scholarly journals Insight into the Role of a Isophthalic Dihydrazide Derivative Containing Piperonylic Acid in Poly(L-lactide) Nucleation: Thermal Performances and Mechanical Properties

2020 ◽  
Vol 57 (3) ◽  
pp. 28-40
Author(s):  
Hao Huang ◽  
Yan-Hua Zhang ◽  
Li-Sha Zhao ◽  
Guang-Ming Luo ◽  
Yan-Hua Cai

This work was aimed at synthesizing the N, N -isophthalic bis(piperonylic acid) dihydrazide (PAID) to be as a new crystallization accelerator for poly(L-lactide) (PLLA), and a detailed investigations of the non-isothermal crystallization, melting behavior, thermal decomposition behavior and mechanical properties of PLLA nucleated by PAID were performed applying differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and electronic tensile tester. The melt-crystallization proved that the PAID could act as a heterogeneous nucleating agent to significantly promote the crystallization in cooling, even the crystallization was still able to be accelerated upon the fast cooling at 50 oC/min. The final melt temperature was another crucial factor for PLLA�s melt crystallization, and when the final melt temperature was 170 oC, the onset crystallization temperature and melt-crystallization enthalpy was almost up to 150 oC and 56.8 J/g upon cooling of 1 oC/min, respectively. Furthermore, the chemical nucleation was proposed to be the nucleation mechanism of PAID for PLLA via the preliminary theoretical calculation. For the cold-crystallization, the addition of PAID exhibited an inhibition for the crystallization of PLLA, but the total crystallization process depended on the heating rate and PAID concentration. The single melting peak after cooling of 1 oC/min indicated that the crystallization had been thoroughly completed in cooling. Additionally, the single melting peak with different locations after full crystallization resulted from the different crystallization temperatures. A comparison in the onset decomposition temperature implied that the presence of PAID only slightly decreased the thermal stability of PLLA. The mechanical testing showed that, in contrast with the elongation at break, the existence of PAID enhanced the tensile strength of PLLA.

e-Polymers ◽  
2016 ◽  
Vol 16 (4) ◽  
pp. 303-311 ◽  
Author(s):  
Yan-Hua Cai ◽  
Li-Sha Zhao

AbstractThe goal of this work was to synthesis a novel aromatic multiamide derivative based on 1H-benzotriazole (PB) as an organic nucleating agent for poly(L-lactic acid) (PLLA), and investigate the effect of PB on the non-isothermal crystallization, melting behavior and thermal decomposition of PLLA. Here, PB was firstly synthesized through 1H-benzotriazole aceto-hydrazide and terephthaloyl chloride, then PB-nucleated PLLA was fabricated via melt-blending technology at various PB concentration from 0.5 wt% to 3 wt%. Finally, the thermal performances were evaluated through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The high thermal decomposition temperature of PB indicated that PB possessed possibility as a nucleating agent for PLLA, and the non-isothermal crystallization behavior confirmed the crystallization accelerating effectiveness of PB for PLLA. Upon optimum concentration of 2 wt%, the onset crystallization temperature, the crystallization peak temperature and the non-isothermal crystallization enthalpy increased from 101.4°C, 94.5°C and 0.1 J·g-1 to 121.3°C, 115.8°C and 35.1 J·g-1, respectively. In addition, the non-isothermal crystallization behavior was also affected by the cooling rate and the final melting temperature. The melting behavior further evidenced the advanced nucleating ability of PB, and the competitive relationship between PB and the heating rate, the nuclear rate and crystal growth rate. Thermal stability measurement showed that PB with a concentration of 1 wt%–2 wt% could slightly improve the thermal stability of PLLA.


