Anda di halaman 1dari 6

J. Chem. Chem. Eng.

7 (2013) 206-211

Effect of Ball Milling Time on the Particle Size and

Morphology of Banana Stem Powder Soaked in
Sodium Hypochlorite Solution

Siti Nuraya Abd Samat1, Baharin Azahari1* and Azura A. Rashid2

1. School of Industrial Technology, Universiti Sains Malaysia, Minden 11800, Pulau Pinang
2. School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Nibong Tebal 14300, Pulau Pinang

Received: Septemper 14, 2012 / Accepted: October 5, 2012 / Published: March 25, 2013.

Abstract: Banana stem powder was soaked in 2% of sodium hypochlorite solution for 24 h at 40 °C then ball milled at variable
milling time to produce banana stem powder dispersions with variable particle size. The effect of ball milling time on the particle size
and morphology of the banana stem powder particles was examined. Results showed the mean particle size of the banana stem
powder reduced progressively with milling time. TEM (transmission electron microscopy) images showed that milling the banana
stem powder at 24 h resulted in the formation of fibre whiskers around the banana stem powder particles.

Key words: Banana stem powder, ball mill, sodium hypochlorite treatment, fiber whiskers, particle size.

1. Introduction postulated that lignin will be softened that leading to

opening of fibres and then the fibre bundles were
Natural fibres are bundles of individual strands of
separated by mechanical action using ball mill [2]. It
fibres. Most of the research has focused on fibre
was found that there was further opening fibres upon
bundles consisting of secondarily thickened, highly
ball milling of treated fibres and the total number of
elongated fibre cells [1]. However, within the walls of
fibres increased for equal weight of fibres.
plant cells, there is a second level of fibre structure on
The ball milling of natural fibre may reduce the
a much smaller scale, held together by bonds of pectin
particle size, disrupt the crystalline structure and break
and lignin, which is a weak bond whose strength is far
down the chemical bonds of the long chain molecules
less than that of the individual fibres. This is the
[3, 4]. Shear forces need to break the bonds and to
limiting factor because that when those bonds fail on
defibrillate the fibres into individual strand of fibres.
application of force, the whole fibre bundle fails. If
In this research, banana stem powder was treated with
these binding materials are removed and individual
2% of sodium hypochlorite and ball-milled at various
fibres are released without damaging them, they can
milling times to form banana stem powder dispersions.
provide high strength of the composites.
The reduction on mean particle size and
Chemical treatment followed by mechanical
morphological behaviour of banana stem powder were
treatment can be used to release individual fibres from
fibre bundles. In this study, initially the fibres were
subjected to chemical treatment with temperature, it is 2. Experiments
Corresponding author: Baharin Azahari, Ph.D., Associate The experiment was divided into two parts. The
Professor, research field: green product. E-mail: first part was done to study the effectiveness of
Effect of Ball Milling Time on the Particle Size and Morphology of 207
Banana Stem Powder Soaked in Sodium Hypochlorite Solution

sodium hypochlorite solution to defibrillate and form Table 1 Formulation of untreated banana stem powder
fibrils/individual strands in comparison with banana
Part by weight (pphr)
stem powder soaked in distilled water (untreated) Ingredients
Dry weight
without further mechanical treatment. The second part Banana stem powder 100
10% Potassium hydroxide 0.5
was done to study the effect of ball milling time with Anchoid dispersing agent 2
combination of sodium hypochlorite treatment on the Distilled water 1,500

