Cement & Concrete Composites 15 (1993) 185-214

Pozzolanic Cements*
Franco Massazza
Italcementi, Via G. Camozzi 124, 24100 Bergamo, Italy

Abstract Natural and artificial pozzolanas have been used to obtain hydraulic binders for over a thousand years. Hardening of pozzolanic cement pastes can result from the reaction between pozzolana and the lime that is added to the mix as hydrated lime or is produced following hydration of portland cement silicates. The pozzolanic reaction does not alter cement clinker hydration; it complements and integrates the hydration process because it results in a lower portlandite content and an increase in calcium silicate hydrates. Besides reviewing the most recent investigations on pozzolana-containing cements, this paper shows that the behaviour of different types of pozzolana can be quite similar when they are blended and become hydrated along with portland cement clinker. Portland cement properties may undergo several qualitative modifications the extent of which substantially depends on the pozzolana/ clinker ratio. So, a maximum is reached in pozzolanic cements. As in the case of pozzolanic cements, for which the current pozzolana content is about one third by weight of cement, the most outstanding variations induced in the behaviour of portland cement can be summarised as follows. Heat of hydration decreases whilst the rate of clinker hydration increases, paste porosity increases and permeability decreases, both portlandite content and Ca/Si ratio in C-S-H decrease and the C-S-H content increases. Chemical and physical properties of pozzolanic cements eventually affect engineering ones. Early strength of both pastes and concretes decreases while ultimate strength is often found to exceed that of the reference portland cement. If cements contain small amounts of very active pozzolana (silica fume, for example), both early
*Keynote paper presented at the International Conference on Blended Cements held in Sheffield in September 1993.

and ultimate strengths may be higher than those of the substituted cement. Creep is found to increase definitely with increasing pozzolana content whereas shrinkage remains practically unaffected. Chemical and microstructural variations in the paste also influence resistance of concretes to environmental attacks. The low basicity and permeability resulting from the presence of pozzolana increase the concrete's resistance to lime leaching, sulphate and sea water attacks, and chloride penetration. Carbonation depth is practically unaffected. Pozzolana containing cements can help avoid expansion induced by alkali-silica reaction. Concrete resistance to freezing is not affected by the use of pozzolanic cement since it basically depends on the entrained air content. The results of a variety of studies introducing a comparison between pozzolana-containing cements and corresponding portland cements can be summarised as follows: cements with appreciable pozzolana contents perform better in the long term rather than at an early age. In most cases, however, the differences between the two types of cements are not so marked and as a consequence both cements are interchangeable especially for the most common building types. Keywords: Pozzolanic cements, chemical reactions, hydration products, microstructure, porosity and permeability, curing, shrinkage and creep, durability, carbonation, chloride penetration, chemical resistance, alkali-aggregate reactivity, frost resistance.

1 POZZOLANAS

The term 'pozzolana' has two distinct meanings. The first one indicates the pyroclastic rocks, essentially glassy and sometimes zeolitised, which

185 Cement & Concrete Composites 0958-9465/94/$7.00 1994 Elsevier Science Limited, England. Printed in Great Britain

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Franco Massazza

occur either in the neighbourhood of Pozzuoli (the ancient Puteoli of the Roman times) or around Rome. ~ The second meaning includes all those inorganic materials, either natural or artificial, which harden in water when mixed with calcium hydroxide (lime) or with materials that can release calcium hydroxide (portland cement clinker). In this review the term 'pozzolana' will be referring to the latter meaning, definitely wider than the former, and will therefore embrace a large number of very different materials in terms of origin, composition and structure. For a long time the use of pozzolanas has been mostly restricted to Italy, where considerable reserves of natural pozzolanas are found. In other countries the interest in these materials is of relatively recent date and has arisen due to the need for the disposal of fly ashes and silica fume. This brief historical background can help explain why so many countries have long distrusted pozzolana-containing cements despite the millenary use of lime-pozzolana mortars and the almost century-old experience in pozzolanic cements. Anyway, the results of a variety of studies have substantially proved that pozzolanic cements, despite the lower initial rate of hardening as compared to portland cements, can yield a higher ultimate strength. Furthermore, they show a greater resistance to the attack of aggressive agents. Literature concerning pozzolanas and pozzolana-containing cements is however too extensive to be summarised in this short review. For more detailed information the reader is referred to the proceedings of the major conferences on both

natural and artificial pozzolana-containing cements.2-t2 A technical classification of pozzolanas, proposed in 1976, is illustrated in Fig. 1.~3 Pozzolanas are formed by 'active' phases, capable of reacting with lime, as well as 'inert' phases, insensitive or little sensitive to its action. As shown in Table 1, all active phases are thermodynamically unstable in as much as they are generally constituted by more or less altered glasses as well as amorphous constituents. The only exception is represented by zeolites which are crystallised minerals. All active phases are rich in silica: this property represents the second most important feature of the materials having pozzolanic behaviour. Some of the typical composition data are summarised in Table 2. The crystalline phase content in pozzolanas varies very appreciably, e.g. between 15% and 35% in fly ashes. 22 The glassy portion of pozzolanas has a variable composition and, in addition to this, in natural pozzolanas it can be more or less altered, zeolitised or clayified. 3 As far as fly ashes are concerned, it is generally agreed that, among the different particles of the same fly ash, differences may also occur in the glass content as well as in the composition of the glass itself. 23-25

2 LIME-POZZOLANA MIXES

Until the last century, lime-pozzolana mixes constituted the only response to the need for hydraulic mortars, i.e. mortars capable of harden-

I,A,o,,LOZZOL J I AS

ROCKS ORIGIN(Altered) ROCKS I ! ! ! I I ICOUEREN|ROCKSI earthsltaIian vhite IHATERIAL$ Of I MATERIALSOf INCOHERENT J $1RPLE OEPO$. [ (Alt,,,~l I I RGRNIC ORIGINI ROCKS Oiatoua~eu~earths C|ays ~(nunactive) italian pozz. I ARGILLIZEO luffasche HATERIAL$ Santurin earth Non active INtXO ORIGIN , Vitreous rhyoI EOEITIZEO Iites Ruler NATERIALS Gaize I NAIR~L [ Trass Naples yellou tuff BURNEDCLAYS.

Canary tuff

Gliezh

I FLY ASH

ARTIFICIAL POZZOLANAS

1 I

.J

Fig. 1. Classificationof pozzolanas.~3

Pozzolanic cements Table 1. Mineralogical composition of some pozzolanas Pozzolana Active phase Passive phase

187

Ref.

Bacoli Barile Salone Gadolini Vizzini Sacrofano Maroc Volvic Neapolitan tuff Reintrass Fly ash Fly ash

Glass Partially decomposed Glass, analcyme Amorphous phase/glass Glass Amorphous phase Opale Glass Hershelite, analcyme (glass) Chabasite, analcyme (glass) Glass Glass

Quartz, feldspars, augite Pyroxenes, olivine, mica, analcyme Leucite, pyroxenes, alkaline feldspars, mica Calcite, quartz, mica, kaolinite, feldspars Feldspar, quartz, olivine, clay Quartz and feldspars Quartz, cristobalite, dolomite Andesine, quartz, diopside, magnetide Feldspar Feldspar Mullite, Fe-spineil, hematite, quartz, carbon Mullite, spinell, quartz, hematite, carbon

14, 15 14 14 14 16 14 15 15 15 15 15 17

Table 2. Chemical analysis of pozzolanic materials Pozzolana SiO, AI_,O~ F e : O , CaO MgO sO, Na,O K,O TiO2 CaCO~ Loss on Insoluble Ref. ignition residue

Bacoli(Naples) Vulture(Potenza) Salone(Rome) Casteggio(Pavia) Vizzini(Catania) Sacrofano(Viterbo) Santorin earth Rheinish trass Opaline shale Diatomite Rhyolite pumicite Fly ash Fly ash Fly ash Fly ash

53.08 44.07 46.84 54.92 50.48 85"50 65"1 55'90 65.4 86"0 65.7 41.49 45.09 48.59 41-94

17.89 19.18 18.44 7.72 16.77 3"02 14.5 16.80 10.1 2"3 15-9 22.14 29"01 28.21 18.44

4.29 9.81 10.25 3-29 11.59 0-44 5.5

9.05 12.25 8.52 13-63 4.86 0.58 3"0 3.20 4.2 4.6 1.8 -2.5 3.4 9.74 9-48 5.37 5'55 5.94 1.15 9-47 14-20

1.23 6.66 4"75 2.53 5.24 tr. 1.1 2.7 0'6 1.3 4.98 0.68 2.15 2.27

0.65 3 . 0 8 tr. 1.64 tr. 1"02 1.93 0.76 0.15 0.87 0.77 0.16

7.61 1.12 6'35 1.50 0.17 0.26 4.70

0.31 0.97 0.06 0.18 0.08 1.22

---22.00 ---

1.24 0 . 9 4 2 . 1 2 1.10 0 . 3 0 1 . 9 9 0.34 0.71 2.33 2.63

0.84 1.44 1.44 1.53

3.05 4.42 3'82 13.68 9.68 7.94 3"5 10.00 6"3 5.2 3.4 7'60 7.34 7.44

25.82 40-85 15.77 20.33 3.75 8"40

14 14 14 14 14 14 18 15 19 19 19 20 20 20 21

ing in water and, at the same time, of resisting the attack of aggressive waters, sea water included. D u e to their slow rate of hardening l i m e - p o z z o lana mixes have gradually been replaced with pozzolanic cements. T h e l i m e - p o z z o l a n a - w a t e r system is in any event simpler than the m o r e complex c l i n k e r - p o z z o l a n a - w a t e r system and its thorough investigation can help with the interpretation of both behaviour and properties of pozzolana-containing cements.
2.1 Pozzolanic reaction T h e t e r m 'pozzolanic activity' covers all reactions occurring a m o n g the active constituents of pozzolanas, lime and water. T h e definition, though approximate, is h o w e v e r acceptable from a technical and practical viewpoint. Notwithstanding the difficulty in following the evolution of pozzolana's active phases throughout the hydration process, the progress of the pozzolanic reac-

tion is c o m m o n l y evaluated in terms of diminution of free lime in the system. T h e term 'pozzolanic activity' includes two parameters, viz. the m a x i m u m a m o u n t of lime that a pozzolana can combine with and the rate at which such combination occurs. Both factors d e p e n d on the nature of the pozzolanas and, m o r e precisely, on the quality and quantity of the active phases. T h e heterogeneity of the pozzolana family as well as the complex p h e n o m e n a occurring during hydration can sufficiently explain the inability to model pozzolanic 'activity' and only enable general tendencies to be identified. It can schematically be affirmed that the overall a m o u n t of c o m b i n e d lime essentially depends on the following: (a) (b) (c) (d) the nature of the active phases their content in the pozzolana their SiO2 content the l i m e - p o z z o l a n a ratio of the mix

