Chemical analysis of ferrous materials - Inductively coupled plasma optical emission spectrometric analysis of unalloyed and low alloyed steels - Determination of Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (total) and Sn [Routine method]

This European Standard specifies an inductively coupled plasma optical emission spectrometry routine method for the analysis of unalloyed and low alloyed steels, whose iron content shall be at least 95 %.
This method is applicable to the elements listed in Table 1 within the ranges shown.
Table 1 - Application ranges
(...)
In all cases, the ranges specified can be extended or adapted (after validation) for the determination of other mass fractions, provided that the iron content in the samples under concern is above 95 %.
Other elements may be included. However such elements and their mass fractions should be carefully checked, taking into account the possible interferences, the sensitivity, the resolution and the linearity criteria of each instrument and each wavelength.
Depending also on the sensitivity of each instrument, suitable dilutions of the calibration and the test sample solutions may be necessary.
Moreover, even if the method described is "multi elemental", it is not absolutely necessary to carry out the determination of all the elements of its scope simultaneously: the measurement conditions have to be optimised by each laboratory, depending on the performances of each apparatus available.
NOTE 1   The accuracy of the method is unsatisfactory for phosphorus contents from 0,05 to 0,1 %.
NOTE 2   The trueness of the method couldn't be checked for vanadium contents below 0,05 %.
NOTE 3   The precision of the method is unsatisfactory for aluminium (total) contents below 0,02 %.

Chemische Analyse von Eisenwerkstoffen - Analyse von unlegierten und niedrig legierten Stählen mittels optischer Emissionsspektrometrie mit induktiv gekoppeltem Plasma - Bestimmung von Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (gesamt) und Sn [Routineverfahren]

Diese Europäische Norm legt ein Verfahren der optischen Emissionsspektrometrie mit induktiv gekoppeltem Plasma (ICP-Emissionsspektrometrie) fest, das routinemäßig zur Analyse unlegierter und niedrig legierter Stähle anzuwenden ist, die einen Eisengehalt von mindestens 95 % haben. Das Verfahren ist auf die in Tabelle 1 aufgeführten Elemente innerhalb der angegebenen Bereiche anwendbar.
Alle angegebenen Bereiche können erweitert oder (nach einer Validierung) so angepasst werden, dass auch andere Massenanteile zu bestimmen sind, sofern die zu analysierenden Proben einen Eisenanteil von mehr als 95 % haben. Das Verfahren darf auch dann angewendet, wenn weitere Elemente enthalten sind. Diese Elemente und ihre Massenanteile sollten jedoch unter Berücksichtigung möglicher Störungen, der Empfindlichkeit, der Auflösung und der Linearitätskriterien für jedes ICP-Emissionsspektrometer und für jede Wellenlänge sorgfältig überprüft werden. Entsprechend der Empfindlichkeit des jeweiligen ICP-Emissionsspektrometers kann es notwendig sein, geeignete Verdünnungen der Kalibrier- und der Untersuchungsprobenlösungen anzuwenden. Obwohl das beschriebene Verfahren zur „Mehrelementbestimmung“ angewendet wird, müssen nicht unbedingt alle im Anwendungsbereich angegebenen Elemente gleichzeitig bestimmt werden; die Messbedin-gungen sind in jedem Prüflaboratorium in Abhängigkeit von den Leistungsparametern der verfügbaren Prüfgeräte zu optimieren. ANMERKUNG 1 Für Phosphorgehalte von 0,05 % bis 0,1 % ist die Genauigkeit dieses Verfahren nicht zufrieden stellend. ANMERKUNG 2 Für Vanadiumgehalte unter 0,05 % konnte die Richtigkeit des Verfahrens nicht überprüft werden. ANMERKUNG 3 Für Aluminiumgehalte (Gesamtgehalte) unter 0,02 % ist die Präzision dieses Verfahrens nicht zufrieden stellend.

Analyse chimique des matériaux ferreux - Analyse des aciers non alliés et faiblement alliés par spectrométrie d'émission optique avec source à plasma induit - Détermination de Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (total) et Sn [Méthode de routine]

La présente Norme européenne spécifie une méthode de routine, par spectrométrie d'émission optique avec
source à plasma induit, pour l’analyse des aciers non alliés et faiblement alliés ayant une teneur en fer d’au
moins 95 %.
Cette méthode s’applique aux éléments listés dans le Tableau 1, dans les domaines de teneur indiqués.
Dans tous les cas, les domaines spécifiés peuvent être étendus ou adaptés (après validation) pour la
détermination des autres teneurs, à condition que la teneur en fer des échantillons concernés soit supérieure
à 95 %.
D'autres éléments peuvent être inclus. Il convient toutefois de contrôler, avec la plus grande attention, ces
éléments et leurs teneurs, en tenant compte des interférences éventuelles, de la sensibilité, de la résolution et
des critères de linéarité de chaque instrument et chaque longueur d'onde.
En fonction, également, de la sensibilité de chaque instrument, des dilutions appropriées des solutions
d’étalonnage et des solutions d’échantillon peuvent être nécessaires.
Qui plus est, même si la méthode décrite est « multiélémentaire », il n’est pas absolument nécessaire de
déterminer simultanément tous les éléments de son domaine d’application : les conditions de mesurage
doivent être optimisées par chaque laboratoire, en fonction des performances de chaque appareil disponible.
NOTE 1 L'exactitude de la méthode n’est pas satisfaisante pour les teneurs en phosphore comprises entre 0,05 et
0,1 %.
NOTE 2 La justesse de la méthode n’a pas pu être vérifiée pour les teneurs en vanadium inférieures à 0,05 %.
NOTE 3 La fidélité de la méthode n’est pas satisfaisante pour les teneurs en aluminium (total) inférieures à 0,02 %.

Kemična analiza železovih zlitin - Analiza z direktno spektrometrijo optične emisije z induktivno sklopljeno plazmo nelegiranih in malolegiranih jekel - Določevanje Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (celotni) in Sn [rutinska metoda]

Ta dokument določa rutinsko metodo z emisijsko spektrometrijo z induktivno sklopljeno plazmo za analizo nelegiranih in malolegiranih jekel.

