METHODOLOGY. This chapter mainly discuss about the procedure in executing the project towards achieving the objective.

Methodology of this project will dived to two which is first part will explain the flow of procedure to prepare polylactic acid/graphene nanocomposite (PLA/GNP and second will explain about characterization of PLA/GNP. Preparation of PLA/GNP. Like carbon nanotubes and many other nanomaterials, a key challenge in the synthesis and processing of bulky quantity graphene is aggregation. Graphene which have a high specific surface area, unless well separated from each other then to form irreversible agglomerates or even restack to form graphite through van der Walls interactions. The graphene agglomerate is not soluble or redispersable in water or other polar solvents, making further processing difficult. This problem will encounter by pre-dispersed. In pre-dispersed, agglomeration graphene will become dispersible graphene with mix agglomeration graphene with solvent that is epoxied plam iols, EPO and than heated and stir until become dispersible graphene that will mix with polylactic acid, PLA to become PLA/GNP The PLA/GNP were prepared by melt blending technique. In this technique we will use Brabender Internal Mixer. The table below is summarized about weight ratios of PLA and GNP for preparation PLA/GNP. PLA/GNP PLA90/GNP10 PLA80/GNP20 PLA70/GNP30 PLA60/GNP40 PLA50/GNP50 PLA40/GNP60 PLA30/GNP70 PLA20/GNP80 PLA10/GNP90 PLA 90 80 70 60 50 40 30 20 10 GNP 10 20 30 40 50 60 70 80 90

The mixture of this elements were added into the mixture chamber. The blends will compress molded and produce sample sheets. This sample sheets were than use for further characterization in form of Dum bell specimen. Below is diagram of Dum bell specimen that will tested.

D E C A B

where A = length of over-all B = width of over-all C = length of narrow section D = length of bench marker E = width of narrow section

Characterization. The PLA/GNP were characterized by Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), and Tensile Measurement. Fourier Transform Infrared Spectroscopy (FTIR) A FTIR spectrometer was used to determine the functional group in the sample. FTIR spectra were recorded using a Perkin Elmer spectrometer. Sample were measured in the form of thin films which were prepared by hot press molding. X-Ray Diffraction (XRD) X-ray diffraction is a useful tool to obtain structural information. XRD measurement was carried out by using a Shimadzu XRD diffractometer with CuK radiation ( = 1.542). Data were collected within the range of scattering angle (2) of 2 to 10. Thermogravimetric Analysis (TGA) Sample will undergo TGA test to get the change in weight of a sample as a function of either temperature. TGA was performed using a Perking Elmer instrument.

Weight (%)

Temperature (%) Scanning Electron Microscopy (SEM). SEM was used to see structural phenomena that important role in determining the properties of a polymer. SEM was done using JEOL Scanning Microscope. Tensile Measurement.

Tensile measurement were carried out by using Instron Mechanical tester. From this test we will get stress-strain data. Evaluation from this data we will get tensile strength, tensile modulus and elongation of break. Usually 7 samples for each composition and an average of 5 result were taken as the resultant value in determining the tensile measurement of specimen. Below is flowchart of methodology in preparation and characterization of PLA/GNP nanocomposite. Agglomerate graphene Dispersible graphene

