scholarly journals Light-curing effects in acrylic-type dental nanocomposites probed by annihilating positrons: the case of loosely monolith Dipol® restoratives

2020 ◽  
Vol 10 (12) ◽  
pp. 4753-4758
Author(s):  
Olha Shpotyuk ◽  
Adam Ingram ◽  
Oleh Shpotyuk ◽  
Jozef Cebulski ◽  
Nina Smolar
Keyword(s):  
Free Volume ◽  
Polymer Matrix ◽  
Light Exposure ◽  
Average Lifetime ◽  
Annihilation Process ◽  
Fractional Free Volume ◽  
Positron Annihilation Lifetime ◽  
Light Curing ◽  
Semi Empirical ◽  
Dental Restorative

AbstractThe possibility of application of positron annihilation lifetime (PAL) spectroscopy to commercially available dimethacrylate-based dental restorative composites Dipol® (Oksomat-AN Ltd, Ukraine) subjected to photopolymerization due to light curing is analyzed. The governing annihilation process in these composites is identified as mixed positron (e+)-positronium (Ps) trapping, where Ps decaying is caused entirely by input from free-volume holes in polymer matrix superimposed on free e+-trapping contribution from interfacial free-volume holes between filler nanoparticles and surrounded polymer matrix. Photopolymerization shrinkage is revealed through decrease in the average lifetime of annihilating positrons due to opposite changes in Ps-decaying and e+-trapping channels. The growing light-activated polymerization is characteristic of both intensities related to the second and third components in the unconstrained ×3-term decomposed PAL spectra, accompanied by decrease in the corresponding lifetimes. This process resulted in enhanced trapping rate in the defects and depressed fractional free-volume saturation with light curing. Light exposure causes smaller voids in composites owing to free-volume fragmentation in Ps- and e+-trapping sites. The microstructure scenario for these transformations includes photo-induced cross-linking of structural chains in the polymer matrix, followed by conversion of o-Ps traps in interfacial free-volume voids near agglomerated filler nanoparticles. A meaningful description of this process is developed on the basis of the semi-empirical model exploring the  ×3– ×2-coupling decomposition algorithm.

scholarly journals Effect of Free Volume on Curcumin Release from Various Polymer-Based Composite Films Analyzed Using Positron Annihilation Lifetime Spectroscopy

Materials ◽  
2021 ◽  
Vol 14 (19) ◽  
pp. 5679
Author(s):  
Jong-Whan Rhim ◽  
Saygin Kuzeci ◽  
Swarup Roy ◽  
Necmettin Akti ◽  
Cumali Tav ◽  
...  
Keyword(s):  
Positron Annihilation ◽  
Free Volume ◽  
Bioactive Compounds ◽  
Polymer Matrix ◽  
Volume Fraction ◽  
Composite Films ◽  
Positron Annihilation Lifetime Spectroscopy ◽  
Positron Annihilation Lifetime ◽  
Biocomposite Films ◽  
Free Volume Fraction

This work reports the effects of free volume on curcumin release in various polymer-based composite films. Curcumin-reinforced biocomposite films were fabricated with natural biopolymers (carrageenan and chitosan) and bioplastics (poly(lactide) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT)) via the solvent casting method. The curcumin release test was performed using an aqueous medium, and it was found that it was released the fastest in the carrageenan film, followed by the chitosan, PLA, and PBAT films, presumably owing to the dissimilarity of the polymer matrix. The free volume of the polymer films was determined using positron annihilation lifetime spectroscopy (PALS) to understand the release phenomena of curcumin. The free volume fraction was varied and reliant on the type of polymer, with the highest in the PBAT-based film followed by the PLA-, chitosan-, and carrageenan-based films. The free volume method helps analyze the release of bioactive compounds in a polymer matrix and may help to achieve a better understanding of the release of bioactive compounds.

scholarly journals Nano-Porous-Silicon Powder as an Environmental Friend

Materials ◽  
2021 ◽  
Vol 14 (15) ◽  
pp. 4252
Author(s):  
Marwa Nabil ◽  
Kamal Reyad Mahmoud ◽  
Raghda Nomier ◽  
El-Maghraby El-Maghraby ◽  
Hussien Motaweh
Keyword(s):  
Porous Silicon ◽  
Positron Annihilation ◽  
Free Volume ◽  
Dye Removal ◽  
Environmentally Friendly ◽  
Silicon Powder ◽  
Chemical Additives ◽  
Fractional Free Volume ◽  
Powder Synthesis ◽  
Positron Annihilation Lifetime

Nano-porous silicon (NPS) powder synthesis is performed by means of a combination of the ultra-sonication technique and the alkali chemical etching process, starting with a commercial silicon powder. Various characterization techniques {X-ray powder diffraction, transmission electron microscopy, Fourier Transform Infrared spectrum, and positron annihilation lifetime spectroscopy} are used for the description of the product’s properties. The NPS product is a new environmentally friendly material used as an adsorbent agent for the acidic azo-dye, Congo red dye. The structural and free volume changes in NPS powder are probed using positron annihilation lifetime (PALS) and positron annihilation Doppler broadening (PADB) techniques. In addition, the mean free volume (VF), as well as fractional free volume (Fv), are also studied via the PALS results. Additionally, the PADB provides a clear relationship between the core and valence electrons changes, and, in addition, the number of defect types present in the synthesized samples. The most effective parameter that affects the dye removal process is the contact time value; the best time for dye removal is 5 min. Additionally, the best value of the CR adsorption capacity by NPS powder is 2665.3 mg/g at 100 mg/L as the initial CR concentration, with an adsorption time of 30 min, without no impact from temperature and pH. So, 5 min is the enough time for the elimination of 82.12% of the 30 mg/L initial concentration of CR. This study expresses the new discovery of a cheap and safe material, in addition to being environmentally friendly, without resorting to any chemical additives or heat treatments.

