196.5-95.pdf

BRITISH STANDARD BS EN196-5:1995

Methods of testing cement —

Part 5: Pozzolanicity test for pozzolanic cements

The European Standard EN 196-5:1994 has the status of a British Standard

BS EN 196-5:1995

This British Standard, having been prepared under the direction of Technical Committee B/516, was published under the authority of the Standards Board and comes into effect on15 March 1995

© BSI 02-1999

The following BSI references relate to the work on this standard:Committee reference B/516Special announcement in BSI News December 1992

ISBN 0 580 21525 3

Cooperating organizations

The European Committee for Standardization (CEN), under whose supervision this European Standard was prepared, comprises the national standards organizations of the following countries:

Austria Oesterreichisches NormungsinstitutBelgium Institut belge de normalisationDenmark Dansk StandardFinland Suomen Standardisoimisliito, r.y.France Association française de normalisationGermany Deutsches Institut für Normung e.V.Greece Hellenic Organization for StandardizationIceland Technological Institute of IcelandIreland National Standards Authority of IrelandItaly Ente Nazionale Italiano di UnificazioneLuxembourg Inspection du Travail et des MinesNetherlands Nederlands Normalisatie-instituutNorway Norges StandardiseringsforbundPortugal Instituto Portuguès da QualidadeSpain Asociación Española de Normalización y CertificaciónSweden Standardiseringskommissionen i SverigeSwitzerland Association suisse de normalisationUnited Kingdom British Standards Institution

Amendments issued since publication

Amd. No. Date Comments

BS EN 196-5:1995

© BSI 02-1999 i

Contents

PageCooperating organizations Inside front coverNational foreword iiForeword 2Text of EN 196-5 3National annex NA (informative) Determination of endpoints Inside back coverNational annex NB (informative) Committees responsible Inside back coverNational annex NC (informative) Cross-references Inside back cover

BS EN 196-5:1995

ii © BSI 02-1999

National foreword

This British Standard has been prepared under the direction of Technical Committee B/516, Cement and lime. It is the English language version of EN 196-5:1994 Methods of testing cement — Part 5: Pozzolanicity test for pozzolanic cement published by the European Committee for Standardization (CEN). EN 196-5 was drawn up by CEN Technical Committee 51, Cement and building limes, as Part 5 of a series on testing cement which was originally accepted by CEN on 15 November 1985 and made available on 12 May 1987. The UK gave a negative vote at the final voting stage and, under the CEN Rules then in force, was not obliged to implement this Part. A second formal vote was taken in November 1992 when the UK again gave a negative vote but, under the CEN Rules now in force, is obliged to implement this Part. This British Standard supersedes clause 15 of BS 4550-2:1970 and this clause is now deleted.In this Part the reference procedure requires the endpoint of titrations to be determined visually. However, for the standardization of the EDTA solution and the determination of the calcium oxide concentration a more satisfactory photometric procedure using the same indicator exists in EN 196-2. In the UK this photometric endpoint determination, as indicated in National annex NA, is preferred as an alternative.A British Standard does not purport to include all the necessary provisions of a contract. Users of British Standards are responsible for their correct application.

Compliance with a British Standard does not of itself confer immunity from legal obligations.

Summary of pagesThis document comprises a front cover, an inside front cover, pages i and ii, the EN title page, pages 2 to 6, an inside back cover and a back cover.This standard has been updated (see copyright date) and may have had amendments incorporated. This will be indicated in the amendment table on the inside front cover.

EUROPEAN STANDARD

NORME EUROPÉENNE

EUROPÄISCHE NORM

EN 196-5

December 1994

ICS 91.100.10 Supersedes EN 196-5:1987

Descriptors: Cements, pozzolans, chemical tests, determination of content, calcium hydroxide, EDTA, chemical reagents, apparatus

English version

Methods of testing cement — Part 5: Pozzolanicity test for pozzolanic cement

Méthodes d’essais des ciments — Partie 5: Essai de pouzzolanicité des ciments pouzzolaniques

Prüfverfahren für Zement — Teil 5: Prüfung der Puzzolanität von Puzzolanzementen

This European Standard was approved by CEN on 1994-12-12. CEN membersare bound to comply with the CEN/CENELEC Internal Regulations whichstipulate the conditions for giving this European Standard the status of anational standard without any alteration.

Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the Central Secretariat or to anyCEN member.

This European Standard exists in three official versions (English, French,German). A version in any other language made by translation under theresponsibility of a CEN member into its own language and notified to theCentral Secretariat has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium,Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy,Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland andUnited Kingdom.

