scholarly journals Physical Properties of Biodegradable Poly(L-lactide) Induced by N, N -Bis(Benzoyl) 1, 3-Cyclohexanedicarboxylic Acid Dihydrazide as Crystallinity Additive

2021 ◽  
Vol 58 (2) ◽  
pp. 48-59
Author(s):  
Li-Sha Zhao ◽  
Ting Deng ◽  
Jun Qiao ◽  
Yan-Hua Cai
Keyword(s):  
Cooling Rate ◽  
Heating Rate ◽  
Melting Temperature ◽  
Crystallization Process ◽  
Melting Behavior ◽  
Cold Crystallization ◽  
Light Transmittance ◽  
Melt Crystallization ◽  
Crystallization Peak ◽  
Crystallization Ability

This work is aimed at synthesizing an organic compound N, N -bis(benzoyl) 1,3-cyclohexane-dicarboxylic acid dihydrazide (CABH) to focus on its effect on the non-isothermal crystallization of poly(L-lactide) (PLLA), meanwhile the melting behavior, thermal decomposition process and optical property of PLLA/CABH samples in different CABH concentrations were also investigated. It was found that CABH acted as efficient heterogeneous nucleating agent for inducing PLLA�s crystallization through comparative analysis of melt-crystallization process of the virgin PLLA with PLLA/CABH samples, and a high amount of CABH played a much more significant role in promoting PLLA�s crystallization. Additionally, the melt-crystallization processes also showed that both the cooling rate and the final melting temperature affected the crystallization behavior of PLLA, an increase of cooling rate could weaken the crystallization ability of PLLA/CABH samples, and the final melting temperature of 180�C made PLLA/CABH exhibit the best crystallization ability. For the cold-crystallization process, the cold-crystallization peak became flatter and shifted toward the lower temperature with increasing of CABH concentration, but an increase of heating rate could prevent the cold-crystallization peak from moving to low temperature because of the thermal inertia. The melting behaviors of PLLA/CABH depended on the previous crystallization and heating rate in heating, and the difference in melting behavior of PLLA/CABH samples effectively reflected the nucleation role of CABH, as well as the double melting peaks behavior of PLLA/CABH was thought to due to the melting-recrystallization. The introduction of CABH led to a drop in light transmittance, moreover, this negative effect were more obvious with an increase of CABH loading. In contrast, the fluidity of PLLA was significantly enhanced due to the existence of CABH.

scholarly journals Heterogeneous Nucleation Effect of N, N'-Adipic Bis(4-phenylbutyric Acid) Dihydrazide on Crystallization Process of Poly(L-lactic Acid)

2019 ◽  
Vol 25 (4) ◽  
pp. 446-454
Author(s):  
Yan-Hua CAI ◽  
Li-Sha ZHAO
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Heterogeneous Nucleation ◽  
Isothermal Crystallization ◽  
Crystallization Process ◽  
Melting Behavior ◽  
Light Transmittance ◽  
Crystallization Peak ◽  
Nucleation Effect ◽  
Phenylbutyric Acid

Enhancing crystallization ability is a fundamental challenges in Poly(L-lactic acid) (PLLA) industry, therefore, the goal of this work was to synthesis a new organic nucleating agent N, N'-adipic bis(4-phenylbutyric acid) dihydrazide (APAD), and investigate its effect on non-isothermal crystallization, isothermal crystallization, melting behavior, thermal stability, and optical property of PLLA. Non-isothermal melt crystallization results showed that APAD acted as more effective nucleating and accelerating agent for the crystallization of PLLA, as a result, upon cooling at 1 °C/min, PLLA/0.5 %APAD had the highest onset crystallization temperature 136.4 °C and the crystallization peak temperature 132.0 °C, as well as the largest non-isothermal crystallization enthalpy 48.1 J/g. However, with increasing of APAD concentration from 0.5 wt.% to 3 wt.%, the crystallization peak shifted to the lower temperature. In contrast, for the non-isothermal cold crystallization process, the effect of APAD concentration on the crystallization behavior of PLLA was negligible. Additionally, the non-isothermal crystallization process was also depended on the cooling rates and the final melting temperature. In isothermal crystallization section, to compare with the primary PLLA, the crystallization half-time of PLLA/APAD could decrease from 254.3 s to the minimum value 29.4 s, with 0.5 wt.% APAD contents at 125 °C. Melting behavior of PLLA/APAD samples under different conditions further confirmed the heterogeneous nucleation effect of APAD for PLLA, and the appearance of the double melting peaks was attributed to the melting-recrystallization. Finally, the addition of APAD decreased the thermal stability to some extent, although APAD could not change the thermal decomposition profile of PLLA. And a drop of PLLA/APAD samples in light transmittance resulted from the double influence of the enhancement of crystallization and the opaqueness of APAD.

