CHARACTERIZATION TECHNIQUE

3.8 Characterization Experiment

The materials that were used in the manufacturing of the filters were sampled for
characterization. These samples include; three clay raw materials (Bombowuha clay,Hossaina
clay,Leku clay) and two combustible materials (sawdust and teff husk).Samples of the finished
filters were also taken for characterization. The characterization experiment was used to
determine the surface morphologies and the elemental compositions, crystalline phase
identification and thermal analysis of the raw samples. The surface morphologies and the
elemental compositions of the samples were characterized using the Scanning Electron
Microscope (SEM) and Energy Dispersive X-ray Spectroscopy (EDS) coupled device, the
thermal stability and fraction of volatile components of the raw materials sample were
analyzed using Differential Thermogravimetric analysis (DTG) device.while the elemental
compositions of the samples were obtained using the X-Ray diffraction (XRD) and the elemental
compositions of the samples were obtained using Energy Dispersive X-ray Spectroscopy (EDS).

Powder X-Ray Diffraction (XRD) analysis

X-ray diffraction (XRD) is widely utilized to elucidate the structure of crystalline
materials. It is a technique used to confirm the structural characteristics of a synthesized
specimen providing with a unique fingerprint of samples under investigation.
In this study,analysis of sample powder of three clay raw materials (Bombowuha clay,Hossaina
clay,Leku clay) were analysed using the X ray powder diffractometer (XRD- 7000S ,Dangil
shimadzu-south Korean corporation product ) operating in Bragg-Brentano geometry with Cu-
Kα radiation and Ni filter and it has a wavelength of 1.54056 Å with 2kw or 3kw which is
controlled by computer software. The instrument setting for each test at room temperature
was: tension = 45 kV, current = 40 mA and a scan rate of 2o per minute, Data collection
will be carried out in the 2θ range 6-82 °, with a scanning step of 0.02 °. Samples for the X-
ray analysis were ground before sieving them through the 270 mesh sieve. Around 0.2-0.5
g of ground/powder samples were then mounted on an aluminum holder before conducting the
XRD analysis and the sample holder surface were smoothed off in order to absorb the X-ray
beam regularly. The crystalline phase identification were carried out by comparing crystal inter
plannar distance or d-spacing in the differentiating pattern to their integrated intensity with
known standards in the JCPDS (joint committee on powder diffraction standards) standard file.
The diffraction pattern was plotted within the XRD machine by generating a scan with
continuous scanning mode for the intensity of peak as the Y-axis versus (2θ) as the X-axis. XRD
was also used to analyse the phase changes that the product filter samples underwent
during different firing or sintering temperature(800°c and 900°)?.
FIG. 1.X-RAY DIFFRACTION PATERN (PAHSE ANALYSIS) OF BOMBOWUHA KAOLIN
CLAY
EXAMPLE

TABLE 1: XRD RESULT OF BULK BOMBOWUHA CLAY SAMPLE SHOWING THE

QUANTITY OF DIFFERENT PHASES
PHASE IDENTIFIED WEIGHT %
FIG. 2. HOSSANA BULK KOLINITE CLAY XRD

FIG.3. LEKU CLAY

OTHER EXAMPLE
XRD was used to analyse the crystalline phases in the suggested formula. In the XRD trial, the
triaxial formulation was mixed for 1 hour in a ball mill before being placed in a sample holder
and the diffraction patterns were recorded.
From jouranl
The mineralogical data were obtained on powdered samples using XRD instrument Phillips
PW1700 series automated powder diffractometer using CuKαradiation at 40 Kv/40mA from
5°<2θ<85° with the step size 0.04 at the counting time of 2 seconds. Both random and oriented
powder samples were studied and were compared with International card for diffractometer data
(ICDD).

XRD Result analysis

RESULTS AND DISCUSSION

Figures 1 to 5 showed the X-ray Diffraction (XRD) of the five clay samples. Asero
1 and Fajo 1 had the highest intensity of Q-Quartz at 10,000 intensity while Agba-
Akin clay 1 had the least intensity of XRD at 27 position (02Theta) copper.
The Ajebo1 clay XRD displayed K-Kaolin as the major content of the clay. From
Figure 6, the five selected clays samples had the same Experimental Physico-
Mechanical Properties but deviated after the compressive length (MPa). Ile Ise
Awo1 (IA1) had the highest Crack Formation while Agba-Akin1 (Onibode had the
least Crack Formation). Ajebo1 (AJ1) and Ile Ise Awo1 (IA1) had almost the same
Experimental Physico-Mechanical Properties.