particle size and morphology of banana stem powder dispersing agent and potassium hydroxide with water
dispersion. first followed by the addition of banana stem powder
2.1 Materials and Ingredients under stirring at a speed of 250 rpm for 20 min at
room temperature. After that, 5% of ammonium
Sodium hypochlorite solution and ammonia hydroxide was added to maintain the stability of
hydroxide were purchased from ZARM Scientific and dispersion.
Supplies (Malaysia) Sdn. Bhd.
2.4 Particle Size Measurement
2.2 Production of Banana Stem Powder
The particle size distribution of the banana stem
Banana stem was cut into small pieces, washed 2 powder dispersions with different milling time was
times with water and shredded by using a blender. The measured using the Malven Mastersizer 2,000 s. From
shredded banana stem was then pressed by using the the output of the machine, the mean particle diameter
hydraulic press to remove excess water followed by (d50) was taken as the average particle size.
drying in the oven at 110 °C for 2 h. After that the
dried banana stem was ground into powder and sieved 2.5 TEM (Transmission Electron Microscopy)
to obtain about of 53 µm of banana stem powder The dispersions containing banana stem powder
particle size and also to remove any foreign matter soaked in sodium hypochlorite solution with different
and large banana stem powder particles. milling times were deposited onto glow-discharged
2.3 Sodium Hypochlorite Treatment/Bleaching carbon-coated grids and allowed to dry. These grids
were then scanned with Philips CM 12 CRYO
About 30 g of the dried and sieved banana stem
transmission electron microscope.
powder was bleached with 450 g of a 2% solution of
sodium hypochlorite at 40 °C for 24 h. After bleaching, 2.6 Optical Microscopy-Dino Lite
the banana stem powder was ball-milled at room
The reductions in banana stem particle size,
temperature for 24 h. About 5% of ammonia
defibrillation and particle distribution in the dispersion
hydroxide was added as a preservative to maintain the
discovered by Dino-Lite digital microscope AM413T5
pH of the dispersion around pH 11 and also to prevent
Dino-Lite Pro with high resolution with supersized
further reaction of sodium hypochlorite solution
magnification at 500 ×.
within the dispersion. Other banana stem powder
dispersions were also prepared by ball-milling at room 3. Results and Discussion
temperature for 48 h and 72 h. Dispersion of banana
3.1 Defibrillation of Banana Stem Powder Soaked in
stem powder treated with the sodium hypochlorite
Sodium Hypochlorite Solution and Distilled Water
without ball-milling was also prepared.
Untreated banana stem powder without ball milling Fig. 1 shows the mean particle size (d50) of banana
was also prepared by using the formulation as shown stem powder, and banana stem powder after soaking
in Table 1. The mixing was done by adding the anchoid in distilled water and sodium hypochlorite solution.
208 Effect of Ball Milling Time on the Particle Size and Morphology of
Banana Stem Powder Soaked in Sodium Hypochlorite Solution

30 particles in the second peak is larger than the fraction

Mean particle size d50 (µm)

25 of particles in the first peak. The first peak

20 characterized by the smaller particle size of banana
15 stem powder, ranged in 0.86 µm to 1.52 µm that may
10 consist of the removal unwanted fiber components.
5 Meanwhile, the banana stem in powder form
0 exhibits a uni-modal particle size distribution
Banana stem Soaked in distilled Soaked in sodium
powder water hypochlorite
(between 0.86-100 µm) with mean particle size
Banana stem powder around 26 µm.
Fig. 1 Mean particle size (d50) of banana stem powder The ability of the fiber bundles to defibrillate and to
soaked in distilled water and sodium hypochlorite solution. form fibrils/individual strands after soaking in sodium
Results showed that the mean particle size of banana hypochlorite solution is shown in Fig. 3c. Result
stem powder soaked in distilled water and sodium shows that sodium hypochlorite treatment was capable
hypochlorite solution reduced from around 26 µm in softening and opening or separating the fiber
(powder form) to around 14 µm. The reduction of bundles to individual strands (fibrils). In contra,
mean particle size of the banana stem powder soaked banana stem powder soaked in distilled water, fiber
in sodium hypochlorite solution is due to the removal bundles of banana stem powder showed in Fig. 3b and
of the amorphous regions such as lignin, this postulated that distilled water is not strong enough
hemicellulose, non-cellulosic materials and surface to separate the fiber bundles to individual strands.
imperfections [5, 6]. However, sodium hypochlorite treatment alone is
As comparison, distilled water is also capable to not strong enough to completely separate the fiber
reduce the banana stem powder particle size and the bundles to individual strand as shown in Fig. 3c, fiber
results show that mean particle size of banana stem bundles still there mingle together with the individual
powder soaked in distilled water is similar with the strand of fibers in the dispersion. Therefore, the
banana stem powder soaked in sodium hypochlorite second part of this research, banana stem powder
solution (~14 µm). This may be due to the water dispersion was prepared with combination of sodium
soluble substances and fully amorphous structure of hypochlorite and mechanical treatment. The main
hemicellulose components that are partly soluble in purpose of ball milling is to achieve a good and stable
water [7] which has been removed and these break up dispersion of the banana stem powder in terms of
the banana stem powder aggregates. particle size distribution and mean particle size.
The particle size distributions of banana stem
powder, and banana stem powder soaked in distilled Banana stem powder
water and sodium hypochlorite solution is shown in
8 Soaked in distilled
Fig. 2. Bimodal particle size distributions in micron
In (%)

6 water
scale are observed for both banana stem powder
Soaked in sodium
soaked in distilled water and sodium hypochlorite hypochlorite
solution. The bimodal particle size distribution is
probably due to the removal of the waxy cuticle layer
0 10 20 30 40 50 60 70 80 90 100
and hydrophilic non-cellulosic components of the
Size (µm)
banana stem powder thus increased the ability of the Fig. 2 Particle size distribution of banana stem powder
fiber to defibrillate [8]. The number fraction of soaked in distilled water and sodium hypochlorite solution.
Effect of Ball Milling Time on the Partic
E cle Size and Morphology
M o
of 2099
Banana Stem m Powder So oaked in Sodium Hypochlo orite Solution


Mean Particle Size d50(µm)

0 24 48 72

Ball milling
m time of treeated banana steem powder
dispeersion (h)

Fig.. 4 Effect of ball

b milling tim
me on the mea an particle sizee
(d50) of banana steem powder soaaked in sodium
m hypochloritee

Fig. 3 Opticcal microscopyy of (a) banan

na stem in pow wder
form, (b) banana stem poowder soaked in distilled water
nd (c) soaked in
(untreated) an i sodium hypoochlorite soluttion.

