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(19)

(11) EP 3 081 921 A1

(12) EUROPEAN PATENT APPLICATION

(43) Date of publication: (51) Int Cl.:

19.10.2016 Bulletin 2016/42 G01N 21/27 (2006.01)

(21) Application number: 15163879.8

(22) Date of filing: 16.04.2015

(84) Designated Contracting States: (72) Inventor: Lammerant, Luc

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB 3582 Koersel (BE)
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO
PL PT RO RS SE SI SK SM TR (74) Representative: Heraeus IP
Designated Extension States: Heraeus Holding GmbH
BA ME Schutzrechte
Designated Validation States: Heraeusstraße 12-14
MA 63450 Hanau (DE)

(71) Applicant: Heraeus Electro-Nite International N.V.

3530 Houthalen (BE)

(54) SPECTROMETER CALIBRATION METHOD AND REFERENCE MATERIAL

(57) The present invention refers to a calibration spectrometer wherein a reference material has a homo-
method for a spectrometer and a reference material. geneous content (1) of elements. Further the reference
It is an object of the present invention to provide a material is protected by an inert coating (2). The refer-
calibration method for a spectrometer and a reference ence material is used for calibration of the spectrometer.
material which facilitates the calibration of a spectrome- The object is further solved by a reference material hav-
ter. ing a homogeneous content of elements which is pro-
The object is solved by a method for calibration of a tected by an inert coating.
EP 3 081 921 A1

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Description ately precede the analysis of any samples, for optimum

accuracy.
[0001] The present invention refers to a calibration [0005] Since the spectral intensity ratio of a target sam-
method for a spectrometer and a reference material. ple to be analysed is incorporated from a previously pre-
[0002] The composition of iron and steel alloys can be 5 pared and known reference calibration curve, the preci-
measured using different analytical techniques. One of sion of the analysis for the target sample depends on the
these techniques, optical emission spectroscopy in- accuracy of the previously generated calibration curve.
volves exciting atoms of a target sample of which knowl- Accordingly, a standard reference material of homoge-
edge of the composition is desired and examining the neous and known elemental content is necessary for ac-
wave length of photons emitted by atoms during transi- 10 curate analysis. These standards should be selected to
tion from an excited state to a lower energy state. Each cover the concentration ranges of all elements for which
element in the periodic table emits a characteristic set of the spectrometer is capable. The standards should also
discrete wave lengths when its atoms return from an ex- match the structure and alloy type being evaluated.
cited state to a lower energy state. By detecting and an- [0006] One such standard reference material used for
alysing these wave lengths the elemental composition of 15 the routine calibration is a circular ingot of for example
a sample can be determined in accordance with a cali- 40 to 60 mm diameter. Prior to each use, the surface of
bration curve showing the relation between the spectral the ingot must be prepared by grinding or milling in order
intensity ratio (absolute radiation power of an element / to obtain a new active surface exhibiting no oxidation or
absolute radiation power of the base metal) and the con- other chemical changes in the surface. In this way accu-
centration of the element in the standard sample. The 20 rate measuring results can be obtained and a consistent
spectral light may be produced by irradiation with elec- calibration curve developed. The procedures and proc-
tromagnetic radiation such as by a laser, x-rays, but is esses to obtain a representative analysis of metals are
generally produced by a short spark produced by a spark well known in the art. In Dulski, T.R. A Manual for the
generator incident upon the target of which knowledge Chemical Analysis of Metals, ASTM International, 1996
of its elemental composition is desired. Irrespective of 25 or the publication ASTM E1009 well describes the anal-
the energy source, the accuracy and reliability of such ysis of carbon and low alloy steel. Reference materials
emission spectrometers is dependent on the accuracy are commercially available and known for example from
and quality of the detector and optics used to receive the the MBH catalogue 2014 from MBH Analytical LTD, Hol-
radiation emitted from the sample. land House, Queens Road, Barnet, EN5 4DJ, England.
[0003] The output of a spectrometer may drift with time. 30 [0007] According to published procedures such as;
Drift correction may be required due to changes in the USA standard ASTM E415 - 14 Standard Test Method
optics, the excitation source, processing electronics and for Analysis of Carbon and Low-Alloy Steel by Spark
even ambient room temperature or humidity. These Atomic Emission Spectrometry or ASTM E716 - 10
changes can cause drifts in the intensity ratios from those Standard Practices for Sampling and Sample Prepara-
recorded during the initial calibration. In order to guaran- 35 tion of Aluminum and Aluminum Alloys for Determination
tee the accuracy, detector and/or optics response should of Chemical Composition by Spectrochemical Analysis,
be checked and the spectrometer recalibrated, if neces- in Japan standard for steel, JIS Z 2611 and JIS Z 2612,
sary, using reference material with a well-defined com- for aluminum JIS H 1305 and European standards for
position. The process of drift correcting the curves has steel DIN 51009 and for aluminum, DIN 14726 all state
many names: normalization, standardization, and re-cal- 40 grinding preparation of the sample and that its surface
ibration. Regardless of the name given the process, the should be free of contamination. Those in the analytical
curves are adjusted back to their state at the time of the field are accustomed to and train to grind the standard
original calibration. reference material even when received in a protective
[0004] If a drift correction is not made, errors will occur shipping container. The referenced national standard
and false concentration readings will result. Timing for 45 procedures dictate that the renewal of the surface of the
implementing drift correction is critical. However, this is same sample provides a continuity of results. It is well
determined by the individual laboratory considering the known in the art that once the sample is prepared the
criticality of the analysis. Some laboratories periodically surface begins to deteriorate due to interaction with the
run check or SPC standards to determine if the instru- environment.
ment is within the allowed tolerances. The stability and 50 [0008] As stated before, that accuracy of the analysis
duty cycle of the instrument determine the period for is dependent upon the quality of the recalibration and this
checking drift. It should at least be checked every hour is dependent upon the quality of the reference standard
or before a batch of samples are run to assure quality of in terms of its composition and more importantly, its prep-
results. If drift detection tolerances are not set up, it is aration prior to analysis. The technique of sample prep-
imperative that drift correction, at a minimum, is accom- 55 aration is known in the art. In some instances it is a totally
plished every shift for laboratory instruments and hourly manual operation that itself is subject to minute variation.
for mobile instruments. If the analyst is unsure about the In a laboratory setting this variation can be controlled to
state of the instrument, drift correction should immedi- an acceptable level. In industrial environments where op-

