Abstract
Photo-polymerisation is now a widely accepted initiation mode for the clinical hardening processes required with a wide range of biomaterials including dental adhesives and restoratives. As we discuss in detail, there is a strong relationship between the progressive phenomenon of photo-polymerisation, with attendant network formation, and shrinkage stresses and strains set up in the material and its host environment.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsReferences
Watts DC, Al Hindi A. Intrinsic “soft-start” polymerisation shrinkage-kinetics in an acrylate-based resin-composite. Dent Mater 1999; 15:39–45
Versluis A, Douglas WH, Cross M, Sakaguchi RL. Does an incremental filling technique reduce polymerization shrinkage stresses? J Dent Res 1996; 75:871–878
Silikas N, Eliades G, Watts DC. Light intensity effects on resin-composite degree of conversion and shrinkage strain. Dent Mater 2000; 16:292–296
Sakaguchi R, Berge H. Reduced light energy density decreases post-gel contraction while maintaining degree of conversion in composites. J Dent 1998; 26:695–700
Pananakis D, Watts DC. Incorporation of the heating effect of the light source in a nonisothermal model of a visible-light-cured resin composite. J Mater Sci 2000; 35:4589–4600
Labella R, Lambrechts P, Van Meerbeek B, Vanherle G. Polymerisation shrinkage and elasticity of flowable composites and filled adhesives. Dent Mater 1999; 15:128–137
Davidson CL, Feilzer AJ. Polymerisation shrinkage and polymerisation shrinkage stress in polymer-based restoratives. J Dent 1997; 25:435–440
Kinomoto Y, Torii M, Takeshige F, Ebisu S. Comparison of polymerization contraction stresses between self-and light-curing composites. J Dent Res 1999; 27:383–389
Hegdahl T, Gjerdet NR. Contraction stresses of composite resin filling materials. Acta Odont Scand 1977; 35:191–195
Condon JR, Ferracane JL. Reduction of composite contraction stress through non-bonded microfiller particles. Dent Mater 1998; 14:256–260
Carvalho RM, Pereira JC, Yoshiyama M, Pashley DH. A review of polymerisation contraction: the influence of stress development versus stress relief. Oper Dent 1996; 21:17–24
Bouchlicher MR, Vargas MA, Boyer DB. Effect of composite type, light intensity, configuration factor and laser polymerisation on polymerisation contraction forces. Am J Dent 1997; 10:88–96
Eick JD, Welch FW. Polymerisation shrinkage of posterior composite resins and its possible influence on postoperative sensitivity. Quintessence Int 1986; 17:103–111
Stansbury JW. Cyclopolymerisable monomers for use in dental resin composites. J Dent Res 1990; 69:844–848
Sakaguchi RL, Ferracane JL. Stress transfer from polymerization shrinkage of a chemical-cured composite bonded to a pre-cast composite substrate. Dent Mater 1998; 14:106–111
Feilzer AJ, Dooren LH, de Gee AJ, Davidson CL. Influence of light intensity on polymerization shrinkage and integrity of restoration-cavity interface. Eur J Oral Sci 1995; 103:322–326
Sakaguchi R, Brust E, Cross M, DeLong R, Douglas W. Independent movement of cusps during occlusal loading. Dent Mater 1991; 7:186–190
Tantbirojn D, Versluis A, Pintado M, DeLong R, Douglas W. Tooth deformation patterns in molars after composite restoration. Dent Mater 2004; 20:535–542
Morin DL, Douglas WH, Cross M. Biophysical stress analysis of restored teeth: experimental strain measurement. Dent Mater 1988; 4:41–48
Opdam N, Roeters F, Feilzer A, Verdonschot E. Marginal integrity and postoperative sensitivity in class 2 resin composite restorations in vivo. J Dent 1998; 26:555–562
