ࡱ> hjcdefgpqrstus hybjbjEE ''R=hh22224f<2m0tp:]]]///////$14R/]@]]]/:'05$5$5$]R(:/5$]/5$5$r0.T"0/:pZqSx25!\.l/=00m0.4#^40/40/<]]5$]]]]]//#F]]]m0]]]]4]]]]]]]]]h p: Studija utjecaja leteeg pepela iz termoelektrane na fizikalno-kemijska svojstva i ponaaanje cementnog kompozita Study on the effect of fly ash from the thermo-electric power plant on the physical and chemical properties and on the behaviour of the cement composite Dra~an Jozi Zavod za anorgansku tehnologiju, Kemijsko-tehnoloaki faultet Sveu iliatza u Splitu, Teslina 10/5, 21000 Split, Hrvatska SA}ETAK Portland cement je jedan od najpopularnijih i airoko primjenjivih graevinskih materijala. Meutim, njegova proizvodnja troai velike koli ine sirovina i energije. Istovremeno u termoelektranama lo~enim ugljenom nastaje ogromna koli ina leteeg pepela, od ega se manji dio koristi, a vei se dio odla~e na odlagaliatima. Obzirom na ekoloake aspekte, tj. velike koli ine osloboenog CO2 tijekom proizvodnje portland cementa i raspolo~ivost leteeg pepela, ije proizvodnje rastu s porastom infrastrukture globalnog razvoja, potrebno je brzo djelovanje radi smanjenja njihovog negativnog utjecaja na okolia. Stoga je cilj ovog rada istra~ivanje utjecaja leteeg pepela iz domae termoelektrane Plomin 2, Plomin, na hidratacijske karakteristike i svojstava ( vrstoa, trajnost i otpornost) portland cementnih kompozita kako s teorijskog tako i prakti nog aspekta. U eksperimentalnom radu primijenit e se serija, kemijskih, kemijsko-fizikalnih, elektrokemijskih, mehani kih i mikrostrukturnih ispitivanja za karakterizaciju i izbor polaznih sirovina, za komponiranje i optimiranje sastava mjeaavine, za ispitivanje njezinog utjecaja na mikrostrukturu nastalih hidratiziranih produkata, te na vrstou, trajnost i otpornost o vrslog cementnog kompozita izlo~enog kemijskoj koroziji sulfata i klorida. Matemati kim modelima opisat e se procesi hidratacije i o vraivanja ato e omoguiti predvianje svojstava i ponaaanja cementnog kompozita u uvjetima njegove primjene. O ekujemo da e rezultati ovih istra~ivanja razviti novi in~enjerski pristup projektiranju i izvoenju sve slo~enijih i zahtjevnijih konstrukcija, posebice za potrebe priobalnog pojasa. Zna aj predlo~enog istra~ivanja je uz o ekivani znanstveni doprinos i njegova primjena u razvoju novih konstrukcijskih materijala ciljanih svojstava uva~avajui kriterije osiguranja kvalitete, zbrinjavanja industrijskog otpadnog materijala, o uvanja energije i prirodnih izvora sirovina, te zaatite okoliaa. Klju ne rije i: letei pepeo, portland cement, hidratacija cementa, matemati ko modeliranje, vrstoa i trajnost, kloridna i sulfatna korozija,koeficijent difuzije, mikrostruktura, XRD, DTA-TG/DTG, FTIR, SEM, SEM/EDS, zbrinjavanje industrijskog otpada, zatita okolia. ABSTRACT Portland cement concrete is the most popular and widely used building material; however, the production of Portland cement is extremely resource and energy intensive process. On the other hand, power station using coal like fuels are worldwide energy sources and then high quantities of fly ash are nowadays generated. Simultaneously, only a small part of these fly ashes is utilised, while the rest of this by-product material is currently dumped in landfills. With the concern on two environmental-related situations, i.e. the high amount of carbon dioxide released to the atmosphere during the production of Portland