Title: Composite
Abstract: A composite comprising a structural component and a matrix component, the structural component comprising structural fibers and a toughening additive comprising non structural fibers of a first thermoplastic material and the matrix component comprising a second thermoplastic material. The structural component is a fabric formed from the structural fibers and the non structural thermoplastic fibers, the fabric comprising non structural thermoplastic fibers which are in fibre form in the final composite. The first and second thermoplastic materials differ as to their molecular weight or are dissimilar.
Patent Number: 6,902,800 Issued on 06/07/2005 to Woolstencroft
| Inventors:
|
Woolstencroft; David Harold (Poulton-le-Fylde, GB)
|
| Assignee:
|
cytec Technology Corp. (Wilmington, DE)
|
| Appl. No.:
|
381540 |
| Filed:
|
September 27, 2001 |
| PCT Filed:
|
September 27, 2001
|
| PCT NO:
|
PCT/GB01/04353
|
| 371 Date:
|
March 25, 2003
|
| 102(e) Date:
|
March 25, 2003
|
| PCT PUB.NO.:
|
WO02/28623 |
| PCT PUB. Date:
|
April 11, 2002 |
| Current U.S. Class: |
428/317.9; 264/112; 264/122; 264/171.1; 264/480; 428/294.7; 428/373; 428/375; 428/396 |
| Intern'l Class: |
B32B 005/22 |
| Field of Search: |
428/3179,373,294.7,374,296.1,119,120
264/112,122,171.1,480
52/273
156/71,92
|
References Cited [Referenced By]
U.S. Patent Documents
| 4911718 | Mar., 1990 | Lee et al.
| |
| 5132394 | Jul., 1992 | Bockrath.
| |
| 5624386 | Apr., 1997 | Tailor et al.
| |
| 5910361 | Jun., 1999 | Guevel et al.
| |
| 6003276 | Dec., 1999 | Hegemier et al.
| |
| 6237292 | May., 2001 | Hegemier et al.
| |
| 6616971 | Sep., 2003 | Evans.
| |
| 6716776 | Apr., 2004 | Morishima et al.
| |
| Foreign Patent Documents |
| 0 539 996 | Oct., 1992 | EP.
| |
| 2 323 322 | Sep., 1998 | GB.
| |
| 04249152 | Apr., 1992 | JP.
| |
Primary Examiner: Dixon; Merrick
Attorney, Agent or Firm: Wasserman; Fran, Neller; Robert
Claims
1. A composite comprising a structural component and a matrix component, the
structural component comprising structural fibres and a toughening additive comprising
non structural fibres of a first thermoplastic material and the matrix component
comprising a second heat-curable thermoplastic material, wherein the structural
component is a fabric formed from the structural fibres and the non structural
thermoplastic fibres, wherein the fabric comprises non structural thermoplastic
fibres which are in fibre form in the final composite, and wherein the first and
second thermoplastic materials are different.
2. A composite as claimed in claim 1 wherein the first and second thermoplastic
materials differ as to their molecular weight.
3. A composite as claimed in either claim 2 wherein the first and second thermoplastic
materials are dissimilar.
4. A composite as claimed in any preceding claim wherein the matrix component
is a low viscosity thermoplastic material.
5. A composite as claimed in any preceding claim wherein at least some of the
thermoplastic fibres are semi-crystalline.
6. A composite as claimed in any preceding claim wherein the percentage by volume
of the toughening additive is more than 2% but less than 50%.
7. A composite as claimed in any preceding claim wherein the volume of the toughening
additive is more than 5% but less than 40%.
8. A composite as claimed in any preceding claim wherein the volume of the toughening
additive is more than 10% but less than 30%.
9. A composite as claimed in any preceding claim wherein the structural component
is provided in the form of a plurality of layers of fabric and at least one veil
is provided between a pair of adjacent layers, the veil comprising a thin layer
of woven or unwoven material.
10. A composite as claimed in any preceding claim wherein the volume fraction
of the structural fibres in the fabric is at least 65%.
11. A composite as claimed in any preceding claim wherein the structural and/or
non structural fibres are continuous or discontinuous.
12. A composite as claimed in any preceding claim wherein the fabric comprises
a hybrid yarn of twisted structural fibres and thermoplastic fibres or yarn of
structural fibres and yarn of thermoplastic fibres.
