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Research Article The effects of disinfectant solutions on the viscoelastic properties of acrylic resins

Perihan Oyar, DDS, PhD,a Gulsen Can, DDS, PhDb aDental Prosthetics Technology, School of Health Service, Hacettepe University, Ankara, Turkey bDepartment of Prosthodontics, Faculty of Dentistry, Ankara University, Ankara, Turkey

ARTICLE INFO ABSTRACT

Article history: Objectives: The aim of this paper was to analysis the effects of disinfectant solutions on Received 09 May 2014 polyoxymethylene viscoelastic properties in comparison with polymethyl methacrylate. Accepted 25 June 2014 Materials and Methods: Polymethyl methacrylate and polyoxymethylene acrylic and 200 mL 5% chlorhexidine gluconate, 2% and one Corega Tabs dissolved in 200 mL water at 40°C were used. The storage modulus, loss modulus, Tanδ and glass transition temperatures of the disinfected acrylic resins were observed with the Thermal Dynamic Keywords: Acrylic resins Mechanical Analyzer. Disinfectant solutions Results: Lower storage modulus values were observed in the disinfectant solutions at Dynamic mechanical thermal analysis polymethyl methacrylate specimens. The storage modulus showed lower values than the Viscoelastic properties control group at chlorhexidine gluconate, higher values at sodium hypochlorite in the disinfectant solutions at polyoxymethylene specimens. While the glass transition temperatures of polymethyl methacrylate in the disinfectant solutions showed proximal values, the glass transition temperatures of polyoxymethylene in the chlorhexidine gluconate showed lower temperatures (approximately 11%). Conclusions: The storage modulus, loss modulus, Tanδ values of polyoxymethylene were lower than those of Polymethyl methacrylate. The Corega Tabs did not affect the viscoelastic properties of polyoxymethylene. Chlorhexidine gluconate and sodium hypochlorite did not affect the viscoelastic properties of polymethyl methacrylate.

INTRODUCTION originating from free resin .1 Acetal resin is a polycrystalline structure and an Ethylene-derived acetal resins 2 have recently come into use as alternatives injection-molded resin. Acetal resin has been to metal substructures for removable shown to have good physical and mechanical partial dentures. These resins are a type properties. The material has been also shown of polyoxymethylene (POM) that have a to have good biocompatibility that’s why branchless, linear chain structure formed it was considered as a framework material by the of for removable partial dentures for patients

Corresponding author at: Peihan OYAR, Dental Prosthetics Technology, School of Health Service, Hacettepe University, 06100 Sıhhıye, Ankara, Turkey. Tel.: +90-312-305 15 87/111, Fax.: +90-312-3102730. E-mail: [email protected]

