Bsi bs en 01744 1 2009 + a1 2012 (2013)

BRITISH STANDARD Tests for chemical properties of aggregates Part 1: Chemical analysis ICS 91.100.15 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW BS EN 1744-1:2009 +A1:2012 BS EN 1744-1:2009+A1:2012 National foreword This British Standard is the UK implementation of EN 1744-1:2009+A1:2012 It supersedes BS EN 1744-1:2009, which is withdrawn The start and finish of text introduced or altered by amendment is indicated in the text by tags Tags indicating changes to CEN text carry the number of the CEN amendment For example, text altered by CEN amendment A1 is indicated by !" The UK participation in its preparation was entrusted by Technical Committee B/502, Aggregates to Subcommittee B/502/6, Test methods A list of organizations represented on this subcommittee can be obtained on request to its secretary This publication does not purport to include all the necessary provisions of a contract Users are responsible for its correct application Compliance with a British Standard cannot confer immunity from legal obligations This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 May 2010 © The British Standards Institution 2013 Published by BSI Standards Limited 2013 ISBN 978 580 76567 Amendments/corrigenda issued since publication Date Comments 31 January 2013 Implementation of CEN amendment A1:2012 EUROPEAN STANDARD EN 1744-1:2009+A1 NORME EUROPÉENNE EUROPÄISCHE NORM November 2012 ICS 91.100.15 Supersedes EN 1744-1:2009 English Version Tests for chemical properties of aggregates - Part 1: Chemical analysis Essais visant déterminer les propriétés chimiques des granulats - Partie 1: Analyse chimique Prüfverfahren für chemische Eigenschaften von Gesteinskörnungen - Teil 1: Chemische Analyse This European Standard was approved by CEN on 17 October 2009 and includes Amendment approved by CEN on 15 October 2012 CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status of a national standard without any alteration Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member This European Standard exists in three official versions (English, French, German) A version in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom EUROPEAN COMMITTEE FOR STANDARDIZATION COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels © 2012 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members Ref No EN 1744-1:2009+A1:2012: E BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) Contents Page Foreword 7 Scope 8 Normative references 8 Terms and definitions 9 4.1 4.2 Reagents 9 General 9 Reagents for determination of water-soluble chloride salts using the Volhard method (Clause 7) 10 4.3 Reagents for determination of water-soluble chloride salts by potentiometry (Clause 8) 11 4.4 Reagent for factory production control determination of water-soluble chloride salts using the Mohr method (Clause 9) 11 4.5 Reagents for determination of water-soluble sulfates (Clause 10) 11 4.6 Reagents for determination of total sulfur content (Clause 11) 11 4.7 Reagents for determination of acid soluble sulfide content (Clause 13) 11 4.8 Reagents for determination of lightweight contaminators (see 14.2) 13 4.9 Reagents for determination of potential presence of humus (see 15.1) 13 4.10 Reagents for determination of fulvo acid content (see 15.2) 13 4.11 Reagents for determination of free lime by complexometry (see 18.2) 14 4.12 Reagent for determination of free lime by conductometry (see 18.3) 14 4.13 Reagents for determination of free lime by acidimetry (see 18.4) 14 4.14 Reagent for the determination of the expansion of steel slag (see 19.3) 15 4.14.1 Silicone oil 15 4.14.2 Hydrochloric acid diluted (1 + 5) 15 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11 5.12 5.13 5.14 Apparatus 15 General requirements 15 Apparatus for general purposes 15 Additional apparatus required for determination of water-soluble chloride salts following Volhard (see Clause 7) 16 Additional apparatus required for potentiometric determination of water-soluble chloride salts (see Clause 8) 16 Additional apparatus required for factory production control determination of water soluble chloride salts following Mohr (see Clause 9) 17 Additional apparatus required for determination of water-soluble sulfates (see Clause 10) 17 Additional apparatus required for the determination of total sulfur content (see Clause 11) 17 Additional apparatus required for determination of sulfide content (see Clause 13) 17 Additional apparatus required for determination of lightweight contaminators (see 14.2) 18 Additional apparatus required for determination of the potential presence of humus (see 15.1) 18 Additional apparatus required for determination of fulvo acid content (see 15.2) 19 Additional apparatus required for determination of organic contaminators by mortar method (see 15.3) 19 Additional apparatus required for determination of free lime by complexometry (see 18.2) 19 Additional apparatus required for determination of free lime by conductometry (see 18.3) 19 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) 5.15 5.16 5.17 5.18 Additional apparatus required for acidimetric determination of free lime (see 18.4) 22 Additional apparatus required for the determination of CaO in steel slag by X-ray diffraction (see 18.5) 22 Additional apparatus required for the determination of dicalcium silicate disintegration of air-cooled blast-furnace slag (see 19.1) 