188

Franco Massazza
LIP = 1/1 L/P = 1/3

whereas the combination rate depends on (e) the specific surface (BET) of the pozzolana and (f) temperature. (a) In order to exemplify the role played by the various types of active phases, it should be remembered that within the zeolite family herschelite is more active than analcyme 26.27 and that zeolitic pozzolanas are considered to be more reactive than glassy ones.~ 5 (b) It is obvious that, other properties being equal, the larger the amount of combined lime, the higher the content in active phases and the lower the content in crystalline phases (quartz, sanidine, mullite, magnetite, etc.). A dependence but not a close relationship has been ascertained between these two properties 2~ inasmuch as the amount of combined lime also depends on: (c) the SiO2 content of the active phases, which can range for instance between c. 45% and c. 85%. -~s Neither the role played by other elements, especially alumina, occurring in pozzolana, nor the long completion time of the pozzolanic reaction should however be neglected. (d) Figure 2 shows that, for each pozzolana, the lime combined with 100 g of pozzolana increases as the lime-pozzolana ratio increases and that for each ratio a different equilibrium between combined and still free lime is established. 29,-~" Figure 2 also highlights the fact that the amount of combined lime varies appreciably according to the different types of pozzolana used and also in relation to the lime-pozzolana ratio. Figure 314 illustrates how after 180 days of reaction pozzolanas have been able to combine with between 40% and 75% of lime with respect to their mass. In pastes, the lime combination is lower inasmuch as the hardened mass hinders the attainment of equilibrium conditions. 2s (e) As shown in Fig. 3, the short-term activity essentially depends on the specific surface (BET) of the pozzolana, whereas in the long term the chemical and mineralogical composition of the pozzolana becomes of the utmost importance. 3~ It has been reported that the reaction rate of pozzolanic materials is proportional to the specific surface area squared/'
A o,I

70~P= .r

3/1|
1

o
o

(g

50
~) BACOLI 1) SALOtlE

UJ U,I

riM. 30 U. O 10 0

3) SEGM
4) SACIROFANO

2 4 6 TIME (DAYS)

Fig. 2. Kinetics of reaction between Ca(OH)2 and some ltalian pozzolanas from: Bacoli (1), Salone (2), Segni (3) and Sacrofano (4), with different initial lime/pozzolana (L/P) weightratio.29

7O

z< so o so
40

30 '
ao

~"
O1

10 o Pozz.n.1 23 4 5 6 m2"/g

HYDiRATION UNOER SHAKING O STATIC HYDRATION

Fig. 3. Calcium hydroxide combined versus specific surface. L/P ratio 80:100, water/solid ratio 2:174

(f)

The temperature increase emphasises the rate of lime-natural pozzolana reaction though it does not modify the differences in behaviour due to the different nature of the pozzolanas. Between 50C and 90C, most lime is already fixed after ! day of reaction 29 whereas, above 70C, combined lime tends to decrease. As is shown in Fig. 4, evidence of this inversion is also found in fly ashes at approximately 60C 3 and is likely to be due to the variation in the composition of hydrated phases. Conversely, the amount of combined pozzolana, expressed in terms of silica which becomes soluble in acid, always

I
4O

Pozzolanic cements

18 9

TIME (DAYS)

Fig. 4. Lime reacted for various times and at various temperatures. CaO :fly ash = 2 0 : 8 0 weight ratio. 3

increases with temperature. Whenever a given temperature is exceeded, the C/S or C/A ratio of hydrated phases tends to decrease. 2.2 The reaction products The reaction between pozzolana and lime basically produces the same compounds which are formed on hydration of the clinker constituents as well as of portland cement. The differences are minor and, in general, affect the amount rather than the nature of the phases. 2. 2. i Natural pozzolanas Natural pozzolanas react with lime forming calcium silicate hydrate (C-S-H) and hexagonal aluminates C4AHI3, 32-34 probably carbonated. 35 When some natural pozzolanas, more or less clayified, react with a saturated Ca(OH)2 solution having a w/s ratio = 100, then tetracalcium aluminate hydrate C4AHt3 , its derived carbonated compound as well as C-S-H and hydrogarnets are formed. Tetracalcium aluminate hydrate is sometimes present with gehlenite hydrate 36 although the presence of both compounds is regarded in contrast with the relations of equilibrium existing in the CaO-AI203-SiO2-H20 system. 37 This coexistence might however result from a metastable equilibrium in as much as the presence of C2ASH ~ and C4AHI3 or (C4AHI3-C3A.C~.HI2) has also been reported by other authors. 26 As a function of time and of the increase in the amount of fixed calcium, hydrogarnet tends to prevail on both aluminate and carboaluminate. 36.37 The variability of the C/S ratio of C-S-H seems to depend on the type of pozzolana, the temperature of curing and the analytical method used. As an example, with an opal-based pozzo-

lana, ratios ranging between 0.87 and 0.75 have been obtained also as a function of the curing temperature, whereas, with a glassy pozzolana, ratios turned out to be substantially higher, namely between 1.35 and 1.75. 6 An electron microprobe has given values ranging between 0.75 and 0.8515 whereas chemical analysis has shown values ranging between 1.2 and 1.7. 28 The variability of the C/S gel ratio can be ascribed to the non-stoichiometry of the C-S-H whilst the existence of different calcium silicate hydrates is evidenced by microscopic examinations. 34 At temperatures between 50C and 90C, the pozzolanic reaction leads to the formation of amorphous C-S-H which is similar to that obtained upon hydration of portland cement. 29 When gypsum occurs in pozzolana-lime pastes, ettringite is formed. 38 Whenever specific percentage contents of calcium sulphate are exceeded, the formation of ettringite causes paste disintegration. 39 2.2.2 Fly ashes mixed with lime When fly ashes are mixed with lime, C-S-H, C4AHI3 and CzSAH 8 are formed. 6 If silicoaluminate fly ashes contain sulphates, besides C-S-H and C4AH13 , ettringite is also formed. 15 CaAH|3 decreases with time whereas the CaAcH12 content increases. 4 High-lime fly ashes can harden without a further addition of lime 41 since they contain variable amounts of free lime which, upon mixing, are transformed into Ca(OH)2. From a practical viewpoint, these fly ashes correspond to the artificial hydraulic limes obtained by mixing hydrated lime with pozzolana. 42 Hardening is therefore the outcome of the pozzolanic reaction and of the occurrence of specific hydraulic compounds which, as in the case of C:S, are formed during coal combustion. When high lime contents occur, also C2ASH8 is also eventually formed. 43 If, however, lime is entirely or mainly combined with A120 3 and SiO2 in the glass, it becomes unreactive. As a consequence, no prominent pozzolanic reaction is evidenced and, at least for three months, no C-S-H is formed. 4 After three days the surface of the fly ashes appears to be slightly covered with hydrates, some of which protrude from the surface of the fly ash particles. 2.2. 3 Silica fume and Ca(OH)2 Data concerning the reaction occurring between silica fume and Ca(OH)2 are rather limited. Owing to the high reactivity of silica fume, free lime dis-

190

Franco Massazza

appears between the 7th and the 28th day 44 therefore earlier than what generally occurs in natural pozzolanas and fly ashes. T h e reaction favours the formation of rather well-crystallised C-S-H I? 4 T h e reaction between silica fume and Ca(OH)2 solutions is very rapid and causes a phase to precipitate and turn into C-S-H very quickly. 45
2.2. 4 Other types o f pozzolana

ing between 15 and 20 A, whereas fly ash-lime mixes show only a slight discontinuity. 48

T h e same c o m p o u n d s are also formed with other types of pozzolana. T h e reaction products of burnt kaolin with lime are mainly gehlenite hydrate (C2ASHs), calcium silicate hydrate (C-SH) and small quantities of calcium aluminate hydrate (C4AHI3). 32,4(''47 At higher temperatures and suitable lime concentrations, the tetracalcium aluminate hydrate turns into cubic C3AH ~.

2.4 Strength of lime-pozzolana pastes T h e most remarkable practical consequence produced by pozzolanic reaction consists in the gradual hardening of the pozzolana-lime pastes (Table 3). 38 Strength increases as the amount of combined lime increases; 28,42 however, as is shown in Fig. 6, 28 there is no general relationship between the two parameters, just a simple correlation within each pozzolana. A n extreme case is represented by clayey materials which, despite their ability to fix lime, do not harden appreciably. A n interesting example referred to in Ref. 6 shows that the strength of a material rich in clay minerals

2.3 Porosity and microstructure T h e specific surface (BET) of the pastes increases gradually with time up to 35-10"0 m2/g after 90 days of curing. 2s T h e hydration products obtained by dispersing lime-pozzolana mixes in water (water-to-binder ratio= c. 12) can be as much as 150 m2/g after 1 year of curing, according to the type of pozzolana and the lime-pozzolana ratiosJ ~ At least up to a ratio of 0.6, combined lime always increases as the ratio increases, whereas the specific surface decreases, sometimes dramatically, once it has attained a peak value. Whatever the type of pozzolana, there always exists a direct relation between porosity and specific surface of hydrated products (Fig. 5).4s A difference has however been evidenced between a typical natural pozzolana and a fly ash: natural pozzolana-lime mixes show a clearly defined discontinuity in pore radii rang-

Table 3. Compressive strength of mortars containing Segni pozzolana3s -- values expressed as kg/cm:
7)'rne 0 2.5 UaSo4 (%) 5 7.5 10

Ca(OH) 2= 15% 7 days 28 days 6 months 1 year 2 years Ca(OH)2 = 25% 7 days 28 days 6 months 1 year 2 years

16 51 122 135 150 8 49 168 190 212

31 85 138 156 165 22 55 175 2(18 239

28 108 175 180 187 30 125 233 266 28(I

56 120 170 181 186 28 144 239 268 275

65 140 180 163 148 51 150 215 2(12 187

200

VIZZINITUFF
0.75

-r" 150 I.-

FLY ASH A D FLY ASH B

BACOLIPOZZ.

4B

ul
i,i > 10C 6

E
>I.0 ~) o.

0.50

iB
0.25

Ae

~ '

II: o.

