AU2016227677B2 - Method for producing a tablet which comprises a sample material - Google Patents

Method for producing a tablet which comprises a sample material Download PDF

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Publication number
AU2016227677B2
AU2016227677B2 AU2016227677A AU2016227677A AU2016227677B2 AU 2016227677 B2 AU2016227677 B2 AU 2016227677B2 AU 2016227677 A AU2016227677 A AU 2016227677A AU 2016227677 A AU2016227677 A AU 2016227677A AU 2016227677 B2 AU2016227677 B2 AU 2016227677B2
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Australia
Prior art keywords
sample material
fluxing agent
tablet
melt
layer
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AU2016227677A1 (en
Inventor
Marc BORNEFELD
Oliver Maier
Jürgen Schneberger
Reinhard Teutenberg
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Thyssenkrupp Polysius GmbH
ThyssenKrupp AG
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Thyssenkrupp Polysius GmbH
ThyssenKrupp AG
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44—Sample treatment involving radiation, e.g. heat
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/2202—Preparing specimens therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
    • G01N2001/2866—Grinding or homogeneising

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

The invention relates to a method for producing a tablet which comprises a sample material, the sample material being mixed at least to some extent with a melting agent, the mixture of sample material and melting agent at least partially being molten and the melt being caused to solidify, the solidified melt having tablet form or being converted to tablet form. Said method is characterized by melting the mixture of sample material and melting agent by means of laser radiation, plasma radiation and/or electron radiation.

Description

The invention relates to a method for producing a tablet which comprises a sample material, the sample material being mixed at least to some extent with a melting agent, the mixture of sample material and melting agent at least partially being molten and the melt being caused to solidify, the solidified meh having tablet form or being converted to tablet form. Said method is characterized by melting the mixture of sample material and melting agent by means of laser radiation, plasma radiation and/or electron radiation.
(57) Zusammenfassung: Ein Verfahren zur Herstellung einer ein Probenmaterial umfassenden Tablette, bei dem das Probenmaterial zumindest teilweise mit einem Schmelzmittel vermischt, die Probenmaterial-Schmelzmittel-Mischung zumindest teilweise aufgeschmolzen und eine Erstarrung der Schmelze herbeigefuhrt wird, wobei die erstarrte Schmelze die Tablettenform aufweist oder in die Tablettenform uberfuhrt wird, ist dadurch gekennzeichnet, dass die ProbenmaterialSchmelzmittel-Mischung mittels Laserstrahlung, Plasmastrahlung und/oder Elektronenstrahlung aufgeschmolzen wird.
WO 2016/139242 Al llllllllllllllllllllllllllllllllllllllllllllllllll^
KZ, RU, TJ, TM), europaisches (AL, AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, KM, ML, MR, NE, SN, TD, TG).
Veroffentlicht:
— mit internationalem Recherchenbericht (Artikel 21 Absatz 3)
2016227677 30 Apr 2018
Method for producing a tablet which comprises a sample material
The invention relates to a method of producing a tablet comprising a sample material intended for use in an analysis of the sample material.
It is known that tablets of this kind can be produced as compressed tablets by grinding the sample material and processing it further to give the tablet with employment of pressure and/or binders. A method of this kind requires the sample material already to be in a physical consistency suitable for the finished tablet prior to the grinding.
It is also known that tablets of this kind can be produced from a melt. This involves mixing the sample material with a fluxing agent, melting this sample material/fluxing agent mixture and pouring the melt into a tablet mold and cooling it therein.
However, such a cooling operation with simultaneous shaping is complex both from an engineering and from an apparatus point of view. Thus, a melt tablet has to be cooled under very controlled conditions, since excessively rapid cooling can lead to fracture of the tablet, whereas the melt would crystallize in the event of excessively slow cooling, as a result of which the tablet would likewise lose its strength.
WO 2015/000571 Al and US 5,257,302 each disclose methods of producing a tablet comprising a sample material, in which a material mixture comprising the sample material is melted and cooled again. The resultant vitreous material is then ground and subsequently compressed to the tablet.
It was an object of the invention to specify an improved method of producing a tablet comprising a sample material.
Advantageous embodiments of these methods will be apparent from the description which follows.
A first aspect provides a method of producing a tablet comprising a sample material, where the sample material is at least partly mixed with a fluxing agent, the sample
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018 material/fluxing agent mixture is at least partly melted and solidification of the melt is induced, where the solidified melt is in tablet form or is converted to tablet form, and where the sample material/fluxing agent mixture is melted by means of laser radiation, plasma radiation and/or electron beams, wherein the melting is monitored in real time using imaging sensors or a pyrometer, whereby, by regulation of the power of a device that generates the laser radiation, plasma radiation and/or electron beams, a regulation of the melting process is achieved.
