SMART MATERIALS

BHAVYA
MDS FINAL
YEAR
 CONTENTS
• INTRODUCTION
• ORIGIN
• CLASSIFICATION
• PROPERTIES
• INFLUENCING FACTORS
• MATERIALS USED IN DENTISTRY
• CONCLUSION
• REFERENCES
 INTRODUCTION
 Smart materials are materials that have properties which may be altered in a controlled
fashion by stimuli, such as stress, temperature, moisture, pH, electric or magnetic fields.

 Smart behavior generally occurs when a material senses some stimulus from the
environment and reacts to it in a useful, reliable, reproducible, and usually reversible
manner.
 DEFINITION
Smart materials in dental restoration is defined as, those which not only esthetically
restore the teeth but are also bio-responsive and helps in preventing
demineralization with release of component like, fluoride into surrounding
environment.
(Anusavice, 1998)
 The different types of smart materials used in the field of dentistry are piezoelectric
materials, shape memory alloys or shape memory polymers, pH sensitive polymers,
polymer gels and others that have shown their own smart behaviour.

 These smart materials can easily sense the changes in the oral cavity and respond
positively to these changes. (are highly responsive and have a great capacity to sense
and respond to any environmental change.)

 Hence these materials are also known as ― Responsive Materials.

 ORIGIN
The use of the terms “smart” and “intelligent”
to describe materials and systems came from the
USA and started in the 1980s.

Early smart material applications started with

magnetostrictive technologies. This involved
the use of nickel as a sonar source during World
War I to find German U-boats by Allied forces.

It was first used in dentistry for SMAs

(Shape Memory Alloys)
 CLASSIFICATION
• Based on the interaction with the oral environment, dental
materials might be classified as:
– Bioinert (passive)
– Bioactive
– Bioresponsive (smart materials)
• Smart materials are of two types passive and active materials.
• Passive Smart Restorative Materials: They sense the external change and react
to it without external control. They also possess self - repairing characteristics.
GIC
Resin Modified GIC
Compomer
Dental Composites

• Active Smart Restorative Materials: Active materials sense change in the environment
and respond to them. Utilize a feedback loop to enable them to functions as a
cognitive response through a controlled mechanism or system.
• Based on the use in Conservative Dentistry and Endodontics:

– Smart materials used in Preventive Dentistry

• ACP
• CPP
• Smart Antimicrobial Peptide
– Smart materials used in Restorative Dentistry
• GIC
• Smart Composites
• Smart Ceramics
• Smart materials in Adhesive dentistry
• Smart fibres for LASER
– Smart materials used in Endodontics
• SMA
• Smart Seal
– Smart materials used in Surgical Endodontics
• Emdogain
• Smart sutures
 PROPERTIES
Smart materials sense changes in the environment around them and responds in a
predictable manner. In general, these properties are:

• Piezoelectric- when a mechanical stress is applied, an electric current is generated.

• Shape memory - can change the shape whenever required and can return back to
original shape once force / pressure applied is removed .
• Thermochromic- these materials change color in response to changes in temperature.
• Photochromic- these materials change color in response to changes in light
conditions.
• Magnetorheological- these are fluid materials become solid when placed in a
magnetic field.
• pH sensitive-when pH of the surroundings gets altered they will change their shape.
• Biofilm formation- presence of biofilm on the surface of material alters the
interaction of the surface with the environment.
 MECHANISM
The “smartness” feature in a material (or system) is determined by two
different mechanisms :

ENERGY EXCHANGE

PROPERTY CHANGE
 • Among Stimuli responsive materials (SRMs), one group is able to change its
macroscopic shape in the presence of a proper stimulus. According to their
moving behavior, it is possible to distinguish:
– Shape changing materials(SCM)
– Shape memory materials(SMM)
Shape-changing materials (SCMs):
characterized by the shape-changing
capability (SCC), which is defined as the
materials’ ability to instantly change their
shape gradually while they are exposed to a
suitable stimulus. They recover their original
shape progressively as soon as the stimulus
is terminated. SCC can be repeated several
times.
Shape-memory materials (SMMs):
characterized by the shape-memory effect
(SME), which is defined as the materials’
capacity to be deformed and fixed in temporary
or dormant shape (programming), which remains
stable until it is exposed to an appropriate
stimulus (recovering).
• The SME typify a distinctive feature of a multiplicity of materials
• In SCM, the extent of shape recovery is sourced as a function of original
molecular structure.

• On the other hand, in SMM, the extent of shape recovery is sourced as a function
of fine programming leading to predefined temporary shape.

