WO2024008241A1 - Matériau de référence pour l'analyse de corps solides, procédé de production du matériau de référence et utilisation du matériau de référence - Google Patents

Matériau de référence pour l'analyse de corps solides, procédé de production du matériau de référence et utilisation du matériau de référence Download PDF

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Publication number
WO2024008241A1
WO2024008241A1 PCT/DE2023/100509 DE2023100509W WO2024008241A1 WO 2024008241 A1 WO2024008241 A1 WO 2024008241A1 DE 2023100509 W DE2023100509 W DE 2023100509W WO 2024008241 A1 WO2024008241 A1 WO 2024008241A1
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Prior art keywords
reference material
acetylacetonate
acrylate
elements
monomer
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PCT/DE2023/100509
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German (de)
English (en)
Inventor
Anika ROGOLL
Carla VOGT
Original Assignee
Technische Universität Bergakademie Freiberg
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Publication of WO2024008241A1 publication Critical patent/WO2024008241A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds

Definitions

  • Reference material for solid state analysis method for producing the reference material and use of the reference material
  • the invention relates to a reference material for solid state analysis, a method for producing the reference material and a use of the reference material.
  • the reference material should have very good homogeneity for the elements introduced and the desired elements should be able to be introduced into the material in a wide concentration range.
  • the reference material should be as simple and solvent-free to produce as possible.
  • the object of the invention is to eliminate the disadvantages of the prior art.
  • a reference material should be specified that has a homogeneous distribution of the element(s) and does not contain any solvents.
  • a method for producing such a reference material should be specified.
  • a reference material for solid state analysis having at least one acetyl acetonate of an element in an acrylate-based polymer.
  • the reference material according to the invention can be produced without using solvents. Details of the preparation of the reference material according to the invention are described below.
  • the reference material according to the invention has a homogeneous distribution of the element(s) in the polymer.
  • the polymer forms a matrix in which the elements are embedded. This matrix is also referred to below as the “organic matrix”.
  • the reference material according to the invention is characterized by a large concentration range of the element or elements compared to the prior art.
  • the reference material according to the invention enables a large selection of elements.
  • the reference material may contain the elements contained in a reference material that conforms to the NIST glass standard.
  • the reference material according to the invention differs from the reference materials that correspond to the NIST glass standard in that the reference material according to the invention has an organic matrix instead of a glass matrix.
  • An organic matrix is advantageous because the properties of glass differ significantly from those of a tissue sample, for example in hardness, thermal conductivity and also in terms of the main components.
  • the organic matrix of the reference material according to the invention is characterized in that the characteristics of a reference material match those of the sample as closely as possible to match. In this way, using the reference material according to the invention, a better analysis result can be obtained compared to the prior art.
  • the reference material according to the invention can be adapted as well as possible to the respective sample. For this reason, it is preferred that only the element or elements that the sample to be examined also possesses are introduced into the organic matrix. In this way it can be achieved that the reference material according to the invention contains exactly the element or exactly the combination of elements for which the sample is to be examined.
  • Acetyl acetonate is a complex former for the ionic element.
  • the ionically present element and the acetyl acetonate form a complex in which the acetyl acetonate is present as a ligand to the element.
  • This complex is referred to below as acetyl acetonate complex or acetylacetonate of an element, both terms being used synonymously.
  • the element is present as an ion.
  • the ionically present element can be the central particle of the complex.
  • a complex can have exactly one central particle and several ligands.
  • Acetylacetonate is also known as “pentanedione-2,4-dione”.
  • Acetylacetonate is also referred to as “acac” below. Since acetylacetonate can form complexes with many elements, it can be used to produce reference materials that can have a very broad spectrum of elements.
  • element describes an element of the periodic table of elements.
  • the element can be present as an ion, with the element preferably being present as an ion.
  • the term “element” therefore also includes the ion or ions of the element.
  • the element is present as an ion.
  • the element is preferably a metal or semi-metal, particularly preferably a metal.
