Biodegradable polymer/graphene oxide composite films

Ashutosh Kumar Department of Mechanical Engineering

Indian Institute of Technology, Patna India

Supervised by Prof. Debes Bhattacharyya Dr.Dongyan Liu

Centre of Advanced Composite Materials(CACM)

University of Auckland, New Zealand 2012

1

Abstract
In the current age of growing environmental awareness and energy crisis situation, biodegradable composites have gained wide acceptance in various facets of engineering. Poly(lactic acid) (PLA) has several applications in various areas such as in woven and non-woven fabrics, paper coatings, food and medicine packaging, and biomedicine (sutures, scaffolds and implants). This aliphatic polyester is prepared from lactic acid (therefore derived from 100% renewable sources, e.g. corn or sugarcane), and is biodegradable and biocompatible. In order to make this material more attractive for some applications, as a strong alternative to petrochemical plastics, some properties should be improved, namely mechanical properties and gas barrier properties. Graphene due its remarkable properties is centre of attraction for most of the researchers these days. Our objective is to use graphene in composite as reinforcement, a single atomic layer of carbon whose existence had been known for a long time but which was produced and identified only as recently as 2004. Andre K. Geim and Konstantin S. Novoselov of the University of Manchester, UK, were awarded the 2010 Nobel Prize in Physics for their ability to isolate this single sheet of carbon atoms. The present work is to manufacture biodegradable polymer (PLA)/Graphene oxide(GO) composites by twin extrusion and compression moulding methods and characterize their mechanical and gas barrier properties. Five types of PLA/GO films of different compositions were prepared and used in this study. Theoretical modelling of gas barrier properties is done to compare the experimental results with the prediction by various models proposed by scientists. Effects of introducing the GO flakes into the matrix have been tried to understand.

Acknowledgement
I sincerely thank The Faculty of Engineering and CACM, The University of Auckland, for providing me with this wonderful opportunity to work on a project that was exciting and enthralling. I thank Prof. Anil K. Bhowmik, my reverend Director, for giving me this opportunity to visit New Zealand and work on a wonderful project. This project has only been possible because of special contribution and great assistance of many people. Prof. Debes Bhattacharyya, your dedication, guidance and feedback, not to forget your extensive manufacturing and composites knowledge, have been invaluable in assisting me throughout my project under your supervision. Its a pleasure to thank Dr. Dongyan Liu for her constant inspiration and valuable inputs in manufacturing and experiments which helped to develop my knowledge base in experimental research and made it possible to complete my work well within time. Without her this never would have been possible.

I am grateful to all the technicians for their kind attention and help. Jos, for
patiently explaining the safety measures vital for working in the lab and helping me out in doing the tensile test of films . Steve for providing essential equipments required at all the stages of manufacturing. Jimmy, Shane and Callum, for their practical inputs and assistance in various stages of manufacturing and processing. My sincere appreciations to my colleagues Kalyan and Vijay for all their support to make this project possible. Last but not the least, I thank my parents and my little sister for their love and support, and for standing by me at all times.

Contents
Abstract.2 Chapter 1 Introduction.5 1.1 Composites.....5 1.2 Film Composites and its applications....5 1.3 Manufacturing techniques and instruments used6 1.3.1 Twin Extruder6 1.3.2 Compression moulding....7 1.3.3 Scanning Electron Microscope..7 1.3.4 Differential Scanning Calorimetry..8 1.3.5 Optical Microscope9 1.4 Permeability10 1.4.1 Factors affecting permeability.13 1.4.2 Applications of permeability to industry..14 1.4.3 Theoretical Modelling of Gas Barrier Properties.14 Chapter 2 Materials19 2.1 PLA............19 2.2 Graphene Oxide..20 Chapter 3 Manufacturing Procedures and its Description...21 3.1 Preparation of Graphene Oxide Film..21 3.2 Preparation of Composite Films.24 Chapter 4 Testing Methods...28 4.1 SEM of Fracture Surface of Films..28 4.2 Films under Optical Microscope....31 4.3 Tensile test...32 4.4 DSC of the films....35 4.5 Permeability test and Theoretical Model....36 Chapter 5 5.1 Results and Discussions45 References..48 Appendices.......50

Chapter 1: Introduction
1.1 Composites
A composite is a material which is a mixture of two or more distinct materials where each material has different physical and chemical properties. Moreover, a composite usually possesses properties superior to its constituents. It consists of a matrix(dispersion phase) and a reinforcement(dispersed phase).Matrix and reinforcement offer different properties. Matrix Transfers load to the reinforcement Holds the dispersed phase Provides chemical and temperature resistance Reinforcement Provides strength and stiffness Impact resistance Enhances gas barrier properties

1.2 Film Composites and its applications

A thin film is a layer of material ranging from fractions of a nanometer (monolayer) to several micrometers in thickness. Films have been used in industry for manifold purposes be it packaging industry, microelectronic integrated circuits, magnetic information storage systems, optical coatings or wear resistant coatings. However, the mechanical performance of these materials tends to depend on fabrication and post-processing parameters. With the purpose of improving the mechanical and gas barrier properties of films a relatively novel idea of mixing GO in PLA matrix is used in this research project. PLA/GO composites can be prepared by melt-blending, solvent-casting or in situ polymerization. In this work twin-extrusion and compression moulding are used to obtain thin films and characterise them.

1.3 Manufacturing techniques and instruments used

1.3.1 Twin Extruder
In the twin extruder, raw material in the form of small beads is gravity fed from a top mounted hopper into the barrel of the extruder [11]. The material enters through the feed throat and comes into contact with the screw. The rotating screw pushes the beads forward into the barrel which is heated to the desired melting temperature of the polymer fed. A heating profile is set for the barrel in which three or more independent PID controlled heater zones gradually increase the temperature of the barrel from the rear. Extra heat is contributed by the intense pressure and friction taking place inside the barrel. At the front of the barrel, the molten plastic leaves the screw and travels through a screen pack to remove any contaminants in the melt. The screens are reinforced by a breaker plate (a thick metal puck with many holes drilled through it). After passing through the breaker plate molten plastic enters the die. The die is what gives the final product its profile and must be designed so that the molten plastic evenly flows from a cylindrical profile, to the product's profile shape. Long continuous strands of polymer are obtained from the extruder that was used. Twin screw extruders are usually run starve fed. There is an independent control of both the feed rate and the screw speed.