205 Oyar and Can: The effect of disinfectant solutions on acrylic resins with allergic reactions to metal alloys. to cause undesirable changes in the These properties make it an appropriate physical properties of the acrylic base.17-19 material for removable partial dentures, Depending on the type and length of complete dentures, provisional bridges, contact, disinfection agents may cause occlusal splints, orthodontic and sleep structural changes in the inner matrix apnea appliances.3-6 Prolonged use requires of the .20,21 Chau et al.22 reported that these materials exhibit chemical and that 1% sodium hypochlorite eliminated mechanical resistance in their surrounding microorganisms from the denture, and environments over time. Numerous factors another study found immersion in affect the mechanical properties of resins, 1% sodium hypochlorite, 4% chlorhexidine including polymer molecular weight; ratio gluconate, or 3.78% sodium perborate for of residual monomers, and 10 minutes produced no change in the cross-linking agents; internal porosity of transverse strength of heat-polymerized the polymer matrix; material thickness; polymethyl methacrylate. Similarly, finishing techniques; contact with chemical Angelillo et al.23 stated that glutaraldehyde- agents; and patient-related factors. Resin based disinfectants provided effective properties may also be affected by loss of disinfection without causing degradation soluble components or water sorption, in and rubber materials. Ayaz tension and temperature changes related et al.24 al stated that the effervescent to hot and cold food intake during clinical denture cleaners (sodium perborate, use.7-10 sodium bicarbonate) may be degradation in polymer structure of acrylic resins and The porous structure of change color of acrylic resin teeth. as well as the presence of any surface scratches or pits allow microorganisms In contrast, other studies have reported to easily attach themselves to an acrylic- changes in the flexural strength of resin resin denture. Thus, in addition to long- immersed in sodium hypochlorite and, term contact with oral tissue, saliva, with heat application, alkaline peroxide.17,25 blood and water in the oral environment, Shenet et al.20 reported softening of resin an acrylic-resin denture also requires surfaces exposed to glutaraldehyde alkaline immersion in a cleaning solution for long disinfection with phenolic buffer for periods of time. Disinfection is necessary 2 hours, with the affect increasing with in order to minimize cross-contamination further exposure, and Peracini et al.18 found between the patient, dental personnel that Corega Tabs caused a considerable and the denture.11-13 McCabe et al.14 reduction in the flexural strength of acrylic stress the need for proper disinfection resin as well as a color change. of all prostheses. This may be achieved DMA is a method used to analyze the using various chemicals, including viscoelastic properties of polymeric materials glutaraldehyde, chlorhexidine gluconate, through the application and measurement alkaline peroxides, alkaline hypochlorites, of controlled sinusoidal stress.26-29 The null diluted and enzymes.15 In addition, hypothesis was that different disinfectant Gronitskey et al.16 have suggested that solutions would affect the viscoelastic sodium perborate products (Corega Tabs) properties of POM and polymethyl may have an antimicrobial effect. methacrylate acrylic resin (PMMA). In order The disinfection process is expected to better understand the effects of hygienic to have no negative effect on denture procedures on the viscoelastic properties of materials; however, a number of studies acrylic resin prosthetics, this study analyzed have reported some disinfectant solutions and compared the effects of 3 different

206 Oyar and Can: The effect of disinfectant solutions on acrylic resins

disinfectant solutions on the viscoelastic N2 atmosphere and temperatures ranging properties of POM and PMMA acrylic resin from -60 to +250°C with heating rate of using DMA. 10°C/min. (POM specimens could not be observed above +160°C because of the melting point of the material). MATERIALS AND METHODS DMA measurements are sensitive Two different types of acrylic resin to micro-level structural changes and [PMMA(QC-20 resin; De trey, Dentsplay, are capable of thoroughly analysing the England) and POM (Dental D;Quatrotti, viscoelastic behaviour of with RovelloPoro, Italy)] and 3 different types of relatively few samples. Because of the disinfectants [5% chlorhexidine gluconate small number of samples in the present (Dental D, Quatrotti, RovelloPoro, Italy); study, a detailed statistical analysis was not 2% sodium hypochlorite (Miyako do Brazil performed. Similar recent studies of the Id e Com; Guarrulhos, Brazil); CoregaTabs viscoelastic properties of dental materials (Stafford Miller; Dungarvan Co, Waterford, have also been conducted without Ireland)] were used in this study. performing statistical analysis.30-34 Acrylic specimens (20 mm × 10 mm × 4 mm) were prepared according to the RESULTS manufacturers’ instructions and divided into the following groups: E’ values are shown in Figure 1-3. Among Aa (n=1) : PMMA/chlorhexidine gluconate PMMA specimens, E’ values of specimens Ab (n=1) : PMMA/sodium hypochlorite immersed in chlorhexidine gluconate (Aa) Ac (n=1) : PMMA/Corega Tabs (Fig. 1) were similar to those of the control Ba (n=1) : POM/chlorhexidine gluconate group (Ad), whereas E’ values of specimens Bb (n=1) : POM/sodium hypochlorite immersed in sodium hypochlorite (Ab) Bc (n=1) : POM/Corega Tabs (Fig. 2) and in Corega Tabs (Ac) (Fig. 3) were Ad (n=1) : PMMA/200 mL distilled water lower than those of the control group. Among (control) POM specimens, E’ values of specimens Bd (n=1) : POM/200 mL distilled water immersed in chlorhexidine gluconate (Ba) (control) (Fig. 1) were lower than those of the control group (Bd), whereas E’ values of specimens Disinfectants were dissolved in 200 mL immersed in sodium hypochlorite (Bb) distilled water at 40°C and thermocycled (Fig. 2) were higher than those of the control (MSCT-3 plus; Marcelo Nucci-ME, Sao group and E’ values of specimens immersed Carlos, Brazil) at 5°-55°C with a 60-second in Corega Tabs (Bc)(Fig. 3) were similar to dwell time. Each specimen was immersed those of the control group.z for 10 minutes in one of the solutions, removed and rinsed for 2 minutes in E’’ values are shown in Figure 4-6. distilled water. This procedure was repeated Instances of decreases in E’ values appear 30 times (to simulate approximately as peaks in E’’ values, with the first peak (β) 6 months of denture usage). in E’’ values observed between +5° to +24°C and the second peak (α) between 120° to A Thermal Dynamic Mechanical 125°C for PMMA, whereas POM peaks Analyzer (Perkin Elmer Pyris Diamond were observed between –10° to –20°C (β) DMA; Model 983 MA) was used to measure and peak between 115° to 127°C (α). the storage modulus (E’), loss modulus (E’’), Tanδ and glass transition temperatures Tanδ (E’’/E’) values are shown in (Tg) of disinfected acrylic resin samples at Figure 7-9. PMMA Tanδ values peaked at

