journal Limited-Dose Electron Microscopy Reveals the Crystallinity of Fibrous JA. Ceram Soe 89 [2 627-632 (2006) DOr 1011115 138129162005 074 C-S-H Phases Christiane RoBler! and Jochen Stark FA, Fingor-Institute for Building Materials Science, Bauhaus-University, 9421 Weimar, Germany Frank Steiniger Centre for Electron Microscopy, Faculty of Medicine, Friedrich Schille-University, 07740 Jena, Germany Willem Tichelaar Department of Biological Scienoes, Imperial College, London SW? 2AZ, UK Using lectron diffraction, we demonstrate that the fibrous calciun-silicate-hydrates (C-S-H) of tricalciumsilicate (CxS) hydration possess was revealed by limiting the electron dose, wl in electron microscopy of biomacromolecules. it oom temperature, the fading of the electron diffraction patterns at -175°C occurs at an electron dose that is about one order of magnitude higher. A combination of low-dose and cryo-protection methods offers the possibility to investigate the structures of water-containing cement phases by high-resolution electron microscopy in a close-to-native state. 1. Introduetion Te Sai phasesand portance Ca(01D,) are hydration produets of the silicate cement clinker minerals CxS and GS, which are the main constituents of Portland cement. These hydration products strongly influence the strength and durabil- ily of conerete. To date, itis not clear whether the fibrous C-5- H phases of C3S and Portland cement hydration possess a erys- talline structure oF not All X-ray and electron éiffraction pattns for C-S-H phases summarized by Gard and Taylor! and Taylor? were determined from phases that had been synthesized at elevated temperatures, and/or at an increased water-to-solid ratio (WS). However, di- Iution of pastes or increase in temperature leads to C-S-H phias- «8 with a lower calcium-to-silicon ratio (Ca/Si) Therefore, its {questionable whether the structures of these low-Ca/Si C-S-H ‘phases can be compared with those of C-S-H phases formed in 3S or coment pastes with clevated Ca/Si. Nevertheless, Gard and Taylor! and Taylor’ assumed that the C-S-H phases ob: tained at elevated temperatures andjor at increased W/S ratios were related to the ones of standard C;S hydration Pioneering. work on collecting electton diffraction patterns and images of cement phases was carried out by Grudemo, who first deseribed the fibrous morphology of C-S-H phases in C:S and Portland cement pastes (hydration at room temperature, ‘normal W/S). From their compilations, Gard and Taylor! and Taylor? de duced thatthe structure of C-S-H in mature C,S and cement pastes can be described as a modified exystal structure of the or naturally ecusng minerals tohermorte and jemi. From Highesiaion magng ste sanamaaion eton micros CHEND, Viclnd eta suggested tat 28-1 pass cna th amorphous maten with nanontaline talon, The Te Mha"homever, eve lee quspioned In awe he eoaeon doses applied (see Richardson,” for a review). As a result of electron radiation, Richardson and Groves* ered couseung of SH phase of conan and 8 B- Gio in the TEME Theoret) wagered us oa Sta po size and a more dtoened Seat bat the ap cation ofa towee cen dos. Appbing catton facton, ower, Barter" onyabsrvel nile fs of cyst Into tbemorte wih ncaa ton dose Tn bts cases The done wer ot quai an tay bea the ons aa tne otaconepeman ha lnifeny over han at the imegng exponent of Recatdoon and Grows Furr ‘more, Moser and Stark® described edge melting of fibrous C-S~ panes ocsnsng re severly tor Nigh acu eo thon inthe sang ehcton mitoscope (EM) than nthe Water vapor cont of thy environmental SEM (ESEM Those ls igs he bets ay be es el preserved son hy re dyed neh nan From detvon mitocpicl work on biomacromalels, which contain Considerable penetage of mater an ae vey Tedationsmive t's tnown thatthe scqution of NO Rierootoon dst eqase the potecion af he eee I Ure to protect te oe apiatdehyraion te mic stop sacuum, in ied. that embed in amorphous ico)" Towelectron dose procedures are followed in ord 10 ‘Sucereton droge an he apecen noon ese st ow teogratars i order To rece tn effec of raaton dare tee nth way, soeuon aryomicreenpy allow hydrated Specimens to be stud ina cows o-atve ste Them hi stdy wos to vette mtr or not C-S- H phases af C8 hydeslon Coun exept WSO) ae Cri Fo ong tines ths hs era question of Signe ‘Gat