Characterization of chemical and physical parameters of post copper slag

Transcription

1 Cent. Eur. J. Phys. 9(2) DOI: /s y Centrl Europen Journl of Physics Chrcteriztion of chemicl nd physicl prmeters of post copper slg Reserch Article Aldon Lowinsk-Kluge 1, Pwel Piszor 2, Jolnt Drul 2, Teres Kntel 1, Pwel Gml 3 1 Institute of Structurl Engineering, Poznn University of Technology, Piotrowo 5, PL Poznn, Polnd 2 Deprtment of Mterils Chemistry, Fculty of Chemistry, Adm Mickiewicz University, Grunwldzk 6, PL Poznn, Polnd 3 KGHM Ecoren S.A., M. Sklodowskiej-Curie 45 A, PL Luin, Polnd Received 30 July 2010; ccepted 21 Jnury 2011 Astrct: Pilot studies concerning industril scle ppliction of post copper slg s nno-dditive for the modifiction of the corrosion resistnce of cement composites hve een descried. The influence of triochemicl tretment on some physicochemicl properties s well s the corrosion resistnce of the otined composites hve een evluted sed on DTG, RTG, nd SEM coupled with EDX mesurements nd chemicl nlysis. It ws oserved tht the so-clled size prticle dditive effect influences the course nd rte of trnsformtions in the formed cement composites, nd my led to specific nd desirle properties. PACS (2008): g, t, Rh, Hk, cp Keywords: cement composites post copper slg nnodditives physicochemicl properties Versit Sp. z o.o. 1. Introduction Recent chievements in nnotechnology hve proved tht tht this technique enles new mterils to e produced, dedicted to specific pplictions [1]. Prticulrly in the uilding industry, new cement composites with high mechnicl strength nd wterproofing, nd freeze, chemicl nd rdition resistnce, s well s low deformility nd temperture stility, hve een otined y the ddition E-mil: ldon.lowinsk-kluge@put.poznn.pl of the proper components in the form of powders. The commonly used definition of nnomterils clssifies them ccording to grin dimeter size which should e elow 0.1 µm. However, in the cse of uilding mterils, etter pproch consists of clssifying them in terms not of their verge grin dimeter, ut y the size for which sustntil chnges in the properties of the finl product re oserved. It is known tht micro- nd nnoscle interctions gretly influence the finl properties of concrete y properly shping its microstructures. For exmple, the ppliction of nnosilicte dditive leds to more compct microstructures with improved mechnicl properties nd more st- 380

2 Aldon Lowinsk-Kluge, Pwel Piszor, Jolnt Drul, Teres Kntel, Pwel Gml le cement mterils [2]. A nnodditive tht contins C-S-H crystllite nuclei reduces the time of concrete setting nd hrdening. Moreover, nnofires used s micro-reinforcement component improve the crcking resistnce of the cement mtrix [3, 4]. Until now, minerl dditives hve een predominntly used for the modifiction of cement mterils. Most often, for these purposes, fly shes, lst-furnce slg, silic dust nd different types wste y-products re pplied. These components re dded in mounts rnging from few to severl dozen percents of the totl cement mss. Independently of their chemicl ctivity, such dditives should modify the physicl nd mechnicl properties of the pste, mortrs nd concretes. It is known tht existing su micron pores in the hydrted cement pste re filled with the gel frction of C-S-H hydrted clcium silictes nd this mteril cn e modified with the use of rective nd nonrective nnoprticles, efficiently incresing the shre of the gel frction [5, 6]. Post copper slg hs een recently proposed s filling mteril for concrete, nd s inding dditive for cement pste production [7 11] s well s for otining composites with higher resistnce to different destructing gents [8]. On the sis of our preliminry results [8], one cn expect tht post copper slg, fter specil triochemicl tretment (up to the nnoscle), cn e useful for the preprtion of highly resistnt cement composites. The post copper slg dditives with prticle dimeters D 50 < 2 µm hve not yet een used for the modifiction of cement composites. The min im of this work ws to investigte nd nlyze post copper slg usefulness for these purposes y RTG, DTG nd SEM coupled with EDX methods. 2. Experiment 2.1. Mterils The test ws conducted with the use of post copper slg tken from the Luin-Glogow copper mine region in Polnd. The smples of slg were prepred on semi technicl scle y triochemicl tretment in fluidl jet mill. In this procedure, the dditive with specific grin size distriution (D 50 < 2 µm) hs een otined. In spite of the fct tht it does not correspond to the commonly used nnomteril definition (D < 100 nm) it hs een referred to s nnodditive. It should serve for modifying the cement composites t nno-scle nd cn e used to significntly lrger extent thn the nno-prticles used efore Methods Definition of triochemicl tretment prmeters of the tested dditives The prmeters of triochemicl tretment of the considered dditives were determined using counter-current fluidl jet mills provided with nti-rsive lining from Hosokw Alpine Compny. The grnulometric composition of the dditives efore nd fter the tretment ws determined using lser prticle nlyzer from the Coulter Compny with the use of wet mesurement module ph mesurement The ph of the extrction wter ws determined for 20% suspension of the dditive. The ph mesurements were conducted using N5170E ph-meter with comined glss electrode Morphology of dditive grins nd their microstructure The microscopic tests were crried out in order to define the morphology nd structure of the dditive grins nd their chnges resulting from the triochemicl tretment. It ws oserved with the VEGA TS5135 MM scnning microscope provided with n X-ry microproe for the following prmeters: ccelerting voltge 25 kv; low vcuum 10 P; BSE reflected electrons. The smples were dusted. Moreover, the EDX X-ry micronlyses were crried out for them. The dditive grins in the initil form (extrcted from n verged smple) were seled in resin in order to determine the element distriution ccording to the distnce from the middle of the grin. The SEM microscopic nlysis ws mde with: the dditives in initil form, i.e. the form used t present in uilding engineering; the sme dditives in the nno-form, otined s result of the triochemicl tretment Chemicl nd phse composition Chemicl composition of the dditives efore nd fter triochemicl tretment ws determined in ccordnce with generlly ccepted stndrd procedures for uilding mterils [12, 13]. 381