cement, and the abundant availability of fly ash, which the rate of their production is increasing with the increasing demand on infrastructure development worldwide, proper attention and action to minimize the impact on their sustainability of environmental are needed. Therefore, the main aim in this work will be the study on the effect of the fly ash from the Croatian Plomin 2 coal-fired Thermal Power Station (Plomin) on the hydration characteristics and changes of properties (strength, durability, resistance) of hydrated Portland cement composites with theoretical and practice aspects. A series of chemical, physical and mechanical experiments will be used to create a cementitious composite material starting from raw material characterisation, design and optimisation of blend proportions, their affect on the microstructure and properties of the hydrated product formed, on chemical resistance and on the durability of cement composites exposed to aggressive media of sulphate and chlorides. The mathematical modelling will be use to describe the processes of hydration and hardening, which could make it possible to quantitative prediction both properties and behaviours of cementitious composites at conditions of their exploitation. We expect results will also provide a new engineering admission in the design and development of new construction materials of high performance in coastal region. The significance of the work proposed lies not only in its expected scientific contributions but also in its application in choosing and composing of mixture composition, in optimising process conditions relative to the product quality required, industrial waste management, resource utilization and energy saving, and the environmental protection. Keywords: fly ash, Portland cement, cement hydration, mathematical modelling, strength and durability, chloride and sulphate corrosion, diffusion coefficient, microstructure, XRD, DTA-TG/DTG, FTIR, SEM, SEM/EDS, waste management, environmental protection. UVOD Djelovanje razli itih industrijski otpadnih materijala (troska visoke pei, filtarska SiO2 praaina, letei pepeo) na svojstva kompozita na bazi cementa/betona stalno je u srediatu prou avanja bilo sa stajaliata upoznavanja mehanizma reakcija hidratacije unutar ovakvih sustava i/ili njihova utjecaja na mehani ke karakteristike, te otpornost i trajnost cementnih kompozita (Zeli, 1997.; Saravanos, 1995.). Letei pepeli nastaju kao otpadni produkti u termoelektranama (TE) lo~enim na ugljen i, pored granulirane troske visokih pei, ubrajaju se meu koli inski najviae uporabljene industrijske mineralne dodatke cementu/betonu. Termin letei pepeo u stru noj literaturi se po prvi put spominje 1937. (Davis i sur., 1937.). Prema definiciji (ASTM C 618:1994.), letei su pepeli ostatci nakon spaljivanja (u energetske svrhe) mljevenog ugljena, ato ukazuje da se svaki pepel ne mo~e izjedna iti s leteim pepelom. Pored toga, letei pepeli imaju specifi ne karakteristike po kojima se bitno razlikuju od ostalih industrijskih mineralnih dodataka. Kemijski sastav leteeg pepela mo~e varirati ovisno o vrsti uporabljenog goriva i tehnoloakim procesima spaljivanja, a prisutnost ugljika, iji sadr~aj mo~e varirati od 2 do 10 mas.