scholarly journals Fluoroalkyl Pentacarbonylmanganese(I) Complexes as Initiators for the Radical (co)Polymerization of Fluoromonomers

Polymers ◽  
2020 ◽  
Vol 12 (2) ◽  
pp. 384 ◽  
Author(s):  
Roberto Morales-Cerrada ◽  
Vincent Ladmiral ◽  
Florence Gayet ◽  
Christophe Fliedel ◽  
Rinaldo Poli ◽  
...  
Keyword(s):  
Visible Light ◽  
Polyvinylidene Fluoride ◽  
Vinylidene Fluoride ◽  
Degree Of Crystallinity ◽  
End Groups ◽  
Radical Initiators ◽  
Alternating Copolymerization ◽  
Kinetics Of ◽  
The Degree Of Crystallinity ◽  
Moderate Yield

The use of [Mn(RF)(CO)5] (RF = CF3, CHF2, CH2CF3, COCF2CH3) to initiate the radical polymerization of vinylidene fluoride (F2C=CH2, VDF) and the radical alternating copolymerization of vinyl acetate (CH2=CHOOCCH3, VAc) with tert-butyl 2-(trifluoromethyl)acrylate (MAF-TBE) by generating primary RF• radicals is presented. Three different initiating methods with [Mn(CF3)(CO)5] (thermal at ca. 100 °C, visible light and UV irradiations) are described and compared. Fair (60%) to satisfactory (74%) polyvinylidene fluoride (PVDF) yields were obtained from the visible light and UV activations, respectively. Molar masses of PVDF reaching 53,000 g·mol−1 were produced from the visible light initiation after 4 h. However, the use of [Mn(CHF2)(CO)5] and [Mn(CH2CF3)(CO)5] as radical initiators produced PVDF in a very low yield (0 to 7%) by both thermal and photochemical initiations, while [Mn(COCF2CH3)(CO)5] led to the formation of PVDF in a moderate yield (7% to 23%). Nevertheless, complexes [Mn(CH2CF3)(CO)5] and [Mn(COCHF2)(CO)5] efficiently initiated the alternating VAc/MAF-TBE copolymerization. All synthesized polymers were characterized by 1H and 19F NMR spectroscopy, which proves the formation of the expected PVDF or poly(VAc-alt-MAF-TBE) and showing the chaining defects and the end-groups in the case of PVDF. The kinetics of VDF homopolymerization showed a linear ln[M]0/[M] versus time relationship, but a decrease of molar masses vs. VDF conversion was noted in all cases, which shows the absence of control. These PVDFs were rather thermally stable in air (up to 410 °C), especially for those having the highest molar masses. The melting points ranged from 164 to 175 °C while the degree of crystallinity varied from 44% to 53%.

Influence of the Crystallisation Kinetics on the Microstructural Properties of α-PVDF

2006 ◽  
Vol 949 ◽  
Author(s):  
Marco Pinto Silva ◽  
Vitor Sencadas ◽  
Anabela G Rolo ◽  
Gabriela Botelho ◽  
Ana Vera Machado ◽  
...  
Keyword(s):  
Vinylidene Fluoride ◽  
Alpha Phase ◽  
Degree Of Crystallinity ◽  
Infrared Transmission ◽  
Crystallisation Kinetics ◽  
Poly Vinylidene Fluoride ◽  
Different Temperatures ◽  
Kinetics Of ◽  
The Degree Of Crystallinity ◽  
Crystallization From The Melt

ABSTRACTThe kinetics of the isothermal crystallization from the melt at different crystallisation temperatures and the melting behaviour of Poly(vinylidene fluoride) (PVDF) in the alpha phase has been investigated. The variation of the microstructure of the samples crystallized at different temperatures was monitored with time by Optical Microscopy. The correlation between microstructure and kinetic parameters allows the tailoring of the microstructure by choosing the crystallisation conditions of the samples. Raman and Infrared Transmission Spectroscopy also show the appearance of the γ-phase for higher crystallisation temperatures. The influence of the crystallisation kinetics on the degree of crystallinity of the samples will be also presented and discussed.

