Australian Dental Journal - 2011 - McCabe - Smart Materials in Dentistry
Australian Dental Journal - 2011 - McCabe - Smart Materials in Dentistry
See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Australian Dental Journal
The official journal of the Australian Dental Association
Australian Dental Journal 2011; 56:(1 Suppl): 3–10
doi: 10.1111/j.1834-7819.2010.01291.x
ABSTRACT
Most dental materials are designed to have a relatively ‘neutral’ existence in the mouth. It is considered that if they are
‘passive’ and do not react with the oral environment they will be more stable and have a greater durability. At the same time,
it is hoped that our materials will be well accepted and will cause neither harm nor injury. This is an entirely negative
approach to material tolerance and biocompatibility and hides the possibility that some positive gains can be achieved by
using materials which behave in a more dynamic fashion in the environment in which they are placed.
An example of materials which have potential for ‘dynamic’ behaviour exists with structures which are partly water-based
or have phases or zones with significant water content and for which the water within the material can react to changes in
the ambient conditions. Such materials may even be said to have the potential for ‘smart’ behaviour, i.e. they can react to
changes in the environment to bring about advantageous changes in properties, either within the material itself or in the
material-tooth complex. The controlled movement of water or aqueous media through the material may cause changes in
dimensions, may be the carrier for various dissolved species, and may influence the potential for the formation of biofilms at
the surface. Some of these issues may be closely interrelated.
Clearly, materials which do not have the capacity for water transport or storage do not have the potential for this sort of
behaviour.
Some materials which are normally resistant to the healthy oral environment can undergo controlled degradation at low pH
in order to release ions which may prove beneficial or protective. It is doubtful whether such behaviour should be classified
as ‘smart’ because the material cannot readily return to its original condition when the stimulus is removed.
Other materials, such as certain alloys, having no means of transporting water through their structure, can display smart
behaviour by undergoing predictable changes in structure in response to applied mechanical or thermal stimuli. It has been
difficult to harness such behaviour to the benefit of patients but progress in this area is slowly being made.
Keywords: Smart materials, fluoride release, fluoride recharging, glass-ionomers, biofilms.
Abbreviations and acronyms: GIC = glass-ionomer cement; HEMA = hydroxyethylmethacrylate; PAA = polyacrylicacid; PAN =
polyacrylonitrile; PVA = polyvinylalcohol; QLF = quantitative light-induced fluorescence; RMGIC = resin modified glass-ionomer cement;
SMA = shape memory alloys.
pH, light or applied voltage. One common example of increase in strain which in ‘normal’ alloys would be
this sort of technology is the light-sensitive sunglasses identified as irreversible yielding.12,13 In the SMA
which darken when exposed to bright sunlight. alloys, however, this ‘yielding’ is related to a reversible
Polymer gels offer a potential for smart behaviour.1,6 change in the crystal structure. The reverse process is
They consist of cross-linked polymer networks which may temperature dependent and this lies at the heart of the
be inflated with a solvent such as water. The labile nature difficulty in harnessing the characteristic for clinical
of the solvent enables a rapid and reversible swelling or benefit as the temperatures required can be very high.
shrinkage in response to a small change in their environ- However, this knowledge has been used in the manu-
ment (e.g. temperature). The most common gel forming facture of wires of similar cross-section but markedly
polymers are polyvinylalcohol (PVA), polyacrylicacid different stiffness. The phase changes involved in
(PAA) and polyacrylonitrile (PAN). Microsized gel fibres the crystal transitions involve a small exothermic ⁄
may contract in milliseconds, while thick polymer layers endothermic response which can be used to monitor or
may require much longer to react. It has been suggested measure the extent of the change. However, the amount
that these gels can potentially deliver a stress equivalent to of energy involved is very small and very sensitive
that of a human muscle of about equivalent size. recording equipment is required (e.g. temperature
modulated differential scanning calorimetry).14 In
order to fully utilize the super-elastic or shape memory
Smart materials by chance or design
characteristics, it would be essential to enable the phase
The future use of smart materials will involve a degree transitions to occur in a controlled fashion at or near
of ‘smart behaviour’ by design. However, smart behav- mouth temperature, and this is now claimed to be
iour was first noted in some materials by chance and the possible by some manufacturers. Wires exhibiting
significance of the special nature may not be recognized shape-memory behaviour at mouth temperature nor-
as being of any practical use until some time later. This mally contain copper and ⁄ or chromium in addition to
was certainly the case for thermo-responsive materials, nickel and titanium.
either shape memory alloys or shape memory polymers.
