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Introduction in to glass reinforced plastics General statement A general definition of a composite is

Introduction in to glass reinforced plastics

General statement

A general definition of a composite is a synergistic combination of two or more materials. More specifically, the composites referred to here comprise a high strength reinforcement in fibrous form, incorporated into and bonded together by a matrix, usually a thermosetting polymer. The term fiber reinforced plastics (FRP) is widely used to describe such materials with glass reinforced plastic (GRP) when the reinforcement is glass fiber. Glass reinforced epoxy (GRE) is used when, as in the case of much composite pipework, epoxy resin is the matrix

The nature of E-glass fibers

Most glass fibers consist of E-glass, a term which once stood for electrical grade glass, as used in insulators and capacitors. This glass, which is transparent and brittle, but of high strength, is

a super-cooled mixture of metallic oxides. Glasses in bulk form

tend to have relatively low strength levels, because of the presence of microscopic surface flaws which act at site for crack

propagation. Glass in fibrous form can be much stronger provided that the surface of the fibers is protected at all times against damage. Glass is produced in a furnace about 1200ºC and spun into fibers by allowing it to drain under its own weight through many heated bushings. Molten glass is quite corrosive, and the bushings must be made from platinum to avoid damage, and to protect the glass from contamination. Each bushing contains many hundreds of holes through which the molten glass must pass before forming fibers of approximately 10 microns in diameter.

The secret of the strength of glass fibers, and of their ability to bond to polymeric matrices is the size which is applied to the surface of the fiber's in the form of an aqueous solution shortly after the fiber's emerge from the bushings. The size contains a polymeric binder which coats the glass surface to protect it and lightly binds together the individual fiber's in each fiber tow to prevent them rubbing against one another during subsequent handling and processing. The size also contains a coupling agent

- 1 - a reactive component, usually an organosilane, which is a

multi-functional molecule. The silane part of the molecule bonds tightly to the surface of the glass while the organic part is designed to attach itself to the polymer matrix. When purchasing glass fiber it is necessary to stipulate the type of resin matrix to be used, since some coupling agents are specifically chosen to be compatible with particular resins. The size also contains a film former to enable it to spread over the glass surface and lubricants to facilitate processing without damage.

Fiberglass-Composite Pipe Group/Europe P.O.Box 6 – 4191 CA Geldermalsen – Holland tel. +31 345 587 587 – fax +31 345 587 561

Despite the presence of the size, every processing or handling operation introduces flaws and reduces the strength of the glass. By the time it has been incorporated into the composite, the effective tensile strength is generally about 1700 Mpa, which is many times tower than its strength immediately after leaving the bushing. After spinning, the glass fiber tows, referred to as rovings 1 are wound at high speed onto cylindrical packages, or cheeses, and placed in a drying oven where the water in the size coating is removed. These cylindrical packages are the basic intermediate from which a wide variety of glass reinforcing products are manufactured. Examples of such products are described in figure 1 and are given in table 1 and 2. The tex of a fiber tow or roving is its weight in g per km.

Undirectional rovings can be used directly in composite manufacture, or they can be converted to other intermediate products. Direct applications include the uni-directional rovings used in process such as spray lay up, filament winding and pultrusion. Alternatively, the glass strands may be chopped, usually to a length of 50 mm, and sprinkled onto a moving belt to make chopped strand mat (CSM), the most widely used reinforcing product for boat building and other general purpose GRP products. CSM contains randomly orientated glass strands, held together by the application of a small amount of polymeric binder. In purchasing CSM, it is important to specify the type of binder: some are soluble in liquid resin, some are not.

More importantly, some binders are unsuitable for use in laminates to be continuously immersed in water. CSM is widely used in contact moulding, resin transfer moulding and other processes.

Continuous strand mat or swirl mat is similar in some respects to CSM, except that the fiber's are continuous. Swirl mat is used in pultrusion, where the reinforcement is required to have sufficient integrity to allow it to be pulled through the process under tension.