50

C]
).00

I I
30

I
20

I
30

I
40

I
60 SPECIFIC S U R F A C E

I
90

I
120x104

10 COMBINED

Ca(OH)2(g/100 g of ~ z z . )

(~'/g)

Fig. 5. Relationship between porosity and specific surface of the hydration products: water/solid = 12.4~

Fig. 6. Mechanical strengths of 17 mm x 17 mm samples against combined calcium hydroxide. Lime-pozzolana pastes (40: 100).2~

Pozzolanic cements

191

can be as much as approximately one third of the strength found in materials having real pozzolanic behaviour. For this reason technical assessment of pozzolana must be carried out by measuring the strength of the lime mix (or portland cement mix) and not by determining the amount of fixed lime present. Fixed lime is only a useful means to help explain the hardening phenomenon. 5,39 The strength of lime-natural pozzolana pastes is remarkably increased by the addition of gypsum (Table 3). This should however not exceed certain levels (e.g. 5%) 49 if disintegration of specimens due to the formation of large quantities of ettringite is to be avoided. High-lime fly ashes behave like hydraulic binders. If they have a suitable composition, they need neither lime nor cement to harden. Such mixes always run the risk of rapid setting and thus require the addition of a suitable setting retarder. If gypsum is added, the strength will vary between 12.4 and 4.34 MPa after 28 days of curing. After 120 days, strengths will still be increasing and practically doubling, s

3 POZZOLANIC CEMENTS AND POZZOLANA CEMENTS When added to a portland cement, pozzolana reacts with the calcium hydroxide formed during hydration of clinker calcium silicates. As a result of this reaction, the final portlandite content of pastes made up of pozzolana-containing cements is always lower than that found in control portland cement pastes. This applies to natural pozzolanas,~ 5.5J fly ashes j 7.52.53and microsilica. 54-56 Pozzolanic cements are by definition mixes of portland cement and pozzolana which, if dispersed in water and kept under certain conditions, eventually produce solutions unsaturated with calcium hydroxide. 57,58 Conversely, pozzolana cements do not comply with this requirement inasmuch as their pozzolana content is insufficient to combine -- in terms of both quality and quantity -- most of the free lime released by calcium silicates thus giving unsaturated solutions.

occurred, 59,6 that is to say, as soon as 80% of alite 60'61 and 60-80% of C3A+C4AF have reacted. 6 This fact influences both the microstructure and properties of pozzolanic cements. This is the reason why the hydration processes of clinker and pozzolana can be investigated separately but always taking into account that the two materials exert a reciprocal influence. As a rule, the addition of pozzolanas accelerates the initial hydration of the clinker contained in pozzolanic cements. This behaviour is neatly apparent whenever the measured parameters, namely rate of heat evolution and total heat of hydration, are referred not to the clinker + gypsum + pozzolana system but to the former two only, i.e. whenever the measured values are multiplied by the dilution factor. In such cases, the second peak of heat evolution is higher than that of the non-diluted cement. This is always true with natural pozzolanas 6 and silica f u m e 56,62 whereas it is not always so with fly ashes, whose peak of heat evolution can be slightly higher, 52 unaltered 63 or lower 62 than that of the control portland cement. In this latter case, the retarding effect can be ascribed to the presence of unburnt coal in the ashes. The progress of hydration in pozzolanic cements cannot be expressed in terms of Ca(OH)2 content, as can be done -- still with some reservations -- with portland cements since the portlandite content in the pastes is the result of at least three concurring phenomena: acceleration of the hydrolisis of the calcium silicates of clinker, pozzolanic reaction, modification in the composition of the hydrated phases. This concurrence can help explain the behaviour of the portlandite content in cement pastes which increases at first and then decreases (see Fig. 7). 2o Consequently, one would be driven to assume that natural pozzolana is more active than the fly ash and calcareous filler inasmuch as they leave smaller amounts of free CaO in the pastes. However, from Figs 8 and 9, 20 where the activity of pozzolana is expressed in terms of both combined water and strength, it is particularly apparent that this conclusion is wrong. For the purpose of obtaining more consistent results, the only conclusion one can draw is that any pozzolanic addition is likely to modify the reaction course, the composition of the hydrated phases as well as the microstructure.

3.1 The hydration of pozzolanic cements Clinker (plus gypsum) and pozzolana show different reaction processes and react at different ages. As is known, the pozzolanic reaction becomes apparent after 7-15 days since mixing

192
14
uJ 12

Franco Massazza

Limestone 30%

10

~8
o o v-

tetracalcium aluminate hydrate (often carbonated), monosulphoaluminate, C-S-H, Ca(OH)2. Ettringite is rapidly formed in cements containing natural pozzolana a~ or fly ashes, i7,64 The persistence of ettringite which has not turned into monosulphate was observed at 28 days in fly-ash containing cements ~7 and at 1 year in cements containing natural pozzolanasJ 9 The picture is actually much more complex than it might seem because ettringite can also disappear after 3 days2 Moreover, its conversion into monosulphate was also observed in SO3-poor fly ashesJ 2 As a consequence, ettringite's conversion into monosulphate depends on the amount of SO 3 available. Tetracalcium aluminate hydrate is often carbonated either because it has been contaminated by the CO2 contained in the atmosphere a9 or because of the occurrence of calcite in cement. ~ 7 The hydration of alite is accelerated by the presence of pozzolanic materials. The formation of C-S-H is so rapid that is already visible after 24 h s and it is even more rapid if pozzolana is made up of microsilica. ~5 The hydration of both C3S and C2S is associated with the formation of portlandite. In pozzolanic cements, besides the C-S-H which is formed due to the hydration of clinker silicates, the C-S-H originating from the reaction between pozzolana and hydrolysis lime also occurs. The composition of this latter type of C-S-H is different from that originating from C3S and C2S, the reason being due to different conditions of formation. In pozzolanic cements the C-S-H has a lower C/S ratio and an alumina content greater than that of portland cement pastes (Table 4). ~ The variability in the composition of C-S-H has also been stressed by methods other than EMPA. As an example, optical microscopy showed that in hydrated pozzolanic cement pastes the calcium silicate hydrate has different refraction indexes
Table 4. Composition of C - S - H in cement pastes with and without 40% blending component (w/c = 0.40, 293 K, age 4 years) by EMPA s

P o z z ~

c~ 6

~4
-r

o o2
I I 1 / I

t~

13 7

28

60

90

TIME (DAYS)

Fig. 7. Free portlandite in blended cement pastes.:"

14 o~

3
uJ

4
2

_z o
0

Q =E

13 7

28

60

9o

TIME (DAYS)

Fig. 8. Combined water in blended cement pastes. -~(~

7o

so

40 3o
~e

o. 0 t,..}

1Q

3~

2'8
TIME

9o
(DAYS)

Fig. 9. Mechanical strengths of blended cements. 2~)

3.2 Hydration products in pozzolanic cements The reaction products formed during the hydration of pozzolanic cements are the same as those occurring in portland cement pastes, although differing in content. They are:

C/S A/C C](S+A) Na20 K,O

OPC 2-03 0-06 Fly ash cement 1.01 0.21 Slagcement 1.62 0.44 1.81 0-84 (I.96 0"03 0.24 0.23 0'1 [ 0.33 0.30

(%)

ettringite,

Pozzolanic cements

193

which clearly indicates a difference in the chemical composition.7] This conclusion is supported by the different degree of polimerization of the silicate anion, greater in pozzolanic cement than in portland cement pastes. 65 In cements containing high-lime fly ashes, C2ASH8 (gehlenite hydrate) besides C-S-H is also f o r m e d . 64 Anyway, if gypsum is added to cements, the gehlenite hydrate gradually decreases and eventually disappears after 60 days. In the short and medium term, the presence of portlandite in hardened pozzolanic cement pastes is justified by a low initial rate of pozzolanic reaction. Only in the long term should the pozzolanic reaction be overwhelming thus making free lime disappear. Table 563 shows however that portlandite does not disappear even after 4 years of curing. It is therefore evident that there must be other reasons beside those mentioned earlier in Section 3.1.
3.3 Portlandite content

must be ascribed not to a lack of pozzolanic reaction but to the difficulties encountered by both portlandite crystals and pozzolana particles in reacting in very stiff pastes where they are found to be covered and shielded by hydrated compounds. This assumption is sustained by the following: Free lime is progressively less in pastes, mortars and concretes respectively, i.e. in materials having increasing a/c ratios and thus greater porosity and permeability (Fig. 10). 51 As portland cement fineness increases, combined lime first increases and then decreases (Fig. 11).67 Combined water is always larger in blended cement pastes than in control cement pastes (Table 6). 17 In spite of the significant Ca(OH)2 content of pastes, pozzolana has substantially and remarkably reacted after 28 d a y s . 6.68 To explain the contradiction between the high free lime content and the considerable progress in
1) Paste u)
"

The overall Ca(OH)2 content of pozzolana containing pastes is always lower than that of control portland pastes when referred to the binder (portland cement+pozzolana). It may however be higher, 17 l o w e r 2,66 o r even the s a m e 52,53"67 when the content is referred to portland cement alone. In any case, in the first month, the portlandite content is more or less equivalent to that formed in portland cement multiplied by the dilution factor. The long-term persistence of portlandite may appear incompatible with the presence of pozzolana since the common Italian pozzolanas, as well as fly ashes, can combine an amount of Ca(OH)z being as much as about 50% of their weightJ 4 Henceforth, the portlandite content of hardened cement pastes should be very low. The reality being different, the persistence of portlandite
Table 5. Free lime content in portland cement with different amounts of pozzolana. Pastes cured for 4 years 63
Free lime A TD method Franke method

2) M o r t a r

3) C o n c r e t e

8
1. I- ~

--3 r U ul

WN

"

0
3 7 28 TIME (DAYS) 60 90 ~

Fig. 10. Free portlandite content of paste, mortar (1:3) and concrete (1:6) samples cured at 40C (water/cement ratio=0.5). 35% of portland cement replaced by two types of pozzolanasP t

FLY ASH M 14

~%)

(%)

o e= o 10 a u.i z ,,n :z 6 o (.)

Portland cement Portland cement + Portland cement + Portland cement + Portland cement + Portland cement +

10% Segni Pozzol. 20% Segni Pozzol. 30% Segni Pozzol. 40% Segni Pozzol. 50% Segni Pozzol.