The use of laser radiation, plasma radiation and/or electron beams may enable very exactly definable, locally delimitable and locally very high introduction of energy into the sample material/fluxing agent mixture to be melted, which may have a positive effect on the melting and especially may also enable simple and simultaneously very exact regulation of the melting process. The locally exactly defined introduction of energy can additionally minimize the loss of heat that occurs in the performance of a method of an embodiment of the invention. It may also be possible through the use of laser radiation, plasma radiation and/or electron beams to achieve comparatively rapid melting of the sample material/fluxing agent mixture intended for the purpose, which can have a correspondingly advantageous effect on the time required for the production of the tablet.
The melting of the sample material/fluxing agent mixture can achieve conversion 20 thereof to a homogeneous or chemically homogeneous melt, which may help to improve analysis of the sample material using the resolidified melt. It may be possible in this way to distinctly reduce or entirely eliminate effects that arise, for example, from the grain size distribution and the density and from mineralogical properties such as crystal structure and crystallinity of the original sample. Dilution of the sample in the fluxing agent may additionally make the sample matrix more homogeneous and hence may greatly reduce what is called the matrix effect.
“Tablet” is understood in accordance with the invention to mean a solid body in a defined spatial form that includes a material mixture comprising the sample material.
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In the performance of a method of an embodiment of the invention, it may preferably be the case that the sample material/fluxing agent mixture is melted selectively by means of the laser radiation, plasma radiation and/or electron beams. “Selective” is understood to mean gradual melting of the sample material/fluxing agent mixture or of the fraction intended for the purpose, in that the laser beam, the plasma beam and/or the electron beam, the coverage of which is smaller than the area covered by the sample material/fluxing agent mixture to be melted, is run across this area, such that the sample material/fluxing agent mixture is gradually melted over this area. In the course of this, as part of the area is being melted, it is already possible for another already partly melted part of the area to solidify again.
It may be possible to influence the melting operation via the number of exposure steps (single or multiple exposure). In the case of single exposure, the laser beam (or else pulsed laser beam) runs over every “point” exactly once (for example only in the forward direction). In the case of multiple exposure, the laser beam may run over every “point” more than once (for example three times). The forward movement may be superposed here by a backward and/or sideways movement. The mode of exposure may be adjustable in a material-dependent manner (depending on factors including the sample material).
It may additionally preferably be the case that the sample material is ground prior to 20 mixing with the fluxing agent, preferably until attainment of a grain size of not more than 100 pm, more preferably of not more than 63 pm. This can have an advantageous effect on the homogenization of the sample material or of the sample material/fluxing agent mixture over the course of melting.
In a preferred embodiment of the method of an embodiment of the invention, it may 25 be the case that the sample material is subjected to preliminary grinding in a first grinding step and, after being mixed with the fluxing agent, to further grinding in a further grinding step. In this case, the grinding of the sample material/fluxing agent mixture can serve the primary purpose of mixing the already ground sample material with the fluxing agent. This may be especially enabled by the fluxing agent in many
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018 cases already being in the form of fine grains. One advantage that can arise from this is that both the grinding of the sample material and the mixing of the sample material with the fluxing agent can be conducted in the same apparatus, namely a suitable (fine) mill. Provision of an additional mixing apparatus can thus be avoided.
Accordingly, “grinding” in accordance with the invention is not necessarily understood to mean a method step in which processing of a material or material mixture is associated with achievement of a reduction in the grain size of the material or material mixture. Instead, such a “grinding” operation can serve exclusively or primarily for mixing of a material mixture, if grinding of the material or material mixture would be possible in principle, i.e. with different method parameters, through the use of the same apparatus (mill) utilized here. The speed of the (fine) mill can be matched to the mixing effect to be achieved (a low speed if appropriate) and can differ from a grinding speed.
Good mixing of the fluxing agent with the sample material may have the advantage in laser melting that any “puddle” (zone which is remelted) is of uniform composition (grain size distribution of sample with respect to fluxing agent always virtually the same).
If appropriate, the fluxing agent may also be mixed with the sample material in dosed form as a solid body, by means of which dosage of sample material and fluxing agent in a predefined ratio can be simplified. In this case, it may be advisable also to grind the solid fluxing agent body in at least one of the grinding steps, i.e. to reduce it to particles of a defined (maximum) grain size.
In a further-preferred embodiment of the method of the invention, it may be the case that the solidification of the melt is induced by forming a vitreous constituent (the resolidified melt) of the tablet. In particular embodiments of the method of the invention, semicrystalline formation of the solidified melt may alternatively be adequate or even advantageous.
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2016227677 30 Apr 2018 “Vitreous” or “vitreous constituent” is understood to mean an amorphous material configuration which, after cooling from the melt, does not have an ordered crystal structure. Conversion of the melt to a vitreous constituent can especially be achieved by cooling the melt with sufficient speed, which prevents crystallization of the molten material.
The vitreous constituent may be particularly advantageously suitable for the analysis of the sample material because the homogeneous mixture that results from the melting of the sample material together with the fluxing agent is conserved therein, and the fluxing agent is dimensionally stable.