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2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.@Chemische Analyse von Eisenwerkstoffen - Analyse von unlegierten und niedrig legierten Stählen mittels optischer Emissionsspektrometrie mit induktiv gekoppeltem Plasma - Bestimmung von Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (gesamt) und Sn [Routineverfahren]Analyse chimique des matériaux ferreux - Analyse des aciers non alliés et faiblement alliés par spectrométrie d'émission optique avec source à plasma induit - Détermination de Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (total) et Sn [Méthode de routine]Chemical analysis of ferrous materials - Inductively coupled plasma optical emission spectrometric analysis of unalloyed and low alloyed steels - Determination of Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (total) and Sn [Routine method]77.040.30Kemijska analiza kovinChemical analysis of metalsICS:Ta slovenski standard je istoveten z:EN 10351:2011SIST EN 10351:2011en,fr,de01-november-2011SIST EN 10351:2011SLOVENSKI

STANDARD
SIST EN 10351:2011
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN 10351
March 2011 ICS 77.140.10; 77.140.45 English Version

Chemical analysis of ferrous materials - Inductively coupled plasma optical emission spectrometric analysis of unalloyed and low alloyed steels - Determination of Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (total) and Sn [Routine method]

Analyse chimique des matériaux ferreux - Analyse des aciers non alliés et faiblement alliés par spectrométrie d'émission optique avec source à plasma induit - Détermination de Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (total) et Sn [Méthode de routine]

Chemische Analyse von Eisenwerkstoffen - Analyse von unlegierten und niedrig legierten Stählen mittels optischer Emissionsspektrometrie mit induktiv gekoppeltem Plasma -Bestimmung von Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (gesamt) und Sn [Routineverfahren] This European Standard was approved by CEN on 15 January 2011.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member.

This European Standard exists in three official versions (English, French, German). A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, 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.

EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre:
Avenue Marnix 17,

B-1000 Brussels © 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 10351:2011: ESIST EN 10351:2011

EN 10351:2011 (E) 2 Contents Page Foreword ..............................................................................................................................................................31Scope ......................................................................................................................................................42Normative references ............................................................................................................................43Principle ..................................................................................................................................................54Reagents .................................................................................................................................................55Apparatus ...............................................................................................................................................86Sampling .................................................................................................................................................87Sample solution preparation ................................................................................................................88Calibration process ...............................................................................................................................99Determination ...................................................................................................................................... 1210Expression of results ......................................................................................................................... 1511Precision .............................................................................................................................................. 1512Test report ........................................................................................................................................... 19Annex A (informative)

Plasma optical emission spectrometer — Suggested performance criteria to be checked ...................................................................................................................................... 20Annex B (normative)

Synoptic of the operations related to Clause 9 ........................................................ 24Annex C (informative)

Test samples used for the validation precision test .............................................. 25Annex D (informative)

Detailed results obtained from the validation precision test ................................ 26Annex E (informative)

Graphical representation of the precision data ...................................................... 35Bibliography ..................................................................................................................................................... 44 SIST EN 10351:2011

EN 10351:2011 (E) 3 Foreword This document (EN 10351:2011) has been prepared by Technical Committee ECISS/TC 102 “Methods of chemical analysis for iron and steel”, 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 by September 2011, and conflicting national standards shall be withdrawn at the latest by September 2011. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, 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. SIST EN 10351:2011

EN 10351:2011 (E) 4 1 Scope This European Standard specifies an inductively coupled plasma optical emission spectrometry routine method for the analysis of unalloyed and low alloyed steels, whose iron content shall be at least 95 %. This method is applicable to the elements listed in Table 1 within the ranges shown. Table 1 — Application ranges Element Mass fraction % min. max. Mn 0,005 2,00 P 0,005 0,05 Cu 0,005 0,80 Ni 0,010 2,00 Cr 0,010 1,60 Mo 0,005 0,80 V 0,002 0,40 Co 0,002 0,10 Al (total) 0,020 0,30 Sn 0,001 0,10

In all cases, the ranges specified can be extended or adapted (after validation) for the determination of other mass fractions, provided that the iron content in the samples under concern is above 95 %. Other elements may be included. However such elements and their mass fractions should be carefully checked, taking into account the possible interferences, the sensitivity, the resolution and the linearity criteria of each instrument and each wavelength. Depending also on the sensitivity of each instrument, suitable dilutions of the calibration and the test sample solutions may be necessary. Moreover, even if the method described is "multi elemental", it is not absolutely necessary to carry out the determination of all the elements of its scope simultaneously: the measurement conditions have to be optimised by each laboratory, depending on the performances of each apparatus available. NOTE 1 The accuracy of the method is unsatisfactory for phosphorus contents from 0,05 to 0,1 %. NOTE 2 The trueness of the method couldn't be checked for vanadium contents below 0,05 %. NOTE 3 The precision of the method is unsatisfactory for aluminium (total) contents below 0,02 %. 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 edition of the referenced document (including any amendments) applies. CEN/TR 10345:2008, Guideline for statistical data treatment of inter laboratory tests for validation of analytical methods SIST EN 10351:2011

EN 10351:2011 (E) 5 EN ISO 14284, Steel and iron — Sampling and preparation of samples for the determination of chemical composition (ISO 14284:1996) ISO 648, Laboratory glassware — One-mark pipettes ISO 1042, Laboratory glassware — One-mark volumetric flasks ISO 5725-1:1994, Accuracy (trueness and precision) of measurement methods and results — Part 1: General principles and definitions ISO 5725-2:1994, Accuracy (trueness and precision) of measurement methods and results — Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method ISO 5725-3:1994, Accuracy (trueness and precision) of measurement methods and results — Part 3: Intermediate measures of the precision of a standard measurement method 3 Principle Dissolution of a test portion with nitric and hydrochloric acids. Filtration and ignition of the acid insoluble residue. Removal of silica with hydrofluoric acid. Fusion of the residue with a mixture of orthoboric acid and potassium carbonate, dissolution of the melt with acid and addition of this solution to the reserved filtrate. After suitable dilution and, if necessary, addition of an internal reference element, nebulisation of the solution into an inductively coupled plasma optical emission spectrometer and measurement of the intensity of the emitted light from each element (including, where relevant, the intensity of the internal reference element). 4 Reagents During the analysis, use only reagents of recognised analytical grade and only distilled water or water of equivalent purity. The same reagents should be used for the preparation of calibration solutions and of sample solutions. 4.1 Hydrochloric acid, HCl (ρρρρ20

= 1,19 g/ml) 4.2 Hydrochloric acid, solution 1 + 1 Add 500 ml of hydrochloric acid (4.1) to 500 ml of water. 4.3 Nitric acid, HNO3 (ρρρρ20 = 1,33 g/ml) 4.4 Nitric acid, solution 1 + 1 Add 500 ml of nitric acid (4.3) to 500 ml of water. 4.5 Hydrofluoric acid, HF (ρρρρ20 = 1,13 g/ml) WARNING — Hydrofluoric acid is extremely irritating and corrosive to skin and mucous membranes producing severe skin burns which are slow to heal. In the case of contact with skin, wash well with water, apply a topical gel containing 2,5 % (mass fraction) calcium gluconate, and seek immediate medical treatment. 4.6 Sulphuric acid, H2SO4 (ρρρρ20 = 1,84 g/ml) 4.7 Sulphuric acid, solution 1 + 1 SIST EN 10351:2011