Technical Bulletin 1 May 1998

Glass fibre manufacture intermediate products and process

Figure 1.

manufacture intermediate products and process Figure 1. Properties of fibres and typical composite materials Table

Properties of fibres and typical composite materials

Table 1. Fibers and metals

   

Density 10 -kg/m 3

3

Modulus

(Gpa)

Tensile

strength

Specific

stiffness

Specific

strength

 

Mpa

(GPa)*

(MPa)*

 

E-glass

 

2.5

70

1700

28

680

carbon

 

1.8

230 to 820

2000 to 820

128 to

1111 to

     

7000

455

3900

 

Ararnid

 

1.4

130

3000

98

2140

Polyethylene

 

0.97

170

3000

175

3090

HT steel

 

7.8

210

750

27

96

Aluminium

 

2.7

75

260

28

96

*Stiffness or strength divided by Specific Gravity

 

Table 2: Material properties

 

Resin

Reinforcement

Possible applications

 

Density

Tensile

Tensile

comp.

Approx. cost ( /kg)

 

3

(g/cm )

strength

Modulus

strength

(Mpa)

(Gpa)

(Mpa)*

Polyester

E-Glass CSM

 

1.44

80-180

7.3.9.3

140-150

1.6

E-Glass WR

General Hand lay-up

 

1.63

210-300

12-21

150-270

1.8

E-Glass uni

 

1.80

410-1180

1241

210480

1.8

S-Glass WR

Increased stiffness

 

1.64

440

20

210

5.6

amid WR

 

1.31

430

26

115

17.1

vinylester

E-Glass WR

General RTM lay up

 

1.89

342

25

355

2,4

Glass WR

 

1.90

=520

=45

--

5.8

Aramid WR

Increased & high stiffness

1.35

=500

=40

--

20.2

Carbon WR

1.50

=600

=85

--

18.0

Epoxy

E-GIass WR

Higher strength, durability Fatigue loading High stiffness

1.92

360

17

240

3.0

E-Glass Uni

1.92

1190

39

1001

3.2

Aramid WR

1.33

517

31

172

20.9

 

1.38

1379

76

276

21.0

High strength & stiffness

1.53

625

73

500

48.3

1.57

2040

134

1000

18.5

Phenolic

E-Glass CSM

Non/semi structural, fire high temperature resist.

1.50

85-150

5-7.5

--

2.1

E-Glass WR

1.65

220-330

13-17

--

2.2

Acrylic

E-Glass WR

Structural, Fire/high

 

170

308

21

292

2.3

temperature resistance

Note: these figures are for guidance only

Technical Bulletin 1 May 1998

Glass fiber rovings may also be woven by standard textile processes into a range of reinforcing fabrics. Such woven rovings can have various types of weave, such as plain, satin or twill, plain being the most common. Woven rovings can be used in processes such as contact moulding, resin transfer moulding and pre-preg manufacture. In their most common form, woven rovings have equal quantities of fiber in the warp and weft directions, giving orthotropic laminates with roughly similar properties in these two directions. It is also possible to produce biased fabrics with different quantities of fiber in the two directions, the extreme case being "unidirectional" fabric, where almost all the reinforcement is the in the warp direction, with lust sufficient stitching in the transverse direction to maintain integrity during processing

Recently, there has been interest in "non-crimp" fabrics, where uni-directional rovings are stitched together in layers. These fabrics produce somewhat stronger, stiffer laminates than woven fabrics, because the rovings do not undulate as they would in a conventional fabric. It is also possible to stitch together layers or plies with different fiber orientation, including ± 45º plies, as well as 90º ones.

C-glass

Other special glass and ceramic fibers

C-glass is chemically resistant glass, used as a protective layer in the manufacture of pipes and other GAP components exposed to aggressive environments. Unlike E-glass, C-glass, which is manufactured by a different process, is not available in the form of continuos rovings. It is supplied as a non- woven mat, known as surface veil. The use of C-glass is intended to provide a resin rich barrier layer between a particular fluid environment and the main stress-bearing part of the laminate.

