scholarly journals Impact of the Surface Properties of Cellulose Nanocrystals on the Crystallization Kinetics of Poly(Butylene Succinate)

Crystals ◽  
2020 ◽  
Vol 10 (3) ◽  
pp. 196 ◽  
Author(s):  
Hatem Abushammala ◽  
Jia Mao

The hydrophilicity of cellulose nanocrystals (CNCs) is a major challenge for their processing with hydrophobic polymers and matrices. As a result, many surface modifications have been proposed to hydrophobize CNCs. The authors showed in an earlier study that grafting alcohols of different chain lengths onto the surface of CNCs using toluene diisocyanate (TDI) as a linker can systematically hydrophobize CNCs to a water contact angle of up to 120° depending on the alcohol chain length. Then, the hydrophobized CNCs were used to mechanically reinforce poly(butylene succinate) (PBS), which is a hydrophobic polymer. As a result of hydrophobization, PBS/CNCs interfacial adhesion and the composite mechanical properties significantly improved with the increasing CNC contact angle. Continuing on these results, this paper investigates the impact of CNC surface properties on the crystallization behavior of PBS using differential scanning calorimetry (DSC). The results showed that the crystallization temperature of PBS increased from 74.7 °C to up to 86.6 °C as a result of CNC nucleation activity, and its value was proportionally dependent on the contact angle of the CNCs. In agreement, the nucleation activity factor (φ) estimated using Dobreva and Gutzow’s method decreased with the increasing CNC contact angle. Despite the nucleation action of CNCs, the rate constant of PBS crystallization as estimated using the Avrami model decreased in general as a result of a prevailing impeding effect. This decrease was minimized with increasing the contact angle of the CNCs. The impeding effect also increased the average activation energy of crystallization, which was estimated using the Kissinger method. Moreover, the Avrami exponent (n) decreased because of CNC addition, implying a heterogeneous crystallization, which was also apparent in the crystallization thermograms. Overall, the CNC addition facilitated PBS nucleation but retarded its crystallization, and both processes were significantly affected by the surface properties of the CNCs.

Polymers ◽  
2020 ◽  
Vol 12 (1) ◽  
pp. 95 ◽  
Author(s):  
Hatem Abushammala

Despite the many interesting properties of cellulose nanocrystals (CNCs), their hydrophilicity is one of the main challenges for their processing with hydrophobic polymers and matrices. To overcome this challenge, this paper describes the preparation of brush-like CNCs with tailored surface properties by grafting alcohols of different chain lengths onto their surfaces. Ethanol, 1-butanol, 1-hexanol, and 1-octanol were grafted on the CNC surface using 2,4-toluene diisocyanate (TDI) as a linker. The CNCs were characterized for their structural, morphological, surface, and thermal properties. Because of the grafting, the water contact angle of the CNCs significantly increased from 32° to up to 120°, which was dependent on the chain length of the grafted alcohol. The thermal stability of the CNCs was also improved, mainly as a result of the reaction of TDI with the CNC hydroxyl groups. Later, the CNCs were used to reinforce films of poly(butylene succinate) (PBS), which were then characterized using dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). An increase of up to two-fold in the storage modulus was observed using DMA, which was dependent on the chain length of the grafted alcohol. However, no change in the glass transition temperature or degradation temperature of PBS was detected. This approach is proved efficient for tailoring the surface properties of CNCs towards excellent interfacial adhesion in their composites.


Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1643
Author(s):  
Ricardo Donate ◽  
María Elena Alemán-Domínguez ◽  
Mario Monzón

Surface modification of 3D-printed PLA structures is a major issue in terms of increasing the biofunctionality and expanding the tissue engineering applications of these parts. In this paper, different exposure times were used for low-pressure oxygen plasma applied to PLA 3D-printed scaffolds. Alkali surface treatments were also evaluated, aiming to compare the modifications introduced on the surface properties by each strategy. Surface-treated samples were characterized through the quantification of carboxyl groups, energy-dispersive X-ray spectroscopy, water contact angle measurements, and differential scanning calorimetry analysis. The change in the surface properties was studied over a two-week period. In addition, an enzymatic degradation analysis was carried out to evaluate the effect of the surface treatments on the degradation profile of the 3D structures. The physicochemical characterization results suggest different mechanism pathways for each type of treatment. Alkali-treated scaffolds showed a higher concentration of carboxyl groups on their surface, which enhanced the enzymatic degradation rate, but were also proven to be more aggressive towards 3D-printed structures. In contrast, the application of the plasma treatments led to an increased hydrophilicity of the PLA surface without affecting the bulk properties. However, the changes on the properties were less steady over time.