  • the element is selected from the group consisting of Al, Ca, Cd, Co, Cr, Fe, La, Mg, Pb, Sr and Zn.
  • the metal or semi-metal is in the acetylacetonate Complex as an ion.
  • the ion may be selected from the group consisting of Al 3+ , Ca 2+ , Cd 2+ , Co 2+ , Cr 3+ , Fe 3+ , La 3+ , Mg 2+ , Pb 2+ , Sr 2 + and Zn 2+ exists.
  • the reference material has at least one acetylacetonate of an element.
  • the reference material preferably has acetyl acetonate of two or more elements.
  • the reference material particularly preferably has acetylacetonates of three or more elements.
  • the reference material according to the invention can therefore contain combinations of several elements. These elements are introduced into the acrylic monomer with one and the same ligand, namely acetylacetonate, during the production of the reference material.
  • organic-based reference materials such as. B. the reference materials provided by Bode
  • a combination of several elements is not possible without any problems because these elements have to be introduced into the oil with different complexing agents.
  • the reference material comprises acetyl acetonate of the elements that are contained in a sample that is to be examined using solid state analysis. These can be the elements that are suspected to be contained in the sample.
  • solid state analysis refers to procedures for analyzing solid samples. Examples of such methods are laser ablation-ICP mass spectrometry (ICP: inductively coupled plasma), X-ray fluorescence analysis (XRF), laser-induced plasma spectroscopy (Laser-Induced Breakdown Spectroscopy, LIBS) or secondary! on mass spectrometry (SIMS).
  • the sample is preferably a solid, particularly preferably a body made of a material that is in the solid state at room temperature (20 °C) and normal pressure. Alternatively or additionally, a solid can be understood as meaning a body made of a material that is in the solid state when examined using a solid-state analysis method.
  • the reference material according to the invention is particularly suitable for the calibration of solid-state analysis methods.
  • acetylacetonate of an element can be carried out according to the method described by M. M. Jones, A New Method of Preparing Some Acetyl acetonate Complexes, J. Am. Chem. Soc. 1959, 81, 13, 3188-3189, described procedures can be carried out.
  • acetyl acetonates of a variety of elements are also commercially available.
  • the acetylacetonate of chromium (Cr(acac)s) is commercially available from the company aber GmbH, Düsseldorf, DE
  • the acetylacetonate of aluminum (Al(acac)s) from the company Merck KGaA, Darmstadt, DE.
  • the reference material has an acrylate-based polymer.
  • the acrylate-based polymer is a polymer obtained by polymerizing at least one monomer containing an ethylenically unsaturated bond and selected from the group consisting of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, ⁇ , ⁇ -ethylenically unsaturated carboxylic acid esters , ⁇ , ⁇ -ethylenically unsaturated carboxamides and mixtures thereof.
  • the acrylate-based polymer is a horn polymer or a copolymer of at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, butyl acrylamide and Ethylhexylacrylamide consists.
  • TerraGloss® UV gloss varnish 8/372 F NVK (Actega Terra GmbH, Lehrte, DE) is used to produce the polymer.
  • TerraGloss® UV gloss varnish 8/372 F NVK contains an acrylate monomer that can be crosslinked using UV radiation to preserve the polymer.
  • the monomer or monomers can be provided in a reaction mixture which, in addition to the monomer or monomers, contains at least one additive, for example a photoinitiator. It can be provided that the proportion of all additives does not exceed 10% by weight, based on the weight of the reaction mixture.
  • the reaction mixture preferably contains no solvent.
  • the reference material contains no components other than the acetyl acetonate of one or more elements and the acrylate-based polymer. In other words, it can be provided that the reference material consists of the acetylacetonate(s) of one or more elements and the acrylate-based polymer.
  • the reference material contains at least one additive. Such an additive may come from the reaction mixture used to prepare the acrylate-based polymer. It can be provided that the proportion of all additives does not exceed 10% by weight, based on the weight of the reference material.
  • the reference material contains the element(s) in a concentration that lies in a range from 1 to 2000 mg/kg, based on the weight of the reference material. This is a concentration range that goes beyond the ranges known from the prior art.
  • the reference material it can be provided that the reference material,
  • the concentration of the element should not exceed 1000 mg/kg based on the weight of the reference material.
  • the concentration of iron is preferably in a range of 1 to 2000 mg/kg, based on the weight of the reference material, particularly preferably in a range of 200 to 2000 mg/kg. For example, it can be 200 mg/kg, 500 mg/kg, 800 mg/kg, 1000 mg/kg, 1100 mg/kg, 1400 mg/kg, 1700 mg/kg or 2000 mg/kg reference material.
  • the concentration of the respective element is preferably in a range from 1 to 1000 mg/kg, based on the weight of the reference material, for example 1000 mg/kg reference material.
