Machbarkeitsstudie zu geeigneten Kandidaten für f r die Herstellung von CRM für r die Bestimmung von Wasserstoff in Festkörpern

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1 BAM mission: Safety in technology and chemistry Machbarkeitsstudie zu geeigneten Kandidaten für f r die erstellung von CRM für r die Bestimmung von Wasserstoff in Festkörpern V.-D. odoroaba, a D. Klemm, b U. Reinholz, a E. Strub, c J. Röhrich, d W. Bohne, d V. offmann b and K. Wetzig b a Bundesanstalt für Materialforschung und -prüfung (BAM), Berlin b Leibniz Institute for Solid State and Materials Research Dresden c Universität zu Köln d ahn-meitner Institute (MI), Berlin

2 Overview on analytical methods for the analysis of hydrogen in solid samples Analytical Method Detection of Quantification of ote NRA Limitations no local information (i.e., no depth profiles) analysed depth of up to only - µm LoD ~ ppm ERDA SIMS lack of -CRM, thin layers GD-OES lack of -CRM (

3 Analytical figures of merit in GD-OES: Limit of Detection (LoD( LoD) ) of GD-OES-Lines for ydrogen Detection (Werkstoffanalytische Verfahren,.-J. unger, Ch. : Glimmentladungsspektroskopie, 99).

4 Analytical figures of merit in GD-OES: Limit of Detection (LoD( LoD) ) of

5 Electrolytically deposited Zn on Steel GD-OES element depth profile depth profile before and after heat treatment C Zn N O Fe line intensity (a. u.) Electrolytical Zn coating as plated annealed Steel St7 substrate GD-anode = mm; V dc = V; p 7 Pa; Zn I. nm; Fe I 7.9 nm; I. nm; C I. nm; N I 9. nm; O I. nm; Ar I. nm GD-anode = mm; V dc = 7 V; I dc = ma; I. nm Samples: OTEK Gmb, Brieselang

6 Requirements for -CRM (CRC) omogeneity of the concentration in the coating (as an alternative to bulk) - lateral - in-depth Stability (!) of the concentration over longer periods of time (i.e. years)

7 Coating as candidates for -CRM (CRC): (i) Electroplated Zn() ) on steel Cyanide-free alkaline Zn electrolyte, low additive concentration Cyanide Zn electrolyte, without additives Acid Zn electrolyte, without additives 9 Fe 9 Zn Fe Fe 7 7 Zn Zn Mn O C N Mn C N O Mn CON Samples: SurTec, Zwingenberg

8 Electroplated Zn() ) on steel; Determination of the concentration by ERDA & NRA; Stability tests immediately after the deposition after months after further months Depth /µm 7 9 ERDA # NRA Zn()# Zn()# Zn()# Depth /µm 7 9 Zn()# Zn()# Zn()# ERDA # Depth /µm 7 9 Zn()# Zn()# Zn()# ERDA # Intensity GD-OES (a. u.) 7 GD-OES content ERDA & NRA (at.-%) Intensity GD-OES (a. u.) 7 GD-OES content ERDA & NRA (at.-%) Intensity GD-OES (a. u.) 7 GD-OES content ERDA & NRA (at.-%) Table Stability tests of the hydrogen concentration in at.-% in three electrolytically deposited zinc coatings determined by ERDA. Sample immediately after the deposition after months after further months Zn() #. ±. 9.7 ±.. ±. Zn() #. ±.. ±.. ±. Zn() #. ±.. ±.. ±. Samples: SurTec, Zwingenberg

9 Electroplated Zn() ) on steel; omogeneity tests; SIMS depth profile of, PI = µm Zn() Steel substrate Samples: SurTec, Zwingenberg

10 Coating as candidates for -CRM (CRC): (ii) Carbon-rich rich hard coatings,, WC() / steel C Cr Fe C Cr Fe W Mn Ni Mo Si W Mn Ni Mo Si The corresponding hydrogen concentrations found by ERDA are. ±. and. ±. at.-%. GD-Anode = mm; V dc = 7 V; I dc = ma; C I, nm; W I, nm; I, nm; Fe I 7,9 nm; Cr I, nm; Mn I, nm; Ni I 9, nm; Mo I, nm; Si I. nm Proben: FhG-IST, Braunschweig

11 Coating as candidates for -CRM (CRC): (iii) Amorphous Si layers, a:si() ) / Si Si() Si Si O N C GD-anode = mm; V dc = 7 V; I dc = ma; I. nm Samples: MI, Berlin & AXO, Dresden

12 Coating as candidates for -CRM (CRC): (iii) Amorphous Si layers, asi: Table Samples used for the calibration curve in Fig.,, asi: asi: asi: asi: Sample asi: asi: asi: asi: Sputter factor SR (µg/s).... (at.-%)..9.. (mass-%) IARM 7B asi: asi: asi: ,,,,,,, IARM 7B... c (%) *SR (µg/s) GD-anode = mm; V dc = V; I dc = ma (IFW Dresden) I. nm Samples: MI, Berlin & AXO, Dresden

13 Coating as candidates for -CRM (CRC): (iii) Amorphous Si layers

14 Coating as candidates for -CRM (CRC): (iii) Amorphous Si layers

15 Resümee / Ausblick At least three classes of reference coatings as successful candidates dates for upcoming certification of the concentration: Electrolytically Zn() ) / steel Carbon-rich rich hard coatings,, WC() / steel Amorphous Si layers, a:si() / Si V.-D. odoroaba,, D. Klemm,, U. Reinholz,, E. Strub,, J. Röhrich,, W. Bohne,, V. offmann and K. Wetzig,, Potential candidates of Certified Reference Material for determination of hydrogen concentration ntration with Glow Discharge Optical Emission Spectrometry (GD-OES) - a feasibility study, J. Anal. At. Spectrom.,,,,,.