DENT2113, unit 2.

3
Denture base materials

Brendan M. Leung, Ph.D.

Department of Applied Oral Sciences

School of Biomedical Engineering

bleung@dal.ca
Parts of a denture

Dentures base material –

biocompatible polymer that
comes in contact with gum
tissue, most commonly
made of acrylic polymer
(PMMA)

Prosthetic teeth –
embedded in denture base
material. Made of
ceramics, porcelain or
plastics. Responsible for
chewing, biting, etc…..
In this module, you will learn about…..

1. Desirable physical and chemical properties of denture

base materials
¨ Mostly acrylic – PMMA
¨ Effects of dental acrylic formulation on denture fabrication and
performance

2. Biocompatibility of poly(methyl methacrylate) (PMMA)

as denture base material
¨ Host response
¨ Materials response
¨ Infection control
General requirements of denture base
material
n Physical properties
¨ Color that matches real gum tissue (dye compatible, and
biocompatibility of dye)

¨ Shape retention during normal use (high Tg)

¨ Good dimensional stability – won’t swell or shrink

¨ Low specific gravity – light weight

¨ High thermal conductivity to enable patient to feel hot and cold

stimuli.

¨ Radiopaque – in case you swallowed it (or parts of it)!

General requirements of denture base
material (con’t)
n Mechanical properties
¨ High elastic modulus – to provide rigidity and prevent
deformation from stress during normal use.

¨ High flexural strength – so they don’t snap in half along the

midline due to repetitive stress and fatigue

¨ High impact resistance – in case of accidental impacts and drops

¨ Wear resistance – protection from daily use and cleaning

Broken denture
Poly(methyl methacrylate),
682
PMMA
U. Ali et al.

Table 1
Physical and some mechanical properties of PMMA.

Property PMMA Re
Color Colorless 1
Density (g/cm3) 1.18 2
Melting Point (! C) 220–240
Surface Hardness (Rockwell) M92, M90-M100 2
Glass Transition Temp. (Tg) 110 to 120 1
Linear Thermal Expansion (£10¡5 mm/mm.k) 6.3
Thermal Expansion Coefficient 20! C (£10¡4 K¡1) 1.8
Thermal Expansion Coefficient 40! C (£10¡4 K¡1) 2.2
Isothermal Compressibilities at 20! C (£10¡5 bar¡1) 2.7
Isothermal Compressibilities at 40! C (£10¡5 bar¡1) 2.9
Mold Shrinkage (%) 0.3–0.6
Water Absorption (%) 0.3
Oxygen Index (%) 19, 17.19 2
Thermal conductivity at 20! C (k(W/mK) 0.12, 0.17 2
Tensile Strength (MPa) 72
Tensile Modulus (GPa) 3.10
Elongation at Break (%) 5

Umar Ali, Khairil Juhanni Bt. Abd Karim & Nor Aziah Buang
(2015) A Review of the Properties and Applications of Poly
(Methyl Methacrylate) (PMMA), Polymer Reviews, 55:4, 678-705
Table 2
PMMA: Resistance to organic solvents.
 Free radical polymerization of methyl
methacrylate into PMMA
Poly (Methyl Methacrylate) 679

Figure 1. The structures of MMA and PMMA.

+
MMA is a promising polymer for applications in optical, pneumatic actuation, sen-
nalytical separation, and conductive devices.4–8 Other applications include the use
MMA in biomedical applications, polymer electrolytes, polymer viscosity, and drug
ery using electro-diffusion or electro-osmotic flow.9–13 Due to its compatibility and
processing as a polymer moiety, PMMA with carbon nanotubes or other inorganic
Benzoyl
ials plays an important role peroxide
in the development of nanotechnology. Wang et al., in
eparation of carbon nanotube polymer composites, used poly (styrene-co-acryloni-
with poly (methyl methacrylate)-g-multi walled carbon nanotubes.14
MMA is the polymer that enhanced the behavior at the interface between the carbon
ube and the copolymer.
MMA can be obtained from its monomer using different techniques of polymeriza-
The monomer undergoes polymerization using the common methods of free radical
nionic initiations by bulk, solution, suspension, and emulsion techniques.15 Follow-
e discovery of a new technique of polymerization by Krzysztof Matyjaszewski in
Major components in dental acrylic kit

n Supplied as a solid-liquid kit

n Powder
¨ Polymer beads – poly(methyl methacrylate) PMMA
¨ Initiator – free radical source, usually a peroxide (benzoyl peroxide)
¨ Pigment – Salts of Cd, Fe or organic dyes

n Liquid
¨ Monomer – methyl methacrylate (MMA)
¨ Cross-linker – Ethyleneglycol methacrylate (1-2% v/v)
¨ Inhibitor – Hydroquinone
¨ Activator - NN-DMPT (N N’ -dimethyl-p-toluidine), used in self-curing
acrylic
Key features of dental acrylic polymerization

n Cured by free-radical polymerization

¨ Contains inhibitor to prevent premature polymerization in storage

n Free radical generated from heat decomposition of

benzoyl peroxide (BPO), “heat cured”
¨ In self-curing, “chemical cured” formulation, an activator
activates peroxide via redox reaction

n Exothermic reaction! Needs proper cooling to prevent

MMA from boiling (100.3oC) and form bubbles in cured
PMMA.
Bulk polymerization vs two-part polymer-
monomer kit
n Bulk polymerization of PMMA can display volumetric
shrinkage up to 21% (r: 0.94 to 1.19 g/cm3)
¨ Why does it shrink?