EN 10351:2011 (E) 6 Add 25 ml of sulphuric acid (4.6) to 25 ml of water and allow it to cool. 4.8 Fusion reagent 4.8.1 Fusion mixture Mix one part by mass of orthoboric acid, H3BO3 and one part of potassium carbonate anhydrous, K2CO3. 4.8.2 Fusion mixture, 100 g/l solution In a suitable beaker, dissolve 25 g of the fusion mixture (4.8.1). Heat if necessary. After cooling, transfer the solution quantitatively into a 250 ml one-mark volumetric flask, dilute to the mark with water and mix well. 4.9 Aluminium, 1 g/l standard solution Weigh (0,5 ± 0,001) g of aluminium (99,99 % purity) and transfer into a 400 ml beaker. Add 50 ml of hydrochloric acid solution (4.2) and heat gently until aluminium is completely dissolved. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Al. 4.10 Chromium 1 g/l standard solution Weigh (0,5 ± 0,001) g of chromium (99,99 % purity) and transfer into a 250 ml beaker. Add 40 ml of hydrochloric acid (4.1) and heat gently until chromium is completely dissolved. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Cr. 4.11 Cobalt 1 g/l standard solution Weigh (0,5 ± 0,001) g of cobalt (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 5 ml of hydrochloric acid (4.1) and 5 ml of nitric acid (4.3). Heat gently until the metal is dissolved and then boil until nitrous fumes have been expelled. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Co. 4.12 Copper 1 g/l standard solution Weigh (0,5 ± 0,001) g of copper (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 10 ml of nitric acid solution (4.4). Heat gently until the metal is dissolved, then boil until nitrous fumes have been expelled. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Cu. 4.13 Manganese 1 g/l standard solution The manganese used to prepare the solution is released from superficial oxide possibly present by introducing a few grams of metal in a 250 ml beaker containing 150 to 160 ml of water and 15 to 20 ml of sulphuric acid (4.6). Shake and after a few seconds, allow the solution to settle and add water. Repeat the water cleaning several times. Remove the metallic manganese and rinse with acetone. Dry the metal in an oven at 100 °C for 2 minutes or with a hair dryer. Cool in a desiccator. Weigh (0,5 ± 0,001) g of this purified manganese and transfer into a 250 ml beaker. Dissolve it in 5 ml of hydrochloric acid (4.1) and 10 ml of nitric acid solution (4.4). Heat gently until the metal is dissolved. After SIST EN 10351:2011

EN 10351:2011 (E) 7 cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Mn. 4.14 Molybdenum 1 g/l standard solution Weigh (0,5 ± 0,001) g of molybdenum (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 10 ml of hydrochloric acid (4.1) and 10 ml of nitric acid (4.3). Heat gently until the metal is dissolved. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Mo. 4.15 Nickel 1 g/l standard solution Weigh (0,5 ± 0,001) g of nickel (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 10 ml of nitric acid solution (4.4). Heat gently until the metal is dissolved, then boil until nitrous fumes have been expelled. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Ni. 4.16 Phosphorus 1 g/l standard solution Weigh (2,197 ± 0,001) g of dried potassium dihydrogen phosphate, transfer into a 250 ml beaker and dissolve it with water. Transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of P. 4.17 Tin 1 g/l standard solution [freshly prepared] Weigh (0,5 ± 0,001) g of tin (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 50 ml of hydrochloric acid (4.1). Heat gently until the metal is dissolved. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Sn. 4.18 Vanadium 1 g/l standard solution Weigh (0,5 ± 0,001) g of vanadium (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 30 ml of hydrochloric acid (4.1) and 10 ml of nitric acid (4.3). Heat gently until the metal is dissolved. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of V. NOTE Standard solutions whose preparations are described under items 4.9 to 4.18 can be replaced by commercial available standard solutions, provided that they are supplied by a recognised producer and their traceability fully documented. 4.19 Internal reference element solution, 1 g/l Choose a suitable element to be added as internal reference and prepare a 1 g/l solution. NOTE Elements as Cd, Fe, Sc and Y were used for this purpose during the validation precision test of this method. SIST EN 10351:2011

EN 10351:2011 (E) 8 4.20 Pure iron The purity of the iron selected shall be at least ten times better than the low limit of the scope of each element included in the present method. 5 Apparatus All volumetric glassware shall be Class A and calibrated, in accordance with ISO 648 or ISO 1042 as appropriate. 5.1 Close texture filter paper and/or 0,45 µm cellulose nitrate filter 5.2 Filter funnel suitable for 0,45 µm filters Two-pieces acid-resistant filter funnel with a support screen between the funnel body and stem, designated for the vacuum filtration of liquids. The stem of the filter is fitted with a ground glass cap stopper or a rubber stopper for insertion into an opening of the vacuum vessel. 5.3 Vacuum vessel With an opening to allow the insertion of the stopper of the filter funnel stem. 5.4 Platinum crucibles and covers 5.5 Optical emission spectrometer, equipped with inductively coupled plasma This shall be equipped with a nebulisation system. The instrument used will be satisfactory if, after optimising in accordance with the manufacturer’s instructions, it meets the performance criteria given in Annex A. 6 Sampling Sampling shall be carried out in accordance with EN ISO 14284 or with an appropriate national standard for steels. 7 Sample solution preparation 7.1 Test portion Weigh, to the nearest 0,001 g, 1 g of the test sample. 7.2 Preparation of the test solution 7.2.1 Dissolution of the test portion Transfer the test portion (7.1) into a 250 ml or 400 ml beaker. Add 5 ml of nitric acid (4.3) and 20 ml of hydrochloric acid solution (4.2). Cover and heat gently until the attack reaction ceases. Heat at a temperature of about 95 °C, for about 5 minutes. Allow to cool. Rinse the beaker cover and the walls of the beaker with water. SIST EN 10351:2011

