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APPLICATIONS AND PERSPECTIVES OF A NEW INNOVATIVE XRF-XRD SPECTROMETER IN INDUSTRIAL PROCESS CONTROL
D. Bonvin, R Yellepeddi ARL Applied Research Laboratories S.A., 1024 Emblem (Switzerland) A. Buman ARC Applied Research Laboratories, Dearborn, MI 48120 (USA) 1. INTRODUCTION

Wavelength Dispersive X-ray fluorescence (WDXRF) is a well established technique for process control in various industries. Its versatility in handling both conducting and nonconducting solids, its accuracy and excellent precision for the majority of the elements and the wide dynamic range (from ppm to 100%) gave WDXRF the place it enjoys in the process and quality control. Elemental analysis of raw materials, intermediate products (sintered, calcinated or electrolysis related) and final products (cement, mining, pure metals and alloys) is routinely carried out using a typical configuration with about 10 to 20 XRF monochromators for rapid analysis and an XI@ goniometer for flexible analysis of other elements. In the metals industry, XRF is employed in conjunction with optical emission techniquesfor a more complete analysis. Due to the ever increasing demand for the detection and reliable analysis of trace elements in the production of pure metals as well as for the tighter control of alloy or final product compositions, there is a need for enhanced sensitivities in XRF and correspondingly lower limits of detection. In addition, there are needs to monitor specific phases or compounds either in the raw materials or in the intermediate products for better utilization and process optimization. Since XRF is essentially capable of measuring total elemental composition only, wet chemical methods are generally used for the analysis of a given compound, for example free lime in cement clinkers, differentiation of iron oxides in terms of magnetite and hematite content, analysis of Fe2+ (FeO) in sinters or alumina related phases etc. These methods are not only time consuming but are usually off-line with respect to the process integration. X-ray diffraction can, in suitable cases,quantify the different forms of iron oxides in ores or the Fe2+in sinters or distinguish alpha-A1203in alumina, or free CaO in clinker, etc. However, a traditional X-ray diffractometer can hardly be justified for such on-line process control applications due to its complexity, its poor repeatability and the maintenance costs involved. The usefulnessof having both XRF and XRD data on the same sample has been discussed earlier. Various combinations using WDX and EDX techniques have been proposed.The possibility of an energy dispersive diffraction/spectroscopy was first developed by Giessen The and Gorden and Buras et.a1.23 occurrence of diffraction peaks in an energy dispersive XRF spectrum has been described4.Prediction and detection of diffraction peaks in an energy dispersive XRF spectrum of a given sample and their exploitation in some applications has been discussed4. Quantitative phase identification and analysis using the data from XRF and XRD has been demonstrated in cases such as synthetic corrosion product, limestone and mullite5. It was hoped that such a combined analysis would become available in a single program5.A combined XRF and XRD instrument for on-line processcontrol applications was described earlier 6. This system is based on a diffraction tube excitation of the sample and

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separate proportional counters to detect diffracted beams and fluorescence radiation. An integrated XRD-XRF system for the on-stream analysis of slurries was also described earlier. Here again, a standard XRD platform is used with fixed geometry goniometer and an EDX detector for the XRF analysis. A combined XRD and XRF system for portable and remote applications (planetary explorations) has been developed . Built around low power excitation and CCD position sensitive detector, such an instrument was shown to be feasible and applicable 2. INSTRIJMENTATION

Taking into account these analytical needs, a new X-ray spectrometer has been developed (Figure 1) which integrates both X-ray fluorescence and X-ray diffraction in one single instrument (Figure 2).