%, mo~e nepovoljno utjecati na reaktivnost leteeg pepela. Stoga su rezultati i zaklju ci dosadaanjih istra~ivanja njegovog utjecaja na hidrataciju cementa neujedna eni, a katkada i potpuno suprotni. Meutim, zadnjih godina uz pomo primjene novih tehnika i metoda ispitivanja dobiva se bolji uvid o kemijskim i fizikalnim promjenama u sustavima cement-voda  letei pepeo. Dosadaanji radovi (Berry i Malhotra, 1980.; Malhotra, 1989., Fraay i sur., 1989.) pokazali su da se viae svojstava cementnog kompozita (mort/beton) mo~e poboljaati dodatkom leteeg pepela. Neka od tih poboljaanja rezultat su fizikalnih efekata povezanih s poveanjem udjela finih estica (veli ina estica leteeg pepela je manja nego portland cementa), dok je dio poboljaanja posljedica pucolanske reakcije. Budui je pucolanska reakcija sporiji proces u odnosu na proces hidratacije cementa, rane vrstoe ovih betona su obi no ni~e nego vrstoe kontrolnog betona na bazi istog cementa. Posebnom obradom leteeg pepela kao ato je mehani ko usitnjavanje (Pay i sur., 1995., 1996. i 1997.), termi ka (Hu i sur., 1997.; Maltais i sur., 1998.) i kemijska aktivacija (Katz, 1998.; Poon i sur., 2001.) mogue je ubrzati pucolansku reakciju a time i porast ranih vrstoa betona koji sadr~e letei pepeo. Sli an u inak kao i kod vrstoa odra~ava se i kod svojstava nepropusnosti cementnog kompozita s dodatkom leteeg pepela. Razlog smanjenja propusnosti cementnih kompozita s dodatkom leteeg pepela le~i u promjeni veih pora u manje i u poveanju diskontinuiteta poroznosti sustava (Patel i sur., 1989), kao posljedica novonastale mikrostrukture. Prema nekim autorima (Bouzouba i sur., 2001.; Thomas i Matthews, 2004.) ovakav cementni kompozit pokazuje i bolju korozijsku zaatitu eli ne armature prema utjecaju klorida, a sama otpornost je funkcija koli ine i sastava leteeg pepela. Iako su sva dosadaanja istra~ivanja utjecaja leteeg pepela usmjerena u cilju poveanja mehani kih vrstoa i trajnosti betona, a letei pepeo se primjenjuje u praksi, njegova uporaba u betonima se joa i danas prihvaa s odreenom dozom opreza (Papayianni,1992.), ato se uglavnom pripisuje promjenjivom kemijskom i granulometrijskom sastavu leteeg pepela tj. njegovoj reaktivnosti (Fu i sur., 1997.). Stoga su rezultati i zaklju ci dosadaanjih istra~ivanja o utjecaju leteeg pepela na hidrataciju cementa neujedna eni, a katkada i potpuno suprotni. Termoelektrana (TE) Plomin 2, Plomin, je jedina TE u Hrvatskoj koja za proizvodnju elektri ne energije koristi ugljen kao gorivo. Tijekom normalnog re~ima rada TE troai 80 t/h ugljena kao goriva, a postupcima desulfurizacije i separacije, iz otpadnih plinova, se izdvaja 7 t/h gipsa i 12,8 t/h leteeg pepela, odnosno, 90000 tona leteeg pepela godianje ( TE Plomin d.o.o., 1999.), ato predstavlja veliki ekoloaki i ekonomski problem. Preliminarna istra~ivanja (Zeli i Jozi, 2005., 2006.) su potvrdila da se letei pepeo iz TE Plomin 2 mo~e svrstati u mineralni dodatak klase F za primjenu u portland cementu/betonu (HRN EN 450:2000; ASTM C 618:1994.). Stoga je cilj ovoga rada istra~iti utjecaj leteeg pepela dobivenog iz filtarskog postrojenja u termoelektrani lo~enoj ugljenom (TE Plomin 2, Plomin, Hrvatska) kao zamjenskog dodatka cementu na ranu hidrataciju industrijskog portland cementa CEM I 42,5R (CEMEX / Dalmacijacement, Kaatel Suurac, Hrvatska) te na fizikalno mehani ka svojstva i ponaaanje o vrslog cementnog kompozita izlo~enog agresivnim sredinama sulfatnih i kloridnih iona, kako s teorijskog aspekta tako i njegove primjene u pripravi cementnih kompozita visokih