GB2478749A

GB2478749A - Composite materials of reduced electrical resistance

Info

Publication number: GB2478749A
Application number: GB1004365A
Authority: GB
Inventors: John Ellis; Emilie Fisset
Original assignee: Hexcel Composites Ltd
Current assignee: Hexcel Composites Ltd
Priority date: 2010-03-17
Filing date: 2010-03-17
Publication date: 2011-09-21
Also published as: US20130005205A1; CN102802944A; BR112012023882A2; EP2547519B1; ES2717612T3; KR101813958B1; JP5813020B2; RU2556658C2; CN102802944B; US9187606B2; EP2547519A1; US10144153B2; CA2788610A1; CA2788610C; GB201004365D0; BR112012023882B1; JP2013522412A; RU2012144030A; AU2011228823B2; WO2011114140A1

Abstract

A prepreg comprises a structural layer of conductive, preferably carbon, fibres comprising thermosetting resin in the interstices and an outer layer of thermosetting resin. The outer layer is populated by some filaments of the structural layer which are free-filaments located at the interface between the structural layer and the outer layer. The prepreg is preferably manufactured by passing the electrically conductive fibres over a disrupter, preferably a spreader bar with an abrasive surface, which breaks the outer fibres of the structural layer, to cause a proportion of the fibres on an external face of the sheet to become free filaments. During heating to curing temperature the resin has reduced viscosity and the free filaments are able to migrate into the outer layer. Free fibres of adjacent layers of a laminate of the layers migrate into the outer/inter-layer and the inter-layer becomes conductive due to a network of contacting free fibres to provide a laminate of reduced electrical resistance through its thickness. The composite is intended for use in applications where lightening strikes are a possibility such as aircraft structures.

Description

Title: Process for Manufacturing Composite Materials

Technical Field

s The present invention relates to a process for manufacture of prepregs comprising fibres and resin matrix which when stacked to form a laminate and subsequently cured, form composite materials, particularly with improved resistance to damage caused by lightning strikes.

io Background

Composite materials have well-documented advantages over traditional construction materials, particularly in providing excellent mechanical properties at very low material densities. As a result, the use of such materials is becoming increasingly is widespread and their fields of application range from "industrial" and "sports and leisure" to high performance aerospace components.

Prepregs, comprising a fibre arrangement impregnated with thermosetting resin such as epoxy resin, are widely used in the generation of such composite materials.

Typically a number of plies of such prepregs are "laid-up" as desired and the resulting laminate is cured, typically by exposure to elevated temperatures, to produce a cured composite laminate.

Such prepregs are typically manufactured by impregnating a sheet-like structure of structural fibres with a thermosetting resin. Such sheet-like structures first need to be prepared from a number of so-called tows of fibres. A fibre tow is a bundle of filaments, e.g. 12,000 filaments, with an approximately rectangular cross-section with dimensions of around a centimetre by a couple of millimetres.

A comsnon method of "spreading" such tows to merge and form a single sheet of structural fibres is to pass them over a sequence of spreader bars, or rollers. EP 1172191 gives an example of improvements in such a process by eliminating the "fuzz" which is generated.

A common composite material is made up from a laminate of a plurality of prepreg fibre layers, e.g. carbon fibres, interleafed with resin layers. Although the carbon fibres have some electrical conductivity, the presence of the interleaf layers means that this is only predominantly exhibited in the composite in the plane of the laminate.

The electrical conductivity in the direction orthogonal to the surface of the laminate, the so-called z-direction, is low.

The lack of conductivity in the z-direction is generally accepted to contribute to the vulnerability of composite laminates to electromagnetic hazards such as lightning strikes. A lightning strike can cause damage to the composite materials which can be quite extensive, and could be catastrophic if occurring on an aircraft structure in flight. This is therefore a particular problem for aerospace structures made from such composite materials.

A wide range of techniques and methods have been suggested in the prior art to provide lightning strike protection to such composite materials, typically involving the addtition of conductive elements at the expense of increasing the weight of the composite material.

