The influence of system compliance and sample geometry on composite polymerization shrinkage stress

The objective of this study was to use finite-element analysis to model tensilometer tests of polymerizing dental composites. A typical sample in polymerization shrinkage stress tests is shaped like a flat disk, that is, has a high aspect ratio (ratio of diameter to height). In the experimental literature it is implied that the induced stress state in the flat disk composite samples is uniaxial. Three published tensilometer tests of curing dental composite samples with similar high aspect ratios (varying from 3 to 5) were modeled, but with test configurations having low, intermediate and high relative compliance (a tenfold variation). With the use of linear elastic finite element analysis, an instantaneous volumetric shrinkage of 1% was applied to the composite via the thermal analogy and the following questions were addressed: 1. Does the numerically predicted state of stress in composite samples tested in this fashion differ substantially from the uniaxial stress state assumed in the experiments?2. How do the numerically predicted stresses compare with the experimentally determined nominal stresses?3. Does compliance of the mountings influence the numerically predicted stress state? The finite-element results predicted a complex triaxial stress state that was strongly influenced by the compliance of the mountings. For the low and intermediate system compliance the model overpredicted the polymerization contraction stress, as would be anticipated due to the inability of the model to account for viscoplastic flow. For high system compliance, the numerical and experimental stress values were in better agreement, mainly because the linear elastic mountings accounted for most of the measured system compliance.     

A mechanism on why slower polymerization of a dental composite produces lower contraction stress

It has been well documented that the rate of polymerization of a dental composite often affects its polymerization contraction stress. In most cases, a slower cure produces a lower stress. To investigate the mechanism behind this, we prepared an unfilled dimethacrylate resin sample and photocured it using two light irradiances, both with the same total irradiation energy. We measured the polymerization-induced shrinkage from the unbonded surface of a class I restoration, contraction stress, extent of polymerization, and flexural modulus. The resin specimens cured under the two irradiances achieved the same extent of polymerization and developed an identical amount of shrinkage from the unbonded surface. But those cured under the lower irradiance possessed a lower contraction stress and a lower flexural modulus than those cured under the higher irradiance. We demonstrated that the stress level did not respond to the extent of viscous flow of the curing resin because the slower polymerization did not produce more shrinkage from the unbonded surface. Instead, the lower stress is likely due to a lower modulus of the cured resin. To explain why the cured resin with an identical extent of polymerization can have different moduli, we proposed that slower polymerization produces a higher level of structural inhomogeneity, which reduces the rigidity of the cured resin.     

Photopolymerization and shrinkage kinetics of in situ crosslinkable N-vinyl-pyrrolidone/poly(epsilon-caprolactone fumarate) networks

Biodegradable, injectable and in situ photocrosslinkable macromers based on fumaric acid and polycaprolactone (PCLF) were prepared and characterized by FTIR, 1HNMR, and 13CNMR spectroscopy. The multifunctional macromers dissolved in N-vinyl pyrollidone (NVP) were photopolymerized by visible light irradiation in the presence of camphorquinone as photoinitiator. The photocrosslinking reaction was monitored by measuring shrinkage strain and shrinkage strain rate. The degree of photopolymerization reaction i.e. degree of conversion (DC%) was traced using FTIR spectroscopy. A three level factorial design was developed to study the effects of initiator concentration, NVP concentration, and molecular weight of PCLF upon photocrosslinking characteristics including degree of conversion and shrinkage strain. Results revealed that although neat PCLF was photopolymerized, but it was putty like after 220 seconds of irradiation and showed a very low degree of conversion (29%). Adding about 20% NVP caused a dramatic increase in its degree of conversion (63.33%). Increasing NVP up to 50% resulted in a decrease in DC% because of lower reactivity of NVP and leaving more unreacted NVP monomers. Sol fraction studies supported these results indicating that at higher NVP concentration, most of NVP and PCLF have not undergone the crosslinking reaction, leading to 55% decrease in DC%. Shrinkage strain measurement also confirmed the FTIR results.     

