Organic Nucleating Agent Research Articles

The Performance Investigation of PLLA/PPAPH: The Influence of PPAPH as Heterogeneous Crystal Nuclei

To overcome PLLA�s poor crystallization capability, using nucleating agent as crystallization improvement strategy was performed in this study. PPAPH as PLLA�s an organic nucleating agent was firstly synthesized, and then PLLA was blended with different PPAPH loading through melting blend method, the resulting influences of PPAPH on PLLA�s performances were investigated using the relevant testing instruments. Melt-crystallization revealed that PPAPH played important role in promoting PLLA�s crystallization through providing effective sites of heterogeneous nucleation, and effect of PPAPH loading on PLLA�s melt-crystallization was very poor, indicating that low PPAPH loading could cause PLLA to possess powerful crystallization capacity. In addition, the relative low final melting temperature was beneficial for PLLA/PPAPH�s crystallization. However, an increase of cooling rate during cooling stage weakened PLLA/PPAPH�s crystallization capacity. PLLA/PPAPH�s cold-crystallization suggested that PPAPH had an inhibition effect on cold-crystallization process to some extent. Melting behaviors depended on heating rate and previous crystallization including melt-crystallization at various cooling rates and isothermal crystallization at various crystallization temperatures. PPAPH enhanced PLLA�s fluidity, tensile modulus and tensile strength. Unfortunately, PLLA�s transmittance was seriously weakened as PPAPH loading increased, as well as the elongation at break continuously decreased.

Self-assembled poly(lactic acid) films with high heat resistance and multi-stage thermochromic properties prepared by blown film-annealing

Developing reversible thermochromic films that can achieve thermochromism from low to high temperatures by simple processes is a goal which carries a great deal of potential. They have potential applications in temperature monitoring, information encryption and anti-counterfeiting. For this work, decanedioic acid, 1,10-bis(2-benzoylhydrazide) (TMC-300) was used as a self-assembled organic nucleating agent and was combined with an annealing process to heat-resistant modify the blown polylactic acid films. The thermochromic films would have a higher upper limit to its detection range. Through this method, we obtained thermochromic films with a dense morphological structure. Additionally, the effects of TMC-300 and annealing on various properties of films were studied in detail. Unexpectedly, we found a hindering effect between thermochromic microcapsule (TCM) and TMC-300 at TMC-300 mass fractions below 0.3 wt%. Subsequently, TCM with different color changes in different temperature ranges was added. Films with thermochromic color change in the range of 25–70 °C were successfully prepared by this method. The color of the films also demonstrated a multi-stage thermochromic transition through brown, orange, and red before eventually becoming colorless. The results showed the crystallinity of the films rose to 45.65 %, while the heat resistance temperature and elongation at break increased by 60 % and 170 %, respectively. The prepared thermochromic films had enough transparency and even after 60 heating–cooling cycles, they exhibited outstanding thermochromic properties. Moreover, we have explored the application of films in fields of information encryption and temperature monitoring by utilising their multi-stage thermochromic properties.

Significantly enhanced crystallization of polylactide Ingeo 4032D by polyethylene ionomer

Poly(lactic acid) (PLA) is the most important biopolymer material due to its excellent biocompatibility, biodegradability, and processability. However, its widespread applications were significantly limited by its low crystallization rate. While adding small molecule organic nucleating agents became a commonly used method in enhancing the crystallization rate, these nucleating agents generally suffer from limited solubility, which caused compromised nucleation efficiency and undesirable product appearance due to their precipitation onto the surface of the PLA products overtime. Here we report an efficient method for improving the PLA crystallization performance by using polyethylene (PE) ionomer as an additive in the PLA/TMC300 (an organic nucleating agent) nucleation/crystallization process. The added ionomer led to enhanced crystallization rate and reduced crystalline grain size. The resulting PLA from crystallization with TMC300 and ionomer showed reduced glass transition temperatures, reduced contact angles, and enhanced elastic modulus without compromising the impact strength and elongation at break. A possible mechanism was proposed for the remarkable synergistic effects of ionomer and TMC-300 in modifying the PLA crystallization process with the ionomer playing the roles of both plasticizer (enhanced PLA chain mobility and crystallization rate) and compatibilizer (enhanced dissolution and dispersion of TMC300 in the PLA matrix). This work offered a promising strategy for crystallization and modification of PLA materials.