23 Additional apparatus required for determination of the volume expansion of steel slag (see 19.3) 23 6.1 6.2 6.3 6.4 6.5 6.6 General requirements for testing 26 Number of tests 26 Repeatability and reproducibility 26 Expression of mass, volume, factors and results 26 Drying of materials 26 Ignitions of precipitates 27 Check for the absence of chloride ions (silver nitrate test) 27 Determination of water-soluble chloride salts using the Volhard method (Reference method) 27 Principle 27 Sampling 27 Preparation of test specimens 27 Preparation of extracts 28 Procedure for the determination of the chloride content of the extracts 28 Calculation and expression of results 29 7.1 7.2 7.3 7.4 7.5 7.6 8.1 8.2 8.3 8.4 9.1 9.2 9.3 9.4 9.5 9.6 9.7 Determination of water-soluble chloride salts by potentiometry (Alternative method) 29 Principle 29 Sampling, preparation of test specimens and extracts 29 Procedure for the determination of the chloride content of the extracts 29 Calculation and expression of results 30 Determination of water-soluble chloride salts using the Mohr method (Alternative method) 30 General 30 Principle 30 Sampling 30 Preparation of test portion 31 Preparation of extracts 31 Procedure for the determination of the chloride content of the extracts 31 Calculation and expression of results 31 10 10.1 10.1.1 10.1.2 10.1.3 10.1.4 10.1.5 10.1.6 10.2 10.2.1 10.2.2 10.2.3 10.2.4 10.2.5 Determination of water-soluble sulfates 31 Determination of water soluble sulfates in natural and manufactured aggregates 31 Principle 31 Sampling 32 Preparation of test portion 32 Preparation of extracts 32 Procedure for the determination of the sulfate content of the extracts 32 Calculation and expression of results 33 Determination of water soluble sulfates in recycled aggregates 33 Principle 33 Sampling 33 Preparation of test specimen 34 Preparation of extracts 34 Procedure for the determination of the sulfate content of the extracts, using a spectrophotometer 34 11 11.1 11.2 Determination of total sulfur content 35 Determination of total sulfur content by acid digestion (Reference method) 35 Determination of total sulfur content by high temperature combustion (Alternative method) 37 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) 11.2.1 11.2.2 11.2.3 11.2.4 11.2.5 Principle 37 Sampling 37 Preparation of test portion 37 Procedure 37 Calculation and expression of results 37 12 12.1 12.2 12.3 12.4 12.5 Determination of acid soluble sulfates 37 Principle 37 Sampling 38 Preparation of test portion 38 Procedure 38 Calculation and expression of results 38 13 13.1 13.2 13.3 13.4 13.5 Determination of acid soluble sulfides 39 Principle 39 Sampling 39 Preparation of test portion 39 Procedure 39 Calculation and expression of results 40 14 14.1 14.1.1 14.1.2 14.1.3 14.2 14.2.1 14.2.2 14.2.3 14.2.4 Determination of components affecting the surface finish of concrete 40 Examination for the presence of reactive iron sulfide particles 40 General 40 Sampling 40 Procedure 41 Determination of lightweight contaminators 41 General 41 Principle 41 Procedure 41 Calculation and expression of results 42 15 Determination of organic components affecting the setting and the hardening of cement 42 15.1 Determination of potential presence of humus 42 15.1.1 Principle 42 15.1.2 Sampling 42 15.1.3 Preparation of test portion 42 15.1.4 Procedure 43 15.1.5 Expression of results 43 15.2 Determination of fulvo acid content 43 15.2.1 Principle 43 15.2.2 Sampling 43 15.2.3 Preparation of test portion 43 15.2.4 Procedure 43 15.2.5 Expression of results 44 15.3 Determination of organic contaminators by mortar method 44 15.3.1 Principle 44 15.3.2 Sampling 44 15.3.3 Preparation of test portions 44 15.3.4 Preliminary treatment of test portions 44 15.3.5 Constituents 45 15.3.6 Mix quantities 45 15.3.7 Mixing procedure 45 15.3.8 Measurement of stiffening time 46 15.3.9 Compressive strength of hardened mortar 46 15.3.10 Calculation and expression of results 46 16 16.1 16.1.1 16.1.2 16.1.3 Determination of water solubility 47 Determination of water solubility of aggregate, excluding filler 47 Principle 47 Sampling 47 Preparation of test portion 47 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) 16.1.4 16.1.5 16.2 16.2.1 16.2.2 16.2.3 16.2.4 16.2.5 Extraction of soluble components 47 Calculation and expression of results 47 Determination of water solubility of filler 48 Principle 48 Sampling 48 Preparation of test portion 48 Extraction of soluble component 48 Calculation and expression of results 48 17 17.1 17.2 17.3 17.4 Determination of loss on ignition 49 Principle 49 Sampling and preparation of test portion 49 Procedure for the determination of loss on ignition 49 Calculation and expression of results 49 18 18.1 18.2 18.2.1 18.2.2 18.2.3 18.2.4 18.3 18.3.1 18.3.2 18.3.3 18.3.4 18.4 18.4.1 18.4.2 18.4.3 18.4.4 18.5 18.5.1 18.5.2 18.5.3 18.5.4 Determination of free lime in steel slag 50 General 50 Determination of free lime by complexometry (Reference method) 50 Principle 50 Sampling and preparation of test portion 50 Procedure 50 Calculation and expression of results 51 Determination of free lime by conductometry (Alternative method) 51 Principle 51 Sampling and preparation of test portion 51 Procedure 51 Evaluation and expression of results 51 Determination of free lime by acidimetry (Alternative method) 51 Principle 51 Sampling and preparation of test portion 52 Procedure 