Polymerization shrinkage of methacrylate esters

The polymerization shrinkage of a range of poly(n-alkyl methacrylates) in the range C1 to C16, some of their isomers and the polymers of cyclic and heterocyclic methacrylates have been measured using densitometry. The percentage volume shrinkage decreases with the size of the substituent side group. This proved to reflect the fact that the change in molar volume on polymerizing a methacrylate ester is reasonably constant at 22 cc/mol irrespective of the geometry of the substituent group. However, the glass transition temperature of the polymer depends very critically on the geometry of the side group. Hence one method for the development of low shrinkage glassy polymers is to investigate methacrylate esters of large molar volume, but with side group geometry that results in a high glass transition temperature. Polymerization shrinkage can be used to determine the degree of conversion of a polymer, using the value of 22 cc/mol as the change in molar volume.     

A theoretical and experimental analysis of polymerization shrinkage of bone cement: A potential major source of porosity

A theoretical basis for understanding polymerization shrinkage of bone cement is presented based on density changes in converting monomer to polymer. Also, an experimental method, based on dilatometry and the Archimedes' principle is presented for highly precise and accurate measurement of unconstrained volumetric shrinkage of bone cement. Furthermore, a theoretical and experimental analysis of polymerization shrinkage in a constrained deformational state is presented to demonstrate that porosity can develop due to shrinkage. Six bone-cement conditions (Simplex-Ptrade mark vacuum and hand mixed, Endurancetrade mark vacuum mixed, and three two-solution experimental bone cements with higher initial monomer levels) were tested for volumetric shrinkage. It was found that shrinkage varied statistically (p< or = 0.05) from 5.1% (hand-mixed Simplex-Ptrade mark) to 6.7% (vacuum-mixed Simplex-Ptrade mark) to 10.5% for a 0.6:1 (polymer g/monomer mL) two-solution bone cement. Shrinkage was highly correlated with initial monomer content (R(2) = 0.912) but with a lower than theoretically expected rate. This discrepancy was due to the presence of residual monomer after polymerization. Using previously determined residual monomer levels, the theoretic shrinkage analysis was shown to be predictive of the shrinkage results with some residual monomer left after polymerization. Polymerization of a two-solution bone cement in a constrained state resulted in pores developing with volumes predicted by the theory that they are the result of shrinkage. The results of this study show that shrinkage of bone cement under certain constrained conditions may result in the development of porosity at the implant-bone cement interface and elsewhere in the polymerizing cement mantle.     

The effect of curing modes on polymerization contraction stress of a dual cured composite

Although a lower curing rate is often cited as the reason why a chemical cured (CC) dental composite produces lower polymerization contraction stress (PCS) than a light cured (LC) composite, the exact mechanism is still unclear. In addition, the comparison is often made by using different brands of composites. The comparison's fairness is questionable because the two composites have different compositions and preparation procedures. The goal of the present work was to determine if the curing mode alone can produce different PCS. We formulated a dual cured composite and prepared it the same way for both CC and LC modes. We measured PCS by a strain gauge method, shrinkage by a video-imagining technique, degree of conversion (DC) by infrared spectroscopy, and flexural modulus by the three-point bending test. The CC specimens showed lower PCS and lower flexural modulus than the LC specimens, although both possessed an identical chemical composition and physical texture before cure. This finding indicates that the curing mode alone can affect PCS. Because the CC and LC specimens produced a similar shrinkage and DC, the lower modulus is considered to be one of the reasons for the lower stress. Using a structural inhomogeneity model, we explained how a resin composite with an identical DC can have different physical properties such as the modulus.     

