Performance of the analytical techniques employed in characterization and certification of stainless...

Performance of the analytical techniques employed in

characterization and certification of stainless steel materials

by

Ingemar GustavssonAnalytical Chemistry Group

Corrosion and Metals Research InstituteDrottning Kristinas väg 48

SE 114 28 Stockholm, SwedenE-mail: [email protected]

•

Definitions of RMs and CRMsaccording to ISO-Guides 30-35

____________________________

• Reference Material (RM)

• A material, sufficiently homogeneous and stable with respect to one or more properties, which have been established to be fit for its intended use in a measurement process

• Certified Reference Material (CRM)

• An RM characterized by a metrologically valid procedure, accompanied by a certificate that states the value of the specified property, its associated uncertainty, and a statement of metrological traceability

Production of certified reference materials (CRM)

Demand of a new CRM is investigated

Producers´ Group-ECRM

Repalcement of an exhausted ECRM

NCRMWG The JK-series

Replacement of an exhausted CRM

YES YES

Supplier is requested (Nordic countries)

Supplier is requested (Nordic, British, French, German)

Bars for homogenity test

Bars for homogenity test

Delivery to SIMR or BAM, BAS, CTIF,

IRSIDDelivery to SIMR

Possibly new homogeneity test


YES

No !

Production of certified reference materials (CRM)

Preparation chips (drillings)

Preparation chips (drillings)

Preanalysis according to ISO-standards

Preanalysis according to ISO-standards

Distribution of chips to laboratories for

certification analysis(20-30)

Distribution of chips to laboratories for

certification analysis(15-20)



4 UK 4 French 4 German Other European

European Nordic International

Characteristic steel elementsConcentrations given in % (m/m)

• C, Si, Mn, P, S, Cr, Mo, Ni, N, (Fe)

• C 0,01 - 2 Si 0,05 - 3

• Mn 0,3 - 12 P 0,001 - 0,02

• S 0,0005 - 0,2 Cr 0,1 - 30

• Mo 0,005 - 5 Ni 0,01 - 30

• N 0,001 - 0,3 Fe 35 - 99

• Low alloy steel C, Si, Mn, P, S, N

• High alloy steel C, Si, Mn, P, S, Cr, Mo, Ni, N

• (Stainless steel)

• Tool steelC, Si, Mn, P, S, Cr, Mo, Ni, N, W, V, Co

• ”Special steel” C, Si, Mn, P, S, Cr, Mo, Ni, N plus

• e.g. Al, Si, Nb, Ti, Cu, Ce

Chemical analysis of stainless steel

• C and S Combustion - infrared detection

• (C - 0,003-4,5 %; S - 0,0005 - 0,2 %)

– Oxidation by oxygen gas at 2100 oC; formation of CO2 and SO2

– Calibration against BaCO3; Na2CO3 or sucrose

– Calibration against K2SO4

– (Calibration against CRMs)


• Si - Spectrophotometry (0,01-0,2%)– Dissolution by H2SO4/HNO3

– Filtartion

– Ignition of acid-insoluble Si with Na2O2

– Add MnO4- - solution - pink solution

– Add MoO4 2- - solution

– Add ascorbic acid solution - formation of molybdosilicate complex (blue)

– Measurement at 810 nm

– Calibration against ”SiO2 -solution”

• Si - Gravimetry (0,1 - 5 %)– Oxidation by HClO4-fuming-formation of SiO2

– Filtration

– Addition of HF - formation of SiF4

– Ignition

– Weighing


• Mn - AAS - flame (0,002 - 2 %)– Dissolution by HCl/HNO3 (HF)

– Add HClO4 - fuming

– Filtration

– Measurement at 279,5 nm

– Calibration against matrix-matched Mn -solution


• P - Spectrophotometry (0,001 - 1,0 %)

– Dissolution by HCl/HNO3 (HF)

– Add HClO4 - fuming

– Cr content > 0,1 % is removed by addition of HCl - formation of volatile CrO2Cl2

