CEMENT and CONCRETE RESEARCH. oI. 4, pp. 13-29, 1974. Perganon Press, Inc. Frintec in the United States THE EFFECT OF SAND GRADING Ox THE CALCIUM SILICATE BRICK REACTION wok teen ay creek TRASEE MP PEE eed gory any Spats, oy Gt tan (Communicated by HF. Ws Taylor) ‘Received duly 24, i973 Calciua silicate brick specimens withdifferent sand gradings were autoclaved at 1.20 W8/a? gauge steam pressure for periods of 2, 4, 6) 8, 12 and 16 hours Ind tested for compressive strength and drying inkage. Their composition has been investigated by essy diffraction and differential thermal Results were in agreoment with existing knowledge that the reaction was faster, the higher the content of fine sand in the speciaen: The development of Lobermorite as indicated by X-ray diffraction was not related to any other properties of the specimens cxamined. Drying shrinkage was correlated with the ‘amount of hydros!licate formed but the strength (ose saxtmun w with a gap grading) w ore probably r 1c dogree to which the Conenting saverial filled the voids: Kalkeandatein-Probestilcke ait verschiedenen Keravertel lunges wurden bei 1210 atll Daspfdruck wiirend Perioden von 2, 4, 6, § 12 und 16 Stunden [Fehiirtee and dann auf brackfestigkett and Trockenachwindung geprife. Ihre Zusamnensetsung wurde mittela RBntgenbeuging und Differentialtherm- ‘nelyse unteraueht- Die Ergebniase stimmton mit der bekannten Erfahrung iberein, dage die Unsetzung umso achneller vor gich geht, Jo grosser der Feinsandgehalt des Probestiickes ine.” Diewdurch RBntgenbeugung angezeigte Entwicklung den Tobermorits var mic kesner der anderen Eigen ‘aften der untereuchten Prosestiicke verbunden” Die Trockenschwindung war nit der Menge, des neugebiideten Hydrosilixate verknipee, aber es ist wahracheinlicher, Gass die Featigheit (deren Maximum mit einer Kornvertefiung ohne Mittelkorn erzielt wurde) vor dem Auagaes abhing?, womit daa Bindemittel die Hoblrdune erfiliie. .1" Vor, 4, Mo, 1 SAND LIME BRICK, REACTION, SAND GRADATION aTRopverroy In experizents on sand grading there have been two main approaches to defining the size distribution. The most complete definition is by means of grading curves. Tt has been found Gieicult, however, to translate these into simple parancters against which the properties of speciens can be plotted. Although natural sands should give straight Line distributions (and hence capable of being defined by two paraneters) on log- norsal or Rosin-Raanler nets, they do not alvays do s0, and the curves are further complicated when blends of Inds are studied. ‘The second approach is to consider the sand in toras of three size ranges, normally defined by outs at only two sieve sizes, and to plot the results on triangular graph paper. Despite its lack of precision, thia approach has been extremely useful in Laboratory experiments and has given a method by which independent investigators have arrived at similar results, From the practical point of view, improvement of sand evading is best achieved by blending and to be effective this needs sands of different gradings than the original. It is unlikely that i would be necessary to blend more than three components together, 40 that this method of representation is of considerable convenience. Previous papers from the author's laboratories (1,2) have considered sands in terms of their fractions above 0.6 mm, between 0.6 and 0.15 am and below 0.15 aa. The limita for the middie Fraction were chosen because aost calciua silicate brick making sands in England have the bulk of their material within this range and it was also known that the higher surface area fraction below 0.15 am was sore reactive and had a large effect on the properties of the bricks, Thus, blends plotted in terms of these Eractions tended to emphasise the effect of particles coarser (e.g. crushed flint) of finer (e.g. fine sand) than normal. German workers have algo used similar triangular diagrans but with the Limits at 0.63 and 0.10 mm, These are of the sant order, the precise values in each ease representing sieve sizes normally used for concrete aggregates in the two countries.Vol. 4, Wo. 1 15 SAND LINE BRICK, REACTEON, SAND GRADATION The Limite chosen are satisfactory for normal sands, but are not necessarily suitable for silicate concrete where fractions such ax 1.0 - 0.1, 0.1 - 0-01 and 0,01 - 0,001 mm, as used by Chernyi and Tonilina (3), aay be more appropriate. In the present work, the autoclaving time as well as the sand grading, was varied. It was thus necessary to present the results ina series of triangular diagrams, one for each autoclaving time. The tine factor was included to see whether differences in grading had a major