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tical emission spectrographs are installed near a metal- [0016] In a preferred embodiment of the invention, the
lurgical process these devices maybe subject to the reference material is kept under an inert gas atmosphere
same rigorous process of recalibration however, a higher or vacuum within the dispensing device which allows a
frequency of recalibration could be necessary due to the long storage of the reference material. Preferably Argon
environmental stress on the instruments. Routinely, one 5 may be used as inert gas.
skilled in the recalibration process must travel to the lo- [0017] In a preferred embodiment of the invention, a
cation of the instrument or in the case of mobile equip- composition of steel is measured by the spectrometer
ment a field calibration is necessary or a return of the after the calibration. Steel is an alloy of iron and carbon.
device to a certified calibration facility. Recalibration is a In a preferred embodiment of the invention, a composi-
labor intensive and necessary endeavor costing a labo- 10 tion of all types of ferrous and nonferrous metals including
ratory a considerable percentage of the analytical cost precious metals, alloys and ferroalloys, including as pow-
involved in the repeated preparation of the reference ma- dered metals are measured by the spectrometer after
terials for calibration. The sample surface must be calibration.
grounded or milled flat, free of residue of this process, [0018] In a preferred embodiment of the invention, the
and with a maximum tool impression on the surface. This 15 inert coating does not comprise elements to be measured
is can be manual or automatic but still requires the loading in the steel or iron alloy in order to avoid falsified results.
and retrieval and segregation of the standard reference [0019] It may further be preferred that an inert gas is
material. used to protect the homogeneous content instead of or
[0009] Shipping reactive materials in inert gas, such in addition to the inert coating.
as bottles or ampoules, is common in the material supply 20 [0020] In a preferred embodiment of the invention, a
industry. The use of protective coatings such a plastic plurality of reference materials, preferably in the form of
covers, paints, oils, ceramic and CVD films are known in coins are inserted into a cassette respectively a container
the art to prevent oxidation and corrosion protection of of cassette comprising a lid prior to the calibration of a
metal parts. spectrometer.
[0010] Metallic coatings are well known in the electrical 25 [0021] In a preferred embodiment of the invention, one
contact industry for corrosion resistance. Silver coatings or more cassettes comprising a plurality of reference ma-
have been used to improve conductivity and provide cor- terials are inserted into a storage and dispensing device
rosion resistance is disclosed in U.S. Patent No. prior to the calibration of a spectrometer, in which the
4,189,204 to Brown et al.. reference materials maybe kept under vacuum or under
[0011] It is an object of the present invention to provide 30 an inert gas atmosphere from a remote supply. An inert
a calibration method for a spectrometer and a reference gas (example argon but others are possible) protects the
material which facilitates the calibration of a spectrome- recalibration surface and the protective coating of a ref-
ter. erence material from environmental contamination.
[0012] The object of the invention is solved by a method [0022] In a preferred embodiment of the invention, a
comprising the features of claim 1 as well as by the sub- 35 new reference material is removed periodically from such
ject matter of the further independent claim. The sub- a cassette and transferred to a spectrometer platen for
claims refer to preferred embodiments of the invention. analysis respectively calibration. The entire operation
[0013] The object is therefore solved by a method for can be performed without human intervention.
calibration of a spectrometer wherein a reference mate- [0023] A reference material for calibration of a spec-
rial has a homogeneous content of elements. Further the 40 trometer has a homogeneous content of elements. The
reference material is protected by an inert coating, which content is protected by an inert coating. In this way, there
protects a repeatable surface of the reference material. is an active surface which can be used for calibration of
The reference material is used for calibration of the spec- a spectrometer.
trometer in the as received condition, without additional [0024] In a preferred embodiment of the invention, the
preparation. "Inert" in the sense of the protective coating 45 inert coating is composed of a metal such as zinc, nickel,
relates not to the absolute involatility of the element but ruthenium, rhodium, palladium, silver, osmium, iridium,
to the practical resistance to environment degradation platinum and gold or any alloys thereof.
and more particularly to oxidation. [0025] In a preferred embodiment of the invention, the
[0014] Due to the coating, it is not necessary to prepare inert coating is composed of a noble metal such as Ag,
a surface of the reference material by grinding or milling 50 Au, Pt, Ir and/or Rh or any alloy thereof. Noble metals
in order to obtain a new active surface exhibiting no ox- are metals that are resistant to corrosion and oxidation
idation or other chemical changes in the surface. Thus, on one side. As a rule, noble metals are not present in
the invention allows reducing the technical effort. an iron alloy or in steel. For these reasons, a noble metal
[0015] Since an elaborate preparation is not required, or any alloy thereof is an appropriate material.
an automatic transfer of the reference material from a 55 [0026] In a preferred embodiment of the invention, the
dispensing device to the spectrometer can take place for homogeneous content of element is formed from steel.
calibration which allows a further reduction of the tech- [0027] In a preferred embodiment of the invention, the
nical effort. thickness of the inert coating is 0,1 to 10 mm, preferably

