c. ~ ~ ral Research Series No. 556

Size: px

Start display at page:

Download "c. ~ ~ ral Research Series No. 556"

Barrie Campbell
5 years ago
Views:

1 10 -X2CJA UILU-ENG S~ ENGINEERING STUDIES c. ~ ~ ral Research Series N. 556 ISSN: COOPERATIVE CALIBRATION AND ANALYSIS OF CEMENT CLINKER PHASES, REPORT 2 By Leslie J. Struble A Reprt t ASTM C DEPARTMENT OF CIVIL ENGINEERING UNIVERSITY OF ILLINOIS AT URBANA-CHAMPAIGN URBANA, ILLINOIS SEPTEMBER 1990

2 Abstract A cperative calibratin was carried ut by ASTM Task Grup C as part 'f an effrt t assess the use f X-ray diffractin analysis fr determining the prprtin f tricalcium aluminate (cubic and rthrhmbic), tetracalcium aluminferrite, and magnesium xide in prtland cement and clinker. That calibratin, including statistical analysis t determine precisin and bias, was described in an earlier reprt. Since that previus re POI4 sme additinal data have been submitted and the statistical analysis repeated. The subsequent analysis shwed that the calibratin precisin were imprved, thugh nly slightly., 'With these additinal data. Based n this statistical analysis, repeatability and reprducibility levels may be specified fr analysis f these 4 phases in unknwn mixtures prepared frm the same materials. Replicate analyses in the same labratry shuld differ by n mre than 1.1 % (relative t the ttal clinker) [the previus level was als 1.1 %]. Replicate analyses in different labratries shuld differ by n mre than 1.7% (relative t the ttal clinker) [the previus level was 1.8%]. Overall, analyses shuld differ frm the knwn value by n mre than 1.7% (relative t the ttal clinker). The measured values differ frm the knwn values by less than the reprducibility standard deviatin, s there appears t be n bias in these results.

3 TABLE OF CONTENTS Abstract. 1. Intrductin 2. Participan.t:s 3. Results 4. Cnclusins Acknwledgements... i Referentt _ Appendix 1. Labratries Participating in the Cperative Calibratin Appendix 2. Summary f Results Appendix 3. Statistical Analysis. 14 ii

4 ~ ~:..; ~~.. UST OF TABLES Table 1. Summary f Statistical Analysis 6 Table 2-1. Results, Labratry 1 Table 2-2. Results, Labratry Table 2-3. Results, Labratry Table 3-1. QXRD Results fr Statistical Analysis. 15 Table 3-2. Cell Averages Table 3-3. Cell Standard Deviatins Table 3-4. Between-Labratry Cnsistency Statistic Values (h-statistic) 17 Table 3-5. Within-Labratry Cnsistency Statistic Values (k-statistic) 19 Table 3-6. Summary f Precisin Parameters iii

5 list OF FIGURES Figure 1. Results frm QXRD analysis f rthrhmbic C~ shwing actual values (lines) and measured values (symbls) fr bth unknwns. 2 Figure 2. Results frm QXRD analysis f cubic C~ shwing the actual values (lines) and measured values (symbls) fr bth unknwns. 3 Figure 3. Results frm QXRD. analysis f C~ shwing actual values (lines) and measured values (symbls) fr bth unknwns. 4 Figure 4. Results frm QXRD analysis f MgO shwing actual values Oines) and measured values (symbls) fr bth unknwns. 5 Figure 3-1. Level f h-value fr each labratry, with critical values indicated by upper and lwer dashed lines Figure 3-2. Level f k-value fr each labratry, with the critical value indicated by a dashed line iv

6 1. Intrductin ASTM: Task Grup C is currently wrking t develp a prpsed test methd t determine the prprtin f varius phases in prtland cement and clinker using quantitative X-ray diffractin (QXRD) analysis. The Thsk Grup, currently chaired by Leslie Struble~ recently cmpleted a cperative calibratin and analysis fr fur phases in cement and clinker: cubic and rthrhmbic tricalcium aluminate (C 3 Al), tetracalcium aluminferrite (C~), and magnesium xide (MgO). Results f that cperative calibratin, including precisin and bias levels fr the test methd, were described in a previus reprt (Struble and Kanare, 1989). Recently, sme additinal data have been submitted fr the cperative calibratin. Therefre all data, including these additinal data, have been statistically analyzed t determine precisin and bias levels; that analysis is the subject f this secnd reprt. 2. Participants Altgether., ten 1a bratries participated in the cperative calibratin and analysis. These labratries are listed in Appendix 1. This reprt refers t all results by labratry number t prvide annymity. 3. Results Three sets f new data are included in this present reprt. One is frm a labratry that did nt participate in the previus reprt (designated Labratry 10). One is a revised set frn1 Labratry 7; riginal data submitted by this labratry were nt used in the previus statistical analysis because replicate values were nt prvided, but the revised data include replicate values fr each determinatin. The third set is als revised data, submitted after ne f the riginal participating labratries (Labratry 1) later decided t repeat the analysis. PJI the indi\~duai results are listed in A-ppendix 2. All data including these three new sets are summarized graphically in Figs. 1 thrugh The fi1wing abbreviatins (cmmn in the cement and cncrete literature) are used: C fr CaO, A fr AI203, F fr Fe203, and S fr SiOl 1

