The use of spent-zeolites to produce mortars influence on physical and

mechanical performance
B. Sena da Fonseca
a
, A.S. Castela
a,b
, R. e!es
b
, R.". #uarte
a,b
, C. "alhano
c
, $.F. $ontemor
a
%
a
&C'$S-#'(, &nstituto Superior T)cnico, *+isboa, ,-./---, +isboa, 0ortu1al
b
'STBarreiro, &nstituto 0olit)cnico de Set2bal, 345/---, Barreiro, 0ortu1al
c
#ep. de Ci6ncias da Terra, Faculdade de Ci6ncias e Tecnolo1ia, *..+., 343/-7,8 Caparica, 0ortu1al
Abstract
This 9or: aims at studyin1 the potential of spent-zeolites as cement additi!e and its impact on rele!ant
mortar properties.
The spent-zeolites 9ere used as recei!ed and are mainly compound by Si and Al, sho9in1 1rain sizes
sli1htly hi1her than those of cement particles.
$ortars modified 9ith different amounts of spent-zeolites re!eal sli1htly hi1her air-permeability,
attributed to less fa!orable 9or:ability and hi1her absorbent capability. As conse;uence, C<3 penetration
is faster, but still the obtained results are ;uite satisfactory. The hi1her porosities also affect solution
upta:e and the concentration of dissol!ed chloride ions. =o9e!er, capillary absorption and dryin1 tests
re!eal that the spent zeolites sho9 acceptable 9ater transport properties. At hi1her spent-zeolites
additions, the effect of a
>
capture o!erlaps the detrimental effect of hi1her porosities concernin1
chloride penetration.
?hen the mortars are submitted to a re1ular cure procedure, at early sta1es the spent-zeolites cause a
decrease the compressi!e stren1th% the effect becomes less important at lon1er times. &n immersed
conditions @potable 9ater and 5AaClB the differences bet9een miCtures are ne1li1ible.
Key-words: spent-zeolites, mortars, compressi!e stren1th, curin1 conditions
1. Introduction
ApproCimately ,3-,--- tons of solid catalysts are used e!ery year, mainly by petroleum industry on its
operations to impro!e the refinery process efficiency . These catalysts 1radually lose their catalytic
acti!ity and are spent 9hen this catalytic acti!ity is eChausted . &t is estimated that only 37.---
5-.--- tDyear are re1enerated and re-used . Today, the construction industry is ma:in1 an effort to
incorporate different types of 9aste into concrete and mortars, contributin1 to materials di!ersification,
decrease of the final costs, and rationale use of ra9 materials . The catalytic crac:in1 catalysts are
mainly zeolites and e!en as spent-catalysts, they ha!e some attracti!e properties that promoted studies
concerned on their incorporation on cementitious miCtures. There are innumerous types of natural and
synthetic zeolites% these materials are porous and ha!e the ability to lose or bound 9ater, to adsorb
molecules by its adsorption properties or to act as molecular sie!es and cation eCchan1ers .
The pozzolanic acti!ity of zeolites and spent-zeolites and its influence on cement hydration has been
reported in literature. as 9ell as their impact, on the mechanical stren1th of blend elements , corrosion
protection and chloride diffusion beha!iour or carbonation resistance .
=o9e!er, some inconsistent results could be found. For eCample, Caputo et al. @3--4B studied the partial
substitution of ordinary 0ortland cement by t9o different types of spent synthetic zeolites in the
percenta1es of 7, ,- and 37A 9ith blendD9ater ratio of -.58 @9D9B. &t has been reported that the
compressi!e stren1ths are lo9er than those of reference specimens until the 34
th
day of cure. =o9e!er the
authors also state that at lon1er reaction times the mechanical resistance of blends may become
comparable or e!en hi1her than those of the reference. <n the other hand, 0erra:i et al. 3-,- found that
at the 34
th
day of cure, the blended mortars 9ith ,-A of natural zeolites display hi1her compressi!e
stren1th compared to reference mortars made from C'$ & .3.7R. After ,4- and 58- days of cure, the
blended specimens sho9ed lo9er stren1th compared to reference specimens.
Althou1h the zeolites and spent-zeolites are hydrated aluminosilicates, thus bein1 an interestin1 additi!e
incorporation in mortar and concrete, it seems that their particular features may cause enormous results
!ariability. The zeolites ha!e different particles sizes, porosities and SiDAl ratios. $oreo!er, particular
characteristics could be ac;uired durin1 its lifetime as catalyst, e.1., modification of its particles size and
porosity bloc:in1 by carbon-based 9astes. #ue to this dispersion, for its incorporation in cementitious
blends, the control of crucial factors such as zeolite characteristics and concreteDmortar manufacture
processes are critical to obtain coherent and reproducible results.