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0,5 to 2 mm. tance for the analysis. Examples (not restricted to these
[0028] In a preferred embodiment of the invention, the only) of suitable materials in the case of reference ma-
reference material is a circular coin in order to facilitate terial used for steel are Ag, Au, Pt, Ir, Rh. The coating
the handling since an alignment is not required when layer is for example applied using sputtering technology
putting the circular coin into a housing or into a spectrom- 5 with high quality target material in order to obtain a pure
eter platen for calibration. layer (so almost without the elements to be measured in
[0029] In a preferred embodiment of the invention, the steel / iron). An appropriate thickness of the layer is 1
diameter of the coin is 10 to 80 mm diameter and/or the mm, but other layer thickness in this range can work also.
height of the coin is 1 to 30 mm. [0036] In order to have enough corrosion resistance
[0030] In a preferred embodiment of the invention, the 10 with silver (Ag) and further noble metals, a few mm is an
purity of the metal or the metal alloy is at least 90% and appropriate layer thickness. Silver is characterized by
is preferably better than 92.5%. poor sulfidation resistance and low hardness. However,
[0031] In another preferred embodiment the reference silver has advantages over other non-oxidizing metals in
material is arranged in a housing, whereby the housing that the element is not routinely analysed as a contami-
is preferably closed gas-tightly. It is of advantage, that 15 nant in irons based samples and its dominant spectral
more than one piece of the reference material is arranged emission line does not interfere with others normally en-
in the housing. The pieces can be arranged separated countered in iron analysis. As a rule, this is also true for
one from another. The housing can have at least two other noble metals.
parts whereby one part can be removed at least partially [0037] The present invention provides the analytical
from the other part. 20 laboratory with a reference standard that is prepared in
[0032] It can also be preferred that the pieces are ar- a predictable fashion, with a predicable surface that is
ranged in the housing one on top of the other. environmentally stable for extended periods of time. The
[0033] The reference material is available for immedi- elimination of the preparation labor, equipment, and con-
ate use, without preparation due to an anti-corrosive sumable supplies provides considerable benefit to the
package, individually housed in an inert gas or vacuum 25 cost of operation of an analytical instrument. The envi-
containing housing providing protection from environ- ronmental stability of the reference standard provides for
mental containments in the ambient environment such a means of recalibration of an instrument installed at the
as atmosphere, particulate and contact contamination in metallurgical process location with the same precision
handling, storage and use. The package or housing is as that of one installed in a controlled laboratory.
sealed until use. Additionally, the portability of this refer- 30 [0038] The use of an automatic standard reference
ence material to remote sites allows calibration of mobile loading apparatus for the recalibration of point of use
units and those installed near the industrial process. spectrometers, i.e., shop floor installed analytical equip-
[0034] The present invention provides an optical emis- ment does not exist in the market. The potential benefit
sion spectro-chemical reference material especially for to the users of point of use analysis equipment is opti-
metals and metal alloys having a homogeneous content 35 mized by an automatic recalibration system and no prep-
of element which is directly usable without preparation. aration samples are a key component to its realization.
Moreover, the present invention refer to a disposable [0039] Another distinct point of difference between this
spectro-chemical material that is available for immediate and all other standard reference materials known in the
use, protected by an anti-corrosive coating and is pref- art is that ready to use prepared surface of the present
erably housed in an inert gas shielded container provid- 40 invention is two sided.
ing protection from environmental containments in the [0040] In the following, the invention is further illustrat-
ambient environment such as atmospheric, particulate ed by the way of examples.
and contact contaminants during handling, storage and
use. It is capable for use in automatic recalibration rou- Fig. 1 is a three dimensional view of a reference ma-
tines of analytical equipment in remote locations as well 45 terial in the form of a coin.
as laboratory settings. Especially, the present invention Fig. 2 is a three dimensional view of a cassette hous-
is used for a metallurgical process. ing for the coins.
[0035] The application of an inert layer allows protect- Fig. 3 is a sectional view of the cassette housing.
ing the recalibration surface during long term storage. Fig. 4 is a housing for one piece of reference material.
This solution may also be combined with an inert atmos- 50 Fig. 5 shows the housing of Fig. 4, opened.
phere. A homogeneous coin of standard reference ma- Fig. 6 shows another kind of housing, for multiple
terial according to the industrial standards known in the coins.
art is prepared with a surface finish according to a known Fig. 7 is another alternative housing.
industrial standard for analysis respectively calibration. Fig. 1 is a view of a reference material in the form of
A protective coating is immediately applied to its surface. 55 a circular coin. The coin consists of known elemental
The protective coating is selected in such a way that this content 1 and a coating 2 composed of silver or gold.
coating material does not influence the analysis of the The diameter of the coin 1, 2 is between 20 to 60
recalibration surface for the elements that are of impor- mm. The height of the coin 1, 2 is between 5 to 30