13. A method of making a composite comprising forming a fabric from structural
fibres and non structural fibres of a first thermoplastic material to provide a
structural component, injecting a liquid resin comprising a second thermoplastic
material into the structural component to provide a matrix component and setting
the matrix component, wherein the first and second thermoplastic materials are
different and wherein the liquid resin is injected at a temperature such that the
final composite includes non structural thermoplastic fibres in fibre form.
14. A method as claimed in claim 13 wherein the fabric is provided in layers
and a veil is provided between at least one adjacent pair of layers prior to addition
of the second thermoplastic material, the veil comprising a thin layer of woven
or non-woven material.
15. A method as claimed in claim 14 comprising distributing binder material on
or in the veil.
16. A method as claimed in any one of 15 wherein the resin injection process
is resin transfer moulding or composite resin injection moulding.
Description
The present invention relates to a composite and a method of composite manufacture.
Composite materials generally comprise an array of reinforcing fibres in
a resin matrix. The present global industries which utilise composite structures,
for example the aerospace industry, predominantly use conventional unidirectional
and fabric-based prepregs. Such prepregs are formed by making a unidirectional
roving of reinforcing fibres, drawing the fibres through a bath of molten resin
material and then drying the resin. The prepreg is then formed into a desired shape,
loaded into a moult which is closed and heated to cure the resin.
Over the last five to seven years in an alternative technology for manufacturing
composite parts has emerged which is generally termed liquid composite moulding.
In liquid composite moulding, a dry fibrous reinforcement is loaded into a mould
or tool and the resin is injected or infused into the fibres and cured.
The reinforcement is termed a "preform" which term is well known to those skilled
in the art of composites as indicating an assembly of dry fibres that constitutes
the reinforcement component of a composite in a form suitable for use in a liquid
composite moulding process. A preform is typically an assembly of various textile
forms such as fabrics, braids or mats, tailored or shaped as necessary, and is
assembled as a specific operation prior to being placed into or on the mould tool.
Liquid composite moulding technologies, such as the RTM (resin transfer moulding),
SCRIMP (composite resin injection moulding or vacuum infusion) methods are perceived
by many to be the solution to the problem of making composite parts in a number
of intractable situations, such as large aerospace primary structures and high
volume structural automotive components. The benefits that liquid composite moulding
technologies are perceived to offer over conventional prepregs are reduced scrap
and lay-up time, non-dependence upon drape and increased shelf life properties.
However, liquid composite moulding does possess its own problems, particularly,
when the end use applications require high toughness and where control of curing
cycle time is critical.
Structural parts require a high degree of toughness for most applications
and this is especially true of aerospace primary components. The solution to introducing
high toughness in an aerospace grade composite has traditionally been to toughen
the matrix—usually by the introduction of a second phase additive such as
a thermoplastic polymer to the base epoxy resin matrix.
Various approaches have been employed for the addition of a thermoplastic
material into the resin. The thermoplastic may be blended with the unreactive thermoset
resin at elevated temperatures to produce a single phase, unreacted melt. A limitation
of this approach is the level of thermoplastic that can be added to enhance toughness.
High molecular weight thermoplastics are used but as these dissolve into the resin,
the viscosity of the blend rises steeply. However the very nature of the injection
process of the resin into the reinforcing fibres requires that the resins rheological
properties, viscosity and elasticity are such as to allow infiltration of the resin
throughout the fabric preform. This is essential if the resulting composite structure
is to be free of voids and long injection times and high injection temperatures
are to be avoided. Conventional toughened epoxies are extremely viscous systems
which means that high pressures and massive tools are required with the necessity
of heating the resins and difficulties in matching curing time and injection-fill cycles.
Thermoplastic may also be added in the form of a continuous solid film
which is placed between two layers of fibre. In such processes the thermoplastic
layer is generally known as the Interleaf layer. A process of this type is disclosed
in European Patent Application No. 0327142 which describes a composite which comprises
a solid continuous layer of a thermoplastic material placed between two layers
of fibre impregnated with thermosetting resin. On heating the thermosetting layers
and the interleaf layers remain as discrete layers.
A problem with the interleaf approach is that the solid thermoplastic film does
not dissolve into the resin during the heat processing stage. As a result, although
the final composite may show the desired increase in toughness, there is a weak
resin-thermoplastic interface. The weak interface between the interlayer and matrix
can cause poor resistance to cracking between plies especially when exposed to
a moist environment.