10.2 7.6 5"3 2.9 1-1"5 1

9"65 7"20 5"4 3"1 1"3 0"9

2
i I I I I I

3000 4o00 sooo sooo rooo 8ooo PORTLAND CEkF.NT FINENESS (cm2/g)

Fig. 11. Ca(OH)2 combined by fly ashes versus the specific surface (Blaine) of control portland cements. 67

194 Table 6. TGA/DTG data for PC-fly ash pastes 7

Franco Massazza

Paste

Age

Ca (OH): (per l OOg) total binder

0-94 6.(t5 15.05 18.12 19.16 23.94 0.40 1.53 11.16 17.76 18.57 18-94 (I 2'45 8"70 12'84 12"94 15-(16 1.(t8 1"34 11.(12 16'47 16.35 20-73 () (t.96 8.91 12.77 12.53 19-42

Content (per lOOg) PC

0.94 6.(t5 15.05 18.12 19.16 23.94 0.46 1.76 12.84 20.44 21.37 21.79 0 3"35 11.89 17'54 17'68 20"57 1-24 1"55 12.70 18'98 18.84 23.89 0 1-32 12.21 17.49 17.16 26.60

Bound water (per lOOg) total binder

2.82 9.(10 14.75 19.53 21.39 26.85 2.34 4.13 13.56 19.55 20'95 24.34 2.44 4.54 12" 17 17-21 19.25 23' 14 2'8(t 4.72 13"82 19-93 20"60 27-9 l 2.23 3.54 14.13 18.94 19.5(/ 22.38

Content (per lOOg) 1'('

2-82 9.00 14.75 19.53 21.39 26.85 2.69 4.75 15.61 22.49 24.11 28.01 3"33 6"20 16"62 23.51 26'29 31'60 3"23 5.43 15"93 22-97 23.74 32.16 3.05 4.85 19.36 25.95 26-72 30.66

Control PC

2h 5h 1 day 3 days 7 days 28 days 2h 5h 1 day 3 days 7 days 28 days 2h 5h 1 day 3 days 7 days 28 days 2h 5h 1 day 3 days 7 days 28 days 2h 5h 1 days 3 days 7 days 28 days

4 515

4 5311

1(/15

1 030

pozzolanic reaction it is necessary to assume that pozzolanas will have to subtract lime from the adjacent C - S - H . 69 As in the case of the C3S-pozzolana mixes, this model requires that: (i) a C/S gradient exists which, starting from portlandite crystals, would cross C-S-H to reach the fly ash particle; and that (ii) the C-S-H in pozzolanic cements has a C/S ratio being lower than that of ordinary cements. Figure 12 70 and Table 4 ~ show how both requirements are complied with. These two conclusions are far from being insignificant, inasmuch as they can contribute to explaining the higher flexural strength of pozzolanic cements as well as their improved resistance to aggressive ions.

3.4 Paste microstructure The paste microstructure reveals the different rates of clinker hydration and pozzolana reaction.

After 1 day, the reaction has only involved clinker and plenty of ettringite crystals as well as C-S-H rims, apparently amorphous, are evident. ~7'7~ It would seem that fly ash particles provide a suitable nucleation site for the growth of the hydrated compounds. ~7 After 28 days, the fibres of C-S-H have filled all pore spacings.~ 7 After 1 day the particles of the pozzolanic materials seem to have been attacked. It is supposed that some chemical interaction between the surface of the pozzolana and the ions dissolved in the mixing water must have occurred. A reaction between a large well-formed crystal of CH in contact with a fly ash particle can also be observed. 7-" Only at later stages does the outer part of the pozzolana particles appear altered and is replaced by a thin layer of newly-formed products. After a 28-day hydration, the outer part of the natural pozzolana's grains is transformed into a rim of new hydrated products. Reflected fight microscopy has shown that in some cases this rim is made by two different layers. 7~

Pozzolanic cements

195

4.0 3.d 2.0 1.0

_o
re

3 days . . . . 2
6

~
13

'

~
14

,~
O

0 1
i

2 3 4 , 91,days
HYDRATES

5
i

6
i

~zl 1 ~ 2 3.11" 1 2.C ~ 1

2 34 5

J3

pozz.

67

1.0

decreasing with time, the porosity is always higher than in portland cements. After a 7-month curing, differences can range between 15% and 60% according to the type of pozzolana. T M The pore size distribution of the two types of cement are different and mesoporosity of pozzolanic cement pastes is displaced towards the smaller pores. In fact, the Maximum Continuous Diameter (MCD) and the Threshold Values (TV) are lower in pozzolanic cement pastes than in portland cement ones. When considering porosity values, it must be taken into account that experimental results could be altered by various factors. O The cumulative mercury intruded pore volume measured on 105C-oven-dried specimens is higher than that found in the same specimens from which water was extracted by solvent replacement. T M Vacuum drying at 70C and drying at 20C with decreasing relative humidities highlight different porosity v a l u e s . 79 From mercury intrusion measurements, the pore distribution in hydrated blended cement mixes is somewhat distorted and the porosity is often overestimated due to the structural damages occurring at high pressure.80,81 Some experimental evidence indicates that part of the pores of cement pastes containing fly ash or silica fume are not intruded by mercury. 66 This would mean that pozzolana-containing cements give a definitely higher porosity. As suggested by test results, pozzolanic cement pastes are relatively richer in larger pores whose entrances are however smaller than in portland cements pastes. Conversely, permeability of pozzolanic pastes is tendentially lower 17,66,74(Table 774). A general correlation might be expected between permeability and porosity since both of them vary with time according to similar equations. In reality, such a correlation is only valid for each single cement. 82 Lack of a general correlation is to be ascribed to differences in the microstructures between pozzolanic and portland cement pastes. The apparent contradiction in terms of (higher) porosity and (lower) permeability of pozzolanic cements can be explained through the following model. 83 In most pozzolanic cements, hydration occurring during the first 7-15 days almost exclusively involves the clinker+gypsum

o ;

~ a ~ ;
D I S T A N C E (p.m)

Fig. 12. C/S ratio in blends of C3S and Beppu white clay pozzolana.TM

SEM examination of fly-ash in cement has suggested that the rims are initially made up of a continuous and uniform layer of calcium hydroxide which is in turn covered with calcium silicate hydrate. 73 As far as hydration of high-lime fly ashes is concerned, a model has recently been produced which can be applied, with only minor changes, to all pozzolanic materials. 64 The fly ash spheres are consumed from the outer surface inwards thus forming a rim of new products. The rim is gradually replaced with radiating bundles of fibrous C-S-H perpendicular to the surface of the particles. This mechanism implies a topochemical action as well as through a solution growth with a thin, amorphous, migrating interfacial region situated between the honeycomb C-S-H and the residual fly ash spheres. Beneath the rims, the surface of the particles is smooth and signs of chemical attack are barely present. This could suggest that the so-called 'inert' phases of pozzolana are also dissolved by a strong alkaline environment. Thus, the progress of the pozzolanic reaction, which in turn determines the progress of the mechanical properties, must take place through this double layer, probably by diffusion of the various ionic species present.

3.5 Porosity and permeability of pozzolanic pastes The total porosity, assessed by mercury intrusion, is generally higher in pozzolanic cement pastes than in portland cement pastes manufactured with the same w/c ratio. 17'66'74-77 Though

196

Franco Massazza

Table 7. Porosity (%) and permeability coefficients (m 2) of cement pastes 74"

Cement paste 7days Porosity

Pti. cement Ptl. cement + filler Ptl. cement + fly ash Ptl. cement + Bacoli pozz. 19.70 26.10 31.90 26"60

Curing 7 months Permeability

2.36 1.29 1.70 1'92 10-17 10-17 10-17 10-17

l'orosity
15"10 15"30 17"40 13"30

l'ermeability
3'00 1"26 0'51 0"77 10-17 10-17 10-17 10-17

"Dried at 70C for 16 h under vacuum at the residual pressure of 5 mbar.

fraction. Within this time c. 80% of alite has

r e a c t e d . 7

Part of the hydration products of clinker is formed and develops on site, whereas the remaining part deposits on the pozzolana particles. When the pozzolana starts reacting, its particles are surrounded by a porous but already stiff structure. Only a part of the hydration products can therefore form on site. Since there is no evidence of a growing pressure, part of their hydrated compounds must form elsewhere and precipitate in the water-filled capillary pores. This process can take place due to the fibrous radial structure of C-S-H which covers the pozzolana particles and allows dissolution and transportation phenomena to occur. The volume of the precipitating mass is small and is therefore unable to fill the larger pores. It is however sufficient in amount to obstruct the thin connections existing between the larger pores or at least to reduce span thereof. As a consequence, the porosity of pozzolanic cements is still higher even after completion of the pozzolanic reaction whereas permeability is reduced. The microstructure of pozzolanic cement pastes is slightly but neatly different from that of portland cement pastes. Nevertheless, the microstructural differences are such that they determine the well-known differences in the engineering properties of both types of cement and mainly regarding: mechanical properties durability 3.6 Mortar and paste strength Pozzolana starts reacting somewhat belatedly with the calcium hydroxide produced by clinker

hydration and therefore, at least initially, it behaves like an inert diluting agent towards the portland cement with which it has been mixed. Consequently the partial replacement of portland cement for pozzolana generally reduces the initial rate of cement hardening, though at longer curing ages the situation can be reversed. This conclusion applies to natural pozzolanas, ~4 high-~5 and low-lime fly ashes ]7,86'87 and silica fume. 88,89 A typical example of this behaviour is given in Fig. 13. 51 The effect of pozzolana on strength depends on a number of factors the most significant of which are: pozzolana content, type of pozzolana, pozzolana grading and specific surface, type of cement, strength class of cement, curing, temperature.

1401
X I'Z 121]

10(] tLJ > u) u) lu 8 E 1.

0 ul 60

>
.,I m 40

1o

20

3o

,~

's'o

POZZOLANA CONTENT iN CEMENT, %

Fig. 13. Effect of substituting portland cement for pozzolana on the compressive strength of ISO mortar. Values expressed as percentage of the 28-day strength of reference cement. -~[

Pozzolanic cements
3.6.1 Pozzolana content Too high pozzolana contents reduce strengths at all ages and must therefore be avoided unless other reasons, such as the need for a low heat of hydration or a greater durability, suggest the opposite. Of course, the real behaviour of a pozzolana-containing cement depends also on the type of portland cement and pozzolana used. In other words, there is an optimum pozzolana content that must be determined on a case-by-case basis and that depends on a number of factors. The 28-day-strength reduction caused by the replacement of pozzolana for portland cement is in any case lower than that obtained by diluting the control portland cement with an inert filler. 9'91 Generally, the optimum pozzolana content refers to the 28-day strength. If the main target to be met is different, i.e. a slower/higher heat of hydration, higher ultimate strength or improved durability, the 'optimum contents' should be varied accordingly.