Studying the Effect of Low α-Radiation Doses on CR-39 Polymers Using Positron Annihilation Lifetime and Mechanical Properties

2012 ◽  
Vol 332 ◽  
pp. 77-83
Author(s):  
M.F. Eissa ◽  
E.M. Hassan ◽  
Emad A. Badawi
Keyword(s):  
Positron Annihilation ◽  
Free Volume ◽  
Alpha Particles ◽  
Polymer Materials ◽  
Fractional Free Volume ◽  
Positron Annihilation Lifetime ◽  
Microhardness Test ◽  
Solid Media ◽  
Free Volume Hole ◽  
Different Doses

Positron annihilation lifetime spectroscopy (PALS) is one of the unique tools for studying free-volume defects in solid media. The microhardness test offers a simple and nondestructive tool for investigating the mechanical behavior of polymer materials. Polyallyl diglycol carbonate (CR-39) track detectors have a variety of applications in science and technology. PALS measurements and microhardness tests were verified for CR-39 irradiated with different doses of alpha particles (0 - 69.20 mGy). The variations in free volume hole size and fractional free volume were obtained by using the PALS method. The small free volume hole sizes were found at doses 27.68 and 44.98 mGy. The microhardness test for the two doses yielded medium values.

scholarly journals Structure dependence of gamma ray irradiation effects on polyurethane and epoxy resin studied by PAL technique

2019 ◽  
Vol 13 (27) ◽  
pp. 157-163
Author(s):  
Hayder S. Hussain
Keyword(s):  
Free Volume ◽  
Gamma Ray ◽  
Cross Linking ◽  
Hole Size ◽  
Irradiation Effects ◽  
Fractional Free Volume ◽  
Structure Dependence ◽  
Positron Annihilation Lifetime ◽  
Gamma Ray Irradiation ◽  
Free Volume Hole

Positron annihilation lifetime (PAL) technique has been employed tostudy the microstructural changes of polyurethane (PU), EUXIT 101and epoxy risen (EP), EUXIT 60 by Gamma-ray irradiation with thedose range (95.76 - 957.6) kGy. The size of the free volume hole andtheir fraction in PU and EP were determined from ortho-positroniumlifetime component and its intensity in the measured lifetime spectra.The results show that the irradiation causes significant changes in thefree volume hole size (Vh) and the fractional free volume (Fh), andthereby the microstructure of PU and EP. The results indicate thatthe γ-dose increases the crystallinity in the amorphous regions of PUand increase the cross-linking of EP.

Influence of Average Free Volume Element Size on the Transport of Gases Through Polymers With Equivalent Total Free Volumes

2002 ◽  
Vol 752 ◽  
Author(s):  
Broderick R. Wilks ◽  
Won J. Chung ◽  
Peter J. Ludovice ◽  
Mary E. Rezac ◽  
Pavla Meakin ◽  
...  
Keyword(s):  
Free Volume ◽  
Defect Size ◽  
Volume Element ◽  
Model Systems ◽  
Average Lifetime ◽  
Fractional Free Volume ◽  
Element Size ◽  
Depth Analysis ◽  
Average Defect ◽  
The Impact

ABSTRACTThe permeability coefficients of gases through glassy polymers have been correlated with the fractional free volume (FFV) of the polymers. In general, polymers with high fractional free volumes have high permeabilities while those with low FFV have low permeabilities. This observation is valid for many, but not all materials. This study evaluates the impact of the average size of a free volume element on the permeability of gases through the polymer.Evaluation of the influence of average free volume element size is only possible by employing model systems in which the chemistry and the total free volume are essentially equivalent. In this study, two stereochemical forms of a methyl-substituted polynorbornene were employed. The isomers are chemically equivalent, with similar total free volumes (0.181 versus 0.188). The average defect size was probed using positron annihilation lifetime spectroscopy. The ortho-positronium lifetimes were measured and it was determined that the difference between the two isomers was approximately 10% with the lower-FFV isomer having the larger average lifetime. For simplicity, the two isomers will be termed Pd and Ni (in reference to the catalysts used in their preparation). The Pd isomer has a slightly lower FFV, but larger average defect size. The Ni isomer has a higher FFV, but smaller average defect size.Transport evaluation indicates that the Pd-isomer has gas permeabilities two to three times those of the Ni-isomer. In depth analysis indicates that the increase in permeability is a result of an increase in both the diffusivity of gases through the polymer and gas solubility.