Effects of NANH as a nucleation agent on the performance of PLLA

In this research, N,N′-bis(nicotinic) 1,4-naphthalenedicarboxylic acid dihydrazide (NANH) as a new synthetic organic nucleating agent was employed to overcome the slow crystallization rate of poly(L-lactide) (PLLA). Melt crystallization showed that the crystallization ability of PLLA was significantly enhanced by NANH, with NANH still being able to accelerate PLLA crystallization at a cooling rate of 50°C/min. Additionally, when the final melting temperature was 170°C, the onset melt-crystallization temperature and melt-crystallization peak temperature of PLLA/3% NANH were up to 160.0 and 155.1°C, respectively. Isothermal crystallization showed that the half-time of the overall crystallization of PLLA/3% NANH was dramatically reduced, from 71.9 min at 135°C for the virgin PLLA to the minimum value of 0.3 min. This advanced nucleation effect was speculated to be due to chemical nucleation through the theoretical analysis of frontier orbital energy. Melting behaviors under different conditions further confirmed the crystallization-accelerating effect of NANH for PLLA crystallization, and the melting processes were affected by the crystallization temperature and heating rate. Although NANH decreased the thermal decomposition temperature of PLLA in air, the thermal decomposition temperatures of all PLLA/NANH blends were higher than 330°C, which could meet daily usage requirements. Finally, the addition of NANH enhanced PLLA fluidity; however, light transmittance was seriously weakened.

Nucleating Agents to Enhance Poly(L-lactide) Crystallization and Melting Behavior of Modified Poly(L-lactide)

Melt processing poly(L-lactide) (PLLA) with a nucleating agent has been thought to be one of the most effective route to enhance PLLA s crystallization and heat resistance. In the current work, a newly-developed organic nucleating agent named N, N -bis(2-picolinyl) 1, 4-naphthalenedicarboxylic acid dihydrazide (NCAPH) was synthesized to investigate its effects on PLLA�s crystallization and melting behaviors. It is proved that NCAPH as an organic crystallization nucleating agent could provide large number of crystallization nucleation sites to improve PLLA�s crystallization, as observed from DSC and POM measurements. The result from melt-crystallization processes further showed that the final melting temperature and cooling rate were two important factors for affecting PLLA�s melt-crystallization behaviors in cooling, and the theoretical calculation result of frontier orbital energy indicated there existed probable intermolecular interaction between N-H of NCAPH and C=O of PLLA, which was proposed as nucleation mechanism of NCAPH for promoting PLLA�s crystallization. The melting behaviors of PLLA/NCAPH after non-isothermal crystallization or isothermal crystallization further confirmed the positive effects of NCAPH and NCAPH�s loading for the crystallization of PLLA, meantime, the melting behaviors depended on the heating rate, crystallization temperature, crystallization time, etc.

Synthesis of symmetric bis-α-ketoamides from renewable starting materials and comparative study of their nucleating efficiency in PLLA.

An efficient and smart synthesis of bis-α-ketoamides has been disclosed. The desired products have been obtained through a Passerini multicomponent reaction using biobased aldehydes, acetic acid and bis-isocyanides (prepared from the corresponding biobased diamides), followed by a deprotection/oxidation step. The effect of the synthesized compounds on the crystallization behavior of poly(l-lactide) (PLLA) has been investigated by differential scanning calorimetry (DSC) in non-isothermal conditions. Among all the synthesized compounds, only a few are able to meaningfully enhance the nucleation of PLLA, as confirmed by a shift of the polymer crystallization peak temperature towards higher values. With the research of active polymer nucleating agents being mostly empirical, the combinatorial synthetic approach proposed herein, coupled with the possibility of a small scale mixing procedure, can potentially represent a useful strategy for the discovery of new efficient biobased polymer additives.