'!en focusin1 only on spent-zeolites, se!eral in!esti1ation approaches could be ta:en, by direct
replacement of cement , addition of other products @e.1. super-plasticizerB , usin1 thermal treatments or
1rindin1 . =o9e!er, most of these procedures may not be compatible 9ith the costs of final product, as
9ell as, loses much of the en!ironmental benefit due to eCtra ener1y demand.
By these reasons, the present 9or: aims at contributin1 for the :no9led1e about the impact of use a spent
zeolite in cementitious mortar miCtures by direct replacement of cement, 9ithout any pre!ious treatment
of the zeolites, 9hich could increase the costs of its use.
2. Experimental plan
2.1. Spent-zeolite study
The spent-zeolites po9der as-recei!ed, 9ere submitted to se!eral tests to assess their physic-chemical
properties.
A scannin1 electron microscopy @S'$B JEOL JSMT330A 9as used to assess the morpholo1y of spent-
zeolite particles, as 9ell as, to assess the semi-;uantitati!e chemical composition. +oss on &1nition @+<&B
9as calculated by 9ei1ht loss after heatin1 the samples at ,---EC for 3 hours.
The particle size distribution of zeolites po9der 9as studied by usin1 t9o different techni;ues. The
fraction of particles 9ith dimensions F,--Gm 9ere analyzed usin1 dry sie!in1 techni;ue @sie!es of
'uropean SeriesB and 1ra!imetric measurements. The fraction of particles 9ith inferior dimension 9as
analyzed by laser diffraction particle size analyzer @Mastersizer 2000). The complement of these t9o
techni;ues enabled to measure the 9hole ran1e of the zeolite particles sizes.
The e!aluation of pozzolanic acti!ity 9as performed accordin1 to the methodolo1y described in . A
saturated solution of Ca@<=B3 9as prepared and :ept under stirrin1 at a temperature of .- ,HC 9hile
measurements of conducti!ity 9ere made until a constant !alue 9as reached @IJmSDcmB. Thereafter 71 of
zeolite po9der 9ere added into the solution and the conducti!ity measurements continued for 8- minutes.
2.2. Specimens preparation
The reference mortar specimens 9ere prepared usin1 0ortland cement type C'$ & .3.7R, natural fine
sand, natural coarse sand and potable 9ater in the 9ei1ht relation of ,D-..4D3.73D-.8-, respecti!ely. To
study the role of spent-zeolite reuse in mortars manufacture, other specimens 9ere prepared 9ith the
same miCture relation but replacin1 5, 8, / and ,39tA of cement by this spent catalyst @table ,B, a
synthetic spent zeolite po9der from the crac:in1 catalytic units @Sines refineryB. The sand used 9as
eCploited in the re1ion of SeiCal in 0ortu1al and has a siliceous nature, mostly composed by ;uartz 1rains.
After the preparation of each miCture and before the castin1, slump flo9 tests 9ere performed accordin1
AST$ C,.5J-,5 to e!aluate the 9or:ability of fresh pastes, the results are depict in table ,. Thereafter,
the miCtures 9ere cast in prismatic @,8C.C.cmB and cubic @.C.C.cmB moulds for physical and
mechanical tests and in cylindrical @5-C,7cmB moulds for chlorides mi1ration and air-permeability @:TB
studies. All the specimens 9ere demoulded after 3. hours of cure and part of prismatic specimens 9ere
submitted to three different en!ironments of cureK immersion in potable 9ater% immersion in 5A aCl
solution and at 3-HCD87AR=.
The remainin1 non-cylindrical specimens 9ere :ept in a chamber at 3-HC and 87A R= until the 34
th
day.
The cylindrical specimens 9ere cut at the J
th
day of cure 9ith a circular sa9 in slices of 7- mm to
perform the tests described belo9.
Table , $iCtures proportions and 9or:ability.
Reerence !ement
"ine
Sand
!oarse
Sand
Additi#e $ater $%! $%!&Additi#e
$or'ability
(cm)
!ontrol ,.-- -..4 3.73 -.-- -.8- -.8- -.8- 35./
*+ -./J -..4 3.73 -.-5 -.8- -.83 -.8- 33./
,+ -./. -..4 3.73 -.-8 -.8- -.8. -.8- 33.8
-+ -./, -..4 3.73 -.-/ -.8- -.88 -.8- 33.-
12+ -.44 -..4 3.73 -.,3 -.8- -.84 -.8- 3,.5
2.*. !ompressi#e stren.t/ tests
To e!aluate the role of spent-zeolites in cure process, the compressi!e stren1th 9as assessed in specimens
cured in an en!ironment of 3-HC and 87A R= after J, 34 and /- days after castin1. To e!aluate the
influence of the incorporation of spent-zeolites in cure of immersed mortars, compressi!e tests 9ere
performed in specimens cured on potable 9ater @from public 9ater systemB and on a solution of 5A aCl,
after 34 and /- days.