52 Calculation and expression of results 52 Determination of CaO in steel slag by X-ray diffraction 52 Principle 52 Procedure of analysis 53 Calibration procedure 54 Analytical results 55 19 19.1 19.1.1 19.1.2 19.1.3 19.1.4 19.1.5 19.1.6 19.2 19.2.1 19.2.2 19.2.3 19.2.4 19.2.5 19.3 19.3.1 19.3.2 19.3.3 19.3.4 19.3.5 19.3.6 Determination of unsoundness of blast-furnace and steel slags 55 Determination of dicalcium silicate disintegration of air-cooled blast-furnace slag 55 General 55 Principle 55 Sampling 55 Preparation of test portion 55 Procedure 55 Expression of results 55 Determination of iron disintegration of air-cooled blast-furnace slag 56 General 56 Principle 56 Sampling 56 Procedure 56 Expression of results 56 Determination of the expansion of steel slag 56 General 56 Principle 56 Sampling 56 Preparation and compaction of the specimens 56 Steam test procedure 58 Calculation and expression of results 58 Annex A (informative) Precision 60 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) A.1 A.2 A.3 A.4 A.5 A.6 Symbols 60 Determination of water-soluble chloride salts using the Volhard method (Reference method) (See Clause 7) 60 Determination of water-soluble chloride salts by potentiometry (Alternative method) (See Clause 8) 60 Determination of water-soluble sulfates in recycled aggregate (See 10.2) 60 Determination of total sulfur content by acid digestion (Reference method) (See 11.1) 60 Determination of acid soluble sulfates (See Clause 12) 61 Bibliography 62 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) Foreword This document (EN 1744-1:2009+A1:2012) has been prepared by Technical Committee CEN/TC 154 “Aggregates”, the secretariat of which is held by BSI This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by May 2012, and conflicting national standards shall be withdrawn at the latest by May 2012 Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights This document supersedes !EN 1744-1:2009" This document includes Amendment 1, approved by CEN on 2012-10-15 The start and finish of text introduced or altered by amendment is indicated in the text by tags ! " This standard forms part of a series of tests for chemical properties of aggregates Test methods for other properties of aggregates are covered by the following European Standards: EN 932 (all parts), Tests for general properties of aggregates EN 933 (all parts), Tests for geometrical properties of aggregates EN 1097 (all parts), Tests for mechanical and physical properties of aggregates EN 1367 (all parts), Tests for thermal and weathering properties of aggregates The other parts of EN 1744, Tests for chemical properties of aggregates, are:  Part 3: Preparation of eluates by leaching of aggregates  Part 4: Determination of water susceptibility of fillers for bituminous mixtures  Part 5: Determination of acid soluble chloride salts  Part 6: Determination of the influence of recycled aggregate extract on the initial setting time of cement According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) Scope This European Standard specifies procedures for the chemical analysis of aggregates It specifies the reference procedures and, in certain cases, an alternative method which can be considered as giving equivalent results Unless otherwise stated, the test methods specified in this standard may be used for factory production control, for audit tests or for type tests This standard describes the reference methods used for type testing and in cases of dispute (and alternatives methods) for chemical analyses of aggregates For the purpose of type testing and in cases of dispute only the reference method should be used For other purposes, in particular factory production control, other methods may be used provided that an appropriate working relationship with the reference method has been established Normative references The following referenced documents are indispensable for the application of this document For dated references, only the edition cited applies For undated references, the latest edition of the referenced document (including any amendments) applies EN 196-1, Methods of testing cement — Part 1: Determination of strength EN 196-2:2005, Methods of testing cement — Part 2: Chemical analysis of cement EN 459-2, Building lime — Part 2: Test methods EN 932-1, Tests for general properties of aggregates — Part 1: Methods for sampling EN 932-2, Tests for general properties of aggregates — Part 2: Methods for reducing laboratory samples EN 932-5, Tests for general properties of aggregates — Part 5: Common equipment and calibration EN 932-6, Tests for general properties of aggregates — Part 6: Definitions of repeatability and reproducibility EN 933-2, Tests for geometrical properties of aggregates — Part 2: Determination of particle size distribution — Test sieves, nominal size of apertures EN 1015-4, Methods of test for mortar for masonry — Part 4: Determination of consistence of fresh mortar (by plunger penetration) EN 1015-9, Methods of test for mortar for masonry — Part 9: Determination of workable life and correction time of fresh mortar EN 1015-11, Methods of test for mortar for masonry — Part 11: Determination of flexural and compressive strength of hardened mortar EN 1097-6, Tests for mechanical and physical properties of aggregates — Part 6: Determination of particle density and water absorption ISO 384:1978, Laboratory glassware — Principles of design and construction of volumetric glassware ISO 385, Laboratory glassware — Burettes BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) Loss on ignition = m13 − m14 × 100 (in %) m13 (18) where m13 m14 is the mass of the initial test portion in grams; is the mass of ignited test portion in grams The temperature of ignition used shall be reported." 