Composites Science and Technology 59 (1999) 459±466

Composites of UHMW polyethylene ®bres in a LD

polyethylene matrix.
I. Processing conditions
E. Devaux*, C. CazeÂ
Ecole Nationale SupeÂrieure des Arts et Industries Textiles, Laboratoire Gemtex, 2 place des Martyrs de la Resistance, 9 rue de l'Ermitage, BP 30329,
59056 Roubaix Cedex 01, France

Received 21 November 1997; received in revised form 1 April 1998; accepted 20 April 1998

Abstract
The use of ultra-high-molecular-weight (UHMW) polyethylene ®bres as reinforcing materials in a composite application is lim-
ited by the non-polar chemical constitution of the polymer which excludes the possibility of establishing covalent links with a
polymer matrix. For this reason, the adhesion between the polyethylene ®bre and another polymer is generally poor, and the global
performance of a composite material reinforced by these ®bres is very low. Nevertheless, owing to the very high strength of this
kind of ®bre, it should be interesting to improve the adhesion between the ®bres and the matrix in order to obtain a high-perfor-
mance composite material. For this purpose, a chemical modi®cation of the ®bre surface is generally used, either by chemical
treatment or plasma treatments. In the following paper, we discuss an attempt to use polyethylene ®bres as a reinforcement for a
highly chemically compatible matrix such as polyethylene itself. The di€erence between the melting points of the ®bre and of the
matrix is exploited in order to ®nd the ideal processing conditions for such a composite material. In these conditions, the matrix has
to be suciently ¯uid in order to ensure good impregnation of the yarns, and the temperature must not be too high in order to
avoid degradation of the ®bres. The high chemical compatibility of the two components allows us to create physico-chemical
interactions which might favour the interfacial adhesion. # 1999 Published by Elsevier Science Ltd. All rights reserved.
Keywords: A. Polymer-matrix composites (PMCs); B. Interphase; B. Surface treatments; B. Thermomechanical properties; D. Di€erential scanning
calorimetry (DSC)

1. Introduction polyethylene ®bres [1±4]. Marked improvements of the

At the present time, high-modulus ultra-high-mole-
cular-weight (UHMW) polyethylene ®bres represent one
of the best performing polymeric materials, combining
high resistance to mechanical loading, low density, bio-
compatibility, hydrophobicity, chemical resistance and
electrical insulation. Industrial applications are being
strongly developed, particularly in domains such as
sport, biomedical prosthesis, and ballistic protection.
However, the utilisation of these ®bres as reinforcing
materials for composite applications remains limited as
a consequence of their total apolarity, and because of
the diculty of obtaining strong interactions with poly-
meric matrices. As a consequence, the constitutive ®bres
are not able satisfactorily to transmit the mechanical
stresses imposed on the composite material. A few
publications are available concerning investigations on
thermoset matrices reinforced with high-modulus
* Corresponding author. Tel.: 0033 20 25 64 64; fax: 0033 20 27 25 97.
interface are obtained after super®cial plasma treat-
ments of the ®bres. These treatments generally increase
the ®bre surface energy, thus favouring wetting by the
liquid matrix, by elimination of the weak boundary
layer generated during the polyethylene yarn processing
[2,5±8]. Concerning thermoplastic matrices, the proces-
sing problems encountered are often dicult to solve
because high temperatures are generally required. Thus,
the relatively low melting temperature of the poly-
ethylene ®bre prevents the reinforcement of many
thermoplastic matrices by these ®bres. Moreover, the
adhesion problems remain similar to those for thermo-
set matrices. All of these factors have led a number of
authors to develop the idea of the embedment of high-
modulus polyethylene ®bres in a polyethylene thermo-
plastic matrix for which the melting temperature is
lower than that of the ®bre [9±13]. In this case, ®bre
matrix adhesion may be realised by the epitaxial crys-
tallization of the molten polymer on the ®bre surface
because of the chemical similarity of the two materials