EX. 3.2. X ray diffraction

The results of all the minerals estimated through X-ray diffraction are given in
Table 2.The nature of the impurities was determined by studying the crude samples
(Figs. 2 and 3); quartz is the dominant impurity (101 reflection at 3.34 Å), all the
more so for the ClaySej1 sample with a small amount of feldspar. The ClaySej2
sample contains quartz and calcite (reflection at 3.03 Å).

The following mineralogical components were identified in the purified

fraction: illite (ICDD reference pattern: 00-002-0050) with a characteristic
reflection at 10 Å, is the principal mineral. The presence of kaolinite (ICDD
reference pattern: 00-001-0527) with a reflections at 7.14 Å and 3.57 Å which
disappear after heating at 500°C.

The mineralogical composition is the same in all cases, mainlyincluding

kaolinite, illite, quartz, calcite and feldspar (Table 2).
RESULT TO EX.

3.5. Study of the thermal behavior by XRD

The mineralogical mutations during the firing process were analyzed by X-ray
diffraction and the X-ray diffractograms of the raw clays after heating at 300, 600,
800, 1000 and 1200 °C for 3 h are given in Figs. 6 and 7.The mineralogical
structure and other physico-chemical properties of various types of clay samples
have been extensively studied and discussed in the literature (Moore and Reynolds,
1997; Aras, 2004;Azzouz et al., 2011). Kaolinite, which is present in both samples,
is not subject to the effect of temperatures below 300 °C and disappears completely
at atemperature of 600 °C. Illite, on the other hand, gradually decreases until 800
°C. The calcite mineral undergoes the same process as illite.From this temperature
on, the destruction of kaolinite coincided with the appearance of an amorphous
product which can be metakaolinite (Kakali et al., 2001).
 [18] Ewelina Klosek-Wawrzyn, Jan Matolepszy, Pawel Murzyn, “Sintering Behaviour of Kaolin with
Calcite”, Procedia Engr, 57. 572-582. 2013
The XRD result for the clay raw material is presented in Figure 4.4.0.
The XRD analysis revealed that, the clay showed strong peaks of a sodium aluminum silicate

compound know as Albite, which is a common feldspar and has the chemical formula of

NaAlSi3O8. The ERD also showed some weak peaks of other elements, which were revealed by the

EDS scan as Potassium (K), carbon (C), Fluorine (F), Calcium (Ca), Iron (Fe), Titanium (Ti) and Magnesium
(Mg).
SCANNING ELECTRON MICROSCOPY (SEM) AND ENERGY DISPERSIVE
SPECTROSCOPY (EDS) ANALYSIS
Scanning electron microscopy (SEM) is one of the most versatile instruments available for the
examination of the morphology of solid materials. SEM works under the principle of interaction
between the specimen and the electron beam producing a signal from secondary electrons
and backscattered electrons which can be used to produce images.
In this investigation, the morphology analysis of CPWF product sample were carried out using
a NOVA NANO SEM 230 (FEI) scanning electron microscope with the VCD detector in high
vacuum. The output voltage from the electrons gun is 3000 V and the actual voltage reaching the
sample is 2000 V. With this detector the signal were collected from both secondary and
backscattered electrons simultaneously. Samples will be sputter coated with gold to reduce
static charging just before SEM analyses. In addition to the morphological analysis, the
elemental composition of CPWF product sample will be analyzed.

In the case of the SEM and EDS analysis, the samples were characterized in their unprocessed
states. Hence, the powdered sawdust, clay and hydroxyapatite samples were characterized
without special specimen preparation. The SEM/EDS analysis was carried out at the Sheddah
Science Center in Gwagwalada, Abuja, Federal Capital Territory, Nigeria. They were conducted
on the Model Zeiss Evo 60 Environment scanning electron microscope (Carl Zeisis Canada Ltd.,
Canada) that was instrumented with a model Bruker AXS Quantax 4010 energy dispersive X-ray
spectroscopy (EDS) system (Carl Zeisis Canada Ltd., Canada).
OTHER EXAMPLE