18 18.1 Determination of free lime in steel slag General Each of the methods specified in this clause determine the presence of free lime (CaO), which is potentially expansive, and hydrated lime (Ca(OH)2) which is not expansive To distinguish between these two forms of lime, extra tests are necessary, such as thermo gravimetric or X-ray diffraction analysis 18.2 18.2.1 Determination of free lime by complexometry (Reference method) Principle Free lime is extracted from a ground sample of aggregate by hot ethanediol The content of calcium ions in the extract is subsequently determined by complexometric titration 18.2.2 Sampling and preparation of test portion Proceed as specified in 11.1.2 and 11.2.3 but crushing the last 20 g until they all pass a 63 µm sieve and take approximately 0,5 g of this material as the test portion Coarse iron fragments remaining on the sieve shall be removed 18.2.3 Procedure Weigh the test portion to the nearest 0,1 mg (m15) and transfer into the conical flask (5.13.1) already containing a PTFE stirrer Measure 50 ml of anhydrous ethanediol (4.11.1) and transfer into the flask Seal the flask with the glass stopper and stir in a 70 °C water bath for 30 after reaching the temperature, using the magnetic stirrer at 300 rpm to 400 rpm Then filter immediately through the sintered glass filter (5.13.4), which has a layer (approximately mm to mm) of firmly rammed filter paper pulp in ethanediol Wash out the flask three times with a total of 50 ml propan-2-ol (4.11.2) Acidify the clear filtrate, containing the dissolved free lime, with 10 ml of hydrochloric acid (1 + 1) (4.11.4) and rinse through with water into the measuring flask (5.13.2) Fill up to the mark and homogenize by shaking In accordance with the presumed content, transfer 50 ml or 100 ml to a glass beaker using a pipette Add ten drops of m-nitrophenol solution (4.11.6) and ten drops of triethanolamine (4.11.5) (to sequester the Mn and Fe ions), and then neutralize with the mol/l NaOH solution (4.11.7); dilute with water to approximately 500 ml and bring the pH-value to greater than 13 by adding about 10 ml of mol/l NaOH solution Add indicator (4.11.8) and titrate with EDTA solution (4.11.9) until the reddish mauve changes to blueish mauve Determine the end point of titration by using the photoelectric titration equipment (5.13.5) A blank value shall always be determined from the ethanediol and the reagents 50 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) 18.2.4 Calculation and expression of results Calculate the free lime content of the aggregate from the following equation: Free Lime = (V11 − V12 )× F ×100 (in % ) m15 (19) where V11 is the volume of EDTA solution added (in ml); V12 is the volume of EDTA solution added for the blank (in ml); F is the EDTA solution factor in mg of CaO per ml; multiply by 0,5 in the case of pipetting 100 ml out of the flask (5.13.2); m15 is the mass of the test portion (in g) The amount of free lime is rounded to the nearest 0,1 % 18.3 18.3.1 Determination of free lime by conductometry (Alternative method) Principle Free lime is extracted from a ground sample of aggregate by hot ethanediol The content of calcium ions in the extract is subsequently determined by conductance measurements 18.3.2 Sampling and preparation of test portion Proceed as specified in 18.2.2 and take (100 ± 0,1) mg of the passing 63 µm material as the test portion 18.3.3 Procedure Preheat 100 ml of ethanediol (4.11.1) to (80 ± 0,1) °C in the measuring vessel (see Figure 2) with the aid of a connected thermostat, stirring with a magnetic stirrer Add the test portion to this solvent and introduce the measuring electrode NOTE By measuring the conductance during extraction time, the dissolution of the free lime can be monitored directly After an extraction time of at least 10 and when no further change in conductance occurs, the extraction process is completed Then read off the final conductance value 18.3.4 Evaluation and expression of results Convert the measured conductivity into free lime content using a calibration graph (see Figure 3) Express the mass percentage of free lime to the nearest 0,1 % 18.4 18.4.1 Determination of free lime by acidimetry (Alternative method) Principle Free lime is extracted from a ground sample of aggregate by boiling in ethyl acetoacetate (Franke method); the extract is titrated with a standard 0,2 mol/l hydrochloric acid solution 51 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) 18.4.2 Sampling and preparation of test portion Proceed as specified in 18.2.2 and take approximately g of the passing 63 µm material as the test portion 18.4.3 Procedure Measure 70 ml of the prepared solvent solution (4.13.5) containing ethyl acetoacetate and 2methylpropan-1-ol in the proportion of to 20, and transfer into the Erlenmeyer flask (5.15.1) Weigh the test portion to the nearest 0,1 mg (m16) and transfer into the flask Adjust the flask in position to the water-cooled condenser, fitted with the upper adapter tube containing the sodium hydroxide (4.13.8) and the molecular