Shape memory alloys3 based upon NiTi alloys have
The role of water
been used in orthodontics for many years and their
remarkable properties have been commented upon Many types of smart behaviour are related to the ability
without any insight into how the properties could be of a gel structure to absorb or release solvent rapidly in
harnessed for a practical purpose. Likewise the response to a stimulus such as temperature. In the oral
potential thermo-responsive smart behaviour of some environment, the key solvent is water and the structures
glass-ionomer cements was first suggested by Davidson7 may be gels or salts which contain water which may be
and was then demonstrated as a result of attempting to bound either strongly or loosely and therefore may be
measure the coefficient of thermal expansion.8–11 absorbed or released at different rates. Some types of
Heating or cooling of these materials may result in smart behaviour may also be defined by any species,
minimal dimensional change as the expected expan- such as fluoride ions dissolved in the water and which
sions (heating) or contractions (cooling) appear to be are capable of undergoing reversible interactions with
offset by a compensating reaction related to the the gel, salt or oral structures. Depending upon the
movement of water in or out of the structure. nature of the water and how strongly it is bound, the
observed changes may be dependent upon the dimen-
sions of the structures.11
Smart alloys – the first smart dental materials
The term ‘smart material’ or ‘smart behaviour’ in the
Smart thermal behaviour
discipline which is now loosely defined as ‘dental
materials science’, was probably first used in connection The vast majority of materials responds to a temper-
with nickel-titanium alloys, or shape memory alloys ature change in a predictable manner. This involves a
(SMAs), which are used as orthodontic wires. Frustrat- dimensional change characterized by the coefficient of
ingly, although these materials were found to have thermal expansion or expansivity. One problem with
fascinating characteristics in relation to the way their dental filling materials is their tendency to expand and
structure ⁄ properties changed in response to strain and contract to a greater extent than the natural tooth tissue
temperature, it has never been clearly expounded how when subjected to hot or cold stimuli. When samples of
their characteristics could be used beneficially during restorative materials were heated in order to determine
patient treatment. The smart behaviour is essentially their values of coefficient of thermal expansion, an
related to the ability of the alloy to initially undergo interesting observation was made. For composite
strain in response to stress in the normal way, but at the materials, expansion and contraction occurred in the
point identified as the yield stress there is a further expected way and a coefficient could readily be
4 ª 2011 Australian Dental Association
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Smart materials in dentistry
determined, and whether testing was done dry or wet way in which this can react to changes in the
made little or no difference.8 For glass-ionomers, little environment. Clearly, there are different ways in which
or no change in dimension was observed when heating water can be retained in and transported through the
and cooling between 20 C and 50 C in wet conditions cement structure. One important feature which may
(Fig 1).9,10 In dry conditions, the materials showed a provide a location for the formation of reservoirs
marked contraction when heated above 50 C. The within the material is porosity. The number and size of
explanation for this behaviour is that the expected pores within a cement can be controlled by the method
expansion on heating is compensated by fluid flow to of mixing and is conveniently measured using micro-CT
the surface of the material to cause a balancing of the scanning.15 Figure 3 shows typical scans of a glass-
dimensional changes. On cooling, the process was ionomer cement mixed mechanically in capsules or
reversed. In dry conditions, the rapid loss of water on handmixed. The volume of bubbles can readily be
heating results in the observed contraction. This calculated and is shown in Table 1.
behaviour is akin to that of human dentine (Fig 2) The results given in Table 1 indicate that both the
where very little dimensional change is observed on method of mixing and the viscosity of the cement have
heating in wet conditions and a marked contraction is an effect on porosity. In the low viscosity material,
noted in dry conditions.11 Both results can be explained handmixing reduces the porosity significantly compared
by flow of fluids in the dentinal tubules. Hence, the to mechanical mixing, either by shaking or rotation.
glass-ionomer materials can be said to be mimicking the For the viscous material the levels of porosity are low
behaviour of human dentine through a type of smart and not significantly affected by mixing. These differ-
behaviour. ences in porosity are reflected in differences in water
absorption (Table 2).11,16 Hence, this aspect of the
The role of porosity
The smart behaviour of glass-ionomers and related
materials is closely linked to their water content and the
Ketac-Cem
Aplicap 2.8 (1.6) 1.8 (1.8) –
Maxicap 2.7 (2.6) 2.1 (2.1) 0.2 (0.2)
Hand – – 0.1 (0.1)
Ketac-Molar
Aplicap 0.2 (0.2) 0.1 (0.1) –
Fig 2. Dimensional change of human dentine when heated under wet Hand – – 0.1 (0.1)
or dry conditions.