In WO 2008/056123 improvements have been made in lightning strike resistance, by adding hollow conductive particles in the resin interleaf layers so that they contact the adjacent fibre layers and create an electrical pathway in the z-direction. However this often requires elaborate processing methods and can reduce fatigue properties.

There therefore remains a need in the art for a conductive composite material which is lightweight and has excellent mechanical properties.

Summary of Invention

The present inventors have surprisingly discovered that improvements in the electrical conductivity of a cured laminate of prepregs can be achieved by manipulating the structural fibres prior to resin impregnation.

Thus, in a first aspect, the invention relates to a prepreg comprising a structural layer of conductive fibres comprising thermosetting resin in the interstices, and a first outer layer of resin comprising thermosetting resin, and comprising a population of s conductive free filaments located at the interface between the structural layer and the outer resin layer which, when cured under elevated temperature, produces a cured composite material comprising a cured structural layer of packed conductive fibres and a first outer layer of cured resin, the outer layer of cured resin, comprising a proportion of the population of conductive free filaments dispersed therein.

Such prepregs are believed to undergo a minor structural transformation as it is heated but before it reaches temperatures sufficient to cause curing of the resin. As the resin is heated its viscosity drops and the free fibres are free to migrate into the resin layer away from the interface. As the temperature rises further, the resin begins to cure, is fixing the free filaments in place distributed within the resin layer.

The free fibres are believed to form electrical contacts between themselves and bridging the resin layer, thus increasing the electrical conductivity in the z-direction of the cured composite material. Thus, the resin layer can be made to become electrically conductive without having to add any conductive elements to it during prepreg manufacture.

In one embodiment, the conductive free filaments may be separately prepared and deposited onto the surface of the structural layer prior to resin impregnation.

However, the inventors have found that manipulation of an outer face of the structural layer of conductive fibres to generate the free fibres by disrupting a proportion of the conductive fibres, is a particularly convenient method of production.

Thus, in a second aspect, the invention relates to a process for producing a prepreg, the process comprising passing a sheet of electrically conductive fibres to a fibre disrupting means to cause a proportion of the fibres on an external face of the sheet to become conductive free filaments and subsequently impregnating the sheet with thermosetting resin and generating an outer layer of resin comprising thermosetting resin in contact with the external face of the sheet comprising the free fibres.

The disrupting means therefore manipulates the fibres at an external face to become s free filaments. The term "free filaments" means filaments which are not physically bound to any other body and are essentially mobile. The free filaments thus formed are not adhered to any other fibres and are freely mobile.

As such the free filaments will also have an upper limit on their length, sufficient to io maintain their free filament nature.

For example, the free fibres typically have a distribution of lengths with a mean length of less than 2.0 cm, preferably less than 1.0 cm, more preferably less than 0.5 cm.

is The layer or sheet of electrically conductive fibres may be in the form of random, knitted, woven, non-woven, multiaxial or any other suitable pattern. However, preferably the electrically conductive fibres are unidirectional. When the conductive fibres are unidirectional a free filament may be generated by a single break in a unidirectional fibre. This single break allows the free filament to migrate about an anchor point, to move into the outer resin layer or interlayer.

The disruption means may generate the free fibres in a number of ways depending on how the structural fibres are arranged, for example by breaking points of adhesion between structural fibres and breaking structural fibres into shorter lengths.

Thus, the invention is highly innovative as it can involve actively generating ftizz or broken fibres, which have hitherto been seen as a problem to be eliminated.

In a preferred embodiment, the conductive fibres are unidirectional fibres and the disruption means involves passing the fibres over an abrasion surface, thereby causing breakage of a proportion of the fibres on the external face passing in contact with the abrasion surface, whilst the fibres not in contact with the abrasion surface remain unbroken.

It has been found that breaking from 0.5 to 5.0 wt% of the fibres in at least one location provides good results.

s As discussed above, unidirectional fibre sheets are typically formed from a plurality of tows of fibres, which are spread out to merge together, prior to impregnation with resin. A common method of achieving this is to pass the fibres over a plurality of sequential spreader bars or rollers.

It is therefore convenient for the abrasion surface to be incorporated in an existing spreader bar arrangement. Thus, in a preferred embodiment, the abrasion surface is the surface of a spreader bar.

