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Microstructure analysis of the structure of materials used for the mixture of

expanded - Clay lightweight concrete with additives of raw material

Article · January 2010

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 MICROSTRUCTURE ANALYSIS OF THE STRUCTURE OF MATERIALS USED
FOR THE MIXTURE OF EXPANDED – CLAY LIGHTWEIGHT CONCRETE
WITH ADDITIVES OF RAW MATERIAL
Romualdas Mačiulaitis, Marija Vaičienė, Ramunė Žurauskienė
Vilnius Gediminas Technical University, Sauletekio ave. 11, LT-10223 Vilnius, Lithuania.
E-mail: romualdas.maciulaitis@vgtu.lt, marija.vaiciene@vgtu.lt, ramune.zurauskiene@vgtu.lt

Abstract. In order to utilise various waste materials as additives in the production of lightweight concretes effi-
ciently, it is necessary to carry out a detailed analysis, to determine their mineralogical, chemical, granulometric
composition. The purpose of this research is to analyse the properties of raw materials, used in the production of ex-
panded-clay lightweight concrete with the catalyst waste, and estimate their influence on the properties of the mixture
of lightweight concrete. Microstructure of the analysed Portland cement and catalyst utilised in the reactor of catalytic
cracking, X-ray structural analysis of waste material is provided in the research. Additionally, the analysis of the
crush resistance of coarse aggregate (expanded-clay) carried out, is described in the research. The granulometric
composition of the sand was determined, as well as the particles' size of the catalyst and cement was analysed. The
hardened expanded clay – lightweight concrete was analysed during the research. Microstructure analysis of the ex-
panded-clay lightweight concrete was carried out.

Keywords: filler aggregate, expanded-clay aggregate, waste catalyst, lightweight concrete, microstructure.

1. Introduction lyst waste is created in the oil refineries, in the equipment

In recent years it is important for the manufacturers
to use cheap raw materials for the production of construc-
tion materials. In order to compete in a market, the manu-
facturers are putting a lot of efforts to lower the produc-
tion costs, because by lowering the costs the
manufacturers can offer their production in the prices,
lower than ones of competitors. During the manufactur-
ing of products from the secondary raw materials the
several problems increasing product's costs are faced.
During the manufacturing of products from the secondary
raw materials it is necessary to follow the same require-
ments applied for the products from the initial raw mate-
rials. Moreover, special requirements related to the usage
of secondary raw materials must be complied with. Addi-
tional problem lies in the negative image of these prod-
ucts, and this image does not contribute to the increase of
demand and selling of the production (Uselytė et al.
2007). However, during the implementation of waste
reprocessing and utilisation programmes in future, part of
the natural materials will have to be replaces by raw ma-
terials. Due to this waste materials must be used instead
of the natural resources where it is possible.
Already a decade scientists from various countries
are analysing the secondary usage of catalyst waste. Cata-
for catalytic cracking. Here the coarse-grained and fine-
grained particles of the utilised catalyst are created. The
coarse-grained particles are created during the filter
cleaning. They consist of more than 55 % of SiO2 and
40 % of Al2O3.
During the scientific investigations it was found, that
when fine-grained catalyst waste is used (Su et al. 2000),
it is possible to replace 15–20 % of the grout of binding
material in the mixtures or 10 % of fine-grained aggre-
gates without worsening grout's qualitative properties.
Due to the special chemical composition and appro-
priate characteristics, this catalyst waste can be used for
the production of fire resistant (Stonys et al. 2008) and
ceramic products (Mačiulaitis et al. 2007), and can be
used as an aggregate in the production of asphalt concrete
or as a pozzolanic component for Portland cement (Fu-
rimsky 1996) as well.
Recently, chemical and active mineral additives are
introduced widely in the concrete production technology.
These additives influence largely water’s binding forms
of and its amount in the concrete mixture or grout,
rheological properties of the mixtures and hydration of
the cement. Active dispersive additives (mostly industrial
waste materials, having large amount of amorphous SiO2)
are used as partial replacement of cement in the concrete