• The possibility to purposeful customize their moving behavior, have increased the
attractiveness of SMM over SCM.

• Shape-memory polymers (SMPs), also called actively moving polymers (AMPs),

are a class of polymeric materials demonstrating SME: they can respond to
several external stimuli such as temperature, magnetism, electricity, specific
wavelength, moisture, pH and some specific chemicals.
MECHANISM FOR THE SHAPE-MEMORY EFFECT IN SHAPE-MEMORY
POLYMERS IS THE DUAL SEGMENT/DOMAIN SYSTEM
 FACTORS INFLUENCING?
• Role of water
• Smart thermal behaviour
• Role of porosity
• Expansion and radial pressure
• Ion release and recharging
• Biofilms and smart behaviour
• Design of smart materials
 ROLE OF WATER
• Many types of smart behaviour are related to the ability of a gel structure to absorb or
release solvent rapidly in response to a stimulus such as temperature.

• In the oral environment, the key solvent is water and the structures may be gels or
salts which contain water which may be bound either strongly or loosely and
therefore may be absorbed or released at different rates.

• Some types of smart behaviour may also be defined by any species, such as fluoride
ions dissolved in the water and which are capable of undergoing reversible
interactions with the gel, salt or oral structures.

• Depending upon the nature of the water and how strongly it is bound, the observed
changes may be dependent upon the dimensions of the structures.
 Smart thermal behavior
• The vast majority of materials responds to a temperature change in a predictable manner.

• This involves a dimensional change characterized by the coefficient of thermal expansion or

expansivity.

• For composite materials, expansion and contraction occurred in the expected way and a
coefficient could readily be determined, and whether testing was done dry or wet made little
or no difference.

• For glass-ionomers, little or no change in dimension was observed when heating and cooling
between 20°C & 50°C in wet conditions.

• In dry conditions, the materials showed a marked contraction when heated above 50°C.
• Both results can be explained by flow of fluids in the dentinal tubules. Hence, the
glass-ionomer materials can be said to be mimicking the behaviour of human
dentine through a type of smart behaviour.
 Role of porosity
• The smart behaviour of glass-ionomers and related materials is closely linked to their
water content and the way in which this can react to changes in the environment.

• One important feature which may provide a location for the formation of reservoirs
within the material is porosity.

• Both the method of mixing and the viscosity of the cement have an effect on porosity.

• In the low viscosity material, hand mixing reduces the porosity significantly compared
to mechanical mixing, either by shaking or rotation. For the viscous material the levels
of porosity are low and not significantly affected by mixing.
 Expansion and Radial Pressure
• Smart materials which combine a special interactive characteristic with an acceptable
durability or longevity are likely to combine some salt or gel characteristic with a resin
component imparting some stability. Manufacturing of such materials presents a
problem of compatibility.

• Traditionally, such problems are solved by also incorporating species with both
hydrophilic and hydrophobic groups which have the function of bridging or coupling the
two distinctly different ingredients.

• Profiles of cavities containing a blend of GIC and resin phases with HEMA constrained
within a cavity show the ‘growth’ of the material out of the cavity and this is combined
with a considerable radial pressure measured as around 26 MPa compared with <3 MPa
caused by the water absorption of a typical resin matrix composite.
 Ion release & recharging
• The efficacy of fluoride release in caries prevention since even products with high initial
fluoride release tend to rapidly lose the ability to release fluoride in significant amounts.
• Even in the case of GICs, the fluoride release rate can become negligible within a week.
• However, the smart behaviour of materials containing GIC salt phases offers some long-
term solutions to this problem.
• In the long term, the fluoride re-released after recharging may be much more important
than the initial ‘burst’ which is sustained only for a short time.
• Another area where ‘smart’ fluoride interactions can have a significant benefit is in the
prevention of demineralization around orthodontic brackets.

• Using fluoride releasing cements can help to prevent demineralization. This has been
studied using quantitative light-induced fluorescence (QLF)
• Other work has shown that the rates of fluoride release and recharging are
temperature sensitive.

• Taking this a stage further, smart composite materials have been developed
which contain amorphous calcium phosphate particles or whiskers which at
low pH provide a source of calcium and phosphate ions which may act to
prevent demineralization of tooth structure and reportedly maintain
acceptable mechanical properties in the process.
 Biofilms and smart behaviour
• Biofilms formed on the surface of materials in the mouth may enhance the smart
behaviour of materials containing fluoride releasing salt phases.

Fluoride release from materials does not prevent

biofilm formation or growth
 The daily fluoride release in natural saliva is
significantly lower than the release into
distilled water or artificial saliva.

