scholarly journals Dielectric, Thermal and Mechanical Properties of l,d-Poly(Lactic Acid) Modified by 4′-Pentyl-4-Biphenylcarbonitrile and Single Walled Carbon Nanotube

Polymers ◽  
2019 ◽  
Vol 11 (11) ◽  
pp. 1867 ◽  
Author(s):  
Fryń ◽  
Bogdanowicz ◽  
Krysiak ◽  
Marzec ◽  
Iwan ◽  
...  
Keyword(s):  
Lactic Acid ◽  
Weight Ratio ◽  
Thermal Response ◽  
Crystal Form ◽  
Optical Microscope ◽  
Poly Lactic Acid ◽  
Scanning Calorimetry ◽  
Single Walled Carbon ◽  
Short Term Strength ◽  
Walled Carbon Nanotubes

We report here the preparation and thermal, electrical and mechanical characterization of binary and ternary films based on l,d-poly(lactic acid) (l,d-PLA) and 4′-pentyl-4-biphenylcarbonitrile (5CB) and Single Walled Carbon Nanotubes (SWCN) with various weight ratio. The transitions for all investigated hybrid compositions detected by differential scanning calorimetry method were shifted to lower temperatures with increasing the concentration of 5CB in the mixture with polymer. Frequency domain dielectric spectroscopy method and thermal imaging together with polarized optical microscope were used to study electric and structural properties of created hybrid compositions. The best electrical conductivity was observed for hybrid composite l,d-PLA:5CB:SWCN with ratio 10:1:0.5 w/w/w - resistance of 41.0 Ω and thermal response up to 160 °C without causing any damages. Films in crystal form are much more inflexible than in amorphous and can be explain by the cold crystallization occurs at heating while the materials changed their physical state. The value of ε’ increases with increasing the 5CB admixture. Moreover, the addition of 5CB to l,d-PLA resulted in increased flexibility of polymeric base films. The best material flexibility and short-term strength were obtained for l,d-PLA sample with 9% 5CB content.

Biodegradable Composite Materials Based on Poly(3-Hydroxybutyrate) for 3D Printing Applications

2019 ◽  
Vol 955 ◽  
pp. 56-61
Author(s):  
Premysl Mencik ◽  
Veronika Melcova ◽  
Sona Kontarova ◽  
Radek Prikryl ◽  
Dagmara Perdochova ◽  
...  
Keyword(s):  
Lactic Acid ◽  
3D Printing ◽  
Cross Sections ◽  
Optical Microscope ◽  
Zinc Stearate ◽  
Poly Lactic Acid ◽  
Mechanical And Thermal Properties ◽  
Scanning Calorimetry ◽  
Biodegradable Composite ◽  
Base Polymer

Presented work deals with the development of bio-source and biodegradable composite material for 3D printing. Polymer blend based on poly (3-hydroxybutyrate) (60 wt%) and poly (lactic acid) (25 wt%) plasticized by tributyl citrate (15 wt%) was used as a matrix. This base blend was filled with 10 vol% of kaolin or limestone. Zinc stearate was used for the surface treatment of the limestone samples. The mechanical and thermal properties of the composites, as well as their behavior during 3D printing process, were compared with unfilled blend and commercial poly (lactic acid) based 3D printing filament. Warping behavior, one of the main problems of 3D printing materials, was studied by means of warp coefficient. Cross-sections of specimens 3D printed under the same processing conditions were observed by the optical microscope. In the case of composite samples, individual filaments were separated. Despite the separation, composites filled with kaolin and with surface treated limestone exhibited satisfying mechanical properties. Scanning electron microscopy analysis confirmed good particle distribution of the samples with kaolin and surface treated limestone. No significant particle agglomerates were formed in the composites with limestone proving good dispergation ability of zinc stearate. Thermogravimetric analysis and Differential scanning calorimetry analysis showed no degradable effect of the used fillers on base polymer matrix. Observed results indicate that kaolin and surface treated limestone are suitable fillers for the bio-source composites used for 3D printing.

scholarly journals Hybrid Materials Based on l,d-Poly(lactic acid) and Single-Walled Carbon Nanotubes as Flexible Substrate for Organic Devices