189
mixtures. Due to high excess of dispersiveness and sur-
face energy, these additives influence the interaction
between water and solid phases in the concrete mixture.
By increasing the surface area of solid phase in the mix-
ture, active dispersive additives increase the amount of
water in the cement paste of normal consistence (Sas-
nauskas et al. 2001).
Fine-grained catalyst waste can be assigned to the
group of filler aggregates, and, considering its influence
during the cement hydration process, to active filler ag-
gregates. In reference (LST EN 1577 1999) it is stated
that active filler aggregates can be produced from the
natural rocks, industrial waste materials. The amount of
active SiO2 in these filler aggregates should not exceed
50 %, and should not be less than 5 % (of the mass).
During our previous research (Mačiulaitis et al.
2009) it was found, that when the catalyst waste (15 %
comparing to the cement mass) from the reactor of cata-
lytic cracking is used for the lightweight concrete, the
density of the analysed expanded-clay lightweight con-
crete and compressive strength (even for the larger wa-
ter/cement ratio) increase, more heat is dissipated during
the hydration of cement and this exothermic effect occurs
several hours earlier.
During the analysis of the expanded-clay lightweight
concrete, where the fractions of coarse aggregates were 5,
15 and 25 mm, scientists (Tommy et al. 2007) have esti-
mated that the highest compressive strength was reached
after 28 days of hardening of 15 mm fraction expanded-
clay. These scientists state that the strength of the con-
crete with the light-weight aggregates depends on the
strength of the utilised light-weight aggregates and on the
strength of hardened cement paste.
The main issue of this research is the utilisation of
technogenic raw materials of oil industry for the produc-
tion of high quality products of lightweight concrete. The
main task of the research is to analyse the fine-grained
catalyst waste and estimate its possible influence on the
properties of the mixture of lightweight concrete. The
analysis of the research shows the possibilities of the
production of lightweight concrete by utilising the secon-
dary resources. To implement this task the properties of
raw materials were analysed, the appropriate content of
formation mixture was selected, the structure of hardened
expanded-clay lightweight concrete was analysed.
2. Experimental methodology and raw materials
2.1 Experimental methodology
The microstructure of Portland cement, waste cata-
lyst, expanded-clay and lightweight concrete particles
was observed by a SEM (EVO LS 25, Zeiss Germany).
The chemical composition of the catalyst were esti-
mated by using the analyser OXFORD Instruments INCA
Penta FET×3.
The X-ray analysis was carried out by X-ray diffrac-
tometer DRON-2 with a cooper anticathode and nickel
filter, the voltage of anode 30 kV, current of anode 8 mA,
slits of the goniometer – 0.5; 1.0; 0.5 mm, the speed of
recording of X-ray diffraction patterns – 600 mm/min. the
190
phase composition was defined using the ASTM card
index of data.
The crush resistance of the grains of expanded-clay
in dry status is estimated according to LST EN 13055-1
„Lightweight aggregates – Part 1: Lightweight aggregates
for concrete, mortar and grout“.
The granulometric composition of the fine-grained
aggregates is estimated according to LST EN 933-1
„Tests for geometrical properties of aggregates – Part 1:
Determination of particle size distribution – Sieving
method”.
The size and granulometric composition of the cata-
lyst and particles of the cement is analysed with the ana-
lyser CILAS 1090 DRY.
The composition of the mixture of expanded-clay
lightweight concrete is calculated by implementing the
methodology described in (Skramtaev et al. 1966). Sam-
ples – cubes (with 10 cm side length), were hardened in
accordance with LST EN 12390-2 2003.
During the analysis of the expanded-clay lightweight
concrete with the additive of catalyst waste, the formation
mixture with the following composition for 1 m3 was
prepared: 292.6 kg of Portland cement, 822.8 kg of sand,
396.5 kg of sand of expanded-clay with the fraction of 0–
4 mm, 215.8 l of water and 30 % of used catalyst was
poured into the mixture (comparing to the amount of the
binding materials), i.e. 125.4 kg. During the analysis of
the expanded-clay lightweight concrete with no additive
of waste materials, the formation mixture with the follow-
ing composition for 1 m3 was prepared: 418 kg of Port-
land cement, 822.8 kg of sand, 396.5 kg of sand of ex-
panded-clay with the fraction of 0–4 mm, and 215.8 l of
water.
2.2 Row materials properties
Cement: Portland-composite cement CEM II/A-L
42.5N (A), from company "Akmenės cementas" AB,
complying with the requirements of the standard LST EN
197-1 "Cement – Part 1: Composition, specifications and
conformity criteria for common cements". The chemical
composition of the Portland cement is provided in Table
1, and mineralogical composition is provided in Table 2.
Table 1. Chemical composition of Portland cement
Chemical composition, %
SiO2 CaO Al2O3 Fe2O3 MgO SO3 CaO1 Others
20.61 63.42 5.45 3.36 3.84 0.80 0.73 0.341
Table 2. Mineral composition of Portland cement
Mineral
C3S C2S C3A C4AF
composition
In % 57.26 15.41 8.68 10.15
Fine aggregate: natural sand with the particles’ size
of 0–4 mm. The granulometric composition of the sand is
provided in Table 3. Table 3 shows that the particles with
the size from 1 to 0.5 mm compose the major part of the
sand, the amount of these particles is approximately 47 %.
Table 3. Sand's granulometric composition 3. Experimental results and discussions
Size of sieve mesh, mm Partial residue, %
form 4 to 2 30.197 3.1. Microstructure and dispersivity analysis of the
from 1 to 0.5 46.73 materials
from 0.25 to 0.125 20.155
‹ 0.063 1.034 The structure of Portland cement used in the re-
search is showed in Fig 2. In the photo it can be noticed
Coarse light-weight aggregate: expanded-clay sand that the shape of the powder of Portland cement is irregu-
with 2–4 mm size particles. Characteristics of the coarse lar, and size varies in a wide range. Such properties are
aggregate are provided in Table 4. typical for Portland cement where the major part is com-
posed of clinker produced by burning the limestone in a
Table 4. Characteristics of the expanded-clay sand rotational furnace and by grinding in a ball mill. Portland
Properties cements of this type are distinguished by open matrix,
Fraction and the microstructure of the products based on such
Density
of ex- Bulk Hol- binding materials is porous. Materials produced by using
of Im-
panded- den- low- Wet- this binding material have larger gas penetratability, and
parti- pregna-
clay sity ness ness % liquids penetrate easier.
cles tion %
kg/m3 %
kg/m3
2–4 mm 473 1020 53.63 13.90 33.55

