Physicomechanical Properties of Agro Waste Filled High Density Polyethylene Bio-Composites

Journal of Institute of Polymer Engineers (JIPE) Vol. 1, No.
2, October, 2017
PHYSICOMECHANICAL PROPERTIES OF AGRO WASTE FILLED HIGH DENSITY

POLYETHYLENE BIO-COMPOSITES
1*
Ogah, A. O. and 2Chukwujike, I.C
1*
Industrial Chemistry Department, Faculty of Science, Ebonyi State University, Abakaliki,
P.M.B. 053, Ebonyi State, Nigeria
2
Department of Polymer and Textile Engineering, Faculty of Engineering, Nnamdi Azikiwe
University, P.M.B. 5025, Awka, Anambra State, Nigeria
*
Corresponding author E-mail address: anselmogah@gmail.com
ABSTRACT
The objective of the study was to characterize and compare flexural, impact, water absorption and
thickness swelling properties of agro waste filled high density polyethylene (HDPE)
biocomposites. The agro wastes utilized include corncob fiber (CCF), rice hull fiber (RHF), walnut
shell fiber (WSF) and flax shive fiber (FSF). The composites were compounded by extrusion
processing technique. The impact and flexural properties, diffusion coefficient and maximum
moisture contents of the composites were investigated. Results indicated that the CCF/HDPE
composites showed higher diffusion coefficient of 8.57 x 10-12m2s-1 while the FSF/HDPE
composites showed least diffusion coefficient of 3.14 x 10-12m2s-1 compared to 7.64 x 10-12m2s-1
for rice hull fiber and 7.97 x 10-12m2s-1 walnut shell fiber composites. The RHF/HDPE composites
showed higher values of thickness swelling of 12 %, while the FSF/HDPE composites showed the
lowest value of thickness swelling of 0.5 % compared to 7% for CCF/HDPE and 6.45% for
WSF/HDPE composites. The flexural modulus (MOE) and un-notched Izod impact strength
increased with a decrease in flexural strength (MOR) of the composites compared to the neat
HDPE. RHF/HDPE composites showed superior MOR of 22.5MPa. FSF/HDPE composites gave
superior MOE of 3.0 GPa and WSF/HDPE composites exhibited superior un-notched Izod impact
strength of 52.5 J/m. The study showed that agro filler sample load of 65 wt. % could be used in
composite formulation with good result.
Keywords: Agro wastes, High density polyethylene, Mechanical properties, Thickness swelling,
Water absorption
1.0 INTRODUCTION
The mounting global environmental and social concern, high rate of decline of petroleum resources
and novel environmental policy has engendered the search for green composite materials which
are environment friendly [1]. Thousands of tons of agro wastes are produced every year globally
consequently these crop residues can serve as a source material for developing bio-based polymer
composites [2]. Today, the utilization of agro waste materials is common in wood-limited countries
and the fight against climate change caused by the felling of trees, since they are easily available
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Journal of Institute of Polymer Engineers (JIPE) Vol. 1, No. 2, October, 2017
and inexpensive. The use of agro fibers derived from annually renewable resources render positive
environmental benefits with respect to final disposability and raw material utilization [3].
Agro fillers have a number of techno-ecological advantages over synthetic fillers since they are
renewable and abundant resources, being less damaging to the environment, and cause less
abrasive wear to processing equipment. There is a wide variety of agro-based materials that can
be used to reinforce thermoplastics. These include wood fibers as well as a variety of agro-based
fibers such as wheat straw, rice husk, corn stover and shells of various dry fruits. The problem
associated with using agro-based fibers in thermoplastic composites is moisture absorption [4].
A moisture build-up in the fiber cell wall can lead to thickness swelling and dimensional changes
in the composite [5]. The thickness swelling can lead to reduction in the adhesion between the
fiber and the polymer matrix. Thus, the water absorption can have undesirable effects on the
mechanical properties of the composites [6]. The water uptake of natural fiber composites can be
reduced considerably by using coupling agents to assist with fiber-matrix adhesion [7]. At low
fiber content, the matrix restrains expansion of the fibers while at high fibers content, there is
insufficient matrix to maintain this restrain and the fibers can take up more water than its weight
in water [8].
Although, there has been considerable research devoted to the physical and mechanical properties
of agro-based fibers thermoplastic composites [9-12], there are no experimental data on the
physical and mechanical properties of agro waste fibers at higher filler loading.
The objective of the study was to characterize and compare flexural and impact, water absorption
and thickness swelling properties of corncob, rice hull, walnut shell and flax shive agro byproducts
based high density polyethylene composites using 65 wt. % filler loading.
2.0 MATERIALS AND METHODS

2.1 Materials
The polymeric matrix used was HDPE (Ineos®HP54-60) of density 0.95g/cm3, MFI=0.35g/10min;
provided by Composite Materials and Engineering Center, Washington State University, Pullman,
USA. Flax shive fiber was supplied by Biolin Research Inc., 161 Jessop Avenue Saskatoon,
Canada, walnut shell fiber was supplied by Composition Materials Co. Inc. USA. The rice hull
fiber was supplied by Rice hull Specialty Products, USA, and corncob fiber by Mt. Pulaski
Products, USA. The agro fibers were of 60-100 mesh size and were used as supplied by the
manufacturers.
2.2 Chemical composition of agro fibers

The basic constituents of the agro fiber samples used in this study were determined according to
TAPPI Test Method [13]. The extractives content was determined through three successive
extractions (soxhlet) with ethanol/benzene, ethanol and water. The determination of the acid-
insoluble lignin was performed in triplicate using sulphuric acid and the ash content was
determined by calcinations at 5000C for 2 hours. The results are presented in Table 1.
2
Table 1: Chemical composition of agro fibers

Composition (%) Corncob Rice hull Walnut shell Flax shive
Cellulose 50.5±0.3 35.0±0.1 47.8±0.3 47.7±0.2
Hemicellulose 31.0±0.2 25.0±0.1 22.1±0.2 17.0±0.2
Lignin 15.0±0.1 20.0±0.1 25.9±0.2 26.6±0.1
Ash 0.3±0.1 17.1±0.1 0.7±0.1 1.0±0.1
Others 3.2±0.1 2.9±0.1 2.5±0.1 7.7±0.1
2.3 Particle size distribution of agro fibers

Agro wastes such as corncob, rice hull, flax shive and walnut shell fiber (60-100 mesh) was used
as received from the manufacturers and sieve analysis was conducted on oven dried (OD) fibers
at a drying temp of 103±2oC. 100 g weigh of each agro fiber type were put on a Mechanical Sieve
Shaker (Model Rx-86) with standard test sieves (50, 60, 70, 80,100,120 mesh) for 10 min
according to the Rotap A method (ASTM D5644-010). See Figure 1 below.
Figure 1: Particle size distribution of agro fibers
2.4 Particle geometry

Particle geometry was investigated by SEM (S-570, Quanta 200F) Hitachi Scientific Instruments.
Fibers were distributed to obtain clear images and the fibers geometry was measured. Fig. 2 shows
the particle geometry of the agro fibers using a magnification of (80X).
3
Figure 2: Particle geometry of agro fibers (80 X) magnification
2.5 Composites preparation

Table 2 shows the formulations for the composite samples used for the study. Fibers were dried at
103oC±2oC in an air circulating oven for 24 h before mixing. The agro fillers (65 wt. %) proportion,
high density polyethylene (32 wt. %) and 3 wt. % lubricant (Lonza® WP4400) were mixed for 5
min at a rotor speed of 47 rpm using a ribbon blender (Charles Ross and Sons Co., USA). After
dry mixing the materials were extruded in a 35 mm intermeshing twin-screw extruder (Cincinnati
Milacron Inc.) equipped with a 37 x 10 mm cross-section die. The extruder temperature was set to
162oC at screw speed of 20 rpm.
Table 2: Composite formulation
Sample code HDPE Rice-hull Corncob Walnut shell Flax-shive WP4400
(Wt %) (Wt %) (Wt %) (Wt %) (Wt %) (Wt %)
A 32 65 - - - 3
B 32 - 65 - - 3
C 32 - - 65 - 3
D 32 - - - 65 3
2.6 Water Absorption and Thickness Swelling Tests

Water absorption and thickness swelling behavior of the composites was conducted according to
the ASTM D 570-98 method. Four specimens of each composite were dried in an oven for 24 h at
103±20C. The dried specimens were weighed with a precision of 0.001 g and their thicknesses
were measured with a precision of 0.001 mm. They were placed in distilled water contained in a
water bath, at predetermined time intervals of 24 h, the specimens were removed from the distilled
water, the surface water was wiped off using blotting paper, and their wet mass and thickness were
4
determined. The water absorption and thickness swellings were calculated using Equations 1 and
2:
Where M is the percentage water absorption, mo and mt denotes the oven-dry weight and weight
after time t, as shown in equation 1.
(𝑚𝑡 − 𝑚0 )⁄
𝑀(%) = 𝑚0 × 100 (1)
(𝑇𝑡 − 𝑇0 )
𝑆(%) = ⁄𝑇 × 100 (2)
0
Where S is the percentage thickness swelling, Tt and To denotes the oven- dry thickness and
thickness after time t as shown in Equation 2.
2.7 Mechanical Characterizations

2.7.1 Flexural testing
The flexural properties of the composites modulus of elasticity (MOE) and modulus of rupture
(MOR) were determined according to ASTM D 790-10 method. Six samples of 203.2 x 38.1 x
10.2 mm were cut and stored for 48 h at 23±2oC and 50±5% relative humidity conditioning room.
The test span was 152.4 mm (6 inches). An Instron Universal Testing Machine (model 4466) was
used for flexural testing. The machine was equipped with 8.5 kN load cell and the support span
was 20 times the depth of the beam with a crosshead speed of 3.8 mm/min.
2.7.2 Izod impact testing
Un-notched Izod impact tests were conducted according to ASTM D 256-97 method. The tests
were performed using a pendulum. Seven samples of 63.5 x 12.7 x 3.2 mm were cut and stored for
48 h at 23±2oC and 50±5% relative humidity conditioning room. The pendulum was calibrated by
running the striker at zero position to compensate for the frictional error. The pointer was always
zero before each test specimen was taken and the value was taken at the point where the upper arm
coincided with the lower arm.
3.0 RESULTS AND DISCUSSION
3.1 Water absorption and thickness swelling of composites
Figures 3 and 4 show the water absorption’s and thickness swelling of composites after immersion
for 56 days in water. Generally, the water absorption and thickness swelling increased with
immersion time, reaching a certain value beyond which no more weight and thickness increased.
CCF/HDPE composites showed higher values of water absorption, followed by WSF/HDPE
composites and RHF/HDPE composites. FSF/HDPE composites showed the lowest value for
water absorption. The higher values of water absorption of corncob composites could be attributed
to the higher chemical constituents of cellulose and hemicelluloses (Table 1).
5
Figure 3: Water absorption of composites at different immersion times
RHF/HDPE composites showed higher values of thickness swelling, followed by corncob

composites and walnut shell flour composites. The higher values of thickness swelling recorded
for rice hull composites could be attributed to the finer particle size distribution of (< 0.125 mm)
and the probability of agglomeration at 65 wt % filler content which increased its ability to retain
water. FSF/HDPE composites exhibited the least value for thickness swelling. Figures 3 and 4
showed that the FSF/HDPE composites showed longer equilibrium time (i.e., time to reach
equilibrium water absorption and thickness swelling). The FSF/HDPE composites swelled and
gained weight very slowly.
Figure 4: Thickness swelling of composites after 56 days immersion in water
The analysis of the water diffusion mechanism in composites was performed based on Fick’s
Theory. Diffusion can be distinguished theoretically by the shape of sorption curve represented by
Equation (3).
𝑙𝑜𝑔(𝑀𝑡 ⁄𝑀𝑠 ) = 𝑙𝑜𝑔𝐾 + 𝑛𝑙𝑜𝑔 𝑡 (3)

Where Mt is the water content at time t, Ms is the water content at the equilibrium, and K and n
are constants. If the value of n is smaller than 0.5, the water absorption behaviour follows the
Fickian diffusion process [3]. To understand the mechanism of the water absorption in the
composite materials, the experimental data were fitted into equation (3).
6
The diffusion coefficient is the most significant parameter in the Fickian model. The water
diffusion coefficient was calculated using the equation (4).
Mt/Ms=4/L (D/π)0.5t0.5 (4)
In the equation (4) Mt is the moisture content at time t, Ms is the moisture content at equilibrium,
L is the thickness of samples, and D is the water diffusion coefficient [4].
Table 3 showed the diffusion parameters for the studied composites. The values of n indicate that
the water absorption in agro filler/HDPE composites followed a Fickian process. It was found that
the diffusion coefficient of composites of corncob fiber was the highest. This result can be related
higher amount of cellulose and hemicelluloses contained in the corncob. The lowest diffusion
coefficient value observed for flax shive fiber composites as filler can be due to chemical
constituents (Table 1).
Table 3: Diffusion parameters of agro fibers filled HDPE
Composites n log k k (h2) D (m2s-1)
CCF/HDPE 0.408 -1.296 0.050 8.57 E-12
RHF/HDPE 0.168 -0.544 0.286 7.64 E-12
WSF/HDPE 0.478 -1.485 0.033 7.97 E-12
FSF/HDPE 0.479 -1.523 0.030 3.14 E-12
3.2 Flexural properties

The flexural strength and modulus of the composites are shown in Figures 5 and 6 as a function of
the filler loading at 65wt. %. The flexural properties of the composites vary significantly with fiber
type. Composites made with rice hull fiber and flax shive fiber showed the highest strength and
modulus of flexural, whereas walnut shell fiber composites exhibited the lowest properties. The
strength of fiber reinforced composites depends on the properties of constituents and the interface
interaction. However, when considering the flexural properties, homogeneity of the overall
composite needs to be taken into account. This is mainly because in bending, the convex side is
compressed [14]. Generally, all the compositions showed a flexural strength and modulus lower
and higher than the pure HDPE respectively.
Figure 5: Flexural strength of agro fibers filled HDPE composites
7
Figure 6: Flexural modulus of agro fibers filled HDPE composites
3.3 Impact strength

Figure 7 shows that the un-notched Izod impact strength of the four agro fiber HDPE composites
increased at 65wt% filler loading compared to the neat HDPE. This means that the energy absorbed
by the specimens increased and with it its toughness also increased. Agro fiber content increased
the impact strength of the composites by almost 55%. The addition of walnut shell to HDPE gave
rise to superior un-notched impact strength compared to the other three agro fiber composites. It
was found that the composites with larger filler particles showed slightly higher impact strength
than those with smaller particles. This is because smaller particles with larger surface area tend to
have more of the poorly adhered interfacial sites. Rahman et al., [15] observed that the smaller the
filler size the lower is the impact strength and the increase in the filler composition lowers the
impact strength.
Figure 7: Un-notched Izod impact strength of agro fibers filled HDPE composites
8
3.4 Morphology characteristics

Scanning electron microscopy (SEM) is an effective media for the morphological investigations
of the composites. Through SEM study, the distribution and compatibility between the fiber and
the matrix could be observed. The differences in the flexural properties of the composites could
be related to the SEM micrographs in Figure 8. The rice hull and flax shive composites that showed
higher strength and modulus of flexural, is because the filler particles are well dispersed in the
matrix polymer, as compared with the composites made with the corncob and walnut shell fibers.
There are some voids where the fibers have been pulled-out. The presence of these voids means
that the interfacial bonding between the fiber and the matrix polymer is weak.
Figure 8: SEM Micrographs of flexure fractured surfaces at 65wt. % (a) corncob (b) rice
hull (c) flax shive and (d) walnut shell
4.0 CONCLUSIONS
The CCF/HDPE composites showed the highest water absorption due to its higher cellulosic
content. The RHF/HDPE composites exhibited the highest thickness swelling and flexural
strength. The FSF/HDPE composites gave the lowest water absorption, thickness swelling and
highest flexural modulus. The flexural strength of the composites was significantly inferior to
those of neat HDPE. The flexural moduli of the composites were significantly higher than those
of neat HDPE. The un-notched Izod impact strength of the composites was superior to those of
neat HDPE. The WSF/HDPE composites exhibited superior un-notched Izod impact strength
9
among the studied composites. The flax shive composite could be used in wet environments due
to its lowest water absorption and thickness swelling properties.
REFERENCES
1. Abilash, N and Sivapragash, M. (2013). Environmental Benefits of Eco-friendly Natural
Fiber Reinforced Polymeric Composites Materials, International Journal of Application or
Innovation in Engineering and Management, 2 (1), 53-59.
2. Nechwatal, A., Mieck, K.P. and ReuBmann, T. (2003).Developments in the
Characterization of Natural Fiber Properties and in the Use of Natural Fibers for
Composites, Journal Composites Science and Technology, 63, pp.1273-1279.
3. Amar, K.M., Manjusri, M. and Lawrence, T.D. (2005).Natural Fibers, Bio-polymers, and
Bio-Composites, CRC Press, Tailor and Francis.
4. Espert A., Vilaplana F. and Karlsson S., (2004). Comparison of Water Absorption in
Natural Cellulosic Fibres From Wood and one-year Crops in Polypropylene Composites
and its Influence on their Mechanical Properties, Composites Part A, 1267-1276
5. Dhakal, H.N., Zhang, Z.Y. and Richardson, M.O.W. (2007). Effect of Water Absorption
on the Mechanical Properties of Hemp Fiber Reinforced Unsaturated Polyester
Composites, Journal of Composites Science and Technology, 67, 1674-16783.
6. Panthapulakkal, S. and Sain, M. (2007). Agro-Residue Reinforced HDPE Composites:
Fiber Characterization and Analysis of Composites Properties, Composites Part A, 38 (6):
1445-1454.
7. Hargital H., Racz I. and Anandjiwala R. (2006). Development of Hemp Fibre-PP Non-
woven Composites. Macromol. Symp, 239: 201-208.
8. Zabihzadeh, S. M. Dastoorian, F. and Ebrahimi, G. (2010). Effects of MAPE on
Mechanical and Morphological Properties of Wheat Straw/HDPE Injection Moulded
Composites,”Journal of Reinforced Plastics and Composites, 24(1): 123-131.
9. Talavera, F.J., Guzman, J.A.S., Duenas, R.S. and Quirarte, J.R. (2007). Effect of
Production Variables on Bending Properties, Water Absorption and Thickness Swelling of
Bagasse/Plastic Composites Boards,’ Ind. Crops and Products, 26 (1): 1-7.
10. Yang, H.S., Kim, H.J., Park, H.J., Lee, B.J. and Hwang, T.S. (2007). Effect of
Compatibilizing Agents on Rice-husk Flour Reinforced Polypropylene Composites,”
Composites Structures, 77 (1): 45-55.
11. Yao, F., Wu, Q., Lei, Y. and Xu, Y. (2008). Rice Straw Fiber-Reinforced High-density
Polyethylene Composites: Effect of Fiber Type and Loading,” Ind. Crops and Products,
28 (1): 63-72.
12. Georgopoulos, S.T., Tarantile, P.A., Avgerinos, E., Andreopoulos, A.G. and Koukios, E.G.
(2005). Thermoplastic Reinforced with Fibrous Agricultural Residues, Journal of Polymer
Degradation and Stability, 90 (2): 303-312.
13. Tappi test method. Acid-insoluble lignin in wood and pulp. TAPPI 2002.
14. Cui, Y., Lee, S. and Noruziaan, B., (2008). Fabrication and Interfacial Modification of
Wood/Recycled Plastic Composites Materials, Composite Part A, 39: 655-661.
15. Rahman, W.A.W.A., Isa, N.M., Rahmat, A.R. et al. (2010). Rice husk/High-density
Polyethylene Bio-composites: Effect of Rice Husk Filler Size and Composition on
Injection Moulding Processability with Respect to Impact Property, Journal Advanced
Material Research, 83-86:367-374.
10
UTILIZATION OF GEOTEXTILES FOR SOIL IMPROVEMENT
Onuegbu, G.C., Okorie, C.C., Anyiam, C.K. and Akanbi, M.N.
Department of Polymer and Textile Engineering, Federal University of Technology, Owerri,

Nigeria.
Corresponding Author: E-mail: gc.onuegbu @ yahoo.com
ABSTRACT
Natural geotextiles which include; coir, plantain pseudo stem and palm fruit empty bunch, were
prepared by decortications process and spun into yarns. The yarns were constructed into woven and
non-woven geotextiles. Ground nut, waterleaf and green were planted on the cleared farm and the
woven and non-woven geotextiles were laid on the farm and monitored. The height of the crops
was measured weekly and the laboratory tests were carried out on the soil after three months to
determine the effect of woven and non- woven geotextiles on the soil nutrients which sodium,
phosphorus, calcium, Magnesium, Organic Carbon and Nitrogen. The results showed that the
geotextile increased the rate of growth of the three crops planted due to the improvement on the
soil nutrients. The woven coir and plantain geotextiles yielded higher amount of sodium, calcium
, and magnesium more than non-woven ones while non-woven geotextiles yielded higher Organic
Carbon, Nitrogen and Phosphorus more than the woven ones. Generally, geotextiles improved the
soil nutrients.
1.0 INTRODUCTION
Exposing soil surfaces leads to soil erosion and instability which contributes to the loss of soil
nutrients, low production yield, land wastage, poor crop /.8growth and endangering of life due to
landslides, [1]. Geotextiles can be used to solve the above problems and improve the soil nutrients.
Geotextiles are relatively thick planar sheet which may be woven, non-woven or knitted. These are
capable of transmitting fluids across or in-plane or in both ways, and retain suspended particles.
Woven geotextiles are manufactured by interlacing yarns, usually at right angles, whereas non-
woven geotextiles are made by mechanical, heat or chemical bonding of directional or randomly
oriented yarns [2].
11
Man-made geotextiles based on petrochemical derivatives such as polyethylene, polyester,

polypropylene have doubtful eco-compatibility and there is slow depletion of the valuable source
and high cost warranting its controlled usage [3].
Due to the need for eco-friendly, renewable, abundantly available and economically viable
alternatives, comes the necessity for use of natural geotextile [4]. Natural geotextile mats might
help to reduce intense solar radiation, suppress extreme fluctuations on soil temperature, reduce
water loss through evaporation and increase soil moisture. All these could assist in creating ideal
conditions for plant growth in many circumstances. As they degrade, natural products add organic
matter and nutrients to the soil. This may enhance soil microbiological activity, promote soil health,
fertility and aggregate stability [5]. Natural geotextiles can be applied in the following soil
situations: Separation application in unpaved roads, shore line stabilization, storm water channels,
slope stabilization in railway & highway cuttings and embankments, water course protection,
reinforcement of unpaved roads & temporary walls, filtration in road drains & land reclamation,
mud wall reinforcement and soil stabilization [6]. Different natural geotextiles have been studied
for soil improvement. These geotextiles include coir [3, 7-9], jute [10], sisal [5], oil palm empty
fruit bunch [11, 12], plantain pseudo stem [13, 14].
In the present research work on the utilization of geotextiles for soil improvement, the central
objectives include, to ascertain the natural geotextiles that are temporary degradable and long-term
non-degradable; to determine the effect of the natural geotextiles (woven and non-woven) on soil
nutrients; to compare and contrast the characteristics of some natural geotextiles and; (iv) to reveal
the advantages of natural geotextiles in agricultural application.
2.0 MATERIALS AND METHOD
2.1 Materials
The coir fibre (coconut husk fibre), plantain pseudo stem fibre, oil palm empty fruit bunch fibre
were obtained from Umuagwo in Ohaji Local Government Area, Umuayo, Eziobodo, Owerri West
Local Government Area, and Umuagbom, Ihitte Okwe of Ngor-Okpala Local Government Area,
Imo State respectively. The seeds (groundnut, water leaf and green (Amaranthus) seeds) were
obtained from Obinze market, Owerri West Local Government Area, Imo State.
12
2.2 Preparation of the samples
The farmland was cleared, the fibres (coir, oil palm bunch and plantain) were decorticated, spun,
woven and constructed into woven and non-woven fabrics. The seeds were planted and the woven
and non-woven geotextiles laid on the soil. The heights of the seedlings were measured and
recorded on weekly basis for two months.
2.3 Testing
The following soil nutrients (Sodium, Calcium, Magnesium, Phosphorus, Organic Carbon and
Nitrogen) were determined in the Soil Science Laboratory, Federal University of Technology,
Owerri.
3.1 The Height of the Plant
Figures 1 and 2 show the heights of the three plants for woven and non-woven geotextiles
respectively. The Figures showed that the rate of growth of ground nut, green and water leaf plant
were improved by the three woven and non-woven geotextiles for the eight weeks. This is due to
the Improvement on soil nutrient and reduction in the rate of evaporation.
Figure 1: The plot of the height of plant for woven geotextiles versus No. of weeks
13
Figure 2: The plot of the height of plant for Non-woven geotextiles versus No. Of
weeks
3.2 The Soil Nutrients
3.2.1 Sodium (Na) content
Figure 3, shows the effect of the woven and non-woven geotextiles on sodium content of the soil.
The decreasing order of sodium content for the geotextiles-laid on the soil is as follows:
Woven coir > non-woven palm bunch > non-woven coir > non-woven plantain fiber > woven palm
bunch > woven plantain > control.
0.09
0.08
Na(cmol/kg)
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
Geotextiles
Figure 3: Effect of geotextiles on sodium content of the soil
14
The amount of sodium initially present on the soil (control) is 0.03mol/kg. It is then observed that
woven coir fiber has the highest sodium content due to the presence of lignin in the coir fiber which
contributed to the low run-off of the soil surface This is in agreement with previous research work
on Coir geotextiles.
Non-woven palm bunch followed in the increment of the sodium content of the soil due to high
degradation rate of the palm bunch fiber. It could be seen that the non-woven coir, non-woven
plantain, woven palm bunch and woven plantain geotextiles also aided in the increment of sodium
content of the soil but not as the woven coir. The bare soil control containing the least sodium
content due to the absence of geotextiles (coir, plantain and palm bunch).
3.2.2 Calcium (Ca) content
Figure 4 shows the effect of woven and non-woven geoxtextiles on the calcium content of the soil.
The decreasing order of calcium content in the geotextile-laid soil is thus:
Woven plantain > Woven palm bunch > Non-woven plantain > Non-woven coir > Control > Woven
coir > Non-woven palm bunch.
7
6
5
Ca(cmol/kg)
4
3
2
1
0
Geotextiles
Figure 4: Effect of geotextiles on calcium content of the soil
The initial calcium content of the soil (control) is 3.2mol/kg. It is observed that woven plantain
geotextile increased the amount of Calcium content on the soil. This is due to increase in the rate
15
of degradation of the plantain fibre and the inherent nutrient of the plantain pseudostem fibre. This
is in agreement with Akpabio et al., (2012).
3.2.3 Magnesium (Mg) content
Figure 5 shows the effect of woven and non-woven geoxtextiles on the Magnesium content of the
soil. The decreasing order of magnesium content on the geotextile-laid soil is:
Woven coir > Woven plantain > Non-woven palm bunch > Non-woven plantain > Woven palm
bunch > Non-woven coir > Control.
The initial magnesium content is 0.4mol/kg. The woven coir geotextile added the highest amount
of magnesium to the soil compared to the other geotextiles which is as a result of the high lignin
content of coir fibre. The other geotextiles; woven plantain, non-woven palm bunch, non-woven
plantain, woven palm bunch and non-woven coir added 1.6mol/kg, 1.6mol/kg, 0.56mol/kg,
1.27mol/kg, 1.1mol/kg and 0.94mol/kg of magnesium respectively. The bare soil control shows the
least amount of Mg content having 0.27mol/kg.
2.5
2 2
2 1.67
Mg(cmol/kg)
1.5
1.5 1.34
0.96
1 0.67
0.4
0.5
Geotextiles
Figure 5: Effect of geotextiles on magnesium content of the soil
3.2.4 Available Phosphorus (P)
16
Figure 6 shows the effect of woven and non-woven geotextiles on the phosphorus content of the
soil. The decreasing order of phosphorus content on the geotextile-laid soil is thus:
Non-woven palm bunch > Woven plantain > Non-woven coir > Control > Woven palm bunch >
Non-woven plantain > Woven coir.
Available P(ppmP/g)
27.3 28.28
19.18
14.28 13.23
12.53 11.06 11.62
Geotextiles
Figure 6: Effect of geotextiles on Phosphorus content of the soil
The initial phosphorus content is 13.23ppmP/g. It is observed that non-woven palm bunch
geotextile yielded the highest amount of phosphorus to the soil due to its ash content and easy
degradation.
3.2.5. Organic Carbon (OC) content
Figure 7 shows the effect of woven and non-woven geotextiles on the organic Carbon content of
the soil. The decreasing order of organic Carbon content on the geotextile-laid soil is thus:
Non-woven plantain > woven coir > control > non-woven coir > non-woven palm bunch > woven
palm bunch > woven plantain.
The initial organic carbon content of the soil is 1.416%. It is observed that non-woven plantain
yielded 0.30% of organic carbon to the soil. The non-woven plantain geotextile contributed the
highest percentage of OC due to the high degradation rate of non-woven plantain geotextile.
17
2 1.716
1.8 1.556 1.556
(%) ORGANIC CARBON