  • the upper concentration limit is element-dependent, since the solubilities of the acetylacetonate complexes with the selected elements are different. With regard to the solubility of the acetylacetonate complexes, the maximum concentration for many elements is approximately 1000 mg/kg reference material. However, acetylacetonate complexes of individual elements, such as iron, can also be solved more easily.
  • the lower concentration limit of an element can be lower than 1 mg/kg reference material, since the liquid solution of the acetylacetonate of the element and the liquid monomer can be further diluted with monomer as desired.
  • concentration information mg/kg refers to the concentration of the respective element in the reference material and is also stated below with the unit “ppm”.
  • the maximum concentration of the respective element in the reference material depends on the solubility of the acetylacetonate complex of the respective element.
  • the reference material according to the invention contains acetylacetonates of the elements Cr, Fe, La and Zn.
  • the reference material preferably contains
  • Acetylacetonate of Fe at a concentration of 1000 mg/kg based on the weight of the reference material
  • Acetyl acetonate of La at a concentration of 1000 mg/kg based on the weight of the reference material
  • This reference material can advantageously be used to analyze a sample that simultaneously contains Cr, Fe, La and Zn without having to provide a separate reference material for each element.
  • a method for producing a reference material according to the invention comprises the steps:
  • the monomer(s) provided in liquid form in step (a) are solvent-free. In this way it is ensured that the reference material according to the invention does not contain any solvents.
  • the solution obtained in step (b) is a solution of the acetylacetonate of one element or the acetylacetonates of several elements in the monomer or monomers provided in step (a).
  • the acetylacetonate or acetylacetonates of one or more elements are introduced into the monomer or monomers without the addition of a solvent. In this way it is ensured that the invention appropriate reference material does not contain any solvents.
  • the acetylacetonate of the element or the acetyl acetonate of the elements are dissolved directly in the monomer or monomers.
  • the solution obtained in step (b) preferably has a homogeneous distribution of the element(s) in the monomer.
  • the solution can be moved, for example stirred.
  • the dissolution of the acetyl acetonate of one element or the acetyl acetonates of several elements is supported by ultrasound. Such support is not absolutely necessary, but ensures a residue-free solution of the acetylacetonate(s). If acetylacetonate is not completely dissolved, there is a risk that the undissolved residues will form inhomogeneities in the form of particles in the reference material.
  • a solid material is obtained, which is the reference material.
  • the acetylacetonates of the elements dissolved in the monomer(s) are included in the polymer. It is possible that the acetylacetonate(s) form units of the polymer, i.e. H. be polymerized. This may be because acetylacetonate has a double bond.
  • the acetylacetone is only present as a ligand in the enol form.
  • the proton of the enol is released during the synthesis of the acetylacetonate complex, which creates a negative charge on an oxygen atom. This leads to binding, i.e. H. for charge balancing, with the metal ion, which is positively charged, during complex formation, with the second bond of the ligand being coordinated. Since the proton is no longer present, a reverse reaction to the keto form is no longer possible.
  • step (c) the polymerization takes place by means of free-radical polymerization.
  • the polymerization of the monomers is preferably brought about by irradiation, for example by UV irradiation.
  • the monomer or monomers can be present in a reaction mixture that contains a photoinitiator.
  • the reference material is formed as a layer. Such a layer is also referred to below as a reference material layer designated.
  • a solid body that has two or more reference material layers is referred to below as a reference material body.
  • the reference material body is a solid body that has layers that consist of the reference material according to the invention.
  • the solution obtained in step (b) can be applied to a surface and the polymerization can then be carried out according to step (c), whereby a reference material layer is obtained.
  • a further layer of the solution can be applied to this reference material layer, which is then polymerized to obtain a second reference material layer. This process can be repeated one or more times, thereby obtaining a reference material body consisting of two or more reference material layers.
  • a reference material body it can be provided that, in order to produce a layer of the reference material, the solution obtained in step (b) is applied to a surface and then the polymerization is carried out according to step (c), whereby a reference material - layer is obtained.
  • An acrylate-based material that does not contain any acetylacetonate of an element and therefore no element can be applied to this reference material layer.
