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119
Jaumat of the Unh'ersityofChemical Technatos)"
and Meta urs), 4j, 4, 2010, 3gt-396
ON THE FORMATIONOF CEMENTPHASESIN THE COURSEOFINTERACTION
OF KAOLINITE \YITH PORTLANDITE
J.Ninov?,
I. Doykovr,
N. Pehovar,
LD.a!sbey',
L. Dimoval
1Cendal Labarator!-of l4ineralogt and Crysta ographt
BulgananAcadery of Sciences,
E-maiI: idancher@aby.
bg: wtw cImc.bas.bg
2Sofa Unhersity "St. Klinent OhridslE",
Fac t.yof Chenistr!
t Unirersity o/ Archikcn|e, Canstnction and Geodesj
Receiyed
29 hl! 20la
Accepted20 Octaber2010
ABSTRACT
The prcsent||ork dealswith a phasecompositionstudy of the prcducts of the po2zolanicreaction of entiched
kaolin fton 'Senovo"deposit(Bulgaia) with saturatedsolutionsof Ca(OH)..Expeine al runsarc caft,ed out at t\vo
tefipeftturcs- 23and l00aC.
The resultsobtainedshowthat at a temperature
of 100'C ttvowe distinguished
ctystalline
hydnte phases
are
fonned:gehletite h4rate and hydrogznet. Both hrdratesare locztedinthe suface layer afthe silica get, vhich foms a
needle-fiberlike shapestucturc. After temination of the rcactionand curing the sanplesin the couneof 3 monthsat a
temperaturcot 2OC in satututedwatervapourmediun. theCehlenitehyd'ate is conveftedinto hydrceanet, tvhichis the
stablephaseundet theseconditions.
The famation of the needle-fiberlike shapesttuctDrc is chancteristic of the reactionprcduct, obtainedat a
temperaturc
of23qC,haveve\rc fotmationofcrtsttllinehldnte phases
is obseled_Thtsb prcbabtydueto a ctecterse
of the Ate of thepozzolzniceaction or to a lawet fite af crystallzation af the secondaryproductstormect.
Kswgllb: Iine-kAolinite reactions.hychogatnet.gehlenitehydrate.needte-fiber- ke Dhas..
T\IRODUCTIOI{
In a recen!work the kineticsof the pozzolanic
reaclionofenrichedkaolinfiom rhe"Senovo' deposit,
Buigaria,wasstudiedin saturaledsolutionsofCa(OH),
Ii]. The phasecomposirionofthe relction produclsis
investigated
in the presentt\ork.
The compositionand lhe structureofthe reuc,
tion productsofkaolinitewi$ hydratedlirnehalebeen
thesubjcctof man) investigations.
basicallythroughthe
preparationand curing of mi\tures of clay, lime and
wrter ai a definiteratio 3t varioustemperatures!
mos!
oiten whhin the inlervalf.om 23 !o 60.C [2-5].B.rsed
on X-ray diflr.rclionanalysisand DTA/TG anallsisof
lhe reactedml\ture the authorshave esmblishedthe
formationofthe lollowlngnewphases:
a poorlycrystallizedgel ofcalcium hydrosilicateand someothercryslalline hydratesconteiningaluminium - C.ASHs
(gehlenite hydra!e), C.AH,. and CrASzH6_,.
(hydrogamet).
Nluchmorearethe arailabledataonthephase
composilionofthe pozzolirnicteaclionproducisin the
systemmetakaoline-por!lirndite-waler
asa rcsultofthe
higherreaciivityofmctakroline.A largenumberofthese
dau is givenin the reviewanicle ofSabir et al. [6]. It is
claimedin theseinvesligations
rhai rhesilicategelconlainingaluminiumis themainproductofthepozzolanic
reaclion.
