The International Journal Of Artificial Organs I Vol. 3 no. 2, 1980 I p.p.
114-118
Composite materials for
biomedical applications
This work was presented in part at the First Interna-
tional Workshop on Artificial Organs, October 3-5, 1979,
Sorrento, Italy.
KEY WORDS
Biomaterials
Polymers
Human tendon
ABSTRACT
The concepts of composite mechanics have been
used to design two materials for potential prosthesis of
biomedical interest. They attain specific physical proper-
ties and use polymers which show a high degree of
biocompatibility.
The materials used were a poly (2-hydroxyethyl-
methacrylate) as matrix and polyesther resin as reinforc-
ing fibers.
The mechanical performance of a uniaxially oriented
composite has been adjusted to match the behaviour of a
human tendon. A laminate composite has been modelled
for use in plastic surgery.
INTRODUCTION
The possibility of using polymeric materials for con-
structing artificial organs has been the object of many
scientific publications and patents (Kronental et al, 1975)
in the past years. However, polymers which are suitable
for particular applications often display undesired side
effects once implanted in the human body. In fact, the
specifications which apply to polymeric materials used as
substitutes for internal organs are very severe. Together
with the specific physical properties which are required
by the particular function, the material must show the fol-
lowing properties (Lyman, 1975):
- high chemical and physical stability to biological envi-
ronments;
- ability of being sterilized;
- absence of any kind of contaminant.
© by Wichtig Editore sri, 1980
C. Migliaresi and L. Nicolais
Istituto di Principi di Ingegneria Chimica
University of Naples
Naples, Italy
Moreover, the polymer must not induce:
- tumor formation;
- antileukotactic response;
- thrombus formation;
- inflammatory encapsulation or cell modification in the
surrounding tissue.
All these requirements strongly reduce the number of
polymers which are potential candidates for biomedical
applications. The most widely used polymers are: silicon
rubbers, polythetrafluoroethylene (PTFE), polypropylene
(PP), polyvinyl alcohol (PVA), polyvinylchloride (PVC),
polyesther resins (PET) and acrylic resins (AR). The sili-
con rubbers display high chemical and biological inertia
coupled with mechanical properties similar to those of
natural tissues. They are used for plastic surgery and for
making prostheses whjch are in direct contact with
blood. One of the oldest uses of such material is in the
Holter hydrocephalus check valves. Also the pacemakers
are generally coated with silicons in order to improve the
resistence to the biological environments. The main prob-
lem connected with this polymer is that the growing liv-
ing tissue cannot adhere on it and consequentely the
formed fibrin cannot be transformed in fibrous tissue. As
a consequence, occlusion of tubes will sometimes occur
especially in the Holter valves. The PFTE based polymers
are mainly used for surgery applications. They show high
biomechanical stability and a high degree of porosity
which permits good adhesion to the organic tissues.
However, the difficulties of processing strongly reduce
their applications. The PVA has been widely used in the
past but since it has shown a tendency to promote cal-
cification, its use is now strongly reduced. The PP and
PET are widely used mainly in fiber form showing good
biomechanical stability. The PVC is very common in arti-
ficial prosthesis but only for short time applications due
to its poor physico-chemical stability in living tissues.
The AR are mainly used in dentistry. Other polymers are
used in small quantities for very specific applications and
most of them are still under investigation for their in-situ
long-term properties.
In the last years, a growing interest in a new class of
biomaterials, the hydrogels, has been shown. These
polymers are swollen extensively in water (30-70%) and
0391-3988/300114-05 $ 01.25/0
Composite materials for biomedical applications
display excellent biocompatibility also for long term ap-
plications (Sprinel et al 1973). They are similar to the
body's highly hydrated tissues and show strong biologi-
cal interactions with them (Hoffman, 1975). In fact, hyd-
rogels appear to absorb proteins and to adhere with cells
more gently than low water content foreign interfaces
(Hoffman, 1975); moreover, the water molecules included
In the polymer seem to be associated within the three-
dimensional network to form a quasi-organized structure
similar to the one formed in the proteins (Bruck, 1973).
This enables rapid ingrowth of cells and capillaries and
permits modelling of all tissue characteristics. In contrast
with this high biocompatibility, the hydrogels generally
display very poor mechanical properties reducing very
much the possibility of their applications as a material for
artificial organs.
In the present paper the possibility of using the con-
cepts of composite materials (Nicolais, 1975), for design-
ing artificial organs is investigated. Structural fiber com-
posite materials with very high specific properties have
been successfully utilized in many engineering applica-
tions (Waddoups, 1975). Because the fibers are so much
stronger than ordinary polymeric materials, they normal-
ly inpart strength to whatever matrix they are in. When
the fibers are all aligned in one direction, maximum
strength is achieved in the composite material along the
direction of the fiber length. By purposely placing or
weaving the fibers into specific directions, strength can
be developed in those directions. It thus becomes possi-
ble to tailor-make specific properties in specific directions