I. II.

add EPO heat & stir

PLA

Melt blending

PLA/GNP nanocomposite

Characterize in tensile FTIR, TGA, & SEM

measurement,

INTRODUCTION. Polymer. Polymer is such a widely used material that some of us take in for granted. If we look closely into our environment, polymer is all around us whether we realizes or not. Essentially, what is polymer actually ? Poly is a prefix from Greeks that means many. The word polymer itself originated come from Greeks polumers which means consisting of many parts. Generally, a polymer is a molecule with extremely high molecular weight constructed from repetition of small and simple chemical unit. These small and simple chemical unit are typically connected by covalent chemical bonds. Polymer exists as natural part of our world as well as synthetic materials which mostly originated from hydrocarbon. Polymer is being utilized in broad area of usage due its board physical and chemical properties. Nanotechnology. Recently researchers around the world discuss and study the ability to build thing from bottom up technique, working at the atom level up to the molecule level using technique and tools to make complete, highly advanced product. This technology is called nanotechnology, as it is dealing with the material at nanoscale level and it has significant impact on almost all industries and all areas of society. It offers better built, longer lasting, safer and smart products for home, communication, medicine, transportation and industry in general. Our country, Malaysia is also concerned with nanotechnology. According to BERNAMA , 19 September 2006, Malaysia will upgrade the existing six nanotechnology center to woo the best scientists locally and from abroad. Our Deputy Prime Ministry Datuk Seri Najib Tun Razak said that under the National Nanotechnology Initiative (center that involved in nanotechnology research and development focus on introducing nanotech in all spheres of economic development), these center will be upgraded to become center of excellence that will attract not only the best talent from within Malaysian but also scientist outside Malaysia. Nanoscience and nanotechnology have tremendous potential to enable the generation of new technologies and products across a vast array of field including health care, information technology, energy production, even in national defense. The impact of nanotechnology on our way of life is believed to reach profound level in the coming decade. In line with government vision, the research on the chemistry of the new nanocomposite (some part of nanoscience and nanotechnology) was carried out. Nanocomposite. Nanocomposite is related with composite. As we know, engineered materials that consist of two or more materials to form the final material is a composite. They are normally engineered to

possess physical and chemical properties of the original materials and most of time bettering them. Generally, a composite consist of matrix and reinforcement. The matrix material surrounds and provides supports for the reinforcement material by maintaining their relative position. The reinforcement then impart special physical (mechanical and electrical properties to enhance the matrix original properties. Most common composites are supported by polymer as the matrix while fillers are the reinforcements materials. The fillers are normally selected according to their properties which are selected based on what is needed from the composite. Function and role of nanocomposite is same as composite but the different is about their size. Nanocomposite is very small compare to composite. According to Mark, 1996, nanocomposite is a new class of the material which is a composite made of an organic polymer and dispersed inorganic filler whose particles have one or more dimension in the nanometer scale. There are three type of nanoscale filler that can be used in formation of nanocomposite. Particle with three dimension in the order of nanometers that are isodimensional nanoparticles such as spherical silica nanoparticles obtained by in-situ sol-gel method or by polymerization promoted directly from their surface. Common example particle with three dimension is graphite. Secondly, particle with two dimension in the nanometer scale and the third are longer forming an elongated structure that are nanotubes for example carbon nanotubes. Third type of nanoparticle are characterized by only one dimension in the nanometer scale where the filler is present in the form of sheets with thickness of one to a few nanometer and length such as sheets of graphene. Last type of nanoparticle is 0 dimention such as buckyballs.

Graphene: Building block of the various form of Carbon Allotropes.(top) Graphene, (bottom from left to right) Graphite, Nanotube and Fullerenes(adapted from Scientific American (2008).

OBJECTIVES. The principal objective of this study is to prepare polylactic acid/graphene nanoplatlet nanocomposite, PLA/GNP nanocomposite and characterized it. Hence the research was undertaken with the following specific objectives : i. ii. Preparation of PLA/GNP nanocomposite by using melt blending techniques. To characterize the prepared nanocomposites by Fourier Transform Infrared Spectroscopy (FTIR), X-Ray diffraction analysis (XRD), Thermogravimetry analysis (TGA), Scanning Electron Microscopy (SEM) and Tensile measurement involving tensile strength, tensile modulus and elongation of break.

Instrument analysis. Fourier Transform Infrared Spectroscopy (FTIR) Atoms or atomic groups in molecules are in continuous motion with respect to each other. These motion are twisting, bending, rotating and vibrational motion of atoms in a molecule. Upon interaction with infrared radiation, portions of the incident radiation are absorbed at particular wavelength. These absorbed wavelength are measured which are specific for particular atom present in a molecule. The multiplicity of vibration occurring simultaneously produces a highly complex absorption spectrum, which is uniquely characteristic of the functional groups of the molecule. X-Ray diffraction analysis (XRD), To identify and characterize solid, X-ray diffraction has conducted. The nature of bonding and the working criteria for distinguishing between short-range and long-range order of crystalline arrangements from the amorphous substances are largely derived from X-ray diffraction and thus it remains as a useful tool to obtain structural information. X-ray diffraction pattern of amorphous polymer will not show any sharp and highly intensed peaks whereas the nanocomposites of amorphous polymer show sharp and highly intensed peaks. This is due to the development of crystallinity in the amorphous polymer. Highly intensed peaks occur in the pattern due to the presence of inserted gamma iron oxide materials in the rubber matrix. X-ray diffraction has been most commonly used for routine characterization as well as for detailed structural elucidation. In order to obtain detailed structural information, knowledge of X-ray diffraction intensities is also essential, the intensities being related to the structure factor. If you want to calculate cell parameter, application of Baggys law must used in this XRD analysis. Baggys law describes the angular position of diffracted beam in terms of distance between lattice dhkl and wavelength, n = 2dhkl sin equation1