0266-3538/99/$ - see front matter # 1999 Published by Elsevier Science Ltd. All rights reserved.
PII: S0266 -3 538(98)00090 -6
460 E. Devaux, C. Caze / Composites Science and Technology 59 (1999) 459±466
in contact. Moreover, partial melting of the ®bre surface
may occur and a co-crystallization process between the
matrix macromolecules and those on the ®bre surface may
take place [14]. Evidence for this epitaxial crystallization
or co-crystallization is shown by the observation of a
transcrystalline interphase by polarised-light optical
microscopy [9±11]. The occurrence of such a phenomenon
proves the existence of interactions between the two
components. It is generally thought that the presence of
a transcrystalline interphase is a factor which may
improve the interfacial adhesion between the ®bre and the
matrix. Moreover, a slight improvement of the thermal
behaviour of the composite material is observed [15].
Because of the relatively narrow range of temperature
required for the processing of this kind of composite
material, preliminary investigations have been carried
out in order to evaluate the behaviour of the reinforcing
®bres as a function of the treatment temperature. To
this end, the crystalline state and the mechanical proper-
ties of Spectra1 ®bres have been studied. These experi-
ments allowed us to de®ne the precise temperature
conditions for processing the polyethylene-reinforced
polyethylene. It should be noted that an acceptable com-
promise must be found in order to obtain sucient matrix
¯uidity for convenient impregnation of the ®bre yarns, and
limited reduction of the reinforcing material properties.
On the other hand, the weak boundary layer gener-
ated during the spinning of the Spectra1 ®bre must be
removed in order to optimise the wetting of the ®bre by
the molten matrix, and to favour interactions between
the two materials. Di€erent methods are proposed in
the literature for eliminating this weak boundary layer,
including plasma treatments and chemical treatments
[16]. We have chosen the second of these approaches,
and we have had to follow the changes in the ®bre
properties depending on the treatment conditions.
2. Experimental materials
The polymer used as the matrix is a low-density
polyethylene supplied by Elf Atochem (reference Lacq-
teÁne1 type 1700 MN 18). This polyethylene has a very
high melt-¯ow index (MFI=70 g/10 min at 190 C),
which is a necessary condition for satisfactory impreg-
nation of the polyethylene ®bre tows. The melting tem-
perature is given as 108 C, while the tensile strength,
elongation at break, and elastic modulus are given as 10
MPa, 120%, and 160 MPa, respectively.
The reinforcing ®bres are ultra-high-strength, high-
modulus polyethylene Spectra1 1000 ®bres supplied by
Allied Signal, and are extracted from a textile fabric.
These ®bres are produced by gel-spinning from UHMW
high-density polyethylene (Mw=1,500,000 g/mol), and
have tensile strength and modulus values of 2.9 and
172 GPa, respectively, according to the manufacturer
speci®cations [17]. These properties result from the
highly oriented crystalline structure of the ®bres. The
melting temperature of the Spectra1 1000 ®bres is
147 C, as obtained by di€erential scanning calorimetry
(DSC) measurements with a heating rate of 10 C/min.
The mono®lament diameter is 28 mm.
3. Variation of the behaviour of polyethylene ®bres
with thermal processing conditions
3.1. Changes in the crystalline state of the Spectra1 ®bre
The remarkable mechanical characteristics of the
Spectra1 ®bres are essentially due to the existence of
fully extended constitutive macromolecules [18]. This
particular disposition of the polyethylene chains pre-
vents the formation of folded-chain molecular struc-
tures, which represent points of weakness in most
polymeric ®bres. The growth of classical crystalline
superstructures, such as spherulites, is therefore not
possible because of the particular gel-spinning process
of the Spectra1 ®bres. The preparation of these ®bres
leads to a very high crystallinity, typically close to 90%.
For the use of Spectra1 ®bres in a composite appli-
cation which requires a relatively high processing tem-
perature, it was interesting to study the changes in the
®bre crystalline state as a function of the treatment
temperature. The investigations were carried out with a
Perkin-Elmer DSC-7 apparatus, and the melting endo-
therms of the ®bres after di€erent thermal treatments
were recorded. The DSC pans used for the experiments
were placed in the DSC oven with an air ¯ow, in order
to work in conditions as close as possible to the real
processing conditions.
10 mg of ®bre is rapidly heated to a variable iso-
thermal temperature, Ti, and maintained for 15 min at
this temperature. The ®bres are not held under con-
straint during this treatment. The sample is then cooled
to room temperature, and heated again at a constant
rate (10 C/min) up to 200 C. The melting endotherms
are recorded during this second step. The DSC signal
obtained for the untreated Spectra1 ®bre is shown in
Fig. 1. The total area measured under the complex
melting peak was
Hf=255.51 J/g, which corresponds
to a crystallinity of 90% for an in®nite enthalpy of fusion