Lopes G, Baratieri L, Monteiro SJ, Vieira L. Effect of posterior resin composite placement technique on the resin-dentin interface formed in vivo. Quintessence Int 2004; 35:156–161
Althof O, Hartung M. Advances in light curing. Am J Dent 2000; 13:77D–81D
Hofmann N, Hugo B, Schubert K, Klaiber B. Comparison between a plasma arc light source and conventional halogen curing units regarding flexural strength, modulus, and hardness of photoactivated resin composites. Clin Oral Investig 2000; 4:140–147
Peutzfeldt A, Sahafi A, Asmussen E. Characterization of resin composites polymerized with plasma arc curing units. Dent Mater 2000; 16:330–336
Blankenau R, Erickson R, Rueggeberg F. New light curing options for composite resin restorations. Compend Contin Educ Dent 1999; 20:122–125
Bennett A, Watts D. Performance of two blue light-emitting-diode dental light curing units with distance and irradiation time. Dent Mater 2004; 20:72–79
Smith F. Optics and photonics, an introduction. Wiley, New York, 2000
Mills RW. Blue light emitting diodes: another method of light curing? Br Dent J 1995; 178:169
Jandt K, Blackwell G, Ashworth S. Depth of cure and compressive strength of dental composite cured with blue light emitting diodes (LEDs). Dent Mater 2000; 16:41–44
Yap A, Soh M, Siow K. Post-gel shrinkage with pulse activation and soft-start polymerization. Oper Dent 2002; 27:81–87
Soh M, Yap A. Influence of curing modes on crosslink density in polymer structures. J Dent 2004; 32:321–326
Hofmann N, Denner W, Hugo B, Klaiber B. The influence of plasma arc vs halogen standard or soft-start irradiation on polymerization shrinkage kinetics of polymer matrix composites. J Dent 2003; 31:383–393
Hofmann N, Markert T, Hugo B, Klaiber B. Effect of high intensity vs soft-start halogen irradiation on light-cured resin-based composites. Part I. Temperature rise and polymerization shrinkage. Am J Dent 2003; 16:421–430
Hofmann N, Markert T, Hugo B, Klaiber B. Effect of high intensity vs soft-start halogen irradiation on light-cured resin-based composites. Part II. Hardness and solubility. Am J Dent 2004; 17:38–42
Bouschlicher M, Rueggeberg F. Effect of ramped light intensity on polymerization force and conversion in a photoactivated composite. J Esthet Dent 2000; 12:328–339
De Lange C, Bausch J, Davidson C. The curing pattern of photo-initiated dental composites. J Oral Rehab 1980; 7:369–377
Watts D, Amer O, Combe E. Characteristics of visible light-cured composite systems. Br Dent J 1984; 156:209–215
Ruyter IF. Methacrylate-based polymeric dental materials: conversion and related properties. Summary and review. Acta Odontol Scand 1982; 40:359–376
Rueggeberg F, Craig R. Correlation of parameters used to estimate monomer conversion in a light-cured composite. J Dent Res 1988; 67:932–937
Ferracane J. Correlation between hardness and degree of conversion during the setting reaction of unfilled dental restorative resins. Dent Mater 1985; 1:11–14
DeWald J, Ferracane J. A comparison of four modes of evaluating depth of cure of light-activated composites. J Dent Res 1987; 66:727–730
Cook WD, Standish P. Cure of resin-based restorative materials. II. White light photo-polymerised resins. Aust Dent J 1983; 28:307–311
Miyagawa Y, Powers J. Prediction of color of an esthetic restorative material. J Dent Res 1983; 62:581
Van Krevelen D. Properties of polymers. Elsevier, Amsterdam, 1976