The formation of a vitreous constituent of the solidified melt can also be assisted by active cooling, for example by means of a gas flow (e.g. air or a protective gas). Regulation of the active cooling can also be provided for to the effect that crystallization is prevented as far as possible.
A fluxing agent usable advantageously in the performance of the method of an embodiment of the invention may, for example, be lithium tetra- or metaborate, sodium tetra- or metaborate, sodium carbonate, potassium disulfate and/or an acid, for example boric acid, or a mixture thereof - with addition of additives as well (e.g. fluxes such as LiBr).
It may further be preferable that the fluxing agent is mixed with the sample material 20 in a ratio of between 40:1 to 2:1, preferably between 10:1 and 2:1.
In an advantageous embodiment of the method of the invention, it may be the case that the sample material/fluxing agent mixture is melted and solidified layer by layer (i.e. successively in multiple layers). This may enable relatively rapid generation of the melt as a result of exactly dosed and very high local introduction of energy into the sample material/fluxing agent mixture (or the fraction thereof envisaged for the melting).
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It may more preferably be the case that the layer-by-layer melting and solidification of the fluxing agent/sample material mixture is utilized as an additive manufacturing method for production of the tablet (or the corresponding constituent thereof). An additive manufacturing method may use a three-dimensional body composed of a pulverulent material in particular that is generated layer by layer, by starting from a base layer and, in a layer-by-layer manner, applying material to this base layer, melting it and solidifying it. A relevant advantage of such an additive manufacturing method is that, by virtue of material being melted in an only relatively thin layer and in a locally limited manner, it may be possible to dispense with accommodation of the melt during the solidification in a negative mold corresponding to the envisaged shape of the resolidified melt (i.e. in the form of the tablet or the corresponding constituent thereof).
Suitable specific embodiments for production of the tablet or a constituent thereof by an additive manufacturing method may be selective laser sintering, which is common knowledge, selective laser melting and (selective) electron beam melting.
Layer-by-layer melting and solidification can also be affected by first melting and solidifying a surface layer, and then melting and solidifying a layer beneath (i.e. a layer which is spatially separated by the surface layer with respect to a radiation source that brings about the melting). This can be continued step-by-step until the intended thickness of the tablet to be produced or of the component of the tablet to be produced has been attained. As the case may be, it may be possible here to exploit different absorption for the laser radiation, plasma radiation and/or electron beams by the sample material/fluxing agent mixture on the one hand and the resolidified melt on the other hand.
In a further-preferred embodiment of the method of the invention, it may also be the case that the solidified melt is ground and then converted to tablet form, and is especially compressed for the purpose. It may thus be the case that a compressed tablet is formed from the melt that has been solidified and then ground. By means of such an embodiment of the method of the invention, the easy producibility of a tablet
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2016227677 30 Apr 2018 comprising a sample material in the form of a compressed tablet may be combined with the homogenization of the sample material by melting which may be advantageous for the later analysis. This procedure may exploit the fact that the homogenization of the sample material which may be advantageously achieved by the melting is not adversely affected (to a relevant degree) by the grinding.
In a further-preferred embodiment of the method of the invention, it may be the case that the sample material/fluxing agent mixture (optionally after mixing-in of a binder) is compressed prior to melting. This may especially be advantageous if there is no intention to form the entire tablet in the form of a resolidified melt and hence no intention to melt the entire sample material/fluxing agent mixture. It may thus be especially possible in principle to form the tablet in the form of a compressed tablet, while only a surface layer envisaged primarily for the later analysis is melted and resolidified, in order to correspondingly improve the analysis by virtue of the vitreous and hence amorphous structure which is preferably to be obtained, and homogenization of the sample material in this surface layer. The surface layer here may advantageously have a thickness of between 30 pm and 300 pm.
The melting of the sample material/fluxing agent mixture by means of laser radiation, plasma radiation and/or electron beams which is envisaged in accordance with an embodiment of the invention can advantageously achieve monitoring and optional regulation of the inducement of the solidification of the melt (and any active cooling used in the process) in real time. It may also be possible to exploit the fact that regulation of the power of the device that generates the laser radiation, plasma radiation and/or electron beams leads very quickly or essentially directly to corresponding regulation of the heat energy introduced into the sample material/fluxing agent mixture. It may thus be possible to achieve very rapid and exact regulation of the melting process.
Corresponding monitoring can advantageously be effected using imaging sensors, for example a CMOS, thermal imaging and/or infrared camera, and/or a pyrometer.
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In a further-preferred embodiment of the method of the invention, it may be the case that a decontaminating agent is ground in a mill and then the sample material to be mixed with the fluxing agent is ground in the same mill. This can serve to decontaminate the mill that may already have been utilized for grinding of a different kind of sample material beforehand, or to deliberately contaminate it with the sample material to be ground subsequently. In this way, it may be possible to as far as possible rule out contamination of the sample material that could lead to distortion of the result of any subsequent analysis of this sample material.