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mm. The thickness of the coating 2 is between 0,5 3. Method according to one of the preceding claims
to 5 mm. characterized in that the reference material is kept
under an inert gas atmosphere or vacuum prior to
[0041] The known elemental content 1 consists of steel calibration.
for example a low alloy steel comprising Fe, C, Si, S, P, 5
Mn, Ni, Cr, Mo, Cu, Sn, Al, V, As, Zn, N, a ferritic and 4. Method according to the preceding claim character-
martensitic stainless steel comprising Fe, C, Si, S, P, Mn, ized in that the inert gas is argon.
Ni, Cr, Mo, Cu, Sn, V, Co, Nb, W, B, N, a high nitrogen
stainless steel comprising Fe, C, Si, S, P, Mn, Ni, Cr, Mo, 5. Method according to one of the preceding claims
Cu, Al, V, W, Co, Nb, B, N. Further examples comprise 10 characterized in that a composition of an iron alloy
Fe, C, Si, S, P, Mn, Ni, Cr, Mo, Cu, Sn, Al, As, Pb, N or or a steel alloy is measured by the spectrometer after
Fe, C, Si, S, P, Mn, Ni, Cr, Cu, Al, Co, Mg, N. the calibration.
[0042] Fig. 2 is a three dimensional view of a cassette
housing 3, 4 for the coins 1, 2. Fig. 3 is a sectional view 6. Method according to the preceding claim wherein
of the cassette housing 3, 4 comprising a plurality of coins 15 the inert coating does not comprise elements to be
1, 2. It is possible to attach the lid 4 to the container 3 by measured in the steel or iron alloy.
one or more bolts 5.
[0043] Each coin 1, 2 is inserted into the cassette hous- 7. Method according to one of the preceding claims
ing composed of a container 3 and a lid 4. The bottom characterized in that an inert gas is used to protect
of the container 3 comprises an inlet 6 for inert gas. There 20 the homogeneous content instead of or in addition
remains slit 7 between the container 3 and the lid 4 which to the inert coating.
allows to remove a coin 1, 2 from the cassette housing
3, 4 in an automatic manner. Further, the slit 7 may serve 8. Reference material for calibration of a spectrometer
as an outlet for inert gas. The side wall of the container according to one of the preceding claims having a
3 may comprise a recess 8 which allows to fix the con- 25 homogeneous content of elements characterized
tainer 3 within a dispensing device. in that the content is protected by an inert coating.
[0044] In an alternative embodiment each coin 12 of
reference material is inserted into a housing 10, Fig. 4. 9. Reference material according to the preceding claim
The inert gas (for example argon, but others are possible) characterized in that the inert coating is composed
purges the internal space of the housing and is sealed 30 of Ag, Au, Pt, Ir and/or Rh or alloys thereof.
by a gas tight closure of the housing which protects the
recalibration surfaces and its protective coating from en- 10. Reference material according to one of the preced-
vironmental contamination. An O-ring 13, as one exam- ing claims characterized in that the homogeneous
ple can be utilized for this purpose. The coin housing 10 content of element is formed from steel.
is opened just prior to use, as shown in Fig. 5. and trans- 35
ferred to the spectrometer for analysis. Use of plastic 11. Reference material according to one of the preced-
bags, Fig. 6, is also contemplated. Multiple coins 12 can ing claims characterized in that homogeneous con-
be housed in a foil backed holder 20, providing dispens- tent of elements (1) does not comprise an element
ing of individual coins 12 without compromising the inert of the coating (2).
gas protection for the remaining coins 12. This embodi- 40
ment is similar to a blister used as pill dispenser. Individ- 12. Reference material according to one of the preced-
ual dispensing of coins 12 provides the operator with a ing claims characterized in that the thickness of the
recalibration surface without the need for preparation inert coating is 0,1 to 10 mm, preferably 0,5 to 2 mm.
equipment. Fig. 7 is a familiar package 21 of multiple foils.
45 13. Reference material according to one of the preced-
ing claims characterized in that the reference ma-
Claims terial is a circular coin.