and thereby satisfy the design requirements of structures
subjected to a variety of multiaxial stresses. It is precisely
this ability to design materials to fit complex require-
ments combined with the improved specific properties
Fig. 1 Photograph of a circular sample of PHEMA, shown by the
arrow.
115
that make fiber-reinforced composites so interesting.
In the present work the composite mechanics has
been applied to design two materials for potential pros-
theses of biomedical interest; i.e. artificial tendons and
reinforced sheets for plastic surgery.
MATERIALS AND METHODS
The hydrogel used in this study is a poly (2-hyd-
roxyethil-methacrylate), PHEMA. developed by Wichterle
and Lim (Wichterle and Lim, 1960) and widely applied for
contact lenses. The 2-hydroxyethyl methacrylate (HEMA)
monomer obtained by Rhom und Haas was redistilled
before use. The radical polimerization was accomplished
at T = 60°C for 2 hors. using 0.5% by weight of
ethylenedimethacrylate (EDMA) as crosslinking agent and
0.1 % by weight of 2-Aso-iso-butyronitrile (AlB) as in-
itiator. Sets of PHEMA were prepared containing respec-
tively 10, 20, 30 and 40 percent by weight of diacetins.
The mixture was poured between two glass plates for
preparing flat specimens with a thickness ranging from
0.25 to 2.5 mm or in a silicon rubber tube of 3 mm inside
diameter for cylindrical samples. Once the reaction was
completed, the samples were dipped in water for two
months at room temperature to eliminate any unreacted
material and to eliminate diacetins in the case of HEMAl
diacetins mixtures. The perfect transparency of the mat-
erial obtained is shown in Figure 1. The fibers used were
PET fibers kindly supplied by Montefibre SpA. The artifi-
cial tendons were obtained by crosslinking the HEMAl
diacetins mixture at 40% diacetins content in a tube in
which the desired amount of uniaxially oriented fibers
was placed. The composite sheets were prepared by
u
cD
"'E LIP 0100 em Hg
~
E
---l
X
-,
°
0'-- :_-----~:_----_____:~ I
:;-;1 I
100 200 300
t hr
Fig. 2 Normalized water flow J x L versus time for a PHEMA mem-
brane obtained by a mixture containing 10% of diacetin.
Migliaresi and Nicolais
placing different numbers of laminae with fibers oriented
at 0°/90° between two glass plates and by filling the
space with the same mixture as above.
Permeability measurements were performed by using
a classical permeability cell apparatus (Refojo, 1965).
Mechanical properties were determined by using
specimens cut into dumbell shape and tested with a con-
stant rate of strain (f = 0.2 min.") and constant tempera-
ture (T = 37°C) with an Instron universal testing machine
Mod. 1112. Throughout tensile test the swollen sample
was immersed in distilled water, kept at constant temp-
erature in a jacketed vessel. The latter moved together
with the lower clamp of the Instron machine and was
connected with a thermostat.
RESULTS AND DISCUSSION
a) Permeability
The water flow, J, expressed as J x L where L is the
membrane thickness, is reported in Figure 2 as a function
of time for a PHEMA membrane at T = 37"C. The be-
haviour is that typical (Matz and Elata, 1970) of a rubbery
material, showing an initial strong decrease of permea-
bility due to membrane compaction. The asymptotic val-
ues measured on membranes prepared from HEMAl
diacetins at different relative content are reported in Fig-
ure 3 as function of the applied pressure. It can be ob-
served that the effect of diacetin content is to increase
the permeability at each value of the applied pressure,
LlP. The permeability coefficient, K, can be calculated
(Refojo, 1965) by:
K = VL1]/tALlP (1)
where V is the volume of water which flows through a
00'
9
300
LIP, em Hg
Fig.3 Asymptotic water flow, J x L, versus applied pressure, AP,
for PHEMA membranes with initial diacetin weight content
of: 0% (a), 10% (b), 20% (c), 30% (d). 40% (e).
membrane of thickness, L, in a given time, t, and 1] is the
water viscosity. The values of K are reported in Table I
for each diacetin content. These results may roughly be
calculated with the average pore radius, r, by using the
equation proposed by Ferry, 1936:
r = y'8KTS (2)
where S is the specific water content.
In Table I the reported r values are very close to those
obtained by Refojo, 1965, for similar systems indicating
that the presence of diacetin modifies only slightly the
permeability properties of PHEMA. Since the maximum
dimensional stability occurs when the diacetin content in
the monomer mixture is 40%, the use of such system as
matrix for composites avoids that stress be induced
around the fibers which would result in dewetting or
damage OT the matrix during the water swelling proce-
dure. In Table I the equilibrium water content is reported
as a function of diacetin concentration in the monomer
mixtures.
b) Mechanical properties
Typical stress-strain curves for different initial diacetin
contents are shown in Figure 4. The presence of diacetin
reduces the elastic modulus, E, (i.e. the initial slope of
the stress-strain curve) and strength, ob, while increases
the elongation at break, eb, In Table I also these
mechanical parameters are reported. All the above re-
sults indicate that the effect of diacetin is that of reducing
the crosslinking density of the PHEMA network.
Photographs of the uniaxially oriented composites are
shown in Figure 5. The tensile behaviour of a human
tendon (Kenedi, 1974) is reported in Figure 6 as a full
line. To match the same performance, the PET fibers in
e
~.
'0
0.5
Fig.4 Stress-strain curves for PHEMA samples at initial diacetin
weight content of: 0% (a), 10% (b), 20% (c), 30% (d), 40% (e).
116
Composite materials for biomedical applications