207 Oyar and Can: The effect of disinfectant solutions on acrylic resins approximately 120°C, whereas no marked and periodic stresses on a daily basis. peak was observed for POM. PMMA Tanδ Depending upon its duration, stress can values were similar for all disinfectant produce a temperature change in the resin, solutions and were lower than those of and as the temperature increases, the the control group. PMMA Tg temperatures polymers may be transformed into a viscous were similar for all disinfectant solutions. structure. If the cross-linking occurring as a result of polymerization is incomplete, However, POM Tg temperatures were the release of side groups of polymer chains lower for chlorhexidine gluconate than for may be observed in the DMA spectrum.27 the other disinfectant solutions (Table I). The E’ value determines its rigidity and depends upon its ability to store mechanical energy, while the E’’ value is DISCUSSION associated with the energy absorbed during dynamic deformation. Tanδ, that is, the As a result of eating and drinking, acrylic resins are exposed to temperature change

Figure 4. E’’ values of disinfectant solutions Figure 1. E’ values of disinfectant solutions for chlorhexidine gluconate. for chlorhexidine gluconate.

Figure 2. E’ values of disinfectant solutions Figure 5. E’’ values of disinfectant for sodium hypochlorite. solutions for sodium hypochlorite.

Figure 3. E’ values of disinfectant solutions Figure 6. E’’ values of disinfectant for Corega Tabs. solutions for Corega Tabs.

208 Oyar and Can: The effect of disinfectant solutions on acrylic resins

Table 1. Glass transition temperatures (Tg) observed in the DMA spectrums. Polymer groups Aa Ab Ac Ad Ba Bb Bc Bd

