Effect of cooling induced crystallization upon the properties of segmented thermoplastic polyurethanes

2017 ◽  
Vol 37 (5) ◽  
pp. 471-480 ◽  
Author(s):  
Daniel Ramirez ◽  
Juliana Nanclares ◽  
Marisa Spontón ◽  
Mara Polo ◽  
Diana Estenoz ◽  
...  

Abstract An investigation on the cooling-induced crystallization in three thermoplastic polyurethanes based on MDI, PTMG, and 1.4-BD as chain extender with different hard segment content is reported. Thermal transitions were determined using differential scanning calorimetry (DSC) measurements at different cooling rates, and thermal stability was studied by thermogravimetric analysis. Changes in Raman spectra were useful to correlate the thermal transitions with changes in the morphology of the polymers. The dissimilarity in the composition gave different rheological behavior in the molten state, indicated by the temperature dependence of the viscosity. The mechanical properties and the crystallinity was influenced not only by the cooling rate but also by the hard segment content. Thermoplastic polyurethanes with more hard segment content formed more crystalline hard domains as evidenced by the DSC and atomic force microscopy results.

e-Polymers ◽  
2020 ◽  
Vol 20 (1) ◽  
pp. 469-481
Author(s):  
Yang Gao ◽  
Jie Lv ◽  
Licheng Liu ◽  
Yingfeng Yu

AbstractIt is low cost and feasible to improve the mechanical properties of polyurethane by using the chain extender with hydrogen bonding function to improve the degree of microphase separation. In this article, hydrazine hydrate was used to react with ethylene carbonate and propylene carbonate, respectively, to synthesize diacylhydrazines as the polyurethane chain extender with amide bonds, which were characterized by 1H nuclear magnetic resonance. Polyurethane with different contents of hard segment were prepared from poly-3,3-bis(azidomethyl)oxetane-tetrahydrofuran as the polyol and 4,4′-diphenylmethane diisocyanate as the isocyanate components. Fourier transform infrared spectroscopy showed that with the increase of the hard segment content, the proportion of hydrogen-bonded ordered carbonyl group increased to 94%, proving that diacylhydrazines could improve the degree of ordered hydrogen bonding, which led to clear microphase separation observed by field emission scanning electron microscopy and higher storage modulus of the polyurethane. Differential scanning calorimetry and dynamic mechanical analysis showed that polyurethane with higher hard segment content is likely to exhibit multiple thermal transitions caused by microphase separation. When the hard segment content was 40%, compared with polyurethane with 1,4-butanediol as the chain extender, the tensile strengths of polyurethanes with diacylhydrazines also improved by 30% and 76%, respectively.


Polymers ◽  
2018 ◽  
Vol 10 (11) ◽  
pp. 1292 ◽  
Author(s):  
Jia-Wun Li ◽  
Hsun-Tsing Lee ◽  
Hui-An Tsai ◽  
Maw-Cherng Suen ◽  
Chih-Wei Chiu

In this study, novel biodegradable long-segment fluorine-containing polyurethane (PU) was synthesized using 4,4′-diphenylmethane diisocyanate (MDI) and 1H,1H,10H,10H-perfluor-1,10-decanediol (PFD) as hard segment, and polycaprolactone diol (PCL) as a biodegradable soft segment. Nuclear magnetic resonance (NMR) was used to perform 1H NMR, 19F NMR, 19F–19F COSY, 1H–19F COSY, and HMBC analyses on the PFD/PU structures. The results, together with those from Fourier transform infrared spectroscopy (FTIR), verified that the PFD/PUs had been successfully synthesized. Additionally, the soft segment and PFD were changed, after which FTIR and XPS peak-differentiation-imitating analyses were employed to examine the relationship of the hydrogen bonding reaction between the PFD chain extender and PU. Subsequently, atomic force microscopy was used to investigate the changes in the microphase structure between the PFD chain extender and PU, after which the effects of the thermal properties between them were investigated through thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Finally, the effects of the PFD chain extender on the mechanical properties of the PU were investigated through a tensile strength test.