sieve (5.15.3); reflux at boiling temperature, stirring on the hot plate (5.2.7) for h Remove the hot plate, allow to cool, then filter under vacuum through the glass microfibre filter (5.15.4), receiving the filtrate in a second flask Wash the first flask and residue with 50 ml of 2-methylpropan-l-ol (4.13.2), using a stirring rod fitted with a rubber policeman to guide the flow Add 10 to 12 drops of the indicator solution (4.13.6) to the filtrate and titrate with the standard 0,2 mol/l hydrochloric acid solution (4.13.7) to a distinct reddish tinge NOTE If the titration is conducted by means of a recording pH meter, the filtration of the extract is not necessary 18.4.4 Calculation and expression of results Calculate the free lime content of the aggregate from the following equation: Free lime = k/1 000 V12/m16 100 (in %) (20) where V12 is the volume of hydrochloric acid added (in ml); m16 is the mass of the test portion (in g); k is the factor defined in 4.13.7, representing the number of mg of free CaO per ml of standardized hydrochloric acid solution 18.5 Determination of CaO in steel slag by X-ray diffraction 18.5.1 Principle In wet chemical analyses “free lime” is determined by selective extraction of the minerals CaO (free lime, in its narrower sense as detrimental slag constituent) and Ca(OH)2 (Portlandite, the hydration 2+ product of CaO) The concentration of Ca ions is analysed and expressed as CaO, i.e “free lime” By X-ray diffraction both minerals (free lime = CaO and Portlandite = Ca(OH)2) can be distinguished due to their different crystal structure The intensities of the measuring signals are proportional to the concentrations of CaO and Ca(OH)2 NOTE The crystal structure of each mineral is a three-dimensional, periodic framework of atoms This framework can be described by different sets of parallel lattice planes Each single set of parallel lattice planes has a constant spacing “d” X-ray diffraction can be understood as reflection of X-rays by the different sets of lattice planes 52 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) Any X-ray diffraction device records a signal – called "peak" in the following text – if Bragg’s law is fulfilled: n λ = d sin θ where n λ θ d = whole number; = wave length of the used X-radiation; = diffraction angle of the reflected X-radiation; = lattice spacing Each mineral is characterized by a set of specific d-values and corresponding intensity ratios These sets are listed in literature, i.e commercially available data files Please note that in X-ray diffraction °θ or °2 θ is frequently used as read-out of the instrument θ or θ is linked to the d-values of a mineral by Bragg’s law and depends on the wavelength of the used Xrays 18.5.2 18.5.2.1 Procedure of analysis Starting and stopping the X-ray powder diffraction device Follow up the procedure in the instruction manual of the X-ray powder diffraction device used 18.5.2.2 Preparing the sample Sample preparation shall be done within short time to prevent further hydration of CaO by humidity Contact with water shall be avoided The laboratory sample taken shall be dried immediately in the laboratory at (110 ± 5) °C until a constant mass (3.4) is reached A sub-sample of at least 30 g shall be crushed until all of it passes a sieve with 63 µm woven wire cloth complying with the requirements of EN 933-2 Then this sub-sample shall be prepared in accordance with the requirements of the X-ray device 18.5.2.3 Analysis Before any operation, make sure that the equipment is in an optimal operational condition (refer to the manual of the X-ray diffraction device) To perform an analysis of free lime (CaO) and Portlandite (Ca(OH)2) in steel slag strong intensities of these minerals shall be used, preferably the intensities at dCpeak = 2,389 Å for free lime (CaO) and dCHpeak = 4,895 Å for Portlandite (Ca(OH)2) X-ray intensities of steel slag minerals usually are broadened peaks, due to imperfect crystals and/or partial substitution of Ca by other elements For this reason a d-range around the above mentioned intensities shall be scanned Make sure that there is no serious interference with other minerals of the slag or of impurities in the steel slag 53 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) Make a background correction for free lime (CaO) and Portlandite (Ca(OH)2), preferably at: dCb1 = 2,427 Å and dCb2 = 2,335 Å for free lime (CaO) and dCHb1 = 4,950 Å and dCHb2 = 4,860 Å for Portlandite (Ca(OH)2) Select measuring times for each background left and right of the peaks and the d-ranges that ensure statistic save analytical results Standard deviation in impulse statistics follows square root (N), with N = counts (number of detected impulses) Make sure that calibration measurements and analyses are performed under identical operational conditions and same d-values for intensities and background Make a correction for loss of intensity of the X-ray tube EXAMPLE An example of a measuring procedure for free lime (CaO) is as follows: Measure the background intensity ICb1 at dCb1 = 2,427 Å for 160 sec Scan the range dCb1 = 2,427 Å to dCb2 = 2,335 Å in steps of 0,01 °2 θ/sec and report the intensity ICRange Measure the background intensity ICb2 at dCb2 = 2,335 Å for 160 sec ICRange shall be at least x square root ((ICb1 + ICb2)/2) Calculate IC = ICRange – (ICb1+ICb2)/2 Use IC for all further calculations EXAMPLE An example of a measuring