Poly(methyl methacrylate) – so-called product as a model is therefore essential to

‘acrylic resin’ – is usually the material of the understanding of the more advanced
choice for full denture bases and and complicated materials which are, in a
‘gumwork’ for removable devices. It has very direct sense, derived from it.
also been the chemical model for many Read full chapter
other material developments in dentistry, Synthetic Polymers
such as restorative materials. The Poly(methyl methacrylate)
properties, behaviour and handling of Poly(methyl methacrylate) (PMMA) (Fig.
poly(methyl methacrylate) likewise form a 33.1F) is a non-degradable polyacrylate
basis for understanding those other and is the most commonly applied non-
materials. metallic implant material in orthopedics.
A polymerization reaction is performed as After being used as an essential ingredient
part of the normal dental procedures in the in making dentures, PMMA was
laboratory, and the proper control of this is introduced to orthopedic surgery in the
important for controlling the properties of mid 1950s (Saha and Pal, 1984). PMMA
the product. It is essential to understand tissue biocompatibility became further
both the heat-cured and cold-cured types, apparent when Plexiglas fragments were
whose properties and limitations differ accidentally implanted in the eyes and
because of their processing differences. other body tissues of World War II fighter
Since the methyl methacrylate monomer is pilots during aircraft crashes.
a very reactive compound, storage is a PMMA can be in situ polymerized and
problem. Its chemistry has a bearing on a crosslinked from a slurry containing
number of issues. PMMA and methyl methacrylate
The mechanical properties are the monomers and is so used as a common
ultimate concern in determining suitability bone grafting material, mainly in the
to task, and the relationship of these to fixation of orthopedic prosthetic materials
processing and service conditions are for hips, knees, and shoulders (Kenny and
clearly important. This topic is dependent Buggy, 2003). PMMA-based bone cements
on the special behaviour of polymers. The can be mixed with inorganic ceramics or
properties of the plain product are not bioactive glass to modulate curing kinetics
ideal, however, and various modifications and enforce mechanical properties.
to the chemistry are possible to obtain Antibiotics can be loaded within the
better behaviour. cement to reduce the risk of prosthesis-
Dental acrylic resin represents a case study related infection. Significant drawbacks of
in polymer science of wide interest in self-curing PMMA cements include that
itself. Even so, there are many points they are not degraded, that their high
which are relevant in other dental materials curing temperatures and toxic monomers
contexts, and a grounding in this type of can cause necrosis of the surrounding
tissue, and that the cements show limited The clinical presentation just described is
interactions with the surrounding bone termed bone implantation syndrome (BIS)
(Hendriks et al., 2004). Therefore, or bone cement implantation syndrome
development of alternative injectable bone (BCIS). Proposed mechanisms for MMA-
cements is directed towards biodegradable induced injury include a neurogenic reflex,
materials with improved curing properties release of vasoactive and myocardial
and osteoconductive interfaces (Yaszemski depressant substances by the cement,
et al., 1996; Hendriks et al., 2004). intravascular thrombin generation in the
Due to its excellent bio- and lungs, direct vasoactive effects of absorbed
hemocompatibility and ease of MMA, and acute pulmonary
manipulation, PMMA is used in many microembolization.
medical devices, including blood pumps After application of
and dialyzers. Its optical properties make it polymethylmethacrylate, unbound MMA
a candidate material for implantable ocular monomer is quickly absorbed into the
lenses and hard contact lenses (Lloyd et systemic circulation and eliminated by the
al., 2001). PMMA also offers physical and lungs. Its peak level is reached in expired
coloring properties that are beneficial for air within 2 to 5 minutes. The extent of
denture fabrication (Hendriks et al., 2004). systemic absorption depends on the area of
Read full chapter contact between the bone cement and
Methylmethacrylate vascularized tissue and on the degree of
Definition curing.