Concentration‐dependent specimen shrinkage in iodine‐enhanced microCT

Iodine potassium iodide (I₂KI) solution can be employed as a contrast agent for the visualisation of soft tissue structures in micro‐computed tomography studies. This technique provides high resolution images of soft tissue non‐destructively but initial studies suggest that the stain can cause substantial specimen shrinkage. The degree of specimen shrinkage, and potential deformation, is an important consideration when using the data for morphological studies. Here we quantify the macroscopic volume changes in mouse skeletal muscle, cardiac muscle and cerebellum as a result of immersion in the common fixatives 10% phosphate‐buffered formal saline, 70% ethanol and 3% glutaraldehyde, compared with I₂KI staining solution at concentrations of 2, 6, 10 and 20%. Immersion in the I₂KI solution resulted in dramatic changes of tissue volume, which were far larger than the shrinkage from formalin fixation alone. The degree of macroscopic change was most dependent upon the I₂KI concentration, with severe shrinkage of 70% seen in solutions of 20% I₂KI after 14 days' incubation. When using this technique care needs to be taken to use the lowest concentration that will give adequate contrast to minimise artefacts due to shrinkage.     

Measurement of composite shrinkage using a fibre optic Bragg grating sensor

Fibre Bragg grating is used to determine resin-based composite shrinkage. Two composite resins (Freedom from SDI and Z100 from 3M) were tested to determine the polymerization contraction behaviour. Each sample of resin was prepared with an embedded fibre Bragg grating. A LED activation unit with wavelength from 430 nm to 470 nm (Dabi Atlante) was used for resin polymerization. The wavelength position of the peak in the optical reflection spectra of the sensor was measured. The wavelength shift was related to the shrinkage deformation of the samples. Temperature and strain evolution during the curing phase of the material was monitored. The shrinkage in the longitudinal direction was 0.15 +/- 0.02% for resin Z100 (3M) and 0.06+/-0.01% for Freedom (SDI); two-thirds of shrinkage occurred after the first 50 s of illumination.     

Preparation of low shrinkage stress Bis-GMA free dental resin composites with a synthesized urethane dimethacrylate monomer

A new urethane dimethacrylate TMA was synthesized through a typical urethane reaction. TMA was used to replace 1,6-bis(methacryloxy-2-ethoxycarbonyl- amino)-2,4,4- trimethylhexane (UDMA) in UDMA based composite partially or totally to prepare TMA containing composites. Critical properties of TMA containing composites were investigated. 2,2-bis[4(2-hydroxy-3-methacryloy- propyloy)phenyl]propane (Bis-GMA) based and UDMA based composites were used as references. FT-IR and ¹H-NMR confirmed the structure of TMA. All of experimental dental resin composites had the similar double bond conversion (p?>?0.05). With a certain amount of TMA, TMA containing composites could have lower volumetric shrinkage (p?<?0.05) and shrinkage stress (p?<?0.05) than control groups. Water sorption, solubility, flexural strength and modulus of TMA containing composites were not worse than those of control groups. All of TMA containing composites and UDMA based composite had the same fracture toughness (p?>?0.05), which was higher than that of Bis-GMA based composite (p?<?0.05). TMA has potential as Bis-GMA substitute to prepare Bis-GMA free dental resin composites with low shrinkage stress.     

Development of highly reactive mono-(meth)acrylates as reactive diluents for dimethacrylate-based dental resin systems

