Effect of modified microcrystalline cellulose on poly(3-hydroxybutyrate) molecular dynamics by proton relaxometry

2020 ◽  
pp. 096739112092607
Author(s):  
Filipe Antonio dos Santos Viegas Ribeiro ◽  
Maxwell de Paula Cavalcante ◽  
Maria Inês Bruno Tavares ◽  
Amanda Ramos Aragão Melo
Keyword(s):  
Molecular Dynamics ◽  
Polymer Matrix ◽  
Degree Of Crystallinity ◽  
Hybrid Films ◽  
Scanning Calorimetry ◽  
Reciprocal Influence ◽  
Proton Relaxometry ◽  
Solution Casting Method ◽  
Cellulose Concentration ◽  
Modified Cellulose

Hybrid films of poly(3-hydroxybutyrate) (PHB) and modified cellulose by solution casting method were prepared, aiming to study the influence of modified cellulose (0.25%, 0.5% and 0.75% w/w) on the structural organization and thermal properties of PHB matrix. The modified cellulose showed good dispersion in polymer matrix, due to the high compatibility between phases explained by similarity of polymer and filler structures. The composites were studied by wide-angle X-ray diffractometry, differential scanning calorimetry, thermogravimetric analysis, and time-domain nuclear magnetic resonance (NMR) spectroscopy. The conjugation of results coming from those techniques allowed to determine the cellulose concentration that had the highest influence on crystalline planes and degree of crystallinity of PHB, that is, the influence in the composite structure. The molecular dynamics obtained by NMR showed a reciprocal influence between polymer matrix and cellulose particles, enhancing the interactions present in the agglomerated particles.

scholarly journals Modification of Laser Marking Ability and Properties of Polypropylene Using Silica Waste as a Filler

Materials ◽  
2021 ◽  
Vol 14 (22) ◽  
pp. 6961
Author(s):  
Artur Kościuszko ◽  
Piotr Czyżewski ◽  
Mateusz Rojewski
Keyword(s):  
Laser Beam ◽  
Polymer Matrix ◽  
Tensile Tests ◽  
Degree Of Crystallinity ◽  
Infrared Range ◽  
Scanning Calorimetry ◽  
Multifunctional Additive ◽  
Strong Concentration ◽  
Laser Marking ◽  
Laser Head

Polypropylene (PP) belongs to the group of polymers characterized by low susceptibility to absorption of electromagnetic radiation in the infrared range (λ = 1064 nm). This research consisted of assessing the possibility of using silica waste from the metallurgic industry as an additive for PP laser marking. The modifier was introduced into the polymer matrix in the range from 1 to 10 wt%. The effects of laser radiation were assessed based on colorimetric tests and microscopic surface analysis. The mechanical properties of the composites were determined during the static tensile tests. The thermal properties were investigated via differential scanning calorimetry. It was found that the introduction of silica waste into polypropylene allows for the effective marking of sample surfaces with the use of a laser beam. The greatest contrast between the graphic symbol and the background was obtained for silica contents of 3 and 5 wt%, with the use of a low-speed laser head and a strong concentration of the laser beam. The application of silica caused an increase in the modulus of elasticity and the tensile strength of the composite samples. Increases in the crystallization temperature and the degree of crystallinity of the polymer matrix were also observed. It was found that silica waste can act as multifunctional additive for polypropylene.

scholarly journals PEG-POSS Star Molecules Blended in Polyurethane with Flexible Hard Segments: Morphology and Dynamics

Molecules ◽  
2020 ◽  
Vol 26 (1) ◽  
pp. 99
Author(s):  
Konstantinos N. Raftopoulos ◽  
Edyta Hebda ◽  
Anna Grzybowska ◽  
Panagiotis A. Klonos ◽  
Apostolos Kyritsis ◽  
...  
Keyword(s):  
Glass Transition ◽  
Star Polymer ◽  
Polymerization Process ◽  
Degree Of Crystallinity ◽  
Dielectric Relaxation Spectroscopy ◽  
Scanning Calorimetry ◽  
Similar System ◽  
Soft Phase ◽  
Hard Segments ◽  
Star Molecules