The decontaminating agent may preferably be or at least comprise a first portion of the sample material (and consist, for example, of the sample material/fluxing agent mixture). It may likewise also be possible to utilize a portion of the solidified melt as decontaminating agent. This may especially be advisable when another portion of the solidified melt is subsequently being ground in the mill in order to form a compressed tablet therefrom. It may thus also be possible to decontaminate a mill by means of a first decontaminating agent preferably comprising a first portion of the sample material for subsequent grinding of a further portion of the sample material, in which case this further portion of the sample material is subsequently mixed with the fluxing agent and melted in accordance with an embodiment of the invention. Subsequently, it may be possible to grind a first portion of the solidified melt in the zu same mill or another mill for decontamination of the mills and then to grind a further portion of the solidified melt in order to form a compressed tablet therefrom.
Alternatively or additionally, however, the decontaminating agent may also be or comprise a material other than the sample material, such as, more particularly, sand, corundum and/or any refractory material (including fireclay-containing material).
In one embodiment of the method of the invention, it may be the case that the ground decontaminating agent is discarded, such that it is at least not utilized any further within the context of the method of an embodiment of the invention. It may especially be the case here that the decontaminating agent is disposed of.
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It may also be possible that the ground decontaminating agent(s) is/are compressed and utilized as base layer for a sample material/fluxing agent mixture to be compressed and/or a portion/amount of solidified and subsequently ground melt to be compressed. In this case, a selection of the decontaminating agent (or at least of a constituent thereof) can also be made with regard to suitability as base layer. Compression of the decontaminating agent(s) can preferably (in each case) be effected in a mold ring. The height of the latter can advantageously be greater and preferably at least twice as great as the layer thickness of the base layer. The unit composed of base layer and mold ring can then serve as vessel-like negative mold (with respect to the tablet form envisaged) for the sample material/fluxing agent mixture or ground solidified melt to be introduced subsequently therein, which can also be processed further, especially compressed and/or melted, therein.
Advantageously, the mold ring may consist at least partly of stainless steel or a refractory metal having a low coefficient of thermal expansion.
In order to assure a reliable hold of the compressed tablet within the mold ring, it may preferably be the case that it forms at least one depression on the inside, into which a material comprising a sample material (sample material/fluxing agent mixture in pulverulent or vitreous form) and/or decontaminating agent can penetrate in the respective compression operation, which can result in formation of a form20 fitting bond between the compressed tablet to be produced and the mold ring.
Another aspect of the invention further relates to a method of analyzing a sample material, wherein a tablet comprising the sample material is produced by means of a method of the first aspect of the invention and then an analysis of the sample material is conducted using the tablet. In the analysis of the sample material, it may especially be possible to conduct an x-ray fluorescence analysis.
The sample material may especially comprise one or more natural rocks, for example silicates, carbonates, sulfates, sulfides, salts and/or oxides. In addition, the sample material may especially comprise industrial process products, for example slag, fly ash, alloys and/or other metal compounds.
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018 ίο
The indefinite article (“a”), especially in the claims and in the description that elucidates the claims in general, should be understood as such and not to mean “one”. Components correspondingly specified therewith should thus be understood such that these are present at least once and may be present more than once.
Embodiments of the invention are elucidated in detail hereinafter with reference to working examples shown in the drawings. The drawings show:
Fig. 1: a schematic of a tablet produced by means of a first embodiment of a method of the invention;
Fig. 2: a schematic of a tablet produced by means of a second embodiment of a method of the invention;
Fig. 3: a schematic of the procedure of a method of the invention in a third embodiment and an apparatus utilized therein; and
Fig. 4: a schematic of the procedure of a method of the invention in a fourth embodiment and an apparatus utilized therein.
Fig. 1 shows a tablet which comprises a sample material and has been produced by means of a first embodiment of a method of the invention.
In this embodiment of a method of the invention, first of all, a first portion (e.g. 5 to 6 g) of the sample material to be processed and analyzed is metered into a fine mill (not shown) and ground therein as purge sample or preliminary sample. This deliberately contaminates the fine mill with the sample material to be processed. This first portion of the sample material therefore serves as decontaminating agent.
The portion of the sample material utilized as decontaminating agent, after grinding in the fine mill, is pressed by means of a tableting press (not shown) into a mold ring 1 made, for example, of stainless steel (cf. fig. 1), in order to form a base layer 2 for a further layer 3 of a mixture of a second portion of the sample material and a fluxing agent (e.g. a molten salt). This further layer 3 or a constituent thereof serves for
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018 subsequent analysis of the sample material. The base layer 2 is unsuitable for this purpose as a result of possible contamination by the impurities present in the fine mill. For the base layer 2, for example, a layer thickness of three to four millimeters may be envisaged. This layer thickness may correspond to about 50% of the height of the mold ring 1. After cleaning of the mold ring 1 and the base layer 2, the unit formed from these two components is rotated by 180° (about a radial axis), such that this unit forms a vessel open at the top into which the further portion of the sample material can be introduced.
