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Anomalous Reduction in Surface Area During Mechanical Activation of Boehmite
Anomalous Reduction in Surface Area During Mechanical Activation of Boehmite
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Sanat K Roy
Indian Institute of Technology Kharagpur
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Article history: Mechanical activation of boehmite (γ-AlOOH), synthesized by thermal decomposition of gibbsite, has been
Received 15 April 2010 carried out in a planetary mill up to 240 min. After an initial decrease in particle size up to 15 min, the particle
Received in revised form 27 November 2010 size shows an increase with further milling; the median size (d50) has increased from 1.8 to 5 μm during 15 to
Accepted 11 December 2010
240 min of milling. Quite unexpectedly, the BET specific surface area of the sample (N2 adsorption method)
Available online 21 December 2010
decreases continuously from 264 m2/g to 67 m2/g with milling. A detailed analysis of N2 adsorption/
Keywords:
desorption isotherms has indicated that the decrease in surface area is associated with: (a) change in narrow
Boehmite slit like pores with microporosity to slit shaped pores originating from loose aggregate of platelet type
Mechanical activation particles; and (b) shift of maxima in pore size distribution plot at ~ 2 nm and ~ 4 nm to dominantly ~ 23 nm
Pore size distribution size pores. Scanning electron microscopy (SEM) studies have revealed that during milling, initial breakage is
Amorphisation followed by agglomeration/fusion of particles with consequent loss in porosity. Amorphisation, decrease in
Microstrain microcrystallite dimension (MCD) and increase in microstrain (ε) are indicated from a detailed analysis of X-
Reactivity ray powder diffraction patterns and Fourier Transform Infrared (FTIR) spectra. Reactivity of samples,
expressed in terms of increase in dissolution in alkali (in 8 M NaOH at 90 °C) and decrease in boehmite to γ-
Al2O3 transformation temperature, increases with milling time. The nature of correlations between reactivity
and physico-chemical changes during milling has been analyzed and discussed.
© 2010 Elsevier B.V. All rights reserved.
0032-5910/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2010.12.010
T.C. Alex et al. / Powder Technology 208 (2011) 128–136 129
behaviour. Attempt has also been made to correlate reactivity with tion. The full widths at half maxima (FWHM) were determined using
physico-chemical characteristics of mechanically activated samples. XRDA software [15]. The instrumental broadening was corrected
using quartz as an external standard. The corrected width (β) was
2. Materials and methods used to determine average micro-crystallite dimension (MCD) and
microstrain (ε) using Williamson–Hall equation [16,17]:
2.1. Synthesis of boehmite
0:9λ
The boehmite used in the study was prepared by thermal decom- β⋅ cos θ = + 4ε ⋅ sin θ ð2Þ
MCD
position of a coarse grained (d50 = 120 μm) gibbsite. The gibbsite
sample was supplied by M/s National Aluminium Company (NALCO),
Bhubaneswar, India. Thermal decomposition of gibbsite was carried MCD and ε were obtained from the intercept and slope of straight
at 350 °C for 2 h in a muffle furnace under static air atmosphere to line fitted to β cosθ vs. sinθ plot for eight strongest peaks. θ and λ
obtain phase pure boehmite. The temperature and time of decompo- correspond to the Bragg angle and wavelength of the X-ray radiation
sition were determined based on exploratory studies involving TG/DTA used.
studies, heating experiments and phase characterization. Fourier Transform Infrared (FTIR) spectra of the boehmite
samples were recorded on a Nicolet 5700 Spectrometer in the region
2.2. Mechanical activation experiments
p 1 ðC−1Þ p
= a + a ð1Þ
na ⋅ðp0 −pÞ nm ⋅C nm ⋅C ⋅ p0
of 4000–400 cm− 1. The samples were mixed with KBr and pressed in
the form of pellets to record the spectra.
Reactivity of the milled samples was evaluated in terms of: (a) its
thermal transformation temperature to γ-Al2O3; and (b) leachability
in alkali under specified condition. A simultaneous TG–DTA appara-
tus (model: SDT Q600, TA Instruments, USA) was used to study the
thermal transformations. Thermal analysis of the milled samples was
carried out at heating rate of 10 °C/min and under a constant flow of
high purity argon gas. The DTA peak temperature corresponding to
boehmite ➝ γ-Al2O3 transition was taken as a measure of reactivity.
Lower the temperature of transformation, higher will be the reac-
tivity. Alkali leaching tests were carried out under following con-
dition: temperature—90 °C, NaOH concentration—8 M, duration—30
min and stirring speed—300 rpm. Reactivity in this case was
expressed in terms of percentage dissolution.
Fig. 2. Size distribution and characteristic diameters of boehmite milled for different
durations.
