Chapter 7 · The Polyethylene History – A. Bellare, M.
Spector
7 The Polyethylene History
A. Bellare, M. Spector
Summary
Our understanding of the wear behavior of polyethylene
(PE) components has deepened over the past few years as
the adverse effects of gamma irradiation (in air) steril-
ization have become understood.This understanding has
led to methods to improve the wear performance of the
polymer using cross-linking. However, it will still be
several years before the clinical benefits of new methods
of processing PE are clear and the benefit-risk ratio is
established.
Introduction
Ultra-high-molecular-weight polyethylene (UHMWPE)
is one of the principal materials employed in total knee
arthroplasty. While the lubrication and friction of the
metal-on-PE articulation provides the low-friction
arthroplasty that Sir John Charnley sought,the wear of PE
yields particulate debris that potentiates an osteolytic
response, which remains a significant problem. The often
rapid and extensive destruction of bone attributable to PE
wear particles is so dramatic, and so challenges revision
arthroplasty, that it has commanded the most attention
in recent years.However,the actual incidence of this prob-
lem remains somewhat in question. This point notwith-
standing, the prevalence of PE wear particle-induced
osteolysis is great enough to warrant changes in how the
material is processed so as to improve its resistance to
wear.Extrinsic factors that contribute to the wear of poly-
ethylene are also being addressed: prosthetic designs that
reduce stresses in the polymer; prosthetic designs and
manufacturing processes that reduce the number of
particles released from modular junctions, which can
participate in three-body wear of polyethylene; and
materials that may allow the production of more scratch-
resistant metallic counterfaces.
It is well known that PE components of total joint
replacement prostheses undergo processes that produce
PE wear debris due to the articulation of the harder
metallic component, usually a cobalt-chromium alloy,
against the softer PE component. The generation of wear
45 7 7
debris not only damages the surface of the PE component
but is also known to elicit a biological response that often
results in bone resorption. This bone loss (referred to as
osteolysis) can eventually lead to loosening of the pros-
thetic device.The location and size of PE particle-induced
osteolytic lesions often greatly complicate revision
surgery. Work in recent years has focused on processing
parameters that serve as the determinants of the resis-
tance of PE to wear. The reduction of the amount of wear
debris from,and surface damage to,PE would prolong the
lifetime of such prostheses.
The objective of this chapter is to review the history
of the use of polyethylene in total joint arthroplasty, as
a basis for understanding the methods being employed
to improve its performance. There are several prior
reviews [26, 27] of this subject that can be accessed for
useful reference.
Polyethylene Molecular Structure
UHMWPE has a very low frictional coefficient against
metal and ceramics and is therefore used as a bearing
surface for joint replacement prostheses. Moreover, the
wear resistance of UHMWPE is greater than that of other
polymers investigated for this application. Low strength
and creep, however, present potential problems.
The term polyethylene refers to plastics formed from
the polymerization of ethylene gas. The possibilities for
structural variation of molecules formed by this simple
repeating unit for different molecular weight (e.g., crys-
tallinity, branching, and cross-linking) are so numerous
and dramatic, with such a wide range of attainable prop-
erties, that the term polyethylene refers to a wide array of
materials. The earliest type of polyethylene was made by
reacting ethylene at high (20 000–30 000 pounds per
square inch) pressure and temperatures of 200°–400°C
with oxygen as catalyst. Such material is referred to as
low-density polyethylene. A great amount of polyethylene
is produced now by newer,low-pressure techniques using
aluminum-titanium (Ziegler) catalysts. This is called lin-
ear polyethylene due to the linearity of its molecules, in
contrast to the branched molecules produced by high-
 46 II . Past Failures
pressure processes. The linear polymers can be used to
make high-density polyethylene by means of the higher
degree of crystallinity attained with the regularly shaped
molecules. Typically, there is no great difference in mole-
cular weight between the low- and high-density varieties,
e.g., 100 000–500 000. However, if the low-pressure
process is used to make extremely long molecules, i.e.,
UHMWPE, the result is remarkably different. This mate-
rial, with a molecular weight between 1 and 10 million, is
less crystalline and less dense than high-density polyeth-
ylene and has exceptional mechanical properties. It is ex-
tremely tough and remarkably wear resistant; a 0.357
magnum bullet fired from 25 feet bounces back from a
l-inch thick slab of UHMWPE. The material is used in
very demanding applications (e.g., ore chutes in mining
equipment) and is by far the most successful polymer
used in total joint replacements. It far outperforms the
7 various acrylics, fluorocarbons, polyacetals, polyamides,
and polyesters which were tried for such purposes.