Crystallization and properties of nucleated poly(l-lactic acid): Effect of cyclopentanecarboxylic acid derivative as a new nucleating agent

2021 ◽  
pp. 089270572110019
Author(s):  
Lisha Zhao ◽  
Xuhua Liu ◽  
Yanhua Cai ◽  
Wei Chen
Keyword(s):  
Lactic Acid ◽  
Cooling Rate ◽  
Melting Temperature ◽  
Tensile Modulus ◽  
Nucleating Agent ◽  
Orbital Energy ◽  
Melt Crystallization ◽  
Promoting Effect ◽  
Crystallization Peak ◽  
Lower Temperature

In this study, the potential effects of N, N’-dodecanedioic bis(cyclopentanecarboxylic acid) dihydrazide (BCADD) as a new additive in poly(L-lactic acid) (PLLA) was estimated. The comparative study on the melt-crystallization showed that the BCADD as heterogeneous nuclei facilitated crystallization of PLLA in cooling, which indicated by the obvious crystallization exotherms and sharp melt-crystallization peak. Unfortunately, with increasing of BCADD from 0.5 wt% to 3 wt%, it is unexpected that the melt-crystallization peak of the BCADD-nucleated PLLA shifted toward the lower temperature and became flatter, evidencing the importance of BCADD loading for PLLA’s crystallization. Additionally, the cooling rate and the final melting temperature were also proved to be important influence factors during PLLA’s melt-crystallization process, but in contrast with the effect of the final melting temperature on the melt-crystallization, a higher cooling rate could more seriously weaken crystallization ability of the BCADD-nucleated PLLA. The chemical nucleation mechanism was proposed to explain the promoting effect of BCADD on the crystallization of PLLA via the analysis of frontier orbital energy. The melting behaviors after crystallization further confirmed the crystallization accelerating role of BCADD, and the melting behaviors were affected by the heating rate, crystallization temperature and BCADD loading. Although the onset thermal decomposition of the BCADD-nucleated PLLA occurred at lower temperature comparing with the pure PLLA, the intermolecular interaction of PLLA with BCADD attempted to prevent the decrease of thermal stability. Overall, the addition of BCADD resulted in the complicated effect on the tensile modulus and tensile strength of PLLA, but the elongation at break continuously decreased when increasing BCADD loading.

scholarly journals N, N’-sebacic bis(hydrocinnamic acid) dihydrazide: A crystallization accelerator for poly(L-lactic acid)

e-Polymers ◽  
2019 ◽  
Vol 19 (1) ◽  
pp. 141-153 ◽  
Author(s):  
Li-Sha Zhao ◽  
Yan-Hua Cai ◽  
Hui-Li Liu
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Isothermal Crystallization ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Cold Crystallization ◽  
Light Transmittance ◽  
Nucleation Density ◽  
Melt Crystallization ◽  
Hydrocinnamic Acid