procedure for Portlandite (Ca(OH)2) is as follows: Measure the intensity ICHb1 at dCHb1 = 4,950 Å for 160 sec Scan the range dCHb1 = 4,950 Å to dCHb2 = 4,860 Å in steps of 0.01 °2 θ/sec and report the intensity ICHRange Measure the intensity ICH2 at dCH2 = 4,860 Å for 160 sec ICHRange shall be at least x square root ((ICH1 or ICH2)/2) Calculate ICH = ICHRange – (ICH1+ICH2)/2 Use ICH for all further calculations 18.5.3 Calibration procedure 18.5.3.1 General A calibration curve shall be established that links the intensity of the diffracted ray with the free lime contents on of reference samples with known concentrations based on one of the following methods 18.5.3.2 Establishing a calibration curve for free lime in steel slag Take reference samples in the converter, by means of a spoon NOTE Considering the temperature of the slag at the moment of the sampling (1 600 °C to 700 °C) it can be assumed that hydrated lime (Portlandite) is totally absent After crushing, these samples are analysed in accordance with 18.2 to determine the contents of free lime The diffracted intensity by free lime (CaO) is measured for each of the samples in accordance with 18.5.2.3 and the calibration curve for the CaO is then established 18.5.3.3 Establishing a calibration curve for Portlandite in steel slag The reference samples used for establishing the calibration curve of free lime (CaO) are hydrated during 48 h in a beaker with excess water After drying, the absence of free lime is confirmed by comparison between the analysis of the hydrated samples and the calibration curve of free lime 54 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) The intensity diffracted by Portlandite (Ca(OH) 2) is measured in accordance with 18.5.2.3 and the calibration curve for (Ca(OH) 2) is then established 18.5.3.4 Establishing a calibration curve for free lime and Portlandite in steel slag Prepare synthetic mixtures of the relevant steel slag and reagent-grade CaO or Ca(OH)2 The intensity diffracted by free lime (CaO) or Portlandite (Ca(OH)2) is measured in accordance with 18.5.2.3 and the calibration curves for free lime (CaO or (Ca(OH) 2) is then established 18.5.4 Analytical results Report the results to an accuracy of % 19 19.1 slag 19.1.1 Determination of unsoundness of blast-furnace and steel slags Determination of dicalcium silicate disintegration of air-cooled blast-furnace General This clause specifies the method of determination of the susceptibility to disintegration of crushed blastfurnace lump slag resulting from the inversion of the metastable ß form of the dicalcium silicate to the γ form This phenomenon is sometimes improperly called "lime disintegration" 19.1.2 Principle Broken slag surfaces fluoresce under ultra-violet light in the range of visible light The aspect and colour of fluorescence enable the detection of slags liable to silicate disintegration 19.1.3 Sampling Proceed as specified in 11.1.2 19.1.4 Preparation of test portion Reduce the laboratory sample to a test portion of at least 30 lumps, then wash and dry the test portion, then split each lump to obtain freshly broken surfaces 19.1.5 Procedure Carry out the dicalcium silicate disintegration test under ultra-violet light (5.17.1) 19.1.6 Expression of results Record the observations made on the appearance of freshly broken surfaces Slags which exhibit numerous or clustered large and small bright spots of a yellow, bronze or a cinnamon colour on a violet background shall be recorded as suspect with respect to disintegration Slags with a uniform shine in various shades of violet and those exhibiting bright spots in a limited number only and uniformly distributed, shall be deemed sound 55 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) 19.2 19.2.1 Determination of iron disintegration of air-cooled blast-furnace slag General This clause specifies the method of determination of the susceptibility to disintegration of crushed blastfurnace slag, resulting from the hydrolysis of iron- and manganese sulfides 19.2.2 Principle The iron disintegration occurring by ageing in a humid atmosphere or in rain, but more rapidly under water, is observed by examining the behaviour of pieces of slag which have been immersed in water 19.2.3 Sampling Proceed as specified in 11.1.2 19.2.4 Procedure Place 30 pieces of slag, with a nominal size between 40 mm and 150 mm, in water at (20 ± 2) °C for two days 19.2.5 Expression of results Record any cracking or disintegration If no pieces disintegrate or crack, the sample shall be regarded as having passed the test If one or two pieces disintegrate or crack, the test shall be repeated with a further 30 test pieces If any pieces disintegrate or crack in the second test the sample shall be regarded as having failed the test 19.3 19.3.1 Determination of the expansion of steel slag General This clause specifies the method of determination of the susceptibility to expansion of crushed steel slag, resulting from the late hydration of dead burned free lime and/or free magnesium oxide The test is accelerated due to the elevated temperature and is designed to generate measurable values of expansion for the purpose of categorizing suitable slag 19.3.2 Principle A compacted slag specimen, combined from known grain sizes, is subjected to a flow of steam at 100 °C in a steam unit at ambient pressure By this means, the necessary moisture for reaction with the free lime and