CEN/TC 187/WG 4 - Chemical analysis

This document specifies analytical techniques for the determination of volatile components by thermal treatment at specified temperatures, and methods for the determination of the total carbon, free carbon, silicon carbide, total and free silicon and free and surface silica content of silicon-carbide, silicon-nitride and silicon-oxynitride containing raw materials and refractory products.

This document describes methods for the determination of mineralogical phases typically apparent in nitride and oxy-nitride bonded silicon carbide refractory products using a Bragg-Brentano diffractometer.
It includes details of sample preparations and general principles for qualitative and quantitative analyses of mineralogical phase composition. Quantitative determination of α-Si3N4, β-Si3N4, Si2ON2, AlN, and β’- SiAlON are described.
For quantitative determination of α-Si3N4, β-Si3N4, Si2ON2, AlN and β’-SiAlON refinement procedures based on the total nitrogen content of the sample are described.
NOTE            ISO 21068-3 is used for the analysis of the total nitrogen content of the sample.

This document specifies analytical techniques for the determination of total nitrogen and nitrogen calculated as silicon nitride, total oxygen, and metallic and oxidic components in silicon carbide raw materials and refractory products.

This document gives definitions and specifies techniques for the preparation of samples for the chemical analysis of silicon-carbide-containing raw materials and refractory products including:
a)       SiC raw materials;
b)       graphite brick containing silicon carbide;
c)        silicon carbide brick (includes the bricks containing silicon nitride, silicon oxynitride, sialon);
d)       refractories containing carbon and/or silicon carbide mixed with clay;
e)       refractories containing carbon and/or silicon carbide mixed with silica (and fused silica);
f)         refractories containing carbon and/or silicon carbide mixed with high alumina material;
g)       refractories containing carbon and/or silicon carbide mixed with magnesia (and dolomite);
h)       refractories containing carbon and/or silicon carbide mixed with chrome mineral or magnesia-chrome materials;
i)         refractories containing carbon and/or silicon carbide except those described in a) to h) above.
The items of analysis described in ISO 21068-2, ISO 21068-3 and ISO 21068-4 are as follows:
—     loss on drying (LOD);
—     loss on ignition (LOI);
—     total carbon, Ctotal;
—     free carbon, Cfree;
—     silicon carbide, SiC;
—     free silicon (Sifree);
—     free aluminium (Alfree);
—     free magnesium (Mgfree);
—     free iron (Fefree);
—     silicon(IV) dioxide (SiO2);
—     aluminium(III) oxide (Al2O3);
—     iron(III) oxide (Fe2O3);
—     titanium(IV) oxide (TiO2);
—     calcium oxide (CaO);
—     magnesium oxide (MgO);
—     sodium oxide (Na2O);
—     potassium oxide (K2O);
—     chromium(III) oxide (Cr2O3);
—     zirconium(IV) oxide (ZrO2);
—     boron oxide (total boron calculated as B2O3);
—     nitrogen;
—     oxygen;
—     nitrides (undifferentiated: Si3N4, AlN, BN, sialon, oxy-nitrides, etc.);
—     mineralogical phases (XRD-methods).

This European Standard defines a method for the determination of the trace element concentrations of Al, Ca, Cr, Cu, Fe, Mg, Ni, Ti, V and Zr in powdered and granular silicon carbide.
Dependent on element, wavelength, plasma conditions and weight, this test method is applicable for mass contents of the above trace contaminations from about 0,1 mg/kg to about 1 000 mg/kg, after evaluation also from 0,001 mg/kg to about 5 000 mg/kg.
NOTE 1   Generally for optical emission spectrometry using inductively coupled plasma (ICP OES) and electrothermal vaporization (ETV) there is a linear working range of up to four orders of magnitude. This range can be expanded for the respective elements by variation of the weight or by choosing lines with different sensitivity.
After adequate verification, the standard is also applicable to further metallic elements (excepting Rb and Cs) and some non-metallic contaminations (like P and S) and other allied non-metallic powdered or granular materials like carbides, nitrides, graphite, soot, coke, coal, and some other oxidic materials (see [1], [4], [5], [6], [7], [8], [9] and [10]).
NOTE 2   There is positive experience with materials like, for example, graphite, B4C, Si3N4, BN and several metal oxides as well as with the determination of P and S in some of these materials.