Thecomposition
andthermountsofrhecrysial-
Jounal of the Univercityof ChemicalTechnolog and Metallutgt, 46, 4, 2011, 369-374
CHARACTERTZATION OF TIIE POZZOULANIC PROPERTIESOF THE FLY ASII
EVOLVEDFROM TPP "Rf,PUBLIKA'. BULGARIA
J. Ninovr,N. Petrova'
LDilooya',L Doykovr,
t Institute of lrliheralog/ and Crystalloyaphy,BAS,
''Acad.G. Ronchev'St/.,bl.l07, ll13 SoJia,Butgaria
Received20 Jul, 2011
Accepted22 Septenber2all
'1UniversityaI Architecture,Constructionand Geodesr,
t Chisto SnimenskiA\,,e.,1t64 Safa, Bulgaria
r Soja Uniilersity 'St.Klinent Ohidski , I James
BouchietAw., t164 Solia,Butsatia
ABSTRACT
Nev dataon the conposition,physicalchenical andpozzouknic prcpertiesot theny ash(FA), generctedat TPP
'I?epublika",are obtainedaftet tbe basicrcconstructionduring 2U7-2008. The quantitiesof the crystallinephasesand
Anoryhous(glassy)phaseare detetminedusingRieteeldrcfin?menLme activity indexb detemined in accodancewith
the BDSEN 450-l rcquircnents.Theconplex analtsescatriedout shoe that the fly ashinprovespozzoulanicprcpefties
and this natefial is apprcpriatefor elTectiyeutilization in the manufactDrcofdiffetent kind building prcducts, without
preIiminary mechanicaI tteatment.
KjryygBE flt ash.pozzoulanicprcpetties, Rietreld relinenent, nineral (phase)conposition, DTA-TG analtsis,
specilicsuiacearca.
I]NTRODUCTION
The combustionof coal for eLectricity
and heat
generxtionproducesa largeamountof wastesthe fly
.tshb€inglhe biggestonewith its shareofabout 90 %
of the solid residue.The total quantityof FA in Bulgarie amountsto about6-7 million tons per yerr. but
only a smallpar! (under5 70)of it is usedin ihe conThe remriningpart is disposed
in on-sitc
sLrLrcrion.
pondsandlandfillscausingseveralecological
problems.
ktons
FA
io
Yearly. nerrly 300
is due lhe coal-fired
TPP "Republiks".whichoperareswith lo$-gradesubbiluminouscoal lrom the Pemik mineregion.In some
previousworks [-,{] the FA from TPP "Republika"is
defiredrs corl il] ashwithlolvcalciumconten!.coarsei
with lo\! con\!iih s:rnd-sizeparticlespredominated,
glxssy
(amorphous)
phase
t.nt of
xnd relativerich in
unburnedcarbon.Therefore.thissolidresiduewasdispos€drs wasresoflow qualitl in two landfilisnearlhe
lown of Pe.nik.
The Vr" stesmgenerulor(l+3 NIw) tlas modernizedin 2007/2003
and equippedwilh ne\r air-mills
precipitator(ESP).
anda newfour-chamber
eiectrostatic
Due to the finer grindingand pulverizationofthe coal
fuel and lhe bettercombusrionin the boiler,the characterislicsof the falling FA and of the flue gasesexwerechanged,
hauslto lhe almosphere
The aim of the presentwork is to providenerv
data on the composition,physicalchemicaland
pozzoulanicpropertiesof the FA, generatedat TPP
''Republika"after the.reconsructionof ils equipment.
The obtainedresultsin rhe studywould p.ovidepossibilidesto utilizetheFA in severalareas.Thestudydoes
no1concernthe bottom ash,which quanlity is loNer
than 5 % from the total wasteresidue.
L\PERI}IFT\T.{I
Nlxterialsnnd methods
The FA samplesare collectedfrom modernized
fuel inslallationofTPP "Republika"at differentperiodsof 2010during ils processingin stablecombustion
pafrmeters.Dry FA is trken from the hoppersof the
mechanicalcollector(MC) and from all lheESPcham-
REMEDIATION OF TI{E REINFORCEDCONCRXTE
STRUCTURESOT METRO STATION 9 AND 10 AND TUIINEL
BETWEEN THENI FROM SECONDMETRO DIAMETER OF
METROPOLITAN SOFIA
NazarskyD.r, PetrovB.2,DoykovI.3, petrov B.a
Kewordsi rcrfiediation,corrosion,acpansionjoifits, recovery
ABSTR4.CT
The articlepres€nts
remedies
successfully
appli€din the EconsFuctionactivitiesof
the elementsof reinforced concrete structure of the second m€tro diameter in the area
between
MS9 andMSl0, built in theearly80softhe rwentiethcenrury.
Measuresfor restoring warerrighhess in the areas of the sructure with leakage
through the concreteare represented.Activiries for r€pair of defectedexpansionjoints are
designed.
For areaswith a defectivestructure
ofconcretenecessary
measures
andmaterialsare
d€finedto preventfuturedevelopm€nt
ofcorosion processes
in ther€inforcement
bals,also
for concrete
r€pairandapplication
of a protective
system.
