Kılıçlı (Şile-İstanbul) killerinin jeokimyasal mineralojik ve fiziksel özelliklerinin incelenmesi
The investigation of the chemical, mineralogical and physical properties of Kılıçlı clay deposits
Yazar: SERPİL GÜL YILMAZ
Danışman: DOÇ.DR. M. SEZAİ KIRIKOĞLU
İstanbul Teknik Üniversitesi / Fen Bilimleri Enstitüsü
Derece: Yüksek Lisans, 1994
Konu: Jeoloji Mühendisliği = Geological Engineering
Dizin: Fiziksel özellikler = Physical properties ; Jeokimya = Geochemistry ; Kil = Clay ; Mineraloji = Mineralogy ; Petroloji = Petrology ; İstanbul-Şile-Kılıçlı = İstanbul-Şile-Kılıçlı

Özet:
DZET Bu çalışma, İstanbul'un kuzeydoğusunda, Şile'ye bağlı Avcı koru köyünün batısında ve 7 km'lik bir alanda yer alan kil yataklarının değerlendirilebilirle olanaklarını ortaya koymak için yapılan kimyasal, mineralojik ve fiziksel araş tırmalar ile sonuçlarını içermektedir. Çalışmada ayrıca Şile killeri ile, rezervleri bakımından ikinci büyük paya- sahip olan Bilecik-Söğüt bölgesindeki ( Yakacık-Alan mevkide ki) killerin karşılaştırılması yapılmıştır. Çalışma sonucunda Şile (Kılıçlı-Kirazlıyatak tepe mevki) killeri kökensel açıdan in-sitü killer ve sedimenter killer olmak üzere iki ana tipte olduğu görüşü bir kez daha ortaya konmuştur. XRD, DTA ve dilatometre ve mikroskopik inceleme ler sonucu in-sitü killerin özellikle ana kayacın yüzeysel alterasyonu sonucu oluştuğu, sedimanter killerin ise detritik malzemeden, özellikle Üst Kretase volkanik kayaçlarının alterasyon profilleri başta olmak üzere, çevre kayaçlardan kaynaklandığı saptanmıştır. İn-situ kilin (2.3) kil boyutun daki bileşenleri başlıca kaalinit (düzenli ve düzensiz tip) ve gibisttir. Sedimanter killerin (2.1,2.4,2.5,2.6,2.7 ve 2.8) kil boyutundaki bileşenleri ise düzensiz kaolinit, il- lit, düşük oranlarda dioktaedral smektit ve çok az kuvarsdan ibarettir. Şile killerinin Üst Kretase yaşlı volkanik (an dezit) katkılı flişler üzerinde, Söğüt killerinin ise Permi- yen yaşlı granit batoliti üzerine gelen Neojen yaşlı gölsel çökeller içersinde oluştuğu belirlenmiştir. Söğüt killeri Şile killerinden farklı olarak, çökelme havzalarında kısa süreli ve hızlı beslenme şeklinde kendini gösteren sedimantasyon koşullarında oluşmuşlardır. Söz konusu killerin teknolojik özellikleri incelendiğinde ise, Şile killeri özellikle yüksek demir (% 2.47-3.03) içeriği nedeniyle seramik sanayiinde kullanılmaları güçtür. Ancak seçimli üretim sonucu istenen limitlere düşürülmesi durumunda 2.4,2.5,2.6 ve 2.7 nolu kil seviyelerinin duvar karosu, 2.1 yer karosu ve bağlama, 2.3 ise refrakter kil olarak kullanılabileceği belirlenmiştir. Söğüt killerinden A-241 -Y yer karosu, A,241-F ve A-241-K (kumlu kil) duvar karosu ve A-241 -D döküm kili olarak kullanılabilecek niteliktedir. vı

Abstract:
THE INVESTIGATION OF THE CHEMICAL, MINERALOGICAL AND PHYSICAL PROPERTIES OF KILIÇLI CLAY DEPOSITS SUMMARY Term clay is usually used in reference f ine-granied, earthy material that becomes plastic when mixed with a small amount of water. With the use of X-ray techniques clays have been shown to consist mainly of a group of crystaline substances known as the clay minerals. They are all essentially hydrous aluminum silicates. In some, Mg or Fe substitute in part for Al and alkalies or alkaline earths may be present as essential constituents, Although a clay may be made up of a single clay mineral, there are usually several mixed with other minerals such as feldispar, quartz, carbonates, and micas. Kaolinit is a common mineral, the chief constituent of clay. Kaolinite shows little compositional variation; for Al2Si2D5(DH)4, AlgGg 39.5,SİÜ2 kk.5, H20 1^.0 %. It is always a secondary mineral formed of by weathering or hydrotermal alteration of aluminium silicates, particularly feldispar. It is a found mixed with feldispar in rocks that are undergoing alteration, in places it form entire deposits where such alteration has been carried to comple tion. As one of the common products of the composition of rock it is found in soils, and transported by water it is deposited, mixed with quartz and other materials, in lakes, and so on in the form of beds of clay. The clay rninerel, dickite and nacrite are of the same composition as kaolinite but differ somewhat in ther structure, they are less important constituents of clay deposits. Anauxite is a also assigned to the kaolinite group but has a higher Si/Al ratio than kaolinite. Halloysite has two forms: One with kaolinite composition, Al2Si205 (OH),, the other with composition Al2Si"0g (OH),. 