nts inthe eld of coment and conte esearch rue to answer ths cuss, we eorded etn fection SutansoFaersepidy cone (2 115C}and uncooled sap tne etron dose athe TEML Tats way we asco he folate nth tlerstuctr fibrous CST phases the Stevon ration induce trvtral damage andthe oe of ‘pase cotng onthe damage poco fie yar of CS ase anayead io the TEM nee unui ena by ESpating thi appearance with ati he ESEM. The ce ton diaion pcs obuaned for Rbvows CSL phase Were compel its he mented sod eaclate action Fulton of obermore ed enn nore oases esa [ial elaons at have ber suggested by Gard and Taylor628 Journal of the American Ceramic Saciets—RaBler etal HL. Experimental Procedure (1) Materials C,S used in this work was prepared according to standard protocols," which include burning of raw materials at 1450°C. Several times. The chemical analysis of the produet showed mi- nor impurities of Aland Fe. The free lime (CaO) content de- termined by chemical analysis was about 0.15% ‘Quartz powder and ree ime were used for the preparation of hydrothermal paste (C8 = 0.4 2) Sample Preparation ‘The CS hydration was performed at a W/S of 0.5. To avoid carbonation, samples were stored in sealed plastic containers. Unless stated otherwise, a hydration period of 14 days was cho- sen to achieve a sullcient degree of hydration with stable rexe- tion products. “The quartz-lime mixture (C|S = 0.4) was prepared by reaction at 170°C for 7 h in a pressure vessel (hydrothermal treatment) (3) Electron Microscopie Specimen Preparation Picoes of the hardened C,S paste were ultrasonically dispersed in 2-propano! (approximately 0.5 g CxS paste, 2 ml. 2-propanel, 2-3 min sonifcaion), One droplet ofthe dispersed liquid was applied to # copper grid covered by a QUANTIFOIL” holey ettboa film (Quantfo Micro Tools GmbH, Jena, Germans). ‘The grid was kept in nitrogen gas atmosphere in order to pre vent carbonation during evaporation ofthe 2propanol Irme- diately after the -propanol had evaporated, the gid was ultra- rapidly gooled by plunging into lguid-nitrogen cooled liquid ethane," transferred into a cooled specimen holder under cold riteogen gas, and inserted into a CM 120 TEM. The tempera- ture ofthe sare holder was kept below —175°C. ‘Allematively, for investigations al room temperature, the specimen was inserted into a TEM (CM 120, Pips, Eindho- ven, the Netherlands, and JEM 3010, JEOL, Tokyo, Japan) ‘without any cooling after the 2-propanol had evaporated. For scanning eeciron_ microscopy (SEM) investigations, freshly fractured pices of hurdened pases were inserted into the microscope chamber (4) Electron Microscopy ‘Transmission electron microscopy was carried out with « CM 120 Philips), operated at 120 RV, and with 2 JEM 3010 EOL), ‘operated at 300 KY; both instruments were equipped with LaB, cathodes. With the CM 120, images and diffraction patterns ‘were recorded using controlled lectron dose. The value forthe applied electron dose was determined with a calibrated CCD ‘Camera (FastScan F114, TVIPS, Gguting, Germany). The dose rates applied were 4 and 27 e-(5. A")-'. Up to 30 s elapsed be- fore the object was centered ané the microscope settings were adjusted for obtaining an electron diffraction image. ‘SEM was carried out with an XL30 ESEM-FEG (Philips) operating at 25 kV and a humidity of about 80% or at 2.5 kV and a high vacuum environment. ‘The software package CaRIne Crystallography 3.1 (ESM- software, Hamilton, OF) was used to ealeulate an electron dif fraction pattern for 11 A tobermorite, (5) X-Ray Diffraction ‘The sample was dried (30°C) and ground to a grain size smaller than 45 ym, Measurements were performed with an X-ray pow der difraciometer in. Bragg-Brentano geometry (D-3000, Siemens, Karlsule, Germany), The Cuka (21.5818 A) radiation was generated at 40 mA and 40 kV, Data were cok lected over a Brage angle range of <0" (20), using an angular slep sizeof 0.05" and 2.5» counting time. DIFFRAC™ EVA 9.0 software (Bruker AXS, Karlsruhe, Germany) in combina. tion with an ICDD Powder Diffection File (PDF 2) were used for qualitative phase identification Vol. 89, No. 2 Fig.l. Environmental scaming electron microscope image (25 kV, 0% humidity) of uncoated fibrous C-S-H phases om C3 grain pee Sand at 20°C; the hydration period was 3 months IIL, Results (1) SEM and