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Road Map for the Selection of Characteristic Parameters of Polymer Matrix Composites for Engineering Applications

Dr.J.Fazlur Rahman1 Mohammed Yunus2 T.M. Tajuddin Yezdani3 and Dr.A.Ramakrishna4 1. Professor Emeritus, Department of Mechanical Engineering, H.K.B.K. C.E., Bangalore, Karnataka State, India. 2. Professor, Department of Mechanical Engineering H.K.B.K.C.E., Bangalore, Karnataka State, India. 3. Professor, Department of Mechanical Engineering H.K.B.K.C.E., Bangalore, Karnataka State, India. 4. Professor and Dean, Department of Mechanical Engineering Andhra University Engineering College, Vishakhapatnam Andhra Pradesh, India.

ABSTRACT An important technological development that has contributed significantly to the growth of the composite is the development of a strong and stiff fibres such as glass, carbon and aramide along with the concurrent development in polymer industry, resulting in various polymeric materials such as epoxy, vinyl ester, phenolic resins, etc. to serve as matrix materials. Over the last few years, usage of FRPs using polymer matrices have seen tremendous growth as they can be tailored to suit specific application. The mechanical and physical properties of FRP depend upon type, shape, length and orientation of the fibres. Generally long fibres transmit loads more effectively through the matrix. In spite of the complexity of their behaviour and the unconventational nature of fabrication, and other aspects, the usage of FRPs in automotive industry, aerospace, marine application, sports equipments, house hold articles, construction of structural frames and many more has been beneficially realised. This paper deals with the charting of strategy for the application of PMCs citing the specific reasons for selecting the particular material systems to its functionality. A brief review of modern FRPs is followed by a general discussion and the logical choice of a particular material system that has gained wide acceptance. With this knowledge as the basis, a material engineer is well placed to create

innovative designs that are having fast effective gains and also material enhanced properties. Keywords: Polymer Matrix Composites-PMC, Mechanical and Physical Properties of FRP, Degradation of PMC, Moulding Processes, Types of Resins, Natural Fibres. 1. INTRODUCTION Recently, many advances have been made in the design, manufacture and application of composite materials which can be very strong and stiff, yet very light in weight, that is strength to weight ratio and stiffness to weight ratio are several times greater than steel and aluminium. These composites also exhibit fatigue and toughness properties better than common engineering materials. A great deal of progress has been made in the field of FRPs which makes them ideal for use in many applications. The most commonly used composite class for load bearing structural applications is the continuous fibre reinforced polymer matrix composite. The most popular material system has been the epoxy based resins reinforced with carbon, glass, or aramid (Kevlar) fibres. FRPs are commonly used in the aerospace, automotive, marine and construction industries[19]. Attention is now focused on expanding the usage of such composites to other areas where temperatures could be higher. As the polymer matrix material is the most affected (rather than the reinforcing fibres) by high temperature, it is the matrix material that has been the focus of attention in the development of high temperature PMCs [8]. The research and development efforts to produce polymer matrices with higher service temperatures (up to 500 C) have shown encouraging trends. Composite materials and layered structures based on natural plant fibres are increasingly regarded as an alternative to artificial fibre reinforced parts [5]. These new FR materials are called as bio-composites. Natural fibres such as hemp, flax, cotton, jute, coir, sisal, kenaf, etc., are generally applied for reinforcement. The various advantages of natural fibres over man made fibres (glass, Kevlar and carbon ) are, low cost, low density and comparable specific tensile properties, recyclability, and biodegradability and their field of application is generally found in the structural components in automotive industries, aerospace, construction, sports and packaging industry [1,2]. The selection of a particular system required to be tailored depends on a host of conflicting requirements, which a system has to satisfy. It is important to note here that the production and the properties of several PMCs either for continuous fibre or discontinuous fibre is profoundly affected by the reinforcement. These property enhancements due to the reinforcement are comparable to the hybrid polymer matrix composites [9]. 1.1 Criteria for the Selection of Polymer Matrix Composites

