Influence of Coupling Agent on the Morphology of Multifunctional, Degradable Shape-Memory Polymers

2013 ◽  
Vol 1569 ◽  
pp. 57-64 ◽  
Author(s):  
Liang Fang ◽  
Wan Yan ◽  
Ulrich Nöchel ◽  
Michael Zierke ◽  
Marc Behl ◽  
...  
Keyword(s):  
Coupling Agent ◽  
Hydrolytic Degradation ◽  
Weight Ratio ◽  
Hexamethylene Diisocyanate ◽  
Degree Of Crystallinity ◽  
Shape Effect ◽  
Scanning Calorimetry ◽  
Thermally Induced ◽  
Force Microscopy ◽  
Surface Morphologies

ABSTRACTMultifunctional polymer-based biomaterials, which combine degradability and shapememory capability, are promising candidate materials for biomedical implants. An example is a degradable multiblock copolymer (PDC), composed of poly(p-dioxanone) (PPDO) as hard and poly(ε-caprolactone) (PCL) as switching segments. PDC exhibits a unique linear mass loss during hydrolytic degradation, which can be tailored by the PPDO to PCL weight ratio, as well as an excellent thermally induced dual-shape effect. PDC can be synthesized by co-condensation of two oligomeric macrodiols (PCL-diol and PPDO-diol) using aliphatic diisocyanates as coupling agent. Here, we investigated whether different morphologies could be obtained for PDCs synthesized from identical oligomeric macrodiols (PCL-diol with Mn = 2000 g·mol-1 and PPDO-diol with Mn = 5300-5500 g·mol-1) with 2, 2(4), 4-trimethyl-hexamethylene diisocyanate (TMDI) and 1, 6-hexamethylene diisocyanate (HDI), respectively. More specifically, atomic force microscopy (AFM) was utilized for an investigation of the surface morphologies in solution casted PDC thin films in the temperature range from 20 °C to 60 °C. The results obtained in differential scanning calorimetry (DSC) and AFM demonstrated that different morphologies were obtained when TMDI (PDC-TMDI) or HDI (PDC-HDI) were used as linker. PCL related crystals in PDC-HDI were more heterogeneous and less ordered than those in PDCTMDI, while HDI resulted in a larger degree of crystallinity than TMDI. This research provides some new suggestions for choosing a suitable coupling agent to tailor the required morphologies and properties of SMPs with crystallizable switching segments.

scholarly journals Synthesis and Characterization of Polycarbonate Copolymers Containing Benzoyl Groups on the Side Chain for Scratch Resistance

2016 ◽  
Vol 2016 ◽  
pp. 1-6 ◽  
Author(s):  
Hohyoun Jang ◽  
Jaeseong Ha ◽  
Jiho Yoo ◽  
Jaeseung Pyo ◽  
Kunyoung Choi ◽  
...  
Keyword(s):  
Methylene Chloride ◽  
Water Drop ◽  
Scratch Resistance ◽  
Scanning Calorimetry ◽  
Force Microscopy ◽  
H Nmr ◽  
Chemical Structures ◽  
Atomic Force ◽  
Rearrangement Reaction ◽  
Surface Morphologies

The purpose of this study was to enhance the scratch resistance of polycarbonate copolymer by using 3,3′-dibenzoyl-4,4′-dihydroxybiphenyl (DBHP) monomer, containing benzoyl moieties on the ortho positions. DBHP monomer was synthesized from 4,4′-dihydroxybiphenyl and benzoyl chloride, followed by the Friedel-Craft rearrangement reaction with AlCl3. The polymerizations were conducted following the low-temperature procedure, which is carried out in methylene chloride by using triphosgene, triethylamine, bisphenol-A, and DBHP. The chemical structures of the polycarbonate copolymers were confirmed by1H-NMR. The thermal properties of copolymers were investigated by thermogravimetric analysis and differential scanning calorimetry, and also surface morphologies were assessed by atomic force microscopy. The scratch resistance of homopolymer film (100 μm) changed from 6B to 1B, and the contact angle of a sessile water drop onto the homopolymer film also increased.