effect on the rate of reaction in the bricks. SPECIMEN PREPARATION AND TESTING ‘The specimens were prepared from commercially supplied fractions of washed quartz sand (as used in the preparstion of standard mortar bars (4))with nominal size ranges of 1.2 - 0-6, 0.6 - 0.3, 0.3 = 0.15 and 0-15 - 0.09 mm and a white hydrated Lime with an available CaO content of 65.4%. AlL mixes contained 7% by weight of Ca0 based on the total available calcium oxide plus sand content. The grading of the snd was altered by changing the proportions of the three size components of over 0.6, 0.6 - 0.15 and below 0.15 mm. The 0.6 ~ 0.15 am component was composed of equal proportions of 0.6 - 0.3 and 0.3 ~ 0.15 mm fractions. Individual gradings ss shown in Figure 1 are represented by letters so that they can be referred to in the text. The water content requiresent was deterained empirically so that it was at a maximin without damaging apecimens in the autoclave. The values shovn in Figure 1 were deterained by a preliminary experinent. The components were mixed dry in a Hobart mixer for one minute followed by four minutes with the requisite amount of water added. 15 test cylinders 51 mm high by 38 am dismeter and four prisas 152 x 38 x approx. 32 mm moulded at 36 MN/a? vere pre- pared from each mix by a method described previously (1). Six cylinders were used for compressive strength testing, #ix forVol. 4, Wo. 1 SAND LIME BRICK, REACTION, SAND GRADATION coarse oe Sem sepium ine ‘SAND SAND 015-06 ‘below O35 mm FIs, 1 Teiangular diagran showing the biends of sands used in the preparation of the specizens. Gradings have been lettered Borvreference. ‘Open figures indicate the percentage water contenes of the mixes. Frost resistance testing and the remaining three were spares analysis. The four prisas were used for drying shrinkage deterainations, ‘The specimens were autoclaved at 1.20 MN/a? gauge steam pressure for perioda of 2, 4, 6, 8, 12 and 16 hours. Nine sets Of apecizens were autoclaved at a tine 0 that tuo separate autoclavings were required for the complete range of gradings for a given autoctaving tine. compressive strength tests were carried out on specimens which had been soaked An water for 24 hours. The load was Increased at a rate of 21 KX/ain and the results were based on means from six cylinders. The frost resistance test was based on the method described in D.T-X. 108 (5) in which specimens were dried at 105°C, soakedVol. 4 No. 1 7 ‘SAO LINE BRICK, REACTION, SAND GRADATION An water and subjected to 25 freeze-thay cycles. They were ‘then tested for compressive strength and those whose strength was ed over S0f of the original strength were considered to have p. the test. Bulk density and water absorption were deterained by weighing the specinens at the appropriate stages in the frost resistance test and determining their volunes by displacenent in The drying shrinkage test was carried out according to the procedure in B.5.187: 1955 (6) in which specimens were dried at 50°C over a aaturated calcium chloride solution. All specimens autoclaved for a given period were tested together. ‘The phase analysis of the samples was carried out by X-ray powder diffraction and differential thermal analysis, ax described elsewhere (7,8). The K-ray analysis wes carried out with 3 hour exposures on an 1148 mm diameter powder camera using nickel-filtered copper radiation at 30 KY and 20 mA. The differential thersal analysis vas carried out on Standata 615 apparatus with a heating rate of 10°C/ain. Stanton RESULTS AND DISCUSSION ‘The results have been presented in the form of triangular Alagrans. Th order to facilitate visual comparison between Aiagrans, and because of space requirenents, in sost cases only high, medium and low ranges of values for each property have been indicated. Differential Thermal Analy: Figure 2, showing D.T.A. curves for specinens autoclaved for specimens autoclaved for § hours, illustrates the form of the traces encountered. The caleiun hydroxide, quartz and high tomperature hydrosilicate peaks are easily distinguishable. A small carbonate peak occurred in all samples and in many there was & broad exothermic peak at about 200°C which probably Andicated loss of interlayer water from the hydrosilicate. Fros earlier work (7), it vas assumed thet the size of the exothernic hydrosilicste peak increased with the anount of hydrosilicate present, at least in the carlior stages in the(a PRRFEL THT |Vol. 4 No. 1 SAND LIKE RI REACTION, SAND GRADATION HYDROSIUCATE PEAK. HEIGHT ¢ s a A ‘ ‘ wr A wh fA tec tm 1D 50-100mm Beet to. 3 ‘Triangular diagrans showing results for the hydrosilicate peak height in terms of proportions of