scholarly journals Effect of Poling on the Mechanical Properties of β-Poly(Vinylidene Fluoride)

2006 ◽  
Vol 514-516 ◽  
pp. 951-955 ◽  
Author(s):  
Carlos M. Costa ◽  
Vitor Sencadas ◽  
João F. Mano ◽  
Senentxu Lanceros-Méndez
Keyword(s):  
Mechanical Properties ◽  
Mechanical Response ◽  
Vinylidene Fluoride ◽  
Degree Of Crystallinity ◽  
Scanning Calorimetry ◽  
Direction Parallel ◽  
Poly Vinylidene Fluoride ◽  
The Stability ◽  
Kinetics Of ◽  
The Degree Of Crystallinity

In this work, mechanical and thermal experimental techniques have been applied in order to relate the mechanical response with the microscopic variations of the material. Stress-strain results along the main directions of β-poly(vinylidene fluoride), β-PVDF, in poled and non-poled samples enables to investigate the influence of the poling process on the mechanical response of the material. Further, differential scanning calorimetry experiments allow the investigation of the effect of poling in the degree of crystallinity of the material as well as on the stability of the crystalline phase. Thermogravimetric analysis was used to investigate the kinetics of the thermal degradation of poled and non-poled β-PVDF samples. The differences observed between the two materials suggest that the poling affects the mechanical properties of the material especially in the direction parallel to the polymeric chains and originates changes at a molecular level that remain beyond the melting of the material.

Studies on thermal and degradation kinetics of cellulose micro/nanoparticle filled polylactic acid (PLA) based nanocomposites

2021 ◽  
pp. 096739112098717
Author(s):  
Achal Bhiogade ◽  
Murugasamy Kannan
Keyword(s):  
Degradation Kinetics ◽  
Thermo Gravimetric Analysis ◽  
Composite Films ◽  
Degree Of Crystallinity ◽  
Hydroxyl Group ◽  
Poly Lactic Acid ◽  
Gravimetric Analysis ◽  
Scanning Calorimetry ◽  
Kinetics Of ◽  
The Degree Of Crystallinity

The aim of this work is to understand the effect of concentration of plasticizer, particle size and wt% of nanoparticles on nanocomposites by fabricating poly lactic acid (PLA) based bio-nanocomposites. The bio-nanocomposites were prepared by a solution casting method with PLA as the matrix, chloroform as solvent and poly ethylene glycol (PEG) as plasticizer. Microcrystalline cellulose (MCC) and cellulose nanocrystal (CNC) were used as reinforcements in 1, 3 and 5 wt% to modify the properties of the bio-nanocomposite. The degradation kinetics of the PLA based composites were determined by using the Coats-Redfern equation over the range of 0-5 wt% of MCC and CNC. Fabricated PLA based composite films were analyzed by differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS) and field emission scanning electron microscopy (FE-SEM). The analyses showed that the amount of PEG, MCC and CNC affected the degree of crystallinity. DSC results showed that the MCC/CNC content level affected the degree of crystallinity compared to neat PLA. The FTIR showed a free hydroxyl group (−OH) present in the system. The TGA analysis showed that the PLA/MCC3%/ PEG 10% composition had the highest stability compared to the other compositions but less than neat PLA.

Effects of LiCF3SO3 on PVDF-HFP/MG49 (70/30) Based Blend Polymer Electrolyte

2013 ◽  
Vol 313-314 ◽  
pp. 117-120 ◽  
Author(s):  
Narges Ataollahi ◽  
Azizan Ahmad ◽  
Harun Haji Hamzah ◽  
Mohd Yusri Rahman ◽  
Nor Sabirin Mohamed
Keyword(s):  
Polymer Electrolyte ◽  
Vinylidene Fluoride ◽  
Solid Polymer ◽  
Degree Of Crystallinity ◽  
X Ray Diffraction ◽  
Poly Vinylidene Fluoride ◽  
Solution Casting Method ◽  
Blend Polymer Electrolyte ◽  
Blend Polymer ◽  
The Degree Of Crystallinity

Poly (vinylidene fluoride-hexafluoro propylene) (PVDF-HFP), Poly (methyl methacrylate)-grafted natural rubber (MG49) (70/30) complexed with different compositions of lithium trifluoromethane sulfonate (LiCF3SO3) based solid polymer electrolyte has been prepared using solution casting method. This work has demonstrated that conductivity values were found to depend upon the concentration of LiCF3SO3. The highest ionic conductivity was 1.97×10ˉ4 S cm-1at 25 wt. % of LiCF3SO3 at room temperature. X-ray diffraction (XRD) indicates decrease in the degree of crystallinity by increasing of salt concentration.

