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Journal of Macromolecular Science, Part C: Polymer

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ULTRA-HIGH MOLECULAR WEIGHT POLYETHYLENE*

a
John M. Kelly
a
Ticona, Houston, Texas, U.S.A.
Version of record first published: 07 Feb 2007.
To cite this article: John M. Kelly (2002): ULTRA-HIGH MOLECULAR WEIGHT POLYETHYLENE*, Journal of Macromolecular
Science, Part C: Polymer Reviews, 42:3, 355-371
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JOURNAL OF MACROMOLECULAR SCIENCE

Part C—Polymer Reviews
Vol. C42, No. 3, pp. 355–371, 2002
ULTRA-HIGH MOLECULAR WEIGHT

POLYETHYLENE*
Downloaded by [Wageningen UR Library] at 21:11 22 October 2012
John M. Kelly
Ticona, Houston, Texas
CONTENTS
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
II. Polymer Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
III. Viscometric Measure of Molecular Weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
IV. UHMWPE Powder Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
A. Compression Molding. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
B. Ram Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
C. Gel Extrusion and Spinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366
V. Modification of UHMWPE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366
A. Process Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
B. Mechanical Property Modifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
VI. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370
I. INTRODUCTION
Ultra-high molecular weight polyethylene or UHMWPE is a linear

homopolymer produced by the polymerization of ethylene gas.
*Reprinted from Polymer Modification: Principles, Techniques, and Applications; Meister, J.J.,
Ed.; Marcel Dekker, Inc.: New York; 2000, 273–291.
355
DOI: 10.1081/MC-120006452 1532-1797 (Print); 1532-9038 (Online)

Copyright # 2002 by Marcel Dekker, Inc. www.dekker.com
356 KELLY
Structurally, UHMWPE is similar to HDPE differing primarily in the

average length of its molecular chains. This class of linear polyethylenes is
appropriately termed ‘‘ultra-high’’ because its average molecular weight is
10–100 times greater than standard grades of HDPE. As defined by ASTM,[1]
UHMWPE must have an average molecular weight in excess of 3.1 million
g/mole. UHMWPE is available commercially with molecular weights of 3–6
million g/mole. By comparison, most high density polyethylenes report
molecular weights well below 300,000 g/mole.
UHMWPE exhibits the best sliding wear resistance and impact
toughness of any polymer.[2] In many applications requiring wear resistance,
UHMWPE routinely replaces steel. Figures 1 and 2 compare the impact
resistance and abrasion resistance of UHMWPE to other competitive

materials.
Figure 1. Comparative izod impact strength.
Figure 2. Comparative sand–slurry abrasive wear resistance.

ULTRA-HIGH MOLECULAR WEIGHT POLYETHYLENE 357
Table 1. UHMWPE Industrial Applications
Industry Segment Applications
Unit conveying Chain guides, star wheels, feed screws

Mining Truckbeds, hopper & bunker liners
Pulp and paper Suction box covers, rollers, foil blades
Medical Knee, shoulder and hip implants
Agricultural Food preparation surfaces
Automotive Lead acid battery separators
Fibers Ballistic cloth, fishing lines and nets
Recreational Snow ski soles, snowmobile boogie wheels
The polymer’s wear and impact resistance is due to the extremely long
molecular chains of the material and its semi-crystalline solid state
conformation. The surface and subsurface structure of the polymer is
highly ordered and the crystal sites offer resistance to deformation and
conformance to a wear mating surface and to sections being torn loose.[3]
UHMWPE does not easily flow when high shear forces are applied due to the
excessive entanglements of the long polyethylene chains.
UHMWPE also shares the lubricity, chemical resistance, and superior
electrical properties of HDPE. Industrial applications, which utilize the
properties of UHMWPE, are presented in Table 1.
II. POLYMER SYNTHESIS
UHMWPE was first synthesized by Karl Ziegler in the early 1950s and
commercially introduced in 1955. The reaction utilizes a highly reactive
organotitanate catalyst to polymerize the feedstock, ethylene gas. The
method of synthesis is similar to that for HDPE except the UHMWPE
chains are polymerized to greater lengths prior to chain termination. The
resultant polymer chains are remarkably linear, with measured branching of
less than 3%.[4]
Despite a tremendous amount of research, the true mechanism of
Ziegler–Natta polymerization is still not entirely clear. The trial-and-error
method is frequently employed in developing new catalysts. Figure 3 depicts
the general Ziegler–Natta mechanism for polyethylene.[5] As shown, the
catalyst generally consists of titanium in combination with aluminum
alkyls. During the reaction, the aluminum alkyls form a titanium alkyl
bond. Ethylene is inserted into this chemical bond by forming a titanium
ethylene alkyl. The chain grows by inserting more ethylene molecules into
this titanium carbon bond. A chain transfer agent such as molecular hydro-
gen is typically employed to control molecular weight because it reacts
358 KELLY
Figure 3. Ziegler–Natta polymerization mechanism.
cleanly, leaves no residue, and is low in cost. A chain transfer agent termi-
nates a growing chain without deactivating (poisoning) the catalyst.
Commercial catalysts are very active. Catalyst particles, suspended in
liquid slurry, serve as the initiation sites for many growing polymer chains.
Typical reaction velocities for this exothermic reaction are in the range
of 103–107. The velocity of chain growth, dependent on the concentration