Fig.1.1- Twin extruder, CACM, University of Auckland.

1.3.2 Compression moulding

It is a manufacturing technique in which the desired object moulds are compressed under high pressure and temperature. The moulds are inserted between the two metallic plates which are connected to hydraulic pumps to apply pressure. The advantage of compression moulding is its ability to mould large, fairly intricate parts. Also, it is one of the lowest cost moulding methods compared to other methods such as transfer moulding and injection moulding; moreover it wastes relatively less material, giving it an advantage when working with expensive compounds. However, compression moulding often provides poor product consistency and difficulty in controlling flashing, and it is not suitable for some types of parts. Fig.1.3 shows hydraulic press for compression moulding.

Fig.1.2- Hydraulic Press (for compression moulding), CACM , University of Auckland

1.3.3 Scanning Electron Microscope

SEM is a type of microscope which enables us to observe morphology of materials at micro and nano-level. In this microscope an electron beam is emitted over the desired region and the sample response is sensed that reflects its topography. The response is due the conductivity of the sample being observed. The signals produced by SEM contain data about its composition, topography and other properties. Wide range of magnification is possible i.e. from 10 to 500,000. Its magnification doesnt depend on the power of the objective lenses.
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The process involves various steps. First thermionic emission of Electron beam from the electron gun, fitted with a tungsten filament, takes place. Then the beam passes through various lenses to converge it in the range of nano meters. Finally, electron beam interacts with the specimen and exchange of energy takes place between the specimen and the beam. This energy exchange results into emission of secondary electrons and electromagnetic radiation which is detected by respective detectors .The signals received are amplified and sent to the monitor to display the topography of the sample.

Fig.1.4- Scanning Electron Microscope (SEM)-courtesy: RCSMS, University of Auckland

1.3.4 Differential Scanning Calorimetry

Differential Scanning Calorimetry (DSC) measures the temperatures and heat flows associated with transitions in materials as a function of time and temperature in a controlled atmosphere. Heat flow is measured with reference to another reference material whose heat capacity within the test temperature range is well known. The specimen and the reference are kept nearly at the same temperature throughout the experiment. DSC experiment gives us a curve of heat flux versus time or temperature. This curve can be used to calculate enthalpies of transitions [10]. This is done by integrating the peak corresponding to a given transition. DSC is widely used to find the following results:
8

Glass Transitions Melting and Boiling Points Crystallization time and temperature Percent Crystallinity Heats of Fusion and Reactions Specific Heat Oxidative/Thermal Stability Rate and Degree of Cure Reaction Kinetics Purity

Fig.1.5- Differential scanning Calorimetry setup, courtesy: CACM University of Auckland

1.3.5 Optical Microscope

Optical microscope is an instrument that uses visible light and a system of lenses to magnify images of small samples. All modern optical microscopes designed for viewing samples by transmitted light share the same basic components of the light path, listed here in the order the light travels through them:

In addition the vast majority of microscopes have the same 'structural' components:

Ocular lens (eyepiece) Objective turret or Revolver or Revolving nose piece (to hold multiple objective lenses)
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Objective Focus wheel to move the stage ( coarse adjustment, fine adjustment) Frame Light source Diaphragm and condenser lens Stage (to hold the sample)

Fig.1.6- Optical Microscope , Plastic Centre, University of Auckland

1.4 Permeability
To quantify and characterize the barrier properties of a polymer film or membrane, the most frequently measured and reported quantity is the permeability P. Permeability P is a measure of the amount of gas that passes through a film of thickness l and area A within a finite amount of time t. =
()()( ) ( )( )

(1-1)

Permeability or transmission rate is dependent upon two factors: the solubility of a gas or vapour and the rate of diffusion through the barrier. In order for
10

permeation to occur, these two mechanisms one thermodynamic (solubility) and the other kinetic (diffusion) must both occur. =

(1-2)

where, D and S represent the diffusion and solubility coefficient respectively and P is the permeability. Diffusion through a polymer occurs by small molecules passing through voids and other gaps between the polymer molecules (free volume) [48]. If the speed at which a molecule diffuses through a polymer obeys Ficks first and second laws, as is the case for oxygen permeating through an MFC under standard conditions, it is termed Fickian diffusion[7,8,9]: Ficks first law: =

(1-3)

where J is the steady-state flux per unit area, D is the diffusion coefficient and C the gas concentration. It is well known that Ficks first law is also analogous to Darcys law, which can be used to predict the permeability of a homogeneous system to gases or liquids.

(1-4)

Solubility is determined by the enthalpy change on dissolution of the molecule in the polymer matrix and the volume available for occupation. The solubility is in particular influenced by the state of the polymer; if it is in the rubbery state then most common gases in polymers follow Henrys law behaviour. However in glassy polymers, Henrys law is observed for the more noncondensable gases (O2, helium, H2, N2, argon) while condensable gases such as CO2 more accurately follow the dual-sorption model [7].

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Four stages are involved in the permeation of a gas through a film or polymer matrix ,and they are [50]: 1. Absorption into the surface of the polymer 2. Solution of the gas or vapour into the polymer matrix 3. Diffusion through the wall along a concentration gradient 4. Desorption from the other surface There are no universally accepted units for gas transmission through polymer films or sheets; however a few common terminologies are defined in the ASTM Standard D3985-05 [51] to report permeability.