2H"0. The second type dehydrates to the first with loss of interlayer water molecules. The mantmorillonite group comprises a number of clay minerals composed of both dioctahedral and trioctahedral type. The outstanding characteristics of members of this Vllgroup is their capacity to absorb water molecules between the seets, the producing marked expansion of the structure, The dioctahedral members are montmorillonite, beidellite and nontronite; the triactahedral members are hectorite and sapanite. Illite is a general term fur the micalike clay minerals. The illites differ from the micas in having less substitution of Al for Si, in containing more water, and in having K partly replaced by Ca and Mg illite is the chief constituent in many shales. Clay is one of the most important natural industrial substances. It is available in every country of the World and Şile is the most important region for the Turkish kaolinitic caly deposits. The Turkish ceramic industry, which is developing rapidly, uses these raw materials for producing floor and wall tiles. The studied area, takes place at the West of. Avcikoru one of Şile's villages which is at the 5D km Northeast of Istan bul. Şile kaolinitic clay deposits take place inside Neogen aged, lacustrine and delta facies units which are discordant over Paleozoic carystalline basin and Upper Cretaceous flysch containing volcanic materialy. This sequence has 1 QOm thickness maximum. These units contain residual clay and transported clay deposits. Residval clay sample numbered 2.3 was generated by the weathering of the volcanic rocks of Upper Cretaceous, under warm and humid climate conditions. The clays was derived particu- lary due to the petrographic character of the parent rock. Transported clays samples numbered 2.1, 2.k, 2.5, 2.6,2.7 and 2.8) was mainly formed by transportation and deposi tion of detritic material in the lacustrine environment Detritic material were supported by the surrounding rocks, mainly by the alteration profiles of Upper Cretaceous. In the side section of mentioned suquence begins with pale grey clay ( with coal, yellowish beiqe clay (2.6 clayey red sand and finishes with cover. Although in the middle sectio Neogone sequence begins with lower cl been formed by the alteration of the the basement, and continues grey clay dark grey clay (2.7), black clay (con organic material), middle coal, beige upper caol, yellowish beige clay (2.6 contains yellow clay levels (2.1) and cover. basin, Neogone 2.3) and continues ), yellow sand. soil n of the basin, ays (2.9) that have andesites forming (2.8), lower coal, taining coal and clay (2. if, 2.5), ), sands, clay that finishes with soil vmCI X-ray p metric, analyse the hea analyse Al 03, metric photome additio ays ouide mec s ar t la s we Fe2D meth try, n, X Na2G. K the ane in studi r diffra hanical e listed ss (fine re done, and Ti ods TNa"D SiD" an RF analy Tia2, Fe ove, SG, sulphur determinate s abı ed a etio and in los by t D2 a and d 50 ze w det r. rea were n, diffe thin sec Table 1 ses) det itrimetr nalyses K"0 ana 4 5y gra as appli SO, and ermınatı characteri rantial the tion analys shown below ermination, ic method u were measur lyses were vimetric me ed for 5İ0" CaG conten an was made zed by chemical rmal, dilato- es. Chemical Following CaD, MgD sing EDTA; ed by colori- done by flame thods. In, MgD, A1203, ds. Excepts with also As it i is about 1.3 presence of hydroxides, other clays tigation are the gibbsite D.63 Si02/Al other sample and high val This situtio and free sil of the clays Thus free si was shown by s known, SiOp/AlpO, rati. Values smaller than thi gibbsite and similar alu where higher values indi and free quartz when the a was evaluated in this content of the 2.3 numb "G3 ratio was proved by s the mentioned ratio is ues in the KpG ve MgO ra n shows the presence of ica (quartz) in the samp of the studied area wer lica ratio changes betws this method. on in pure kaolinite s ratio show the minium oxide and cate the presence of clays of the inves- aspect, first of all ered clay which owns this method. In the greater than 1. 