CHA P T E R

19
Prosthetic Polymers and Resins

O UTLINE KEY TER M S

Dentures and Denture Base Resins Inhibitor—A component that prevents or inhibits undesirable polymerization of the monomeric liquid
during storage, in order to prolong shelf life. An unintended positive effect of inhibiting or prevent-
Fabrication of Dentures ing premature polymerization is the increase in working time.
Acrylic Resins Liner—The polymeric material used to replace the tissue-contacting (intaglio) surface of an existing
denture.
Heat-Activated Denture Base Resins Long-term soft liner—A resilient polymeric material that is bonded to the tissue-contacting surface
of a denture for cushioning and/or improved retention. Intended for up to a year of service, they
Compression Molding Technique
are typically heat-processed, and thus, they are more durable than chemically cured, short-term
Chemically Activated Denture soft liners and tissue conditioners. See also “Denture soft liner.”
Base Resins Rebasing—The process of replacing the entire denture base of an existing complete or partial denture.
Relining—The process of replacing the tissue-contacting surface of an existing denture.
Light-Activated Denture Base Resins
Denture soft liner—A polymeric material that is placed on the tissue-contacting surface of a denture
Physical Properties of Denture base to absorb some of the mastication impact energy by acting as a type of “shock absorber”
Base Resins between the occlusal surfaces of a denture and the underlying oral tissues. A denture soft liner
also may be used to engage natural or prosthetic undercuts so as to provide retention, stability,
Miscellaneous Resins and Techniques and support.
Resin Teeth for Prosthetic Applications Short-term soft liner (tissue conditioner)—A resilient polymeric material that is employed for brief
periods (up to 14 days) to absorb masticatory impact and adapt to changing ridge contours (e.g.,
Materials for Maxillofacial Prosthetics following the extraction of teeth or surgical alteration of an edentulous or partially edentulous
ridge.) Such materials are typically chemically activated polymers that contain plasticizers.

T his chapter surveys the materials and techniques used to fabricate prosthetic denture
devices and other denture-related materials, as well as prosthetic materials used to
replace portions of the facial complex. The emphasis is on the polymeric materials used
in denture base resins and denture teeth, plus an overview of the resilient materials used
to fabricate maxillofacial prostheses.

DENTURES AND DENTURE BASE RESINS

The Glossary of Prosthodontic Terms (The Academy of Prosthodontics, 2005) defines a
complete denture as a removable dental prosthesis that replaces the entire dentition and
associated structures of the maxilla or mandible. Such a prosthesis is composed of arti-
ficial teeth attached to a denture base. In turn, the denture base derives its support
through contact with the oral tissues, teeth, or dental implants.
Although individual denture bases can be formed from metals, the majority of
denture bases are fabricated using common polymers. Such polymers are chosen based
on availability, dimensional stability, handling characteristics, color, and compatibility
with oral tissues.
A description of commonly used denture base polymers is presented in this chapter.
Considerable attention is given to individual processing systems and polymerization
techniques. In addition, methods for improving the fit and dimensional stability of
resin-based prostheses are provided.

474
 Heat-Activated Denture Base Resins 475

a powder-liquid system. The liquid contains mostly nonpo-

FABRICATION OF DENTURES
lymerized methyl methacrylate and the powder contains pre-
Several processing techniques are available for the fabrication dominantly prepolymerized polymethyl methacrylate resin
of denture bases (Figures 19-1 to 19-11). Each technique in the form of micro-sized beads (or spheres). When the
requires a suitable impression of the associated dental arch liquid and powder are mixed in the proper proportions, a
followed by fabrication of an accurate gypsum cast. In turn, workable mass is formed. The material is introduced into a
a resin record base is fabricated on the cast. Wax is added to properly formed mold cavity and polymerized. The chemical
the record base, and prosthetic teeth are positioned in the basis for this reaction is described in Chapter 6.
wax, related to the opposing dentition, and evaluated in the
patient’s mouth before proceeding.
HEAT-ACTIVATED DENTURE BASE RESINS
In the laboratory, a brass denture flask is chosen, and the
completed tooth arrangement is encased in a suitable invest- Heat-activated materials are used in the fabrication of
ing medium. Subsequently, the denture flask is opened and nearly all denture bases. The thermal energy required for
the wax is eliminated. After a thorough cleansing of the mold, polymerization of such materials can be provided using a
a resin denture base material is introduced into the mold water bath or microwave oven. The emphasis in this chapter
cavity and polymerized. Following polymerization, the is on heat-activated systems because of the prevalent use of
denture is recovered and prepared for clinical placement. these resins.

COMPOSITION
ACRYLIC RESINS
As previously noted, most polymethyl methacrylate resin
Since the mid-1940s, the majority of denture bases has systems include powder and liquid components (Figure
been fabricated using polymethyl methacrylate resins. Pure 19-1). The powder consists of prepolymerized spheres of
polymethyl methacrylate is a colorless transparent solid. To polymethyl methacrylate and a small amount of benzoyl
facilitate its use in dental applications, the polymer can be peroxide, termed the initiator, which is responsible for start-
tinted to provide almost any color, shade, and degree of trans- ing the polymerization process. The liquid is predominantly
lucency. Its color, optical characteristics, and dimensional nonpolymerized methyl methacrylate monomer with small
properties remain stable under normal intraoral conditions, amounts of hydroquinone. Hydroquinone is added as an
and its physical properties have proven to be adequate for inhibitor, which prevents undesirable polymerization or
dental applications. “setting” of the liquid during storage. Inhibitors also retard
One decided advantage of polymethyl methacrylate is the the curing process and thereby increase working time.
relative ease with which it can be processed. Polymethyl A cross-linking agent can also be added to the liquid. Glycol
methacrylate denture base material is commonly supplied as dimethacrylate is used commonly as a cross-linking agent in
polymethyl methacrylate denture base resins. Glycol dimeth-
acrylate is chemically and structurally similar to methyl
methacrylate. Therefore, it can be incorporated into growing
polymer chains (Figure 19-2). One should note that methyl
methacrylate possesses one carbon-carbon double bond per
molecule and glycol dimethacrylate possesses two double
bonds per molecule. As a result, an individual molecule of
glycol dimethacrylate can participate in the polymerization
of two separate polymer chains that unites the two polymer
chains. If sufficient glycol dimethacrylate is included in the
mixture, several interconnections can be formed and solvent
swelling may occur, such as that caused by exposure to
ethanol in alcoholic beverages. These interconnections yield
a netlike structure that provides increased resistance to defor-
mation. Cross-linking agents are incorporated into the liquid
component at a concentration of 1% to 2% by volume.

STORAGE
Manufacturers of heat-activated resin systems generally rec-
ommend specific temperature and time limits for the storage
of powder and liquid components. Strict observance of such
recommendations is essential. If recommendations are not
FIGURE 19-1  A representative heat-activated resin. The majority of followed, components can undergo changes that may affect
heat-activated resins are supplied as powder-liquid systems. (Courtesy working properties of these resins as well as the chemical and
of Lang Dental Mfg. Co., Inc. Wheeling, IL) physical properties of processed denture bases.
476 CHAPTER 19  Prosthetic Polymers and Resins

Methyl Glycol
methacrylate dimethacrylate Crosslinked poly(methyl methacrylate)

Activator
Initiator

FIGURE 19-2  Chemical basis for the formation of cross-linked polymethyl methacrylate. Glycol dimeth-
acrylate is incorporated into polymethyl methacrylate chains and may “bridge” or “interconnect” such
chains.

COMPRESSION MOLDING TECHNIQUE

After the stone has hardened, the record base and wax
As a rule, heat-activated denture base resins are shaped via must be removed from the mold. To accomplish this task, the
compression molding. Therefore, the compression molding denture flask is immersed in boiling water for 4 min. The
technique is described in detail below. flask is then removed from the water and the appropriate
segments are separated. The record base and softened wax
PREPARATION OF THE MOLD remain in the lower portion of the denture flask while the
Before mold preparation, prosthetic teeth must be selected prosthetic teeth remain firmly embedded in the investing
and arranged in a manner that will fulfill both esthetic and stone of the remaining segment (Figure 19-3, E). The record
functional requirements. In turn, the completed tooth base and softened wax are carefully removed from the surface
arrangement is sealed to the master cast. of the mold. Residual wax is removed from the mold cavity
At this stage, the master cast and completed tooth arrange- using wax solvent. The mold cavity is subsequently cleaned
ment are removed from the dental articulator (Figure 19-3, with a mild detergent solution and rinsed with boiling water.
A). The master cast is coated with a thin layer of separator to
prevent adherence of dental stone to the master cast during
the flasking process. The lower portion of a denture flask is ? CRITICAL QUESTIONS
filled with freshly mixed dental stone, and the master cast is What is the purpose of a separating medium that is used during
placed into this mixture. The dental stone is contoured to denture base fabrication? What is the chemical basis for popular
facilitate wax elimination, packing, and deflasking proce- separating media?
dures (Figure 19-3, B). Upon reaching its initial set, the stone
is coated with an appropriate separator.
The upper portion of the selected denture flask is then posi- SELECTION AND APPLICATION OF
tioned atop the lower portion of the flask. A surface tension- A SEPARATING MEDIUM
reducing agent is applied to exposed wax surfaces and a second The next step in denture base fabrication involves the applica-
mix of dental stone is prepared. The dental stone is poured into tion of an appropriate separating medium onto the surfaces
the denture flask. Care is taken to ensure that the investing of the mold cavity. This medium must prevent direct contact
stone achieves intimate contact with all external surfaces of the between the denture base resin and the mold surface. Failure
mounted teeth. The investing stone is added until all surfaces to place an appropriate separating medium can lead to two
of the tooth arrangement and denture base are completely major difficulties: (1) If water is permitted to diffuse from the
covered. Incisal and occlusal surfaces are minimally exposed mold surface into the denture base resin, it can affect the
to facilitate subsequent deflasking procedures (Figure 19-3, polymerization rate as well as the optical and physical proper-
C). The stone is permitted to set and is coated with separator. ties of the resultant denture base. (2) If dissolved polymer or
At this point an additional increment of dental stone is free monomer is permitted to soak into the mold surface,
mixed and the remainder of the flask is filled. The lid of the portions of the investing medium can become fused to the
flask is gently seated and the stone is allowed to harden denture base. These difficulties often produce compromises
(Figure 19-3, D). in the physical and esthetic properties of processed denture
 Compression Molding Technique 477

A B

C D

E F
FIGURE 19-3  Steps in mold preparation (compression molding technique). A, Completed tooth arrangement prepared
for flasking process. B, Master cast embedded in properly contoured dental stone. C, Occlusal and incisal surfaces of the
prosthetic teeth are exposed to facilitate subsequent denture recovery. D, Fully flasked complete maxillary denture.
E, Separation of flask segments during wax elimination process. F, Placement of alginate-based separating medium.