  • the acrylate-based material is then polymerized to obtain another layer. This layer is also called the element-free layer. This process can be repeated once or several times. Using this procedure, a reference material body can be obtained which alternately consists of reference material layers and element-free layers.
  • the acrylate-based material preferably corresponds to the monomer or monomers provided in liquid form in step (a), ie the reference material layers only differ from element-free layers in that the monomer or monomers in step (a) are used to produce the reference material layers (a) are provided, with an acetylacetonate of one element or acetylacetonates of several elements.
  • a reference material body is therefore provided.
  • the reference material body can have one or more layers which consist of the reference material according to the invention. It can be provided that the reference material body has at least one layer that is an element-free layer. It can be provided that the layers made of the reference material and the element-free layers are arranged alternately in the reference material body. It can be provided that the layers made of the reference material and the element-free layers each have a thickness that lies in a range of 10 to 1000 m.
  • the reference material layers - or the reference material layers and the element-free layers - adhere to one another. This is a particular advantage over the reference materials based on oil standards known from the prior art. Due to the oil content of these standards, layers of this material did not adhere to each other, causing the layers to peel away from each other. Therefore, oil standards cannot be used as a reference material for depth-resolved measurements such as: B. a confocal micro X-ray fluorescence analysis (“confocal micro X-ray fluorescence, CXRF) can be used.
  • the reference material according to the invention is stackable, i.e. H. Layers of reference material adhere to one another. This also applies to layers of the reference material and element-free layers.
  • the reference material according to the invention is therefore also suitable for depth-resolved measurements, such as. B. a confocal micro-X-ray fluorescence analysis, suitable.
  • the process according to the invention is based on the knowledge that acetylacetonates of the elements dissolve directly in the monomer or monomers, which is why the process according to the invention is less complex and the homogenization is very simple. Since the use of oil standards can be dispensed with, all disadvantages that could arise from the oil are eliminated. For example, several reference material layers can be hardened one on top of the other without any problems. In addition, the reference material according to the invention is better suited for vacuum methods because there is no solvent that can escape from the reference material in a vacuum. Since acetyl acetonate is available for many metals, the standards can be used depending on the question, ie the respective solid state analysis procedure and/or the sample.
  • the method according to the invention is particularly suitable for the production of reference materials which are intended for the spatially resolved measurement of solid samples. This can be attributed to the fact that for many metals, depending on the element, concentrations in the polymer standard can be covered from the lowest ppm range up to approx. 1000 ppm, and depending on the element also > 1000 ppm.
  • the use of a material that has at least one acetylacetonate of an element in an acrylate-based polymer is also provided as a reference material for solid state analysis of a sample.
  • the material is the reference material according to the invention, to the description above which reference is made.
  • 1 is a diagram showing a calibration series of iron in reference materials according to the invention determined by micro-X-ray fluorescence analysis (pXRF); 2 is a diagram showing the signal intensity of the K X-ray fluorescence line of iron (Fe-K), determined by micro-X-ray fluorescence analysis (pXRF), as a function of the relative depth for a layered reference material;
  • pXRF micro-X-ray fluorescence analysis
  • FIG. 3 shows a schematic sectional view of a first embodiment of a reference material body according to the invention.
  • Fig. 4 is a schematic sectional view of a second embodiment of a reference material body according to the invention.
  • iron(III) acetylacetonate (Fe(acac)3)
  • 5 g of FeCL • 6 H2O were dissolved in 50 ml of distilled water.
  • 6.1 ml of acetylacetone was added dropwise, after which 8.1 ml of ammonia (concentrated aqueous solution) was added dropwise.
  • the reaction mixture was stirred for 30 min.
  • Iron(III) acetylacetonate precipitated as a red solid, which was filtered, washed three times with 10 ml of distilled water and then dried.
  • Example 2 describes the production of a reference material according to the invention which contained an element, namely 1000 ppm Fe. This reference material is referred to as RFFeiooo.
  • Example 4 To demonstrate the stability of the reference material produced in Example 1 during a measurement, a layer system was kept at 20 mbar for 4 hours. The layer thickness was determined before and after, but no changes could be detected. In addition, 100 point measurements were carried out using micro-X-ray fluorescence analysis on exactly the same location. This took a little more than 3 hours, and no damage or similar to the material was found. A measurement of 1800 repetitions (60 h measuring time) on exactly the same location achieved a relative standard deviation of 0.7%, whereby the temperature change in the room also had an influence on the measurement result.