The crush resistance of 2–20 mm fraction grains of

the expanded-clay was estimated. The results of the
analysis of crush resistance of dry expanded-clay are
provided in Table 5.
Table 5. Crush resistance of expanded-clay
Crush resistance, MPa
Fraction of the expanded-clay, mm
Dry
2–4 3.25
4–10 2.64
10–20 1.39
Filler aggregate: fine-grained catalyst waste from
the reactor of catalytic cracking. These particles are pro- Fig 2. Structure of Portland cement grains
duced by using filters. The chemical composition of this
catalyst waste is as follows: SiO2 – 55.15 %, Al2O3 –
120
40.94 %, Fe2O3 – 0.90 %, TiO2 – 1.48 %, P2O5 – 0.11 %,
Cumulative values, %

100
La2O3 – 1.41 %.
Fig 1 shows the X-ray diffraction diagram of cata- 80

lyst waste, indicating that this catalyst is a crystalline 60

material with some amorphous phase in the structure. The 40
crystallized phase identified is mainly faujasite (Na2, Ca, 20
Mg)3.5Al7Si17O48·32H2O.
0
Results of the analysis of elements' composition in
0,3
0,9
1,5
2,4
3,6
5,3
8
13
19
28
40
60
85
130
190
280
460

the catalyst waste showed that the following materials

Diameter, µm
exist: Fe – 0.14 %, S – 0.10 %, C – 24.31 %, La –
0.22 %, Ti – 0.10 %, Cu – 0.06 %, O2 – 70.06 %.
Fig 3. Particle size distribution of the Portland cement
grains
1600 +
1400
+ Faujasite
1200 + According to results of the analysis of granulometric
Intensity (a. u.)