Nanomaterials ◽  
2020 ◽  
Vol 10 (12) ◽  
pp. 2564
Author(s):  
Amparo López-Rubio ◽  
Adriana Blanco-Padilla ◽  
Kristiina Oksman ◽  
Sandra Mendoza

In this work, two different strategies for the development of amaranth protein isolate (API)-based films were evaluated. In the first strategy, ultrathin films were produced through spin-coating nanolayering, and the effects of protein concentration in the spin coating solution, rotational speed, and number of layers deposited on the properties of the films were evaluated. In the second strategy, cellulose nanocrystals (CNCs) were incorporated through a casting methodology. The morphology, optical properties, and moisture affinity of the films (water contact angle, solubility, water content) were characterized. Both strategies resulted in homogeneous films with good optical properties, decreased hydrophilic character (as deduced from the contact angle measurements and solubility), and improved mechanical properties when compared with the neat API-films. However, both the processing method and film thickness influenced the final properties of the films, being the ones processed through spin coating more transparent, less hydrophilic, and less water-soluble. Incorporation of CNCs above 10% increased hydrophobicity, decreasing the water solubility of the API films and significantly enhancing material toughness.


2013 ◽  
Vol 33 (2) ◽  
pp. 111-119
Author(s):  
Yiming Liu ◽  
Qing Liu ◽  
Bing Meng ◽  
Zhihua Wu

Abstract Polycaprolactone (PCL)-coated micro kaolin and nano-titania were prepared by high-speed hybrid mechanical coating. Poly(butylene succinate) (PBS)-coated inorganic particle composites were prepared by the melt-blending process. The influence of coated kaolin microparticles on the dynamic rheological behavior, non-isothermal crystallization behavior, micromorphology, and mechanical behavior were investigated. The effect of coated nano-titania on the mechanical properties of PBS-coated kaolin composites was also studied. A dynamic rheological property indicates that the complex viscosity of PBS-coated kaolin microcomposites is higher than neat PBS. Differential scanning calorimetry (DSC) implies that the micrometric size of kaolin particles restrains the crystallization of PBS. Scanning electronic microscopy (SEM) reveals a well dispersed state of coated kaolin in the polymer matrix. The impact strength of PBS-coated kaolin microcomposites is improved, while the tensile strength and elongation at break is decreased, but still appreciable. The introduction of coated nano-titania improves the impact strength dramatically, and the elongation at break of composites is considerable.


1995 ◽  
Vol 383 ◽  
Author(s):  
M. R. Houston ◽  
R. T. Howe ◽  
K Komvopoulos ◽  
R. Maboudian

ABSTRACTThe surface properties of diamond-like carbon (DLC) films deposited by a vacuum arc technique on smooth silicon wafers are presented with specific emphasis given to stiction reduction in microelectromechanical systems (MEMS). The low deposition temperatures afforded by the vacuum arc technique should allow for easy integration of the DLC films into the current fabrication process of typical surface micromachines by means of a standard lift-off processing technique. Using X-ray photoelectron spectroscopy (XPS), contact angle analysis, and atomic force microscopy (AFM), the surface chemistry, microroughness, hydrophobicity, and adhesion forces of DLC-coated Si(100) surfaces were measured and correlated to the measured water contact angles. DLC films were found to be extremely smooth and possess a water contact angle of 87°, which roughly corresponds to a surface energy of 22 mJ/m2. It is shown that the pull-off forces measured by AFM correlate well with the predicted capillary forces. Pull-off forces are reduced on DLC surfaces by about a factor of five compared to 10 nN pull-off forces measured on the RCA-cleaned silicon surfaces. In the absence of meniscus forces, the overall adhesion force is expected to decrease by over an order of magnitude to the van der Waals attractive force present between two DLC-coated surfaces- To further improve the surface properties of DLC, films were exposed to a fluorine plasma which increased the contact angle to 99° and lowered the pull-off force by approximately 20% over that obtained with as-deposited DLC. The significance of these results is discussed with respect to stiction reduction in micromachines.


Polymers ◽  
2021 ◽  
Vol 13 (18) ◽  
pp. 3177
Author(s):  
Moein Zarei ◽  
Miroslawa El Fray

Polymeric materials have numerous applications from the industrial to medical fields because of their vast controllable properties. In this study, we aimed to synthesize series of poly(butylene succinate-dilinoleic succinate-ethylene glycol succinate) (PBS-DLS-PEG) copolymers, by two-step polycondensation using a heterogeneous catalyst and a two-step process. PEG of different molecular weights, namely, 1000 g/mol and 6000 g/mol, was used in order to study its effect on the surface and thermal properties. The amount of the PBS hard segment in all copolymers was fixed at 70 wt%, while different ratios between the soft segments (DLS and PEG) were applied. The chemical structure of PBS-DLS-PEG was evaluated using Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. Gel permeation chromatography was used to determine the molecular weight and dispersity index. The results of structural analysis indicate the incorporation of PEG in the macrochain. The physical and thermal properties of the newly synthesized copolymers were also evaluated using water contact angle measurements, differential scanning calorimetry and dynamic thermomechanical analysis. It was found that increasing the amount of PEG of a higher molecular weight increased the surface wettability of the new materials while maintaining their thermal properties. Importantly, the two-step melt polycondensation allowed a direct fabrication of a polymeric filament with a well-controlled diameter directly from the reactor. The obtained results clearly show that the use of two-step polycondensation in the melt allows obtaining novel PBS-DLS-PEG copolymers and creates new opportunities for the controlled processing of these hydrophilic and thermally stable copolymers for 3D printing technology, which is increasingly used in medical techniques.