1.476 1.456 1.496 1.496 1.416
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
GEOTEXTILES
Figure 7: Effect of geotextiles on organic carbon content of the soil
3.2.6. Nitrogen (N) content
Figure 8 shows the effect of woven and non-woven geotextiles on the Nitrogen content of the soil.
The decreasing order of Nitrogen content on the geotextile-laid soil is thus:
Non-woven plantain > Woven coir > Non-woven coir > Non-woven palm bunch > Woven palm
bunch > Woven plantain > Control. The initial N content of the soil (before laying of geotextile) is
0.118%. It is observed that non-woven plantain added 0.038% N to the soil. The non-woven
plantain geotextile contributed the highest percentage of N. This proved that both woven and non-
woven geotextiles have effect on the Nitrogen content of the soil.
(%) Nitrogen
0.144 0.156
0.136 0.129 0.14 0.138
0.12 0.118
Geotextiles
Figure 8: Effect of geotextiles on the Nitrogen content of the soil
18
4.0. CONCLUSION
Geotextiles affected the soil nutrients such as Na , P, Ca, Mg, Organic Carbon and N. From the
analysis, woven coir geotextile yielded the highest amount of sodium (Na) and magnesium (Mg)
content .Woven plantain pseudostem geotextile gave the highest amount of calcium (Ca) while
non-woven plantain pseudostem geotextile yielded more Organic Carbon (O.C) and Nitrogen (N)
contents on the soil. Moreover, non-woven palm bunch geotextile yielded the greater amount of
phosphorus (P) content on the soil. The woven and non-woven plantain pseudo stem and oil palm
fruit empty bunch geotextiles decomposed after two months while the woven and non-woven coir
geotextiles were unable to decompose. Therefore, the coir geotextile is a long-term non-degradable
geotextile while the plantain pseudo stem and oil palm empty fruit bunch geotextiles are short-term
degradable geotextiles. This is due to the high lignin content found in the coir fibre.
ACKNOWLEDGEMENT
The authors express their gratitude to Pastor Simon Nti, the Chief Technologist, Soil Science
Department, Federal University of Technology, Owerri, Imo state, Nigeria, who assisted in
determining the soil nutrients.
REFERENCES
[1] Ranjan B. (2009) Utilization of Palm-mat Geotextiles for Soil Conservation on Arable
Loamy Sands in the United Kingdom. A thesis submitted in partial fulfilment of the
requirements of the University of Wolverhampton for the degree of Doctor of
Philosophy, 9-267.
[2] Gopan Mukkulath and Santosh G. Thampi (2012). Biodegradation of Coir Geotextiles. Journal
of Bioremediation and Biodegradation 3:1-4.
[3] Ghosh,M.,Koerner, R.M. and Hejay, S.M. (2009).Development of Jute-Based Aspalt Overlay
Fabric, Journal of Applied Polymer Science, 54:117-122
[4] Chen W.F. and Richard J.Y (2002). Geotextile. The Civil Engineering Hand book ,4: 750-781.
[5] Raghuvanshi R., Shukla, E. Peters, S. and K. Prasad (2009). Application of Geotextiles in
Erosion Control -A Field Experiment. Journal Of Arid Land Studies, 249-252.
19
[6] Beena K.S. (2013). Case Studies on Application of Coir Geotextiles for Stabilization,
International Conference on Case Histories In Geotechnical Engineering, 7: 1-7.
[7] Rao G.V. and Balan K. (2000) Coir geotextiles-emerging trends. The Kerala State Coir
Corporation Ltd, Kerala, India.
[8] Tiwari A. and Mahiyar H. K. (2014). Experimental Study on Stabilization of Black Cotton
Soil by Fly Ash, Coconut Coir Fiber & Crushed Glass. International Journal of Emerging
Technology and Advanced Engineering, Volume 4, Issue 11.
[9] Singh, H.P. (2013). Strength and Stiffness Response of Itanagar Fly Ash Reinforced
with Coir Fiber. International Journal of Research in Science, Engineering Innovative and
Technology, 2: 9.
[10] Kiran K. and Jagan B. (2016). A Critical Review on Applications of Natural Jute Fibres ,
International Journal of Civil Engineering and Technology 7(3), 200–210.
[11] Ibeawuchi, I.I., E.B. Etuk and J.C. Obiefuna (2007). Palm Bunch Refuse (PBR) Mulch-
Manure in Yam/ Maize/ Cassava Crop Mixture. Proceedings of the third National
Conference on Organic Agriculture, UDU Sokoto, Nigeria.
[12] Okoli, N. A. (2010). Relevance of Empty Fruit Bunch and Palm Bunch Ash in Organic
Agricultural Production in Nigeria. Report and Opinion 2(12), 52-54.
[13] Akpabio, U.D., Udiong, D.S. and Akpakpan, A.E. (2012). The Physicochemical
Characteristics of Plantain (Musa Paradisiaca) and Banana (Musa Sapientum) Pseudostem
Wastes, Advances in Natural and Applied Sciences, 6: 167-172.
[14] Ogofure, A.G. and Emoghene, A.O. (2016). Evaluation Of Proximate, Phytochemicaland
Antibacterial Properties Of The Pseudostem (Musa paradisiaca). Nigerian Journal of Agriculture,
Food and Environment, Volume 12, No.2, 19-26.
20
MECHANICAL PROPERTIES OF NATURAL RUBBER VULCANISATE FILLED

WITH RICE HUSK POWDER
R.A. Adetola1, M.I. Ugbaja1, D.O. Adeoye2
1
Department of Polymer Technology, Nigerian Institute of Leather and Science Technology,
Zaria.
1
Zaria.
2
Directorate of Research and Development, Nigerian Institute of Leather and Science
Technology, Zaria.
Corresponding Author: ugboajamichael@yahoo.com, 08138995080
ABSTRACT
Characterization of natural rubber vulcanisate filled with rice husk (powder) was carried out. The
rice husk has a pH of 4.2 and was sieved using a mesh size of 350 um. Six samples of the natural
rubber vulcanisates were prepared incorporating varying proportions of the rice husk powder (0 g
- 50 g) using a laboratory scale two- roll mill. The prepared vulcanisates were cured using a
hydraulic press and samples of the cured vulcanisates were cut out accordingly for testing. The
mechanical properties namely tensile properties, hardness and abrasion resistance were
investigated. It was observed that hardness of the vulcanisates increased with increase in filler
loading to a maximum of 85, while the abrasion resistance, tensile strength, percentage elongation
and modulus decreased with increasing filler loadings. Water absorption also increased as the filler
loading was increased while the n-hexane solvent absorption was decreased as the filler loading
increases.
Keyword(s): Mechanical properties, Natural Rubber (NR), Rice Husk (RH).
1.0 INTRODUCTION
The demand for polymers in many applications has experienced a steady growth over the years.
Rubber, being a major form of polymers have not been left out, the application of these rubbers in
various area make it mandatory that they possess some minimum basic requirements in terms of
properties, so as to be able to perform effectively in specified areas. In order to have useful
properties, rubber must be reinforced with small filler particles which influence crosslinking
reactions and consequently stiffness and compressive strength. They control shrinkages, thermal
expansion as well as reduce the cost of the rubber goods [1].
21
Petroleum based carbon black is typically used as the reinforcing filler in the rubber industry [2
3]. Environmental impact, sustainability and life cycle analysis are new factors that must be
considered alongside cost and technical performance when developing new materials, products
and processes. The increasing desire by societies for products to be environmentally friendly has
led to manufacturers exploring means of producing products entirely or mostly from renewable
resources. The objective is to replace materials from non-renewable feedstock, by materials
derived from renewable agricultural or biomass feedstock. Recent examples in tyre manufacture
include the use of starch as filler [4, 5] in their Biotechnology, applied in the Good year GT3 tyres,
and in the development by SRI Dunlop of an environmentally friendly tyre with only 30%
petroleum based materials [6].
Rice husk (RH) which is a major agricultural waste has been utilized as a filler material
extensively. The RH has a huge potential as a possible fibre because rice production worldwide is
700 million tons [7] of which around 22% i.e. 154 million tons is husk [8] and this husk has no
potential use and its disposal otherwise is very difficult. It contains cellulose, hemicelluloses,
lignin, and ash. According to Marti-Ferrer [9] the lignin and hemi-cellulose contents of rice husk
are lower than wood whereas the cellulose content is similar. For this reason, rice husk flour can
be processed at higher temperatures than wood. Therefore, the use of rice husk in the manufacture
of polymer composites is attracting much attention.
Rice husk has mostly been employed as flour however researchers have also utilized chopped rice
husk [10]. Different polymers have been used as matrix material. RH was incorporated in
polypropylene by Yang et al. [11], Premalal et al. [12], Dimzoski et al. [13], Rosa et al. [9] to name
a few. Besides polypropylene rice husk has also been used with other polymeric materials.
Ghofrani et al. [14], Atuanya et al. [15], Rahman et al. [16], Nawadon et al. [17] have used
polyethylene, Attharangsan et al. [18], Ramasamy et al. [19] have used rubber as the matrix.
Besides these matrix materials rice husk has also been used with polyurethane [20], resin [21],
poly-lactic acid [22], vinyl ester [23], tires [24] etc. All studies on rice husk have focused on the
effect of filler loading on the mechanical properties. In most of the studies it was observed that
with addition of fillers most of the mechanical properties decreased. The tensile strength, flexural
strength, impact strength and hardness were seen to decrease, however there was an increase in
Young’s Modulus with filler loading. The incorporation of filler also made material brittle.
22
However, keeping in mind the advantage of using rice husk as filler material, there is still scope
of utilization of rice husk as reinforcing agent [25], which is actually the objective of this study.
2.1 Materials
The two major materials used in this work include natural rubber (NR) which was provided by the
Latex Laboratory, Department of Polymer Technology, NILEST, Zaria; and rice husk (RH) which
was sourced from local rice mill in Samara, Zaria, Kaduna State.
2.2 Methodology
2.2.1 Preparation of rice husk filler
The rice husk was sourced from a local rice mill in Samaru community, washed with water to
remove dirt and then sun-dried to remove moisture. After drying, the dried rice husk was then
grinded with a Thomas Wiley Laboratory Mill (Model 4) Philadelphia, PA, USA, and was sieved
using a mesh size of 350 µm.
2.2.2 Sample Preparation

Samples for testing were prepared first by compounding using a laboratory scale two-roll mill at
70 oC for 7 minutes, and secondly hot pressed with a manually operated hydraulic press at a
temperature of 150 oC and pressure of 5 tons for 5 minutes. The compounding materials which
was weighed based on parts per hundred of rubber (Pphr) was introduced into the compounding
mill in the order as presented in Table 1 to give the required number of samples labeled A to E.
Table 1: Typical Formulation for Natural Rubber Filled Vulcanisates.
Samples (g)
S/N Ingredients A B C D E F
1. Natural Rubber (NR) 100 90 80 70 60 50
2. Zinc Oxide 5 5 5 5 5 5
3. Stearic Acid 2.5 2.5 2.5 2.5 2.5 2.5
4. TMQ 1.5 1.5 1.5 1.5 1.5 1.5
23
5. MBTS 2.0 2.0 2.0 2.0 2.0 2.0
6. Rice husk (RH) 0 10 20 30 40 50
7. Processing oil 2.0 2.0 2.0 2.0 2.0 2.0
8. Sulphur 2.5 2.5 2.5 2.5 2.5 2.5
2.3 Sample Testing
2.3.1 Tensile
The tensile test was carried out using advance material testing machine in accordance with
ASTMD 412 method.
2.3.2 Shore (A) Hardness

The Shore (A) hardness test was carried out using a durometer. A flat sheet of the samples were
placed under the indentor and the reading was recorded.
2.3.2 Abrasion Resistance

The test samples were first weighed, W1 and then placed under an abrader for two minutes, and
then was reweighed W2. The difference in weights was used to calculate their percentage weight
loss which is a measure of their abrasion resistance.
2.3.3 Water and n-hexane absorption

The water absorption test (ASTM D750-95) was carried out by immersing the test samples
completely in distilled water at room temperature for 24 hours. The weights before, W1 and after,
W2 immersion were determined respectively and the difference in values was used to calculate
the percentage water absorption. The procedure was repeated for the n-hexane absorption test.
3.1 Tensile Strength

The results of the effect of rice husk content on the tensile strength of natural rubber vulcanisates
is shown in Figure 1. From the figure, it could be seen that the tensile strength of the vulcanisates
decreases with increasing filler loading. Similar results were also reported by previous researchers
24
[11-13]. The decrease of tensile strength with increasing filler loading is due to the decrease in the
worsening interfacial bonding between the matrix (hydrophobic) and fibre (hydrophilic). It has
also been shown that for irregularly shaped fibres the strength of the composites could decrease
due to the inability of the filler to support stress transferred from the polymer matrix [26]. The
decrease in strength could also be attributed to one of the characteristic of rice husk flour that is
agglomeration due to which voids could be generated between filler and matrix [27].
6
Tensile Strentgh ( N/mm2)
5
4
3
2
1
0
0 10 20 30 40 50 60
Filler Loading (g)
Figure 1: Effect of RH content (g) on the tensile strength of NR vulcanisate (N/mm2)
3.2 Percentage Elongation

Figure 2 shows the effect of rice husk content on the percentage elongation of natural rubber
vulcanisates. The observed decrease in the percentage elongation as the rice husk content was
800
% Elongation
750
700
650
600
550
500
0 10 20 30 40 50 60
Filler Loading (g)
Figure 2: Effect of RH content on the percentage elongation of NR vulcanisate
Increased which could be attributed to the presence of voids which obstructs stress propagation
and induce increased brittleness [11].
25
3.3 Tensile Modulus
The Young’s Modulus also decreases with increase in filler loading as observed in Figure 3. The
Young’s Modulus for natural rubber is 75 MPa and it reduces to about 63-32 MPa, with a reduction
of about 43 % for 50 wt% filler loading. This behavior might be understood from the fact that as
the filler content increased more load is transferred from the matrix to the filler but since there is
no proper adhesion between the filler and matrix there is slippage between the filler and matrix
and hence the decrease in the stiffness [25].
80
Young Modulus (N/mm2)
70
60
50
40
30
0 10 20 30 40 50 60
Filler Loading (g)
Figure 3: Effect of RH content on the tensile modulus of NR vulcanisate
3.4 Hardness
The hardness of the natural rubber vulcanisate was increased gradually with increasing rice husk
content as shown in Figure 4. The minimum hardness value of 53 and a maximum hardness value
of 85 were obtained at the extreme ends of the filler loadings respectively. This clearly shows the
hardening effect which the rice husks have on the natural rubber vulcanisates especially when
increased in quantity.
90
80
Hardness (o)
70
60
50
0 20 40 60
Filler Loading (g)
Figure 4: Effect of RH content on the Hardness of NR Vulcanisates.
26
3.5 Abrasion Resistance

The results of the percentage loss in mass of the natural rubber vulcanisates at varying rice husk
content is presented in figure 5. It can be seen that at 0 g and 10 g filler loadings, the samples have
almost the same value of about 15 % loss in mass. Beyond this point it increases drastically to 35
% loss in mass at 20 g filler loading, and then to a maximum of 46 % loss in mass at 30 g and 40
g filler loadings, and finally drops slightly to 45 % loss in mass at 50 g filler loading. It is important
to note that the percentage loss in mass inversely measures the abrasion resistance of the samples.
50
40
% lost in mass
30
20
10
0
0 10 20 30 40 50 60
Filler Loading (g)
Figure 5: Effect of RH content on the Abrasion Resistance of NR Vulcanisates.
3.6 Water and n- hexane Absorptivity
The results of the water absorption property of the natural rubber vulcanisates at varying rice husk
content employed is presented in Figure 6. The control sample did not absorb any water for the
duration under study. However, at higher loadings of the rice husk content the percentage water
absorption of the filled vulcanisates increases accordingly to a maximum of 120 % at 50 g filler
loading. This can be attributed to the hydrophilic nature of the rice husk filler.
150
% Water Absorption
100
50
0
0 10 20 30 40 50 60
Filler Loading (g)
27
Figure 6: Effect of RH content on the Water absorptivity of NR Vulcanisates.
For the test on n-hexane, the result is presented in Figure 7. The absorptivity decreases with
increasing rice husk content as the control sample has the maximum value of 1.2 g.
1.4
n-hexene Absorption (g)
1.2
1
0.8
0.6
0.4
0.2
0
0 10 20 30 40 50 60
Filler Loading (g)
Figure 7: Effect of RH content on the n-hexane absorptivity of NR Vulcanisates.
4.0 CONCLUSION
The mechanical properties of natural rubber vulcanisates filled with rice husk powder have been
investigated in this work. The pH of the rice husk filler was 4.2 which mean the filler is acidic in
nature and in effect retards vulcanisation. The tensile properties such as tensile strength, percentage
elongation and tensile modulus of the vulcanisates were reduced as a result of the introduction of
the rice husk powder. It clearly shows that the rice husk powder has no reinforcing effect on the
tensile properties of natural rubber vulcanisates. Again the abrasion resistance of the natural
vulcanisates was reduced especially beyond the 10 g rice husk powder loading. However, the
hardness of the samples increases with increasing filler content of the rice husk powder suggesting
that the resulting composites is suitable for applications such as table tops where hardness is a
priority.
REFERENCES
[1] Byars, J.A., Jong, L. 2009. Flow propertiesof natural rubber composites filled with defatted
soy flour: Journal of applied polymer science,111(4): 2049-2055
28
[2] Sadakne, G., White, J.L. 1973. An experimentalstudy of adsorption of polymers on activated
carbon: Butadiene - styrene polymers and poly(methyl methacrylate): Journalof Applied Polymer
Science, 17: 453-469.
[3] Furtado, C.R.G., Leblanc, J.L., Nunes,R.C.R. 1999. Fatigue resistance of micacarbonblack-
styrene butadiene rubber(SBR) compounds. European Polymer Journal,35(7): 1319-1325.
[4] Goodyear tyre and rubber companypress release 2001. Goodyear reinvents thewheel: The
world’s first tyre using extract ofcorn.
[5] Corvasce, F.G., Fottrgon, F.A.J. 2005.U.S patent No 6,878,760.
[6] Sumitomo Corporate news 2005, ENASAVEES 801,non-petroleum tire to sell inafter market.
[7] Trade and Markets Division. Food and Agriculture Organization of the United Nations”, FAO
Rice Market Monitor. Bull; 2010.
[8] E. C. Beagle. Rice-husk conversion to energy: FAO Agric. Serv. Bull.; 1978.
[9] Simone Maria Leal Rosa, EviliseFonsecak Santos, Carlos Arthur Ferreira et al. Studies on the
Properties of Rice Husk filled PP composites-effect of Maleated PP, Journal of Materials
Research, 12(3), 2009, 333-338.
[10] Mohammad Razavi Nouri, FatemehJafarzadeh-Dogouri, AbdulrasoulOromiehie et al.
Mechanical properties and water absorption behaviour of chopped rice husk filled polypropylene
composites, Iranian Polymer Journal, 15(9), 2006, 757-766.
[11] Han-Seung Yang, Hyun-Joong Kim, Jungil Son et al. Rice husk flour filled polypropylene
composites, mechanical and morphological studies, Composite Structures, 63, 2004, 305-312.
[12] Hattotuwa GB Premalal, H Ismail, A Baharin. Comparison of the mechanical properties of
the rice husk powder filled polypropylene composites with talc filled polypropylene composites,
Polymer testing, 21, 2002, 833-839.
[13] B. Dimzoski, G. Bogoeva-Gaceva, G. Gentile, M. Avella et al. Polypropylene-based Eco-
composites Filled with Agricultural Rice Hulls Waste, Chemical and biochemical Engineering,
23(2), 2009, 225–230.
[14] Mohammad Ghofrani, SakinehPishan, Mohammad Reza Mohammad et al. A study on Rice-
husk/Recycled high density polyethylene Composites- their physical and mechanical properties,
Environment Sciences, 9(1), 2012, 99-112.
29
[15] Atuanya. U., Olaitan S.A., Azeez T.O. et al. Effect of rice husk filler on the mechanical
properties of polyethylene matrix composite, International Journal of current research and
review, 05(15), 2013, 111-118.
[16] Md. Rezaur Rahman, MdNazrul Islam, MD MonimulHuque et al. Effect of chemical
treatment on the Rice Hush (RH) Reinforced Polyethylene Composites, Bio-Resources, 5(2), 2010,
854-869.
[17] NawadonPetchwattana, SirijutaratnaCovavisaruch, SirapatChanakul. Mechanical properties,
thermal degradation and natural weathering of high density polyethylene/ rice hull composites
compatibilized with maleic anhydride grafted polyethylene, Journal of Polymer Research, 19(7),
2012, 1-9.
[18] SupalakAttharangsan, Hanafi Ismail, Mohamad Abu Bakar et al. The Effect of Rice Husk
Powder on Standard Malaysian Natural Rubber Grade L (SMR L) and Epoxidized Natural Rubber
(ENR 50) Composites, Polymer Plastics Technology and Engineering, 51(3), 2012, 231-237.
[19] ShamalaRamasamy, Hanafi Ismail & Yamuna Munusamy. Tensile and Morphological
Properties of Rice Husk Powder Filled Natural Rubber Latex Foam, Polymer Plastics Technology
and Engineering, 51(15), 2012, 1524-1529.
[20] H. D. Rozman, L. G. Ang, G. S. Tay et al. The Mechanical Properties of Rice Husk-
Polyurethane Composites, Polymer Plastics Technology and Engineering, 42(3), 2003, 327-343.
[21] Michael IkpiOfem, Muneer Umar and Friday AjeOvat. Mechanical properties of rice husk
filled cashew nut shell liquid Resin composites, Journal of Material Science Research, 1(4), 2012,
89-97
[22] A. A. Yussuf, I. Massoumi, A. Hassan. Comparison of Polylactic Acid/Kenaf and Polylactic
Acid/Rise Husk Composites: The Influence of the Natural Fibres on the Mechanical, Thermal and
Biodegradability Properties, Journal of Polymers and Environment, 18(3), 2010, 422–429. [23] D.
Shivappa, Ananda.G.K, Shivakumar.N. Mechanical Characterization of Rice Husk Flour
Reinforced Vinylester Polymer Composite, International Journal of Innovative Research in
Science, Engineering and Technology, 2(11), 2013, 6271-6277.
[24] D Garcia, J. Lopez, R. Balart et al. Composites based on sintering rice husk-waste tire
rubbermixtures, Materials and Design, 28, 2007, 2234-2238.
30
[25] NeerajBisht, Prakash Chandra Gope. Mechanical Properties of Rice Husk Flour Reinforced
Epoxy Biocomposite, NeerajBisht Int. Journal of Engineering Research and Applications, 5(6),
2015, 123-128.
[26] Han-Seung Yang, Hyun-Joong Kim, Hee-Jun Park et al. Effect of compatibilizing agents on
rice-husk flour reinforced polypropylene composites, Composite Structures, 77, 2007, 45–55.
[27] Yang HS, Kim HJ, Park HJ et al. Water absorption behavior and mechanical properties of
lignocellulosic filler-polyolefin bio-composites. Composite Structures, 72, 2006; 72:429-437.
31
MODELING ANALYSIS OF THE EFFECTS OF DOLOMITE FILLERS AND

COMPATIBILIZATION ON THE MECHANICAL PROPERTIES OF POLYPROPYLENE
COMPOSITES
M.N. Akanbi*, O. Ogbobe, M.U. Obidiegwu, H.C. obasi, G. C. Onuegbu and

B.C. Aharanwa
Department of Polymer and Textile Engineering, Federal University of Technology, P.M.B 1526, Owerri
Imo State, Nigeria.
*Corresponding Author: magdalene910@yahoo.com
ABSTRACT
The effects of dolomite filler and compatibilizer on the mechanical properties of polypropylene have been
investigated using the filler loadings of 5 – 20 wt% and the polypropylene grafted maleic anhydried (PP-g-
MA) compatibilzer content of 1.5 wt%. The compatibilized and uncompatibilized composites were
produced using an injection moulding machine. The mechanical properties tested were tensile strength at
yield, elongation at break (EB), Brinell hardness and flexural strength (FS). The results obtained revealed
that higher filler loadings beyond 15 wt% of the dolomite mineral without a compatibilizer, resulted in poor
tensile strength at yield. The EB was observed to reduce with increasing filler loading and worsened with
the incorporation of the PP-g- MA consequent to the enhanced interfacial interactions between the
polypropylene matrix and the dolomite filler. Moreover, the hardness and flexural properties were improved
and showed an increasing trend with increased filler loading. The incorporation of the compatibilizer
ultimately improved this trend. The tensile strength at yield was seen to increase with about 37%, flexural
strength 40% and hardness with 40.02% at 20% filler loading and 1.5 weight % PP-g-MA. The properties
of the compatibilized composites investigated, increased in this order: Hardness > Flexural > Tensile
strength at yield. The research was modeled with Matlab modeling software to obtain optimal results for
values beyond the filler contents investigated in the research. The Modeled equation for tensile strength
was given as TS = -0.0007467x3+0.01029x2+0.09095x+5.046, also EB = -0.0003714x2-0.08357x+5.775
and the Modeled equation of FS for the compatibilized composite was given as FS =
0.01457x2+0.1762x+5.011.
32
Keywords: Dolomite, Polypropylene, compatibilizer, maleic anhydride, filler.
1.0 INTRODUCTION
Presently in this century, Polymers have high acceptability in almost every field and stages of human life
and activities: from cradle to grave, in constructions, house hold items, automobiles, medicine, electronics,
food processing, agriculture etc. Polymers are often enhanced with fillers to improve or attain the desired
properties. These fillers are a host of materials which can be minerals, metals, ceramics or bio based. Some
mineral fillers include Calcite (CaCO3), Dolomite (CaCO3MgCO3), Carbon black, Wollastonite (CaSiO3)
[1] etc. Functional fillers are incorporated into polymers for palpable reasons such as to induce conductivity,
retard flammability, improve processibility, mechanical, optical properties etc. [2]. Based on this, myriad
researchers have delved deeply into polymer reinforcements with functional fillers and obtained credible
results. Some of these include; polypropylene filled with fly ash [3], polypropylene filled calcium carbonate
composite [4, 5], flammability of Polyethylene filled with Alstonia boonie wood [6], also, polyethylene
filled with Snail shell powder [7], among many others. However this work is poised to investigate the
effects of the mineral filler, Dolomite, of natural origin and specific gravity of 2.85, Moh hardness of 3.5,
with refractive indices of 1.5 and 1.68 [8] in Polypropylene (-C3H6-)n matrix using Maleic anhydride
grafted polypropylene MA - g- PP as Compatibilizer.
2.0 EXPERIMENTAL
The following materials were used in the present study:
- Polypropylene
- Maleic Anhydride grafted polypropylene
- Dolomite CaMg(CO3)2
A commercial grade polypropylene of density 910 kgm-3 and melt flow index (MFI) 12g/10mm was
supplied by Ceeplast Industries Nigeria Limited, Aba in Abia State, was employed in this research.
Maleic Anhydride Grafted- polypropylene PP-g-MA was used as the compatibilizer. It was obtained from
Sigma-Aldrich Chemicals, Germany, with the melting point of 156oC and density of 0.934gcm-3. It was
used as supplied. The Apparatus used were: An Injection moulding machine (size =100 tons, injection
pressure of 1570kg/cm), Instron testing machine M-500-25KN, Brinell Hardness tester and flexural tester.
The Hardness of the composites was calculated using the relationship:
𝐹(𝑘𝑁)
𝐻= (1)
𝜋𝐷 0 (𝐷 0 − √𝐷 0 − 𝐷 𝑖 )
33
Where F: Force (kN); D0: Diameter of indentation ball; Di:Diameter of indentation made on various
samples, 𝜋: constant.
The dolomite filler was incorporated into polypropylene at filler weigths of 5 to 20 weight % with and
without the incorporation of the compatibilizer. The compatibilizer was used at 1.5wt% for all the filler
weight compositions. Some mechanical tests e.g. tensile strength at yield, elongation at break, hardness and
flexural strength of the prepared composites were carried out.