– Add NaNO2 - reduction of dichromate

– Add H3BO4 - formation of tertafluoroboric acid

– Add metavanadate and heptamolybdate solutions-formation of phosphovanadomolybdate complex

– Extraction with 4-methyl-2-pentanone

– Measurement of organic solvent at 355 nm

– Calibration against KH2PO4

(orthophosphate) - solution


• Cr and V - Potentiometric titration Cr (1 - 30 %); V (0,5 - 10 %)

– Dissolution by HCl/HNO3/HF in aTeflon pressure vessel in micro-wave assisted system

– Add H3PO4/H2SO4 - oxidation to Cr(VI) and to V(V), respectively

– Titration with Fe(II) giving Cr(III) and V(IV)

– Oxidation with MnO4- -solution giving V(V)

and not Cr(VI)

– Excess of MnO4- is reduced by NO2

-

– Excess of NO2- is eliminated by urea

– Standardisation using pure K2Cr2O7


• N - Melt extraction - Thermal Conductivity (0,002 - 0,6 %)

– Melt extraction at 2700 oC in graphite crucible and purging helium

– Calibration against KNO3



• O - Melt extraction - Infrared detection (0,0001 - 0,02 %)

– Melt extraction at 2200 oC in graphite crucible and purging helium

– Calibration against KNO3

– Calibration against Dy2O3 alt TeO2



• Trace elements (< 0,01 %)

• Li, Be, B...Ti…Nb, Mo…Sn, Sb… Ce, La…W…Pb, Bi, Th, U

– Dissolution in HCl/HNO3/(HF) in a Teflon pressure vessel using a micro-wave assisted system

– Dilution to suitable analytical volume

– Addition of internal standard (usually 1- 3) of Y, Rh, In, Re, Ir, Tl

– Calibration against matrix-matched elemental solutions

E C I S SE U R O P E A N C O M M IT T E E F O R IR O N A N D S T E E L S T A N D A R D IZ A T IO N

C O M IT É E U R O P É E N D E N O R M A L IS A T IO N D U F E R E T D E L ’A C IE RE U R O P Ä IS C H E S K O M IT E E F Ü R E IS E N -U N D S T A H L N O R M U N G

E U R O P E A N C E R T IF IE D R E F E R E N C E M A T E R IA L ( E U R O N O R M – C R M )C E R T IF IC A T E O F C H E M IC A L A N A L Y S IS

