Natural Zeolites, an option as a partial replacement for Ordinary Portland Cement, a Review R eview Cristian A. Flórez a , Jorge Iván Tobón b , Oscar J. Restrepo c. a,b,c
Departamento de ateriales ! inerales, "r#po del Cemento ! ateriales de Constr#cción, $niversidad %acional de Colombia.
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%at#ra %at#rall zeolit zeolites es are are *!drat *!drated ed al#mi al#min#m n#m silica silicate te minera minerals ls it* it* a tetra*edral cr!stalline str#ct#re *ic* ma-e t*em di//erent /rom ot*er s#pplementar! cementitio#s materials li-e /l! as*, silica /#me among ot*ers. )ome advantageo#s properties o/ zeolites are t*eir reg#lar 0*one!comb1 str#ct#re, large *ig* s#r/ace area, large inner speci/ic s#r/ace area, #ni/orm size pores, good strong adsorption capacit!, among ot*ers. 2e#landite and clinoptilolite bot* monoclinical zeolite minerals are t*e most ab#ndant zeolites t!pes in nat#re. 3eolites are pozzolans t*at are composed b! a *ig* reactive )iO 4 and Al4O5 and are able able to combin combine e it* it* portla portlandi ndite te 0Ca0O2 0Ca0O21141, a b!6p b!6pro rod# d#ct ct o/ cement cement *!dration. *!dration. As s#pplement s#pplementar! ar! cementiti cementitio#s o#s material, material, zeolite zeolite en*ances t*e d#rabilit!, red#ce t*e *eat o/ *!dration, increase t*e resistance to s#l/ate attac- and red#ce t*e energ! cost per cement #nit.
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7e!ords+ %at#ral 3eolite Clinoptilolite 8ozzolan Cement
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Introd#ction................... Introd#ction................................ ........................... ........................... ........................... ............................ ........................... ........................... ............................. ............... 4
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A#t*ors and aterials.................. aterials............................... ........................... ............................ ........................... ........................... ............................ ...........................5 .............5
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Concl#sions................... Concl#sions................................. ........................... ........................... ............................ ........................... ........................... ............................ ........................... ............. =
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Re/erences..................... Re/erences.................................. ........................... ........................... ........................... ............................ ........................... ........................................ ........................... =
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1. Introduction )ince ancient times, zeolites *ave been generall! #sed as an additive in constr#ctions aro#nd t*e orld. It is idel! -non t*at p ozzolans can improve some properties li-e give a d#rabilit! increase, decrease t*e *eat o/ *!dration, en*ance t*e resistance to s#l/ate attac- and red#ce t*e energ! cost per cement #nit 07oca-, Tasci, 7a!a, 4@951. %oada!s, more t*an <@ nat#ral and 9<@ s!nt*etic zeolite minerals are -non and #sed in di//erent ind#stries 0A*madi )*e-arc*i, 4@9@1. %at#ral zeolites are *!drated al#minosilicate minerals it* a tetra*edral cr!stalline str#ct#re, *ic* ma-e t*em di//erent /rom ot*er s#pplementar! cementitio#s materials. T*e most ab#ndant and most common t!pe o/ nat#ral zeolite minerals on eart* are clinoptilolite, *e#landite, analcime, c*abazite, and mordenite. 2oever in t*is revie e are :#st going to tal- abo#t *e#landite and clinoptilolite mostl!.
t*ree di//erent t!pes o/ c*annel, A, (, and C 0ise )anta, 4@@<1. It is generall! -non t*at nat#ral zeolites are an especial t!pe o/ nat#ral pozzolan *ic* *as been recentl! applied in vario#s cement and concrete man#/act#ring plants aro#nd e#rope and some ot*er co#ntries li-e iran, c#ba, c*ina, inter alia. T*ese nat#ral zeolites *as a s#bstantial pozzolanic activit! despite t*eir noticeable cr!stalline str#ct#re. 8ozzolanic activit! o/ nat#ral zeolites *as been generall! associated to dissol#tion o/ t*ese zeolitic cr!stals #nder t*e attac- o/ O26 ions available in *!drating cementitio#s s!stem *ic* are composed b! t*reedimensional microporo#s *one!comb str#ct#res t*at o//ers large internal and eBternal s#r/aces. T*e large #antit! o/ reactive )iO 4 and Al4O5 in zeolite c*emicall! combines it* t*e calci#m *!droBide prod#ced b! t*e *!dration o/ cement to /orm additional C)2 gel and al#minates, res#lting in t*e improvement o/ microstr#ct#re o/ *ardened cement 0A*madi )*e-arc*i, 4@9@1. Replacement o/ nat#ral zeolites as a s#pplementar! cementitio#s materials can improve some mec*anical properties o/ cement and concrete composites b#t also increases ater demand d#e to zeolites porosit!. Despite o/ t*eir several advantages, nat#ral zeolites *as not been researc*ed as deep as ot*er pozzolans. According to )cop#s, #sing -e!ords as zeolites and nat#ral pozzolans, Fig. 2 s*o #s t*e p#blications n#mber per !ear, *ic* con/irms t*at t*ese zeolites *as not been eBtensivel! researc*ed.