Oxygen transmission rate (OTR) is the quantity of oxygen gas passing through a unit area of the parallel surfaces of a plastic film per unit time under the conditions of test. The SI unit for OTR is mol/m2 s, however it is usually recorded as cm3. (STP)/m2 day [12, 15]. Oxygen permeance (PO2) takes into account the pressure difference between the two sides of the film as shown in Equation (2-4) . The SI units of Permeance are mol/(m2 .s.Pa). PO2 =

(1-5)

Permeance does not take into account the thickness of the material and hence is only useful when comparing specimens of similar thickness. Oxygen permeability coefficient (P) is the product of permeance and thickness. P = PO2 x t (1-6)

While the SI unit is mol/m2s Pa, authors in literature usually report permeability as cm3 (STP).mm/m2 day.atm which is the same as saying a cubic
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centimeters of gas that passes through a square meter of film in a day when the gas pressure differential on one side of the film, at a specified temperate, is one atmosphere greater than that on the other side[13,14].

1.4.1Factors influencing permeability

There are a number of factors which influence diffusion and solubility and hence permeability. These include: 1. Crystallinity 2. Filler particle 3. Molecular orientation 4. Temperature 5. Pressure 6. Humidity Crystallinity affects permeability as the chains are highly ordered in crystalline regions compared to amorphous regions and hence there should be very little free volume and the path should be extremely tortuous. The amount of free volume depends on density and polymer characteristics. In crystalline regions this provides less free volume while amorphous regions will depend upon the direction of the penetrant [20].

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Filler material also affects the diffusion behaviour because if the particle is impenetrable as it creates a more tortuous path for the diffusing molecule. The reason for this is for every 5C increase in temperature, a 30 to 50% rise in permeability occurs. From the mass transport equation, the flow of a gas and partial pressure difference is affected by temperature changes. At the molecular level, increasing temperature leads to a rise in the mobility of the molecular chains and thermal expansion leads to a reduction in density. This results in more free volume and thus higher solubility since free volume is directly proportional to free volume [19].

1.4.2Applications of permeability to industry

Gas barrier properties are most important to the packaging industries. One of the requirements of the packaging material is to prevent passage of gases like oxygen to prevent degradation of stored material. There is also water and other gases such as carbon dioxide and nitrogen which are important factors to consider in packaging materials. Preventing oxygen from entering a package is an important requirement for most food products. If oxygen is allowed in the package, this will break down organic materials initiating or accelerating the decay process which is the mechanism for staleness and loss of nutritive value. On the other hand, to maintain the bright red colour in meat, a high rate of oxygen transmission is required while a low water transmission rate is required to prevent drying the meat .Oxygen permeability plays an important role in maintaining the quality of milk. High oxygen permeability of package will accelerate the oxidation reaction of inside milk and in turn causes quality deterioration.

Factors under consideration during modelling would include the dispersed phases aspect ratio, orientation, dispersion, shape and volume fraction, as well as the density and crystallinity of the matrix and the affinity between the constituent polymers and diffusing species [16, 17, 18] .

1.4.3 Theoretical modelling of Gas Barrier Properties

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The majority of models found in literature only take into account a couple of the variables mentioned above.

Nielsens model for filled polymer systems

Nielsens model is based on the tortuosity factor where the filler particles are impenetrable to a diffusing gas or liquid molecule, resulting in the diffusing molecules following a tortuous path through the polymer. The relation is as follows:

where, P and Pm are the permeability of the composite and pure polymer, is the volume fraction of the matrix polymer and is the tortuosity factor which is the ratio of the distance a molecule must travel to get through the film to the shortest route. If the filler particles are circular or rectangular the tortuosity factor is represented by the following: where, L the length of the filler, W is the filler thickness and is the volume fraction of the filler or reinforcement. This model represents the ideal case where the particles are completely exfoliated and uniformly dispersed along the preferred orientation in the polymer matrix. = 1 + (
2

(1-7)

(1-8)

Series and parallel model

The series and parallel models represent the upper and lower bounds for permeability modelling. The upper bound is represented by the parallel model where the reinforcing phase is orientated parallel to the direction of permeation. The series model is the lower bound case where the reinforcing phase is orientated across the direction of permeation [25]. Parallel model: = +

(1-9)

15

Series model:

where, P is the permeability, is the volume fraction and the subscripts m and f denote the matrix and reinforcing polymers.

(1-10)

Geometric Mean Model

If one assumes a random distribution of phases, the film permeability can be estimated using the weighted geometric mean of the polymer permeabilities via a model known as the Geometric Mean Model[26]: = +

(1-11)

Generalised Maxwell-Rayleigh relationship

There also exists the Rayleigh relation for cylinders. This differs from Maxwells equation[26] (also known as Maxwells relation for spheres) only by the value of the shape factor defined in the following generalised equation as f, which is equal to 1 for Rayleighs relation and 2 for Maxwells relation.

where, f is the shape factor in this equation. When f approaches infinity Equation (1-11) reduces down to the parallel model (1-9). For f = 0 the equation becomes the Series model (1-10). When f = 2, the equation represents Maxwells equation for spheres. Lastly if f = 1, we get Rayleighs relation [66] for long transverse cylinders.

= 1 +

( +) ( 1)

(1+) ( 1)

(1-12)

Lewis and Nielsen equation for two-phase systems

A theoretical model developed by Nielsen [24, 26] to predict the elastic modulus of two phase systems has also been applied by others to the prediction of electrical and thermal conductivity. Likewise, permeability can be predicted from component values using this model:
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where A = ke - 1, where ke is the Einstein coefficient and is equal to 1.5 for fibres and 2.5 for spheres. Also: =

1 +

1+

(1-13)

(1-14)

where represents the maximum fibre packing fraction. This value is 0.785 for square packing, 0.82 for random packing and 0.907 for hexagonal packing.

