applications of borate fusion for x-ray … no. 63 applications of borate fusion for x-ray...

Abstract No. 63

Applications of Borate Fusion for X-Ray Fluorescence Analysis Author: Dr. Rainer Schramm, FLUXANA GmbH & Co. KG, Borschelstr.3, 47551 Bedburg-Hau, Germany Tel. +49 2821 99732-0, Fax +49 2821 99732-29, www.fluxana.com, [email protected] Abstract In steel industry x-ray fluorescence analysis (XRF) is a well established analytical method. Beside the direct measurement of metal samples, other samples will be measured as pressed pellets or fused beads. This presentation will present state of the art fusion technique for different applications in steel industry. A comparision of traditional gas based fusion systems and new modern electric fusion systems will be given. Based on different applications like raw materials, ferro alloys, slags or continuous casting powder all important analytical parameters will be discussed. A new development for the determination of volatile elements like fluorine, chlorine or sulphur from fused beads will be presented.

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FLUXANA®Applications of Borate Fusion for X‐RAY

Fluorescence Analysis

Rainer Schramm

CETAS 2015, 9th International Conference, Düsseldorf

© 2015 Dr. Rainer Schramm

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FLUXANA®


Company Portfolio

• Commercial XRF AnalysisDIN EN ISO/IEC 17025 Accreditation for XRF from DAkkS(flexibel accreditation)

• Application development

• Sample Preparation machines

• Production and sales of Reference Materials

• Proficiency tests

• ServiceCETA

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FLUXANA®

XRF Laboratory: 2 PerformX and 1 QuantX

WDRFA / EDRFA


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Method developmentbased on gas fusionsystems

Method developmentbased on pressed pellets

FLUXANA®


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FLUXANA®


Method development based on electrical fusion systems

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• Development of newcertified reference materials

• Organisation of proficiencytests

• XRF contract analysis asservice (DIN EN ISO/IEC 17025)

FLUXANA®


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Applications related to Steel Industry


• Raw materials

• Ferro alloys

• Slags

• Continuous casting powder

FLUXANA laboratory:

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Application Raw Materials

• XRF Application of raw materials

• Sample preparation: electrical or gas fusion system

• XRF: WDXRF

• Standards: available as CRM

• glass beads


Materials:• Sand, limestone, clay, gypsum, iron ore, dolomite, alumina, etc.CE

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Sample preparation ‐ fusion


Sample preparation:

• Preparation as dublicates

• Dilution 1:8

• FX‐X65 (66% LIT : 34% LIM)

• Electrical fusion system

• 1200 ‐ 1250°C

XRF instrument:

• Thermo PerformX WDXRF

Calibration:

• Fundamental parameter

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Example: Application Raw OxidesSet of standards used for calibration (all CRMs) 1/2

RAW 01b RAW 02 RAW 03a RAW 04a RAW 05a RAW 06 RAW 07 RAW 08 RAW 09a RAW 10 RAW 11 RAW 12 RAW 13

Dolomite Granite Slag Phosphate Bauxite Limestone Limestone Clay Fe2O3 Gypsum Gypsum Sand Iron ore

Al2O3 0,20 12,17 6,24 4,96 89,470 3,85 0,212 35,93 0,130 2,57 0,036 12,463

BaO 0,013 0,14 0,006 0,006 0,05 0,003 0,013

CaO 57,46 0,786 31,39 23,72 0,081 77,89 98,02 0,193 41,17 35,66 0,006 4,599

Cr2O3 0,002 0,004 0,018 0,07

Fe2O3 0,86 2,01 0,79 3,76 1,914 1,41 0,080 1,18 99,998 0,060 1,370 0,012 55,737

K2O 0,050 5,03 0,38 3,212 0,020 0,720 0,035 2,54 0,030 0,680 0,005 0,693

MgO 40,71 0,060 19,01 8,70 0,121 1,10 0,265 0,341 0,230 2,19 0,001 1,732

Mn2O3 0,173 0,023 0,873 0,04 0,151 0,019 0,001 0,3663

Na2O 3,38 0,24 0,171 0,020 0,180 0,035 0,387 0,010 0,090 0,003 0,108

P2O5 0,024 7,402 0,222 0,196 0,009 0,081 0,010 0,030 2,368

SiO2 0,51 76,26 39,24 47,39 5,018 14,19 1,24 58,10 0,560 11,00 99,84 20,87

SO3 1,44 0,031 57,810 46,41 0,302

SrO 0,067 0,105 0,034 0,138 0,228

TiO2 0,008 0,091 0,392 0,586 3,133 0,213 0,016 1,23 0,017 0,567

ZnO 0,016

Sum 100,01 99,87 100,14 100,00 100,15 100,01 100,01 100,05 100,00 100,15 100,24 99,92 99,88


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Example: Application Raw OxidesSet of standards used for calibration (all CRMs) 2/2