CEN

European Committee for StandardizationComité Européen de NormalisationEuropäisches Komitee für Normung

Central Secretariat: rue de Stassart 36, B-1050 Brussels

© 1994 Copyright reserved to CEN membersRef. No. EN 196-5:1994 E

EN 196-5:1994

© BSI 02-19992

Foreword

This European Standard was drawn up by Technical Committee CEN/TC 51, Cement and building limes, of which the secretariat is held by IBN.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 time and soundness. ENV 196-4, Methods of testing cement — Part 4: Quantitative determination of constituents. EN 196-5, Methods of testing cement — Part 5: Pozzolanicity test for pozzolanic cements. 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 196-21, Methods of testing cement — Part 21: Determination of the chloride, carbon dioxide and alkali content of cement. 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 June 1995, and conflicting national standards shall be withdrawn at the latest by June 1995.This European standard supersedes EN 196-5:1987.According to the CEN/CENELEC Internal Regulations, the following countries are bound to implement this European Standard: Austria, Belgium, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland, United Kingdom.

Contents

PageForeword 2

1 Scope 32 Normative references 33 General requirements for testing 34 Preparation of a cement sample 35 Principle 36 Reagents 37 Apparatus 48 Standardization of solutions 49 Procedure 5

10 Results 6Figure 1 — Diagram for assessing pozzolanicity 6

EN 196-5:1994

© BSI 02-1999 3

1 ScopeThis European Standard describes the method of measuring the pozzolanicity of pozzolanic cements conforming to ENV 197-1. This standard does not apply to Portland pozzolana cements or to pozzolanas.This method constitutes the reference procedure.

2 Normative referencesThis European Standard 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 Standard 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 cement. EN 196-7, Methods of testing cement — Part 7: Methods of taking and preparing samples of cement. ENV 197-1, Cement — Composition, specifications and conformity criteria — Part 1: Common cements. ISO 385-1:1984, Laboratory glassware — Burettes — Part 1: General requirements. ISO 835-1:1981, Laboratory glassware — Graduated pipettes — Part 1: General requirements. ISO 3534:1977, Statistics — Vocabulary and symbols.

3 General requirements for testing3.1 Expression of masses, volumes and factors

Express masses in grams to the nearest 0,0001 g and volumes from the burette in millilitres to the nearest 0,05 ml. Express the factors of solutions, given by the mean of three determinations, to three places of decimals.

3.2 Number of tests

The number of tests shall be two (see also 3.3).

3.3 Expression of results

Express the results of the determinations in millimoles per litre to the nearest 0,1 mmol/l.Give the final result as the mean of two determinations to one place of decimals.

If the difference between two determinations is more than twice the standard deviation for repeatability, repeat the test and take the mean of the two closest values.

3.4 Repeatability and reproducibility

The standard deviation of repeatability gives the closeness of agreement between successive results obtained with the same method on identical material tested under the same conditions (same operator, same apparatus, same laboratory and short intervals of time1)).The standard deviation of reproducibility gives the closeness of agreement between individual results obtained with the same method on identical material but tested under different conditions (different operators, different apparatus, different laboratory and/or different time1)).The standard deviations of repeatability and reproducibility are expressed in millimoles per litre.

4 Preparation of a cement sampleTake a sample by the method described in EN 196-7. Treat this laboratory sample as described in EN 196-2.

5 PrincipleThe pozzolanicity is assessed by comparing the quantity of calcium hydroxide present in the aqueous solution in contact with the hydrated cement, after a fixed period of time, with the quantity of calcium hydroxide capable of saturating a solution of the same alkalinity. The test is considered positive if the concentration of calcium hydroxide in the solution is lower than the saturation concentration.Experiment has shown that a mixture of 20 g of cement and 100 ml of water at 40 °C achieves equilibrium after a period of 8 days or 15 days2).To evaluate the results it is therefore necessary to know the solubility at 40 °C of calcium hydroxide in a solution of which the alkalinity varies from 35 to about 100 mmol OH– per litre.

6 ReagentsUse only reagents of recognized analytical quality and freshly boiled water, distilled or of equivalent purity, during the analysis.6.1 Concentrated hydrochloric acid (HCl), approximately 12 mol/l (ï = 1,18 g/cm3 to 1,19 g/cm3).

1) Definitions taken from ISO 3534.2) 8 days are sufficient if the test is positive at this stage (see 10.2).