EN 10351:2011 (E) 9 7.2.2 Filtration of the test solution 7.2.2.1 Including total aluminium determination Place a 0,45 µm cellulose nitrate filter (5.1) on the support screen of a filter funnel (5.2). Moisten the filter with water and join the body and stem of the funnel. Insert the stopper of the filter funnel stem into a vacuum vessel (5.3). Apply vacuum gently to the vacuum vessel and filter the solution. Wash the funnel sides and residue with warm water several times. Stop the vacuum gently. Wipe the funnel sides with a close texture filter paper, then place the cellulose nitrate filter in this filter paper and fold them. Transfer the folded filters into a platinum crucible (5.4) and cover with a suitable platinum cover. Transfer the filtrate quantitatively into a 200 ml one-mark volumetric flask. 7.2.2.2 Excluding total aluminium determination Filter the solution through a close texture filter paper and collect the filtrate into a 200 ml one-mark volumetric flask. Wash the filter paper and residue with warm water several times and collect the washings in the volumetric flask. Transfer the filter into a platinum crucible (5.4) and cover with a suitable platinum cover. 7.2.3 Treatment of the insoluble residue Introduce the crucible in a COLD furnace, then switch it on in order to reach a temperature of about 900 °C. Allow to stand at 900 °C for about 15 min. Cool the crucible. Add into the crucible 0,5 to 1,0 ml of sulphuric acid solution (4.7) and 2 ml of hydrofluoric acid (4.5). Evaporate to dryness and cool. Add 1,0 g of the fusion mixture (4.8.1). Fuse the content of the crucible in a muffle furnace at 1 000 °C for

15 min to 20 min. Cool the crucible and add 20 ml of hydrochloric acid solution (4.2) to the solidified melt. Heat gently, in order to dissolve the fusion products. Allow the crucible to cool and add this solution quantitatively to the filtrate in the 200 ml volumetric flask. If an internal reference element is used add, with a calibrated pipette, 10 ml of the internal reference element solution (4.19). NOTE 1 Depending on the instrument performances, the volume and/or the concentration of the internal reference element solution may be different. Dilute to the mark with water and mix. NOTE 2 Depending on the instrument performances, suitable dilutions of the sample solution and of the calibration solutions may be necessary. 8 Calibration process 8.1 Steps The calibration process is subdivided into calibration and drift compensation by re-calibration. SIST EN 10351:2011

EN 10351:2011 (E) 10 8.2 Preparation of the multi-elemental calibration solutions Weigh the quantities of pure iron (4.20) shown in Table 2 and introduce them into each of a series of 250 ml or 400 ml beakers. Add 20 ml of the hydrochloric acid solution (4.2) to each beaker. Cover with a watch glass and heat gently. When the attack reaction ceases, add 5 ml of nitric acid (4.3). Heat until nitrous fumes have been expelled. Rinse the cover and the walls of the beaker with water and heat to boiling. Allow to cool and transfer each calibration solution into a 200 ml one-mark volumetric flask. With calibrated pipettes, add the quantities (volumes) of the mono-elemental standard solutions (4.9 to 4.18) or of commercial available mono-elemental standard solutions of each element shown in Table 2. Add to each volumetric flask 10 ml of the fusion mixture solution (4.8.2) and 10 ml of hydrochloric acid (4.1). If an internal reference element is used add, with a calibrated pipette, 10 ml of the internal reference element solution (4.19). NOTE 1 Refer to NOTE 1 under 7.2.3. Dilute to the mark with water and mix. NOTE 2 Refer to NOTE 2 under 7.2.3. Following this same procedure, also prepare a pure iron solution (labelled F0 in Table 2), to be used to control if the lowest content for each element is enough high to be considered as "different from the zero point". Strong care should be taken in order to ensure that the quantity of acids remains about the same in the calibration solutions (namely when commercially available standard solutions are used), in the sample solutions and in the Certified Reference Materials solutions prepared to check the trueness of the calibration. The calibration curves obtained may be stored within a computer, connected to the inductively coupled plasma optical emission spectrometer. NOTE 3 The trueness of these calibration functions should be checked by measuring at least two suitable Certified Reference Materials or Internal Reference Materials sample solutions (just above the low point and just below the high point of each calibration range). SIST EN 10351:2011

EN 10351:2011 (E) 11 Table 2 — Composition of the multi-elemental calibration solutions Element Label F0 F1 F2 F3 F4 Fe 1 000,0 mg 100,00 % 958,3 mg 95,83 % 979,7 mg 97,97 % 971,2 mg 97,12 % 989,7 mg 98,97 % Mn (4.13)

------ 20 mg [2,0 %]
20 ml 2 mg [0,2 %]
2 ml 0,02 mg [0,002 %]
a 0,2 mg [0,02 %] b P (4.16)
------ 0,05 mg [0,005 %] c 0,1 mg [0,01 %] d 0,5 mg [0,05 %]
e 1 mg [0,1 %]
1 ml Cu (4.12)
------ 0,5 mg [0,05 %]
f 8 mg [0,8 %]
8 ml 0,05 mg [0,005 %]
g 1 mg [0,1 %]
1 ml Ni (4.15)
------ 20 mg [2,0 %]
20 ml 5 mg [0,5 %]
5 ml 0,05 mg [0,005 %]
h 0,5 mg [0,05 %]
i Cr (4.10)
------ 0,05 mg [0,005 %] j 0,5 mg [0,05 %]
k 16 mg [1,6 %]
16 ml 5 mg [0,5 %]
5 ml Mo (4.14)
------ 0,05 mg [0,005 %] l 0,5 mg [0,05 %]
m 8 mg [0,8 %]
8 ml 1 mg [0,1 %]
1 ml V (4.18)
------ 0,02 mg [0,002 %] n 4 mg [0,4 %]
4 ml 0,2 mg [0,02 %]
o 1 mg [0,1 %]
1 ml Co (4.11)
------ 0,02 mg [0,002 %] p 0,1 mg [0,01 %] q 1 mg [0,1 %]
1 ml 0,05 mg [0,005 %] r Al (4.9)
------ 0,03 mg [0,003 %] s 0,1 mg [0,01 %] t 3 mg [0,3 %]
3 ml 0,5 mg [0,05 %]
u Sn (4.17)
------ 1 mg [0,1 %]
1 ml 0,05 mg [0,005 %] v 0,01 mg [0,001 %]

w 0,1 mg [0,01 %] x a 2 ml of a 0,01 g/l manganese standard solution m 5 ml of a 0,1 g/l molybdenum standard solution b 2 ml of a 0,1 g/l manganese standard solution n 2 ml of a 0,01 g/l vanadium standard solution c 5 ml of a 0,01 g/l phosphorus standard solution o 2 ml of a 0,1 g/l vanadium standard solution d 1 ml of a 0,1 g/l phosphorus standard solution p 2 ml of a 0,01 g/l cobalt standard solution e 5 ml of a 0,1 g/l phosphorus standard solution q 1 ml of a 0,1 g/l cobalt standard solution f 5 ml of a 0,1 g/l copper standard solution r 5 ml of a 0,01 g/l cobalt standard solution g 5 ml of a 0,01 g/l copper standard solution s 3 ml of a 0,01 g/l aluminium standard solution h 5 ml of a 0,01 g/l nickel standard solution t 1 ml of a 0,1 g/l aluminium standard solution i 5 ml of a 0,1 g/l nickel standard solution u 5 ml of a 0,1 g/l aluminium standard solution j 5 ml of a 0,01 g/l chromium standard solution v 5 ml of a 0,01 g/l tin standard solution k 5 ml of a 0,1 g/l chromium standard solution w 1 ml of a 0,01 g/l tin standard solution l 5 ml of a 0,01 g/l molybdenum standard solution x 1 ml of a 0,1 g/l tin standard solution