Hf1=282.15 J/g according to Wu et al. [19]. The
endotherm of the polyethylene ®bre may be divided into
three principal peaks. A slight shoulder is detectable at
137 C, and corresponds to the melting of the lamellar
crystals overgrown from the shish-kebab ®brils during
the gel-spinning of the ®bre [20]. This kind of crystalline
superstructure is created by the lowest molecular mass
macromolecules and is generally located in the periphery
of the ®bre. The principal peak at 147.5 C corresponds
to the melting point of the main constitutive oriented
 E. Devaux, C. Caze / Composites Science and Technology 59 (1999) 459±466
Fig. 1. DSC scan of the untreated Spectra 1
®bre during heating at
10 C/min.
orthorhombic crystals of the ®bre. A solid-state trans-
formation of the previous crystals is mentioned during
this same step, transforming a part of the orthorhombic
phase in an hexagonal form. This phenomenon is
masked by the principal endothermic peak of fusion [20].
Finally, a second shoulder around 155 C is due to the
melting of the hexagonal form of the polyethylene gen-
erated in the latter step.
Fig. 2 shows the di€erent melting endotherms of the
Spectra1 ®bres obtained consecutively for a thermal
treatment at Ti. It can be established that up to
Ti=140 C, the crystalline state of the polyethylene
macromolecules does not change signi®cantly. Above
this temperature, a rearrangement occurs and the
oriented ®brillar orthorhombic lattice which is con-
cerned with the principal melting peak previously
described, transform into the spherulitic orthorhombic
classical form of the polyethylene. Moreover, the
shoulder at 155 C disappears for thermal treatments
above Ti=150 C, and the originally hexagonal form
also transforms into the spherulitic orthorhombic form.
The enthalpies of fusion after di€erent treatments at Ti
Fig. 2. DSC scans of Spectra1 ®bres with a heating rate of 10 C/min,
after thermals treatments at di€erent temperatures.
461
Fig. 3. Variation of the enthalpy of fusion of the Spectra1 ®bre as a
function of thermal treatment temperature, Ti.
are shown in Fig. 3. It can be seen that this curve can be
divided into three parts. Up to Ti=135 C, the crystal-
linity of the ®bre does not change and no crystalline
rearrangement can be detected. When Ti varies between
135 C and 155 C, the enthalpies dramatically decrease
because of the partial melting and recrystallization of
the extended chains in the material. Thus, this curve
shows that a processing temperature above Ti=135 C
for a composite material reinforced with polyethylene
®bres cannot be used without a marked transformation
of the ®bre structure. Above a treatment temperature of
Ti=155 C, the polyethylene which has totally crystal-
lised in the spherulitic orthorhombic form, shows a
relatively low crystallinity. It should be noted that the
enthalpy of fusion in the third part of the curve slightly
increases with Ti. This phenomenon is probably due to
the nonlinear cooling rate of the samples in the DSC
oven after 15 min at the temperature Ti.
These ®rst results show that the use of Spectra1 ®bres
as reinforcing materials in a composite application calls
for a processing temperature below 135 C. On the other
hand, the melting point of the polyethylene used as the
matrix being 108 C, the composite material must be
processed between these two critical temperatures.
However, the processing temperature chosen must be
the close to 135 C in order to use the thermoplastic
matrix as ¯uid as possible.
