Composires Part A 27A (1996) 1089-1095 Copyright 0 1996 Elsevier Science Limited

ELSEVIER

S1359-835X(%)00070-X

Printed in Great Britain All rights reserved 1359-835X/96/$15.00

Fabrication of woven carbon fibre/ polycarbonate repair patches

F. C. Smith*,

L. D. Moloney

and F. L. Matthews

Centre for Composite Materials, Imperial College of Science, Technology and Medicine, Prince Consort Road, London SW7 2BY, UK

and J. Hodges
Structural Materials Centre, DRA Farnborough, Farnborough, Hampshire GU14 6TD, UK (Received 10 December 1995; revised 16 April 1996)

In-field repair of composite aircraft is often performed in difficult conditions and hence needs to be as simple as possible. Current repair techniques generally involve the application of composite patches based on thermosetting epoxy resin via either wet lay-up, prepreg stacking over a film adhesive, or bonding precured patches. These methods of repair are very effective, but a complex cure cycle under controlled conditions is required and the use of epoxy resin means that storage must be taken into consideration. Composites patches based on thermoplastic resins overcome both of these problems; they do not require curing, and have no special storage needs. Thermoplastics can also be thermoformed and can hence be produced in sheet form and formed to the correct shape in situ during adhesive bonding to the surface to be patched, using vacuum and heat. With its low thermoforming temperature and good mechanical properties, polycarbonate is a good candidate for use as a thermoplastic matrix, with woven carbon fibre fabric as the reinforcement to produce patch laminates. The present paper describes the use of solution impregnation together with film stacking to produce patches of acceptable quality and how these patches were formed without any wrinkling using double diaphragm forming. Copyright 0 1996 Elsevier Science Limited (Keywords:repair patches; wovencarbon fihre/polycarbonate composite; fabrication)

INTRODUCTION Current composite repair techniques generally involve the application of patches based on thermosetting epoxy resins, these being fabricated using either in situ wet layup, prepreg stacking over a film adhesive or by bonding precured patches. These methods give a good quality patch but a complex cure cycle under controlled conditions is needed to achieve optimum results. For the quick in-field repair of battle damaged aircraft, often performed in difficult conditions, thermoplastic based patches offer two potential advantages over thermosets: they need no special storage conditions prior to use and, having no lengthy cure cycle, they can be more quickly applied. Further, since thermoplastics can be thermoformed, it may be possible, using an appropriate thermoplastic matrix and adhesive, to develop a system whereby the patch forming and the bonding of the patch on to the damaged surface take place together
* To whom correspondence should be addressed

in a single process. An ideal thermoplastic patch for this in-field repair involving the minimum of equipment will be able to be thermofomred and bonded in place using only vacuum and heat. The most widely used high performance thermoplastics currently commercially available are polyetheretherketone (PEEK), polyethersulfone (PES) and polyetherimide (PEI). Given their superior mechanical properties at elevated temperatures it would obviously be advantageous to use them. However, since the patch should be thermoformed and bonded directly over the damage site, the problem of forming temperatures arises. The thermoforming temperatures of these materials are too high for use with in situ forming on composite aircraft panels since the panel being repaired may suffer extensive heat damage to both its matrix and any sealant present on its internal surface. So, a thermoplastic with a lower forming temperature must be used, with any reduction in mechanical properties accepted, for this sort of repair process to be viable. From the previous work in this area*, two possible

1089

Fabrication

of woven carbon fibrelpolycarbonate

repair patches: F. C. Smith et al.

Figure 1 Chemical reaction to produce polycarbonate

thermoplastic matrices were identified: polycarbonate and acrylonitrile-butadiene-styrene (ABS), both mentioned as having a thermoforming temperature below 175C. The work described in the present paper is based on two MSc projects performed at Imperial College213.In addition to optimizing the process of patch production, the bondability of patches to epoxy matrix composites was also studied; only the former aspects are discussed here. The initial study2 assessed the suitability of both polycarbonate and ABS. It proved impossible to fabricate acceptable panels using solution impregnation and hot pressing of ABS in the granular form available. It was concluded that the use of powder or, possibly, film might prove more successful. Acceptable laminates were, however, produced from polycarbonate by a combination of solution impregnation and film stacking, although the pressures and temperatures that had to be used were too high for field repairs. In the second project3 only polycarbonate was studied. The techniques used before were improved upon and the requirements for thermoforming were evaluated.