Thermoplastic material may also be introduced in a powdered form. An
example of this technique is disclosed in European Patent Application No. 0274899
where the thermoplastic material is either added to the resin before the prepreg
is prepared or sprinkled onto the prepreg surface.
The use of powders presents a problem in that it is difficult to ensure that
an even distribution of powder is supplied to the resin. There is therefore an
uneven loading of the thermoplastic material with the result that the composite
will have regions of different toughnesses. Furthermore, incorporation of powdered
thermoplastic material in the resin is not suitable for liquid composite moulding
techniques because the viscosity of the resin is increased when the particles are
added to it according to standard Newtonian theory with all the consequent disadvantages
as discussed above.
Whether the powdered thermoplastic is added to the resin or to the prepreg,
the amount which can be incorporated is limited. Thus, so too is the toughening
effect and, in general, to achieve a reasonable improvement in toughness, expensive
structural thermoplastics have to be employed.
It has been proposed, in Japanese Patent Application 6-33329, to include thermoplastic
in the form of fibres. The Application discloses a reinforcement fibre mix comprising
99.80% by weight of carbon fibres or graphite fibres and 1-20% by weight of thermoplastic
resin. This approach is disclosed solely as useful in a classic prepreg technique.
A good composite is one having a combination of physical properties particularly
suited to a specific application. The physical properties of the composite product
are determined by, amongst other things, the physical properties of the solidified
resin matrix material and the structural material, and the uniformity of distribution
of the matrix material and the structural material in the composite. Best results
are achieved where the matrix material is intimately in contact with all of the
structural material.
It is therefore desirable that the resin matrix material is of such a consistency
(viscosity) that it covers (wets) all of the structural material and, if necessary,
fills the interstices formed in the structural material. Uniform wetting is particularly
difficult to achieve where the structural material is of complex structure, for
example where it is a preform, or where the ratio of the matrix material to support
is particularly low.
The viscosity of the matrix material is affected by the number and types of additives.
There therefore arises the problem that, although a liquid or a gel matrix material,
comprising one or more additives may possess suitable physical properties when
solidified, the viscosity of the liquid or gel matrix material may be too high
to facilitate its even distribution around the support material, particularly where
the support is complex. This results in a composite product lacking the physical
characteristics expected.
Normally to achieve a good combination of properties a composite material
will consist of a number of constituents. Typically for an aerospace grade prepreg
there will be a high performance reinforcement preform combined with a complex
polymeric resin matrix mix. This matrix mix normally consists of a thermosetting
epoxy resin blended with various additives. These latter additives enhance the
toughness of the basic resin. Such systems have complex flow characteristics and
whilst they can be easily combined with fibres in a prepreg form, their use in
other manufacturing techniques is limited. As for instance an attempt to use such
a complex resin in an injection or resin transfer process in a complex fibre preform
may result in the filtering out of additives and a non uniform product.
There is therefore a need for a method of composite manufacture which overcomes
the above mentioned problems particularly for large complex structures.
EPA 0539 996 describes a fabric for lamination or moulding comprising reinforcing
fibres such as carbon fibres and yarns of high and low molecular weight polyether
either ketone resin. On application of heat, the low molecular weight yarns melt
and enter the gaps between the fibres and the high molecular weight yarns.
In accordance with a first aspect of the present invention there is provided a
composite comprising a first structural component and a second component, the structural
component comprising structural fibres and a toughening additive comprising non
structural fibres of a first thermoplastic material and the second component comprising
a second thermoplastic material, wherein the structural component is a fabric formed
from the structural fibres and the non structural thermoplastic fibres, wherein
the fabric comprises non structural thermoplastic fibres which are in fibre form
in the final composite, and wherein the first and second thermoplastic materials
are different, characterised in that the second component is a matrix component
formed by injecting the structural component with a liquid resin comprising the
second thermoplastic material.
The term "structural fibre" as used herein refers to fibres which add to the
strength of the ultimate composite such as glass or carbon fibres and which therefore
have a modulus of elasticity greater than 50 GPa.
The term "non-structural fibre" as used herein refers to fibres which are not
provided for increasing the strength of the ultimate composite as they have a modulus
of elasticity less than 40 GPa. Thus known strengthening fibres formed from materials
such as Kevlar are not non-structural fibres within the terms of the present Application.