Il&pl:g.~. ( h.Y.S .%?oiotI of 1he itr!egl~rl/ed XIU~AK/ 1 .yec/mniefer

fTiprr 2: Irl/e.gralior/ nairrtnwnt:

L7~lCllj5l.S

qf Xh!F ami XfW IN /he .sarne me xample, one it~slrunwr~l, one

The salient features of this new X-Ray instrument are listed below: . Modular construction enabling the selection of analytical devices such as XRF goniometer, XRF monochromators and integrated XRD system. Most appropriate conligurations can be defined to achieve speed of analysis, sample throughput or limits of detection as required. . High sensitivity thanks to optimized X-ray optical design for monochromators and goniometers. . Latest generation end-window tube with Rh anode providing broad spectrum excitation. Extra-thin window (75 micrometers) increases sensitivity for light elements. 70 kV excitation provides higher sensitivity for heavy elements. . Geometry with X-ray tube above sample preventing damage to instrument in case of defective samples (pressed pellets) and ensuring high uptime in routine use. . Fast, simple and highly reliable sample introduction system. . Fast gearless XRF goniometer with such positioning accuracy that precision is equivalent to tixed channels. Allows also semi-quantitative and standardless analysis through state-of-theart QuantAS and UniQuant software options. . Integrated XRD system providing XRD measurements with the same tube on the same sample. . High stability of analysis thanks to global and local thermal control systems. . WinXRF software compatible with Windows TM NT environment, integrating analytical i expertise in its Analytical Assistant to help the operator through the use of the spectrometer. . Modem support available to prevent or diagnose instrument or analytical problems.

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3.

APPLICATIONS

3.1. IRON AND STEEL INDUSTRY The analytical needs of the modern iron and steel industry (see Figure 3 below) increasingly demand more comprehensive and process-integrated instrumentation. Two trends seem to emerge in the way the analytical instruments are positioned in this industry: there is a clear move towards decentralization of the measurements and there is a need for higher levels of information content from each analytical instrument. Indeed, most iron and steel manufacturers would like to see that the analytical capability moves closer to the process where the answer is truly needed
TOTAL IRON X-RAY ANALYZER mplele an- I&immiy In a d&c hstmment Iron ores
Hematitqhlagnetite)

Low dKh$

dloy

:;,; .* $

Coating thiekness(nqh2)y
monoelemcnt on shd plate Eli,

Fiqure 3: Typicul applications in the iron and steel industry for an integrated XRF-XRll

spectrometer

3.1.1 Analysis of hematite and magnetite in iron ores Figure 3 shows an XRD scan on three iron ore samples. Two distinct peaks can be seen: the peak around 2.96 Ang. is due to magnetite (Fe303) while the peak around 2.7 Ang. is due to hematite (Fe,O,). The peak intensities are quite high allowing their use for quantitative analysis based on peak intensities as there is no observable peak shift as seen in Figure 4. However, the XRD program allows a search for the exact position of the peak before measuring the intensity. This is particularly useful if iron ores of different origin are mixed and slightly varying polymorphic structures exist. It is also possible to do a peak integration with or without suitable background correction.
40 M F JI 2 18 .$ II g *o 1 II II 8 I 0 1
50 7 p $6 r -I j JO

Bare currr witho, correctionr

I
-,A+

Fe304-II ,-&&J&.& 3.0 2.9

dspocing

3.1

2.8
(Alptrom,

2,

2.6

Fiqure 4: XRD scans on 3 iron ore samples showing the hemafite and magnetite phases