Subsequently, a further portion of the sample material is metered into the fine mill and ground in a first grinding step therein. The speed with which the fine mill is operated and the grinding time can be adjusted according to the sample material to be processed. After the conclusion of the first grinding step, a fluxing agent (e.g. lithium tetraborate) is mixed into this ground portion of the sample material in accordance with a defined mixing ratio (for example with a mixing ratio of 1:5, i.e., in the case of an amount of the further portion of the sample material of 2 g, an amount of the fluxing agent of 10 g). Subsequently, this sample material/fluxing agent mixture is ground in the fine mill in a second grinding step and mixed as thoroughly as possible. The sample material/fluxing agent mixture is then introduced into the vessel formed by the mold ring 1 and the base layer 2 and compressed in the zu tableting press. The compressed tablet thus formed consists of two layers at first, namely the base layer 2 consisting of the optionally contaminated first portion of the sample material, and of the further layer 3 which is to be the subject in the subsequent analysis, consisting of the compressed sample material/fluxing agent mixture.
The free surface of this further layer 3 is then irradiated and melted by means of a laser (not shown in fig. 1). The corresponding surface is remelted/fused in full or in small sections by means of continuous or pulsed laser radiation (for example by means of a fiber laser). After solidification of this melt as a result of cooling, the tablet to be produced comprises a vitreous layer 4 characterized by a very homogeneous material configuration. This vitreous layer 4 is advantageously suitable
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2016227677 30 Apr 2018 for a subsequent analysis of the sample material in, for example, an x-ray fluorescence analyzer (not shown).
In one possible variant, the laser beam is used to scan the surface of the further layer 3 point by point (area by area). This produces very small “melt puddles” which solidify again in vitreous form a short time later. As a result of the flowing process resulting from the movement of the laser, the entire surface is homogeneously fused and converted to a vitreous layer 4.
The point of the melt fusion is to convert the sample material together with a fluxing agent to a homogeneous melt which solidifies in vitreous form on cooling. The fusion eliminates or at least reduces effects on the intensity of the fluorescence radiation within the x-ray fluorescence analysis that are caused by the grain size distribution and the mineralogical original state of the sample material. The fusion leads to a homogeneous binding form of the elements and, through dilution, reduces the effect of the elements on one another through secondary excitation and absorption.
Remelting is a chemical operation. The fluxing agent breaks down the compounds of the sample material and chemically converts them. Silicates, aluminates, carbonates and sulfates of the sample material (if present) thus become borates, for example. Remelting or fusion of, for example, Fe2C>3, Fe3C>4, FeO, FeCh, FeS2, FeCC>3 with tetraborate gives rise to iron borates. Through conversion to iron borates, the influences of the chemical bonding are minimized.
In an alternative embodiment of the above-described method of producing a tablet comprising a sample material (according to fig. 2), no base layer 2 is generated. Instead, a compressed tablet is formed exclusively from the sample material/fluxing agent mixture. For this purpose, a first portion of the sample material is again first ground as purge sample or decontaminating agent, but then discarded. On completion of decontamination of the mill, a second portion of the sample material (e.g. 2 g) is again processed in two grinding steps. In the first grinding operation, only this second portion of the sample material is ground. For the second grinding step, in a
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018 very exact ratio of, for example, 1:5 (sample material to fluxing agent), a fluxing agent is then added and ground together with the sample material in order to achieve very thorough mixing of these components. The mixture of the sample material and the fluxing agent is then transferred to a tableting press (not shown). The mixture is compressed therein to a layer 3 corresponding essentially to the form of the tablet to be produced. Subsequently, the melting and solidification of a surface layer of the compressed tablet can be conducted in accordance with the above-described embodiment of a method of the invention in order to form a vitreous layer 4.
The mold ring 1 utilized in the course of performance of the above-described methods has, on its inside, two circumferential V-shaped depressions 5. One of the depressions 5 is in the upper axial half and the other depression 5 in the lower axial half of the mold ring 1. The mold ring 1 has, for example, an (axial) height of
8.5 mm. One of the depressions 5, proceeding from one of the axial ends of the mold ring 1, is, for example, at an axial height of 2.5 mm, and the other depression (proceeding from the same axial end of the mold ring 1) at an axial height of 6 mm.
Fig. 3 shows, in schematic form, the procedure for a method of the invention in a third embodiment, and an apparatus utilized in the performance of this method.
This embodiment of a method of the invention is based on the method of selective laser melting (SLM). The powder processed consists of a mixture of a sample material and a fluxing agent. This powder is processed in accordance with the procedure in the two above-described embodiments of method of the invention, i.e., after possible decontamination of a fine mill (not shown), a portion of the sample material is ground in the fine mill in a first grinding step and subsequently mixed with the fluxing agent, and then the sample material/fluxing agent mixture is mixed in the fine mill in a second grinding step.
