1、PUBLISHED DOCUMENT PD CEN/TR 196-4:2007 Methods of testing cement Part 4: Quantitative determination of constituents ICS 91.100.10 PD CEN/TR 196-4:2007 This Published Document was published under the authority of the Standards Policy and Strategy Committee on 30 November 2007 BSI 2007 ISBN 978 0 580
2、 61119 3 National foreword This Published Document is the UK implementation of CEN/TR 196-4:2007. The UK participation in its preparation was entrusted by Technical Committee B/516, Cement and lime, to Subcommittee B/516/12, Sampling and testing. A list of organizations represented on this committee
3、 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. Amendments issued since publication Amd. No. Date CommentsTECHNICALREPORT RAPPORTTECHNIQUE TECHNISCHERBERICHT CEN/
4、TR1964 September2007 ICS91.100.30 SupersedesENV1964:1993 EnglishVersion MethodsoftestingcementPart4:Quantitativedetermination ofconstituents MthodesdessaisdescimentsPartie4:Dtermination quantitativedesconstituants PrfverfahrenfrZementTeil4:QuantitativeBestimmung derBestandteile ThisTechnicalReportwa
5、sapprovedbyCENon14April2007.IthasbeendrawnupbytheTechnicalCommitteeCEN/TC51. CENmembersarethenationalstandardsbodiesofAustria,Belgium,Bulgaria,Cyprus,CzechRepublic,Denmark,Estonia,Finland, France,Germany,Greece,Hungary,Iceland,Ireland,Italy,Latvia,Lithuania,Luxembourg,Malta,Netherlands,Norway,Poland
6、,P ortugal, Romania,Slovakia,Slovenia,Spain,Sweden,SwitzerlandandUnitedKingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2007CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnati
7、onalMembers. Ref.No.CEN/TR1964:2007:E2 Contents Page Foreword 3 1 Scope. 5 2 Normative references6 3 General requirements for testing . 7 3.1 Number of tests 7 3.2 Determination of constant mass 7 3.3 Expression of masses and results. 8 3.4 Repeatability and reproducibility.8 4 Preparation of a ceme
8、nt sample. 8 5 Reagents. 8 6 Determination of the contents of cement constituents . 8 6.1 General 8 6.2 Selective dissolution method . 9 7 Determination of the contents of constituents for cements with three constituents16 7.1 General 16 7.2 Determination of the slag content 16 7.3 Determination of
9、the siliceous fly ash content . 26 7.4 Determination of the natural pozzolana content 28 CEN/TR 196-4:20073 Foreword This document (CEN/TR 196-4:2007) has been prepared by Technical Committee CEN/TC 51 “Cement and building limes”, the secretariat of which is held by NBN. Attention is drawn to the po
10、ssibility 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 ENV 196-4:1993. This European Technical Report was drawn up by Technical Committee CEN/TC
11、 51 “Cement and building limes“ the Secretariat of which is held by NBN. It is based on a revision of the European Pre- standard ENV 196-4 of July 1993. The main aim of this document is to quantitatively verify the compositions (analysis of the constituents) of all the cements included in EN 197-1:2
12、000 (Cements Part1: composition, specifications and conformity criteria for common cements) as set out in Table 1 “The 27 products in the family of common cements”. Further to this objective, original methods of analysis were devised, firstly, for cements with 3 constituents and then a reference met
13、hod for cements with more constituents. Following the progress of work on EN 197-1, cements with blastfurnace slag, siliceous fly ash and natural pozzolans have been successively studied. As a result the first draft of ENV 196-4 was published in December 1989, followed by the ENV 196-4 in July 1993.