3.2 Effect of Ball Millinng Time on the

t Particle Size
and Morphoology of Bannana Stem Poowder Soakeed in
Sodium Hyppochlorite Sollution

The resultts obtained from

fr the first part of the sttudy Fig.. 5 Optical microscopy
m of the particles of
o the bananaa
showed that sodium hypoochlorite soluution was cappable stem
m powder dispersions, ball m milled at variou
us times: (a) 0
h, (b
b) 24 h, (c) 48 h,
h (d) 72 h, respectively.
in softeningg and openiing or sepaarating the fiber f
bundles to individual strands
s (fibrils) comparedd to
distilled watter. Thereforee in the seconnd part, the efffect
of ball millling time (00, 24, 48 annd 74 h) on the
particles size and morphoology of banana stem pow wder
soaked in sodium
s hypocchlorite soluution for 24 h at
40 °C was exxamined.
Fig. 4 shoows the meann particle sizee of banana stems
powder soakked in 40 °C of sodium hyypochlorite at a 24
h soaking timme followed by variable ball b milling tiimes.
The mean particle
p size decreases prrogressively with w
increasing milling
m time from
f around 13.82 µm too 6.1 Fig.. 6 TEM imaages of banan na stem powder dispersionss
balll milled at variious milling tim
me: (a) 0 h, (b)) 24 h, (c) 48 h,,
µm. It shoows that ball b milling after chem mical
d (d) 72 h, respeectively.
modificationn is not onlly effective in reducing the
particle sizee but also caapable of brreaking the fiber f the point of colllision betweeen balls as well
w as on thee
bundles (cryystalline areaa) to fully am morphous areea of highh grinding ennergy obtained due to th he centrifugall
banana stem m powder as shown in i Figs. 5 and actiion in a ball mill
m [9] and tthis facilitatess the openingg
6. During baall milling process,
p enerrgy is releaseed at of the
t banana stem s powder particles alo ong the fiberr
210 Effect of Ball Milling Time on the Partic
E cle Size and Morphology
M o
Banana Stem m Powder So oaked in Sodium Hypochlo orite Solution

diameter dirrections and also along the fiber lenngth

directions too form fibre whiskers
w at siignificant millling
time (in this study at 24 h milling timee).
Gorton and
a Pendle [10]
[ showedd that increaasing
milling timee clearly decreased the average parrticle
size of the dispersions. On the otherr hand, Blackley
[11] reported that time ofo milling haad relatively little
effect upon the average particle
p size of
o the disperssion. Fig.. 8 Stability studies
s of banaana stem powd der dispersion
afteer soaking in soodium hypochhlorite solution
n with variablee
In addition, Liang and co-workers
c [12] reported that balll milling (a) 0 h and (b) 72 h
h, after 24 h storage time att
longer the milling tim me reduced the degreee of room m temperaturee.
crystallinity and after milling to longeer time whichh the
shown in Fig. 8.article
8 of bbanana stem powder, thee
fiber becomes completelyy amorphous.
ble the colloid stability off the banana stem powderr
It can be seen from Figs.
F 5 and 6 that millingg the
disppersion as shoown in Fig. 88.
banana stem m powder lonnger than 24 h resulted inn the
T colloidal stability oof banana stem powderr
formation ofo less fibre whiskers and no more fiber f
disppersion with 0 and 72 h baall mill after 24 h soakingg
bundles in the dispersioons. The redduction is maaybe
time in sodium hypochlorite
h solution is shown in Fig..
due to the breakage of thhe whiskers fromf the partiicles
8. A stable colloidal systeem is one in n which thee
as a result of more mechanical acction of the ball
partticles resist fllocculation orr aggregation n and exhibitss
milling proccess. As reporrted by Liangg and co-worrkers
a lo
ong shelf-life.. This dependds upon the balance
b of thee
[12], the lonnger milling time
t up to 722 h, the degreee of
repu ulsive and attractive
a foorces that ex xist betweenn
crystallinity of the fiberr bundles beccome compleetely
partticles. However, if the pparticles havee little or noo
amorphous as a shown in Figs.
F 5d and 6d.
repu ulsive forcee then instaability mech hanism willl
The partticle size diistribution of o banana stem s
eveentually take place
p sedimenntation.
powder soakked in sodium m hypochlorrite solution with w
Inn this case, banana
b stem ppowder dispeersion with 0
variable millling time (FFig. 7), shows that the lonnger
h ball millingg shows unnstable disp persion withh
the milling time up to 72 h, reduced the average
sedimentation phenomenon. Sedimentatio on occurs byy
particle sizee of banana stem
s powder as evident from f
setttling of susppended particcles under th he action off
the narrowerr particle sizee distributionn. The finer thhe p
grav vity. Howeveer, the sedimeentation is not observed inn
ability of the
t banana stem powdeer dispersionn as
the banana stem m powder diispersion witth 72 h balll
14 milling (Fig. 8bb). The reduuction of parrticle size off
12 0h bannana stem powder after 72 h ball milling hass
10 24 h produced mutuual repulsionn that resultts in stablee
48 h bannana stem pow wder dispersion.
In (%)