Polymers ◽  
2018 ◽  
Vol 10 (11) ◽  
pp. 1271 ◽  
Author(s):  
Patryk Fryń ◽  
Krzysztof Bogdanowicz ◽  
Natalia Górska ◽  
Jakub Rysz ◽  
Piotr Krysiak ◽  
...  
Keyword(s):  
Carbon Nanotubes ◽  
Lactic Acid ◽  
Hybrid Materials ◽  
Thermal Imaging ◽  
Flexible Substrate ◽  
Single Walled Carbon Nanotubes ◽  
Poly Lactic Acid ◽  
Single Walled Carbon ◽  
Organic Devices ◽  
Walled Carbon Nanotubes

We report on the application of l,d-poly(lactic acid) (l,d-PLA) with dispersed Single-Walled Carbon Nanotubes (SWCN) as a flexible translucent electrode for organic devices. We used commercially available nanotubes in various weight ratios from 0 to 8% dispersed in chloroform polymeric solution by ultrasonication and were drop cast. The created hybrid materials were investigated by differential scanning calorimetry to determine the influence of SWCN content on the thermal behavior, while polarizing optical microscope was used to find the effect of mechanical deformations on the textures. Drop-cast films were studied by optical transmittance, conductivity, dielectric properties and by thermal imaging under applied potential. Thermal imaging provided evidence of visible voltage-activated conduction. Simple mechanical deformation such as bending with stretching at edge to ca. 90 and elongation test were performed. Moreover, interactions between l,d-poly(lactic acid) and SWCN were investigated by FT-IR and NMR spectroscopy. Finally, we can conclude that the thermographic examination of created films permits fast, simple and inexpensive localization of defects on the surface of l,d-PLA:SWCN film, together with the electrical properties of the films.

Preparation and Isothermal Crystallization Behavior of Poly(lactic acid)/Graphene Nanocomposites

2011 ◽  
Vol 284-286 ◽  
pp. 246-252 ◽  
Author(s):  
Yan Hua Chen ◽  
Xia Yin Yao ◽  
Zhi Juan Pan ◽  
Qun Gu
Keyword(s):  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Graphene Nanosheets ◽  
Nucleating Agent ◽  
Optical Microscope ◽  
Poly Lactic Acid ◽  
Scanning Calorimetry ◽  
Avrami Model ◽  
Graphene Nanocomposites ◽  
Solution Blending

Poly(lactic acid) (PLA)/graphene nanocomposites were prepared by solution blending using chloroform as a mutual solvent. Transmission electron microscopy (TEM) was used to examine the quality of the dispersion of graphene in the PLA matrix. The isothermal crystallization behaviors of PLA and PLA/graphene nanocomposites were investigated by differential scanning calorimetry (DSC). The isothermal crystallization kinetics were analyzed by Avrami model based on the DSC data. The results showed that the well dispersed graphene nanosheets could act as a heterogeneous nucleating agent and lead to an acceleration of crystallization during the PLA isothermal crystallization process. According to the Arrhenius equation, the activation energies were found to be -106.9 and -46.6 kJ/mol for pure PLA and PLA/0.1 wt % graphene nanocomposite, respectively. The crystal morphology were characterized with polarizing optical microscope (POM).

Effect of Poly(D-Lactic Acid)-co-Polyethylene Glycol on the Crystallization of Poly(L-Lactic Acid)

2017 ◽  
Vol 751 ◽  
pp. 283-289 ◽  
Author(s):  
Ployrawee Kaewlamyai ◽  
Amornrat Lertworasirikul
Keyword(s):  
Lactic Acid ◽  
Polyethylene Glycol ◽  
Weight Ratio ◽  
Crystallization Rate ◽  
Heat Stability ◽  
Nucleating Agent ◽  
Degree Of Crystallinity ◽  
Poly Lactic Acid ◽  
Infrared Spectrometry ◽  
Scanning Calorimetry