ª 2011 Australian Dental Association 5
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JF McCabe et al.
Fig 7. Pre and post-demineralization QLF images around orthodontic brackets showing significant demineralization around a non-fluoride releasing
cement and minimal demineralization around cements with ‘large’ or moderate fluoride release or recharging capacity.
ª 2011 Australian Dental Association 7
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JF McCabe et al.
Fig 10. Surface profiles of a GIC at baseline and after brushing in acidified saliva (natural or artificial). This illustrates the protective effect of the
biofilm formed in natural saliva.
competing during the setting of an RMGIC material, it 7. Davidson CL. Glass ionomer cements, intelligent materials. Bull
Group Int Rech Sci Stomatol Odontol 1998;40:38–42.
is possible to conceive of means of controlling the
extent to which one or other of the processes dominates 8. Sidhu SK, Carrick TE, McCabe JF. Temperature mediated coef-
ficient of dimensional change of dental tooth-coloured restorative
and hence to influence the structure and properties of materials. Dent Mater 2004;20:435–440.
the set material. 9. Yan Z, Sidhu SK, Carrick TE, McCabe JF. Response to thermal
stimuli of glass ionomer cements. Dent Mater 2007;23:597–600.
10. Yan Z, Sidhu SK, McCabe JF. The influence of microstructure on
ACKNOWLEDGEMENT thermal response of glass ionomers. J Mater Sci Mater Med
2007;18:1163–1166.
The authors are grateful to Professor Seiji Ban, editor of
11. Yan Z. Smart materials in dentistry. Newcastle University, United
the Dental Materials Journal, for permission to repro- Kingdom, 2006. PhD thesis.
duce large parts of this paper which was originally 12. Gil FJ, Planell JA. Shape memory alloys for medical applications.
presented at the International Dental Materials Con- Proc Inst Mech Eng H 1998;212:473–488.
gress, Bangkok in 2003 and published in Dent Mater J 13. Gil FJ, Planell JA. Effects of copper addition on the superelastic
2009;28:37–43. behaviour of Ni-Ti shape memory alloys for orthodontic appli-
cations. J Biomed Mater Res 1999;48:682–688.
14. Brantley WA, Iijima M, Grentzer TH. Temperature-modulated
REFERENCES DSC provides new insight about nickel-titanium wire transfor-
mations. Am J Orthod Dentofacial Orthop 2003;124:387–394.
1. Zrinji M, Szilagyi A, Filipcsei G, Feher J, Szalama J, Moczar G.
15. Nomoto R, Komoriyama M, McCabe JF, Hirano S. Effect of
Smart gel-glass based on the responsive properties of polymer
mixing method on the porosity of encapsulated glass ionomer
gels. Polym Adv Technol 2001;12:505–510.
cement. Dent Mater 2004;20:972–978.
2. Allameh SM, Akogwu O, Collinson M, Thomas J, Soboyejo WO.
16. Yan Z, Sidhu SK, Mahmoud GA, Carrick TE, McCabe JF. Effects
Piezoelectric generators for biomedical and dental applications:
of temperature on the fluoride release and recharging ability of
effect of cyclic loading. J Mater Sci Mater Med 2007;18:
glass ionomers. Oper Dent 2007;32:138–143.
39–45.
17. McCabe JF. A laboratory evaluation of the water and fluoride
3. Gil FJ, Planell JA. Shape memory alloys for medical applications.
equilibrium characteristics of reactmer giomer. International
Proc Inst Mech Eng 1998;212:473–488.
Meeting Proceedings, Shofu Inc., 2001.
4. Lendlein A, Langer R. Biodegradeable, elastic, shape-memory
18. McCabe JF, Rusby S. Water absorption, dimensional change and
polymers for potential biomedical applications. Science
radial pressure in resin matrix dental restorative materials. Bi-
2002;296:1673–1676.
omaterials 2004;25:4001–4007.