7 ~" 4.0,.._--,..--r----,.-...,...-,--.,..--r----r-...,...-,---, s. a e O--~cnn ~cnn1 a. ~ C) ~ a e t:.' ~ ' e 7 sa 10 labrat%'7 num.ber Figure 1. Results frm QXRD analysis f rthrhmbic C3A shvving actual "alues (lines) and measured values (symbls) fr bth unknwns. ~;. 2

8 " ~ ~ IG.O l~.o & a. 1 0 X. '7.0 j. 0 t s. -- a.j:lknwn UJ:I.k:D.wn it -~ A t & &... G G 7 e _ 10 labll'at.~ Q\1ZDbar Figure 2. Results frm QXRD analysis f cubic C 3 A shwing the actual values (lines) and measured values (symbls) fr bth unkn\vils. 3

9 13.0 1& t ~.. T.O ;.0 8.0,; ~. 0 l. ~ '-> ~.O.. : ~ LO 1.0 e.g 1. a.. e e 7 8 e 10 labrat.0t7 li:uuzaber 1 l } t.. ::.. 4. ~. t. ~ Figure 3. Results frm QXRD analysis f C~ shwing actual values (lines) and measured values (symbls) fr bth unknwns. 4

10 unla:1wu UU&::nOWU & g 0 0 ~-.--!-Jl-~ a a 4 ~ e., II 8 10 Labratr'7 :a.uznmr Figure 4. Results frm QXRD analysis f MgO shwing actual values (lines) and measured values (symbls) fr bth unknwns. In the previus statistical analysis, tw sets f data were nt included because they did nt include replicate values (Labratries 4 and 7). A..s nted abve, replicate data have nw been prvided fr ne (Labratry 7). Hwever, when repeating the statistical analysis it \vas decided t include the ther set (Labratry 4) in the determinatin f between-labratry variatin~ thugh nt in the determinatin f within-labratry variatin. The results were analyzed statistically t estimate precisin and bias fllwing the prcedure described in ASTM E 691 (as was als dne fr the previus reprt). Details f the statistical analysis are presented in Appendix 3 and results are summarized in Table 1. As in the previus reprt, results in Table 1 are expressed as a percent f a hypthetical starting clinker, whereas results in Appendices 2 and 3 are expressed as a percent f the mixture f the fur phases (this mixture was cnsidered t represent 17 percent f the hypthetical clinker). This analysis did nt include Labratry 3 because results frm Labratry 3 'were previusly fund t exceed the critical values f the cnsistency statistics (Struble and Kanare, 1989). 5

11 The measured values agree well with the knwn values (Table 1). (It shuld be nted that the knwn values in the previus reprt were calculated incrrectly; values in the present reprt have been crrected, and therefre differ slightly frm thse previus values). In every case the measured values agree with the knwn values by well within the reprducibility standard deviatin (SR in Table 1). Thus there appears t be n bias in these results. Table 1. Summary f Statistical Analysis (percent f clinker) Standard Deviarin 95% Limit Phase Unknwn Average Mea- Knwn Number sured Value Value' sr a SR b ~ Rd rthrhm bic C3A cubic C3A C 4 AF MgO arepeatability (within-labratry) standard deviatin breprducibility (between-labratry) standard deviatin Crepeatability limit (2.8 times sr) drcprducibil ity limit (2.8 times SR) The estimated levels f repeatability standard deviatin (within-labratry standard deviatin, Sr in Table 1) allw us t estimate the verall repeatability expected fr this analysis. Instead f Sn we use the limit fr 95 percent repeatability (r in Table 1, 2.8 times sr)' This parameter ranged frm 0.25 t 2.16 and averaged 1.1 percent fr the 8 phases tested, the same value determined in the previus statistical analysis. Likewise, the estimated levels f reprducibility (between-labratry standard deviatin, SR in Table 1) and the limit fr 95 percent reprducibility (R in Table 1) indicate the verall reprducibility expected fr this analysis. The 95 percent reprducibility ranged frm 0.38 t 3.22 and averaged 1.7 percent fr the 8 phases tested, slightly lwer than the average f 1.8 percent determined in the previus statistical analysis. The higher value f these tw parameters (r r R), in this case the 95 percent reprducibility value f 1.7 percent, prvides a measure f precisin fr this analysis. 6