The compression tests 9ere made in a $atest press 9ith t9o independent load cells @maCimum measurin1
ran1e of 37-: and ,7:B and touch screen control unit. At least three specimens of each condition 9ere
tested and all 9ere submitted to a constant loadin1 rate of ,.7 $0aDsec.
2.0. 1/ysical and durability tests
All the determinations described belo9 9ere performed on specimens a1ed bet9een 34 and /- days.
The 9ater absorption of each type of mortar 9as determined by !acuum immersion method, the
specimens stayed under !acuum for 3. hours, maintainin1 the !acuum it 9ere immersed in distilled 9ater
for 3. hours and after this period the pressure 9as increased until atmospheric pressure and :ept under
9ater for another 3. hours. "ra!imetric measurements of specimens 9ere made in its dry, saturated state
and under9ater. The procedure is described in the specification +'C '5/7 .
The 9ater absorption by capillary suction 9as performed in prismatic specimens @J-C.-C.-mmB 9ith
lateral faces sealed 9ith an epoCy coatin1. Three specimens of each miCture 9ere placed inside a closed
container upon a pile of filter papers of approCimately ,- mm thic:ness and partially immersed in 9ater.
This setup allo9s the material to absorb 9ater up9ard by capillary forces . The mass of specimens 9ere
recorded after ,, 7, ,-, 3-, 5- and 8- minutes, subse;uent measurements 9ere ta:en e!ery hour up to 4
hours after the first contact 9ith 9ater. The initial capillary absorption !alues @SiB 9ere calculated
accordin1 the results from the first day. To be possible to calculate the secondary absorption @SsB, the
succeedin1 measurements 9ere ta:en once a day in the follo9in1 4 days.
After9ards, the same specimens 9ere saturated by full immersion to perform the e!aporation tests, a
chamber at 37HC 9ith an e!aporation potential of -., mmDh 9as used. The 1ra!imetric measurements
9ere carried out e!ery hour durin1 the first 4 hours and then t9ice a day in the first 9ee:.
Cylindrical slices 9ith 7 cm thic:ness 9ere used for the assessment of air-permeability throu1h the test
method de!eloped by Torrent @,//3B . Four measurements in different surfaces 9ere ta:en from fairly dry
cylindrical specimens of each miCture. This test starts 9ith the creation of a !acuum inside a t9o chamber
cell, 9hich is sealed on the material surface by means of concentric rubber rin1s, creatin1 t9o separate
chambers. ?hen !acuum reaches 5- mbar, the !al!e of inner chamber is closed. The air in the pores
flo9s throu1h the material into the inner chamber, raisin1 its pressure. The rate of pressure rise 9ith time
is directly lin:ed to the coefficient of air-permeability @:TB of the material surface . The :T !alue on
concrete ha!e re!ealed some interestin1 relationships 9ith other transport and durability properties .
0rismatic mortars 9ere prepared by isolatin1 four opposite surfaces 9ith aluminum tape for accelerated
carbonation test. The specimens 9ere placed on a carbonation chamber 9ith a concentration of 7A of
C<3 at 3-HC and 87A R= up to . months. To measure the front of carbonation depth the specimens 9ere
crac:ed in three parts, the crac:ed surfaces 9ere sprayed 9ith an indicator solution, ,3 measurements in
each specimen 9ere ta:en.
Considerin1 that C<3 diffusion is based on Fic: la9, the carbonation rate is proportional to the s;uare
root of the time of eCposure and the accelerated carbonation coefficients @:caB could be achie!ed usin1 the
e;uation , K
@,B
9here X is the carbonation depth @mmB and t is the eCposure time @yrB.
The non steady state mi1ration test 9as performed by usin1 cylindrical mortars @,7-C7-mmB saturated
9ith lime solution. A t9o compartment cell 9as attached on each specimen% one side 9as filled 9ith a
,-A aCl solution @cathodic solutionB and the other 9ith a ,.3A a<= solution @anodic solutionB. Spiral
electrodes of stainless steel 9ere used in each compartment to impose an initial electric potential of 5- L.
The electric current 9as read and the potential adMusted accordin1 +'C '.85-3--. recommendations.
#ue to the similarity amon1 specimens, in all cases an electric potential bet9een ,-L and 3- L 9as
applied for 3. hours. Thereafter, each specimen 9as split and the crac:in1 surfaces 9ere sprayed 9ith a
-.,$ A1<5 solution to allo9 the measurements of the chloride penetration depth, made in 58 points.
The non-steady-state mi1ration coefficients @#nsB 9ere calculated by usin1 the e;uation 3 .
@3B
9here, T is the temperature a!era1e in solutions @HCB, L is thic:ness of the specimen @mmB, xd a!era1e
!alue of the penetration depths @mmB, t is the test duration @hB and U is the absolute !alue of the applied
!olta1e @LB.