2017 ◽  
Vol 15 (1) ◽  
pp. 248-254 ◽  
Author(s):  
Yan-Hua Cai ◽  
Li-Sha Zhao

AbstractThe introduction of a nucleating agent in semi-crystalline polymers is a frequently utilized way to improve the crystallization performance, and the use of a nucleating agent has a very great effect on the performance of the polymer in other areas including thermal stability and mechanical properties. In this investigation, barium phenylphosphonate (BaP) was prepared as a crystallization accelerator for Poly(L-lactic acid) (PLLA), and the non-isothermal crystallization behavior, thermal stability, and mechanical properties of PLLA modified by BaP were investigated using differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and electronic tensile testing. Non-isothermal crystallization analysis showed that the BaP could significantly accelerate the crystallization of PLLA, and the non-isothermal crystallization peak shifted to a higher temperature with increasing concentration of BaP, however, the corresponding crystallization peak became wider. XRD results after non-isothermal crystallization confirmed the non-isothermal crystallization DSC results. Additionally, the addition of BaP did not change the crystal form of PLLA. A comparative study on thermal stability indicated that BaP decreased the onset decomposition temperature of PLLA, resulting from the formation of more tiny and imperfect crystals. Whereas the influence of BaP on the thermal decomposition profile of PLLA was negligible. In terms of mechanical properties, the tensile strength and elastic modulus of PLLA/BaP increased compared to the virgin PLLA, unfortunately, the elongation at break decreased.


2021 ◽  
Author(s):  
Lisha ZHAO ◽  
Yanhua CAI

N, N'-oxalyl bis(piperonylic acid) dihydrazide (PAOD) was obtained through the amination of piperonylic acid chloride and its structure was characterized by Fourier transform infrared spectrometer and nuclear magnetic resonance. Melting blend technology was used to prepare the modified poly(L-lactic acid) (PLLA) containing the various loading PAOD as a new organic nucleating agent. The thermal performances including crystallization, melting behavior and thermal decomposition process, as well as the fluidity of PAOD-nucleated PLLA were investigated via a series of tests. The DSC results showed that, in comparison to DSC curve of the virgin PLLA, the DSC curves of all PLLA/PAOD appeared the sharp melt-crystallization peak, and a higher PAOD concentration caused the melt-crystallization to occur in the higher temperature region and reduced the negative effect of the high cooling rate on the melt-crystallization process. However, with increasing of PAOD concentration, the cold-crystallization enthalpy decreased from 24.4 J/g to 16.7 J/g. The melting peak after melt-crystallization depended on the heating rate and the PAOD concentration; and the double melting peaks appeared after isothermal crystallization in low temperature region was thought to be due to the melting-recrystallization. The addition of PAOD decreased the onset decomposition temperature of PLLA, but the onset decomposition temperature was determined by the PAOD concentration and the intermolecular interaction of PLLA and PAOD. Additionally, the PAOD could considerably improve the fluidity of PLLA.


Molecules ◽  
2020 ◽  
Vol 25 (9) ◽  
pp. 2158
Author(s):  
Nanci Vanesa Ehman ◽  
Diana Ita-Nagy ◽  
Fernando Esteban Felissia ◽  
María Evangelina Vallejos ◽  
Isabel Quispe ◽  
...  

Bio-polyethylene (BioPE, derived from sugarcane), sugarcane bagasse pulp, and two compatibilizers (fossil and bio-based), were used to manufacture biocomposite filaments for 3D printing. Biocomposite filaments were manufactured and characterized in detail, including measurement of water absorption, mechanical properties, thermal stability and decomposition temperature (thermo-gravimetric analysis (TGA)). Differential scanning calorimetry (DSC) was performed to measure the glass transition temperature (Tg). Scanning electron microscopy (SEM) was applied to assess the fracture area of the filaments after mechanical testing. Increases of up to 10% in water absorption were measured for the samples with 40 wt% fibers and the fossil compatibilizer. The mechanical properties were improved by increasing the fraction of bagasse fibers from 0% to 20% and 40%. The suitability of the biocomposite filaments was tested for 3D printing, and some shapes were printed as demonstrators. Importantly, in a cradle-to-gate life cycle analysis of the biocomposites, we demonstrated that replacing fossil compatibilizer with a bio-based compatibilizer contributes to a reduction in CO2-eq emissions, and an increase in CO2 capture, achieving a CO2-eq storage of 2.12 kg CO2 eq/kg for the biocomposite containing 40% bagasse fibers and 6% bio-based compatibilizer.


