Microstructures of Nanocellulose and Reinforcement in Nitrile

Butadiene Rubber (NBR) Composites

Mohamad Nurul Azman Mohammad Taib 1*, Nurhidayatullaili Muhd Julkapli2 ,

Wageeh Abdulhadi Yehye3 and Sharifah Bee O.A. Abdul Hamid4
Nanotechnolgy & Catalysis Research Centre (NANOCAT), Institute of Postgraduate Studies (IPS),
University of Malaya, 50603 Kuala Lumpur MALAYSIA
azman04@um.edu.my

Keywords: Field Emission Scanning Electron Microscopy (FESEM), Nano crystalline cellulose
(NCC), polymer composites, microstructure.

Abstract. This study was done to investigate the microstructures of nanocrystalline cellulose (NCC)
after hydrolysis with mineral acid concentrated. The optimum NCC was achieved through acid
hydrolysis and the NCC was used as a reinforcement in nitrile butadiene rubber composites. The
Field Emission Scanning Microscopy (FESEM) was used to study the structures and surfaces of the
NCC and composites produced. The NCC that was synthesis from microcrystalline cellulose (MCC)
found to be more individual and agglomerated due to hydrogen bonding between the NCCs, the
more individual NCC produced would create more surface area to be bonded with NBR as a
reinforcement. More surface area of NCC was good to create physical bonding with NBR and
increase mechanical performance of composites. The NCCs in NBR composite found to form
agglomeration caused by different properties that exhibited by both materials. This can restrict and
reduce the performance of composite produced. A combination of these materials can be used as a
reinforcement but need more attention on the modification to make these materials more
compatible. Further research can be done to find the best way to prevent agglomeration between
these both materials.

Introduction
Cellulose can be extracted from various sources such as cotton fibre, corn starch, bamboo, bagasse
pulp and other agricultural residues [1]. The advantages of this NCC are from natural abundant
resources, biodegradable, high tensile strength, high mechanical properties, low gas permeability
and dimensional stability[2,3]. This material is suitable to be used as a reinforcement in other
matrices because of light weight for adhesives, in electronic devices, biomaterials, foams, aerogels
and textiles [2]. Inorganic materials such as carbon black, silica and clays are incorporated with
rubber is still limited in term of mechanical properties since the large increases of the weight of
rubber composites produce and thus limits the loading of these inorganic materials[2].
Nitrile butadiene rubber (NBR) is in a family of unsaturated copolymers of 2-propenenitrile and
various butadiene monomers (1, 2-butadiene and 1, 3-butadiene). NBR is a synthetic polymer or
elastomer that was originally oil-resistant synthetic rubber. NBR is used in many products such as
films, tapes, ropes, hoses, belt and mats. NBR has been studied as a matrix for various nano
composites such as with carbon nanohorns, nanographite and nanokaolite [4,5]. The NBR
composite that produces from these materials increases the weight of composites produced which
limited in expanding use in high force load bearing field.
Nano-reinforced polymer composites are widely used in many engineering applications as
reported in the previous study by [2] and the element such as microscopic and microstructure of the
material is one of the most important element that can be studied to determine what exactly happen
on the material and the structure of material. Various equipment can be used but an advance
equipment nowadays such as field emission scanning electron microscopy (FESEM) is widely used
to do the investigation. The data obtain can be used to disseminate by researchers and engineers for
further studies and applications. Based on our knowledge, no research paper on morphology
structure of NCC and NBR composites by dipping process has been reported in literature to date. In
this paper, we reported NBR reinforced with NCC at low loading level and studied the
morphological structure properties. Further research can be done to expand the application of NCC
as reinforcement or as a filler in synthetic or natural rubber.

Materials and Method

Commercial microcrystalline cellulose (MCC), Hydrochloric acid (HCl) 37 wt.% for synthesis of
NCC were purchased from a local supplier. Nitrile butadiene rubber, ammonia, sodium dodecyl
benzene sulfonate (SDBS), zinc dibutyldithiocarbamate (ZDBC), sulphur, zink oxide (ZnO),
titanium oxide (TiO), were supplied by the local manufacturer. All materials were used without
further purification.

Hydrolysis of MCC to NCC. MCC (5g) was mixed with HCl of 5M concentration. The mixture
was then hydrolyzed at 100°C for 60min with continuous stirring (500 rpm). After finish, the
mixture was quenched in ice tube to stop the reaction. Then, the mixture was washed with distilled
water and centrifuged for 30 minutes at 3000 rpm by using repeated centrifugation. This action was
repeated for five times. After that, the supernatant was dialysis with distilled water until the pH of
wash water was constant at pH 7. Then, resultant suspension was stored at room temperature before
further process and analysis. NCC (0.05g) was dispersed in 100ml of distilled water under
continuous stirring and then ultrasonicated for 30 min using ultrasonic homogenizer with an output
power 1200W, equipped with a sonication probe. To avoid overheating of suspension, the beaker
with NCC suspension was placed in ice bath. Then, NCC suspension was sent to further analysis.