The composite uses a thermoplastic resin as the matrix. The thermoplastic material
may be expected to provide good chemical resistance and a degree of toughness in
the final part. However, in order to achieve low viscosity which will be desirable
if the thermoplastic resin is to be injectable, it may be necessary to reduce the
molecular weight of the resin. Toughness of a thermoplastic is closely linked to
the molecular weight such that a decrease in molecular weight will result in a
decrease in toughness. It is therefore proposed that in addition to the use of
a thermoplastic matrix, the composite is further toughened by the incorporation
of thermoplastic fibres into the fibre preform.
Alternatively considered, the form of the reinforcement component enables
a reduction in the toughening to be provided by the matrix resin thus allowing
use of low viscosity systems. In other words, by providing for toughening of the
composite by the fibres, the molecular weight of the thermoplastic resin can be
made lower and so it may have a lower viscosity. This makes impregnation of large
parts feasible with sensible pressures, lightweight low cost tooling and manageable
cycle times. Furthermore a significantly greater amount of toughening additive
can be included without compromising any of the processability aspects of liquid
composite moulding techniques.
The thermoplastic fibres may be produced from a similar thermoplastic material
to that of the matrix but with a higher molecular weight to introduce toughness.
Alternatively, the fibres may be produced from a dissimilar thermoplastic material.
Combinations of thermoplastic fibres may also be used in order to achieve
a mix of optimum properties. The properties of the composite will be dependent
on the mechanical properties of the matrix, the additional thermoplastic fibres
and the interfacial bonding between all components.
By toughening is meant the ability to absorb fracture, which may manifest itself
in the ability to absorb impact. Such ability may be measured by suitable impact
testing methods which will be known to the skilled man. Thermoplastic polymers
are known to increase the ability to absorb impact energy in structural composites.
By suitable formation of the fabric they may be dispersed throughout the final
composite to give homogenous impact resistance.
In accordance with another aspect of the invention, there is provided a method
of making a composite comprising forming a fabric from structural fibres and non
structural fibres of a first thermoplastic material to provide a structural component,
injecting a liquid resin comprising a second thermoplastic material into the structural
component to provide a matrix component and setting the matrix component, wherein
the first and second thermoplastic materials are different and wherein the liquid
resin is injected at a temperature such that the final composite includes non structural
thermoplastic fibres in fibre form.
The hybrid approach to the production of preforms for liquid composite moulding
involves integrating the mechanism that provides toughening into the novel textile
preforms rather than being an additive in a thermosetting resin. The net result
of this is that the improved properties are achieved without compromising the manufacturability
of the systems. This also has manufacturing benefits and in addition to providing
a tougher part it also simplifies the manufacturing process and allows the potential
for faster manufacturing make span times and hence greater tool utilisation. This
has the further benefit of potentially reducing the most expensive element of a
new composite programme: the up front investment required to meet rate production
and hence provides the potential for lower cost entry into a new product programme.
Preferably, the toughening additive is a thermoplastic material whose
latent heat of melting may absorb a proportion of the heat of the resin but which,
upon completion of setting, reverts to its solid form without loss of toughening
capacity. Alternatively, the thermoplastic resin and thermoplastic additive may
be selected to allow absorption of some of the energy of setting in melting or
phase change of the additive.
Injection of low viscosity resins can decrease the injection-fill part
of the processing cycle. However, it is also desirable to decrease the remaining
cycle time. By using very hot low viscosity thermoplastic resins, the injection-fill
part can be accelerated but the risk is the generation of a long cooling cycle—particularly
in thick parts, and also excessive heating, again particularly in thick parts,
which could lead to a degraded, distorted or damaged final part.
A very rapid cycle can be affected without risking excessive cool-out times if
semi-crystalline thermoplastic fibres are used as the toughening additive. Heat
from the cooling of the thermoplastic matrix can be used to generate crystalline
melting with the fibres. The latent heat of crystalline melting will absorb the
excess energy thereby accelerating the cooling cycle and ensuring that it happens
at a uniform rate within the bulk of the product thereby eliminating the potential
for distortions to occur within the part. The selection of toughening fibres with
appropriate crystalline melting temperature allows the cycle time to be minimised
without risk of composite damage. The semi-crystalline fibres themselves will simply
revert to their original condition on cooling and the process will not affect the
ultimate toughness of the parts.