Furthermore, it has been found that if the abrasion surface spreader bar is positioned is late in the sequence of spreader bars, then further improvements in conductivity can be obtained. Thus, preferably the abrasion surface spreader bar is in the last three, preferably in the last two, and most preferably is the last spreader bar in the sequence.

The abrasion surface may be made from any suitable material, such as metal or ceramic, however tungsten carbide is preferred.

In a preferred embodiment, the process of the invention involves passing the sheet of electrically conductive fibres to a second fibre disrupting means to cause a proportion of the fibres on the other external face of the sheet to become free fibres.

Thus, at least two spreader bars may comprise abrasion surfaces, each one in contact with each of the external faces of the sheet of conductive fibres.

A number of factors determine the breakage rate of fibres passing over the abrasive surface. For example the relative speed of movement over the surface, the roughness of the surface, the tension in the fibres, the area and the time spent in contact with the surface. Also the material properties of the fibres will be a factor, particularly their sizing type and percentage.

However, it has been found that the roughness of the abrasive surface is a key parameter and thus preferably the abrasive surface has an Ra roughness of at least 1.5 micrometres, more preferably at least 2.5 micrometres.

Another important factor is the relative speed of movement over the surface.

Preferably the relative speed of movement is from 2 to 20 rn/mm.

Once the sheet of electrically conductive fibres comprising free fibres on one or both io external faces is prepared, the next stage is resin impregnation.

Resin impregnation may be carried out in a wide variety of ways which will be known to the person skilled in the art. Typically it involves bringing into contact with a face of the fibres a first layer of resin, comprising thermosetting resin. This is generally is followed by compressing the resin and fibres to cause impregnation to occur.

In a particularly preferred embodiment the resin is applied to a roller, the fibre sheet passing over a surface of the roller and the resin detaching from the roller to the fibre sheet. Compression can conveniently be carried out also by means of passing over rollers, which can be arranged as desired.

Traditionally there are two main ways of introducing resin to the fibre sheet for impregnation. The first involves introducing all the resin to the fibres in a single stage. The second involves introducing part of the resin in a first stage and the remainder in a second stage. Such one-stage and two-stage processes have been widely employed. One advantage of the two-stage process is the opportunity to introduce different materials in each of the two resin compositions, in order to achieve desired effects.

For example, a widely-used two-stage process involves a first stage of impregnating the fibres with resin followed by a second stage of bringing into contact with the impregnated resin another resin composition comprising thermoplastic toughener particles. This process produces two distinct layers in the prepreg, one of impregnated fibres and one of resin comprising the thermoplastic particles. Once a plurality of such prepregs are laid-up then an alternating layered structure is formed, comprising alternate layers of impregnated structural fibres with resin interlayers comprising toughener particles. Such an arrangement is known to give good mechanical properties following curing.

The good mechanical properties are generally attributed to the presence of these so-called interlayers which are free of structural fibres. However, as discussed, these interlayers also contribute to the poor electrical conductivity through the thickness of io the laminate, essentially because they provide a spacing between adjacent layers of conductive fibres.

In the present invention, this problem of the interlayer causing low electrical conductivity is overcome, without affecting the good mechanical performance is provided by the interlayer. Thus the impregnation process can be either a one-stage or two-stage process as desired.

It is highly desirable that particulate material be dispersed within the outer resin layer or interlayer.

The particulate material can be made from a wide variety of materials, however preferably they provide an additional useful function such as improved toughness or conductivity. Materials which are suitable include polyamide 6, polyamide 6/12, polyamide 12, conductive coatings on particulates formed from resins such as phenolic resins or from glass beads, coatings such as silver, carbon particles and/or microparticles and others.

Once prepared, the prepregs according to the invention are typically laid-up to produce a curable laminate or prepreg stack. Due to the flexible nature of the prepregs they are able to take the form of structural bodies having a wide range of shapes and contours.

Typically the orientation of the fibres will vary throughout the stack, for example by arranging for unidirectional fibres in neighbouring layers to be orthogonal to each other in a so-called 0/90 arrangement, signifiying the angles between neighbouring fibre layers. Other arrangements such as 0+451-45/90 are of course possible, among s many other arrangements.