SIST EN 10351:2011

EN 10351:2011 (E) 12 8.3 Re-calibration Drifts in the spectrometer readings shall be corrected by using the re-calibration procedure described in the manufacturer's instruction manual. For that purpose the synthetic multi-elemental solutions (8.2), used for the calibration or suitable Certified Reference Materials or Internal Reference Materials solutions may be used. It is strongly recommended to carry out a re-calibration of the instrument before the analysis of each set of unknown samples. 9 Determination 9.1 Synoptic

The synoptic of the operations described in this paragraph is given in Annex B. 9.2 Adjustment of the apparatus Start the inductively coupled plasma optical emission spectrometer and let it stabilise in accordance with the manufacturer’s instructions before taking any measurements. At the wavelengths of the analytical lines specified in Table 3, adjust all relevant instrumental parameters, as well as the pre-spraying and the integrating times, according to the instrument manufacturer’s instructions while aspirating (for each element) the highest concentration calibration solution. Table 3 — Wavelengths for determinations related with unalloyed and low alloyed steels Element Wavelength (nm) Mn 257,6 or 293,1 P 178,2 Cu 324,7 or 327,4 Ni 231,6 Cr 205,6 or 206,6 or 267,7

Mo 202,0 or 281,6 V 309,3 or 310,2 or 311,1 Co 228,6 or 230,8 Al 394,4 or 396,2
Sn 189,9 Cd 214,1 Fe 271,4 Sc 361,4 Y 371,0

NOTE 1 Depending on the instrument configuration these parameters may include the outer, intermediate or central gas flow-rates, the torch position, the entrance slits, the exit slits and the photomultiplier tubes voltage. NOTE 2 Other wavelengths may be used, provided that interferences, sensivity, resolution and linearity criteria have been carefully investigated. SIST EN 10351:2011

EN 10351:2011 (E) 13 Prepare the software for measurements of the intensity, and for the calculation of the mean value and relative standard deviation corresponding to each analytical line. Each time the internal reference element is used, prepare the software to calculate the ratio between the intensity of each analyte and the intensity of the internal reference element. 9.3 Spectrometric measurements of the calibration solutions Carry out the spectrometric measurements of the calibration solutions (8.2). A simultaneous spectrometer shall be available for measurements using internal reference element (ratio mode). For each calibration solution, three to five integrations are necessary in order to calculate the mean intensities or the mean ratioed intensities. Establish the calibration curves using the measured mean intensities or ratioed mean intensities and the corresponding analyte amounts, expressed in percentage (mass fraction). Use a software suitable for regression calculations and calculate the relevant correlation coefficients: these coefficients should be, at least, 0,999. If this criterion is not conforming, check eventual discrepancies within the multi-elemental standard solutions preparation, or adapt the analytical range(s) either by performing suitable dilutions of the calibration standard solutions or by adapting the analytical range itself. If some calibration curves are second degree mathematical functions within the range of content, the number of multi-elemental calibration solution should be increased. The trueness of these calibration functions shall be checked by measuring at least two suitable Certified Reference Materials (or Internal Reference Materials) sample solutions (just above the low point and just below the high point of each calibr

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2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Analyse chimique des matériaux sidérurgiques - Analyse des aciers faiblement alliés par spectrométrie d'émission optique avec source à plasma induit - Détermination de Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (total) et Sn [Méthode de routine]Chemical analysis of ferrous materials - Inductively coupled plasma optical emission spectrometric analysis of low alloyed steels - Determination of Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (total) and Sn [Routine method]77.040.30Kemijska analiza kovinChemical analysis of metalsICS:Ta slovenski standard je istoveten z:prEN 10351oSIST prEN 10351:2009en,fr01-september-2009oSIST prEN 10351:2009SLOVENSKI

STANDARD
oSIST prEN 10351:2009

EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMDRAFTprEN 10351June 2009ICS 77.140.10; 77.140.45 English VersionChemical analysis of ferrous materials - Inductively coupledplasma optical emission spectrometric analysis of low alloyedsteels - Determination of Mn, P, Cu, Ni, Cr, Mo, V, Co, Al (total)and Sn [Routine method]Analyse chimique des matériaux sidérurgiques - Analysedes aciers faiblement alliés par spectrométrie d'émissionoptique avec source à plasma induit - Détermination de Mn,P, Cu, Ni, Cr, Mo, V, Co, Al (total) et Sn [Méthode deroutine]This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee ECISS/TC 20.If this draft becomes a European Standard, CEN members are bound to comply with the CEN/CENELEC Internal Regulations whichstipulate the conditions for giving this European Standard the status of a national standard without any alteration.This draft European Standard was established by CEN in three official versions (English, French, German). A version in any other languagemade by translation under the responsibility of a CEN member into its own language and notified to the CEN Management Centre has thesame status as the official versions.CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, 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.Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are aware and toprovide supporting documentation.Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without notice andshall not be referred to as a European Standard.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre:

Avenue Marnix 17,

B-1000 Brussels© 2009 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. prEN 10351:2009: EoSIST prEN 10351:2009

prEN 10351:2009 (E) 2 Contents Page Foreword ..............................................................................................................................................................41Scope ......................................................................................................................................................52Normative references ............................................................................................................................53Principle ..................................................................................................................................................64Reagents .................................................................................................................................................64.1Hydrochloric acid, HCl (ρρρρ20

