesirable structural effects on the sample and could affect the determination of phosphorus and chromium, in particular. Matrix effects exist between the elements listed. To compensate for those inter-element effects, mathematical corrections shall be applied. A variety of computer program
22、s for corrections is commonly used and included in the software package from the manufacturers. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest e
23、dition of the referenced document (including any amendments) applies. EN ISO 10280, Steel and iron Determination of titanium content Diantipyrylmethane spectrophotometric method (ISO 10280:1991) ISO 17054:2010(E) ISO 2010 All rights reserved2 EN 10315:2006 (E) 5 EN ISO 10700, Steel and iron Determin
24、ation of manganese content Flame atomic spectrometric method (ISO 10700:1994) EN ISO 10714, Steel and iron Determination of phosphorus content Phosphovanadomolybdate spectrophotometric method (ISO 10714:1992) EN ISO 14284, Steel and iron Sampling and preparation of samples for the determination of c
25、hemical composition (ISO 14284:1996) CR 10299, Guidelines for the preparation of standard routine methods with wavelength-dispersive X-ray fluorescence spectrometry ISO 4829-1, Steel and cast iron Determination of total silicon content Reduced molybdosilicate spectrophotometric method Part 1: Silico
26、n contents between 0,05 and 1,0 % ISO 4829-2, Steel and iron Determination of total silicon content Reduced molybdosilicate spectrophotometric method Part 2: Silicon contents between 0,01 and 0,05 % ISO 4937, Steel and iron Determination of chromium content Potentiometric or visual titration method
27、ISO 4938, Steel and iron Determination of nickel content Gravimetric or titrimetric method ISO 4942, Steel and iron Determination of vanadium content N-BPHA spectrophotometric method ISO 4946, Steel and cast iron Determination of copper content 2,2-Diquinolyl spectrophotometric method ISO 9441, Stee
28、l Determination of niobium content PAR spectrophotometric method ISO 11652, Steel and iron Determination of cobalt content Flame atomic absorption spectrometric method ISO/TS 13899-1, Steel Determination of Mo, Nb and W contents in alloyed steel Inductively coupled plasma atomic emission spectrometr
29、ic method Part 1: Determination of Mo content 3 Principle The sample is finished to a clean uniform surface and then irradiated by an X-ray beam of high energy. The secondary X-rays produced are dispersed by means of crystals and the intensities are measured by detectors at selected characteristic w
30、avelengths. The measuring time is set to reach below a specified counting statistical error. Preliminary concentrations of the elements are determined by relating the measured intensities of unknown samples to analytical curves prepared from reference materials, CRM or RM, of known compositions. The
31、 final concentrations are calculated by using the results obtained by measuring a CRM of the same grade. The correction is made for the elements of interest by using the difference between the certified value and the value obtained during the measurement of the CRM (the “near by technique“). A fixed
32、 channel or a sequential system may be used to provide simultaneous or sequential determinations of element concentrations. 4 Reagents 4.1 P10 gas (90 % argon mixed with 10 % methane) for the gas-flow proportional detector. 4.2 A set of Certified Reference Materials (CRM). All reference material use
33、d for calibration or calibration verification shall be certified by internationally recognized bodies (see NOTE). ISO 17054:2010(E) ISO 2010 All rights reserved3EN 10315:2006 (E) 6 NOTE A complete set of internationally recognised CRMs to cover all elements at all concentration levels may not be ava
34、ilable. Other CRMs could be used if the material is certified by referee procedures based on SI units. 4.3 Reference materials used for standardization or for statistical process control (SPC samples) of the method need not to be certified, but adequate homogeneity data shall be available. Select th
35、e standardization samples in such a way that they cover at least the low and top end of the concentration range for each element. 4.4 Pure ethanol. 5 Apparatus 5.1 Sample preparation equipment For the final preparation, use a surface grinder with 180-grit or finer aluminium oxide (see NOTE) belts or
36、 discs. Other preparation procedures are also possible (turning, for example). But in each case, the surfaces of CRMs, RMs and samples shall be prepared under the same conditions. NOTE Paper made of silicon carbide will disable Si determinations and paper made of zirconium oxide will disable Zr dete
37、rminations, and aluminium determinations also sometimes as zirconium oxide is often contaminated by aluminium oxide. 5.2 X-ray fluorescence spectrometer A simultaneous or sequential wavelength dispersive spectrometer. This test method is written for use with commercially available instruments. 5.3 X
38、-ray tube Tube with a high-purity element target. Rhodium is recommended for analysis of steel. 5.4 Analysing crystals To cover all elements specified in this method, flat or curved crystals made of LiF(200) and PE (for light elements, atom no. approximately 22) are required. Crystals made of LiF(22
39、0) and Ge or other crystals optimized for individual elements may also be used. 5.5 Collimators For sequential instruments, a two collimator system is necessary: a coarse collimator for light elements (atom no. approximately 22) and a fine collimator for heavy elements. 5.6 Detectors One scintillati
40、on detector for heavy elements and one gas-flow proportional detector for light elements (atom no. approximately 22). Sealed proportional detectors may also be used. The combination of detectors and how to use them, in single or dual mode, depends on the equipment used. See the operation manual for
41、the equipment in question. 5.7 Vacuum system A vacuum system capable of keeping the pressure at a constant level below at least 40 Pa during the measurement. ISO 17054:2010(E) ISO 2010 All rights reserved4 EN 10315:2006 (E) 7 5.8 Measuring system An electronic circuit capable of amplifying and integ
42、rating pulses received from the detectors. A computer system with an adequate software package for the calculation of concentrations based on the measured intensities. 6 Safety precautions They shall be in accordance with national regulations for X-ray equipment. X-ray equipment shall be used only u
43、nder the guidance and supervision of a responsible, qualified person. 7 Sampling Carry out sampling in accordance with EN ISO 14284 or appropriate national standards for iron and steel. 8 Final sample preparation 8.1 Preparation of CRMs and test samples Grind the samples on a surface grinder (see 5.
44、1) or turn them until the surface is flat and has a uniform finish. The minimum sample size is approximately 25 mm in diameter and with a thickness of at least 5 mm. Before measurement, clean the surface with pure ethanol to avoid dust on the exposed sample surface. If the samples have been stored i
45、n air for more than a day, always prepare the surface before the measurement. 8.2 Preparation of standardization samples and check samples Samples used as standardization samples or used for checking the instrument performance should be prepared in the same way as were done during the calibration of
46、 the routine method. It is recommended that those samples should have a mirror like surface in order to avoid any influence from the sample preparation. The samples should be stored in a desiccator between measurements. Clean the surface before measurement with pure ethanol. 9 Procedure 9.1 Preparat
47、ion of apparatus Prepare the instrument for operation according to the manufacturers instructions. Since most of the instruments are used for routine analyses, it is assumed that they are running and in most cases also already are calibrated for steel. If the instrument has been turned off for a lon
48、g period (several hours), ensure that the conditions have stabilized before starting the measurements, e.g. temperature and vacuum. Verify the calibration status by analysing the SPC samples or CRMs. ISO 17054:2010(E) ISO 2010 All rights reserved5EN 10315:2006 (E) 8 9.2 Measurements 9.2.1 ”Near by t
49、echnique” method Select a Certified Reference Material (CRM) with a composition close to the composition of the unknown sample. The required closeness in composition of the CRM is specified in 13.2. Load and measure the unknown sample and the CRM in a close sequence according to the instrument users manual. Be sure that the sample is properly fixed in the sample cup. It is assumed that the instrument is equipped with a sample spinner in order to avoid effects from grinding striation