EN 196-5:1994

4 © BSI 02-1999

6.2 Dilute hydrochloric acid: about 0,1 mol/l. Using the 50 ml precision burette (7.8), add 8,5 ml of concentrated hydrochloric acid (6.1) to a 1 litre volumetric flask (7.10) containing about 500 ml of water. Then make up the volume with water.6.3 Dilute hydrochloric acid (1 + 2): add 250 ml of concentrated hydrochloric acid to 500 ml water.6.4 Methyl orange (dimethylaminoazobenzene p-sodium sulfonate).6.5 Methyl orange indicator: dissolve 0,02 g of methyl orange in water and make up to 1 000 ml.6.6 Sodium hydroxide (NaOH).6.7 Sodium hydroxide solution: dissolve 100 g of sodium hydroxide in water and make up to 1 000 ml.6.8 Calcium carbonate (CaCO3): dried at 110 °C.6.9 Potassium chloride (KCl): dried at 110 °C.6.10 Murexide (ammonium purpurate).6.11 Murexide indicator: grind and mix 1 g of murexide with 100 g of dry potassium chloride.6.12 EDTA (disodium dihydrate salt of ethylenediaminetetra-acetic acid).6.13 EDTA solution about 0,025 mol/l : dissolve 9,306 g of EDTA in water and make up to 1 000 ml.6.14 Sodium carbonate (Na2CO3): dried at 260 °C.

7 Apparatus7.1 500 ml cylindrical polyethylene container of about 70 mm diameter with a pressure seal-plug locked by a screw plug.7.2 Wide stem funnel7.3 Porcelain Buchner funnel of 60 mm inner diameter.7.4 Filter paper with low porosity (mean pore diameter of about 2 4m).7.5 250 ml vacuum flask.7.6 250 ml and 400 ml beakers.7.7 50 ml and 100 ml precision pipettes (class A of ISO 835-1:1981).7.8 50 ml precision burette (class A of ISO 385-1: 1984).7.9 Uniform temperature enclosure controlled thermostatically at (40 ± 0,5) °C.7.10 500 ml and 1 000 ml volumetric flasks.7.11 250 ml conical flask.

8 Standardization of solutions8.1 Standardization of the EDTA solution

Weigh approximately 1 g of calcium carbonate (6.8) to the nearest 0,0001 g and introduce into the 250 ml beaker (7.6). Add approximately 100 ml of water and, very carefully, 50 ml of dilute hydrochloric acid (6.3) keeping the beaker covered with a watch glass.Stir with a glass rod and ensure that dissolution is complete. Then transfer the solution into the 500 ml volumetric flask (7.10), wash the beaker and watch glass carefully with water, adding the washings to the solution and make up the volume with water.Pipette 50 ml of the solution into the 400 ml beaker (7.6), dilute with approximately 150 ml of water and add the quantity of sodium hydroxide solution (6.7) necessary to achieve pH 13 (check the pH by means of a pH meter or by indicator papers).Add approximately 50 mg of murexide indicator (6.11) and titrate by means of the burette (7.8) against the EDTA solution (6.13) until there is a steady colour change from purple to violet. From the volume of EDTA solution used, calculate the factor f1 of the EDTA solution by the formula:

where

8.2 Standardization of the 0,1 mol/l solution of hydrochloric acid

Weigh approximately 0,2 g of sodium carbonate (6.14), add it to the 250 ml flask (7.11) and dissolve it in 50 ml to 75 ml of water. Add five drops of the methyl orange indicator (6.5) to the solution and titrate with the 0,1 mol/l dilute hydrochloric acid (6.2) until the colour changes from yellow to orange.

(1)

f1 is the factor of the ETDA solution;

m1 is the mass of calcium carbonate, in grams;

V1 is the volume of EDTA solution used for the titration, in millilitres;

100,09 is the molecular mass of calcium carbonate.

EN 196-5:1994

© BSI 02-1999 5

Calculate the factor f2 of the hydrochloric acid solution by the formula:

where

9 Procedure9.1 Storage and filtration

Pipette 100 ml of freshly boiled water into the polyethylene container (7.1) and place the sealed container in the thermostatic enclosure (7.9) until equilibrium is reached (about 1 h). Remove the container from the thermostatic enclosure. Pour (20 ± 0,01) g of the cement to be examined into it, using the wide stem funnel (7.2). Immediately seal the container hermetically.Shake vigorously for about 20 s to avoid formation of cement lumps. A horizontal rotary motion has to be used to prevent any part of the sample or liquid being thrown up and remaining separated from the rest of the solution.Replace the container in the thermostatic enclosure, making sure that its base is perfectly horizontal so that the deposited layer of cement has a uniform thickness. Perform all operations outside the thermostatic enclosure as quickly as possible (in 1 min maximum) to avoid any appreciable lowering in temperature of the contents of the container.After a period of 8 days or 15 days3) in the thermostatic enclosure, remove the container and filter the solution immediately under vacuum through the Buchner funnel (7.3) into the vacuum flask (7.5) using dry double filter paper (7.4) in less than 30 s (to avoid absorption of atmospheric carbon dioxide and any appreciable lowering in temperature of the solution). Seal the vacuum flask immediately and let the filtrate cool to room temperature.