performanci (mehani ke vrstoe, otpornosti i trajnosti) uva~avajui kriterije zaatite okoliaa, osiguranja kvalitete i ekonomi nosti. Ovo istra~ivanje bi imalo viaestruko zna enje kako sa stajaliata temeljnih istra~ivanja tako i njegove prakti ne primjene u razvoju novih konstrukcijskih materijala ciljanih svojstava koriatenjem otpadnih materijala kao mineralnih dodataka cementu/betonu s aspekta odr~ivog razvitka, o uvanja energije i prirodnih izvora sirovina te zbrinjavanja industrijskog otpada. METODE ISTRA}IVANJA U svrhu ostvarenja postavljenih ciljeva istra~ivanja primijenit e se niz fizi ko-kemijskih metoda i tehnika. Primjenom mikrokalorimetrijskih mjerenja, temeljenih na toplinskim efektima reakcija, pratit e se reakcije hidratacije cementa bez i s razli itim zamjenskim dodatkom (10-40 mas. %) leteeg pepela te e kineti kom analizom odrediti utjecaj dodatka na mehanizam i kineti ke parametre hidratacijskih procesa. Napredovanje procesa hidratacije i fizikalno-kemijske promjene nastale tijekom hidratacije u istra~ivanim reakcijskim sustavima cement-voda-letei pepeo su praene neprekidnim mjerenjima promjene elektri ne provodnosti elektrokemijskim metodama te odreivanjem promjene koncentracije Ca2+ iona u tekuoj fazi za razli ita vremena hidratacije kemijskim metodama Pomou toplinskih metoda (DTA-TG/DTG) odreivat e se koli ina slobodnog kalcijevog hidroksida i kvantificirati pucolanska aktivnost leteeg pepela. Otpornost uzoraka prema prolazu kloridnih iona ispitat e se odreivanjem dubine prolaza i izra unavanjem koeficijenata migracije kloridnih iona kroz nepomi ni sloj morta, prema standardu NT Build 492. Za identifikaciju nastalih hidratacijskih produkata te strukturne promjene u uzorcima izlo~enim utjecaj $ :<&Y[e%%d'f'p'"($(\****,-@-^-4*4,449\9x9996:<=`==8>@>L>AABBFFPGGGHHHIzL"QJQTٹhB*phh6]aJ h6]h5\mH sH haJmH sH h5aJmH sH hmH sH  haJ h5 hH*h+6 h5\h<  6 & ( 8 Z[d%d'f'p'*/3CPGh`h$`a$$h`ha$ & F$a$`$a$gdNgd+6PG:NQ Q"QJQehhhhJo`bd~PR`^$h`ha$$ & Fa$$`a$$`a$$ & Fa$$a$$h`ha$TVV^W"ZZdeffggggggBgDgFgHghhhhllJop"pvv,v.v0v2v4v6v\v^v¶٩ٕ{o٩jhEHUaJ h6aJh5H*\h h5\hCJaJjhEHUaJj$oJ hUVaJjhEHUaJj$oJ hUVaJjhUaJ haJUhB*phhB*H*aJphhB*aJph&u sulfata primijenit e se metode pretra~ne elektronske mikroskopije (SEM), rendgenska difrakcija (XRD) na polikristalnom uzorku, infracrvena spektroskopija (FTIR) i toplinska analiza (TG/DTG-DTA). Matemati ki programski paket Mathcad 2000 Professional koriaten za razvoj i testiranje pretpostavljenih modela. Shematski prikaz kineti kog modeliranja procesa hidratacije (NR EMBED Equation.3 I EMBED Equation.3 D) prikazan je blok dijagramom na slici 1, a matemati ko modeliranje utjecaja rane faze hidratacije na razvoj tla ne vrstoe o vrslog cementnog kompozita na slici 2. REZULTATI ISTRA}IVANJA Rezultati istra~ivanja procesa hidratacije slo~enog heterogenog sustava industrijski portland cement  letei pepeo ukazuju na dvostruku ulogu leteeg pepela. Tijekom rane hidratacije letei pepeo djeluje kao punilo (fizi ka uloga), tj. kao nukleacijsko mjesto gdje se talo~e hidratacijski produkti ime poti e reakciju hidratacije, dok u kasnijim vremenima pucolanskom reakcijom s hidratacijom nastalim Ca(OH)2 stvara nove C-S-H faze (kemijska uloga) koje doprinose veoj vrstoi i zguauju cementni matriks. Ovo kaanjenje pucolanske reakcije vjerojatno je razlog da se najvee rane vrstoe cementnog morta posti~u uz zamjenski dodatak leteeg pepela od 