Magnetic Properties of Irradiated Nickel Ferrite Thermoplastic Natural Rubber Nanocomposite

2014 ◽  
Vol 879 ◽  
pp. 206-212 ◽  
Author(s):  
Sivanesan Appadu ◽  
Sahrim Hj. Ahmad ◽  
Chantara Thevy Ratnam ◽  
Meor Yahaya Razali ◽  
Moayad Husein Flaifel ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
Thermal Properties ◽  
Natural Rubber ◽  
Weight Ratio ◽  
Xrd Analysis ◽  
Degree Of Crystallinity ◽  
Scanning Calorimetry ◽  
Magnetic Microstructure ◽  
Sem Image ◽  
Thermoplastic Natural Rubber

The effect of electron beam (EB) irradiation at different doses on the magnetic, microstructure, morphological and thermal properties of NiFe2O4/Thermoplastic Natural Rubber (TPNR) nanocomposite was investigated. The NiFe2O4/TPNR nanocomposite samples were prepared by using a Haake mixer in weight ratio of 12:88. The TPNR matrix consists of natural rubber (NR), liquid natural rubber (LNR) and high density polyethylene (HDPE) in weight ratio of 20:10:70. The samples were irradiated using a 2 MeV EB machine in doses from 0 - 200 kGy. Magnetic properties studied by using the vibrating sample magnetometer (VSM) at room temperature showed that the values of saturation magnetization (MS), remanence magnetization (MR) and the coercivity (HC) value increased with increasing doses of irradiation. The increase in MSand MRvalues is attributed to the increase in concentration of Fe3+ions at octahedral B-site and decrease of concentration at the tetrahedral A-site in the NiFe2O4cubic structure. X-ray diffraction (XRD) analysis of the samples showed that peak intensities decreased and the width of the peaks increased with increasing doses of irradiation. Scanning electron microscope (SEM) image of the nanocomposite cross section showed the presence of defects which is more visible with increasing doses of irradiation. In the case of thermal properties, differential scanning calorimetry (DSC) analysis showed that the crystallization temperature (Tc) and the degree of crystallinity (Xc) of the nanocomposite samples decreased with increasing doses of irradiation due to crosslinking of polymeric chains which hinders the growth of crystals.

scholarly journals Synthesis of thermoplastic poly(ester-olefin) elastomers

2004 ◽  
Vol 58 (10) ◽  
pp. 444-449
Author(s):  
Branka Tanasijevic ◽  
Salem Elkhaseh ◽  
Marija Nikolic ◽  
Jasna Djonlagic
Keyword(s):  
Soft Segment ◽  
Weight Ratio ◽  
Soxhlet Extraction ◽  
Thermoplastic Elastomers ◽  
Molecular Structures ◽  
Degree Of Crystallinity ◽  
Molar Ratio ◽  
Mechanical Spectroscopy ◽  
Scanning Calorimetry ◽  
High Boiling Solvent

A series of thermoplastic poly(ester-olefin) elastomers, based on poly(ethylene-stat-butylene), HO-PEB-OH, as the soft segment and poly (butylene terephthalate), PBT, as the hard segment, were synthesized by a catalyzed transesterification reaction in solution. The incorporation of soft hydrogenated poly(butadiene) segments into the copolyester backbone was accomplished by the polycondensation of ?, ?-dihydroxyl telechelic HO-PEB-OH, (PEB Mn = 3092 g/mol) with 1,4-butanediol (BD) and dimethyl terephthalate (DMT) in the presence of a 50 wt-% high boiling solvent i.e., 1,2,4-trichlorobenzene. The molar ratio of the starting comonomers was selected to result in a constant hard to soft weight ratio of 60:40. The synthesis was optimized in terms of both the concentration of catalyst, tetra-n-butyl-titanate (Ti(OBu)4), and stabilizer, N,N'-diphenyl-p-phenylenediamine (DPPD), as well as the reaction time. It was found that the optimal catalyst concentration (Ti(OBu)4) for the synthesis of these thermoplastic elastomers was 1.0 mmol/mol ester and the optimal DPPD concentration was 1.0 wt-%. The extent of the reaction was followed by measuring the inherent viscosity of the reaction mixture. The effectiveness of the incorporation of the soft segments into the copolymer chains was proved by Soxhlet extraction with chloroform. The molecular structures, composition and the size of the synthesized poly(ester-butylene)s were verified by 1H NMR spectroscopy, viscometry of dilute solutions and the complex dynamic melt viscosity. The thermal properties of poly(ester-olefin)s were investigated by differential scanning calorimetry (DSC). The degree of crystallinity was also determined by DSC. The thermal and thermo-oxidative stability were investigated by thermogravimetric analysis (TGA). The rheological properties of poly(ester-olefin)s were investigated by dynamic mechanical spectroscopy in the melt and solid state.