3 Chrcteriztion of chemicl nd physicl prmeters of post copper slg Phse composition of the dditives efore nd fter triochemicl tretment, s well s fter DTA tests, ws determined using BRUKER D8 ADVANCE X-ry diffrctometer. The X-ry diffrctogrms of the smples were crried out for identifying the phse composition. Powder smples were tested using CuK α1 rdition in the Brgg ngle rnge: 2θ: 5 to 70, 14 to 54 nd 14 to 70. The goniometer ws displced with the step of 0.02 ; pulse cquisition time ws settled for 4.5 s. A silicon strip detector ws used for the mesurement purpose. Therml differentil nlysis ws crried out for the smples efore nd fter the triochemicl tretment. It ws done with the use of the Setsys TG-DSC15 derivtogrph from the SETARAM Compny (Frnce) under the following conditions: mesurement temperture rnge: C, furnce temperture growth rte: 10 C/min, reference sustnce: Al 2 O 3, furnce tmosphere: N Results nd their nlysis Chemicl composition nd selected properties of the exmined slg re shown in Tle 1. As ws expected, oth the chemicl composition nd density of the slg did not chnge fter tretment. However, the ph of the extrction wter chnged from the vlue of 6.3 to 9.8. Tle 1. Chemicl composition nd selected properties of the post copper slg smples. Component CO SiO 2 Al 2 O 3 Fe 2 O 3 MgO N 2 O e K 2 O Density ph-rection of ph-rection of [%] [%] [%] [%] [%] [%] [%] [Mg/m 3 ] the initil slg the treted slg The results of the SEM oservtion of the post copper slg efore (1) nd fter tretment (1) re presented in Fig. 1. Smll locl vritions in the distriution of elements cn indicte the presence of crystl nuclei with nerly the sme chemicl composition, which re seprted when heting the smple. It is known tht even smll mount of some compounds (s well s ions) my influence how crystlliztion tkes plce nd its direction y lowering the temperture nd incresing the rte of crystlliztion [14]. For proper setting of the triochemicl tretment prmeters, the prticle size distriution nd content of prticulr frctions were lwys mesured for ech smple. Figure 1. SEM BSE imge of post copper slg, (A) efore tretment, (B) fter tretment. As is evident, such kind of tretment leds to the homogeniztion of the slg structure, nd formerly invisile prts of the grins re now exhiited. The EDX nlysis llowed for the comprison of the liner distriution of chosen elements in post copper slg grin Fig. 2. The results of the prticle size distriution of post copper slg efore (3) nd during the tretment (3) re shown in Fig. 3. The second (Fig. 3) ell curve confirms more uniform homogeneity of the treted slg in the prticle size rnge of 0 µm < D < 10 µm. The results of structurl chnges of the post copper slg grins fter triochemicl tretment were confirmed lso y XRD nd DTA mesurements (Fig. 4, 5 nd 6) respectively. 382