Preferred toughening additives include:—polypropylene, nylon 6,
6, styrene-butadiene, butadiene, polyether imide, polyethylketone, PET, polyether sulphone.
Preferably, the percentage by volume of the toughening additive in the
final composite is more than 2%, more preferably, more than 5%, most preferably,
more than 10%.
Preferably, the percentage by volume of the toughening additive in the
final composite is not more than 50%, more preferably, not more than 40%, most
preferably, not more than 30%. It is particularly preferred that the percentage
toughening additive by volume in the final composite is not more than 25%.
The percentage by volume of structural fibres in the fabric is preferably at
least 65%. The minimum value of 65% ensures that there is sufficient structural
fibres to give the required strength. However the proportion of toughening fibres,
that is, the thermoplastic fibres is high particularly in comparison to known methods
in which thermoplastic is added in particulate form and so the toughening effect
is commensurately much greater than that achieved with those known methods.
Preferably, the melt temperature of the toughening additive is not the
same as the melt temperature of the resin component. It can be between 80-350°
C., more preferably between 100-250° C., but its final selection will depend
upon the parameters of the base matrix material.
The ability of the composite to be produced using a low viscosity resin will
implicitly increase the rate at which a mould can be filled. However, the problem
of controlling resin cycle times remains. A key factor always in thermoplastic
resin injection is ensuring that the resin fills the mould and wets the reinforcement
totally before it sets. However fill time and setting time are linked and the resin
begins to set as soon as it leaves the injection port, and this process continues
throughout the injection cycle.
In an alternative method, the injection and setting stages of the process are
separated by incorporating the matrix thermoplastic resin in solid form into the
preform. The resin may be in fibrous or particulate form. This has the benefit
that the application of heat is all that is required to enable the matrix resin
to flow and wet the part out and this will enable even greater convenience in the
manufacturing process.
A further preferred feature is the use of a textile veil as part of a laminate
by being sandwiched between layers of the structural component. The veil preferably
has a greater absorbency rate and the structural component layer(s) either due
to its thinness or the inherent absorbency or structure of the veil material or
a combination of these characteristics. Accordingly, in some embodiments, it is
preferred that a veil layer is provided sandwiched between the structural layers
and provides means to increase the rate of filtration of resin into the structure.
Advantageously, by this means, the resin may be preferentially directed into the
centre of thicker structures than has hitherto been possible.
Advantageously, by the use of a fibrous veil, toughness and delamination
suppression, are achieved with fibre bridging effects. However, preferably, the
veil has a toughening additive incorporated therein to further enhance toughening
of the composite. It is envisaged that the veil may also include thermoplastic
fibres as a toughening additive. However, it is particularly preferred that when
the veils are made by the papermaking route, the toughening additive is added in
particulate form as this is particularly well adapted for use in the paper-making process.
Preferably, the matrix resin is a thermoplastic material with low viscosity
such as an EMS Chemie Grilamid Polyamide 12.
The fibres may be continuous or discontinuous. If discontinuous, such as are
produced by stretch breaking, they will be used in the form of a continuous yarn
formed from the discontinuous fibres.
The structural component fabric may be woven or non-woven and may comprise a
hybrid yarn i.e. structural fibres and toughening fibres twisted in a hybrid yarn
or the fabric may comprise structural yarn and toughening yarn mixed in a single fabric.
The basic concept of using hybrid yarns can be varied considerably. It is possible
to replace all yarns in a textile with a hybrid yarn, or alternatively to replace
a selection. Furthermore a large preform may consist of zones of conventional or
toughened fabrics according to the needs of the part. This offers a processing
advantage in that a single resin system can be used for a large part but the properties
of the composite can differ in terms of toughness, and temperature capability from
place to place—hence making one shot moulding of complex structures more feasible.
The properties of the composite can be varied widely by making the preform of
different forms. For example, with a woven fabric the pattern in which the structural
fibres and the thermoplastic fibres are provided will have an effect on the overall
behaviour of the composite. The use of a structural reinforcement in the form of
a textile therefore enables great versatility.