toxicity. Pyridine, cresylic acid solvents and p-dioxane are the non-halogenated solvents. Hydrocarbons and aliphatic alcohols, esters and ketones do not dissolve polycarbonates. Chlorobenzene is an adequate high temperature solvent, but the polymer may crystallize and set to a hard gel state on cooling. Acetone promotes rapid crystallization of the normally amorphous polymer, and causes catastrophic failure of stressed polycarbonate parts. The glass transition temperature Tg of 149C for bisphenol A polycarbonate is unusually high compared to that of polystyrene (lOOC), nylon-6,6 (45C) and polyethylene (-45C). A high Tp indicates excellent dimensional stability and resistance to creep under load. Bisphenol A polycarbonate becomes plastic at a reported melting range of 215-225C and it may then be shaped with sufficient pressure. The viscosity continues to decrease with increasing temperature and over its normal injection moulding range, of 270-315C, the melt viscosity drops from 1100 to 360 Pas. For comparison purposes, the melt viscosity of poly(ethylene terephthalate) of similar molecular weight is five times lower over the same temperature range. Bisphenol A polycarbonate exhibits outstanding thermal stability. The dry polymer may be held for hours in the molten state up to 320C and for short times up to 330-350C with minimum degradation. Decomposition begins at an appreciable rate above the latter temperature and rapid cracking and loss of volatile fragments occurs above 400C. The outstanding thermal stability coupled with a high degree of aromaticity combine to make bisphenol A polycarbonate resistant to burning.

PRODUCTION COMPOSITES

OF THERMOPLASTIC

MATRIX

Solution impregnation

POLYCARBONATE The economically most important polycarbonate is 2,2bis(4-hydroxyphenyl) propane polycarbonate, also termed bisphenol A polycarbonate (BPA-PC). The great commercial success of BPA-PC is due to its unique combination of properties: extreme toughness, outstanding transparency, excellent compatibility with several polymers and high heat distortion resistance4. Few details of commercial polymerization have been disclosed, but the basic chemistry is shown in Figure 1. The reaction may be run in solution employing a polymer solvent such as methylene chloride and an acid acceptor such as pyridine. The polymer (MW 12 000-l 5 000) may be recovered as a methylene chloride solution after multiple aqueous washes to remove the pyridine hydrochloride formed and excess pyridine. Chloroform, c&l-2-dichloroethylene, sym-tetrachloroethane and methylene chloride are the preferred solvents for polycarbonate. Methylene chloride is an excellent solvent with the advantages of low flammability and

The most frequently tried approach to impregnation is to dissolve the polymer in a suitable solvent and use that low viscosity medium to wet the fibres. The preferred solution concentration is about 10% by weight of polymer. The impregnation operates at ambient temperature and is followed by drying to eliminate the unwanted solvent. The wetting process itself relies mainly on surface tension forces. The process is relatively easy to operate, provided that a suitable solvent is available for the polymer matrix. Despite many arguments in favour of solution technology, for many years it was a relatively unused technique. The reasons against solution impregnation are:
l

the use of solution technology usually leads to a sensitivity to solvents in service; the presence of residual solvents compromises processing and reduces service performance, particularly at high temperature; because the fibre wetting process is determined by

1090

Fabrication

of woven carbon fibrelpolycarbonate

repair patches: F. C. Smith et al.

surface tension forces, the fibre distribution is not easily controlled; and the fibre-matrix interface produced in the solution process is inadequate.