RAW 14 RAW 15 RAW 16 RAW 17a RAW 18b RAW 19cRAW 20c RAW 21 RAW 22 RAW 23 RAW 24 RAW 25

Dolomite Bauxite P Cement Cement P Cement Cement Clinker P Cement P Cement Al Cement Al Cement Cement

Al2O3 0,63 77,81 4,85 5,55 4,62 5,56 4,84 4,10 6,29 69,74 39,24 4,43

BaO 0,004

CaO 56,56 0,026 70 64,48 64,70 61,45 64,94 63,46 61,78 29,39 39,39 65,30

Cr2O3 0,067 0,003 0,008 0,02 0,009 0,006 0,113

Fe2O3 0,52 12,42 0,300 2,62 2,72 3,32 4,15 1,96 2,90 0,08 14,71 3,96

K2O 0,195 0,013 0,11 0,81 0,68 0,95 1,08 0,21 1,12 0,01 0,05 0,50

MgO 39,71 0,017 0,42 1,48 2,11 3,05 1,82 4,10 2,88 0,19 0,51 0,95

Mn2O3 0,034 0,006 0,057 0,065 0,049 0,120 0,003 0,060 0,064

Na2O 0,055 0,100 0,22 0,11 0,15 0,14 1,05 0,49 0,299 0,021 0,084

P2O5 0,008 0,071 0,12 0,163 0,124 0,31 0,003 0,070 0,192

SiO2 2,13 5,41 21,8 20,95 21,53 22,19 22,09 21,27 18,91 0,24 4,02 21,25

SO3 0,21 2,25 2,98 3,07 2,66 0,39 2,88 4,69 2,96

SrO 0,014 0,11 0,285 0,649 0,327 0,019 0,024 0,086

TiO2 3,77 0,04 0,283 0,330 0,335 0,242 0,198 0,270 0,020 1,790 0,243

ZnO 0,001 0,051 0,003 0,068

Sum 99,87 99,83 100,16 99,95 99,88 99,67 99,70 100,06 100,16 100,00 100,00 100,00

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Calibration – Raw Materials


CaO with electrical fusion machine

SEE: 0,30%

• 24 CRMs as duplicates (green)

• 7 control samples (orange)CETA

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Control samples for CaO – Raw materials


Sample preparation:

• Mean value of 3 duplicates

Control samples Certificate Results

CRM CaO % u(Cref) 95% CaO % bias %

NIST 1413 sand 0,74 0,04 0,75 0,01

GYP‐C gypsum 41,04 0,94 41,11 0,07

BAS 683‐1 iron ore 7,98 0,11 7,87 ‐0,11

GBW 7108 rock 54,13 0,38 54,23 0,10

BAS 513 limestone 98,58 0,28 98,59 0,01

FX CRM 101 cement 48,24 0,15 48,19 ‐0,05

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Application Ferro Alloys

• XRF application of ferro alloys

• Sample preparation: gas or electricalfusion system

• XRF: WDXRF

• Standards: available as CRM + synthetic

• glass beads


Materials:

• FeSi, FeSiMn, FeSiMnP, FeMo, FeTi, FeV, FeW, FeNbCE

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Ferro Alloys ‐ Sample Preparation


• Direct method:sample, oxidizer and flux at once in crucibleone fusion program with oxidation step

• 2 step method:sample and oxidizer in cruciblefusion program for oxidation onlyaddition of fluxmain fusion program

• Internal standard method:addition of an internal standard element

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Example FeSi


Sample preparation:

• Preparation as duplicates

• 0.2g sample

• 1g V2O5, 8g LIT

• WO3 int. Standard

• Gas fusion system VULCAN

XRF instrument:

• WDXRF

Calibration:

• empiric

Calibration standards:

• SARM33, HC 14606, HC 14607, BS 140/1, BS 140/2, BS 140/3, BS 140/4, F3/3

• 5 synthetic standards tofill gaps

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Control sample FeSi


2 certified reference materials:

HC25627 Al Ca Cu Fe Mn P Si

Certificate 1,8 0,3 0,172 0,023 76,741 1,88 0,31 0,03 21,47 0,175 0,024 76,62

2 1,90 0,28 0,04 20,33 0,172 0,014 76,70

3 1,89 0,32 0,03 20,78 0,180 0,021 76,72

4 1,88 0,29 0,04 20,52 0,184 0,024 76,77

5 1,91 0,30 0,03 20,38 0,168 0,021 76,57

6 1,90 0,29 0,03 20,36 0,178 0,021 76,74

Mean 1,90 0,30 0,03 20,64 0,176 0,021 76,69STDEV 0,01 0,013 0,003 0,44 0,006 0,003 0,08

bias 0,10 0,02 0,32 ‐0,01 ‐0,001 0,001 0,00

IPT70 Al Ca Cu Fe Mn P Si

Certificate 0,21 0,16 0,066 54,1 0,283 0,018 44,71 0,23 0,13 0,08 53,67 0,298 0,027 44,82