Limited-Dose TEM of C-S-H Phases (A) C-S-H Phases of C38 Paste Prepared at 20°C and WIS=05. Figure | shows an SEM image of uncoated fi brous C-S-H phases. These fibers ere approximately 2m long and their tips measure several nanometzes across. The TEM. image in Fig. 2 shows an ultrarapidly cooled C-S-H fiber over 4 hole in a support film at ~175°C after exposure to a cumu- lative electron dose of ~8 x 10" e{A2, A characteristic morpho- logical feature isthe tration parallel to the longitudinal axis of a CST fibre. Other morphological features of the fibers are their sharp edges and pointed ends (not shown). Fig.2. ‘Transmission eletron mierostope image of a C-S-AT fiber of (C'S hydration rvordad at 175°C. The fer (center) i spanning a hole in the support fi righ). The fiber was exposed to a cumulative electron dose of 8x10" GIA" (sce text for further details). Hydration cond tions: WIS =05, 20February 2006 Fig.3. Environmental seznning electron microscope image (2.5 KV, vacuum) of ribbor-iype C-S-H phases of a hydrothermally treated (B)_ CASH Phases of Hydrothermally (170°C) Cured Quarts-Lime Paste (C|S=04): An SEM image of uncoated hydrothermally teated quart-lime paste is showa in Fig. 3. Is microstructure is characterized by a C-S-H maitix made up of ribbor-ype phase, which attain a length of approximately 20 tum. Contrary to the Sbrous C-S-H phases of C38 paste, the hbon-type C-SHT phases do not show an intemal station in the TEM (results not shown). However, the fingy short side of te ribbons indicates that, similar to the fibrous C-S-H phases, these ribbons could be made up of agaregaes of several individ ual erst (2) Limited-Dose Electron Diffraction of Ultra-Rapily Cooled C-S-H Phases (A) C-S-H Phases of C58 Paste Prepared at 20°C and WiS=05: An electon diffraction pattern that indicates & cexystalline structure of a C-S-H fiber of a C3S paste prepared at ‘anormal W/S and at room temperature is presented in Fig. (a). Te has been recorded after a cumulative electron dose of ~8 x 10" e/A” and ata temperature of —175°C. The d-spacings setermined are indicated in Fig. a) and listed in Table tthe ‘maximum deviation from the given mean values is ~0.03 (B) Comparison of Fibrous with Ribbon-Type C-S-Ht Phases: In order to compare the d-spacings observed in the case of the C-S-H fibres (C3S hydration, 20°C) with those of the ribbons (quartz-lime mixture, C/S=034, 170°C), an electron iffraction pattern of the latter was laid over one of the former in Fig. 4(6). Both patterns were recorded at — 175°C. The d- spacings determined for the ribbons are also listed in Table I An X-ray powder pattern of a hydrothermally crystallized (quarte-lime mixture is displayed in Fig. 5. The pattern shows that tobermorite is the main produet of the reaction. Therefore, \we overlaid the electron diffraction pattern ofa ribbon-type C= S-H (recorded at ~175°C) with the calculated pattern for 11 A toberorie viewed along the [21] axis in Fig. (estructural data by Merlino et ai). Whereas these two patterns corre: spond reasonably well, no correspondence was found with eal- culated diffraction patterns of jennite (results not shown; structural data of Bonaccorsi et al." (3) Electron Beam Damage of C-S-H Phases (A) Observations in Imaging Mode: In TEM images re corded at room temperature, the longitudinal striations of fi ‘brous C-S-H phases (Fig. 2) were observed at doses lower than 64 10° e/A*, A three to four times higher dose could be ap: plied at low temperature (175°C). The disappearance of the The Crystallinity of Fibrous C-S-H Phases 9 (a) Fig, Fleazondiraction putes of C-S-H phases record at “sic. (a) A patern a a vous SHH phase of CS bya, hye ation conitons: W/S= 0.3, 20 C. (by The ater in () (white so) Superimposed y pattem of hydrotbeaalyerysalied (C'S 0.8 TC, Thy, bbondype CEH phases (ack spot). (2) Pati of 2 "bbon-ype CH paws (whe spot) superimposed By eels, Jnexod patter for ILA tobermonte viewed slong the (21) ax the Calton was cartied out on the basis of srutaral data from Merino fal’ Inthe case of all hee ates the objet was expose lo 4 uulatve easton dose of “8.108 GA"630 Journal of the American Ceramic Society—RaBler etal. ‘Table1. d-Spacings Caleulated from Electron Diffraction Patterns of C-S-H Phases Fibous SHA) Ribhonype SH A) 095 092 121 119 = 149 