In addition to E-glass, there is range of glassy reinforcements of alternative composition, designed to give either superior mechanical performance or resistance to certain types of environment. These types of glass reinforcement are more expensive than E-glass, by a factor of 5 to 30, depending upon the material. S-glass, S2-glass and A-glass offer substantial strength and small stiffness improvements over E-glass, while ECR- glass offers enhanced resistance to certain types of corrosive environment. The use of these special glasses offshore is not currently significant, but could grow.

Silica and aluminia fiber's have much better high temperature performance than E-glass, which softens well below 1000 0 C. Benefits can therefore be achieved by combining small amounts of these fiber's with E-glass when hydrocarbon fire resistance is needed.

Technical Bulletin 1 May 1998

The nature of thermosetting resins

Polymers consist of long organic chain molecules. They are held together by two types of bond: the strong covalent bonds joining the atoms within the chains and the weak Van der Waals bonds which are between adjacent chains. If the chains are linear, the polymer can be melted or softened to allow it to be shaped, then cooled again.

Resins of this type are known as thermoplastics. If, on the other hand, the chains are bridged or cross-linked to form a molecular network, a polymer is obtained which cannot be melted and cannot be easily deformed without either fracture or decomposition taking place. This type of polymer is known as a thermoset.

Although there is interest in using thermoplastic polymers as the basis for composites, thermoplastics matrix composites are still at an early stage of development, and hence are unsuitable for large structures. All the resins of current interest for offshore use are of the thermosetting type.

Typical characteristics of thermosetting polymers are that they

usually have stiffness values in the range 2-4 GPa, depending on the degree of cross linking, with strength values around 40-70

MPa and, being bound together chemically, they are capable of

relatively little plastic deformation. Hence they cannot be shaped by flow or plastics deformation. It follows that when fabricating composite parts. from thermosetting polymers the shaping operation must be carried out at the same time as the chemical reaction that establishes the cross linked network. The cross- linking process, known as curing, can be carried out in two different ways. In the case of cold curing, the cross-linking reaction is started by mixing together components which react. In hot curing, the sequence of reactions which produces cross- linking is initiated by raising the temperature.

The cure reaction often fails to go to completion initially. In

C most cases, the properties of the composites are

considerably improved if a post-curing operation is carried

out. This is usually done by placing the component in an oven for several hours at elevated temperature. Sometimes, however, the

size or shape of the component may prevent this.

Thermosets become softer as temperature is increased, but do not melt in the way that thermoplastics do. At an elevated temperature, large segments of the molecules eventually become mobile and the Modulus falls to a low value. The temperature where the Modulus drops most sharply is called the glass transition temperature or Tg. This temperature is often taken as an approximate indication of the maximum service temperature of the resin. Eventually, at some temperature in excess of the glass transition temperature, the resin will begin to decompose.

Technical Bulletin 1 May 1998

Polyesters

These are the resins most commonly used in the manufacture of thermosetting composites in the uncured state they consist of a polymer, an unsaturated polyester resin. Unsaturated means that the backbone chain contains some carbon-carbon double bonds. The polyester is dissolved in a reactive monomor, usually styrene. To cure the resin, a peroxide initiator must be added, which decomposes to produce free radicals which act on the styrene monomor, causing it to polymerise. The polymerisation takes place by the opening up of the double bonds in the styrene and the double bonds in the polyester chain are also involved in this reactions, leading to a molecular network where the polyester chains are cross-linked by polystyrene ones, as shown schematically in figure

2.

Scheme of the filament winding process

Figure 2. Schematic representation of the cure mechanism of polyester resins

representation of the cure mechanism of polyester resins In cold -cured polyesters, the decomposition of the

In cold -cured polyesters, the decomposition of the peroxide initiator is catalysed by adding an accelerator, usually a cobalt salt. In hot-cured resins the peroxide decomposition is triggered simply by increasing the temperature.

The constituents of the polyester chain can be varied to confer the desired properties on the final polymer. For instance, the density of the cross-links can be controlled by varying the number of double bonds in the chain, known as the reactivity of the resin. Resins with high reactivity produce highly cross-linked products which have a high glass transition temperature and good chemical resistance, but which are somewhat brittle at room temperature. Low reactivity resins give a lower level of cross-linking, a lower Tg and less chemical resistance, but are tougher at room temperature.