Effects of initial crystallization process on piezoelectricity of PVDF-HFP films

2015 ◽  
Vol 35 (5) ◽  
pp. 451-461 ◽  
Author(s):  
Bin Hu ◽  
Ning Hu ◽  
Liangke Wu ◽  
Feng Liu ◽  
Yaolu Liu ◽  
...  
Keyword(s):  
Crystallization Process ◽  
Vinylidene Fluoride ◽  
Degree Of Crystallinity ◽  
Slow Cooling ◽  
Poly Vinylidene Fluoride ◽  
Cooling Speed ◽  
Solution Casting Method ◽  
Heating Pattern ◽  
The Degree Of Crystallinity ◽  
Initial Crystallization Temperature

Abstract The effects of some important factors in the initial crystallization process of the solution casting method on the piezoelectricity of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) films were extensively explored. The experimental results revealed that there is an optimal initial crystallization temperature at around 90°C. The slow cooling speed can moderately enhance the degree of crystallinity. The most important finding was that a bilayer crystalline structure caused by an asymmetrical heating pattern can enhance the formation of packed micro-fibrillar morphologies after drawing. These three points can increase the piezoelectricity of the PVDF-HFP films, indicating the increase of the extended-chain crystals (β-phase).

scholarly journals Thermal and Mechanical Studies of Biofiller/Poly-3-Hydroxybutyrate Biocomposites

2019 ◽  
pp. 302-310
Author(s):  
Evgeniy G. Kiselev ◽  
Andrew P. Kuzmin ◽  
Ivan V. Nemtsev
Keyword(s):  
Construction Industry ◽  
Wood Flour ◽  
Degree Of Crystallinity ◽  
Scanning Calorimetry ◽  
Polyester Resins ◽  
X Ray ◽  
Biodegradable Poly ◽  
Kinetics Of ◽  
The Degree Of Crystallinity ◽  
Physical Mixtures

Biodegradable poly-3-hydroxybutyrate [P(3HB)] and birch wood flour (as filler) were used to prepare powdered blends and then pellets and granules. Pellets were produced by cold pressing of polymer and filler powders; granules were produced from the powders wetted with ethanol. The properties of the initial P(3HB) and filler and the blends thereof were studied using IR spectroscopy, differential scanning calorimetry, X-ray analysis, and electron microscopy. No chemical bonds between the components were revealed; the blends were physical mixtures. The degree of crystallinity of the blends was lower than that of the initial polymer, suggesting different crystallization kinetics of the blends. The introduction of increasing amounts of filler into the polymer progressively decreased the mechanical strength of the pellets, as confirmed by a decrease in Young’s modulus. The resulting composite, based on biodegradable polymers and wood flour, is a promising nontoxic material for the production of wood-based panels for the construction industry and the manufacture of furniture in place of materials produced using toxic polyester resins

scholarly journals Estimation of the Age of Architectural Heritage Objects by Microstructural Changes of Calcite in Lime Mortars of Ancient Brickwork and Masonry

Buildings ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 240
Author(s):  
Vladimir Kotlyar ◽  
Victoria Pishchulina ◽  
Alexey N. Beskopylny ◽  
Besarion Meskhi ◽  
Yury Popov ◽  
...  
Keyword(s):  
18Th Century ◽  
Degree Of Crystallinity ◽  
Architectural Heritage ◽  
Natural Conditions ◽  
Relative Age ◽  
Lime Mortars ◽  
Powder Samples ◽  
Diffraction Patterns ◽  
Cultural Monuments ◽  
The Degree Of Crystallinity

