Effect of Different Types of Graphene and Graphene Loadings on the Properties of Nitrile Rubber NBR and XNBR Compounds

Anna Marzec, Anna Laskowska, Marian Zaborski Institute of Polymer and Dye Technology, Technical University of Lodz, ul. Stefanowskiego 12/16 90-924 Lodz, Poland anna.marzec@p.lodz.pl, anna.laskowska@p.lodz, marian.zaborski@p.lodz.pl

1.

Introduction

Graphene is a monolayer of carbon atoms closely packed in a honeycomb lattice and is the basic unit of all the three dimensional (3D) carbon nanostructures. Graphene and its derivatives have been widely used to produce a lot of electronic devices [1-6] and also as reinforcement filler in polymer composites [7]. Previous research demonstrates that the addition of graphene into a polymer matrix can remarkably enhance polymer properties such as mechanical, thermal, and reduce permeability of composites [8-11]. Although incorporation of graphene into thermoplastic matrix such as poly(methyl methacrylate), polycarbonate, poly(ethylene oxide) has been very successful [12,13] application of graphene nanoplatelets in relatively non-polar polymers as rubber has not been extensively reported. For example chemically exfoliated GO nanosheets were incorporated into HXNBR by simple solution-mixing method and produced GO/HXNBR composites [14]. Composite of PDMS and exfoliated graphite for a compliant electrode exhibited a low percolation threshold and moderate conductivity [15]. Other example involve incorporation of graphene into PU matrix [16]. The current study mainly focuses on studying whether the presence of graphene can enhance mechanical properties, crosslink density and protect against UV ageing of acrylonitrile-butadiene rubber NBR and carboxylated acrylonitrile-butadiene rubber.

2. Experimental 2.1. Materials The nitrile rubber NBR was Perbunan 2845F (nitrile content 28%) and carboxylated acrylonitrile-butadiene rubber was Krynac X7.50 (carboxyl groups content 7% wt., bound acrylonitrile content 27% wt) were purchased from Lanxess Deutschland GmbH. The composition of rubber compounds was presented in Table 1 whereas the NBR and XNBR rubber chain structures were shown in Fig. 1.

Table 1. Compositions of nitrile rubber compounds NBR Ingredient NBR rubber Graphene Zinc oxide Sulphur Mercaptobenzothiazole Stearic acid amount, phr 100 5, 10, 15 5 2 2 1
CN COOH CH 2 CH 2 HC CH 2 CH 2 H 2C

XNBR Ingredient XNBR rubber Graphene Zinc oxide amount, phr 100 5, 10, 15 5

CN HC CH2 CH CH 2 HC CH2 CH 2 CH 2
HC CH 2 CH CH 2

HC CH 2

(a)

(b)

Fig.1 NBR (a) and XNBR (b) chain structure

Flake graphene with average particle thickness around 2 nm, average particle diameter larger than 2 microns and different specific surface areas varying from 300 to 750 m2/g were purchased from XG Science Inc. USA. We used three types of graphene nanoplatelets known as: xGnP-C-300, xGnP-C-500, xGnP-C-750 which have respectively 300, 500, 750 m2/g of specific surface area.

2.2.

Experimental methods

Mixing of the graphene nanoplatelets (5, 10 and 15 phr loadings) and vulcanizing system with the rubber was carried out in a laboratory size open two-roll mixing mill at room temperature. Rubber mixes were subjected to a curing study with a moving die rheometer ALPHA PMDR 2000. The rheometric studies were conducted at 160C for 60 min. The rubber compounds were subsequently cured under pressure at 160 C for optimum cure time. Thickness of the compression mould was lower than 1 mm. The stress-strain tests were performed with a universal material testing machine (Zwick model 1435) with a crosshead speed of 500 mm/min according to ISO-37 standard. Swelling of vulcanized samples was measured in toluene at room temperature for 48h to achieve equilibrium swelling and then dried to constant weight. Crosslink density was calculated from the swelling data using Flory-

Rehner equation [17]. The morphology of the graphene nanoplatelets and their dispersion in the elastomer matrix were estimated using Scanning Electron Microscopy with a LEO 1530 SEM microscope. The samples were UV irradiated (Atlas UV 2000). Measurement lasted for 120 h and consisted of two alternately repeating segments with the following parameters: daily segment (radiation intensity 0.7 W/m2, temperature 600 C, duration 8h), night segment (no UV radiation, temperature 500C, duration 4 h) after that tensile properties values were measured. The UV-ageing coefficients were calculated according to the relationship: S= [TSEB] /[TS*EB], where TS tensile strength [MPa], EB elongation at break [%], TS, EB corresponding values after ageing.

3. Results and discussion Graphene nanoplatelets were shipped as a black bulk powder. SEM images of xGnP-C fillers show that each individual particle has an irregular shape and a clean surface, however the size of layer diameter is getting smaller with increasing of specific surface area. We could observe a standard shape of two dimensional plates which lie flat upon one another with a high tendency to agglomeration. The effect of graphene on vulcanization kinetic of rubber mixes was dependent on the type and composition of rubber compounds. It was noted that in case of NBR mixes, time of vulcanization was longer in the presence of graphene in comparison to the unfilled rubber. Opposite effect was observed in case of XNBR compounds cured with zinc oxide. The tensile measurements evidently indicated the reinforcement effect of graphene as filler in the XNBR matrix. The results confirm that the tensile strength of XNBR/graphene composites is much superior even at such small concentration of filler as 5 phr, up to 31 MPa, in comparison to unfilled rubber. A decrease of EB parameter clearly refer to an increased crosslinking density, and this effect is the most pronounced in case of XNBR/xGnP-C-750 at the highest loading of filler, 15 phr. This can be attributed to the increment in crosslink density as the EB parameter is gradually going down with the increase of amount of filler in elastomer. Opposite effect is observed in case of compounds filled with xGnP-C-300 where higher concentration of filler results in enhancement of tensile strength.

4. Conclusions NBR and XNBR rubber showed a significant improvement in mechanical properties even when a small amount around 5 phr of graphene nanoplatelets was incorporated, however in case of XNBR reinforcing effect of graphene was more evident. Graphene filler with as high specific surface area as 300, 500 and 750 cm2/g effected on increase in tensile strength, stress at 100, 200 and 300% elongation and also crosslink density of nitrile rubber composites. It was also found that NBR and XNBR compounds filled with graphene exhibited enhanced UV stability in comparison to unfilled rubber material.

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