= 1,19 g/ml) ...............................................................................................64.2Hydrochloric acid, solution 1 + 1 .........................................................................................................64.3Nitric acid, HNO3 (ρρρρ20 = 1,33 g/ml) .........................................................................................................64.4Nitric acid, solution 1 + 1 ......................................................................................................................64.5Hydrofluoric acid, HF (ρρρρ20 = 1,13 g/ml) .................................................................................................64.6Sulphuric acid, H2SO4 (ρ20 = 1,84 g/ml) .................................................................................................74.7Sulphuric acid, solution 1 + 1 ...............................................................................................................74.8Fusion mixture .......................................................................................................................................74.9Aluminium, 1 g/l standard solution ......................................................................................................74.10Chromium 1 g/l standard solution .......................................................................................................74.11Cobalt 1 g/l standard solution ..............................................................................................................74.12Copper 1 g/l standard solution .............................................................................................................74.13Manganese 1 g/l standard solution ......................................................................................................74.14Molybdenum 1 g/l standard solution ...................................................................................................84.15Nickel 1 g/l standard solution ...............................................................................................................84.16Phosphorus 1 g/l standard solution ....................................................................................................84.17Tin 1 g/l standard solution [freshly prepared] ....................................................................................84.18Vanadium 1 g/l standard solution ........................................................................................................84.19Internal standard solution, 1 g/l ...........................................................................................................94.20Pure iron .................................................................................................................................................95Apparatus ...............................................................................................................................................95.1Close texture filter paper and/or 0,45 µm cellulose nitrate filter .......................................................95.2Filter funnel suitable for 0,45 µm filters ...............................................................................................95.3Vacuum vessel .......................................................................................................................................95.4Platinum crucibles and platinum covers .............................................................................................95.5Atomic emission spectrometer, equipped with inductively coupled plasma (ICP) ........................96Sampling .................................................................................................................................................97Sample solution preparation ............................................................................................................. 107.1Test portion ......................................................................................................................................... 107.2Preparation of the test solution ......................................................................................................... 108Calibration process ............................................................................................................................ 118.1Preparation of the multi-elemental calibration solutions ............................................................... 118.2Standardization or re-calibration ...................................................................................................... 129Determination ...................................................................................................................................... 139.1Adjustment of the apparatus ............................................................................................................. 139.2Spectrometric measurements of the calibration solutions ............................................................ 139.3Analysis ............................................................................................................................................... 1410Expression of results ......................................................................................................................... 1511Precision .............................................................................................................................................. 1612Test report ........................................................................................................................................... 19oSIST prEN 10351:2009

prEN 10351:2009 (E) 3 Annex A (informative)

Optical emission spectrometer (OES) — Suggested performance criteria to be checked ........................................................................................................................................... 20Annex B (normative)

Synoptic of the operations related to § 9 ................................................................... 23Annex C (informative)

Test samples used for the precision test ................................................................. 24Annex D (informative)

Detailed results obtained from the precision test ................................................... 25Annex E (informative)

Graphical representation of the precision data ....................................................... 34Bibliography ...................................................................................................................................................... 39 oSIST prEN 10351:2009

prEN 10351:2009 (E) 4 Foreword This document (prEN 10351:2009) 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 document is currently submitted to the CEN Enquiry. oSIST prEN 10351:2009

prEN 10351:2009 (E) 5 1 Scope This document specifies an inductively coupled plasma emission spectrometry routine method for the analysis of unalloyed and low alloyed steels, whose iron content should be at least 95 %. This method is applicable to the elements listed in Table 1 within the ranges shown. Table 1 — Application ranges Element Mass fraction % min. max. Mn 0,005 2,00 P 0,005 0,05 Cu 0,005 0,80 Ni 0,010 2,00 Cr 0,010 1,60 Mo 0,005 0,80 V 0,002 0,40 Co 0,002 0,10 Al (total) 0,020 0,30 Sn 0,001 0,10

In all cases, the ranges specified can be extended or adapted (after validation) for the determination of other mass fractions, provided that the iron content in the samples under concern still is above 95 %. Other elements may be included. However such elements and their mass fractions should be carefully checked, taking into account the eventual interferences, the sensitivity, the resolution and the linearity criteria for each instrument and each wavelength. Depending also on the sensitivity of each instrument, suitable dilutions of the calibration and the test sample solutions may be necessary. Moreover, even if the method described is a "multi elemental" method it is not absolutely necessary to carry out the determination of all the elements of its scope simultaneously: the measurement conditions have to be optimised by each laboratory, depending on the performances of each apparatus available. NOTE 1 The accuracy of the method is unsatisfactory for phosphorus contents from 0,05 to 0,1 %. NOTE 2 The trueness of the method couldn't be checked for vanadium contents below 0,05 %. NOTE 3 The precision of the method is unsatisfactory for aluminium (total) contents below 0,02 %. 2 Normative references This working draft incorporates by dated or undated reference, provisions from other publications. These normative references are cited at the appropriate places in the text and the publications are listed hereafter. For dated references, subsequent amendments to, or revisions of any of these publications apply to this working draft only when incorporated in it by amendment or revision. For undated references, the latest edition of the publication referred applies (including amendments) EN ISO 14284, Steel and iron — sampling and preparation of samples for the determination of chemical composition. oSIST prEN 10351:2009

prEN 10351:2009 (E) 6 ISO 648, Laboratory glassware — One mark pipettes. ISO 1042, Laboratory glassware — One mark volumetric flasks. ISO 3696, Water for analytical laboratory use — Specification and test methods. ISO 5725-1:1994, Accuracy (trueness and precision) of measurement methods and results — Part 1: General principles and definitions. ISO 5725-2:1994, Accuracy (trueness and precision) of measurement methods and results — Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method. ISO 5725-3:1994, Accuracy (trueness and precision) of measurement methods and results — Part 3: Intermediate measures of the precision of a standard measurement method. CEN/TR 10345:2008, Guideline for statistical data treatment of inter laboratory tests for validation of analytical methods. 3 Principle Dissolution of a test portion with nitric and hydrochloric acids. Filtration and ignition of the acid insoluble residue. Removal of silica with hydrofluoric acid. Fusion of the residue with a mixture of orthoboric acid and potassium carbonate, dissolution of the melt with acid and addition of this solution to the reserved filtrate. After suitable dilution and, if necessary, addition of an internal reference element, nebulisation of the solution into an inductively coupled plasma emission spectrometer and measurement of the intensity of the emitted light (including, eventually, that of the internal reference element). 4 Reagents During the analysis, use only reagents of recognised analytical grade and only distilled water or water of equivalent purity. The same reagents should be used for the preparation of calibration solutions and of sample solutions. 4.1 Hydrochloric acid, HCl (ρρρρ20