Embodiments of the present invention will now be further described with
reference to the accompanying examples and drawings in which:
FIG. 1
a shows a schematic laminar composite in accordance with the present invention;
FIG. 1
b shows the upper layer of the laminar composite of FIG. 1
a
with a schematic impact region;
FIG. 1
c shows the schematic construction of the upper layer of the laminar
composite of FIG. 1
a;
FIG. 1
d shows an exploded schematic view of yield zone 2 shown
in FIG. 1
b;
FIG. 2
a shows a hybrid veil sandwiched between two structural layers
in a laminate;
FIG. 2
b shows a possible construction for the hybrid veil of FIG. 2
a;
FIG. 2
c shows an alternative construction for the hybrid veil of FIG.
2
a;
FIG. 3 shows absorbed energy versus volume fraction x thickness for various
examples, and
FIGS. 4 to 6 show plots of impact strength as a function of thickness
x volume fraction of fibres for a composite formed from glass fibres alone, FIG.
4, glass fibres and polypropylene fibres, FIG. 5, and glass fibres and polyamide
fibres, FIG. 6.
FIG. 1
a shows a composite with a laminar structure of three superimposed
identical flat rectangular layers: upper layer
3a; middle layer b
and lower layer c. The internal structure is shown more clearly by FIG. 1
c which
is an explosion of inset
4. The explosion shows each layer is formed from
a hybrid fabric comprising yarns of structural fibre, e.g. carbon fibre interspersed
with yarns of thermoplastic fibre set in a thermoplastic resin matrix.
FIG. 1
b and FIG. 1
d show schematically the effect of an impact
on the surface of the upper layer
3a. In particular, FIG. 1
b reveals
a series of diagonal linear yield zones from the theoretical impact and FIG. 1
d
shows an explosion of a linear yield zone
2 and reveals that the yield
zone corresponds to a thermoplastic yarn extending in the composite layer.
Referring to FIG. 2, this shows a schematic laminar composite construction
similar to that of FIG. 1 but with a hybrid veil sandwiched between two layers
of textile. The sandwiched veil introduces toughening into the textile composite.
Two alternatives of the veil construction are shown in FIGS. 2
b and
c.
FIG. 2
b shows schematically the construction of mixed structural and non-structural
fibres and thermoplastic powder whereas FIG. 2
c shows a singular construction
of carbon fibres and thermoplastic powder. In both cases the delamination resistance
and some toughening is provided by fibre bridging between the textile layers and
the fibrous veil. However this is greatly enhanced by the presence of thermoplastic
in the veil layer.
By appropriate design of the interply veil, the resin flow rate across the veil
may be enhanced relative to the flow rate across the upper and lower structural
layers and thus improve the rate of injected resin impregnation into the composite.
There will now be described a number of examples of a composite having a structure
as illustrated in FIG. 1 but employing a matrix of a thermosetting resin. The examples
therefore serve to illustrate the effect of employing thermoplastic fibres as the
toughening additive and so are illustrative of the invention even though not fully
in accord with it.
The most dramatic benefits of the thermoplastic fibre toughening additive can
be seen in the improved impact resistance of the composites. This is often illustrated
by plotting the absorbed energy in through penetration impact tests as a function
of volume fraction of fibres multiplied by thickness—a combination of parameters
that yields a master curve for conventional composite systems irrespective of matrix
type and detailed fibre orientation (assuming the fibres are arranged in a broadly
in-plane isotropy or at worse a 0.90 arrangement). The master curve has been found
to hold for materials with very different matrices, including brittle cold cure
resins and tough thermoplastic matrices, such as polypropylene. Composites with
the thermoplastic fibre toughening additive exhibit a surprising increase in toughness
as shown by a considerable deviation from the master curve. This is also evidenced
by greater damage allotment in the impact specimens.
EXAMPLE 1
A composite was prepared from a fabric preform that consisted of glass fibres
commingled
with polypropylene fibres in a quadriaxial non crimp fabric. The fabric was impregnated
with a low viscosity unsaturated polyester resin and the laminate was cured at
room temperature followed by a post cure at 80° C. in accordance with the
resin supplier's specification.
The plate was 3 mm thick and the volume fractions of the three components as follows:—
- glass fibres 0.2 v/v;
- polypropylene fibres 0.2 v/v; and
- polyester resin 0.6 v/v.
The laminate was subjected to a falling weight impact test to measure its energy
absorption. The specific test configuration used produces absorbed energy results
for glass fibre composites that fall in a master curve determined by the thickness
of the laminate and the volume fraction of fibres. The energy absorbed by the laminate
prepared from the preform with polypropylene fibres added as toughening agents
was 100 J.