scholarly journals On the Mutual Relationships between Molecular Probe Mobility and Free Volume and Polymer Dynamics in Organic Glass Formers: cis-1,4-poly(isoprene)

Polymers ◽  
2021 ◽  
Vol 13 (2) ◽  
pp. 294
Author(s):  
Helena Švajdlenková ◽  
Ondrej Šauša ◽  
Sergey V. Adichtchev ◽  
Nikolay V. Surovtsev ◽  
Vladimir N. Novikov ◽  
...  
Keyword(s):  
Free Volume ◽  
Spin Probe ◽  
Hyperfine Coupling Constant ◽  
Organic Glass ◽  
Molecular Probe ◽  
Positron Annihilation Lifetime ◽  
Broadband Dielectric Spectroscopy ◽  
Relaxation Modes ◽  
Reorientation Dynamics ◽  
In Cis

We report on the reorientation dynamics of small spin probe 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) in cis-1,4-poly(isoprene) (cis-1,4-PIP10k) from electron spin resonance (ESR) and the free volume of cis-1,4-PIP10k from positron annihilation lifetime spectroscopy (PALS) in relation to the high-frequency relaxations of cis-1,4-PIP10k using light scattering (LS) as well as to the slow and fast processes from broadband dielectric spectroscopy (BDS) and neutron scattering (NS). The hyperfine coupling constant, 2Azz′(T), and the correlation times, τc(T), of cis-1,4-PIP10k/TEMPO system as a function of temperature exhibit several regions of the distinct spin probe TEMPO dynamics over a wide temperature range from 100 K up to 350 K. The characteristic ESR temperatures of changes in the spin probe dynamics in cis-1,4-PIP10k/TEMPO system are closely related to the characteristic PALS ones reflecting changes in the free volume expansion from PALS measurement. Finally, the time scales of the slow and fast dynamics of TEMPO in cis-1,4-PIP10k are compared with all of the six known slow and fast relaxation modes from BDS, LS and NS techniques with the aim to discuss the controlling factors of the spin probe reorientation mobility in polymer, oligomer and small molecular organic glass-formers.

scholarly journals Shape and Temperature Expansion of Free Volume Holes in Some Cured Polybutadiene-Polyisoprene Rubber Blends

2021 ◽  
Vol 22 (3) ◽  
pp. 1436
Author(s):  
Giovanni Consolati ◽  
Eros Mossini ◽  
Dario Nichetti ◽  
Fiorenza Quasso ◽  
Giuseppe Maria Viola ◽  
...  
Keyword(s):  
Free Volume ◽  
Radial Direction ◽  
Volume Fraction ◽  
Spherical Shape ◽  
Suitable Model ◽  
Positron Annihilation Lifetime ◽  
Rubber Blends ◽  
Free Volume Fraction ◽  
Hole Model ◽  
Best Fit

The free volume fraction of a macromolecular structure can be assessed theoretically by using a suitable model; however, it can also be evaluated from experimental data obtained from dilatometry and positron annihilation lifetime spectra. In this second case, a regular geometry of the sub-nanometric cavities forming the free volume has to be assumed, although in fact they are irregularly shaped. The most popular approach is to guess spherical holes, which implies an isotropic growth of these last with temperature. In this work, we compared the free volume fraction, as obtained from experiments in a set of polybutadiene and polyisoprene cured rubbers and their blends, with the analogous quantity expected by using the lattice-hole model. The results allowed us to obtain insights on the approximate shape of the holes. Indeed, a cylindrical flattened geometry of the cavities produced a better agreement with the theory than the spherical shape. Furthermore, the best fit was obtained for holes that expanded preferentially in the radial direction, with a consequent decrease of the aspect ratio with temperature.

Preliminary Positron Lifetime Results on Free Volumes in Cyclodextrins

2010 ◽  
Vol 666 ◽  
pp. 99-102 ◽  
Author(s):  
Maria Fatima Ferreira Marques ◽  
A.M.G. Moreira Da Silva ◽  
P.M. Gordo ◽  
Z. Kajcsos
Keyword(s):  
Positron Annihilation ◽  
Free Volume ◽  
Positron Lifetime ◽  
Positron Annihilation Lifetime Spectroscopy ◽  
Positron Source ◽  
Lifetime Component ◽  
Positron Annihilation Lifetime ◽  
Long Lifetime

Positron annihilation lifetime spectroscopy was used to study the free-volume parameters in various pure -, - and -cyclodextrins samples and, in the case of β-cyclodextrin, with inclusion of S-carvone and thymoquinone. The results clearly indicate the presence of long lifetime components related to Ps-formation. The data show that the addition of S-carvone to β-cyclodextrin results in a decrease of o-Ps lifetime that we ascribe to a reduction of free volume holes from 81.8 to 63.7 Å3. The long lifetime component disappears when thymoquinone is added to -cyclodextrin, indicating this substance acts as an o-Ps quencher. For all samples studied, a decrease in the long lifetime component values was observed with increasing source in situ time, a result that might be attributed to the irradiation of the sample by the 22Na positron source.

Sign in / Sign up

Export Citation Format

Share Document