free magnesium oxide is continuously conveyed to the test specimen Any change in the volume caused by this reaction is read off from a displacement indicator directly at the top of the specimen The increase in volume is given as the result, calculated in % volume in relation to the original volume of the compressed slag specimen The values are not directly indicative of those expected in the field, i.e % expansion in the test does not equate to % uniform expansion in the field 19.3.3 Sampling The laboratory sample shall be taken in accordance with the procedures specified in EN 932-1 19.3.4 Preparation and compaction of the specimens The laboratory sample taken shall be dried immediately in the laboratory at (110 ± 5) °C until a constant mass (3.4) is reached 56 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) For the steam test use mm to 22 mm test portions of dried mineral mixtures of slag, which have been combined in accordance with the Fuller parabola The proportions of mass for the individual grain size classes are given in Table Table — Proportions of mass per grain size class Sizes Percentage mm in mass to 0,5 15 0,5 to 15 to 5,6 20 5,6 to 10 to 11,2 11 11,2 to 16 14 16 to 22 15 Total 100 NOTE if there are great differences in the particle densities of the individual grain size classes, the mineral mixture can be combined using proportion of volume The individual grain size classes shall be taken from the crushed aggregates The sample reduction shall be carried out in accordance with the procedures specified in EN 932-2 The expansion shall be determined on at least two test specimens Each individual test portion shall be combined separately with the above-mentioned size distribution The amount of material required for each individual sample is 4,5 kg In addition, a sample shall be combined for the determination of the pre-dried particle density, in accordance with EN 1097-6 Cover the perforated base of the test cylinder with a circular filter (fabric mat) and, using a laboratory scoop, transfer the prepared test portion to the cylinder (5.18.1) illustrated in Figure Then dynamically compact the dry specimen on the vibrating table (5.18.5) for at a frequency of (48 ± 3) Hz (amplitude ± 1,5 mm) and a static load of 0,035 N/mm², produced for example by hydraulic pressure Under these test conditions, a void content of (25 ± 3) % volume remains in the slag specimen, values conforming to the practice Alternatively, the sample can be compacted by any other method capable of achieving the same degree of compaction, such as a Proctor hammer or a hand-held power hammer If water is added to the sample to facilitate compaction, testing shall commence within 24 h of the completion of the compaction process After compaction, determine the volume of the slag specimen VS, which is the difference between the volume of the cylinder VC and the volume of air VA between the slag specimen and the top edge of the cylinder Calculate VC and VA from height measurements with the sounding rod (5.18.6) and taking the average of four readings on the extremity of two at right angles crossing diameters plus at minimum four additional readings distributed over the specimen surface Finally, cover over the surface of the slag specimen with a circular filter (fabric mat) and then with a layer of glass beads (5.18.3) which have been lubricated before the test with silicone oil to reduce friction between the individual beads Adjust the mass of the layer of beads so that the total mass of the surcharge, the surcharge support, the perforated plate and the glass beads equals (7,5 ± 0,01) kg Distribute the glass beads evenly within the test cylinder so that they give a level surface NOTE 1,5 g of silicone oil is sufficient for the batch of 1,5 kg of beads 57 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) Repeat the lubrication of the glass beads after each steam test As lime is deposited on the glass beads during the steam test, it is furthermore necessary to clean off the lime after every fourth steam test with dilute hydrochloric acid 19.3.5 Steam test procedure After the slag test specimen has been covered with the layer of glass beads, attach the test cylinder to the steam equipment and fit the heating jacket to the outer wall of the test cylinder Then lay the perforated plate, the surcharge support and the surcharge on top of the beads Adjust the displacement indicator vertically in the centre of the perforated plate and fix it to a rigid support on the steam unit After switching on the heating jacket and the steam unit, the slag test specimen then starts heating up with an expansion of its volume In order not to register the lifting movements associated with this, not begin recording the displacement until steam is passing freely through the sample The testing time in the steam test depends of the composition of slag When the MgO content determined in accordance with EN 196-2 is not greater than or equal to %, the testing time shall be 24 h When the MgO content is more than %, the testing time shall be 168 h NOTE The total MgO content is used as a measure of free MgO, in the absence, at present of a reliable method of determining the content of free MgO In the event of a reliable method being developed, the types should be redefined in terms of free MgO content MgO values declared by steel producers are acceptable for use in determining testing time