Polymethylmethacrylate bone cement is a
MMA is a peripheral vasodilator.
polymer formed by mixing highly volatile
However, the amount released during
liquid methylmethacrylate (MMA)
reaming in joint replacement is 10- to 20-
monomer with an accelerator,
fold less than that required to produce
polymethylmethacrylate powder. This
hypotension in experimental models.
bone cement is used during orthopedic
Further, studies have demonstrated that
surgery to implant prostheses for joint
hypotension also occurs in the absence of
replacement. MMA has been implicated as
the polymer. Thus, the most likely
a cause of adverse cardiopulmonary events
explanation of the pathogenesis of this
observed most frequently during hip
syndrome is acute pulmonary
replacement surgery. Symptoms include
microembolization. During implantation of
hypoxemia, bronchoconstriction,
the cement and prosthesis, the high
pulmonary hypertension, and right
intramedullary pressure generated in the
ventricular failure with hypotension. Fatal
long bone marrow cavity forces medullary
cardiac arrest, though rare, has been
contents into the venous circulation, with
reported in 0.6% to 1% of patients in some
embolization to the lungs. The pathologic
case series.
nature of the emboli is not certain; it may
be fat, marrow, thrombus, air, or bone pulmonary effect of MMA in the absence
cement. Emboli appear as echogenic of pulmonary embolization is not well
masses during reaming, cementing, defined. However, indirect evidence
prosthesis placement, and manipulation of suggests that it may trigger
the bone. Pulmonary embolization bronchoconstriction.
activates the clotting cascade and triggers Read full chapter
the production of proinflammatory
Structure of Polymer
substances. Further, cemented prostheses
Glasses: Short-range Order
are associated with a longer duration of
5 Polymethylmethacrylate
embolization, larger emboli, and a higher
Atactic polymethylmethacrylate is widely
percentage of right atria filled by emboli
used in optical components for a high level
compared with noncemented prostheses.
of clarity and structural rigidity. The
Intramedullary pressure peaks are 680 mm
intermediate level order of
Hg in humans with cemented arthroplasty,
polymethylmethacrylate has been
compared with peaks of less than 100 mm
extensively studied since the steric
Hg with noncemented arthroplasty.
crowding along the chain leads to a curved
There are also chronic issues related to backbone conformation. These proposals
MMA and other polymers used in have been confirmed using wide-angle x-
orthopedic surgery. Controlled ray scattering measurements (Lovell and
occupational exposure to MMA has not Windle 1981, Waring et al. 1982). These
been shown to affect workers' mortality and more recent broad Q neutron
from colon and rectal cancer. The scattering studies coupled with molecular
recommended maximum exposure of modeling support the view of a persistent
MMA vapor is 100 parts per million over chain conformation in an otherwise highly
the course of an 8-hour workday. Acute disordered material (Ward and Mitchell
exposure to extremely high levels of MMA 1995). Gabrys et al. (1986) reported the
vapor can cause liver necrosis, pulmonary existence of some short-range order in
edema, and pulmonary emphysema. glassy polymethylmethacrylate using spin
Occupational exposure of medical polarization neutron scattering, although
personnel is well below the levels their contentions are not supported by
necessary to elicit these toxic effects. molecular models (Gabrys et al.