Once formed, the interleaf layers are typically much thinner than the structural fibre layers. Thus, the ratio of the total thickness of the structural layers to the total thickness of the interleaf layers is from 10:1 to 3:1.

The structural fibres may comprise cracked (i.e. stretch-broken), selectively discontinuous or continuous fibres.

The structural fibres may be made from a wide variety of materials, provided they are electrically conductive, such as carbon graphite, metallised polymers aramid and mixtures thereof Carbon fibres are preferred.

Likewise the free fibres may be made from the same selection of materials. In a preferred embodiment the free fibres are the same material as the structural fibres.

Typically the fibres in the structural layer and the free fibres will generally have a circular or almost circular cross-section with a diameter in the range of from 3 to 20gm, preferably from S to l2im.

The curable resin may be selected from epoxy, isocyanate and acid anhydride, for example. Preferably the curable resin is an epoxy resin.

Suitable epoxy resins may comprise mono fUnctional, difunctional, triftinctional and/or tetraftinctional epoxy resins.

Suitable difunctional epoxy resins, by way of example, include those based on; diglycidyl ether of Bisphenol F, Bisphenol A (optionally bromianted), phenol and cresol epoxy novolacs, glycidyl ethers of phenol-aldelyde adducts, glycidyl ethers of aliphatic diols, diglycidyl ether, diethylene glycol diglycidyl ether, aromatic epoxy resins, aliphatic polyglycidyl ethers, epoxidised olefins, brominated resins, aromatic glycidyl amines, heterocyclic glycidyl imidines and amides, glycidyl ethers, fluorinated epoxy resins, or any combination thereof.

Difunctional epoxy resins may be preferably selected from diglycidyl ether of Bisphenol F, diglycidyl ether of Bisphenol A, diglycidyl dihydroxy naphthalene, or any combination thereof.

io Suitable trifunctional epoxy resins, by way of example, may include those based upon phenol and cresol epoxy novolacs, glycidyl ethers of phenol-aldehyde adducts, aromatic epoxy resins, aliphatic triglycidyl ethers, dialiphatic triglycidyl ethers, aliphatic polyglycidyl ethers, epoxidised olefins, brominated resins, triglycidyl aminophenyls, aromatic glycidyl amines, heterocyclic glycidyl imidines and amides, is glycidyl ethers, fluorinated epoxy resins, or any combination thereof.

Suitable tetrafunctional epoxy resins include N,N, N' ,N'-tetraglycidyl-m-xylenediamine (available commercially from Mitsubishi Gas Chemical Company under the name Tetrad-X, and as Erisys GA-240 from CVC Chemicals), and N,N,N,N -tetraglycidylmethylenedianiline (e.g. MY72 1 from Huntsman Advanced Materials).

Once prepared the laminates are cured by exposure to elevated temperature, and optionally elevated pressure, to produce a cured laminate.

As discussed above, a proportion of the free fibres migrate from the region sandwiched between the structured fibre layer and the adjacent resin layer to become dispersed within the resin layer itself This occurs as the laminate is heated up but before curing occurs, as the viscosity of the resin drops dramatically.

Once in the resin layer, or interlayer, curing begins as the temperature rises still higher. The curing process prevents further migration of the free fibres which become locked in place in the interlayer.

Thus the interlayer becomes electrically conductive due to the network of contacting free fibres. Additionally the good mechanical performance provided by the interlayer is not negatively affected.

It has been found that excellent electrical conductivity can be achieved when the interlayer comprising from 1 to 15 wt% of free fibres, preferably from ito 10 wt%.

The cured laminates produced according to the invention have remarkably low io electrical resistance, with a 3mm thick laminate of twelve plies of prepreg having an electrical resistance of less than 3, preferably less than 2, more preferably less than 1 being possible, as measured in the Z-direction according to the test method described below.

is Thus, in a third aspect, the present invention relates to a process of raising the temperature of a prepreg according to the present invention below that where curing occurs but sufficient to reduce the viscosity of the resin in the prepreg, and for a sufficient duration to allow a proportion of the free fibres to migrate into the outer layer of resin.