Determining the age of ancient architectural and cultural monuments is a significant scientific problem. An approach based on the transformation of portlandite into calcite and subsequent recrystallization of calcite is considered, which allows for estimating the relative age of ancient brickworks for local groups of historic buildings based on the results of diffraction studies of powder samples of carbonate mortars and measurements of samples with a known age. This article presents the results of the study of lime mortars of ancient brickwork. Under natural conditions, the process of transformation of portlandite into calcite takes from 100 to 200 years. The rate of this process is influenced by temperature, humidity, peculiarities of interaction with carbon dioxide contained in the air, etc. Examples show that portlandite is completely transformed into calcite in masonry mortars of the 18th century and that portlandite is not found in older mortars. It was determined that after the transformation of portlandite into calcite, an increase in the degree of recrystallization of calcite is observed, which manifests itself in powder diffraction patterns in the relative broadening of the diffraction peak of calcite hkl 104. In a detailed study, an estimate of the peak width at half maximum (FWHM) associated with the degree of crystallinity is effective. The actual data are given, which show that in older lime mortars the degree of recrystallization of calcite is higher than in younger ones. This fact makes it possible to indirectly determine the relative age of brickwork and masonry of various buildings of architectural heritage, which is especially relevant for the objects with the use of lime mortars of the northern provinces of the Byzantine Oecumene and other periods of various cultures.

scholarly journals Preparation and Electrochemical Characterization of Organic–Inorganic Hybrid Poly(Vinylidene Fluoride)-SiO2 Cation-Exchange Membranes by the Sol-Gel Method Using 3-Mercapto-Propyl-Triethoxyl-Silane

Materials ◽  
2019 ◽  
Vol 12 (19) ◽  
pp. 3265 ◽  
Author(s):  
Li ◽  
Li ◽  
Li ◽  
Guan ◽  
Zheng ◽  
...  
Keyword(s):  
Membrane Potential ◽  
Oxidative Stability ◽  
Water Uptake ◽  
Polyvinylidene Fluoride ◽  
Vinylidene Fluoride ◽  
Sol Gel ◽  
Synthesis Method ◽  
Co2 Production ◽  
Inorganic Hybrid ◽  
Poly Vinylidene Fluoride

A new synthesis method for organic–inorganic hybrid Poly(vinylidene fluoride)-SiO2 cation-change membranes (CEMs) is proposed. This method involves mixing tetraethyl orthosilicate (TEOS) and 3-mercapto-propyl-triethoxy-silane (MPTES) into a polyvinylidene fluoride (PVDF) sol-gel solution. The resulting slurry was used to prepare films, which were immersed in 0.01 M HCl, which caused hydrolysis and polycondensation between the MPTES and TEOS. The resulting Si-O-Si polymers chains intertwined and/or penetrated the PVDF skeleton, significantly improving the mechanical strength of the resulting hybrid PVDF-SiO2 CEMs. The -SH functional groups of MPTES oxidized to-SO3H, which contributed to the excellent permeability of these CEMs. The surface morphology, hybrid structure, oxidative stability, and physicochemical properties (IEC, water uptake, membrane resistance, membrane potential, transport number, and selective permittivity) of the CEMs obtained in this work were characterized using scanning electron microscope and Fourier transform infrared spectroscopy, as well as electrochemical testing. Tests to analyze the oxidative stability, water uptake, membrane potential, and selective permeability were also performed. Our organic–inorganic hybrid PVDF-SiO2 CEMs demonstrated higher oxidative stability and lower resistance than commercial Ionsep-HC-C membranes with a hydrocarbon structure. Thus, the synthesis method described in this work is very promising for the production of very efficient CEMs. In addition, the physical and electrochemical properties of the PVDF-SiO2 CEMs are comparable to the Ionsep-HC-C membranes. The electrolysis of the concentrated CoCl2 solution performed using PVDF-SiO2-6 and Ionsep-HC-C CEMs showed that at the same current density, Co2+ production, and current efficiency of the PVDF-SiO2-6 CEM membrane were slightly higher than those obtained using the Ionsep-HC-C membrane. Therefore, our novel membrane might be suitable for the recovery of cobalt from concentrated CoCl2 solutions.

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.

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