3.1 Tensile Strength
The plots in Figure 1, obtained, reveal that the Tensile Strength at Yield of Polypropylene/ Dolomite
Composites improved with increased filler weight but declined at filler loadings above 15%. This is in line
with literature, Chris De Armitt [1] a slight loss of yield strength may be observed when Isotropic fillers
are employed in a polymer matrix. Also, this decrease in tensile strength at yield is in agreement with the
previous findings [9].
20
Tensile Strength at Yield (MPa)
COMP. PP/DOL
15 y = 0.5478x + 4.156
R² = 0.9596
10
UNCOMP. PP/DOL
0
0 5 10 15 20 25
y = -0.1252x + 5.093
Filler Wt (%) R² = 0.9951
Figure 1: Tensile Strength vs % Filler Weight of Compatibilised and Uncompatibilised PP/DOL

Composites
3.1.1 Modeled results of tensile test for the uncompatibilised composite
Coefficients (with 95% confidence bounds):
Goodness of fit:
34
SSE: 0.1851
R-square: 0.9535
Adjusted R-square: 0.8139
RMSE: 0.4303
Model equation is given as TS = 0.0003067x3-0.02323x2+0.2559x+4.96 (2)
The graph of Predicted Tensile strength (TS) of the uncompatibilized Dolomite filled Polypropylene
composite is shown in Figure 2. An upward deviation was observed at 5wt% and 15wt% and a downward
deviation at 10wt% loading of Calcium diphosphate It was also observed that there is proximity at 20wt%.
The analysis of fit for the predicted data is shown in Figure 3. The equation of the graph is shown in
Equation (2).
6.4
Ex perimental data1
6.2 Predic ted data2
Tensile Strength (MPa)
5.8
5.6
5.4
5.2
0 2 4 6 8 10 12 14 16 18 20
Filler Content (wt%)
Figure 2: Plot of Predicted tensile strength at yield of the Polypropylene-Dol

uncompaitibilized composite
Analy s is of fit "fit 1" for datas et "ts vs . x"
7
fit 1
6 ts vs . x
Fit
4
0.5
1st deriv
-0.5
150
Integral from 0
100
50
0
0 2 4 6 8 10 12 14 16 18 20
Figure 3: Analysis of Fit for Predicted tensile strength at yield of the Polypropylene - Dol
3.1.2 Modeled Results of Tensile Test for the compatibilized composites
35
Goodness of fit:
SSE: 0.0593
R-square: 0.9992
RMSE: 0.1722
The mathematical model equation is given as f(x) = 0.01883x2+0.1712x+5.097 (3)
The plot of predicted tensile strength at yield of the Polypropylene-Dol compaitibilized composite is shown
in Figure 4. It was observed that there is a great proximity between 0- 20wt%. The analysis of fit for the
predicted data is shown in Figure 5. The equation of the graph is Equation 3.
18
Experimental data1
16 Predicted data2
Tensile Strength (MPa)
14
12
10
4
0 2 4 6 8 10 12 14 16 18 20
Figure 4: Plot of Predicted tensile strength at yield of the Polypropylene-Dol compaitibilized

composite
Analysis of fit "fit 1" for dataset "Ts vs. x"
20
fit 1
15 Ts vs. x
Fit
10
5
1
1st deriv
0.5
0
200
Integral from 0
100
0
0 2 4 6 8 10 12 14 16 18 20
Figure 5: Analysis of Fit for Predicted tensile strength at yield of the Polypropylene-Dol
compaitibilized composite
3.2 Elongation at Break
36
Pragmatically from the plots obtained, there is a decline in the Elongation at Break with increasing filler
loading with and without the incorporation of compatibilizer. This can be attributed to the reduction in the
deformation of a rigid interface between the fillers and the Polypropylene matrix. Consequently, the
incorporation of the PP-g-MA compatibiliser enhanced the interfacial interactions between the
Polypropylene matrix and the Dolomite filler resulting to a stronger interfacial bonding which enhanced
rigidity and decreased ductility [3].
7
ELLONGATION AT BREAK
6 UNCOMP
PP/DOL
5
4 y = -0.104x + 5.902
(MM)
3 R² = 0.8575
COMP PP/DOL
2
1
0 y = -0.1004x + 5.788
0 5 10 15 20 25 R² = 0.9994
FILLER WT. (%)
Figure 6: Elongation at Break versus Filler weight of the Uncompatibilised and Compatibilised
PP/Dol Composites
3.2.1 Modeled Results of Elongation at Break for the uncompatibilised composites
The model equation is f(x) = -0.0003714x2-0.08357x+5.775 4.30 (4)
Coefficients (with 95% confidence bounds): Goodness of fit:
SSE: 0.0002629
R-square: 0.9999
RMSE: 0.01146
The Plot of Predicted Elongation at Break of the Polypropylene-Dol uncompatibilized composite is shown
in Figure 7. It was observed that there is a close proximity between 0 – 20wt% filler loading. The Analysis
of Fit for the Predicted Elongation at Break is shown in Figure 8. The equation of the graph is Equation 4.
37
Figure 7: Plot of Predicted Elongation at Break of the Polypropylene-Dol uncompaitibilized

composite
Figure 8: Analysis of Fit for the Predicted Elongation at Break of the Polypropylene-Dol
3.2.2 Modeled Results of Elongation at Break for Compatibilised PP/Dol composites
The model equation is given as EB=-0.1004x+5.788 4.33 (5)
Goodness of fit:
SSE: 0.00148
R-square: 0.9994
RMSE: 0.02221
The Plot of Predicted Elongation at Break of the Polypropylene-Dol compatibilized composite is shown in
Figure 9. It was observed that there is a close proximity between the experimental and predicted data at 0
38
– 20wt% filler loading. The Analysis of Fit for the Predicted Elongation at Break is shown in Figure 10.
The equation of the graph is Equation 5.
Figure 9: Plot of Predicted Elongation at Break of the PP/DOL at 1.5 wt (%) compatibilizer
Figure 10: Analysis of Fit for Predicted Elongation at Break of the Compatibilized PP/DOL
composite
3.3 Flexural Strength
From the Figure 11, it is apparent that the Flexural strength increased with increase in filler loading and
significant increases were recorded with the incorporation of the 1.5%wt PP-g- MA compatibilizer. From
similar report [4], an increased Flexural Stress in their research on Effect of Titanate coupling agent on the
mechanical properties of calcium carbonate filled Polypropylene.
20
FLEXURAL STRENGTH
15 UNCOMP PP/DOL
10
(N/mm2)
y = 0.2496x + 4.68
5 R² = 0.9793
0 COMP PP/DOL
0 5 10 15 20 25 y = 0.6328x + 3.952
FILLER WT. (%) R² = 0.9587
39
Figure 11: Plot of Flexural Strength versus Filler weight (%)of the Uncompatibilised and
Compatibilised PP/Dol Composites
3.3.1 Modeled Results for Flexural Strength of the Uncompatibilised PP/Dol composites
The model equation is f(x) = 0.00614x2+0.1273x+4.986 (6)
Goodness of fit:
SSE: 0.002166
R-square: 0.9999
RMSE: 0.03291
The Plot of Predicted Flexural strength (FS) of the Polypropylenel-Dol uncompatibilized composite is
shown in Figure 12. It was observed that there is a great proximity between the experimental and predicted
data at 0 – 20wt% filler loading. The Analysis of Fit for the Predicted Flexural strength (FS) is shown in
Figure 13. The equation of the graph is Equation 6.
10
Ex perimental data1
Predic ted data2
9
Flexural Strength (MPa)
4
0 2 4 6 8 10 12 14 16 18 20
Figure 12: Plot for Predicted Flexural strength (FS) of the Polypropylenel-Dol uncompatibilized
composite
Analy s is of fit "fit 1" for datas et "fs vs . x"
10
fit 1
8 fs vs . x
Fit
4
0.4
1st deriv
0.2
0
150
Integral from 0
100
50
0
0 2 4 6 8 10 12 14 16 18 20
40
Figure 13: Analysis of Fit for Predicted Flexural strength (FS) of the Polypropylene-Dol
uncompatibilized composite
3.3.2 Modeled Results for Flexural Strength of the Compatibilised PP/Dol composites
Linear model Poly2:
The model equation is FS = 0.022x2+0.1936x+5.05 4.42 (7)
Goodness of fit:
SSE: 0.07168
R-square: 0.9993 Adjusted R-square: 0.9986
RMSE: 0.1893
The Plot of Predicted Flexural strength (FS) of the Polypropylenel-Dol compatibilized composites is shown
in Figure 14. It was observed that there is a close proximity between the experimental and predicted data at
0 – 20wt% filler loading. The equation of the graph is Equation 7. The Analysis of Fit for Predicted Flexural
strength (FS) of the Polypropylene-Dol compatibilized composites is shown in Figure 15.
Figure 14: Plot for Predicted Flexural strength (FS) of the Polypropylenel-Dol-compatibilized
composites
Analy s is of fit "fit 1" for datas et "Fs vs . x"
20
fit 1
Fs vs . x
Fit
10
0
1
1st deriv
0.5
0
200
Integral from 0
100
0
0 2 4 6 8 10 12 14 16 18 20
Figure 15: Analysis of Fit for Predicted Flexural strength (FS) of the Polypropylene-Dol
compatibilized composites
41
3.4 Brinell Hardness Test (BHN)
The hardness increased significantly with Dolomite concentration range of 5 – 20wt%, also the addition of
1.5wt% of the maleic anhydride grafted polypropylene (MAPP) compatibilizer followed a greater trend.
Invariably, the incorporation of MAPP enhanced the interfacial bonding between the PP matrix and the
micro structure of the surrounding Dolomite filler leading to greater increase in composite hardness. This
increase in the hardness with increased filler loading indicates enhancement of abrasion of the composites
[10].
40
HARDNESS (BHN)
30
COMP PP/DOL
20
y = 1.1442x + 6.024
10 R² = 0.9468
UNCOMP PP/DOL
0
0 5 10 15 20 25
y = 0.965x + 6.388
FILLER WT. (%) R² = 0.9553
Figure 16: Hardness vs filler weight % of the Compatibilised and Uncompatibilised PP/Dol of
compt.
3.4.1 Modeled Results for Hardness Test of the Uncompatibilised PP/Dol composites
Linear model Poly2:
The mathematical model equation for PP/DOL is given as H = 0.03494x2+0.2661x+8.135 (8)
Goodness of fit:
SSE: 0.1977
R-square: 0.9992; Adjusted R-square: 0.9984 and RMSE: 0.3144
42
The R2 of 0.9992 shows that a high correlation exists between the experimental and predicted values. Also,
from the graph below Figure 17, it is asserted that a high close relationship exists between the experimental
and predicted values.
28
Experimental data1
26
Predicted data2
24
22
Hardness(BHD)
20
18
16
14
12
10
8
0 2 4 6 8 10 12 14 16 18 20
Filler Content( wt%)
Figure 17: Graph of Predicted/Experimental Hardness for the uncompatibilized PP/DOL

Composites
3.4.2 Modeled Results for Hardness Test of the Compatibilised PP/Dol composites
Linear model Poly3: f(x) = p1*x^3 + p2*x^2 + p3*x + p4
Goodness of fit:
SSE: 0.1537
R-square: 0.9996
RMSE: 0.392
The response surface model for the hardness of 1.5%wt compatibilized PP/DOL Composites is given as
f(x) = 0.001987x3-0.01506x2+0.6805x+7.953 (9)
The R2 of 0.9996 shows that high correlation exists between the experimental and predicted values. From
the graph in Figure 18 it is asserted that a high close relationship exists between the experimental and
predicted values. The equation of the graph is Equation 9.
43
35
Experimental data1
Predicted data2
30
25
Hardness 20
15
10
5
0 2 4 6 8 10 12 14 16 18 20
Figure 18: Plot of Predicted/Experimental Hardness for 1.5%wt compatibilized PP/DOL

composites
4.0 CONCLUSION
The mechanical properties of Polypropylene filled Dolomite mineral composites have been conducted and
the effects of the filler and compatiblizer on polypropylene have also been investigated. This study has
further established the fact that compatibilizers enhance the mechanical properties of Polymer composites.
The results obtained revealed that higher filler loadings beyond 15wt% of the dolomite mineral without a
compatibilizer, resulted in poor tensile strength at yield of PP/Dol Composite. The elongation at break was
observed to reduce with increasing filler loading and worsened with the incorporation of the PP-g-MA
compatibilizer consequent to the enhanced interfacial interactions between the polypropylene matrix and
the dolomite filler. Moreover, the hardness and flexural properties were improved and showed an increasing
trend with increased filler loading; more so, the incorporation of PP-g-MA compatibilizer ultimately
improved this trend. The Modeled equation for Tensile strength was given as TS = -
0.0007467x3+0.01029x2+0.09095x+5.046, also EB = -0.0003714x2-0.08357x+5.775 and the Modeled
equation of FS for the compatibilized composite was given as FS = 0.01457x2+0.1762x+5.011. This report
therefore, depicts that the composite can play vital roles in applications demanding high hardness over
elastic property.
REFERENCES
[1] Chris De Armitt, Applied Plastic Engineering Handbook pg 455 – 468.
[2] Tong Chen and Dr. Alex Isarov 2005, Functional Fillers for Plastics
[3] Jitendra Gummadi,G. V ijay Kumar, Gunti Rajesh (2012) Evaluation of flexural properties of fly
ash filled polypropylene composites. International Journal of Modern Engineering Research (IJMER) 2 (4),
pp – 2584 – 2590.
[4] Doufnoune R. et al (2010) Doufnoune .R., Chebira F. & Haddasomi N. (2010). Effect of Titanate
coupling agent on the mechanical properties of calcium carbonate filled Polypropylene. International
Journal of Polymer Material, 52, 967 – 984.
[5] David, J. Tucker, P.L., Lear, G.S., Atkinson, S.I. & Seung J. L. (2000) use of Polymeric Compatibilizers
in Polyprophylene/Calcium Carbonate Composites. Korean Journal of Chemical Engineering 17, PP. 506-
509.
44
[6] M. U. Obidiegwu and O. Ogbobe, Mechanical And Flammability Properties Of Low Density
Polyethylene/Kola Nitida Wood Fibre Composites Academic Research International Vol. 2, No. 3, May
2012.
[7] Anyanwu, P. I. & Ogbobe, O. (2007). Effect of Pulverized Snail Shell on Mechanical Properties of High
Density Polyethylene, Inter. Res.Jour. In Engr. Sc. & Tech (IREJEST),4(2), pp 177-183.
[8] R. N. Rothon, Particulate fillers for Polymers, pages 17 – 29; ISBN: 1-85957 – 310-X.
[9] Rozman, H. D., Lim, P. P., Abusamah, A., Kumar, R. N., Ismail, H and Mohd Ishak, Z (1999). The
Physical Properties of Oil Palm Empty Fruit Bunch Composites made from Various Thermoplastic.
International Journal of Polymer Materials 44 (1 & 2), 179 – 195.
[10] Onuegbu G.C., Madufor I.C and Ogbobe O. (2012). Studies On Effect Of Maleated Polyethylene
Compatibilizer On Some Mechanical Properties of Kola Nut Filled Low Density Polyethylene Aca. Res.
Int. 3 (1), 406 -412.
DEVELOPMENT OF LUFFA CYLINDRICA FIBRE REINFORCED LOW DENSITY

POLYETHYLENE COMPOSITES
1Nwosu-Obieogu, K., *1Aguele, Felix O., 2Nwanorh, Kieran O., 1Adekunle, Kayode F.
1Department of Chemical Engineering, Michael Okpara University of Agriculture,
Umudike, Abia State, Nigeria.

2Department of Chemistry, Imo State University, Owerri, Imo State.
*Corresponding author: foaguele@gmail.com

ABSTRACT
The drive to search for renewable sources to compliment or possibly replace the conventional
fillers for polymer composite production at a reduced or no cost and having no negative effect on
the environment forms the basis of this research. In this work, Luffa cylindrica fibre was modified
with NaOH solution at a constant time of 18 hours. Different NaOH concentrations of 3%, 4% and
5% were used for the fibre modification and a part of the fibre was left unmodified. The modified
and unmodified luffa fibres were used to prepare two sets of composite with low density
polyethylene as the matrix phase. The fibre volume was varied from 0 to 50pph, at intervals of 10
during the composite preparation. The mechanical properties of the composites were investigated
and from the results, it was found that the 4% NaOH modified fibre-LDPE composites had the
best reinforcing properties than the rest composites, where other concentrations (3%, 5%) of NaOH
were used to modify luffa fibre. Also it was observed that generally, the modified luffa fibre-LDPE
composites were better than the unmodified, which showed little or no reinforcement.
Keywords: Renewable fibre, Luffa cylindrica, NaOH, Polyethylene, Composites.
1.0 INTRODUCTION
Natural fibres offer many technical and ecological benefits for its use in reinforcing composites. It
presents many advantages such as light weight, low cost, high specific strength, high modulus,
reduced tool wear and safe manufacturing process when compared to synthetic fibres which makes
them attractive as reinforcements in composite materials [1,2] . They come from abundant and
renewable resources, which ensures a continuous fibre supply and a significant material cost
45
saving. Its use is gaining popularity in many sectors especially in the automotive and plastic
industries.
Natural fibres have limitless areas of application; they are biodegradable, recyclable and can be
easily converted into thermal energy through combustion leaving little or no residue [3-5]. Their
biodegradability can contribute to a healthier ecosystem and their low cost and reasonable
performance fulfil economic interest of various industries [1, 6-7].
The use of plant fibres as reinforcements in composite materials requires extra care regarding
fibre/matrix adhesion particularly when the matrix is hydrophobic and the fillers are hydrophilic
in nature, hence it is recommended that the fibres be treated before they are used for reinforcement
to improve interfacial compatibility with the matrix. [8-10]. Although Luffa fibre offers a unique
potential than other natural fibres due to its availability as a weed, naturally woven and thick
stands, there is still need to study its behaviour during surface treatment. The use of different kinds
of physical or chemical surface treatment such as mercerization, grafting, silane-coupling agents
etc., lead to change in the fibre surface structure and ensure improvement of the tensile properties
and absorption characteristics [8,11]. Several authors have investigated fibre-matrix adhesion in
composites involving luffa cylindrical [12-17].
Although there has been extensive research on luffa fibre reinforced composites, much study has
not been carried out on its reinforcement with LDPE which is a popular conventional polymer.
Hence, this paper presents a study which tends to analyse the mechanical properties of luffa
reinforced low density polyethylene composites varying sodium hydroxide concentration during
the treatment of the fibre.
Plate 1: Dried luffa cylindrical in its natural woven form.
2.1 Preparation of the fillers
The luffa fibre combs were collected and the dried seeds shaken out. It was then washed with
distilled water, dried under atmospheric condition and then divided into three parts, which were
immersed in already prepared 3%, 4% and 5% of sodium hydroxide respectively for 18 hours to
undergo mercerization process, it was washed again with distilled water to remove any unreacted
sodium hydroxide from luffa substrate. The sundried material was ground to effectively reduce
size to a range of 800 – 1100µm before being used in the composites.
46
2.2 Preparation of the Composite
The various forms of luffa fibre were incorporated into Low density polyethylene as the matrix, to
produce reinforced composites and using an injection moulding machine, the composite was
moulded into shapes. The filler loading was varied from 0 to 50pph at intervals of 10, for the
3%,4% and 5% modified and unmodified luffa fibre respectively, so that four different sets of
composite were produced at a processing temperature of 150oC.
2.3 Moisture content determination
The moisture content was done in accordance with ASTM 789standard. Moisture content was
computed using equation 1.
𝑤𝑜 −𝑤𝑓
𝑀𝑜𝑖𝑠𝑡𝑢𝑟𝑒 𝑐𝑜𝑛𝑡𝑒𝑛𝑡 = ( 𝑤𝑜
) × 100 (1)
Where: wo is the original weight of fibre; wf is the final weight of fibre after drying and Moisture
content is in percentage.
2.4 FT-IR Spectroscopy Characterisation
A Fourier transform infrared spectrophotometer was used for the structural determination of
functional groups present in the modified and unmodified luffa fibres. In carrying this operation,
the Shimadzu IR Affinity spectrometer was used.
2.5 Hardness Test
This was carried out with Rockwell Hardness testing machine, in accordance with standard
method: ISO 6508-200 M015. The test samples were prepared into appropriate shapes in readiness
for the test. Then the samples were placed on the anvil of the equipment placing the test point
directly under the indentor. The machine was set by lifting the anvil to set the preloading force.
2.6 Impact Test
The impact test was done with the impact testing machine “Samuel Denison” using the Charpy
test method: ISO 148-200M014. The test samples were prepared into appropriate rectangular rod
shape of 7.5cm by 3.0 cm in readiness for test. Then samples were placed on the anvil of the
equipment. The equipment operates by swinging pendulum method and the sample is fracture by
single overload event as a result of impact from the pendulum. A pointer is used to record how far
the pendulum swings back after fracturing the sample.
2.7 Flexural Test
47
The flexural test was carried out using flexure instron. The standard test process used is given in
ASTM D- 790. The specimen is supported on two knife edges as a simple beam and load is applied
at its mid-point. This method of measuring flexure behaviour of materials subjected to simple
beam is called a transverse beam test. Maximum fibre stress and maximum strain are calculated
for increment of loads.
3.0 RESULTS AND DISCUSSIONS
Table 1: Moisture content of luffacylindrica
Type of Luffa Fibre Sample Moisture Content

Unmodified 6.5%
3% NaOH modified 7.2%
The moisture content of the samples was determined as 6.5%, 7.2%, 7.5% and 7.8% for the
unmodified, 3% NaOH modified, 4% NaOH modified and 5% NaOH modified respectively. These
values for moisture actually agreed with expectation, since it indicated that the modified luffa fibre
still holds more moisture than the unmodified luffa fibre as shown in Table 1. During
mercerisation, most of the hydrogen bonds are broken from the cellulose. However, mercerisation
increases the number of hydroxyl groups on the cellulose, as the alkali (NaOH) penetrates the
cellulose fibres, it makes the cellulose to swell and more amorphous regions are created on the
fibre. Absorption of moisture is higher in these regions than crystalline regions. This explains why
the mercerised cellulose absorbed more moisture than the unmercerised samples. This agrees with
findings of other research works [18].
However, the alkali treatment is able to improve the mechanical properties as was observed in this
study. This agreed with the observation of other researchers (22). The observation is attributed to
the fact that interfacial interaction is enhanced between the fibre (luffa) and polymer matrix
(polyethylene)
by fibre surface cleaning
done during alkali
modification, which dignified
the fibre.
48
Figure 1: FT-IR spectra for untreated luffa fibre
From the FT-IR spectra as shown in Figures 1 and 2, a broad absorption band between 500 to 2000
cm-1 region is characteristic of polymeric association of the –OH groups and hydrogen bonded-
OH stretching vibration present in cellulose and lignin. It can be noted that the broadness of the –
OH band decreased more in the alkali treated fibre between 3600cm-1 and 3500cm-1. For the
modified fibres, the intensity of the band reduced at 1058 cm-1because of the formation of
glycosidic bonding, also the intensity of bands at 1608cm-1 from carbonyl stretching was reduced
or almost absent due to removal of hemicelluloses during mercerisation. The decrease of the
intensity of the band at 1207 cm-1 can be explained by the removal of -OH bonding in the absorbed
water molecules by mercerization.
Figure 2: FT-IR spectra for treated luffa fibre
Generally, varying the filler volume in a composite affect the physical properties as was also
observed during this study. In addition, modification of the cellulosic reinforcement by
mercerisation further influenced the mechanical properties of the final composite samples. The
modified luffa fibre exhibited higher mechanical properties than the unmodified fibres. The strands
were also observed to be tougher during the grinding process indicating that mercerization
increased the strength of the fibre.
49
700
600
hardness test
500
400
300 Modified
200
Unmodified
100
0
0 10 20 30 40 50
filler volume
Figure 3: Bar chart of hardness versus filler volume of composites (3% NaOH modified)
800
600
hardness test
400 Modified
200 Unmodified
0
0 10 20 30 40 50
filler volume
Figure 4: Bar chart of hardness versus filler volume of the composites (4% modified)
700
600
hardness test
500
400
300 Modified
200
Unmodified
100
0
0 10 20 30 40 50
filler volume
Figure 5: Bar chart of hardness versus filler loading of the composites (5% modified).
For the hardness test results in Figures 3, 4 and 5, reinforced LDPE composites where the 3%
NaOH modified filler was used showed more reinforcement than the unmodified and the
50
reinforcement was observed to progress with increase filler volume as stated earlier. The
reinforced samples exhibited the best mechanical properties with 50% filler volume. The
observations were generally similar for 4% and 5%NaOH modified fibre reinforced LDPE
composites. This observation was found to be in agreement with the report of other researchers [3-
5, 19]. However, for the 4% NaOH modified fibre, the property reduced at 50% filler volume,
giving highest value at 40% filler volume.
10.00
8.00
impact test
6.00
4.00 Modified
2.00 Unmodified
0.00
0 10 20 30 40 50
filler volume
Figure 6: Bar chart of impact versus filler volume of composites (3% NaOH modified)
10.00
8.00
impact test
6.00
4.00 Modified
2.00 Unmodified
0.00
0 10 20 30 40 50
filler volume
Figure 7: Bar graph of impact test versus filler volume of the composites (4% modified).
The impact strength was observed to fall generally as filler volumes were increased. See Figures
6, 7 and 8. For the impact test, of the 3% NaOH modified, the unmodified had more impact than
the modified. As it progressed with volume of filler, the impact of the modified reduced more than
the unmodified composites. For the 4% and 5% NaOH modified fibre reinforced composites they
had more impact than the unmodified at any given filler volume. This signifies that the unmodified
luffa fibre reinforced composites absorb more energy during fracture than the modified luffa fibre
reinforced composites though with a slight variation for 4% and 5% NaOH modified luffa fibre
composites.
51
10.00
8.00
impact test
6.00
4.00 Modified
Unmodified
2.00
0.00
0 10 20 30 40 50
filler volume
Figure 8: Bar chart of impact test versus filler volume of composites (5% modified).
100.00
80.00
flexural test
60.00
40.00 Modified
20.00 Unmodified
0.00
0 10 20 30 40 50
filler volume
Figure 9: Bar chart of flexural test versus filler volume of composites (3% NaOH modified)
100.00
80.00
flexural test
60.00
40.00 Modified
Unmodified
20.00
0.00
0 10 20 30 40 50
filler volume
Figure 10: Bar graph of flexural test versus filler volume of composites (4% modified).
52
100.00
80.00
flexural test
60.00
40.00 Modified
Unmodified
20.00
0.00
0 10 20 30 40 50
filler volume
Figure 11: Bar chart of flexural test versus filler volume of composites (5% modified).
For the flexural test, unmodified luffa composites had better flexural properties than the 3%, 4%
and 5% modified luffa composites. This is shown in Figures 9, 10 and 11 above. This signifies
that unmodified luffa composites experience a higher stress at its moment of yield than the
modified luffa composites. More so, this behaviour is attributed to the fact that as modification
enhanced the hardness, stiffness and rigidity, the property of toughness is sacrificed. Hence the
flexure was reducing for the modified more than the unmodified as the filler volume was being
increased. This observation falls in line with results of previous researchers [19-21].
4.0 CONCLUSION
Increasing environmental concern along with the drive to find substitutes for synthetic fibre and
value added applications for low cost and renewable plant fibre have led to the development of
composites based on bio-based materials. One of the drawbacks encountered in such exercise is
the lack of adhesion between the incorporated plant fibre and synthetic polymeric (hydrophobic)
matrices. Luffa fibre offers unique characteristics to composite processing than other fibres due to
its naturally woven form, thick strands and renewability. It grows naturally as a weed in tropical
regions. This study demonstrated that mercerization treatment on the luffa fibre has a positive
effect on the composite preparation with reference to the variation in modification of the fibre. The
modification effects were exhibited as improvement to different extents on the mechanical
properties of resultant composites.
At present, Luffa fibres are highly underutilized despite its abundance in our environment. It is
regarded as a non-viable material economically. The discovery of its unique potential gave the
initial motivation for this work.
REFERENCES
1. Kalaprasad, G., Pradeep, P., George M., Pavithran, C., Sabu, T. (2000). Thermal
conductivity and thermal diffusivity analyses of low-density polyethylene composites
53
reinforced with sisal, glass and intimately mixed sisal/glass fibres. Composites Science and
Technology, 60:2967-2977
2. Mokoena, M. A., Djoković, V., Luyt, A. S. (2004). Composites of linear low density
polyethylene and short sisal fibers: The effects of peroxide treatment. Journal of Materials
Science, 39:3403-3412.
3. Idicula, M., Malhorta, S.K., Joseph, K., Thomas, S. (2005). “Dynamic mechanical analysis
of randomly oriented intimately mixed short banana/sisal hybrid fiber reinforced polyester
composites”. Composites Science and Technology, 65:1077-1087.
4. Bledzki, A.K., Abdullah, A. And Volk, M.J. (2010) “physical, chemical and surface
properties of wheat husk, rye husk and soft wood and their propylene composite,” Compos.
Part A 41, 480-488.
5. Abdul Khalil H. P. S., Hanida S. and Kang C. W. (2007). “Agro-hybrid composite: The
effects on mechanical and physical properties of oil palm fibre (EFB)/glass hybrid
reinforced polyester composites”, Journal of Reinforced Plastics and Composites, Vol. 26,
p. 203.
6. Joseph, P.V. Rabello, M.S. Mattoso, L.H.C. Joseph, K. Thomas, S. (2002) “Environmental
effects on the degradation behaviour of sisal fibre reinforced polypropylene composites”,
Compos. Sci. Technol. 62 (10/11) 1357–1372.
7. Nwosu-Obieogu K, Ejim I.F and Adekunle K.F (2016) “Mechanical properties of rice husk
reinforced low density polyethylene composite”. International Journal of Research in
Advanced Engineering and Technology (IJRAET) , 2(1): 10-15
8. Adekunle K. F. (2015) “Surface treatment of natural fibres- A Review”: Part 1. Open