Technical Bulletin 1 May 1998

The advantage of the free radical cure mechanism is its ease of control. The uncured resins are fairly stable and have a long shelf life but when they are required to cure, the reaction may be brought about rapidly and controllably. The period of time for which the resins remain processable after the curing system has been added is known as the pot life. Different pot lives are required according to the size of the laminating operation and the process used. The rate of cure can be varied by changing the amount of curing agent added, and additionally, a delay in the onset of curing, which may be needed for instance when laminating large structures, can be achieved by adding an inhibitor. The polyesters also have some disadvantages. The cure reaction is temperature sensitive, so the environmental temperature must be held within certain limits. The resins also tend to emit styrene vapour during processing, which is undesirable from a health and safety viewpoint. Good ventilation is required when laminating large areas.

Epoxy Vinylesters

These resins are, to a certain extent, a chemical compromise between epoxies and polyesters. The unsaturated polyester is replaced by an epoxy-like one, which is much more chemically and thermally resistant. Moreover, the styrene content is decreased. The curing mechanism is similar to that of the polyesters, although more accurate control of the quantities of curing agent added is essential, as the cure reaction is less tolerant of compositional variations than in the case of polyesters. Epoxy vinylesters, or simply vinylesters or variants of this system are used in place of polyester when improved toughness and chemical resistance is needed.

Epoxies

Epoxy resin systems generally consist of two separate ingredients which must be mixed immediately prior to processing. One of these is the epoxide or “resin” part of the system. Although the constituents of the molecule may be varied to achieve certain final properties, the key characteristic is the epoxide or ring like structure at each end of the molecule, and the fact that there are a number of -OH groups present on the chain. The cross-linking reaction may involve both the end groups and the hydroxyl (-OH) groups.

The second ingredient of the resin is the hardener, which is frequently a primary or secondary amine or an acid anhydride. For wet laminating and filament winding, the main offshore uses, amine cured epoxies are preferred. Two different types of amine may be used; aliphatic amines or aromatic amines.

Aromatic amines give the highest T a values, and the best mechanical and chemical properties at high temperature, but they are most expensive. Aliphatic amines are less expensive and below 100ºC their cured resin properties are at least as good as those of aromatic amines. They do, however, require careful post curing.

Technical Bulletin 1 May 1998

Unlike the polyester resins, epoxies lake longer to cure during processing. Anhydride cured epoxies have excellent properties and are used in prepeg systems for aerospace and also in large quantities in piping Systems.

In the case of epoxy prepregs, the reinforcement is impregnated with resin and cure allowed to progress to an intermediate B-stage where it is halted. The prepeg is then kept at low temperature until it is needed for moulding. Prepreg systems are much more expensive than composites produced by the "wet resin route", but they do produce products with excellent properties. Some companies with in-house pre-pregging facilities are beginning to use prepeg systems for marine construction.

Phenolics

These are the oldest class of synthetic polymers. Recently, many improvements have taken place in the chemistry of these resins, which have rendered them suitable for use in composites. There are two main types of phenolic resin which am distinguished by the type of curing agent used.

The majority of the liquid resins processed by cold cure are hardened by the addition of a strong acid catalyst. The catalyst can cause problems with corrosion of mould tooling and there can also be difficulties with the alkali content of glass fiber reinforcements from certain sources, which can interfere with the action of the curing agent. Most phenolic resins contain a certain amount of water, and further water is evolved during the cure reaction. Although most of the water can be removed by a high temperature post cure, this usually leaves the matrix with a number of microvoids. Despite this, and despite the fact that the matrix is relatively brittle in the un-reinforced state, phenolic resin composites have good mechanical properties, which at room temperature are comparable to those of composites based on isophtalic polyester. Because of the presence of the microvoids, phenolics show a higher level of water absorption than the other resins but there is little evidence as yet that this causes any long term deterioration of properties.