= 1,19 g/ml) 4.2 Hydrochloric acid, solution 1 + 1 Add 500 ml of hydrochloric acid (4.1) to 500 ml of water. 4.3 Nitric acid, HNO3 (ρρρρ20 = 1,33 g/ml) 4.4 Nitric acid, solution 1 + 1 Add 500 ml of nitric acid (4.3) to 500 ml of water. 4.5 Hydrofluoric acid, HF (ρρρρ20 = 1,13 g/ml) WARNING — Hydrofluoric acid is extremely irritating and corrosive to skin and mucous membranes producing severe skin burns which are slow to heal. In the case of contact with skin, wash well with water, apply a topical gel containing 2,5 % (mass fraction) calcium gluconate, and seek immediate medical treatment. oSIST prEN 10351:2009

prEN 10351:2009 (E) 7 4.6 Sulphuric acid, H2SO4 (ρ20 = 1,84 g/ml) 4.7 Sulphuric acid, solution 1 + 1 Add 25 ml of sulphuric acid (4.6) to 25 ml of water. 4.8 Fusion mixture Mix one part by mass of orthoboric acid, H3BO3 and one part of potassium carbonate anhydrous, K2CO3. 4.8.1 Fusion mixture, 100 g/l solution In a suitable beaker, dissolve 25 g of the fusion mixture (4.8). Heat if necessary. After cooling, transfer the solution quantitatively into a 250 ml one-mark volumetric flask, dilute to the mark with water and mix well. 4.9 Aluminium, 1 g/l standard solution Weigh (0,5 ± 0,001) g of pure aluminium (99,99 % purity) and transfer into a 400 ml beaker. Add 50 ml hydrochloric acid solution (4.2) and gently heat until aluminium is completely dissolved. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Al 4.10 Chromium 1 g/l standard solution Weigh (0,5 ± 0,001) g of pure chromium (99,99 % purity) and transfer into a 250 ml beaker. Add 40 ml hydrochloric acid (4.1) and gently heat until chromium is completely dissolved. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Cr. 4.11 Cobalt 1 g/l standard solution Weigh (0,5 ± 0,001) g of pure cobalt (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 5 ml hydrochloric acid (4.1) and 5 ml of nitric acid (4.3). Heat gently until the metal is dissolved and then boil until nitrous fumes have been expelled. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Co. 4.12 Copper 1 g/l standard solution Weigh (0,5 ± 0,001) g of pure copper (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 10 ml of nitric acid solution (4.4). Heat gently until the metal is dissolved, then boil until nitrous fumes have been expelled. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Cu. 4.13 Manganese 1 g/l standard solution The manganese used to prepare the solution is released from superficial oxide possibly present by introducing a few grams of metal in a 250 ml beaker containing 150 to 160 ml of water and 15 to 20 ml of sulphuric acid (4.6). Shake and after a few seconds, allow the solution to settle and add water. Repeat the water oSIST prEN 10351:2009

prEN 10351:2009 (E) 8 cleaning several times. Remove the metallic manganese and rinse with acetone. Dry the metal in an oven at 100 °C for 2 minutes or with a hair dryer. Cool in a desiccator. Weigh (0,5 ± 0,001) g of this purified manganese and transfer into a 250 ml beaker. Dissolve it in 5 ml hydrochloric acid (4.1) and 10 ml of nitric acid solution (4.4). Heat gently until the metal is dissolved. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Mn. 4.14 Molybdenum 1 g/l standard solution Weigh (0,5 ± 0,001) g of pure molybdenum (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 10 ml hydrochloric acid (4.1) and 10 ml of nitric acid (4.3). Heat gently until the metal is dissolved. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Mo. 4.15 Nickel 1 g/l standard solution Weigh (0,5 ± 0,001) g of pure nickel (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 10 ml of nitric acid solution (4.4). Heat gently until the metal is dissolved, then boil until nitrous fumes have been expelled. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Ni. 4.16 Phosphorus 1 g/l standard solution Weigh (2,197 ± 0,001) g of dried potassium dihydrogen phosphate and transfer into a 250 ml beaker and dissolve it with water. Transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of P. 4.17 Tin 1 g/l standard solution [freshly prepared] Weigh (0,5 ± 0,001) g of pure tin (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 50 ml hydrochloric acid (4.1). Heat gently until the metal is dissolved. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of Sn. 4.18 Vanadium 1 g/l standard solution Weigh (0,5 ± 0,001) g of pure vanadium (99,99 % purity) and transfer into a 250 ml beaker. Dissolve it in 30 ml hydrochloric acid (4.1) and 10 ml of nitric acid solution (4.3). Heat gently until the metal is dissolved. After cooling, transfer the solution quantitatively into a 500 ml one-mark volumetric flask, dilute to the mark with water and mix well. 1 ml of this solution contains 1 mg of V. NOTE Standard solutions whose preparations are described under items 4.9 to 4.18 can be replaced by commercial available standard solutions, provided that they are supplied by a recognised producer and their traceability full documented. oSIST prEN 10351:2009

prEN 10351:2009 (E) 9 4.19 Internal standard solution, 1 g/l Choose a suitable element to be added as internal reference and prepare a 1 g/l solution. NOTE Elements as Cd, Fe, Sc and Y were used for this purpose during the precision test of this method. 4.20 Pure iron The purity of the iron selected shall be at least ten times lower than the low limit of the scope of each element included in the method. 5 Apparatus All volumetric glassware shall be class A and calibrated, in accordance with ISO 648 or ISO 1042 as appropriate. 5.1 Close texture filter paper and/or 0,45 µm cellulose nitrate filter 5.2 Filter funnel suitable for 0,45 µm filters Two-pieces acid-resistant filter funnel with a support screen between the funnel body and stem, designated for the vacuum filtration of liquids. The stem of the filter is fitted with a ground glass cap stopper or a rubber stopper for insertion into an opening of the vacuum vessel. 5.3 Vacuum vessel With an opening to allow the insertion of the rubber stopper of the filter funnel stem. 5.4 Platinum crucibles and platinum covers 5.5 Atomic emission spectrometer, equipped with inductively coupled plasma (ICP) This shall be equipped with a nebulisation system. The instrument used will be satisfactory if, after optimising in accordance with the manufacturer’s instructions, it meets the performance criteria given in Annex A. 6 Sampling Sampling shall be carried out in accordance with EN ISO 14284 or an appropriate national standard for steel. oSIST prEN 10351:2009