The problem of solvent sensitivity can be addressed in one of three ways: the use of the composite can be constrained to those applications where solvent exposure is not critical or, in use, those solvents to which it is susceptible can be avoided; the polymer can, after the composite is formed, be crosslinked to make it insensitive to solvents; and the solvent used can itself be a monomer and be subsequently polymerized. Elimination of solvents from the composite takes place in two stages. The removal of the bulk of the solvent (increasing the polymer concentration from about 15 to 95%) and removing the final traces of the solvent. The presence of residual solvent may, on occasion, be exploited. It can be used to soften the composite to make it drapable and tacky and hence suitable for hand lay-up; in this case the residual solvent must be removed during the final processing stage. Failure to remove the residual solvent leads to bubbles or blisters in the composite, and high temperature properties may be affected. The presence of even traces of residual solvent may also provide a path for accelerated attack by solvents in service. The interface between the fibres and matrix is a critical feature of thermoplastic matrix composites, and in composites prepared by solution impregnation this interface is usually not very good. The reasons for this are not exactly known, but there are currently three possible explanations:
l l l

This process can take several hours to fully wet-out the fibres. The high pressure applied can also lead to the problem of fibre damage, especially in the case of woven fabrics where the fibres cross one another. Since film stacking is based on flat film, it is well adapted to making flat sheets, but it can be adapted to shaping complex forms. Despite its problems film stacking is still widely used, and when used with reinforcing fibres which have been pre-impregnated to some degree with thermoplastic the problem of poor wet-out can be reduced. Hence, a combination of solution impregnation followed by melt processing appears to be a good way to place fibres within a thermoplastic resin as the unwetted fibres after solution impregnation would be easily wetted by a subsequent melt process.

PATCH LAMINATE

FABRICATION

Initial studies2 showed that solution impregnation of the fibres followed by film stacking and hot pressing produced laminates with the fewest defects. Several variations of both processes were investigated before a satisfactory procedure was established. One difficulty encountered was that polycarbonate could only be obtained in granular, rather than powder, form.
Solution impregnation

detachment of the interface during solvent extraction; concentration of residual solvent at the interface; and phase separation of low molecular weight species at the surface of the fibres.

During removal of the solvent from the interface, the natural escape route is through the surface layers, but an alternative course is for the solvent to move to the fibrematrix interface, detach the interface, and then move along the fibres surface until it reaches the surface of the composite.
Film stacking

Film stacking was, for a long time, the standard method for producing thermoplastic composites. Layers of reinforcing fibres are interposed between layers of thermoplastic sheet, and then the stack is compressed at a temperature above the Tg of the thermoplastic to pressures of at least 10 bar. The major problem with this technique is achieving good fibre wet-out. In the melt form the thermoplastic is still highly viscous and high pressure must be applied to force this melt through the tiny gaps between the fibres.

It was found.2 that 5% w/w of polycarbonate granules in dichloromethane gave a relatively fast dissolving solution which gave good impregnation. Since the evaporation of the dichloromethane during dissolution was a problem, the mixture needed to be placed in a tight capped bottle. This had the added advantage that the mixture could be shaken to accelerate its dissolving. To prevent it disintegrating during impregnation the woven carbon fibre fabric* was fastened to a wooden picture-frame of 500mm side length. The fabric in the frame was placed in a bath containing 2dm3 of the solution and gently massaged with a brush. After removal from the solution, the fabric in the frame was slowly rotated to prevent the solution dripping to one end. When dry, the fabric was removed from the frame, weighed, and the mass compared with the original mass of fabric. After a number of impregnations, the average weight fraction of polycarbonate in the fabric was 12.08%. The only problem with this technique was that although it was initially taut in the frame, on immersion in the solution the fabric stretched. This meant that on drying the fabric was no longer flat. Various attempts to solve this, such as drying against a Perspex sheet, were unsuccessful.
satin *Five-harness 5 13 1 yarn supplied weave fabric, SC516,283 by Sigmatex grn- using Tenax HTA

1091

Fabrication

of woven carbon fibrelpolycarbonate

repair patches: F. C. Smith et al.

--I_

O/90
-_

+I-45
O/90

-= poly&nate film O&O = impregaated fabric in O/W direction I-45 = impregnated fabricin +A45direction

+I-45 -0190

+/a
O/90 ---__

+/a -Figure 2
Initial lay-up 0190 --_

+/-45 __--_O/90 +I-45 -___I_+/-a5 __-_-_ O/90 l-45 _-I-_-_ 0190 __-----__ Figure 3
Symmetrical stacking sequence

Originally the impregnated fabric was left for a couple of hours at room temperature until it felt dry. After investigation, it was found that leaving the impregnated fabric in a vacuum oven for two weeks at 80C produced a laminate which was almost completely free of bubbles. The problem of fibre distortion was resolved by processing a symmetrical lay-up, as shown in Figure 3. It should be noted that better results were obtained with an enclosed press. With an open press, which was also used, the edges of the mould were cooler than the centre, resulting in poorer consolidation around the periphery of the laminate. One laminate was produced in an autoclave. The schedule followed was the same as for the laminates produced in the press. The resultant laminate was very well consolidated, with no visible bubbles. The C-scan showed that the quality of the laminate was more consistent than for those prepared in the hot-press. This result showed that if the patch laminates were to be manufactured before being taken into the field, they could be prepared in bulk in an autoclave.