197

The strength loss caused by the partial replacement of cement for pozzolana is sooner or later recovered, depending both on the type and content of pozzolana. For example, a cement containing 15% of rhyolitic glass slightly exceeds the strength of the control portland cement already after 7 days. 88 Owing to its fineness and composition, microsilica is even more effective since, when added in amounts ranging between 5 and 10% by weight of cement, strengths are increased by 15-25% after 7 days of curing and by 4-12% after one year. Conversely, with certain poorquality materials the strength-pozzolana content ratio curve lacks the maximum peak and the strength of the control portland cement is always higher than that of blended cements. 93

3.6.2 Type of pozzolana Figure 14 9~ s h o w s that the strength development of pozzolanic cements depends on the type of pozzolana used 86"91,92 and that the strength of mixes containing 20% of pozzolana is always higher than that of the control sample which contains 20% of ground quartz. 9 The case of Sacrofano pozzolana illustrated in Fig. 14 must be considered as particular and not as common since this type of pozzolana is very active.

Silica fume

so/
/

f /
~

~Ot,tom.earth

3.6.3 Pozzolana particle size distribution In the short and long term a remarkable reduction in strength is associated with a decrease in pozzolana f i n e n e s s . 85'86'92 The role played by the particle size distribution is illustrated in Fig. 15. 92 The effect is even more pronounced at earlier ages. Figure 16 s5 shows that the 0-20 fraction reduces 7-day strengths by 50% and 90-day strengths by 15%. The fractions with higher particle diameters reduce the initial strength extensively and neither after 90 days of curing is this loss of strength recovered. ~5 In the latter case, high-lime fly ashes behave slighly better probably because they contain hydraulic constituents. Conversely, the strength is substantially improved if ground fly ash instead of graded fractions of fly ashes is used. In this case, if the grinding fineness of the fly ash has proven suitable (Blaine Specific Surface = 453 m2/kg), the 90-day

Seg.I
o,ro,
A

" rl c 30

Sacrofano

75 ~ 7 ~tm

20

50

2O

10

25

46

0 10 20 TIME (DAYS) 30 40 0 30 60 90 120

Fig. 14. Strength development of different pozzolanacement pastes. 20% replacement; 4 x 4 x 16 specimens. Curing: 77 h in water and then in air at 65% RH at 20C. 9

PERIOD OF CURE (DAYS)

Fig. 15. Mortar strength development rates for fly ashes of various median diameters. (~m)? 2

198

Franco Massazza

too ]
80 60

[%]

r].,,ce
Fractions
[~ 0-20pm

80 o. "1" I-

--m

ftc = 0 f / c = 0.25 f / c = 0.50

l~ 20-40pm
D 40-60pm

0 Z uJ
m Iu) uJ > U) (n m O. :i 0 0

6O

40

40 ~

~] > 60pm

20

w / ( + t ) = 0.50 8 d i l f e r e n t fly ashes ~ 28 AGE (DAYS)

0 0 7

7 days

28 days

90 days

90

Fig. 16. Relative compressivestrength of binders containing 30% fractionizedlow-calciumfly ash.~

Fig. 17. Compressive strength of mortars without (w) and with fly ash (f) added to portland cement (c)?6

strength can be higher than that of the control cementY 5 When, however, the fineness of fly ashes exceeds certain limits, the compressive strength will decrease instead of increasing. 85 The substitution of 5% of a active materials (fly ashes, slags) -- accounting for 30% of the cements under examination -- for silica fume does not improve the 7-90 day strengtas whereas the substitution of practically inert materials (crystalline slags, ground quartz) causes a neat improvement already at 28 days. 9~

100

=~ 90

....--1+2 3

80 I~ 70 ul
--> -,

endslcm21g)
Series 1 3450 3920 4640 Series 2 4080 4550 5420 S e r i e s 3 6810 7110 7590
3

5O

3.6.4 Type of cement

The strength of mortars depends not only on fly ash properties but also on the portland cement used. Partial replacement of portland cements of the same strength class, with a 28 day compressive strength ranging between 45,5 and 49,7 MPa for the same fly ashes leads to compressive strengths that do not match those of the control cements. ~6 This means that the behaviour of a pozzolana cannot be assessed by using a portland cement alone and confirms the difficulty of using a given cement class to set up a reference mortar. The partial substitution of blasffurnace slag cements for fly ashes reduces the strength to a greater extent than what usually happens in portland cements. ~('

TIME (DAYS)

Fig. 18. Mean values of relative compressivestrengths, with respect to control portland cements.Series 1, 2 and 3 made with blends of one portland cement and one fly ash, ground separately at three differentfinenesses. 95

With the class 45 portland cement, mortars containing fly ashes were not capable of attaining the same strengths as the control cement even after 90 days. 86 In other words, it would seem that the lower the fineness of the control cement, the sooner pozzolanic cements reach or approximate to the strength of the control cements. 95

3.6.6 Length of curing

The strength drops when pozzolana partially replaces portland cement. Figure 1895 shows that the substitution of 30% of cement for fly ashes can reduce the early strength of the control cement by 50%, therefore exerting a greater effect than that calculated by dilution rule. 95 For this reason the curing of pozzolanic concretes and mortars needs more care than the curing of portland cements. Provided that curing is correctly carried out, the difference in strength between pozzolanic and portland cements decreases with age and eventually disappears or changes in sign. The moment of

3.6.5 Cement strength class

Fly ashes in cements have different effects according to the strength class of portland cement being used. A n example is given by 86 who blended a 35 and 45 class portland cement made with the same clinker with 25% of 8 different types of fly ash. All mortars containing the former cement reached the same strength as the control fly ashfree mortars after approximately 60 days and exceeded it after 90 days (see Fig. 17). 86

Pozzolanic cements
recovery depends on the fineness of both portland cement 95 and pozzolana. 85 The lower hardening rate caused by the replacement of portland cement for pozzolana does not create major problems when pozzolanic cements are prepared directly at the cement works, because here the cement manufacturer takes all necessary steps to ensure that blended cements have strength values complying with standard specifications. When pozzolana is added to cement at the building site where the properties of pozzolana and cement cannot be further modified, the only possible corrective measure for optimizing the properties of the mix is to increase the cement content.

199

both pastes and mortars. In this case, obviously, the influence exerted by aggregates -- which constitute most part of the concrete -- as well as by the cement content must also be considered.

3.6. 7 Plasticising and superplasticising admixtures The workability is only slightly affected when pozzolanic cements contain natural pozzolanas or fly ashes. When, however, cements contain very fine materials such as microsilica and diatomaceous earths, batches require the addition of large amounts of superplasticisers. Although the dosage of admixtures increases proportionally to the quantity of microsilica present, it is still possible to replace portland cement for silica fume (s.s.-20 m2/g) and very finely ground silica (s.s. = 12 and 20 m2/g SiO2 = 87%) up to 25%. In spite of the presence of the admixture, microsilica reduces the initial compressive strength in virtually all mixes. This loss is gradually attenuated and after 28 days the strength of all mixes is higher than that of the control cement. 86 It is reported that the highest strengths have been obtained not with silica fume but with finely ground silica of equal fineness. 89 Even when associated with superfluidising admixtures, silica fume requires an optimum dosage. Generally, an amount of about 15% is sufficient, this value being far lower than those required by natural pozzolanas and fly ashes. 89 The addition of a superplasticiser (condensed sulphonate melamine) to pastes containing between 20 and 35% of fly ashes does not change the strength but allows a lower w/c ratio to be used and thus higher strengths to be attained. 96

4.1.1 Optimum content As far as pastes and mortars are concerned, concretes also need an optimum content of pozzolana to attain the best performances. After 3 days of curing, a 15% replacement of a portland cement for 15% fly ash gives in the majority of cases a higher compressive strength than that of the control c e m e n t s However better development of early strengths is to be attributed to a physical rather than chemical cause. As is known, in fact, the pozzolanic reaction has already started at 3 days but it has certainly not progressed very far. A twofold substitution, amounting to as much as 30% of fly ash, reduces early strengths and the strength loss is recovered only after 40-90 d a y s . 97 Owing to its high reactivity, the pozzolanic effect of silica fume starts earlier, i.e. after 7 days at 2 0 C 98'99 and after 2 days at 3 5 C . 98 4.1.2 Chemical and mineralogical composition The chemical and mineralogical composition of both natural and artificial pozzolanas varies noticeably from type to type and this can help explain why, even by using the same portland cement, concrete strength depends on the type of pozzolana used.~ 00 The decrease in early strengths -- a typical feature of concretes containing siliceous fly ashes -- may not occur despite a considerable replacement of cement with high-lime fly ash (CaO=30.3%), 1~ (CaO=22%)J 2 If 30% of portland cement is replaced, increases in strength amounting to as much as 85% and 35% can be obtained by a 28-day and 8-year curing respectivelyJ 3 This behaviour of high-lime fly ashes depends on their content in hydraulic compounds. The reactivity of microsilica is basically pozzolanic in character and therefore more similar to that of the most common vitreous pozzolanas and fly ashes. Up to 7 days, the 5, 10 and 20% substitution of a portland cement for silica fume does not substantially modify the strength of concretes containing 300 kg/m 3 of cement and having a w/c ratio of 0.7 although, with respect to the control cement, workability is noticeably reduced. Subsequently, the difference between the strengths of the four cements is the more substantial, the larger the amount of silica fume (Fig. 19).99

4 POZZOLANA CONTAINING CONCRETE

4.1 Concrete strength

The strength of pozzolana-concretes is affected by the same factors influencing the strength of

200
60
A

Franco Massazza
F l y ash ~ ~ ~20%

~ so
40

-4 3 2 ~ ~

50 40 30
20

.._..--- ~

~--40%
u% 20%

zo

~
. / f /7 "

-- _ ~

..... ---" -

40%

Slgca fume Slump

UJ

10
I I

- I

Grade 25
I I

ha
o

20

(1) (2) (3) (4)

300/0 285115 270/30 240160

15 14 10 6
I 9O

20

40

60

80

100

AGE (DAYS)

28

TIME (DAYS)

Fig. 20. Effect of concrete grade and fly ash content on compressive strength. Portland cementreplaced by 20 and 40% fly ash.~~

Fig. 19. Concrete strength versus time. Cement composition and slumpindicated in the figure;w/c = 0.7; no plasticiser.99

Silica fume gives a major contribution to strength development between the 3rd and the 28th day at 20C. 14

4.1.3 Curing Every concrete -- and the same applies therefore to pozzolana-containing concretes -requires proper curing which is essential to exploit all potential capabilities of the cement used. The strength development of concretes containing pozzolanas is more adversely affected by very short curing periods under water than plain portland cement-containing concretes. H~,l4 Such behaviour depends on the fact that, at least during the first 7 days of curing, the most common pozzolanas do not take part in the hydration process and they solely act as a diluting agent and increase de facto the w/c ratio. It is not by chance that the weight loss of air stored concrete diminishes as the fly ash content is decreased 15 and the curing period is prolonged. Fly-ash-containing concretes, initially moist cured for 7 days and subsequently stored at 65% R.H. for 90 days, were able to attain and exceed the strength of the control portland cement concrete.~5 As far as curing of pozzolanic cements is concerned, emphasis is generally laid on the relatively lower early strengths while other aspects are often forgotten. Concretes containing pozzolanas in general and fly ashes in particular ~6 continue increasing their strength even after 28 days, an age which is commonly taken as a reference for concrete quality. After 7 years of water curing, a concrete containing 46.6% of fly ashes was found to have developed a more than twofold strength as compared to that found at 28 days.