E U R O N O R M – C R M N o . 2 7 4 -1 V A N A D IU M S T E E L

L A B O R A T O R Y M E A N S (4 V a l u e s ) m a s s c o n te n t in %

L in e N o C S i M n P S C r M o N i C u N V W O (* ) A l to t1 1 .5 4 5 0 1 .0 2 7 3 0 .3 8 4 8 0 .0 1 3 4 0 .0 0 8 6 7 .9 5 8 0 - 0 .0 6 7 0 - 0 .0 7 2 4 - 0 .0 0 7 2 0 .0 0 1 7 0 .0 0 0 52 1 .5 4 9 9 - 0 .3 8 8 1 0 .0 1 4 0 0 .0 0 8 7 7 .9 9 5 0 - 0 .0 7 3 5 0 .0 2 6 7 0 .0 7 4 4 - 0 .0 0 7 3 0 .0 0 2 1 0 .0 0 1 53 1 .5 5 0 0 1 .0 3 9 0 0 .3 8 8 7 0 .0 1 4 4 0 .0 0 8 7 8 .0 0 1 2 1 .3 9 3 0 0 .0 7 4 0 0 .0 2 6 7 0 .0 7 5 3 3 .9 5 7 8 0 .0 0 7 5 0 .0 0 2 1 0 .0 0 1 84 1 .5 5 4 7 1 .0 4 6 7 0 .3 9 0 0 0 .0 1 4 4 0 .0 0 8 8 8 .0 1 0 5 1 .4 1 7 7 0 .0 7 4 2 0 .0 2 6 7 0 .0 7 6 0 3 .9 6 2 5 0 .0 0 7 8 0 .0 0 2 1 0 .0 0 2 45 1 .5 5 8 0 1 .0 4 9 6 0 .3 9 0 5 0 .0 1 4 5 0 .0 0 9 3 8 .0 1 3 4 1 .4 2 9 3 0 .0 7 5 0 0 .0 2 7 1 0 .0 7 6 2 3 .9 6 6 6 0 .0 0 8 1 0 .0 0 2 2 0 .0 0 2 56 1 .5 5 8 6 1 .0 5 2 6 0 .3 9 0 7 0 .0 1 4 5 0 .0 0 9 4 8 .0 1 5 2 1 .4 3 2 0 0 .0 7 6 4 0 .0 2 7 8 0 .0 7 6 4 3 .9 7 0 3 0 .0 0 8 4 0 .0 0 2 3 0 .0 0 2 67 1 .5 6 0 0 1 .0 5 3 7 0 .3 9 2 0 0 .0 1 4 6 0 .0 0 9 5 8 .0 1 5 3 1 .4 4 8 0 0 .0 7 7 5 0 .0 2 7 9 0 .0 7 7 0 3 .9 8 7 9 0 .0 0 8 4 0 .0 0 2 6 0 .0 0 2 68 1 .5 6 2 0 1 .0 5 5 8 0 .3 9 5 8 0 .0 1 4 6 0 .0 0 9 5 8 .0 3 8 1 1 .4 4 8 7 0 .0 7 7 7 0 .0 2 8 1 0 .0 7 7 0 3 .9 9 6 8 0 .0 0 8 6 0 .0 0 2 6 0 .0 0 2 99 1 .5 6 4 5 1 .0 5 9 1 0 .3 9 7 2 0 .0 1 4 7 0 .0 0 9 8 8 .0 4 6 1 1 .4 5 5 3 0 .0 7 7 9 0 .0 2 8 2 0 .0 7 7 2 3 .9 9 7 3 0 .0 0 8 6 0 .0 0 2 6 0 .0 0 3 0

1 0 1 .5 6 6 0 1 .0 6 3 2 0 .3 9 8 2 0 .0 1 4 7 0 .0 0 9 8 8 .0 4 9 1 1 .4 5 8 6 0 .0 7 8 1 0 .0 2 8 2 0 .0 7 7 2 3 .9 9 7 5 0 .0 0 8 8 0 .0 0 2 8 0 .0 0 3 71 1 1 .5 6 6 7 1 .0 6 4 9 0 .3 9 9 1 0 .0 1 5 0 0 .0 0 9 8 8 .0 5 9 1 1 .4 5 9 5 0 .0 7 8 3 0 .0 2 8 4 0 .0 7 7 2 4 .0 0 2 4 0 .0 0 9 0 0 .0 0 2 9 0 .0 0 3 91 2 1 .5 7 1 7 1 .0 6 8 5 0 .4 0 1 7 0 .0 1 5 2 0 .0 0 9 9 8 .0 7 3 4 1 .4 6 5 0 0 .0 7 8 8 0 .0 2 8 5 0 .0 7 7 7 4 .0 0 4 2 0 .0 0 9 3 0 .0 0 3 0 -1 3 1 .5 7 4 0 1 .0 6 9 2 0 .4 0 2 4 0 .0 1 5 4 0 .0 0 9 9 8 .0 8 4 0 1 .4 6 7 9 0 .0 7 9 5 0 .0 2 8 5 0 .0 7 8 0 4 .0 0 6 0 0 .0 1 0 0 0 .0 0 3 0 -1 4 1 .5 7 5 8 1 .0 7 2 4 0 .4 0 3 0 0 .0 1 5 9 0 .0 1 0 4 8 .0 9 0 0 1 .4 7 3 7 0 .0 8 0 4 0 .0 2 8 8 0 .0 7 9 4 4 .0 1 4 6 0 .0 1 0 7 0 .0 0 3 01 5 1 .5 7 6 0 1 .0 7 7 1 0 .4 0 7 0 0 .0 1 6 5 0 .0 1 0 9 8 .0 9 2 2 1 .4 8 5 8 0 .0 8 0 5 0 .0 2 8 8 0 .0 7 9 5 4 .0 1 9 7 0 .0 1 1 2 0 .0 0 3 21 6 1 .5 7 6 1 - 0 .4 0 7 8 - 0 .0 1 1 0 - 1 .4 9 1 6 - 0 .0 2 9 0 0 .0 8 0 0 4 .0 4 1 3 - 0 .0 0 3 21 7 0 .4 0 9 7 1 .5 0 0 2 0 .0 8 6 8 0 .0 2 9 6 4 .0 4 6 11 8 4 .0 6 2 31 9 4 .0 6 6 22 0 4 .0 8 0 0M M 1 .5 6 3 0 1 .0 5 6 8 0 .3 9 7 0 0 .0 1 4 8 0 .0 0 9 6 8 .0 4 0 4 1 .4 5 5 1 0 .0 7 7 0 0 .0 2 8 2 0 .0 7 7 0 4 .0 1 0 0 0 .0 0 8 7 0 .0 0 2 6s M 0 .0 1 0 0 0 .0 1 3 9 0 .0 0 7 5 0 .0 0 0 8 0 .0 0 0 7 0 .0 4 0 4 0 .0 2 8 7 0 .0 0 4 2 0 .0 0 0 8 0 .0 0 1 9 0 .0 3 6 6 0 .0 0 1 2 0 .0 0 0 4s W 0 .0 0 6 0 0 .0 0 5 9 0 .0 0 3 5 0 .0 0 0 4 0 .0 0 0 3 0 .0 2 2 4 0 .0 0 8 5 0 .0 0 1 3 0 .0 0 0 4 0 .0 0 0 8 0 .0 1 8 5 0 .0 0 0 3 0 .0 0 0 2