3 tios were observed, illite, montmorillonit le. Rational analysis e also performed, en 2.G7 and 17.78 % Uhen Table 1 is examined, it can be understood that ignition losses of the samples change between 7.k and 20.13 %. High ignition loss in related with hidroxides, organic substance and sulphur quantity. For example, 2.3 numbured clay's high ignition lass must be dependent upon it's gibbsite content which is taa much, where 2.8 clay's high ignition loss depends upon high organic substance and sulphur. The evaluation of whale rock ana clays are important npt only because geological and mineralagical informat provides valuable information about a they are used especially about the ce Besides silica and aluminium which ar components of the clay, the connect d which cause unpureness such as iron usage is necessary. If a few example high silica content effects in such a decreases the plasticity and free res lysis results of the it gives various ians but also for it ther fields where ramie industry, e the 2 main elementer iscovery of components and sulphur, before s are ta be given, way that it istance. As seen in IXcn +> ?H tn a a w a >> ca r-H C_3 QJ.H.H uy CU ? in tn > ro c u o ce ? x: _j CD eC J" ? tn CM CO tD tn a CM CO CM tn CD CM. CM ?.H in o CO a) a. E CO in ? CM CM CM CM CMin-d-CMCMOCMa,-J-tnCM<- CMCMCO CM D CD CD CD CD CM CM CM cm tn in CD r- tn j- in vd r-> m cn.......? CMCMCMCMCMCMCMCMour 2 that sampl sampl anly high tion tian uiashi TİG", ta Be.3 hi the c e 2.8 es ca diffi iran of se in th ng. CaO, ahay gh A lays can n be cult cant lect e ar The MgD ed i lZ°3 can be use y is ents ive ea o unpu, Na n th and law Si be used as used as bin d caarse se their (sam This can mining meth r by are er renesses ca nQ and SO, 2. k. e ceramxc ı 0" and Fe"B^ contents show refraktar clay. Although ding clay, but the other ramie clays. However the pies 2.1, 2.4, 2.5, 2.6,2.7) be improved by the applica- ads during the clay praduc- ichment methods containing used by oxides such as are not out of limit needed ndustry. investigation area is kaolinite and illite accomponies the paragenesis. In the sample the presence of diocta- hedral simectite was discovered. The numbere of 2.3 is kaolinite and gibbsite accompanies the paragenesis with important ratio. Differential thermal analyses (DTA) and dilatometry of samples support the conclusions from X-ray examina tions. In DTA curves, without exception in all samples, while endothermic reactions are given at about 1 GO C and 57G C, exothermic reactions are seen at about 960 C. The mentoneol picks show that the main clay mineral is irregjlar kaolinite and there are lots of coarse grained materials. Endothermic picks given between 200 and 450°C at the curves indicate 1G the presence of burning organic metarial. Besides, as a result of the investiga tion af TG curves. It was observed that the weight losses of the samples change between k and 13.3 %. Theoretical crystal water ratio of kaalinitic clays is about 14 %. As the weight loss of samples are this level, the clays are not pure kaalinitic clay. Dilatometry curves indicates to continous until o about 56Q C. After this value, there is a decrease in expansion with little angle. This shrinkage, observed as the endothermic reaction in the DTA curve, indicates kaolinite's transformation to metakaolinite furthermore, as there is also free quartz in the sampler, typical expansion at 573 C shows the transformation from alpha- quartz to beta-quartz. In the samples clay, permanent XIc o Dİ oı a: L» H tn u oı c > CO CJ m x: tn u.