1.62 133 188 184 2.05 = = 252 299) 298 3.09 378 internal stration was accompanied by edge melting and fol- lowed by the occurrence of bubbling (Fig. 6). (B)_ Observations in diffraction mode: Figure 7 depicts the fading ofthe diffraction patterns of both fibrous and ribbon type C-S-H phases with electron dose at —175°C, and at room temperature. The fading is given as the maximum attainable resolution of diffraction patterns, ie. the smallest cdspacings that can be identified for the particular doses applied, Ribbon-type C-S-H phases appeared to be more radiation resistant than fibrous ones. The patterns of the ribbon-type C S-H phases remained unaffected at low temperature until the fend of the measuring period (9 min), at which a total dose of ~24% I ‘was reached, while they started to fade at ~8 10" @/A® at room temperature, Whereas the fading of the pattems of fibrous C-S-H phases commenced at ~ 1.5 10° eA" at room temperature, it only started at ~24% 10" e/A? at Tow temperature. In other words, at low temperature, the fibrous C-S-H phases can endure an electron dose that is about one order of magnitude higher than that at room temperature, ‘AL still higher electron doses than those documented in Fig. 7, electron diffraction patterns indicating an amorphous structure were recorded for specimens of fibrous and ribbon type C-S-H at room temperature. Those amorphous ring pat- terns did not occur during the observation period when working at low temperature. IV. Discussion We have demonstrated that erystalline electron dlraetion pat- tems of fibrous C-S-H phases of CxS paste prepared with nor- Vol. 89, No. 2 Fig.6._ Transmission electron miroscope image of fibrous C-S-H ther with the typical beam damage structure of bubbles, recorded at 20°C, patterns is thatthe applied electron dose be i patterns extending toa resolution of 1.05 A =175°C, ithe dose is kept below 2.4 10° efA*. At doses higher than 64% 1 e/A? at room temperature, diffraction patterns consisting of amorphous rings, similar to those shown by Gru- demo,’ are obtained, The electron dose that ean be applied be- fore a particular spatial frequency of the diffraction pattern is, Jost at low temperature is about one order of magnitude higher than at room temperature. This eryo-protection factor is lightly higher than the one found in the case of bigmacromolecules, which is about half an order of magnitude.” Fibrous C-S-H phases appear 10 be more radiation sensitive then ribbon- type ones. In images of both fibrous and ribbon-type C-S-H phases, at least three different kinds of structure deterioration caused by ‘beam damage are observed: (1) loss of the striations in the case ofthe fibers, 2) rounding ofthe tips and edges (edge melting). and (3) formation of bubbles. The internal striations of C-S-H ‘Phases are visible inthe images as long as spots are observed in the diffraction patterns, For the applied dose rates the internal striations are maintained over an approximately three times mal W/S (0.5) and at room temperature (~20°C) can be pe A acquired. A prerequisite for obtaining these electron diffraction iter We ee rg tease eed) 2 mien ype CHOC wtb CS-H20C ” = 19 | x oe Diaconate 2-Theta Fig.5._ X-ray diffcacton pater of hydrothermally treated quartz-lime mixture (C/S= 04, 170°C, 7h, Interferences marked! with “tare at- tebuted 1011 A tobermonite; "gz" indicates diftaetion interferences For squacz 0! iw oe 1 electron dose (fA) ‘maximum resolution of eiration patorn [1A], Fig.7. Graph depicting the effect of electron dose on the maximum attainable resolution (fading stops) of electron diffraction pattems of ‘brows and ribbonsype C'S-H phases, at 17S" and 20°CFebruary 2006 Jonger illumination period at low temperature when compared with room temperature. This factor probably explains why the intemal stration of C-S-H phases has so far rarely been ob served at room temperature. A further improvement in eryo- protcction by a factor of about two can be expected if the spec men is kept at liquid-belum instead of liqud-aitrogen temper ature.” Bubbling fas been explained as the hindered escape of ‘volatiles that are a result of radistion-induoed bond ruptures in the specimen"; in the ease of our specimens, the bubbles may indicate the presence of structural water. The observed ede ‘melting