THERMOFORMING Thermoforming was originally developed as a fast, low technology means of shaping unreinforced thermoplastic sheets, requiring only simple equipment. Thermoplastics, in sheet form, are heated to a plastic state in which the sheet retains its integrity throughout a heating and stretching sequence. Combinations of vacuum, air pressure and mechanical force are used to shape the heat-plasticized sheet to a mould. The addition of long-fibre reinforcement can seriously complicate the thermoforming of thermoplastics. The most severe situation arises in advanced composites which involve the use of continuous, straight, parallel fibres, crossplied and packed to a high volume fraction. In such composites in-plane flexibility is much reduced, local thickness reductions cannot occur without major rearrangement of fibres, local wrinkling may occur, and the position of the fibres is difficult to control. Of the various heating methods available infrared (i.r.) heating has been proven to be a good choice for thin, well compacted flat sheets, or gentle contours in a continuous oven feeding a moulding process. For loosely compacted plies convection heating is an effective method. Impingement heating in which many high velocity jets of heated air impinge on the surface, and contact heating using, say, a heater mat are alternative methods. Radio frequency heating can be effective, but is very dependent upon part composition and geometry and requires specialized design and set-up experience. The choice of a forming method depends on the level of capital investment desired and the effect of the method on the quality of the final part. The major processing methods currently being used in thermoforming are6 matched-die press forming, diaphragm

Film stacking and hot pressing

Initial study of the manufacture of polycarbonate/ carbon fibre laminates using film stacking and hot pressing found that six layers of pre-impregnated fabric separated by five layers of polycarbonate film (plus two layers at each outer surface) gave the best laminate, possessing good fabric impregnation and a good surface finish. This was used as the basis for further trials3 with the laminates produced containing 11 layers of polycarbonate film (two on each outer surface), as shown in
Figure 2.

The stack of fabric and film was inserted in a release coated metal mould and then placed in a heated press for 20min at 1.24MPa and 265C. Apart from the central region the quality of the resultant laminate was poor when checked by eye, with ultrasonic C-scanning and using microscopy. The major fault was bubbles in the upper surface layer of polycarbonate, although there was also distortion of the weave pattern at the edges of the laminate. Other combinations of film and prepreg stacking failed to produce a satisfactory laminate. The process thought to be causing the bubbles in the top surface of the laminate was excess solvent from the impregnated fibres being driven off during the hot pressing and not being able to escape from the mould.

1092

Fabrication

of woven

carbon

fibrelpolycarbonate

repair patches:

F. C. Smith

et al.

-----

=mould = breather cloth = releasecloth =vacuumbGIg = kmmcouple

Figure 4

Set-up used to thermoform

the patch laminate

using a heater mat and vacuum

forming, hydroforming, autoclave forming, forming and rubber pad press forming.

vacuum

THERMOFORMING

OF PATCHES

As previously stated, one constraint on in situ thermoforming is that the patch should not be allowed to exceed temperatures of about 110C. The reason for this limitation is that when applying a patch to an aircraft, using the aircraft as a mould, the substructure and seals of the aircraft could undergo thermal degradation at temperatures in excess of 110C. Since the normal forming temperature of polycarbonate is quoted4 as 191C, and the lower forming temperature is given as 168C, unless the patch laminates could be made to form at significantly lower temperatures than these, some form of insulation would have to be used between the patch laminate and the mould to prevent the mould from becoming too hot.
Initial studies