This part of ISO 14720 defines a method for the determination of sulfur in powdered and granular non-oxidic ceramic raw materials and materials, which are completely oxidized at a higher temperature in an oxygen atmosphere, e.g. carbon and graphite materials.
For materials which are not completely oxidizable under these conditions, it is possible to determine sulfur that can be released under these conditions, e.g. the adherent sulfur.
This part of ISO 14720 is applicable for materials with mass fractions of sulfur ≤ 10 % and mass fractions of ash  < 20 %, The defined method is limited for materials with mass fractions of barium < 10 mg/kg, because the sulfur bonded in barium sulfate is not detectable with this method.
For the lower detection limit of this method, a mass fraction of sulfur of 0,5 mg/kg in the case of inductively coupled plasma optical emission spectrometry (ICP/OES) and 5 mg/kg in the case of ion chromatography (IC) has to be considered as a recommended value.

ISO 14720-1:2013 defines a method for the determination of sulfur in powdered and granular non-oxidic ceramic raw materials and materials, such as silicon carbides, silicon nitrides, graphites, carbon blacks, cokes, carbon powders. If proved by the recovery rate, this method can also be applied for other non-metallic powdered and granular materials, e.g. silicon dioxide.
ISO 14720-1:2013 is applicable for materials with mass fractions of sulfur from 0,005 % to 2 %.
ISO 14720-1:2013 can also be applied for materials with higher mass fractions of sulfur after verification of the particular case.

ISO 14719:2011 specifies a spectral photometric method with 1,10-phenanthroline for the quantitative determination of Fe2+ and Fe3+ in oxidic raw and basic materials for ceramics, glass and glazes, e.g. feldspar, kaolinites, clay, limestone, quartz refractory materials. ISO 14719:2011 could be extended to other aluminosilicate materials, providing that uncertainty data is produced to support it. However, there might be problems in the decomposition of high-purity alumina and chrome ore samples.
The method is not suitable for reduced materials, such as silicon carbide, graphite-magnesia, etc.

ISO 12677:2011 specifies a method for the chemical analysis of refractory and technical ceramic raw materials, intermediates and products, by means of the X-ray fluorescence (XRF) fused cast-bead method. Typical materials that can be analysed by ISO 12677:2011 are given in Clause 3. ISO 12677:2011 is not applicable to non-oxide materials, such as silicon carbides or nitrides, etc. The method is applicable to a wide range of materials containing a wide range of elements.

This European Standard describes the method for the analysis of mass fractions of the impurities Al, B, Ca, Cr, Cu, Fe, Mg, Ni, Ti, V and Zr in powder  and grain-shaped silicon carbide of ceramic raw and basic materials. This application can also be extended to other metallic elements and other similar non-metallic powder  and grain-shaped materials such as carbides, nitrides, graphite, carbon blacks, cokes, carbon, as well as a number of further oxidic raw and basic materials after appropriate testing.
NOTE   There are positive interferences for materials such as e.g. graphite, B4C, BN, WC and several refractory metal oxides.
This testing procedure is applicable to mass fractions of the impurities mentioned above from approximately
1 mg/kg up to approximately 3 000 mg/kg, after verification. In some cases it may be possible to extend the range up to 5 000 mg/kg depending on element, wavelength, arc parameter, and sample weight.

ISO 20565-2:2008 specifies traditional (“wet process”) methods for the chemical analysis of chrome-bearing refractory products and raw materials.

ISO 10058-2:2008 specifies traditional (“wet process”) methods for the chemical analysis of magnesite and dolomite refractory products and raw materials.

ISO 20565-3:2008 specifies flame atomic absorption spectrometry (FAAS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) methods for the chemical analysis of chrome-bearing refractory products and chrome-bearing raw materials.