4.1.4 Quality The lower quality of fly ashes seen in recent years has suggested that fines in fly ashes should be separated from coarser particles. Strength is thus improved as a consequence of the decrease in the maximum diameter of the particles (20, 10 and 5/am) and a 15% replacement of cement can give concretes having 7-day strengths roughly equivalent to that of the addition-free control concrete. After 91 days of curing, all fly-ash-containing concretes yielded strengths equal to or, if finer, greater than those of the control specimens.l7 4.1.5 Temperature Blended cements are more sensitive to temperature than portland cements. Anyway, if the mixes have been proportioned so to give concretes having the same 28-day strength, the 1-3 day strength of pozzolana-containing concrete will not substantially differ from that of concrete containing portland cement only. 9~ 4.1.6 Partial substitution The partial substitution (20-40%) of a cement for fly ashes exerts a different effect according to the cement content. For example, with a cement content of 285 kg/m 3, the 91-day strength is lower than in the control concrete, whereas with a cement content of 345 kg/m 3 it is increased between 28 and 91 days. In any case, the initial strength was shown to be lower than that of the control specimen (Fig. 20). L8 4.1.7 Plasticizers and superplasticisers Plasticizers and superplasticisers are often used in concrete technology on account of the many advantages they offer in terms of strength, workability and durability. When concrete contains microsilica, their utilisation becomes essential as

Pozzolanic cements
the water demand increases almost linearly with increasing microsilica contents in cement (see Fig. 21). 14 Furthermore, microsilica renders concrete more cohesive and viscous. 14 Since the use of admixtures is often associated with variations in the mix composition it is rather difficult to relate their effects with other parameters of the concrete itself. Loss of strength in concretes, for example, caused by replacing portland cement with 30% fly ashes, can be recovered by adding silica fume, and a water reducing agent (Fig. 22109). Conversely, a ligninsulphonate-based plasticising admixture was not able to regain the strength loss caused by a 10% addition of silica fume to cements containing either 10% or 25% of fly ashes. 98 This clearly indicates that a successful outcome is related to the type of admixture selected. A parameter that should not be neglected is the aggregate inasmuch as a cement containing 25%

201

of fly ashes and tested with various aggregates has given different strengths. With a 10% addition of silica fume, strengths are found to decrease with some aggregates whereas they are increased with certain others. In the former case, the diminution is not recovered even after 2 years of water storage whereas in the latter two cases the positive effect is maintained, l In the presence of microsilica equal slump does not mean equal workability) 4 In order to ensure the same workability it is always recommended that microsilica-containing concrete should have a slump higher than 3-5 cm.

4.1.8 Early strengths

Fly ashes and microsilica are usually added to concrete to replace part of the cement content. Often cost-effective, this practice raises some perplexities from a technical viewpoint since the early strengths are remarkably reduced. Conversely, the use of pozzolanas to compensate for any deficiency in fines in the aggregates is always advantageous and in some cases necessary. At least between 2 and 91 days, concrete strengths are increased if fine aggregates instead of portland cement are replaced. The amount of aggregate to be replaced with fly ashes in order to obtain better results depends on curing as well as on the w/c ratio.110

~ 5o
z so

No admixtures

j R ; 3 8

i .
m 2o

~ lO

~
r

SP 30

4.1.9 High strength concretes

I

I 10

20

I 30

40

50

MICROSILICA CONTENT (kg/m3)

Fig. 21. The influence of microsilica addition on the water demand of mixes with no water reducing admixtures. Cements: OPC (SP 30), RHC (RP 38), pozzolana cement (RP 38 containing 20% fly ash). 14

Control+20% silica

fume
--20%

i '
3 [/
tJ

In pozzolana-containing concretes the relatively low rate of initial hardening does not prevent concretes with 28-day strengths higher than 60 MPa, i.e. high strength concretes, from being manufactured. As shown in Fig. 23,111 this can also be obtained by replacing 50% of portland cement with fly ashes. In order to achieve the best results the binder content must be high, the w/c+f.c, ratio low, the workability improved through a superplasticiser, the fines content adequate. When evaluating the advantages of a large substitution of the portland cement, one should consider that the heat of hydration, shrinkage and creep will also be reduced. 111

c e m' ~ e n t - " ~ " ~ '" "

70% PII cem.+30% fly ash (com'eol,)

4.1.10 Efficiency factor

Sometimes the replacement of portland cement for pozzolana is not effected as a simply ponderal equivalence but it is best accomplished by using the so-called efficiency factor K, generally assumed to be 0.3. The efficiency factor K is defined as the mass of portland cement that makes the same contribution to the strength of

,3 ~

2'.

5~
AGE (DAYS)

9'1
with

Fig. 22. Compressive strength of concrete w/(c + f) = 0.60, superplasticiser and A E A ) 9

202
WATER/(CEMENT+PFA)RATIO ~" 10(] a, I so 0.32 i 0.421 ! I 0.614 I Fog curing i

Franco Massazza

.--.
t

400

28-day water cured

,
I I
365 d

~300
~ 200
Fly ash ontscd (%)

40

/~01

o
Cement 233
233 659 C o m s e 1035 PFA 174 174 133 kg 133 " 761 " 1121 " 1.7 % 163 kg

20

4O

6O

80

DRYING TIME (DAYS) Fig. 24. Drying shrinkage versus age of concretes having different fly ash contents. Grade 35 mixes."~s

Fines

720
1093 1.8 148

SuperpL
(%C+PFA)I.8 Water 145

Fig. 23. Mix proportioning chart for fly ash concrete containing a superplasticiser and 50% cement replacements, t~

Table 8. Shrinkage and expansion after 2 years of concretes having different composition and similar workability ~~ 2

concrete as a unit mass of fly ash. According to this procedure, portland cement is not replaced with the same amount of fly ashes on a weight basis but with a given amount of ash multiplied by K.IO5

Target W/C Binder strength content" (MPa) (kg/m 3)

Shrinkage h Environment Laboratory Outside sheltered

Expansion (10 -~)

20 40 60

0'615 0-423 0'320

266 348 466

485 460 475

422 385 393

260 233 201

4.2 Drying shrinkage

Shrinkage, expansion and creep are widely recognised as fundamental properties of concrete. It is therefore necessary to know exactly how pozzolanas can influence these parameters. In this respect, it should be remembered that a large percentage of cracks forming in the concrete structures is due to the restraints opposed to the shrinkage.t ~ 2 It is generally assumed that drying shrinkage is not substantially influenced by pozzolanas in themselves. Variations, if any, should be ascribed to changes occurring in the water demand and in the microstructure of cement pastes (Fig. 24). ,~8 Shrinkage does not depend on the strength of the concrete: this is true either if the binder (cement +fly ash) content and the w/c ratio are constant "~7,~s or if the workability is kept constant by modifying the composition and thus the strengths.J J2 As a rule, shrinkage depends on the cement content and the w/c ratio. 114 Variations with the same sign in both parameters make shrinkage increase or decrease, whereas variations having opposite signs contrast reciprocally. Table 8 ~2 shows that the shrinkage of three concretes having different compositions and strengths is basically the same due to the contrasting action exerted by

"50% Portland cement -- 50% fly ash. ~'Superplasticiser 1.8% of binder content.

the cement content and the diminution of the w/c ratio. This diminution has been brought about by the use of a superfluidising agent. The independence of shrinkage from concrete strength is remarkable inasmuch as it is obtained by substituting 50% portland cement for fly ashes. ~i2 Table 8 shows that expansion of concretes stored in a fog chamber (RH= 95%) is neatly lower in concretes with higher strengths. In this case the difference could be ascribed to the lower w/c ratio of the high strength concrete and therefore to the lower capillary porosity which hinders and reduces water penetration from the outside. Curing conditions exert a noticeable effect on shrinkage since, as illustrated in Table 8, air storage of specimens being only protected against rainfalls or sunlight has caused a lower shrinkage. In conclusion, the final shrinkage of fly-ashcontaining concretes having different compositions lies in the 100 x 10 -6 interval./12 Air-classified fly ashes (<20, < 10 and <5 ktm) have given similar results since shrinkage differences never exceeded 100 10- 6107

Pozzolanic cements

203

T=ble 9. Typicalvaluesof concrete shrinkage(#m/m)84

g00

l
4

Cement 1 3

Storage (days) 7 28 90
700
Z ,< u~ 0. w tu n0 500

325 Portland 425 Portland 525 Portland 325 Pozzolanic 425 Pozzolanic

33 37 60 44 44

86 86 114 97 100

170 158 180 206 185

360 354 358 480 420

476 501 497 609 540

300

f.a.
(3) (4) 30 % -

(control) replac.

so % "
I I I

100
I I I

Replacement of various amounts of fly ash (20%, 30% and 50%) in cement does not substantially modify the drying shrinkage since the differences fall within the 50 x 10 -6 interval. ~~ Drying shrinkage is larger for cements replaced by 20 and 40% of fly ashes as compared to the control cement but only when the curing period is short (7 days for example).~8 Shrinkage is larger in concretes made up with natural-pozzolana- containing cements (see Table 9). 84 This feature, which distinguishes natural pozzolanas from fly ashes, can be ascribed to the much more porous microstructure of natural pozzolanas. Water reducing agents have diminished shrinkage in both concretes, either with or without fly ashes.~ ~ 5
4.3 Creep