In contrast, a similar laminate produced from identical polyester resin 0.8 v/v
but reinforced with a fabric that was totally produced from glass fibres of a fibre
volume fraction of 0.2 v/v and a thickness of 3 mm absorbed an average of approximately
40 J. This demonstrates that addition of the thermoplastic fibres into the preform
provides a considerable toughness benefit.
EXAMPLE 2
A glass fibre epoxy composite was prepared from a DGEBA epoxy resin (digylcidyl
ether of bisphenol-A cured with an amine hardener [Shell Epikote 828 cured with
Ciba HY932 aromatic amine]) and a plain weave woven fabric of E-glass fibres. The
fabric occupied approximately 50% by volume of the composite. A similar composite
was prepared with the same level of fabric but where the fabric component contained
70% (by volume) E-glass fibres and 30% by volume of a semi-crystalline polymeric
fibre, with a crystalline melting temperature of 210° C.
The composites were produced by impregnating the fabrics and laminating to a
thickness of 6 cm thick and cured in an oven set at 190° C. Thermocouples
embedded in the centre of the laminate monitored the temperature rise in the materials
as they initially equilibriated to the oven temperature and then experienced further
temperature rises due to the exothermic curing process.
The laminate with just glass fibres exhibited a temperature rise well beyond
the 190° C. oven temperature which became rapid and reached a peak value of
300° C. at which point significant degradation of the epoxy was observed.
The laminate with semi-crystalline thermoplastic fibre also exhibited a temperature
rise due to the exothermic cure but once this temperature reached the crystalline
melting temperature of the thermoplastic fibres, the overall temperature rise was
halted and the epoxy resin did not noticeably degrade.
EXAMPLE 3
A carbon fibre composite, 3 mm thick, was prepared from a plain weave fabric
and
an epoxy resin (digylcidyl ether of bisphenol A cured with an amide hardener [Shell
Epikote 828 cured with Ciba HY932 aromatic amine]). The fabric contained 70% by
volume carbon fibres (Torayca T300) and 30% by volume nylon 6.6 fibres. The fabric
was impregnated with the liquid epoxy resin and cured at room temperature for 24
hours followed by a post cure at 100° C. for 4 hours. The cured laminate contained
approximately 50% carbon fibres by volume and 21% of nylon fibres by volume. The
remaining 29% of the composition was cured epoxy resin. A similar composite was
prepared by impregnating a fabric produced exclusively from carbon fibres. In this
case the plain weave carbon fibre occupied 50% of the volume of the composite and
the epoxy resin matrix occupied the remaining 50%.
Both laminates were subjected to excess energy, falling weight impact tests.
The laminate comprising just carbon fibres and an epoxy matrix absorbed 50 J of
energy. The laminate with the carbon fibres, nylon fibres and epoxy matrix absorbed
85 J.
EXAMPLES 4 TO 7
Tests have been conducted with a series of medium volume fraction glass fibre
composites which exhibit impact toughness (energy absorbed during drop weight impact
with full penetration) which is enhanced by a factor of 2-3 times by inclusion
of thermoplastic fibres in comparison to the unmodified analogues. Tests have also
shown a remarkable lack of sensitivity to notches in open hole tension tests on
the same materials.
The impact results of two materials against two control samples are shown in
FIG. 3 and Table 1 defines the materials tested.
| TABLE 1 |
| Comparison of toughened and non-toughened composite laminates. |
| |
|
% Volume Fraction |
|
| Examples |
Product |
Structural Component |
Structural components |
| Example 4 |
(F394) |
22-23 |
Glass/polypropylene/ |
| |
|
|
polyester |
| Example 5 |
(F404) |
41 |
Glass/polyester |
| Example 6 |
(F384) |
22-23 |
Glass/polypropylene/ |
| |
|
|
polyester |
| Example 7 |
(F389) |
25 |
Glass/polyester |
The structural components each comprised about 50:50, glass to toughening additive,
by volume.
FIG. 3 shows the impact results for the Examples 4-7 as a plot of absorbed energy
against thickness x volume of fibres. The impact master curve for SMC (sheet moulding
composite), GMT's (glass mat thermoplastics) and prepreg etc. has been superimposed
for comparative purposes. The absorbed energy for the polypropylene and polyester
containing composites is significantly improved by comparison with analogous composites
having no toughening additive.