The initial studies reported here involved simply heating the patch laminates with a heater mat or in an oven and pressing the laminate by hand on to a mould. A laminate was placed on top of a double curvature mould (with radius of curvature of 100 mm) with a heater mat on top. Thermocouples were placed on the top and bottom surface of the laminate and the top surface of the mould and the temperatures were monitored constantly as the temperature of the heater mat was increased. With pressure applied by hand no deformation of the laminate occurred until the setpoint of the heater mat was increased to 150C. A small amount of deformation remained when the pressure was relieved, but the bottom surface of the laminate was severely wrinkled. The major problem with this method of thermoforming the patch laminates appeared to be the large temperature difference between the top and bottom surfaces of the laminate, due to the low through-thickness thermal conductivity of the laminate. In order to get the bottom of the laminate to a temperature at which it would form readily, the top of the laminate would have to be at a very high temperature. Following the above, a laminate was placed in an oven in order to produce even heating. After being left in an oven at 160C for 1 h the laminate was removed, placed

immediately on the mould and again pressed by hand. On removal from the oven the laminate cooled very rapidly and, on placing it on the mould where the thermocouple on the surface of the laminate read 12OC, the laminate could not be bent. Since the problems with the previous methods appeared to be the poor through-thickness thermal conductivity of the patch laminates, and the high cooling rate, the next method tried involved enclosing the laminate in a vacuum bag during heating which would help prevent cooling, and the vacuum could be used to provide the forming pressure rather than having to form by hand. Figure 4 shows the set-up used. The heater mat and vacuum were controlled by a hot bonding machine which gave a read-out every 2 min of the thermocouples and the level of vacuum. Initially the vacuum was set at 125 mm Hg, but as the laminate began to form, this was increased to 625 mm Hg. With a single curvature mould (with radius of curvature of 1.50mm). the laminate began to form at between 140 and 15OC, and it was at this point that the vacuum was increased and pulled the laminate down on to the mould. The laminates were held like this for - 10min and then cooled down with the vacuum still applied. On removing the vacuum, the laminates retained the shape of the mould, but were wrinkled on the bottom surface (next to the mould). A second mould was tried which contained two 90 bends. With the setpoint of the heater mat at 160C the laminate formed to the shape of the mould. The inner surface of the laminate showed severe wrinkling at the 90 bends. From the above results it can be seen that the polycarbonate formed at rather lowe temperatures than the quoted literature value7 of 168C. It was clear that the wrinkling seen was due to the bottom (or inner) surface of the laminate being in compression during forming. One way to solve this is by diaphragm forming, which involves encasing the laminate under vacuum between two diaphragms which keeps the laminate slightly in tension during forming. This approach was investigated at DRA Farnborough. following the studies at Imperial College.
Double diaphragm forming and consolidation

Double diaphragm forming has evolved from the vacuum forming of thermoplastic sheet and the superplastic forming of metals. The main principles of the

1093

Fabrication

of woven carbon fibrefpolycarbonate

repair patches: F. C. Smith et al.

Glasschordto

Mould

cooling process was started. On removal from the mould the laminate was well consolidated and matched the shape of the mould perfectly with no wrinkles. During experimentation with the forming process it was found that if the preform was too large the excess material around the edges of the mould prevent movement during forming and caused wrinkling at the edges of the mould. By simply ensuring that the correct amount of preform was used this problem was eliminated. I

............... Ucl@Jl

--_----~gm
Figure 5 process

-=kYtape
-laminate

pJ_cld

clamping-

DISCUSSION The work2>3reported here has shown that it is feasible to produce, on a laboratory scale, patches of acceptable quality from woven carbon fibre fabric and polycarbonate. The issues underlying impregnation and consolidation have been studied and patches produced via a procedure involving solution impregnation and film stacking, using either a heated press or an autoclave. There is no obvious reason why the method could not be scaled up for batch production, enabling aircraft operators to maintain a store of patches for further use. It has also been shown that such patches can be satisfactorily shaped using double diaphragm forming. Simple forming using a heater mat, or an oven, was not satisfactory. Of course, whilst diaphragm forming may be possible at a major maintenance depot, its use in the field is questionable. For in-field repair there are two alternative solutions: if the radius of curvature required was shallow it may be possible to form the polycarbonate patches using a heater mat and vacuum bag without wrinkling of the patches occurring. Alternatively, patches formable at lower temperatures than those required by polycarbonate could be used in conjunction with a heater mat. On the wider issue of using thermoplastic matrix patches for repair, one needs to consider both the bonding of the patch to the parent composite, and the durability of the repair. The former issue appears not to be a serious problem according to results obtained on bonded lap joints at Imperial College3. The durability issue is perhaps more serious. As noted above, polycarbonate is soluble in a number of solvents, some of which could well be encountered in the operating environment of civil and military aircraft. One result of contamination could be embrittlement of the polycarbonate matrix resulting in a possible lossof strength of the repair. Clearly the patch could be covered with a protective layer, or the use of the more damaging solvents prohibited. However, such issues would need to be addressed before the use of such materials could be certificated.