prEN 10351:2009 (E) 10 7 Sample solution preparation 7.1 Test portion Weigh, to the nearest 0,001 g, 1 g of the test sample. 7.2 Preparation of the test solution 7.2.1 Dissolution of the test portion Transfer the test portion (7.1.1) into a 250 ml or 400 ml beaker. Add 5 ml of nitric acid (4.3) and 20 ml of hydrochloric acid (4.2). Cover and heat gently until the attack reaction ceases. Heat at a temperature of about 95 °C, for about 5 minutes. Allow to cool. Rinse the beaker cover and the walls of the beaker with water. 7.2.2 Filtration of the test portion 7.2.2.1 Including total aluminium determination Place a 0,45 µm cellulose nitrate filter (5.1) on the support screen of a filter funnel (5.2). Moisten the filter with water and join the body and stem of the funnel. Insert the stopper of the filter funnel stem into a vacuum vessel (5.3). Apply vacuum gently to the vacuum vessel and filter the solution. Wash the funnel sides and residue with warm water several times. Stop the vacuum gently. Wipe the funnel sides with a close texture filter paper, then place the cellulose nitrate filter in this filter paper and fold them. Transfer the folded filters into a platinum crucible (5.4) and cover with a suitable platinum cover. Transfer the filtrate into a 200 ml one-mark volumetric flask. 7.2.2.2 Excluding total aluminium determination Filter the solution through a close texture filter paper and collect the filtrate into a 200 ml one-mark volumetric flask. Wash the filter paper and residue with warm water several times and collect the washings in the volumetric flask. Transfer the filter into a platinum crucible (5.4) and cover with a suitable platinum cover. 7.2.3 Treatment of insoluble residue Introduce the crucible in a COLD furnace, than switch it on in order to reach a temperature of about 900 °C. Allow to stand at 900 °C for about 15 minutes. Cool the crucible. Add into the crucible 0,5 to 1,0 ml of sulphuric acid (4.7) and 2 ml of hydrofluoric acid (4.5). Evaporate to dryness and cool. Add 1,00 g of the fusion mixture (4.8). Fuse the content of the crucible in a muffle furnace at 1000 °C for 15 to 20 minutes. Cool the crucible and add 20 ml of hydrochloric acid (4.2) to the solidified melt. Heat gently, in order to dissolve the fusion products. Allow the crucible to cool and transfer the solution quantitatively to the filtrate in the 200 ml volumetric flask. oSIST prEN 10351:2009

prEN 10351:2009 (E) 11 If internal standard is used, add, with a calibrated pipette, 10 ml of the internal standard solution (4.19). NOTE 1 Depending on the instrument performances, the volume and/or the concentration of the internal standard solution may be different. Dilute to the mark with water and mix. NOTE 2 Depending on the instrument performances, suitable dilutions of the sample solution and of the calibration solutions may be necessary. 8 Calibration process The calibration process is subdivided into calibration and drift compensation by re-calibration. 8.1 Preparation of the multi-elemental calibration solutions Weigh the quantities of pure iron (4.20) shown in Table 2 and introduce them into each of a series of 250 ml or 400 ml beakers. Add 20 ml of the hydrochloric acid (4.2) to each beaker. Cover with a watch glass and gently heat. When the attack reaction ceases, add 5 ml of nitric acid (4.3). Heat until nitrous fumes have been expelled. Rinse the beaker cover and the walls of the beaker with water and heat to boiling. Allow to cool and transfer each calibration solution into a 200 ml one-mark volumetric flask. With calibrated pipettes, add the quantities (volumes) of the mono-elemental standard solutions (4.9 to 4.18) or of commercial available mono-elemental standard solutions of each element shown in Table 2. Add to each volumetric flask 10 ml of the fusion mixture solution (4.8.1) and 10 ml of the hydrochloric acid (4.1). If internal standard is used, add, with a calibrated pipette, 10 ml of the internal standard solution (4.19). NOTE 1 Refer to NOTE 1 under § 7.2.3. Dilute to the mark with water and mix. NOTE 2 Refer to NOTE 2 under § 7.2.3. Following this same procedure, also prepare a pure iron solution (labelled F0 in Table 2), to be used to control if the lowest content for each element is enough high to be considered as "different from the zero point". Strong care should be taken in order to ensure that the quantity of acids stays about the same in the calibration solutions (namely when commercially available standard solutions are used), in the sample solutions and in the CRMs solutions prepared to check the trueness of the calibration. The calibration curves obtained may be stored within a computer, integrated to the ICP atomic emission spectrometer. NOTE The trueness of these calibration functions should be checked by measuring at least two suitable CRMs or IRMs sample solutions (just above the low point and just below the high point of each calibration range. oSIST prEN 10351:2009

prEN 10351:2009 (E) 12 Table 2 — Composition of the multi-elemental calibration solutions Element Label F0 F1 F2 F3 F4 Fe 1000,0 mg 100,00 % 958,3 mg 95,83 % 979,7 mg 97,97 % 971,2 mg 97,12 % 989,7 mg 98,97 % Mn

------ 20 mg
2,0 % 2 mg
0,2 % 0,02 mg
0,002 % 0,2 mg
0,02 % P
------ 0,05 mg
0,005 % 0,1 mg
0,01 % 0,5 mg
0,05 % 1 mg
0,1 % Cu
------ 0,5 mg
0,05 % 8 mg
0,8 % 0,05 mg
0,005 % 1 mg
0,1 % Ni
------ 20 mg
2,0 % 5 mg
0,5 % 0,05 mg
0,005 % 0,5 mg
0,05 % Cr
------ 0,05 mg
0,005 % 0,5 mg
0,05 % 16 mg
1,6 % 5 mg
0,5 % Mo
------ 0,05 mg
0,005 % 0,5 mg
0,05 % 8 mg
0,8 % 1 mg
0,1 % V
------ 0,02 mg
0,002 % 4 mg
0,4 % 0,2 mg
0,02 % 1 mg
0,1 % Co
------ 0,02 mg
0,002 % 0,1 mg
0,01 % 1 mg
0,1 % 0,05 mg
0,005 % Al
------ 0,03 mg
0,003 % 0,1 mg
0,01 % 3 mg
0,3 % 0,5 mg
0,05 % Sn
------ 1 mg
0,1 % 0,05 mg
0,005 % 0,01 mg
0,001 % 0,1 mg
0,01 %

8.2 Standardization or re-calibration Drifts in the spectrometer readings shall be corrected using a standardization or re-calibration procedure as described in the manufacturer's instruction manual. For that purpose the synthetic multi-elemental solutions (8.1), used for the calibration or suitable CRM or IRM solutions may be used. It is strongly recommended to carry out a standardization of the instrument before the measurements of a set of unknown samples. oSIST prEN 10351:2009

prEN 10351:2009 (E) 13 9 Determination A synoptic of the operations described in this paragraph is given in Annex B. 9.1 Adjustment of the apparatus Start the ICP-OES and let it run for about half an hour before taking any measurements. Adjust all the instrumental parameters, each gas flow rate (outer, intermediate or central), torch position, entrance slits, exit slits, photomultiplier tubes voltages, wavelengths of the analytical lines specified in Table 3, pre-spraying time and integrating time, according to the manufacturer’s instructions, while aspirating (for each element) the highest concentration calibration solution. Table 3 — Wavelengths for determinations in low alloyed steels Element Wavelength (nm) Mn 257,6 or 293,1 P 178,2 Cu 324,7 or 327,4 Ni 231,6 Cr 205,6 or 206,6 or 267,7

Mo 202,0 or 281,6 V 309,3 or 310,2 or 311,1 Co 228,6 or 230,8 Al 394,4 or 396,2
Sn 189,9 Cd 214,1 Fe 271,4 Sc 361.4 Y 371,0
NOTE Other wavelengths may be used, provided that interf
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