The invention will now be illustrated, by way of example, and with reference to the following figures, in which:-Figure 1 is a schematic representation of a spreader bar arrangement.

Figure 2 is a schematic is a schematic representation of another spreader bar arrangement.

Figure 3 is an image of a cross-section through a cured laminate made up of plies of prepreg according to the present invention.

Figure 4a to 4d are images of cross-sections through a cured laminate made of plies of prepreg according to the present invention.

Figure 5a to 5d are images of cross-sections through a cured laminate made of plies of prepreg outside the scope of the invention.

Examples

Resistance of composite laminates test method A panel is prepared by autoclave cure that is 300mm x 300mm x 3mm in size. The io layup of the panel is 0/90. Specimens (typically three to four) for test are then cut from the panel that are 36mm x 36mm. The square faces of the specimens should be sanded (for example on a on a Linisher machine) to expose the carbon fibres. This is not necessary if peel ply is used during the cure. Excess sanding should be avoided as this will penetrate past the first ply. The square faces are then coated with an is electrically conductive metal, typically a thin layer of gold via a sputterer. Any gold or metal on the sides of the specimens should be removed by sanding prior to testing.

The metal coating is required to ensure low contact resistance.

A power source (TTi EL3O2P programmable 30V/2A power supply unit, Thurlby Thandar Instruments, Cambridge, UK) that is capable of varying both voltage and current is used to determine the resistance. The specimen is contacted with the electrodes (tinned copper braids) of the power source and held in place using a clamp (ensure electrodes do not touch each other or contact other metallic surfaces as this will give a false result). Ensure the clamp has a non-conductive coating or layer to prevent an electrical path from one braid to the other. A current of one ampere is applied and the voltage noted. Using Ohm's Law resistance can then be calculated (V/I). The test is carried out on each of the cut specimens to give range of values. To ensure confidence in the test each specimen is tested two times.

Example 1

A continuous sheet of unidirectional carbon fibres was passed through the roller arrangement shown in figure 1. The rollers have a chrome surface with a very low surface roughness Ra of less than 1.0 micrometres. The rollers were fixed in a non-rotating manner.

The carbon fibres were then impregnated with an epoxy resin formulation comprising polyamide particles in a single stage, producing a prepreg having a layer of resin impregnated carbon fibres and an outer layer of resin comprising the polyamide particles.

The prepregs were then cut to size and stacked together in a 0/90 arrangement io symmetric from the centre, with 12 plies. They were then cured by heating until fully cured.

The resulting cured laminate was then tested for its electrical conductivity according to the above method.

Subsequently, the rollers marked A and B were exchanged for tungsten carbide rollers having roughened surfaces of 3.0 micro metres and 6.0 micro metres in a variety of combinations and composite laminates made and tested in the same manner.

The results are shown in table 1 below.

Table 1

Spreader bar A Spreader bar B Electrical resistance, ohms Smooth Smooth 1.47 Rough, 6 jim Smooth 0.87 Rough, 3 jim Smooth 0.96 Rough, 6 im Rough, 3pm 0.47 The dramatic effect of providing roughened spreader bars on the electrical resistance of the eventual cured laminate can be clearly seen.

Example 2

A continuous sheet of unidirectional carbon fibres was passed through the roller arrangement shown in figure 2. The rollers have a chrome surface with a very low surface roughness Ra of less than 1.0 micrometres. The rollers were allowed to freely rotate.

The prepregs were then cut to size and stacked together in a 0/90 arrangement, symmetric from the centre with 12 plies. They were then cured by heating until fully cured.

Subsequently, the rollers marked A and B and C were exchanged for tungsten carbide rollers having roughened surfaces of 3.0 micrometres and 6.0 micrometres in a variety of combinations and composite laminates made and tested in the same manner. Some of the laminates were also tested for their mechanical performance; The results are shown in table 2 below.