bases. Hence the importance of employing an appropriate Subsequently, the mold sections are oriented to prevent
separating medium should not be overlooked. “pooling” of separator, and the solution is permitted to dry.
Currently, the most popular separating agents are water-
soluble alginate solutions. When applied to dental stone ? CRITICAL QUESTIONS
surfaces, these solutions produce thin, relatively insoluble Why do denture base resin systems contain polymer beads? How
calcium alginate films. These films prevent direct contact of does the inclusion of polymer beads affect volumetric shrinkage?
denture base resins and the surrounding dental stone, thereby
eliminating undesirable interactions.
Placement of an alginate-based separating medium is rela- POLYMER-TO-MONOMER RATIO
tively uncomplicated. A small amount of separator is dis- Proper polymer-to-monomer ratio is of considerable impor-
pensed into a disposable container. Then a fine brush is used tance in the fabrication of well-fitting denture bases with
to spread the separating medium onto the exposed surfaces desirable physical properties. Unfortunately, most discus-
of a warm, clean stone mold (Figure 19-3, F). Separator sions of polymer-to-monomer ratio provide little practical
should not be permitted to contact exposed portions of information for dental personnel. Furthermore, these discus-
acrylic resin teeth, since its presence interferes with chemical sions do not address relationships between molecular events
bonding between acrylic resin teeth and denture base resins. and gross handling characteristics of denture base resins. The
478 CHAPTER 19  Prosthetic Polymers and Resins

following paragraphs are intended to provide practical, uncoil, thereby increasing the viscosity of the mix. This stage
unambiguous information. is characterized by “stringiness” or “stickiness” when the
The polymerization of denture base resins results in volu- material is touched or drawn apart.
metric and linear shrinkage. This is understandable when Subsequently, the mass enters a doughlike stage. On a
one considers the molecular events occurring during the molecular level, an increased number of polymer chains enter
polymerization process. the solution. Thus, monomer and dissolved polymer are
Envision two methyl methacrylate molecules. Each mol- formed. It is important to note that a large quantity of swollen,
ecule possesses an electrical field that repels nearby mole- but undissolved polymer also remains. Clinically, the mass
cules. Consequently, the distance between molecules is behaves as a pliable dough. It is no longer tacky and does not
significantly greater than the length of a representative adhere to the surfaces of the mixing vessel or spatula. The
carbon-to-carbon bond. When the methyl methacrylate physical and chemical characteristics exhibited during the
molecules are chemically bonded, a new carbon-to-carbon later phases of this stage are ideal for compression molding.
linkage is formed. This produces a net decrease in the space As a result, the material should be introduced into the mold
occupied by the components. cavity during the latter phases of the doughlike stage.
Research indicates that the polymerization of methyl Following the doughlike stage, the mixture enters a
methacrylate to form polymethyl methacrylate yields a 21% rubbery or elastic stage. This is because monomer is dissi-
decrease in the volume of material. As might be expected, a pated by evaporation and by further penetration into remain-
volumetric shrinkage of 21% would create significant difficul- ing polymer beads. The mass rebounds when compressed or
ties in denture base fabrication. To minimize dimensional stretched. Because the mass no longer flows freely to assume
changes, resin manufacturers prepolymerize a significant the shape of its container, it cannot be molded by conven-
fraction of the denture base material. This can be thought of tional compression techniques.
as “preshrinking” the selected resin fraction. Upon standing for an extended period, the mixture becomes
In practice, the prepolymerized fraction is encountered as stiff. This can be attributed to continued evaporation of unre-
a powder, and is commonly referred to as polymer. The non- acted monomer. From a clinical standpoint, the mixture
polymerized fraction is supplied as a liquid, and is termed a appears very dry and is resistant to mechanical deformation.
monomer. When the powder and liquid components are
mixed in the proper proportions, a doughlike mass results. DOUGH-FORMING TIME
Commercial products generally use a polymer-to-monomer The time required for the resin mixture to reach a doughlike
ratio of approximately 3 : 1 by volume. This ratio provides stage is termed the dough-forming time. American National
sufficient monomer to thoroughly wet the polymer particles Standards Institute/American Dental Association (ANSI/
but does not contribute excess monomer that would produce ADA) Specification No. 12 (ISO 20795-1:2008: Dentistry—
increased polymerization shrinkage. Using a 3 : 1 ratio, the Base polymers—Part 1: Denture base polymers) for denture
volumetric shrinkage can be limited to approximately 7%. base resins requires that this consistency be attained in less
The initial setting expansion of the gypsum mold and swell- than 40 min from the start of the mixing process. In clinical
ing of the polymerized acrylic resin after exposure to water use, the majority of denture base products reach a doughlike
in the denture flask and later, further compensate this shrink- consistency in less than 10 min.
age. The polymerization shrinkage of denture base resin is
discussed in depth later in the chapter. WORKING TIME
Working time is defined as the time a denture base material
? CRITICAL QUESTIONS remains in the doughlike stage. This period is critical to the
What are the five physical stages through which properly mixed compression molding process. ANSI/ADA Specification No.
denture base resins pass? During which stage should compression 12 requires the dough to remain moldable for at least 5 min.
molding be initiated? The ambient temperature affects the working time. Hence
the working time of a denture resin can be extended via refrig-
POLYMER-MONOMER INTERACTION eration. A significant drawback associated with this technique
When monomer and polymer are mixed in the proper is that moisture may condense on the resin when it is removed
proportions, a workable mass is produced. Upon standing, from the refrigerator, which may degrade the physical and
the resultant mass passes through five distinct stages. These esthetic properties of a processed resin. Moisture contamina-
stages can be described as (1) sandy, (2) stringy, (3) dough- tion can be avoided by storing the resin in an airtight con-
like, (4) rubbery or elastic, and (5) stiff. tainer. Following removal from the refrigerator, the container
During the sandy stage, little or no interaction occurs on should not be opened until it reaches room temperature.
a molecular level. Polymer beads remain unaltered, and the
consistency of the mixture can be described as “coarse” or PACKING
“grainy.” Later, the mixture enters a stringy stage. During this The placement and adaptation of denture base resin within
stage, the monomer attacks the surfaces of individual polymer the mold cavity are termed packing. This process represents
beads and is absorbed into the beads. Some polymer chains one of the most critical steps in denture base fabrication. It is
are dispersed in the liquid monomer. These polymer chains essential that the mold cavity be properly filled at the time of
 Compression Molding Technique 479

polymerization. The placement of too much material yields a teased away from the body of resin that occupies the mold
denture base that exhibits excessive thickness and resultant cavity (Figure 19-4, C). Care is taken not to chip the gypsum
malpositioning of prosthetic teeth. Conversely, the use of too surfaces of the mold. Pieces of gypsum that have become
little material leads to noticeable denture base voids or poros- dislodged must be removed so that they are not incorporated
ity. To minimize these difficulties, the mold cavity is packed into the processed denture base.
in a well-defined sequence. A fresh polyethylene sheet is placed between the major
While in a doughlike state, the resin is removed from its portions of the flask, and the flask assembly is once again
mixing container and rolled into a ropelike form. Monomer placed in the press. Trial closures are repeated until no flash
is painted over the necks of the denture teeth to promote is observed.
bonding to the denture base. Subsequently, the resin form is When flash is no longer apparent, the mold is closed for
bent into a horseshoe shape and placed into the portion of the last time with no polyethylene sheet interposed. The mold
the flask that houses the prosthetic teeth (Figure 19-4, A). A sections are properly aligned and placed in the flask press.
thin polyethylene separator sheet is placed over the master Again, pressure is incrementally applied. Following definitive
cast, and the flask is reassembled. closure, the flask is transferred to a flask carrier (Figure 19-4,
The flask assembly is placed into a specially designed press D). The flask carrier maintains pressure on the flask assembly
and pressure is applied incrementally (Figure 19-4, B). Slow during denture base processing. A cross-sectional representa-
application of pressure permits the resin dough to flow uni- tion of the denture flask assembly is presented in Figure 19-5.
formly throughout the mold space. Excess material is dis-
placed eccentrically. The application of pressure is continued INJECTION MOLDING TECHNIQUE
until the denture flask is fully closed. Next the flask is opened In addition to compression molding techniques, denture
and the polyethylene packing sheet is removed from the bases can be fabricated via injection molding using specially
surface of the resin with a rapid, continuous tug. designed flasks. One half of the flask is filled with freshly
Excess resin will be found on the relatively flat areas sur- mixed dental stone, and the master cast is settled into this
rounding the mold cavity. This excess resin is called flash. mixture. The dental stone is appropriately contoured and per-
Using a gently rounded instrument, the flash is carefully mitted to set. Subsequently, sprues or ingates are attached to

A C

FIGURE 19-4  Steps in resin packing (compression

molding technique). A, Properly mixed resin is bent into a
horseshoe shape and placed into the mold cavity. B, The
flask assembly is placed into a flask press, and pressure is
applied. C, Excess material is carefully removed from the
flask. D, The flask is transferred to a flask carrier, which
B D
maintains pressure on the assembly during processing.
480 CHAPTER 19  Prosthetic Polymers and Resins

posterior palatal seal area is shown for injection molding than

for any of the other molding processes.
From a clinical perspective, this requires greater (i.e.,
deeper) preparation of the post-palatal seal area (on the
dental cast) to ensure contact of the polymerized denture base
with the patient’s palatal tissues.

POLYMERIZATION PROCEDURE
As previously noted, denture base resins generally contain
benzoyl peroxide. When heated above 60 °C, molecules of
benzoyl peroxide decompose to yield electrically neutral
species containing unpaired electrons. These species are
termed free radicals. Each free radical rapidly reacts with
an available monomer molecule to initiate chain-growth
polymerization. Since the reaction product also possesses an
unpaired electron, it remains chemically active. Consequently
additional monomer molecules become attached to individ-
ual polymer chains. This process occurs very rapidly and
terminates by either (1) the direct connection of two growing
chains (i.e., combination) or (2) the transfer of a single hydro-
gen ion from one chain to another. (See also Figures 6-7, 6-8
and 6-9 in Chapter 6).
In the system under discussion, heat is required to cause
decomposition of benzoyl peroxide molecules. Therefore,
heat is termed the activator. Decomposition of a benzoyl per-
oxide molecule yields two free radicals that are responsible
FIGURE 19-5  A cross-sectional representation of the denture flask and for the initiation of chain growth. Hence, benzoyl peroxide is
its contents.
termed the initiator.
During denture base fabrication, heat is applied to the
the wax denture base, which lead to an inlet or pressure port resin by immersing a denture flask and flask carrier in a water
(Figure 19-6, A). The remaining half of the flask is positioned, bath. The water is heated to a prescribed temperature and
and the investment process is completed (Figure 19-6, B). maintained at that temperature for a period suggested by the
Wax elimination is performed as previously described (Figure manufacturer.
19-6, C), and the flask is reassembled. Subsequently, the flask
is placed into a carrier that maintains pressure on the assem- TEMPERATURE RISE
bly during resin introduction and processing. The polymerization of denture base resins is exothermic, and
Upon completion of the foregoing steps, resin is mixed the amount of heat evolved can affect the properties of the
and injected into the mold cavity (Figure 19-6, D). The flask processed denture bases. Representative temperature changes
is then placed into a water bath for polymerization of the occurring in water, investing stone, and resin are presented
denture base resin if a heat-curing resin is used. Upon com- in Figure 19-7. The temperature profile of the investing stone
pletion, the denture is recovered, adjusted, finished, and (identified as “plaster”) closely parallels the heating curve for
polished. the water. The temperature of the denture base resin lags
Currently there is some debate regarding the comparative somewhat during the initial stages of the heating process. This
accuracy of denture bases fabricated by compression molding can be attributed to the fact that the resin occupies a position
and those fabricated by injection molding. Available data and in the center of the mold and therefore heat penetration takes
clinical information indicate denture bases fabricated by a longer time.
injection molding can provide slightly improved clinical As the denture base resin attains a temperature slightly
accuracy. above 70 °C, the temperature of the resin begins to increase
However, the advantages of injection molding are not rapidly. In turn, the decomposition rate of benzoyl peroxide
straightforward. For example, although tooth movement is is significantly increased. This sequence of events leads to
minimized, resin viscosity must be considerably lower than an increased rate of polymerization and an accompanying
that used in compression molding in order to facilitate increase in the exothermic heat of reaction. Because resin and
injection. dental stone are relatively poor thermal conductors, the heat of
This requires a substantially smaller polymer-to-monomer reaction cannot be dissipated. Consequently, the temperature
ratio, and consequently results in increased curing shrinkage. of the resin rises well above the temperatures of the investing
Hence, the palatal fit is compromised. This is illustrated in stone and surrounding water. This can cause the monomer to
Figure 19-12D, below, in which a greater opening at the boil and produce porosity within the processed resin.
 Compression Molding Technique 481

