U.S. DEPARTMENT OF COMMERCENational Technical Information Service

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Investigation of AcceleratedMethods for the Determination ofAvailable Alkali in Pozzolans 3

Army Engineer Waterways Experiment Station Vicksburg Miss

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MISCELLANEOUS PAPER C-74-1

INVESTIGATION OF ACCELERATEDI METHODS FOR THE DETERMINATION OF

AVAILABLE ALKAU! IN POZZOLANS

I W. G. Miller

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1.F.~mary 1974 U. S DPRTMENT OF COMERCE

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%-Adct Ex .S ryEgierWtrasIperiment Stationk Concrete Laboratory

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U. S. Army Engineer Waterways Experiment Station Unc~assified

Vicksburg, Mississippi

3.' REPORT TITLE,

INVESTIGATION OF ACCELERATED METHODS FCR THE DETERMINATION OF AVAILABLE ALKALI IN

POZZOLANS

Final rprS. AU TORIS) (Plet r mO . SAIIlc ItNhltI. 1"Of RNeO)

William G. Miller

SREPORT CATS 7 TOTAL No or PA642, 70I. No. OF REPrSFebruary 1974.. _ 5

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.PROJECT NO. Miscellaneous Pdper C-74-1

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Is ,",o", The porocedure spe 0f%( in acceptance testing of pozzo] njz for the d.3termina-tion of the available alkali released by a p~oz.-)an requires the. lime-poz. olan paste to

be stored for a period o. 23 days prior to test. In order to inventigate the possibil-ity of reducing the storage time of the paste prior to te..t, six pozzolans were testedfor av la)'le alkali releice rate by subjecting the paste to three conditions of storadtime a /or temperature. The three conditions were as follc- s: a. Condition 1, Stan-

dard Condition, 28 days at ?8 C; b. Condition 2, seven . at 38 C; c. Condition 3,seven days at 65.5 C. The results of these tests are s fot]l¢s: a. The highect avail-able alkali values for all pozzolans were obtaind under Stor,.e Crandition 1. b. Allpozzolans, except e alcined tuff, produced higher values for CJ ,dition 3 thtui for Condi-tion 2. c. All pozzolans, except calcined tuff, produced av-ilable ilkalM values forCondition 3 that were in excess of t-wo-thirdF of the v lues produced for Condition 1.Results of this study indicate that if the avall-bl, alkali value cf a pozzolan is 1.0percent or less when the paste is stored at 65.5 C f,." scrvc- irys, the maximt= specifi-cation limit of 1.5 percent vill not be exceeded when the pozzolir. In eva)xited by the.present Standard Condition, 8 days at 38 C. In order to reduce the storage time of th,lime-pozzolan paste to seven days, storage Condition 3 w'ti .. maximum limit of 1.0 pe'-cent available alkali is rce;4mnded as an opti. 'l method for the acceptance testingof pozzolan.

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K9 ODILINK A LINK 0 LINK CK KY W00305ONOLS | NTOL. WT MOLI WT

Acceptance testsAlkaliesLime-pozzolan pastes

Pozzolans

- _ Unclassif~yd

MISCILLANEOUS PAPER C-74-1

INVESTIGATION OF ACCELERATEDMETHODS FOR THE DETERMINATION OF

AVAILABLE ALKALI IN POZZOLANS

W. G. Miller

IIa!

OCT, 20 g976ri

Foebruary 1974

I~ Soored by Office, Chi~l: of Engineer=, U. S. Army,

Conducled by U. S. Army :ngiuew Waterways Experiment StationL.V . Ocre!te Labor UEtoryVickibulrg, Misslisippi

A464V-MRC VtCKsmuma. m4iss

APPROVED FOR PUC:IC RELEASE: G;SRIBUTION UNLIMITED

771?

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Foreword

The investigation reported herein was authorized by the Office,

Chief of Engineers (OCE)), by bhe first indorsement, dated 30 March 2970,

to a letter frou OCE to the U. S. Army EngLeer Waterways Experiment

Station (ES), dated 25 February 1970, subject: "Project Plan for In-

vestigation of Accelerated Methods for the Determination of Available

Alkali in Pozzolans."

The work was conducted by the Concrete Laboratory, WES, under the

direction of Mr. Bryant Mather and under the supervision of Mr. R. V.

Toy, Jr. This report was prepared by Mr. W. G. Miller.

PC, E. D. Peixotto, CE, and COL G. H. Hilt, CE, wre Directors of

WES duxtng the preparation and publication of the report. Mr. F. R.

Brown was Technical Director.