5 mas. %. Produljenjem vremena hidratacije vrstoe mortova s veim dodatkom rastu i vee su u odnosu na vrstoe referentnog uzorka, morta bez dodatka leteeg pepela. Iz eksperimentalnih -t krivulja provedena je kineti ka analiza procesa hidratacije po modelu Bezjak-Jeleni. Ovim modelom mogue je razlu iti vremenske razmake u kojima se odvijaju pojedini procesi hidratacije od nukelacije i rasta prvih produkata (NR) preko interakcije na granici faza (I) do procesa difuzije (D). procesa D.Vrijednosti dobivenih kineti kih parametara i vremena prijelaza jednog kontrolirajueg procesa u drugi potvruju da poveani udjel leteeg pepela produljuje vrijeme reakcija hidratacije: ubrzava proces NR, a usporava proces I zbog ega slijedi kasnija pojava procesa D. Usporedbom eksperimentalnih i modelom odreenih -t krivulja utvreno je najbolje slaganje u podru ju u kojem je sveukupna brzina hidratcije kontrolirana procesom NR. Za pretpostaviti je da su uo ena odstupanja posljedica pojednostavljenog sukcesivnog modela ((NR EMBED Equation.3 I EMBED Equation.3 D) koji ne uzima u obzir sve parametre koji djeluju na hidrataciju cementa, pa su vjerojatno mogue i druge kombinacije procesa. Na temelju uzajamnih vrijednosti fizikalno-mehani kih svojstava (tla na i savojna vrstoa, skupljanje suaenjem, dinami ki modul elasti nosti) uzoraka cementnog morta bez i s zamjenskim dodatkom leteeg pepela (5 - 40 mas. %) naene su matemati ke ovisnosti promjena svojstva cementnog morta o zamjenskom dodatku leteeg pepela. Utjecaj rane faze hidratacije na svojstva potpuno o vrslog cementnog kompozita istra~en je Knudsen-ovom relacijom. Funkcionalana ovisnost stupnja hidratcije () o tla noj vrstoi (fc) ukazuje na lineranu zakonitost. Definirani model omoguava prognoziranje i programiranje tla ne vrstoe i/ili stupnja hidratacije u bilo kojem vremenu hidratacije, te daje mogunost za razvoj i kreiranje cementnih kompozitnih materijala ciljanih svojstava. Ispitivanjem otpornosti uzoraka morta u agresivnoj otopini sulfata je utvreno da su uzorci s veim dodatkom leteeg pepela (iznad 20 mas. %) otporniji prema koroziji u odnosu na referentni uzorak. vrstoe referentnog uzorka opadaju ve nakon 120 dana boravka u otopini sulfata zbog vee koli ine nastalih produkata korozije, gipsa i etringita, ato je potvreno analizom difrakcijskih slika. Uzorci morta s veim dodatkom leteeg pepela (iznad 20 mas. %) takoer pokazuju i manju propusnost kloridnih iona u odnosu na referentni uzorak. Izra unati koeficijenti migracije kloridnih iona se kreu od 7,2910-12 m2s-1 (referentni mort) do 6,310-13 m2s-1 (uzorak morta s 30 mas. % leteeg pepela). O ito je, da optimalni dodatak leteeg pepela cementu CEM I 42,5R ovisi o namjeni cementnog kompozita (mort/beton) i o uvjetima njegove eksploatacije u prirodnom okoliau sulfata i/ili klorida. 4. ZAKLJU AK Ovaj rad predstavlja izvorno znanstveno djelo, u kojem se viaestranim pristupom istra~uje utjecaj leteeg pepela na ranu hidrataciju i na stabilnost cementnog kompozita. Istra~ivanja su usmjerena u dva pravca: prvo, prou ava se djelovanje leteeg pepela na tijek rane hidratacije cementa uvoenjem kineti ke analize kroz ra unalnu obradu rezultata u cilju iznala~enja matemati kog modela koji najbolje opisuje kinetiku i mehanizam procesa hidratacije i, drugo, ispituju se posljedice pucolanske reakcije na promjene fizikalno-mehani kih svojstava i stabilnost o vrslog cementnog