A B

C D
FIGURE 19-6  Steps in mold preparation (injection molding technique). A, Placement of sprues for intro-
duction of resin. B, Occlusal and incisal surfaces of the prosthetic teeth are exposed to facilitate denture
recovery. C, Separation of flask segments during wax elimination process. D, Injection of resin and place-
ment of assembly into water bath.

INTERNAL POROSITY stages of polymerization. Rapid heating of the resin mass may
As indicated earlier, the polymerization process is exother- cause the monomer to boil, producing porosity within the
mic. Because resin is an extremely poor thermal conductor, polymerized denture base. Fortunately this process can be
the heat generated in a thick segment of resin cannot be dis- controlled by heating the resin more slowly during the poly­
sipated. When heating is poorly controlled, the peak tempera- merization cycle.
ture of this resin can rise well above the boiling point of The relationship between the rate of heating and tempera-
monomer (100.8 °C). This causes boiling of unreacted ture rise within the denture base resin is illustrated in Figure
monomer and produces porosity within the processed 19-8. The polymerization cycle represented by curve C prob-
denture base. ably would yield porosity in thick portions of the denture,
since the temperature of the resin exceeds the boiling point
? CRITICAL QUESTIONS of the monomer (100.8 °C). On the other hand, the polym-
What causes porosity in denture bases? How can these defects be erization cycle represented by curve A probably would result
minimized? in the presence of unreacted monomer, since the resin
temperature fails to reach the boiling temperature of the
POLYMERIZATION CYCLE monomer (100.8 °C). Thus, it is logical to assume that an
The heating process used to control polymerization is termed optimum polymerization cycle lies somewhere between
the polymerization cycle or curing cycle. This process should curves A and C.
be carefully regulated to avoid the effects of uncontrolled Research has led to the development of guidelines for
temperature rise. polymerization of denture base resins. The resultant polym-
The curing cycle presented in Figure 19-7 is unsatisfactory erization cycles have been quite successful for denture bases
because of the marked temperature increase during the early of various sizes, shapes, and thicknesses.
482 CHAPTER 19  Prosthetic Polymers and Resins

140

120

Acrylic
100
Temperature (°C)

80
Water

60

Investing plaster
A
40

20
0 20 40 60 80 100
Time of heating (min)

FIGURE 19-7  Temperature-time heating curves for the water bath,

investing plaster, and acrylic resin during the polymerization of a
25.4-mm cube of denture resin. (Modified from Tuckfield WJ, Worner HK,
Guerin BD: Acrylic resins in dentistry. Aust Dent J 47:119–121, 1943.
Reproduced with permission from the Australian Dental Journal.)

120
C
B
100
Temperature (°C)

A
ter
Wa

80

te r B
60 Wa
FIGURE 19-9  A representative nonmetallic microwave flask (A) and
40 microwave resin (B). (Courtesy of GC America, Inc. Alsip, IL.)

20
20 40 60 80 100 120 3 hrs.
temperature. Rapid cooling can result in distortion of the
Heating time (min)
denture base because of differences in thermal contraction of
FIGURE 19-8  Temperature changes in acrylic resin when subjected to resin and investing stone. To minimize potential difficulties,
various curing schedules. (Modified from Tuckfield WJ, Worner HK, the flask should be removed from the water and bench cooled
Guerin BD: Acrylic resins in dentistry. Aust Dent J 47:119–121, 1943. for 30 min. Subsequently, the flask should be immersed in
Reproduced with permission from the Australian Dental Journal.) cool tap water for 15 min. The denture base can then be
deflasked and prepared for delivery. To decrease the probabil-
One technique involves processing the denture base resin ity of unfavorable dimensional changes, the denture should
in a constant-temperature water bath at 74 °C (165 °F) for 8 h be stored in water until it is placed in the oral cavity.
or longer, with no terminal boiling treatment. A second tech-
nique consists of processing in a 74 °C water bath for 8 h and POLYMERIZATION VIA MICROWAVE ENERGY
then increasing the temperature to 100 °C for 1 h. A third Polymethyl methacrylate resin can be polymerized using
technique involves processing the resin at 74 °C for approxi- microwave energy because the methyl methacrylate molecule
mately 2 h and increasing the temperature of the water bath is asymmetric. This technique employs a specially formulated
to 100 °C and processing for 1 h. resin and a nonmetallic flask (Figure 19-9). A conventional
Following completion of the chosen polymerization cycle, microwave oven is used to supply the thermal energy required
the denture flask should be cooled slowly to room for polymerization.
 Chemically Activated Denture Base Resins 483

The major advantage of this technique is the speed with terparts. This imparts greater dimensional accuracy to chemi-
which polymerization can be accomplished, but overheating cally activated resins.
can occur in thick sections, causing the monomer to boil and The color stability of chemically activated resins generally
produce porosity. Available information indicates the physical is inferior to the color stability of heat-activated resins. This
properties of microwave resins are comparable to those of property is related to the presence of tertiary amines within
conventional resins. Furthermore, the fit of denture bases the chemically activated resins. Such amines are susceptible
polymerized using microwave energy is comparable to those to oxidation and accompanying color changes that affect the
processed via conventional compression molding techniques. appearance of the resin. Discoloration of these resins can be
minimized via the addition of stabilizing agents that prevent
? CRITICAL QUESTION such oxidation.
What are the main benefits and drawbacks of denture base resins
TECHNICAL CONSIDERATIONS
cured by a chemical-activation process compared with those that
are heat-activated? Chemically activated denture base resins are most often
molded using compression techniques. Therefore, mold prep-
aration and resin packing are essentially the same as those
CHEMICALLY ACTIVATED DENTURE BASE RESINS
described for heat-activated denture resins.
As already noted, heat and microwave energy can be used to Polymer and monomer are supplied in the form of a
induce denture base polymerization. The application of powder and a liquid, respectively. These components are
thermal energy leads to decomposition of benzoyl peroxide mixed according to the manufacturer’s directions and permit-
and the production of free radicals. The free radicals formed ted to attain a doughlike consistency. The working time for
as a result of this process initiate polymerization. chemically activated resins is shorter than for heat-activated
Chemical activators can also be used to induce denture materials. Therefore, special attention must be paid to the
base polymerization. Chemical activation does not require consistency of the material and rate of polymerization.
the application of thermal energy. Therefore, it can be com- A lengthy initiation period is desirable since this provides
pleted at room temperature. As a result, chemically activated adequate time for trial closures. One method for prolonging
resins often are referred to as cold-curing, self-curing, or auto- the initiation period is to decrease the temperature of the
polymerizing resins. resin mass. This can be accomplished by refrigerating the
As discussed in Chapter 7, in most instances, chemical liquid component and/or mixing vessel before the mixing
activation is accomplished through the addition of a tertiary process. When the powder and liquid are mixed, the polym-
amine, such as dimethyl-para-toluidine, to the denture base erization process slows down. As a result, the resin mass
liquid (i.e., monomer). Upon mixing of the powder and liquid remains in a doughy stage for an extended period and the
components, the tertiary amine causes decomposition of working time is prolonged.
benzoyl peroxide. As a result, free radicals are produced and Mold preparation and resin packing are accomplished in
polymerization is initiated. Polymerization progresses in a the same manner described for heat-activated resins. In cases
manner similar to that described for heat-activated systems. of chemically activated resins with minimal working times, it
It should be noted that the fundamental difference between is doubtful that more than two trial closures can be made.
heat-activated resins and chemically activated resins is the Therefore, extreme care must be taken to ensure that a proper
method by which benzoyl peroxide is divided to yield free amount of resin is employed and a minimal number of trial
radicals. All other factors in this process (e.g., initiator and closures are needed.
reactants) remain the same.
As might be expected, denture bases fabricated using PROCESSING CONSIDERATIONS
chemically activated resins and heat-activated resins are quite Following definitive closure of the denture flask, pressure must
similar. Nonetheless, chemically activated resins exhibit be maintained throughout the polymerization process. The time
certain advantages and disadvantages that are worthy of required for polymerization will vary with the material chosen.
discussion. Initial hardening of the resin generally will occur within
As a general rule, the degree of polymerization achieved 30 min but polymerization continues for an extended period.
using chemically activated resins is not as complete as that To ensure sufficient polymerization, the flask should be held
achieved using heat-activated systems. This indicates there is under pressure for a minimum of 3 hours.
a greater amount of unreacted monomer in denture bases The polymerization of chemically activated resins is never
fabricated via chemical activation. This unreacted monomer as complete as the polymerization of heat-activated materials.
creates two major difficulties. First, it acts as a plasticizer, Resins polymerized via chemical activation generally display
resulting in decreased transverse strength of the denture 3% to 5% free monomer, whereas heat-activated resins exhibit
resin. Second, the residual monomer serves as a potential 0.2% to 0.5% free monomer. Therefore, it is important that
tissue irritant, thereby compromising the biocompatibility of the polymerization of chemically activated resins be as com-
the denture base. plete as possible. Failure to achieve a high degree of polym-
From a physical standpoint, chemically activated resins erization will predispose the denture base to dimensional
display slightly less shrinkage than their heat-activated coun- instability and can lead to tissue irritation.
484 CHAPTER 19  Prosthetic Polymers and Resins