Journal of Polymer Chemistry, 5, 41-46.
9. Nwosu-Obieogu Kenechi, Chiemenem Linus, AdekunleKayode.(2016) “ Utilization of
Rice Husk as Reinforcement in Plastic Composites Fabrication- A Review”. American
Journal of Materials Synthesis and Processing. Vol. 1, No. 3, 2016, pp. 32-36
10. Gassan, J., Bledzki, A.K., (1999); Alkali treatment of jute fibres: relationship between
structure and mechanical properties, J. Appl. Polym. Sci. 71 (4) 623–629.
11. Bledzki, A.K., Gassan, J., Composites reinforced with cellulose based fibres, Prog. Polym.
Sci. 24 (2) (1999) 221–274.
12. Tanobe O.A.U, Syndenstricker H.D.T, Munaro, M and Amico S.C (2005) “ A
comprehensive characterization of chemically treated brazillian sponge gourds (luffa
cylindrica) Polymer Testing 24: 474–482.
54
13. Ichetaonye S.N, Madufor I.C, Yibowei, M.E and Ichetaonye D.N (2015) “ Physico-
mechanical properties of luffa aegyptiaca fibre reinforced polymer matrix composite.Open
Journal of Composite Materials, 5, 110-117.
14. Mohanta, N. And Acharya S.K (2015) investigation of mechanical properties of luffa
cylindrical fibre reinforced epoxy hybrid composite, International Journal of Engineering,
Science and Technology Vol. 7, No. 1, 2015, pp. 1-10.
15. Sousa, A.M.F, Escocio, A.V, Elen B.A.V.P, Visconte L.L.Y, Cavalcante, A.P, Soares,
G.A, Junior, M.F Motta, C.C.L and Britta, G.F.C. (2013); “Design of experimental design
tool for the processing and characterization of HDPE composites with sponge-gourds
(Luffa cylindrical) Agro-fibre residue)Journal of Sustainable Development; Vol. 6, No. 4.
ISSN 1913-9063 E-ISSN 1913-9071.
16. Saw K.S, Purwar, R., Nandyy, S, Ghose J and Gautan S (2013) “Fabrication,
Characterization and Evaluation of luffa cylindrical Fibre Reinforced Epoxy Composites”
Bioresources 8(4); 4805-4826.
17. Ubi, P.A. and Asipita, S.A.R., (2015) “Effect of Sodium Hydroxide Treatment on the
Mechanical Properties of Crushed and Uncrushed Luffa cylindrical Fibre Reinforced LDPE
Composites” World Academy of Science, Engineering and Technology International
Journal of Chemical, Molecular, Nuclear, Materials and Metallurgical Engineering Vol:9,
No:1.
18. Mohamed E. Khalifa (2017); “Mercerisation of cotton yarn fibres. Optimisation of caustic
soda concentration via degree of mercerisation,dyability and mechanical properties”. Intl
Journ. Textile Sci., Vol 6, No 1, 15-19.
19. Aguele, F. O., Madufor, C. I. (2012); “Effects of Carbonised Coir on Physical Properties
of Natural Rubber Composites” American Journ Pol Sci., 2(3): 28-34.
20. Bledzki, A.K., Gassan, J. (1999); “Composites Reinforced with Cellulose Based Fibres”
Journ Progress Pol. Sci., vol. 24, No. 2, 221-274.
21. Chadramohan D., Marimuthu k. (2011); “Tensile and Hardness Tests on Natural Fiber
Reinforced Polymer Composite Material”. Intl. Journ. Advanced Eng. Sci. and Technol,
vol 6, 97-104.
22. Xue Li, Lope G. Tabil, Satyanarayan Panigrahi (2007); “Chemical Treatments of Natural
Fiber for Use in Natural Fiber-Reinforced Composites: A Review”. J Polym Environ.
15:25–33
55
PREPARATION AND CHARACTERISATION OF DECOLOURED NOVATEIN® AND

MODIFIED PLA BLENDS
Sandra C. P. Izuchukwua*, Casparus J. R. Verbeeka, and James Michael Bierb

a
School of Engineering, University of Waikato, Private bag 3105, Hamilton 3240, New Zealand
b
Aduro Bioploymers LP, Private Bag 3105, Hamilton 3240, New Zealand
*
Corresponding author; sciokoro@gmail.com, scpi1@students.waikato.ac.nz
ABSTRACT
Modified Poly (lactic acid) (PLA) was blended with Decoloured Novatein® (DNTP), a
thermoplastic protein material using reactive extrusion to produce a degradable material with
improved properties compared to neat Decoloured Novatein®. PLA was modified through free
radical grafting of itaconic anhydride to create reactive side-chain groups. Varying ratios of DNTP/
PLA-g-IA or PLA were prepared. Blending DNTP with PLA was found to increase tensile strength
between 22% to 538% and modulus between 201 GPa to 3193 GPa, whereas the strain at break
decreased between 80% to 94% depending on the blend ratio. The glass transition temperature of
the blends which was measured as the tan δ peak, also revealed an increase when compared to neat
DNTP. Scanning electron microscope revealed an enhanced interfacial adhesion between the two
phases in the blends with PLA-g-IA suggesting a more homogenous microstructure. WAXS result
revealed an insignificant decrease in the crystallinity of the blends compared to neat DNTP,
indicating that blending with PLA had no structural effect on DNTP. The results show the
possibility and feasibility of blending DNTP with PLA for use in agricultural and packaging
applications.
56
1. INTRODUCTION
The rise in the cost of petroleum based polymer has led to an increased trend in the replacement
of the synthesic polymer with bio-based polymers. PLA, protein, starch and gluten are among the
bio-based polymers that are very attractive as replacement due to their availability and properties
[1-3]. PLA has experienced substantial growth in its application as a result of its unique properties
such as glossy optical appearance, biodegradability, compostability, high tensile strength and good
barrier properties toward carbon dioxide, oxygen and water [4-6]. PLA is a biodegradable
thermoplastic polyester derived from corn starch, with several applications in biomedical and
pharmaceutical fields as a material used in surgical operations, tissue regeneration, and drug
delivery systems [7]. PLA is also considered suitable for high-volume packaging applications [4,
8] because of its good barrier properties to aromas and permeability to carbon dioxide, oxygen and
water vapour compared to synthetic polymers. However, PLA is expensive and has low heat
deflection temperature which remains as limitations for wider application. Therefore PLA has
often been blended with other polymers to reduce cost and improve blends properties [4, 9-11]
Decoloured Novatein thermoplastic protein (DNTP) is a newly developed biopolymer using

bloodmeal as starting material [12, 13]. DNTP is best suited for agricultural and horticultural
applications such as weasand clips, weed mat pegs, biodegradable plant pot and seedling trays.
DNTP is a protein polymer consisting of complex molecules with strong intra- and intermolecular
interactions. These strong interactions make the melt processing of DNTP such as extrusion and
injection moulding very difficult unless an adequate amount of plasticizers are added to promote
mobility and flexibility of the protein chains enabling flow and consolidation during processing.
Low molecular weight polyols such as glycerol, propylene glycol, ethylene glycol and their derivatives
[13-17] are used as plasticizers for proteins to reduce intermolecular interactions and glass transition
temperature Tg. However, the amount of plasticizer used affects the material’s mechanical properties as
well as leads to phase separation [5, 9]. Previous research has shown that DNTP can be successfully
processed using the extrusion and injection moulder [18]. However, like every other protein polymer,
moisture evaporates during processing which leads to a highly brittle material and loss of functionality.
Blending DNTP with other polymers can improve its processability and mechanical properties. Researches
has shown that blending protein with other hydrophobic thermoplastic is an alternative to increase the
processability and moisture resistance of the protein based polymer products [9, 19-23]. Therefore, DNTP
will be blended with PLA. However, the problem with this blend system is the poor interfacial interaction
between the hydrophilic DNTP and hydrophobic PLA. Compatibilizer such as poly-2-ethyl-2-oxazoline
(PEOX) [9, 24], polymeric methylene diphenyl diisocyanate (pMDI) [5, 25], maleic anhydride [21, 26],
methylene diphenyl diisocyanate (MDI) [27, 28] and itaconic anhydride [29] have been used to enhance
the interfacial interaction between PLA and other protein polymers.
Research on compatibilized blends of protein thermoplastics and polybutylene succinate reported an

improvement in water resistance and tensile strength [5]. Blends of soy protein and PLA was found to
increase tensile strength, reduced water absorption of soy plastic and a co-continuous phase was observed
for soy protein concentrate (SPC) and PLA [9]. Blends of cereal protein and poly (hydroxyl ester ether)
without compatibilizer was reported to exhibit acceptable mechanical properties due to the strong hydrogen
57
bonding between the two components [30]. Using a small amount of maleic anhydride (MA) grafted on
low-density polyethylene (LLDPE), An improvement in the compatibility between Novatein thermoplastic
protein (NTP) was observed as well as improved tensile strength and reduction in water absorption of NTP
[25].
Itaconic anhydride (IA) is a highly reactive monomer in free radical grafting as it has the abililty to produce
tertiary radicals [31]. Although IA has not been extensively studied but it has been used as a renewable
monomer for synthesing bio-based copolymers through conventional copolymerization [32], also can be
used for acetylating lysin, tyrosine and cysteine [33]. IA is extremely stable when reacted with proteins
compared to MA.
In this study, blends of DNTP and PLA compatibilized with itaconic anhydride
were investigated. The main objective of this study was an attempt to demonstrate that DNTP can be used
for PLA blends, as other proteins and starch has already been used for PLA blends. It also considered the
improvement of processibility and properties of DNTP based plastic through blending with PLA. The
morphology, thermal, mechanical and water absorption properties of DNTP/PLA blends were investigated.
2. EXPERIMENTAL
2.1. Materials
Bloodmeal was obtained from Wallace Corporation Limited, New Zealand and used as received. Analytical
grade itaconic anhydride (IA), dicumyl peroxide (DCP), acetone, 30 wt % hydrogen peroxide, technical
grade sodium dodecyl sulphate (SDS), triethylene glycol (TEG) were purchased from Sigma Aldrich NSW,
Australia. Peracetic acid (Peraclean 5) was purchased from Evonik Industries, Morrinsville, New Zealand.
Poly(lactic acid) (PLA) grade 3051D was purchased from NatureWorks Ltd in pellet form. Distilled water
was produce onsite at the University of Waikato New Zealand.
2.2. Sample preparation

2.2.1. Interfacial modification of PLA
PLA was modified through free radical grafting of itaconic anhydride [6] to create reactive side-chain
groups. PLA was dried at 80 ºC for 4 hours to control moisture. 4.2 parts per hundred PLA (pph) itaconic
anhydride and 0.8 pph dicumyl peroxide were dissolved in 30 mL acetone. The preformed solution was
poured over the oven dried PLA and was keep in the fuse hood for 2 hours. The solution was decanted
before oven drying the PLA for 3 hours at 50 ºC. The modified PLA (PLA-g-IA) was extruded using a
LabTech twin screw co-rotating extruder having a screw diameter of 20 mm and L/D ratio of 44:1, at
temperature profile of 145 (feed zone), 145, 165, 165, 180, 180,180, 180, 160, 160, 155 ºC (die zone). A
constant screw speed was maintained at 150 rpm. A vaccum pump was attached on the 7th heating zone of
the extruder to get rid of vapour generated during extrusion. To avoid the crystallization of the extruded
PLA-g-IA, it was collected in a water bath upon exiting the die and afterwards pelletized. The pelletized
PLA-g-IA was oven dried at 60 ℃ for 12 hours prior to blending with Decoloured Novatein (DNTP) to
minimise hydrolysis during melt processing.
2.2.2. Bloodmeal decolouring and Decoloured Novatein preparation

Bloodmeal was decoloured using the standard method with solution of peracetic acid (PAA) [34, 35]. 4
wt% PAA solution was prepared by diluting 5 wt% stock solution with distilled water with a constant
percentage ratio of 80:20 respectively. 150 g bloodmeal was decoloured by adding 450 g of 4 wt% PAA in
58
a high speed mixer. The mixture was allowed to mix continuously for 5 min to ensure homogenous
decolouring of bloodmeal. 450 g of distilled water was added and mixed for another 5 min to ensure
complete dilution of the slurry. The slurry was neutralized by adjusting to pH = 7 with sodium hydroxide.
The neutralized slurry was filtered using a wire mesh sieve with aperture size 60 and subsequently washed
by adding another 450 g of distilled water. The decoloured bloodmeal was dried approximately 15 hours in
a oven temperature of 75 ºC.
Decoloured Novatein (DNTP) was formulated by dissolving 6 part per hundred decoloured bloodmeal
(pphD) SDS in 40 pphD water heated to 60 ºC while stirring . the solution was added to decoloured
bloodmeal powder in a high speed mixer and mixed for 5 min. 30 pphD TEG was added to the mixture
and mixed for another 5 min to ensure homogeneous mixture is obtained. The mixed material was stored
in an air tight bag overnight in a 2 ºC fridge to equilibrate.
Different formulations of DNTP were prepared based on varying the additives. Water was varied between
30 and 40 pphD, TEG was between 20 and 30 pphD and SDS was between 3 and 6 pphD to produce four
sample formulations known as F1, F2, F3 and F4.
2.2.3. Blends preparation

DNTP was formulated prior to blending. Blends containing 30:70, 50:50, 70:30 and 90:10 (w/w)
DNTP/PLA-g-IA or PLA were prepared. The performed DNTP and PLA-g-IA or PLA blends were then
compounded using a twin screw co-rotating extruder (LabTech). The extruder barrel had eleven heating
zones and the screw speed was maintained at 150 rpm. The compounding extrusion temperature varied
from 100 (feed zone) to 180 ºC (die zone) depending on the DNTP content which required a reduction in
compounding temperature with an increase in DNTP content as it’s formulation contained 40 parts of water
that could lead to PLA hydrolysis. The extrudate was granulated using a Tri-blade granulator from Castin
Maunfacturing Limited.
2.2.4. Test specimens preparation

ASTM D638-14 Standard tensile test samples [36] and ISO 179-1:2010 impact test samples [37] of the
blends were injection moulded using a BOY 35A injection moulding machine. The samples were injected
through a cold runner into a 60 ºC water heated mould. The injection moulder has five heating zones
including the feed and the die zones. The feed temperature remained constant at 100 ºC, the barrel
temperature varied between 100 to 140 ℃ and the die temperature varied between 120 to 140 ℃ depending
on the formulation. The screw speed was constant at 150 rpm. The sample specimens produced were also
used for water absorption, thermal and morphology testing.
2.3. Sample Analysis

All samples were conditioned for 7 days at 23 ºC and 50 % relative humidity before testing except otherwise
stated.
2.3.1. Mechanical properties
The mechanical testing was performed according to ASTM D638 using Instron Universal Testinf machine
(model 33R4204) at a crosshead speed of 5 mm/min and an extensiometer guage length of 50 mm. 10
replicates were tested for each sample type to obtain an average value.
59
The impact testing bars produced from the injection moulder had diameter of 80 x 10 x 4 mm3. Charpy
edgewise impact strength was performed according to ISO 179-1:2010 using a RAY-RAN Pendulum
Impact System. The bars tested were notched according to standard. 10 bars were tested to obtain average
impact strength of the material.
2.3.2. Thermal analysis
Dynamic mechanical analysis (DMA) was conducted using Elmer DMA 8000 fitted with a high
temperature furnace and cooled with liquid nitrogen. Rectanglar samples (30 x 9 x 4 mm) were cut from
injection moulded samples and tested in a single cantilever fixture using free length of 12.5 mm and
scanning temperature from -80 to 150 ºC at 2 ºC/min . data was collected at multiple oscillation frequencies
(0.1 – 30 Hz). Tan δ peak values were recorded as glass transition temperatures.
2.3.3. Wide angle X-ray scattering measurement (WAXS)
WAXS was used to measure the XRD pattern of the blends. WAXS was performed with a philips X-ray
diffractometer operating at 40 Kv and 40 mA using CuKα radiation. The diffraction data was collected
from 2θ values of 4º to 40º with a step size of 0.013º. a fixed 7.5 mm anti-scatter slit, fixed incidence beam
mask of 10mm and a soller slit of 0.04 rad were used. The data collected was baseline corrected from 5-40º
and amorphous halo was fitted to this region to determine crystallinity of the blends.
2.3.4. Fracture morphology
The phase structure of the blends was investigated using Hitachi S-4700 field emission scanning electron
microscope (SEM). The injection molded specimens were cryofractured using liquid nitrogen. The
specimens were sputter coated with platinum using Hitachi E-1030 Ion sputter before scanning.
3. RESULTS AND DISCUSSION
Formulation 1 Formulation 2
Formulation 3 Formulation 4
Figure 1: Injection moulded samples produced from different DNTP formulations
Different formulations of DNTP were accessed for blend suitability with PLA based on ease of processing,
mechanical and visible colour of produced sample. Formulation 2, 3 and 4 had ease of processing and were
easily reproducible compared to formulation 1. They were easy to pull out of the mould and most were self-
ejected. They showed reduced injection time and barrel refill time compared to formulation 1, which was
faced with spur and mould blockage. Comparing the visible clarity of samples, formulation 2, 3 and 4 were
60
more transparent. Compromising tensile strength, formulation 2, 3 and 4 showed low modulus, impact
strength and strain at break greater when compared. Similar mechanical properties have been reported for
bioplastic produced from decoloured bloodmeal [13].
Figure 2: Mechanical properties of DNTP formulation with varying amount additives.
Flexibility, toughness and enlongation are very important when considering a material for sheet production
as they describe the material’s ductility and are useful in the prediction of material performance during
handling and storage. Therefore, formulation 4 was chosen to be investigated further as blends with PLA
because it produced better extrudate, injection mouldable and brighter samples, having better strain at break,
low modulus and good impact strength.
3.1 Blending and processing

Two different blend approaches were used to determine the best approach for DNTP/PLA-g-IA or PLA
blends. In the first variation, PLA-g-IA or PLA was blended with pre-extruded granules of DNTP and the
second variation was to blend PLA-g-IA or PLA with DNTP powder.
3.1.1. Extrusion processing of the blended material

Extruding the blends of DNTP/PLA-g-IA or PLA produced either consolidated or semi-consolidated
extrudate with semi or reasonably smooth surface. Extrudate flowed out of the extruder with moderate
torque and pressure. The produced extrudate was flexible and rubbery prior to cooling. Small surface
defects such as cracks and shark skinning were observed with the blends with high ratio of DNTP. The
produced extrudate were granulated and injection moulded.
3.1.2. Injection moulding of the blended material

Injection moulding of blended DNTP granules and PLA-g-IA or PLA
The blends with pre-granulated DNTP could not be injection moulded due to excessive blockage of the
injection moulder barrel and protein degradation. Adding of Struktol processing aid had no effect on the
blend processing as it became more difficult to feed through the barrel. This was considered an effect of
lack of plasticizer in the blend, which might be as a result of excess heat run on DNTP resulting to loss of
61
plasticizers, considering that moisture was also controlled to avoid the hydrolysis of PLA. Therefore an
approach to reduce DNTP heat run during processing was considered leading to blends of DNTP powder
and PLA-g-IA or PLA.
Injection moulding of blended DNTP powder and PLA-g-IA or PLA
The injection moulding of DNTP powder and PLA-g-IA or PLA worked well without processing aid and
produced flexible and consolidated sample bars. The injection of blends produced three type of sample bars
as shown in Table 1.
Table 1: description of injection processing of blends
Injection type Description
1 not self ejected out of the mould, longer injection time and barrel refill time, very
difficult to pull out of the mould due to spur block.
2 not self injected out of the mould, reduced injection time and barrel refill time,
easy to pull out of the mould unit and spur section.
3 mostly self injected out of the mould and easy to remove from the mould unit
manually, reduced injection time and barrel filling time.
Injection type 1 was observed mainly for blend having high amount of PLA while for blends having lower
amount of PLA injection type 2 and 3 were observed and injection type 3 was observed for 50:50 blends.
Blending PLA and DNTP powder was injection mouldable and showed ease of processing, therefore the
second variation was chosen to be the optimal method for processing DNTP/PLA blends. The properties of
the sample produced were investigated.
3.2 Phase morphology

The study of polymer blend morphology is important as it is related to the mechanical and barrier properties
of the blend [14, 38] and it is essential in understanding property-structure relationship of the material. Most
polymer blends are immiscible therefore produce a heterogeneous morphology [38]. Compatibilizers are
used to reduce the interfacial tension in polymer blends thereby stabilizing the morphology, often resulting
in a co-continuous structure [5]. Co-continuous morphology exhibits a combination of both polymer
components characteristics [39], this is formed mainly around the point of phase inversions such that the
matrix is undistingishable from the dispersed phase.
Figure 3 shows the cryofractured phase structure of DNTP/PLA and DNTP/PLA-g-IA blends with DNTP/
PLA-g-IA or PLA ratio varying between 30:70 to 90:10 (w/w). A dispersed phase morphology was
observed with blends without itaconic anhydride showing one phase which is rich in DNTP and another
that is rich in PLA (Figure 3.c, d, e). Also, the interstices between the DNTP phase and PLA matrix were
clearly observed for the uncompatibilized blend indicating poor interfacial adhesion. This is expected, as
DNTP contains 90% protein which is highly polar and hydrophilic while PLA is hydrophobic therefore will
lead to poor interfacial interaction between the two phase. Blend of Novatein and polybutylene succinate
(PBS) without compatibilizer was reported to have poor interfacial adhesion [5]. As DNTP content
increased, the diameter of DNTP rich phase increased for blends without IA. This is attributed to the poor
62
interfacial adhesion between DNTP and PLA phase. However, the addition of IA (Figure 3. c’, d’, e’)
showed an improved even dispersion of DNTP within the matrix. Even at high DNTP content (Figure 3.
e’), a virtually undistinghable DNTP phase was observed. Although some interstices were still observed in
the compatibilized sample but they are fewer and smaller compared to the uncompatiblized blends.
The improved dispersion observed with blends compatibilized with IA arose from the formation of
branched and crosslinked macromolecules initiated by the reaction of the anhydride group of PLA-g-IA
with the amino groups of DNTP. Same phenomena had been reported for compatibilized PLA blends with
protein and starch [10, 26]. It has been reported that addition of PEOX improved the interfacial adhesions
between SPC/PLA blends resulting to finer structure and homogeneous phase structure [9]
Compatibilization showed no clear effect on 30:70 blend ratio (Figure 3. b and b’), this is believed to be
due to the overwhelming effect of high PLA content in the matrix. This was further explored using thermal
analysis and wide angle X-ray scattering (WAXS).
63
Figure 3: SEM micrographs of cryo-fractured surface of DNTP/ PLA-g-IA or PLA blends.

a and a’: PLA and DNTP; b and b’: 3070DP and 3070DgP; c and c’: 5050DP and 5050DgP;
d and d’: 7030DP and 7030DgP; e and e’: 9010DP and 9010DgP
3.3. Dynamic mechanical properties
Understanding thermal transition of a polymer material is very important in the predictation of the
material’s performace under different end use conditions. DMA have been commonly used to study the
molecular relaxation processes in polymers [14] and to determine inherent flow and mechanical properties
such as modulus and damping of viscoelastic material over a spectrum of time (frequency) and temperature
[40]. Figure 4 show the tan δ and storage modulus (E’) of neat PLA, PLA-g-IA and DNTP. PLA and DNTP
showed broad and low damping peaks (Tg) while PLA-g-IA exhibited a sharp and high damping peak. The
high damping peaks is suggested to be due to PLA-g-IA low crystallinity which makes it very soft when
the temperature is above its α-transition. Similar observation have been reported for PLA grade used for
blends with soy protein composites [9, 26].
Figure 4: Tan  and storage modulus (E’) of neat PLA, PLA-g-IA and DNTP
The damping peak of PLA and PLA-g-IA in the blends were observed to be lower than that of the neat PLA
and PLA-g-IA alone. This suggests that the DNTP component was still in glassy state in the α-transition
range of PLA and PLA-g-IA. The compatibilized blends (Figure 5. a’) show broader peaks compared to
the uncompatibilized blends (Figure 5. a), which suggested that the blends had improved interactions
between PLA and DNTP. The damping peak height decreased with increasing DNTP ratio, this is probably
attributed to the effective contribution of the DNTP phase to the storage modulus in the rubbery region of
PLA [9, 26, 41]. The decrease in Tg observed with the blends is thought to be due to the migration of small
molecules of plasticisers from DNTP phase to the PLA matrix during compounding. No significant
difference was observed in the Tg of the compatibilizer and the uncompatibilizer blends therefore it
suggests that compatibilization has no significant influence on the melting point of PLA in the blends.
64
Figure 5: Tan  and storage modulus (E’) of blends. a and b: DNTP/ PLA, a’and b’: DNTP/
PLA-g-IA
Two transitions (peak and a shoulder) was observed for the 30:70 and 50:50 blends (Figure 5. a). the first
peak correspounds to the α-transition of PLA region and the second peak could be associated with the α-
transition of the DNTP region in the blends. 30:70 and 50:50 blends with PLA-g-IA (Figure 5. a’) showed
a shift in the α-transition of DNTP region towards a lower temperature while the PLA region showed a
slight change with compatibilization. This change is suggested to be due to the improved compatibility
between both regions or as a result of miscibility of DNTP and the compatibilizer. Jinwen Zhang et al
observed same trend with soy protein isolate/PLA compatibilizer with PEOX [9]. At higher content of
DNTP, only a single peak was observed and no shift in peak temperature was observed. The storage
modulus of the uncompatibilized blends dropped when the Tg of DNTP ( ≈ 60 ºC) was reached, and then
recovered to a significant degree between 90 and 95 ºC due to the cold crystallization of PLA. However,
this recovery was not observed with the compatibilized blends. The compatibilized blends showed a lower
storage modulus than both DNTP and PLA (Figure 4. a’) at temperature below α-transition of PLA region.
This might be associated with the compatibilization effect of IA on DNTP in the blends making DNTP
more flexible in the blends. Ning Wang et al suggested that the addition of maleic anhydride improved the
plasticization of starch in starch/PLA blends [10].
3.4. Wide angle X-ray scattering (WAXS) measurement

