‘ALASSESSNENT OF THE LOWG-TERM DURABILITY OF (CONCRETE IN RADIOACTIVE WASTE REPOSITORIES A. ATKINSON, 01d. GOULT AND. J:A. HEARNE Naterials DeveTopment Division, BuiTding 552, AERE Harwell, Didcot, Oxfordshire, OF11 OPA, United Kinadom. postRact A prelininary assessment of the long-term durability of concrete in a Gxpertence of concrete structures and both flelé and laboratory studies. It ‘siatso supported by resuits of the examination of a concrete sample which had-been buried {n clay for #3 years. ‘The enaineerine Tifetine of a 1'n thick reinforced concrete slab. with cone face in contact with clay, and the way in'which fn. the repository as a'whote 1s'Titely to vary with tine have Soth been estinated from available fata, “The estinates indicate that enginesring Tifetines of about 10° years fare expected (providine thet suTphate resisting cement. fs Used) and thoe pi AS"vikety to remain ahove 10.5 for about 10" years. aopUCTION any conceptual desians for repositories for dispose} of radioactive waste propose extensive use of hyaraulfe cenents. and coneretes. These meteriats ray be used for the vaste form matrix fteelfy 95 9 construction’) Meterfal for walls and floor, we. prast to hack-Fill pane between wast, Backages and 95.2 sealant of shofts. and tunnels. A sinplifiee desten Ti) fore repouitory being considered in the ile iz show in Fg. Te. his parcicutar example 1s-9 shollow structure, sited in clay, for the disposal Sf py uastes having very ion Tevels of gcenitting isotopes. Concrete, te bide"to proviae casts for the aruns of vaste and’ the structure. tsel? 1s essentfally’a box with walls of reinforced concrete. The cuter surface of 3 wail Ts in contact with the clay. The cenent. and’ concrete repasitory components serve mary useful functions; such as-controlt iow maler flow thy having Tor permeability) ane ‘radionicTige mieracion {hy navine Tow diffusion coefficients and. sone Sorptton capacity for radfonscl ees) tn the nese Field. The prineipa? fFanetions of the concrete are, however, probably mechantcel and chemical . Nechantcatly, the strictura! Componente moet cuppert the recotved leeds 30 that the repository structure #oes not col lapee.” The-chenical function 4 tovmeintatn the ph in the near field ot 2 high value for as Tong as possible. "In'the relatively. short term this provices en environment which fininises the corrosion of steel contatners ang. in the lona term. ensures Ter soveous sofuntt ity Times. for any traces ef lonociSved ration saess In this: paper we consiser how Tong the cener® and concrete in the repository will be able to fUIftl thece mechorteal ond enenfeal functions. For'the mechanical function, we consider the Hehaviaur of 0 1'm thick Feinrorces concrete’ well wnose cuter sUrrace 1s" tn contace with clay at the ge of the repository. The estinated Tifetine ts based on recorded fiperience with reel structures, accelerated Taboretory teste and field experiments. The predicted behaviour 1a supported by examination of Eonercee which hos been exrumee after being buried for ad years tn's clay Formation. For’ the chenfcal function we estinate how the pl of 3 reposttory as @ whole 15 Iikely to evolve over very lona tinescaTes.” The estimates are Kena on sinnte grounduntor franchort madele and The chomictry af canunt Systems240 ASSESSMENT OF ENGINEERING LIFETIPE OF CONCRETE Studies of ancient structures (e.9. Ronan), in which celcareous cements vere used, ave fnateated the potential Tonerity of cetent, and mmeterfals are, however, Tikely to be different fran those which wil? (determine the performance of modern naterials in very different Environments. For example, ancient cements show extensive carbonation by Fesction with CO, from the’ atmosphere, whereae Tn undergraund repositortes The environmental reactions wiTl he with oroundwater constituents. Tt ts therefore necessary to constder the processes which may Tead to chenaes {nthe concrete in the environment in ouestion. once only persite 9 brief description of the ascescrent, the detatls ‘of whichvere’ reported elseuhere {2]<" the following causes of” concrete Slteration were considered; (3). internal changes (e.g. crystallisation, aTkali-aggregate tions), (b) Teacttons with the environment (clay) through groundwater, (2) physical changes from wet/dry or Freeze/thaw cycles, {3} Corrosion of reinforcenent, (2) action of wicro-orgent ses, (5) Taatetton effects (rodialysts, vadtation damage) of these st wae concluded that (b) and {d) were the most likely sources of deterioration of the concrete