Kubelka P, Munk F. A contribution to the optics of pigments. Z Technol Phys 1931; 12:593
Miyagawa Y, Powers J, O’Brian W. Optical properties of direct restorative materials. J Dent Res 1981; 60:890
Cook W, McAree D. Optical properties of esthetic restorative materials and natural dentition. J Biomed Mater Res 1985; 19:469
Taira M, Yamaki M. Studies on optical properties of a visible-light-cured dental composite resin by diffuse reflectance measurements. J Mater Sci Lett 1995; 14:198
Wozniak W, Siew E, Lim J, McGill S, Sabri Z, Moser J. Color mixing in dental porcelain. Dent Mater 1993; 9:229
Lee Y, Powers J. Color and optical properties of resin-based composites for bleached teeth after polymerization and accelerated aging. Am J Dent 2001; 14:349–354
McCabe J, Carrick T. Output from visible-light activation units and depth of cure of light-activated composites. J Dent Res 1989; 68:1534–1539
Suzuki H, Taira M, Wakasa K, Yamaki M. Refractive-index-adjustable fillers for visible-light-cured dental resin composites: preparation of TiO2-SiO2 glass powder by the sol-gel process. J Dent Res 1991; 70:883
Moad G, Chiefari J, Mayadunne R et al. Initiating free radical polymerization. Macromol Sympos 2002; 182:65–80
Dart E, Nemcek J. British Patent 1975:1 408 265
Taira M, Urabe H, Hirose T, Wakasa K, Yamaki M. Analysis of photo initiators in visible light-cured dental composite resins. J Dent Res 1988; 67:24–28
Tsai L, Charney E. The triplet states of a-Dicarbonyls. J Phys Chem 1969; 73:2462–2463
Stansbury J. Curing dental resins and composites by photopolymerization. J Esthet Dent 2000; 12:300–308
Peutzfeldt A, Asmussen E. Effect of propanal and diacetyl on quantity of remaining double bonds of chemically cured BisGMA/TEGDMA resins. Eur J Oral Sci 1996; 104:309–312
Peutzfeldt A, Asmussen E. In vitro wear, hardness, and conversion of diacetyl-containing and propanal-containing resin materials. Dent Mater 1996; 12:103–108
Chae K-H, Sun G-J. Phenylpropanedione; a new visible light photosensitizer for dental composite resin with higher efficiency than camphorquinone. Bull Korean Chem Soc 1998; 19:152–154
Sun G, Chae K. Properties of 2,3-butanedione and 1-phenyl-1,2-propanedione as new photosensitizers for visible light cured dental resin composites. Polymer 2000; 41:6205–6212
Park Y-J, Chaec K-H, Rawlsa HR. Development of a new photoinitiation system for dental light-cure composite resins. Dent Mater 1999; 15:120–127
Ferracane J, Greener E. Fourier transform infrared analysis of degree of polymerization in unfilled resins: methods comparison. J Dent Res 1984; 63:1093–1095
Ferracane JL, Greener EH. The effect of resin formulation on the degree of conversion and mechanical properties of dental restorative resins. J Biomed Mater Res 1986; 20:121–131
Eliades GG, Vougiouklakis GJ, Caputo AA. Degree of double bond conversion in light-cured composites. Dent Mater 1987; 3:19–25
Ruyter I, Oysaed H. Analysis and characterization of dental polymers. Crit Rev Biocompat 1988; 4:247–279
Cox C, Keall C, Keall H, Ostro E, Bergenholtz G. Biocompatibility of surface-sealed dental materials against exposed pulps. J Prosth Dent 1987; 57:1–8
Vankerckhoven H, Lambrechts P, Van Beylen M, Vanherle G. Unreacted methacrylate groups on the surfaces of composite resins. J Dent Res 1982; 61:791–795
Ruyter IE, Svendsen S. Remaining methacrylate groups in composite restorative materials. Acta Odontol Scand 1978; 36:75–82
Asmussen E. Factors affecting the quantity of remaining double bonds in restorative resin polymers. Scand Dent Res 1982; 90:490–496