of active catalyst and monomer, can be expressed by Eq. (1)[6]:
Vchain growth ¼ kp Ms C ð1Þ
where
Vchain growth ¼ velocity of chain growth
C* ¼ number of active growing chains (catalyst activity)
Ms ¼ concentration of monomer (i.e., ethylene)
kp ¼ propagation rate constant
The polymerization rate is also controlled by the particle geometry, mass-
transfer coefficient at the polymer surface, and the diffusivity of the monomer
through the layer of polymer coating the primary catalyst particles. The
catalyst chemistry influences such polymer attributes as average molecular
weight and distribution, bulk density, degree of crystallinity, particles size
and morphology.
The polymer attributes are also affected by such process parameters as
the reaction temperature, pre-activation of the catalyst and concentration of
alkyls. Ziegler–Natta polymerization does not easily allow for secondary
reactions to the basic polymer. In-situ modification of the UHMWPE homo-
polymer, although possible, is not practiced.
The Ziegler–Natta reaction is inherently ‘‘clean’’ and the polymer
requires no purification beyond removal of the slurry diluent by staged
dryers. The virgin polymer is white in color and opaque due to the deflection
of light by the polyethylene crystallites. It is commercially available with
average particle diameters ranging from 50 to 250 micrometers. Visually,
the particles are roughly spherical although on the microscopic level the
individual particles are porous and finely webbed.[7] Figure 4 shows scanning
electron micrographs of UHMWPE particle at a) 500 magnification and
b) 5,000 magnification.
III. VISCOMETRIC MEASURE OF MOLECULAR WEIGHT
It is difficult to measure the molecular weight of UHMWPE because the

long molecular chains are too entangled to permit measurable shear flow.
Standard melt viscosity methods, such as parallel plate or capillary rheome-
try do not work. For example, virgin UHMWPE powder would report a
value of zero flow by means of standard capillary rheometry. Instead, dilute
solution viscosity must be used to measure the average size of the polymer
molecules. The methodology,[8] as the name infers, requires dissolving the
polymer in a solvent (decahydronaphthalene) and measuring the kinematic
viscosity by a capillary viscometer. An increase in the solution viscosity is related
to the length of the molecular chain. This measure of solution viscosity is
360 KELLY
Figure 4. Scanning electron micrographs of UHMWPE particle. Ticona GURÕ grade 4130
a) 500 magnification b) 5,000 magnification. Source: Hoechst AG Research Laboratory
(Frankfurt, Germany).
referred to as the polymer’s relative viscosity [rel ] as it compares the polymer

solution viscosity against the viscosity of the pure solvent. The relative
viscosity is defined by Eq. (2):
Relative viscosity ¼ ½rel ¼ ðts k=ts Þ=ðt0 k=t0 Þ ð2Þ
where
k ¼ viscometer kinetic energy correction constant
ts ¼ solution flow time, seconds
t0 ¼ pure solvent flow time, seconds
Equations 3 and 4 relate the relative viscosity of the polymer to the
average molecular weight of the polymer through the intrinsic viscosity:
Intrinsic viscosity ¼ ½ ¼ f½2Crel 2 lnð1 þ rel CÞ1=2 g=C ð3Þ