A star polymer with a polyhedral oligomeric silsesquioxanne (POSS) core and poly(ethylene glycol) (PEG) vertex groups is incorporated in a polyurethane with flexible hard segments in-situ during the polymerization process. The blends are studied in terms of morphology, molecular dynamics, and charge mobility. The methods utilized for this purpose are scanning electron and atomic force microscopies (SEM, AFM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and to a larger extent dielectric relaxation spectroscopy (DRS). It is found that POSS reduces the degree of crystallinity of the hard segments. Contrary to what was observed in a similar system with POSS pendent along the main chain, soft phase calorimetric glass transition temperature drops as a result of plasticization, and homogenization of the soft phase by the star molecules. The dynamic glass transition though, remains practically unaffected, and a hypothesis is formed to resolve the discrepancy, based on the assumption of different thermal and dielectric responses of slow and fast modes of the system. A relaxation α′, slower than the bulky segmental α and common in polyurethanes, appears here too. A detailed analysis of dielectric spectra provides some evidence that this relaxation has cooperative character. An additional relaxation g, which is not commonly observed, accompanies the Maxwell Wagner Sillars interfacial polarization process, and has dynamics similar to it. POSS is found to introduce conductivity and possibly alter its mechanism. The study points out that different architectures of incorporation of POSS in polyurethane affect its physical properties by different mechanisms.

scholarly journals Crystallization Behavior and Mechanical Properties of Poly(ε-caprolactone) Reinforced with Barium Sulfate Submicron Particles

Materials ◽  
2021 ◽  
Vol 14 (9) ◽  
pp. 2368
Author(s):  
Hegoi Amestoy ◽  
Paul Diego ◽  
Emilio Meaurio ◽  
Jone Muñoz ◽  
Jose-Ramon Sarasua
Keyword(s):  
Barium Sulfate ◽  
Thermal Studies ◽  
Polarized Light ◽  
Optical Microscope ◽  
Submicron Particles ◽  
Degree Of Crystallinity ◽  
Scanning Calorimetry ◽  
Nucleation Effect ◽  
Crystal Fraction ◽  
Light Optical Microscope

Poly(ε-caprolactone) (PCL) was mixed with submicron particles of barium sulfate to obtain biodegradable radiopaque composites. X-ray images comparing with aluminum samples show that 15 wt.% barium sulfate (BaSO4) is sufficient to present radiopacity. Thermal studies by differential scanning calorimetry (DSC) show a statistically significant increase in PCL degree of crystallinity from 46% to 52% for 25 wt.% BaSO4. Non-isothermal crystallization tests were performed at different cooling rates to evaluate crystallization kinetics. The nucleation effect of BaSO4 was found to change the morphology and quantity of the primary crystals of PCL, which was also corroborated by the use of a polarized light optical microscope (PLOM). These results fit well with Avrami–Ozawa–Jeziorny model and show a secondary crystallization that contributes to an increase in crystal fraction with internal structure reorganization. The addition of barium sulfate particles in composite formulations with PCL improves stiffness but not strength for all compositions due to possible cavitation effects induced by debonding of reinforcement interphase.

scholarly journals Study on Structure, Thermal Behavior, and Viscoelastic Properties of Nanodiamond-Reinforced Poly (vinyl alcohol) Nanocomposites

Polymers ◽  
2021 ◽  
Vol 13 (9) ◽  
pp. 1426
Author(s):  
Tomáš Remiš ◽  
Petr Bělský ◽  
Tomáš Kovářík ◽  
Jaroslav Kadlec ◽  
Mina Ghafouri Azar ◽  
...  
Keyword(s):  
Electron Microscopy ◽  
Mechanical Analysis ◽  
Single Step ◽  
Poly Vinyl Alcohol ◽  
Scanning Calorimetry ◽  
X Ray Scattering ◽  
Transmission Electron ◽  
Primary Particles ◽  
Solution Casting Method ◽  
Average Size

In this work, advanced polymer nanocomposites comprising of polyvinyl alcohol (PVA) and nanodiamonds (NDs) were developed using a single-step solution-casting method. The properties of the prepared PVA/NDs nanocomposites were investigated using Raman spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). It was revealed that the tensile strength improved dramatically with increasing ND content in the PVA matrix, suggesting a strong interaction between the NDs and the PVA. SEM, TEM, and SAXS showed that NDs were present in the form of agglomerates with an average size of ~60 nm with primary particles of diameter ~5 nm. These results showed that NDs could act as a good nanofiller for PVA in terms of improving its stability and mechanical properties.

scholarly journals The Correlation between Physical Crosslinking and Water-Soluble Drug Release from Chitosan-Based Microparticles