Subsequently, a sufficient amount of the sample material/fluxing agent mixture is supplied via an inlet 6 to a metering device 7 of the apparatus utilized for the performance of this embodiment of a method of the invention and stored here. In the region of an outlet 8, the metering device 7 has two metering valves 9, 10 spaced
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018 apart in a parallel manner, which, in a known manner, enable separation of a defined volume of sample material/fluxing agent mixture from the total amount of the sample material/fluxing agent mixture held in the metering device 7, in that, with the lower metering valve 9 closed, the upper metering valve 10 is opened, such that sample material/fluxing agent mixture can fall into the metering space 11 formed between the metering valves 9, 10. By closing the upper metering valve 10, a portion of the sample material/fluxing agent mixture corresponding to the volume of the metering space 11 is then separated from the remaining amount of the sample material/fluxing agent mixture retained in the metering device 7. This separated portion can then be discharged from the metering device 7 by opening the lower metering valve 9.
A portion of the sample material/fluxing agent mixture discharged in this way drops onto a plate 12 of a receiving apparatus 13 arranged beneath the metering device 7. The plate 12 is movable in vertical direction within a guide system 14 of this receiving apparatus 13. The receiving apparatus 13 further comprises a vibrator 15, by means of which the receiving apparatus 13 can be set in oscillation. This serves to loosen up the portion of the sample material/fluxing agent mixture lying on the plate 12, and for a first areal distribution of this portion on the plate 12.
Subsequently, by means of a distributor valve 16, the sample material/fluxing agent mixture is distributed on the plate 12 in a layer of very substantially homogeneous thickness, and excess sample material/fluxing agent mixture is guided into a sample container 18 via a sample ejector 17. This excess sample material/fluxing agent mixture can be conveyed from the sample container 18 back into the metering device 7 for reuse. For this purpose, the sample container 18 can be removed by means of an automatic handling device, for example a robot (not shown), and moved to the inlet 6 of the metering device 7. Alternatively, it may also be the case that the excess sample material/fluxing agent mixture is removed from the sample container 18, for example sucked out by means of a suction apparatus 19, and then optionally disposed of.
The layer of the sample material/fluxing agent mixture lying in smoothed form on the plate 12 of the receiving apparatus 13 is subsequently irradiated and selectively
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018 melted by means of a laser 20. For this purpose, a mirror 21 pivotable in an automated manner is provided, the pivoting motion of which enables gradual irradiation and resultant melting of a defined region of the layer of the sample material/fluxing agent mixture by means of a laser beam generated by the laser 20 (alternatively possible without mirrors, direct introduction of energy). Solidification of the melt thus generated gives rise to a vitreous layer. This vitreous layer may already be the tablet to be produced. Alternatively, it is possible to form a multitude of such (cohesively bonded) vitreous layers one on top of another layer by layer, in that application of a metered portion of the sample material/fluxing agent mixture to the plate 12 of the receiving apparatus 13, distribution/smoothing of this portion and melting and solidifying of this portion are each conducted in succession, with downward movement of the plate 12 for each cycle by a distance corresponding substantially to the envisaged layer thickness of the vitreous layer to be formed.
The vitreous layer(s) thus generated can then optionally be applied to a base layer (not shown), in order to increase the dimensional stability of the tablet to be produced.
By means of a transport apparatus 22, for example a suction gripping element, the tablet or the vitreous layer(s) can then be removed from the receiving apparatus 13 and transferred into an analyzer (not shown), for example an x-ray fluorescence analyzer. As the case may be, the vitreous layer(s) thus generated (if appropriate in conjunction with the base layer) may also have been inserted into a sample carrier 23 beforehand, in order to improve the ease of handling of the tablet produced in the context of the analysis.
Fig. 4 shows, in schematic form, the procedure for a method of the invention in a fourth embodiment, and an apparatus utilized in the performance of this method.
This embodiment of a method of the invention is also based on the method of selective laser melting (SLM). The powder processed again consists of a mixture of the sample material and a fluxing agent. This powder is processed in accordance with the procedure in the above-described embodiments of method of the invention, i.e.,
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018 after possible decontamination of a fine mill (not shown), a portion of the sample material is ground in the fine mill in a first grinding step and subsequently mixed with the fluxing agent, and then the sample material/fluxing agent mixture is mixed in the fine mill in a second grinding step.