FLUID RESIN TECHNIQUE assembly is cooled. (See the section on Agar [Reversible
The fluid resin technique employs a pourable, chemically Hydrocolloid] in Chapter 8) Following gelation of the hydro-
activated resin for the fabrication of denture bases. The colloid, the cast with the attached tooth arrangement is
material is supplied in the form of powder and liquid removed from the flask (Figure 19-10, B). At this stage, sprues
components. When mixed in the proper proportions, these and vents are cut from the external surface of the flask to the
components yield a low-viscosity resin. This resin is poured mold cavity (Figure 19-10, C).
into a mold cavity, subjected to increased atmospheric Wax is eliminated from the cast with hot water. The pros-
pressure, and allowed to polymerize at ambient temperature. thetic teeth are retrieved and carefully seated in their respec-
Laboratory aspects of the fluid resin technique are described tive positions within the hydrocolloid investing medium.
in the following paragraphs. Subsequently, the cast is returned to its position within the
Tooth arrangement is accomplished using accepted mold (Figure 19-10, D).
prosthodontic principles. The completed tooth arrangement The resin is mixed according to the manufacturer’s direc-
is then sealed to the underlying cast and placed in a specially tions and poured into the mold via the sprue channels (Figure
designed flask (Figure 19-10, A). The flask is filled with a 19-10, E). The flask is then placed in a pressurized chamber
reversible hydrocolloid investment medium, and the (i.e., a pressure pot) at room temperature and the resin is

A B

C D

E F

FIGURE 19-10  Steps in mold preparation (fluid resin technique). A, Completed tooth arrangement positioned in a fluid
resin flask. B, Removal of tooth arrangement from reversible hydrocolloid investment. C, Preparation of sprues and vents
for the introduction of resin. D, Repositioning of the prosthetic teeth and master cast. E, Introduction of pour-type resin.
F, Recovery of the completed prosthesis.
 Physical Properties of Denture Base Resins 485

permitted to polymerize. According to available information, polymerized base. A high-intensity light source is used to
only 30 to 45 minutes are required for polymerization. polymerize the tooth-setting resin, thereby maintaining pros-
Nevertheless, a longer period is suggested. thetic teeth in the desired positions. Next, a contouring resin
Following completion of the polymerization process, the is used to generate the desired final surface form. The resul-
denture is retrieved from the flask (Figure 19-10, F) and the tant prosthesis is placed into the light chamber to complete
sprues are removed. The denture/cast assembly is returned the denture base fabrication process. The denture is then
to the articulator for correction of processing changes. Sub- removed from the cast, finished, and polished in a conven-
sequently, the denture base is finished and polished. After tional manner.
finishing and polishing, the denture should be stored in water
to prevent dehydration and distortion.
PHYSICAL PROPERTIES OF DENTURE
Advantages claimed for the fluid resin technique
BASE RESINS
include (1) improved adaptation to underlying soft tissues,
(2) decreased probability of damage to prosthetic teeth and The physical properties of denture base resins are critical to
denture bases during deflasking, (3) reduced material costs, the fit and function of removable dental prostheses. Charac-
(4) and simplification of the flasking, deflasking, and finish- teristics of interest include polymerization shrinkage, poro­
ing procedures. sity, water absorption, solubility, processing stresses, and
Potential disadvantages of the fluid resin technique include crazing. These characteristics are addressed in the following
(1) noticeable shifting of prosthetic teeth during processing, sections.
(2) air entrapment within the denture base material, (3) poor
bonding between the denture base material and acrylic resin POLYMERIZATION SHRINKAGE
teeth, and (4) technique sensitivity. When methyl methacrylate monomer is polymerized to form
In general, denture bases fabricated in this manner exhibit polymethyl methacrylate, the density of the mass changes
physical properties that are somewhat inferior to those of from 0.94 to 1.19 g/cm3. This change in density results in a
conventional heat-processed resins. Nonetheless, clinically volumetric shrinkage of 21%. When a conventional heat-
acceptable dentures can be obtained using fluid resins. activated resin is mixed at the suggested powder-to-liquid
ratio, about one third of the mass is liquid monomer. The
remainder of the mass is prepolymerized polymethyl meth-
LIGHT-ACTIVATED DENTURE BASE RESINS
acrylate. Consequently, the volumetric shrinkage exhibited by
Visible light-activated denture base resins have been available the polymerized mass should be approximately 7%. This
to the dental community for several years. These materials figure is in agreement with values observed in laboratory and
have been described as resin-based composites having matri- clinical investigations.
ces of urethane dimethacrylate (Chapter 6, Figure 6-18), There are several possible reasons why materials exhibiting
microfine silica, and high-molecular-weight acrylic resin such high volumetric shrinkages can be used to produce
monomers. Acrylic resin beads are included as organic fillers. clinically satisfactory denture bases. It appears the shrinkage
Visible light is the activator, while a photosensitizing agent exhibited by these materials is distributed uniformly to all
such as camphorquinone serves as the initiator for polymer- surfaces. Hence the adaptation of denture bases to underlying
ization. Single-component denture base resins are supplied in soft tissues is not significantly affected, provided the materials
sheet and rope forms and are packed in lightproof pouches are manipulated properly.
to prevent inadvertent polymerization (Figure 19-11, A). In addition to volumetric shrinkage, one also must con-
As might be expected, denture base fabrication using a sider the effects of linear shrinkage. Linear shrinkage exerts
light-activated resin is significantly different from denture significant effects upon denture base adaptation and cuspal
base fabrication using a heat-activated or chemically activated interdigitation.
resin. A light-activated resin cannot be flasked in a conven- By convention, the magnitude of linear shrinkage is deter-
tional manner since the opaque investing media prevent the mined by measuring the distance between two predetermined
penetration of light. Instead, the denture base is molded on an reference points in the second molar regions of a completed
accurate cast and subsequently the teeth are positioned (Figure tooth arrangement. Following polymerization of the denture
19-11, B). In turn, the denture base is exposed to a high- base resin and removal of the prosthesis from the master cast,
intensity visible light source for an appropriate period (Figure the distance between these reference points is measured once
19-11, C). Following polymerization, the denture is removed again. The difference between pre- and postpolymerization
from the cast, finished, and polished in a conventional manner. measurements is recorded as linear shrinkage. The greater the
The most recent generation of light-activated denture linear shrinkage, the greater is the discrepancy observed in
base resins consists of three resins. These include (1) a base- the initial fit of a denture.
forming resin, (2) a tooth-setting resin, and (3) a contouring
resin. The base-forming resin is adapted to the dental
cast. The cast and denture base are placed into a high-intensity ? CRITICAL QUESTION
Why is the relatively high volumetric shrinkage of a denture base
light chamber to induce polymerization. Subsequently, the
resin not usually considered as a significant clinical problem?
tooth-setting resin is used to attach the prosthetic teeth to the
486 CHAPTER 19  Prosthetic Polymers and Resins

C
FIGURE 19-11  Steps in denture fabrication (light-activated denture base resins). A, Representative light-
activated denture base resin. Sheet and rope forms are supplied in light-proof pouches to prevent inad-
vertent polymerization. B, Teeth are arranged and the denture base sculpted using light-activated resin.
C, The denture base is placed into a light chamber and polymerized according to the manufacturer’s
recommendations. (Parts A and C courtesy of Densply International, York, PA.)
 Physical Properties of Denture Base Resins 487

TABLE 19-1 Polymerization Shrinkage of Maxillary activated resins appear to provide significant advantages over
Denture Bases heat-activated resins. However, there are several other factors
that affect the overall dimensional characteristics of pro-
Material Linear Shrinkage (%)
cessed denture bases including the type of investing medium,
High-impact acrylic resin 0.12 method of resin introduction, and temperature used to acti-
Vinyl acrylic resin 0.33 vate the polymerization process.
Conventional acrylic resin 0.43 On completion of the polymerization process, individual
denture bases and master casts are retrieved and returned to
Pour-type acrylic resin 0.48
their respective dental articulator(s). Dimensional changes
Rapid heat-cured acrylic resin 0.97
are assessed with respect to the proposed vertical dimension
Data from Stafford GD, Bates JF, Huggett R, Handley RW: A review of the properties of occlusion.
of some denture base polymers. J Dent 8:292, 1960. Fluid resin techniques used in conjunction with hydrocol-
loid investing media generally yield decreases in vertical
Based on a projected volumetric shrinkage of 7%, an dimension. Conversely, dentures processed using heat-
acrylic resin denture base should exhibit a linear shrinkage of activated or chemically activated resins in conjunction with
approximately 2%. In reality, linear shrinkage rarely exceeds compression molding techniques usually display increases in
1% (Table 19-1). overall vertical dimension. Minimal increases in vertical
Examination of the polymerization process indicates dimension are considered desirable since they permit a return
thermal shrinkage of resin is primarily responsible for the to the proposed occlusal vertical dimension via occlusal
linear changes observed in heat-activated systems. During grinding procedures. Dimensional changes occurring in
the initial stages of the cooling process, the resin remains denture bases fabricated from various resins are illustrated in
relatively soft. Consequently, the resin mass contracts at about Figure 19-12. Additional dimensional factors include setting
the same rate as the surrounding dental stone. expansion of the gypsum product used to make the master
As cooling proceeds, the soft resin approaches its glass cast and investing component and expansion from water
transition temperature, Tg (see Chapter 6, Dental Polymers). sorption of the cured acrylic resin after polymerization is
The glass transition temperature is a thermal range in which complete.
the polymerized resin passes from a soft, rubbery state to a
rigid, glassy state. Cooling the denture base resin beyond the
glass transition temperature yields a rigid mass. As might be ? CRITICAL QUESTIONS
expected, this rigid mass contracts at a rate different from that What are the causes of porosity when fluid resin denture fabri­
of surrounding dental stone. The shrinkage occurring below cation techniques are used? How can these difficulties be
the glass transition temperature is thermal in nature and minimized?
varies according to the composition of the resin.
To illustrate the effect of thermal shrinkage, consider the
following example. The glass transition temperature for poly- POROSITY
methyl methacrylate is approximately 105 °C. Room tem- The presence of surface and subsurface voids can compro-
perature is 20 °C. The generally accepted value for linear mise the physical, esthetic, and hygienic properties of a pro-
coefficient of thermal expansion, α, for polymethyl methac- cessed denture base. It has been noted that porosity is likely
rylate is 81 ppm/°C. Therefore, as the denture base resin cools to develop in thicker portions of a denture base. Such porosity
from the glass transition temperature to room temperature, results from the vaporization of unreacted monomer and
it undergoes a linear shrinkage, which can be expressed as: low-molecular-weight polymers when the temperature of a
resin reaches or surpasses the boiling points of these species.
Linear shrinkage = α∆T = (81 ppm/ °C)(105 °C − 20 °C)(100%)
(1) Nonetheless, this type of porosity may not occur equally
= 0.69% throughout the affected resin segments.
This value is in agreement with linear shrinkages of 0.12% to To facilitate our understanding of these effects, consider
0.97% reported for various commercial denture resins (see the specimens in Figure 19-13, A, no porosity, and 19-13,
Table 19-1). B, localized subsurface porosity. Specimens B and C were
Complete dentures constructed using chemically activated flasked in such a manner that the section displaying porosity
resins generally display better adaptation than those con- was nearer the center of the investment mass, whereas the
structed using heat-activated resins. This phenomenon can nonporous section was nearer the surface of the metal flask.
be attributed to the negligible thermal shrinkage displayed by As might be expected, the metal of the flask conducts heat
chemically activated resins. Processing shrinkage has been away from the periphery with sufficient rapidity to prevent a
measured as 0.26% for a representative chemically activated substantial temperature rise. As a result, the low-molecular-
resin, compared with 0.53% for a representative heat-activated weight species does not boil and porosity does not develop.
resin. In contrast, resin specimens occupying central positions in
Given the preceding information regarding polymeriza- the mold are surrounded by larger amounts of gypsum.
tion shrinkage and denture base adaptation, chemically Because gypsum is a poor thermal conductor, heat was not
488 CHAPTER 19  Prosthetic Polymers and Resins

A B

C D
FIGURE 19-12  Dimensional changes resulting from polymerization. A, Chemically activated resin, pour technique.
B, Microwave resin, compression molding. C, Conventional heat-activated resin, compression molding. D, Heat-activated
resin, injection molding. (Demonstration and photographs courtesy of Dr. Rodney Phoenix).