1:37
Nominal molecular weight ¼ 53,700½ ð4Þ
where
C ¼ solute concentration (typically 0.02%)
k ¼ viscometer kinetic energy correction constant
Measurement of molecular weight by solution viscosity is only accurate
for virgin UHMWPE powder that has not been subjected to temperatures
above its crystalline melting point (138–142 C). UHMWPE, which has been
processed into solid shapes by means of heat and pressure, is too insoluble,
due to autocrosslinking, to allow for measurement by solution techniques.
The degree of autocrosslinking induced in the polymer by exposure to heat is
low but sufficient to inhibit complete dissolution of the material in hot sol-
vent. The solution technique is described by the ASTM test method D4020.
IV. UHMWPE POWDER PROCESSING
UHMWPE has a melt viscosity in the region of 1010 Pa s and therefore

cannot be processed by standard high shear methods.[9] If subjected to shear,
these molecularly immobile molecules will undergo chain scission to the
extent that the polymer’s final impact and abrasion properties are reduced.
Shear processes such as injection molding, screw extrusion, or blow molding
require materials with a melt viscosity between 104 and 106 Pa s. Instead, a
low flow process such as sintering is used to form UHMWPE powder into
solid shapes. Two sintering processes commonly employed are ram extrusion
and compression molding. Metal powders, PTFE and some ceramics are
sintered in a similar fashion.[10,11] Sintering uses heat and high pressure to
compact and fuse the free flowing powder. Under sufficient pressure, the
rough UHMWPE particle morphology allows for a dense packing structure.
Initially, compaction occurs by realignments of the particles. As the compac-
tion pressure builds, the particles elastically deform. For particulate solids the
relationship[12] between pressure and porosity is given by Eq. (5):
E ¼ Eo ekP ð5Þ
where
E ¼ compacted powder porosity
Eo ¼ uncompacted powder porosity
P ¼ compaction pressure
k ¼ compressibility constant
Under typical compaction pressure, the bulk density of UHMWPE
powder is relatively high and the void content is low. Much of the final
molded density can be reached by application of pressure alone. For
example,[13] UHMWPE powder cold pressed at 9 MPa attained a bulk
density of 0.80 g/cm3 while the fused polymer density is 0.935 g/cm3.
362 KELLY
Under typical commercial compaction pressures of 3–5 MPa, UHMWPE

powder (e.g., Ticona GURÕ 4000 series) attains a bulk density of
0.60–0.65 g/cm3. Once compacted, very little material melt flow is required
to sinter the powder. The numerous particle to particle contact points of the
compacted powder exhibit sufficient flow to achieve fusion after melting.
Typical sintering pressures and temperatures for UHMWPE are 3–5 MPa
and 180–220 C respectively.
Cooling of the fused form can begin when a core temperature of roughly
180 C is reached. With a 4–6% shrinkage rate for UHMWPE, the rate of
cooling is critical to the final dimensional stability of the molded part. To
prevent warping, the molded form must be slowly cooled under pressure. If
cooled too rapidly, the differential shrinkage between the faster cooling sur-
face layer and still molten core will create frozen-in stresses. Often, an anneal-
ing step is added to the process to eliminate differential shrinkage. The
annealing process involves reheating the molded part above the polymer’s
crystalline melting point and then slowly cooling (10–20 C/min) the part to
allow for stress relaxation.
It has proven difficult to accurately model the UHMWPE particle fusion
process. Present models[14–16] describe interparticle fusion by mechanisms
based on surface tension as the sintering driving force and viscosity as resisting
the coalescence process. They assume the compacted particles are smoothly
spherical but, as seen in Figure 4, the average UHMWPE particle is anything
but smooth. Rather, the typical UHMWPE particle consists of an aggregate of
nodular units interconnected by a porous fibrillar network. Consequently the
actual surface to volume ratio is much higher than a value based on particle
diameter and leads to highly erroneous calculated results.
A. Compression Molding
Large UHMWPE sheets (1.2-m 3.0-m) are commercially produced by

compression molding. The process, in schematic form, is depicted in Fig. 5.
The process consists of filling the unheated bottom cavity with UHMWPE
powder then inserting a top plate. The closed die is then inserted into a press,
which can apply a controlled pressure and temperature cycle. Figure 4 depicts
how the melt front begins at the heated surfaces of the platens and moves
toward the center of the compacted form. Once the center of the fused form
has reached at least 180 C, the mold is slowly cooled to below the polymer’s
crystalline melting point before opening the mold and removing the part.
A variation of standard compression molding is direct compression
molding or DCM. The DCM process compacts and fuses the particles in
two steps rather than one. The powder is first cold compacted into a ‘‘green’’
preform and next transferred to an oven where it is heated, under pressure
and allowed to fuse. Since UHMWPE does not flow, the green preform