4 1

20

JO

60

80

100

bure 5: CRD calibration curve of Fe203 in a series _ ot u-on ore samples

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Figure 5 presentsthe calibration curve for the hematite phase in a series of iron ore samples. The accuracy of the XRD measurementreflects that of the wet chemical method. One of the most important aspects of the integrated XEW system is its reproducibility and long term stability. The XRD measurementsbenefit from the same optical encoder technology used on the XRF goniometer as well as from the vacuum environment and the high precision of the sample positioning system. Apart from the quantification of different mineral species in the iron ore, the XRF part of the instrument is also used for analysis of trace elements or oxides presentin the sample. 3.1.2 Analysis of Fe0 in sinters: Analysis of Fe0 in sinters can be made much faster and on-line with the help of the integrated XRD system,typically in less than 100s with very good precision. A series of sinter samples were measured to establish the calibration curve using concentrations determined by wet chemistry. A typical range of Fe0 may be between 4 to 9%. This means that very high sensitivities are necessaryto achieve good precision. Thanks to the closely coupled optics, the integrated XRD system offers the necessary peak to background intensities to achieve satisfactory performance. Figure 6 shows a calibration curve obtained for a series of sinter samples. Excellent correlation is obtained between the XRD intensities and the chemical concentrations of FeO. Table 1 provides the corresponding regression results. A typical standard error of estimate (accuracy) of around 0.2% is achieved.
4.4 8 h % I P 2 4.2 3.8 4.0 3.6 3.4 3.2 if 2.6 3.5 4.0 4.5 5.0 5.5 P/o> 6.0 6.5 7.0 Base Curve wihtoutCar,ectionr

Fe0 Concentration

Figure 6: XRD calibration for Fe0 in sinters

Inten--Concentration of PC sity Nr. Calcul. Nominal Kcps 1 3.5583 5.41 5.0 2 3.5384 5.3 5.38 4.4 4.27 3 2.9626 4 3.5743 5.4 5.44 5 4.8 4.79 3.2299 5.6 5.78 6 3.7489 7 5.49 5.5 3.5981 3.4294 5.2 5.17 8 6.4 6.09 9 3.9115 6.2 5.93 10 3.8248 5.6 5.77 11 3.7422 5.74 5.8 3.7274 12 4.6 4.51 13 3.0838 0.20 Standar Error of Estimate:

Sinter

l-

Difference Absolute 0.41 0.08 -0.13 0.04 -0.01 0.18 -0.01 -0.03 -0.3 1 -0.27 0.17 -0.06 -0.09

Table I: XRLI calibration results of Fe0 in sinters

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Table 2 shows short term repeatability results on a sinter sample. Since the instrument is capable of analysing all the elements or oxides by XRF together with the Fe0 concentration by XRD in the same sample, one can effectively combine the results from the two methods and exploit the synergy between total elemental concentration and the specific phase content of the same element. The standard deviation shown in Table 2 for most of the constituents doesconfirm the suitability of the instrument in a typical processcontrol environment.
Run I> 2> 3> 4> 5> 6> 7> 8> 9> lO> ll> A% Fe0 8.32 8.31 8.30 8.32 8.30 8.32 8.30 8.30 8.29 8.31 8.32 8.31 0.01 0.13 Fe Total 56.25 56.24 56.25 56.25 56.26 56.27 56.27 56.27 56.27 56.27 56.28 56.26 0.01 0.02 SiOz 5.81 5.82 5.81 5.82 5.83 5.82 5.82 5.83 5.82 5.83 5.82 5.82 0.01 0.10
A1203

CaO 10.21 10.21 10.20 10.21 10.20 10.21 10.20 10.20 10.21 10.20 10.20 10.20 0.00 0.04

Ml@
1.78 1.79 1.79 1.79 1.79 1.79 1.79 1.79 1.78 1.79 1.79 1.79 0.00 0.17

TiOz 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.22 0.00 0.39

Mn 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.00 0.39

S 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.004 0.000 1.748

P 0.098 0.098 0.098 0.097 0,099 0.097 0.098 0.099 0,099 0.097 0.099 0.098 0.001 2.130

V 0.029 0.028 0.029 0.029 0.030 0.029 0.030 0.028 0.030 0.029 0.030 2.43 0.00 0.11

2.14 2.13 2.13 2.14 2.14 2.13 2.13 2.13 2.14 2.14 2.14 2.14 0.00 0.23

Sd Sd%
Table2. -*

Short term repeatability results on sinter sample using the integrated XRD-XRF spectrometer