ISO 20565-1:2008 specifies methods for the chemical analysis of chrome-bearing refractory products and chrome-bearing raw materials, using traditional (“wet”) methods, ICP-AES spectrometry and FAAS spectrometry. It covers apparatus, reagents, dissolution and determination of gravimetric silica.

ISO 10058-1:2008 specifies apparatus, reagents, dissolution and gravimetric silica analysis for the chemical analysis of magnesite and dolomite refractory products and raw materials.

ISO 10058-3:2008 specifies atomic absorption spectrometry (AAS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) methods for the chemical analysis of magnesite and dolomite refractory products and raw materials.

ISO 21079-1:2008 specifies methods for the chemical analysis of AZS (alumina, zirconia, and silica) refractory products (containing 5 % to 45 % of ZrO2) and raw materials, using traditional ("wet") methods, inductively coupled plasma atomic emission (ICP-AE) spectrometry and flame atomic absorption (FAA) spectrometry. It covers apparatus, reagents and dissolution methods.
ISO 21079-1:2008 is not applicable to MgO-based refractories.
ISO 21079-1:2008 gives alternatives to the X-ray fluorescence (XRF) method given in ISO 12677.

ISO 21079-3:2008 specifies flame atomic absorption spectrophotometry (FAAS) and inductively coupled plasma emission spectrometry (ICP-AES) methods for the analysis of AZS (alumina, zirconia, and silica) refractory products (containing 5 % to 45 % of ZrO2) and raw materials.
ISO 21079-3:2008 is not applicable to MgO-based refractories.
ISO 21079-3:2008 gives alternatives to the X-ray fluorescence (XRF) method given in ISO 12677.

ISO 21079-2:2008 specifies methods for the chemical analysis of AZS (alumina, zirconia, and silica) refractory products (containing 5 % to 45 % of ZrO2) and raw materials, using traditional ("wet") methods.
ISO 21079-2:2008 is not applicable to MgO-based refractories.
ISO 21079-2:2008 gives alternatives to the X-ray fluorescence (XRF) method given in ISO 12677.

ISO 26845:2008 specifies apparatus, reagents, sampling, sample preparation, terms and definitions, basic procedures, loss on ignition and reporting of results applicable to the following standards, which are used for the chemical analysis of refractory products and raw materials by wet chemical, AAS and ICP-AES:
ISO 10058-1, ISO 10058-2 and ISO 10058-3;
ISO 20565-1, ISO 20565-2 and ISO 20565-3;
ISO 21079-1, ISO 21079-2 and ISO 21079-3;
ISO 21587-1, ISO 21587-2 and ISO 21587-3.

ISO 21078-1:2008 specifies methods of determining boron(III) oxide in refractory products and raw materials, in mass fractions of 0,01 % or greater. It is applicable to the determination of total boron(111) oxide in oxidic materials for ceramics, glass and glazes.

ISO 21078-2:2006 specifies procedures of chemical analysis for the determination of boron(III) oxide used as a binder component added to aluminosilicate refractories, using an acid extraction method.
It is applicable for refractories containing less than 1 % (mass fraction) of boron(III) oxide.

ISO 21587-1:2007 specifies reagents, dissolution and gravimetric silica analysis for the chemical analysis of aluminosilicate refractory products and raw materials.
ISO 21587-1:2007 gives alternatives to the X-ray fluorescence (XRF) method given in ISO 12677:2003.