2021 ◽  
Vol 36 (2) ◽  
pp. 137-143
Author(s):  
S. A. Awad

Abstract This paper aims to describe the thermal, mechanical, and surface properties of a PVA/HPP blend whereby the film was prepared using a solution casting method. The improvements in thermal and mechanical properties of HPP-based PVA composites were investigated. The characterization of pure PVA and PVA composite films included tensile tests, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The results of TGA and DSC indicated that the addition of HPP increased the thermal decomposition temperature of the composites. Mechanical properties are significantly improved in PVA/HPP composites. The thermal stability of the PVA composite increased with the increase of HPP filler content. The tensile strength increased from 15.74 ± 0.72 MPa to 27.54 ± 0.45 MPa and the Young’s modulus increased from 282.51 ± 20.56 MPa to 988.69 ± 42.64 MPa for the 12 wt% HPP doped sample. Dynamic mechanical analysis (DMA) revealed that at elevated temperatures, enhanced mechanical properties because of the presence of HPP was even more noticeable. Morphological observations displayed no signs of agglomeration of HPP fillers even in composites with high HPP loading.


2017 ◽  
Vol 37 (6) ◽  
pp. 607-616 ◽  
Author(s):  
Xiwei Jing ◽  
Weiguang Gong ◽  
Zhongjun Feng ◽  
Xin Meng ◽  
Baicun Zheng

Abstract A comb-like copolymer poly (styrene-co-maleic anhydride)-graft-poly (ε-caprolacton) (SMA-g-PCL, SP) with carboxyl group as an anchoring group and polycaprolactone as a solvent chain was used as an effective dispersant for CaCO3 in the polypropylene (PP) matrix. The effects of CaCO3 concentration on crystallization behaviors, mechanical properties, and thermal stabilities were studied systematically. The results revealed that the dispersion of CaCO3 in the PP matrix was markedly improved owing to the steric hindrance effect caused by PCL, and the SP-coated CaCO3 was a very effective nucleating agent for PP. Proper CaCO3 concentration corresponded to the improvement of crystallization temperature, crystallinity, and crystallization rate of PP. There was only a slight improvement in yield stress but great improvement in Young’s modulus, flexural modulus, and impact strength. However, the excessive CaCO3 filler deteriorated the mechanical properties. The good dispersion of SP-coated CaCO3 in the PP matrix also accounted for the improvement of thermal stability. The initial decomposition temperature of the PP/CaCO3 composite with 7.4 wt.% CaCO3 increased 35°C compared with neat PP.


2020 ◽  
Vol 42 (3) ◽  
pp. 383-383
Author(s):  
Li Sha Zhao and Yan Hua Cai Li Sha Zhao and Yan Hua Cai

In this study, a 1H-benzotriazole derivative, N, Nand#39;-bis(1H-benzotriazole) succinic acid acethydrazide (SABHA), was synthesized to nucleate Poly(L-lactic acid) (PLLA). A series of comparative studies on the melt-crystallization, the cold-crystallization, the melting behavior, the thermal stability, as well as the fluidity between the pure PLLA and PLLA/SABHA were performed. The melt-crystallization behavior revealed that the SABHA as a heterogeneous nucleating agent could significantly facilitate the crystallization of PLLA, and a larger amount of SABHA concentration exhibited the better nucleation effect. However, for the cold-crystallization process, the crystallization peak shifted toward the lower temperature with increasing of SABHA concentration. The melting behavior after crystallization at different crystallization temperatures showed that the melting process of PLLA/SABHA samples depended on the crystallization temperature, and the appearance of the double melting peaks was attributed to the melt-recrystallization. The thermal decomposition profile of PLLA was not affected by SABHA, but the addition of SABHA reduced the thermal stability of PLLA. Fortunately, the presence of SABHA improved the fluidity of PLLA, and the effect of SABHA concentration on the fluidity was positive.