= 1 +

1 2

(1-15)

Bttcher formula
Bttcher gave a formula that was originally applicable for random dispersion of spherical particles which was later modified to a more general form that could be applied to ellipsoidal shaped particles. This equation is [21]:
+( ) ( )

where A is related to the shape of the reinforcement, A=1/3 for spheres and A=0.5 for rods.

+( )

( )

=0

(1-16)

17

Bruggeman formula
The differential effective medium (DEM) theory was introduced by Bruggeman to estimate the effective thermal conductivity of composites at high volume fractions [27]. Bruggeman formula for spherical particles is given by:

The permeability for random-oriented laminated flat particles is:

13

+2 +2

= 1

= (1 ) 1

(1-17)

(1-18)

Higuchi Model
Higuchi demonstrated when particle-particle interactions were neglected, the model led to the well known Rayleigh-Clausius-Mosotti equation (labelled Maxwell equation in this report). In another paper by Higuchi et al. [23] the same principles from an earlier paper were used to derive a model to predict the permeability of two-phase mixtures. His model is represented by: = 1 + [1
2 (1 ) ]

The quantity K involves the distribution function for random spheres and is a function of the volume fraction of the reinforced polymer. Higuchi found K = 0.78 provided a good fit between the experimental data and the predicted model. When K = 0, this model reduces down to the Maxwell equation for random spheres. is a measure of the permeability difference between the two phases and is given by:

(1-19)

+2

(1-20)

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Chapter 2: Materials

2.1 PLA(Poly-lactic Acid)

PLA [22] stands for poly-lactic acid and is a thermoplastic aliphatic polyester derived from renewable resources, such as corn starch, tapioca products (roots, chips or starch) or sugarcanes. It can biodegraded under certain conditions, such as the presence of oxygen, and is difficult to recycle.Bacterial fermentation is used to produce lactic acid from corn starch or cane sugr.

PLA polymer 2002D[28] , that we are using , is a clear sheet grade and processeseasily on conventional extrusion and thermoforming equipment.Its specific gravity is 1.24.Its glass transition temperature is in between 60-65 C .Its melting temperature is 210 C. Its tensile yield strength at 60MPa.PLA is PLA is used to make clear compostable containers and PLA lining is used in cups and containers as an impermeable liner. PLA is biodegradable, and fully compostable. It uses 65 percent less energy to produce than conventional oilbased plastics and generates 68 percent fewer greenhouse gasses and contains no toxins.

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Fig. 2.1- PLA Pellets, CACM, University of Auckland

2.2 Graphene Oxide (GO)

Graphene oxide is oxidised form of Graphene , the two dimensional sheet of sp2 hybridised carbon atoms which has evolved as a material with remarkable mechanical, electrical and thermal properties. Heaps of research has been carried out and still being carried out to derive various applications of graphene and its derivatives in the field of nano electronic devices, composite materials and gas sensors,biomedical applications and energy storage devices. Graphene oxide sheets have been used to prepare a strong paper-like material. Graphene oxide is prepared by oxidation with strong oxidizers. It typically preserves the layer structure of the parent graphite, but the layers are buckled and the interlayer spacing is about two times larger (~0.7 nm) than that of graphite. Besides oxygen, epoxide groups (bridging oxygen atoms), other functional groups experimentally found are: carbonyl (=CO), hydroxyl (-OH), phenol groups [2,3,4] attached to both sides.

20

Fig.2.2 Graphene Oxide structure

Highly oxidized Graphene oxide is insulating where as graphene is exceptionally conducting this is mainly due to the extensive presence sp3 carbon atoms of oxygen (highly electronegative) containing functional groups which do not allow free movement of electrons.[29]It is almost a semiconductor, with differential conductivity between 1 and 510-2 S/cm at a bias voltage of 10 V.[31]Its conductivity can be varied by varying the level of oxidation, temperature and other environmental factors.[30] Graphene oxide sheets have tensile modulus of 32 GPa [32] whereas of graphene its 130GPa.[33]Its spring constant is also very high. Such chemically and structurally tuned graphene sheets hold significant promise for novel sensors, membrane based NEMS devices, transparent conductors for optoelectronic applications, smart composite materials, and others.

Chapter 3: Manufacturing Procedures and its Description 3.1 Preparation of Graphene Oxide film Modified Hummers Method Procedure:
1. First of all, 2g. of powdered Graphite and 1.5g. of sodium nitrate are taken and poured into a flask containing H2SO4(concentrated 66%). 2. Then, the mixture is stirred for 30min.at 600 rpm using magnetic stirrer. 3. Then the flask is transferred to an icebath which had been cooled down to 0o C.
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4. 6 g. of KMnO4 is slowly added to the flask at room temparatue. 5. Then, the flask is transferred to a water bath to maintain a temperature of 35 3o C for 60 min. 6. Then the suspension is diluted with 100 ml. of water very slowly causing violent effervescence and increase in temperature. 7. The temperature is maintained at 80oC in hot waterbath for 15 min. 8. The solution is again diluted to 300ml. with warm water 9. Followed by, addition of 10 ml. of H2O2(30%) which results in the colour change of the suspension to yellow. 10.Then, 200 ml. of HCl (20%) is added to the suspension. 11.The suspension is left overnight.

Fig.3.1-GO suspension, Chemistry Lab. , CACM, University of Auckland.

12.Filtration and of the suspension is done till the pH of the suspension turns neutral.

Fig.3.2 Filtration by suction

13.After filtration centrifugation of the GO is done.

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Fig.3.3-Centrifugation at Chemistry Lab., University of Auckland, Tamaki Campus.

14.Then, ultrasonification of GO particles is done to break them into finer particles.

Fig.3.4 Ultrasonification at Chemisty Lab. ,University of Auckland, Tamaki Campus.

Fig.3.5 Ultrasonifier

15.The Graphitic oxide is heated in the oven for drying.

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Fig. 3.6 Oven Dryer @ Chemistry Lab.,University of Auckland, Tamaki Campus.

16.The film that we get is as shown below.