structure. For the purpose of the assesssent we define the ‘engineering 1ifetine! of the ronrrafe cection az the tine by whieh Its Toad-beartne capacity has Seen reduced by 2 factor of two. Reactions with groundwater Potential reactions betwoen the constituents of a clay groundwater and concrete are summarised in Table Ty tonether wth thelr deletortous onscauerces. Reported experience of corerete stryctures in siofTar Shriromenes [40 Tidicstes thet rescetons with Rae and 80,°"-tqpe sre SThety'te'be the most severe.” The S0,°" fone, topethor with Ca"™ from the omert environment, ateact the hydrate calclim aluminstes to form SuTphor Sitminates: 3¢20.A1,0, 81,0 + CaS0, + 1,0 = 3Ca0.A1,0,(C9S0,).124,0 (1) inondsitphat’) Yonosvlphate + 2950, + 2,0 = 3C0,A.0,.3(6880,).201,0 (2) 10 = san ctdetaghtel These reactions involve considerable increases in the volume of solfd, which leads to gigruption of the concrete ‘rhe gh Fone attace. alt the Ua-containing matertat wo produce sot id vig(ou)?, which ts far Tess soluble than Ca(OH), and hydrated magnesium silicates. Since the Ca compounds are responsible for binding the concrete, the reactions resuTtin Toss of strength. fn 1970 the Building Research Exeabifchnent (Hatford, U.K.) initiated = ‘long-term proaraeme to assess the performance of various concretes under exposure to sulphete-bearing oroundvater.. The progranse enplayed both Taboratory and field tests and the results of exposure for up to 5 years have been reported [5]. In the laboratory, the attack was accelergted by fnereasing the sulphate concentration in the water to 0.19 mole 1-1, which Hyon order of magnitude greater than expected in a clay environment. Tt Should be noted that such cceleration may change the dominant mechantsns of alteration, The accelerated laboratory tests resulted in 9 visibie ALEErFeration zone whose depth, Noy 8 given approximately by the enprricarat expression [3]. Xglem) = 0.55.c9(2).(CH0) + (90,)-(y). 0 In this equation Cy 1s the percentage (by weight) of 3C00.1,0, in the nhydrated cenent tnd’ it appears beceuse {ts hydration produété are those high are principally under attack. The fon concentrations are in mole £-! nd t fe the tine in years. The variability observed in the laboratory feats es toptcTy'S88 751 (Spanning mexima and tnt depths of attack). = ‘able 1, Summary of pouentiet iy veteterfuus tnterections between ‘ehay-erounavaterané concrete Grounduater Constituent | Concrete Constituent | Possible Tansequence | Cone tn clay water Pele w | $0.-- 300.410, 64,0 | Expansion and cracking, xu «] w, cao = sto, = 4,0 vet | Loss uF we rete» | not catow, Loss of strength * and pe S #0 soluble cat Loss of strenoth and pi. sxioe |, Steel reinforcement | Loss of strenath. Expanston ana cracking. axiom | at, Kt SiO, aggregate Expansion and ersckings ih atest file grit a agseted ty enue ups TSE Cileae ire a rng’ ta 2 exe ‘tation tstacGy Sect ft iets £3, pretting toprocetay PESPWIAL SGp cptet fee Sys in i evvtroment ere tl» tee intl Mons therefore aed tn cleat orange of eeterng vical emetic Se See tte Se on given in Tabie I and the results are susmartsed in Table IT. Ordinary Ferd Ean’ Bsn etn do Sab oct te Syriana Pee Wie stn fuel Gate Tre eu eae th te ores nt wri ETP pois i served intuit bene, iG Stiles heen carcrte tevin rythmes” ssbb derby SFR elie f lft Bee2a Nn cee mamnsen Fio. 1 Conceptual destgn of a shallow repository ina clay hed for the ElSponad of tntermeeiate Vevel waste having tow accelvity (ref. Fig. 2 Scnenatic dtagram shovina the composition end depth of the Biteration zane on concrete which had been buried in Oxford clay for 43 years. (The sulphur concentrations are in percentave of cement by weight.) Figs 3 Concentratfon of sulphur in covent ohase (determined sent~ ‘uantitatively ty electron probe microanalysis) as 2 function of depth into Concrete after Burial in clay for 43 yearsemaa Tale II. Estimated engineering 1ifetine™ of an average revntorced meretemeay eorerete Wr eTay Lifetine veoral Degradation Process coments win. | Probable | Pax. sulphate atteck | 180 | 400 | 800 | ordinary Portland Cerent 100 | 2500 | - | suiphate Resisting Conent| Corroston of 800 cracking reinforcenent 2000 | Wo ereckine + Tine for the loss of half the load-bearing capactty of a 1 metre thick rection: reovired to improve on this. Nevertheless, superior longevity of SRPC Eonerete, as opposed to OPC concrete. in clay environments < clearly indicated. Examination of concrete buried in clay Samples of a 2 x 2x 2m hock of concrete, which has been