12 The next effrt f Task Grup C is an interlabratry analysis fr the prprtins f cubic C3A, rthrhmbic C3A, C4AF, and MgO in a set f standard clinker samples. This analysis utilizes results f the cperative calibratin described in this present reprt. The interlabratry analysis is current1y underway. 4. Cnclusins A cperative calibratin and analysis were carried ut and reprted previusly fr quantitative X-ray diffractin determinatin f the prprtins f cubic C3A, rthrhmbic CA C 4 AF, and MgO in prtland cement clinker. Subsequently, additinal data have been submitted and a new statistical analysis has been perfrmed. This new statistical analysis indicates greater repeatability and reprducibility than did the previus analysis. Based n these results, the fllwing repeatability and reprducibility levels may be specified fr analysis f these phases in mixtures f phases used fr the calibratin: 1. Replicate analyses in the same labratry shuld differ by n mre than 1.1 % (relative t the ttal clinker). 2. Replicate analyses in different labratries shuld differ by n mre than 1.7% (relative t the ttal clinker). 3. Analyses shuld differ frm the knwn value by n mre than 1.7% (relative t the ttal clinker). 4. The measured values differ frm the knwn values by less than the reprducibility standard deviatin, s there appears t be n bias in these results. 5. Ackn,\'Iedgements This reprt summarizes the effrts f all the members f ASTM Task Grup C ,vh participated in the cperative calibratin. These effrts are gratefully acknwledged. 6. Reference L. Struble and H. Kanare, 1989, Cperative Calibratin and Analysis f Cement Clinker Phases.. Natinal Institute f Standards and Technlgy (U.S.), NISTIR , 34 pp. 7

13 APPENDICES 9

14 1. LABORATORIES PARTICIPATING IN THE COOPERATIVE CALIBRA TION LD.Adams Suthwestern Prtland Cement PO Bx 937 Victrville, CA H. Chen Canada Cement Lafarge Ltd. Research Center 6150 Ryalmunt Mntreal, Quebec, CANADA J.T. Cnway Santee Cement Cmpany PO Bx 698 Hlly HIll, SC Dr. R. Davies Cuncil fr Scientific and Industrial Research Natinal Building Research Institute PO Bx 395 Pretria 0001 SOUTIIAFRICA S. DeHayesIP. Hawkins CaLMat C. PO Bx 947 Cltn, CA w. Gutteridge British Cement Assciatin Wexham Springs Slugh, UK H. KanarelF. Tang CTL, inc Old Orchard Rad Skkie., II L Keller Camet Research Inc. 318 Twlefth St. Santa Mruca, CA G. McPhersn HallibwtD Services PO Bx 1431 Dun~ OK

15 2. SUMMARY OF RESULTS 2.1 Labratry N Specified Methd Internal standard: Ti0 2, NIST SRM 674 Mixing methd: Bleuler mill, g mixture and g Ti0 2 Instument: cmputerized diffractmeter Peaks ( 28) fr eu Ka: rthrhmbic C:0: 20.2 cubic C~ 21.8 c~: 12.2 MgO: 42.9 Peak intensities: measured by cmputer Table 2-1. Results, Labratry 1 T T... '(,... "'... 1 UUl\.UUYVll J.. (percent f mixture) UnknO\\712 cubic C3A rthrhmbic C 3 A C~ MgO

16 2.2 Labratry N Specified Methd Internal standard: Si (12 percent) Mixing methd: Bleuler mill, g mixture, g Si, and 5 ml 1,1,1-trichlrethane fr 6 min Instument: cmputerized diffractmeter (Phillips APD 3600) Peaks ( 26) fr Cu Ka: rthrhmbic C3A: 21.0 cubic C:>A: 21.8 c~: 12.1 MgO: 42.9 Peak intensities: measured using prfile fitting prgram QPROF Results: nrmalized t 100 percent and averaged Table 2-2. Results, Labratry 7 (percent f mixture) Unknwn 1 Unknwn 2 cubic C 3 A rthrhmbic C 3 A C~ MgO