Reactive diluents such as triethyleneglycol-dimethacrylate (TEGDMA) have been widely used with bisphenol-A-glycidyl-dimethacrylate (Bis-GMA) to achieve restorative resins with appropriate viscosity and higher conversion. However, additional water sorption and polymerization shrinkage were also introduced. The aim of this work is to investigate whether the cure and material properties can be improved in dental resins containing novel mono-(meth)acrylates as reactive diluents so that these Bis-GMA-based copolymers have reduced polymerization shrinkage but higher overall double bond conversion. Several ultra-high-reactivity mono-(meth)acrylates that contain secondary functionalities have been synthesized and investigated. The polymerization rate and double bond conversion were monitored using photo-FTIR. Polymerization shrinkage, dynamic mechanical analysis, and flexural strength were characterized. Compared with the Bis-GMA/TEGDMA control, the Bis-GMA/mono-methacrylate systems studied showed higher final conversions, faster curing rates, and decreased polymerization shrinkage. Our optimum system Bis-GMA/morpholine carbamate methacrylate achieved 86% final conversion (vs. 65%), a polymerization rate 3.5 times faster, and a 30% reduction in polymerization volumetric shrinkage. These results indicate that certain highly reactive, novel mono-(meth)acrylates possess very promising potential to replace TEGDMA as reactive diluents and can readily be applied to develop superior dental resins.     

Nondestructive quantification of leakage at the tooth–composite interface and its correlation with material performance parameters

Current methods to determine debonding/leakage at the tooth–composite interface are qualitative or semi-quantitative. Our previous work introduced a 3D imaging technique to determine and visualize leakage and its distribution at the interface of cavity wall and composite restoration in model cavities. In this study, an automated program was developed to quantify leakage in terms of area and volume. 3D leakage distribution obtained via the image analysis program was shown to have excellent agreement with leakage visualized by dye penetration. The relationship between leakage and various material performance parameters including processability, shrinkage, stress, and shrinkage strain-rate was determined using a series of experimental composites containing different filler contents. Results indicate that the magnitude of leakage correlated well with polymerization stress, confirming the validity of the common approach utilizing polymerization stress to predict bonding durability. 3D imaging and image analysis provide insight to help understand the relations between leakage and material properties.     

Contraction behaviors of dental composite restorations--finite element investigation with DIC validation

The objective of this study was to examine the effects of cavity configuration on the polymerization shrinkage and stress of light-cured composite restorations by combining local strain measurement and a finite element analysis (FEA). Dental mesio-occluso-distal cavities of various widths and depths (each for 2 vs. 4 mm), representing different configuration factors, were prepared on extracted molars. The displacements of the bonded tooth cusps and cavity floors, caused by polymerization shrinkage of composite restorations, were assessed utilizing a digital-image-correlation (DIC) technique. The cervical marginal microleakage was investigated by examining the resin replicas of these restorations under SEM. The local material properties of the polymerized composite along the curing depth were defined by the nanoindentation test and applied in the subsequent FEA. In the FEA, four models were generated to correspond with the experimental restorations. In the DIC measurement results, the 4(w)×4(D) mm cavity presented the greatest values of inward displacements at the cusp and floor. The cavity depth, rather than the cavity width, was found to significantly correlate to the floor deformation, the location of shrinkage centers, and also the cervical microleakage ratio. The FEA simulation results showed that the 2(w)×4(D) mm cavity presented the maximal von Mises and principal stress located respectively on the cervical margins and cavity floor. Additional safety factor analysis showed a high risk of bond failure over the cavity floor in the 4-mm deep cavity. With the experimental validation, the simulation revealed that the cavity depth was significant to the formation of contraction stress and the incidence of interfacial debonding.     

Über die anionische copolymerisation der methacrylate, 2. Polymerisation des 2-methoxyäthylmethacrylats

The anionic polymerization of 2-methoxyethyl methacrylate initiated with lithium tert-butoxide in a nonpolar hydrocarbon medium was investigated. The polymerization conversion curve of an unusual shape consists of two growth regions separated by a plateau on the conversion curve. Changes in the course of the polymerization are accompanied by pronounced changes in the microstructure of the forming polymer which from predominantly isotactic in the first growth stage turns to syndiotactic during the plateau on the conversion curve and the second growth stage. The polymerization rate in the first stage is several times higher than in the second stage. The absolute magnitude of both polymerization rates and the length of the plateau on the conversion curve are functions of the concentration conditions. Both the weight and number average molecular weight in the first stage increase proportionally to conversion. During the plateau on the conversion curve there is a decrease in the molecular weight, whereas in the second stage of the polymerization course the molecular weight increases again with increasing conversion. Similar changes can also be observed in the investigation ofthe intrinsic viscosities of the polymers. These findings, along with the increase in polymer polydispersity in the second growth stage, led to the conclusion that each growth stage of the polymerization is controlled by a separate type of active centres differing both kinetically and by their stereospecific capacity. The anomalies described in the paper, however were not observed with sodium terr-butoxide as initiator.     