where is the diffraction angle. By combining the Baggy equation with expression for d-spacing for cubic system, equation 1 become 1 d2hkl
=

h2 + k2 + l2 a2

equation 2

where a is cell parameter, and when n = 1, equation 2 become

sin2 =

2 4a2

h2 + k2 + l2

equation 3

by solving equation 3 for with data from XRD analysis, cell parameter can be calculated where is the Baggys diffraction angle and is the wavelength of X-ray.

Thermogravimetry analysis (TGA) TGA is an analytical technique used to determine a materials thermal stability and its fraction of volatile component by monitoring the weight change that occurs as a specimen is heated. So by thermal analysis we can measurement of physical and chemical properties of materials as a function of temperature. Scanning Electron Microscopy (SEM). SEM is one of the most widely used instruments in materials research laboratories SEM is central to microstructure analysis and therefore important to any investigation relating to the processing, properties and behavior of materials that involve their microstructure. Microstructure analysis in this work was carry out to study the surface morphology and also to identify the particles size of the samples prepared. Tensile Measurement. Tensile measurement were studies using Instron Mechanical tester. The tensile measurement were determine using average of 5 from 7 samples (ignored maximum and minimum value). Tensile strength, tensile modulus or young modulus and elongation of break properties were obtained from the tensile test. Tensile strength, = F 9.81(m/s2)A(m2) where F = load, A = cross sectional area. According to Shah, 1984 the tensile modulus is a measure of stiffness of a material in the initial deformation stage of a sample undergoing tensile test and can be determined from a stress-strain diagram (slope of diagram) The elongation of break (Eb) is the strain on a sample when it breaks. This usually expressed as a percentage . ) 100 Eb = ( Where is change of length, is original length

LITERATURE RIVIEW. This chapter will explain all the related fields and knowledge regarding to the completion of the thesis. This chapter able to help us to understand the project better. Graphene. Graphene is the basic structural unit of some carbon allotropes, including graphite, carbon nanotubes and fullerenes. It is a monolayer of sp2-hybridized carbon atoms arranged in a twodimensional lattice, has attracted tremendous attention in recent years owing to its exceptional thermal, mechanical, and electrical properties. One of the most promising applications of this material is in polymer nanocomposites, polymer matrix composites which incorporate nanoscale filler materials. Graphene has a rich history which spans over forty years of experimental work Pristine graphene (a single, purely sp2-hybridized carbon layer free of heteroatomic defects) has been produced by several routes including growth by chemical vapor deposition (both of discrete monolayers onto a substrate and agglomerated powders), micro-mechanical exfoliation of graphite, and growth on crystalline silicon carbide. While these approaches can yield a largely defect-free material with exceptional physical properties, current techniques of making powdered samples of graphene do not yield large enough quantities for use as composite filler. Table below show physical properties of graphene nanoplatelets. Physical Properties Diameter Thickness Specific Area 40-60 m2/g Surface Density ~2.25 g/cm3 Electrical Conductivity 8000-10000 S/m Tensile Strength 5 GPa