L in e N o A s C o P b S n T i S b1 0 .0 0 1 3 0 .0 2 1 2 0 .0 0 0 0 6 0 0 .0 0 0 8 1 0 .0 0 0 6 0 .0 0 0 1 8 52 0 .0 0 1 3 0 .0 2 1 3 0 .0 0 0 0 6 5 0 .0 0 0 9 3 0 .0 0 1 2 0 .0 0 0 1 9 03 0 .0 0 1 4 0 .0 2 2 6 0 .0 0 0 0 6 8 0 .0 0 0 9 5 0 .0 0 1 4 0 .0 0 0 2 0 04 0 .0 2 6 6 0 .0 0 1 5 0

A d d i t io n a l v a lu e fo r in fo r m a t io n : B ~ 5 g /gV a lu e s g iv e n i n ita li c ty p e a r e fo r in fo r m a t io n o n ly

M M : M e a n o f th e la b o r a to r y m e a n s , s M : S ta n d a rd d e v ia t io n o f th e la b o r a t o r y m e a n s s M = 4/22b wss

s w : In t r a la b o r a t o r y s ta n d a rd d e v ia t io n , s b : In te r la b o r a to r y s ta n d a rd d e v ia t io nT h e la b o ra to r y m e a n v a lu e s h a v e b e e n e x a m in e d s ta t is t ic a lly to e l im in a t e o u tly in g v a lu e s .

W h e r e a ” - " a p p e a rs in th e ta b le it in d ic a te s t h a t a n o u t ly in g v a lu e h a s b e e n o m it te d b y e ith e r th e C o c h ra n o r G ru b b s T e s t.

(* )V a lu e s r e fe r t o s o l id s a m p le s ; t h u s o x y g e n d e te r m in a t i o n s h a l l o n l y b e d o n e o n d is c s a m p le s e x c lu d in g a c e n t re d i a m e t e r o f 6 m m .