2011 ◽  
Vol 31 (2-3) ◽  
Author(s):  
Abhinay Mishra ◽  
Pralay Maiti

Abstract Structural variation and its effect on the properties of aromatic polyurethanes (PUs) with different chain structures have been reported. Polarized optical microscopic studies of aromatic PUs demonstrate the development of micro clusters with increasing hard segment content (HSC). Higher crystallinity has also been proven from differential scanning calorimeter (DSC) and X-ray diffraction (XRD) studies. A globular pattern has been observed through atomic force microscopy (AFM) and the pattern depends on the type of diisocyanate used to prepare the PU. The difference in surface morphology is evident for two different PUs. The tensile modulus increases systematically with increasing HSC while toughness decreases, due to the presence of bigger crystallites in higher HSC polymer. Both the modulus and toughness vary on the type of diisocyanate present in PUs.


2010 ◽  
Vol 45 (6) ◽  
pp. 621-630 ◽  
Author(s):  
Mihaela Alexandru ◽  
Carmen Racles ◽  
Maria Cazacu ◽  
Alexandra Nistor ◽  
Ana-Maria Macsim

Polydimethylsiloxane-α,ω-diols with different contents of pendant chloromethyl groups were reacted with an aromatic diamine (3,3′-dimethoxybenzidine) when cross-linking occurred. The reactions were performed in silica — generating sol— gel system; so two interconnected networks (silica and cross-linked polydimethylsiloxane) were formed. The resulting structures were investigated by FT-IR and 1H-NMR spectroscopies. Differential scanning calorimetry was used to emphasize the thermal transitions of the resulted materials and the water sorption capacity was investigated by dynamic vapor sorption, the obtained values being influenced by the amount of polar groups. Atomic force microscopy was used to evaluate the morphology and surface topography in dry as well as in swollen state in water and heptane.


Polymers ◽  
2021 ◽  
Vol 13 (6) ◽  
pp. 878
Author(s):  
Krystyna Wnuczek ◽  
Andrzej Puszka ◽  
Łukasz Klapiszewski ◽  
Beata Podkościelna

This study presents the preparation and the thermo-mechanical characteristics of polymeric blends based on di(meth)acrylates monomers. Bisphenol A glycerolate diacrylate (BPA.GDA) or ethylene glycol dimethacrylate (EGDMA) were used as crosslinking monomers. Methyl methacrylate (MMA) was used as an active solvent in both copolymerization approaches. Commercial polycarbonate (PC) was used as a modifying soluble additive. The preparation of blends and method of polymerization by using UV initiator (Irqacure® 651) was proposed. Two parallel sets of MMA-based materials were obtained. The first included more harmless linear hydrocarbons (EGDMA + MMA), whereas the second included the usually used aromatic copolymers (BPA.GDA + MMA). The influence of different amounts of PC on the physicochemical properties was discussed in detail. Chemical structures of the copolymers were confirmed by attenuated total reflection–Fourier transform infrared (ATR/FT-IR) spectroscopy. Thermo-mechanical properties of the synthesized materials were investigated by means of differential scanning calorimetry (DSC), thermogravimetric (TG/DTG) analyses, and dynamic mechanical analysis (DMA). The hardness of the obtained materials was also tested. In order to evaluate the surface of the materials, their images were obtained with the use of atomic force microscopy (AFM).