0.5 - 20 5 - 25 nm m

The applications of graphene nanoplatelets, GNP is as high performance composite additives in PPO, POM, PPS, PC, ABS, PP, PE, PS, Nylon and rubbers. Beside that GNP can improve composite tensile strength, stiffness, corrosion resistance, abrasion resistance and antistatic and lubricant properties.GNP also as mechanical properties modifications, conductivity modification and fuel tank coating.In sporting goods, graphite-based composites are stronger and stiffer and lighter than comparable materials. GNP can be dispersed in a wide variety of materials to add electrical conductivity and surface durability in coatings and paints Graphene as a nanofiller in polymer matrixes may be preferred over other conventional nanofillers (Na-MMT, LDH, CNT, CNF, EG, etc.) owing to its high surface area, aspect ratio, TS, thermal conductivity and electrical conductivity. For these reasons, graphene is considered the best carbon nanofiller among the traditional fillers available. Graphene/graphite-based polymer nanocomposites. In recent years, a variety of processing routes have been reported for dispersing both GNP into polymer matrices. Many of these procedures are similar to those used for other nanocomposite systems, although some of these techniques have been applied uniquely to

graphene-based composites. For example according to Kuilla T and his friends (prepare Epoxy/graphene nanocomposites) Graphene sheet-incorporated epoxy composites were prepared and the level of thermal expansion was examined using a thermo-mechanical analyzer. The epoxy resin showed very poor thermal conductivity but the inclusion of graphene sheets resulted in significant improvements. The addition of 1 wt.% Graphene to the epoxy resins had a similar effect on improving the thermal conductivity to that of filling with 1 wt.% of SWNT. A 5 wt.% Graphene-filled epoxy resin showed a thermal conductivity of ~1W/mK, which is 4 times higher than that of the neat epoxy resin. Zhang K, Zhang LL, Zhao XS, Wu J reported that polyaniline, PANI/graphene oxide composites with different mass ratios were reduced to a graphene composite by hydrazine monohydrate followed by reoxidation and reprotonation of the reduced PANI to give the PANI/graphene nanocomposites. By using in situ polymerization in situ polymerization PANI/graphene nanocomposites was prepared by aniline monomer in the presence of graphene oxide under acidic conditions. TGA analysis showed that the pure graphene lost only 23% weight in the temperature range of 100600 C, indicating that most of the oxygen containing groups of graphene had been removed during the chemical reduction process. At the same time, the PANI and the PANI/graphene composite samples showed 40% and 25% mass loss, respectively, over the same temperature range. Beside that, tris(2,2bipyridyl) ruthenium (II) (Ru(bpy)32+)/ nafion/graphene modified electrodes were prepared by the solution mixing of graphene and nafion. This research was carried by Li H, Chen J, Han S, Niu W, Liu X, Xu G. The resulting electrode was immersed in a 1M Ru(bpy)32+solution for 30 min to obtain a Ru(bpy) 32+ modified electrode. CV of the nafion/graphene modified electrode suggested that the conducting graphene facilitates electron transfer. From this research they get the presence of TPA causes an increase in the anodic peak current, indicating that the Ru(bpy)32+)/nafion/graphene composite film electrochemically catalyzes the oxidation of TPA. The modified electrode was also used to detect the presence of oxalate ion in urine, and showed good sensitivity, selectivity and stability. Another research that use graphene as composite was done by Xu Y, Wang Y, Jiajie L, Huang Y,MaY,WanX, et al. In this research, they prepared poly(3,4-ethyldioxythiophene) (PEDOT)/sulfonatedgraphene composite by in situ polymerization. From this research, the novel hybrid material showed excellent transparency, electrical conductivity and good flexibility, as well as high thermal stability, and was easily processed in both aqueous and organic solvents. PEDOT/graphene films with a thickness of 33, 58, 76 and 103 nm had an optical transmittance of 96%, 76%, 51% and 36%, respectively, at a wavelength of 550 nm. The conductivity of the composite films deposited on quartz and PMMA substrates was 7 and 10.8 Sm1, respectively, and was independent of the film thickness. The material was robust, flexible and retained its original conductivity after deformation. It has been suggested that these composites are suitable for many applications of transparent conducting materials. The potential applications of PEDOT/graphene composites are quite promising because of its improved thermal stability. The composite materials showed very little mass loss below 297 C, and ~19% mass loss below 325C. The conclusion is in addition, the PEDOT/graphene composite was thermally more stable than that of the PEDOT/PSS composites. From the studies have been conducted that make graphene/graphite-based polymer nanocomposites, the mechanical properties can be summarized in table below