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Contents

PassForeword . 0 0 * 0 * 0 0 . 0 0 0 *

Summary *............ ............ vit

Background . . . . . ... ......... .o * 1

Purpose sn4 Scope of Investigation . .o ....... o 1

Materials and Test ethods ..... ........ ..... 2

Presentation and Analyses of Test kesqlts .. 3.... . 3

Conclusions ....... . . . ... o * • • * *

Literature Cited o. . o.. . . . . . . . . . 6

Tables 1-3

v

ISummary

The procedure apecified in acceptance testing of pozzilans forthe determination of the availaLle alkali released by a pozzolan re-quires the lite-pozzolan paste to be stored for a period of 28 daysprior to test. In order to investigate the possibility of reducingthe storage time of the paste prior to test, six pozzolans were testedfor available alkali release rate by subjecting the paste to threeconditions of storage time and/or temperature. The three conditionswere as follows:

a. Condition 1, .'andard Condition, 28 days at 38 C.

b. Condition 2, s:ven days at 38 C.

c. Condition 3, secn days at 65.5 C. IThe results of these tests are as follows:

a. The highest available alkali values for all pozzolans Iwere obtained under Storage Condition 1.

b. All pozzolans, except calcined tuff, produced highervalues for Condition 3 than for Condition 2.

c. All pozzolans, except calcined tuff, produced available Ialkali_ values for Condition 3 that were in excess of Itwo-thirds of the values produced for Condition 1.

Resu.lts of this study indicate that if the available alkali valueof a pozzolan is 1.0 percent or less when the paste is stored at 65.5 Cfor ieven days, the maximum specification limit of 1.5 percent wifll notbe exceeded when the pozzolan is evaluated by the present Standard Con-

dition, 28 days at 38 C.

In order to reduce the storage time of the lime-pozzolan paste toseven days, storage Condition 3 with a maximum limit if 1.0 percentavailable alkali is recommended as an optional method for the acceptancetesting of ozzolan.

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INVESTIGATION OF ACCELERATED METHODS FOR THE DETERMINATIONOF AVAILABLE ALKALI IN POZZOLANS

Background I1. The Corps oa" Engineers Standard Guide Specification for Concrete,

CE 1401.01,I requires the follovrng conditions for release for shipment

and approval for use of tested pozzolans: "Release for shipment and

approval for use will be based on compliance with seven-day lime-pozzolan

strength tequirements and other physical and chemical and "ormity re-

quirements for which test can be completed by the time the seven-day lime-

pozzolan strength test is completed. kelease for shipment and approval

for use on the above basis will be contingent on continuing compliance

with the other requirements of the specifications." The applicable por-

tion of CRD-C 263, Corps of Engineors Herhod for Sampling and Testing

Pozzolan for Use in Portland Cement Concrete,2 for the determination of

available alkali requires 23 days storage of the lime-pozzolan paste.

Under current shipping and construction practices, most tested pozzolan

is incorporated in the project construction prior to the completion of

the above test.

2. This investigation was conducted as part of the responsibility

assigned to the Waterways Experiment Station (.IES) for the technical

surveillance of cement and pozzolan procurement acceptance testing function

of the Corps of Engineers as outlined in ER 1110-1-8100.3

Purpose and Scope of Investigation

3. The investigation reported herein was undertaken to determvne

the alkali release rate of pozzolans and war confined to the effect of

Ii

storage time and temperature conditions on the available alkali released

by lime-pozzolan paste prepared with pozzolans meetLig the requirements

of CRD-C 262, Corps of Engineers Specifications for Pozzolan for Use in

Portland Cement Concrete.2

4. This report describes the materials tested, test methods used,

results obtained, and conclusions derived therefrom.

Materials and Test Methods

Materials

5. Pozzolans. From the many pozzolans available for use, six

(four natural and two fly ash) were selected and identified as follows:

a. Volcanic cinders (Vol C)

b. Calcined Keasey Shale (CK Sh)

c. Calcined Diatomaceous Shale (CD Sh)

d. Calcined Tuff (CT)e. F

e. Fly Ash (FA I) '

f. Fly Ash (FA II)

6. Each pozzolan was blended in a one-quart blender for four hours.

Approximately 150 grams of each material was placed in a staled Jar end

retained for chemical analysis and preparation of lime-pozzolan paste for

determination of available alkali. The remaining portion was placed in

a plastic bag, sealed, and retuined for use in the preparation of physical

test specimens.