17 2.3 Labratry N Specified Methd Peaks (02e) fr eu K~: rtllrhmbic C3A: 20.8 albic C3A: 21.6 c~: 24.2 MgO: 42.9 Results: nrmalized t 100 percent and averaged Table 2-3. Results, Labratry 10 (percent f mixture) Unkn\VI1 1 Unkn\VI12 cubic C3A rthrhmbic C 3 A C~ MgO

18 3. STATISTICAL ANALYSIS The statistical analysis was carried ut accrding t ASTM E691. Of the riginal 10 participating labratries, ne (Labratry 3) was nt included (as discussed in the previus reprt., Struble and Kanare, 1989). The analysis included ne participant (Labratry 4) that did DOt nt prvide replicate results fr any phases and ne participant (Labratry 10) that did nt prvide replicate results fr Unknwn #2. Each phase in each unkn\vil 'Was treated as a separate material in the statistical analysis. Therefre there were 8 materials. Data frm 9 labratries were used in this analysis (Thble 3-1). Hwever, ne f these labratries did nt reprt replicate values (Labratry 4h s nly 8 labratries were used fr calculatins f within labratry variatin (cell standard deviatin and k-statistic). In the present analysis, ne f the labratries exceeded the critical value f the between-labratry cnsistency statistic (h-statistic, shwn in Table 3-4 and'fig. 3-1) fr ne phase. It was decided nt t reject the data frm this labratry due t the single high value. likewise, a few labratries exceeded the critical value f the 'Within-labratry cnsistency statistic (k-statistic, shwn in Table 3-4 and Fig. 3-2), but nly fr ne phase in each case 7 s n labratry was excluded frm the calibratin based n the k statistic.. Results f the statistical analysis are shwn in Tables 3-2 thrugh 3-6, Figure 3-1 and Figure

19 Table 3-1. QXRD Results fr Statistical Analysis (percent f mixture) Lab- ra MgO r MgO cub C~ C,0F ell ratry C3A C:0 C3A C3A IDA arthrhmbic bcubic - 15

20 Table 3-2. Cell Averages. (percent f mixture) Lab- ~ MgO r MgO cub C~ C \F ell ratry C:>A C~ C0 C 3 A x.c d Sx arthrhmbic bcubic cverall average f cell averages dstandard deviatin f cell averages 16

21 Table 3-3. Cell Standard Deviatins (percent f mixture) Lab- ~ MgO r MgO cub C.0F C~ ell ratry C0 C~ C3A C3A arthrhmbic bcubic Table 3-4. Between-Labratry Cnsistency Statistic Values (h-statistic) (percent f mixture) Lab- ra MgO r MgO cub C0F C.0F eu ratry C3A C0 C3A C3A () L. L u.uu nan v."tv Critical value at 0.5% significance is 2.23 (ASTM E691, Table 12) arthrhmbie beubic 17

22 " labrat~ nuznber Figure 3-1. Level f h-value fr each labratry, with critical values indicated by upper and lwer dashed lines. 18

23 Table 3-5. Within-Labratry Cnsistency Statistic Values (k-statistic) (percent f mixture) Lab- f'i MgO r MgO cub C0F C0F ell ratry C3A C0 C3A C3A S ~ Critical value at 0.5% significance is 2.06 (.ASTM E691, Table 12) arthrhmbic bcubic 19

24 II g 10 labrat~ nuxnber Figure 3-2. Level f k-value fr each labratry, with the critical value indica ted by a dashed iine. 20

25 Table 3-6. Summary f Precisin Parameters (percent f mixture) Lab- ~ MgO r MgO cub C0F C0F ell ratry C 3 A C 3 A C 3 A C:>A s/ SR d arthrhrnbic bcubic 'repeatability standard deviatin dreprducibility standard deviatin 21

METHOD OF TEST FOR THE DETERMINATION OF POTENTIAL ALKALI-CARBONATE REACTIVITY OF. CARBONATE ROCKS BY CHEMICAL COMPOSITION

Labratry Testing Manual Date., 96 5 1 Page 1 f 5 METHOD OF TEST FOR THE DETERMINATION OF POTENTIAL ALKALI-CARBONATE REACTIVITY OF. CARBONATE ROCKS BY CHEMICAL COMPOSITION 1. SCOPE 1.1 This methd cvers