n One way to minimize the effect of shrinkage is to introduce

pre-polymerized particles (powder)
¨ MMA penetrate outer layer pf PMMA, once polymerized come tightly
tangled and bound
¨ Considers as composite materials in some textbooks

n Polymer-monomer ratio usually 3:1

¨ This limits volumetric shrinkage to 7% (linear shrinkage <1%)

n Soaking in water post-fabrication further reduce shrinkage

Alternative curing method
n Polymerization by microwave energy
¨ Require specially formulated resin kit
¨ 👍: quicker than using water bath
¨ 👎: uneven heating, increased porosity
n Chemically activated resin
¨ Decomposition of peroxide by adding tertiary amine (NN-DMPT)
¨ 👍: less shrinkage
¨ 👎: incomplete polymerization, weaker denture (monomer act as
plasticizer), monomer leaching causing tissue irritation
n Light-activated resin
¨ Photo-initiator to generate free radical
¨ 👍: denture repair
¨ 👎: need specialized mold (transparent), thickness dependent
Leachable substance from dental acrylic
Factors affecting leachable
substance release include:

1. Mechanism of free radical

initiation
2. Polymerization time
3. Polymerization
temperature
4. Surface finish
Biocompatibility - Systemic toxicity of
PMMA/MMA
n Like many polymer-monomer systems, MMA is far more
toxic than PMMA
¨ Related to difference in reactivity and size between MMA and
PMMA

n Some residual MMA due to incomplete reaction

¨ 3-5 wt.% in chemically cured resin
¨ 0.1-1.5 wt. % in heat cured resin

n Other major toxic leachable substances include

formaldehyde and benzoyl peroxide
Biocompatibility - Systemic toxicity of
PMMA/MMA
n LD50 of MMA in rat is 9 g/kg body weight (low systemic
toxicity)

n In rat oral model (tube to stomach)

¨ Found in blood stream 5min post admin, peaked at 10-15min
¨ No significant effects on organs

n Low acute MMA toxicity due to rapid hydrolysis of MMA

by enzymes in blood stream

n Half-life of MMA in human blood stream is 20-40 min

Biocompatibility - Systemic toxicity of
MMA vapor
n MMA inhalation toxicity including cardiovascular effect, inhibited
peristalsis and gastric motor function reported in rat model
¨ Relevant when making denture. Good ventilation is key!
¨ LC50 in rat is 7093ppm

n MMA also cause embryo and fetus malformation in rat when injected
intraperitoneally

n ‘there is no evidence, however, that serious problems may be

caused by inhaling PMMA ingredients, although MMA may irritate
eyes, skin, and respiratory system.’
Biocompatibility – Local toxicity and tissue
compatibility
n Significant cytotoxicity towards oral
epithelial cell (KB) and oral mucosal
fibroblast (BF) on day 1.

n Generally, toxicity decreases with time.

n Also depends on type of resin

¨ self-curing is worse, heat and light cured
resins are less toxic
 Local compatibility and tissue response -
Allergies
n Skin contact with PMMA and MMA may result in allergenic reactions.
 Biocompatibility – ocuupational hazards

nSkin contact with PMMA and MMA may result in allergenic reactions.
n‘one dentist had to quit his profession due to severe allergy to MMA’
nSome numbers: survey of 251 dentists in Berlin showed:
¨14 dentists
¨9 assistants
¨78 patients suffer from allergy to acrylates.
nBesides MMA, almost all other components of PMMA can cause allergy.
nEGDMA and HQ are important contact allergens.
nAnimal experiments confirm that after MMA sensitization, cross allergies to other
acrylates may develop.
nData from the literature indicate a disproportionately high increase in
occupationally exposed dental personnel, since more and more resins
are used.
Microbial colonization
n PMMA can promote the growth of C. albicans, E. coli, P.
aeruginosa.
¨ Generally due to poor oral hygiene
¨ Can be promoted by roughening of PMMA surface

n C. albicans plays a role in etiology of denture stomatitis

n Experimental antimicrobial PMMA using Ag or antibiotic

carrier nanoparticles
Are there any alternatives to PMMA?
 Conclusions
n 0.1-5% releasable residual monomers and additives.

n Components of PMMA resins are allergenic. Cross-sensitizations occur. MMA is the most
significant allergen.

n Toprevent allergy, a best possible monomer-polymer conversion rate is critical. Therefore heat
polymerized materials should be preferred to autocure materials.

n Denture
bases should be stored in water for 24hrs prior to use to reduce amount of residual
monomer.

n Asa professional you need to ensure you and your team should be scrupulous in avoiding skin
contact with unset resin or individual components - it may cause occupational disability. Gloves do
not sufficiently protect skin against contact with monomers.

n Rooms where resins are processed need to be appropriately ventilated.

n Alternatives exist, but data is limited.