3.1.3 Direct Reduced Iron: Direct Reduction (DR) has been defined as the processof reduction of iron oxides to metallic iron using a lower temperature than required for a conversion to liquid state. The iron oxides can be in the form of sized ores, concentrates,pellets or mill scale etc. The reduction process itself can be gas based or coal based.Direct Reduced Iron (DRI) is a metallic product which is used as a feedstock for electric arc furnace steelmaking, in blast fwnaces, and in other iron and steelmaking applications. Its main advantagesare a low level of impurities and chemical and physical consistency.Hot Briquetted Iron (EIBI) is a densified form of DRI. The DRI process is being implemented in various parts of the world thanks to its many advantages.Since the process involves reducing the iron ore directly using a gas mixture of carbon monoxide and hydrogen, for example, the analysis of iron ore as it goes through a seriesof reactors would allow a continuous control of the reduction process.It is obvious that the concentration of iron oxide (hematite for example) decreases near zero levels when the to most of the iron is in the metallic form. The integrated XRF-XRD spectrometer,named in this case Total Iron X-ray Analyzer may be used to monitor this processby measuring the oxide content by XRD, total Fe content by XRF and the difference accounting for the metallic Fe.

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3.2. ALUMINIUMINDUSTRY Production of aluminium involves electrolysis of aluminium oxide. Starting from the raw materials (bauxite, aluminium bearing minerals) through alumina to aluminium metal and its alloys, XRF can be positioned in different areasof processand quality control in this industry (see Figure 7 below). X-ray diffraction (XRD), on the other hand, is commonly used, for example, to perform the electrolytic bath analysis in addition to any other off-line applications.
luEAL ALUMINIUM X-RAY ANALYZER
Acompleteanntysislaboratoryiuasingle~

Alumlns
(a-Al203)

Electrolyte Bath ;cess AlF3,C&?, BR:

Alumtntum metal Alloys

,Fisure 7: Typical applications in the aluminium industry for an integrated XRF-Xm spectrometer

Figures 8 and 9 show as examples the calibration curves for the excessAlF3 and total calcium respectively, using the integrated XRD system of the Total Aluminium X-Ray Analyzer. Figure 10 shows the calibration curve obtained for a-Al203 in a series of alumina samples using the sameXRD system.
MVR Graphical Results: XRD for excess AIF sase curve WIthoUt CorreCtloB

E f B
0 2 4 s Cancmtratlan [%, 8

23.6 23.2 t 228 22.4 $ 22 D 21.6

21.2

Concentration ml : I 1 Figure 8: XRD calibration curvefor the excessof AlF3 in Figure 9: XRF calibration curve for the total calcium a series of bath samples in the bath samples
II

i-:r:-:

4.8

4.9 6

5.1 6.2

MVR Graph14 XRD of Alpha4203

Results: in Alumina

Base Curve without Corrections

Figure IO: XRD calibration curve for the a-AlJO in a series of alumina samples

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3.3 CEMENT INDUSTRY The analytical requirements of the cement industry have evolved in the past few years to encompass a wide range of materials and qualities. While it is difficult to substitute the different physical and chemical methods used in a cement laboratory by a single technique, most cement manufacturers are looking for rationalization and integration of analytical methods. This is in accordancewith the drive to (a) optimize the use of raw materials and additives, (b) reduce the production costs, (c) improve and stabilize the quality and (d) keep the maintenance and running costs under control. In addition, environmental issues are becoming more and more important in the cement industry both in terms of using the kiln to incinerate and eliminate waste products and using by-products from other industries as fillers, i.e. coal ash, metallurgical slags, silica dust etc.
TOTAL CEMENT ANALYZER

A~pMecementat+slshbora~inazin~madtb~e

(Slags, Fly Ash, Limestone, etc.)

(Heavy mctsl, In du.st)

Cement

Fiaure 11: Typical applications in the cementindustryfor an integrated XRF-Xm spectrometer

While the role of XRF in the analysis of major and minor oxides in the raw materials, clinker, cement and additives is universally accepted, the use of XRD for the analysis of free lime in clinkers and other crystalline phases such as limestone in the process of precalcination or as an additive in cement has been limited until recently. Only an integrated XRD system can be justified in such online process control applications due to its simplicity of use, high repeatability and the low maintenance costs involved. A summary of various applications in the cement industry is given in Figure 11 and in Table 3.