Pharmaceutics ◽  
2020 ◽  
Vol 12 (5) ◽  
pp. 455
Author(s):  
Emilia Szymańska ◽  
Katarzyna Woś-Latosi ◽  
Julia Jacyna ◽  
Magdalena Dąbrowska ◽  
Joanna Potaś ◽  
...  
Keyword(s):  
Drug Release ◽  
Polymer Matrix ◽  
Drug Loading ◽  
Water Soluble ◽  
Dissolution Behavior ◽  
Complex Nature ◽  
Prolonged Release ◽  
Scanning Calorimetry ◽  
Burst Effect ◽  
The Impact

Microparticles containing water-soluble zidovudine were prepared by spray-drying using chitosan glutamate and beta-glycerophosphate as an ion crosslinker (CF). The Box–Behnken design was applied to optimize the microparticles in terms of their drug loading and release behavior. Physicochemical studies were undertaken to support the results from dissolution tests and to evaluate the impact of the crosslinking ratio on the microparticles’ characteristics. The zidovudine dissolution behavior had a complex nature which comprised two phases: an initial burst effect followed with a prolonged release stage. The initial drug release, which can be modulated by the crosslinking degree, was primarily governed by the dissolution of the drug crystals located on the microparticles’ surfaces. In turn, the further dissolution stage was related to the drug diffusion from the swollen polymer matrix and was found to correlate with the drug loading. Differential Scanning Calorimetry (DSC) studies revealed the partial incorporation of a non-crystallized drug within the polymer matrix, which correlated with the amount of CF. Although CF influenced the swelling capacity of chitosan glutamate microparticles, surprisingly a higher amount of CF did not impact the time required for 80% of the drug to be released markedly. The formulation with the lowest polymer:CF ratio, 3:1, was selected as optimal, providing satisfactory drug loading and displaying a moderate burst effect within the first 30 min of the study, followed with a prolonged drug release of up to 210 min.

scholarly journals Melt-Cast Films Significantly Enhance Triamcinolone Acetonide Delivery to the Deeper Ocular Tissues

Pharmaceutics ◽  
2019 ◽  
Vol 11 (4) ◽  
pp. 158
Author(s):  
Akshaya Tatke ◽  
Narendar Dudhipala ◽  
Karthik Janga ◽  
Bhavik Soneta ◽  
Bharathi Avula ◽  
...  
Keyword(s):  
Triamcinolone Acetonide ◽  
Polymer Matrix ◽  
Rabbit Model ◽  
In Vivo Studies ◽  
Invasive Technique ◽  
Content Uniformity ◽  
Scanning Calorimetry ◽  
Ocular Tissues

Delivering an effective drug load to the posterior section of the ocular tissues, while using a non-invasive technique, has always been a challenge. In this regard, the goal of the present study was to develop sustained release triamcinolone acetonide (TA) loaded polymeric matrix films for ocular delivery. The TA-films were prepared in two different polymer matrices, with drug loadings of 10% and 20% w/w, and they were evaluated for ocular distribution in vivo in a conscious rabbit model. A 4% w/v TA suspension (TA-C) was used as a control for in vitro and in vivo studies. The TA-films, prepared with melt-cast technology, used polyethylene oxide (PEO) and Soluplus® as the polymer matrix. The films were evaluated with respect to assay, content uniformity, excipient interaction, and permeability across isolated rabbit sclera. The distribution of TA in the ocular tissues, post topical administration, was determined in New Zealand male albino rabbits as a function of dose, and was compared against TA-C. The assay of the 10% and 20% w/w film was in the range from 70–79% and 92–94% for the Soluplus® and PEO films, respectively, and content uniformity was in the range of 95–103% for both the films. The assay of the TA from Soluplus® films was less compared with the PEO films and showed an interaction with TA, as revealed by Differential Scanning Calorimetry (DSC). Hence, Soluplus® films were not selected for further studies. No interaction was observed between the drug and PEO polymer matrix. The enhancement of trans-scleral flux and permeability of TA was about 1.16 and 1.33-folds, respectively, from the 10% w/w PEO and 3.5 and 2.12-folds, respectively, from the 20% w/w PEO films, as compared with TA-C formulations. The in vivo studies demonstrate that significantly higher TA levels were observed in the anterior and posterior segments of the eye at the end of 6h with the PEO films. Therefore, the PEO based polymeric films were able to deliver TA into the back of the eye efficiently and for prolonged periods.

scholarly journals Preparation and Characterization of Talc Filled Thermoplastic Polyurethane/Polypropylene Blends

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Emi Govorčin Bajsić ◽  
Vesna Rek ◽  
Ivana Ćosić
Keyword(s):  
Thermal Properties ◽  
Thermoplastic Polyurethane ◽  
Mechanical Analysis ◽  
Degree Of Crystallinity ◽  
Scanning Calorimetry ◽  
Polypropylene Blends ◽  
Pp Blends ◽  
The Degree Of Crystallinity ◽  
Better Than

