CEN/TR 196-4:2007

SLOVENSKI STANDARD
01-marec-2008
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SIST ENV 196-4:1995
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Methods of testing cement - Part 4: Quantitative determination of constituents
Prüfverfahren für Zement - Teil 4: Quantitative Bestimmung der Bestandteile
Méthodes d'essais des ciments - Partie 4 : Détermination quantitative des constituants
Ta slovenski standard je istoveten z: CEN/TR 196-4:2007
ICS:
91.100.30
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL REPORT
CEN/TR 196-4
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
September 2007
ICS 91.100.30 Supersedes ENV 196-4:1993
English Version
Methods of testing cement - Part 4: Quantitative determination
of constituents
Méthodes d'essais des ciments - Partie 4 : Détermination Prüfverfahren für Zement - Teil 4: Quantitative Bestimmung
quantitative des constituants der Bestandteile
This Technical Report was approved by CEN on 14 April 2007. It has been drawn up by the Technical Committee CEN/TC 51.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,
Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2007 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 196-4:2007: E
worldwide for CEN national Members.

Contents Page
Foreword. 3
1 Scope. 5
2 Normative references.6
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 cement 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 the siliceous fly ash content . 26
7.4 Determination of the natural pozzolana content . 28

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 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 ENV 196-4:1993.
This European Technical Report was drawn up by Technical Committee CEN/TC 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 197-1:2000 (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 method 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.
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 analytical
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 calculations.
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 being
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 by
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 current 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 methods of testing cement comprises the following Parts:
EN 196-1 Methods of testing cement — Part 1: Determination of strength
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
EN 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 hydration — 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
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 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 cement’s constituents, generally of an unknown number,
where they are not available separately 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 is derived from Table 1 of EN 197-1.
Table 1 — Common cement types specified in EN 197-1
(1)
Type of Designation Notation Excluding
cement
CEM I Portland cement I
Portland-slag cement II/A-S
(with blastfurnace slag) II/B-S

Portland-silica fume cement II/A-D

Portland pozzolana cement II/A-P

(with natural pozzolana) II/B-P

Portland-fly ash cement II/A-V

(with siliceous fly ash) II/B-V
CEM II
Portland-limestone cement II/A-L or LL*
II/B-L or LL*
Portland-composite cement II/A-M limestone
II/B-M Burnt shale
III/A
CEM III Blastfurnace cement III/B
III/C
CEM IV Pozzolanic cement IV/A
IV/B
CEM V Composite 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 constituents will be
necessary before the method can be applied.
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 determined ‘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
undertaken 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 statistical 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 the 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 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’;
 ‘natural 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 reference 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 incorporated 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, Cement — Part 1: Composition, specifications and conformity criteria for common cements
ISO 3534, Statistics — Vocabulary and symbols

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 made 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 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 each 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
deviation 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 determination of constituents, in particular for clinker.
Likewise, for the methods of analysis f
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