The selection of the materials comprising the PMC is by no means a random process. The systematic selection apart from the composition of the component comprising the PMC also takes into account the optimization factor, where the so called merit parameters play a significant role in analysing the competitiveness between the materials that are functionally related to material properties such as density, tensile strength, stiffness, resistance to corrosion, resistance to temperature besides, cost and value of weight savings. In the aerospace sector, cost is not necessarily the governing factor because of the low production volume and profit realized by weight savings. The continuous fibre reinforced PMCs have low density, more stiff and strong [7], are known to have weight optimized performance and are performance oriented design. As far as the automotive sector is concerned, cost plays a vital role. Since large volume prevails and as such material cost will significantly affect the competitiveness of the component produced. A great deal of progress has been made in the field of FRPs which makes them ideal for use in many applications [19]. The matrix materials used for reinforced plastics are epoxy, polyester and vinyl ester resins. The most popular material systems have been epoxy based resins reinforced with carbon, glass or aramide (Kevlar fibres). The application of reinforced plastic include, acid resistant tanks made of phenolic resins and asbestos fibres, boats made of epoxies with glass fibre, advanced fibres made with glass or carbon fibre. For high temperature (up to 5000C) application, components of aircraft and rockets, helicopter blades, automobile blades and pressure vessels and vessels, ladders etc., [6]. Aluminium application in aircraft has been replaced by graphite epoxy reinforced plastics with reduced weight and cost with improved resistance to corrosion and fatigue. 1.2 Selection of Right Polymer Matrix The role of matrix in a fibre-reinforced composite is to transfer stress between the fibres, to provide a barrier against an adverse environment and to protect the surface of the fibres from mechanical abrasion [15]. The matrix plays a major role in the tensile load carrying capacity of the composite structure. The binding agent or matrix in the composite is of critical importance. Four major types of matrices have been reported: Polymeric, Metallic, Ceramic and Carbon. Most of the composites used in the industry today are based on polymer matrices. Polymers are generally classified into two classes, thermoplastics and thermosetting. Thermoplastics currently dominate as matrices for bio-fibres (forming bio-composites). The most commonly used thermoplastics for this purpose are Polypropylene (PP), Polyethylene , High density Polyethylene (HDPE), Low density Polyethylene (LDPE) ( processing temperature less than 230 degrees C), and Poly vinyl- Chloride (PVC). By heating, thermoplastic resins are softened from solid state before processing (i.e., before making a composite) without chemical reaction. Thermoplastics return to solid state (matrix) once processing is done. The primary advantage of thermoplastic resin over thermoset resins is their high impact strength and fracture toughness. Thermoplastic resins also provide higher strains-to-failure, which is manifested by better resistance to micro cracking in the matrix of a composite. Some of the other advantages of thermoplastic resins are [24, 25]:

1. Unlimited storage (shelf) life at room temperature. 2. Shorter fabrication time. 3. Postformability (e.g., by thermoforming) 4. Ease of repair by (plastic) welding, solvent bonding, etc. 5. Ease of handling (no tackiness). 6. Recyclability. 7. Higher fracture toughness and better delamination resistance under fatigue than thermosets such as epoxies. Depending on the application, there are 3 types of thermosetting resins used polyester, vinyl ester, and epoxy. 1.2.1. Polyester resin, tends to have yellowish tint, and is suitable for most backyard projects. Its weaknesses are that it is UV sensitive and can tend to degrade over time, and thus generally is also coated to help preserve it. It is often used in the making of surfboards and for marine applications. Its hardener is a MEKP, and is mixed at 14 drops per oz. MEKP is composed of methyl ethyl ketone peroxide, a catalyst. When MEKP is mixed with the resin, the resulting chemical reaction causes heat to build up and cure or harden the resin. 1.2.2. Vinyl ester resin tends to have a purplish to bluish to greenish tint. This resin has lower viscosity than polyester resin, and is more transparent. This resin is often billed as being fuel resistant, but will melt in contact with gasoline. This resin tends to be more resistant over time to degradation than polyester resin, and is more flexible. It uses the same hardener as polyester resin (at the same mix ratio) and the cost is approximately the same. 1.2.3. Epoxy resin is almost totally transparent when cured. Epoxy Resins are thermosetting resins, which cure by internally generated heat. Epoxy systems consist of two parts, resin and hardener. When mixed together, the resin and hardener activate, causing a chemical reaction, which cures (hardens) the material. Epoxy resins generally have greater bonding and physical strength than do polyester resins. In the aerospace industry, epoxy is used as a structural matrix material or as structural glue. In working with epoxies, the resin to hardener ratio is very important and should never be adjusted in an attempt to slow down or speed up the curing process. The importance of epoxy resin can be more fully understood by studying the following table. Table 1. Characteristics of different resins
Characteristics Flexural Strength Tensile Strength Elongation % Water Absorption Hardness Pot Life Working Time Above Waterline Below Waterline Major Construction General Repairs Shelf Life Polyester Resin Good Good Good Good Good 4 7 Minutes 20 30 Minutes Yes Yes Yes Yes 18 24 Months Epoxy Resin Best Best Lowest Lowest/Excellent Best 14 20 Minutes - 6 Hours Yes Yes Yes Yes 2 Year +