Processing of Polyethylene
Implants of polyethylene are usually manufactured by the
machining of components from bulk stock fabricated
from as-synthesized polyethylene powder using mainly
ram extrusion or compression molding. These processes
involve application of heat and pressure to consolidate the
powder into bulk components, followed by machining of
the implant components, packaging, and sterilization.
Various grades of UHMWPE resins have been avail-
able for orthopedic implant application, primarily from
Ruhrchemie AG, which later changed its name to
Hoechst, and is currently called Ticona. The early
UHMWPE resin used by John Charnley was called RCH-
1000 for (R)uhr (CH)emie. This resin is similar to the
current GUR 1020 UHMWPE resin. RCH-1000 was clas-
sified as a form of HDPE (high-density polyethylene),
which is why earlier papers refer to UHMWPE as HDPE
[26]. Later, the orthopedic grade of polyethylene was
called CHIRULEN. Since the 1990s, the UHMWPE resin
used in implants has been called GUR or (G)ranular
(U)HMWPE (R)uhrchemie. Common examples of poly-
ethylene resins used today are GUR 1050 and GUR 1020.
The numbers following GUR refer to the following: the
first digit refers to approximate or loose density (1); the
second digit refers to presence (1) or absence (0) of cal-
cium stearate, which has been used as a lubricant to as-
sist processing; the third digit refers to molecular weight
(2=2 million g/mole and 5=5 million g/mole), and the
fourth digit (0) refers to the resin grade. Calcium
stearate is no longer added to orthopedic-grade poly-
ethylene, since reports showed increased levels of oxi-
dation and fusion defects associated with calcium
stearate [24, 40, 43, 46]. Another source of UHMWPE
was Montell (Formerly Himont), which produced the
Hi-Fax 1900H, a resin that has different structure and
properties compared to the Hoechst resins [45]. How-
ever, Hi-Fax is no longer available, and GUR 1050 and
GUR 1020 remain the only grades of polyethylene used
in orthopedic implants.
The as-synthesized polyethylene resin particles are
approximately 100 µm, but can be submicrometer in size
as well. The broad size distribution of GUR 4150 (the dig-
it “4” refers to the country code, USA, which was the
nomenclature used for GUR resins.) powder particles
have been measured by Pienkowski et al. [35, 36]. Each
powder particle contains 10- 30-µm diameter aggregates
comprising approximately 1-µm diameter nodules con-
nected to each other by fibrils.Olley et al.[34] have shown
that voids or defects remain along the resin boundaries
even after the powder is "fully” consolidated into bulk
components. The likely reason for the presence of defects
is the high viscosity associated with the ultra-high mole-
cular weight of the polyethylene that is required for high
wear resistance. The incomplete consolidation of high-
molecular-weight polyethylene resin compared with low-
molecular-weight polyethylenes, however, is not a major
concern. Gul et al. showed that there was no correlation
between the degree of consolidation of UHMWPE pow-
der particles and the rate of generation of particulate
wear debris under the processing conditions that they
used [23].
The nascent UHMWPE powder contains extended-
chain crystals (thick lamellae) as well as thin lamellae
[16]. The high melting temperature of 141°C observed us-
ing a differential scanning calorimeter suggests that the
powder contains mostly extended-chain crystals, as pre-
sent in high-pressure crystallized UHMWPE. However, a
study utilizing morphological, chemical, and molecular
techniques indicated that a dual lamellar structure exist-
ed.It is postulated that the fibrils of the polyethylene resin
powder contain thick, extended-chain crystalline lamel-
lae, while 20-nm thick lamellae (such as those present in
bulk components manufactured using molding or ram
extrusion) exist in the spherical domains [16].It is unclear
why the powder morphology contains fibrils connecting
spherical domains (sometimes referred to as the “cauli-
flower” morphology). The presence of fibrils in the
powder suggests that the as-synthesized powder has
UHMWPE macromolecules trapped in a low-entangle-
ment, aligned state compared with melt-crystallized
UHMWPE. This low entanglement would assist in con-
solidation of powder during molding or ram extrusion
processes.A highly entangled state would make it harder
to consolidate the powder, since it would require the
chains from powder particles to disentangle and then re-
entangle with the chains of the adjacent powder particles.
The most common processes used to consolidate
polyethylene powder particles into bulk stock are com-