  • Example 4 To demonstrate the stability of the reference material produced in Example 1 during a measurement, a layer system was kept at 20 mbar for 4 hours. The layer thickness was determined before and after, but no changes could be detected. In addition, 100 point measurements were carried out using micro-X-ray fluorescence analysis on exactly the same location. This took a little more than 3 hours, and no damage or similar to the material was found. A measurement of 1800 repetitions (60 h measuring time) on exactly
  • Example 4 describes the production of a reference material according to the invention which contained four elements, namely 1000 ppm Fe, 1000 ppm Cr, 1000 ppm La and 1000 ppm Zn. This reference material is referred to as RFpeioooocrioooLaiooozniooo.
  • Examples 6 to 15 describe the production of further reference materials according to the invention, each of which contained 1000 ppm of exactly one element.
  • the preparation of these reference materials was carried out as described in Example 2, except that instead of 0.0632 g of iron (III) acetylacetonate, an acetylacetonate of the corresponding element was used, in an amount required to achieve a concentration of 1000 ppm can be achieved.
  • the metal acetyl acetonates listed in Table 1 were commercially available or were prepared as described in Example 1, except that instead of FeCh
  • a calibration series was produced which consisted of seven reference materials according to the invention.
  • the reference materials each contained exactly one element, namely Fe.
  • the calibration series consisted of the reference materials shown in Table 2, which contained Fe at the concentration shown in Table 2.
  • 0.5 g of the solution prepared in step a) was mixed with 4.5 g of TerraGloss® UV gloss varnish 8/372 F NVK (ACTEGA Terra GmbH, Lehrte, DE). 3 ml of this solution were applied to a glass plate using an automatic film applicator (e.g. 200 pm squeegee, film applicator “automatic film applicator S” from BYK-Gardener GmbH) and left to rest for 10 minutes. The polymerization was then started by placing the glass plate containing the sample in a UV chamber for 12 minutes and turning it on. After polymerization was completed, the resulting reference material RFF 6 2OO was removed from the glass plate.
  • an automatic film applicator e.g. 200 pm squeegee, film applicator “automatic film applicator S” from BYK-Gardener GmbH
  • the reference materials of the calibration series were examined using micro-X-ray fluorescence analysis. 25 randomly distributed points per concentration were examined, each with a measuring time of 2 minutes per point.
  • the exact concentration of all reference materials in the calibration series was determined using ICP-OES (optical emission spectrometry with inductively coupled plasma) after microwave digestion. This differed only minimally from the values calculated from the initial weights. From this information, the calibration curve shown in FIG. 1 was set up, which has a very good coefficient of determination.
  • a reference material body consisting of eleven layers was produced.
  • the reference material body had alternating iron-containing layers and iron-free layers.
  • the iron-containing layers are reference material layers, the iron-free layers are element-free layers.
  • 3 ml liquid TerraGloss® UV gloss varnish 8/372 F NVK (ACTEGA Terra GmbH, Lehrte, DE) were applied to the existing layer using an automatic film applicator (e.g. 200 pm squeegee, film applicator “automatic film applicator S” from BYK-Gardener GmbH) and left to rest for 10 min.
  • the polymerization was then started by placing the glass plate containing the solution in a UV chamber for 10 minutes and turning it on. After the polymerization was completed, the layer was left on the glass plate.
  • a total of 11 layers were applied alternately, alternating between iron-containing and iron-free layers. This resulted in a total of 6 iron-containing and 5 iron-free layers. The entire sequence of layers was then removed from the glass plate, resulting in the reference material body.
  • Example 18 To demonstrate its suitability as a reference material for depth-sensitive measurements, the reference material body produced in Example 18 was examined using confocal micro-X-ray fluorescence analysis. Points at a distance of 10 pm (in the z direction) were put together to form a depth profile with a measuring time of 2 min per point (see Fig. 2).
  • the iron-containing layers could still be distinguished from iron-free layers up to a depth of almost 2 mm.
  • the reference material body is suitable as a reference material for depth-sensitive calibration.
  • FIG. 3 illustrates a first embodiment of a reference material body 1. This is a solid body which consists of five layers 2 of a reference material according to the invention.
  • Example 21
  • FIG. 4 illustrates a second embodiment of a reference material body 1. This is a solid body which alternately consists of layers 2 of a reference material according to the invention and element-free layers 3.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Medical Uses (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)