2008 ◽  
Vol 8 (4) ◽  
pp. 1658-1668 ◽  
Author(s):  
Defeng Wu ◽  
Liang Wu ◽  
Lanfeng Wu ◽  
Bin Xu ◽  
Yisheng Zhang ◽  
...  

The isothermal cold and melt crystallization behavior of intercalated polylactide (PLA)/clay nanocomposites (PLACNs) were studied using differential scanning calorimetry (DSC), polarized optical microscope (POM), X-ray diffractometer (XRD) and Fourier Transform Infra-Red Spectrometer (FT-IR). The results show that the degree of crystallinity of PLA matrix decreases monotonously with increasing clay loadings for both the cold and melt crystallization. The cold crystallized sample shows a double melting behavior and lower melting temperature compared to that of melt-crystallized sample, especially in the presence of clay. The crystallization kinetics was then analyzed by the Avrami and Lauritzen-Hoffman methods for further comparison between these two crystallization behaviors. The results reveal that PLA and its nanocomposites present higher activation energy in melt crystallization than that in cold crystallization due to the reptation of entire polymer chains. The addition of clay facilitates the overall kinetics of melt crystallization, which is attributed to both the nucleation effect of clay and enhanced diffusion of PLA chains. However, for cold crystallization, only very small amounts of clay can slightly increase the kinetics, while larger amounts impede the process. The presence of clay leads to a diffusion-controlled growth of nucleation of PLA matrix in the cold crystallization process and, the hindrance effect of clay hence becomes the dominant factor gradually with increasing clay loadings in the case of high-rate nucleation.


2012 ◽  
Vol 624 ◽  
pp. 264-268 ◽  
Author(s):  
Duo You Zhang ◽  
Peng Liu ◽  
Chun Fa Ouyoung ◽  
Qun Gao ◽  
Kang Sheng Zheng ◽  
...  

PNA012 is a new nucleating agent on polybutylene terephthalate. The effect of different dosage of PNA012 on crystallization and mechanical properties were investigated by means of differential scanning calorimetry, universal testing machine, melt flow indexer and vicat softening testing machine. It was revealed that the PNA012 could substantially accelerate the crystallization of PBT. Compared with the pure PBT,the crystallization temperature of PBT/PNA012 rises from 196.3 °C to 199.7 °C and crystallization degree from 34.2% to 39.9%. The tensile Strength of PBT/PNA012 is increased 9.7%. The Bending Strength has a rise of 9.3% and the heat distortion temperatures of PBT/PNA012 is increased from 115.07°C to 125.94°C.


2018 ◽  
Vol 38 (8) ◽  
pp. 759-765
Author(s):  
Muhammad Remanul Islam ◽  
Md. Dalour H. Beg

Abstract Multi-walled carbon nanotube (MWCNT) reinforced polyester-based composites were prepared by mixed blending in a solvent. Orthophthalic unsaturated polyester was blended individually with different types of non-functionalized and functionalized MWCNTs. Two types of functional groups: hydroxyl (-OH) and carboxyl (-COOH) were introduced with MWCNTs for the nanocomposites. The mechanical properties of the composites, like tensile, three-point bending and impact energy were evaluated. Fourier transform infrared spectroscopy was used for the functional group analysis. The dispersion characteristics of the samples were observed by transmission electron microscopy and field-emission electron microscopy. In addition, the thermal decomposition and melting behavior of the samples was assessed by differential scanning calorimetry and thermogravimetric analysis. The properties were varied due to the variation of the functional groups. The result analysis showed that the entangled agglomerations of hydroxyl-functionalized MWCNTs were destroyed to relatively smaller clusters. The hydroxyl-functionalized MWCNTs were more effective for homogeneous dispersion and contributed for better mechanical properties of the composites, compared to non-functionalized and carboxyl group-functionalized MWCNTs.


Sign in / Sign up

Export Citation Format

Share Document