CEN/TC 187 - Refractory products and materials

This document describes the procedure for the preparation of test panels from refractory materials by gunning through pneumatic nozzle mixing type guns at ambient temperatures. The test pieces are for the determination of properties on as-gunned products prepared under either “standard conditions” (as required for quality assurance or product development) or “site conditions”. In the case of “site conditions”, the purpose of the testing is to establish the properties pertaining to a given installation or a given set of installation conditions. In this case, the panel can be obtained during the on-site installation. Parameters such as ambient temperature, gunning elevation, air pressure and curing conditions (temperature, orientation of the panel) applicable during the preparation of the panel are as near as possible to the respective parameters pertaining to the site installation.
It is also possible to simulate certain “site conditions” by gunning panels off-site, for example, in a laboratory setting. This is acceptable under this document, by agreement between interested parties.
This document does not apply to plastic gunning mixes and to those mixes that contain aggregates that are susceptible to hydration.
This document does not apply to shotcrete type mixes, which are dealt with in ISO 18886.

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 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 specifies three methods for the determination of the bulk density of granular refractory materials (grain density) having a grain size larger than 2 mm:
—    Method 1: mercury method with vacuum;
—    Method 2: arrested water absorption method;
—    Method 3: vacuum method with spin dryer option according to ISO 5017.
Method 1 is intended as the reference method.
NOTE       Depending on the nature of the material tested, the three methods can give different results. Any statement of the value of a bulk density can therefore be accompanied by an indication of the method used or to be used in case of dispute.
The same method can be used for the determination of the volume of the sample, for selecting and preparing the sample, for calculating the bulk density and for presenting the test report.

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 document specifies three methods for the determination of the permanent change in dimensions on heating of dense shaped refractory products.
NOTE   The methods can be applied to materials sensitive to oxidation. However, some of these materials can be affected during the test in such a way as to make the measurement of the dimensional changes impossible to carry out to the required accuracy.

This Part of EN 993 specifies a method for the determination of the modulus of rupture of dense and insulating shaped refractory products at ambient temperature, under conditions of a constant rate of increase of stress.

This document specifies a method of determination of the cold crushing strength of dense shaped refractory products.

This document specifies a method for the determination of the bulk density, apparent porosity and true porosity of dense shaped refractory products.
NOTE   For shaped insulating refractory products, the bulk density and true porosity are determined in accordance with EN 1094-4.

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.

ISO 10081-4:2014 specifies the classification and designation of dense shaped refractory products of special composition including oxide products, oxide and non-oxide products, non-oxide silicon carbide or carbon-based products, and further special products which are only designated but not classified, for example non-oxide products, such as boride, nitride or further combinations of the series given above.

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 1927-6:2012 specifies methods for the determination of properties of unshaped materials from test pieces prepared and stored according to ISO 1927-5:2012.
The methods are applicable to dense and insulating castables and to ramming materials (including plastics) as defined in ISO 1927-1:2012 before and after firing.

ISO 1927-4:2012 describes methods for the determination and measurement of the consistency of dense and insulating castables as defined in ISO 1927-1:2012. It is applicable to all types of dense regular castables, dense deflocculated castables and insulating castables to determine the liquid addition necessary for preparing test pieces according to ISO 1927-5:2012.

ISO 1927-8:2012 specifies methods for the determination of the properties of unshaped refractory materials from test pieces prepared and stored in accordance with ISO 1927-5. The methods complement those described in ISO 1927-6.
The methods have been adapted from standards for shaped refractory products to make them applicable to dense and insulating castables, and ramming materials as defined in ISO 1927-1, before and after firing.

ISO 1927-3:2012 specifies the methods for the characterization of monolithic (unshaped) refractory materials as received and for checking the homogeneity of a delivery of a product. It is applicable to castables (dense and insulating), gunning materials tap hole clay, injection mixes, dry vibrating mixes, and ramming materials, as defined in ISO 1927-1.