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.

scholarly journals Impact of Water and UV Irradiation on Nonwoven Polylactide/Natural Rubber Fiber

Polymers ◽  
2021 ◽  
Vol 13 (3) ◽  
pp. 461
Author(s):  
Yulia Tertyshnaya ◽  
Maria Podzorova ◽  
Maksim Moskovskiy
Keyword(s):  
Natural Rubber ◽  
Uv Irradiation ◽  
Hydrolytic Degradation ◽  
Thermal Characteristics ◽  
Degree Of Crystallinity ◽  
Scanning Calorimetry ◽  
Melt Flow Rate ◽  
Phase Transition Temperatures ◽  
Nonwoven Fiber ◽  
The Degree Of Crystallinity

A nonwoven fiber made of polylactide/natural rubber with a rubber content from 0 to 15 wt.% was obtained by electrospinning from a solution. The water sorption test showed that the addition of natural rubber into the polylactide matrix did not significantly affect the degree of water absorption of the fibers, which was in the range of 48.9–50.6%. The melt flow rate only increased by 0.5 g/10 min at a content of 15 wt.% natural rubber. The thermal characteristics after 120 days of degradation in distilled water and UV irradiation (50 h) at a wavelength of 365 nm were determined using differential scanning calorimetry. Changes in the values of the phase transition temperatures and the degree of crystallinity were determined. It was determined that the fiber samples from all compositions retained the propensity for photo- and hydrolytic degradation.

scholarly journals Synthesis of thermoplastic poly(ester-siloxane)s in the melt and in solution

2005 ◽  
Vol 70 (12) ◽  
pp. 1469-1485 ◽  
Author(s):  
Biljana Dojcinovic ◽  
Vesna Antic ◽  
Marija Vuckovic ◽  
Jasna Djonlagic
Keyword(s):  
1H Nmr Spectroscopy ◽  
Hard Segment ◽  
Soft Segment ◽  
Weight Ratio ◽  
Thermoplastic Elastomers ◽  
Degree Of Crystallinity ◽  
Mechanical Spectroscopy ◽  
Scanning Calorimetry ◽  
Melting Temperatures ◽  
High Boiling Solvent

Two series of thermoplastic elastomers, based on poly(dimethylsiloxane) PDMS, as the soft segment and poly(butylene terephthalate), PBT, as the hard segment, were synthesized by catalyzed transesterification, from dimethyl terephthalate, DMT, silanol-terminated poly(dimethylsiloxane), PDMS-OH Mn=1750g/mol, and 1,4-butanediol, BD. The mole ratio of the starting comonomers was selected to result in a constant hard to soft weight ratio of 55:45. The first series was synthesized in order to determine the optimal mole ratio of BD and DMT for the synthesis of high molecular weight thermoplastic poly(ester-siloxane)s, TPESs. The second series was performed in the presence of the high-boiling solvent, 1,2,4-trichlorbenzene in order to increase the mixing between the extremely non-polar siloxane prepolymer and the polar reactants, DMT and BD, and, therefore, avoid phase separation during synthesis. The structure and composition of the synthesized poly(ester-siloxane)s were verified by 1H-NMR spectroscopy, while the melting temperatures and degree of crystallinity were determined by differential scanning calorimetry (DSC). The effectiveness of the incorporation of the silanol-terminated poly( dimethylsiloxane) into the polyester chains was verified by chloroform extraction. The rheological properties of the poly(ester-siloxane)s were investigated by dynamic mechanical spectroscopy (DMA).

scholarly journals Tuning the mechanical properties and degradation properties of polydioxanone isothermal annealing

2020 ◽  
Vol 44 (5) ◽  
pp. 1430-1444
Author(s):  
Xiliang LIU ◽  
Shaomin FENG ◽  
Xin WANG ◽  
Jin QI ◽  
Dong LEI ◽  
...  
Keyword(s):  
Tensile Strength ◽  
Isothermal Annealing ◽  
Hydrolytic Degradation ◽  
Degree Of Crystallinity ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
Optical Micrograph ◽  
Potential Applications ◽  
Degradation Properties ◽  
The Degree Of Crystallinity

Polydioxanone (PPDO) is synthesized by ring-opening polymerization of p-dioxanone, using stannous octoate as the catalyst. The polarized optical micrograph (POM) shows thes pherulite growth rate of PPDO decreases with an increase in the isothermal crystallization temperature. PPDO is compression-molded into bars, and PPDO bars are subjected to isothermal annealing at a range of temperatures (Ta = 50, 60, 70, 80, 90, and 100 °C), and correspond to three different annealing times (ta = 1h, 2h, 3h). The effect on PPDO is investigated by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). With an increase in Ta and ta, the grain size and the degree of crystallinity also increase. Meanwhile, the tensile strength is significantly improved. The PPDO bars (90 °C, 2 h) reach the maximum crystallinity (57.21%) and the maximum tensile strength (41.1 MPa). Interestingly, the heat treatment process does not result in serious thermal degradation. It is observed that the hydrolytic degradation of the annealed PPDO is delayed to some extent. Thus, annealed PPDO might have potential applications, particularly in the fields of orthopedic fixation and tissue engineering.