Fig. 4 shows a Spectra1 1000 ®bre embedded in the
polyethylene matrix. This sample is observed by polar-
ised-light optical microscopy, and it has been obtained
after slow cooling at 1 C/min from 130 C. Evidence is
shown for the growth of a transcrystalline interphase in
the vicinity of the reinforcement, which con®rms the
existence of physico-chemical interactions between the
two constituents.
We have shown that the crystalline state of the
Spectra1 ®bre was not a€ected for a processing tem-
perature lower than 135 C. The change in its mechanical
performance as a function of the thermal treatment has
also to be followed.
462 E. Devaux, C. Caze / Composites Science and Technology 59 (1999) 459±466
Fig. 4. Transcrystallization of the polyethylene matrix in the vicinity
of a Spectra1 ®bre as observed with polarized-light optical micro-
scopy, after cooling at 1 C/min.
3.2. Change in the mechanical properties of the
Spectra1 ®bre
The elastic modulus and tensile strength of the poly-
ethylene ®bre have been measured in order to quantify
the damage caused by high temperatures. The mechan-
ical characteristics measurements were carried out after
di€erent thermal treatments in a precision oven. For a
given temperature, the maximal thermal gradient is
‹1 C between two points in the oven. The ®bres are
isothermally treated at di€erent temperatures, Ti, with-
out any mechanical stress during the treatment, then
tested on a tensile apparatus after cooling at room tem-
perature. For these experiments, the mono®lament
length was 120 mm and the tensile testing rate was 10
mm/min. Fig. 5 shows the change in the elastic modulus
with the treatment temperature, Ti. For the untreated
®bres, a value of 98 GPa is obtained, which is quite low
for this kind of material. However, the very long gauge
length used for the tests and the fact that the ®bres
have been extracted from the warp direction of a woven
Fig. 5. Variation of the Young's modulus of the Spectra1 ®bre after
thermal treatments at di€erent temperatures.
Fig. 6. Variation of the maximum tensile strength of the Spectra1
®bre after thermal treatments at di€erent temperatures.
textile may explain this unexpected result. The tensile
and friction stresses imposed on the yarns during weav-
ing are indeed very high. The elastic modulus of the
Spectra1 ®bre remains stable up to a thermal treatment
at Ti=100 C. It decreases slightly up to a treatment
temperature corresponding to the melting temperature
of the ®bre. It can be seen that after 15 min at 130 C, a
loss of 25% in the modulus is observed. Nevertheless,
the tensile strength of the polyethylene ®bres (Fig. 6)
remains constant up to 130 C, then falls dramatically in
the vicinity of the melting temperature. The results pre-
sented in Fig. 7 show that the elongation at break
increases regularly as a function of the isothermal
treatment temperature, up to a temperature close to the
melting point. This behaviour gives evidence of a prob-
able solid±solid transition in the crystalline state of the
constitutive molecules of the ®bre. The annealing
operation indeed tends to fold the extended macro-
molecular chains. One of the consequences is to improve
the elongation at break by favouring the molecular
movements in the crystalline lattice. Thus, the modulus
decreases whereas the tensile strength remains constant.
Fig. 7. Variation of the elongation at break of the Spectra1 ®bre after
thermal treatments at di€erent temperatures.
 E. Devaux, C. Caze / Composites Science and Technology 59 (1999) 459±466 463

