Water sorption and solubility of resin-based composites

Interaction of resin-based composites with water is a continuous process from the early stages of composite placement. Water plays an important role in the long-term stability of composite fillings and may induce hygroscopic expansion of the material, hydrolytic degradation of intra- and intermolecular bonds within the resin matrix and at the resin-filler interface, plasticization of polymer chains, elution of leachable substances and reduction in mechanical properties.

The importance of composite-water interaction has been acknowledged in the ISO standard 4049 which states the maximum values for water sorption and concurrent solubility for resin-based materials (composites and cements). In order to comply with this ISO standard, resin-based materials must have  water sorption and solubility values equal or lower than 40 micrograms per cubic milimetre (sorption) and 7.5 micrograms per cubic milimetre (solubility) for specimens 15 mm in diameter and 2 mm thick.

Water sorption and solubility values are based on mass changes of the samples before (m1) and after immersion (m2) in water and after dessication (m3) until constant mass is achieved.  Mass changes m2-m3 are divided by sample volume to calculate water sorption and m1-m3 divided by sample volume give solubility values. 

Recent papers* published in Dental Materials investigated water sorption and solubility and hygroscopic dimensional changes of several resin-based composites:

low-shrinkage Filtek Silorane

universal Gradia Kalore

micro-hybrid Gradia Direct Anterior and Posterior and

self-adhering flowable Vertise Flow.

After 150 days of storage in de-ionized water, the lowest sorption of about 13 μg/mm³ was found for Filtek Silorane and the greatest of about 72 μg/mm³ was found for Vertise Flow. Vertise Flow also showed the greatest solubility of about 16 μg/mm³ whereas other materials showed either negative values (Filtek Silorane and Gradia Kalore) or values below 4 μg/mm³. The authors suggested that the negative solubility values for Filtek Silorane and Gradia Kalore meant that the dessication was not sufficient or that some water was irreversibly bound to the resin matrix.

Hygroscopic dimensional expansion as the result of water sorption over the 150-day period was lowest for Filtek Silorane (about 0.7%) and highest for Vertise Flow (about 4.8%) whereas the values for Gradia composites were between 1.5 and 2%. Hygroscopic expansion may compensate to a certain extent polymerization shrinkage which was found to be 0.99% for  Filtek Silorane, 1.7-2.4% for Gradia composites and  4.4% for Vertise Flow. However, this expansion occurs over a much slower time scale than shrinkage and its effect on the clinical performance of resin-based composite is yet to be determined.

The greatest stability in the aqueous environment found for Filtek Silorane may be explained by the hydrophobic siloxane and low-shrinkage ring-opening oxirane units of the silorane monomer. Furthermore, cationic polymerization is relatively oxigen-insensitive with the potential of reaching higher degree of conversion than methacrylate-based composites.

On the other hand, aqueous instability of Vertise Flow was attributed to the hydrophilic monomer, GPDM, which is responsible for the self-adhesive property of Vertise Flow but also seems to attract more water uptake by the resin matrix compared to other resin-based composites.


* Wei YJ, Silikas N, Zhang ZT, Watts DC. Hygroscopic dimensional changes of self-adhering and new resin-matrix composites during water sorption/desorption cycles. Dent Mater. 2011 Mar;27(3):259-66.

Wei YJ, Silikas N, Zhang ZT, Watts DC. Diffusion and concurrent solubility of self-adhering and new resin-matrix composites during water sorption/desorption cycles.Dent Mater. 2011 Feb;27(2):197-205.

[Reprints of the cited papers may be obtained from the corresponding authors]

Click here for more on Vertise Flow.
 

Silorane technology in restorative dentistry - material properties and clinical application

I recently published a review article in the Serbian professional journal "Stomatolog" ["Dentist"] on Filtek Silorane material properties and clinical application steps. The article is in Serbian but I would be happy to translate it to English for interested colleagues. Contact me at vesna.miletic@gmail.com

Abstract

Polymerization shrinkage remains one of the main weaknesses of composite materials. Silorane technology significantly reduces material shrinkage compared to methacrylate composites. This review article compares chemical composition and polymerization process of methacrylate- and silorane-based composites. Systematically are reviewed studies on mechanical, aesthetic, antibacterial and chemical properties of Filtek Silorane, as well as its interaction with tooth tissues. Lower polymerization shrinkage and microbial adherence and comparable mechanical properties have been reported for Filtek Silorane compared to methacrylate-based composites. In the only clinical study that has been published so far, marginal adaptation of Filtek Silorane was found to be inferior than the nanocomposite Ceram.X  However, low inter-examiner reliability questions the results of this clinical study and scientific literature lacks more information on clinical performance of Filtek Silorane. 