6 72 h
4. Conclusion
C ns
S of banana steem powder in sodium m
hyppochlorite sollution promoote the remov val of lignin,,
0 100 20 30 40
4 50 60 70 80 90 100
hemmicelluloses and
a artificial impurities frrom the fiberr
Size (µm)
surffaces which promotes
p the defibrillation
n of the fiberr
Fig. 7 Partiicle size distriibution of ban
nana stem pow wder
bunndles to formm individual strands whicch makes thee
soaked in sod dium hypochloorite solution with variable ball
milling time. fibrrils less dense and rigidd. However, soaking thee
Effect of Ball Milling Time on the Particle Size and Morphology of 211
Banana Stem Powder Soaked in Sodium Hypochlorite Solution

banana stem powder in sodium hypochlorite alone is 2005, 40, 4271-4278.

[3] Miuett, M. A.; Effland, M. I.; Caulfield, D. F. Influence
not strong enough to completely separating all the
of the Fine Grinding on the Hydrolysis of Cellulosic
fibers bundles to individual strands. Combination of Materials-Acid vis Enzymatic. Adv. In Chem. Ser. 1979,
sodium hypochlorite treatment with further ball 181, 7.
milling was introduced. Soaking the banana stem [4] Earland, C.; Raven, D. J. The Influence of Grinding on
the Structure of Cellulose. J. Textile Inst. 1977, 68, 69.
powder in sodium hypochlorite solution weakened the
[5] Howard, R. W. The Bleaching of Pulp Technical
fiber and helped their milling and reduced further the Association of the Pulp and Paper Industry; Lexington
mean particle size of the banana stem powder. Ball Avenue: New York, 1963; pp 104-115.
milling not only reduces the particle size but also [6] Mohanty, A. K.; Khan, M. A.; Hinrichsen, G. Influence
of Chemical Surface Modification on the Properties of
produces fiber whiskers around the particles and
Biodegradable Jute Fabrics-Polyester Amide Composites.
prolonging the milling time to more than 24 h, Composite Part A: Appl. Sci. Manufac. 2000, 31,
destroys some of these fiber whiskers. 143-150.
[7] Bledzki, A. K.; Mamun, A. A.; Lucka-Gabor, M.;
Acknowledgments Gutowski, V. S. The Effects of Acetylation on Properties
of Flax Fibre and Its Polypropylene Composites. Express
The authors would like to thank the Universiti Sains Polymer Letters 2008, 2, 413-422.
Malaysia for providing financial support. This work is [8] Ivan, J. D. S. Physicochemical Changes of Cellulose
supported under the Research University grant No. Subjected to Oxidative Conditions. Master Degree Thesis,
McGill University, December 1999.
[9] Prasad, B. M.; Sain, M. M.; Roy, D. N. Properties of Ball
Milled Thermally Treated Hemp Fibers in an Inert
Atmosphere for Potential Composite Reinforcement.
[1] Hornsby, P. R.; Hinrichsen, E.; Tarverdi, K. Preparation Journal of Materials Science 2005, 40, 4271-4278.
and Properties of Polypropylene Composites Reinforced [10] Gorton, A. D. T.; Pendle, T. D. Natural Rubber
with Wheat and Flax Straw Fibres: Part II Analysis of Technology 1981, 12, 21.
Composite Microstructure and Mechanical Properties. J. [11] Blackley, D. C. Polymer Latices; Chapman and Hall:
Mater. Sci. 1997, 32, 443. North London, 1997; Vol. 3, pp 24-25.
[2] Prasad, M. B. Properties of Ball Milled Thermally [12] Liang, X. H.; Gu, L. Z.; Ding, E. Y. Recrystallization
Treated Hemp Fibers in an Inert Atmosphere for Potential Behavior of Cellulose and Lignocellulose from Pinus
Composite Reinforcement. Journal of Material Science Massoniana. Wood Sci. Technol. 1993, 27, 461.