ISO 1927-5:2012 specifies methods for the preparation and treatment (curing, drying and firing) of test pieces from monolithic (unshaped) refractory materials.
The methods are applicable to dense and insulating castables and to ramming materials with the four types of chemical composition defined in ISO 1927-1:2012.
The dimensions of the test pieces are specified and the preparation of the mixture, compaction methods, storage and post-treatment of the test pieces are described.

ISO 1927-7:2012 specifies methods for the testing of as-delivered pre-formed shapes. It applies to shapes fabricated from dense and insulating castables and ramming materials as defined in ISO 1927-1.

ISO 1927-2:2012 gives guidance on the sampling of monolithic (unshaped) refractory materials for the purpose of inspection and testing for quality and general information on the reduction and treatment of samples prior to testing. It covers all materials formulated as monolithic refractory materials.

ISO 1927-1:2012 defines terms relating to monolithic (unshaped) refractory products and establishes a classification for the various types of product.
Raw materials and crushed or granulated refractory materials, which do not contain any binder, are excluded.

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.

This part of ISO 8894 describes the hot-wire methods (“cross-array” and “resistance thermometer”) for the determination of the thermal conductivity of non-carbonaceous, dielectric refractory products and materials.
This methods are applicable to dense and insulating refractories (shaped products, refractory castables, plastic refractories, ramming mixes, powdered or granular materials) with thermal conductivity values less than 1,5 W/m×K (“cross-array”) and less than 15 W/m×K (“resistance thermometer”) and thermal diffusivity values less than 5 x 10-6 m2/s.

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 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 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 20565-2:2008 specifies traditional (“wet process”) methods for the chemical analysis of chrome-bearing 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 10058-2:2008 specifies traditional (“wet process”) methods for the chemical analysis of magnesite and dolomite refractory products and raw materials.

ISO 1893:2007 specifies a method for determining the deformation of dense and insulating shaped refractory products, when subjected to a constant load under conditions of progressively rising temperature (or refractoriness under load), by a differential method. The test may be carried out up to a maximum temperature of 1700 °C.

ISO 16282:2007 specifies a method intended primarily for the determination of the abrasion resistance of shaped refractory materials at ambient temperature. It can also be used for unshaped refractory materials. It provides an indication of the suitability of the material for service in abrasive or erosive conditions.

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 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 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.

This European Standard defines terms for those refractory products and materials which are classed as high temperature insulation wools (HTIW). It also establishes the classification of insulating refractory products made from HTIW and specifies methods for determining the thickness, bulk density, resilience, permanent linear change and tensile strength of HTIW products.
It applies to HTIW bulk wool, blankets, felts, mats, boards, pre-formed shapes and papers, with the exception of products delivered in a wet state.
Further test procedures are in development and will be included once they have been ratified. These include a 3 point bend test for boards, a length weighted fibre diameter measurement technique by Scanning Electron Microscope, shot content measurement (dry and wet methods) and thermal conductivity measurement. There is a shot content method described in BS ISO 10635 and there is a thermal conductivity technique described in ASTM C201.

This European Standard describes two alternative methods for determining the resistance to thermal shock of dense shaped refractory materials by an air quenching method, which proved to give the most reliable results when compared with the behaviour of refractories in furnace linings.
Method B can also be applied to unshaped refractory materials.

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 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.

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

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.

ISO 12680-1:2005 specifies a method for determining the dynamic Young's modulus of rectangular cross-section bars and circular cross-section specimens of refractories by impulse excitation of vibration. The dynamic Young's modulus is determined using the resonant frequency of the specimen in its flexural mode of vibration.

ISO 8895:2004 specifies a method for determining the cold crushing strength of shaped insulating refractory products.

These guidelines introduce the principles, testing and assessment of corrosion of refractories by liquids (molten metals, metallurgical slags, glasses, fluxes etc.) and describe four commonly used test methods.
-   Method A: Corrosion testing by the crucible test;
-   Method B: Corrosion testing by the finger-dip test;
-   Method C: Corrosion testing by the rotary slag test;
-   Method D: Corrosion testing by the induction crucible test.