A B C D E
FIGURE 19-13  Heat-activated denture base resin exhibiting different types and degrees of porosity.
A, Properly polymerized; no porosity. B and C, Rapid heating, relatively small subsurface voids. D, Insuf-
ficient mixing of monomer and polymer; large voids resulting from localized polymerization shrinkage.
E, Insufficient pressure during polymerization; relatively large, irregular voids. (From Tuckfield WJ, Worner
HK, Guerin BD: Acrylic resins in dentistry. Aust Dent J March 1943.)

readily dissipated. Consequently low-molecular-weight packing until this consistency has been reached. A third type
species are vaporized and noticeable porosity is produced. of porosity can be caused by inadequate pressure or insuffi-
Porosity can also result from inadequate mixing of powder cient material in the mold during polymerization (Figure
and liquid components. If this occurs, some regions of the 19-13, E). Voids resulting from these inadequacies are not
resin mass will contain more monomer than others. During spherical; they assume irregular shapes. These voids may be
polymerization, these regions shrink more than adjacent so abundant that the resultant resin appears significantly
regions, and the localized shrinkage tends to produce voids lighter and more opaque than its intended color.
(Figure 19-13, D). A final type of porosity is most often associated with fluid
The occurrence of such porosity can be minimized by resins. Such porosity results from air entrapment during
ensuring the greatest possible homogeneity of the resin. mixing and pouring procedures. If air inclusions are not
Proper polymer-to-monomer ratios and well-controlled removed, sizable voids may be produced in the resultant
mixing procedures are essential. Because the material is more denture bases. Therefore careful mixing, spruing, and venting
homogeneous in the doughlike stage, it is wise to delay are essential.
 Physical Properties of Denture Base Resins 489

WATER ABSORPTION To test water absorption, a disk of material with specified

Polymethyl methacrylate absorbs small amounts of water dimensions is prepared and dried to a constant weight. This
when placed in an aqueous environment. This water exerts weight is recorded as a baseline value. The disk is then soaked
significant effects on the mechanical and dimensional prop- in distilled water for 7 days. Again, the disk is weighed, and
erties of the processed polymer. this value is compared with the baseline value. According to
Although absorption is facilitated by the polarity of poly- the specification, weight gain following immersion must not
methyl methacrylate molecules, a diffusion mechanism is pri- be greater than 0.8 mg/cm2. Additional information regard-
marily responsible for the ingress of water. As water molecules ing ANSI/ADA Specification No. 12 is presented in subse-
penetrate the polymethyl methacrylate mass, they occupy quent sections.
positions between polymer chains. Consequently, the affected
polymer chains are forced apart. The introduction of water SOLUBILITY
molecules produces two important effects. First, it causes a Although denture base resins are soluble in a variety of liquids,
slight expansion of the polymerized mass. Second, water mol- they are virtually insoluble in the fluids commonly encoun-
ecules interfere with the entanglement of polymer chains and tered in the oral cavity. ANSI/ADA Specification
thereby act as plasticizers (see the section, Solvation and Dis- No. 12 prescribes a testing regimen for the measurement of
solution Properties in Chapter 6, Dental Polymers). resin solubility. This procedure is a continuation of the water
Polymethyl methacrylate exhibits a water sorption value of sorption test described in the preceding section. Following the
0.69 mg/cm2. Although this amount of water may seem incon- required water immersion, the test disk is permitted to dry
sequential, it produces significant effects in polymerized resins. and is reweighed. This value is compared with the baseline
It has been estimated that for each 1% increase in weight pro- value to determine weight loss. According to the specification,
duced by water absorption, acrylic resin exhibits a linear expan- weight loss must not be greater than 0.04 mg/cm2. Such a loss
sion of 0.23%. Laboratory trials indicate the linear expansion is negligible from a clinical perspective. Non-cross-linked
caused by water absorption is approximately equal to the polymethyl methacrylate dentures made in the 1940s swelled
thermal shrinkage encountered as a result of the polymerization and warped when exposed to ethanol in the diet. Addition of
process. Hence, these processes very nearly offset one another. cross-linking agents (see Figure 6-2, Chapter 6, Dental Poly-
As previously noted, water molecules can also interfere mers) to the resin composition has solved this problem.
with entanglement of polymer chains and thereby change the
physical characteristics of the resultant polymer. When this ? CRITICAL QUESTIONS
occurs, polymer chains generally become more mobile. This What are the causes of processing stresses? What are the clinical
permits the relaxation of stresses incurred during polymer- implications of these stresses if any?
ization. As stresses are relieved, polymerized resins may
undergo changes in shape. Fortunately, these changes are
relatively minor and do not exert significant effects on the fit PROCESSING STRESSES
or function of the processed bases. Whenever a natural dimensional change is inhibited, the
Because the presence of water adversely affects the physical affected material sustains internal stresses. If stresses are
and dimensional properties of denture base resins, diffusion relaxed, distortion of the material can occur. This principle
coefficients also warrant consideration. The diffusion coeffi- has important ramifications in the fabrication of denture
cient (D) of water in representative heat-activated denture bases, since stresses are always induced during processing.
acrylic resin is 0.011 × 10−6 cm2/s at 37 °C. For a representative For purposes of this discussion, consider the events that
chemically activated resin, the diffusion coefficient is 0.023 × occur during denture base polymerization. As previously
10−6 cm2/s. Since the diffusion coefficients of water in repre- noted, a moderate amount of shrinkage occurs as individual
sentative denture resins are relatively low, the time required monomers are linked to form polymer chains. During this
for a denture base to reach saturation can be considerable. process, it is possible that friction between the mold walls and
This is dependent upon the thickness of the resin as well as the soft resin may inhibit normal shrinkage of these chains. As a
storage conditions. A typical denture base may require a result, the polymer chains are stretched and tensile stresses
period of 17 days to become fully saturated with water. exist within the material.
Results of laboratory investigations indicate there are very Stresses also are produced as the result of thermal shrink-
slight differences in the dimensions of heat-activated and age. As a polymerized resin is cooled below its glass transition
chemically activated denture bases following prolonged temperature, the resin becomes relatively rigid. Further
storage in water. Compression-molded heat-activated denture cooling results in thermal shrinkage. The clinician must
bases are slightly undersized when measured from second remember that a denture base resin generally is encased in a
molar to second molar. Conversely, compression-molded rigid investing medium, such as dental gypsum, during this
chemically activated denture bases are slightly oversized process. Since denture base resins and dental stone contract
when measured in the same regions. The clinical significance at markedly different rates, a contraction differential is estab-
of this difference is negligible. lished. This disparity in contraction rates also yields stresses
ANSI/ADA Specification No. 12 identifies guidelines within the resin. Additional factors that may contribute to
regarding the testing and acceptance of denture base resins. processing stresses include improper mixing and handling of
490 CHAPTER 19  Prosthetic Polymers and Resins

8
Condition in Tested in
7 Air 32% R.H. Water
Air 32% R.H. Air
6 Water Water
Water Air
5

Deflection (mm)
4

1
FIGURE 19-14  Crazing around porcelain teeth.
0
the resin and poorly controlled heating and cooling of the 0 1 2 3 4 5 6 7 8
flask assembly. Load (kg)

CRAZING FIGURE 19-15  Transverse deflection-load curve for a typical denture

base resin, showing the influences of different conditioning procedures
Although dimensional changes can occur during relaxation
and testing environments. All specimens were conditioned for 3 days as
of processing stresses, these changes generally do not cause
indicated before testing. (Data from Swaney AC, Paffenbarger GC, Caul
clinical difficulties. In contrast, stress relaxation can produce HJ, Sweeney WT: American Dental Association Specification No. 12 for
small surface flaws that may adversely affect the esthetic and denture base resin, ed. 2, J Am Dent Assoc 46(1):54–66, 1953. Reprinted
physical properties of a denture. The production of such by permission of ADA Publishing, a Division of ADA Business Enterprises,
flaws, or microcracks, is termed crazing. Inc.) (R.H. = relative humidity.)
In a clinical setting, crazing is evidenced by small linear
cracks that appear to originate at a denture’s surface. Crazing
in a transparent resin imparts a “hazy” or “foggy” appearance. STRENGTH
In a tinted resin, crazing imparts a whitish appearance. In The strength of an individual denture base resin is dependent
addition to esthetic effects, these surface cracks predispose on many factors. These factors include composition of the
a denture resin to fracture. resin, processing technique, and conditions presented by the
From a physical perspective, crazing may result from stress oral environment.
application or from partial dissolution by a solvent. Tensile To provide acceptable physical properties, denture base
stresses are most often responsible for crazing in denture base resins must meet or exceed the standards presented in ANSI/
applications. It is believed that crazing is produced by ADA Specification No. 12. A transverse test is used to evalu-
mechanical separation of individual polymer chains that ate the relationship between the applied load and resultant
occurs upon application of tensile stresses. deflection in a resin specimen of prescribed dimensions.
Crazing generally begins at the surface of a resin and is Typical deflection-load results are presented in Figure 19-15.
oriented at right angles to tensile forces. Microcracks formed Inspection of Figure 19-15 reveals a curvature to each
in this manner subsequently progress internally. An example component of the deflection load plot. Since no straight-line
of crazing is presented in Figure 19-14. portion is evident, one may assume that plastic deformation
As noted, crazing can also be produced as a result of solvent (i.e., irreversible deformation) occurs during the loading
action. Microcracks produced in this manner are oriented process. Some elastic deformation (i.e., recoverable deforma-
more randomly than those depicted in Figure 19-14. Solvent- tion) also occurs. From a clinical standpoint, this means that
induced crazing generally results from prolonged contact with load application produces stresses within a resin and a change
liquids such as ethyl alcohol. The development of improved in the overall shape of the denture base. When the load is
acrylic resin teeth and cross-linked denture base resins has released, stresses within the resin are relaxed and the denture
resulted in a decreased incidence of denture base crazing. base begins to return to its original shape. Nevertheless,
plastic deformation prevents complete recovery and some
permanent deformation will remain.
? CRITICAL QUESTIONS
Perhaps the most important determinant of resin strength
What variables reduce the strength of acrylic resin denture bases? is the degree of polymerization exhibited by the material. As
What processing method is most likely to produce denture bases
the degree of polymerization increases, the strength of the
with decreased fracture resistance?
resin also increases. In this regard, the polymerization cycle
 Miscellaneous Resins and Techniques 491