the composite system are not fully extended but rather 100
they are suitably crimpled in order to give a low initial
modulus together with a high rigidity for a strain of 0.5.
The volumetric fiber content is <I> = 0.2 and the cross-
section is 7 rnm-,
The experimental results reported in Figure 6 indicate
that this composite system well reproduces the mechani-
cal behaviour of the human tendons. Studies on creep z
behaviour and fatigue (Migliaresi et al, 1980) confirm the
strong similarities between natural and artificial tendons.
-g 50
In order to achieve a «quasi-isotropic» behaviour of o
.....J
fiber composite (i.e. materials with stiffness and strength
approximately uniform in all directions of a plane) it is
necessary to build composite sheets with laminae having
fiber at 0°, 90° and ±45° with respect to the direction of

TABLE 1-PROPERTIES OF PHEMA OBTAINED FROM HEMA/DIACE-

TIN MIXTURES AT DIFFERENT DIACETIN CONTENT

Initial X x 10'· r Equilibrium E ab

5
2
diacetin (crns) (A) water
content
(N/m 2 ) (N/m 2 ) E x 10
content
(wt.%) (vol.%) Fig. 6 Tensile behaviour of a human tendon (full line) compared
with experimental results for a uniaxially oriented PHEMAI
0 0.69 3.8 38.5 6 2.14 0.36 PET composite.
10 0.87 4.5 40.1 4.8 1.58 0.46
20 1.08 5.0 40.2 4.2 1.47 0.55
30 1.17 5.2 41.0 2.4 1.40 0.74 Fig. 7 Photographs of PET/PHEMAcomposites at volumetric filler
40 1.19 5.2 42.1 2.3 1.20 0.89 content = 0.0035 (a) and 0.0180 (b) respectively.