14、 The main aim of the revision of the Pre-standard was to adapt the reference method in such a way that it would be qualitative and quantitative whatever the constituent materials, including blastfurnace slag (which had not been included in the 1989 draft ENV 196-4). This entailed revising the analyt
15、ical procedure and the calculation of the constituents. The opportunity was taken at the same time to unify the presentation of the different methods, reference and alternative, endeavoring to standardize the notational symbols to eliminate all ambiguities in the interpretation of the formulae for c
16、alculations. Table 1 of ENV 197-1:1992 introduced further new constituent materials. One of them, silica fume, could be routinely determined by the reference method, while calcareous fly ash and burnt shale, being composites of several minerals, react partially like other constituents capable of bei
17、ng determined by the reference method. Where these materials are constituents it has proved not to be possible to determine the mass composition of the cement but only to obtain an overall bulk analysis. Almost all of the cements manufactured in Europe can be correctly characterized and quantified b
18、y the reference method. However, for cements containing burnt shale (CEM II/A-T and B-T) or calcareous fly ash (CEM II/A-W and B-W) it would be necessary to undertake further research in order to obtain an acceptable reference method. For cements having constituents that can be analyzed by the curre
19、nt reference method as defined in section 1 “Scope” the method will be adequate. Where other constituents are known, or suspected, to be included it will be necessary to develop additional methods for the quantitative determination of those particular constituents. The European Standard on the metho
20、ds of testing cement comprises the following Parts: EN 196-1 Methods of testing cement Part 1: Determination of strength CEN/TR 196-4:20074 EN 196-2 Methods of testing cement Part 2: Chemical analysis of cement EN 196-3 Methods of testing cement Part 3: Determination of setting times and soundness E
21、N 196-5 Methods of testing cement Part 5: Pozzolanicity test for pozzolanic cement EN 196-6 Methods of testing cement Part 6: Determination of fineness EN 196-7 Methods of testing cement Part 7: Methods of taking and preparing samples of cement EN 196-8 Methods of testing cement Part 8: Heat of hydr
22、ation Solution method EN 196-9 Methods of testing cement Part 9: Heat of hydration Semi-adiabatic method. NOTE A previous Part, EN 196- 21: Methods of testing cement Part 21: Determination of the chloride, carbon dioxide and alkali content of cement, has been revised and incorporated into EN 196-2 C
23、EN/TR 196-4:20075 1 Scope This European Technical Report describes procedures for determining the contents of most of the constituents of the cements that fall within the scope of EN 197-1. In principle, the method described in Clause 6 applies to all cements, whatever the number and nature of their
24、 constituents, but in practice is limited to the cements identified in Table 1. The method in clause 6 should be considered to be the method of choice and is based on a sequential selective dissolution of the cements constituents, generally of an unknown number, where they are not available separate
25、ly for analysis at the same time as the cement. The method of choice enables the quantitative determination (by mass) of: Portland cement clinker, blastfurnace slag, siliceous fly ash, natural pozzolans, limestone, silica fume and set regulators in cements of the types identified in Table 1. Table 1
26、 is derived from Table 1 of EN 197-1. Table 1 Common cement types specified in EN 197-1 Type of cement Designation Notation Excluding (1)CEM I Portland cement I Portland-slag cement (with blastfurnace slag) II/A-S II/B-S Portland-silica fume cement II/A-D Portland pozzolana cement (with natural pozz
27、olana) II/A-P II/B-P Portland-fly ash cement (with siliceous fly ash) II/A-V II/B-V Portland-limestone cement II/A-L or LL* II/B-L or LL* CEM II Portland-composite cement II/A-M II/B-M limestone Burnt shale CEM III Blastfurnace cement III/A III/B III/C CEM IV Pozzolanic cement IV/A IV/B CEM V Compos
28、ite cement V/A V/B *The method is incapable of distinguishing between limestones of type L and LL NOTE 1 Where cements contain calcareous fly ash, burnt shale and/or constituents that partly contain mineral phases, similar to those of clinker, further investigation into the characteristics of those
29、constituents will be necessary before the method can be applied. CEN/TR 196-4:20076 The method of choice has limitations, as indicated earlier, and cannot be considered to be a means by which clinker content can simply be determined in isolation from any other constituent. Clinker content is determi
30、ned by difference and other constituents contain, in part, mineral phases similar to those present in clinker and can cause interferences that lead to difficulties in interpretation of the results. Where apparently anomalous results are obtained, it is recommended that further investigations are und
31、ertaken in accordance with the procedure given in Section 6.2.5.4. Any other method with the same objectives, and intended for use where the constituents are unavailable for separate analysis, can be considered to be an alternative to the method of choice when it is shown that, with appropriate stat