Preparation of nitrile butadiene rubber (NBR) solution and reinforcement with NCC. First,
nitrile butadiene rubber (NBR) with a solid content of 23% was used. 200 ml of NBR latex and
ammonia that was diluted to 25% were mixed together. Ammonia was added as an anti coagulant
to prevent the NBR solution from coagulated. Then, SDBS was pipet into solution. After 1 hour,
the mixture of ZDBC, sulphur, ZnO and TiO2 was mixed together with the solution. TiO2 was added
as a white pigment and UV absorber. The mixed NBR solution was left at room temperature with
continuous stirred and proper cover for overnight. After left overnight, the NBR solution with a
quantity of 200 ml was mixed with NCC. NBR/NCC composites were prepared with the
composition range from one to five parts per hundred rubber (phr). NCC was stirred in NBR
solution until a homogenous mixture was obtained. The solution was put into the dipping tank for
the dipping process. The ceramic former was used as a forming for NBR composites. Further test
and examination was done using INSTRON according to ASTM D412 (tensile strengh by four
replication) and Field emission scanning electron microscope (FESEM).

Results and Discussion

Fig 1 shows result for tensile strength of NBR after reinforced with NCCs. The mean value of
tensile strength was increase with increment of NCCs phr loading. No significant results were
observed from one phr to three phr when compared to NBR. The reason could be due to
agglomeration and strong hydrogen between NCCs itself. Fig 2(a) shows the structure of MCC
observed by FESEM. From Fig 2(a) indicated the MCC was long with curled and soft-flat shape
with an average width of 20µm. The surface looked rough with some pits. The diameter of MCC
was in accordance with research reported by [6]. Fig. 2(b) shows the NCC that was produced from
MCC after being hydrolyzed by HCl acid at 5M concentration. The NCC was found agglomerated
between each other caused by the strong hydrogen bonding between the NCCs itself. After
hydrolyzed, the MCCs turn into NCCs and become smaller and thick. When these particles turn into
NCCs most of them agglomerated between each other. This was due to the cleavage of glycosidic
bond and strong hydrogen bonding in NCCs. The estimation of size cannot be done precisely by
FESEM because the agglomerated between the NCCs. After NCC was produced, the NCC was used
as a reinforcement in NBR polymer to produce NBR composites.

20
16.58

18

16 13.61
Tensile strength (MPa)

14

12 9.105
8.264 8.779
10 7.259
8

0 NBR 1phr 2phr 3phr 4phr 5phr

Type

Fig. 1 Tensile strength of NBR and NBR/NCC composite films

(a) (b)

(c) (d)

Fig. 2(a) FESEM of Micro crystalline (MCC) structure (1000x); (b) Nano crystalline (NCC)
structure (500x); (c) MCC structure (5000x); (d) NCC structure (5000x)

From Fig. 3 shows that the NBR that act as a control sample, it shows a clean and smooth
surface with some element probably from the accelerator. After reinforced with NCC the structure
looked different with the control sample, the NCCs were observed in NBR composite. NBR
composite at 5phr shows aggregated NCC filled and embedded in NBR. This NCC would become
more abundantly and scattered when the phr was increased. Aggregated NCC can lead to poor
dispersion in NBR matrix and result in reduction in performance. The NCC and NBR have
different properties, NCC was more hydrophilic and tend to create strong hydrogen bonding
between the NCCs as seen on Fig.2(b). More agglomerated of NCC was observed on NBR matrix
and create some thicker ball as in Fig.3(b) when compared to Fig. 3(a). Whereas, the NBR is a
polymer and tends to be more hydrophobic. These both properties exhibited would create a
compatibility problem when mixed. This incompatibility within NBR matrix will reduce the
performance when the NCC was added with higher phr.
(a) (b)

Fig.3 (a) FESEM of Nitrile butadiene rubber (NBR) fracture surface (20000x); (b) FESEM
of NBR composite at 5phr (20000x)

Conclusion

In a nutshell, the NBR composites produced with reinforcement of NCC can be used to improve the
performance of NBR in mechanical properties. Further research can be done to obtain more
homogenous mixture between both materials. The results and findings from this research can create
a further understanding and can be used as a reference for researchers.

Acknowledgement

The authors would like to thank Ministry of Science and Technology (MOSTI) Malaysia as a
financial supporter of this project. This project was financially supported by Science Fund (SF013-
2013: Modification of NCC for production of NCC polymer and rubber composite).

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