buried 1n lay since 1942, have been stuctes to assess the extent oF chemco? interaction after 43 years of exposure. The techniques whieh hove boon Used inelude Xeray df ffraction, electron and optical microscony, thersogravinetry and differential scanning Cglorimetry.” The concrete contains” two aggregates: a sand with particle size ~ 1 am and a coarse agaregate (up t0 20 mm) which fs mainly Tinestone With sone flint ond feldspar. The concrete shnws" tuo reaction zones at indicated in Fig. 2. The outermost layer is most Iikely the result of carbonation and’ sulphate attack and fs very thin (< 1mm): The second zone ("10mm thick) ts rich in sulphur (Fie. 3} and is probably the result oF reaction with sulphate fran the clay. The materfal in this zone 1s, Inechanically sound and 15 not as frfable as the alteration zone produced by artificially accelerated sulphate attack. The varfation of aqueous chenistry with depth into the concrete was Studied by taking slices frow a specimen and equilibrating each with a ten= Told enceas of water {uy meiuht) fur 20 days~ The compostcion oF the aqueous phase, a5 8 function of depth, 1s shown in Fig. 4. The magnitudes Of the concentrations. and their variation with depth are difficult to Interpret because of the large nurber of possible chemfeal reactions Which say be participating tn the overall eoufTibrium.. For cxampley the pil end ‘concentrations of Ca and St in equt]fbriun with a stice tron i cn below the Surface are consistent with the C-S-H get having a Ca/St ratio close to 107 (Fi. 6) as expected in-unaltered cement. On the other hand, the results fron’? 1m below the surface indicate that inthis repion the fa/St ratio, in ‘the gel 1s close to its mininun value of 0.6 (Fig. 6) and that interaction with groundwater has removed Ca from the ocl. These experinents therefore Biso Insteate an alteration zone abot I em in thicksas. rom equation (3) we would predict, that after 40 years fn clay the Untenress SP thecarueraton zane! ueut'be"aecacen'1 an"3"cn depending onegy) ee | ema Fig. 4 The composition of the Fig. 6 The composition ot the favcous phase when slices, taken from Gifferent. depths Below the surface of ‘concrete (buried for 43 years in ‘aoucous phase when solids in the Ca0-st0,.#,0 system, having various Ca/St rétiés, ore eouilibrated with Efayi are eauttiprates with a ten- water (ref. 8}+ X denotes Co or St. fold excess of water by wefght. The composition of the tnterstitiai water extracted from the clay 1s sho«n on the lefts lid f tog, (time /years a a a Fig. 5 The corroston of an array of steel reinforcing bars in concrete contrat led by. the imard eiFfuston of 0, dissolved {nthe groundwater. Fig. 7 The estinated time dependence of pH within 9 repository of radius 20.m containing 185 ko ar covent and situated fn'a-oroundvater flux density of 10-10"pe (3.2 wm yt). The phases which control varfous pil regions are Sndfcated. The broken curve 1s for. & roundwater contatning 10-® pole 1"? of Sreecttve® species crys yore245 the tricalctum atusinate content of the coment. Since we have not yet been able to detersine this, we conclude thet eoustion (3) gives elther @ correct lestinate or an overestinate of the rate of sulphate attack. Corrosion of rein nent The potential effects of reinforcenent corrosfon in concrete are reduction tn Teadshearing capacity, through lace of reinforcement, snd racking of the concrete by the extra volune of the corrosion products. Corrosion of the reinforcenent. in-a repository will be very slow (in comparison with corrasfon im reinforced concrete structures above ground) land controlled by oxyaen supply to the steel surface. We-have estinated the Raxihun corrosion rate which oxygen, diffusing Fras the clay ‘srounvater ‘through the concrete to the steel, could sustain For a reinforcenent. array as shown in Fig. 5. Assuming an axyoen diffusion coefficient of 10"? me f=! land oxygen concentration In the groundwater equal to. x 10" mole 2-1, the woxinun rate of corrosion of the first layer of reinforcenent $2 estindtee, to be 10'um yt [3]. The resulting deoradation sequence depends on whether the corrosion procucts will crack the conerete at this low corrosion rate: Unfortunately,” there are no data available vaich can be used to predict. hether cracking wil? occur or nats. Conzeaventiy, we hove estientes £3] the Tifetine both on the assumption that no eracking eccurs, in which case the result fs 3000 y, and on the assunption that corrosion of S02 of @ Feinforcing bar is capable of extensively cracking