Figure 5. Schematic diagram of the compression molding process.
maintains its shape during sintering. DCM offers the ability to produce
intricate parts without intermediate machining. However, because it is diffi-
cult to apply pressure uniformly, this technique is generally limited to dimen-
sionally symmetrical parts.[17] DCM can also be used to prepare open-cell,
porous UHMWPE structures for filtration applications. Limiting the applied
pressure throughout the compaction and sintering stages can vary the inter-
particle porosity.
B. Ram Extrusion
Rods, tubes and more intricate continuous profiles are produced by ram
extrusion. Ram extrusion can be thought of as a continuous compression
molding process. A schematic of a typical ram extruder is depicted in Fig. 6.
The process employs a reciprocating ram to compact and transfer the
UHMWPE powder through a heated die. For example, to extrude a solid
rod, UHMWPE powder is fed into the machine, via a feed hopper, and the
‘‘charge’’ is compressed into the die by a hydraulic ram. When the ram is
reversed, fresh powder flows into the vacated cavity and the process is again
repeated. As the die slowly fills, the compacted powder begins to soften by
conduction from the heated die walls. The compacted and fused powder moves
through the die as a succession of charges formed into a continuous profile.
Although the term extrusion is used in referring to this method, it is
quite different than the more common melt extrusion processes. It must be
emphasized that no shear mixing of the polymer takes place in a ram extru-
der. Rather, the polymer transits through the die as a compacted plug. Unlike
melt extruders, back pressure in ram extruders is not developed by constric-
tion of the die channel. Rather, the drag friction of the compacted powder
364 KELLY
Figure 6. Schematic diagram of the ram extrusion process.
and melted polymer against the die walls generates sufficient back pressure to
compact the UHMWPE powder. The expansion of the heated polymer also
contributes to back pressure. These pressures are quite high. The back pres-
sures developed in most commercial ram extruders are generally higher than
the pressures generated in compression molding by means of a matched die
mold and a compressing piston.
Heat input is achieved by conduction from the die walls; shear heating is
negligible. Increasing the die surface temperature or available die surface area
can increase the heat input. The minimum residence time is a function of the
heated die length as described in Eq. (6):
Minimum die residence time ¼ L=Vmax ð6Þ
where
L ¼ heated die length, meter
Vmax ¼ maximum output speed, meter/hour
The thermal conductivity of a packed polymer powder bed is normally
referred to as the effective thermal conductivity. Typical values for solid
polymers are two or three magnitudes lower than for most metals. For poly-
mer powders the thermal conductivity is even lower. For UHMWPE
powder,[18] the effective thermal conductivity at 20 C is 0.42 W/(m K).
Most ram extruder designs allow for interchangeable dies. The
hydraulic unit used to drive the ram should be sized to handle the pressure
requirements of the largest or most intricate profile contemplated. The axial
die pressures during compaction are high, approximately 44 MPa.
The compaction force (Fz) required to advance the compacted plug can be
expressed by Eq. (7):[19]
Fz ¼ F0 eðKf ZC=AÞ ð7Þ
where
F0 ¼ axial force
C ¼ die circumference
A ¼ cross-sectional area of the die’s cavity
K ¼ Poisson’s ratio (0.3–0.4 for polymers)
Z ¼ compacted bed length

f ¼ static coefficient between the resin and steel (0.4)
In practice, the available hydraulic pressure of the ram limits the die
length and the maximum die temperature is limited by the polymer’s thermal
stability. Excessively high hydraulic pressures also accelerate the wear rate of
the ram and die seals during operation. Replacement of a seal or ram is costly
as such repairs can only be conducted when an extruder is off-line. Generally,
for a cylindrical profile, the minimum die residence time required to suffi-
ciently sinter a UHMWPE profile is calculated from the following relation-
ship as shown by Eq. (8):[20]
timemin ¼ kD2 ð8Þ
where
timemin ¼ minimum residence time
D ¼ extrudate diameter
k ¼ 1.6
This general relation is based on an analytical solution of unsteady heat
conduction in an infinite cylinder with constant thermophysical properties. A
similar relationship is applicable to a rectangular profile where the extrudate
diameter is replaced by the half-sheet thickness.
Because heat input is achieved only by conduction from the die walls,
the output rates of ram extruders are very slow in comparison to twin or
single screw extruders. For example,[21] to produce a 7.6 cm diameter solid
extrudate using a ram extruder with a heated die length of 419 cm, the max-
imum output would be approximately 3.8 cm/s or 0.16 kg/s.
UHMWPE powder compaction and sintering by either ram extrusion or
compression molding yields similar values in terms of the polymer’s final
mechanical properties. The resultant molded semiforms can be easily
shaped. They can be cut, turned, sawed, milled, or punched using standard
machine tools. Although difficult to bond by means of adhesives, UHMWPE
parts can be joined effectively by means of butt-welding or mechanical
366 KELLY
fasteners. Thin films of UHMWPE can also be produced from molding by