Poly (lactic acid) (PLA) is a biopolymer derived from renewable resources and can be disposed of without creating harm to the environment. PLA can be formed by thermoplastic processes and has good mechanical properties. However, its disadvantages are a high crystallization temperature, slow crystallization rate, poor heat stability and low ductility. In the past, it was found that poly (D-lactic acid) (PDLA) can form complexes with poly (L-lactic acid) (PLLA) and the complexes could accelerate the crystallization and increase the degree of crystallinity of the PLA, but decrease the ductility. It is known that polyethylene glycol (PEG) can improve the ductility of PLLA. In this research, PDLA was copolymerized with PEG in an attempt to improve both crystallization behavior and ductility of PLLA. Poly (D-lactic acid)-co-polyethylene glycol (PDEG) was synthesized by ring opening polymerization using D-lactide and PEG at a D-lactide:PEG weight ratio of 10:3. The PDEG was blended with PLLA with a PDEG content of 0wt% to 50wt% by melt blending process. Fourier transform infrared spectrometry (FT-IR) and X-Ray diffractometry (XRD) confirmed the stereocomplex formation between PDEG and PLLA. Characterization by differential scanning calorimetry (DSC) revealed that crystallization temperatures of the blends were decreased in the presence of PDEG. Storage moduli and tan of the blends obtained from dynamic mechanical analysis (DMA) decreased as PDEG content increased. Polarized optical microscopy (POM) micrographs of blends with PDEG content of 1wt% to 5wt% obviously showed that crystallization rate was increased. PDEG has the potential to be an effective nucleating agent and efficient plasticizer for PLLA.

Towards the Enhancement of the Crystallization Kinetics of a Bio-Sourced and Biodegradable Polymer PLA (Poly (Lactic Acid))

2014 ◽  
Author(s):  
Zakariaa Refaa ◽  
Mhamed Boutaous ◽  
Shihe Xin ◽  
Patrick Bourgin
Keyword(s):  
Lactic Acid ◽  
Crystallization Kinetics ◽  
Biodegradable Polymer ◽  
Original Description ◽  
Optical Microscope ◽  
Complete Characterization ◽  
Poly Lactic Acid ◽  
Crystallization Time ◽  
Scanning Calorimetry ◽  
Wide Range

PLA (Poly Lactic Acid) is a bio-sourced and a biodegradable polymer. It represents an interesting substitute for some petrochemical based polymers, especially because of its wide range of applications in the biomedical, agriculture and packaging fields. Unfortunately, PLA exhibits slow crystallization kinetics, limiting the amount of crystallinity in the final product, which is a handicap in order to extend its use. Many authors have investigated the crystallization of polymers; nevertheless several physical mechanisms remain not yet understood. This work aims a complete characterization of PLA in order to improve the understanding of its crystallization kinetics. The quiescent crystallization was investigated using Differential Scanning Calorimetry (DSC) measurements in isothermal and non-isothermal conditions for PLA and PLA with 5wt % talc. The flow effect on crystallization was studied using a thermocontrolled hot-stage shearing device (Linkam) coupled with an optical microscope. The number of activated nuclei and the growth rate were measured as functions of temperature. In addition, the linear viscoelastic properties were obtained from a rheometer with plate-plate geometry. The enhancement of the crystallization was quantified and analyzed in terms of the half crystallization time t1/2. This characteristic time t1/2 is found to be drastically decreased by both the talc and the flow which promote supplementary nucleation leading to various crystalline microstructures. The flow is known to orient and stretch molecules leading to an extra nucleation. An original description of this phenomenon is proposed using two characteristic Weissenberg numbers; based on the definition of Rousse and reptation times. Finally, we have proposed a semi-empirical model to quantify the thermal and flow contributions on the crystallization.

Foaming behavior of microcellular poly(lactic acid)/TPU composites in supercritical CO2

2017 ◽  
Vol 31 (1) ◽  
pp. 61-78 ◽  
Author(s):  
Daifang Xu ◽  
Kejing Yu ◽  
Kun Qian ◽  
Chul B Park
Keyword(s):  
Lactic Acid ◽  
Cell Structure ◽  
Thermoplastic Polyurethane ◽  
Optical Microscope ◽  
Expansion Ratio ◽  
Poly Lactic Acid ◽  
Free Energy Barrier ◽  
Scanning Calorimetry ◽  
Melt Strength ◽  
Cell Nucleation

This article presents the effects of thermoplastic polyurethane (TPU) on the crystallization and melt strength of poly(lactic acid) (PLA) and on the enhancement of cell nucleation and expansion ratio to manufacture microcellular thermoplastic PLA foams in supercritical carbon dioxide. Addition of TPU increased the crystallinity and decreased the crystallite size as observed by differential scanning calorimetry and polarized optical microscope. The formed crystal domains worked as cross-linking points to increase the melt strength of a polymer that potentially affected the cell growth. Scanning electron microscope confirmed the immiscibility between PLA and TPU, and TPU was dispersed as islands in the PLA matrix. This phase morphology further influenced the cell structure of the PLA/TPU foams. TPU acted as a nucleating agent to enhance heterogeneous cell nucleation that is caused by the decrease in free energy barrier. Tensile stress that generated around the TPU and in some local regions surrounding the crystals and crystallization was dominant to induce cell nucleation.