Subsequently, a sufficient amount of the sample material/fluxing agent mixture is supplied via an inlet 6 to a metering device 7 of the apparatus utilized for the performance of this embodiment of a method of the invention and stored here. In the region of an outlet 8, the metering device 7 has two metering valves 9, 10 spaced apart in a parallel manner, which, in a known manner, enable separation of a defined volume of sample material/fluxing agent mixture from the total amount of the sample material/fluxing agent mixture held in the metering device 7, in that, with the lower metering valve 9 closed, the upper metering valve 10 is opened, such that sample material/fluxing agent mixture can fall into the metering space 11 formed between the metering valves 9, 10. By closing the upper metering valve 10, a portion of the sample material/fluxing agent mixture corresponding to the volume of the metering space 11 is then separated from the remaining amount of the sample material/fluxing agent mixture retained in the metering device 7. This separated portion can then be discharged from the metering device 7 by opening the lower metering valve 9.
A portion of the sample material/fluxing agent mixture discharged in this way drops 20 onto a plate 12 of a receiving apparatus 13 arranged beneath the metering device 7.
The plate 12 is movable in vertical and horizontal direction within a tubular guide system 14 of this receiving apparatus 13. The receiving apparatus 13 further comprises a vibrator 15, by means of which the receiving apparatus 13 can be set in oscillation. This serves to loosen up the portion of the sample material/fluxing agent mixture lying on the plate 12, and for a first areal distribution of this portion on the plate 12.
Subsequently, by means of a distributor valve 16, the sample material/fluxing agent mixture is distributed on the plate 12 in a layer of very substantially homogeneous thickness, and excess sample material/fluxing agent mixture is guided into a sample
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018 container 18 via a sample ejector 17. This excess sample material/fluxing agent mixture can be conveyed from the sample container 18 back into the metering device 7 for reuse. For this purpose, the sample container 18 can be removed by means of an automatic handling device, for example a robot (not shown), and moved to the inlet 6 of the metering device 7. Alternatively, it may also be the case that the excess sample material/fluxing agent mixture is removed from the sample container 18, for example sucked out by means of a suction apparatus 19, and then optionally disposed of.
The layer of the sample material/fluxing agent mixture lying in smoothed form on the plate 12 of the receiving apparatus 13 is subsequently irradiated and selectively melted by means of a laser 20. For this purpose, a mirror 21 pivotable in an automated manner is provided, the pivoting motion of which enables gradual irradiation and resultant melting of a defined region of the layer of the sample material/fluxing agent mixture by means of a laser beam generated by the laser 20 (alternatively possible without mirrors, direct introduction of energy). Solidification gives rise to a molten and cooled layer. It may be possible to form a multitude of such (cohesively bonded) layers one on top of another layer by layer, in that application of a metered portion of the sample material/fluxing agent mixture to the plate 12 of the receiving apparatus 13, distribution/smoothing of this portion and melting and solidifying of this portion are each conducted in succession, with vertical zu (downward) movement of the plate 12 for each cycle by a distance corresponding substantially to the envisaged layer thickness of the molten layer which is about to be formed.
After the formation of one or more molten, cooled layers, the plate 12 is moved horizontally, as a result of which the molten, cooled layer(s) fall into a receiving vessel 24. As soon as a sufficient amount of molten, cooled material (i.e. the molten layer(s) 4, optionally broken into fragments) is present in the receiving vessel 24, the receiving vessel 24 is removed by means of an automatic handling apparatus, for example a robot, and sent to a precomminuting apparatus 25. For this purpose, the molten, cooled material can, for example, be precomminuted in the receiving vessel
24 by means of a mortar or a suitable impactor. Subsequently, the precomminuted
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018 particles are sent to a fine mill and ground therein. After the grinding, the previously molten, cooled material is used to produce an analysis-ready compressed tablet in a tableting press. For this purpose, the molten, cooled and then ground material can be compressed in a mold ring, as has been described with reference to figs. 1 and 2.
In all the embodiments described, rather than melting of the sample material/fluxing agent mixture by means of laser radiation, melting can also be conducted by means of plasma radiation or electron beams, without having to alter the other method steps described for the purpose. Under some circumstances, individual process steps can also proceed under protective gas (e.g. argon).
In principle, in all methods of the invention and hence also in the above-described embodiments of methods of the invention, it may be advantageously possible to conduct additional method steps that especially serve to assure adequate quality of the tablet to be produced. It may especially be the case here that the melting of the sample material/fluxing agent mixture and the re-solidification of the melt are monitored regularly or continuously, especially by means of measurement of the temperature of the melt, for example by means of a pyrometer (not shown) and/or by means of monitoring of the heat distribution of the melt, for example by means of a thermal imaging camera (not shown) and corresponding image processing software. It may likewise be possible to observe the melting operation by means of a camera (especially CMOS; not shown). It may likewise also be possible by means of a camera (not shown) to conduct monitoring of the formation of the molten layer or examination of the quality of the glass formed. Some or all of these steps can advantageously also be provided, in one configuration, in the form of real-time monitoring (online system).