Fig.3.7 GO film

3.2Preparation of Composite Films

Five different types of films have been prepared. 1. 2. 3. 4. 5. Pure PLA PLA + 0.5 % GO (Master Batch) PLA + 1% GO (Master Batch) PLA + 0.5 % GO (Non-master Batch) PLA + 1% GO (Non-master Batch)

24

Preparation of Master Batch Master Batch is prepared by mixing 0.5 g. and 1 g. of GO and 19.5 g. and 19 g. of PLA respectively in solvents DMF+THF in the ratio 1:1 . GO and PLA are dispersed in the solvent and they are dried in an oven under vacuum conditions. We get solid stuff as show in the figure.

Fig.3.8 Master Batch

Procedure :
1. First PLA pellets are ground into smaller granules (<5 mm) using granuliser.

2. GO and Master Batch (PLA + GO) is also ground into powdered form using the machine shown in the figure.
Fig.3.9-Pallettizer 25

3. GO is mixed with PLA in 1 and 0.5 weight percent for the non master batch. 4. For master batch we mix 80 gm of PLA granules to each concentration (0.5 and 1 wt. per cent). 5. The mixtures are again grinded in a grinder for proper mixing. 6. Pure PLA and the four mixtures are first extruded into long strands using twin extruder (see figure).

Fig.3.10-Grinder

7. Then, the strands are cut into smaller size pieces using palletizer.
Fig.3.11- Long strands of PLA/GO being enrolled.

26

8. After pelletisation keep the pelletised pieces are kept in vaccum oven for 3 hours .
Fig.3.13- Palletized PLA, PLA+GO(0.5%)& PLA+GO(1%)

9. 2.5 gm of each concentration (including pure PLA pallets) are weighed and hot compression moulded into thin sheets using the hydraulic press.

Fig.3.14-Vacuum Drier, CACM, University of Auckland.

Fig.3.15 -Films after compression moulding.

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Chapter 4: Testing Methods 4.1 SEM of Fractured surface of Films

SEM samples were prepared by cutting films into thin strips. These strips were dipped into Liquid nitrogen and were fractured inside the liquid nitrogen. These fractured surfaces were observed under Scanning Electron Microscope(SEM) and following images were obtained. GO samples were also observed under SEM.

Pure PLA

PLA + 0.5 % GO(MB)

28

PLA + 1 % GO(MB)

PLA + 0.5 % GO(NMB)

PLA + 1 % GO(NMB)

29

GO film

GO suspension

Reduced GO

30

4.2Films under Optical Microscope

Films were reviewed under optical microscope, since after SEM test the two phases (matrix and reinforcement) we not separately visible. So, under 100x and 400x magnification films were observed and picture of the morphology were capture which as shown below.

PLA + 1 % GO

PLA + 0.5 % GO

Pure PLA

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4.3 Tensile Test

The films were cut into thin strips of 13mm width using the click press machine(fig.4.1) , which were then again cut into dumbbell shaped strips using the dumbbell shaped blades and a press machine.These strips are then tested in the INSTRON 5660 where the gauge length fixed is 25 mm , full scale load is 1000N.

Fig.4.1Click press

Fig.4.2 Stress v/s Strain Graph obtained for PLA

Fig.4.3 Stress v/s Strain Graph obtained for PLA/GO(0.5%)

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Fig.4.4 Stress v/s Strain Graph obtained for PLA/GO(1%)

Fig.4.5 Stress v/s Strain Graph Fig. obtained for PLA/GO(1%)MB

Fig.4.6 Stress v/s Strain Graph obtained for PLA/GO(0.5%)MB

Fig.4.6-Comparison of the three films stress-strain curves

Tensile stress v/s Tensile strain 70 Tensile stress (MPa) 60 50 Master Batch(PLA+ 1%GO) 40 30 20 10 0 -0.05 0 0.05 0.1 Tensile strain 33 0.15 0.2 Master Batch(PLA+0.5%GO)

To summarize the results obtained in the tensile test, we got the best set of properties for PLA+0.5%GO .The mechanical properties are almost identical for both master batch and non master batch films. Not much improvement is observed by introducing GO in the matrix by twin extrusion and hot compression moulding method, this is owed to the fact that above 150 o C there is some change in the properties of GO .The table shows the results obtained from the test.

Table4.1 Tensile Test Results Material Modulus (GPa) Yield Strength (MPa) 52.92 57.83 53.30 56.70 54.04 Ultimate Tensile Strength (MPa) 53.03 57.83 53.30 56.70 54.07 Maximum Load (N) 30.60 32.43 31.96 32.10 31.95

Pure PLA

3.16 3.83 3.50 3.52 3.39

PLA+0.5%GO (MB) PLA+ 1%GO (MB) PLA + 0.5% GO (NMB) PLA + 1% GO (NMB)

34

4.4 DSC Test for the Films

Differential scanning calorimetry (DSC) was done on the twin-extruder and compression moulded films of PLA and GO in order to determine the thermal behaviour of the films.52 mg. of each of the three films(PLA,PLA+0.5% GO MB,PLa+1% GO MB ) was cut and sealed to be tested and loaded in the machine. The results are presented in Figure below.

Fig.4.7.DSC Test graphs obtained after analysis

35

Table4.2 DSC Test Results Summary

S. No. Material Glass Onset of Degree of Transition Crystallization Crystallinity Temperature Temperature (%) 56.40oC 56.77oC 105.74o C 97.80o C 108.32oC 0.27 0.86 4.12

1. 2. 3.

Pure PLA PLA+0.5%GO PLA + 1% GO

55.48o C

DSC tests reveal that the glass transition temperature of all the films remain very close to 56oC with not much variation. From this result it is inferred that there is not much of a strong interaction or bonding between the interface of the materials. Though the increase in concentration of GO in the matrix has led to a decrease in the onset of crystallisation temperature i.e. presence of GO induces nucleation in the matrix. Also, crystallinity of the films has increased with increase in the concentration of GO in the films.