However, other less dramatic effects might 1986). Miller et al. (1984) obtained wide-
occur. MMA is known to be a potent angle x-ray scattering from systematic
allergenic sensitizer and can cause local series of amorphous acrylate and
reactions with dermal exposure. It is also methacrylate polymers with differing alkyl
known to be a potential pulmonary toxin, side groups. The regular variation of the
with chronic exposure causing positions of the diffuse peaks in the
occupational asthma. The direct
scattering patterns with alkyl length led to Read full chapter
the proposal of local ordered structures. Synthetic Biomaterials for
Read full chapter Regenerative Medicine
Acrylic bone cements for Applications
joint replacement Satyavrata Samavedi, ... Aaron
Z. Sayeed, ... K.J. Saleh, in Biomedical S. Goldstein, in Regenerative Medicine
Composites (Second Edition),2017 Applications in Organ
9.3.2 Storage Transplantation, 2014
Polymethylmethacrylate is packaged in the 7.3.3.1 Polymethylmethacrylate
form of a liquid monomer and powder Polymethylmethacrylate (PMMA) is a
copolymer constituent. Both components strong but lightweight polymer possessing
are mixed at the time of arthroplasty and a compressive strength between 85 and
undergo polymerisation to form a viscous 110 MPa and a tensile strength between 30
mouldable biomaterial that can be inserted and 50 MPa [44]. PMMA possesses a
into areas needing fixation. It is imperative relatively high coefficient of thermal
that cement curing time is available so that expansion, and during polymerization in
it can be manipulated and inserted before situ, temperatures can reach values as high
the cement is unusable. The time frame of as 40 and 56°C [45,46]. Consequently, the
PMMA from a liquid to a useable paste is curing process in vivo can result in a
relatively short and sets as a solid in shrinkage of around 6–7% [45] and cause
approximately 9 min from mixing (Turner tissue necrosis. The mechanical properties
et al., 1981). The storage of PMMA of PMMA can be tuned by varying the
constituents affects the structural mixing ratios of monomer and initiator
properties of cement. Lewis and Son during polymerization. PMMA can absorb
(2008)describe an ambient temperature of water over several weeks at body
21°C for storage of cement constituents to temperature [45] and properties such as
be used in surgery. Cement constituents tensile strength and fatigue strength,
stored in warmer temperatures set more decrease upon water absorption. Despite
quickly and may cause procedural burden this seemingly poor stability, PMMA
(Lewis and Son, 2008). Additionally, the degrades very little in aqueous
powder copolymer is sterilised with environments. In addition to strength and
ethylene oxide gas and is thermally stable stability in aqueous environments, PMMA
(Lewis and Son, 2008; Lewis and Mladsi, possesses excellent optical properties [47].
1998). Gamma-irradiated powders should Due to its biocompatible nature and
be stored for a period of at least 3 weeks in tunable mechanical and optical properties,
ambient environment to allow for the PMMA has been widely used in bone
proper utilisation post-sterilisation (Lewis cements, as intraocular lenses and as
and Son, 2008; Lewis and Mladsi, 1998). screws in bone fixation [48]. Although
PMMA’s use as bone cement has certain 2.3.2 Polymethyl methacrylate (bone
disadvantages, such as causing thermally cement)
induced necrosis, chemically induced Polymethyl methacrylate (PMMA), also
necrosis due to the release of unreacted called bone cement, is another commonly
monomer, shrinkage after setting and used polymer in orthopedic surgery. The
inflammation due to particles released successful use of PMMA bone cement was
from the cement, bone cement continues to perhaps the most important event in the
enjoy popularity in orthopedic surgery and history of modern joint replacements.
is used under six commercial formulations PMMA had been in use for dental
in the United States [48]. Concurrently, applications before its successful
bone cements have also been used adaptation as the fixation material of
extensively in percutaneous choice in artificial hips. Sir John Charnley
vertebroplasty [49]. Since PMMA does not developed the successful combination of
play a role in inducing new bone PMMA cement fixation and high-density
formation, recent work has investigated the polyethylene as the acetabular bearing
addition of small quantities of bioactive surface (Charnley, 1960; Charnley, 1964).
glass, ceramics, and osteogenic growth As mentioned previously, high-density
factors to PMMA resulting in the polyethylene has been replaced by
formation of “bioactive” bone UHMWPE. Although there have been
cements [49]. Apart from use as bone modifications to the bone cement used by
cement, PMMA has also found widespread Sir Charnley, the bone cement used in
application as hard contact lenses due to its current cemented artificial joints is similar.