.NazarckyD. PhD.Prot SofiaUACG.razarskirAva1oo.com
2
Petrov8., PhD,Assoc.pror.,
-Doykov1.,PhD,ChiefAssist,sona ult6l@!g
SofiaUAC3,doykoff@abv.bg
- Petrov
8., Assist.SofiaUACG,petrov-uacg@gmait.com
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45
Jownal ofchenical Technotog/and tvletalurs, 48, t, 2At3, 5J-60
ON TIIE CONSUMPTIONOF LIME BY METAKAOLIN, FLYASH
AND KAOLINE IN MODEL SYSTEMS
I. Dojkov',S.Stoyanov:,
J.Ninov:,B. Petrov'
t Uniretsitr ofArchtectwe, Ctuil Engenee ng
and Geades),,I "ChUsto6niUte^tki" Elyd.,
l16l Sofd, Bulgaia
'St. "Kl
:Sofa Unii)ersit.y
Ochibki", Faculq,
ofcheniscy, I "J. Botrchier" blrd., B garia,
Eanail: sve injstoiano!@ab, bg
oeceiyed
2l LIa, 2012
Accepted30 k ayember
2012
ABSTRACT
The knetics of the pozzokmic reactions in the q,stems LIK - C^OH),- vate. FA - Ca(OH),- water and
EK - ca(olr.- water wassndied. For thatpnwse. thepoz.olana-time mirlures waspressectas cylindricat specinens
ond cwedjbr a prclonged tine in closed chanbers, at canstant temperatureof 23"C and hieh RH.
It has been.fouhdthat the rcaction MK - ca(o$),pracee^
high rute in thefrst 3 to z dar-sand the rcaction
",ith
FA - Ca(OH)" respecti'elj.- with a maderute rate. The process, which takesplace in the s),sten EK - Ca(OH)1tater is chatucterized as cansisting af tua consecttive stages; modifcation ofthe clat,nineral, and its chemical
degr.tdation b! the reaction *ith lime. on the basisafthe obtained t,sutts the possibitityof ajoint tuseof LIK and
F) in MK - FA - PC blehded cementsisjtlstifed.
Ke*t ords: kirc tics,pozzoldnic reaction. metakaolin,ff ash, enriched kaolin, Iinte.
INTRODUCTION
The lime. releasedbv the hldrurionof cenenl,
decreases
the durabiliw of the concretesand the cemenl mo ars undeanaturalconditions,due to its
paftial solubili!.vin waler and its abiliw to react\4'irh
acidic substances.In order to reducethe contentof
lime, additionsof pozzolana,which combineparl of
the lime ro cementproductswith low basicilvareused.
Thea(ificial pozzolana.
thatcanfindpraciicallyapplica,
tion in Bulgaria-arenetakaolin(NIK) andny ash(F,{).
The processes
involvedintheir interactionin concreres
andcementmorta$havebeenstudiedmanydmes.under
differente\perimentalconditions.
Dataon thekineticsof
-Ca(OH).
thereactionslvlK
andFA-Ca(OH). proceeding in theseproductsare often considerablvdifferent
or controversialI l, 21.This is dueto th. complexir\of
lhe studieds)stems,characterized
by themulti-mineral
54
(phase)compositionof cementand pozzolanicin$edients.and by the simultaneous
pfoceedingoftrvo opposingin time heterogeneous
reactions:
thehydrationof
clinkermine.als,accompanied
by releasingof lime and
thepozzolanicreaction.bywhichthislime is consume.t.
The kineticsofthe studiedpozzolanicreactionsis affectedbv variousadditionalfactorc,mostlyrelaledto the
composition
andpropenies
olthe startingmaterialsused.
As heterogeneous
reactions
ofthe t-vpesolid-liquid.
the pozzolana-limereactionshave a complexmechanism.Theiroverall.aiecouldbe limitednotonly by the
rateofthe chemicalreaction.but also by the diffusion
oflhe Iime reagentthroughthelayerofcementproducts
depositedonlhe surfaceof particlesor. respectiveh,.
by
dissolution
andtrar$portofalime re€ent inthesotution.
The foregoingshorvs.that for the knowledgeand
thecontfolofthe lV1KandFAbehaviorin concreres
aDo
cementmortars,furlhef researchon lhe regularitiesof