Lay-up placed in autoclave in double diaphragm forming

process are: the unconsolidated preform is placed between two thin plastically deformable diaphragms; the diaphragms are clamped around the edge of the mould and the application of vacuum maintains the composite preform in a state of biaxial tension; and the preform and tooling are heated to the processing temperature of the polymer matrix and the diaphragms are stretched over a die by the application of a differential hydrostatic pressure. Since the diaphragms maintain the preform in a state of biaxial tension during the forming problems such as wrinkling, splitting and thin spots are eliminated in the final laminate. The double diaphragm forming carried out at DRA Famborough used both impregnated woven fabric with polycarbonate film and dry woven fabric with polycarbonate film. When the impregnated fabric was used, eight plies of the fabric and nine sheets of polycarbonate film were used, whereas with the dry fabric eight plies of fabric and 18 sheets of polycarbonate film were used (two sheets of film between each ply of fabric and two sheets on each outer edge). The mould used during the forming process was a half-cylinder with a radius of curvature of 100 mm and tapered ends. The material was laid up as shown in Figure 5 with section B under vacuum to keep the preform in a state of biaxial tension and the vacuum in section A was used to help consolidate and form the laminate. Bagging material was used as the diaphragm, a knotted piece of glass chord was placed in the vacuum port of section B to prevent any excess resin blocking the port, and a thermocouple was placed on the clamping frame (not on the laminate to prevent marking) to record the temperature. The set-up was placed in an autoclave and vacuum was applied to section B. The autoclave was heated to 220C and left to soak for 10min after which vacuum was applied to Section A. After 5 min 1 bar of pressure was applied and after a further 5 min this was increased to 3 bar. This pressure was held for 10min and then the

CONCLUSIONS Using a combination of solution impregnation, stacking and hot pressing, polycarbonate/carbon film fibre

1094

Fabrication

of woven carbon fibrelpolycarbonate

repair patches: F. C. Smith et al.

laminates were produced that were well consolidated and had a relatively low void content. It was shown that thermoforming of polycarbonate based laminates can be performed at lower temperatures than those previously reported, with forming beginning between 140 and 150C when a heater mat and vacuum bag were used. This method, however, produced severe wrinkling on the bottom surface of the formed laminate. Double diaphragm forming was shown to be an effective method to produce well formed, wrinkle free polycarbonate/carbon fibre laminates.

contract monitors acknowledged. REFERENCES

and other DRA staff is gratefully

ACKNOWLEDGEMENTS The bulk of the work described here was performed at Imperial College by the first two authors whose MSc studies were funded by the DRA Farnborough (Contracts 2037/402MA and 2037/402). The assistance of the

Murphy, D. Development of damage repair techniques: use of low temperature thermoplastic composites, Report No. C325A, Royal Aircraft Establishment (Fdmborough), prepared under Contract no. A91B/211 Amendment No. 3, 1990 Moloney, L. Repair of composites using thermoplastic composite patches. MSc Project Report, Centre for Composite Materials, Imperial College, 1993 Smith, F.C. Repair of composites using thermoplastic composite patches. MSc Project Report. Centre for Composite Materials, Imperial College, 1994 International Encyclopaedia of Composites, Vol. 4, VCH Publishers Ltd, New York, USA, 1991, pp. 141-156 Encyclopaedia of Chemical Technology, Vol. 18, WileyInterscience, 1982, pp. 480-494 Okine, R.K. Analysis of forming parts from advanced thermoplastic composite sheet materials. SAMPE J. 1989, 25(3) 9-19 Throne, J.L. Thermoforming, Hanser Publishers, Munich, Germany, 1987

1095