4.3 Permeability Modelling and oxygen gas barrier results:

Permeability testing was successfully done using the MOCON OX-TRAN 2/10 machine.The films were cut from the edges to fit in the fixture for testing and the process took around 10 hours for completion. The films under exposure to the oxygen were 50 cm2 and thickness varied with each film. Ambient temperature fixed was 23oC and the standard procedure of testing was followed which involved 10 cycles of 30 minutes each and a conditioning period of 3 hours. The results obtained are shown in Table In section 1.4.3 a brief description of the various models found in literature was provided. Most of the models are conductivity or elasticity models for two phase materials modified because of their close analogy to permeability. To check the applicability of the models, the models were plotted against experimental data found in table 4.3. All these models use the permeability of
36

matrix. The reinforcement is highly impermeable as found in literature so the permeability value for GO is taken to be zero.

Table4.3 Permeability Test Results

Sample Transmission rate cc/[m2-day] Pure PLA 74.95 PLA+0.5%GO 69.14 PLA+1 % GO 70.10 Permeability cc-mm/[m2-day] 35.41 13.27 12.75 Permeability cc-mil/[m2-day] 548.96 522.64 502.30

These models provide a good starting point for predicting the permeability in MFC. Each of them follows the same downward trend seen in the experimental data and with some modification to the gradient; these models should provide a more accurate representation of the data. As earlier mentioned in section 4.1.3 the parallel and series model give the upper and lower bound of the gas permeability value of composites. Fig.4.8 shows the plot of oxygen permeability v/s GO volume fraction. It can be seen from the figure that the experimental data falls well within the upper and lower bounds predicted by the models.
600

500 Oxygen Permeability (cc-mil/[m2-day)

400

300

Experimental Parallel Series

200

100

0 -0.002 -100 Reinforcement(GO) concentartion(vol%) 0 0.002 0.004 0.006 0.008 0.01

Fig.4.8 Permeability v/s GO volume fraction 37

Fig.4.9 shows the comparison of experimental and predicted oxygen gas permeability values by the Maxwell-Rayleigh model and geometric mean model for the composite. Though all the models overestimate the permeability values for the composite, the geometric mean model is the closest of the existing models.
560

550 Oxygen Permeability (cc-mil/[m2-day])

540

530

Experimental Geometric mean Maxwell Rayleigh

520

510

500

490 0 0.002 0.004 0.006 0.008 0.01 Reinforcement(GO) concentration (vol %)

Fig.4.9 Permeability v/s GO volume fraction

Four other models were used for prediction of oxygen gas permeability of the composite films (Lewis-Nielson, Bottcher, Bruggeman and Higuchi) shown in fig. 4.10. All these models over predict the permeability for low contents of PET. The permeability values predicted by these models are within the same vicinity of each other. The predicted values of oxygen gas permeability by Bottcher and Bruggeman are almost coinciding and the hence the graphs of the two models are overlapping.

38

560 550 Oxygen Permeability (ccmil/[m2-day]) 540 530 520 510 500 490 0 0.002 0.004 0.006 0.008 0.01 Reinforcement(GO) concentration (vol %) Experimental Lewis-Nielsen Bottcher Bruggeman Higuchi

Fig.4.10Permeability v/s GO volume fraction

Modification of models
In this section each of the models listed in section 4.1.3 have been modified to make them more applicable to the composite film. This is done by fitting the models to the experimental results by changing the various factors present in the models. The equations or formula listed in table 4.4 have been modified to fit the experimental results.

Table 4.4 S.No. 1. Model Name Maxwell-Rayleigh equation Lewis and Nielsen equation for two-phase systems
= 1 +

Equation /Formula Involved 1 + = 1

2.

(1 + ) ( 1) ( + ) ( 1)

39

3. 4. 5.

Bottcher formula Bruggeman Formula Higuchi model

13 = (1 ) 1 3 = 1 + [1 (1 )2 ]

( ) ( ) + =0 + ( ) + ( )

Maxwell-Rayleigh equation The generalised Maxwell-Rayleigh equation takes into account the models derived by Maxwell and Rayleigh for spheres and long transverse cylinders respectively, through a shape factor that also incorporates the parallel and series models. A recap of which model corresponds to the relevant shape factor is given in Table 4-4.

Table 4.4 Model Shape factor (f)

Maxwell Rayleigh Parallel Series 2 1 0

Using the shape factors predicted by Maxwell and Rayleigh the value of permeability found out exceeds that of the experimental results. The shape factor is determined to fit the experimental results and is found out to be f = 0.094.

40

560

550 Oxygen Permeability (ccmil/[m2-day])

540

530 Experimental 520 f = 0.0944 Maxwell(f = 2) 510 Rayleigh( f = 1)

500

490 0 0.002 0.004 0.006 0.008 0.01 Reinforcement(GO) concentration (vol %)

Fig.4.11 Permeability v/s GO volume fraction

Lewis and Nielsen equation for two-phase systems The Lewis and Nielsen equation is based on the model derived by Halpin and Tsai. They extended the Halpin-Tsai equation to include maximum packing fraction of the filler which is considered to be important for viscosity of suspensions and they pointed out the relation between the shape factor constant (A) and the generalised Einstein coefficient. The shape factor constant A = Ke1 and the value of Ke is found out to be 1.095 that best fits with the experimental data.