Maffezzoli A, Terzi R. Thermal analysis of visible-light-activated dental composites. Thermochim Acta 1995; 269/270:319–335
Ferracane JL. In vitro evaluation of resin composites. Structure-property relationships. Development of assessment criteria. Trans Acad Dent Mater 1989; 2:6–35
Scherzer T. Real-time FTIR-ATR spectroscopy of photopolymerization reactions. Macromol Sympos 2002; 184:79–97
Oréfice R, Disacciati J, Neves A, Mansur H, Jansen W. In situ evaluation of the polymerization kinetics and corresponding evolution of the mechanical properties of dental composites. Polymer Testing 2003; 22:77–81
Stansbury J, Dickens S. Determination of double bond conversion in dental resins by near infrared spectroscopy. Dent Mater 2001; 17:71–79
Louden J, Roberts T. Cure profiles of light-cured dental composites by Raman spectroscopy. J Ram Spec 1983; 14:365–366
Pianelli C, Devaux J, Bebelman S, Leloup G. The micro-raman spectroscopy, a useful tool to determine the degree of conversion of light-activated composite resins. J Biomed Mater Res (Appl Biomater) 1999; 48:675–681
Emami N, Soderholm K-JM, Berglund L. Effect of light power density variations on bulk curing properties of dental composites. J Dent 2003; 31:189–196
Tsuda H, Arends J. Raman spectroscopy in dental research: a short review of recent studies. Adv Dent Res 1997; 11:539–547
Miyazaki M, Onose H, Moore B. Analysis of the dentin-resin interface by use of laser Raman spectroscopy. Dent Mater 2002; 18:576–580
Heatley F, Pratsitsilp Y, McHugh N, Watts D, Devlin H. Determination of extent of reaction in dimethacrylate-based dental composites using solid-state 13C m.a.s. n.m.r. spectroscopy and comparison with FTi.r. spectroscopy. Polymer 1995; 36:1859–1867
Pereira S, Nunes T, Kalachandra S. Low viscosity dimethacrylate comonomer compositions [Bis-GMA and CH3Bis-GMA] for novel dental composites; analysis of the network by strayfield MRI, solid-state NMR and DSC & FTIR. Biomaterials 2002; 23:3799–3806
Teshima W, Nomura Y, Tanaka N, Urabe H, Okazaki M, Nahara Y. ESR study of camphorquinone/amine photoinitiator systems using blue light-emitting diodes. Biomaterials 2003; 24:2097–2103
Anseth KS, Anderson KJ, Bowman CN. Radical concentrations, environments, and reactivities during crosslinking polymerizations. Macromol Chem Phys 1996; 197:833–848
Mizuta Y, Morishita N, Kuwata K. Propagating radicals in photo-initiated polymerization as detected by time-resolved CW-and FT-ESR spectroscopy. Chem Lett 1999:311–312
Selli E, Oliva C, Galbiati M, Bellobono I. EPR investigation of radical formation and decay in photopolymerization of difunctional monomers. J Chem Soc Perkin Trans 1992; 2:1391–1395
Jancar J, Wang W, Benedetto A di. On the heterogeneous structure of thermally cured bis-GMA/TEGDMA resins. J Mater Sci Mater Med 2000; 11:675–682
Leung RL, Fan PL, Jonston WM. Post-irradiation polymerization of visible light-activated composite resin. J Dent Res 1983; 62:363–365
Hansen EK. After polymerization of visible light-activated resins: surface hardness vs light source. Scan J Dent Res 1983; 91:406–410
Watts DC, McNaughton V, Grant AA. The development of surface hardness in visible light-cured posterior composites. J Dent 1986; 14:169–174
Johnson WM, Leung RL, Fan PL. A mathematical model for post-irradiation hardening of photo-activated composite resins. Dent Mater 1985; 1:191–194
Braem M, Lambrechts P, VanHerle G, Davidson CL. Stiffness increase during the setting of dental composite resins. J Dent Res 1987; 66:1713–1716