TOTAL CEMENT ANALYZER XRF Fixed channels

l

Goniometer
l l

XRD System
l l

Simultaneous and rapid analysis (<4Os) CaO, SiO,, AJO,, Fe203, MgO, SO,, etc. Higher throughput Dedicated programs

l l

Sequential and flexible analysis Analysis time (analysis of major & minor oxides) (~2 min) Analysis of sulfide versus sulfate in slags (as additive in cement) Semi-quantitative programs QuantAS and Uni-Quant for standardless analysis of samples from : quarry, coal ash, additives (like fly ash: alumino-silicates, pozzolans, slags, by-pass (Na, Cl, S ...) gypsum (minors & traces), heaw metals on electro-filter dust. etc.

l l

Free Lime in clinkers Limestone additions in cement Pozzolan additions Clinker phases (C,S, C,S, C,A and C,AF) Hot meal (CaO vs CaCO,) Gypsum phases, etc.

Table 3: Summaryof typical applications using the ARL s Total CementAnalyzer

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3.4. STANDARD-LESS ANAL YSIS From the analyst point of view, one of the most useful recent developments in WDXRF has been the availability of semi-quantitative or so called standard-less analysis programs. These programs enable to handle all kinds of samples irrespective of the availability of matching standardsand calibrations. A universal goniometer covering most of the elements from Boron to Uranium is used for this purpose. The semi-quantitative analysis can be based on a global scan followed by spectral processing (QuantAS) or peak and background measurementsat fixed spectral positions followed by intensity processing(UniQuant@).The accuracy and reliability of these programs is improving constantly as more efticient matrix correction algorithms, overlap and background correction models are developed. Applications such as alloy sorting or characterization of specialty alloys, on-the-spot analysis of raw materials, analysis of irregular solids etc. can be handled using these programs. Indeed, both QuantAS and UniQuant@ programs bring a very high value to the XRF goniometer by fully exploiting its flexibility, precise angular positioning and optimized collimator-crystal-detector combinations. Although the X-ray instruments in any industrial process control are predominantly applied for the analysis of routine samples, there is still a need for flexibility to handle ad hoc or occasional samples.For example, the quality of the incoming raw materials or fluxes or coal or environmental dust or any other specialty products may need to be characterizedfrom time to time. Difficulty arises when these non-routine samples do not fit into any of the calibrated programs. Semi-quantitative programs can handle such situations and report the concentrationsdirectly. The following three examples (tables 4, 5 and 6) illustrate the typical performance of such programs in comparison with certified concentrations