This con®rms that the processing time at a given tem-

perature must be as short as possible in order to avoid
the folding of the macromolecules.

4. Behaviour of the polyethylene ®bres after a chemical

surface treatment

4.1. Mechanical properties of the treated ®bres

During the gel-spinning and the subsequent crystal-

lization of the Spectra1 ®bres, the lowest molecular
masses are rejected to the periphery of the ®bre. Thus, a
particular structure surrounding the ®bre is generated, Fig. 8. Variation of the Young's modulus of the chemically treated
the properties of which are very di€erent from the bulk. Spectra1 ®bre as a function of the treatment time.
This structure can prevent optimal adhesion to a poly-
mer matrix and constitutes the so-called weak boundary
layer. In order to improve interfacial adhesion in a and tensile strength of the ®bres are measured by the
composite application with a polyethylene matrix, this method mentioned previously.
layer has to be removed. An oxidising surface treatment In Figs. 8 and 9, it can be seen that both the modulus
has been used for this purpose, consisting in a chromic and the tensile strength dramatically decrease for very
acid solution (K2Cr2O7:H2O:H2SO4=4.4:7.1:88.5 by short treatment times, then increase again for treatment
weight). Blais et al. [21] have already highlighted that times up to 2 min. For oxidising treatments longer than
this kind of oxidising treatment is very e€ective on var- 2 min, the mechanical characteristics slightly decrease.
ious polymer surfaces such as low-density polyethylene, This particular behaviour may be discussed in terms of
high-density polyethylene, or polypropylene. Treating super®cial degradation and chemical reactions in the
polymers by this solution promotes an etching of the vicinity of the ®bre surface. In the ®rst part of the curves
surface and increases the surface energy of the material (<1 min), the strong oxidising power of the solution
[22]. Moreover, chemical changes are detected on poly- tends to remove the weak boundary layer and to graft
ethylene where the build-up of hydroxyl, carbonyl and reactive chemical functions on the surface. Moreover,
sulphate groups is pointed out. The various con- the ®bre is somewhat corroded to a more or less great
sequences of such a chemical treatment on the surface depth. These phenomena have important consequences
properties of the ®bre are important for adhesion to a on the mechanical behaviour of the material. Reduc-
polymer matrix: in the mechanical adhesion theory, an tions in the tensile strength and the elastic modulus of
interlocking of liquid polymer into the pores of the 10% and 20%, respectively are recorded.
substrate occurs. Thus, the chemical etching of the ®bre For treatment times longer than 30 s, increases in
surface can generate a suitable roughness for the tensile strength and elastic modulus are noted. After 2
anchorage of the matrix in the asperities. Moreover, a min, the values of the studied parameters are nearly the
marked enhancement of the substrate surface energy same as the original ones, and an increase in the rigidity
occurs, which considerably improves the wetting of the
®bres by the liquid matrix, and thus favours the inter-
actions between the two materials in contact. Finally,
the weak boundary layer which is responsible of the
poor adhesion to the ®bre surface is removed by this
chemical operation.
However, surface modi®cation of the ®bre may have
an in¯uence on its mechanical characteristics. The
chemical degradation must be ecient in order to
improve the adhesion, but it must be suciently gentle
to avoid too marked a decrease in the tensile behaviour
of the ®bre. To study this, di€erent samples have been
treated by the oxidising solution mentioned above for
various durations. The ®bres are immersed in the
chromic acid bath at room temperature. They are
removed after a time between 30 s and 30 min, then Fig. 9. Variation of the tensile strength of the chemically treated
carefully rinsed in pure methanol. The elastic modulus
464 E. Devaux, C. Caze / Composites Science and Technology 59 (1999) 459±466

of the ®bre is observed. Actually, the chemical groups
grafted onto the surface are likely to have reacted, and a
cross-linked super®cial layer generated. Experimental
evidence for this phenomenon is given by dissolving the
treated ®bre in hot trichlorobenzene. In the case of the
non-surface-oxidised material, the whole polyethylene is
soluble in the solvent. By contrast, the cross-linked layer
behaves as a insoluble gel, and only the ®bre core is
dissolved in the trichlorobenzene. After separation of
the gel from the solution, we obtain a gel content of
approximately 3%. This corresponds to a thickness of
0.22 mm on a 28 mm diameter ®bre, con®rming that only
the extreme surface of the polymer is concerned. As a
comparison, Tissington et al. [1] have published a value
of 0.9% for the cross-linked layer thickness after an
oxygen plasma treatment of polyethylene for 2 min at a
power of 120 W, con®rming that the greater degree of
cross-linking in Spectra1 1000 comparing to other
®bres was related to its very high molecular weight.
4.2. Observation of the treated ®bres surface by atomic
force microscopy (AFM)
The optimisation of the adhesion between a ®bre and
a matrix can be obtained by modifying a certain number
of super®cial physico-chemical parameters. A plasma or

Fig. 10. Untreated Spectra1 ®bre surface as observed by AFM.