Catalyst Cure Time

MEKP 6 8 Hours

2-Part System 5 7 Days

The properties of typical thermoplastic polymers and thermoset polymers used in fiber reinforced composites are given in the Table-2. Table 2. properties of thermoplastic and thermoset polymers used in FRP
Property Density(g/cm2) Tensile strength (MPa) Elastic modulus (GPa) Elongation (%) Water absorption 24hrs (%) Izod impact strength(J/M) PP* 0.8990.920 26-41.4 0.95-1.77 15-700 0.01-0.02 21.4-267 LDPE* 0.9100.925 40-78 0.0550.38 90-800 <0.015 >854 HDPE* 0.94-0.96 14.5-38 0.4-1.5 2.0-130 0,01-0,2 26.7-1068 PS* 1.04-1.06 25-69 4-5 1-2.5 0.03-0.10 1.1 Nylon6 1.12-1.14 43-79 2.9 20-150 1.3-1.8 42.7-160 Nylon6.6 1.13-1.15 12.4-94 2.5-3.9 35->300 1.0-1.6 16-654 Polyester resin 1.2-1.5 40-90 2-4.5 2 0.1-0.3 0.15-3.2 Vinyl ester resin 1.2-1.4 69-83 3.1-3.8 4-7 0.1 2.5 Epoxy 1.1-1.4 35-100 3-6 1-6 0.1-0.4 0.3

*PP=Polypropylene, LEDP=Low density polyethylene, HDPE=High density polyethylene, PS=Polystyrene. 1.3. Selection of Right Fibres

Fibre reinforced plastics are made using fibres of glass, carbon ( graphite, aramide or boron) in a matrix of polyester or epoxy and have very high toughness and strength to weight ratio and stiffness to weight ratio. The mechanical and physical properties of reinforced plastics depend on type, shape, length and orientation of fibres. Long fibres transmit loads more effectively through the matrix. The important properties of different types of fibres used in reinforced plastics are given in the followings. 1.3.1 Carbon fibres Carbon fibres have low density, high strength and high stiffness but are costlier than glass fibres. Carbon fibres are usually 80 to 85 % carbon, whereas graphite fibres are more than 99% carbon. Conductive graphite fibres are available which give enhanced electrical thermal conductivity to the reinforced plastic components. Carbon fibres [14] are used for reinforcing certain matrix materials to form composites. Carbon fibres are unidirectional reinforcements and can be arranged in such a way in the composite that it is stronger in the direction, which must bear loads. The physical properties of carbon fibre reinforced composite materials depend considerably on the nature of the matrix, the fiber alignment, the volume fraction of the fiber and matrix, and on the molding conditions. Several types of matrix materials such as glass and ceramics, metal and plastics have been used as matrices for reinforcement by carbon fibre. Carbon fibre composites, particularly those with polymer matrices, have become