41

560

550 OxygenPermeability(cc-mil/[m2-day])

540

530 Experimental 520 Lewis-Nielson Modified Lewis-Nielson 510

500

490 0 0.002 0.004 0.006 0.008 0.01 Reinforcement(GO) concentration (vol %)

Fig.4.12 Permeability v/s GO volume fraction

Bottcher formula Bttcher derived a formula to correlate the dielectric behaviour of powder with bulk based on the earlier derivation from Bruggeman. Figure 4.13 shows the plot of permeability v/s GO volume fraction in which the shape factor A assumed was 1/3 and which is modified to 0.905 to match the experimental results so that the best fit is obtained. Table 4.5 Shape of dispersed phase Sphere Rods Experimental fitting

Shape factor A 1/3 1/2 0.905

42

560

550 Oxygen Permeability (cc-mil/[m2-day])

540

530 Experimental 520 Bottcher Modified Bottcher 510

500

490 0 0.002 0.004 0.006 0.008 0.01 Reinforcement(GO) concentration (vol %)

Fig.4.13 Permeability v/s GO volume fraction

Bruggeman Formula Bruggemans formula was originally developed to predict the conductivity in spherical particles. The formula proposed is shown below.

Fig. shows that the above formula over predicts the value of oxygen gas permeability. Modification made in the above formula so that it can be is changed to 0.54 to match with the experimental results obtained.

applicable for flaky GO particles in the PLA matrix is that the index of =

= (1 ) 1

1 3

43

560

550 Oxygen Permeability (cc-mil/[m2 -day])

540

530 Experimental 520 Bruggeman Modified Bruggeman 510

500

490 0 0.002 0.004 0.006 0.008 0.01 Reinforcement(GO) concentration (vol%)

Fig.4.14 Permeability v/s GO volume fraction

Higuchi model Higuchi derived his model from the theory used to develop his new relationship for dielectric properties of two-phase mixtures. The quantity K is considered to be the shape factor in this model and the value used in 0.78 was based on dielectric constant data for powders and suspensions. Using the results from experiment, the constant K was modified to fit the experimental data and was found to be 3.49.

44

560 550 Oxygen Permeabilty (cc-mil/[m2-day]) 540 530 Experimental 520 510 500 490 0 0.002 0.004 0.006 0.008 0.01 Reinforcement(GO) concentration (vol%) Higuchi Modifiied Higuchi

Fig.4.14 Permeability v/s GO volume fraction

5.1 Results and Discussion:

Films of PLA(Poly-Lactic Acid) and Graphene oxide were successfully manufactured and their mechanical, thermal and oxygen gas barrier properties were characterised. The results can be summarised as follows: 1. Tensile Test results show that the modulus of elasticity , yield strength and ultimate tensile strength improved with the addition of 0.5(wt%) GO in the PLA matrix. Though the improvement was not significant in the light of the fact that the tensile strength of Graphene is remarkable ~1GPa, nevertheless, the properties did not deteriorate on addition of GO. It was also observed that the increase in the concentration of GO in the PLA matrix led to a decline in the mechanical strength. 1% GO in PLA showed lower values of modulus of elasticity, yield strength,
45

ultimate tensile strength and maximum load. This behaviour of the PLA/GO film is owed to the fact that the increase in GO content led to non-uniform dispersion, agglomeration and formation of lumps increasing the non-homogeneity of the samples. 2. To gain more insight of the trends in mechanical strength of the samples, the SEM test for the fractured surface of the films was done. The pure PLA fracture surface showed a more regular pattern of scaly surface. The roughness of surface increases with increase in GO content. This, in a way, testifies for the formation of lumps and nonhomogeneity in the films with the increase in GO content. But, the main objective of this test was to observe the GO particles inside the PLA matrix, which could not be done as the two phases (matrix and reinforcement) were not distinguishable, may be due to less resolution. Difference in the surfaces of Master Batch and nonmaster batch is due to the process of manufacture, one being more dispersed due to use of solvent and the other being directly incorporated. 3. Due to our inability to observe the GO particles dispersed in PLA distinctly, we took resort to optical microscope to explore more. The two phases of films were, now, clearly distinguishable and the GO matter dispersed in the PLA matrix could be easily viewed. The GO was randomly distributed in the PLA matrix and looked like dark patchy flat paper or flaky structured. The large GO particles were easily visible while there were many smaller particles dispersed but could not be seen properly. 4. After the morphology of the films became clear, the thermal properties of the films were tested by DSC technique. The results obtained were quite satisfactory and in congruence with the trends observed in the mechanical strength of the films. The glass transition temperature of all the three films was around 56oC, which shows that the interaction at the interface of the two materials is not strong enough to bring about much improvement in mechanical properties. Another interesting feature observed was the decrease in the onset of crystallisation temperature of the films with the increase in the GO content in the matrix. This shows that the presence of GO induces the
46

nucleation process to occur faster. The %crystallisation of films was calculated using the data obtained in the test and it was found that with increase in GO concentration it increased. 5. The oxygen gas barrier properties testing was the last test conducted on the films, as the material under consideration was perceived to be a potential material to be used in packaging industry. The permeability of pure PLA film was found to be 548.96 cc-mil/[m2-day] which is quite high very close to the value in the other reference texts. The addition of 0.5% GO (MB) showed around 10% decrease in permeability which as a matter of fact is astounding looking the amount of GO used. The value of permeability found was 489.08 ccmil/[m2-day]. But, further increase in GO content led to a decrease in barrier properties and hence, rise in the permeability value for 1% GO (MB) in PLA matrix. The actual value that was observed for 1% GO film was 500.3271 cc-mil/[m2-day]. This was not expected in light of the permeability theories given by researchers (Lewis-Neilson, MaxwellRayleigh, Higuchi). The oxygen gas barrier test for the non- master batch samples was also done. The permeability value for GO(0.5%) in PLA was found out to be 522.64 cc-mil/[m2-day] and that of GO(1%) in PLA was found to be 502.30 cc-mil/[m2-day], which was in accordance of the theoretical gas barrier models which predict that with increase in the reinforcement percent the gas barrier properties increases. 6. In Section 6.2, some of the models found in literature were used to predict the oxygen gas permeability value of the composite films and was matched with the experimental data of non-master batch PLA/GO films. Each of the models were modified to make them more applicable to the experimental data for PLA/GO(NMB) composite films. None of the modified shape factors provided an ideal fit to the data in particular for models like Lewis-Nielsen, Maxwell-Rayleigh, Bottcher and Bruggeman. Shape factors or indices were changed to fit the formulae to match with the experimental data.