+
1000 + + composition (Fig 3), the size of the particles of Portland
+ + + +
800 +
+ cement analysed varies from 0.3 to 140 µm. The distribu-
+
600 + + tion of the particles depending on their size is uneven, the
400 size of 50 % of particles of Portland cement is 7 µm and
200 smaller. The sizes of other 40% particles vary from 7 µm
0
to 50 µm. The remaining particles (10%) are larger than
4
8
11
15
18
22
25
29
32
36
39
43
46
50
53
57
61
64

2 Theta: degrees
50 µm.

Fig 1. X-ray diagram of catalyst

191
 Fig 4. Microstructure of the waste catalyst grains Fig 6. Microstructure of the expanded-clay grain

Fig 4 shows a scanning electron micrograph of cata- The statement that there are little pores in the surface
lyst waste, which indicates that catalyst particles are of the expanded-clay is confirmed in Fig 6. In this figure
spherical. The granulometric composition of the catalyst it can be noticed the diameter of pores is very small, from
waste is showed in Fig 5. 5 µm to 60 µm, and the largest surface area of expanded-
clay is occupied by agglomerated clay minerals. Cement
1,2
stone should adhere firmly to this agglomerated and
Cumulative values, %

1 rough surface. In order to get more detailed view of ex-

0,8 panded-clay pores (to verify whether they are closed or
0,6 open), the image of expanded-clay pore was zoomed in
0,4
(enlargement of the view of pore located in the centre of
Fig 6). After more exhaustive analysis of expanded-clay
0,2
pores we can notice (in Fig 7) that the internal micropores
0
of expanded-clay are not closed. Therefore, the statement
0,04
0,5
1,1
2
3,2
4,6
7
11
17
23
36
53
75
112
170
240
400

that water does not reach them, as it is stated in reference

Diameter, µm (Gailius et al. 2009), cannot be confirmed. It can be seen
that the structure of pores on the surface of expanded-clay
Fig 5. Particle size distribution of the catalyst waste is similar to the pore structure of foam glass. Water
passes into the expanded-clay through this structure of
During the analysis of the granulometric composi- the adjacent pores. However, the number of these pores is
tion (Fig 5) it can be noticed that the size of particles of not high, and the internal part of the expanded-clay is
catalyst waste varies from 0.2 to 112 µm. Major part of dominated by closed pores and capillaries. During the
the particles of this material has larger diameter than the selection of the required amount of water for the mixture
ones of the Portland cement (Fig 3), size of 80% of the of expanded-clay lightweight concrete it must be consid-
particles in the used catalyst varies from 30 µm to ered that the additional amount of water would be re-
112 µm. When particles of the used catalyst are compared quired to pour into the mixture to moisten the surface of
with the particles of binding material (Green Cement the expanded-clay granules. However, during the harden-
Technology), it can be noticed that the particles of the ing this amount of water would be returned gradually to
catalyst are similar to the ones of the pozzolanic cement the cement stone.
(where volcanic ash is used for the production). Both
have the same shape, but the latter have 4 times smaller
diameter. Specific surface area of the particles (showed in
Fig 5) of used catalyst is smaller than the one of Portland
cement in Fig 3.
Considering the results of microstructure and X-ray
analysis of used catalyst, it can be stated that this material
can replace a part of the binding materials and behave as
an active mineral additive.
Microstructure analysis of the surface of coarse ag-
gregate – 2–4 mm fraction expanded-clay was carried
out. In Fig 6 the microstructure's photo of the surface of
grain of expanded-clay is provided. Fig 7. Microstructure of the expanded-clay pore