the use of skiving blades.
C. Gel Extrusion and Spinning
Several processes are based on blends of UHMWPE and oil[22] where

the oil acts as a diluent rather than a solvent. The UHMWPE particles
imbibe the oil, swell and form gels. Unlike UHMWPE alone, the resulting
gel can then be extruded on modified plastic screw extruders and fiber lines.
Subsequent extraction of the oil from the formed sheets results in a porous
material suitable for battery electrode plate separators or filter membranes.

The majority of automotive lead acid batteries manufactured today contain
UHMWPE electrode plate separators produced in this manner.
Orientation prior to extraction of oil from gel filaments can also
produce fibers. The flexible and random chains of linear polymers can be
successfully drawn into highly oriented and extended conformations. Total
draw ratios up to 350 have been obtained in the laboratory.[23] This so-called
gel spun UHMWPE yields the highest specific tensile properties of any poly-
meric fiber. Systematic studies[24–26] of gel spun UHMWPE fibers have
reported a maximum tensile modulus of 220 GPa and maximum tensile
strength 6.0 GPa.
V. MODIFICATION OF UHMWPE
The general properties[27] of virgin UHMWPE are listed in Table 2.

UHMWPE semiforms are often produced without the addition of additives.
With the exception of chemical crosslinking, little reactive modification of the
base polymer is carried out commercially. Most additives to UHMWPE are
inert fillers. However, UHMWPE does undergo thermally initiated autocross-
linking during molding but the degree of crosslinking is quite low. The
origins of autocrosslinking in polyethylene are still the subject of some dis-
cussion. It is generally assumed that primary radicals are formed through the
action of heat or through the combined actions of heat and mechanical stress
during processing. Additionally, catalyst residues in the polymer from manu-
facturing may also initiate thermal oxidation. To obtain a significant degree
of crosslinking, dicumyl peroxides are added to UHMWPE to improve creep
resistance and surface hardness. For optimum effect, a gel content of 80–90%
is desired.[28] Peroxide additives are typically dry-blended with the
UHMWPE powder prior to processing to insure fine dispersal. The cross-
linking reaction is initiated by heat during the UHMWPE sintering process.
UHMWPE is commonly modified by the addition of non-reactive addi-
tives or fillers prior to processing. As a rule, the addition of additives or
Table 2. Typical Properties of Virgin UHMWPE
Property Unit Typical Values
Mechanical
Density g/cm3 0.926–0.934
Bulk density g/cm3 0.350–0.500
Tensile strength @ yield MPa 20–22
Tensile strength @ fail MPa 41–44
Elongation @ fail % 350–450
Poisson’s ratio 0.4
Izod impact strength kJ/m2
single 45 notch no break
double 15 notch
100
Young’s modulus MPa 1050
Hardness Shore D 62–66
Coefficient of friction against steel
dry 0.10–0.22
wet 0.05–0.10
Relative solution viscosity dL/g 2.3–3.5
Thermal

Crystalline melting range C 135–138
Linear thermal expansion K (20–100 C)
1
0.0002
Latent heat of fusion J/g 170–180
Specific heat J/(g K) at 20 C 1.84
Thermal conductivity W/(m K) at 20 C 0.42