the dominant advanced composite materials for aerospace, automobile, sporting goods and other applications due to their high strength, high modulus, low density, and reasonable cost for application requiring high temperature resistance as in the case of spacecrafts. 1.3.2. Glass fibres Glass fibres are most widely used being least expensive. E-type fibres have tensile strength about 3500 MPa and lowest cost. S-type fibres are costlier and have tensile strength of about 4600 MPa. E-ECR fibres have high resistance to elevated temperatures and acid corrosion. Glass fibres are the most common of all reinforcing fibres for polymeric (plastic) matrix composites (PMCs). The principal advantages of glass fiber are low cost, high tensile strength, high chemical resistance and excellent insulating properties [19, 26]. The two types of glass fibres commonly used in the fiber reinforced plastics industries are E-glass and S-glass. Another type known as Cglass is used in chemical applications requiring greater corrosion resistance to acids than is provided by E-glass. 1.3.3. Aramides / Kevlar fibres Aramide are the toughest fibres with highest strength to weight ratio of all fibres. Absorption of moistures by these fibres degrades the properties of the composite. Kevlar belongs to a group of highly crystalline aramide (aromatic amide) fibres that have the lowest specific gravity and the highest tensile strength to weight ratio among the current reinforcing fibres. They are being used as reinforcement in many marine and aerospace applications [3, 12]. The use of natural fibres for the reinforcement of the composites has received increasing attention both by the academic sector and the industry. Natural fibres have many significant advantages over synthetic fibres. Currently, many types of natural fibres have been investigated for use in plastics including flax, cotton, hemp, jute straw, wood, kenaf, ramie, sisal, coir and many more. Annual production of some of the natural fibres and its source are given in the table-3 below. Table 3.Annual production of natural fibres and their origin
Fiber source Cotton lint Jute Flax Hemp Kenaf Ramie Sisal Coir World production (103 tons) 18500 2500 810 215 770 100 380 100 Origin Stem Stem Stem Stem Stem Stem Stem Fruit

Table 4. The properties of various natural and manmade fibres.

Fiber Density Elongation Tensile Elastic

Cotton Jute Flax Hemp Kenaf Ramie Sisal Coir E-glass S-glass Kevlar29 Kevlar49 Carbon High Strength Carbon High Modulus Carbon Ultra High Modulus

(g/cm2) 1.5-1.6 1.3 1.5 1.47 1.45 N/A 1.5 1.2 2.6 2.5 1.44 1.44 1.8 1.9 2.0-2.1

(%) 7.0-8.0 1.5-1.8 2.7-3.2 2-4 1.6 3.6-3.8 2.0-2.5 3.0 2.4 2.9 2.8 1.8 1.1 0.5 0.2

Strength(MPa) 400 393-773 500-1500 690 930 400-938 511-635 593 1720 2530 2270 2270 2840 1790 1300-1310

Modulus(GPa) 5.5-12.6 26.5 27.6 70 53 61.4-128 9.4-22 4.0-6.0 72 87 83/100 124 230 370 520-620

2. SHAPING PROCESS FOR POLYMER MATRIX COMPOSITES Many of the shaping processes are slow and labour incentive. In general the techniques for shaping composites is less efficient than for other materials as composites are more complex than other materials consisting of two or more phases and particularly for FRPs the fibres must be correctly oriented. The shaping processes of FRPs can be categorized as Open mould Processes: Manual procedures for laying resins and fibres onto forms. In this, successive layers of resin and reinforcement are manually applied to an open mould to build the laminated FRP to the desired thickness. This is then followed by curing and part removing. Curing is required in all thermosetting resins used in FRP composites. Curing cross links the polymer, transforming it from its liquid or highly plastic condition into a hardened product. The various open mould processes are [16, 17] 1) Hand-lay process. 2) Spray-up process. 3) Vacuum bagging 4) Automated tape- laying machines. Close mould process: Molding takes place in moulds consisting of two sections that open and close after each molding cycle. Cost is double that of open mould process, but it gives a good surface finish, higher production rates, and has close control over tolerance. The various close moulding processes are 1) Compression moulding. 2) Transfer moulding. 3) Injection moulding. Filament winding: continuous filaments are dipped into liquid resin and wrapped on a mandrel in a helical pattern. The operation is repeated to form additional layers each having criss-cross pattern with the pervious until desired part thickness is obtained for

producing rigid hollow cylindrical shape. The resin is then cured and the mandrel removed. Pultrusion: it is similar to extrusion but only adapted to include continuous fiber reinforcement. The classification of manufacturing processes of FRPs is shown in fig.1.