192
3.2. Microstructure analysis of the structure
of hardened expanded-clay lightweight concrete
Optical microscope was used to analyse the internal
structure of the samples. The following location of the
hardened product was selected: contact area of the used
catalyst with the formed cement stone. After the analysis
of contact location of catalyst waste with the cement
stone (after 2 days of hardening period), it can be noted
(Fig 8) that granule of the catalyst is adhered firmly to the
formed cement stone and fragmentation occurs through
the cement stone. Catalyst's granule is not over crystal-
lised itself, its structure remains unchanged. However, its
surface has formed firm bonds with the newly formed
minerals of the cement stone. These bonds are stronger
than the granule's extraction force. During the compres-
sion of the sample of expanded-clay lightweight concrete,
when tension appears, at first, bonds break between the
newly formed minerals of cement stone, but not between
the catalyst and cement stone. The compressive strength
of our expanded-clay lightweight concrete analysed is
5.1 MPa after 2 days of hardening.
Ageev et al. (1963) probed that when the amount of
cement is altered from 315 kg/m3 to 533 kg/m3, cubic
compressive strength increases by 46%. Bulk density of
expanded-clay varied in a range from 325 kg/m3 to
700 kg/m3. The increase of expanded-clay density by
115 % determines the increase of cubic compressive
strength of the samples by 67 %. The decrease of the
amount of expanded-clay determines the increase of cu-
bic compressive strength of the samples by 233 %. When
the amount of expanded-clay is decreased, the compres-
sive strength increases by 1.6 times. The main factor
determining compressive strength and deformability of
the expanded-clay lightweight concrete is the density of
expanded-clay and expanded-clay lightweight concrete.
The density of our analysed expanded-clay lightweight
concrete after 2 days of hardening is 1596 kg/m3, and
after 28 days of hardening – 1569 kg/m3. This can be
explained by the fact that in former case 30% of the cata-
lyst (comparing to the amount of cement) was used.
1
2 1
Fig 8. View of adhered catalyst waste and cement
stone (where: 1-cement stone; 2-catalyst)
In order to get more detailed view of cement stone in
the contact area, its view was zoomed in (Fig 8). Results
of the analysis with electronic microscope show that in
193
early cement's hardening stages together with ettringite
the syngenite is created, which fragments later. Further,
during hydration, needle C-S-H microcrystals (Fig 9) are
created within 24 hours. Due to their optimal spacial
arrangement and adherence, they form the core of the
strength of cement stone (Sasnauskas et al. 2001).
Fig 9. View of formed C-S-H microcrystals
After 28 days of hardening, the results of the ana-
lysed contact area between expanded-clay granule and
cement stone show (Fig 10) that expanded-clay granule is
fully adhered (through its full surface) to the newly
formed mass of cement stone, and large surface pores of
the expanded-clay are filled with the minerals of cement
stone. Adherence strength between expanded-clay gran-
ule and cement stone is larger than the strength of ex-
panded-clay granule, and, during the compression, the
sample fragments through the coarse aggregates and ce-
ment stone. Sand grains are adhered to the cement stone
completely in other way. Sand in such conventional hard-
ening conditions does not create strong bonds on its sur-
face. Cement stone, existing in the contact area between
sand and cement stone, at first looses contact with the
surface of sand grain. In order to improve the contact
strength between these materials, the hydrothermal hard-
ening conditions should be maintained. Chemical bonds
between sand and cement stone can be created only after
the processing in autoclave and after mechanical activa-
tion of the surface. The compressive strength of our ex-
panded-clay lightweight concrete analysed after 28 days
of hardening is 19.91 MPa.
Fig 10. Photo of microstructure of contact area be-
tween expanded-clay granule and cement stone
(where: 1-cement stone; 2-expanded-clay)
 Conclusions
Grains of the fine-grained catalyst waste are larger