Development of three-dimensional printing filaments based on poly(lactic acid)/hydroxyapatite composites with potential for tissue engineering

2021 ◽  
pp. 002199832098856
Author(s):  
Marcela Piassi Bernardo ◽  
Bruna Cristina Rodrigues da Silva ◽  
Luiz Henrique Capparelli Mattoso
Keyword(s):  
Tissue Engineering ◽  
Lactic Acid ◽  
Fused Deposition Modeling ◽  
Three Dimensional ◽  
Poly Lactic Acid ◽  
Scanning Calorimetry ◽  
Three Dimensional Printing ◽  
Fused Deposition ◽  
Deposition Modeling ◽  
3D Printed

Injured bone tissues can be healed with scaffolds, which could be manufactured using the fused deposition modeling (FDM) strategy. Poly(lactic acid) (PLA) is one of the most biocompatible polymers suitable for FDM, while hydroxyapatite (HA) could improve the bioactivity of scaffold due to its chemical composition. Therefore, the combination of PLA/HA can create composite filaments adequate for FDM and with high osteoconductive and osteointegration potentials. In this work, we proposed a different approache to improve the potential bioactivity of 3D printed scaffolds for bone tissue engineering by increasing the HA loading (20-30%) in the PLA composite filaments. Two routes were investigated regarding the use of solvents in the filament production. To assess the suitability of the FDM-3D printing process, and the influence of the HA content on the polymer matrix, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were performed. The HA phase content of the composite filaments agreed with the initial composite proportions. The wettability of the 3D printed scaffolds was also increased. It was shown a greener route for obtaining composite filaments that generate scaffolds with properties similar to those obtained by the solvent casting, with high HA content and great potential to be used as a bone graft.

scholarly journals Comparison of the Dielectric Properties of Ecoflex® with L,D-Poly(Lactic Acid) or Polycaprolactone in the Presence of SWCN or 5CB

Materials ◽  
2021 ◽  
Vol 14 (7) ◽  
pp. 1719
Author(s):  
Patryk Fryń ◽  
Sebastian Lalik ◽  
Natalia Górska ◽  
Agnieszka Iwan ◽  
Monika Marzec
Keyword(s):  
Oleic Acid ◽  
Dielectric Properties ◽  
Polymer Matrix ◽  
Liquid Crystalline ◽  
Weight Ratio ◽  
Poly Lactic Acid ◽  
Relaxation Processes ◽  
The Matrix ◽  
Walled Carbon Nanotubes ◽  
Hybrid Layers

The main goal of this paper was to study the dielectric properties of hybrid binary and ternary composites based on biodegradable polymer Ecoflex®, single walled carbon nanotubes (SWCN), and liquid crystalline 4′-pentyl-4-biphenylcarbonitrile (5CB) compound. The obtained results were compared with other created analogically to Ecoflex®, hybrid layers based on biodegradable polymers such as L,D-polylactide (L,D-PLA) and polycaprolactone (PCL). Frequency domain dielectric spectroscopy (FDDS) results were analyzed taking into consideration the amount of SWCN, frequency, and temperature. For pure Ecoflex®, two relaxation processes (α and β) were identified. It was shown that the SWCN admixture (in the weight ratio 10:0.01) did not change the properties of the Ecoflex® layer, while in the case of PCL and L,D-PLA, the layers became conductive. The dielectric constant increased with an increase in the content of SWCN in the Ecoflex® matrix and the conductive behavior was not visible, even for the greatest concentration (10:0.06 weight ratio). In the case of the Ecoflex® polymer matrix, the conduction relaxation process at a frequency ca. several kilohertz appeared and became stronger with an increase in the SWCN admixture in the matrix. Addition of oleic acid to the polymer matrix had a smaller effect on the increase in the dielectric response than the addition of liquid crystal 5CB. Fourier transform infrared (FTIR) results revealed that the molecular structure and chemical character of the Ecoflex® and PCL matrixes remained unchanged upon the addition of SWCN or 5CB in a weight ratio of 10:0.01 and 10:1, respectively, while molecular interactions appeared between L,D-PLA and 5CB. Moreover, adding oleic acid to pure Ecoflex® as well as the binary and ternary hybrid layers with SWCN and/or 5CB in a weight ratio of Ecoflex®:oleic acid equal to 10:0.3 did not have an influence on the chemical bonding of these materials.

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