7. Lime. !he lime conformed with the requirements of ASTM Designa-

tion C6-49, "Standard Specifications for Normal Finishing Hydrated Lime."4

2

8. Cement. The cement conformed with the requirements of CRD-C 200,

'Federal Specification Cement, Portlaud."2

Test Methods

9. Tests conductea or each Pozzolan were as follows:

a. Evalution of each .terial for complience with the require-ments of CPJD-C 262.-

b. Determination of the total acid soluble alkali in accordancewith the rocedure outlined in CRD-C 209, Method 1401.1par 4.1. U i

c. Determination of water soluble alkali in accordance withthe procedure outline in ASTH C 114, "Chemical Analysisof Hydraulic Cement."

d. The available alkali of lime-pozzolan paste was determined jin accordance with the procedure outlined in CRD-C 263. -

Three rounds of test were conducted, a round consisting ofthe determination of the available alkali of each lime-pozzolan paste after exposure to the following storage con-ditions:

Condition 1, 28 days @ 38 C (Standard Condition)Condition 2, 7 days ( 38 CCondition 3, 7 days @ 65.5 C

*!

Presentation and Analyses of Test Results i

-1 10. The results of tests for compliance with CRD-C 262, anid soluble I

alkali,* and water soluble alkali are shown in table I.

a. All the pozzolans, except the CK Sh and CT, met the require-.j aents of CRD-C 262. The CK Sh and CT failed ta comply withI the minimum 75 percent of control for pozzolanic strength of -

cement-pozzolan mortar at 28 days.

* The method used was that used for cement. In order to determine the

total alkali content of a pozzolan, the material must be rendered solubleby fusion with ammonium chloride and calciun carbonate or some otherappropriate material.

3

C U

progress of the pozzolanic reaction or the additLonal exchange of calcLum

for potassium and sodium. At 65.5 C storage temperature the diffusion

rates are more rapid and this is particulArly true for the monovalent

cations which have larger diffusion rates. Thus if the early calcium

for potassium and sodium exchange takes place, the reverse exchange takes

place to a more complete extent and less water-soluble alkali is available

at seven days.

Conclusions

13. Most pozzolans that produce an available alkali content of

less than 1.0 percent when stored under Condition 3 would be expected to

meet the specification requirement of 1.5 percent maximum when stored

under Condition 1. Method 3 allows the completion of the test for avail-

able alkali in seven days and is recommended as an optional method in

the acceptance testing of fly ash pozzolans. Method 3 is also recommended

I as an optional method for testing natural pozzolans which have been shown

not to contain a zeolite.

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Literature Cited

1. Department of the Army, Office, Chief of Engineers, "StandardGuide Specifications for Concrete," C1 1401.01.

2. U. S. Army Engineer Waterways Experiment Station, CE, Handbookfor Concrete and Cement, August 1949 (with Quarterly Supplements),Vicksburg, Miss.

3. vepartment of the Army, Office, Chief of Engineers, ER 1110-1-

8100, "Laboratory Investigation and Material Testing for Militaryj{ and Civil Works Construction Projects."

4. ASTI, "Standard Specification for Normal Finishing Hydrated Lime,"

Designation C6-49, 1968 Book of ASTM. Standards, Part 9, 1968,SPhiladelphia Pa.

5. ASTM, "Chemical Analysis of Hydraulic Cement," Designation C 114,1968 Book of ASTDI Standards, Part 9, 1968, Philadelphia, Pa.

6

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TABLE 3

Results of Tests for Available Alkali of Pozzolans

Storge Conditions of Lime-Pov? .lan Paste

Condition i Condition #2 Condition #3San4)le 23 days at 38 C 7 days at 38 C 7 days at 65.5 CSybl Av. % Std. Dev. Av._ Std. Dev. Av. %, Std. Dev,

Vol C 1.43 0.065 0.64 0.053 1.01 0.0as0

CK Ah 0.57 0.035 0.29 0.047 0.48 0.029

CD Sh 0.73 0.035 0.48 0.024 0.67 0.018

CT 0.93 0.024 0O. *S6 0.044 0.48 0.019

Ft. 1 0.81 0.120 0.11 0.012 0.76 0.035

FA 11 1.13 0.071 0.27 0.024 0.80 0.012

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75576

In accodance with 1R 70-2-3, p ragrph 6c(.)(b),dated 15 february 1973, a facsimile catalog cardin Libray of Congress fert is reloduced below.

Miller, Wilia GInvestigation of acc-\erated methods for the deter-

mination of available ±kali in pozzolans, by W. G.Miller. Vicksburg, U. S. Army Engineer WaterwaysExperiment Station, 1974.

1 v. (various Intrns) iflui. P7 -m. (U. S.Waterways Experiment Station. Hlis:elaneous paperC-74-l)

Sponsored by Office, Chief of Engineers, U. S. Army.Includes bibliography.

1. Acceptance tests. 2. Alkalies. 3. i]me-pozzolanpastes. 4. Pozzolans. I. U. S. Army. Corps ofEngineers. (Series: U. S. Waterways ExperimentStation, Vicksburg, Miss. Miscellaneous paper C-74-I)TA . W34m no.C-7T-1

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