kompozita. Meusobno se povezuju rezultati dobiveni razli itim metodama i uspjeano se postavljaju odreene zakonitosti po kojima se vladaju kemijske i fizikalno-mehani ke promjene ispitivanog sustava. Rezultati istra~ivanja proairuju spoznaje o utjecaju leteeg pepela na kinetiku i mehanizam procesa u ranim vremenima hidratacije, definiraju imbenike koji bitno utje u na kasnija vremena hidratacije i na stabilnost cementnog kompozita, te ukazuju na uvjete odvijanja procesa i mogunosti kontrole korisnih u inaka leteeg pepela kao dodatka cementu. Danim rjeaenjima, dat je novi pristup u prou avanju tehnologije cementa i cementnih kompozitnih materijale kao doprinos razvoju procesnog in~enjerstva i zaatiti okoliaa. ZAHVALA Prikazani rezultati proizaali su iz znanstvenog projekta Primjena leteeg pepela u novim anorganskim vezivnim materijalima uz potporu Ministarstva znanosti, obrazovanja i aporta Republike Hrvatske. LITERATURA ASTM C 618:1994, Standard specification for coal fly ash and raw or calcined natural pozzolan for use as a mineral admixture in portland cement concrete. Berry, E.E., Malhotra, V.M., Fly ash for use in concrete  A critical review, ACI Jour. Proc., 77 (1980) 59-73. Bouzouba, N., Zang, M.H., Malhotra,V.M., Mechanical properties and durability of concrete made with high-volume fly ash blended cements using a coarse fly ash, Cement and Concrete Research, 31 (2001) 1393-1402. Devis, R.E., Carlson, R.W., Kelly, J.W., Davis, H.E., Properties of cements and concrete containing fly ash, ACI Journal, 33 (1937) 577-612. Fraay, A.L.A., Bijen, J.M., de Haan,Y.M., The reaction of fly ash in concrete  A critical examination, Cement and Concrete Research, 19 (1989) 235-246. Fu,Y., Ding, J., Beandoin, J.J., Expansion of Portland cement mortar due to internal sulfate attack, Cement and Concrete Research, 27 (1997) 1299-1306. HRN EN 450:2000, Letei pepeo kao dodatak cementu. Definicije, zahtjevi i nadzor nad kakvoom. Hu, W., Neufeld, R.D., Vallejo, L.E., Kell, C., Latona, M., Strength properties of autochlaved cellular concrete with high volume fly ash, J. Energy Eng., 123 (1997) 44-54. Jozi, D., Zeli, J., The effect of fly ash on cement hydration in aqueous suspension, Ceramics-Silikty, 50 (2006) 98- 105. Katz, A., Microstructure study of alkali-activated fly ash, Cement and Concrete Research, 28 (1998) 197-208. Malhotra,V.M., Pozzolanic and cementitous by-products in cocrete-another look, Procee. 3rd Inter. Conf. On the use of fly ash, silica fume, slag and natural pozzolans in concrete, ACI, (1989) 1-43. Maltais,Y.M., Marchand, J., Influence of curing temperature on cement hydration and mechanical strength development of fly ash mortas, Cement and Concrete Research, 27 (1998) 1009-1020. Papayianni, J., Concrete with high-calcium fly ash, Suppl. Papers of the 4th Inter. Conf. On the use of fly ash, silica fume, slag and natural pozzolanic in concrete, Istanbul, (1992) 261-284. Patel, H.H., Pratt, P.L., Parrott, L.J., Porosity in the microstructure of blended cements containing fly ash, MRS Syimp. Proc., 137, Pittsburg, PA (1989) 381-390. Pay, J., Monzo, J., Bornachero, M.V., Paris-Mara, E., Mechanical tretment of fly ashes: Part I, Part II, Part III, Cement and Concrete Research, 25 (1995) 1467-1470; 26 (1996) 225-235; 27 (1997) 1365-1377. Poon, C.S., Kou, S.C., Lam, L., Lin, Z.S., .Activation of fly ash/cement systems using calcium sulfate