X-ray diffraction (XRD) is a technique used to measure the atomic arrangement of a material. The XRD
data of polymers can be used to study the material’s phase change. The WAXS of neat PLA, DNTP and
DNTP/PLA blends with and without compatibilizer are shown in Figure 6. An amorphous peak at 16º 2θ
was observed for PLA without a crystal and long-range order. PLA-g-IA clearly presents crystalline peaks
at 2θ = 16º and 22º. The 2θ at 16º was recognized as (110)/(200) reflection of α-form homo-crystal structure
and 2θ at 22º was recognized as (100)/(-120)/(-210) of stereo-complex crystals [42-44]. DNTP is semi-
crystalline with less aggregated β-sheet and high number of disordered structure [13]. The peak at 2θ = 9º
corresponds to helical spacing and inter- β-sheet and the peak at 2θ = 22º corresponds to repeated distance
within each structure.
65
Figure 6: WAXS diffractograms of PLA, DNTP, PLA-g-MA and DNTP/PLA blends

without (a) and with compatibilizer (a’)
The summation of DNTP and PLA diffractogram looks exactly like the diffractogram of DNTP/PLA blends
of both with and without compatibilizer. This suggests the existance of three phases in the blends, the
amorphous DNTP, amorphous PLA and crystalline PLA. The compatibilized blends showed a slight
reduction in the amorphous region suggesting an intergration of both PLA and DNTP amorphous region.
This is probably due to the reduction in DNTP aggromerate observed with SEM thermogram (Figure 3).
No change was observed in 2 for the two peak at 16º and 22º with the addition of compatibilizer. This
suggests that Itaconic ahydride had no compatibilizing effect with the crystal region of the blend therefore
may not be a good compatibilizer for DNTP/PLA blends or the degree of PLA grafting is not sufficient to
compatibilize DNTP/PLA blends.
3.5 Mechanical properties

Mechanical testing provides valuable information on material’s flexibility, toughness and elongation which
is useful in the prediction of its performance during processing, handling, storage and final product
performance. The mechanical peoperties of PLA, DNTP and DNTP/PLA blends are shown in
Figure 7. PLA has been reported to have high tensile strength, impact strength, modulus and low elongation
[45] while DNTP has low tensile strength, impact strength, modulus and high elongation [18]. Mechanical
properties might be used to assess polymer blends miscibility as it depends on the intermolecular interaction
chain stiffiness and molecular symmetry of the individual polymer in the blend matrix [46]. Willemse et al.
suggested that tensile modulus of polymer blends depends strongly on the composition and morphology of
the blends [47].
Both DNTP/PLA blends with and without compatibilizer showed rigid and brittle behaviour. The modulus
of the blends was higher than that of neat DNTP due to the incorporation of rigid PLA.
66
Figure 7: Mechanical properties of DNTP, PLA and DNTP/PLA blends with and without
compatibilizer
Tensile strength observed for DNTP/PLA blends were inferior compare to neat PLA. This is as a result of
weak interfacial adhesion between the two phases even with the addition of compatibilizer. Previous
researches have reported inferior tensile strength for blends of PLA/Novatein [29] and PLA/soy protein
[26]. However, all blends showed an improvement in tensile strength compared to DNTP. Further
improvement was observed for 50-50 and 70-30 blends with the addition of itaconic anhydride. The
mechanical properties of 30-70 compatibilized blends were very poor compared to the uncompatibilized
blends while 90-10 blend showed no significant effect. It is assumed that below 50% and above 70% DNTP
cotent, DNTP overwhelm the compatibiling effect of itaconic anhydride resulting in poor tensile strength.
The anhydride groups of Itaconic anhydride were likely to react with the amino groups of DNTP protein
therefore enhancing the interfacial adhesion as observed with the SEM micrographs (Figure 3) which
played a role in reducing the size of DNTP phase in the compatibilzed blends. However, this interfacial
adhesion is considered to be very weak therefore wasn’t strong enough to effect significant improvement
in the mechanical properties. This is thought to be probably due to insufficient amount of compatibilizer
(i.e. low degree of grafting) or an indication that Itaconic anhydride is not a suitable compatibilizer for
DNTP/PLA blends. Rui Zhu et al, reported an increase in both tensile strength and elongation of PLA/Soy
protein composite with an increase in compatibilizer content [26].
4. CONCLUSION
DNTP/PLA blends were successfully prepared by extrusion mixing. The processibility and flowability of
DNTP increased after blending with PLA and it was injection mouldable without processing aids. The
DNTP/PLA blends showed a co-continuous phase morphology with a wide range of compositions. Blends
of DNTP/PLA compatibilized with itaconic anhydride led to significant change in morphology improving
the interfacial adhesion between the blended material phases. however, the adhesion between the phases
67
was not strong enough to improve mechanical properties. DMA results, WAXS diffractograms and
mechanical properties indicated compatibility of PLA with DNTP and the possiblilty of improving their
interfacial interactions. Itaconic anhydride can be used as compatibilizer for DNTP/PLA blends, leading to
improved mixing of the two phases. However, the two transition observed in the blend’s DMA (although
the second transition shifted to lower temperature for 30:70 and 50:50 blends ratio) suggests that the amount
of IA in PLA-g-IA is probably not sufficient enough to effect a significant improvement in the blend’s
mechanical properties. All blends showed low elongation at break and high brittle behaviour thereby
creating room for material plasticization and toughening in future investigations. Investigation of DNTP
formulation and plasticization will be necessary to optimize process and material’s properties.
REFERENCES
1. Sue, H.-J., S. Wang, and J.-L. Jane, Morphology and mechanical behaviour of engineering
soy plastics. Polymer, 1997. 38(20): p. 5035-5040.
2. Vaidya, U.R. and M. Bhattacharya, Properties of blends of starch and synthetic polymers
containing anhydride groups. Journal of applied polymer science, 1994. 52(5): p. 617-628.
3. Mohamed, A.A., et al., Thermal characteristics of polylactic acid/wheat gluten blends.
Journal of food quality, 2006. 29(3): p. 266-281.
4. Huneault, M.A. and H. Li, Morphology and properties of compatibilized
polylactide/thermoplastic starch blends. Polymer, 2007. 48(1): p. 270-280.
5. Ku‐Marsilla, K. and C. Verbeek, Compatibilization of Protein Thermoplastics and
Polybutylene Succinate Blends. Macromolecular Materials and Engineering, 2015. 300(2):
p. 161-171.
6. Marsilla, K.K. and C. Verbeek, Modification of poly (lactic acid) using itaconic anhydride
by reactive extrusion. European Polymer Journal, 2015. 67: p. 213-223.
7. Gorrasi, G. and R. Pantani, Effect of PLA grades and morphologies on hydrolytic
degradation at composting temperature: assessment of structural modification and kinetic
parameters. Polymer degradation and stability, 2013. 98(5): p. 1006-1014.
8. Auras, R., B. Harte, and S. Selke, An overview of polylactides as packaging materials.
Macromolecular bioscience, 2004. 4(9): p. 835-864.
9. Zhang, J., et al., Morphology and properties of soy protein and polylactide blends.
Biomacromolecules, 2006. 7(5): p. 1551-1561.
10. Wang, N., J. Yu, and X. Ma, Preparation and characterization of thermoplastic
starch/PLA blends by one‐step reactive extrusion. Polymer International, 2007. 56(11): p.
1440-1447.
11. Suyatma, N.E., et al., Mechanical and barrier properties of biodegradable films made from
chitosan and poly (lactic acid) blends. Journal of Polymers and the Environment, 2004.
12(1): p. 1-6.
12. Verbeek, C.J.R., M.C. Lay, and A.W.K. Low, Methods of manufacturing plastic materials
from decolorized blood protein. 2013, Google Patents.
13. Low, A., Decoloured bloodmeal based bioplastic. 2012, University of Waikato.
68
14. Hernandez‐Izquierdo, V. and J. Krochta, Thermoplastic processing of proteins for film

formation—a review. Journal of food science, 2008. 73(2).
15. Gennadios, A., Protein-based films and coatings. 2002: CRC Press.
16. Zhang, J., P. Mungara, and J.-l. Jane, Mechanical and thermal properties of extruded soy
protein sheets. Polymer, 2001. 42(6): p. 2569-2578.
17. Pickering, K.L., et al., Plastics material. 2012, Google Patents.
18. Verbeek, C.J.R., et al., Processability and mechanical properties of bioplastics produced
from decoloured bloodmeal. Advances in Polymer Technology, 2017.
19. Rhim, J.-W., J.H. Lee, and P.K. Ng, Mechanical and barrier properties of biodegradable
soy protein isolate-based films coated with polylactic acid. LWT-Food Science and
Technology, 2007. 40(2): p. 232-238.
20. Rhim, J.-W., et al., Preparation and properties of biodegradable multilayer films based on
soy protein isolate and poly (lactide). Industrial & engineering chemistry research, 2006.
45(9): p. 3059-3066.
21. John, J. and M. Bhattacharya, Properties of reactively blended soy protein and modified
polyesters. Polymer international, 1999. 48(11): p. 1165-1172.
22. Mungara, P., et al., Processing and physical properties of plastics made from soy protein
polyester blends. Journal of Polymers and the Environment, 2002. 10(1): p. 31-37.
23. Graiver, D., et al., Biodegradable soy protein–polyester blends by reactive extrusion
process. Journal of applied polymer science, 2004. 92(5): p. 3231-3239.
24. Smith, M.J. and C.J. Verbeek, The relationship between morphology development and
mechanical properties in thermoplastic protein blends. Advances in Polymer Technology,
2017.
25. Marsilla, K. and C.J.R. Verbeek, Properties of Bloodmeal/Linear Low‐density
Polyethylene Blends Compatibilized with Maleic Anhydride Grafted Polyethylene. Journal
of Applied Polymer Science, 2013. 130(3): p. 1890-1897.
26. Zhu, R., H. Liu, and J. Zhang, Compatibilizing effects of maleated poly (lactic acid)(PLA)
on properties of PLA/Soy protein composites. Industrial & Engineering Chemistry
Research, 2012. 51(22): p. 7786-7792.
27. Zhong, Z. and X.S. Sun, Properties of soy protein isolate/polycaprolactone blends
compatibilized by methylene diphenyl diisocyanate. Polymer, 2001. 42(16): p. 6961-6969.
28. Huang, J., et al., Soy protein isolate/kraft lignin composites compatibilized with methylene
diphenyl diisocyanate. Journal of applied polymer science, 2004. 93(2): p. 624-629.
29. Walallavita, A., C.J. Verbeek, and M. Lay. Blending Novatein® thermoplastic protein with
PLA for carbon dioxide assisted batch foaming. in AIP Conference Proceedings. 2016.
AIP Publishing.
30. Wang, C., C. Carriere, and J. Willett, Processing, mechanical properties, and fracture
behavior of cereal protein/poly (hydroxyl ester ether) blends. Journal of Polymer Science
Part B: Polymer Physics, 2002. 40(19): p. 2324-2332.
69
31. Sharabasht, M.M. and R.L. Guile, Copolymerization Parameters of Itaconic Anhydride in
Free-Radical Polymerization. Journal of Macromolecular Science: Part A-Chemistry,
1976. 10(6): p. 1039-1054.
32. Okuda, T., et al., Renewable biobased polymeric materials: facile synthesis of itaconic
anhydride-based copolymers with poly (L-lactic acid) grafts. Macromolecules, 2012.
45(10): p. 4166-4174.
33. Fischer, L. and F. Peissker, A covalent two-step immobilization technique using itaconic
anhydride. Applied microbiology and biotechnology, 1998. 49(2): p. 129-135.
34. Low, A., C.J.R. Verbeek, and M.C. Lay, Treating Bloodmeal with Peracetic Acid to
Produce a Bioplastic Feedstock. Macromolecular Materials and Engineering, 2014.
299(1): p. 75-84.
35. Hicks, T.M., et al., The role of peracetic acid in bloodmeal decoloring. Journal of the
American Oil Chemists' Society, 2013. 90(10): p. 1577-1587.
36. Properties, A.S.D.o.M. Standard test method for tensile properties of plastics. 1996.
American Society for Testing and Materials.
37. ISO, E., 179-1 (2010).". Plastics. Determination of Charpy impact properties. Part. 1.
38. Willemse, R., et al., Co-continuous morphologies in polymer blends: a new model.
Polymer, 1998. 39(24): p. 5879-5887.
39. Xie, H.-Q., J. Xu, and S. Zhou, Polymer blends with two kinds of elastomeric ionomers.
Polymer, 1991. 32(1): p. 95-102.
40. Menczel, J.D. and R.B. Prime, Thermal analysis of polymers: fundamentals and
applications. 2014: John Wiley & Sons.
41. Sumita, M., et al., Dynamic mechanical properties of polypropylene composites filled with
ultrafine particles. Journal of applied polymer science, 1984. 29(5): p. 1523-1530.
42. Furuhashi, Y., Y. Kimura, and H. Yamane, Higher order structural analysis of
stereocomplex‐type poly (lactic acid) melt‐spun fibers. Journal of Polymer Science Part B:
Polymer Physics, 2007. 45(2): p. 218-228.
43. Tsuji, H., H. Takai, and S.K. Saha, Isothermal and non-isothermal crystallization behavior
of poly (l-lactic acid): effects of stereocomplex as nucleating agent. Polymer, 2006. 47(11):
p. 3826-3837.
44. Mittal, V., et al., PLA, TPS and PCL binary and ternary blends: structural characterization
and time-dependent morphological changes. Colloid and Polymer Science, 2015. 293(2):
p. 573-585.
45. Martin, O. and L. Averous, Poly (lactic acid): plasticization and properties of
biodegradable multiphase systems. Polymer, 2001. 42(14): p. 6209-6219.
46. Joseph, S. and S. Thomas, Modeling of tensile moduli in polystyrene/polybutadiene blends.
Journal of Polymer Science Part B: Polymer Physics, 2002. 40(8): p. 755-764.
47. Willemse, R., et al., Tensile moduli of co-continuous polymer blends. Polymer, 1999.
40(24): p. 6645-6650.
70
MECHANICAL PROPERTIES OF RECYCLED LOW DENSITY POLYETHYLENE

FILLED WITH LUFFA SPONGE
J.W. Danjuma1, M.I. Ugbaja1, W.U. Eze1 and D.O. Adeoye2

1
Zaria
2
Directorate of Research and Development, Nigerian Institute of Leather and Science
Technology, Zaria
Corresponding Author: ugboajamichael@yahoo.com; 08138995080
ABSTRACT
The mechanical properties of recycled low density polyethylene (RLDPE) filled with Luffa sponge
(LS) was evaluated in this work. A luffa sponge fibre of 2 cm length was used. The RLDPE /LS
composites was compounded using a laboratory scale two- roll mill in the ratio of 100:0, 90:10,
80:20, 70:30, 60:40 and 50:50 in grams respectively. Samples for testing were prepared by
compressing the compounded samples using a manually operated hydraulic press. The prepared
samples were tested for tensile, flexural, hardness, and solvent absorption properties. The result
showed that the tensile strength decreases from 58.0 N/mm2 at 0 % filler loading to 27.0 N/mm2
at 30 % filler loading which then increases slightly to 31.0 N/mm2 at 40 % filler loading and then
71
drops finally to 9.0 N/mm2 at 50 % filler loading. The tensile modulus almost followed a similar
trend; however peak values of 250.0 N/mm2 and 102.0 N/mm2 were observed at 10 % and 40 %
filler loadings respectively. The results also showed a gradual decrease in flexural strength from a
value of 4.25 N/mm2at 0 % filler loading to 0.40 N/mm2 at 50 % filler loading, while the flexural
modulus had a maximum value of 14.0 N/mm2 at 10 % filler loading which then decreases
gradually but attempts to increase again to a value of 6.0 N/mm2 at 40 % filler loading but then
finally drops to 2.9 N/mm2 at 50 % filler loading. The hardness of the filled composites was
increased with increase in filler loading which was significantly noticed at the 30 % and 50% filler
loadings. The results of the solvent tests showed that there was a significant rise in percentage
absorption for acetone at 20 % and 50 % filler loadings, while that for toluene and water did not
show any observable change in percentage absorption for all the filler loadings used.
Keyword(s): Recycled low density polyethylene, Luffa Sponge, Mechanical Properties.
1.0 INTRODUCTION
Many modern technologies require material, with unusual combinations, which exhibits superior
properties than the individuals. Composites have concerned considerable importance as a potential
operational material. Low cost, light weights, high specific modulus, renewability and
biodegradability are the most basic and common attractive features of composites that make them
useful for industrial applications [1]. With low cost, and high specific mechanical properties
natural fiber signifies a worthy renewable and biodegradable substitute to the most common
synthetic reinforcement. Composites have already proven their worth as weight-saving materials,
the current challenge is to make them cost effective [1]. Now the focus to produce economically
attractive composite components has resulted in several innovative manufacturing techniques
currently being used in the composites industry. Fibre reinforced composite is one such material,
which has revolutionized the concept of high strength. Most of the natural composite materials
grow from the forest and agriculture. Luffa-cylindrica locally called as “sponge-gourd” is one such
natural resource whose potential as fiber reinforcement in polymer composite has not been
explored till date for tribological applications [2].
It has a ligneous netting system in which the fibrous cords are disposed in a multidirectional array
forming a natural mat. This fibrous vascular system is composed of fibrils glued together with
natural resinous materials of plant tissue. It contains 62 % cellulose, 20 % hemicellulose and 11.2
% lignin [3]. The fruit of the sponge-gourd (L. cylindrical) plant with fruit which is of the
Curcubitacea family. It has a thick peel and the sponge-gourd, which has a multidirectional array
72
of fibers comprising a natural mat, presents an inner fiber core. Fibres are basically two types they
are natural and synthetic fibers. Cotton, Jute and Sisal are some examples for Natural Fibres and
Glass, some of the examples for Synthetic Fibres are carbon and Nylon [2]. The Natural fibres are
renewable [4] and cheaper but their mechanical properties are much lower than the synthetic fibers.
The synthetic fibres exhibit good mechanical properties but they are costlier and non-renewable
[5].
Methods of waste reduction and recycling are the preferred options when managing waste. Many
environmental benefits such as reduction or prevention of greenhouse gas emissions, reduction in
the release of pollutants and conservation of resources can be derived from the use of these
methods. In addition, they save energy and reduce the demand for waste treatment technology and
landfill space. Therefore, it is advisable that these methods be adopted and incorporated as part of
the waste management plan. Plastic recycling is a process of changing plastic waste into new
products. Manufacturers have adopted the use of recycled plastics in the manufacturing of products
such as vineyard posts, decking boards for children play ground, garden sleepers etc. [6]. Despite
the advantages that plastics have over the conventional materials, there are also some challenges
that they pose to the industrial world. Many parts of the world, including Nigeria face serious
problems of managing the generation and disposal of plastic waste. At present, plastics account
for roughly a quarter of all solid waste by volume in U.S.A., Nigeria and many countries of the
world [7]. At the present rate, landfill capacity could be exhausted in a few decades mostly in the
urban settlements. To reduce the volume of plastic wastes that goes to landfills or litters the
environment, there are three alternatives: recycling, incineration and land filling [7]. There are
disadvantages in the use of recycled plastics when used in the manufacturing of products compared
to the use of virgin polymer as natural resources; they exhibit low stiffness and strength and this
limit their use in high load bearing application [6]. To improve mechanical properties of recycled
plastic products, manufacturers usually add fillers to reinforce the polymer matrix which affect the
morphology and the structure of the polymer [6]. Fillers are defined as materials that are added to
a polymer formulation to lower the compound cost or to improve properties [8].
Low density polyethylene (LDPE) is semi-rigid and translucent material. Its advantageous
properties include toughness, flexibility, resistance to chemicals and low water absorption. It is
resistant to organic solvent at room temperature, has a high impact resistance and excellent
corrosion resistance [9]. However, LDPE has a poor ultraviolet (UV) resistance, low strength and
73
stiffness. Its maximum working temperature is also low and it is susceptible to environmental
stress attack. Previous researches have demonstrated that certain fillers such as clay, kenaf powder
and calcium carbonate can be added to recycled low and high density polyethylene (LDPE /
HDPE) to improve their mechanical properties but it has also been established from those works
that increase in filler content reduces the tensile strength of recycled polyethylene due to the
inability of filler to support stresses transferred from polymer matrix [10].
This paper examines the mechanical properties of recycled low density polyethylene filled with
chopped luffa fiber which is environmentally- friendly and recyclable.

2.1 Materials
The major materials include: Recycled low density polyethylene popularly known as pure water
sachet which was collected from the Samaru metropolis and luffa sponge which harvested from a
local farm in Kaduna.
2.2 Methodology
2.2.1 Collection and Preparation of the Luffa Sponge Fibre and Recycled Low Density
Polyethylene
The luffa sponge was harvested and soaked in water in order to peel the bark, and was splitted to
remove the seeds, after which it was washed, dried, cut into 2 cm lengths and treated using 5%
NaOH solution for four hours. After treatment, the luffa sponge was dried in an oven at a
temperature of 100oC for 8 hrs. The recycled low density polyethylene was prepared by collecting
pure water sachets from samaru community. They were washed to remove dirts, dried and then
shredded before taken for compounding.
2.2.2 Compounding and Preparation of Sample for Testing
Six samples were prepared. The materials were weighed as shown in Table 1, and then
compounded accordingly for each sample using a laboratory scale two-roll mill at a temperature
of 150 o C. The compounded samples were then placed in a 350 mm x 350 mm mould and then
pressed using a manually operated hydraulic press at a temperature of 160 o C with a pressure of
10 MPa for 10 minutes.
Table 1 Sample Composition by Weight
S/n Sample RLDPE (g) LS (g)
74
1 A 100 0
2 B 90 10
3 C 80 20
4 D 70 30
5 E 60 40
6 F 50 50
2.3 Sample Testing
2.3.1 Tensile
The tensile property test was performed according to ASTM D 638 using a universal testing
machine. Tensile strength and tensile modulus of the dumb-bell shaped specimens were
determined from the data generated.
2.3.2 Flexural
The flexural test was carried out according to standard to determine the flexural strength and
flexural modulus of the rectangular shaped test specimens.
2.3.3 Hardness
The hardness test of the test specimens was carried out using a Durometer. Flat sheet of the samples
for testing was placed one after the other under the hardness tester and indentation was made on
the sample and the respective values read out from the scale of the machine. Average of three
values for each sample was taken.
2.3.4 Solvent absorption
The water absorption test was carried out according to ASTM D2842-12, 2012 using the Kubelka
apparatus. The interior surface of the apparatus was rinsed with distilled water, after which the
water was poured away. The apparatus was then filled with distilled water to the zero mark (25
ml) at 20 ± 2oC. The sample was then weighed and placed in the apparatus. The apparatus was
closed with a rubber stopper to prevent evaporation losses. After 24 hours, the water level was
observed and the sample was further weighed to determine the change in weight. Percentage water
𝑣
absorption was calculated as; P= 𝑉 x 100; where P = water absorbed in ml of water per 100 of
samples, v = volume of water absorbed in ml, and V = volume of the sample.

For absorption in toluene and in acetone, the specimens were immersed in solvent for 24 hrs and
the solvent absorption of composites was measured by the weight gain of the materials at regular
75
intervals. The percentage of solvent absorption is expressed as the ratio of increase in mass of the
specimen to the initial mass.
𝑀𝑜−𝑀1
Therefore; P (%) = (1)
𝑀1
Where; Mo = Final weight; M1= Initial weight.

3.1 Tensile and Flexural Strength
The results of the tensile strength and flexural strength test are shown in fig 1 and fig 2 respectively.
It can be seen from the figures that the tensile strength and flexural strength of the samples
decreases with increasing content of the luffa sponge fibre. It is important to note here that the
physical interaction and immobilization of the polymer matrix in the presence of mechanical
restraints may be responsible for these behaviours.
70
TENSILE STRENGTH (N/mm2)
60
50
40
30
20
10
0
0 20 40 60
FILLER LOADING (g)
Figure 1: Effect of LS loading on the tensile strength of RLDPE composite

5
Flexural strength
4
(N/mm2)
3
2
1
0
0 20 40 60
Filler Loading (g)
76
Figure 2: Effect of LS loading on the flexural strength of RLDPE composites.
3.2 Tensile and Flexural Modulus

Figures 3 and 4, shows respectively the results of the tensile modulus and flexural modulus of the
test samples. For both moduli, significant increase was observed at 10 g of the luffa fibre content
which then decreased as the fibre content was subsequently increased. This behavior can be
attributed to the fair distribution of the luffa sponge in the matrix at 10 g filler loading which
efficiently hinders chain movement during deformations leading to high particle orientation. This
mechanism will increase the stiffness of the composite as well as the modulus. The high modulus
value supports the use of the developed composites in general purpose application. The decrease
in modulus suggests that, there will be no stress transfer across the polymer-particles interface
which will prevent movement in the area around each particle contributing to the decrease in the
modulus.
300
TENSILE MODULUS (N/mm2)
250
200
150
100
50
0
0 20 40 60
FILLER LOADING (g)
Figure 3: Effect of LS loading on the tensile modulus of RLDPE composites.
77
16
Flexural Modulus (N/mm2)

14
12
10
8
6
4
2
0
0 10 20 30 40 50 60
Filler Loading (%)
Figure 4: Effect of LS loading on the flexural modulus of RLDPE composites.
3.3 Hardness
The result of the effect of the luffa sponge (LS) fibre on the hardness of recycled low density
polyethylene (RLDPE) is presented in figure 5. The hardness as shown increased with increasing
LS fibre content in the matrix. The substantial improvement in hardness values obtained in the
reinforced polymer matrix in comparison with the unreinforced RLDPE matrix can be attributed
to the increase in percentage of the luffa sponge fibre in the matrix, and also to the difference in
the thermal expansion between the luffa fibre and RLDPE matrix.
94
Degree Of Hardness
93
92
91
(IRHD)
90
89
88
87
86
85
84
0 10 20 30 40 50 60
Filler Loading (%)
Figure 5: Effect of LS loading on the hardness of RLDPE composite
3.4 Solvent Absorption
78
Three solvents namely acetone, toluene and water were selected and the results are presented in
figure 6 as shown below. It can be seen that the acetone was absorbed more compared to water
and toluene which in this case is the least absorbed. The percentage absorption for acetone
increased significantly with increasing content of the luffa sponge fibre in the matrix, slight
increase for water while for toluene there was no observable increase in the percentage absorption.
Absorption of water in case of luffa is minimum compared to agro based composite materials. This
may be attributed to the effect of alkaline treatment of the luffa sponge fibre.
2000
1500
PERCENTAGE
ABSORPTION
1000 ACETONE
TOLUENE
500
WATER
0
0 10 20 30 40 50 60
-500
FILLER LOADING (g)
Figure 6: Effect of LS loading on the percentage solvent absorption of RLDPE Composites.
4.0 CONCLUSION
The mechanical properties of recycled low density polyethylene filled with luffa sponge fibre have
been carried out. From the results obtained, luffa sponge did not improve the tensile and flexural
properties of the recycled low density polyethylene; however, there was improvement of its
hardness. The presence of the luffa sponge in the matrix increased the absorption of acetone and
that of water while there was no observable absorption in toluene.
REFERENCES
[1] Lassaad Ghali, slah Msahli, Mondher Zidi, Faouzi Sakli, “Effects of fiber weight ratio,
structure and fiber modification onto flexural properties of Luffa polyester composites”. Advances
in Materials Physics and Chemistry, 2011, 78-85.
[2] Oboh, I. O., Aluyor, E. “Luffa Cylindrica-an emerging cash crop”, African Journal of
Agricultural Research, 2009, 4(8): 684-688.
79
[3] K.G Satyanarayana, J.L. Guimara, F.Wypych, “Studies on Ligno-cellulosic fibers of Brazil.
Part I: source, production, morphology, properties and applications, composites, part a 38, 2007,
1694-1709.
[4] S. Biswas, G. Srikanth and S. Nangia, “Development of Natural Fibre Composites in India”,
Convention and trade show composite fabricators Association, 2001, October 3-6 Tampa, FL,
USA.
[5] Boynard CA, D’Almedia J R M,: Water absorption by sponge-gourd (Luffa-cylindrica)-
polyester composite materials, J.Mater.Sci.1999, Lett.18:1789-1791.
[6] Li, K. Environmental effects on recycled Plastics. Published M.Sc. thesis of the University of
Adelaide Australia, 2010.
[7] Eze, I.O. Effects of Bamboo powder on some Mechanical properties of Recycled Low Density
Polyethylene Composites. Journal of Natural and Applied Science 4(1):24-35, 2013.
[8] Chandramohan, D. and Marimuthu, K. A review of natural fibre. Elsevier, New York. 2011.
[9] Du, H.; Wang, W.; and Zhang, Q. Effects of pigments on the UV degradation of wood-
flour/HDPE composites. Journal of applied polymer science, 118(2):1068-1078, 2010.
[10] Ismail, H.; Edyham, M.R. and Wirosento, B. Bamboo fibre filled Natural Rubber Composites:
effects of loading and bonding. Journal of Polymer testing, 21(2):139-144, 2002.
ASTM D2842-12 (2012): Standard Test Method for Water Absorption of Cellular Plastics.
A STUDY ON THE REINFORCING PROPERTIES OF NATURAL RUBBER COMPOSITES