On the kinetics of emulsion copolymerization of methyl methacrylate and ethyl acrylate in the presence of hydrocarbons

The emulsion copolymerization of methyl methacrylate with ethyl acrylate initiated by ammonium peroxodisulfate in the presence of a blend of anionic and non-ionic emulsifiers was investigated at 60°C. The polymerization under batch conditions was conducted to both low and high conversion. The kinetics of the emulsion copolymerization was studied in both the absence and the presence of diluents such as toluene and octane. Unexpectedly both diluents strongly reduced the rate of copolymerization. This reduction increased with increasing diluent concentration. The rate of polymerization was found to increase with increasing conversion up to high conversion. The average particle size increased very slightly with increasing concentration of the diluent. The average number of radicals per particle was found to increase with increasing conversion and to decrease with increasing diluent concentration. The decrease of the radical concentration with diluent concentration was attributed to the desorption of monomer radicals from a polymer particle and to the increase of the termination rate. It is proposed that the hydrophilicity of the monomeric radicals is the driving power of the desorption process.     

使用二维小波收缩法去除弹性成像蠕虫噪声

本文研究使用二维小波收缩去噪法去除弹性成像过程中产生的蠕虫噪声。先使用Sym8小波函数对含有蠕虫噪声的应变估计值矩阵进行3级二维离散小波分解,并使用Birg-éMassart算法获取二维小波变换的域值;然后分别使用硬域值函数和软域值函数对各尺度的水平方向、垂直方向、对角方向的高频系数进行量化;最后将第3层低频系数和各层被量化后的高频系数进行二维小波重构产生去噪后的弹性图像。仿真结果显示,提出的技术有效去除了弹性成像的蠕虫噪声,增强了弹性图像的信噪比(SNRe)和对比度噪声比(CNRe),提高了弹性图像与理想弹性图的相关系数(е);与二维低通滤波去噪法相比,使用二维小波收缩法产生的弹性图像有更高的SNRe和CNRe,能更清晰地显示硬物边界。同时,仿真结果也表明该技术对不同应变量的弹性图像的蠕虫噪声均能有效抑制。本研究表明二维小波收缩去噪法能有效去除弹性图像的蠕虫噪声并提高弹性图像性能。     

Synergistic actions of pemphigus vulgaris IgG, Fas-ligand and tumor necrosis factor-alpha during induction of basal cell shrinkage and acantholysis

This study tested a recently proposed "Basal Cell Shrinkage" hypothesis of pemphigus acantholysis through a quantitative analysis of individual and cooperative effects of pemphigus vulgaris (PV) IgG, Fas-ligand (Fas-L) and tumor necrosis factor-alpha (TNFalpha) on keratinocyte (KC) volume (i.e. cell size) and adhesive properties. Exposure of KC monolayers and MatTek EpiDermFT tissues cultures to the physiologic concentrations of Fas-L, TNFalpha or IgGs from two PV patients resulted in various degrees of reversible changes, which were not observed in control cultures either exposed to normal IgG or left intact. Within 12-24 h of exposure, basal cells in experimental cultures lost their ability to form stress fibers, retracted cytoplasmic aprons and formed keratin aggregates, indicating that their cytoskeleton collapsed. The cell volume decreased significantly (p < 0.05) as the polygonal cell shape changed to a round one. The shrunk cells detached from their neighbors and the substrate, resulting in a reciprocal increase of both the areas of acantholysis and the number of detached KCs, respectively. Since in the skin of PV patients, KCs are targeted by autoantibodies concomitantly with being exposed to autocrine and paracrine pro-apoptotic and pro-inflammatory cytokines, we combined PV IgG with Fas-L and/or TNFalpha in the cell culture experiments. This amplified several fold an ability of PV IgG to cause basal cell shrinkage and detachment. The obtained results demonstrated for the first time that PV IgG works together with Fas-L and TNFalpha to induce acantholysis via basal cell shrinkage, which provides a novel mechanism explaining successful treatment of PV patients with TNFalpha inhibitors.     