*. Results and 2iscussion
*.1. Raw materials and paste wor'ability
S'$D'#S 9as used to assess the elemental chemical composition and to assess the morpholo1ical
features of spent-zeolites. The results re!ealed sphericalDelliptic particles and some particles clusters, as
can be seen in micro1raph of fi1ure ,.
Fi1ure 3 sho9s the particles size distribution of cement, spent-zeolites and both types of sand in the
miCture proportions. The three components ha!e sli1htly distinct 1ranulometric cur!es patterns and in
1eneral the particles sizes are si1nificantly different. The table 3 eChibits the 1ranulometric parameters of
each component. The spent-zeolites are mainly composed by particles 9ith diameters bet9een 3--7--
Nm, 9hereas the cement @C'$ & .3.7RB ha!e particles 9ith sizes ran1in1 bet9een -..-5-- Nm. This
contrast is ;uite noticeable by mean 1rain size !alue @d7-B, the cement ha!e a mean 1rain size !alue of 53
Nm and the zeolites a !alue of 4J Nm, 9hich is almost 5 times hi1her. To e!aluate the particles 1radation,
the uniformity coefficient @CuB and coefficient of cur!ature @CcB 9ere calculated. As eCpected, the results
ma:e clear that the cement is considered a 9ell-1raded material% contrarily spent-zeolites are uniformly
1raded, i.e., its particles sizes are much more similar.
Fi1ure , S'$ microphoto1raphy sho9in1 the morpholo1y of the zeolites
Fi1ure 3 #istribution of 0articles size distribution in !arious mortar components.
Table 3 "ranulometric parameters from miCture components.
d13 (4m) d*3 (4m) d53 (4m) d,3 (4m) !u !c
Sand 3/-.-3 ./7.58 J8-.3. 4/5.5/ 5.-4 -./7
Oeolites .7.54 88.37 48./7 /J.-/ 3.,. ,.--
Cement .../ ,4.5- 5,.4/ 5/.7- 4.4, ,.4/
The chemical composition of spent-zeolites 9as proposed considerin1 the '#S analysis - the maMor
elements found 9ere Al, Si, <. =o9e!er other minor elements 9ere found as 9ell. Based on this
analysis the chemical composition is presented on table 5. The spent-zeolites seem mainly
composed by Si<3 and Al3<5 and residual amounts of other compounds. Accordin1 to literature
zeolites are crystalline aluminosilicates defined by a typical frame9or:, 9hich consists mainly of
Si<. and Al<. tetrahedra connected t/rou./ oxy.en atoms6 t/e tetra/edra are lin'ed in a
manner t/at produces lar.e pores and channels. Their dimension is associated to the number of
Si<. or Al<. tetrahedra in the rin1 9hich circumscribes the pore . Typically, the pores !olume !aries
bet9een -.,- and -.57 cm
5
D1, 9hich means, !ery lar1e surface areas . &n particular, the porous
net9or: of used zeolites @fauMasiteB is composed by cuboctahedral ca1es lin:ed by oCy1en atoms to
form lar1er ca!ities, 9hich in turn are tetrahedral connected producin1 a unit cell 9ith ei1ht
supercages and ei1ht sodalite ca1es . These c/aracteristics .i#e to t/ese zeolites excellent
molecular sie#in. proprieties.
&n 1eneral, the zeolites also ha!e 1ood ion-eCchan1e capacities and such ability !aries 9ith the SiDAl
ratio, lo9er SiDAl ratio increases the ion-eCchan1e capability . The SiDAl ratio !aries from one fauMasite to
another , the used zeolites are aluminum-rich fauMasite, ha!in1 a SiDAl atomic ratio sli1htly inferior to ,. &t
has been su11ested that hydration reactions are controlled by silica and alumina contents @amon1 othersB
and hi1her SiDAl ratios produce faster reactions .
7able * 8 Estimated c/emical composition in terms o oxides percenta.e.
Si92 Al29* "e29* :.9 :n9 !a9 ;a29 K29 S9* <.9.I.
A ...83 ./.-, ,..3 -.-. ,.5- -.74 -.-8 -..7 -.75 3.38
+ar1e ;uantities of Si<3 and Al3<5 are typical from pozzolanic materials% these oCides react 9ith Ca@<=B3
to form additional C-S-= 1el 9ith a hydraulic binder character , increasin1 the mechanical stren1th ,
durability and sulphate attac: resistence . The AST$ C8,4-,3 specifies the chemical re;uirements of fly
ash and natural pozzolans as supplementary cementitious materials, the materials are classified by the
!alue resultin1 from the sum of Si<3, Al3<5 and Fe3<5 9hich should be superior to J-A, by the +<&
9hich should be less than 8A and the S<5 maCimum content admissible is 7A. #espite the studied
particles are not classified as fly ash or natural pozzolan, the same primary and limitati!e criteria could be
applied. The spent-zeolites are mainly comprised by these three oCides satisfyin1 the first condition, no
other compounds 9ere found in si1nificant amounts, includin1 the detrimental S<5 and the +<& is lo9er
than limit !alue. Therefore, the material meets all of these re;uirements.