Journal of Esthetic and Restorative Dentistry gets its first impact factor

A Miletic et al. study among the top 5 cited papers

In the latest list of SCI Journal Impact Factors 2009 published by Thomson Reuters, Journal of Esthetic and Restorative Dentistry is listed with the impact factor of 0.797. The Journal thanks all authors, reviewers and readers and allows free access to the top cited articles. Easy online submissions through ScholarOne Manuscripts are encouraged as this speeds up the review process. Hopefully, the Journal will maintain a growing influence in the scientific literature and increase its impact factor in the future.


It was a pleasure to see that one of the papers I did with my colleagues at the University of Belgrade School of Dentistry was among the top 5 cited articles in the Journal of Esthetic and Restorative Dentistry.

Miletic V, Ivanovic V, Dzeletovic B, Lezaja M.
Temperature Changes in Silorane-, Ormocer-, and Dimethacrylate-Based Composites and Pulp Chamber Roof during Light-Curing.

I look forward to submitting the results of my current studies to the Journal of Esthetic and Restorative Dentistry.

Filtek Silorane composite: temperature changes during light-curing

Some time ago, my colleagues and I published a paper on temperature changes during curing of Filtek Silorane, Admira (ormocer) and Herculite XRV (microhybrid, control) composites. It was interesting to notice substantially higher temperature rise in Filtek Silorane compared to the other two materials. However, there was no difference in the temperature rise inside the pulp chamber, probably due to the insulating effect of the remaining dentine.

The abstract of this paper may be found on MEDLINE and I will be happy to email the full text to anyone interested in this subject. Feel free to contact me at vesna.miletic@gmail.com

J Esthet Restor Dent 2009;21(2):122-31.
Temperature changes in silorane-, ormocer-, and dimethacrylate-based composites and pulp chamber roof during light-curing.
Miletic V, Ivanovic V, Dzeletovic B, Lezaja M.

STATEMENT OF THE PROBLEM: Light-curing of resin-based composites (RBCs) is associated with temperature increase in the pulp chamber, which may have a detrimental effect on the vital pulp.
PURPOSE: The purpose of the study was to evaluate temperature changes of silorane-, ormocer-, and dimethacrylate-based RBCs at the bottom surface of the RBC and in the pulp chamber roof dentin (PCRD) during curing.  
MATERIALS AND METHODS: In part A, temperatures were measured for Filtek LS (3M ESPE, St. Paul, MN, USA), Admira (Voco GmbH, Cuxhaven, Germany), and Herculite XRV (Kerr Corp., Orange, CA, USA) with a high-power light-emitting diode (LED) unit by placing thermocouples in contact with the bottom surface of the material in standardized acrylic molds. In part B, temperature changes in PCRD were measured in extracted molars during light-curing of adhesives and RBCs in 2-mm-deep cavities with a remaining dentin thickness (RDT) of 1 mm.
RESULTS: Filtek LS showed a different temperature curve compared with Admira and Herculite XRV. Significantly higher temperatures were recorded for Filtek LS (p < 0.001) than for Admira and Herculite XRV in acrylic molds. Temperature rises recorded in PCRD for adhesives and RBCs were between 4.1 and 6.4 degrees C. No significant differences in PCRD temperatures were found between the three groups during adhesive curing and RBC curing (p > 0.05).  
CONCLUSIONS: Filtek LS showed a different heat-generation pattern from and significantly higher temperatures than Admira and Herculite XRV when the materials were tested in acrylic molds. Similar temperatures were recorded in the PCRD during curing of adhesives and RBCs.
CLINICAL SIGNIFICANCE: Although a substantial temperature rise in the bulk material occurred during light-curing of the three resin-based composites, a remaining dentin thickness of 1 mm caused a significant reduction in pulp chamber roof dentin temperatures. Temperatures measured in the pulp chamber roof dentin corresponding to the zone occupied by the postmitotic odontoblast layer were not statistically different for the three types of resin-based composites.

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Filtek Silorane by 3M ESPE

In 2007, 3M ESPE launched a new resin-based composite, Filtek Silorane (FS), and its adhesive system. Both the composite and the adhesive system contain a unique resin monomer based on the combination of siloxanes and oxiranes so it is apparent where the term "silorane" comes from. The polymerisation of FS differs from methacrylate-based composites and adhesives and is claimed to result in reduced polymerisation shrinkage. The cationic polymerisation of FS occurs via the ring opening of the C-O-C epoxide group which ends up in less reduction in molecule distances compared to the free radical polymerisation of methacrylate-based composites. In the latter, monomer interaction via methacrylate C=C groups results in the greater reduction of inter-molecular distances and subsequently greater polymerisation shrinkage.

Most recent studies have shown reduced shrinkage and shrinkage stress and strain for FS compared to methacrylate-based composites. Microleakage and nanoleakage were also reported for FS. Ongoing studies will reveal other properties of FS that may affect its clinical performance.