ISO 12677-3:2007 specifies inductively coupled plasma/atomic emission (ICP/AE) spectrometry and flame atomic absorption (FAA) spectrometry methods for the chemical analysis of aluminosilicate refractory products and raw materials.
The methods are applicable to the determination of the following:
silicon(IV) oxide (SiO2)aluminium oxide (Al2O3)iron(III) oxide (total iron oxide calculated as Fe2O3)titanium(IV) oxide (TiO2)manganese(II) oxide (MnO)calcium oxide (CaO)magnesium oxide (MgO)sodium oxide (Na2O)potassium oxide (K2O)chromium(III) oxide (Cr2O3)zirconium oxide (ZrO2)phosphorous(V) oxide (P2O5)
This part of ISO 12677 gives alternatives to the X-ray flluorescence (XRF) method given in ISO 12677:2003

ISO 12677-2:2007 specifies traditional ("wet") methods for the chemical analysis of aluminosilicate refractory products and raw materials.
The methods are applicable to the determination of the following:
silicon(IV) oxide (SiO2)aluminium oxide (Al2O3)iron(III) oxide (total iron oxide calculated as Fe2O3)titanium(IV) oxide (TiO2)manganese(II) oxide (MnO)calcium oxide (CaO)magnesium oxide (MgO)sodium oxide (Na2O)potassium oxide (K2O)chromium(III) oxide (Cr2O3)zirconium oxide (ZrO2)phosphorous(V) oxide (P2O5)
This part of ISO 12677 gives alternatives to the X-ray fluorescence (XRF) method given in ISO 12677:2003.

This standard describes the methods for the analysis of all refractory products containing nitride and oxynitride bonded silicon carbide, irrespective of the silicon carbide level. It includes details of sample preparation, general principles of chemical analysis and detailed methods for the determination of carbon, silicon carbide, free aluminium, free silicon, total nitrogen and oxygen.

This standard describes methods for the determination of mineralogical phases typically apparent in nitride and oxy-nitride bonded silicon carbide refractory products using a Bragg-Brentano diffractometer.
It includes details of sample preparation and general principles for qualitative and quantitative analysis of mineralogical phase composition. Quantitative determination of -Si3N4, -Si3N4, Si2ON2, AlN, and SiAlON are described.
NOTE   For the refinement procedures the total nitrogen content, analysed in accordance with EN 12698-1 is needed.

This European Standard describes a method for the spectrometric determination of chromium (VI) in chrome bearing refractories, before and after use. It is applicable to fired magnesia-chrome products (containing natural chromite, fused grain or co-clinker) and to unfired materials (with refractory cement or chemical bonds) although it is not to be restricted to these types of refractory. The method is applicable to concentrations up to 500 mg/kg of chromium (VI).
This range may be extended or reduced by modifying the dilution factors.

This International Standard specifies a method for determining the comparative resistance of refractory materials to
carbon monoxide disintegration.
The test is intended to be more severe than conditions encountered in service in order to enable probable behaviour
of refractory materials to be assessed in a relatively short time.

This document describes a method for the analysis of mass fractions of the impurities Al, B, Ca, Cr, Cu, Fe, Mg, Ni, Ti, V and Zr in powdered and grain-shaped silicon carbide of ceramic raw materials and ceramic materials. This application can also be extended to other metallic elements and other similar non-metallic powdered and grain-shaped materials such as carbides, nitrides, graphite, carbon blacks, cokes, carbon, as well as a number of further oxidic raw and basic materials after appropriate testing.
NOTE   There is positive experience with materials such as, for example, graphite, boron carbide (B4C), boron nitride (BN), tungsten carbide (WC) and several refractory metal oxides.
This testing procedure is applicable to mass fractions of the impurities mentioned above from approximately 1 mg/kg up to approximately 3 000 mg/kg, after verification. In some cases, it is possible to extend the range up to 5 000 mg/kg depending on element, emission lines, DCArc parameters, and sample mass.