There are se!eral methods to study the pozzolanic acti!ity of materials, +2Can et al. proposed the method
described before, in 9hich the conducti!ity !ariations of a saturated lime solution reflects the de1ree of
pozzolanic reaction bet9een Ca
3>
and <=
-
ions and the material in study. This method has been
successfully used to assess the pozzolanic acti!ity of se!eral types of materials, includin1 different types
of zeolites .
Fi1ure 5 eChibit the conducti!ity e!olution of the saturated lime solution after addin1 the zeolites po9der.
&n the early sta1es a si1nificant decrease on electrical conducti!ity of the suspension is obser!ed. This
beha!ior is eCplained by a decrease of Ca@<=B3 concentration in solution due to the pozzolanic reaction.
Accordin1 to +2Can et al. @,/4/B , the 1reater the reduction, the better the pozzolanicity of material and if
the conducti!ity decreases more than ,.3- mSDcm on the firsts 3 minutes, the material has 1ood
pozzolanicity, 9hich is the case - decrease of 3.3, mSDcm after 3 minutes. #espite not mentioned in *zal
et al. @3-,-B and Rosell-+am et al. @3-,,B , the capture of some ions from initial solution by the zeolite
particles could also influence its conducti!ity, ho9e!er it is belie!ed that these phenomenon has a minor
impact on the o!erall decrease of conducti!ity, hence the zeolites ha!e indeed rele!ant pozzolanic
acti!ity. These findin1s are in accordance 9ith pre!ious in!esti1ations, 9here the pozzolanic acti!ity of
similar zeolites 9as studied by other methods .
#ue to these reasons, and from a theoretical perspecti!e, the addition of spent-zeolites po9der 9ithout
any treatment to cementitious miCtures is appropriate and should impro!e the o!erall performance of
cured elements.
<n the other side, the fresh blends sho9 a decrease of spread diameter 9ith the increasin1 incorporation
of spent-zeolites @table ,B, from 35./ cm in control paste to 3,.5 cm in ,3A paste, 9hich re!eals a
reduction of 9or:ability and compaction. This is eCplained by a set of t9o reasonsK iB the lar1e surface
area of zeolites 9hich is the basis of their hi1hly absorbent nature and iiB the lar1er particle size of
zeolites in relation to cement particles.
To a!oid this issue, some procedures could be ta:enK add more 9ater in the miCture decreasin1 the
mechanical stren1th of hardened mortar , use of superplasticizers increasin1 the costs or reduce the
particles dimension by 1riddin1, 9hich also increases the manufacture costs and ener1y consumption. The
use of more 9ater or need of superplasticizers 9ill introduce other !ariables in the miCtures that could
hide the direct and real effect of cement replacement by zeolites and ma:e more difficult any
interpretation about its role. Furthermore, one important assumptions of this 9or: is to study a product
9ith a lo9er manufacture price and en!ironmentally friendly.
Fi1ure 5 '!olution of lime solution conducti!ity after addin1 the zeolite po9der.
*.2. :ec/anical Stren.t/
Fi1ure . sho9s the e!olution of mortars compressi!e stren1th alon1 cure at 3-HC and 87A of R=. All
miCtures, from the J
th
day to 34
th
days of cure re!eal a important stren1th increase. After9ards a
stabilization occurs and no si1nificant modifications could be un!eil until at least the /-
th
day of cure. The
de!elopment of cement mortar stren1th occurs throu1h a series of hydration reactions. The hydration of
each compound of 0ortland cement ta:es place independently and thus the reactions are not linear
throu1h time. The tricalcium silicates @@Ca<B5@Si<3B - C5SB and dicalcium silicates @@Ca<B3@Si<3B - C3SB
are maMor compounds% the C5S contributes for stren1th de!elopment on first month, 9hile C3S reacts
slo9ly and is responsible for the lon1-term stren1th . Amon1 others, both phases react 9ith 9ater and
form calcium hydroCide @Ca@<=B3B and a calcium silicate hydrate 1el @C-S-=B accordin1 to K
3@Ca<B5@Si<3B > =3< P @Ca<B5@Si<3B3 Q .@=3<B > 5Ca@<=B3 @5B
3@Ca<B3@Si<3B > 7=3< P @Ca<B5@Si<3B3 Q .@=3<B > Ca@<=B3 @.B
The partial substitution of 0ortland cement by spent-zeolites produces a considerable stren1th diminution
at the early sta1es of cure @at J daysB. As the zeolites percenta1e increases, an almost linear decrease on
compressi!e stren1th 9as found. Ta:in1 as reference the !alue of reference mortars, the stren1th
reduction !aries bet9een JA in specimens 9ith lo9er zeolites content @5AB and 37A in specimens 9ith
the hi1her zeolites content @,3AB.