Decomposition temperature C 300
Electrical
Volume resistivity
cm >1014
Dielectric strength kV/cm 900
Dielectric constant 2.30
Dissipation factor, tan
at 50 Hz 0.00019
at 1 kHz 0.0005
at 0.1 MHz 0.00025
fillers, whether liquid or solid, tends to improve some material properties at

the expense of others. Additives are often added to improve the sliding wear
resistance and coefficient of friction of the base polymer. Choice of filler is
often dependent on the polymer’s end use. For example, food applications
often require prior FDA, USDA, 3-A, or kosher approval of a material and
its additives. Since UHMWPE is hydrophobic and biologically inert, such
approval is easily obtained, but many additives can not be used for food
contact applications. For example, UHMWPE compounds which contain
fillers such as glass fiber, glass beads, or metallic powders can not be used
for applications involving food contact as wear debris may contaminate the
food or food preparation area.
368 KELLY
Standard polymer additives such as lubricants, flame-retardants, ultra-

violet stabilizers, pigments, and mineral fillers are used to modify specific
polymer properties. Generally, additives used for HDPE can also be used
for UHMWPE. Additive levels are generally kept below 5% by weight since
higher concentrations can hinder UHMWPE particle fusion during molding
and degrade the polymer’s ultimate wear and impact properties. As stated
previously, no mixing occurs during sintering so additives must be finely
dispersed into the UHMWPE powder prior to processing.
For a free-flowing mixture, the method of blending should be chosen to
suppress the segregation of the individual particles. High intensity blenders
(e.g., Henschel style blender) or low intensity mixers (e.g., ribbon blender) are
commonly employed. High intensity blenders are generally considered better

at dispersing fillers than low intensity blenders. Common additives for
UHMWPE are listed in Table 3.
A. Processing Additives
Process additives are most often employed in the ram extrusion process
to minimize the back pressure exerted on the ram by the surface friction of
the compacted powder on the die walls. Lubricants can be added which will
migrate to the die surface during sintering to create a slip layer between the
die wall and moving polymer plug. Typical lubricants are silicones, polar
waxes and lower molecular weight polyethylenes.
B. Mechanical Property Modifiers
Polyethylenes because of their carbon–carbon backbones are relatively

flexible. Inert fillers are often added to increase flexural modulus. However,
inert fillers often increase stiffness at the expense of abrasion and impact
Table 3. Common Additives of UHMWPE
Property Enhancement Typical Additives
Surface lubricity Silicone oil, molybdenum disulfide, carbon

black, graphite, polar waxes, vegetable oils,
mineral oils
Abrasion resistance Dicumyl peroxide
Surface hardness Talc, hollow glass spheres, kaolin, short
glass fiber, wood flour
UV resistance Carbon black, hindered amine stabilizers
Heat resistance Metal flakes, phosphite based stabilizers
Electrical conductivity Carbon black, graphite
resistance and, therefore, filler concentrations are kept low. Particulate fillers
are most often used since fibrous fillers tend to cause extensive warping and
highly anisotropic properties.[29] Resultant additive properties such as density
or flexural modulus can be approximated for a two component blend by the
rule of mixtures.[30] Equation 9 demonstrates how the density of a blend can
be determined from the concentration and density of its components:
Xblend ¼ ðwtA ÞðXA Þ þ ðwtB ÞðXB Þ ð9Þ
where
Xblend ¼ density of AB blend, g/cc
wtA ¼ weight fraction of component A
XA ¼ density of component A, g/cc

wtB ¼ weight fraction of component B
XB ¼ density of component B, g/cc
It is often assumed that UHMWPE would effectively serve as a lubri-
cating agent or wear resistant additive to other polymers. However, the
polymer’s chemical inertness, coarse particle size and inability to undergo
melt flow causes it to a poor additive for most polymer systems. Generic
polyethylene compatabilizers such as epoxies or polybutadienes do enhance
the adhesive bond strength of UHMWPE but do not totally offset the poor
interfacial adhesion created by the differential shrinkage upon cooling
between UHMWPE filler and continuous polymer matrix. Attempts to
improve the surface adhesion by increasing the total surface area of the
UHMWPE particles by cryogenic grinding have proven unsuccessful.
Particle reduction to less than 30 mm, by brittle fracture grinding, is prevented
by the polymer’s ductility at low temperatures.
VI. SUMMARY
The exceedingly long molecular chains of the UHMWPE molecule yield

a material with excellent impact strength, sliding wear abrasion resistance
and cold temperature properties. In applications requiring such properties,
UHMWPE is the material of choice. The long chains are also responsible
for the high chain entanglements that hinder application of thermoplastic
process methods such as screw extrusion or injection molding. Instead, par-
ticle sintering techniques, such as compression molding and ram extrusion,
are employed.
EXERCISES
1. The viscosity of a 0.02% solution of polyethylene powder in

decahydronaphthalene was measured by means of an Ubbelohde capillary
370 KELLY
viscometer. The measurement yielded an average solution flow time of