excellent optical properties [2]. However, Commercially available bone cements are
PMMA’s use as long-term lenses is limited a two-component system: a powder and a
due to its low oxygen permeability. This liquid. The powder is made of PMMA
limitation can be overcome by beads, sometimes combined with different
copolymerizing methylmethacrylate co-polymers, a polymerization initiator
with methacrylate-functionalized (e.g., benzoyl peroxide), and a
siloxanes. PMMA has also been used in radiographic contrast material
intraocular implants and as intrastromal (radiopacifier) like barium-sulfate (BaSO4)
corneal rings due to its superior or zirconium dioxide (ZrO2). Different
mechanical and optical properties and manufacturers have different proprietary
biocompatibility [50,51]. formulations for their bone cements
Read full chapter (Kühn, 2012). The liquid component
typically consists of methyl methacrylate
Biomaterials in orthopaedic
monomer, a stabilizer (hydroquinone), and
implants an activator (N,N-dimethyl-p-toluidine).
L.C. Jones, ... A.K. Tsao, in Mechanical
Some bone cements contain a coloring
Testing of Orthopaedic Implants, 2017
agent, like chlorophyll, or antibiotics.
The liquid and powder components are materials that is created and formed-to-
mixed together, and the liquid monomer shape in situ, like its namesake, structural
begins to polymerize, or cure. The cement/concrete. The pores and
polymerization reaction is exothermic, irregularities of the adjacent bone surface
generating and releasing heat into the become the mold that the bone cement
surrounding tissue. Once the flows into to take its final shape after it
polymerization is complete, the resulting cures.
solid PMMA can be considered a four- In the operating room, the bone cement is
phase material containing (1) PMMA often mixed in a vacuum system to
beads that were originally in the powder decrease the number of air bubbles trapped
(they do not dissolve), (2) a new PMMA in the cured cement, thus increasing its
matrix formed by the polymerized methyl fatigue resistance. Vacuum mixing may
methacrylate, (3) the radiopacifier, and (4) also help to maintain consistent material
pores formed during the curing process. properties while improving ease of
Each of the phases may contribute to the application. A side benefit is the ability to
mechanical properties of the bone cement, limit toxic fumes which are potentially
and through those to the long-term success carcinogenic and associated with birth
of the implant (Topoleski et al., 1993). For defects in utero. The surgical technique is
example, increased porosity may decrease often equally important to the material to
the fatigue performance of the bone allow fixation between the host bone and
cement, rendering it more likely to sustain the implant. The quality and integrity of
a fatigue fracture. Antibiotics can be added the interface of bone to cement and cement
to the bone cement, making the cement a to implant directly affect the longevity of
drug carrier allowing the gradual release of the in vivo implant.
the drug into the bone and joint space. It is
Read full chapter
commonly used to treat an infected bone
or joint and also used in index surgery
Surface coatings for
procedures for high-risk patients. microfluidic-based
Mechanical properties can also be biomedical devices
influenced by the addition of antibiotics B.G. Abdallah, A. Ros, in Microfluidic
(Lewis, 2015). Devices for Biomedical Applications, 2013
Bone cement holds a prosthesis in place 2.2.2 Polymethylmethacrylate
through mechanical fixation; it is not an (PMMA) devices
adhesive or glue. It is unique because the Polymethylmethacrylate (PMMA) is also a
polymer powder and liquid monomer are very popular material for microfluidic
mixed in prescribed proportions within the applications. A variety of different surface
operating room environment. Bone cement activation and coupling procedures
is one of the few non-adhesive structural addressing a broad range of functionalities
have been reported for PMMA. Several of
these methods are aimed at introducing functionalized with amines, followed by a
amine functionalities on PMMA surfaces ligase detection reaction with immobilized
(see Fig. 2.4). One example of this is a primers to induce hybridization detection.
poly(ethyleneimine) (PEI) coating, which Additionally, PMMA can be silanized to
is an amine-bearing polymer that can incorporate a larger variety of functional
enhance antibody binding to the surface of groups on the surface such as specialized
PMMA (Bai et al., 2006). An improved amines for the immobilization of
antibody surface coverage with up to a ten- biomolecules. A procedure using lithium
fold increase in overall binding was aluminum hydride (LAH) to expose
demonstrated with this immobilization hydroxyl groups on the PMMA surface
strategy, leading to significant can be applied for further functionalization
improvements in immunoassay with organosilanes that facilitate the
performance. immobilization of DNA oligos for DNA
microarray analysis (Cheng et al., 2004).