** Data from Tapas Kuilla, Sambhu Bhadra, Dahu Yao, Nam Hoon Kim, Saswata Bose, Joong Hee Lee There are three preparation method of polymer/graphene nanocomposite. First is In situ intercalation polymerization. In situ intercalation polymerization method, graphene or modified graphene is first swollen within the liquid monomer. A suitable initiator is then diffused and polymerization is initiated either by heat or radiation [Zheng W, Lu X, Wong]. A variety of polymer nanocomposites have been prepared using this method, such as polystyrene (PS)/graphene [Ye L, Meng XY, Ji X, Li ZM, Tang JH. and Zheng W, Lu X, Wong], poly(methyl methacrylate) (PMMA)/EG [Chen G, Wu D, Weng W, Wu C.], polystyrene sulfonate (PSS)/LDH [Kornmann, X], etc. Second method is solution intercalation. According to Stankovich S, Dikin DA, Dommett GHB, Kohlhaas KM, Zimney EJ, Stach EA, et al. this method is based on a solvent system in which the polymer or pre-polymer is solublized and graphene or modified graphene layers are

allowed to swell. Graphene or modified graphene can be dispersed easily in a suitable solvent, such as water, acetone, chloroform, tetrahydrofuran (THF), dimethyl formamide (DMF) or toluene, owing to the weak forces that stack the layers together. The polymer then adsorbs onto the delaminated sheets and when the solvent is evaporated, the sheets reassemble, sandwiching the polymer to form the nanocomposites. This strategy can be employed to synthesize epoxybased nanocomposites but solvent removal is a critical issue. The driving force for polymer intercalation from solution is the entropy gained by the desorption of solvent molecules, which compensates for the decrease in conformational entropy of the intercalated polymer chains. Therefore, a relatively large number of solvent molecules need to be desorbed from the filler to accommodate the incoming polymer chains. The main advantage of this method is that it allows the synthesis of intercalated nanocomposites based on polymers with low or even no polarity. Polymer nanocomposites based on polyethylenegrafted maleic anhydride (PE-g-MA)/graphite [Hussain F, Hojjati M, Okamoto M, Gorga RE.], epoxy/LDH [Shen JW, Huang WY, Zuo SW, Hou J.and , Hsueh HB, Chen CY.], poly(vinyl alcohol) (PVA)/graphene [Liang J, Huang Y, Zhang L, Wang Y, Ma Y, Guo T, et al.], etc., have been prepared using this method. Melt intercalation or melt blending is last method in preparation polymer/graphene nanocomposite This method was introduced by Vaia, et al.by using polystyrene (PS) aspolymer matrix. In the melt intercalation technique, no solvent is required and graphite or graphene or modified graphene is mixed with the polymer matrix in the molten state. [Kim SK, Kim NH, Lee JH.] reported a thermoplastic polymer is mixed mechanically with graphite or graphene or modified graphene at elevated temperatures using conventional methods, such as extrusion and injection molding. The polymer chains are then intercalated or exfoliated to form nanocomposites. This is a popular method for preparing thermoplastic nanocomposites. Polymers, which are unsuitable for adsorption or in situ polymerization, can be processed using this technique. A wide range of polymer nanocomposites, such as PP/EG [Kalaitzidou K, Fukushima H, Drzal LT], HDPE/EG [Kim S, Do I, Drzal LT.], PPS/EG [Chen G, Wu C, Weng W, Wu D, Yan W.] PA6/EG [Weng W, Chen G, Wu D.], etc., have been prepared using this method. Among this three methods used for preparation of polymer/graphene nanocomposite, the melt intercalation or melt blending technique has been the most attractive one compared to the In situ intercalation polymerization and solution intercalation. [Fornes] This because melt blending is more efficient, environmental friendly and economical favorable method for industry from a waste perspective due to the absence of organic solvent. [Fornes]

MOHD FENDI B AHMAT NAZRI

PREPARATION AND CHARACTERIZATION OF PLA/GNP NANOCOMPOSITES Introduction Objective Literature review Methodology To : Mr Chieng BASL 101