---IZn _--. Al

>
1 I 25.3% 5.10% 25.2% 5.18% Cl Al Ca 650o~m 530ppm 1 / I 740ppm 650o~m 540ppm / I

~~~

Table 4: Sample BERM CDA 863 - Copper Alloy

Table 5: Sample NlsT 195 - Ferro-Silicon ---------->

1Oppm

31 wm

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Concentrations
Element Given
1 31.2% /

UQ
30.8%

j QuantAS
I 30.5% I

Fe

2.83% 2.38% 1 Mn Ta -. Si Al La Ti v Cl 1 0.910% 0.752% 0.382% 0.134% 265ppm 232ppm_.---_--1

2.82% 2.20% 0.928% 0.807% 0.198% 0.164% 102ppm 292 ppm 202 ppm 1 0.941% 0.790% 0.414%0.240% 280ppm 270ppm 180ppri____-170 ppm --___

Table 6: Sample BS 162 - Maraging Steel

4.

LINKING THE INSTRUMENT AUTOMATION

TO THE PROCESS THROUGH

There exists in process control industries requirements for simple automation requirements where samples are available only in one single form, typically pressedpellets in steel rings or cylindrical metallic samplesof identical size. In these casesa large sample changerpositioned directly in front of the instrument can be linked to a transport belt which brings the prepared samplesfrom the automatic preparation machines to the instrument. The griper of the sample changer can move on both X and Y axis in order to position itself precisely at desired positions above the surface of the magazine. The griper picks up the sample from the belt and brings it to the loading port of the instrument to be introduced into the vacuum chamber of the spectrometer. The sample identification and the analytical program selection can be done through software connection from a remote PC using the standardanalytical software. Alternatively an external computer system can act as master of the whole automation system. Automation of analysis can be performed not only for production samples but also for control standards,setting-up samples and type standards. After the analysis the sample can be returned to the same transport belt or to a secondtransport belt (Figure 12) or filed in three classification baskets

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Belt from the right of instrument

Belt from the rear and left of instrument

transport

belts

Belt from the left of instrument L

&we

12: Illustration

qf the various possibilities to link rrausport hrlt.r to the X-Y sumpIt changer.

When full automatic operation is required, the instrument can be connected to automatic preparation machines through a robotic sample manipulation system (Figure 13). This flexible tool for automation works as the brain and arm of the whole analysis process. Thanks to the use of an industrial robot for all manipulation operations, it can handle multiple sample forms. It manages the sample introduction, registration, preparation and analysis, as well as the priorities between analysis of production samples, measurement of control standards, running of setting-up samples, type standards or manual samples. Sample sorting, marking or filing are performed quickly and efficiently. The automatic sample manipulation system works in order to minimize sample turnaround time. Instrument control through on-line Statistical Process Control (SPC) and standardization are tasks which are integrated in the normal routine work of the automation system. They are only performed when required and at times when analy: <is C

I~?~wrr 13: The roboil the .spectrometer

to /he loadit~g port of

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5.

CONCLUSIONS

In conclusion, the ARL 9800 X-ray spectrometeroffers the state-of-the-art instrumentation to meet the present and the future analytical requirements of process control industries, in particular in the iron and steel, aluminium and cement industries. The modularity, reliability, reproducibility and the ease of use through total integration are the key features of this new instrument. The integration of the well establishedXRF technique in conjunction with XRD is realized in a single instrument with a view to facilitate the most comprehensiveanalysis of raw materials and products. The instrument can be configured and optimized with various analytical modules to handle fast routine elemental analysis as well as analysis of non-routine samples, The compact size of this new instrument is compatible with its integration into simple or state-of-the-art automated systems linking it to automatic sample preparation equipment.

6.

REFERENCES Ray Analysis, Vol. 2 I, pp 7-21, 1978 B. C. Giessen and G.E. Gorden, Sci., Vol. 159, p. 9 73, 1970 8. Buras et al, Report 894/l l/PS, Inst. of Nut. Res., Mar. 1968 R. G. Tissot and R. P. Goehner, Diffraction peaks in X-ray spectroscopy: friend or FOE?, Advances in X-Ray Analysis, Vol. 36, pp 89-96, 1993J. P. Engelbrecht, M,F. Garbauskas and R. P. Goehner, Complete quantitative analysis using both X-Ray Fluorescence and X-Ray Diffraction, Advances in X-Ray Analysis, Vol. 25, pp 285-288, 1982 M. Hietala and D.J. Kalnicky, Applications of on-line XRF and XRD analysis techniques to industrial process control, Advances in X-Ray Analysis, Vol. 32, pp 49-57, 1989 J. P.R. de Villiers and SW. w. de Bruyn, The on-stream X-ray analysis of slurries for process control, Advances in X-Ray Analysis, Vol. 35A, pp 661-672, 1992 J.A. Kerner and E.D. France, Combined XRD and XRF analysis for potfable and remote applications, Advances in X-Ray Analysis, Vol. 38, pp 319-324, 1995

1. R. Jenkins, Interdependence of X-Ray Diffraction and X-Ray Fluorescence data, Advances in X2. 3. 4. 5. 6. 7. 8.