Thermal and Structural Characterization of Furfuryl Palmitate Coated Fly Ash Reinforced Recycled Polypropylene Matrix Composites

2012 ◽  
Vol 584 ◽  
pp. 551-555 ◽  
Author(s):  
Shubhalakshmi Sengupta ◽  
Dipa Ray ◽  
Aniruddha Mukhopadhyay
Keyword(s):  
Fly Ash ◽  
Coupling Agent ◽  
Low Cost ◽  
Weight Ratio ◽  
Xrd Analysis ◽  
Matrix Composites ◽  
Scanning Calorimetry ◽  
Melt Mixing ◽  
Recycled Polypropylene ◽  
Composite Samples

Abstract: The fly ash (FA) particles were coated with furfuryl palmitate (FP) in different weight % like 1, 2, 3 and 5. The FP coated fly ash particles were incorporated as filler in recycled polypropylene (RPP) matrix composites by melt mixing in 1:1 weight ratio. X-ray diffraction (XRD) analysis, Dynamic Mechanical Analysis, Differential scanning calorimetry (DSC), and Thermogravimetric analysis (TGA) of the composite samples were carried out. The presence of the coupling agent FP resulted in changes in the packing order and structural properties of the composites. It also influenced the alignment of RPP molecules with better filler –matrix interaction in 2 wt % FP coated composite as ascertained from the DSC and DMA analysis. Distinct shift in the glass transition temperature was also observed in 2 wt % FP coated composite samples. However significant improvement in the thermal stability was not observed. Thus, an unconventional, renewable, low cost coupling agent FP was found to influence the structural and thermal properties of the RPP/FA composites significantly.

scholarly journals The Influence of Mucin-Based Artificial Saliva on Properties of Polycaprolactone and Polylactide

Polymers ◽  
2019 ◽  
Vol 11 (11) ◽  
pp. 1880 ◽  
Author(s):  
Dawid Łysik ◽  
Joanna Mystkowska ◽  
Grzegorz Markiewicz ◽  
Piotr Deptuła ◽  
Robert Bucki
Keyword(s):  
Oral Cavity ◽  
Artificial Saliva ◽  
Hydrolytic Degradation ◽  
Scanning Calorimetry ◽  
Force Microscopy ◽  
Atomic Force ◽  
Porcine Gastric Mucin ◽  
Rate Of Hydrolysis ◽  
Effects Of Temperature ◽  
Phosphate Buffered Saline

Polycaprolactone (PCL) and polylactide (PLA) are the two most common biodegradable polymers with potential use in oral applications. Both polymers undergo mainly slow hydrolytic degradation in the human body. However, specific conditions of the oral cavity, like elevated temperature, low pH, and presence of saliva affect the rate of hydrolysis. The study examined the properties of solid samples of PCL and PLA subjected to degradation in phosphate buffered saline (PBS) and artificial saliva (AS) at temperatures of 37 or 42 °C, and pH values 2 or 7.4. A number of tests were performed, including measurement of the degree of swelling, weight loss, molecular weight, differential scanning calorimetry, and thermogravimetry of polymers, as well as hardness and tensile strength. Additionally, topography and stiffness of surfaces using atomic force microscopy are presented. It has been noticed that in the artificial saliva, the processes of polymer degradation occur slightly more slowly, and the effects of temperature and pH are less pronounced. We believe that a layer of porcine gastric mucin from artificial saliva that adsorbed on the surface of polymers may have a key role in the observed differences; this layer resembles protective mucin coating tissues in the oral cavity.

Effect of temperature on structure, morphology and crystallinity of PVDF nanofibers via electrospinning

e-Polymers ◽  
2008 ◽  
Vol 8 (1) ◽  
Author(s):  
Fenglin Huang ◽  
Qufu Wei ◽  
Jiaxi Wang ◽  
Yibing Cai ◽  
Yubo Huang
Keyword(s):  
Thermal Properties ◽  
Ambient Temperature ◽  
Vinylidene Fluoride ◽  
Effect Of Temperature ◽  
Scanning Calorimetry ◽  
Ambient Temperatures ◽  
Force Microscopy ◽  
Poly Vinylidene Fluoride ◽  
Different Temperatures ◽  
Surface Morphologies

Abstract Influence of temperature on morphology, structure and crystallinity of Poly (vinylidene fluoride) (PVDF) nanofibers was investigated in this study. The Wehilmy technique and viscosity testing apparatus were used to evaluate the surface tension and viscosity of electrospun solutions at various ambient temperatures. Surface morphologies and diameters of nanofibers were examined by Field-emission Scanning Electron Microscopy (FE-SEM) and atomic force microscopy (AFM). It was found that the surface morphologies were obviously affected by ambient temperature. This dependence was attributed to the change of the properties of Poly (vinylidence fluoride) solutions with temperature. The thermal properties and crystal structures of the PVDF nanofibers electrospun at different temperatures were also studied by differential scanning calorimetry (DSC), and Xray diffraction (XRD). The results revealed that the crystallinity and thermal properties were improved by increasing the ambient temperature during electrospinning

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