COMPOUNDED WITH PALM FROND FIBER: A COMPARATIVE APPROACH
1
Aguele, Felix O., 2Madufor, Innocent C., 1Nwosu-Obieogu K., 1Chiemenem, Linus I., 2Obasi, Henry C.,
3
Moneke, U.U.
1
Chemical Engineering Department, Michael Okpara University of Agriculture, Umudike, Abia State,
Nigeria.
2
Polymer and Textile Engineering Department, Federal University of Technology, Owerri, Imo State,
Nigeria.
3
Project Management Technology Department, Federal University of Technology, Owerri, Imo State,
Nigeria.
Corresponding Author: foaguele@gmail.com
ABSTRACT
80
This research involved the use of palm frond fibre as filler from renewable source for
reinforcement of rubber composites. This is expected to draw attention towards a possible
renewable resource, which would create commercial values for the agricultural wastes that can
possibly be used in rubber products manufacture. In this study, palm frond fibre (PFF) and carbon
black (CB) were separately used to compound Natural Rubber (NR) samples while filler
concentrations for all were varied between 0 and 50 phr at intervals of 10 phr. The physical
properties of the various composite samples produced were tested. From test results obtained for
samples, it was observed that for hardness, the results obtained from NR-PFF composites were
good relative to the NR-CB composites. The graph of hardness versus filler quantity for both
composites presented rising values of hardness with increase in the filler quantities. For the tensile
strength and modulus there were no sharp increases shown with increase in filler volumes, though
a trend of marginal increases were observed, they were poor relative to the CB reinforced
composites. The results from test for elongation at break, compression set and flex fatigue showed
falling trends for both the PFF and CB filled rubber. This trend indicates reinforcement potential
as expected, since more reinforcement would reduce the values for these properties.
Key words: Composites, Polymer, Reinforcing, Rubber, Renewable resources, Fibre and
Fillers.
1.0 INTRODUCTION
Use of polymers and their composites in various applications have experienced a steady growth
over the years. It is difficult for most contemporary designers to overlook the array of polymer
materials available in different forms for various applications, such as aerospace, automotive,
structures, military, sports, communications, home appliances, etc. [1-3]. The desire to meet
applications and performance target is one of the background driving forces behind the heightened
interest and researches in polymer composites [4-8]. Rubber composites are unique in their
properties; the reason they are called flexible composites. This informs the areas of application of
natural or synthetic rubber, where they are subjected to large deformations [9-12]. The various
materials used for rubber composites depend on targeted goals [8,10-11,13-14].
Environmental awareness and desires for sustainable and green environment has generally increased
worldwide. This has greatly affected the researches in polymer composites to look into natural fibre
reinforcements, being both renewable and environmentally friendly [15-16]. Different materials have been
successfully employed as fillers in polymers. Common among them are carbon black and China clay,
aluminium oxide, calcium carbonate, silica, talc, glass fibre and some synthetic polymer-based fibres
(polyethylene therephthalate, aramides), etc [3, 17-19]. These are not renewable. Price of oil, the main
source of carbon black is galloping and oil reserves are gradually being depleted by the day [20]. More so,
the reinforcement are not biodegradable and the after use wastes become difficult to handle. In the search
for inputs which are environmentally friendly and biodegradable, cellulosic fibres from renewable resources
readily come to mind. Many agro-based materials, such as jute, raffia, kenaf fibre, coconut fibre, rice husk,
81
groundnut shell, rubber seed shell, coir, flax, sisal and wood fibre are being investigated for their potentials
as the reinforcement phase in polymers [3,10-13,19, 21-38].
Natural fibres have a lot of advantages over the commonly used traditional reinforcements. For example,
they have low costs, low densities; they are non-toxic and environmental friendly, biodegradable, non-
abrasive and recyclable [39-42]. For instance, some natural fibres, such as Flax and sisal have been found
to even exhibit some mechanical properties which are comparable to those of glass fibre [43-44]. Many
researchers have explored various aspects of the potentials of natural fibres as reinforcements for different
polymer matrices, including rubbers [45-48]. Others have studied the different methods of modifications
done on natural fibres in attempt to make them more valuable and compatible as composite components in
polymer matrices [17, 49-52]. This paper presents a study of one of such agricultural materials, palm frond
fibre (PFF) for its properties enhancement potentials in natural rubber composites.

2.1 Materials
The main material used for this work was natural rubber (NR). Natural rubber crumb of grade
NSR–10 (Nigeria Standard Rubber) was obtained from Rubber Research Institute, Iyanomo, Benin
City, Edo State, Nigeria. This rubber grade also conforms to TSR-10 (Technically Specified
Rubber). The palm frond fibre (PFF) was obtained from Oil Palm Company, Ewohimi, Edo State,
Nigeria. The other compounding ingredients and additives used were zinc oxide, processing oil,
tetramethyl thiuram disulphide (TMTD), mercaptobenzothiazole sulphanamide (MBTS),
trimethyl quinoline (TMQ), stearic acid, carbon black (N330 HAF) and sulphur. These
compounding agents are of chemical grade produced by British Drug House (BDH) and were used
as obtained from various chemical outlets (Jonaz industrial chemicals, Rovet and Stinpex
chemicals) in Benin, Edo State, Nigeria.
2.2 Methods
2.2.1 Preparation of the Filler
After collection, the palm frond stuck was scraped, cut and split into lengths of about 10cm each
for easy handling and sun-dried. The material was then ruffled to remove lignin from the material
mass. Mortar and pestle was used to pound the sun-dried material so that the fibre is separated,
exercising caution not to grind the fibres at this stage. The material was then dried in an oven at a
temperature of 125oC for 30 minutes. After drying, the PFF was ground using electrically powered
plate grinding machine to attain fine particles size, as shown in Plate 1 (a) and (b). Graduated mesh
sieves (100-300 µm) were used to determine the particle size of fillers.
82
a b
Plate 1: The ground (a) PFF and (b) CB
2.2.2 Preparation of composites

The rubber was masticated and mixed with the additives in a two-roll mill for all the composites
[53]. Two sets of composites (NR-PFF and NR-CB) were prepared and filler volume was varied
from 0 to 50 phr, as presented in Table 1. The NR-CB set of composites actually served as a basis
for comparison, since carbon black (N330 HAF) is a known reinforcing filler.
Table 1: Formulations for reinforced Natural Rubber composites.

Ingredient Content by weight (phr)
Natural rubber 100
Zinc oxide 5.0
Stearic acid 2.5
TMQ 1.0
Processing oil 2.0
Sulphur 2.5
TMTD 1.0
MBT 1.0
Filler (PFF and CB) 0-50
phr – Parts per hundred rubbers (by weight)
2.3 Characterization of the Fillers
During this study, the PFF was characterized using the parameters of moisture content, ash content,
loss on ignition, pH value and particle size, as presented in Table 2.
2.3.1 Vulcanization
The rubber composites were vulcanized in the laboratory using a press moulding machine and
different moulds so that test pieces could be cut for further tests/analyses. Curing was done at a
temperature of 140 oC for fifteen minutes and sulphur was used as the vulcanizing agent. The
composite samples prepared and moulded into different forms and shapes for various analyses.
Test pieces were cut for analysis and tests as shown in Plates 2 and 3.
83
Plate 2: PFF-NR Composite Plate 3: CB-NR Composite
2.3.2 Hardness test

Rubber hardness is the relative resistance of surface to indentation by an indenter of specified
dimension under a specified load. A round disc sample was used for hardness test and recorded as
International Rubber Hardness Degree (IRHD). Test carried out according to standard method
[54].
2.3.3 Tensile strength

This is often referred to as the “Ultimate Strength” of the material and it is measured as the force
applied at the time of rupture per unit of original cross sectional area. The ends of samples (test
pieces prepared in dumb bell shape) were griped by the heads of instron tensometer driven at a
speed of 50 cm/min and specimens strained until they ruptured [55]. Modulus and Elongations at
break were also obtained for each of the samples.
2.3.4 Abrasion resistance test
A round disc sample was also cut for Abrasion resistance test using Akron abrader machine [56].
2.3.5 Compression set test

Compression set is the residual strain left in a test sample after it has been subjected to stress for a
given time and allowed to recover on removing the deforming load. Temperature is maintained at
a constant value during the test. Wallace compression set machine was used [57].
2.3.6 Flex fatigue test
This refers to the ability of samples to withstand fatigue, which results from repeated distortions
by bending, compression or extension. De Mattia flexing machine was used [58].

Initial characterization of the filler was done to enable a proper identification of materials, giving
insight to the expected effects of fibre on vulcanizates. The moisture content (%), ash content (%),
loss on ignition, pH and particle sizes were determined (see Table 2). These parameters are
determinants of levels of distribution and dispersion of fillers in rubber compounds and hence the
final properties of products [27-28].
84
Table 2: Filler characteristics

Parameter PFF CB
Moisture content (wt%) 10.60 2.40
Ash content (%) 5.20
Loss on ignition (875 oC) 52.00 92.60
pH 6.40 6.50
Diameter (μm) 200.00
The moisture content was determined as 10.60% and 2.40% for PFF and CB respectively. Moisture
content is known to affect the properties of polymeric products. High moisture content could lead
to product defects, such as voids and blisters. In this study however, blisters were not observed in
any of the samples produced even though the moisture content of PFF was observed to be quite
higher values than that of CB as shown in Table 2. This means that the moisture level of cellulosic
PFF used in this research was reasonable.
The pH value is another important parameter, which was evaluated during the study. It has been
known that pH value can influence speed of vulcanization. High values of pH (basic condition)
would increase the speed of vulcanization, making the materials to act as if it is an accelerator. In
that case, vulcanization reaction takes less time. While low pH values (acidic condition) retards
the speed of vulcanization. During this research, the pH of the PFF and CB were determined to
be 6.40 and 6.50 respectively, which though were slightly acidic, were within close range and as
such, no marked difference in vulcanization speed was noticed.
Loss on ignition is a parameter that points to the level of carbon contents of fillers and its
effectiveness as reinforcement in composites. During this study, the losses on ignition were
obtained for both fillers as 52.00 and 92.60 for PFF and CB respectively. The effect of this was
evident in the reinforcement properties imparted by the fillers as exhibited by the composites. See
Figures 1 and 2. The tensile strength and modulus for the NR-CB composites were clearly at higher
levels than those of NR-PFF composites at any given volume of filler experimented. These were
attributed to the higher carbon content of CB as indicated by their losses on ignition.
85
Tensile Strength (mN/m2)

40
35
30
25
20 PF
F
15
10
5
0
0 10 20 30 40 50
Filler Volume (phr)
Figure 1: Chart of Tensile Strength Versus Filler Volume

Modulus at 100% (GPa)
3 PF
F
2
0
0 10 20 30 40 50
Filler Volume (phr)
Fgure 2: Chart of Modulus Versus Filler Volume
Particle size was also obtained for the filler during this research; this parameter has been known
to influence the reinforcement efficiency of fillers. Smaller particles have larger surface area for
interactions with the matrix. On this basis, it was said that “the smaller the particle size, the better
its reinforcement properties”. The particle size for the PFF used during this study was 200µm. This
was much greater than particle size of CB, which though was not determined, was far smaller.
Observation of results obtained during this study showed that filler volume variations generally
affected all the physical properties tested. Figures 1, 2 and 3 for effects of PFF volume on tensile
strength, modulus and hardness respectively. The results are pointers to the potentials of the
studied filler (PFF) towards reinforcement. However, although the extent of influence on any of
the measured physical properties was found to depend on volume fraction of fillers, also the
reinforcement was generally lower in NR-PFF than the NR-CB composites.
86
60
Rubber Hardness
PFF
40
CB
(IRHD)
20
0
0 10 20 30 40 50
Filler Volume (phr)
Figure 3: Chart of Rubber Hardness

Versus Filler Volume
The hardness of the composites samples (NR-PFF) spanned between a minimum of 38 and a
maximum of 52 IRHD corresponding to filler volumes between 10 and 50phr (Figure 3). This
trend was attributed to the fact that as more filler was incorporated into the rubber matrix, the
composite became more rigid because of the progressive reduction of rubber chain elasticity.
However, the hardness values obtained for the NR-CB composites for the same range of filler
volume between 10 and 50phr were clearly higher than those of the NR-PFF composites. The
hardness ranged correspondingly from 38 to 52 and 41 to 55 IRHD for the NR-PFF and NR-CB
respectively. It suffices to say on the basis of hardness results here, that the renewable fibre (PFF)
performed relatively well in comparison to the commercially available filler (CB) used.
The tensile strength results for PFF filled composites were observed to show only marginal
increases between 7 and 9MNm-2 for the corresponding increments of filler quantity range of 10
and 50phr respectively (Figure 2). These values as observed were quite low relative to the tensile
strength obtained for the CB-filled composites, which showed a clear rise of tensile strength
between 17 and 38 MNm-2 for the same range of filler volume. The poor strength reinforcement
was attributed to the large particle size, nature, structure and low surface activity of the PFF used
as the test filler. These are major parameters and determinants of the matrix-fibre interfacial
interactions in the composites [59-60].
The modulus results for the PFF also exhibited a marginal increase between 1.2 and 1.8 GPa
corresponding to filler volumes of 10 and 50 phr respectively. Whereas the modulus of CB-filled
composites were determined to be between 1.8 and 5.7 GPa for the same range of filler volume.
These values as were determined showed a clear rise of modulus for NR-CB relative to the NR-
PFF composites, which maintained lower values.
The results led to the inference that there is adhesion between the filler and rubber matrix phases,
which gave rise to the observed increase in stiffness, rigidity, strength and hence modulus of the
composites. Also it has been established that larger particles have smaller surface areas to interact
with any given matrix. The PFF as used in this study, having relatively larger particle size than
carbon black, explains for the lower level of modulus it imparted on the composites. Another
finding of this study asserted for the low enhancement of physical properties by PFF is that it has
more tendencies for filler agglomeration, which makes its dispersion and distribution in the rubber
matrix more difficult.
87
From the graph of compression set, elongation at break and flex fatigue versus filler volume, they
presented downward trends generally for both NR-PFF and NR-CB composites (Figures 4-6).
However, in these cases, values from NR-CB composites maintained lower levels for each filler
quantity. As the filler volume were increased rigidity and hardness were increased, leading to
downward trends of rubber chain mobility and flexibility, which subsequently reduced those
observed properties of compression set, elongation at break and flex in Figures 4-6. This means
that high values of compression set, elongation at break and flex fatigue indicate low
reinforcement. This finding as was observed in this study agreed with results of some previous
researches [26, 61]
45
Compression set (%)
40
35
30
25
PFF
20
15 CB
10
5
0
0 10 20 30 40 50
Filler Volume (phr)
Figure 4: Chart of Compression Versus Filler Volume
Elongation at Break (%)
1000
800
600 P
400 F
7 F
200
0
0 10 20 30 40 50
Filler Volume (phr)
Figure 5: Chart of Elongation Versus Filler Volume

Flex Fatigue
25000
20000
15000 PFF
10000 CB
5000
0
0 10 20 30 40 50 Filler Volume (phr)
Figure 6: Chart of Flex Fatigue Versus Filler Volume
88
Abrasion Resistance
60
Index (ARI)
50
40
PFF
30
CB
20
10
0
0 10 20 30 40 50Filler Volume (phr)
Figure 7: Chart of Abrasion Resistance Index (ARI)
Versus Filler Volume
The result of abrasion resistance tests as were observed during this study was unique (Figure 7).
This result implied that filler volume increase may not continuously increase the abrasion
resistance index of the composites. As the filler volume was increased, a level was reached when
the abrasion resistance index formed a plateau, meaning that there is a maximum level of filler
volume input for optimum performance. Beyond this level of filler volume in the composites, the
property did not show any additional increase. However, in this study, a clear maximum was not
observed, but rather, an irregular plateau.
4.0 CONCLUSIONS
This study investigated the possibility of property enhancement of natural rubber composites by
incorporating PFF, which was from renewable source, as filler. In doing this, a comparative
approach was adopted using carbon black. The study was motivated by a drive to search for
possible alternatives to carbon black as filler for natural rubber products and also to reduce the
cost of final products. It is expected that success in this direction would reduce the
pressure/demands for carbon black, which is derived from petroleum. It was found that palm frond
fibre (PFF) has potential for enhancing the reinforcing properties of rubber composites as
evidenced from results obtained in this study. However, comparing the performance of the PFF
and CB viz a viz their reinforcement enhancement capacity, the CB was observed to be quite better.
REFRENCES
1. M.A. Bello, Polymers: The Chemistry and Technology of Modern Materials. Concept
Publications Ltd, Lagos. 2001.
2. E.M. Katchy, Principles of Polymer Science. 1st Edition. El’Demak Publishers, Enugu, Nigeria.
2000.
3. F.O. Aguele and C.I. Madufor, American Journal of Polymer Science, 2(3), 28-34, 2012.
4. F. Ashby Michael and R.H. David Jones, Engineering Materials 2: An Introduction to
Microstructures, Processing and Design. 2nd Edition. Butterworth-Heinemann, Oxford, 1998.
5. H.E. Peply, Engineered Materials Handbook, T. J. Reinhart (Ed), ASM International, Ohio, USA, 1987,
Volume 2.
6. C.T. Herakovich, Mechanics of Fibrous Composites, J. Wiley and Sons Inc., New York, 1998.
7. G. Akovali (Ed). Handbook of Composites Fabrication, Rapra Technology, 2001, pp 3-4.
8. A. K. Kaw, Mechanics of Composite Materials. 2nd Ed, Taylor and Francis Group, NY., 2006,
p 2.
9. S.Y. Lou and T.W. Chou, Composite Applications – The Role of Matrix, Fibre and Interface, T.L. Vigo and
B.J. Kinzig (Eds), VCH Publishers Incorporated, New York, USA, 1992.
89
10. E.J. Asore, An Introduction to Rubber Technology, Joseg Books, Benin City, Ngeria, 2000.
11. E.M. Katchy, Introduction to Polymer Technology, 1st Edition. El’Demark, Enugu, Nigeria,
2000.
12. M.S. Bhantnagar, A Textbook of Polymers: Chemistry and Technology of polymers;
(Processing and Applications) Vol. II 1st Edition. S Chand New Delhi, 2004.
13. M. E. Cain, Engineering Design with Natural Rubber, Malaysian Rubber Producers’ Research
Association, Hertford, England, 1974.
14. A. A. Kumar and K.R. Gupta, Fundamentals of Polymers. International Edition. McGraw Hill,
Singapore, 1998.
15. E. Jayamani, S. Hamdan, S. K. Heng, M. R. Rahman, M. K. Bakri, A. Kakar Australian Journal
of Basic and Applied Sciences. 8(15), 332-340, 2014.
16. J. Rout, M. Misra, S. Tripathy, S.K. Nayak, A.K. Mohanty, Composites Sci Technol.
61(9),1303–1310, 2001.
17. X. Li, L. G. Tabil, S. Panigrahi, J Polym Environ, 15, 25-33, 2007. DOI 10.1007/s10924-006-
0042-3
18. R. Gachter, H. Muller, Plastics Additives, 3rd Edition. Hanser Publishers, 1990.
19. F.O. Aguele, C.I. Madufor, K.F. Adekunle, Open Journal of Polymer Chemistry. 4, 73-82,
2014. http://dx.doi.org/10.4236/ojpchem.2014.43009
20. K.B. Ski, Engineering Materials: Properties and Selection, Reston Publishing, New York,
1970.
21. K. Oksman, M. Skrifvars, J.F. Selin, Composites Sci Technol. 63, 1317, 2003.
22. A.C.N. Singleton, C.A. Baillie, P.W.R. Beaumont, T. Peijs, Composites B: Eng. 34, 519, 2003.
23. A.K. Rana, S. Mandal, S. Bandyopadhyay, Composites Sci Technol. 63, 801, 2003.
24. A. Valadez-Gonzalez, J.M. Cervantes-Uc, R. Olayo, Composites B: Eng. 30, 321, 1999.
25. A. Keller, Composites Sci Technol. 63, 1307, 2003.
26. F.E. Okieimen and J.E. Imanah, J. Polym. Materi 22(4), 409, 2005.
27. F.E. Okieimen and J.E. Imanah, Nig. J. Polym. Technol. 3(1), 201, 2003.
28. P.A. Egwakhide, E.E. Akporhonor and F.E. Okieimen, Int. J. Phys. Sci. 2(2), 39, 2007.
29. D. Rouison, M. Sain, M. Couturier, Composites Sci Technol 64, 629, 2004.
30. A.K. Bledzki, J. Gassan, Prog Polym Sci 24, 221, 1999.
31. A. Paul, K. Joseph, S. Thomas Composites Sci Technol. 57(1), 67, 1997.
32. A.M. Mohd Edeerozey, Hazizan Md Akil, A.B. Azhar, M.I. Zainal Ariffin, Materials Letters
61, 2023–2025, 2007.
33. T. Sen, H. N. Jagannatha Reddy, International Journal of Innovation, Management and
Technology, 2(3) June 2011.
34. F. Aguele, Idiaghe, J. A. Ekebafe, L. O. International Journal of Material Science Innovations
(IJMSI) 1 (5), 244-255, 2013.
35. M.D. Ayo, C.I. Madufor, M.N. Chukwu L.O. Ekebafe, International Journal of Chemistry.
21(1), 55-58, 2011.
36. B.F. Adeosun, Nig. J. Polym. Sci. Technol. 1 (1), 58, 2000.
37. J.A. Brydson, Plastic Materials. 4th Edition, Butterworth, London, 1985.
38. W. Wafwoyo, C.W. Seo and W.E. Marshall, J. Chem.. Technol. Biotechnol. 74, 1117, 2001.
39. A.K. Mohanty, A. Wibowo, M. Misra, L.T. Drzal, Composites A: Appl Sci Manuf. 35, 363,
2003.
40. C. Baley, Composites A: Appl Sci Manuf 33,939, 2002.
90
41. B. van Voorn, H.H.G. Smit, R.J. Sinke, B. de Klerk Composites A: Appl Sci Manuf 32, 1271,
2001.
42. S. Kalia, K. Thakur, A. Celli, M.A. Kiechel and C.L. Schauer, Journal of Environmental
Chemical Engineering, 1(3), 97-112, 2013.
43. K. van de Velde, P. Kiekens, J Appl Polym Sci 83, 2634, 2002.
44. T.W. Frederick, W. Norman, Natural fibers plastics andcomposites. Kluwer Academic
Publishers, New York, 2004.
45. A.K. Mohanty, M. Misra, L.T. Drzal, Natural fibers, biopolymers, and biocomposites. Boca
Raton (FL): CRC Press/Taylor & Francis Group, 2005.
46. K. Pickering, Properties and performance of natural-fiber composites. Cambridge: Woodhead
Publishing, ISBN: 13: 978 1 84569 267 4. 2008.
47. C. Baillie, Green composites: polymer composites and the environment. Cambridge:
Woodhead Publishing Limited, ISBN: 1-85573-739-6. 2004.
48. R.R. Franck, Bast and other plant fibers. Boca Raton (FL): CRC Press. ISBN:0-8493-2597-8.
2005.
49. M.M. Kabir, H. Wang, K.T. Lau, F. Cardona, Composites: B, 43, 2883–2892, 2012.
50. A.M. Mohd Edeerozey, Hazizan Md Akil, A.B. Azhar, M.I. Zainal Ariffin, Materials Letters
61, 2023–2025, 2007. doi:10.1016/j.matlet.2006.08.006.
51. H.S. Lee, D. Cho, S. Han, Macromolecular Research, 16(5), 411-417, 2008.
52. A.K. Mohanty, M. Misra, L.T. Drzal, Composite Interfaces, 8(5), 313-343, 2001.
53. ASTM-D 3184-80. Standard Methods for Compounding Rubber.
54. ASTM-D1415 – 06. Standard Test Methods for rubber Property – Hardness.
55. ASTM-412. Standard Test Methods for rubber Property – Tensile Strength and Elongation.
56. ASTM-5963-04(2010) Standard Test Methods for rubber Property – Abrasion Resistance.
57. ASTM-D395-03(2008) Standard Test Methods for rubber Property – Compression Set.
58. ASTM-D430 Standard Test Methods for rubber Property – Flex Fatigue.
59. M.Q. Paterman, Rubber World. 194, 38, 1986.
60. M. Morton, Rubber Technology. 3rd Edition. Van Nostrand New York. 1987.
61. Z.A.M. Ishak and A.A. Baker, Eur polym. J. 31(3), 259, 1995.
91
PREPARATION OF CARBOXYMETHYL CELLULOSE FROM ALTERNATIVE

SOURCES AND ITS APPLICATION IN TEXTILE PRINTING: A REVIEW
Obele, Chizoba May and Ibenta, Martin Emeka

Department of Polymer & Textile Engineering, Nnamdi Azikiwe University, Awka.
Email: cm.obele@unizik.edu.ng; ibentaemeka@gmail.com
ABSTRACT
Cellulose, an abundant naturally occurring polymer, houses a large number of derivatives. One of
the most important of such derivatives is Carboxymethyl cellulose (CMC). CMC is a water soluble
polymer whose high demand is mostly met from imported products, and it is usually synthesized
by alkali catalyzed reaction between monochloroacetic acid and cellulose. Considering the need
to reduce the economic and environmental setbacks of over dependence on cotton and wood for
CMC production. This paper seeks to facilitate the sustainable and local production of this polymer
by reviewing various sources of cellulose, the properties of cellulose, together with researches on
the synthesis of Carboxymethyl cellulose, (CMC) including the various characterization
techniques such as estimation of degree of substitution, FTIR, XRD, DSC, TGA and SEM, as well
as the various applications of CMC with emphasis on its behavior and performance when used as
a thickener and flow improver in textile printing.
Keywords: Cellulose Sources, Carboxymethyl Cellulose, Characterization and Textile printing
1.0 INTRODUCTION
Recently, there is an overwhelming increase in the consumption of chemicals and additives whose
demands are mostly met from imported products; one of such chemicals is carboxymethyl
cellulose, a cellulose-derived water soluble polymer, extensively used in various industrial
products as physical property enhancer, and usually produced by alkali catalyzed reaction between
monochloroacetic acid and cellulose [1,2].
Cellulose is a naturally occurring polymer which has become a subject of interest among
researchers. It is considered the most abundant organic compound available because it is the major
substance that makes up the plants cell wall. In nature, cellulose polymer is a linear chain of
anhydro-glucose monomer units joined to each other through 1,4-β-linkages [3], and whose
structure is held by hydrogen bonds. It is widely used as a raw material in the paper industry for
paper production and in numerous other applications, and can be chemically modified to yield
cellulose derivatives [4]. Cellulose and its derivatives are among the ingredients frequently used
for various purposes in industries [5]. Cellulose derivatives display beneficial behavior such as
thickening, thermal gelation, surfactancy, film formation, and adhesion. Further they are
kinetically and thermodynamically more stable and appear easy to synthesize and characterize.
The two essential value-added cellulose derivatives with a broad range of applications are cellulose
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esters (which include, cellulose acetate, cellulose nitrate, etc.), and cellulose ethers (such as
carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethylcellulose [5-8].
Carboxymethyl Cellulose, which belongs to cellulose ethers, is usually produced as sodium
carboxymethyl cellulose and generally used as physical property enhancer in the formulations of
products such as food, pharmaceuticals, cosmetics, drilling fluid, liquid detergent, textile, paint,
ceramics e.t.c [2,9,10]. As a thickener, it is useful in the formulation of printing pastes [11].
Carboxymethyl Cellulose is commonly produced for commercial purpose from very expensive
agricultural products such as cotton linter and wood pulp, resulting in the need for more
economically viable alternatives. However, cellulose-rich biomass such as weeds, fibers,
bamboos, and wastes from agriculture and forests have acquired great significance, as alternative
chemical raw materials, since they are made up of cellulose, hemicellulose, and lignin, which
contain the functional groups (hydroxyl groups) suitable for chemical functionalization [6]. The
functional properties of sodium carboxymethyl cellulose are dependent on the molecular weight
of the polymer, degree of substitution of the hydroxyl groups per monomer unit, as well as the
distribution of carboxymethyl substituent along the chainlength of the cellulose backbone [12,13].
Some researchers have reported the production of carboxymethyl cellulose (CMC) from various
cellulose sources such as Corn cubic agricultural waste [13], Sugarcane Bagasse [14], Pistachio
Shells [15], Palm Kernel Cake [16], Corncob [17], Papaya peel [18].
2.0 CELLULOSE
Cellulose whose chemical formula is [C6H10O5]n, is an organic compound which consists of a
linear chain D-glucose units linked by 1,4-β-linkages [3]. It is a high molecular weight polymer
and a biodegradable material [18]. Cellulose is a long chain polymer consisting of many
anhydroglucose units containing both crystalline and amorphous structures and its degree of
polymerization (DP) varies according to its sources, acquiring processes and further treatments
[19].
Figure 1: Glucose monomer unit Figure 2: Linear Structure of cellulose [19]
2.1 Sources of Cellulose