cannot be explained by a local temperature rise. For the investigated sample material and the microscope parameters used with the CM. 120, a temperature rise by less than | K is, approximated.” In genera, electron bear-induced specimen hating is not considered to be csiticl ia the TEM." A tem- perature rise may only, become significant at dose rates higher than ~6% 10"e: (6A?) “The images of fibrous C-S-H phases presented here showing the striations, and the diffraction patterns of these phases that show the high-resolution reflections, were recorded from spec mens that had been ultra-rapidly cooled and inserted into the microscope cold. However such images and diffection patterns can also’ be obtained ai room temperature provided. that the clectcon. dose. is low enough (2~64% 10° C/A‘, and <~1.5x 10° efA%, respectively). This result implies that the structure of the fibrous C-S-H phases is not alfected by the ‘vacuum of the microscope at the resolution a:tained. Such ro ‘bustness of specimen with respect to dehydration in the vacuum, cavironment is unlike the situation with biological spscimens. In that case, high-resolution data can only be obtained i the struc tures are well preserved in amorphous ice" or in other sub: stances with chemical ané physical properties similar to those of water, except that they are non-volatile, such as sugars." The necessity 10 vitnly the sample (oF to apply other kinds of em bedding) has to be assessed if other kinds of C-S-H oF cement hhydrates are investigated, espovally i they contain more water than the ones investigated here. Moreover, vitfieation may be advantageous with C-S-H. phases containing more water than the ones investigated here, “There is some agreement between the 188, 3.09, and 3.78 A Jawice spacings that we determined for fibrous C-S-H phases (Fig. 4(2); Table 1) and the spacings determined by Gard and "Taylor" and Grudemo® for theie C-S-HT phases that were syn thesized at high W/S or at high temperature. Further corre spondence is found by comparison of the paticms of C-S-H phases of C38 paste and hytrothermally treated. quartz-lime rnixture, especively, in Fig. 4b), and the comparison of spacings in Table I. Although tobermorites one of the ydrate phases in the cage of the quartzalime mixture (Fig. (0), the Structure of 1A tobermorite cannot be considered @ model structure for C-S-H grown in C38 paste. First, forthe fibrous CSI phases, ou diffraction patterns do not allow a structural analysis to be carried out, as they only consist of maximum nine <-spacings and five diferent angles. Second, the deviation of the determincd angles and d-spacings from the calculated pattern is at least 6%, Thied and most important, the Ca/Si of tobermorite Js 0483, whereas that for C-S-H. phases in CS pastes is 7 1.8." From a crystallographic point of view, itis impossible to includ these extra calcium ions i the tobermorite structure (E. Bonaccors, personal communication). Gard and Taylor intro- duced the mineral jennite for the structure of C-S-H phases principally because ofthe low calcium content of tobermorie. Because the CaSi of jenpite (1.5) is sill lower than the one measured by Richardson! for C-S-H phases of CoS paste, the Stcucture of jenite could only be a basis fr structure determi nation. Calculated diffaction pattems for jennite (Structural data of Bonaccorsi er al.'*) show less correspondence with meas- ured diffraction patterss of fibrous C-S-Hi phases than ealeu lated dilfraction patterns for tobermorite Since neither tobermorite nor jennite alone ean constitute the structure of C-S-H in C3S/Portiand cement pastes, generally two types of elaborate models have been proposed. ‘The first The Crystallinity of Fibrous C-S-H Phases 631 suggest that C-S-H is made up of nanocrystal regions of tobermorite and portiandite. In that mode, C-S-H is ot re- garded as an individual phase.‘ The second kind of models var- ies parameters the sbct silicate strotre of tobermorite snd allows calcium rich layer to be incorporated into the strut. ‘Aroview is given by Richardson). A further open point inthe discussion about the structure of C-S-H ts how the fibrous C-S-H is related to the dense inner product C-S-H."