Tg (°C) 120.78 121.52 121.27 125.46 114.98 124.85 122.99 127.05

and inelastic components to the overall behaviour of the material.29 A high tanδ indicates high molecular mobility, while a low tanδ indicates less mobility in the material. As temperature increases, the tanδ value and molecular mobility increases and the material approaches the rubbery.35 Tanδ corresponds to Tg, a Figure 7. Tanδ values of disinfectant physical transformation in which a viscous solutions for chlorhexidine gluconate. or elastic material becomes a fragile glass. The midpoint of this transformation (the glass transition temperature) determines the temperature interval within which the material is suitable for use, with significant chain movements within the acrylic resin still occurring at the upper threshold of this interval. The Tg value of a polymer provides an indication of its cross-linking .26 and depends mainly upon the flexibility of the main chain. Other factors Figure 8. Tanδ values of disinfectant affecting Tg include the affinity between solutions for sodium hypochlorite. molecules, the addition of plasticizers or monomers with a different Tg, molecular weight, the amount of residual and the density of polymerization. Moreover, any absorbed water acts like a , affecting the affinities between the molecules, thereby lowering the Tg value and thus affecting the mechanical properties of the polymer.33,34 Orsiet et al.8 state that heating of the polymer Figure 9. Tanδ values of disinfectant resin that occurs during the polishing solutions for Corega Tabs. process creates a surface film that reduces water sorption, with residual monomers ratio between E’’/E’, and the temperature remaining within the internal porosities of at which polymer chains acquire the ability the resin matrix. This residual monomer to move freely within a polymetric mass, act as a plasticizer, adversely affecting the represents the temperature at which the resin’s mechanical properties and making resin is transformed from a fragile glass it highly susceptible to deformation with limited mobility to a totally fluid when subjected to stress.7,9 Hamanaka system.32 Tanδ also provides an indication et al36 investigated the influence of water of the relative contribution of the elastic sorption on certain mechanical properties

209 Oyar and Can: The effect of disinfectant solutions on acrylic resins of injection-molded thermoplastic denture According to Ruyter et al.38 long distances base resins. They reported that the water between methacrylate groups contribute sorption significantly decreased the to more complete polymerization because flexural strength and elastic modulus. of the high reactivity of the secondary methacrylate groups, which can be expected The main peaks in E’’ and the tan δ curves to contribute to a high degree of conversion show α relaxation in the main polymer and thus an increase in Tg. A decrease in chain. The peaks in the E’’ curve at low the storage modulus value is an indication temperatures indicate γ and β relaxation of an increase in flexibility.39 While PMMA within the side groups and/or chain E’ and E’’ values showed no changes in 5% segments.28 A relatively low tanδ value chlorhexidine gluconate, when PMMA was indicates low molecular mobility and high immersed in sodium hypochlorite and a elasticity, whereas higher tanδ values Corega Tabs solution, both these values indicates greater molecular mobility as well decreased, indicating a slight increase in as viscosity.37 In this study, the lower tanδ resin flexibility. Previous studies have values (approximately 9 times in +70 to shown 1% sodium hypochlorite and 4% +160°C) observed for POM in comparison chlorhexidine gluconate to have no negative to PMMA. Thus, this study indicates POM effects on the flexural strength or hardness to be an acrylic with greater elasticity. of acrylic resin,7,11 whereas CoregaTabs PMMA specimens immersed in have been found to significantly reduce the 5% chlorhexidine gluconate, 2% sodium flexural strength of acrylic resin.18 Asad hypochlorite and Corega Tabs exhibited et al.,17 however, found that immersion in similar Tg values, all of which were lower 0.5% chlorhexidine gluconate for seven days (approximately 3%) when compared to did not result in any significant changes in the control group. These similar Tg values the flexural strength of acryclic resins, but indicate that crosslinking of the material did lead to changes in surface hardness, inhibits the mobility of side groups, so that whereas the flexural strength of non-cross- only the main chain exhibits movement linked homopolymer resin specimens was in response to an increase in temperature. significantly affected by immersion in Moreover, the β transitions observed in alcohol-based disinfectants when compared the spectrums indicate a free release in to distilled water. molecules from the polymer chains, whereas Peutzfeldt et al.40 observed changes in α transitions are indications of cross linking acrylic surfaces as a result of contact with in the material and mobility in the main chlorhexidine digluconate and sodium chain but no release of molecules.37 The use hypochlorite, but not sodium perborate. of 5% Chlorhexidine gluconate led to lower The present study reported no changes Tg (approximately 11%) in the POM. The use in POM E’ or E’’ values with Corega Tabs, of 2% sodium hypochlorite and Corega Tabs but found that POM E’ values decreased led to lower Tg (approximately 3-4%) in the with chlorhexidine gluconate, indicating POM. an increase in flexibility, and that both Cross-linked polymers have lower E’ and E’’ values increased with sodium flexibility and higher Tg values than hypochlorite, indicating an increase in non-cross-linked polymer resins.33 The rigidity. Neppelenbroke et al.15 stated that differences found between PMMA and POM 4% chlorhexidine gluconate, 1% sodium Tg values may be due to the fact that PMMA hypochlorite and 3.78% sodium perborate has a cross-linked structure, whereas POM all led to significant decreases in the is comprised of linear, branchless chains. hardness of acrylic resin; however, this