C E R T IF IE D V A L U E S m a s s c o n t e n t i n %

C S i M n P S C r M o N i C uM M 1 .5 6 3 1 .0 5 7 0 .3 9 7 0 .0 1 4 8 0 .0 0 9 6 8 .0 4 1 1 .4 5 5 0 .0 7 7 0 .0 2 8 2C (9 5 % ) 0 .0 0 5 0 .0 0 8 0 .0 0 4 0 .0 0 0 4 0 .0 0 0 4 0 .0 2 3 0 .0 1 6 0 .0 0 2 0 .0 0 0 4

N V W OM M 0 .0 7 7 0 4 .0 1 0 0 .0 0 8 7 0 .0 0 2 6C (9 5 % ) 0 .0 0 1 0 0 .0 1 8 0 .0 0 0 7 0 .0 0 0 2

T h e h a lf -w id th c o n f id e n c e in t e r v a l C ( 9 5 % ) = t x s M / n

w h e r e t is th e a p p r o p r ia t e S tu d e n t ’s t v a lu e a n d n is th e n u m b e r o f a c c e p ta b le m e a n v a lu e s .F o r fu r th e r in fo rm a tio n re g a r d in g th e c o n f id e n c e in t e r v a l f o r th e c e r t i f ie d v a lu e s e e IS O G u id e 3 5 : 1 9 8 9 s e c t io n 4 .

T h is r e fe r e n c e m a te r ia l w a s p r e p a r e d in a c c o r d a n c e w i th t h e r e c o m m e n d a t io n s s e t o u t in IS O G u id e s 3 0 – 3 5 a n d is s u e d b y :

S w e d is h In s t i t u t e fo r M e t a ls R e s e a r c h (S IM R ) D r o t tn in g K r i s t i n a s v ä g 4 8 , S E - 1 1 4 2 8 , S to c k h o l m , S w e d e n O n b e h a lf o f : T h e I r o n a n d S te e l N o m e n c la tu r e C o - o r d in a tin g C o m m it t e e ( C O C O R ) o f th e E C IS S ,

a f t e r a p p r o v a l b y a ll t h e p a r t i c ip a t in g la b o r a to r i e s a n d a ll th e p ro d u c in g o r g a n i s a tio n s .( F r a n c e - IR S ID /C T IF ; G e r m a n y - Ir o n a n d S te e l C R M W o r k in g G r o u p : V D E h , B A M & M P I f ü r E i s e n f o r s c h u n g ; U K - B A S L t d ; N o rd ic C o u n t r i e s -N o r d ic C R M W o r k in g G r o u p )

C e r t if ie d IS O 1 7 0 2 5In s t i tu te A c c r e d i te d

L a b o r a to r yD E C E M B E R 2 0 0 3

Round-Robin test. Concentrations of 30 elements in a high alloy steel - JK 37.

n = number of participating laboratories; concentrations in g/g

Major element n Cert.value

Mn 17120 35 3 17300

Micro elementsSi 1350 100 3 1410P 157 6 4 160V 740 35 5 750Co 601 29 4 580Ce 1213 65 5 1230Pr 141 11 5 -Nd 365 9 5 -

Trace elementsB 9 2 3 12Al 77 19 5 80Ti 39 6 5 37Ga 45 9 5 As 40 1 4 36Nb 13 1 5Sb 6.1 1.5 5Te 2.9 2.3 4W 84 8 5Pb 1.32 0.23 5

(Cert.values (%) : Cr-26.72;Ni-30.82;Mo-3.55)

Cont`d

Round-Robin test. Concentrations of ultra-trace elements in a high alloy steel - JK 37.

n = number of participating laboratories; concentration in g/g

Ultra-trace elements n Cert.value

Be <0.1 4Pd <1 2Ag <0.4 4Ba <1 4Ta <0.2 5Ir 0.20 0.03 5Pt <0.2 5Tl <0.2 4Bi 0.33 0.13 5

Trace or ultra-trace elements ?