ı-l -P tn.H M 01 ?P CJ ra u ta x: u.H tn # CM t^ CM CM CM CM CM tn cı C^ J- -d- CD i> j- in tn m c^ cn ? j-in»»»»» r-. tn t- cd cn CD t- cm j- t- J- j- in tn D. U >..P ?r-l tn D u cn D- --, ^--^ \ Î& 01 D1CD '-s Dl ^ ? to cm aı.v -P Dl C x: - to -H Dl-P _¥ U ?h 4- c x: oi cu.i-i in 3.H h x: cn h m oi e 01 > "-I.P 01 > P.,-!.r-l M -H E e M- U Dl Xllexpansion mas observed between the temperatures 600-900 C, This shows that so the samples contain an expanding mineral. This mineral should be mica and so the samples must be named as kaolinitic clay cantains illit (kaalino- illitic clay). But, the number 2.8 the proportion of kaolinite mineral is higher, however it has the lowest proportion of illite and free quartz. The day samples numbered 2.3 shows different minera- logical, chemical and physical praporties, that the others. So, the sample gives an important endothermic pick at about 320 C. The second endothermic pick at 5B0 C, is watched. Kaolinite has transformed into meta- kaolinite. The exothermic pick observed at 975°C shows the passage the spinel spase. Besides, the materials, which are not clay consti tuents, greater that 200 micron size were investigated through the binocular microscope, and th'en they were, also frozen in the spofix and they were investigated again using polarising microscope. It can be understood that they have similar mineralogical composition except the specimen defined as 2.3. These materials consist of quartz, quartzite, arkosic sandstone fragments, coal, iron oxide and hydroxide and mica, feldspar, fragments belonging tn different magmatic and metamorfic rocks. The sample 2.3 consists largely of gibbsite and also largely of amorphous cliachite with crystalline gibbsite in cavities. In this work, physical properties of the mentioned clays have been described and the results were shown at Table 2. When the clays are evaluated in the aspect of their physical properties shown in Table 2, it can be said that they can be used for various purposes in the ceramic sector. So, 2.4,2.5,2.6 and 2.7 numbered clays can be used as wall tiles, 2.1 numbered clay can be used as floor tiles and also binding clays, 2.B numbered clay is suitable for binding clays production, and 2.3 numbered clay is suitable far refractor clays. The second important subject of this work is chemical, mineralogical and physical characteristics of the clay deposits of ' Yakacik-Alan area in Bilecek- Söğüt. In the investigated area, Neogene sediments contaning continental clay deposits are Miyocene aged and are found discordan on Permian (Paleozoic) aged and xmtn.w en a a. tu Q to.p.a o :? in Ü3 > i-H (0 C u o a r. 3 co Ixl m a: CD CM CO CD CM CD CO CO tn CM CM CM in to in CM tn CM CJ\ m >- ü_ I I CM CM I I I-» CM tn CM to ? ? V£J 1X3 in tn CD CD tn tn ca vd va va I I x - t - CM CM I I d et XIVgranite bathalite. Transported clays mere mainly formed by transportation and deposition of detritic material in the lacustrine environment. Detritic material which has been transported by flood mere supported by the surrounding rocks. The clays in Söğüt mere characterized by chemical, XRD, DTA dilatametric and thin section analysis. As a result of the mineralogical investigation of the clay samples were found out that the clayey constituents mainly consist of kaolinite and mica(and / or illite). On the other hand, the other materials contain mainly quartz and different magmatic and meta- morphic rock fragments and partially contain feldspars, iron oxides and mica. As a result of the studies, for clay types have been identified; A-241-Y, A-241-F, A-241-D and A-241 -K coded clays. The chemical analysis were given in Table 3. As shown in Table 3, their SiCU/Al^CU ratio (between 2.47-2.77) is greater than the clay of Şile area due to high quartz content. High silica content decreases the placticity and fire resistance. It-can be said that the clays in the studied area are more suitable for casting clays. The physical properties of the mentioned clays were determined and the results of the analyses were given in Table k. Of the four types of the mentioned clays, coded A-241-Y is suitable far floor tiles, A-241-F can be used for wall tiles, A-241 -D can be used for casting clays, and the fourth, A-241 -K is a sandy clay, can be used for wall tiles. xv-p en i CM I in cm ud c-» in t-- r» vn ? CM s- s-. GTi to -p :u :a en 1 J- CM 1 m in D cd yj ixi d in. tn cd v-.... o>. cm co in CO CM CO D r-r t- t- x: tn CM ? CO CD -H tu.... >> oi ? co o\ t- cu.>-» t- cm tn u tu CU XI tu x: 4- a tn u CM CU ?P U CO U CO x: CJ to u cn > x: D_ LU tn u.H -P tn.H f-l tu -P U to u CO x: XVI