The dedicated adhesive system is designed to bridge the gap between hydrophilic dentine and hydrophobic FS composite. It contains the Primer and the Bond in separate bottles which are cured as separate layers, unlike any other two-step self-etch adhesive system, where primer and bond are mixed before curing. In Filtek Silorane adhesive system, these layers are not visible on SEM but can be detected using micro-Raman spectroscopy (Santini & Miletic, 2008) At the BSDR symposium on Dental materials it was reported, that after 6 months of storage, the type of failure for FS changes from the adhesive to cohesive as the fracture occurs within the adhesive system. The intermediate zone between FS Primer and Bond of about 1 micron may be the weak link in the failure mechanism and certainly needs further investigation.

Surface roughness of resin-based composites

The study "Surface characterisation of resin-based composite materials using atomic force microscopy" was successfully presented by Ana Ergic and Dejan Nedeljkovic at the IADR-CED conference in Munich. Click on the image to enlarge the poster. Ana and Dejan are my former students who were involved in this study as part of their student research project. They have recently graduated at the University of Belgrade School of Dentistry.
I'd like to point out that a custom-made device was used in this study to standardise mechanical aging which was performed as a series of brushing cycles using commercial toothbrushes and abrasive toothpaste.

More recent RBCs showed lower surface roughness values before and after aging compared to the control mycrohybrid RBC, Filtek Z250. Surface roughness for N'Durance was found to be similar before and after aging whilst Tetric EvoCeram and Filtek Silorane showed increased roughness after aging.
Keywords: dental materials, resin-based composites, roughness, AFM

BSDR Conference in Glasgow

As previously announced, the BSDR Conference is taking place in Glasgow. The Santini Miletic Research Group presented a study entitled "The ratio of carbon-carbon double bonds in different BisGMA/HEMA mixtures". Click on the image.
Prior to the poster session, I attended the Ceramics session chaired by professor Richard Van Noort. Several very interesting studies were presented regarding CAD-CAM ceramic strength, ceramic reinforcements, fluoride-containing bioactive glasses, leucite glass-ceramic crystallisation, coating materials for zirconia ceramics and wear quantification using profilometry. It was quite impressive to see the very high standard of research carried out at various universities in the UK.

Sponsored by 3M ESPE, the Dental Materials Group Symposium was held during the afternoon session. After the opening remarks by Dr Garry Fleming and Professor R. Van Noort, lectures were given by Dr Rainer Guggenberger (The chemistry of new resin systems), Professor David Watts (The measurement of shrinkage and contraction stress), Professor Tim Watson (The quality of adhesion) and Professor Trevor Burke (Early thoughts of clinical experience using the novel silorane-based composite material). The lectures increased our knowledge on various aspects of resin-based composites and the silorane-based material in particular. The 'non-shrink' resin composites are still not a reality but dental technology has made substantial improvements towards this goal.

Featured article

Degree of conversion of Filtek Silorane Adhesive System and Clearfil SE Bond within the hybrid and adhesive layer: An in situ Raman analysis.

Chiara O. Navarra, Milena Cadenaro, Steven R. Armstrong, Julie Jessop, Francesca Antoniolli, Valter Sergo, Roberto Di Lenarda and Lorenzo Breschi

Dental Materials 2009:25(9):1178-1185

Abstract

Objectives: To examine the degree of conversion (DC) of the adhesive interfaces created by Filtek Silorane Adhesive and Clearfil SE Bond using micro-Raman spectroscopy.

Methods: The adhesives were applied on human dentin in accordance with manufacturer's instructions. Specimens were cut to expose the bonded interfaces to the micro-Raman beam (Ranishaw InVia; laser wl 785 nm). Raman spectra were collected along the dentin/self-etching primer/adhesive interface at 1 μm intervals. The relative intensities of bands associated with mineral (P–O functional group at 960 cm−1) and adhesive (C–C–O group at 605 cm−1) components within the bonded interface were used to detect monomer penetration into the dentin matrix and to calculate the degree of conversion (Cdouble bond; length as m-dashC at 1640 cm−1 as reaction peak, C–C–O at 605 cm−1 as reference peak). Data were statistically analyzed with two-way ANOVA.

Results: DC of Filtek Silorane Adhesive was 69 ± 7% in the adhesive layer, increasing (p<.05) to 93 ± 5% in the primer and 92 ± 9% in the hybrid layer. Clearfil SE Bond showed a DC of 83 ± 3% in the hybrid and 85 ± 3% in the adhesive layer. Thus, Filtek Silorane Adhesive showed a higher DC than Clearfil SE Bond in the hybrid layer (p<.05), but a lower DC in the adhesive (p<.05).

Significance: As high DC is a fundamental pre-requisite for the stability of the bond over time, this study supports the hypothesis that optimal stability of Filtek Silorane Adhesive can be obtained. However, further research is needed to investigate the mechanical properties of the hybrid layer created by Filtek Silorane Adhesive and its long-term stability.