anhydrite (CaSO4), Cement and Concrete Research, 31 (2001) 873-881. Saravanos, E.M., Engineering proprties of high performance concrete containing large volume of Class F fly ash, Ph.D. Thesis, University of Saskatchewan, Canada, 1995. Thomas, M.D.A., Matthews, J.D., Performance of pfa concrete in a marine enviroment  10-year results, Cement and Concrete Composites, 26 (2004) 5-20. Zeli, J., Studija utjecaja amorfnog SiO2 na ranu fazu hidratacije i stabilnost cementnog kamena, Doktorska disertacija, Kemijsko-tehnoloaki fakultet Sveu iliata u Splitu, Split, 1997. Zeli, J., Jozi, D., Fly ash as an active mineral addition to Portland cement and concrete, in Book: Environmental Management; Contribution to Solution, (ed.) N. Koprivanac, Zagreb, 2005. pp.191-198.  Slika 1. Shematski prikaz kineti kog modeliranja procesa hidratacije (NR EMBED Equation.3 I EMBED Equation.3 D)  Slika 2. 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J !Lnw 0w`$|p|8|||8$p|pZ|!! o00GDICxP5wx'###''pw#(wHodv% F(GDIC~# ?Ӈ?DC$$?Ӈ?DC# ŀ CúADC$$ŀ CúADC# ?Ӈ?DC$$?Ӈ?DC# ?y?DC$$?y?DC&% '%     RpTimes New Roman2|H|8|||88|||`' !D( 2||8|2|||' !D|(H,(w#%``@L(w,#dv%    Rp Symbol88|||`' !D( 2||8|2|||' !D|(H,(w#%``@L(w,#dvH,(w#%` `@L(w#dv%  %  % TTDGLV}tAALPa  % TXLHYV}tAA LPID   TXjHvV}tAA(LPCI   Rp Times New Roman' !DCI8|2|||' !D|(H,(w#%``@L(w,#dvH,(w#%` `@L(w#dvH,(w#%`h#`#`L(w#dv% TTHV}tAAHLP1 %  TXHV}tAA]LPKI   T`HV}tAAnLTtID   RpSymbol' !DtIDw#%``@L(w,#dvH,(w#%` `@L(w#dvH,(w#%`h#`#`L(w#dvH,(w#%`<#4#`L(w#dv%  TTGV}tAAjLP  %  %  TTGV}tAARLP-  % Rp MS Sans Serif' !D-(w#%` `@L(w#dvH,(w#%`h#`#`L(w#dvH,(w#%`<#4#`L(w#dvH,(w<#%` `@(w ' !Ddv% % TTHV}tAACLP(TTHV}tAALP) Rp Times New Roman' !D)(w#%`h#`#`L(w#dvH,(w#%`<#4#`L(w#dvH,(w<#%` `@(w ' !DdvH,(w#%`,$$$`L(wx$dv%  RpTimes New RomanH,(w#%`<#4#`L(w#dvH,(w<#%` `@(w ' !DdvH,(w#%`,$$$`L(wx$dvH,(w$%` `@L(w$dv% TTCN}tAA LP3 %  %  %  TTzGV}tAA8LP-  %  %  TX\GfV}tAALP:=  %   % &% ( '% (    % % Rp"Systemwyw!$#w! T$P@nw 0w`wPaw$|p|m|Z|m|(wto%00$w !D'w!%h9w!dv% K( ( ( ( ( ( ( ( ( FGDIC" " % ( ( " F$!!EMF+,@$?K{?HD C*@$??@ p l{ EMFp ,nF GDICC y  --  Times New Romanxww 0wkf^-. !CD   Symbol (xww 0wkf^- - -!a$ -!ID,  Times New Romanxww 0wkf^-!1S - !KDh  !tID~  SymbolF $Pxww 0wkf^-.!z. - -.!-]. - MS Sans Serif '--!(N!) Times New Romanxww 0wkf^- Times New Romanxww 0wkf^-!3  - - ---Symbol' Pxww 0wkf^- . I!I' I!I'.- --Symbol' Qxww 0wkf^- . I!' 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TH%$P@nw 0w`wPaw$|p|m|Z|m|(wp%00$w !D'w!%h9w!dv% K( ( ( ( ( ( ( ( ( FGDIC" " % ( ( " FPDEMF+,@$Œ?K{?: D$C*@$??@  l<W EMF D,nFGDIC] w G--  Times New Romanxww 0w0f-. !CD  Times New Romanxww 0w0f- !1.259" ----$@@ B B@- SymbolF $@xww 0w0f-.!=. -.  MS Sans Serif 'L---   @ @ G&% '%     RpTimes New Roman2|xH|8|||88|||`, !+( 2||8|2||, !+|(,:2|_:,(w4+$%``@L(wd+$dv%   TXDA6ALPCD   RpTimes New Roman, !+CD8|||`, !+( 2||8|2||, !+|(,:|_:,(w4+$%``@L(wd+$dv2|_:,(w,$%` -$-$`L(wh-$dv% Tl9DA6A"LX1.259 % &% '% %  V0:< @@ B B@ % (  RpSymbol, !+1.2592||t| @Q|m|A4+$%`@L(wd+||p|m|Z|m| 0n 0ww(w, !+/$|p|m|-w0n, !+L(w,0$dv%  TTDA6ALP=  %   Rp MS Sans Serif, !+=A4+$%`@L(wd+||p|m|Z|m| 0n 0ww(w, !+/$|p|m|-w0n, !+L(w,0$dv/$|,(w,2$%` `@L(wD2$dv% % ( '% (    % % 0 % K( ( ( ( ( ( @@4EB?ZADBC)DBCDYC!b !!s % % % 0        : # ?1?DC$$?1?DCs `Rp"Systemwdw ! 4w pp&! TH%$P@nw 0w`$|p|8|||8$p|pZ|!!p00GDICxP5w'"'$'$'$""pw'$(w+pdv% F(GDIC@# ?1?DC$$?1?DC# BADC$$BADC# ?1?DC$$?1?DC# h{?[#p?DC$$h{?