AbstractDeveloping more organic nucleating agent with different molecular structure is very instructive to improve the crystallization of poly(L-lactic acid) (PLLA) and explore the crystallization mechanism. In this study, N, N’-sebacic bis(hydrocinnamic acid) dihydrazide (HAD) was synthesized to serve as a nucleating agent for PLLA. The effects of HAD on the non-isothermal crystallization, melting behavior, thermal stability and optical performance of PLLA were investigated by differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), and light transmittance meter. The melt crystallization behavior showed that HAD was able to promote the crystallization of PLLA via heterogenous nucleation in cooling, and it was found that, upon the cooling of 1°C/min, the incorporation of 1 wt% HAD made the crystallization temperature and non-isothermal crystallization enthalpy increase from 94.5°C and 0.1 J/g to 131.6°C and 48.5 J/g comparing with the pure PLLA. Additionally, the melt crystallization significantly depended on the cooling rate and the final melting temperature. For the cold crystallization, when the nucleation density from HAD and PLLA itself was saturated, the influence of the HAD concentration on the cold crystallization process of the PLLA/HAD samples is negligible. The melting behavior after isothermal or non-isothermal crystallization further confirmed the crystallization accelerating effect of HAD for PLLA, and the appearance of the double melting peaks was attributed to the melting-recrystallization. Unfortunately, the addition of HAD decreased the thermal stability and light transmittance of PLLA.

scholarly journals The Crystallization, Melting Behavior, and Thermal Stability of Poly(L-lactic acid) Induced byN,N,N′-Tris(benzoyl) Trimesic Acid Hydrazide as an Organic Nucleating Agent

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Yan-Hua Cai ◽  
Yan-Hua Zhang
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Cooling Rate ◽  
Acid Hydrazide ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Crystallization Peak ◽  
Trimesic Acid ◽  
Neat Plla ◽  
Thermal Stability Of

N,N,N′-Tris(benzoyl) trimesic acid hydrazide (TTAD), as a novel nucleating agent of poly(L-lactic acid) (PLLA), was synthesized and characterized by FT-IR and1H NMR. The crystallization, melting behavior, and thermal stability of PLLA induced by TTAD were investigated through DSC, TGA, depolarized-light intensity measurement, and so forth. The crystallization behavior indicated that the presence of TTAD accelerated the overall PLLA crystallization. Compared to neat PLLA, the crystallization onset temperature of PLLA/1%TTAD increased from 101.36°C to 125.26°C, the melt-crystallization peak temperature increased from 94.49°C to 117.56°C, crystallization enthalpy increased from 0.1023 J·g−1to 33.44 J·g−1at a cooling rate of 1°C/min from melt, and the crystallization half-time of PLLA/TTAD decreased from 2997.2 s to 108.9 s at 110°C. Moreover, the nonisothermal crystallization measurements also indicated that the crystallization peak became wider and shifted to a lower temperature with increasing cooling rate. With the presence of TTAD, the melting behavior of PLLA was affected significantly, and a double-melting peak occurred due to melting-recrystallization. Thermal stability research showed that there existed one degradation stage of PLLA and PLLA/TTAD samples, and the thermal degradation temperature of PLLA/TTAD decreased compared to neat PLLA.

scholarly journals Thermal properties of radiolytically synthesized PVA/Ag nanocomposites

2007 ◽  
Vol 61 (3) ◽  
pp. 129-134 ◽  
Author(s):  
Aleksandra Krkljes ◽  
Zorica Kacarevic-Popovic
Keyword(s):  
Thermal Properties ◽  
Heating Rate ◽  
Melting Temperature ◽  
Melting Behavior ◽  
Melting Peak ◽  
Degree Of Crystallinity ◽  
High Heating Rate ◽  
Half Time ◽  
The Degree Of Crystallinity ◽  
Peak Melting Temperature