TABLE II - EXPERIMENTAL MODULUS (E) AND THEORETICAL

MODULUS (ET), CALCULATED BY USING THE LAMINATION
THEORY, FOR PHEMAIPET COMPOSITES

Filler content E (N/m 2 ) ET(N/m 2 )

(vol.%)

0.25 1.6 x 10· 1.2 x 10.

1.00 4.0 x 16. 4.1 x 10.
3.00 6.5 x 10· 6.3 x 10.

Fig.5 Photographs of uniaxially oriented composites.

117
Migliaresi and Nicolais

the applied load (Nicolais, 1975). Obviously one must be
careful to make laminates which are symmetrical and
balanced to avoid deformations in the laminate plane. In
this work we have confined ourselves to 0/90 laminates.
The photographs of PET/PHEMA composites at 0 =
1.8% and 0 = 0.35% are presented in Figure 7. The elas-
tic moduli, E, obtained from tensile tests on laminates at
different filler contents are reported in Table II together
with the value, Et, calculated by using the lamination
theory, successfully applied to high performance compo-
sites (Nicolais, 1975). The complete development of the
theory is not reported here but its use permits to predict
the moduli of the laminates with a good approximation.
It should also be observed that the values of the laminate
moduli reported in Table II are already 10 times larger
than that of the unfilled PHEMA also for the smaller filler
content.
CONCLUDING REMARKS
6. Lyman, D.J.: Biomedical Polymers - An Introduc-
tion. In: Polymers in Medicine and Surgery, Plenum
Press, 29, 1975.
7. Matz, R., Elata, C.: Hydrodynamic Aspects of Desali-
nation by Reverse Osmosis. O.S.W. Research and
Development Progue, Report No. 543, June 1980.
8. Migliaresi, C., Nicolais, L., Kolarik, J., Stol, M.: Artifi-
cial Tendons. Submitted to Macro lupac, September
1980, Florence.
9. Nicolais, L.: Mechanics of Composites. Polym. Eng.
Sci., 15, 137, 1975.
10. Sprinel, L., Vacik, J.: Biological Tolerance of
lonogenic Hydrophilic Gels. J. Biomed. Mater., Res.,
7, 123, 1973.
11. Waddoups, M.E.: Characterization of Advanced Com-
posite Materials for Structural Design. Polym. Eng.
Sci, 15, 160, 1975.
12. Wichterle, 0., Lim, D.: Hydrophilic Gels for Biological
Use. Nature, 165, 117, 1960.

It has been shown that the concepts of composite

mechanics can be useful to design materials with the
desired physical properties for potential biomedical ap-
plications. The use of continuous biocompatible filaments
for reinforcing weak matrixes with very high physico-
chemical stability to biological environments has brought
to the development of potential prostheses with interest-
ing properties. Work is in progress to investigate the long
term performance of such materials in in-situ applica-
tions.

Reprint requests to
Dr. C. Migliaresi
Istituto di Principi di Ingegneria Chimica
University of Naples
80125 Naples, Italy

REFERENCES

1. Bruck, S.D.: Aspects of Three Types of Hydrogels for

Biomedical Applications. J. Biomed. Mater. Res., 7,
387, 1973.
2. Ferry, J.D.: Ultrafilter Membranes and Ultrafiltration.
Chemical Reviews, 18, 373, 1936.
3. Hoffman, A.S.: Hydrogels - A Broad Class of
Biomaterials - In: Polymers in Medicine and
Surgery, Plenum Press, New York 33,1975.
4. Kenedi, R.M., Gibson, T., Evans, J.H., Barbenel, J.C.:
Tissue Mechanics. Phys. Med. BioI. 20, 699,1975.
5. Kronental, R.L., Oser. Z., Martin, E.: Polymers in
Medicine and Surgery, Plenum Press, New York,
1975.

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