Fig. 11. Spectra1 ®bre surface observed by AFM following chemical treatment for 10 min.
 E. Devaux, C. Caze / Composites Science and Technology 59 (1999) 459±466
chemical treatment generally promotes an increase in
the surface energy, which improves substrate wetting by
the molten matrix. Moreover, amongst the consequences
of the previous treatment on the super®cial properties of
the Spectra1 1000 ®bre, the modi®cation of the surface
topography is an important parameter. The change in
the surface morphology caused by chemical etching has
been investigated by atomic force microscopy. The
anchorage of the liquid matrix is indeed favoured by the
roughness and the porosity of the substrate, by increas-
ing the contact area between the two materials.
Fig. 10 shows the untreated polyethylene ®bre surface
as observed by AFM, and Fig. 11 is the same sample
observed following a 10 minute chemical treatment. For
shorter treatment times, no signi®cant changes of the
super®cial topography were observed. The sample
roughness can be easily characterised by calculation of
the absolute roughness coecient, Ra (centre line aver-
age). The evolution of Ra as a function of the chemical
treatment time shows that for the ®bre as-received,
Ra=18.3 nm, whereas it increases to 49.7 nm after 10
min. The latter value remains stable for longer treat-
ment durations. Taking these results into account, it is
likely to be most appropriate to treat the Spectra1 1000
®bres with the oxidising solution for 10 min, before their
incorporation into a polyethylene matrix. This surface
treatment will be applied in order to remove the weak
boundary layer, to increase the surface energy, and to
optimise the super®cial roughness of the ®bre.
5. Conclusion
The utilisation of UHMW polyethylene ®bres as
reinforcing materials for composite applications is of
the greatest interest, but remains limited owing to the
lack of chemical reactivity of their constitutive macro-
molecules. Thus, the possibility of reinforcement of a
strongly compatible matrix such as polyethylene by this
kind of material has to be investigated. Because of the
marked di€erence between the melting points of the
Spectra1 ®bre and the low-density polyethylene, there
exists a temperature window where the reinforcing
material is still unmolten while the matrix is suciently
¯uid to impregnate the yarn satisfactorily. Under such
conditions, the polyethylene matrix is able to tran-
scrystallize in the vicinity of the ®bre, giving evidence of
physico-chemical interactions between the two materials
present. Phenomena such as co-crystallization or epi-
taxial crystallization do indeed occur close to the ®bre
surface.
The variations in the ®bre physical properties follow-
ing processing in the previous temperature window
show that up to 135 C, the crystalline state of the ®bre
does not signi®cantly change. Moreover, after a thermal
treatment at 130 C during 15 min, no change in the
465
tensile strength is observed, whereas a loss of 25% of
the elastic modulus is noted.
However, the ®bre crystallization during spinning
promotes the formation of a weak boundary layer on its
surface. This particular structure has to be eliminated in
order to favour matrix adhesion to the ®bre surface. To
achieve this, the ®bre was immersed in an oxidising
solution of K2Cr2O7, H2O, and H2SO4 (4.4:7.1:88.5 by
weight). The principal e€ects of this chemical treatment
were to increase the surface energy and the roughness. It
has been shown that the mechanical characteristics of
the ®bre remain stable after this kind of treatment.
Moreover, a marked increase in the super®cial rough-
ness is observed, which is an important parameter
because it increases the speci®c surface of the ®bre, and
will thus likely favour the anchorage of the matrix onto
the ®bre surface.
As a conclusion, these investigations have highlighted
the interest in using high-performance polyethylene
®bres as reinforcing materials for a polyethylene matrix.
The processing conditions chosen are 130 C for 15 min.
In addition, a chemical oxidising treatment of the ®bre
for 10 min before its incorporation in the matrix will
probably improve the wetting of the ®bre by the molten
matrix, and increase the adhesion phenomena between
the two materials. These aspects are investigated in the
next paper.
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