32、istical validity, it gives equivalent results. In individual cases, where the laboratory has been formally advised that: the cement contains only two constituents, the method is greatly simplified because it is sufficient to determine the set regulator content (R) in order to be able to calculate th
33、e clinker content by difference; the cement contains only three constituents, i.e. a set regulator, clinker and one of the following three: slag, pozzolana or siliceous fIy ash. Some of the methods in clause 7 are variations on the method of choice whereas others are based on physical separation of
34、constituents and different analytical principles. NOTE 2 This European Technical Report adopts the following use of terms for major constituents: Portland cement clinker as defined in EN 197-1 is referred to as clinker; granulated blastfurnace slag as defined in EN 197-1 is referred to as slag; natu
35、ral pozzolans as defined in EN 197-1 is referred to as pozzolans; siliceous fly ash as defined in EN 197-1 is referred to as fly ash; calcium sulfate as defined in EN 197-1 is referred to as set regulator. 2 Normative references This European Technical Report incorporates by dated or undated referen
36、ce provisions from other publications. These normative references are cited at the appropriate places in the text and the publications are listed hereafter. For dated references, subsequent amendments to or revisions of any of these publications apply to this European Technical Report only when inco
37、rporated in it by amendment or revision. For undated references the latest edition of the publication referred to applies. EN 196-2, Methods of testing cement Part 2: Chemical analysis of cements EN 196-7, Methods of testing cement Part 7: Methods of taking and preparing samples of cement EN 197-1,
38、Cement Part 1: Composition, specifications and conformity criteria for common cements ISO 3534, Statistics Vocabulary and symbols CEN/TR 196-4:20077 3 General requirements for testing 3.1 Number of tests To carry out the calculation for the contents of the cement constituents, two tests shall be mad
39、e for each. The following analytes are determined: for the method of choice by selective dissolution (clause 6): sulfuric anhydride and carbon dioxide contents, residues after EDTA and nitric acid dissolution and sulfide contents in the cement and in the EDTA residue; for the methods of analysis for
40、 cements with three constituents (clause 7): sulfuric anhydride and carbon dioxide contents, loss on ignition, calcium oxide, magnesium oxide and manganese oxide contents, sulfide contents and insoluble residues. Depending on the method used, only some of these analytes can be determined. If, for ea
41、ch analyte, the difference between the two values obtained is less than twice the standard deviation for repeatability for this analyte, the value to take for further calculations is the arithmetic mean of the two values. If the difference between the two values is greater than twice the standard de
42、viation for repeatability, a third test shall be carried out and the value to be taken for further calculations shall be the arithmetic mean of the two closest values. Hence, for the method of choice by selective dissolution, only one calculation will need to be carried out for the quantitative dete
43、rmination of constituents, in particular for clinker. Likewise, for the methods of analysis for cements with three constituents, a single calculation will enable the content of hydraulic or pozzolanic constituent to be determined. The standard deviations for repeatability of the various analytes to
44、be considered, most of which can be found in EN 196-2: 2005, are as follows: Analyte Standard deviation for repeatability (s rin % by mass) SO 30,07 CO 20,07 a (EDTA residue) 0,50 b (HNO 3residue) 0,11 S 2-0,02 CaO 0,18 MgO 0,15 MnO 0,003 insoluble residue 0,10 loss on ignition 0,04 3.2 Determinatio
45、n of constant mass Constant mass shall be determined by making successive 15 min ignitions, followed each time by cooling and then by weighing. Constant mass is reached when the difference between two successive weighing is less than 0,0005 g. CEN/TR 196-4:20078 3.3 Expression of masses and results
46、Express masses in grams to the nearest 0,0001 g. Express the values for the analytes, given by the mean of two determinations (see 3.1) as the contents of constituents calculated in percentages, to one decimal place. 3.4 Repeatability and reproducibility Repeatability - Precision under repeatability
47、 conditions where independent test results are obtained with the same method on identical test items (material) in the same laboratory by the same operator using the same equipment within short intervals of time. Reproducibility - Precision under reproducibility conditions where test results are obt
48、ained with the same method on identical test items (material) in different laboratories with different operators using different equipment. Repeatability and reproducibility in this document are expressed as repeatability standard deviation(s) and reproducibility standard deviation(s) in absolute percent and relate to clinker contents for the general method of determination of the constituents by selective dissolution and to hydraulic and pozzolanic contents for the methods of analysis of cement with three constituents 4 Preparation of a cement