for steel slag At the end of this period the rise in the test specimen surface is read off and calculated in % volume in relation to the original volume (see 19.3.6) The water container in the steam unit normally is of a size that makes it necessary to top up with water during the test Therefore, care shall be taken to prevent a drop in temperature which would interrupt the production of steam NOTE In many cases, it is useful to record the development of the increase in volume as dependent on time As the movements at the beginning of the steam test occur sharply, it is recommended that the movements be read off at intervals of 15 After h the interval can be extended to 60 If the increase in volume is taken as a function of the time, a detailed interpretation of the test results can be undertaken by means of the graph (starting climb, asymptotic approach to a limit value) For factory production control purposes, it is possible to shorten the test duration by calculating the end point value using regression 19.3.6 Calculation and expression of results Calculate the volume of the slag test portion VS, before the steam test, from the following equation: VS = VC - VA (21) where VS is the volume of the slag test specimen after compaction in the test cylinder (in mm³); VC is the volume of the cylinder (in mm³); VA is the volume of air between the slag specimen and the top edge of the cylinder (in mm³); VC and VA are calculated from the height measurements with the sounding rod and the diameter of the cylinder (210 mm) 58 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) After compaction determine the bulk dry density and the void content of the compacted mixture as follows: ρM = 100 × M ×1 000 and V S × (100 + w) Va = (1 − ρM ) ×100 ρ (22) (23) where ρM is the bulk density of the compressed mixture (in Mg/m³); M is the mass of the compressed mixture (in g); Va is the void content of the compressed mixture (in % volume); VS is the volume of the slag test specimen after compaction in the test cylinder (in mm³); ρ is the pre-dried particle density of the slag, determined as specified in EN 1097-6 (in Mg/m³); w is the water content of the sample (in percentage mass) After completing the test, calculate the expansion in volume % from the rise of the specimen read off the displacement indicator, and from the internal diameter of the test cylinder (210 mm) from the following equation: Expansion = π × h× d2 ×V S × 100 (24) where h is the rise of the specimen after the steam test (in mm); d is the internal diameter of the test cylinder (210 mm) Record the result as the arithmetical mean of the expansion of the two test specimens, rounded to the nearest 0,1 % volume 59 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) Annex A (informative) Precision A.1 r1 Symbols is the repeatability limit as defined in EN 932-6 R1 is the reproducibility limit as defined in EN 932-6 X is the average of the test results A.2 Determination of water-soluble chloride salts using the Volhard method (Reference method) (See Clause 7) The precision of the determination of water-soluble chlorides is stated (in terms of the chloride ion content, as a percentage by mass of the aggregate) as: r1 = 0,000 + 0,029 X and R1 = 0,000 + 0,124 X A.3 Determination of water-soluble chloride salts by potentiometry (Alternative method) (See Clause 8) The standard deviation for repeatability r is 0,001 % The standard deviation for reproducibility R is 0,003 % A.4 Determination of water-soluble sulfates in recycled aggregate (See 10.2) Repeatability r1 and reproducibility R1 have been determined by a French cross testing: two repetitions in eight laboratories Repeatability r1 = 0,022 + 0,018 X Reproducibility R1 = 0,047 + 0,016 X where X is the value T SO4 between 0,2 % and % A.5 Determination of total sulfur content by acid digestion (Reference method) (See 11.1) The precision of the determination of total sulfur content is stated (in terms of the sulfur content, as a percentage by mass of the aggregate) as: r1 = 0,017 + 0,081 X and R1 = 0,062 + 0,204 X 60 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) A.6 Determination of acid soluble sulfates (See Clause 12) The precision of the determination of acid soluble sulfate content is stated (as the percentage SO3 by mass of the aggregate) as: r1 = 0,021 + 0,200 X and R1 = 0,000 + 0,812 X NOTE These values were derived using a test portion of g 61 BS EN 1744-1:2009+A1:2012 EN 1744-1:2009+A1:2012 (E) Bibliography [1] 62 EN 197-1, Cement — Part 1: Composition, specifications and conformity criteria for common cements This page deliberately set blank British Standards Institution (BSI) BSI is the independent national body responsible for preparing British Standards and other standards-related publications, information and services It presents the UK view on standards in Europe and at the international level BSI is incorporated by Royal Charter British Standards and other standardization products are published by BSI Standards Limited Revisions Information on standards British Standards and PASs are periodically updated by amendment or revision Users of British Standards and PASs should make sure that they possess the latest amendments or editions It is the constant aim of BSI to improve the quality of our products and services We would be grateful if anyone finding an inaccuracy or 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