60

160 TIME (DAYS)

260

360

Fig. 25. Influenceof creep of a high-limefly ash as a replacement;w/(c + f) = 0.38J l cretes with slightly different compositions designed to attain the same workability have shown that samples containing fly ashes had a specific creep approximately 50% higher than that found in fly-ash-free samples. ]]5

5 DURABILITY Though it might seem oversimplified, we could affirm that while the salient property of portland cements is their higher rate of hardening, the main property of pozzolanic cements is their greater resistance to chemical attacks. As is known, the durability of concrete depends on a number of chemical and physical causes, the most outstanding of which are: (a) carbonation, (b) leaching, (c) chlorides, (d) sulphates, (e) reactive aggregates, (f) freeze/thaw, (g) thermal variations As far as items (b)-(e) are concerned, pozzolanic cements behave better than portland cements, whereas with respect to items (a), (f) and (g) neither cement shows substantial differences. When concrete is attacked by external chemical agents, the first and most useful defence is impermeability. In this respect, as mentioned earlier in Section 3.4, pozzolanic cements behave far better than portland ones.
5.1 Carbonation

The deformation under load (creep) of concrete is an important time-dependent parameter involving structural mechanics inasmuch as creep influences the loss of pretension, the long-term deformation of structures and the load displacement from the concrete to the reinforcement. Factors affecting creep are various and can be distinguished as internal or external. Internal factors depend on the properties of concrete, while external ones are related to environmental conditions. In the first group the composition of concrete and therefore of the cement itself is found. Creep generally increases as the replacement for fly ash increasesJ z Sometimes, however, the effect is more marked for small than for large replacementsJ 8 Also in fly ash-containing concretes, creep increases as the strength decreases as well as load and time increase. Figure 25 ~0~illustrates the influence exerted by high-lime fly ashes on creep. With regard to creep, the behaviour of blended cements is substantially different from that observed for the strength and shrinkage of concretes. Substitutions up to 50% for fly ashes cause minor variations in strength and shrinkage but modify creep heavily. 11 Con-

The carbon dioxide contained in the air is potentially dangerous to concrete inasmuch as

204

Franco Massazza

CO 2 is capable of attacking all hydrated compounds of cement. In the cement-water-carbon dioxide system the stable phases are calcium carbonate, silica, alumina and iron oxide hydrates. 116 In dense and strong concretes, however, carbonation reduces porosity and permeability while increasing strength and resistance to sulphates. Carbonation is more detrimental to the existing reinforcement than to the concrete in itself inasmuch as it reduces the pH of the pore solution. As a consequence, should carbonation reach the reinforcement, the iron is no longer protected by the alkalinity of the pore solution and, in the presence of oxygen and humidity, it oxidises and becomes corroded. The reaction of cement paste with carbon dioxide can nonetheless improve several properties of concrete. In dense and compact concrete, actually, carbonation reduces total porosity and specific surface of cement pastes as well as permeability. ~3 Carbonation increases the resistance to sulphates z~7 and to the attack of aggressive ions in general. ]~s Carbonation is a time-dependent phenomenon but once this parameter has been fixed it will also depend on the following: cement content, w/c ratio, curing period, ambient humidity, partial pressure of CO2, temperature, microcracks,

that is to say, on all the factors affecting the density, compactness and permeability of concrete. According to some researchers,J ~')-~2J the depth and rate of carbonation also depend on the type of cement although more recent experiments have demonstrated that concretes made up of pozzolana-containing cements behave in the same way as portland cements provided that: (a) the curing period is long enough, (b) the strengths of concretes containing different types of cements are the same. Whenever the depth of carbonation is to be reduced, a correct curing is a primary requirement for all concretes but it becomes particularly important for all blended cements which have a relatively slow rate of initial hardening. As a matter of fact, if wet curing is limited to 1, 3 and 7 days, fly-ash containing cements carbonate to a greater extent than portland cements ~22 and espe-

cially if carbonation is forced (4% of CO~, H R = 5 0 % ) . 121 If the substitution of portland cement for fly ash is modest (16%), differences in the carbonation depth are also small. J2~ After 14.5 months the carbonation depth of concretes is sligthly lowered by the addition of 10% of silica fume. If the mixing water is reduced through a suitably devised plasticiser, so as to keep workability constant, a 20% replacement also makes carbonation depth diminish.12~ Carbonation depth definitely increases with increasing replacement of portland cement for silica fume. This is valid for both 1 day and 28 day curing but it should be remembered that the water content increases as replacement increases. ~25 These conclusions could be criticised inasmuch as they were obtained with concretes having different composition and strength or by accelerated carbonation procedures. It seems unreasonable to measure strengths on wet-cured specimens after 28 days and carbonation depth on wet-cured specimens after 1-7 days only and then stored in a dry ambient for a long time. If pozzolana -~2~' or fly-ash-containing ~27 cements are compared on the basis of the concrete strength, carbonation depth is shown to diminish linearly as the 28-day strength of the concrete decreases (Figs 2612j and 2712s). The converse relation between compressive strength and carbonation depth is not valid as in the case of silica fume because substitution up to 30% of the control portland cement makes the strength of both mortars and concretes, as well as carbonation depth, increase proportionally. ~ 29

5.2 Leaching
Water can decompose any of the hydrated compounds present in cement. ~3 For this reason,
Series A
3C CONTROL WATER-REOUCEO FLY ASH L1

Series B

o_
20
7-DAY MOIST CURED

0 Z

10

oo-~v MOmT

90-DAY MOIST CUREO (PLAIN, W-R)

2;0

2;0

3;0

3;0
(kg/m3)

CEMENT C O N T EN T

Fig. 26. Depth of carbonation versus cement content of fly ash concretes (acceleratedtesting).~ 2~

Pozzolanic cements
MATTHEWS

20 5

50 I ,~ OPC concrete - - - - Pfa concrete CC = correLcoeff. 4

el
S

n.
o. = 20

0~

u)

9 \
\

20

40

60

80

10J0

cc-o.87

"~

34
o

CC-0.79
IO-DA WAYER-C~ED/

cc.o.' c-o-AtR-STORED CUBES I

;3
2 1 0 0

I~

~
20

A
B

UNBRUSHED SAMPLES
I

10 20 30 40 DEPTH OF CARBONATION (ram)

50

40

60

80

100

DAYS IN ACID WATER

Fig. 27. Depth of carbonation versus 28-day compressive strength.12~

Fig. 28. Mass loss of concretes exposed to carbonic acid water. Mix A, OPC 312 kg/m3; mix B, OPC 170 kg/m3 +fly

ash 170kg/m3.135 if the concrete is porous and water is abundant or continually renewed, all the lime -- including the one present in silicates and aluminates -- will be leached and the residue will be made up of SiO2'xH20 and AI203"YH20. The leaching of lime increases both the porosity and the permeability of the cement paste. This increase, in turn, accelerates the leaching of the lime. The amount of lime extracted from pozzolanic cement pastes is far less than the amount of lime released by portland cement. TM Leached lime decreases as the pozzolana/clinker ratio increases. ~ 32 As compared to portland cements, hardened pastes made up of pozzolanic cements are more leaching-resistant due to three closely related reasons: (a) they contain only 3-6% of Ca(OH) 2 (Ref. 51) as against the 20-22% of portland cement pastes; (b) they contain more calcium silicates and aluminates in gel-like form: (c) they have reduced permeability. The above reasons reduce the progress of hydrolysis. 51 Although acid waters containing aggressive CO2 increase the rate of lime leaching, pozzolanic cements still behave better than portland o n e s . j33:34 Figure 28135 shows that as in the case of unbrushed samples the mass loss is c. 40% higher in portland concretes than in pozzolanic ones. Obviously, even with pozzolanic cements, the more delayed cement hydrolysis and lime leaching are, the less permeable is the concrete.

5.3 Chloride penetration

Both concrete and reinforcement can be harmfully affected by chloride action. In the first case the most important consequence is represented by the leaching of the free calcium hydroxide 136-~39 which makes concrete more porous and less strong. In this respect, pozzolanic concretes are more resistant to leaching because they are less permeable and the only leachable lime is the fraction not yet combined with pozzolana 139 and still accessible to water.14 More dangerous and harmful is the chloride which, when penetrating into concrete, reaches as far as the reinforcement. If the C1-/OH- ratio near the reinforcement steel dips below a treshold limit of 0.3,~41 passivation is destroyed and corrosion becomes inevitable, if water and oxygen are present. To protect reinforcement from chlorides, therefore, less permeable concretes and adequate cover thicknesses are required. In addition to these general precautions, efficacious protection is provided by the type of cement used, particularly by cements containing natural pozzolanas, ~42:43 fly a s h e s 137"144-147 or silica
fume.89,129,147-151

Figure 29129 shows how sensitively lower chloride penetration is in cement pastes containing silica fume. 15 There are several reasons underlying such good behaviour of pozzolanic cements. In general, these are to be ascribed to the slower rate at which chloride ions diffuse throughout pozzolanic cement pastes. 145,]48A49,151-~54The lower penetra-

206
A

Franco Massazza
4

g
UJ 0 n-

weeks

weeks

20 Silica fume

Table 11. Coefficients for diffusion of chloride ion into concretes ~ 5~

Sample
15

D(cm-'s ' x I0 '~)

1'65 3.24

Temp.

111//(

o o o

.J "r U.

(c)
Ptl cem. concr. (vibrated) Ptl cem. concr. (non-vibrated) 25 25 0'5 0'6

2; IO. .1 0 Z

10

nI.W O.