coarse (C), medium (M) and Fine (F) sand in the mix LHYOROSIUCATE PEAK TEMPERATURE or 50°C Desa Bi scree Fie. 4 Triangular diagrans showing results for the hydrosilicate peak temperature in terms of proportions of coarse (C), medium (M) fané fine (F) sand in the mix2 Vol. 4, Wo. 1 ‘SAND LINE BRICK, REACTION, SAID GRADATION reaction. The growth of these peaks is illustrated in Pigure 3, where it can be seen that the size of the peak increased in size faster, the more fine sand there was in the sample. These peaka reached 2 maximum height of 120 - 150 mn after which no significant growth occurred. tthe change in the form of the hydrosilicate peaks has been described previously (7,8). Initially, a broad ill-defined exotheraic peak at about 870°C is foraed and as the reaction proceeds the temperature of the peak drops, a double peak occurs, and then @ sharp well-defined peak is formed at about 830°C. The temperatures of the peaks in each trace are indicated in Figure 4, their behaviour following that of the peak height. A histogram of the temperatures of the hydrosilicate peale in Figure 5 shows a preponderance of peak temperatures at £30°C, ‘This would tend to indicate some very distinct change at this AIG. Distribution of temperatures Of the exothernic hyarosili- Sate peaks.” Unshaded portions of the columns Tepresont subsidiary peaks 20 on larger peaks. 8 of sho #70 240 abo azo m0 ATOVol. #5 No. 1 a ‘5980 LIME BRICK, REACTION, SAND GRADATION temperature and, by inference, a distinct composition of the C-S-H phase. By contrast, the temperatures of the peaks in the range 880 - 830°C were more evenly distributed suggesting that before the 830°C peak was formed the composition and/or the structure of the hydrosillcate was very variable although previous work had indicated that C-S-H(I) could be distinguished from C-S-H(TE) according to whether or not the peak temperature vas below about 850% (9). The occurrence of the low temperature endothermic tinter- layer-water' peak (not plotted on triangular diagrans here) wa less consistent than that of the other peaks. In general, st tended to be sore prominent and had s higher temperature when there was 4 well defined exotheraic peak. The presence of free lime, as indicated by the D.T.A. traces, ie shown in Pigure 6, The abgence of calcium hydroxide PHASE ANALYSIS ¢ ¢ 2h an ? c tm ? Ti ee me by xd, Bp tobermorte ciftetion nes [Tl] tee ime by dite. } no cashor free ime EE] coh citrction ines troction Ue Fic. 6 ‘Triangular dlagrana showing the phase analysis remults in terms Of proportions of coarse (C), megium (W) and fine (F) wand am2 Wor. 4, fo. 1 ‘SAID LIME BRICK, REACTION, SAID GRAOATION peaks for gradings Q and R at 2 hours autoclaving is not indicated on this diagram, however. The contours for the height of the Pree Lime peak tended to follow the inverse of the contours for the height of the hydrosilicate peak Double peaks occurring #5 shoulders on the Lime peak and attributed to C,SH(A) (8) vere recorded in isolated cases, ‘suggesting that this phase can sonetines occur. Rav Diffraction Analy: Not all the K-ray results were in entire agreement with those from the differential theraal analysis ALL films showed strong Lines due to quartz (i.e, the les) and the only other components ected sand in the a recorded were calcium hydroxide and hydrosilicates of the Lobermorite group. On no Films were both Lime and hydrositicate Lines recorded together. Im sone cases, neither calcium hydroxide aor hydrosiitcate Lines were recorded. This did not mean that there was no binder present; merely that most of the Lime had reacted but there vas ‘an inguffieient asount and/or crystallinity of the hydrosilicate to give diffraction lines. To label such hydrosilicate as tamorphous! is probably incorrect. These phases lack erystalli- nity and represent 4 small proportion of the sample. Their non~ identification is probably due to a limitation of the technique. ‘the results for free Lime (in Figure 6) indicate how slowly it reacted with the coarse sand and, in general, bear out the ples after 2 D.T.A. results, The distribution of Lime-free hours autoclaving as deterained by X-ray diffraction, however, id not agree with that detersined by D.T.A.; gradings Ly M and X showed no calcius hydroxide Lines on the K-ray Fila while by D.T.A. gradings Q and R were the only ones without a Lise poak. ‘The lack of calcium hydroxide Lines on the X-ray fila coineided with the appearance of C-S-H Lines at these gradings. In all other instances the D.T.A. resulta for free lime shoved the sane trends as the X-ray results but had » higher sensitivity. The C-S-H lines first appeared at gradings Land M afterWor. 