When samples are stored in acidified (pH 4) saliva

the rate of fluoride release is markedly increased
 When the specimens are cycled through both acidic and
neutral conditions, an increase in fluoride release is seen
at day 1 and then also at day 2 after placing into acidic
conditions

This offers some proof that fluoride becomes

concentrated within the biofilm and is made available
when the film is disturbed.

The formation of biofilms and the way in which this changes the interaction of the
materials with the environment represents a clear example of smart behaviour for these
materials.
Biofilms can protect surfaces from abrasive forces and at the same time concentrate
fluoride which is liberated through a change in pH or mechanical debridement.
MATERIALS WITH SMART
BEHAVIOUR
Amorphous Calcium Phosphate (ACP):
• Aaron S. Posner had described ACP for first
time in 1963 .

• At or below 5.8 (critical pH), ACP converts into

crystalline Hydroxyapatite (HAP), thus
replacing the HAP crystal lost to the acid.

• These free ions gets merged in ,forming gel-like

structure within seconds. Within 2 minutes this
gel-like structure releases calcium and
phosphate ions.

• These calcium and phosphate ions neutralizes

and buffers the pH

• Enamel Provarnish
Enamel Pro Varnish resulted in lowest bacterial
adhesion.This study showed that resin
infiltration of enamel lesions could arrest lesion
progress.

Duraflor™ and Enamel Pro® Varnish can be

considered for use in clinic as an effective
method to prevent or reduce demineralization
during orthodontic treatment, especially in
patients with poor oral hygiene.
Casein Phosphopeptide (CPP) :
• It is a milk derivative , in combination with
ACP is used for the remineralisation of
incipient white spot lesions in some
dentifrices (under the name ReCaldent)

• It is marketed as GC tooth mousse plus®-

(The University of Melbourne, Victoria,
Australia)
Smart Antimicrobial Peptide:
• Pheromone-guided ―smart antimicrobial peptide, which are targeted against
Streptococcus mutans.

• Majority of AMPs are amphipathic mixtures of α– helical and β–sheet structures with a
cationic charge.

• The action of AMPs typically involves binding to the negatively charged functional groups
of microbial membranes (e.g, lipopolysaccharides) and creating a disruption by inserting
into the membranes.

• Specifically targeted antimicrobial peptides (STAMP’s) could be delivered in current oral

care products such as mouthwash, toothpaste, or dental floss and could help with the
suppression of cariogenic bacteria.
Mechanism of Action:
• AMPs disrupt the cell membrane’s structure, inhibit proteins, interfere DNA synthesis,
repress cell processes including protein folding or cell wall synthesis or metabolic
turnover and so they have strong antimicrobial activity in the nanomolar (nM)or
micromolar (μM) range against a broad spectrum of microorganisms, including both types
of Gram-stained bacteria, fungi, and viruses.

• Reducing oral bacterial load and plaque by the usage of broad-spectrum antimicrobial
methods lowers caries risk but allows a competitive environment for pathogenic as well as
normal commensal to establish new biofilms and they hardly have any clinical evidence of
long-term caries prevention
Smart Prep Burs:
• Smart Prep Burs are polymer burs which have ability
to cut only infected dentin.
• The affected dentin which has the ability to
remineralize is left intact.
• The cutting blades will deflect and deform upon
encountering normal or partially decalcified dentin,
thereby enabling the reduction of cutting efficiency.
• The time required for caries removal may be slightly
longer, but when considered against the benefits they
are awesome.
 Both polymer bur and Carie-Care were efficient
caries removal agents when assessed clinically and
microbiologically. Polymer bur was found to be
more effective than Carie-Care when assessed
microbiologically.

The differences between complete caries excavation,

pain reaction and need for local anesthesia using both
the techniques were statistically insignificant.
Whereas the time taken for caries removal using Carie
-Care was significantly less than Smart burs (P =
0.001).
 The smart bur ΙΙ had significantly lower caries removal
efficiency when compared to conventional carbide bur.
The smart bur ΙΙ required significantly longer caries
removal time when compared to conventional carbide bur.

Efficiency was statistically insignificant. However,

Brix 3000 took more time than Smart burs for caries
removal
Smart GIC:

• Davidson first observed the smart behavioural property of

GiC.
• GiCs are described as “smart materials” with respect to their
thermal behaviour, since it is a desired feature, when
restorative materials undergo thermally induced volumetric
changes close to those of the tooth substance

• Mahmud GA et al. 2007 stated that the use of fluoride

releasing cement can minimize the demineralisation around
orthodontic brackets & demineralisation does not dependent
upon the amount of fluoride released.