124 seconds vs. 72.3 seconds for the pure solvent. A Hagenbach (k) correc-
tion factor of 2.02 seconds was previously determined for this particular
viscometer. What is the nominal molecular weight of the polyethylene
sample? Would this polyethylene be classified as an UHMWPE?
2. A slide bearing to be used in a water treatment plant is to be made
from a molded UHMWPE compound containing powdered brass filler
(25% by weight). The brass powder has been added to improve heat transfer
created by the friction from a rotating shaft. Assuming the brass powder has
a density of 8.59 g/cc, what would be the estimated density of the molded
part? What would be the maximum amount of brass powder that could be
added if the design specifies the UHMWPE compound must be able to float
on water?
3. A ram extruder is fitted with a die capable of producing a 10 cm
diameter UHMWPE rod. At an operating temperature of 200 C, what is
the estimated minimum amount of time needed to sufficiently sinter this
profile? For a die length of 3 meters, what is the estimated output rate
(kg/hr) for this die?
REFERENCES
1. Annual Book of ASTM Standards; Vol. 08.03, Plastics, Method D4020, 1991.
2. Kanamoto, T.; Sherman, E.S.; Porter, R.S. Polym. J. 1979, 11, 5497.
3. Zachariades, A.E.; Logan, J.A. J. Appl. Polym. Sci. 1983, 28, 1837.
4. Chauh, H.H.; Kanamoto, T.; Porter, R.S. Measures for Polymer Chain
Extension, in High Modulus Polymers: Approaches to Design and Development;
Zachariades, A.E., Porter, R.S., Eds.; Marcel Dekker: New York, 1988; p. 259.
5. Berthold, J. TH K-1 and TH K-2 Process for HDPE, Polyolefins Industries
Ltd. Technical Report.
6. Rosen, S.L. Fundamental Principles of Polymeric Materials; John Wiley & Sons:
New York, 1993; 190–191.
7. Siegman, A.; Raiter, I.; Narkis, M.; Eyerer, P. J. Mater. Sci. 1986, 21, 1180.
8. Annual Book of ASTM Standards; Vol. 08.03, Plastics, Method D4020, 1991.
9. Agassant, J.-F.; Avenas, P.; Sergent, J.-Ph.; Carreau, P.J. Polymer Processing:
Principles and Molding; Carl Hanser Verlag: Munich, 1991.
10. Lee, C.C.; Tucker, C.L. J. Non-Newt. Mech. 1987, 24, 245.
11. Hynn, K.S.; Spalding, M.A. Polym. Eng. Sci. 1959, 30 (10), 571.
12. Tadmor, Z.; Gogos, C. Principles of Polymer Processing; John Wiley & Sons:
New York, 1979.
13. Halldin, G.W.; Kamel, I.L. Polym. Eng. Sci. 1977, 17, 21.
14. Frenkel, J. J. Phys., USSR 1945, 9, 385.
15. Kuczynski, J.C. J. Met. (Met. Trans.) 1949, 1, 169.
16. Eshelby, J.D. Met. Trans. 1949, 185, 796.
17. Siegmann, A.; Raiter, I.; Narkis, M.; Eyerer, P. J. Mater. Sci. 1986, 21, 1180.
18. Langecker, G.R.; Rantenbach, R. Powder Technol. 1976, 15, 39.
19. Rosenzweig, N. Polymer Technology; Rosenzweig, N., Narkis, M., Eds.; John
Wiley & Sons: New York, 1995.
20. Science, 22 February 1991, p. 845.
21. Hoechst Plastics, HostalenÕ GUR Technical Publication, June 1987.
22. Sano, A.; Iwanami, Y.; Matsura, K.; Yokoyama, S.; Kanamoto, T. Interna-
tional Symposium on Macromolecules, Book of Abstracts, Session 2.26,
Montreal, 8–13 July, 1990.
23. Griswold, P.D.; Zachariades, A.E.; Porter, R.S. J. Polym. Sci., Polym. Phys.
1979, 17, 859.
24. Sakurada, I.; Ito, I.; Nakamae, K. J. Polym. Sci. 1966, 615, 75.
25. He, T.; Porter, R.S. Polymer 1987, 28, 946.
26. Wang, L.H.; Ottani, S.; Porter, R.S. Polymer 1991, 32, 1776.
27. Hoechst Plastics, HostalenÕ GUR Technical Publication, June 1987.