4, Ho. 1 2 SIND LINE BRICK, REACTION, SAND GRADATION 2 hours autoclaving and after § hours autoclaving the gradings showing C-S-ll lines formed a band across the diagram from gradings L and 0 to grading G. The absence of C-S-H lines from 2 = 12 hours autoclaving for gradings Q and Rwa unexpected, 23 the D.T.A. results indicated the formation of C-S-H(I) and both atrength and shrinkage increased over this period. The absence of these Iines over five auc considered co-ineidental and attributed to bad saxpling or sone auch cause. After 2 hours, no free Line was recorded for the ive autoclave cycles cannot be gradings and it aust therefore be considered to have reacted. Tt is concluded that the al due to a structural effect which did not affect the thermal properties of the sample. nce of these diffraction lines wae After 12 hours tobermorite appeared in samples whose gradings were represented by a band acroas the triangular diagraa and by this time most other gradings, with the exception of thos containing a high proportion of fine sand, gave C-5-H lines on the filme. The toberaorite lines were particularly well marked For gradings B, F, G, J and K. The occurrence of tobermorite for this purpose was defined when the diffuse C-S-H line at approximately 3% split into a doublet with an extra Line at 2.98 R (9,10). This change wee tise accompanied by en increase in intonaity of the HLA Lines The tobermorite, therefore, representa » nore crystalline variety of hydrositieate. Scanning electron aicroscope studies on other caleium silicate brick specimens (not yet published) suggest that the appearance of the extra diffraction line is due to well-formed crystals growing into the larger void spaces in the specimen. These crystal add nothing to the strength of the speciaens but, because of their better crystallinity, give stronger X-ray reflections which do not necessarily represent increased quantities of binding material, Brving Shrinkage The drying shrinkage results in Figure 7 showed « consistent. pattern with the highest shrinkage values for a given autoclaving2 Vol. 4, to, SAND LIME BRICK, REAL ON, SAND GRADATION DRYING SHRINKAGE 1 beiow o120% TB oca0-o0asx Th or ons: FIG. 7 Triangular diagrans shoving the drying aheikage ceaulte in teraa of proportions of coarse (C), wedium (N) and fine (F) sand in the #13. aux waree waren oenty ABEORFTION ABSORPTION by weight by volume: 5 ¢ + & Se [C1 blow 1850 kg/m? below Okg/100kg below 20ms/h00m? EE] ersotcin? rosie 20-25 moon? Hover 1950 kim? ‘over 15 kg/00kg ‘over 25 3/1003 ‘riangular diagrams showing bulk density and water absorption Tomita in terms of proportions of coarse (C)y medium (W) and Fine (F) Send in the aix 1Vol. 4 No. 1 8 SAND LIME BRICK, REACTION, SAND GRADATION tine corresponding to the highest proportions of fine aggregate as reported previously (2). The shrinkage increased with autoclaving time up to 12 hours but appeared to decrease after 16 hours (this decrease requires confirmation and could possibly be attribuced to incorrect drying oven conditions). ‘The drying shrinkage (other than for the 16 hour results) appeared to parallel hyérosilicate growth as indicated by the height of the hydrosilieate peak on the D.T.A. traces. bulk Density and Mater Absorpt: ‘The values for these properties, shown in Figure 8, were based on means for all apectnens with a given grading. Maxieun bulk density occurred when there war a high proportion of coarse aggregate with the finer sand and the lime f4iling the voids becween the coarse particles sn the green bricks. The water absorption, expressed both by weight and by volune,, showed similar relationanips with respect to the grading After 4 hours most specizens had a satisfactory frost resistance (see Figure 9) but specimens containing only coarse aggregate alvays disintegrated during testing. The triangular diagrams in Figure 10 show that in the Anitial stages of the reaction, the strength increased fastest in specimens with high contents of fine sand, 10 Mi/a” being attained within 2 hours in many instances, The major pattern, as reported in previous work (1, 2), could be seen after 8 hours autoclaving where strengths of over 20 N/a? were recorded with gradings E, T, 3, Land M. The maximum recorded strength wae 26 MN/m®. These strengths are lower than those reported previously, because of t) lower moulding pressure used in the current investigation. ‘The actual maximim strength values after 2 and 4 hours autoclaving occurred with gradings L and 0, whereas at 6 hours and longer autoclaving times the maxima tended to occur at gradings H and L. Thue, for practical purposes, the optima26 Vol. 4 Ne. 1 SSMIO LIME BRICK, REACTION, SAND