2 0,23 0,12 0,09 53,78 0,298 0,019 44,85

3 0,23 0,13 0,09 53,38 0,288 0,021 44,83

4 0,22 0,13 0,09 53,78 0,294 0,017 44,71

5 0,24 0,14 0,08 53,64 0,292 0,024 44,74

6 0,20 0,12 0,08 54,19 0,303 0,015 44,62

7 0,22 0,13 0,08 53,98 0,299 0,019 44,63

8 0,22 0,13 0,08 55,05 0,298 0,014 44,82

Mean 0,22 0,13 0,09 53,93 0,296 0,019 44,75STDEV 0,01 0,006 0,004 0,51 0,005 0,004 0,09

bias 0,01 0,02 0,32 ‐0,01 ‐0,001 0,001 0,00

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Electrical fusion system


Special functions for ferro alloys

• Observation of the oxidation

• Opening of the furnace on top to let gases going out to avoidlong‐term contamination

• Use of a lid to avoid spittingin the furnace

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Application Continuous Casting Powders

• XRF application of continuous castingpowders

• Sample preparation: electrical fusionsystem

• XRF: WDXRF

• Standards: available as CRM

• glass beads


Materials:

• Products of continuouscasting powder (up to 20% carbon)

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Sample preparation ‐ fusion


Sample preparation:

• Preparation as duplicates

• Dilution 1:8

• FX‐X65 (66% LIT : 34% LIM)

• Electrical fusion system

• 1200°C

XRF instrument:

• WDXRF

Calibration:

• Fundamental parameter

Calibration standards:

• DH‐SX 30‐05, DH‐SX 30‐13, DH‐SX 30‐11, DH‐SX 30‐12, NIM‐G, No. 7‐1‐007, 7212, CRM101, BCS 348, NIST 1883 A, NIST 1882 A

• 11 synthetic standards tofill gaps

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Calibration – CC Powder and RAW materials


F in CaF2 with electrical fusion machine

SEE: 0,27%

LOC Mg, Fe

• 8 Standards as duplicates

Certified concentration [%]

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Control sample Continuous Casting Powder


DH‐SX 30‐40 F Al2O3 CaO Fe2O3 K2O MgO MnO2 Na2O P2O5 SiO2 TiO2

Certificate 6,01 7,19 39,19 0,32 0,256 0,779 0,053 7,09 0,034 41,35 0,028

1 6,176 7,204 39,445 0,312 0,251 0,769 0,054 7,006 0,035 41,129 0,039

2 6,055 7,189 39,458 0,310 0,260 0,775 0,055 6,967 0,035 41,134 0,038

3 6,175 7,151 39,425 0,313 0,262 0,759 0,053 6,999 0,039 41,093 0,039

4 6,398 7,189 39,516 0,318 0,255 0,776 0,054 7,032 0,033 41,187 0,040

5 6,221 7,248 39,595 0,313 0,255 0,778 0,051 6,993 0,032 41,233 0,036

6 5,914 7,224 39,498 0,312 0,252 0,777 0,053 7,067 0,038 41,261 0,037

7 6,011 7,178 39,475 0,316 0,261 0,791 0,052 7,052 0,036 41,132 0,041

8 6,234 7,207 39,527 0,312 0,250 0,766 0,054 7,026 0,038 41,358 0,038

9 5,981 7,231 39,520 0,314 0,253 0,808 0,054 7,182 0,035 40,970 0,038

10 6,236 7,243 39,620 0,312 0,258 0,799 0,051 7,234 0,035 41,231 0,039

Mean 6,14 7,20 39,51 0,313 0,255 0,780 0,053 7,05 0,035 41,17 0,038

STDEV 0,147 0,031 0,063 0,002 0,004 0,015 0,001 0,086 0,002 0,106 0,001

bias 0,13 0,02 0,32 ‐0,01 ‐0,001 0,001 0,000 ‐0,034 0,001 ‐0,18 0,010

Mean 6,07 7,18 39,03 0,321 0,244 0,782 0,059 7,18 0,032 41,16 0,035STDEV 0,544 0,084 0,064 0,012 0,005 0,016 0,002 0,150 0,003 0,094 0,001

bias 0,06 ‐0,01 ‐0,16 0,001 ‐0,012 0,003 0,006 0,097 ‐0,002 ‐0,19 0,007

Comparison with VULCAN gas fusion system:

Electrical fusion system:

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Summary


Fusion applications related to steel industry in the FLUXANA laboratory

• Raw materials – pressed pellets and fusion

• Ferro alloys ‐ fusion

• Slags – pressed pellets and fusion

• Continous casting powder ‐ fusion

• Gas – and electrical fusion systems complementary

• Further development of CRMs

• Organisation of PT

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Thank you for your attention!


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applications of borate fusion for x-ray … no. 63 applications of borate fusion for x-ray...

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