2.5. Correlations
3.2. Mechanical milling and characterization
Binary correlation (rxy) between reactivity (y) and physicochem-
ical characteristics of the samples (x), namely, median diameter (d50), 3.2.1. Particle size distribution
geometrical specific surface area (SSAgeo), BET surface area (SSABET), The particle size distribution and characteristic diameters, d90, d50
microcrystalline dimension (MCD) and microstrain (ε) were calcu- d10 of the milled and original samples are given in Fig. 2. The d90, d50,
lated to understand the nature of correlation. The correlation was and d10 values for the original sample were 153.4, 110.2 and 77.0 μm
calculated by dividing covariance between x–y with variance x and y respectively. The variation of characteristic diameters with time
[18]. indicates that the particle size decreases during initial stages of
milling (~15 min) and with further milling an increase, especially in
d90 and d50, is observed. Between 15 and 240 min, d50 shows an
3. Results and discussion increase from 1.8 μm to 5 μm and d90 increases from ~30 μm to 42 μm.
These results are in sharp contrast with the particle size results
3.1. Boehmite reported by Tsuchida and Horigome [8] which showed an initial
decrease in particle size followed by a steady size. As reported by
SEM micrographs in Fig. 1 show the morphology of the boehmite Juhasz and Opoczky [20,21], it is likely that the fine particles undergo
synthesized after thermal decomposition of gibbsite. The boehmite aggregation and agglomeration during prolonged milling which leads
particles were of uniform size (Fig. 1(a)) and preserved the agglomerate to an increase in particle size.
structure (Fig. 1(b)) of the precursor gibbsite. The particles showed
large number of slit shaped pores (Fig. 1(c)). These slit shaped pores 3.2.2. Surface area and porosity
are unique to the sample. The pores are developed during thermal The BET surface area of the boehmite samples obtained after
decomposition as a result of water removal preferentially along the different durations of milling is given in Fig. 3. Fig. 3 also shows the
interlayer regions [1,2,19]. The sample showed a very high BET surface geometrical surface area as determined from particle size analysis
area (264 m2/g) which is attributed to the unique pore structure present assuming spherical geometry for the particles. It is striking to note
in the sample. that the BET surface area decreases exponentially from 264 m2/g, by
Fig. 3. Variation of specific surface area (SSABET and SSAgeo) with milling.
T.C. Alex et al. / Powder Technology 208 (2011) 128–136 131
Fig. 6. Typical SEM micrographs of boehmites milled for different durations: (a), (b) 3 min; (c), (d) 60 min; (e), (f) 240 min.
Fig. 9 shows the variation of micro-crystallite dimension (MCD) bending mode and is a characteristic of physically adsorbed water
and microstrain (ε) with milling time. It is observed that MCD [27,29].
decreases exponentially with milling time. The microstrain (ε) shows Milling has induced changes in IR spectrum. IR peaks for Al–O–H,
a reverse trend. The microcrystallite boundaries indicate high energy especially in the region of 3000–3500 cm−1, show a decrease in
regions. A decrease in MCD and an increase in ε signify an increase in intensity and become less and less resolved with milling time. This is
the stored energy of the material [25]. indicative of decrease in crystallite size and amorphisation [28]. This
observation supports X-ray results (Figs. 7–9). IR peaks, at 475, 597 and
3.2.5. FTIR spectra 744 cm−1, corresponding to AlO6 are also affected. In the initial stages
Fig. 10 gives IR spectra of boehmite before and after milling for of milling (after 15 min), these peaks are better resolved and have
different durations, up to 240 min. As indicated in Table 1, all the IR become equally prominent. With further milling, the peaks at 475 and
peaks in the spectra of the unmilled sample have been assigned to 744 cm−1 decrease in intensity and almost merge with the central peak
boehmite, based on published literature [26–30], and confirmed its at 597 cm−1. It is also observed that the peak at 475 cm−1 progressively
purity. The spectrum has essentially three parts. IR peaks at 3430, shifts to 518 cm−1 after 240 min of milling. These changes in the AlO6
3300, 3090, 1150, 1070 and 744 cm−1 can be assigned to various Al– IR peaks result from a combination of phenomena, including loss of
O–H vibration modes. IR peaks at 475, 597, and 744 cm−1 correspond crystallinity, microstrain and amorphisation as indicated by the analysis
to vibration modes of AlO6. The peak at 1640 corresponds to H–O–H of XRD results (Figs. 7–9).
T.C. Alex et al. / Powder Technology 208 (2011) 128–136 133
Fig. 9. Variation of microcrystallite dimension (MCD) and microstrain (ε) with milling time.
134 T.C. Alex et al. / Powder Technology 208 (2011) 128–136
Fig. 10. FTIR spectra milled for different durations 0, 15, 30, 60, 90, 120, 180 and 240 min.
Table 1 Table 2
Assignment of various IR peaks in the spectra of the unmilled boehmite. Peak Binary correlations (rxy) between reactivity (y) and physicochemical characteristics (x)
assignment is based on published literature [26–30]. of the samples.
Prof. Sanat K Roy, Head, Metallurgical & Materials Engineer- Prof. Surya Pratap Mehrotra, Professor, Indian Institute
ing at Indian Institute of Technology (IIT), Kharagpur (India) of Technology (IIT), Kanpur (India) obtained his B.Tech and
holds bachelor and doctoral degrees in Metallurgical En- P.hD in Metallurgical Engineering from IIT, Kanpur. He has
gineering from IIT, Kharagpur, and has 40 years of teaching over three decades of teaching and research experience.
and research experience. His main areas of interest include During the period, 2002–2008, he served as a Director at
Mineral Processing, Extractive Metallurgy, Environmental National Metallurgical Laboratory, Jamshedpur (India). His
Degradation of Materials, Laser Processing of Materials and research interest includes mineral processing and extractive
Nano-ceramics. metallurgy, process design & development and mechanical
activation of solids.