employed with a heat-activated resin is extremely important. activated resin is somewhat lower (0.78 J). The impact
Figure 19-16 reveals the effects that processing cycles exert strength of high-impact resins such as Lucitone 199 can be
upon deflection-load properties. Note that increased dura- twice as high as the values reported for conventional poly-
tion of the polymerization cycle appears to yield improved methyl methacrylate resins. Increased impact strength of
physical properties. these products is associated with the addition of a rubbery,
In comparison with heat-activated resins, the chemically branched comonomer such as butyl acrylate. Clinicians
activated resins generally display lower degrees of polymer- should recognize that these figures are useful only for com-
ization. As a result, chemically-activated resins exhibit parison of products, since the energy absorbed by an indi-
increased levels of residual monomer as well as decreased vidual specimen is dependent on specimen size and geometry,
strength and decreased stiffness. Despite these characteris- distance between specimen supports, and the presence or
tics, heat- and chemically activated resins display similar absence of notching.
elastic moduli. The Knoop hardness for heat-activated resins may be as
high as 20, whereas chemically activated resins generally
CREEP display a Knoop hardness between 16 and 18.
Denture resins display viscoelastic behavior. In other words,
these materials act as rubbery solids. When a denture base
resin is subjected to a sustained load, the material may exhibit ? CRITICAL QUESTION
deformation with both elastic (recoverable) and plastic (irre- What is the optimal technique for repairing a fractured acrylic
coverable) components. If this load is not removed, addi- denture base?
tional plastic deformation can occur over time. This additional
deformation is termed creep. MISCELLANEOUS RESINS AND TECHNIQUES
The rate at which this progressive deformation occurs is
termed the creep rate. This rate can be elevated by increases REPAIR RESINS
in temperature, applied load, residual monomer, and the Despite the favorable physical characteristics of denture base
presence of plasticizers. Although creep rates for heat- resins, denture bases sometimes fracture. In most instances,
activated and chemically activated resins are very similar at these fractures can be repaired using compatible resins.
low stresses, creep rates for chemically activated resins Repair resins may be light-, heat-, or chemically activated.
increase more rapidly as stresses are raised. To accurately accomplish repair of a fractured prosthesis,
the clinician must realign and lute components together
MISCELLANEOUS PROPERTIES using an adherent wax or modeling plastic. When this has
The Charpy impact strength for a heat-activated denture resin been accomplished, a repair cast is generated using dental
can range from 0.98 to 1.27 J, whereas that for a chemically gypsum. The denture is then removed from the cast and the
kg

10
g

kg
.3 k
– 5.7

6.5

9
–6
2.5 h

5k h–
h
5.5

8
g
.

g
6

7
24 h –

FIGURE 19-16  Deflection-load curves for samples

6. 6.5
kg
–

of polymethyl methacrylate polymerized for differ-

18
Deflection (mm)

kg
8

6 9 ent periods at 71 °C (160 °F). Processing times and

6.
–
h

– fracture loads are noted on individual curves. (Data

48

h
5 72 from Harman IM: Effects of time and temperature
on polymerization of a methacrylate resin denture
4
base. J Am Dent Assoc 38(2):188–203, 1949.
Reprinted by permission of ADA Publishing, a Divi-
3
sion of ADA Business Enterprises, Inc.)
2

0
2 3 4 5 6 7
Load (kg)
492 CHAPTER 19  Prosthetic Polymers and Resins

luting medium is eliminated.Then, the fracture surfaces are a chemically activated resin is usually chosen. The selected
trimmed to provide sufficient room for repair material. The material is mixed according to the manufacturer’s recom-
gypsum cast is coated with separating medium to prevent mendations, placed into the mold, compressed, and permit-
adherence of repair resin, and the denture base sections are ted to polymerize. Finally, the denture is recovered, finished,
repositioned and affixed to the cast. and polished.
At this point a repair material is chosen. Chemically acti- If a chemically activated resin is selected for relining the
vated resins are generally preferred over heat- and light- existing denture, a specialized mounting assembly may be
activated resins despite the fact that chemically activated used in lieu of flasking. This assembly maintains the correct
resins display lower transverse strengths. The principal vertical and horizontal relationships between the cast and the
advantage of chemically activated resins is that they can be denture while eliminating the need to encase the remaining
polymerized at room temperature. Heat- and light-activated denture base in dental gypsum. This facilitates recovery of
repair materials must be placed in water baths and light the denture at the end of the relining process.
chambers, respectively. Heat generated by water baths and Several manufacturers offer chemically activated resins for
light chambers often causes stress release and distortion of relining dentures intraorally. Unfortunately many of these
previously polymerized denture base segments. materials generate enough heat to injure oral tissues. To
The following sequence is employed to accomplish denture receive ADA approval, materials must comply with ANSI/
base repair using a chemically activated resin. A small amount ADA Specification No. 17, which places limits on the rate of
of monomer is painted onto prepared surfaces of the denture temperature rise and maximum acceptable temperature.
base to soften and swell the old resin and thereby facilitate Relining can also be accomplished using resins that are
bonding of the repair material. Increments of monomer and activated by heat, light, or microwave energy. In all of these
polymer are added to the repair area using a small sable-hair instances, significant heat can be generated and distortion of
brush or suitable substitute. A slight excess of material is the existing denture base will be more likely.
placed at the repair site to account for polymerization shrink- Some materials are manufactured for repair as well as
age. The assembly is placed in a pressure chamber and allowed relining purposes. Practitioners should be extremely cautious
to polymerize. The repair site is then shaped, finished, and in using such products. Some of these materials comply with
polished using conventional techniques. ANSI/ADA Specification No. 13 for repairs but fail to meet
The minimum requirements for chemically activated temperature requirements set forth in ANSI/ADA Specifi­
resins used in repair applications are identified in ANSI/ADA cation No. 17. Other materials comply with Specification
Specification No. 13. No. 17 but fail to meet the requirements of Specification
No. 13. Such materials often discolor, harbor microorgan-
isms, and separate from underlying denture bases.
? CRITICAL QUESTION
Similar materials are marketed for home use. Unfortu-
Why are denture reliner materials considered temporary-use
products?
nately, the majority of patients do not possess adequate
knowledge to manipulate these materials correctly; therefore
the use of such products can result in damage to the oral
RELINING RESIN DENTURE BASES tissues. Thus, the purchase and use of such products should
Because ridge contours change during denture service, it is be discouraged.
sometimes necessary to alter tissue surfaces of prostheses to
ensure proper fit. In some instances, this can be achieved by REBASING RESIN DENTURES
selective grinding procedures. In other instances, tissue sur- The steps required in denture rebasing are similar to those
faces must be replaced by relining or rebasing existing described for relining. An accurate impression of the soft
dentures. tissues is made using the existing denture as a custom tray.
Relining involves replacement of the tissue surface of an Subsequently, a gypsum cast is fabricated in the impression.
existing denture, whereas rebasing involves replacement of The cast and denture are mounted in a device designed to
the entire denture base except for the denture teeth. In both maintain the correct vertical and horizontal relationships
instances an impression of the soft tissues is made using the between the stone cast and surfaces of the prosthetic teeth.
existing denture as an impression tray. A gypsum cast is gen- The resultant assembly provides indices for the occlusal sur-
erated in the impression, and the resultant assembly is faces of the prosthetic teeth. After these indices have been
invested in a brass denture flask. Subsequently, the flask established, the denture is removed and the teeth are sepa-
is opened and prepared for the introduction of resin. rated from the existing denture base. The teeth are reposi-
If the denture is to be relined, the impression material is tioned in their respective indices and held in their original
removed from the denture. The tissue surface is cleaned to relationships to the cast while they are waxed to a new
enhance bonding between the existing denture base and the baseplate.
reline material. Next, an appropriate resin is introduced and At this point, the denture base is waxed to the desired
shaped using a compression molding technique. form. The completed tooth arrangement is sealed to the cast,
For relining, a low polymerization temperature is desirable and the assembly is invested as previously described. Follow-
to minimize distortion of the remaining denture base. Hence, ing elimination of the wax and removal of the baseplate, resin
 Miscellaneous Resins and Techniques 493

is introduced into the mold cavity. The material subsequently As polymethyl methacrylate is replaced by higher meth-
is processed. After processing, the denture is recovered, fin- acrylates (e.g., ethyl, n-propyl, and n-butyl), the Tg becomes
ished, and polished. The completed prosthesis consists of a progressively lower. As a result, less plasticizer is required and
new denture base in conjunction with teeth from the patient’s the effects of leaching can be minimized.
previous denture. Vinyl resins have also been used in soft liner applications.
Unfortunately plasticized polyvinyl chloride and polyvinyl
? CRITICAL QUESTION acetate are subject to leaching and will harden during sus-
Under what conditions might soft denture liners be used rather tained use.
than rebasing an acrylic denture base? Perhaps the most successful materials for soft liner appli-
cations have been the silicone rubbers. These materials are
not dependent upon leachable plasticizers; therefore, they
SHORT- AND LONG-TERM SOFT DENTURE LINERS retain their elastic properties for prolonged periods. Unfor-
The purpose of a soft denture liner is to absorb some of the tunately, silicone rubbers may lose adhesion to underlying
energy produced by masticatory impact. Hence a soft liner denture bases.
serves as a “shock absorber” between the occlusal surfaces of Silicone rubbers may be chemically activated or heat-
a denture and the underlying oral tissues. The most com- activated. Chemically activated silicones are supplied as
monly used liners are plasticized acrylic resins. These resins two-component systems that polymerize via condensation
can be heat-activated or chemically activated and are based reactions.
on addition polymerization chemistry that are described Placement of chemically activated soft liners is not com-
previously and in Chapter 6. plicated. The denture base is relined to permit an acceptable
Chemically activated soft liners generally employ poly- thickness of the chosen material. A special adhesive is then
methyl methacrylate or polyethyl methacrylate as principal applied to the surface of the denture base to facilitate bonding.
structural components. These polymers are supplied in The resilient material is mixed, applied to the denture base
powder form and subsequently are mixed with liquids con- via compression molding, and permitted to polymerize.
taining 60% to 80% of a plasticizer. The plasticizer commonly Then, the denture is recovered, finished, and polished.
is a large molecular species such as dibutyl phthalate or an Heat-activated silicones are one-component systems sup-
alcohol for short-term tissue conditioners. The distribution plied as pastes or gels. These materials are applied and con-
of large plasticizer molecules reduces entanglement of toured using compression molding techniques. Heat-activated
polymer chains, thereby permitting individual chains to “slip” silicones can be applied to polymerized resin bases, or they
past one another. This slipping motion permits changes in the can be polymerized in conjunction with freshly mixed resins.
shape of the soft liner and provides a cushioning effect for the To promote adhesion between silicone soft liners and rigid
underlying tissues. It is important to note that the liquids denture base materials, rubber-polymethyl methacrylate
used in such applications do not contain acrylic monomers. cements often are used. These cements serve as adhesive
Consequently the resultant liners are considered short-term intermediates that bond to both soft liners and denture resins.
soft liners or tissue conditioners. At least one silicone liner does not require an adhesive
Unlike chemically activated soft liners, heat-activated when it is cured together with an acrylic denture base mate-
materials generally are more durable and can be considered rial. This material is actually a silicone copolymer that con-
long-term soft liners. Nonetheless, these materials degrade tains components capable of bonding with acrylic resins.
over time and should not be considered permanent. Laboratory procedures for heat-activated silicones are
A number of heat-activated soft liners are supplied as similar to those described for other chemically activated
powder-liquid systems. The powders are composed of acrylic materials. Bases are invested and mold spaces prepared as
resin polymers and copolymers, whereas the liquids consist required. Relief is provided to permit an acceptable thickness
of appropriate acrylic monomers and plasticizers. When of the chosen material(s). Packing, compression molding, and
mixed, these materials form pliable resins exhibiting glass processing are performed in accordance with manufacturer’s
transition temperatures (Tg) below mouth temperature. recommendations. The denture is then recovered, finished,
Although plasticizers impart flexibility, they also present and polished.
certain difficulties. Plasticizers are not bound within the resin All of the described liners display certain shortcomings.
mass. Therefore they may be “leached out” of soft liners. As For instance, silicone liners adhere poorly to denture base
this occurs, soft liners become progressively more rigid. Con- resins. Silicone liners are also porous, which allows water
sequently, it is advantageous to use liners that are less prone uptake and harbors fungal growth. Many soft liners bond
to leaching phenomena. well to denture bases but become progressively more rigid as
In recent years the phthalate esters plasticizer have raised plasticizers leach from the liner materials. Hardening rates
concerns, as they mimic estrogenic hormones in the body for these liners are associated with the initial plasticizer
after they are released from the liner. Alternatives are now in content. As the plasticizer content is increased, the probabil-
use, including trimellitates, aliphatic dibasic esters, phos- ity for plasticizer loss also is increased. Hence materials
phates, benzoates, citrate esters, polymeric plasticizers, sul- exhibiting high initial plasticizer content tend to harden
fonic acid, chloroparaffins, and sorbitol. rather rapidly.
494 CHAPTER 19  Prosthetic Polymers and Resins