Scanning Electron Microscope and Energy-dispersive Spectroscopy (SEM/EDS): A

scanning electron microscope (SEM) Sigma advance analytical scanner with simultaneous
EDS (Carl Zeis NTS GmbH Germany) was utilized to analyse the powders (particle shape,
level of agglomeration) and also the microstructure evolution of the fired samples. The
EDS analysis was undertaken simultaneously with the microstructure observations, which
supports identification of the phases. EDS quantifies the elemental composition of a sample
by measuring the wavelength and intensity of X-rays generated within a Scanning Electron
Microscope. The X-rays are generated as a result of interaction of the electron beam with the
electronic orbitals of the atoms. Each element emits a characteristic set of X-rays under
electron bombardment, and these are detected to identify the elements in the sample. The
final samples were fired to different temperatures and the Microstructure evolution was
investigated by scanning electron microscopy, energy-dispersive spectroscopy and x-ray
diffraction analysis. At temperatures in the 850-1150°C range.
The preparation of green bodies for microstructural analysis is more difficult than for dense
fired samples, since they are weaker and tend to break up during grinding and polishing.
For this reason, the green ceramic specimens were manually broken and a flat ceramic surface
was prepared for analysis by manual grinding in order to reduce the amount of crumbling of
the surface layers. The samples were then cleaned with an air jet, attached to an
aluminium disc and PVD coated with gold to ensure that their surface was electrically
conductive.

SEM result analysis

 3.4.1 DIFFERENTIAL THERMOGRAVIMETRIC(DTG) ANALYSIS
Differential Thermogravimetric analysis (DTG) is the method in which the effect of heat on the
mass of a sample with time is studied to obtain quantitative information. It is an analytical
technique used to determine a material’s thermal stability and its fraction of volatile
components by monitoring the weight change that occurs as a specimen is heated. The
measurement is normally carried out in air or in an inert atmosphere, such as helium or argon,
and the weight is recorded as a function of increasing temperature.
In this particular study, the differential thermal analysis (DTA) was performed on three clay raw
materials (Bombowuha clay,Hossaina clay,Leku clay) and two combustible materials (sawdust
and teff husk) and filter product powder samples were carried out in air with a Dangil shimadzu
DTA unit DTG-60(south Korea) instrument in the temperature range of 50-1500°C and at a
heating rate of 20°C/min in air atmosphere by taking sample of 4 to 5 mg weight.
Differential thermal analysis (DTA) was performed on the porcelain stoneware powder, using a
Setaram (Labsys) DTA unit in air atmosphere. The test was carried out at a heating rate of
50ºC/min, in platinum crucibles and calcined alumina as reference.

DTG analysis result

Fig.1.TGA/DTA analysis of Bombowuha bulk clay

Fig.1.TGA/DTA analysis of Hossana bulk clay
fig .3.TGA/DTA analysis of eucalyptus saw dust

Changes in chemical or physical properties of material as a function of temperature in a controlled

atmosphere may be determined by thermal analysis, (NadiyeTabbiruka and Dandy 1975) which covers
changes in energy, weight, crystal dimension and evolved volatiles. This enables clays to be classified
according to their heating patterns. For this study, only differential thermal analysis (DTA, Mackenzie,
R.C; (1970).) and thermogravimetric analysis (TGA) were used.
 o Nadiye-Tabbiruka, M.S., and Dandy, A.J., (1975). The effect of heat in vacuo on the
microporosity of sepiolite. Clays and clay minerals 23:428-432.

Lumps of the clay were collected from different location and different depths around the dam. To make
laboratory-sized sample, the lumps were mixed and crushed together so that a representative sample
can be used for analysis. The crashed clay was mixed with de-ionized double distilled water and stirred
with a motorized stirrer at 1000 revolutions per minute over night to concentrate the clay particles. The
suspension was left to settle for twenty four hours and the top layer was decanted, filtered and dried in
an oven at about 373K for a day.
IThe resultant structural formula for the clay sample was deduced to be FeAl6SiO10(OH)6and it account
for crude kaolinite containing quartz and microcline. And according to Ekosse G (2001), pure kaolinite
has a theoretical chemical composition of 46.55 wt.% SiO2, 39.49 wt.% Al2O3and 13.96 wt.% H2O, and
in nature it is hardly found in pure form. It is always associated with two types of impurities resulting
from accessory minerals that adhere to the surface of kaolinite, and those resulting from isomorphous
substitution of an element into the kaolinite structure.
 o Ekosse, G.; (2001); Provenance of the Kgakgwe kaolin deposit in southeastern Botswana and its
possible utilization; Applied Clay Science;20:137-152.
o Lanson Bruno; (1997). Decomposition of experimental x-ray diffraction patterns (profile fitting):
A convenient way to study clay minerals; Clays and Clay Minerals; 45:132-146.
o Blakemore, L.C., Searle, P.L., Daly, B.K., (1987). Methods for chemical analysis of soils. N.Z. Soil
Bureau. Sci. Rep. 80. Soil Bureau, Lower Hutt, New Zealand.
o Grim, R.E., 1968. Cation Exchange Capacity of clay minerals in Clay Mineralogy McGraw-Hill,
New York.
o Grim, R.E.
o Velde, B; 1992. Introduction to clay minerals; First edition; Chapman and Hall; UK.
o INSLEY,H. AND EWELL, R.H., THERMAL BEHAVIOR OF KAOLIN MINERAL:NAT. BUREA OF
SATNDARDS, JOUR. OF RESEARCH, VOL. 14,1935