GRADATION A AAA Rost RESSTANCE > Fon Fis. 9 Telenmular diagrans showing frost resistance results in terms ek proportions of coarse (c), mediua 0) and fine (F) sand in the aie " « a 7 compressive stesnord ove maint 1B w-r0nnint Hh cwr200in? FIG. 10 ‘Triangular diagrans shoving compressive strength results in Teeaso# proportions of cosrse {e), sodium (¥) and fine (F)Wor. 4, to. 1 a ‘INO LINE BRICK, REACTION, SAND GRADATION grading does not vary significantly with the period of autoclaving. Differences in strength remults between 8, 12 and 16 hours autoclaving were not great and the variations do not necessarily represent aaxina and minima of strength with time. Specimens containing only coarse sand (grading A) vere very weak, @ strength of 4 MN/a? never being achieved, whores: arading B gave strengths up to 14 MN/=? Ie the triangular diagrams for compressive strength are studied it will be seen that the area of maximim strength corresponds neither to that of maximum bulk density, nor to maximin formation of hydrosilicate as indicated by differential theraal analysis but ies between these two areas. Tt seons probable, however, that the strength is related An gone way to the degree to which the cementing material fills tthe available pore space in the specimen. The data in this paper is inauéficient to test thie directly. If, however, the ratio of the height of the hydrosilicate peak on the D.T.A. trace to the water absorption of the epecimen is taken az a measure to ‘nM eo fe. mm /, aa aN a + en ao, ‘Triangular diagrane shoving the ratio of the hydrositicate peak height to water absorption in terms of proportions of Soarse (C); sedium (M) end fine (F) sand in the mix.2 Vol. 4, No. 1 SAV LINE BRICK, REACTION, SAND GRADATION which the void space is Filled with conenting material, then there is sone correspondence between the contours for this ratio (Jn Pigure 11) and those for compressive strength. Te is not clear how the X-ray results for C-S-H and tobermorite are related to the strength. The patterns on the triangular diagrams show some similarities to those for strength, Both may possibly be related to void apace in the specimen and the degree to Which It is £Lled, if the hypothesis of Gundlach et al (11) is relevant in this situation. concLustoxs 1. Differential thermal analysis results are in accordance with general experience that the reaction proceeds Eastest when there is more fine sand in the specimens. The size of the hydrosilicate peak increases with the consumption of free lise and the peak tenperature indicates a constant phase for the end product 2. Koray diffraction analysis showed maximum growth of C-S- Linea (and, after 12 hours autoclaving, tobermorite Lines) for gradings represented by @ band across the triangular diagram. Specimens with a high content of fine sand showed a rapid reaction with the lime but did not show any C-S-i diffraction Lines on the X-ray fflm. 3. The drying shrinkage appeared to be related to the amount of hydrosilicate formed, as indicated by differential thermal analysis. 4. Maximus strength was achieved with a gap grading and corresponded to neither maximun bulk density nor to maximum hydrosiicate formation. Tt was probably related to the degree to which the hydrosilicate cementing material filled the voids, The optiqua grading for strength was found to be the sane for different autoclaving times under practical conditionsVol. 4 No, 1 2 SSAIO LINE BRICK, REACTION, SAND GRADATION ACKNOWLEDGMENTS. ‘The author wishes to acknowledge the contributions aade to the work by Mes. G.R. Smith, M. Baker, A.G. Cruttenden and G.R. taylor, This paper was presented at the Third International Symposium on Autoclaved Calcium Silicate Building Products in Utrecht on 26th September 1973. REFERENCES 1. GLB. Bessey and ¥.J. Purton, Autoclaved Calcius Silicate butlding Products, pris. Society of Chealeal Industry, Tondon (1967). 2, J.M, Coldrey and H.X. Lee, Chem. and Ind., (8), 260 (1970). 3. Tel, Chernyt and T., Tonilina, Sbornik auch, Rabot.» Yauch, Ieeled, inst. Seroit: Materdalov Belorus, 8.5.R., (Sy 85 (959). B.S, 4551: Part 2. British Standards Institution, London (2330), 5. D.T.N, 108, Deutachen Normenausechuss, Berlin (1962). 6. BLS. 187. Britieh Standards Institution, London (1955). JM. Coldrey and M.J. Purton, J. Appl. Chom., 28, 353 (1968). 8. M.3. Purton, J. Appl. chem., 20, 293 (1970). 9. Mad. Purton and J.M. Coldrey, Trane. Brit. Ceraa. Soe, 59, 03" (1970) 20. Ya. Mt. Butt and L.N, Rashkovich, Tverdenie Yyazhushchileh pri Povyshennykh Temperaturakh, ind edn., p.Ol, Stroiizdat, Moscow (1965) 11, H. Gundiach, £. WBretor and G. Rademacher, Tonindustric Zeitung, 93, 107 (1969).