2013 ◽  
Vol 464 ◽  
pp. 9-13 ◽  
Author(s):  
Zan Li ◽  
Xia Wang ◽  
Ying Li ◽  
Wei Chain ◽  
Jiao Jiao Hu

Fluorinated polyurethanes (FPU) was prepared using fluorinated polyether polyol (FPO) as the soft segment, 4,4`-diphenylmethane diisocyanate (MDI) as the hard segment, 1,4-butanodiol (BDO) as the chain extender and catalysts. Tin metal catalysts were used to catalyze the polyurethane reaction of polyether polyols and isocyanate. The effect of different catalysts including stannous octoate (T-9) and dibutyltindalautrate (DBTDL) on the structure, surface properties and thermal properties of FPU was studied. The structural elucidation of the synthesized FPU was performed by Fourier transform infrared (FT-IR) and discovered that with decreasing catalyst efficiency or without catalyst, the strength of hydrogen bounds were enhanced. The FPU films surface was characterized by contact angle (CA) and atomic force microscopy (AFM) and it was found that the phase separation was increasing with increasing catalyst efficiency. The thermal property was exhibited by Thermo gravimetric (TG) and showed that joining catalyst improved stability significantly.


2015 ◽  
Vol 1754 ◽  
pp. 69-74
Author(s):  
Ravi Gaikwad ◽  
Tinu Abraham ◽  
Aharnish Hande ◽  
Fatemeh Bakhtiari ◽  
Siddhartha Das ◽  
...  

ABSTRACTAtomic force microscopy is employed to study the structural changes in the morphology and physical characteristics of asphaltene aggregates as a function of temperature. The exotic fractal structure obtained by evaporation-driven asphaltene aggregates shows an interesting dynamics for a large range of temperatures from 25°C to 80°C. The changes in the topography, surface potential and adhesion are unnoticeable until 70°C. However, a significant change in the dynamics and material properties is displayed in the range of 70°C - 80°C, during which the aspahltene aggregates acquire ‘liquid-like’ mobility and fuse together. This behaviour is attributed to the transition from the pure amorphous phase to a crystalline liquid phase which occurs at approximately 70°C as shown by using Differential Scanning Calorimetry (DSC). Additionally, the charged nature of asphaltenes and bitumen is also explored using kelvin probe microscopy. Such observations can lead to the development of a rational approach to the fundamental understanding of asphaltene aggregation dynamics and may help in devising novel techniques for the handling and separation of asphaltene aggregates using dielectrophoretic methods.


2020 ◽  
Vol 40 (2) ◽  
pp. 136-142 ◽  
Author(s):  
Homa Maleki ◽  
Hossein Barani

AbstractThe stereocomplex formation is a promising method to improve the properties of poly(lactide) (PLA)-based products due to the strong interaction of the side-by-side arrangement of the molecular chains. Recently, electrospinning method has been applied to prepare PLA stereocomplex, which is more convenient. The objective of the current study is to make stereocomplexed PLA nanofibers using electrospinning method and compare their properties and structures with pure poly(l-lactide) (PLLA) fibers. The stereocomplexed fibers were electrospun from a blend solution of high molecular weight PLLA and poly(d-lactide) (1:1 ratio). The morphology of the obtained electrospun fibers was examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Differential scanning calorimetry was applied to study their thermal properties and crystallinity. Fourier transform infrared spectroscopy (FTIR) test was conducted on the samples to characterize their chemical properties. The SEM and AFM images indicated that smooth uniform fibers with a cylindrical structure were produced. Besides, the FTIR results and thermal properties confirmed that only stereocomplex crystallites formed in the resulting fibers via the electrospinning method.


2011 ◽  
Vol 197-198 ◽  
pp. 1196-1200
Author(s):  
Kun Peng Wang ◽  
Li Ting Yang

A series of polyols (GSOLs) with a range of hydroxyl numbers based on epoxidized soybean oil (ESO) were prepared by ring opening with glycol. These Polyols of hydroxyl (OH) numbers ranging from 111 to 162 mg KOH/g were obtained. The environmentally friendly soybean-oil-based waterborne polyurethane dispersions (SPU) with very promising properties have been successfully synthesized from a series of soybean-oil-based polyols (GSOLs) with different hydroxyl numbers by a polyaddition reaction with toluene 2,4-diisocyanate (2,4-TDI). The structure and thermophysical properties of the resulting SPU films have been studied by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and hardness testing. The experimental results showed that the functionality of the GSOLs and the hard segment content play a key role in controlling the structure and the thermophysical properties of the SPU films.


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