than the particles of Portland cement, and their shape is
spherical (contrary to Portland cement). Size of 80 % of
the particles in the used catalyst varies from 30 µm to
112 µm. Catalyst waste analysed belongs to the group of
zeolites. After the X-ray structural analysis it was identi-
fied that it is faujasite.
The size of Portland cement particles varies from 0.3
to 140 µm, 50% of Portland cement articles have size of
7 µm. When particles of used catalyst are compared with
the particles of binding materials, we can notice that cata-
lyst particles are similar to the particles of binding mate-
rial. They are of the same shape, but the diameter of the
latter ones is 4 times smaller. The amount of sand parti-
cles with the size from 1 to 0.5 mm in the mixture is
equal to 46.73 %, from 4 to 2 mm – 30.2 % and from
0.25 to 0.125 mm – 20.16%. The size of the particles of
coarse aggregate is 2–4 mm.
Considering the results of microstructure and X-ray
analysis of used catalyst, it can be concluded that this
material can replace a part of binding materials and be-
have in the formation mass as an active mineral additive.
The contact in the expanded-clay lightweight con-
crete between the catalyst waste, granule of expanded-
clay and cement stone is strong. During the compression
of the samples, coarse aggregates and cement past start to
break after 28 days of hardening.
Acknowledgements
The authors are grateful for the support of this work
by the Forensic Science Centre of Lithuania Gabrielė
Juodkaitė-Granskienė, Vytautas Jonaitis and Jonas
Mincevičius.
Referentes
Furimsky, E. 1996. Spent refinery catalysts: environment, safety
and utilization, Catalysis Today 30(4): 223–286.
doi:10.1016/0920-5861(96)00094-6
Gailius, A.; Vėjelis, S. 2009. Termoizoliacinės medžiagos ir jų
gaminiai [Thermal insulating materials and their produc-
tion]. Vilnius: Technika, 247 p.
194
View publication stats
Green Cement Technology. Cement Types. [online], [vieved on
December 21, 2009]. Available on the Internet:
<http://www.ceratechinc.com/cement.asp>
LST 1577:1999. Concrete and mortar fillers. Technical re-
quirements. Vilnius. 1999. 6 p.
Mačiulaitis, R.; Žurauskienė, R. 2007. Mažo poringumo staty-
binė keramika iš vietinių ir technogeninių žaliavų [Low
Porosity Building Ceramics Produced from Local Tech-
nogenic Raw Materials]. Vilnius: Technika. 220 p.
doi:10.3846/1398-M
Mačiulaitis, R.; Vaičienė, M.; Žurauskienė, R. 2009. The effect
of concrete composition and aggregates properties on per-
formance of concrete, Journal of Civil Engineering and
Management 15(3): 317–324.
doi:10.3846/1392-3730.2009.15.317-324
Sasnauskas, K.; Skripkiūnas, G. 2001. Vandens ir kietosios
dispersinės fazės sąveika statybiniuose mišiniuose [Inter-
action of water and solid disperse phase in buildings mix-
tures]. Chemical technology (Cheminė technologija)
4(21): 25–30.
Stonys, R.; Pundienė, I.; Antonovič, V.; Goberis, S.; Alek-
nevičius, M. 2008. The effect of waste oil-cracking cata-
lyst on the properties of MCC-type castable, Materials
Science (Medžiagotyra) 14(1): 59−62.
Su N.; Fang H.-Y.; Chen Z.-H.; Liu F.-S. 2000. Reuse of waste
catalysts from petrochemical industries for cement substi-
tution, Cement and Concrete Research 30(11): 1773–
1783. doi:10.1016/S0008-8846(00)00401-4
Tommy, Y. Lo.; Tang, W. C.; Cui, H. Z. 2007. The effects of
aggregate properties on lighweight concrete, Building and
Environment 42(8): 3025–3029.
doi:10.1016/j.buildenv.2005.06.031
Uselytė, R.; Silvestravičiūtė, I.; Karaliūnaitė, I. 2007. Atliekų
panaudojimo naujiems produktams gaminti ir šių pro-
duktų įteisinimo galimybių studija. Ataskaita [Used waste
to produce a new products and theirs products validation
possibility studio. Report] 89 p.
Агеев, Д. Н.; Щеканенко, Р. А.; Заботин, Ю. Н. 1963.
Влияние состава керамзитобетона на его прочность
и деформации [Composition influence expanded-clay
lightweight concrete on its strength and deformations]
Бетон и железобетон [Concrete and ferroconcrete] 3:
83–88.
Скрамтаев, Б. Г.; Щубенкин, П. Ф.; Баженов, Ю. М. 1966.
Способы определения состава бетона различных
видов [Ways of definition of structure of concrete of vari-
ous kinds]. Москва: Издательство литературы по
строительству. 158 с.