Additional hydration reactions o9in1 to pozzolanic zeolites incorporation are li:ely. Oeolites react 9ith
calcium hydroCide erst9hile produced and 9ater to form supplementary C-S-= and hydrated aluminate
phases . Therefore, it 9as eCpected that the presence of zeolites 9ould result in a stren1th increase%
ho9e!er, the pozzolanic materials at ordinary temperatures delay the reactions and initially it could
beha!e as an inert a1ent . Conse;uently, as displayed, the partial substitution of cement 1enerally reduces
the hardenin1 rate in early sta1es .
Fi1ure . Compressi!e stren1ths of mortars at different a1es.
At lon1er curin1 times, 34 days or e!en /- days, the specimens containin1 zeolites sho9 lo9er
compressi!e stren1th compared to reference specimens. e!ertheless, at this sta1e the maMor stren1th
raise occurs in specimens 9ith hi1her zeolites content and the stren1th reduction in specimens 9ith ,3A
of zeolites replacement is only around ,-A. This hi1hli1hts some pozzolanic acti!ity and additional
hydration reactions. The results are interpreted to be a conse;uence of 9orst 9or:ability and compaction,
o9in1 to particles 9ith lar1e surface area that consume more 9ater durin1 the miCin1 and the lar1er size
of particles. As it 9ill be seen later, this fact results in more porous mortars and presentin1 lo9er
mechanical stren1th. Any9ay, it seems unanimous that stren1th reduction due to cement replacement by a
pozzolanic material is in any case lo9er than the obtained by usin1 an inert filler, such as limestone @9ith
e;ui!alent 1ranulometric featuresB .
&n 9hat concerns to the influence of curin1 en!ironment, fi1ure 7 sho9 the comparati!e results of
compressi!e stren1ths after 34 and /- days under 3-HCD87A R=, immersion in tap 9ater @at 3-HCB and
immersion in 5A aCl solution @at 3-HCB.
After 34 days the mortars 9ithout cement replacement and immersed cures re!eal lo9er compressi!e
stren1ths, especially the cure on salt solution 9hich has ,7A less stren1th.
As seen before, the cement replacement produces in 3-HCD87AR.=. cured specimens, a si1nificant
decrease at the 34
th
day% contrarily, in the case of immersed specimens such decrease is not so e!ident and
all mortars cured under immersed conditions in a 5A aCl solution display compressi!e stren1ths around
.7 $0a.
&n fact, is consensual that 9ater has an important role in hydration reactions% it influences the C-S-=
structure and beha!ior in a manner that C-S-= becomes more stable and resistant. <n the other side, the
slo9ness of pozzolanic reactions re;uired a eCtended moist cure for a total ad!anta1e on its use .
&nterestin1ly, both cures re!eal a si1nificant increase on mechanical stren1th from the 34
th
to the /-
th
day.
Furthermore, also in both, the differences bet9een miCtures are minimal 9ith no rele!ant pattern due to
the increasin1 amount of zeolites, i.e., after /- days of 9ater curin1, a mortar containin1 spent-zeolites
ha!e de!eloped, at least, e;ui!alent stren1th 9hen compared to that found in cement mortars. &t seems
that in these cases, the pozzolanic acti!ity has compensated someho9 the stren1th loss o9in1 to the
poorer 9or:ability.
The stren1th of mortars cured under9ater continues to increase e!en after 34 days, such increase is e!en
more noticeable 9hen spent-zeolites 9ere added. These findin1s are in accordance 9ith statements found
in literature .
&n any case, the presence of aCl affects ad!ersely the mortars stren1th @9hen comparin1 both immersed
curesB, its eCistence cause the formation of C5A Q CaCl3 Q ,-=3< and some loss in stren1th could happen .
Fi1ure 7 - Compressi!e stren1ths of mortars at different curin1 conditionsK aB after 34 days cure% bB after
/- days cure.
*.*. 1/ysical and durability properties
The performance and durability of hardened cement materials is stron1ly influenced by its ability to
mana1e the in1ress of harmful a1ents in terms of ;uantity and penetration depth. Althou1h related, the
intrinsic physical and chemical characteristics are t9o maMor aspects controllin1 its de1radation
susceptibility.
The 9ater absorption and permeability are ruled by porous microstructure and 1i!es primary indications
about durability once it controls the rate of entry and mo!ement of a11ressi!e chemicals throu1h 1as or
moisture form. These properties 9ere assessed in the !arious mortar miCes and are displayed on table ..