47

References
[1]Wikipedia. [2] Lipatov YS. Interfacial effects in polymer blends. Review. Polymer Science USSR (English Translation of Vysokomolekulyarnye Soyedineniya Series A) 1978;20(1):1-18. [3] Jeong H-K, Lee YP, Lahaye RJWE, Park M-H, An KH, Kim IJ, et al. Evidence of graphitic AB stacking order of graphite oxides. J Am Chem Soc 2008;130:13626. [4] Szab T, Berkesi O, Forg P, Josepovits K, Sanakis Y, Petridis D, et al. Evolution of surface func-tional groups in a series of progressively oxidized graphite oxides. Chem Mater 2006;18:27409. [5] Lerf A, He H, Forster M, Klinowski J. Structure of graphite oxide revisited. J Phys Chem B 1998;102:447782. [6] Massey, L K, "Permeability Properties of Plastics and Elastomers", 2003, Andrew Publishing. [7] W.F. Smith, Foundations of Materials Science and Engineering 3rd ed., McGraw-Hill (2004) [8] H.C. Berg, Random Walks in Biology, Princeton (1977) [9] R.B. Bird, W.E. Stewart, E.N. Lightfoot, Transport Phenomena, John Wiley & sons, (1976) [10] Skoog, Douglas A., F. James Holler and Timothy Nieman (1998). Principles of Instrumental Analysis (5 ed.). New York. pp. 805808. [11] Rauwendaal, Chris (2001), Polymer Extrusion, 4th ed, Hanser. [12] Hanne Larsen, Achim Kohlr and Ellen Merethe Magnus, "Ambient oxygen ingress rate method", John Wilew & Sons, Packaging Technology and Science, Volume 13 Issue 6, Pages 233 241. [13] F2622 Standard Test Method for Oxygen Gas Transmission Rate Through Plastic Film and Sheeting Using Various Sensors. [14] ASTM. Standard Test Method for Oxygen Gas Transmission Rate Through Plastic Film and Sheeting Using a Coulometric Sensor. D3985-02. p. 458-463. [15] Yam, K. L., "Encyclopedia of Packaging Technology", John Wiley & Sons, 2009. [16] Shields, R.J, Bhattacharyya, D., Fakirov, S., Oxygen permeability analysis of micro-fibril reinforced composites from PE/PET blends, Composites Part A: Applied Science and Manufacturing, Accepted, 2008;39:940-949. [17] Gas barrier properties of PP/EPDM blend nanocomposites
48

Masoud Frounchi , Susan Dadbin , Zahra Salehpour , Mohsen Noferesti. [18] Gas transport properties of polyacrylate/clay nanocomposites prepared via emulsion polymerization Jose M. Herrera-Alonso, Zdenka Sedlakova, Eva Maranda. [19] Gas Permeability and Free Volume of Highly Branched Substituted Acetylene Polymers byYu. P. Yampolskii, A. P. Korikov, V. P. Shantarovich, K. Nagai, B. D. Freeman, T. Masuda, M. Teraguchi and G. Kwak. [20] Moisture Permeability of Polymers. I. Role of Crystallinity and Orientation by S. W. LASOSKI, JR., and W. H. COBBS, JR., E.I. du Pont de Nemours and Company, Film Department, Buffalo, New York. [21] Effective Medium Theories for Artificial MaterialsComposed of Multiple Sizes of Spherical Inclusions in a Host Continuum William M. Merrill, Student Member, IEEE, Rodolfo E. Diaz, Michael M. LoRe, Mark C. Squires, and Nicolaos G. Alexopoulos, Fellow, IEEE [22] Sdergrd, Anders; Mikael Stolt (February 2002). "Properties of lactic acid based polymers and their correlation with composition". Progress in Polymer Science 27 [23] Physical models of diffusion for polymer solutions, gels and solids by L. Masaro, X.X. Zhu. [24] Models for the Permeability of Filled Polymer Systems by Lawrence E. Nielsen at CENTRAL RESEARCH DEPARTMENT, MONSANTO COMPANY ST., LOUIS, MISSOURI. [25] Polymer blends, Lloyd M. Robinson , Hanser. [26] Characterisation of the Mechanical and Oxygen Barrier Properties of Microfibril Reinforced Composites by Ryan John Shields. [27] Generalized Bruggeman Formula for the Effective Thermal Conductivity of Particulate Composites with an Interface Layer by J. Ordez-Miranda J. J. Alvarado-Gil , R. Medina-Ezquivel. [28]Techical Data shee_2002D, by NatureWorks. [29] Boukhvalov, D. W.; Katsnelson, M. I. J. Am. Chem. Soc. 2008, 130, 10697. [30] Tunable Electrical Conductivity of Individual Graphene Oxide Sheets Reduced at Low Temperatures Inhwa Jung, Dmitriy A. Dikin,, Richard D. Piner, and Rodney S. Ruoff. [31] C. Gomez-Navarro et al. (2007). Nano Letters, volume 7, issue 11, page 3499 doi: 10.1021/ nl072090c [32] "Graphene Oxide Paper". Northwestern University. Retrieved 2011-02-28. [33] Lee, C. et al. (2008). "Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene".Science 321 (5887): 385. Bibcode 2008Sci...321..385L

49

Appendix
Calculation of volume fraction:
Volume fraction of GO in the matrix is calculated from mass fraction of GO used and density of PLA and GO. Where, = volume fraction of GO w = mass fraction of GO = + (1 )

= density of PLA matrix = 1.24 g/cc = density of GO = 1.48 g/cc.

Calculation of percent crystallinity:

=

Where,

= enthalpy of 100% crystalline sample of the polymer = 93 J/g.

= enthalpy of melting

= per cent crystallinity

100

= enthalpy of cold crystallization

= mass fraction of polymer in the matrix.

50