The radiolytic method was used to synthesize two types of nanocomposites with silver, PVA/Ag by film casting and PVA hydrogel/Ag nanocomposites. This method is particularly suitable for generating metal nanoparticles in solution. The radiolytic species (solvated electrons and secondary radicals) exhibit strong reducing properties such that metal ions are reduced at each encounter. Metal atoms then tend to grow into larger clusters. It was found that solid or swollen polymers are able to stabilize small crystallites against spontaneous growth via aggregation. Using differential scanning calorimetry (DSC), the melting behavior and kinetics of the PVA/Ag nanocomposites were investigated and compared to those of pure PVA. The melting as well as crystallization behavior of polymers is crucial because it governs the thermal properties, impact resistance and stress strain properties. Understanding the melting behavior is significant not only to tailor the properties of nanocomposites but to investigate the interactions between the constituents. The DSC curves of pure PVA and prepared nanocomposites show only one melting peak between 175 and 230?C, indicating that the melting behavior of these two systems are analogous. In both cases, with increasing heating rate, the melting peak shifts to a higher temperature, but with increasing Ag content the peak melting temperature is lower. When specimens are heated at high heating rate, the motion of PVA molecular chains cannot follow the heating temperature on time due to the influence of heat hysteresis, which leads to a higher peak melting temperature. When Ag nanoparticles are added they increase the heat transfer among the PVA molecular chains decreasing the melting temperature. The Ag content is a major factor affecting the degree of crystallinity. It was observed that at low nanofiller content, up to the 0.5 wt%, the degree of crystallinity of the nanocomposites increased, while at a higher content the crystallization was retarded. The half time of melting is non-linearly dependent on the amount of nanofiller. In the range from 0.25 to 1 wt% Ag it slightly increases, because at a low Ag content the nanoparticles act as a heterogeneous nucleation agent during the crystallization process. For large amounts of nanofiller, the half time of melting is markedly higher than for pure PVA. At a higher Ag content, the nanoparticles act as a barrier that restricts the thermal motion of PVA molecular chains and the half time of complete melting increases. The significantly lower melting activation energy of the nanocomposites with high amount of nanofiller compared to pure PVA, calculated by the Kissinger method, indicated that nanoparticles reduced the heat barrier for the melting process. .

A 1H-Benzotriazole Derivative Nucleated Poly(L-lactic acid): Thermal Behavior and Physical Properties

2020 ◽  
Vol 42 (3) ◽  
pp. 383-383
Author(s):  
Li Sha Zhao and Yan Hua Cai Li Sha Zhao and Yan Hua Cai
Keyword(s):  
Thermal Stability ◽  
Lactic Acid ◽  
Melting Process ◽  
Nucleating Agent ◽  
Melting Behavior ◽  
Cold Crystallization ◽  
Melt Crystallization ◽  
Nucleation Effect ◽  
Lower Temperature ◽  
Thermal Stability Of

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.

Comparison Between Isothermal Cold and Melt Crystallization of Polylactide/Clay Nanocomposites

2008 ◽  
Vol 8 (4) ◽  
pp. 1658-1668 ◽  
Author(s):  
Defeng Wu ◽  
Liang Wu ◽  
Lanfeng Wu ◽  
Bin Xu ◽  
Yisheng Zhang ◽  
...  
Keyword(s):  
Melting Behavior ◽  
Optical Microscope ◽  
Polymer Chains ◽  
Cold Crystallization ◽  
High Rate ◽  
Degree Of Crystallinity ◽  
Dominant Factor ◽  
Clay Nanocomposites ◽  
Melt Crystallization ◽  
Scanning Calorimetry

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.