Fig. 1 2one!comb /rameor- o/ *e#landite and clinoptilolite, composed b! impermeable s*eets 0i.s.1 *ic* are cross6lin-ed, /orming
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Fig. 2 Researc* articles p#blis*ed /rom 9E<9 to 4@9>.
2. Objective )t#d!, compare and anal!ze di//erent res#lts t*at can prove t*at nat#ral zeolites can be #sed as a s#pplementar! cementitio#s material.
3. Authors and Materials aterials #sed b! 0A*madi )*e-arc*i, 4@9@1 ere a A)T T!pe II 8ortland cement, nat#ral zeolites 0Clinoptilolite t!pe1 /rom Iran at di//erent percentage concentrations 0<, 9@, 9<, 4@1, silica /#me it* 0<, 9@, 94.<1 percentage concentrations and %ap*t*alene s#perplasticizer 0;@ solid1 *en t*e! or-ed it* concrete. Abo#t mortars tests t*e! or-ed it* t*e same nat#ral zeolites percentages b#t instead silica /#me t*e! #sed /l! as* at 09@, 4@, 5@, ;@1 percentage concentrations. T*e a#t*ors aim as to eval#ate di//erent e//ects o/ nat#ral zeolites on concrete properties.
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According to 08erra-i, 7ontori, Tsivilis, 7a-ali, 4@9@1, t*e! monitored properties o/ cement replaced it* nat#ral zeolites 0*e#landite t!pe6II1 /rom "reece at 9@ and 4@ or-ing it* 8ortland Cement 0C' I ;4.< % and C' I <4.< %1 #p to one !ear ma-ing t*eir tests on mortars onl!. T#r#is* nat#ral zeolites clinoptilolite t!pe, replacing 8ortland cement 0C' I ;4.< R1 it* <, 9@, 9<, 4@ and 5@ b! eig*t ere t*e materials #sed b! 0(ilim, 4@991 /or *is tests to eval#ate t*e e//ect o/ t*is nat#ral pozzolan on mortars. 07oca- et al., 4@951 or-ed it* nat#ral zeolites /rom t#r-e! to determine t*eir e//ect and test some properties on pastes and mortars, replacing C' II ;4.< R portland cement it* Clinoptilolite at <, 9@, 9<, 4@ b! eig*t. Researc*ers /rom &it*#ania 0%agroc-iene "irs-as, 4@9>1 #sed a replacement o/ Clinoptilolite nat#ral zeolite t!pe at 4.<, <, =.<, 9@, /or C' I ;4.< R cement in order to analize concretes #sing 8ol!carboB!lic resin6based s#perplasticizers
[email protected] 4.<1.
a!le. 1 Di//erent t!pes o/ cement and nat#ral zeolites at di//erent concentrations. Fig. " Comparison beteen )F and %3 pozzolanic reactivit! 0A*madi )*e-arc*i, 4@9@1.
4. Results and Discussion 0A*madi )*e-arc*i, 4@9@1 Fig. " establis*ed t*at pozzolanic reactivit! o/ silica /#me 0)F1 pastes are better t*an nat#ral zeolites, beca#se at 9; da!s t*e silica /#me react 9@@ *ile t*e nat#ral zeolite 0%31 ta-es 4G da!s to react it* t*e total amo#nt o/ Ca0O214. All t*e zeolite replacements obtain *ig*er compressive strengt*s in concrete t*an control miBt#res, *oever t*e best option /or zeolites is t*e one it* a replacement o/ 9< d#e to it *as similar res#lts to silica /#me in 9@ and 94.<. Abo#t ater absorption 0concrete1 and mortar bars eBpansion d#e to A)R, all t*e nat#ral 8 á g i n a ; ? 9@
zeolites miBes s*o loer val#es t*an control miBt#re. Res#lts obtained b! 08erra-i et al., 4@9@1 in compressive strengt*s ere loer t*an control miBes eBcept at 4G and E@ c#ring da!s it* 8ortland cement C' I ;4.< % H 9@ zeolites, 8ortland cement C' I <4.< % H 9@ zeolites and 8ortland cement C' I <4.< % H 4@ zeolites. Compressive and /leB#ral strengt*s since = to E@ c#ring da!s /or all mortars containing zeolites at <, 9@, 9<, 4@, 5@, ere *ig*er t*an re/erence miB and t*e relation beteen ater adsorption and porosit! as lineal according to 0(ilim, 4@991.