Soft liners also exert significant effects on associated denture Each system has advantages and disadvantages. Light-
bases. As the thickness of a soft liner is increased, the thickness activated materials eliminate methyl methacrylate exposure,
of the accompanying denture base must be decreased, and this but are more expensive and require high-intensity light units
results in decreased denture base strength. Furthermore, for polymerization. Chemically activated resins are less expen-
materials used in conjunction with soft liners (e.g., adhesives sive but have been associated with contact dermatitis, particu-
and monomers) may cause partial dissolution of denture larly in laboratory personnel. Because each material exhibits
bases. This can result in fracture during clinical service. advantages and disadvantages, the choice of custom tray mate-
Perhaps the greatest difficulty associated with long- and rial is commonly based upon individual preference.
short-term silicone soft liners is that these materials cannot The steps in custom tray fabrication are described as
be cleaned effectively. As a result patients often report dis- follows: A preliminary impression is made using a stock tray
agreeable tastes and odors related to these materials. Research and an appropriate impression material. In turn, a gypsum
indicates that the liners themselves do not support mycotic cast is generated. A suitable spacer is placed on the stone cast
growth, but such growth is supported by debris accumulating to provide the desired relief. Subsequently a separating
in the pores of these materials. The most common fungal medium is applied to the surface of the cast. At this stage,
growth that develops on soft liners is Candida albicans. fabrication techniques for light-activated materials and
Several cleaning regimens have been used in conjunction chemically activated materials become divergent.
with soft liners; however, these regimens have met with Light-activated resins are supplied in sheet and gel forms.
limited success. Both oxygenating and hypochlorite-type Sheet forms are preferred for custom tray fabrication because
denture cleansers have been employed. Unfortunately, these of their favorable handling characteristics. Individual sheets
agents can cause color change and significant damage to soft are pliable and can be adapted to the associated casts and
liners, especially the silicone materials. spacers with relative ease. A handle is added to facilitate
Mechanical cleaning of soft liners may lead to damage, but removal of the tray from the mouth and the entire assembly
such debridement is often necessary. If mechanical cleaning is placed in a light chamber and the resin is polymerized.
is undertaken, a soft brush should be used in conjunction Chemically activated resins typically are polymethyl
with a mild detergent solution or nonabrasive dentifrice. methacrylates and are supplied as powder-liquid systems. The
In attempts to address potential problems, antimycotic components are mixed to form a dough-like mass. The dough
agents have been incorporated into soft liners. Although this is then rolled into a sheet approximately 2 mm thick, adapted
approach is promising, the limited duration of antimycotic to the diagnostic cast with a handle as above, and allowed to
activity is far from ideal. Therefore additional research is polymerize.
warranted. Upon completion of the fabrication process, both light-
Based on the preceding information, none of the soft liner activated and chemically activated custom trays are removed
materials discussed above are completely satisfactory for from the associated casts and mechanically trimmed. The
other than short-term applications. However, a material suit- peripheries are rounded to make sure that patients will not
able as a permanent soft liner was introduced in 1989 (Gettle- be harmed by sharp or irregular edges. At this point, trays
man et al., 1989; Gettleman, 2004) following extensive can be evaluated intraorally and refined as necessary.
NIH-supported research and clinical trials. This soft liner
material uses a polyphosphazene fluoroelastomer (PNF, a DENTURE CLEANSERS
polymer with –[–P=N–]– as the main chain, and fluorocar- Patients use a wide variety of agents for cleaning artificial den-
bon side groups). PNF forms an interpenetrating network tures. These include dentifrices, proprietary denture cleansers,
with di- and trifunctional cross-linking acrylics, formulated mild detergents, household cleansers, bleaches, and vinegar.
with barium sulfate filler for radiopacity. The liner material is The most common commercial products are based upon
compression molded in the laboratory, polymerized in hot immersion techniques. These cleansers are marketed in
water, and bonded to new or existing acrylic denture bases. powder and tablet forms containing alkaline compounds,
It has no plasticizers that can leach out of the liner surface. detergents, sodium perborate, and flavoring agents. Dissolved
Therefore, the liner stays soft permanently, provides comfort in water, sodium perborate decomposes to form an alkaline
by absorbing chewing forces due to its high-energy damping, peroxide solution. This solution subsequently releases oxygen,
is nonporous to resist fungus growth, and is easily adjusted which loosens debris via mechanical means.
to customize fit. (NovusTM Resilient Liner, Lang Dental Man- Household bleaches (hypochlorites) also are used in
ufacturing Co, Wheeling, IL) denture cleaning applications. Dilute bleach solutions can be
used to remove certain types of stains. Unfortunately, pro-
RESIN IMPRESSION TRAYS AND TRAY MATERIALS longed use of bleach-containing solutions can remove color
Resin trays are often used in dental impression procedures. from denture base and relining materials.
Unlike stock trays, resin impression trays are fabricated to fit Bleaches and bleach solutions should not be used for
the arches of individual patients. Therefore, resin impression cleaning metal prostheses such as removable partial denture
trays are commonly called custom trays. frameworks. These solutions produce significant darkening of
The overwhelming majority of custom trays are fabricated base metals and can damage the serviceability of affected
using light-activated and chemically activated resin systems. prostheses irreparably.
 Resin Teeth for Prosthetic Applications 495

The use of brushes and abrasive cleansers can produce concentration of monomer in freshly mixed resins may
a range of effects on resin surfaces. Toothbrushes alone produce local irritation and serious sensitization of the
produce minimal wear of resin surfaces. Toothbrushes in fingers.
conjunction with most commercial dentifrices, mild deter- Finally, it should be noted that inhalation of monomer
gents, and soaps also appear to be relatively nondestructive. vapor may be detrimental. Therefore, the use of monomer
Conversely, household cleansers, such as kitchen and bath- should be restricted to well-ventilated areas.
room abrasives, are definitely contraindicated. Prolonged use
of such cleansers may cause noticeable wear of resin surfaces TOXICOLOGY
and adversely affect the function and esthetics of these pros- There is no evidence that commonly used dental resins
theses. Therefore, patients should be educated regarding the produce systemic toxic effects in humans. As previously
care and cleaning of resin prostheses. noted, the amount of residual monomer in processed poly-
methyl methacrylate is extremely low. To enter the circulatory
INFECTION-CONTROL PROCEDURES system, residual monomer must pass through the oral mucosa
Care should be taken to prevent microbial and viral cross- and underlying tissues. These structures function as barriers
contamination between patients and dental personnel, that significantly diminish the volume of monomer reaching
including personnel in the dental laboratory. New appliances the bloodstream.
should be disinfected before leaving the dental laboratory. Residual monomer that does reach the bloodstream is
Existing prostheses should be disinfected before entering the rapidly hydrolyzed to methacrylic acid and excreted. It is
laboratory and after completion of laboratory procedures. All estimated that the half-life of methyl methacrylate in circulat-
materials used for finishing and polishing should be handled ing blood is 20 to 40 minutes.
according to established infection-control guidelines. Items Metal oxide (cadmium/selenium) red pigments were used
such as rag wheels should be autoclaved, and materials for many years to color denture base resins. Although toxic
such as pumice should be used according to unit-dose in all concentrations, the pigments are locked within the
recommendations. denture base polymer network and used in very small con-
centrations. Nevertheless, most manufacturers have switched
to organic pigment systems, i.e., cromophtal red BRN, to
? CRITICAL QUESTION
avoid such effects.
Which components of denture resins are most likely to cause an
allergic reaction?