Separation of electrocardiographic and encephalographic components based on signal averaging and wavelet shrinkage techniques

During ambulatory monitoring, it is often required to record the electroencephalogram (EEG) and the electrocardiogram (ECG) simultaneously. It would be ideal if both EEG and ECG can be obtained with one measurement. We introduce an algorithm combining the wavelet shrinkage and signal averaging techniques to extract the EEG and ECG components from an EEG lead signal to a noncephalic reference (NCR). The evaluation using simulation data and measured data showed that the normalized power spectrum unvaried in all frequency bands for the EEG components, and the sensitivity and specificity of R-wave detection for the ECG component were nearly 100%.     

Volumetric contraction and methacrylate conversion in photo-polymerized amorphous calcium phosphate/methacrylate composites

Because of its relatively high solubility in aqueous media and its rapid transformation to hydroxyapatite, amorphous calcium phosphate (ACP) has been utilized as the filler phase of resin-based bioactive composites that have remineralization potential. The objectives of this study were to determine how various methacrylate resins and various types of ACP fillers affect acrylic vinyl conversion and polymerization shrinkage (PS). Several types of photo-crosslinkable resin systems were prepared and admixed with a mass fraction of 40% of either unhybridized, silica- or zirconia-hybridized ACP. After visible light-activated photo-polymerization ACP composites were assessed by near infrared spectroscopy for degree of vinyl conversion and by mercury dilatometry for PS. It was found for these composites that vinyl conversion was independent of filler type but strongly dependent on the type and composition of the resin phase. PS, on the other hand, showed more complex dependence both on the resin type and composition and, in some cases, on the type of ACP. In order to obtain ACP/methacrylate-based composites with maximal vinyl conversion, resin type and composition are of primary importance. However, in order to minimize volume contraction on polymerization it appears necessary to consider both the resin and filler type of these bioactive composites.     

Separation of EEG and ECG components based on wavelet shrinkage and variable cosine window

During ambulatory monitoring, it is sometimes required to record an electroencephalogram (EEG) and an electrocardiogram (ECG) simultaneously. It would be ideal if both EEG and ECG could be obtained with one measurement. Here, we introduce an algorithm that combines the wavelet shrinkage and variable cosine window operation to separate the EEG and ECG components from an EEG signal recorded with a noncephalic reference (NCR). Evaluation using simulated data and actual measured data showed that accurate frequency analysis of EEG and an R-R detection-based heart rate analysis were feasible with our proposed algorithm, which improved the signal-averaging based algorithm so that ECG components containing ectopic beats can be applied.     

Separation of EEG and ECG components based on wavelet shrinkage and variable cosine window

During ambulatory monitoring, it is sometimes required to record an electroencephalogram (EEG) and an electrocardiogram (ECG) simultaneously. It would be ideal if both EEG and ECG could be obtained with one measurement. Here, we introduce an algorithm that combines the wavelet shrinkage and variable cosine window operation to separate the EEG and ECG components from an EEG signal recorded with a noncephalic reference (NCR). Evaluation using simulated data and actual measured data showed that accurate frequency analysis of EEG and an R-R detection-based heart rate analysis were feasible with our proposed algorithm, which improved the signal-averaging based algorithm so that ECG components containing ectopic beats can be applied.