The 9ater absorption @AbB mean !alues are in all specimens bet9een 3- and 33A, bein1 the 0ortland
cement specimens the ones that present the lo9est !alues. These results are in accordance 9ith the
mechanical beha!ior and pre!ious statements% this performance 9as eCpectable since the replacement of
cement by lar1er and more absorbent particles results into 9orse initial compaction and conse;uently
more !oids inside the mortars. e!ertheless, the 9ater absorption increases as conse;uence of
spent-zeolites incorporation, bein1 in all cases inferior to ,-A 9hen compared to reference specimens,
9hich are minor de!iations.
&n 9hat concerns to air-permeability @:TB, the differences are apparently much more si1nificant% the
replacement of cement by ,3A zeolites produces more than t9ice the !alue of control specimens.
=o9e!er, such analysis is misleadin1 and the data interpretation should be made accordin1 the
specificities of the method . There are 7 1rades of Rco!ercreteS ;uality based on coefficient of air-
permeability that are specified% the ;uality is considered eCcellent 9hen :TT-.-,% !ery 1ood 9hen
-.-,F:TF-.,% fair 9hen -.,F:TF,% poor 9hen ,F:TF,- and !ery poor 9hen :TF,- . Based on this
assumption, the replacement of cement by spent-zeolites up to ,3A sli1htly increases the air-permeability
and despite the differences, all miCes fall into the R!ery 1oodS ;uality inter!al. Therefore, in practical
terms its performance is e;ui!alent.
Fi1ure 8 eChibit the mean cur!es of 9ater absorption of each miCture, they present fairly similar
beha!iors. The !alues of initial capillary absorption @SiB are bet9een -.55 and -..4 :1Dm.h
-.7
, 9hile
secondary absorption @SsB are in the ran1e bet9een -.,J and -.3, :1Dm
3
.h
-.7
. The results re!eal a trend to
intensification of capillary suction 9ith increasin1 amount of spent-zeolites. e!ertheless, all mortars
miCtures present capillary absorption !alues belo9 -.7 :mDm.h
-.7
, considered the threshold !alue in '
,7-.-5 9hich specifies the performance re;uirements for structural and non-structural repair products.
Fi1ure 8 - ?ater absorption by capillary suction of
all mortars miCtures.
Fi1ure J '!olution of residual amount of 9ater
9ithin the specimens dryin1 cur!es.
&n construction materials the dryin1 characteristics are reflected by initial e!aporation @#&B, 9hich is
mana1ed by eCternal conditions and ob!iously by the eCternal porosity, i.e. the area of 9ater surface in
contact 9ith the atmosphere. Cimentitious materials such as concrete or mortar, ha!e lo9 li;uid
conducti!ity and 1enerally sho9 a short first dryin1 phase% its determination corresponds to the ne1ati!e
slope of the initial linear part of dryin1 cur!e usin1 at least 7 successi!e ali1ned points. Fi1ure J, sho9 a
;uite short first phase and its calculation usin1 only 5 points 9ould be inaccurate and meanin1less. Thus,
it 9as considered that the second dryin1 phase characterizes 9ell the o!erall dryin1 beha!ior of mortars.
This dryin1 coefficient 9as calculated throu1h linear re1ression of the ,- points after the first day of
eCperiment and the results are eChibit in table .. $inor differences are obser!ed bet9een miCtures. The
!alues are all 9ithin the same order of ma1nitude, ran1in1 bet9een them not more than ,4A, 9hich could
not be considered si1nificant !ariations.
Accordin1 to the abo!e results, the partial cement replacement by spent-zeolites produces mortars 9ith
acceptable hydric and transport properties and from this perspecti!e no si1nificant modifications are
eCpected in terms of 9ater transport and residence permanency 9hich is a 1ood indicator about the mortar
beha!ior 9hen in ser!ice.
Concernin1 carbonation resistance, for the same time inter!al, deeper carbonation fronts, 9ere measured
for mortars 9ith spent-zeolites compared to control specimens. This beha!ior has been attributed to a
reduction of portlandite @al:alineB reser!es 9ithin the mortars, o9in1 to the additional pozzolanic
reactions. This produces a lo9er bufferin1 capacity a1ainst carbonation . =o9e!er, in the present case,
this assumption is less li:ely. "i!en the increasin1 9ater absorption @related to porosityB and air-
permeability these results 9ere eCpected, probably in a 1reater eCtent, because hi1her porosity induces
easier C<3 penetration into the material. &n fact, the :T !alues correlates 9ell the carbonation resistance
and based on abundant eCperimental data a relationship has already been established . '!en considerin1
the reco1nized dispersion on these relations, the ran1e of !alues determined in both tests are in 1ood
a1reement 9ith those found else9here .