The effect of the addition of talc on the morphology and thermal properties of blends of thermoplastic polyurethane (TPU) and polypropylene (PP) was investigated. The blends of TPU and PP are incompatible because of large differences in polarities between the nonpolar crystalline PP and polar TPU and high interfacial tensions. The interaction between TPU and PP can be improved by using talc as reinforcing filler. The morphology was observed by means of scanning electron microscopy (SEM). The thermal properties of the neat polymers and unfilled and talc filled TPU/PP blends were studied by using dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The addition of talc in TPU/PP blends improved miscibility in all investigated TPU/T/PP blends. The DSC results for talc filled TPU/PP blends show that the degree of crystallinity increased, which is due to the nucleating effect induced by talc particles. The reason for the increased storage modulus of blends with the incorporation of talc is due to the improved interface between polymers and filler. According to TGA results, the addition of talc enhanced thermal stability. The homogeneity of the talc filled TPU/PP blends is better than unfilled TPU/PP blends.

Molecular Dynamics Simulation of a Pullout Test on a Carbon Nanotube in a Polymer Matrix

2014 ◽  
Vol 1700 ◽  
pp. 61-66
Author(s):  
Guttormur Arnar Ingvason ◽  
Virginie Rollin
Keyword(s):  
Molecular Dynamics ◽  
Polymer Matrix ◽  
Large Scale ◽  
Md Simulations ◽  
Dynamics Simulation ◽  
Atomistic Simulations ◽  
Polymer Molecules ◽  
Molecular Potential ◽  
Pull Out ◽  
Walled Carbon Nanotubes

ABSTRACTAdding single walled carbon nanotubes (SWCNT) to a polymer matrix can improve the delamination properties of the composite. Due to the complexity of polymer molecules and the curing process, few 3-D Molecular Dynamics (MD) simulations of a polymer-SWCNT composite have been run. Our model runs on the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS), with a COMPASS (Condensed phase Optimized Molecular Potential for Atomistic Simulations Studies) potential. This potential includes non-bonded interactions, as well as bonds, angles and dihedrals to create a MD model for a SWCNT and EPON 862/DETDA (Diethyltoluenediamine) polymer matrix. Two simulations were performed in order to test the implementation of the COMPASS parameters. The first one was a tensile test on a SWCNT, leading to a Young’s modulus of 1.4 TPa at 300K. The second one was a pull-out test of a SWCNT from an originally uncured EPON 862/DETDA matrix.

scholarly journals Post-Processing Time Dependence of Shrinkage and Mechanical Properties of Injection-Molded Polypropylene

Materials ◽  
2020 ◽  
Vol 14 (1) ◽  
pp. 22
Author(s):  
Artur Kościuszko ◽  
Dawid Marciniak ◽  
Dariusz Sykutera
Keyword(s):  
Mechanical Properties ◽  
Impact Strength ◽  
Injection Molding ◽  
Accelerated Aging ◽  
Mold Temperature ◽  
Degree Of Crystallinity ◽  
Injection Mold ◽  
Secondary Crystallization ◽  
Scanning Calorimetry ◽  
Injection Molded

Dimensions of the injection-molded semi-crystalline materials (polymeric products) decrease with the time that elapses from their formation. The post-molding shrinkage is an effect of secondary crystallization; the increase in the degree of polymer crystallinity leads to an increase in stiffness and decrease in impact strength of the polymer material. The aim of this study was to assess the changes in the values of post-molding shrinkage of polypropylene produced by injection molding at two different temperatures of the mold (20 °C and 80 °C), and conditioned for 504 h at 23 °C. Subsequently, the samples were annealed for 24 h at 140 °C in order to conduct their accelerated aging. The results of shrinkage tests were related to the changes of mechanical properties that accompany the secondary crystallization. The degree of crystallinity of the conditioned samples was determined by means of density measurements and differential scanning calorimetry. It was found that the changes in the length of the moldings that took place after removal from the injection mold were accompanied by an increase of 20% in the modulus of elasticity, regardless of the conditions under which the samples were made. The differences in the shrinkage and mechanical properties of the samples resulting from mold temperature, as determined by tensile test, were removed by annealing. However, the samples made at two different injection mold temperature values still significantly differed in impact strength, the values of which were clearly higher for the annealed samples compared to the results determined for the samples immediately after the injection molding.

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