Abstract

L'invention concerne un matériau de référence pour l'analyse de corps solides, le matériau de référence comprenant au moins un acétylacétonate d'un élément dans un polymère à base d'acrylate.
PCT/DE2023/100509 2022-07-06 2023-07-05 Matériau de référence pour l'analyse de corps solides, procédé de production du matériau de référence et utilisation du matériau de référence WO2024008241A1 (fr)

Applications Claiming Priority (2)

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DE102022116898.0A DE102022116898A1 (de) 2022-07-06 2022-07-06 Referenzmaterial für die Festkörperanalytik, Verfahren zur Herstellung des Referenzmaterials und Verwendung des Referenzmaterials
DE102022116898.0 2022-07-06

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WO2024008241A1 true WO2024008241A1 (fr) 2024-01-11

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Citations (3)

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Publication number Priority date Publication date Assignee Title
US20050267229A1 (en) * 2002-09-10 2005-12-01 National Institute Of Advanced Industrial Science And Technology Method for producing poly(methyl methacrylate)-metal cluster composite
US20160040062A1 (en) * 2009-10-28 2016-02-11 Mitsubishi Rayon Co., Ltd. Production method of thermoplastic resin composition, molded body, and light emission body
DE102018206995A1 (de) * 2018-05-04 2019-11-07 Merz Dental Gmbh Härtbares röntgensichtbares Material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050267229A1 (en) * 2002-09-10 2005-12-01 National Institute Of Advanced Industrial Science And Technology Method for producing poly(methyl methacrylate)-metal cluster composite
US20160040062A1 (en) * 2009-10-28 2016-02-11 Mitsubishi Rayon Co., Ltd. Production method of thermoplastic resin composition, molded body, and light emission body
DE102018206995A1 (de) * 2018-05-04 2019-11-07 Merz Dental Gmbh Härtbares röntgensichtbares Material

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Title
ACTEGA COATINGS AND SEALANTS: "TerraGloss UV Lacke", September 2014 (2014-09-01), pages 1 - 8, XP093078755, Retrieved from the Internet <URL:https://www.actega.com/de/de/TERRAGLOSS-UV-Glanzlack-G-8-372-F-NVK-060/p/330112631> [retrieved on 20230905] *
BIRKA M.WENTKER K, ANALYTICAL CHEMISTRY, vol. 87, no. 6, 2015, pages 3321 - 3328
BODE, J., FREIBERG, 2021
M. JONES: "A New Method of Preparing Some Acetylacetonate Complexes", J AM. CHEM. SOC., vol. 81, no. 13, 1959, pages 3188 - 3189
MCNEILL I C ET AL: "The effect of metal acetylacetonates on the thermal degradation of poly(methyl methacrylate): Part II-Manganese (III) acetylacetonate", POLYMER DEGRADATION AND STABILITY, BARKING, GB, vol. 37, no. 1, 1992, pages 25 - 32, XP024144100, ISSN: 0141-3910, [retrieved on 19920101], DOI: 10.1016/0141-3910(92)90088-M *
OLEG YURCHENKO ET AL: "Investigation of chromium(III) acetylacetonate as a calibration reference material for atomic absorption spectroscopy", MICROCHIMICA ACTA ; AN INTERNATIONAL JOURNAL ON MICRO AND TRACEANALYSIS, SPRINGER-VERLAG, VI, vol. 160, no. 1-2, 28 September 2007 (2007-09-28), pages 109 - 112, XP019592113, ISSN: 1436-5073 *

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