According to 07oca- et al., 4@951 compressive and /leB#ral strengt*s in mortars ere loer t*an control miB, t*eir setting time does not *ave signi/icant c*anges /or all zeolites additions.
Fig. $ Concrete adsorption increasing nat#ral zeolites concentrations. 0%agroc-iene "irs-as, 4@9>1
Fig. # Concrete $ltrasonic velocit! at = and 4G c#ring ages. 0%agroc-iene "irs-as, 4@9>1 0%agroc-iene "irs-as, 4@9>1 reported t*at compressive strengt* 0concrete1 a/ter = and 4G da!s o/ c#ring ere signi/icantl! *ig* /or all nat#ral zeolites additive content. (esides, *e also meas#red t*e concrete #ltrasonic p#lse velocit! and its ater adsorption. Fig. #, Fig. $.
0(ilim, 4@991 also reported *o t*ese /leB#ral and compressive strengt*s c*ange, a/ter eBpose t*e miBes to *ig* temperat#res and /reezet*a tests. Fig. %, Fig. &. Comparing mortars compressive strengt*s res#lts beteen 07oca- et al., 4@951 and 0(ilim, 4@991 e can see in Fig. ' t*at t*e! obtain ver! di//erent res#lts as t*e! increased t*e nat#ral zeolite 0Clinoptilolite1 replacements.
Fig. % Decreasing compressive strengt*s at *ig* temperat#res. 0(ilim, 4@991
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Fig. & Decreasing /leB#ral strengt*s at *ig* temperat#res. 0(ilim, 4@991.
Fig. ' %at#ral zeolites blended it* di//erent cement t!pes. 07oca- et al., 4@951 vs 0(ilim, 4@991. 8 á g i n a > ? 9@
5. Conclusions 3eolite t!pe 0Clinoptilolite 6 2e#landite1 co#ld a//ect or improve blended cement properties, giving *ig*er or loer compressive and /leB#ral strengt*s t*an control miBes. %at#ral zeolites can improve blended cement properties li-e pozzolanic reactivit! and get *ig*er compressive strengt*s 0mortars and concretes1 t*an control miBes. %at#ral zeolites on mortars and concrete properties ill c*ange according to *is c*emical composition. Depending on zeolites porosit! *is ater adsortion ill increase or do not.
6. Acno!led"#ents )pecial t*an-s to Cement and Constr#ction aterials /or t*eir amazing s#pport.
$. Re%erences A*madi, (., )*e-arc*i, . 04@9@1. $se o/ nat#ral zeolite as a s#pplementar! cementitio#s material. Cement and Concrete Composites. 'lsevier &td. *ttp+doi.org
[email protected]@9>:.cemconcomp.4@ @E.9@.@@> (ilim, C. 04@991. 8roperties o/ cement mortars containing clinoptilolite as a s#pplementar! cementitio#s material. Construction and Building Materials. 'lsevier &td. *ttp+doi.org
[email protected]@9>:.conb#ildmat.4@9 9.@4.@@> 7oca-, ., Tasci, '., 7a!a, $. 04@951. T*e e//ect o/ #sing nat#ral zeolite on t*e properties and *!dration c*aracteristics o/ blended cements. Construction and Building Materials. 'lsevier &td. *ttp+doi.org
[email protected]@9>:.conb#ildmat.4@9 5.@<.@55 %agroc-iene, D., "irs-as, ". 04@9>1. Researc* into t*e properties o/ concrete modi/ied it* nat#ral zeolite addition. 8 á g i n a = ? 9@
Construction & Building Materials. 'lsevier &td. *ttp+doi.org
[email protected]@9>:.conb#ildmat.4@9 >
[email protected] 8erra-i, T., 7ontori, '., Tsivilis, )., 7a-ali, ". 04@9@1. T*e e//ect o/ zeolite on t*e properties and *!dration o/ blended cements. Cement and Concrete Composites. *ttp+doi.org
[email protected]@9>:.cemconcomp.4@ @E.9@.@@; ise, . )., )anta, C. 04@@<1. )tr#ct#re o/ 3eolites. Encyclopedia of Geology .
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