It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
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2016227677 30 Apr 2018
In the claims which follow and in the preceding description, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018
Reference numerals:
mold ring base layer layer of a sample material/fluxing agent mixture vitreous or molten, cooled layer depression inlet of the metering device metering device outlet of the metering device lower metering valve upper metering valve metering space plate of the receiving apparatus receiving apparatus guide system of the receiving apparatus vibrator distributor valve sample ejector sample container suction apparatus laser mirror transport apparatus sample carrier receiving vessel precomminuting apparatus
10116218_1 (GHMatters) P106821.AU
2016227677 30 Apr 2018

Claims (15)

  1. Claims:
    1. A method of producing a tablet comprising a sample material, where the sample material is at least partly mixed with a fluxing agent, the sample material/fluxing agent mixture is at least partly melted and solidification of the melt is induced, where the solidified melt is in tablet form or is converted to tablet form, and where the sample material/fluxing agent mixture is melted by means of laser radiation, plasma radiation and/or electron beams, wherein the melting is monitored in real time using imaging sensors or a pyrometer, whereby, by regulation of the power of a device that generates the laser radiation, plasma radiation and/or electron beams, a regulation of the melting process is achieved.
  2. 2. The method as claimed in claim 1, wherein the sample material/fluxing agent mixture is selectively melted.
  3. 3. The method as claimed in claim 1 or 2, wherein the sample material is ground prior to mixing with the fluxing agent.
  4. 4. The method as claimed in claim 3, wherein the sample material is subjected to preliminary grinding in a first grinding step and, after being mixed with the fluxing agent, to further grinding in a further grinding step.
  5. 5. The method as claimed in any one of the preceding claims, wherein the solidification is induced by forming a vitreous constituent of the tablet.
  6. 6. The method as claimed in any one of the preceding claims, wherein the fluxing agent is a molten salt and/or an acid.
  7. 7. The method as claimed in any one of the preceding claims, wherein the sample material/fluxing agent mixture is melted and solidified layer by layer.
  8. 8. The method as claimed in any one of the preceding claims, wherein the solidified melt is ground and then converted to tablet form.
    10116218_1 (GHMatters) P106821.AU
    2016227677 30 Apr 2018
  9. 9. The method as claimed in any one of the preceding claims, wherein the inducement of the solidification of the melt is monitored in real time.
  10. 10. The method as claimed in claim 9, wherein the monitoring is conducted using imaging sensors or a pyrometer.
  11. 11. The method as claimed in any one of the preceding claims, wherein a decontaminating agent is ground in a mill and then the sample material to be mixed with the fluxing agent or the solidified melt is ground in the same mill.
  12. 12. The method as claimed in claim 11, wherein the decontaminating agent comprises a first portion of the sample material or the solidified melt.
  13. 13. The method as claimed in claim 11 or 12, wherein the decontaminating agent comprises a material other than the sample material.
  14. 14. A method of analyzing a sample material, comprising the production of a tablet comprising the sample material according to any one of the preceding claims and the subsequent analysis of the sample material using the tablet.
  15. 15. The method as claimed in claim 15, further comprising an x-ray fluorescence analysis.
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DE102015122408A1 (en) * 2015-12-21 2017-06-22 Thyssenkrupp Ag Method and installation for analyzing a sample material
CN109387532B (en) * 2017-08-02 2021-06-15 浦项(张家港)不锈钢股份有限公司 Method for measuring nickel cold milling by intermediate frequency melting sample preparation-X-Ray fluorescence spectrometry
CN112310516A (en) * 2019-07-23 2021-02-02 佛山市南海区和顺城锋冲轧有限公司 Preparation method of anti-radiation battery catalpic shell
CN115073203B (en) * 2022-07-27 2023-08-04 安徽工业大学 Foam ceramic wall material with good hanging function and preparation method thereof

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DE4428920A1 (en) * 1994-08-16 1996-02-22 Krupp Polysius Ag Material prepn. and application of X=ray fluorescence analysis

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DE2216035C3 (en) * 1972-04-01 1974-10-24 Schunk & Ebe Gmbh, 6301 Heuchelheim Process for the production of orodispersible tablets for X-ray fluorescence analysis
US5257302A (en) 1987-08-31 1993-10-26 Ngk Insulators, Ltd. Fluorescent X-ray analyzing system
DE102005048314B4 (en) * 2005-10-06 2009-02-12 Laserinstitut Mittelsachsen E.V. Device for selective laser sintering
DE102008021507A1 (en) * 2008-04-30 2009-11-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for the production of ceramic objects by means of selective laser melting
DE102010041284A1 (en) * 2010-09-23 2012-03-29 Siemens Aktiengesellschaft Method for selective laser sintering and equipment suitable for this method for selective laser sintering
DE102013106998A1 (en) 2013-07-03 2015-01-08 Thyssenkrupp Industrial Solutions Ag Method and device for producing a tablet

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DE2021667A1 (en) * 1970-05-02 1971-11-25 Siemens Ag Process for the crucible-free digestion of powdered dry material
DE4428920A1 (en) * 1994-08-16 1996-02-22 Krupp Polysius Ag Material prepn. and application of X=ray fluorescence analysis

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