4 Aldon Lowinsk-Kluge, Pwel Piszor, Jolnt Drul, Teres Kntel, Pwel Gml Figure 3. Prticle size distriution of post copper slg, () efore triochemicl tretment; () during determintion of the tretment prmeters. smll mount crystlline frction, wheres fter tretment (Fig. 4-IC) n morphous phse is only oserved. Such homogeniztion of the smple s result of the triochemicl tretment is confirmed y existence on the DTA nlysis digrm (Fig. 5) one pek only, t temperture 850 C insted of severl overlpping peks in the rnge C for untreted smples (Fig. 5) [15]. Figure 2. EDX micronlysis of single post copper slg grin: ) metllogrphic specimen of the initil grin with the line long which the EDX micronlysis hs een mde; ) liner distriution of elements s function of the distnce from the grin edge qulittive nlysis. Moreover, for the untreted slg (Fig. 4-IA) one cn see on the XRD spectr very wek diffrction lines coming from X-ry investigtions were lso performed for the sme smples during its nneling in the tempertures close to occurrence of the exothermic effects (determined from DTA curves), i.e. t temp. 680 C nd 860 C (Fig. 6, 6). In the results of these experiments vrious sinters hve een otined for the finl product efore nd fter the tretment. The X-ry diffrctogrms of the sinters otined y this wy for finl products heted up to 1000 C re shown on the Fig. 7. Denottion I 1 nd Ic 1 nneling temperture 680 C; I 2 nd Ic 2 nneling temperture 860 C; I s nd Ic s nneling temperture 1000 C. 383

5 Chrcteriztion of chemicl nd physicl prmeters of post copper slg Figure 4. X-ry diffrctogrms of post-copper slg: ) efore nneling; ) fter nneling up to 1000 C; IA) the initil form; IC) fter triochemicl tretment to the nno-scle. Figure 5. Results of therml nlysis of the post-copper slg for the temperture intervl up to 1000 C: ) for the slg efore tretment; ) for the slg fter the triochemicl tretment leding to nno-size. Figure 6. Results of therml nlysis of the post-copper slg for the temperture rnge up to 860 C: ) for the slg efore tretment; ) for the slg fter the triochemicl tretment leding to nno-size. 384

6 Aldon Lowinsk-Kluge, Pwel Piszor, Jolnt Drul, Teres Kntel, Pwel Gml Record No: (I); Akermnite; C 2 Mg(Si 2 O 7 ), Record No: (D); Augite; luminin C(Mg,Al,Fe)Si 2 O 6, Record No: (D); Hemtite; syn Fe 2 O 3, Record No: (C); Iron Cron; CFe 15.1, suject to tretment (Ic 2 Fig. 7) the following my e identified (ccording to PDF se): Figure 7. Comprison of X-ry diffrctogrms of the post-copper slg nneled t vrious tempertures ) efore the tretment I; ) fter the triochemicl tretment Ic. Finl nneling products, oth in the cse of the slg efore nd fter tretment (denoted y I s nd Ic s ) pproximte ech other. The min phses of the finl product (eing heted to 1000 C) hve een mtched y comprison with PDF se dt nd they re s follows: Record No: ; Diopside ferriin, syn C (Mg Fe )(Si 1.75 Fe 0.24 )O 6, Record No: (I); Akermnite; C 2 Mg(Si 2 O 7 ), Record No: (I); Potssium Aluminum Silicte; KAlSiO 4. On the other hnd, for the sinters otined y nneling t temperture of 860 C (denoted s I 2 nd Ic 2 ) nd corresponding pproximtely to the verge exothermic effect chieved t the DTA curves (Fig. 6 nd 6) for the smple: not suject to tretment (I 2 Fig. 7) the following my e identified (ccording to PDF se): Record No: (D); Augite; luminin C(Mg,Al,Fe)Si 2 O 6, Record No: (C); Aluminum Iron Silicon; Al 0.7 Fe 3 Si 0.3, Record No: (D); Iron; Fe, Record No: (D); Aluminum Oxide; Al 2 O 3, Record No: (A); Stishovite; SiO 2, Record No: (I); Akermnite; C 2 Mg(Si 2 O 7 ), Record No: (I); Potssium Aluminum Silicte; KAlSiO 4, Record No: (D); Mghemite; syn Fe 2 O 3. The intermedite products otined for vrious nneling tempertures in cse of the slg efore nd fter the tretment differ significntly (Figs. 7 nd 7). The mteril, suject to triochemicl tretment, is distinguished y higher numer of crystllite phses nd quicker rrngement of its structure. 4. Summry The XRD, DTA, SEM nd EDX mesurements provided vlule informtion concerning undergoing chnges during triochemicl tretment of the post copper slg in terms of its possile ppliction for modifying of cement mterils. These results clerly indicte tht fter triochemicl tretment of the slg, the smples re highly homogenous nd show desirle properties for further use s n dditive for otining composites. The oserved grin size effect influences the direction of the chnges nd my e used for otining desirle properties of cement composites [8]. 385

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