Odén A, Ruyter IE, Øsaed H. Creep and recovery of composites for use in posterior teeth during static and dynamic compression. Dent Mater 1988; 3:147–150
Oster G, Yang N. Photopolymerisation of vinyl monomers. Chem Rev 1968; 68:125–151
Odian GG. Principles of polymerization. Wiley, New York, 1981
Cook WD. Photopolymerization kinetics of dimethacrylates using the camphorquinone amine initiator system. Polymer 1992; 33:600–609
Burns W, Dainton F. Two factors affecting the use of the rotating sector in photochemical experiments. Trans Faraday Soc 1950; 46:411
Watts DC. Kinetic mechanisms of visible-light-cured resins and resin composites. In: Proc Setting Mechanisms of Dental Materials. Cameron House, Loch Lomond, Scotland, 1992, pp 1–26
Watts DC, Cash AJ. Kinetic measurements of photo-polymerisation contraction in resins and composites. Meas Sci Technol 1991; 2:788–794
Watts DC, Cash AJ. Determination of polymerization kinetics in visible-light cured materials: methods development. Dent Mater 1991; 7:281–287
Andrzejewska E. Photopolymerization kinetics of multifunctional monomers. 2001; 26:605–665
Davidson CL. Conflicting interests with posterior use of composite materials. In: Vanherle G, Smith DC, eds. Posterior composite resin dental restorative materials. Peter Szulc, Amsterdam, 1985, pp 61–65
Davidson CL, de Gee AJ. Relaxation of polymerisation contraction stresses by flow in dental composites. J Dent Res 1984; 63:146–148
Suliman AA, Boyer DR, Lakes RS. Polymerisation shrinkage of composite resins: comparison with tooth deformation. J Pros Dent 1994; 71:7–12
Dauvillier B, Aarnts M, Feilzer A. Developments in shrinkage control of adhesive restoratives. J Esthet Dent 2000; 12:291–299
Feilzer AJ, De Gee AJ, Davidson CL. Curing contraction of composites and glass-ionomer cements. J Pros Dent 1988; 59:297–300
Miyazaki M, Hinoura K, Onose H, Moore BK. Effect of filler content of light-cured composites on bond strength to bovine dentine. J Dent Res 1991; 19:301–303
Culbertson BM, Wan QC, Tong YH. Preparation and evaluation of visible light-cured multi-methacrylates for dental composites. J Macromol Sci Pure Appl Chem A 1997; 34:2405–2421
Davy KW, Kalachandra S, Pandain MS, Braden M. Relationship between composite matrix molecular structure and properties. Biomaterials 1998; 19:2007–2014
Feilzer A, de Gee A, Davidson C. Setting stress in composite resin in relation to configuration of the restoration. J Dent Res 1987; 66:1636–1639
Feilzer AJ, De Gee AJ, Davidson CL. Quantitative determination of stress reduction by flow in composite resin restorations. Dent Mater 1990; 6:167–171
Choi KK, Condon JR, Ferracane JL. The effects of adhesive thickness on polymerisation contraction stress of composite. J Dent Res 2000; 79:812–817
Chen H, Manhart J, Kunzelmann K-H, Hickel R. Polymerization contraction stress in light-cured compomer restorative materials. Dent Mater 2003; 19:597–602
Armstrong S, Keller J, Boyer D. The influence of water storage and C-factor on the dentin-resin composite microtensile bond strength and debond pathway utilizing a filled and unfilled adhesive resin. Dent Mater 2001; 17:268–276
Bouillaguet S, Ciucchi B, Jacoby T, Wataha J, Pashley D. Bonding characteristics to dentin walls of class II cavities, in vitro. Dent Mater 2001; 17:316–321
Loguercio A, Reisa A, Ballester R. Polymerization shrinkage: effects of constraint and filling technique in composite restorations. Dent Mater 2004; 20:236–243