28. Di-Cup Dicumyl Peroxide Technical Data; Hercules, Inc.: Wilmington,
Delaware, Bulletin ORC-201C, 1979.
29. Riedel, T. In Plastics Additives; Gächter, R., Müller, H., Eds.; Carl Hanser
Verlag: New York, 1990; 426–429.
30. Freidman, E.M.; Porter, R.S. Trans. Soc. Rheol. 1975, 19, 493.

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This article was downloaded by: [Wageningen UR Library]

On: 22 October 2012, At: 21:11

Journal of Macromolecular Science, Part C: Polymer

ULTRA-HIGH MOLECULAR WEIGHT POLYETHYLENE*

Version of record first published: 07 Feb 2007.

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JOURNAL OF MACROMOLECULAR SCIENCE

ULTRA-HIGH MOLECULAR WEIGHT

Ticona, Houston, Texas

Ultra-high molecular weight polyethylene or UHMWPE is a linear

DOI: 10.1081/MC-120006452 1532-1797 (Print); 1532-9038 (Online)

Structurally, UHMWPE is similar to HDPE diﬀering primarily in the

resistance and abrasion resistance of UHMWPE to other competitive

Figure 1. Comparative izod impact strength.

Figure 2. Comparative sand–slurry abrasive wear resistance.

ULTRA-HIGH MOLECULAR WEIGHT POLYETHYLENE 357

Table 1. UHMWPE Industrial Applications

Industry Segment Applications

Unit conveying Chain guides, star wheels, feed screws

II. POLYMER SYNTHESIS

Figure 3. Ziegler–Natta polymerization mechanism.

ULTRA-HIGH MOLECULAR WEIGHT POLYETHYLENE 359

of 103–107. The velocity of chain growth, dependent on the concentration

III. VISCOMETRIC MEASURE OF MOLECULAR WEIGHT

It is diﬃcult to measure the molecular weight of UHMWPE because the

referred to as the polymer’s relative viscosity [rel ] as it compares the polymer

Intrinsic viscosity ¼ ½ ¼ f½2Crel 2 lnð1 þ rel CÞ1=2 g=C ð3Þ

ULTRA-HIGH MOLECULAR WEIGHT POLYETHYLENE 361

IV. UHMWPE POWDER PROCESSING

UHMWPE has a melt viscosity in the region of 1010 Pa s and therefore

Under typical commercial compaction pressures of 3–5 MPa, UHMWPE

Large UHMWPE sheets (1.2-m  3.0-m) are commercially produced by

ULTRA-HIGH MOLECULAR WEIGHT POLYETHYLENE 363

Figure 5. Schematic diagram of the compression molding process.

Figure 6. Schematic diagram of the ram extrusion process.

Minimum die residence time ¼ L=Vmax ð6Þ

ULTRA-HIGH MOLECULAR WEIGHT POLYETHYLENE 365

Fz ¼ F0 eðKf ZC=AÞ ð7Þ

Z ¼ compacted bed length

timemin ¼ kD2 ð8Þ

fasteners. Thin ﬁlms of UHMWPE can also be produced from molding by

C. Gel Extrusion and Spinning

Several processes are based on blends of UHMWPE and oil[22] where

material suitable for battery electrode plate separators or ﬁlter membranes.

The general properties[27] of virgin UHMWPE are listed in Table 2.

ULTRA-HIGH MOLECULAR WEIGHT POLYETHYLENE 367

Table 2. Typical Properties of Virgin UHMWPE

Property Unit Typical Values

ﬁllers, whether liquid or solid, tends to improve some material properties at

Standard polymer additives such as lubricants, ﬂame-retardants, ultra-

commonly employed. High intensity blenders are generally considered better

B. Mechanical Property Modiﬁers

Polyethylenes because of their carbon–carbon backbones are relatively

Table 3. Common Additives of UHMWPE

Property Enhancement Typical Additives

Surface lubricity Silicone oil, molybdenum disulﬁde, carbon

ULTRA-HIGH MOLECULAR WEIGHT POLYETHYLENE 369

XA ¼ density of component A, g/cc

The exceedingly long molecular chains of the UHMWPE molecule yield

1. The viscosity of a 0.02% solution of polyethylene powder in

viscometer. The measurement yielded an average solution ﬂow time of

Intrinsic viscosity ¼ ½ ¼ f½2Crel 2 lnð1 þ rel CÞ1=2 g=C ð3Þ

Large UHMWPE sheets (1.2-m 3.0-m) are commercially produced by