Ca <12 4Zn <5 2Se <10 2

ICP-TOFMS - LECO Renaissance

Laser Ablation SystemCETAC LSX-200 plus

Instrument installation

ICP-TOFMSFlight tube

Element Fly time (ns)7Li 675024Mg 12150

48Ti 1702289Y 23020115In 26110138Ba 28558140Ce 28762208Pb 34972209Bi 35056238U 37382

LECO - RenaissanceTypical fly times for ten elements

Element HO 047-Ovako Steel ABBall Bearing Steeln = 8

ECRM 090-1BASLow Alloy Steeln = 7

Value determin. Value determ. Cert. valueTi 14.0 0.3 19.7 0.3Zn 16.2 1.2 21.6 1.5 20.9Ga 27.0 0.2 22.0 0.2 22.8Nb 4.69 0.06 4.3Sn 46.9 0.9 44.0 0.04Sb 0.28 0.04 8.14 0.08 9.0Te <1 <1 <2La <0.076 <0.076Ce <0.045 <0.045Pr <0.028 <0.028Nd <0.048 <0.048Gd <0.22 <0.22Ta <0.048 0.061 0.010Ir <0.068 0.08 0.01Pt <0.14 0.12 0.04Tl <0.059 <0.059 <1Pb 0.79 0.03 23.6 0.3 23.9Bi <0.047 <0.2U <0.028 <0.028

ICP-TOFMSAnalysis of wet-digested low alloy steel samples

Concentrations given in µg/g (ppm)

Element SDN 1021AB Sandvik SteelHigh alloy steeln = 4

CRM JK 37Jernkontoret/SIMRHigh Alloy Steeln = 9

Value determined Value determined Cert. value *Ti 89.4 0.8 42.2 0.2 38Ga 27.9 1.3 28.8 0.4 30Nb 35.2 0.9 12Sn 11.1 0.1 14.5 0.2 18Sb 0.98 0.07 5.6 0.1 5Te <1 <1 <2La 18.4 0.5 357 12 371Ce 130 5 1170 40 1230Pr 14.8 0.1 103 5 129Nd 19.7 0.3 306 7 347Gd 1.5 0.1 59 1 68Ta <0.048 0.051 0.004 <0.2Ir <0.068 0.23 0.01 0.2Pt <0.14 0.14 0.01 0.1Tl <0.059 <0.059 <0.1Pb <0.059 1.32 0.02 1Bi 0.10 0.01 0.32 0.01 0.3U <0.028 0.087 0.006 0.09

*Figures in italics refer to earlier determinations carried out by five different laboratories

ICP-TOFMSAnalysis of wet-digested high alloy steel samples

Concentrations given in µg/g (ppm)

Laser AblationCopper scanning- spot size 200 µm

Laser Ablation Analysis of Copper

Copper samples:BAM 381 BAM 383BAM 382 BAM 385

All BAM samples above have been determined in a traditional wet chemical way

by ICP-TOFMS

LASER measurements:

Calibration with BAM 381, 384 and 385Internal standard Sn118 or Ag107 Determination of BAM 383

Element Laser Traditionalppm ppm

Ag109 5.15 4.86Bi209 1.18 1.08Cd114 1.73 1.67Co59 1.82 1.44Mg26 2.86 2.64Mn55 1.37 2.08Sb121 1.04 1.29Sn118 4.74 4.60Te126 1.46 1.52

LA-ICP-TOFMS and ICP-TOMSComparison of trace element determinations

Laser AblationAnalysis of Steel

Steel Samples:

JK 1C Pure IronECRM 090-1 Carbon SteelEZRM 179-2 Tool SteelHOØ47 (Ovako) Ball Bearing Steel

Calibration with:

JK 1C, ECRM 090-1, EZRM 179-2

Internal standards: Ga and Ni

Samples analysed: HOØ47 (Ovako)

HOØ47 (Ovako)Element Laser OES

% %Cu 0,075 0,07Cr 1,28 1,43Ni 0,07 0,06Mo 0,016 0,02

Laser Traditionalppm ppm

Zn 16,3 16,2

Laser AblationComparison of determinations

Laser AblationAnalysis of Zircaloy

Zircaloy samples:9 authentic samples

Calibration with:

Jaeri-Z11 and two in-door samples

Internal standards:

)(1061690PdOZr and )(1071691

AgOZr

1690OZr

Laser Ablation - Zircaloy samples

Calibration for Cr50 with internal standard

Laser Ablation - Zircaloy samples

Calibration for Cr50 with no internal standard

Sample A B D E G H I Jaeri-Z11

Cr50 0.123 0.117 0.118 0.124 0.11 0.103 0.117 0.041meas. 0.121 0.119 0.121 0.132 0.129 0.129 0.123 0.048

Ni58 0.061 0.06 0.002 0.062 0.051 0.062 0.06 0.021meas. 0.061 0.066 0.007 0.069 0.063 0.070 0.065 0.023

Co59 <5 6 <5 <5 <5 8 7 6meas. 5.0 5.1 4.9 5.1 5.1 5.1 5.1 6.0

Cu63 <10 <10 <10 10 <10 15 14 40meas. 12.1 9.4 9.1 15.1 11.5 10.1 8.5 40.2

Hf176 50 50 50 55 50 50 50 71meas. 51.7 53.2 61.6 56.5 57.6 52.8 54.6 73.4

Ti48 <5 <5 <5 6 5 9 6 28meas. 0.4 8.8 8.8 6.9 9.9 2.7 4.4 27.6

U238 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 0.8meas. 0.05 0.06 0.18 0.15 0.2 0.12 0.09 0.74

Pb208 2 2 2 2 2 2 12meas. 2.2 2.4 2.5 2.3 2.1 2 2 12.8

Laser Ablation - Zircaloy samplesComparison of trace element determinations

Laser AblationDepth profiling analysis of Al

Parameters: Al-layer content:(100 µm thickness)

Spot size 50 µm Si 7.4 ± 0.2 %Energy 3.8 mJ Mn <0.01 %Frequency 20 Hz Mg <0.01 %Integ. time 102 ms Pb 0.01 %Data points 1760 / isotope Ti <0.01 %

0 20 40 60 80 100 120 140 160 1800

500

1000

1500

2000

2500

3000

3500

Co

un

ts

Time (s)

Mg Mn Pb Si Ti

Laser AblationDepth profiling graph for

two Al-layers

Thickness of coating layers according to:- TiN 1 µm- Al2O3 4 µm- Ti (C, N) 1 µm

Three coating layers of a cutting tool

0 20 40 60 80 100 12010

100

1000

Inst

rum

en

tal s

ign

al (

LO

G m

V)

Time (s)

Al (Analog) Co (Analog) Ti (Analog) W (Analog)

0 10 20 30 40 50 60 70 80 90 100 110 12010

100

1000

Inst

rum

en

tal S

ign

al (

LO

G m

V)

Time (s)

Al (Analog) Co (Analog) Ti (Analog) W (Analog)

Laser Ablation - Transient signals of the elements Al, Co, Ti and W on a cutting tool

40 60 80 100 120

0

200

400

600

800

Sig

na

l (co

un

ts)

Time (s)

Hg (Counts)

BV 232

0 5 10 15 20 250

200

400

600

800 BV 232

Sig

nal (

coun

ts)

Djup (µm)

Hg (Counts)

Laser Ablation - Depth profile curve for Hgof an old zinc coated steel sheet

Thickness ofHg-layer - 16.3µm

0 5 10 15 20 25 300

20

40

60

80

100

120

140

160

180

200

Weldox 9601

Sig

na

l (co

un

ts)

Djup (µm)

Hg (Counts)

40 60 80 100 1200

20

40

60

80

100

120

140

160

180

200

Sig

na

l (co

un

ts)

Tid (s)

Hg (Counts)

Weldox 9601

Laser Ablation - Depth profile curve for Hgof a scrap steel sample

Thickness ofHg-layer - 3.8 µm

Conclusions LA-ICP-TOFMS vs ICP-TOFMS:

- a fast method compared with wet chemical analysis- a fast method for depth profile analysis- a tool for trace element determinations in steel and metals- a promising tool for determination of inhomogenieties (inclusions) in steel and metals

Performance of the analytical techniques employed in characterization and certification of stainless...

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