0 0 10 20 30

10

20

3o

lo

3'o

Pozz. cem. concr. (vibrated) Pozz. cem. coner. (non-vibrated)

1.05 2-26

25 25

0-5 0'6

SILICA FUME CONTENT (%)

Fig. 29. Effect of silica fume content on penetration depth of chloride ion? 29

Table 10. Coefficients for diffusion of chloride ion into cement pastes ~ ~ -~'

Sample
Portland cement

D(cm's / x lO"~) W/C Temp. Ref

1-23 2-51 4"85 0"83 0'90 0'97 10 25 40 10 25 40 155

0"4

Pozzol.cement

Portland cement (RHPC) Fly ash cement (22% PFA) Portland cement
(SRPC)

19.2 13.2 28.3 9'2 11"6 13'7 15.1

19-3 37-0 4.47

0-5

20 30 50 20 30 50 20
30 50 25

154

ferent conditions, it is quite clear how efficacious pozzolana-containing cements can be in hindering chloride ion penetration. The fact that the Decf coefficient decreases with increasing pozzolana content would recommend the use of pozzolanic cements, in which pozzolana amounts to approximately 33%, instead of using pozzolana-containing cements, in which the pozzolana content is lower and not well defined. Decf coefficients are still lower in concretes made with pozzolanic cements than in those manufactured with portland cements (see Table 11 ).~55

5.4 Sulphate
Calcium, sodium, magnesium and ammonium sulphates are, in increasing order of hazard, harmful to concrete as they can lead to concrete swelling and, consequently, cracking. The degree of deterioration depends on the intensity of the attack as well as on the characteristics of the concrete. CaS04 reacts with calcium aluminate hydrates thus forming expansive ettringite (3CaO'A120 3"3CaSO 4"32H20). Na2SO4 reacts with calcium hydroxide and forms expansive gypsum (CaSO 4- 2H20) which, in the presence of aluminates, may in turn lead to the formation of ettringite. MgSO 4 reacts with all cement compounds, thus decomposing cement and subsequently forming gypsum and, at a later stage, ettringite. Since the fundamental condition enhancing the formation of expansive compounds is the occurrence both of aluminate hydrates and calcium hydroxide in the paste, low C3A contents are needed for minimising the risk of sulphatic expansion. In Italy, pozzolanic cements are preferred 49 because the C 3 A content of the clinker is diluted by pozzolana and because the pastes contain lower amounts of Ca(OH)2. Ferric-pozzolanic

Portland cement (OPC)

156

Pozzol.cement (070 OPC/30 PFA) Slag cement (35 OPC/65 BFS) Portland cement (SRPC)

1-47 0.41 10'00

0-5

25

25
25

bility of the C1- ion into pozzolana containing cement pastes indiscriminately involves natural pozzolana] 52,~55 fly ashes 151A 53,154,156 and silica fume.~49.153 The effective diffusion coefficient Deee of chloride is reduced as the pozzolanic material content increases. For example, 30% substitution of a portland cement for fly ash decreases the Decf by one order of magnitude. ~53 Effective diffusion coefficients measured by several authors on cement pastes are given in Table 10.126 Though data are not directly comparable as samples were prepared in different ways and tested under dif-

Pozzolanic cements

207

cements, made with c 3 m - f r e e clinker are recommended in case of very strong attacks. Figures 3051 and 31 ]57 illustrate the positive action exerted by natural pozzolanas and fly ashes. Also a 20-25% substitution of an ASTM type F cement for different high-lime fly ashes decreases sulphate expansion. Concretes immersed in a 10% Na2SO4 solution for 27 months gave expansion values ranging between 0.008 and 0.116%, therefore substantially lower than those of the control c o n c r e t e ( 0 . 7 2 8 % ) . 15s,159 The effect of pozzolana is more or less marked depending on the type and quantity of pozzolana being used. The greater sulphate resistance of pozzolanic cements is probably related to the composition and structure of the pores in hydrated pastes. Also an interaction between sulphates and capillary pores is very likely to occur.
5.5 Sea water Sea water has a high salt content which is dangerous to the durability of both ordinary and
/~m/m +10000 Ptl cem. - - - - - - - ~ / Ptl cem.+10% pozz.

reinforced concretes. Although sea-water-induced deterioration is less intense than one would assume from its composition, CI-, SO42- and Mg 2+ still represent a danger and require a properly designed and manufactured concrete. An important contribution to concrete protection is afforded by pozzolanic cements. The major role played by these cements was stressed in 1951 during a survey of maritime structures built at several Italian harbours with pozzolanic m o r t a r s 16 and has since been repeatedly confirmed. 161 It has actually been shown that portland cements allow a chloride penetration from two to fivefold higher than that of blended cements. 162 F i g u r e 32,163 in which the variation in chloride concentrations with depth in sea walls is given, shows that the use of fly ashes in concrete can reduce C1- concentrations. It can thus be said that, history, experiments and research all recommend pozzolanic instead of portland cements for maritime works.
5.6 Alkali-aggregate reaction Over the past 50 years, several harmful chemical reactions between aggregates and portland cements have been noted. The most common reaction is the one occurring between some types of silica (opal, chalcedony and tridymite) and cement alkalis. From this reaction a gel made of alkaline and alkaline-earth silicates is formed which tends to absorb water and therefore to swell. There is no complete agreement about this conclusion; it is however assumed that the expansive reaction does not occur with portland cements containing less than 0.6% of Na:O alkali

z O

~ z + 5000
X w 0

" +

" +3o~ " - ~ / \ .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

200o

,;

~o

ioloo2;o

' ' ' ' 500 1000 2000 5000

STORAGE TIME (DAYS)

Fig. 30. Effect of substituting portland cement for pozzolana on the expansion of 1:3 mortar. Samples 2 cm 4 cm 25 cm stored in 1% MgS04 solution? ~

0.20

1 0 % s o a k test (1) (2) (3) (4) (5) 25% M-6498 25% M-6569 25% M-6730 25% M-6754 No fly ash

Q
.o

0.16

OPC concrete

0.1(

o c .~5

g
~ v z w FZ 0 U ~ nO ,.J 0 2000 0.10

\ \

m Pfa concrete

0.1;

) Z 0.08 4

\
0.05

0.04 -1 0.00 0 400 800 1200 1600 TIME (DAYS)

I 5

I 10

I 15

I 20

i 25

I 30

AVERAGE OEPTH OF SAMPLE (mm)

Fig. 31. Sulphate expansion of concretes containing lowcalcium fly ash (soak test)? 57

Fig. 32. Chloride concentration profiles for concretes from Aberthaw sea wail. ~63

208

Franco Massazza

equivalent. Unfortunately, technology and antipollution regulations in force in many countries make this target too expensive. ~59 On the other hand, the problem cannot be always solved by changing aggregates. A solution is however offered by cements containing fly ashes or natural pozzolanas. This might seem a contradiction because natural pozzolanas can contain up to 11% of alkalis and fly ash up to 5%. In practice, however, expansion is actually reduced and brought down within acceptable levels. 164-166 The final result will depend on the quality and quantity of the addition. Pozzolana and fly ashes shall therefore be chosen and their contents proportioned with the utmost care. 5t,]64,165 Figure 33167 highlights on the one hand the efficacy of pozzolanas in reducing expansion and on the other the different effects according to the type selected. Similar curves are given in Refs 168 and 169 for natural pozzolanas. In Italy there are only few examples of alkali/ aggregate reactions, despite the existence of reactive aggregates. This condition could partly be due to the wide use of pozzolanic cements. So far there is no established explanation for the better behaviour of pozzolanic cements with respect to the alkali-silica reaction. It has however been suggested that the presence of free ~ crystal7o line iT( Ca(OH)2 can be a prerequisite for the development of a destructive alkali-silica reaction. This condition can help explain why the inhibition of expansion requires a large replacement of portland cement for pozzolana. It also implies that a pozzolanic cement with a substantially higher pozzolana content must be used instead of pozzolana cement.

5.7 Frost action As a rule, concrete does not have a good frost resistance due to the presence of water-filled capillary pores. If water freezes, concrete increases in volume and tends to expand. The opposite happens when the temperature rises above 0C. Repeated freeze/thaw cycles accelerate the material's decay. A suitable protection against frost can easily be obtained by introducing microscopic air bubbles into concrete which are able to accommodate water being pushed forward by the ice in the process of being formed. For this reason, natural p o z z o l a n a s , 172 fly ashes j45 and silica fume ~49,t53 present in cement do not reduce frost resistance, provided that the concretes have a suitable entrained-air content and similar strengths. This behaviour is exemplified in Fig. 34 H)~ which shows that only a 50% substitution of portland cement for fly ashes ultimately decreases frost resistance. A large replacement of portland cement for silica fume (20-30%) makes the freeze/thaw resistance decrease also in the presence of e n t r a i n e d air. 173'174 The reason for this lies perhaps in the differences involving the specific surface as well as the factor of air void spacings in concretes.~7~ Laboratory test results have been confirmed in the field. In the Alpine regions of Italy, many dams built with pozzolanic cements are in an excellent state of preservation after decades of service despite the large number of freeze/thaw cycles they are subjected to yearly. ~75 As a matter of course,

100 y
1.5

D- 98 3: (~ Lu ~e 1.0 u) Z
0.,

Fly ash

a/c = 3.5

06
.J

/
II ""3

E Z 94 Oo 92 ~U ' ~ 0 5 i 200 0 i 400 i 600 % l 800 ~'30%

ao~

i / 1000 1200

100 200 TIME(DAYS)

3()0

NUMBEROF CYCLES
Fig. 34. Residual weight of air entrained concrete versus number of freeze-thaw cycles. Percentages of cement replacement for fly ash are indicated. Samples cured for 14 days before exposure. 1"~

Fig. 33. Expansion with age for specimens in which part of the aggregate had been replaced by an equal volume of pfa such that pfa/(c + pfa) = 0.3 (by weight)J 6y

Pozzolanic cements

209

when employing pozzolanic cements, one should remember that due to the slow initial hardening, frost exposure of pozzolanic concretes should be somewhat delayed as compared to portland cements.

6 CONCLUSIONS
The properties of pastes, mortars and concretes made up with pozzolanic cements are not qualitatively different from those obtained from portland cements. This is the reason why pozzolanic cements can be used in most applications as an alternative to portland cements. The differences between the properties of the two types are mainly quatitative and must be thoroughly known to attain the best performances. Compared to portland cements, pozzolanic cements show: lower early strengths, higher ultimate strengths, similar shrinkage, higher creep, lower heat of hydration, greater porosity, lower permeability, greater resistance to lime leaching, greater resistance to sulphate and sea water expansion, inhibition of the alkali-silica expansion, similar freeze/thaw resistance. All these properties are linked to differences involving the chemical and mineralogical composition of cement, the mechanism of hydration, the composition and microstructure of the paste. In conclusion, portland cements are preferred whenever the rapid attainment of high strengths is deemed useful or necessary, while pozzolanic cements find their best applications when requirements of durability are regarded as a priority. In most cases, however, both cements are interchangeable.

REFERENCES
1. Sersale, R., Structure des pouzzolanes et des cendres volantes et hydratation des ciments aux pouzzolanes et aux cendres volantes, in 7th Int. Congr. on the Chemistry of Cement(Paris, 1980), vol. 1, IV-1/1-21 2. Lea, EM., The chemistry of pozzolanas, in Proc. of the Syrup. on the Chemistry of Cements (Stockholm, 1938), 460-90

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