Materials ◽  
2020 ◽  
Vol 13 (14) ◽  
pp. 3196
Author(s):  
Marta Piątek-Hnat ◽  
Kuba Bomba ◽  
Jakub Pęksiński ◽  
Agnieszka Kozłowska ◽  
Jacek G. Sośnicki ◽  
...  

The purpose of this research was synthesis and electron beam modification of novel ester elastomers consisting of sugar alcohol–succinic acid block and butylene glycol–succinic acid block. Four different alditols were used in the synthesis—sorbitol, erythritol, xylitol, and glycerol. The materials were irradiated with doses of 50, 100, and 150 kGy in order to determine which dose is the most beneficial. As expected, irradiation of the materials has led to the cross-link density becoming higher and improvement of the mechanical properties. Additionally, the materials were also sterilized in the process. The great advantage of elastomers described in the paper is the fact that they do not need chemical cross-linking agents or sensitizers in order to undergo radiation modification. The following tests were performed on cross-linked poly(polyol succinate-co-butylene succinate) elastomers: quasi-static tensile test, determination of cross-link density, differential scanning calorimetry (DSC), dynamic thermomechanical analysis (DMTA), wettability (water contact angle), and Fourier transform infrared spectroscopy (FTIR). In order to confirm successful synthesis, prepolymers were analyzed by nuclear magnetic resonance spectroscopy (1H NMR and 13C NMR).


2017 ◽  
Vol 268 ◽  
pp. 87-91
Author(s):  
Syarinie Azmi ◽  
Ramli Arifin ◽  
Sib Krishna Ghoshal

Economically viable and maintenance free glass surfaces with improved hydrophobicity are highly demanding in the recent nanotechnology era. Deposition of pollutants and dirt on glass surface that not only causes visual obscurity but also damages the cultural heritages are still to be researched intensely. It is documented that excellent hydrophobic surfaces (with contact angle greater than 90o) can be achieved by controlling the surface wettability, where liquid droplets remain spherical on such surfaces. Selection of materials and the preparation method play a significant role towards such accomplishments. Stirred by this idea, we explored the feasibility of fabricating super-hydrophobic tellurite glass systems by facilely varying the compositions of different constituents. Highly transparent and thermally stable ternary tellurite glass system with chemical composition of (80-x)TeO2 – xSiO2 – 20ZnO, where x = 0.00 to 0.20 mol% are synthesized via conventional melt-quenching method. Samples are characterized using Atomic Force Microscopy (AFM) and contact angle measurements. The impact of SiO2 concentrations variation on the surface roughness, surface energy, and hydrophobic properties are inspected. Glass surface roughness as much as 9.885 nm is attained. The optimal value of water contact angle is discerned to be 101.02° for 0.1 mol% of SiO2 incorporation into the amorphous tellurite host matrix. Besides, the surface energy revealed an inverse proportionality to the water contact angle. This achieved contact angle (greater than 90°) makes this hydrophobic glass surface beneficial for diverse applications. It is established that the present glass composition may be prospective for the development of super-hydrophobic surfaces.


Polymers ◽  
2021 ◽  
Vol 13 (16) ◽  
pp. 2706
Author(s):  
Minghui Xu ◽  
Xianming Lu ◽  
Ning Liu ◽  
Qian Zhang ◽  
Hongchang Mo ◽  
...  

In order to enhance the application performance of glycidyl azide polymer (GAP) in solid propellant, an energetic copolyurethane binder, (poly[3,3-bis(2,2,2-trifluoro-ethoxymethyl)oxetane] glycol-block-glycidylazide polymer (PBFMO-b-GAP) was synthesized using poly[3,3-bis(2,2,2-trifluoro-ethoxymethyl)oxetane] glycol (PBFMO), which was prepared from cationic polymerization with GAP as the raw material and toluene diisocyanate (TDI) as the coupling agent via a prepolymer process. The molecular structure of copolyurethanes was confirmed by attenuated total reflectance-Fourier transform-infrared spectroscopy (ATR–FTIR), nuclear magnetic resonance spectrometry (NMR), and gel permeation chromatography (GPC). The impact sensitivity, mechanical performance, and thermal behavior of PBFMO-b-GAP were studied by drop weight test, X-ray photoelectron spectroscopic (XPS), tensile test, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA), respectively. The results demonstrated that the introduction of fluoropolymers could evidently reduce the sensitivity of GAP-based polyurethane and enhance its mechanical behavior (the tensile strength up to 5.75 MPa with a breaking elongation of 1660%). Besides, PBFMO-b-GAP exhibited excellent resistance to thermal decomposition up to 200 °C and good compatibility with Al and cyclotetramethylene tetranitramine (HMX). The thermal performance of the PBFMO-b-GAP/Al complex was investigated by a cook-off test, and the results indicated that the complex has specific reaction energy. Therefore, PBFMO-b-GAP may serve as a promising energetic binder for future propellant formulations.


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