• It has been confirmed by using Quantitative Light-induced

Fluorescence (QLF).
• It was also observed that the Fluoride releasing capacity of GiC increased with the
increase in temperature. This can be attributed to the fact that the diffusion coefficient
of GiC increases with the increase in temperature.

• Resin modified Glass Ionomer Cement, compomer or Giomer also exhibit these
smart characteristics.
Ex: GC Fuji IX GP EXTRA (Zahnfabrik Bad Säckingen, Germany)
MODIFICATIONS
• GICs incorporated with nanoparticles or nano glass which act as nucleating centres and
increase the surface area.
• In the polymeric component, inclusion of amino acid-functionalised monomers,
poly-N-vinylpyrrolidone, N-vinylpyrrolidone-modified acrylic acid copolymers and
star-shaped polymers have been done.
• The inclusion of N-vinylpyrrolidone in GIC enhances mechanical properties such
as compressive, biaxial and diametral tensile strength, attributed to enhanced
wettability of the glass particles by the polymers.
Smart Ceramic:
• Smart Ceramics deliver outstanding aesthetics
without reservations or compromise.
• These are metal — free and biocompatible.
• The Cercon system offers advantages like
strength, toughness, reliability, and
biocompatibility of zirconium oxide.
• It is the ultra-thin monolithic material, which
provides maximum strength.
• Ex: Cercon Zirconium Smart Ceramic System
Transformation toughened zirconia, involves an additional
mechanism not found in other polycrystalline ceramics.

Zirconium oxide is transformed from one crystalline state to

another during firing. At firing temperature, zirconia is
tetragonal and at room temperature monoclinic, with a unit
cell of monoclinic occupying about 4.4% more volume than
when tetragonal.

Although stabilized at room temperature, the tetragonal

form is really only “metastable,” meaning that trapped
energy still exists within the material to drive it back to the
monoclinic state.
Smart Composites:
• They are alkaline, nano-filled glass
restorative material and are activated.
• When intra-oral pH drops below 5.5,
calcium, fluoride and hydroxyl ions are
released. These released ions helps in
remineralization.
• Ex: Ariston pH control - introduced by
Ivoclar -Vivadent (Liechtenstein) Company
• Nano-composites containing amorphous nanocalcium phosphate (NACP) particles
have a combination of favorable mechanical properties and acid neutralization
enhancing tooth remineralization.
• It was demonstrated that nano-particulate ACP composites had flexural strength and
modulus of elasticity equal or higher than those of commercial composites.
• They have the remineralizing ability and can be considered as anti-caries
restorations.
• They also have strength higher than RMGiC and inhibit the growth of S. mutans and
decrease the risk of secondary caries.
 ACP at neutral or high pH remains as
ACP.

When low pH values (at or below 5.8) occur during

a carious attack, ACP converts into HAP and precipitates,
thus replacing the HAP lost to the acid.

These ions merge within

Seconds to form a gel. In less than 2 minutes, the gel becomes
amorphous crystals, resulting in calcium and phosphate ions
Self-Healing Composite
A Glycidyl Methacrylate (BisGMA) (1: 1: 1) at 45% w/w with silane 0.7 灰 glass was
formulated with a self-healing system consisting of encapsulated dicyclopentadiene and
Grubbs catalyst.

The results suggested that despite the highly filled nature of dental composites, these
materials could recover mechanical properties by the incorporation of embedded
monomers and catalyst.
BONDING SYSTEMS
Modern Strategies to Deal with Bond Degradation
• Type I collagen plays a significant role in the restoration of dentine since resin
infiltration and subsequent modification are key to dentine bonding.

• Matrix metalloproteinases (MMP) are known to be present in mineralised dentine, and

exposed collagen fibrils are susceptible to intrinsic collagenolytic MMP activity

• Mazzoni et al. have correlated collagenous areas of poor resin infiltration with the
activation of dentine-bound MMP by the acidic components of ‘etch-and-rinse’
adhesives.

• The introduction of MMP inhibitors at the resin dentine interface is an approach that may
assist in extending the longevity of the resin-dentine bond.
Biomimetic Remineralisation Strategies of Dentine

• The ‘bioremineralisation’ process in dentine is related to creating an inorganic,

mineral- like material at the bonding interface that is in turn able to protect the
exposed collagen and decrease void formation, thus minimizing the effects of the
hydrolytic degradation.