the concrete between 1t and the surface of the wall- in which race the reeult fe 2M) yeare.Thace estimates are compared with’ those expected from sulphate attack in Table Tl TIME OEFEMPENCE OF pet IN IH REPOSITORY The alkaline environsent jin cerant an cqgerete ts generated, in the Tong tern, by calctiun compounds whieh form Cat ane OF” fon in aaueous Ueluttons’ The'mgst. abundant canpounds are in the CaQ-S4Do™1,0 (essen) system and Fi. 6 shows how the composition of the aqueoul pface depends on the composition of the solids, expressed by the Ca/St ston ratio. Most, conents have Ca/SI etween 2 and 3 and therefore, fron Fig. 6, the aqueous hase is essentfally. in equilibrium with snifa Ex(QH), at j= Teese ttm Sone nateriats the pi may be even greater due to NooH‘and fCH in solutfon.) then the: coment 1s part of a concrete raposttery buried in the. ground the plwit! "tend to fall with time a5 0 result. oft a)" Toss at Ca: fran’ the repository by #i¢tuston or advection, (3) resctionjqith sreundvater constituents eartng into Bre repost tory feng. mot, 00"), (c)_ slén'reactions‘wlth other repository constituents (e.0. Sf0, in agoresates). ve nano stietd [67 ne may In enten pt W111 be reauces wien tine ror processes’ (a)-and (0) above. The repository nes approxinete as 0 sphere of radius. 20 m with an average’ cenent content of 185 kg ="! (this Ts eautvelent {0 half its volume being occupted by 2 good quality concrete). The eraund- seater Five doneity war assumed to be 10! no"ty which'is'a Tikely upper Bound fora tyotcel repository (e.o. sited in oh arpiTTaceous foreation with 2° nyarautte gradient (7)}-. The. Ca/S\ ratio. in the repository was ateuleted asa: function of ine using the data tn Pigr by for the Eomosttion of the eoueeus phase, and assuming Togs of Ca'hysavection tn fhe? loving groundsaters. The result ts shou tn Flay 7 wnich indicates that, Im this case, the pl 1s expected to be above 10,5 for 4 x 10" years. 1F the groundwater'ts assuned to contain 10°? nates 3"! of dissolved species which can react with the Ca-containing phases the of dependence. Te ogtinated Yo'sGi Fou he"brOnen tne. ana°ene timeseate: For GH°to fall Seow L0c8 1s246 reduced to 0.9 x 10° years. ‘These tinescales are far in excess of that predicted for the engineering Tifetine of the repository walls. Hovever, the i! buffering cepacity does not rely on structural ‘integriiy of the material; only. on its Cotitinues presence’ in” che Pepos TeOry. The calculations described above have also assuved sufficient dt ffusive transport within the repository to maintain the contents at uniform pi This may not be true in reality since the pH will tend to be reseed preferentially on the sige of the repository Facing the incident meter flow. If there 15 negligible diffusion within the repository then 2 similar calculation [6] estinates that the pH = 10.5 front moves into the repost tory ata rate of 1 m every 1.5 x 10> years (assunina a groundwater flur density fof 10"! mst and’ na treactive! cnactec! couctustoms fn engineering 1itetine in excess of 1000 years {s estinated for 3.1 9 thick reinforced concrete section in clay provided that sulphatesresisting cenent {5 used in the concrete, The Vite-tiniting process may be either sulphate attack or corrosion of the retnforcenents Exomination of concrete buried in clay for 43 years hes revealed an alteration zone, which is rich in sulphur, approximately I-em in depth. This 3 not greater than the depth estinated from the empirics] model on which the estinate of engineering 1iftine = based. "The ft'in tha ronnettnry will Ra mointstned ai. ¢ high Yevel by the cement "for a mich longer tine than the engineering Tifetine.. Fora Fepresentative case it fs estinated that the pH will renain above 10.5 for about 10° years. ACKHOWLEDGENENT ‘The authors wish to thank NIPEX for finencfal support. REFERENCES. "WIRE bratneare’, Cok, Langton ond BW. Roy, Mat. Ree. Symp. 1 Noverber 1983, p. 5, NIPEX, Harwell U 2 31 AL deeincon and.Jui, Hearne, Uske Atomte’ 2 4 2, 543 (1504). S73) huthority Report ‘epE-Roi266s [10R8). Fo. Lea, The Chontitry of Cenent ond Concrete, ard Faftion, (aver Arn 5. WH Harrison and + Teychenné, Sulphate Resistance of Aurted Concrete: Second Interim Report on Long Tere Tnvestfaat¥an ot Vorthwrei Pare, (hutTatea Vesesreh-EstanTrsmments WH StatTotery Office, sh. Greenberg and T.N. Chang, J. Phys. Chen., 69, 182 (1965). AL Atkinson, Usk, Atomic Eneray Authority Report AERE-R11777_ (1985). AL Atkinson, Miciear-and Chemical Waste Management, 5, 203 (1985).