210 Oyar and Can: The effect of disinfectant solutions on acrylic resins effect was reversed following immersion in 5% chlorhexidine gluconate. water for 15 days. The present study found slight Pisani et al. investigated effect of differences in PMMA tanδ values observed cleaner solutions for denture cleaning on among disinfectant solutions. These the properties of acrylic resin teeth. They differences may be due to variations in the found that 1% sodium hypochlorite caused rate at which these solutions impact upon alterations on the hardness, rougness and the resin surface film and thus differences color of acrylic resin teeth.41 Paranhos in amounts of water absorption. et al. reported that the alkaline peroxide The null hypothesis was accepted and alkaline hypochlorite did not alter because chlorhexidine gluconate and the flexural strength and 1% sodium sodium hypochlorite affected the hypochlorite solution caused increase viscoelastic properties of POM, and Corega in surface rougness of acrylic resin.42 Tabs affected the viscoelastic properties of Campanha et al. evaluated the effect of PMMA. The results of this study indicate long-term disinfection procedures on that neither chlorhexidine gluconate the hardness of acrylic resin denture nor sodium hypochlorite are suitable for teeth. 4% Chlorhexidine gluconate and cleaning POM prosthetics, whereas Corega 1% sodium hypochlorite and microwave Tabs should not be used to clean PMMA sterilization decrease the hardness of prosthetics. the resin teeth.43 Pisani et al. evaluated colour stability, hardness and rougness of The current study is limited in that acrylic soft denture liners after immersion only 2 type of acrylic resin and 3 type of in denture cleaners. They found that 1% disinfectant solutions are investigated. sodium hypochlorite caused on increase in In order to identify the factors leading to roughness.44 Polyzois et al.3 investigated changes in the Tanδ and Tg values of PMMA the effect of peroxide and hypochlorite and POM, future studies should investigate cleansers on gloss, colour and sorption factors such as polymer structure, cross- of acetal denture resins. The immersion link density, water sorption and residual of acetal resin in NaOCl 5.25% showed monomers. clinically unacceptable and higher sorption and should be avoided or should be managed with care. Alaa Al-Haddad et al.45 CONCLUSIONS showned that Chlorhexidine reduced Within the limitations of this study, the fracture toughness of the acrylic base following conclusions were drawn: (PMMA). 1. E’ (approximately 0.5 to 5 times), E’’ In this study, the E’ values of PMMA (approximately 1.5 to 2.5 times) and specimens were higher (approximately 0.5 tanδ (approximately 9 times) values of to 5 times) than those of POM specimens POM are lower than those of PMMA. and PMMA specimen immersed in 5% 2. The use of Corega Tabs, 5% chlorhexidine gluconate had the highest E’ Chlorhexidine gluconate, 2% sodium values (approximately 5 times). Thus, this hypochlorite disinfectant solutions led result indicates that PMMA was more rigid to lower Tg (approximately 3%) in the acrylic than POM. The E’’ values of PMMA PMMA. The use of 5% Chlorhexidine specimens were higher (approximately gluconate led to lower Tg (approximately 1.5 to 2.5 times) than those of POM 11%) in the POM. The use of 2% sodium specimens. The highest E’’ values was hypochlorite and Corega Tabs led to observed in PMMA specimen immersed in lower Tg (approximately 3-4%) in the

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How to cite this article: Perihan Oyar, Gulsen Can. The Effects of disinfectant solutions on the viscoelastic properties of acrylic resins. Cumhuriyet Dent J 2014;17(3):205-214.

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