• Reactive calcium silicate powders, ion-leaching calcium silicate cements have

been reported to exhibit biomimetic remineralization activities.
Shape Memory Alloys (SMA):
• Shape memory alloys (SMA) are the metals with the ability to recover the
original shape/length when subjected to the thermo- mechanical load.
• These alloys show properties like super elasticity, shape memory, good
resistance to fatigue and wear and relatively good biocompatibility.
• Ex: Nickel -Titianium
Nickel Titanium Alloy:
• Greniger and Mooradian in 1938, first noticed shape
memory property of copper- zinc and copper tin alloys
• Nickel-Titanium was developed 50 years ago by Buehler
et al. in the Naval Ordinance Laboratory (NOL) in
Silver Springs, Maryland.
• Walia et al. in 1988 introduced Ni- Ti to Endodontics
where 55wt% Ni and 45 wt% Ti are commonly used,
referred to as ―55NiTiNOL.‖
• It allows more centered canal preparations with less
canal transportation and a decreased incidence of canal
aberrations.
• Nitinol shows stress-induced thermoelastic
transformation.
EVOLUTION OF NiTi INSTRUMENTS
Smart Fibres for Laser Dentistry:

• Laser radiation of high- fluency can be delivered by Hollow-core Photonic-

Fibers (PCFs) which can ablate tooth enamel been developed.

• These photonic fibers are known as Smart Fibres.

• Photonic Crystal Fibre are not only to transport the high power laser pulse to a
tooth surface, but can be used for detection and optical diagnosis through transmit
plasma emission.

• Care should be taken while using these fibers as laser light may escape and can
harm healthy tissue.
SMART SEAL OBTURATION SYSTEM
• The C Point system (EndoTechnologies, LLC, Shrewsbury, MA, USA) is a point-and-paste root
canal filling technique that consists of
– premade, hydrophilic endodontic points
– an accompanying sealer.

• The inner core of C Point is a mix of two proprietary nylon polymers: Trogamid T and Trogamid
CX.

• The polymer coating is a cross-linked copolymer of acrylonitrile and vinylpyrrolidone, which has
been polymerised and cross-linked using allyl methacrylate and a thermal initiator.

• This nonisotropic lateral expansion is said to enhance the sealing

ability of the root canal filling, thereby reducing the possibility of
reinfection and potentiating the long-term success of root canal
treatment.
• Smartpaste bio is a resin-based sealant designed to swell through the addition of ground polymer.

• Smartpaste bio produces calcium hydroxide and hydroxyapatite as by-products of the setting
reaction, rendering the material both antibacterial while setting and very biocompatible once set.

• It has a delayed setting time (4–10 hr) and is hydrophilic in nature, allowing the propoint to
hydrate and swell to fill any voids.

• Economides et al. (2011) evaluated, ex vivo, the push-out bond strength of Smartseal compared
with gutta-percha/AH-26. The study revealed no significant differences (䐰 > 0.05) between
the mean bond strengths of the various groups, thus indicating that there was no difference in
adhesion to dentine between the Smartseal systemand gutta-percha/AH- 26 applied using either
the single cone or lateral condensation technique
EMDOGAIN:
• EMD is a protein extract from unerupted porcine tooth buds that contains approximately 90%
amelogenins and smaller amounts of tuftelin, ameloblastin, enamelin, and other nonamelogenin
proteins.

• Its main clinical application is to stimulate new periodontal attachment formation, which includes
the periodontal ligament (PDL), acellular cementum, and alveolar bone.

• The full properties and potential of EMD in regenerative endodontics are still not fully understood
although it has been shown to play an important role in odontogenesis via up-regulation of
Osterix and Runx2 transcription factors

• EMD also increases the expression of markers for odontoblast-/osteoblastlike cells in human
dental pulp cells, and this property may improve pulp tissue repair and regeneration. Other
properties of EMD include dentinogenesis, cementogenesis, and angiogenesis.
Smart Sutures:

• They are made up of thermoplastic polymers that have

both shape memory and biodegradable properties.

• Smart sutures made of plastic or silk threads covered

with temperature sensors and micro-heaters can detect
infections.

• Sutures are loosely tied, once the temperature is

increased above the thermal transition temperature;
sutures gets shrinked and tightened.

• Ex: Novel MIT Polymer (Aachen, Germany).

 CONCLUSION
• Smart materials have numerous applications and doing wonders in the field of
dentistry.
• Advances in form of these biosmart dental materials are paving the future of
dentistry.
• The most sophisticated class of smart materials in the foreseeable future will be that
which can mimic the biological systems.
• These materials could have the ability to anticipate challenges based on the ability to
recognize, analyze, and discriminate.
• Thus these innovations in the material science have marked the beginning of an era
of bio-smart dentistry, a step into the future!!
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THANK YOU!!