ALLERGIC REACTIONS
? CRITICAL QUESTIONS
What precautions should be taken in using porcelain teeth in a
Possible toxic or allergic reactions to polymethyl methacry- denture? What are the clinically relevant differences between
late have long been postulated. Reactions can occur following porcelain teeth and acrylic resin teeth?
contact with the polymers, residual monomers, benzoyl
peroxide, hydroquinone inhibitor, pigments, or a reaction
product between some component of the denture base and
RESIN TEETH FOR PROSTHETIC APPLICATIONS
its environment.
Clinical experience indicates that true allergic reactions The majority of preformed artificial teeth sold in the United
to acrylic resins seldom occur in the oral cavity. Irritation is States is made of acrylic or vinyl-acrylic resins. As might be
slightly more common and is related to residual monomer. expected, the majority of resin teeth are based on polymethyl
Irritation reactions are relatively rare, since the residual methacrylate compositions.
monomer content of a properly processed denture is less than Polymethyl methacrylate resins used in the fabrication
1%. Furthermore, surface monomer is completely eliminated of prosthetic teeth are very similar to those used in
following storage in water for 17 hours. denture base construction. The degree of cross-linking at the
Reactions to residual monomer should occur shortly after occlusal and incisal surfaces of prosthetic teeth is much
prosthesis delivery. However, the majority of patients report- greater that that exhibited by polymerized denture base mate-
ing sore mouth due to denture wear have worn the offending rials. The increased cross-linking of prosthetic teeth in con-
prostheses for months or even years. Clinical evaluation of junction with the addition of inorganic filler yields enhanced
these cases indicates that tissue irritation is commonly related stability, increased wear resistance, and improved clinical
to 24-h denture wearing and fungus overgrowth under the properties.
denture, other unhygienic conditions, or trauma caused by Cervical portions of prosthetic teeth often exhibit reduced
poorly fitting denture bases. cross-linking. This facilitates chemical bonding with denture
Repeated or prolonged contact with monomer can also base resins. Additional retention may be achieved by remov-
result in contact dermatitis. This condition is most commonly ing the glossy “ridge-lap” surfaces of resin teeth preparing
experienced by personnel involved in the manipulation of mechanical undercuts.
denture resins. Hence dental personnel should refrain from Chemical bonding between resin teeth and heat-activated
handling such materials with bare hands. The high denture base materials has proven extremely effective.
496 CHAPTER 19  Prosthetic Polymers and Resins

Nevertheless, bond failures can occur if ridge-lap surfaces Resin teeth display greater impact resistance and ductility
are contaminated by residual wax or misplaced separating than porcelain teeth. As a result, resin teeth are less likely to
media. To optimize bonding, gypsum molds must be flushed chip or fracture on impact, as when a denture is dropped.
with hot water and the exposed cervical portions of prosthetic Furthermore, resin teeth are easier to adjust and display
teeth must be thoroughly cleaned with mild detergent solu- greater resistance to thermal shock. In comparison, porcelain
tions. Separating media must be applied to gypsum teeth display better dimensional stability and increased wear
mold surfaces but should not extend onto the exposed sur- resistance. Unfortunately, porcelain teeth often cause signifi-
faces of resin teeth. As a final measure, ridge-lap surfaces cant wear of opposing enamel, metal, and resin tooth
should be wet with monomer immediately before resin surfaces, especially when contacting surfaces have been
introduction. roughened. Therefore, porcelain teeth should not oppose
More recently, manufacturers have introduced “hybrid” such surfaces, and if they are used, they should be polished
teeth to enhance the wear resistance of prosthetic dentitions. periodically to reduce abrasive damage.
These teeth include composite resin-based and polymethyl As a final note, resin teeth are capable of chemical bonding
methacrylate components. Composite resins are found pri- with commonly used denture base resins. Porcelain teeth,
marily on occlusal and incisal surfaces of the prosthetic teeth, however, do not form chemical bonds with denture resins
and are intended to provide improved wear resistance. Unfor- and must be retained by bonded pins, mechanical undercuts,
tunately, chemical bonding between composites and heat- and/or silanization. Leakage at the tooth-denture base junc-
activated denture base materials is inferior to that which tion can be seen as a dark line when food and microbes
occurs between resin teeth and such denture base materials. penetrate the interface.
To address this shortcoming, manufacturers have incorpo-
rated polymethyl methacrylate at the ridge-lap and lingual
surfaces of hybrid teeth. The presence of polymethyl methac- ? CRITICAL QUESTION
rylate on these surfaces facilitates predictable bonding with What are the benefits and drawbacks of materials used in the
construction of maxillofacial prostheses?
heat-activated polymethyl methacrylate denture base resins.
Nevertheless, operators must be certain not to eliminate the
polymethyl methacrylate surfaces while setting the prosthetic
MATERIALS FOR MAXILLOFACIAL PROSTHETICS
teeth.
As might be expected, the laboratory steps prescribed For centuries, prostheses have been used to mask maxillofa-
for hybrid teeth in conjunction with heat-activated resins cial defects. The ancient Egyptians and Chinese used waxes
are identical to those prescribed for resin teeth used in and resins to reconstruct missing portions of the craniofacial
combination with heat-activated resins. Proposed bonding complex. In the sixteenth century, the French surgeon
surfaces such as ridge-lap areas must be free from residual Ambroise Paré described a variety of simple prostheses used
wax, separating media, and other contaminants. To facilitate for the cosmetic and functional replacement of maxillofacial
chemical bonding, these surfaces should be wet with structures. During subsequent years, restorative techniques
monomer immediately before denture base resin is intro- and materials were improved and refined. Casualties in World
duced in place. Wars I and II established an increased need for maxillofacial
Despite shared chemistries, chemically activated poly- prosthetics, and the dental profession assumed a major role
methyl methacrylate denture base resins and their heat- in maxillofacial reconstruction and rehabilitation processes.
activated counterparts display distinct differences. Notably, Despite improvements in surgical and restorative tech-
mechanical retention is the primary method for securing niques, the materials used in maxillofacial prosthetics are far
resin teeth to chemically activated denture base materials. from ideal. An ideal material should be inexpensive, biocom-
While chemical bonding also may be used, it requires a dis- patible, strong, and stable. In addition, the material should be
tinct modification of the fabrication process. To achieve pre- skinlike in color and texture. Maxillofacial materials must
dictable chemical bonding, a mixture of equal volumes of exhibit resistance to tearing, and should be able to withstand
methylene chloride and chemically activated methyl methac- moderate thermal and chemical challenges. Currently, no
rylate monomer is applied to the necks of resin teeth for material fulfills all of these requirements. A brief summary
approximately 5 minutes. Excess solution is then removed. of maxillofacial materials is included in the following
This treatment softens and swells the resin and facilitates paragraphs.
development of an interpenetrating network between the
denture teeth polymers and those of the denture base during LATEXES
polymerization. The resultant bond strengths are similar to Latexes are soft, inexpensive materials that can be used to
those obtained between resin teeth and heat-activated denture create lifelike prostheses. Unfortunately, these materials are
base resins. weak, degenerate rapidly, and exhibit color instability. There-
Despite the current emphasis on resin teeth, prosthetic fore, latexes are rarely used in the fabrication of long-term
teeth also can be fabricated using dental vacuum- or pressure- maxillofacial prostheses.
fired porcelains. Hence a comparison of resin and porcelain One synthetic latex is a terpolymer of butyl acrylate,
teeth is provided in the following photographs. methyl methacrylate, and methyl methacrylamide. Superior
 Selected Readings 497

to natural latex, this material is nearly transparent. Colorants growth and fraying at the featheredge margins, so a process
are sprayed onto the reverse or tissue side of the prosthesis, of bonding to a sheet of polyurethane on the tissue surface
thereby providing enhanced translucency and improved has been developed. However, the urethane may discolor over
blending. Despite these advantages, the associated technical time.
processes are lengthy and the resultant prostheses last only The major disadvantage of heat-curing silicones is the
a few months. Therefore, synthetic latexes have limited requirement for a milling machine and a press. Furthermore,
applications. a metal mold normally is used, and fabrication of the mold
is a lengthy procedure. A stone mold may be housed within
VINYL PLASTISOLS a brass denture flask, but this increases the risk of damage to
Plasticized vinyl resins sometimes are used in maxillofacial the silicone material during deflasking.
applications. Plastisols are thick liquids composed of small
vinyl particles dispersed in a plasticizer. Colorants are added POLYURETHANE POLYMERS
to these materials to match individual skin tones. Subse- Polyurethane also can be used in maxillofacial prosthetics.
quently, vinyl plastisols are heated to impart desired physical Fabrication of a polyurethane prosthesis requires accurate
characteristics. Unfortunately, vinyl plastisols harden with proportioning of three components. The material is placed
age as a result of plasticizer migration. Ultraviolet light also in a stone or metal mold and allowed to polymerize at room
has an adverse effect on these materials. For these reasons, temperature. Although a polyurethane prosthesis has a
the usefulness of vinyl plastisols is limited. natural feel and appearance, it is susceptible to rapid deterio-
ration and fungus growth.
SILICONE RUBBERS
Silicones were introduced in the mid-1940s and have CHLORINATED POLYETHYLENE
been used in maxillofacial applications since the 1950s. In an effort to overcome the deficiencies of the latex, vinyl
Both heat-curing and room-temperature–curing silicones plastisol, silicone, and polyurethanes as maxillofacial materi-
are in use today, and both exhibit advantages and als, a thermoplastic elastomer based on chlorinated polyeth-
disadvantages. ylene (CPE) was investigated in the 1970s and 1980s. With
Room-temperature–curing silicones are supplied as further development, CPE was shown to provide higher edge
single-component materials that cure by evaporation of acetic strength, permanent elasticity, and minimal fungus growth
acid. They are “characterized” by a natural flesh-like appear- (Gettleman, 1992). In a recent randomized, controlled clini-
ance by using dyed rayon fibers, dry earth pigments, and/or cal trial, it was found that the material was equally preferred
oil paints. Prostheses are polymerized by bulk packing in by patients who had never worn facial prostheses before, but
two- or three-part gypsum molds made from the sculpting of patients who had worn silicone rubber prostheses in the past
the facial part, but more durable molds have been made from favored that material in the trial. Methods of layering the
epoxy resins or metals. prosthetic material in the molds to develop color at depth
Heat-curing silicones are supplied as semisolid or putty- were also reported, which may be useful when future maxil-
like materials that require milling, packing in two- or three- lofacial prosthetic materials are introduced (Kiat-amnuay
part molds under pressure, and a 30-minute heat application et al., 2010).
cycle at 180 °C. Pigments are milled into these materials. Thus Additional information may be found in a review by
intrinsic color can be achieved. Heat-curing silicones display Lemon et al. (2005), which presents current concepts regard-
better strength and color stability than room-temperature– ing facial prosthetic rehabilitation of patients with head and
curing silicones. All of the silicones are susceptible to fungus neck cancer and facial prosthetic biomaterials.

S ELECTED READINGS
Arima T, Murata H, Hamad T: The effects of cross-linking agents on Chai J, Takahashi Y, Takahashi T, et al: Bonding durability of con-
the water sorption and solubility characteristics of denture base ventional resinous denture teeth and highly crosslinked denture
resins. J Oral Rehabil 23:476, 1996. teeth to a pour-type denture resin. Int J Prosthodont 13:112, 2000.
Bartoloni JA, Murchison DF, Wofford DT, et al: Degree of conver- Clancy JMS, Boyer DB: Comparative bond strengths of light-cured,
sion in denture base materials for varied polymerization tech- heat-cured, and autopolymerizing denture resins to denture
niques. J Oral Rehabil 27:488, 2000. teeth. J Prosthet Dent 61:457, 1989.
Blagojevic V, Murphy VM: Microwave polymerization of denture Compagnoni MA, Barros Barbosa D, de Souza RF, et al: The effect
base materials: A comparative study. J Oral Rehabil 26:804, 1999. of polymerization cycles on porosity of microwave-processed
Caswell CW, Norling BK: Comparative study of the bond strengths denture base resin. J Prosthet Dent 91:281, 2004.
of three abrasion-resistant plastic denture teeth bonded to a Cunningham JL, Benington IC: An investigation of the variables
cross-linked and a grafted, cross-linked denture base material. which may affect the bond between plastic teeth and denture
J Prosthet Dent 55:701, 1986. base resin. J Dent 27:129, 1999.