FIGS. 4 to 6 are plots showing impact strength, that is, energy absorbed
during penetration, as a function of thickness x volume fraction of fibres. Each
plot has data from three different thermoset matrices—two epoxies and a
polyester. The first plot of FIG. 4 shows the results achieved when glass fibres
alone are used with the volume fraction of glass fibres in the composite being
between 30 to 50%. The second and third plots of FIGS. 5 and 6 show the results
when the portion of the glass fibres is replaced by polypropylene, FIG. 5, and
polyamide, FIG. 6. The plots demonstrate that the inclusion of the thermoplastic
polymers provide significant benefits in terms of improved impact strength.
The resins used in the study which produced the plots of FIGS. 4 to 6
included an unsaturated isophthalic polyester resin (UP), Crystic 272 (a product
of Scott Bader plc) and two epoxy systems, EP1 was a cold cure epoxy resin (digylcidyl
ether of bisphenol A cured with an amide hardener (Shell Epikote 828 cured with
Ciba HY932 aromatic amine) and EP2 was a low single-part, low-viscosity epoxy resin
supplied by Cytec-Fiberite, Cycom 823, which was cured at 120° C.
The experimental procedure in all of these tests involved the use of an instrumented
falling weight impact test in which a striker equipped with a 20 mm diameter hemispherical
tip is allowed to fall onto a plate specimen of the test composite. The composite
specimen is a thin plate, typically 3 mm thick, and 60 mm×60 mm in size which
is simply supported on a steel ring with an internal diameter of 40 mm. The striker
is dropped from a height of 1 m and has sufficient mass such that the kinetic energy
is sufficient for the striker to completely penetrate the specimen. The test records
the forces during the impact event and the energy absorbed is calculated from the
force time record and the measured velocity of the striker as it impacts the specimen.
As noted in the discussion of the above examples, the use of thermoplastic fibres
incorporated into the resin matrix provides a significant toughening effect. The
thermoplastic fibres give a mechanism for plastic deformation and yielding which
is not possible in an unmodified thermosetting resin. It has now been found that
the same mechanism and so toughening effect is produced in a composite having a
thermoplastic resin matrix which means that the effect is primarily fibre dominated.
This makes it possible to form a composite having a thermoplastic resin matrix
by a liquid composite moulding technique. The desirable qualities of a thermoplastic
matrix, including good chemical resistance and contribution to toughness of the
final part, can be obtained without wetting problems. The reason for this is that
the presence of the toughening additives in the form of the thermoplastic fibres
in a structural component means that a lower molecular weight thermoplastic can
be used for the matrix than would be the case if the matrix was solely to provide
the necessary toughness. A reduction in molecular weight results in a reduction
in viscosity and therefore ready impregnation of the preform.
The fibre thermoplastic may differ from the matrix thermoplastic by molecular
weight with a relatively higher molecular weight thermoplastic being used for the
fibres and a relatively lower molecular weight thermoplastic for the matrix. This
can be achieved by using two different thermoplastics or the same thermoplastic
but of two different molecular weights. However, it should be noted that the fibre
thermoplastic whilst having a higher molecular weight than the matrix thermoplastic
does not have such a high molecular weight as to make the modulus such that the
fibres are structural. There is no need to use materials such as Kevlar or other
structural thermoplastics. Lower modulus, and therefore lower cost, thermoplastics
will provide the necessary toughening effect.
The cycle time is key in modem manufacturing. The faster a tool is used, the
greater the tool utilisation which reduces tooling costs and so upfront investment
in a manufacturing program. Whilst the composite with a thermoplastic matrix and
thermoplastic fibre toughening additive is preferably formed by a liquid composite
moulding technique, tool throughput may be increased if another technique is employed
which does not involve an injection step. One possibility would be combine the
reinforcement component consisting of the structural and non-structural fibres
with further thermoplastic fibres having a melting point lower than the thermoplastic
fibres of their reinforcement component. The hybrid preform containing the three
types of fibres: structural fibres and thermoplastic fibres of higher and lower
melting points would be heated under pressure to cause the low melting point fibres
to melt and impregnate both the structural fibres and the high melting point thermoplastic
toughening fibres. For maximum efficiency, the tool would be heated to a temperature
close to the lower melting point prior to positioning the hybrid preform therein.
The low melting point thermoplastic could alternatively be in powder form with
identical processing being employed.
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