Cellulose can be derived from a variety of sources such as woods, annual plants, microbes, and
animals. These include seed fiber (cotton), wood fibers (hardwoodsand softwoods), bast fibers
(flax, hemp, jute, ramie), grasses (bagasse, bamboo), algae (Valencia ventricosa), and bacteria
(Acetobacter xylinum) [20-22], as well as leaf fibers (e.g. Sisal). The cellulose content varies for
different species of plants. Cotton has the highest content of cellulose (90~99%), wood (40~50%),
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jute (60~70%) and flax fibers (~80%) are all major sources of cellulose [23]. The Cellulose content
in hardwood is a little higher than that in softwood [19]. The wood cell wall contains lignin and
hemicelluloses, with lignin acting as the binding component.
2.2 Extraction of cellulose

The extraction of cellulose in its highly pure form has been the subject of extensive studies for
many years due to the complex nature of plants’ cell wall structure [24]. The combination of the
chemical and the mechanical treatments is required for the dissolution of lignins, hemicelluloses,
as well as other non-cellulosic substances [25]. Nuruddin et al., (2011) [26] extracted cellulose
from agricultural waste (Dhaincha, corn stalks, rice straw and wheat straw); the agricultural wastes
were treated with formic acid under the conditions of 90% (v/v) formic acid concentration; and
120 min reaction time at boiling temperature. The fibres were filtered in a buncher funnel and then
washed with fresh formic acid, followed by hot distilled water. Delignification of the mass by
peroxyformic acid (i.e. a mixture of 90% formic acid and 4% H2O2) treatment at 80oC for 120
minutes was done, followed by filtration and washing with 80% formic acid solution. The
bleaching pH was adjusted to 11, by adding NaOH. Using 64% w/w sulphuric acid solution the
mass was hydrolysed for 5 h at 45 °C, with constant stirring. Washing of the resulting mixture with
cold water and repeated centrifugation was done, and the residue was dried in a vacuum oven to
constant weight for 48 hr. Nazir et al., (2013) [3] extracted cellulose from oil palm empty fruit
bunches; eco-friendly reagents with low concentrations of 20% (v/v) formic acid and 10% (v/v) of
30% hydrogen peroxide were employed at 85oC for the extraction and the yield of 64% (w/w) was
achieved.
3.0 CARBOXYMETHYL CELLULOSE (CMC)

Among the product type (i.e. cellulose ether), the carboxymethyl cellulose segment occupied a
significant portion of the cellulose ether market in 2015 and is projected to maintain its leading
position during the forecast period [27]. It is one of the most important cellulose derivatives, which
have an immense importance to the industry and also in our everyday life [28]. Carboxymethyl
cellulose is a linear, long chain, water soluble, anionic polysaccharide derived from cellulose [16].
The Carboxymethyl groups (-CH2COOH) of CMC are bound to some of the hydroxyl groups of
the glucopyranose monomers that make up the cellulose backbone and CMC is often used as its
sodium salt (sodium Carboxymethyl cellulose) [21]. Figure 3, shows the unit structure of
carboxymethyl cellulose;
Figure 3: Unit structure of Carboxymethyl cellulose (DS = 1)
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Carboxymethyl cellulose in its pure form is a white to cream colored, tasteless, odorless, free-
flowing powder [29].
3.1 Preparation of Carboxymethyl Cellulose

Carboxymethyl cellulose is a derivative of cellulose obtained by the chemical modification of
natural cellulose, generally prepared through the reaction of alkali cellulose with
monochloroacetate or its sodium salt in an organic medium [2]. The process involves alkalization
and etherification [16].
Cell−OH + NaOH Cell−O-Na+ + H2O (1)
(Alkali cellulose)
The alkali cellulose formed is now available to be accessed by monochloroacetic acid,
which is added in the second step (equation ii)
Cell−O-Na+ + NaOH + ClCH2COOH Cell−O−CH2COONa + NaCl + H2O (2)
(Monochloroacetic acid) (Na-CMC)
Hydrolysis of Monochloroacetic acid occurs as a side reaction (as shown in equation iii),
forming glycolate and sodium chloride and hydrochloric acid, respectively.
NaOH + ClCH2COOH HO-CH2COONa + NaCl (3)
(Sodium glycolate) (sodium Chloride)
3.1.1 Reports by various other researchers on the preparation of carboxymethyl cellulose

Cellulose powder was converted to carboxymethyl cellulose (CMC) by alkalization and
etherification [1], two reactions were reported to occur simultaneously during the process, namely;
carboxymethylation (which is the primary reaction that produces the pure CMC) and side reaction
(that produces undesired sodium glycolate). The carboxymethylation reaction was optimized
against the reaction temperature, reaction time, sodium monochloroacetate concentration, NaOH
concentration and the solvent ratio (ethanol:isopropanol). The optimized Degree of Substitution,
viscosity and yield obtained were 0.9424, 10.1 cP and 22.1024 g respectively.
Carboxymethyl cellulose (CMC) was prepared from cellulose extracted from palm kernel cake
[16]. Acidified sodium chlorite process was employed to extract 65.66% of the cellulose from the
palm kernel cake, while the optimum carboxymethylation condition for pure cellulose resulted in
a CMC whose degree of substitution (DS), yield and viscosity were 0.67, 1.6475g/g and 66.6cP
respectively. In alkalization pretreatment, 5g of palm kernel cellulose was weighed and added to
250 ml Schott bottle followed by 100ml of isopropanol. Drop-wise addition of 20 mL of 17.5%
aqueous sodium hydroxide was done, while it is stirred for an hour at 300C. After alkali treatment,
etherification reaction was continued by addition of 6g of sodium monochloroacetate (SMCA) in
reaction mixture and after which the mixture was placed in a water bath with horizontal shaker.
The reaction mixture was heated up to reaction temperature of 50ºC and shaken for 2 hours of
reaction time. Longer reaction time has the effect of increasing degradation of polymer and will
reduce the DS value as well. Soaking of the slurry in methanol was done overnight. The slurry was
neutralized the next day with 90% of acetic acid until the pH reaches 6-8 and then filtered.
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Purification of the CMC was done by washing with 70% ethanol for five times to remove undesired
byproduct. Then the CMC was filtered and dried at 600C in an oven for 24 hours.
Carboxymethyl cellulose was synthesized from oil palm fronds. Alkalization of 15 g of bleached
oil palm fronds cellulose powder was done at 300C for 60 min in water bath shaker with various
concentrations of 50 ml NaOH (37.9, 40, 45, 50 and 52.1 %) in 450 ml isopropanol (solvent) [30].
After the alkalization process, the process was followed by the addition of various amount of
monochloroacetic acid (10.7, 12, 15, 18 and 19.2 g.) at 50oCfor 3h. Filtration of the slurry was
done after which the solid was suspended in methanol and then neutralized with 90% acetic acid.
The CMC solid obtained was washed by 80% ethanol for four times to remove undesirable
byproducts. The CMC products were dried at 600C for 6 h. The yield was calculated based on the
amount of cellulose used and expressed as a percentage as shown in equation (iv) below:
Yield of CMC(%) = weight of CMC(g) X 100 (4)
weight of cellulose(g)
The reaction condition was optimized using response surface methodology (RSM). It was found
that at optimum condition: 52 % NaOH and 10.7 g of MCA, at reaction temperature of 500C with
3 h of reaction time, the highest yield of 170.1 % CMC was obtained. The CMC obtained at this
condition was characterized and reported to have the degree of substitution of 1.1, purity of 97.3
%, and the viscosity (of 1% w/v CMC solution) was 685 cP.
Caboxymethylated starch (CMS) was prepared from Sago starch; Sago starch was slurred in 300
ml of isopropanol in a 1 litre covered round-bottomed reactor flask equipped with stirrer, reflux-
condenser and burette [31]. The loss of organic liquid was prevented using the reflux-condenser.
Aqueous NaOH in an estimated amount ranging from 10-30% was added into the reactor flask
over a period of 20 min. The mixture was then stirred for 30 minutes followed by the addition of
sodium monochloroacetate. Subsequently, the flask was heated to the temperature of reaction
which varied from 35°C to 75°C. After cooling, suspension of the mixture in methanol and
neutralization with acetic acid were done. The CMS obtained was then washed with methanol,
filtered and dried overnight at 60°C.The reaction condition for the process was optimized against
degree of substitution and reaction efficiency. The amount of sodium hydroxide in the system, the
time taken for complete reaction, the reaction temperature, and the ratio of the anhydroglucose
unit to sodium monochloro acetate were used to determine the optimized reaction conditions; it
was obtained that 20% concentration of NaOH, 1hr reaction time, 55oC reaction temperature and
1.5:1.0 sodium monochloro acetate to anhydroglucose unit ratio produced a degree of substitution
value of 1.05 and reaction efficiency of 85.9%.
galactamannan gum isolated from seeds of sesbania to carboxymethylation in non-aqueous
medium using monochloroacetic acid under the catalytic action of sodium hydroxide [32]. The
concentration of monochloroacetic acid was varied and the degree of substitution was observed to
increase with increase in monochloroacetic acid concentration.
3.2 Characterization Techniques
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3.2.1 Estimation of degree of substitution (DS) and reaction efficiency (RE) values of
CarboxymethylCellulose
Degree of Substitution Values
The degree of substitution (DS) value is defined as the average number of substituents per
anhydroglucose unit (AGU) and varies between 0 and 3 [31]. The DS is a major factor in the water
solubility of Na-CMC, below approximately 0.4 the polymer is swellable but insoluble; above this,
the polymer is fully soluble with its hydro affinity increasing with increasing DS [33]. The DS
value is often determined by standard method based on acid-based titration [34].
The degree of substitution of carboxymethylated sago starch (CMS) had been determined [31]. A
sample of 4 g of CMS in 75 ml of ethanol was mixed and stirred until good slurry was obtained.
The mixture was converted to an insoluble acid by using 5 ml concentrated nitric acid and boiled
for 5 min. Ethanol (80%) that had been heated to 60°C was used to wash the precipitate.
Diphenylamine reagent was then used to test the removal of acid and salts from the sample. Then,
the sample was dried in an oven and the CMS in acid form was weighed and mixed with 100 ml
of water and 25 ml of standardized sodium hydroxide (0.5 N). This solution was heated and boiled
for 15 to 30 min. The excess of sodium hydroxide was titrated while solution was still hot with 0.5
N of standard hydrochloric acid to a neutral point. Each sample was run triplicate. The DS for
CMS was calculated, using the following equations in agreement with ASTM (1992) [34]:
DS = (0.162 x A) . (5)
[1-(0.058 x A)]
A = (BC – DE)/F; Where: A = the milli equivalent of acid consumed per gram sample; B = the
sodium hydroxide solution added (ml); C = the normality of NaOH; D = the HCl required for
titration (ml); E = the normality of HCl; F = CMS in acid form (g); 0.162kg (= 162g) is the
molecular mass of anhydroglucose unit of starch, and 0.058kg (= 58g) is the net increase in
molecular mass of AGU for each CH2COOH group substituted
Reaction Efficiency
The percentage of reaction efficiency, RE (%), for carboxymethyl starch can be calculated as
follows [31]:
RE(%) = (W2 – W1)/(W3 X 100) (6)
Where, W1 is the initial weight of cellulosic material (or starch in the case of carboxymethylated
starch); W2, the weight of carboxymethyl Cellulose (or carboxymethylated starch; if starch is used)
and W3 is the weight of sodium monochloroacetate.
3.2.2 Fourier Transform Infrared (FTIR) Spectroscopy
Figure 4, displays the spectrum obtained for the FTIR spectroscopy of carboxymethyl cellulose
from palm kernel cake [16]. The new and strong absorption band at 1604.16 cm-1 was reported to
be present due to the COO- group, which is an evidence that hydroxyl group of cellulose was
replaced with carboxyl group when carboxymethylation reaction took place. It also proved that the
sample is CMC since it has a fingerprint region for CMC bonds.
97
Figure 4: FTIR spectrum for CMC from PKC [16].
Similarly, Figure 5, is the FTIR spectrum of carboxymethyl cellulose synthesized from waste
cotton ginning industry [36]; the sample was reported to have shown that the carboxymethyl and
hydroxyl functional groups are found at wavelengths of 1620,1423and1328cm– 1respectively. It
was also explained that: the broad absorption band at 3423cm−1 was due to stretching frequency of
hydroxyl group (OH), the band at 2920cm−1was as a result of carbon–hydrogen (CH) stretching
vibration, the strong absorption band presentat1620cm−1, confirmed the presence of COO−, the
bands around 1423 and 1328cm−1 were assigned to CH2 scissoring and hydroxyl group (OH)
bending vibration, respectively, while the band at 1054cm−1 was reported as a result of >CH-
O-CH2 stretching.
Figure 5: FT-IR spectrum of carboxymethyl cellulose produced from cotton waste ginning
industry [36].
98
3.2.3 X-Ray Diffraction

X-ray diffraction techniques belong to the methods used to evaluate the degree of crystallinity
[37]. Size and perfection of crystals, orientation, order and packaging. The investigation of their
atomic or molecular arrangements is also determined by X-ray diffraction (XRD) techniques.
Katchy (2008) [38] opined that the special usefulness of X-ray diffraction in the study of solid
substances depends on its ability to distinguish ordered from disordered states. If a beam of
monochromatic X-rays of known wavelengths λ falls on a crystal, it will be diffracted at definite
angles according to Bragg’s equation:
2dsinθ ＝ nλ (7)
Where d = the distance between two diffracting planes; n = an integer representing the order of
diffraction and θ = angle of incidence of the X-ray beam.
The recording of the direction and intensity of the diffracted rays is done either by a radiation
counter or diffractometer or through the use of a camera using special x-ray films”.
3.2.4 Thermogravimetric Analysis, TGA
Thermogravimetric analysis is the study of the relationship between a sample mass and its
temperature and it is useful in the study of any physical effect (such as evaporation) or chemical
effect (such as thermal degradation) that causes a material to lose volatile gases [38]. In the process,
experiments are mostly carried out under conditions where there is linear increase in temperature
with time.
3.2.5 Differential Scanning Calorimetry (DSC)
Differential Scanning Calorimetry is a technique used to measure the thermal properties of
polymers on the basis of the rate at which they absorb heat energy compared to a reference material
[40]. Important parameters are usually obtained by plotting the graph of heat flow rate against
temperature. Differential scanning calorimetry is effective for characterizing the physical
properties of a polymer and it enables the determination of melting, crystallization and
mesomorphic transition temperature, characterization of glass transition and effects that exhibit
changes in heat capacity [41].
3.2.6 Scanning Electron Microscopy
Scanning electron microscopy is an extremely useful technique employed for visual confirmation
of surface morphology and the physical state of the sample surface [42]. It is a very essential
imaging technique that uses a beam of electron to acquire high magnification images of specimens.
In order to obtain images, the electrons generated with a thermionic filament must interact with
the sample, escape from the sample and be detected. The process requires extremely high vacuum
to avoid the damage of the beam filament as a result of air ionization caused by interaction between
the electrons and air molecules. The electron microscope consists of an electron gum which
produces the electrons and an assembly of lenses which are all enclosed in a column held under
high vacuum [38].
99
4.0 APPLICATIONS OF CARBOXYMETHYL CELLULOSE

Carboxymethyl cellulose (CMC) has many desirable applications, such as in coatings, the
formation of emulsions and suspensions, and for water retention [2]. It is also widely used as anti-
caking agent, stabilizer, dispersing agent, thickener, and gelling agent [16]. Hence, CMC has found
applications in areas such as medicine, food, paper making, printing and dyeing, adhesives,
protective colloid thickener and in dispersion in aqueous solvents,cosmetics, textiles, water-based
paints, oil well drilling [2], [9], [10]. CMC is essential in food industry because of high viscosity,
non-toxicity, and non-allergic nature [9]. In laundry detergents, CMC is used as a soil suspension
polymer that is designed to deposit onto cotton and other cellulosic fabrics creating a negatively
charged barrier to soils in the wash solution [9], [43]. It is used as a lubricant in non-volatile eye
drops (artificial tears), as well as an ingredient of drilling mud, where it acts as a viscosity modifier
and water retention agent, and referred to as Poly-anionic cellulose or PAC [9]. Carboxymethyl
cellulose lithium (CMC-Li) is used as binder in batteries [44].
4.1 Grades of Carboxymethyl Cellulose (CMC)
The initial alkali catalyzed reaction of cellulose with Chloroacetic acid produces about 60% CMC
plus 40% salts (sodium chloride and sodium glycolate) [43]. This product is the so-called technical
CMC which is used in detergents, textiles, oil drilling fluid, paper products, etc.If further
purification process of the technical grade Carboxymethyl cellulose is employed, these salts are
removed to obtain the pure CMC used for food, pharmaceutical, and dentifrice (toothpaste)
applications [43], [45]. Food grade Carboxymethyl cellulose is widely used in drinks, milk products,
flouring products, seasoning, etc. with its function of toughness, stabilizing, thickening, water
maintaining, emulsifying, mouthfeel improving, and sold under the E-number, E-466.
4.2 Behaviour of Carboxymethyl Cellulose Thickeners in Textile Printing

Sodium carboxymethyl cellulose can be used as thickeners or flow improvers in reactive printing
are those which have a degree of substitution of 2 or higher, this is because, carboxymethyl
cellulose (CMC) with a lower degree of etherification (or degree of substitution) reacts with the
dye via remaining OH groups, and causes the hardening of the handle of the textile fabric, which
occurs after printing” [46,47]. Sodium CMC prepared by a special method can be employed in
textile printing formulation without the need of high degrees of substitution, and that this behavior
appears to be achieved by size reduction which is carried out as a dry grinding or wet grinding,
and that improved ease of dissolution can be obtained by grinding the additive just before use.
Printing inks can be described as coloured liquids or pastes formulated to transfer and reproduce a
design pattern or an image from a printing surface.
4.2.1 Rheological Studies

The rheological properties of carboxymethyl sesbania Galactamnnan gum derivatives (pastes) was
earlier studied [32]. Their evaluation as thickeners in printing cotton fabrics with reactive dyes
showed that highly substituted derivatives could be used successfully as thickening agents in
100
printing cotton fabrics either alone or when mixed with sodium alignate (another thickening agent).
With the help of rheograms, it was observed that the relation between the shearing stress and the
shear rate was not linear, thereby revealing that all the pastes examined exhibited non-Newtonian
behaviour, as seen in Figures 6-8. The non-Newtonian behaviour according to the studies was
observed to be pseudoplastic (or shear thinning) in which a decrease in apparent viscosity occurred
with increasing shear rate. The homogeneity of the molecular structure of the pastes was revealed,
and the researchers observed that the pastes were capable of rebuilding themselves and retaining
their original state on removal of the applied force. The sample of lowest D.S. (0.35) was reported
to have shown the lowest degree of pseudoplasticity. As the value of D.S. increased from 0.35 to
0.58, the positions of the rheograms were far from the shear rate axis, showing higher values of
apparent viscosity, followed by subsequent lower values on further increase in the D.S. values
(from 0.58 to 0.95).
Figure 6: Rheograms of pastes of carboxymethylated sesbania galactomannan gum samples

acquiring different D.S. values, freshly prepared, [32].
After storing the pastes for 3 and 7 days respectively, previous work reported that the rheograms
showed practically no effect on the rheological characteristics of the pastes, and each of them
continued to exhibit non-Newtonian pseudoplastic behaviour after storing [32]. And that as a result
of influence of carboxymethyl group on the stability of sesbania galactomanan gum polymer, the
apparent viscosity values of the pastes nearly remained unaltered after storing for 24 hours or more.
101
Figure 7: Rheograms of pastes of carboxymethylated sesbania galactomannan gum samples

acquiring different D.S. values, after storing for 3 days (the graph on the left side)) and 7
days (the graph on the right side) [32].
.
Figure 8: Log-log plots of the viscosity, η vs. shear rate, γ of freshly prepared
Carboxymethyl Sesbania pastes of different D.S. values (concentration 15%) compared to
those of sodium alginate (concentration 3%) [32].
5.0 CONCLUSION
Various sources and properties of cellulose, synthesis of carboxymethyl cellulose (CMC),
characterization techniques such as FTIR, XRD, DSC, TGA and SEM, as well as the applications
of carboxymethyl cellulose with emphasis on its behaviour as a thickener and flow improver in
102
textile printing have been reviewed in this paper; reports showed that avoidance of over-
dependence on cotton and wood for extraction of cellulose for CMC production could be reduced
by considering that other cellulosic rich biomass such as flax, hemp, jute, ramie, sugarcane
bagasse, algae, bacteria, sisal, waste cartons, oil palm empty fruit bunch, corn stalks, rice straw,
wheat straw, etc. which are majorly agricultural wastes are very economically viable alternatives.
Cellulose have been reported to be a biodegradable organic polymer which consists of a linear
chain of D-glucose units linked by 1-4 β-linkages, and whose degree of polymerization varies
according to its sources, acquiring processes and further treatments. It has been reported that
carboxymethyl cellulose which is an important derivative of cellulose is prepared through alkali-
catalyzed reaction between cellulose and monochloro acetic acid in an organic medium. On the
characterization techniques, reports have revealed that: the functional properties of CMC can be
determined by estimation of its degree of substitution which is the average number of substituents
per anhydroglucose unit; identification of certain functional groups in the molecule is achievable
through Fourier transform infrared (FTIR) spectroscopy; the degree of crystallinity can be
estimated by X-ray diffraction (XRD); thermal stability can be evaluated by thermo gravimetric
analysis (TGA); thermal properties such as melting temperature, glass transition, heat capacity,
etc. can be determined through differential scanning calorimetry (DSC); while scanning electron
microscopy (SEM) is a useful technique for confirmation of surface morphology and physical
state of the polymer sample. Carboxymethyl cellulose due to its properties has been noted to be
useful as anti-caking agent, stabilizer, dispersing agent, thickener, gelling agent, and have been
reported to find applications in areas such as medicine, food, cosmetics, paper making, adhesives,
protective colloids, drilling fluids, battery binder, pesticides, laundry detergent, printing, dyeing
and so on. Highly substituted derivatives have been noted to be suitable for successful use as a
thickening agent in textile printing, either alone or when mixed with other thickeners such as
sodium alignates.
REFERENCES
[1] Ismail, N.M., Bono, A., Valintinus, A.C.R., Nilus , S. and Chng L.M. (2010). Optimization
of reaction conditions for preparing carboxymethylcellulose. Journal of Applied Sciences,
10: 2530-2536.
[2] Boruvkova, K. and Wiener, J. (2011). Water absorption in carboxymethyl cellulose. Autex
Research Journal, 11 (4).
[3] Nazir, M. S., Wahjoedi, B. A., Yussof, A. W. and Abdullah, M. A. (2013). Cellulose from oil
palm empty fruit bunches. Journal of Bio Resources 8(2): 2161-2172.
[4] Mari, G. (2009). Cellulose derivatives: Synthesis, properties and applications. (Academic
dissertation), University of Helsinki Finland. ISBN 978-952-10-5485-3.
[5] Marques-Marinho, F. D. and Vianna-Soares, C. D. (2013). Cellulose and its derivatives: Use
in the pharmaceutical compounding practice. Theo van de Ven and Louis Godbout (Eds),
Intech Open Science.DOI: 10.5772/56637.
103
[6] Varshney, V. K. and Naithani Sanjay (2011). Chemical functionalization of cellulose derived
from nonconventional sources. S. Kalia et al. (Eds.). Cellulose Fibers: Bio- and Nano-Polymer
Composites, DOI 10.1007/978-3-642-17370-7_2, Springer-Verlag Berlin Heidelberg.
[7] Vlaia, L., Coneac, G., Olairu, I., Vlaia, V. and Lupuleasa, D. (2016). Cellulose derivatives
based hydrogels AS Vehicles for Dermal and Transdermal Drug Delivery. Intech Open
Science, pp. 159-200. DOI: 10.57772/63953.
[8] Shokri, J. and Adibkia, K. (2013), Application of cellulose and cellulose derivatives in
pharmaceutical industries. Theo van de Ven and Louis Godbout (Eds). Intech Open Science,
ISBN 978-953-51-1191-7. DOI: 10.5772/55178.
[9] Kalia, S., Kaith, B. S. and Kaur, T. (2011). Cellulose fibers: Bio- and nano- polymer
composites. Green Chemistry and Technology. Springer Heidelberg Dordrecht London New
York. DOI: 10.1007/978-3-642-17370-7.
[10] Asep, H. S., Linnisa Q., and Alia, Badra P. (2014). Synthesis and characterization of
carboxymethyl cellulose (CMC) from water hyacinth using ethanol-isobutyl alcohol mixture
as the solvents. International Journal of Chemical Engineering and Applications, 5 (1).
[11] Fijan, R., Bastille, M., Lapasan, R., and Sostar-Turk, S. (2009). Rheological properties of
printing pastes and their influence on quality-determining parameters in screen printing of
cotton with reactive dyes using recycled polysaccharide. Journal of Carbohydrate Polymers,
78: 25-35. DOI: 10.1016/j.carbpol.2009.03.022.
[12] Singh, R. K. and Khatri, O. P. (2012). A scanning electron microscope based new methods
for determining degree of substitution of sodium carboxymethyl cellulose. Journal of
Microscopy, 246(1): 43-52.
[13] Singh, R. K. and Singh, A. K. (2013). Optimization of reaction conditions for preparing
carboxymethyl cellulose from corn cubic agricultural waste. Journal of Waste and Biomass
Valorization, 4(1): 129. DOI 10.1007/s12649-012-9123-9.
[14] Ge, Y. and Li, Z. (2013). Preparation and evaluation of sodium carboxymethyl cellulose from
sugarcane bagasse for applications in coal-water slurry. Journal of Macromolecular Science,
Part A, Pure and Applied Chemistry, 50: 757-762.
[15] Tufan, M., Uraz E., Tosu, C., and Gercel, H. (2015). Synthesis and characterization of
carboxymethyl cellulose film from pistachio shells. Proceeding 16th of ISERD International
Conference, Prague Czech Republic.
[16] Bono, A., Ying, P.H., Yan, F.Y., Muei, C.L., Sarbatly, R., Krishnaiah D. (2009). Synthesis
and characterization of carboxymethyl cellulose from palm kernel cake. Journal of Advances
In Natural and Applied Sciences, 3 (1): 5-11.
[17] Fang, J., Hong-jie, L., and Guo-gang, Z. (2016). Preparation of carboxymethyl cellulose from
corncob, International Conference on Waste Management and Technology, Procedia
Environmental, 31: 98-102.
[18] Pornchai, R. (2009). Blended films of carboxymethyl methyl cellulose from papaya peel
(CMCp) and corn starch. Kasetsart Journal of Natural Sciences, 43:259-266.
104
[19] Wang, H. H. (2002), Cellulose and pulp, forests and forest plants. Encyclopedia of Life Support
Systems (EOLSS), 2: 158-177.
[20] Nevell, T. P. and Zeronian, S. H (1985). Cellulose chemistry and its applications. Ellis
Horwood, Chichester New York.
[21] Lavanya, D., Kulkarni, P.K.I. and Dixit, M. (2011). Sources of cellulose and their applications:
A review. International Journal of Drug Formulation and Research (IJDFR), 2(6).
[22] Samia B. H., Bey, B. H. M., Scheherazade, K. and El-Amine, A. A. S. (2016). Physicochemical
analysis of cellulose from microalgae nannochloropsis gaditana. African Journal of
Biotechnology, 15(24): 1201-1207. DOI: 10.58977/AJB2016.15321.
[23] Muna, H. A. (2013). Extraction of cellulose from some industrial and plant’s waste and its
hydrolysis using new heterogeneous catalyst. (Master’s Thesis), University of Baghdad.
https://www.scbaghdad.edu.iq/library/Chemistry/MS.C/2013/Extraction%20of%20Cellulos
e%20from%20some%20Industrialpdf. Accessed on May 22, 2017.
[24] Brendel, O., Iannetta, P.P.M. and Stewart, D., (2000). A rapid and simple method to isolate
pure alpha-cellulose. Journal of Phytochemical Analysis, 11 : 7–10.
[25] Sun, R.C. and Hughes, S., (1998). Fractional extraction and physico-chemical
characterization of hemicelluloses and cellulose from sugar beet pulp. Journal of
Carbohydrate Polymers, 36: 293–299.
[26] Nuruddin, M., Chowdhury, A., Haque, S. A., Rahman, M., Farhad, S. F., Sarwarjahan, M. and
Quiayyum, A.(2011). Extraction and characterization of cellulose microfibrils from
agricultural wastes in an integrated biorefinery initiative. Journal of Cellulose Chemistry and
Technology, 45(5-6), pp. 347-354.
[27] Transparency Market Research (2016). Cellulose ether market: Global industry analysis, size,
share, growth, trends, and forecast 2016 – 2024.
http://www.transparencymarketresearch.com/cellulose-ether-market.html. Accessed June 5,
2017.
[28] Al-Bermany, A. J. (2014). Study the effect of adding polyacrylamide on rheological and
mechanical properties of carboxymethyl Cellulose Polymer as aqueous solutions. Journal of
Chemical and Process Engineering Research, 22, ISSN 2225-0913.
[29] Mario, P., Adinugrada, D.W., Haryadi, M. (2005). Synthesis and characterization of sodium
carboxylmethyl cellulose from Cavendish banana pseudo stem (Musa cavendishii
LAMBERT). Journal of Carbohydrate Polymers, 62(2): 164-169.
[30] Tasaso, P. (2015). Optimization of reaction conditions for synthesis of carboxymethyl
cellulose from oil palm fronds. International Journal of Chemical Engineering and
Applications, 6(2): pp. 101-104.
[31] Yaacob, B., Amin, Mohd C. I. M., Hashim, K. and Bakar, B. A. (2011). Optimization of
reaction conditions for carboxymethylated sago starch. Iranian Polymer Journal, 20(3): 195-
204.
105
[32] Rekaby, M. M., El-Thalouth, I. A., Rahman, A. A. H., and El-Khabery, A. E. (2010).
Technological evaluation of carboxymethyl sesbania galactomannan gum derivatives as
thickeners in reactive printing, Journal of BioResources, 5(3), pp. 1517-1529.
[33] Togrul, H. and Arslan, N. (2003). Production of carboxymethyl cellulose from sugar beet pulp
Cellulose and rheological behaviour of carboxymethyl cellulose. Journal of Carbohydrate
Polymers, 54: 73–82.
[34] American Standard of Test Method ASTM (1992). Standard test method for sodium
carboxymethyl cellulose. 6 : 249-256.
[35] Jaggi, N. and Vij, D. R. (2015). Fourier transform infrared spectroscopy. Handbook of Applied
Solid State Spectroscopy, pp. 411-450, National institute of Technology, Kurukshetra.
[36] Haleem, N., Ashad M., Shahid M., and Tahir, M. A. (2014). Synthesis of carboxymethyl
cellulose from waste cotton ginning industry. Journal of Carbohydrate Polymers, 113: 249-
255.
[37] Evseev, I. G., Haminiuk, Charles W. I., and Waszczynskyj, N. (2012). Addition of
carboxymethyl cellulose in gelified caseinomacropeptide systems: NMR, X-ray diffraction
and rheology. Journal of Food and Nutrition Research, 51 (4) 207–216.
[38] Katchy, E. M. (2008). Principles of polymer science, Second Edition. El’ Demark Publishers,
9 Ani Street, Ogui New Layout, Enugu, Enugu State Nigeria.
[39] Price, D. M., Hourston, D. J. and Dumont F. (2000). Thermogravimetry of polymers.
Encyclopedia of Analytical Chemistry. RA Meyers (Ed), pp. 8094-8105.
[40] Ashraf, A. A. (2015). Thermal analysis of polymers by differential scanning calorimetry
(DSC) technique. DOI: 10.13140/2.1.1558.0963.
https://www.researchgate.net/publication/271841055, Accessed on June 6, 2017.
[41] Schizk, C. (2009). Differential scanning calorimetry (DSC) of semicrystalline polymers.
Journal of Analytical and Bionalytical Chemistry, 395(6): 1589-611.
[42] Sathiyanarayan, P., Karunakaran, J. R., Gomathi, T. and Sudha, P. N. (2015). Synthesis and
characterization of carboxymethyl cellulose/polyethylene glycol/montmorrillonite clay
blends. International Journal of Novel Trends in Pharmaceutical Sciences, ISSN: 2277 -
2782.
[43] Al-Bermany, A. J., and Sahib, Nadia H. (2013). Study of some mechanical properties of high
viscosity carboxymethyl cellulose using ultrasonic wave system. Journal of Babylon
University/Pure and Applied Sciences, 21(4).
[44] Qui, L., Shao, Z., Wang, D., Wang, W., and Wang, J. (2014). Carboxymethyl cellulose
lithium (CMC-Li) as a novel binder and its electrochemical performance in lithium ion
batteries. Journal of Cellulose, 21(4): 2789-2796.
[45] Bahramparvar, M. and Mazaheri, T. M. (2011). Application and Functions of Stabilizers in
Ice Cream. Food Reviews International Journal, 27 (4): 389–407.
[46] Kniewske, R., Kiesewetter, R., Reinhardt, E., and Szabikowski, K. (1995). US Patent No.
5463036A. https://www.google.com/patents/US5463036. Accessed on June 14, 2017.
106
[47] Fink, J. K., (2011). Hand book of engineering and specialty thermoplastics, Water soluble
polymers, (Vol.2): pp. 80-85, Scrivener Publishing LLC.
EFFECTS OF COMPATIBILIZATION AND FILLER CONTENT