Development of the Glassy State of Benzophenone and Effect of Heating Rate from the Glassy State on Solidification

1996 ◽  
Vol 455 ◽  
Author(s):  
Paul E. Thoma ◽  
John J. Boehm
Keyword(s):  
Phase Transformation ◽  
Solid State ◽  
Cooling Rate ◽  
Heating Rate ◽  
Melting Temperature ◽  
Glassy State ◽  
Equilibrium Structure ◽  
Solidification Temperature ◽  
Additional Heating ◽  
Solid State Phase Transformation

ABSTRACTBenzophenone supercools to a glass when cooled to −100°C. In fact, it is difficult to freeze benzophenone on cooling. In this investigation, the effect of cooling rate and the minimum cooling rate to obtain benzophenone as a glass is determined. From the glassy state, the influence of heating rate on the solidification temperature of benzophenone is determined. When heated at 3°C/min., solidification starts at about −29°C. Upon additional heating, melting usually starts at about +24°C, which is 23°C lower than the solid equilibrium structure melting temperature of 47°C. Occasionally the solid that forms at about −29°C undergoes a solid state phase transformation at about +22°C, when heated at 3°C/min. If this solid state phase transformation occurs, then the solid benzophenone starts to melt at 47°C. When solid benzophenone with the equilibrium structure is cooled to −100°C, no solid state phase transformation occurs. It appears that the structure that solidifies at −29°C is metastable.

scholarly journals Crystallization and Melting Behavior of Biodegradable Poly(L-lactic acid)/Talc Composites

2012 ◽  
Vol 9 (3) ◽  
pp. 1569-1574 ◽  
Author(s):  
Yan-Hua Cai
Keyword(s):  
Lactic Acid ◽  
Heating Rate ◽  
Isothermal Crystallization ◽  
Crystallization Rate ◽  
Melting Behavior ◽  
Melting Peak ◽  
Melt Crystallization ◽  
Biodegradable Poly ◽  
Crystallization And Melting Behavior ◽  
Double Melting Peak

Crystallization and melting behavior of Poly(L-lactic acid)(PLLA)/Talc composites with different talc content were investigated in detail. The addition of talc can increase the overall crystallization rate of PLLA, 5%talc makes the melt-crystallization peak temperature of PLLA increase from 96.28 °C to 105.22 °C, and the crystallization enthalpy increases from 1.379 J•g-1to 28.99 J•g-1. The melting behavior of PLLA/5%talc composites at a different heating rate during non-isothermal crystallization at different cooling rate shows that heating rate can affect the melting behavior of PLLA, with increasing of heating rate, the double melting peak degenerates to single melting peak. Melting behavior after isothermal crystallization and after cold isothermal crystallization and hot isothermal crystallization indicates that the double-melting peak of PLLA/5%talc composites results from melting-recrystallization.

scholarly journals Melting Kinetics of Nascent Poly(tetrafluoroethylene) Powder

Polymers ◽  
2020 ◽  
Vol 12 (4) ◽  
pp. 791
Author(s):  
Fotis Christakopoulos ◽  
Enrico Troisi ◽  
Theo A. Tervoort
Keyword(s):  
Kinetic Model ◽  
Heating Rate ◽  
Melting Temperature ◽  
Melting Behavior ◽  
Slow Heating ◽  
Heating Rates ◽  
Scanning Calorimetry ◽  
Exponential Factor ◽  
Melting Kinetics ◽  
Kinetics Of

The melting behavior of nascent poly(tetrafluoroethylene) (PTFE) was investigated by way of differential scanning calorimetry (DSC). It is well known that the melting temperature of nascent PTFE is about 344 ∘ C, but reduces to 327 ∘ C for once molten material. In this study, the melting temperature of nascent PTFE crystals was found to strongly depend on heating rate, decreasing considerably for slow heating rates. In addition, during isothermal experiments in the temperature range of 327 ∘ C < T < 344 ∘ C, delayed melting of PTFE was observed, with complete melting only occurring after up to several hours. The melting kinetics of nascent PTFE were analyzed by means of the isoconversional methodology, and an apparent activation energy of melting, dependent on the conversion, was determined. The compensation effect was utilized in order to derive the pre-exponential factor of the kinetic model. The numerical reconstruction of the kinetic model was compared with literature models and an Avrami-Erofeev model was identified as best fit of the experimental data. The predictions of the kinetic model were in good agreement with the observed time-dependent melting of nascent PTFE during isothermal and constant heating-rate experiments.

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