* Our electron diffraction patemns were oblained from single SAH fibers The occurence of strikes in the diffaction pat terns indicates a lamelar or twin tractor on the nanoscale of the exjstals This findings support the sect silicate model forthe Structure of C-S-H fibers. Abit i iffcult to establish a CaySi fatio of 1-7 ina tobermorite structure, a new analysis forthe Structure of fibrous C-S-H shouldbe carried out. Oa the bass of our protocol fr sample preparation and eifraction exper ‘nents with mite electron dose i shouldbe possible to obtain tore high-resolution diffaction data. Another way could be to tise a synchrotron X-ray soure for an extended X-ray absorp- tion fine structure, with, Xray radial dintbution function Calculation to determine the strate of fibrous C-S-H Ve Conclusions 1, Fibrous C-S-H. phases of trcalumsiieate hydration prepared with a normal water-o-slid ratio (0.5) and at room femperature 20°C) possess a crystalin structure. 2 Tis erystlige nature canbe reveled by applying Jimited-dose gletron diffraction; above an electron dose of 6410" e/A® at room temperature, the crystalline structure destroyed and dilraction patteros that show amorphous rings are detected. 5. At =175'C, the electron dose that can be applied before the high-resolution diffraction spots disappear is about one order of magnitude higher 4. Anadverseellect of specimen dehydration inthe vacuum ofthe microscope was not detected 5. For samples with a higher water content, however, the Jose dose and eryo-protetion methods applied in this work may have to be complemented by the technique of vitrification. 6 Fibrous C-S-H phases of trcaleumilieate hydration appear to be more radiation sensiive than ribbonype ones formed under hydrothermal conditions. "Following previous structural models, itis proposed that fibrous C-S-H phases of trcaleiumsilcate hydration possess shoot sicateke structure. Acknowledgments ‘he autor woul keto thnk Dr eae Thomas (Lbs Ente for Sob State and Materia Rewrch, Dresden, German) as) Mathias Stan {vIPS, Gauming, Gomany) for hepa ctsson, and Dr Mari Blt (Giovani Bozzeo Sp. Fag, 1a) for cobs eading of he manus References "a A, Gard and HLF. W. Taylor, “Calum Siate Hyate (1) CS ly, Com. Cones Re, 68 1970) SH. FW. Tesla “Propose Siete for Calum Site Hyleate Gel” J Are Coram Sic, 89, 451 (988), "A Gredemo, "The Mirostartres of Cement Gel Phases” Trans &. Ist Tega (Stockh Sed), 282-24 138287 (965 “Sp Vahand, de Lis Ld. Yaa, a Z. Xa, "Mexnrture of Calan Si sete Hyarte (@-S-H) Gab in Poand Canent Paste: Short Range Oneriog sea 1950) " A1.G. Rchadion, “Eltron Microscopy of Cements pp 00-56 in Since and Perfomance of Comets, ii by J. Bexsod and P Bases, Spon Pres of Faréened Ordinary Potand Cement Pases” Morey. "S0, 28 26277 (isp. Ewart F Glas, G. Groves Japp, RMCrobaa, PT. Mos, S. ‘Technology Harwel, AFRE Repor R 13800, 1990. "Miser and J. Suk, “High Resolution Tmaiog of Wer Bung Materia Samples in ew Naural Sse Using Ensronmental Scaning Fletton Mito632 Journal of the American Ceramic Saciets—RaBler etal ope" pp 28930, 261-78 in Proce of 1, Fed by G. Griese and G. ‘Ogens, Hone, Sout Ac, 203 SRA Talo and RSE. Glne, “Eicon Diao of Frame, Hyéeated Prin Cyn” Sen 86, 10067 (978), Sy. 'Dabochei, M. Adan, JJ. Chang, J-C. Homo, J. Lena, A. MeDonal, and P. Shula, "Cryo. Bletron Misscopy of Vitel Spasinens, Tes Bhs 2, 128238 (1988). NUT Unter and R Heaueron, “Molealar Suuctuse Deternination by Mecon Mirowopy af Unesne’ Catalin Specimens” Mol Diol. 94 250 195) "SG. Siege, "The Infusnce of Low Temperatures on she Raiaton Darage of ‘gate Costa by 00 La Elcionn” 2 None Tx 32582 (97), RM. Ghee? and KA Taye, “Ruciaton Danas Transmision trou, Micoscopy of ‘Blog! ‘Specimens at Low Temperature: A Review” J Mire 1, 1238 (878). Vol. 89, No. 2 "4H F.W. Taso, Cement Choy, raion, pp SIH8, Tord Pubiching, Ux, bm, "SS iMetian, # Boman, and. Azabrster, “The Real Suuctae of Mosietions” fur! Mina 1 17-90 (0), "Sp BonaccorsS. Merino, and HF. W. Tayo, “The Cs structure of Sie, C4540 (OH) SHO," Com. Con. Re 4, 1381-8210. iL Res,Trawoni Heron ears, 3, Splge, Be, 1993 ‘Cayent Paes” Com Contr Carp 32, 97-115 00) "HL'G. Rehardoo,"Tobermortedeuate abd Tobermorit Cali Hyon ide -Bused Model fo the Siete of Appleby to Hatdened Pass of Ti (Slow Site, f-Dislsam Siete, Dorin Cement sd Blends of Poland ‘Cement wth ie-Forace Sap. Metakaoin, Shea Fume Com Con er seine cs) 3