3.4. Differential thermal analysis (DTA) and thermo-gravimetry (TG)

The differential thermal analysis (DTA) and thermo-gravimetry (TG) measurements of the ClaySej1 and
ClaySej2 are given in Fig. 5.As canbe observed in the DTA curves, five consecutive endothermic peaks
appeared for all the clays and one exothermic peak for the ClaySej1 sample at 950 °C. These first
endothermic peaks were at a temperature lower than 250 °C, proving the removal of weakly-bound
water. The peaksof the ClaySej2 at 314 °C and 375 °C show the existence of impurities;while the
endothermic peak found at about 488 °C indicates the dehydroxylation of the kaolinite.The
decarbonation reaction of calcite (686 °C) was detected in the structure as well as the formation of
quasi-amorphous materials in the ClaySej2 sample. The total mass loss of the ClaySej1 and ClaySej2
samples was 9.2% and 14.6% respectively (Fig. 5). The greater mass loss for the ClaySej2 compared to
that of ClaySej1 is justified by its mineralogical composition and its content of alkaline earth oxides.
4.1.3 Hardness
4.1.3.1 Vickers Hardness
The variation of material hardness with applied load is shown in Figure 4.12. The
average of at least 10 measurements was used for each data point. From this figure, the ZTA
showed a hardness of 1700 HV at 1 kgf that drops to 1509 HV at higher test loads (2 kgf to 50
kgf). SiC also showed load dependent hardness with a value of 2596 HV at 1 kgf which is
higher than the plateau value of 2413 HV measured at higher loads of 2 kgf to 10 kgf. This is
an indication of indentation size effect (ISE), which is primarily caused by incomplete and
reversible deformation at low loads as shown in Figure 4.13. The load independent values
1509 HV and 2413 HV were taken as the hardness of ZTA and SiC, respectively.
SiC displayed excessive cracking and spalling at loads beyond 3 kgf as shown in
Figures 4.14, which adds to measurement uncertainties. Hence, its test result was limited to
10 kgf load. On the other hand, measurements on ZTA are compromised by high porosity that
made indentation diagonals partly invisible especially at low loads, as shown in Figure 4.15.
RESULTS
The XRD analysis of the hydroxyapatite-doped filter shows peaks that reveal the compound

cancrinite. This is a complex carbonate and silicate compound of sodium, calcium and aluminum. It

has the formula Na

Ca2 [(CO

3
Al6

Si6O24)].2H

2O

(http://en.wikipedia.org/wiki/cancrinite). There were a few weak peaks that were not identified in

the XRD scan. The EDS analysis of the hydroxyapatite-doped filters also revealed evidence of

Potassium (K), Titanium (Ti), Iron (Fe), Magnesium (Mg) and Phosphorus (P). All the elements

identified both in the EDS and XRD scan of the filter sample were also found in the clay analysis,
expect for phosphorus, which is found in the hydroxyapatite.
In the XRD analysis of the filter without hydroxyapatite, two major compounds were found. The

first one being Allophane, is an amorphous hydrous aluminum silicate clay mineral with the

formula Al

2O32SiO
23H

O. The second compound identified in the XRD peaks is a potassium

aluminum silicate hydroxide compound with the formula K

0.7

Al2

(SiAl)

4O10(OH). The EDS analysis

also revealed the presence of Titanium (Ti) and Iron (Fe).

SEM images of the two types of filters are presented in Figure 4.4.8. The two materials have similar

layered microstructure morphologies. There was also evidence of porosity and some inclusion

particle formation on the surface of the two filters.