5. Stayton PS, El-Sayed ME, Murthy N, et al. Smart delivery systems
19. Momoi Y, McCabe JF. Hygroscopic expansion of resin based
for biomolecular therapeutics. Orthod Craniofac Res
composites during 6 months of water storage. Br Dent J
2005;8:219–225.
1994;176:91–96.
6. Prabaharan M, Mano JF. Stimuli responsive hydrogels based on
20. Shaw A, McCabe JF, Carrick TE. Fluoride release from glass
polysaccharides incorporated with thermo-responsive polymers
ionomers and compomers. J Dent 1998;26:355–360.
as novel biomaterials. Macromol Biosci 2006;8:991–1008.
21. Momoi Y, McCabe JF. Fluoride release from light-activated 32. Xu HHK, Weir MD, Sun L. Nanocomposites with Ca and PO4
glass ionomer restoration cements. Dent Mater 1993;9:151– release: effects of reinforcement, dicalcium phosphate particle size
154. and silanization. Dent Mater 2009;23:1482–1491.
22. McCabe JF, Carrick TE, Sidhu SK. Determining low levels of 33. Antonucci JM, Fowler BO, Weir MD, Skrtic D, Stansbury JW.
fluoride released from resin based dental materials. Eur J Oral Sci Effect of ethyl-a-hydroxymethylacrylate on selected properties of
2002;110:380–384. copolymers and ACP resin composites. J Mater Sci Mater Med
23. Al Naimi OT, Itota T, Hobson RS, McCabe JF. Fluoride 2008;19:3263–3271.
release for restorative materials and its effect on biofilm forma- 34. Namen FM, Galen J, De Deus G, Cabreira RD, Filho FC. Effect
tion in natural saliva. J Mater Sci Mater Med 2008;19:1243– of pH on the wettability and fluoride release of an ion-releasing
1248. resin composite. Oper Dent 2008;33:571–578.
24. Itota T, Carrick TE, Yoshiyama M, McCabe JF. Fluoride release 35. Xu HHK, Sun L, Weir MD, et al. Nano DCPA-whisker com-
and recharge in giomer, compomer and resin composite. Dent posites with high strength and Ca and PO4 release. J Dent Res
Mater 2004;20:789–795. 2006;85:722–727.
25. Mahmoud G, Pretty IA, Gordon PH, McCabe JF. Effect of 36. Al Naimi OT. Surface interaction of biomaterials with biological
fluoride release on enamel de-mineralisation adjacent to ortho- fluids. Newcastle University, United Kingdom, 2005. PhD thesis.
dontic brackets. Proceedings BSDR 2007, Abstract 217. 37. Rolland SL, McCabe JF, Robinson C, Walls AWG. In vitro bio-
26. Larmour CJ, McCabe JF, Gordon PH. An ex vivo assessment of film formation on the surface of resin-based dentine adhesives.
resin-modified glass ionomer bonding systems in relation to Eur J Oral Sci 2006;114:243–249.
ceramic bracket debond. J Orthod 2000;27:329–332. 38. Friend C. Smart materials: the emerging technology. Materials
27. Itota T, Al-Naimi OT, Carrick TE, Yoshiyama M, McCabe JF. World 1996;4:16–18.
Fluoride release and neutralizing effect by resin-based materials. 39. McCabe JF. Resin-modified glass ionomers. Biomaterials
Oper Dent 2005;30:522–527. 1998;19:521–527.
28. van Dijken JWV. Three-year performance of a calcium-, fluoride-,
and hydroxyl-ions- releasing resin composite. Acta Odont Scand
2002;60:155–159.
Address for correspondence:
29. Heintze SD. A new material concept for inhibiting the formation
of secondary caries. Am J Dent 1999;12:S4–S7.
Professor JF McCabe
30. Skritic D, Antonucci JM, Eanes ED. Amorphous calcium phos-
School of Dental Sciences
phate bioactive composites for mineralized tissue regeneration. J Newcastle University
Res Nat Inst Stand Tech 2003;108:167–182. NE2 4BW
31. Xu HHK, Weir MD, Sun L. Calcium and phosphate ion releasing United Kingdom
composite: effect of pH on release and mechanical properties.
Email: [email protected]
Dent Mater 2009;25:535–542.