1. Method for calibration of a spectrometer character- 14. Reference material according to the preceding claim
ized in that a reference material is used for calibra- 50 wherein the diameter of the coin is 10 to 80 mm di-
tion of the spectrometer wherein the reference ma- ameter and/or the height of the coin is 1 to 30 mm.
terial has a homogeneous content of elements (1)
which is protected by an inert coating (2). 15. Reference material according to one of the preced-
ing claims characterized in that the purity of the
2. Method according to the preceding claim character- 55 steel is at least 90% and is preferably better than
ized by an automatic transfer of the reference ma- 92.5%.
terial (1, 2) from a dispensing device to the spec-
trometer for calibration. 16. Reference material according to one of the preced-

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ing claims characterized in that it is arranged in a

housing, whereby the housing is preferably closed
gas-tightly.

17. Reference material according to claim 16, charac- 5

terized in that more than one piece of the reference
material is arranged in the housing.

18. Reference material according to claim 17, charac-

terized in that the pieces are arranged separated 10
one from another.

19. Reference material according to one of the claims

16 to 18, characterized in that the housing has at
least two parts whereby one part can be removed at 15
least partially from the other part.

20. Reference material according to claim 17, charac-

terized in that the pieces are arranged one on top
of the other. 20

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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 4189204 A, Brown [0010]

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