The outstanding feature of phenolic resins, which has proved the driving force behind the development of more easily processed grades, is their fire performance. They possess relatively good levels of integrity at high temperatures, have low smoke and toxicity as well as low levels of heat release. For these reasons, they may well be the only resin systems which can be tolerated in laminates facing in critical area's such as accommodation modules and safe havens. The reason for the good performance of these resins in tire is that instead of decomposing and volatilising at high temperatures, the aromatic ring structure in phenolics condenses progressively, eventually producing a carbonaceous char, which persists for some time. However, a disadvantage of phenolics in fire is that any water present in the laminate can sometimes lead to violent delamination when it volatiles.

Technical Bulletin 1 May 1998

Because of their generally attractive attributes in fire, there have been attempts recently to develop grades or resin that can be processed by pultrusion. These have met with some limited success, and there are now two manufacturers in Europe offering phenolic matrix pultrusions. Phenolic resins are also used as the basis for foams, which have excellent insulating properties, combined with low toxicity. They are unfortunately very friable, which greatly restricts their feasibility for use as a core for sandwich panels.

There are, however, a number of phenolic based syntactic core materials which contain various lightweight mineral fillers bonded together in a phenolic matrix. Some of these materials have exceptionally good burn-through characteristics are therefore viable core materials for heat and blast protections panels.

In addition to the acid-cured phenolics, there is another class, known as novolacs, which are cured by alkaline agents. These resins are favoured for hot cure processes such as press and prepeg moulding. Recently, to overcome the problems of both acid and base cured resins, new "neutral” curing systems have been introduced.

Filament-Winding

This is the process by which composite pipework is manufactured, but which has also the potential to be used for large complex structures. There are several configurations, but in the most common one, shown in Figure 3, continuous tows of reinforcement are drawn through a resin bath to wet them and then applied, via a transversing feed eye, to a rotating mandrel. The speed of the feed eye relative to that of the mandrel determines the winding angle. For pressure piping, a winding angle of t 550 is normally used. Modern winding machines are numerically controlled to lay down a precisely controlled number of covers of reinforcement. For chemical resistance, pipes are usually provided with a resin rich inner linen This is applied to the mandrel in the form of a non-woven scrim, soaked in resin. The reinforcement in the scrim may be either C-glass of non- woven polyester fabric.

Filament winding is not limited to simple cylindrical shapes:

pipes with bell ends may be wound, as may pressure vessels or storage tanks with wound in ends. Large structures such as storage tanks and silos may also be produced by filament winding. In some cases as with large tanks, the process may be simplified to one of hoop winding, to minimise the rate at which the feed eye must transverse the mandrel. When this is done, spray lay-up of randomly oriented fiber's is often employed in addition to the hoop winding to give the structure the necessary transverse strength.

Technical Bulletin 1 May 1998

The process is not limited to axi-symmetric structures:

prismatic shapes and more complex parts, such as tee-joints may be wound on machines equipped with the appropriate number of degrees of freedom. Complex shapes which have been successfully filament wound include rocket motor casings 1 aircraft fuselages and railroad hopper cars.

In the introduction of pipework, impregnated lows are wound onto waxed, preheated steel mandrels. After winding these are removed from the machine to an oven for curing and post curing, during which the mandrel is continuously rotated to maintain uniformity or resin content around the circumference. After curing, the pipe is removed from the mandrel, either by a hydraulic extractor or by the application of internal pressure. Although most filament winding operations are batch processes, it is possible to filament wind continuous pipework.

Figure 3. Scheme of the filament winding process

RECIPROCAL FILAMENT WINDING PROCESS

filament winding process RECIPROCAL FILAMENT WINDING PROCESS Source 1994 Marinetech Research, Project CP 275, General

Source

1994 Marinetech Research, Project CP 275, General Principals and Guidance for the Application of Glass Reinforced Composites Offshore.

Edited by

Contributors: M.J. Cowling, T. Hodgkiess, T.Y. Reddy.

: D.A. Spagni and A.G. Gibson.

Technical Bulletin 1 May 1998