[#p?DC&% '%     RpTimes New Roman2|xH|8|||88|||`, !+( 2||8|2||, !+|(,:2|_:,(w4+$%``@L(wd+$dv%   TXbtDA6ALPCD   Rp Times New Roman, !+CD8|||`, !+( 2||8|2||, !+|(,:|_:,(w4+$%``@L(wd+$dv2|_:,(w,$%` -$-$`L(wh-$dv% TlDA6A"LX1.259 % & % '% %  V0@@ B B@ % (  RpSymbol, !+1.2592||t| @Q|m|A4+$%`@L(wd+||p|m|Z|m| 0n 0ww(w, !+/$|p|m|-w0n, !+L(w,0$dv%  TTw~DA6ALP=  %   Rp MS Sans Serif, !+=A4+$%`@L(wd+||p|m|Z|m| 0n 0ww(w, !+/$|p|m|-w0n, !+L(w,0$dv/$|,(w,2$%` `@L(wD2$dv% % ( '% (    % % Rp"System!+/$|p|m|-w0n , !+Lnw 0w`wPaw$|p|m|Z|m|(w8p%00$w !D'w!%h9w!dv% K( ( ( ( ( ( FGDIC" " % ( ( " F EMF+,@$g??DBC*@$??@ l{ EMF ,nF GDICiO s  --  Times New Romanxww 0wf-.  Symbol (xww 0wf- - -!a -!nr   !a  MS Sans Serif 'X--!(!)  Times New Romanxww 0wf-!16 - !expK  !Knrp  !a  SymbolF $xww 0wf-.!. ---!(k!) Times New Romanxww 0wf- !n   - -!-d - ---Symbol0 Qxxww 0wf-. ]!]' ]!]'.---Symbol0 Rxxww 0wf-. ]!' ]!'.- - -.!-@. - -.!:=(. -. ---     &% '%     RpTimes New Roman2|AH|8|2|||p8|||`F !( 2||8|2|||F !(]|,(w<$%``@L(w=$dv%    RpSymbol8|||`F !( 2||8|2|||F !(]|,(w<$%``@L(w=$dv,(w>$%` `@L(w>$dv%  %  % TT :AALPa  % TX :AA LPnr  TT:AALPa Rp MS Sans SerifF !ar8|2|||F !(]|,(w<$%``@L(w=$dv,(w>$%` `@L(w>$dv,(w@$%`@A$8A$`L(wA$dv% % TT:AALP(TT :AA LP) RpTimes New RomanF !)(w<$%``@L(w=$dv,(w>$%` `@L(w>$dv,(w@$%`@A$8A$`L(wA$dv,(wC$%`|C$tC$`L(wC$dv% TT16:AA6LP1 %  T`DT:AAKLTexp  T`ew:AApLTKnr   TT{:AALPa  RpSymbolF !anrw>$%` `@L(w>$dv,(w@$%`@A$8A$`L(wA$dv,(wC$%`|C$tC$`L(wC$dv,(wE$%`F$F$`L(wG$dv%  TTwy:AALP  % % % TT`c:AAkLP(TT:AALP) RpTimes New RomanF !)(w@$%`@A$8A$`L(wA$dv,(wC$%`|C$tC$`L(wC$dv,(wE$%`F$F$`L(wG$dv,(w0I$%`I$I$`L(wI$dv%  TT :AA LPn  %  % TTZ`:AAdLP- %  % % % Rp SymbolF !-(wC$%`|C$tC$`L(wC$dv,(wE$%`F$F$`L(wG$dv,(w0I$%`I$I$`L(wI$dv,(wL$%` `@(w F !dv%  !] TTTY :AA]LP" !] TTT Y:AA]LP"  % ( % % Rp SymbolF !(wE$%`F$F$`L(wG$ ,(w0I$%I$I$``w`wP|p|m|Z|m| oA 0w<8w b0|,(w\O$%` `@(w F !dv%  !] TT :AALP" !] TT :AALP"  % (  %  %  TT:@:AA@LP-  %  %  TX$-:AA(LP:=  %   % & % ( '% (    % % 0 % K( ( ( ( ( ( ( ( @@4KCeA D8 D55D8 D D8D!b !!s % % % 0        : # ݌?Ӈ?@ D@ D$$݌?Ӈ?@ D@ Ds 51Rp"Systemwdw ! 4w pp&! , !+Lnw 0w`$|p|8|||8$p|pZ|!!:p00GDICxP5w'@"4$4$4$@"@"pw4$(w[pdv% F(GDIC# ݌?Ӈ?@ D@ D$$݌?Ӈ?@ D@ D# CúA@ D@ D$$ CúA@ D@ D# ݌?Ӈ?@ D@ D$$݌?Ӈ?@ D@ D# }?y?@ D@ D$$}?y?@ D@ D&% '%     RpTimes New Roman2|AH|8|2|||p8|||`F !( 2||8|2|||F !(]|,(w<$%``@L(w=$dv%    Rp Symbol8|||`F !( 2||8|2|||F !(]|,(w<$%``@L(w=$dv,(w>$%` `@L(w>$dv%  %  % TT77?F:AALPa  % TX?8IF:AA LPnr  TTO8TF:AALPa Rp MS Sans SerifF !ar8|2|||F !(]|,(w<$%``@L(w=$dv,(w>$%` `@L(w>$dv,(w@$%`@A$8A$`L(wA$dv% % TTJ8MF:AALP(TTT8XF:AA LP) RpTimes New RomanF !)(w<$%``@L(w=$dv,(w>$%` `@L(w>$dv,(w@$%`@A$8A$`L(wA$dv,(wC$%`|C$tC$`L(wC$dv% TTk8qF:AA6LP1 %  T`8F:AAKLTexp  T`8F:AApLTKnr   TT8F:AALPa  RpSymbolF !anrw>$%` `@L(w>$dv,(w@$%`@A$8A$`L(wA$dv,(wC$%`|C$tC$`L(wC$dv,(wE$%`F$F$`L(wG$dv%  TT7F:AALP  % % % TT8F:AAkLP(TT8F:AALP) Rp Times New RomanF !)(w@$%`@A$8A$`L(wA$dv,(wC$%`|C$tC$`L(wC$dv,(wE$%`F$F$`L(wG$dv,(w0I$%`I$I$`L(wI$dv%  TT3>:AA LPn  %  % TT7F:AAdLP- %  % % % RpSymbolF !-(wC$%`|C$tC$`L(wC$dv,(wE$%`F$F$`L(wG$dv,(w0I$%`I$I$`L(wI$dv,(wL$%` `@(w F !dv%  !] TT3<:AA]LP" !] TT=E:AA]LP"  % ( % % RpSymbolF !(wE$%`F$F$`L(wG$ ,(w0I$%I$I$``w`wP|p|m|Z|m| oA 0w<8w b0|,(w\O$%` `@(w F !dv%  !] TT3<:AALP" !] TT=E:AALP"  % (  %  %  TTu7|F:AA@LP-  %  %  TX]7gF:AA(LP:=  %   % &% ( '% (    % % Rp"Systemwyw!R$#w! 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