This document defines a method for the determination of the mass fractions of the elements Al, Ca, Cr, Cu, Fe, Mg, Ni, Ti, V and Zr in powdered and granular silicon carbide.
Dependent on element, emission lines, plasma conditions and sample mass, this test method is applicable for mass fractions of the above trace contaminations from about 0,1 mg/kg to about 1 000 mg/kg, after evaluation also from 0,001 mg/kg to about 5 000 mg/kg.
NOTE 1   Generally for optical emission spectrometry using inductively coupled plasma and electrothermal vaporization (ETV-ICP-OES) there is a linear working range of up to four orders of magnitude. This range can be expanded for the respective elements by variation of the sample mass or by choosing emission lines with different sensitivity.
After adequate verification, this document is also applicable to further metallic elements (excepting Rb and Cs) and some non-metallic contaminations (like P and S) and other allied non-metallic powdered or granular materials like carbides, nitrides, graphite, soot, coke, coal, and some other oxidic materials (see [1], [4], [5], [6], [7], [8], [9] and [10]).
NOTE 2   There is positive experience with materials like, for example, graphite, boron carbide (B4C), silicon nitride (Si3N4), boron nitride (BN) and several metal oxides as well as with the determination of P and S in some of these materials.

This part of EN 12698 describes the methods for the analysis of all refractory products containing nitride bonded silicon carbide, irrespective of the Silicon carbide level.  It includes details of sample preparation, general principles of chemical analysis and detailed methods for the determination of carbon, silicon carbide, free aluminium, free silicon, total nitrogen and oxygen.  
Silicon nitride, silicon oxynitride, silicon, free silica and silicon aluminium oxynitride (sialon) can be determined by XRD.

ISO 21068-2:2008 specifies analytical techniques for the determination of change in mass by thermal treatment at specified temperatures, and methods for the determination of the total carbon content, free carbon, silicon carbide, silicon, total silica and free silica content of silicon-carbide-containing raw materials and refractory products.

ISO 21068-3:2008 specifies methods for the determination of total nitrogen and nitrogen calculated as silicon nitride, total oxygen, and free metallic and oxidic components in silicon carbide raw materials and refractory products.
It applies only to silicon carbide materials that are not bonded with nitrogen. Nitride-bonded silicon carbide refractories are covered in EN 12698-1.

ISO 21068-1:2008 gives definitions and specifies techniques for the preparation of samples for the chemical analysis of silicon-carbide-containing raw materials and refractory products.

This European Standard defines a method for the determination of the trace element concentrations of Al, Ca, Cr, Cu, Fe, Mg, Ni, Ti, V and Zr in powdered and granular silicon carbide.
Dependent on element, wavelength, plasma conditions and weight, this test method is applicable for mass contents of the above trace contaminations from about 0,1 mg/kg to about 1 000 mg/kg, after evaluation also from 0,001 mg/kg to about 5 000 mg/kg.
NOTE 1   Generally for optical emission spectrometry using inductively coupled plasma (ICP OES) and electrothermal vaporisation (ETV) there is a linear working range of up to four orders of magnitude. This range can be expanded for the respective elements by variation of the weight or by choosing lines with different sensitivity.
After adequate verification, the standard is also applicable to further metallic elements (excepting Rb and Cs) and some non-metallic contaminations (like P and S) and other allied non-metallic powdered or granular materials like carbides, nitrides, graphite, soot, coke, coal, and some other oxidic materials (see [1], [4], [5], [6], [7], [8], [9] and [10]).
NOTE 2   There is positive experience with materials like for example graphite, B4C, Si3N4, BN and several metal oxides as well as with the determination of P and S in some of these materials.

ISO 12677:2003 specifies a method for chemical analysis of refractory products and materials, and technical ceramics composed of oxides, including the determination of oxide at levels between 0,01 % and 99 % by means of the XRF fused cast bead method.

This European Prestandard applies to refractory materials in the alumino- silicate familiy. It is intended for the determination of the following constituents within the following range: SiO2: 40 to 93 %; Al2O3: 1 to 60 %; Fe2O3: 0 to 10 %; TiO2, CaO, MgO, K2O, Na2O: 0,01 to 5 %. Note 1: Though Fe2O3 contents higher than 5 % are quite unusual in refractory materials, the field of application of this standard extends to 10 % Fe2O3. Note 2: Using FAAS, K andNa are determined in emission mode.

This part of EN 955 describes methods for chemical analysis of refractories containing predominantly silica (SiO2) and/or alumina (AL2O3) using wet methods.Annex A gives the instrument calibration requirements associated with the test method.