9.2 Determination of the hydroxyl ion concentration

Shake the vacuum flask (7.5) to homogenise the filtrate and pipette 50 ml of the solution into the 250 ml beaker (7.6). Add five drops of methyl orange indicator (6.5) and determine the total alkalinity with the dilute hydrochloric acid (6.2). The titration end-point corresponds to the colour change from yellow to orange.Calculate the hydroxyl ion concentration [OH– ] by the formula:

where

9.3 Determination of the calcium oxide concentration

To the same solution remaining after completing 9.2, add 5 ml of sodium hydroxide solution (6.7), approximately 50 mg of murexide indicator (6.11) and titrate the calcium oxide with EDTA solution (6.13) by means of the burette (7.8) until there is a steady colour change from purple to violet.Before and after titration, the pH value of the solution shall be at least 13, if not, add the requisite amount of sodium hydroxide solution.Calculate the calcium oxide concentration [CaO] by the formula:

where

(2)

f2 is the factor of the hydrochloric acid;

m2 is the mass of sodium carbonate, in grams;

V2 is the volume of hydrochloric acid used for the titration, in millilitres;

105,989 is the molecular mass of sodium carbonate.

3) 8 days are sufficient if the test is positive at this stage (see 10.2).

(3)

[OH– ] is the hydroxyl ion concentration in millimoles per litre;

V3 is the volume of 0,1 mol/l hydrochloric acid solution used for the titration, in millilitres;

f2 is the factor of 0,1 mol/l hydrochloric acid solution, in grams per millilitre.

(4)

[CaO] is the calcium oxide concentration in millimoles per litre;

V4 is the volume of EDTA solution used for the titration, in millilitres;

f1 is the factor of the EDTA solution.

EN 196-5:1994

6 © BSI 02-1999

10 Results10.1 Expression of results

Plot the mean concentrations (see 3.3) of hydroxyl ions and calcium oxide in the solution, obtained in accordance with 9.2 and 9.3, as a point on Figure 1 which shows the saturation concentration of calcium oxide in the solution as a function of the hydroxyl ion concentration at 40 °C.

10.2 Assessment of results

The cement satisfies the pozzolanicity test when the point plotted is below the curve of calcium oxide saturation concentration shown on Figure 1.

10.3 Repeatability and reproducibility

The standard deviation for repeatability is:for calcium oxide : 0,2 mmol/l;for hydroxyl ion : 0,5 mmol/l.

The standard deviation for reproducibility is:for calcium oxide : 0,5 mmol/l;for hydroxyl ion : 1,0 mmol/l.

Figure 1 — Diagram for assessing pozzolanicity

BS EN 196-5:1995

© BSI 02-1999

National annex NA (informative) Determination of endpointsNA.1 Standardization of the EDTA solutionA standardized solution of EDTA (see 8.1) is required for the determination of the calcium oxide concentration (see 9.3). This standard specifies that the titration endpoint is determined visually, using murexide as the indicator. However, the method described in 4.53.3 a) of BS EN 196-2:1995 utilizes a photometric endpoint detector (see 5.11 of that standard), set at 620 nm when murexide indicator is used, and is the preferred technique for EDTA standardization in the UK.NA.2 Determination of the calcium oxide concentrationThe determination of calcium oxide in cement (see 9.3) is described in 13.14 of BS EN 196-2:1995. That method also utilizes a photometric endpoint detector (see NA.1) and is the preferred technique for calcium oxide determination in the UK.

National annex NB (informative) Committees responsibleThe United Kingdom participation in the preparation of this European Standard was entrusted by Technical Committee B/516 Cement and lime, to Subcommittee B/516/4, upon which the following bodies were represented.

British Cement AssociationBritish Civil Engineering Test Equipment Manufacturers’ AssociationBritish Ready Mixed Concrete AssociationCementitious Slag Makers’ AssociationDepartment of the Environment (Building Research Establishment)Electricity AssociationQuality Ash AssociationSociety of Chemical Industry

National annex NC (informative) Cross-references

The British Standards corresponding to the European Standards referred to in the text are identical in number and title with those given in clause 2.

Publication referred to Corresponding British Standard

ISO 3534:1977 BS 5532 Statistical terminology Part 1:1978Glossary of terms relating to probability and general terms relating to statistics

BSI389 Chiswick High RoadLondonW4 4AL

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