Fig.1.Classification of manufacturing processes of FRP

3. Advantages of FRPs over conventional materials Merits of FRP over steel and suitability of application of FRP with respect to various desired properties are tabulated [5, 6].
Table 5. Merit Comparison and Ratings for FRP and Steel Merit/Advantage (Rating) FRP Steel Strength/stiffness 4-5 4 Weight 5 2 Corrosion resistance/ 4-5 3 Environmental Durability Ease of field construction 5 3-4 Ease of repair 4-5 3-5 Fire 3-5 4 Transportation/handling 5 3 Toughness 4 4 Acceptance 2-3 5 Maintenance 5 3 Property (Parameter)

Note: Higher rating indicates better desirability of the property Note: Different Rating Scales 1: Very Low, 2: Low, 3: Medium, 4: High, 5: Very High.
Table 6. Merits and suitability of applications of FRP

Table 7. suitability for marine applications and use of FRPs

4. DISCUSSION AND CONCLUSION: Based on previous researchers work, on the characterization of fiber reinforced polymer composites, the following have been inferred for future studies. 1. Natural fibers due to their low cost fairly good mechanical properties, high specific strength, not abrasive, eco friendly and bio degradable characteristics, they are exploited as a replacement for conventional fiber, such as glass, aramid and carbon. The tensile properties of the natural fiber reinforced polymers are generally influenced by the inter-facial addition between the matrix and the fibers. Several chemical modifications are employed to improve the interfacial matrix-fiber bonding for the enhancement of tensile properties. In general, the tensile strength of the natural fiber reinforced. Polymer composite increased with the increase in fiber content up to an optimum value and then the value will drop. The youngs modulus of the natural PMC increased with increase in fiber loading [3, 12 and 14]. 2. The PMC have been used in structures subjected to for a variety of applications such as structural members of airplanes, automobiles, marine applications, sports equipments, chemical plants etc. since they are outstanding performances such as lighter weight, high strength and good fatigue properties and corrosion resistance but material characterization and failure evaluation of the PMCs is in compression is still an item of research [6, 13 and 19]. 3. Glass reinforced plastics have wide applications but is being proposed for critical marine components such as Moisture resistance in submarine control surfaces transmission shaft propellers and super structures, submarine casings etc. due to limited durability in under water shock loading [27].

4. The long term durability and the residual life of the composites depends upon the degradation of the PMC composites under hostile environments and service conditions which often limits the service life of the component. Degradation occurs as the results of environment dependent chemical or physical attack by degradation agents. The various causes of degradation of polymeric components are [28, 29] a) Photo oxidation b) Thermal decomposition c) Hydrolytic attack d) Attack by pollutants e) Mechanical degradation and f) Stress - aided chemical degradation. 5. The selection the materials comparatively the polymer matrix materials such as polyester resins, vinyl ester resins and epoxy resin depends upon the various properties for a specific application involving the various factors such as density, tensile strength, stiffness, resistance to corrosion and resistance to temperature and also the cost and value of weight savings, which is highlighted in detail aspects in table 1 and 2. The selection of right fibers namely glass, carbon, aramid or boron in a matrix of polyester or epoxy depends upon three main factors namely high toughness, strength o weight ratio and stiffness to weight ratio. The mechanical and physical properties of reinforced plastics depend on the type, shape, length and orientation of fibers. Generally the long fibers transmit loads more effectively through the matrix, the various properties of different types of fibers are given in table 3 and 4. The merits and demerits of the different moulding processes namely open mould and close mould processes of FRPs are highlighted with regards to dimensional accuracy of the components surface finish produced, production rate and the cost. Lastly, the merit comparison along with the rating for both FRP and steel is presented in a tabular column 5.

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