Prati C, Nucci C, Davidson CL, Montanari G. Early marginal leakage and shear bond strength of adhesive restorative systems. Dent Mater 1990; 6:195–200
Retief DH, O’Brien JA, Smith LA, Marchman JL. In vitro investigation and evaluation of dentin bonding agents. Am J Dent 1988; 1:176–183
Bandyopadhyay S. A study of the volumetric setting shrinkage of some dental materials. J Biomed Mater Res 1982; 16:135–144
Venhoven BAM, de Gee AJ, Davidson CL. Polymerization contraction and conversion of light-curing bisGMA-based methacrylate resins. Biomaterials 1993; 14:871–875
de Boer J, Visser R, Melis G. Time-resolved determination of volume shrinkage and refractive index change of volume shrinkage and refractive index change of thin polymer films during photopolymerization. Polymer 1992; 33:1123–1126
Ensaff H, O’Docherty D, Jacobsen P. Polymerization shrinkage of dental composite resins. Proc Inst Mech Engrs 2001; 215:367–375
Shlesinger MF. Williams-Watts dielectric relaxation: a fractal time stochastic process. J Stat Phys 1984; 36:639–648
Williams G, Watts DC. Non-symmetrical dielectric relaxation behaviour arising from a simple empirical decay function. Trans Faraday Soc 1970; 66:80–85
Braga R, Ferracane J. Contraction stress related to degree of conversion and reaction kinetics. J Dent Res 2002; 81:114–118
Loshaek S, Fox T. Cross-linked polymers. I. Factors influencing the efficiency of cross-linking in copolymers of methyl methacylate and glycol dimethacrylate. J Am Chem Soc 1953; 75:3544–3550
Patel MP, Braden M, Davy KWM. Polymerisation shrinkage of methacrylate esters. Biomaterials 1987; 8:53–56
Gilbert J, Hasenwinkel J, Wixson R, Lautenschlager E. A theoretical and experimental analysis of polymerization shrinkage of bone cement: a potential major source of porosity. J Biomed Mater Res 2000; 52:210–218
Rose E, Lal J, Green R. Effects of peroxide, amine and hydroquinone in varying concentrations on the polymerization rate of polymethyl methacrylate slurries. J Am Dent Assoc 1958; 56:375–381
Castille YP. Physical properties of monomers. The polymer handbook, 1st edn. In: Brandrup J, Immergut E, McDowell W, eds. Wiley, New York, 1975, section VIII-16
Silikas N, Al-Kheraif A, Watts DC. Influence of P/L ratio and peroxide/amine concentrations on shrinkage-strain kinetics during setting of PMMA/MMA biomaterial formulations. Biomaterials 2005; 26:197–204
Asmussen E, Peutzfeldt A. Influence of pulse-delay curing on softening of polymer structures. J Dent Res 2001; 80:1570–1573
Watts DC, Marouf AS, El Hejazi A, Al Hindi A, Ibrahim A. Evolution of shrinkage and expansion stresses in dental resin composites. Proc Soc Exper Mech 2001:96–98
Watts DC, Marouf AS, Al Hindi AM. Photo-polymerization shrinkage-stress kinetics in resin-composites at standardized compliance: methods development. Dent Mater 2002; 18
Thompson VP, Williams EF, Bailey WJ. Dental resins with reduced shrinkage during hardening. J Dent Res 1979; 58:1522–1532
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2005 Springer-Verlag Berlin · Heidelberg
About this chapter
Cite this chapter
Watts, D., Silikas, N. (2005). In Situ Photo-Polymerisation and Polymerisation-Shrinkage Phenomena. In: Eliades, G., Watts, D., Eliades, T. (eds) Dental Hard Tissues and Bonding. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-28559-8_6
Download citation
DOI: https://doi.org/10.1007/3-540-28559-8_6
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-23408-1
Online ISBN: 978-3-540-28559-5
eBook Packages: MedicineMedicine (R0)