The non steady state chloride diffusion coefficients sho9 that the mortars 9ith percenta1es of spent-
zeolites up to /A display e;ui!alent chloride resistance in comparison to reference mortars. The
,3A mortars ha!e a relati!ely lo9er diffusion coefficient, re!ealin1 hi1her chloride bidin1 capacity.
0re!ious results ha!e su11ested a porosity increase as the amount of zeolites increases and therefore
it 9as eCpected a decrease on chloride biddin1 resistance. =o9e!er, since non-steady state diffusion
coefficient is affected by both, porosity and bindin1 capacity , the achie!ed !alue is consistent 9ith
the hi1her o!erall Al3<5 content 9hich produces hi1her chloride bindin1 capacity of mortars 9ith
si1nificant amount of spent-zeolites. The aluminum presence imparts char1e defects 9hich are
compensated by eCternal cations @a
>
B , its capture circumscribe the Cl
-
penetration due to ionic
attraction bet9een both. &t seems that in the mortars 9ith hi1her spent-zeolites content this action
o!erlaps the detrimental effect of hi1her porosities a1ainst chloride penetration. At lo9er
percenta1es, the results su11est that the chloride bindin1 capacity of the blend has been rapidly
eChausted, re!ealin1 e;ui!alent resistance to reference mortars.
Table . $ortars properties estimated from eCperimental measurements.
Ab
(+)
'7
(x13
-1,
m
2
)
Si
('.%m
2
./
3.5
)
Ss
('.%m
2
./
3.5
)
2II
('.%m
2
/
3.5
)
'ca
(mm%yr
3.5
)
2ns
(x13
-2
m
2
%s)
3+ 3-.35U-.// -.-34U-.--5 -.55U-.-7 -.,JU-.-. -.-.JU-.--7 3J..5J 3,.8
*+ 3,.8/U-.43 -.-58U-.--. -.5JU-.-8 -.3-U-.-3 -.-7-U-.--5 3/.J-8 3,.4
,+ 33.3,U-.43 -.-.7U-.--5 -..3U-.-, -.3-U-.-, -.-.4U-.--7 5,./8J 33.,
-+ 3,.75U-..J -.-./U-.--. -.5/U-.-. -.,/U-.--@.B -.-75U-.--3 5-.,53 3,.J
12+ 3,./7U-.-/ -.-8.U-.--8 -..4U-.-, -.3,U-.--@5B -.-..U-.--8 5-.J/8 ,4.-
0. !onclusions
Spent-zeolites particles mainly compound by Si<3 and Al3<5 ha!e different 1ranulometric sizes 9hen
compared to cement particles, includin1 a lar1er mean 1rain size. This fact, to1ether 9ith its hi1hly
absorbent capacity, ma:es the 9or:ability of miCtures less fa!orable. At curin1 conditions of 3-HC and
87A R=, the replacement of cement 9ith spent-zeolites, at early sta1es decreases the compressi!e
stren1th, 9hich is less remar:able at lon1er times due to delayed hydration reaction.
&n immersed conditions of cure @potable 9ater and 5A aClB, the differences bet9een miCtures are
minimal o9in1 to the interaction bet9een zeolites and 9ater. &n saline en!ironments the mortars
containin1 spent-zeolites de!eloped at least e;ui!alent stren1th 9hen compared to that found in control
mortars.
The 9ater absorption of mortars is sli1htly affected by the partial cement replacement by spent-zeolites,
ho9e!er, it produces mortars 9ith fairly acceptable hydric and transport properties. From this perspecti!e,
no si1nificant modifications are eCpected in terms of 9ater transport and residence in practical terms.
"i!en the increase of 9ater absorption and air-permeability the C<3 penetration is faster, still the obtained
results are ;uite satisfactory and accordin1 to the standardized :T ;uality 1rades, all miCtures fall 9ithin
the !ery 1ood ;uality ran1e.
The ion-eCchan1e properties allo9s eCchan1e of aluminum promotin1 the capture of a
>
. This effect
reduces the free Cl
-
content due to ionic attraction bet9een both. &n mortars 9ith hi1her spent-zeolites
contents this action o!erlaps the preMudicial effect of hi1her porosities a1ainst chloride penetration.
Therefore, cement replacement by spent-zeolites do not add additional ris: under eCternal chloride attac:.
The partial replacement of cement by spent-zeolites is technolo1ically feasible and some ne9 interestin1
possibilities 9ere found, amon1 9hich are the under9ater applications. Thus, it is a 1ood solution to
reduce the final product costs, as 9ell as, a 1ood solution to reuse a 9aste produced on lar1e scale.
Ac'nowled.ments
The authors are 1rateful to FCTVFundaWXo para a Ci6ncia e Tecnolo1ia @0T#CD'C$D,-7.3JD3--4B for
the financin1 of this in!esti1ation and to "A+0 'ner1ia for pro!idin1 the spent-zeolites.
5. =iblio.rap/y