ON THE FLAMEABILITY OF POLYPROPYLENE / CALCIUM DIPHOSPHATE
COMPOSITE AND IT’S MODELLING
Akanbi M. N
Department of Polymer and Textile Engineering, Federal University of Technology, P.M.B. 1526,
Owerri, Imo State, Nigeria.
Corresponding Athour: magdalene910@yahoo.com
ABSTRACT
The effects of compatibilization and Calcium Diphosphate filler on the flammability of

polypropylene have been investigated at filler contents of 0 - 20 weight%. The effect of Maleic
Anhydride grafted Polypropylene (PP-g-MA) used as the compatibilzer was also investigated at a
constant weight of 1.5 wt% at filler compositions of 0 – 20 weight percent and at varied
compatibilization of 2.5, 3.5, 4.5 and 5.0 weight % at aconstant filler weight of 5%. The
compatibilized and uncompatibilized Polypropylene/Calcium Diphosphate (PP/CAPHOS)
composites were prepared using an injection-moulding machine. The results showed that Calcium
Diphosphate filler gave significantly improved flame retardant properties on polypropylene at
composition of 20% weight filler content. The Matlab modeled curve equation for the ignition
time of Uncompatibilized PP/CAPHOS Composite is given as: f(x) = 0.3113x3-
5.714x2+32.6x+156.8, while for Compatibilized is f(x) = 0.026x3+0.2286x2-0.1214x+162.9. The
incoporation of a compatibilizer to the composite compositions reduced the ignition time of the
PP/CAPHOS composites, thus showing that the compatibilizer had a negative effect on the flame
retardant properties of Calcium Diphosphate filled Polypropylene.
Key words: Calcium diphosphate, Compatibilization, Uncompatibilised, Polypropylene, Maleic

Anhydride, Filler, Comatibilized, Compatibilizer.
1.0 INTRODUCTION
Fire is significantly the cause of property damages and death in the big cities in Nigeria, United
States, and the world at large. It had been reported that about 4,500 deaths and 29,000 injuries
resulting from over 3 million fires each year in the U.S .Jash and Wilkie, (2005) [1]. This led to
the loss of billions of dollars and properties. The losses were sequel to the presence of clothes, wall
coverings, and household items in the residential buildings. Hence, safety consequences call for
fire resistant and safety polymer products and their resistance performances. To meet the fire safety
standards, products made of synthetic materials (plastics) are modified with flame retardants.
Flame retardants (FRs) are chemicals which when added to polymeric materials entirely prevent
the combustion of polymerics or delay the rate of spread of fire in that material after ignition.
Kemmlein et al (2003) [2]. It is known that most thermoplastics are flammable; burning easily
when heated to a high enough temperature. Plastics being hydrocarbons, combust through a
process that begins as heat in the pre-ignition phase and progresses to fire, which breaks down
107
their long-chain structure into volatile hydrocarbons, hydrogen, and hydroxyl-free radicals. These
elements formed during decomposition are high in energy and react with oxygen, releasing heat
and causing fire to spread.
Plastics containing flame retardants are found in homes and office buildings, cars and mass transit
vehicles, furnishing, fibers household appliances, and many other areas and applications.
Examples of the diverse plastic products that require flame retardants include constructions fabrics,
banner films, ceiling insulation, carpet backing, automotive fabrics, components in trains and
planes, tent materials, stadium seating, mattress covers, television and computer housings, electric
wiring, power cable etc. This makes it imperative that Polymer products to be used in such
environments must be designed to protect life and property in case of fire accidents. Several
methods have been developed to enhance the flame resistance of polymeric consumer goods,
which would provide protective coatings against fire and equally improve the escape time during
the occurrence of fire.
This present study investigates the effects of Calcium diphosphate filler on the flammability of
Figure1: Chemical structure of Calcium diphosphate
Polypropylene with and without the incorporation of the Maleic Anhydride grafted Polypropylene
(PP-g-MA) compatibilizer.
Flame retardants are generally classified according to their chemical makeup. The most common
classes of flame retardants are: Bromine, Phosphorus, Nitrogen and Chlorine containing based
retardants as well as organic based flame retardants. The flame retardants containing phosphorus
interrupt the combustion process by promoting “charring.” In the presence of a heat source,
Phosphorus flame retardants release phosphoric acid which causes the material to char and form a
thick glassy layer of carbon. This carbonated char stops the decomposition process (pyrolysis) and
prevents the release of flammable gases, essentially cutting off fuel to the flame. It also provides
a barrier between the material and the heat source [3]. Phosphorus flame retardants are used in
some upholstered furniture, foam mattresses, textiles, television casings, rubber and plastics.
2.0 Experimental
2.1 Materials
The following materials were used in the study:
Polypropylene
Maleic Anhydride grafted Polypropylene (PP-g-MA)
Calcium Diphosphate
2.2 Flame Tests

With the aid of a retort stand, the test samples were positioned above a Bunsen burner to provide
flame/heat source according to ASTM D568. Three displacements (0-3cm, 3-6cm and 6-9cm)
were marked on the test specimens.
This test was used to determine the ignition time and flame propagation rates.
108
2.2.1 Ignition Test

The test samples were held at 3.0cm above the flame source (ASTM D1929). The ignition time
was obtained as the time which elapsed between the turning on of the flame source and a visible
flame appearing on the test sample, using a stop watch.
2.2.2 Flame Propagation Test
In determining the flame propagation rate, the test samples were clamped at the constant distance
of 3cm above the flame source (ASTM D5868) and three marks of 3.0cm apart made on these
samples. Then, the time taken for the flame to get to each of the three marked points was noted
and the time taken for the flame to travel from one marked points to the other was also noted and
used to assess the rate of flame propagation on each composite sample. The Flame Propagation
Rate is the ratio of the distance from the end of the sample and the flame propagation time.
FPR = X (1)
FPT
Where X is the propagation distance and FPT is the flame propagation time.
2.2.3 Time Rate of Distance Travelled
This is the Time Distance Graph whose reciprocal will give the Velocity of the flame which is
the slope of the graph.
3.1 Ignition Time (I.T)
The flame properties of the composites were assessed by determining the ignition time,
Propagation rate and their percentage decrease.
It can be observed from Figure 2 that the curves have upward trends which depict that the ease of
ignition decreased with increasing filler loading for the uncompatibilized composites investigated.
This shows that the filler would reduce the ease at which the substrate would ignite and is therefore
acting as a flame retardant. This observation is in agreement with the report of Hanu L.G et al,
2006 [3] on the use of mineral filler (Mica) which is said to be known to delay the time taken for
a polymer to ignite. Their report also stated that mineral fillers improve the thermal stability of
composites.
It can be deduced also from figure 2 that the introduction of the compatibilizer reduced the IT for
all compositions of the composites which is obvious when compared with the curve of the
uncompatibilized. This is not surprising because the compatibilizer contains oxygen atoms which
we should expect would support combustion. Although PP-g-MA may have affected adhesion
between filler and PP, it severely escalated its flammability. The results of the I.T obtained showed
that the ease of ignition of the 1.5wt% compatibilizer composites decreased with increasing filler
loading with respect to the neat PP, but this is not the case with respect to the uncompatibilized
composites.
1500
IGNITION TIME (S)
1000
500 Uncompt. PP/Caphos

Compt. PP/Caphos
0
0 5 10 15 20 25
FILLER WEIGHT %
109
Figure 2: Ignition Time versus Filler weight for the compatiblized and uncompatibilized
PP/Caphos Composites.
Furthermore, there was rather an increase in the ease of ignition which also could be traced to the
PP molecules in the PP-g-MA compatibilizer which increased the quantity of the PP molecules
present in the composites. The introduction of the maleic anhydride-grafted Polypropylene,
introduced more sites of the combustible hydrocarbon via the grafted polypropylene molecules,
since ignition depends on the availability of combustible gaseous hydrocarbon. Obidiegwu et al,
2012 [4].
3.1.1 Modelling of Polypropylene-Calcium Diphosphate Uncompatibilized Composite

The model and experimental curves for PP/CAPHOS Uncomatibilized composites are shown in
Figure 3. The experimental curve has a downward deviation at 5 wt% and 15 wt% and an
upward deviation at 10 wt%. The optimum filler is between 18 – 20 wt%.
Goodness of fit:
SSE: 1903
R-square: 0.9962
RMSE: 43.63
The Model Equation is given as f(x) = 0.3113x3-5.714x2+32.6x+156.8 (2)
1100
Experimental data
1000 Predicted data
900
800
Ignition Time(s)
700
600
500
400
300
200
100
0 2 4 6 8 10 12 14 16 18 20
Filler Content(g)
Figure. 3 Experimental and Predicted (model) of the Ignition Time of Polypropylene Calcium
Dihosphate uncompactibilized Composite .
3.1.2 Modeling of Ignition Time (IT) for Polypropylene- CAPHOS Composites at constant
1.5 wt % Compatibilizer
Goodness of fit:
SSE: 60.36
R-square: 0.999
RMSE: 7.769
The Model Equation is f(x) = 0.026x3+0.2286x2-0.1214x+162.9 (3)
110
The modeled (predicted) graph is shown in Figure 4 while the Analysis Curve is in Figure 5.
From the modeled graph, there was a slight downward derivation at 10wt % and the optimum
filler weight for the optimum result is observed at 20wt%.
500
Experimental data
Predicted data
450
400
Ignition Time(s) 350
300
250
200
150
0 2 4 6 8 10 12 14 16 18 20
Filler Content(g)
Figure 4: Experimental and Predicted Curves of Ignition Time for the PP/CAPHOS at 1.5 wt%
Compatibilizer.
Analysis of fit "fit 1" for dataset "it vs. x"

600
fit 1
400
Fit
200
0
50
1st deriv
-50
6000
Integral from 0
4000
2000
0
0 2 4 6 8 10 12 14 16 18 20
Figure 5 : Analysis of Fit for PP/CAPHOS for PIT @Constant 1.5 wt% Compatibilizer
3.1.3 Modelling of PP/CAPHOS Composites at varied compatibilizer and constant Filler content
Goodness of fit:
SSE: 0.345
R-square: 0.9973
RMSE: 0.5873
The Model Equation is f(x) = -0.3045x4 + 3.579x3 – 15.06x2 + 24.33x + 162 (4)
From the curve in Figure 6, it is observed that there is proximity between the experimental and
predicted data from 0-1.5 wt%, an upward deviation at 2.5 wt% and 4.5 wt% while a downward
deviation is observed at 3.5 wt%. the optimum comactibilization is observed at 1.5wt%.
111
176
Ex perimental data
Predic ted data
174
172
Ignition Time(s) 170
168
166
164
162
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Filler Content(g)
Figure 6: Experimental and Predicted Plot of Ignition Curve and Model of PP/CAPHOS at varied
Compatibilization
Analysis of fit "fit 1" for dataset "it vs. x"
400
fit 1
300
Fit
200
100
0
1st deriv
-50
-100
1500
Integral from 0
1000
500
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
Figure 7 Analysis of Fit for PP/CAPHOS for varied Compatibiliser and Constant Compatibiliser
3.2 Flame Propagation Rate

The flame propagation rate is used to investigate the spread of combustion and its kinetics. It
determines how rapidly the flame travels on the burning material. The results of the flame
propagation rate and its propagation rate respectively are shown in figures 8 - 9. Figure 8 shows
the plot of the flame propagation rate against filler wt. % for both compactibilized and
uncompatibilzed composites. It is evident from this graph that both curves had a downward trend,
meaning that there was a decrease in the flame propagation rate with increase in filler weight. The
Uncompactibilized had a lower rate of propagation than the Compactibilized composites. This
could be from the fact that the PP- G - MA Compatibilizer introduced more polyolefin burning
sights into the composites.
The flame propagation rate % decrease of the composites is represented in figure 9. The curves of
the uncompatibilized composites had upward trends. The propagation rate % decrease curves were
seen to increase with the increase in filler wt. %.The burning speed decreased, this depicts that the
flame spread is not accelerating. And a non-accelerating flame is a good sign of flame propagation
resistance of the composite materials. This trend is in good accord with literature T. Wittek and T.
Tanimoto (2008) [5]. There was a significant 100% decrease in the flame propagation rate at
20wt% filler content.
112
0.04
Flame Propergation
0.03
Rate (cm/s)
0.02
PP/CAPHOS UNCOMPT.
0.01
PP/CAPHOS COMPT.
0
0 5 10 15 20 25
Filler Weight (%)
Figure 8: Flame propagation rate of Compatibilised and Uncompatibilsed PP/CAPHOS

Composites.
150
FPR % DECREASE
100 PP/CAPHOS
50 UNCOMPT.
0 PP/CAPHOS
0 10 20 30 COMPT.
FILER WEIGHT (%)
Figure 9: The Percentage Decrease of the Flame Propagation Rate (FPR) of the Compatibilsed and
Uncompatibilised PP/CAPHOS Composites.
3.2.1 Modeling of Flame propagation Rate (FPR) of the Calcium Diphosphate-Polypropylene
Composite at 1.5(wt %) Compatibilization
Linear model Poly3:
Goodness of fit:
SSE: 2.721e-006
R-square: 0.9858
RMSE: 0.001649
The Model Equation is f(x) = -0.0000008x3-0.000015x2-0.0002271x+0.0339 (5)
From the modeled curve in Figure 10, there is an upward deviation at filler weight of 5% and a
downward deviation at 10 wt%. The optimum result would be observed at filler composition of
20wt%.
113
0.04
Experimental data
Predicted data
Flame Propagation Rate(cm/s)

0.035
0.03
0.025
0.02
0.015
0 2 4 6 8 10 12 14 16 18 20
Filler Content (g)
Figure 10: Experimental and Predicted Flame propagation Rate (FPR) of the Calcium
Diphosphate-Polypropylene Composite at 1.5(wt %) Compatibilization
Analysis of fit "fit 1" for dataset "fpr vs. x"
Fit with 95% pred bounds
0.1
fit 1
95% prediction bounds
0
-3
-0.1 x 10
0
1st deriv
-1
-2
1
Integral from 0
0.5
0
0 2 4 6 8 10 12 14 16 18 20
Figure 11: Analysis of Fit for Predicted Flame propagation Rate (FPR) of the Calcium Diphosphate-
Polypropylene Composite at 1.5(wt %) Compatibilization .
3.3 The Time Rate of Distance travelled

The distance of the flame travelled with respect to time is represented on Figure 12 – 13for
compatibilized and uncompatibilized composites respectively. The reciprocal of the time –
distance graph gives the velocity of the flame which is the slope of the graphs.
For the uncompatibilized Polypropylene filled with Calcium Diphosphate composites under
investigation, it took a longer time for the flame to propagate through a short distance which is
evident in Figure 12 and this depicts that the fillers were able to delay the rate at which the flame
burned the substrates. This was quite obvious in the uncompatibilized PP/CAPHOS composite at
20% filler weight. The PP/CAPHOS composite of 20% filler weight ignited but did not propagate
beyond the 3cm mark after propagation. The flame propagated through the zero mark to the 3cm
mark and stopped. A hard crust char was formed over the composite, this could be due to the
presence of phosphorous ion in the filler. When phosphorous is heated, it reacts, and forms a
polymeric form of Phosphoric acid. This acid causes a char layer which shields the material from
oxygen in that way, preventing the flammable gases Ike Van Der Veen et al 2012 [6].
From Figures 13, it could be observed that the propagation time increased with the increase in
filler loading that is the more the filler content the longer the time of the flame to travel through
the substrates.
114
1200
0wt%
5wt%
1000 10wt%
15wt%
20wt%
800
600
Time (s)
400
200
0 2 4 6 8 10
Distance (cm)
Figure 10: Time versus Distance Covered of Uncompatibilised Calcium Diphosphate filled
550 0wt%
500 5wt%
10wt%
450 15wt%
400 20wt%
350
300
Time (s)
250
200
150
100
50
-50
0 2 4 6 8 10
Distance (cm)
Polypropylene composite
Figure 11: Time versus Distance Covered of constant 1.5 wt % compatibiliser Calcium
Diphosphate filled Polypropylene composite.
4.0 CONCLUSION
In conclusion, it abounds that Polyolefins which are basically fuels burning easily when ignited
and the traditional flame retardants meant to salvage this problem are toxic and environmentally
unfriendly. This present study has revealed that the mineral filler Calcium Diphosphate can be
used in this regard. Also, from the results obtained it is deduced that the use of compatibilizers is
obviously not necessary for the purpose of flame retardance, in composite preparation, despite the
proper adhesion it introduced between the two compounds. More so with the incorporation of
Maleic anhydride Graphted Polypropylene (PP-g-MA) compatibilizer as this will interfere with
the retardance effectiveness of the filler.
REFERENCES
1. Jash and Wilkie, (2005) Methods, systems, and compositions for fire retarding substrates
US 7736696 B2 http://www.google.com/patents/US7736696
115
2. Kemmlein, S., Hahn, O., Jann, O., (2003). Emissions of organophosphate and
brominated flame retardants from selected consumer products and building materials.
Atmo. Environ,
3. Hanu, L.G., Simon, G.P. & Cheng, Y.B. (2006). Thermal stability and flammability of
silicone polymer composites.Polym. Degrad. Stabil., 91, 1373–1379.
4. Obidiegwu M. U. (2012). Mechanical and flammability property of low density
Polyethlene /Alstonia boonei wood fire. Asian Journal of nature and applied sciences.
5. T. Wittek and T. Tanimoto (2008), “Mechanical Properties And Fire Retardancy Of
Bidirectional
Reinforced Composite Based On Biodegradable Starch Resin And Basalt Fibres” EXPRESS
Polymer Letters Vol.2, No.11810–822.
6. Ike van der Veen & Jacob de Boer (2012).“ Phosphorus flame retardants: Properties,
production, environmental occurrence, toxicity and analysis ”Chemosphere Vol 88 Issue
10,Pages 1119 – 1153.
116

Physicomechanical Properties of Agro Waste Filled High Density Polyethylene Bio-Composites

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Journal of Institute of Polymer Engineers (JIPE) Vol. 1, No.

PHYSICOMECHANICAL PROPERTIES OF AGRO WASTE FILLED HIGH DENSITY

2.0 MATERIALS AND METHODS

2.2 Chemical composition of agro fibers

Table 1: Chemical composition of agro fibers

2.3 Particle size distribution of agro fibers

Figure 1: Particle size distribution of agro fibers

2.4 Particle geometry

Figure 2: Particle geometry of agro fibers (80 X) magnification

2.5 Composites preparation

2.6 Water Absorption and Thickness Swelling Tests

2.7 Mechanical Characterizations

Figure 3: Water absorption of composites at different immersion times

RHF/HDPE composites showed higher values of thickness swelling, followed by corncob

Figure 4: Thickness swelling of composites after 56 days immersion in water

𝑙𝑜𝑔(𝑀𝑡 ⁄𝑀𝑠 ) = 𝑙𝑜𝑔𝐾 + 𝑛𝑙𝑜𝑔 𝑡 (3)

3.2 Flexural properties

Figure 5: Flexural strength of agro fibers filled HDPE composites

Figure 6: Flexural modulus of agro fibers filled HDPE composites

3.3 Impact strength

3.4 Morphology characteristics

UTILIZATION OF GEOTEXTILES FOR SOIL IMPROVEMENT

Onuegbu, G.C., Okorie, C.C., Anyiam, C.K. and Akanbi, M.N.

Department of Polymer and Textile Engineering, Federal University of Technology, Owerri,

Man-made geotextiles based on petrochemical derivatives such as polyethylene, polyester,

2.0 MATERIALS AND METHOD

2.2 Preparation of the samples

3.0 RESULTS AND DISCUSSION

3.1 The Height of the Plant

3.2 The Soil Nutrients

3.2.1 Sodium (Na) content

Figure 3: Effect of geotextiles on sodium content of the soil

3.2.2 Calcium (Ca) content

Figure 4: Effect of geotextiles on calcium content of the soil

3.2.3 Magnesium (Mg) content

Figure 5: Effect of geotextiles on magnesium content of the soil

3.2.4 Available Phosphorus (P)

Figure 6: Effect of geotextiles on Phosphorus content of the soil

3.2.5. Organic Carbon (OC) content

(%) ORGANIC CARBON

Figure 7: Effect of geotextiles on organic carbon content of the soil

3.2.6. Nitrogen (N) content

Figure 8: Effect of geotextiles on the Nitrogen content of the soil

MECHANICAL PROPERTIES OF NATURAL RUBBER VULCANISATE FILLED

R.A. Adetola1, M.I. Ugbaja1, D.O. Adeoye2

Keyword(s): Mechanical properties, Natural Rubber (NR), Rice Husk (RH).

2.2.2 Sample Preparation

Table 1: Typical Formulation for Natural Rubber Filled Vulcanisates.

1. Natural Rubber (NR) 100 90 80 70 60 50

3. Stearic Acid 2.5 2.5 2.5 2.5 2.5 2.5

4. TMQ 1.5 1.5 1.5 1.5 1.5 1.5

5. MBTS 2.0 2.0 2.0 2.0 2.0 2.0

6. Rice husk (RH) 0 10 20 30 40 50

7. Processing oil 2.0 2.0 2.0 2.0 2.0 2.0

8. Sulphur 2.5 2.5 2.5 2.5 2.5 2.5

2.3 Sample Testing

2.3.2 Shore (A) Hardness

2.3.2 Abrasion Resistance

2.3.3 Water and n-hexane absorption

3.0 RESULTS AND DISCUSSION

3.1 Tensile Strength

3.2 Percentage Elongation

Figure 2: Effect of RH content on the percentage elongation of NR vulcanisate

Linear model Poly3: f(x) = p1x^3 + p2x^2 + p3*x + p4