Oxidation for carboxylic acid functionality
has also been reported as a suitable
covalent immobilization strategy for
PMMA. For example, McCarley et
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al. (2005) discussed a device to capture
2.4. Amination on PMMA is shown via activation of a
and concentrate cells and proteins using
short bifunctional amine. Other methods exist to
treatments for patterning polymers to
create aminated PMMA, as discussed in the text.
substrate surfaces. For this purpose,
Amine groups can further be used to link other
carboxylic acid groups can be patterned on
functional molecules, such as that shown in the
a PMMA surface with UV treatment in an
reaction with the bifunctional glutaraldehyde and
oxygen rich environment, onto which
subsequent immobilization of amine-bearing
antibodies are immobilized for the
molecules, such as proteins.
detection of cells (for example MCF-7
Another example surface treatment of
breast cancer cells) and other proteins in
PMMA with amine functionalities is based
solution. Antibody linkage for
on an activation procedure with lithiated
immunoassays has also been reported via a
diamines to link alkylcyanates to PMMA
sol-gel immobilization strategy (Wang et
(Henry et al., 2000). This method was
al., 2008). Sol-gel films are first adsorbed
further employed by Hashimoto et
to substrate surfaces in which
al. (2005, 2006) for improved detection of
biomolecules can be immobilized within
single DNA base mutations. Similar
the gel networks. The mildness of this
activation strategies can be used to detect
procedure is beneficial in that bioreactivity
low abundance mutations in DNA using a
is preserved, non-specific adsorption is
microarray (Wang et al., 2003). Primers
reduced, and effective immobilization of
are linked to a PMMA surface
target analytes can be achieved for devices in which DNA probe attachment is
immunosensing with low detection limits. a crucial step. It was shown that the
For example, this method has been applied Reacti-Bind™ method is the least effective
in a microreactor for proteolysis via of the three, whereas the CTAB method
trypsin immobilization on a sol-gel coated provides improved immobilization of
PMMA microchannel surface (Huang et amine modified DNA oligos and the
al., 2006). SurModics procedure is the most effective
An indirect approach to immobilize in producing high quality spots along the
antibodies within a PMMA/polycarbonate array with the least amount of surface
microfluidic device to perform ELISA is pretreatment. As a whole, all of these
also possible using functionalized carbon methods can improve DNA-oligomer
nanotubes (CNT) (Sun et al., 2010). In this immobilization and consequently chip
example, a pressure-driven device was efficiencies, hybridization kinetics, and
used and antibody immobilization was detection limits.
achieved via linkage onto carbon Read full chapter
nanotubes functionalized with Cement Extraction
poly(diallyldimethylammonium chloride). Techniques
This functionalization step renders a Gurdeep S. Biring, Bassam A. Masri,
positive charge on the coated CNTs, in Surgical Treatment of Hip
therefore immobilization is achieved via Arthritis, 2009
electrostatic interactions with a negatively Hand-Held Tools
charged antibody. The developed ELISA Polymethylmethacrylate bone cement has
was used to detect bacterial toxins such as mechanical properties that allow it to
staphylococcal enterotoxin B (SEB) with withstand forces several times body
detection limits comparable to weight. It is much weaker than cortical
conventional ELISA, leading to a point-of- bone and is weaker in tension than in
care device that could perform with high compression. The various revision
sensitivity. instruments rely on disrupting this
Various other coating procedures based on interface once the implant has been
commercial coating agents have been removed without compromising the
reported including the chemical SurModics integrity of the underlying bone.