Table 2

A B C Electrical ILSS Multiangle UTS (2980 resistance, (88MPa) tensile (1240 MPa) ohms MPa) Smooth Smooth Smooth 3.8 93 1154 2676 6pm Smooth Smooth 1.1 106 1159 2518 6pm 8pm Smooth 1.0 --- 6pm 8pm 9pm 1.05 98 1173 2704 9pm Smooth Smooth 1.2 --- 9 pm 8 pm Smooth 0.8 ---The dramatic effect of providing roughened spreader bars on the electrical resistance of the eventual cured laminate can be clearly seen. Additionally breakage of a proportion of the structural fibres has no measurable effect on mechanical performance.

The laminate produced with spreader bar A at 6 micrometres was sectioned and an io image of its cross-section taken, as shown in Figure 3. Figure 3 clearly shows the presence of free filaments in the interlayer of the laminate.

Figures 4a to 4d show further images of a sample of cross-secions, at a variety of scales, of laminates produced with rough spreader bars as shown in table 2. The is presence of free filaments in the interlayer can be clearly seen.

Figures 5a to Sd show images of a sample of cross-sections, at a variety of scales, of laminates produced with smooth spreader bars as shown in table 2. No filaments can be seen in the interlayer region.

Claims

Claims 1. A prepreg comprising a structural layer of conductive fibres comprising thermosetting resin in the interstices, and a first outer layer of resin comprising thermosetting resin, and comprising a population of conductive free filaments s located at the interface between the structural layer and the outer resin layer which, when cured under elevated temperature, produces a cured composite material comprising a cured structural layer of packed conductive fibres and a first outer layer of cured resin, the outer layer of cured resin, comprising a proportion of the population of conductive free filaments dispersed therein.
2. A prepreg according to claim 1, wherein the free fibres have a distribution of lengths with a mean length of less than 2.0 cm, preferably less than 1.0 cm, more preferably less than 0.5 cm.
3. A prepreg according to claim 1 or claim 2, wherein the electrically conductive fibres are unidirectional.
4. A prepreg according to any one of the preceding claims, wherein particulate material is dispersed within the outer resin layer or interlayer.
5. A prepreg according to any one of the preceding claims, wherein the free filaments are the same material as the structural fibres.
6. A cured composite material obtainable by the process of curing a prepreg according to any one of the preceding claims by exposure to elevated temperature, and optionally elevated pressure.
7. A cured composite material according to claim 6, wherein the outer layer of resin comprises from 1 to 15 wt% of free filaments, preferably from 1 to 10 wt%.
8. A process for producing a prepreg, the process comprising passing a sheet of electrically conductive fibres to a fibre disrupting means to cause a proportion of the fibres on an external face of the sheet to become free filaments and subsequently impregnating the sheet with thermosetting resin and generating an outer layer of resin comprising thermo setting resin in contact with the external face of the sheet comprising the free filaments.
9. A process according to claim 8, wherein the conductive fibres are unidirectional fibres and the disruption means involves passing the fibres over io an abrasion surface, thereby causing breakage of a proportion of the fibres on the external face passing in contact with the abrasion surface, whilst the fibres not in contact with the abrasion surface remain unbroken.
10. A process according to claim 9, wherein from 0.5 to 5.0 wt% of the fibres are is broken in at least one place.
11. A process according to claim 9 or claim 10, wherein the abrasion surface is the surface of a spreader bar.
12. A process according to claim 11, wherein the abrasion surface spreader bar is in the last three, preferably in the last two, and most preferably is the last spreader bar in the sequence.
13. A process according to any one of claims 8 to 12, which involves passing the sheet of electrically conductive fibres to a second fibre disrupting means to cause a proportion of the fibres on the other external face of the sheet to become free filaments.
14. A process according to claim 13 wherein at least two spreader bars comprise abrasion surfaces, each one in contact with each of the external faces of the sheet of conductive fibres.
15. A process according to any one of claims 9 to 14, wherein the abrasive surface has an Ra roughness of at least 1.5 micrometres, more preferably at least 2.5 micrometres.
16. A process according to any one of claims 9 to 15, wherein the relative speed of movement is from 2 to 20 mlmin.
17. A process of raising the temperature of a prepreg according to any one of claims 1 to 7, below that where curing occurs but sufficient to reduce the io viscosity of the resin in the prepreg, and for a sufficient duration to allow a proportion of the free fibres to migrate into the outer layer of resin.