(a company specializing in surface Femur
coatings for medical applications) and In the femur the instruments are used in
Reacti-Bind™ procedures (Liu and Rauch, the plane along the longitudinal axis of the
2003). These methods and the bone, using T or V splitters or offset
cetrimonium bromide (CTAB) surfactant circular chisels without entering the
were tested in the development of cortical bone (Fig. 41-4). These splitters
microfluidic hybridization array (MHAC) have to be used with extreme caution if the
cement mantle is thick. In such situations before the plug, it is best to repeat this
we prefer to thin the cement mantle to a steps multiple times rather than risk an
manageable thickness first with a high- uncontrolled perforation. Once the plug
speed bur and then to use the splitters. The has been drilled, an appropriately sized tap
T splitter is ideally suited to disrupting a is threaded into the hole, and with reverse
well-bonded cement-bone interface. The tapping the cement or plastic fragment
vertical limb of the T acts as a cutting captured by the tap is removed in a
chisel to break the cement, and the retrograde fashion. Any remnants of
horizontal limb of the T acts as a shovel to cement or restrictor can be removed with
scoop the underlying broken cement. As reverse cutting hooks, which come in
already stated, this is not effective if the different sizes (Fig. 41-6). An olive-tipped
cement mantle is thick. The V splitter is guidewire can be used as a feeler to make
useful for creating stress longitudinal sure the cortex has not been breached.
fractures in the cement to allow piecemeal
removal of the cement. The debris is
removed with gouges so that third body
particles are not dispersed, and irrigation is
used to prevent excess heat buildup when
high-speed burs are used. All instruments
have extended shafts so that more distal
diaphyseal cement can be removed, and
this is aided by the use of long-handled
fluorescent lights and grasping forceps.
Once the cement has been removed, the
distal cement restrictor or plug can be
drilled and extracted with special taps
(Fig. 41-5). For this to be accomplished,
the medullary canal is sized and an
appropriately sized drill guide that fills the
medullary canal is used. A drill is then
inserted centrally through the guide into
the medullary canal to allow central
drilling of the cement. It must be noted
that this is not a foolproof method, and the
surgeon must exercise extreme caution to Sign in to download full-size image
make sure that the drilling of the plug FIGURE 41-4. Selection of hand-held instruments
remains central to avoid a cortical including standard and offset chisels and splitters.
perforation. For a thick cement column
Sign in to download full-size image
FIGURE 41-5. Specialized taps for distal cement plug
and restrictor extraction.

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FIGURE 41-7. Acetabular osteotomes and chisels.
Pneumatic impact wrench devices are
available for difficult acetabular revisions,
and these systems deliver repetitive
rotatory loads to the acetabular component
that create shear stresses at the cement-
prosthesis or cement-bone interface,
thereby loosening the
component. Judicious use is appropriate
3,4

in the presence of osteolysis. There are

Sign in to download full-size image studs measuring 6 mm by 6 mm on the
FIGURE 41-6. Reverse cutting hooks for retrieval of pneumatic wrench. Grooves are cut in the
restrictors, disruption of pedestals, and removal of cup with a high-speed bur so that the two
retained cement. can be mated. A torque of 276 to 1379 kPa
Acetabulum is delivered through an arc of 15 degrees
On the acetabular side, curved instruments for 30 seconds and then reversed. This
that follow the contour of the outer typically loosens the cup, but the greatest
diameter of the implant allow the cement- use has been in extracting cementless
implant interface to be approached. This shells, as other methods of extraction
interface is developed, and the cup is usually suffice in the cemented situation.
removed (Fig. 41-7). However, these devices have not gained
popularity and are not in widespread use,
and pelvic fractures have been reported.3
In the acetabulum, burs can be used to
section the polyethylene cup, which then
becomes flexible and can be easily
removed, revealing the cement mantle.
Cement plugs in large and small holes
used to achieve a macrolock in the primary
operation can be burred away. It is unwise
to chase any intrapelvic extensions of
cement, because of the close vicinity of
vascular structures, without appropriate
angiography to delineate the proximity,
and it is pertinent to consider a
retroperitoneal approach to provide access
to retrieve any extruded cement.
Problems
In the presence of osteopenia there is a
high risk of fracture, and careful technique
is required with all modalities of
extraction. The instruments are sharp, and
metaphyseal bone is easily penetrated.