Influence of sericin‐g‐PLA as an organic nucleating agent for preparing biodegradable blend films

AbstractHere for the first time, this work indicated that the sericin‐g‐polylactide (SS‐g‐PLA) copolymer can be potentially used as an organic nucleating agent to improve the crystallinity and biodegradability of polylactide (PLA). The properties of blended films containing SS‐g‐PLA mixed with virgin PLA polymer were highly evaluated. The water vapor permeability (WVP), thermal behavior, dynamic mechanical properties, crystal structure, and biodegradability of the PLA/SS‐g‐PLA‐blended films were characterized and compared with a commercial PLA film. The results clearly indicated that the incorporation of SS‐g‐PLA copolymer in the PLA matrix had a significant effect on the properties of PLA/SS‐g‐PLA‐blended films. The WVP values of PLA/SS‐g‐PLA‐blended films were lower than that of commercial PLA film by about 2–3 g·mm/m2·day·atm, and their thermal behaviors (e.g. Tg, Tcc, and Tm) were also decreased. Adding SS‐g‐PLA can increase the crystallinity of PLA. The degree of crystallinity (%χc) of the series of PLA/SS‐g‐PLA‐blended films was increased to about 2–4 times that of the commercial PLA film (3%). Interestingly, biodegradation results revealed that the percent of biodegradability of PLA/SS‐g‐PLA‐blended film was 80% in 43 days under a compost environmental temperature of 58 ± 2°C. This evidence indicated that the SS‐g‐PLA copolymer can improve the biodegradability of PLA.

Poly (L-lactic acid) Modified by N, N -bis(Stearic acid)-1,4-Dicarboxybenzene Dihydrazide: Studies of Crystallization, Melting Behavior and Thermal Decomposition

In this study, a new organic nucleating agent N, N -bis(stearic acid)-1,4-dicarboxybenzene dihydrazide (PASH) to improve crystallization behavior of poly(L-lactic acid) (PLLA) along with the effect of PASH on melting behavior, thermal stability of PASH-nucleated PLLA was holistically reported. The melt-crystallization process illustrated that PASH as an effective heterogeneous nucleating agent could boost PLLA�s crystallization rate, but increasing PASH concentration and cooling rate conversely inhibited melt-crystallization process of PLLA in this study. With respect to melt-crystallization process, a larger amount of PASH leaded to a shift of cold-crystallization peak to lower temperature level. Isothermal crystallization revealed, in comparison to pure PLLA, that the half time of overall crystallization of PLLA/PASH was significantly decreased with PLLA containing 3 wt% PASH having the minimum t1/2= 67.3 s at 105şC. The different melting behaviors of PLLA/PASH under different conditions were attributed to the nucleating effect of PASH within PLLA. In particular, the melting behavior at a heating rate of 10�C/min after isothermal crystallization depended primarily on the crystallization temperature. Whereas, the impact of crystallization time on melting behavior was negligible. Nonetheless, the melting behavior was influenced by the heating rate after non-isothermal crystallization. The thermal stability of PLLA was detrimental with the addition of PASH owing to a typical drop in onset thermal decomposition temperature.

Thermal Performances and Fluidity of Biodegradable Poly(L-lactic acid) Filled with N, N'-Oxalyl Bis(piperonylic acid) Dihydrazide as a Nucleating Agent

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.

Preparation of Organic Crystal Seed and Its Application in Improving the Functional Period of Biodegradable Agricultural Film

White pollution caused by agricultural films has recently attracted great attention. In some areas, the content of micro plastic in the soil has reached 30 kg/ha. The most effective way to solve this problem is to replace traditional polyethylene agricultural films with degradable agricultural films. The consistency between the degradation rate and the crop growth period has become the biggest obstacle for the wide application of such novel agricultural films. In this paper, crystallinity regulation is used to adjust the functional period of degradable agricultural films. In addition, an organic nucleating agent of polyethylenimine (PEI) is selected by doping it to poly(butylene adipate-co-terephthalate) (PBAT) polymers using a double-screw extruder. The PBAT doped with 1 wt% PEI films revealed a significant increase in mechanical properties, water holding capacity, and crystallinity compared with the pure PBAT film. There was a 31.9% increase in tensile strength, a 30.5% increase in elongation at break, a 29.6% increase in tear resistance, a 30.9% decrease in water vapor permeability, and a 3.1% increase in crystallinity. Furthermore, the induction period of PBAT doped with 1 wt% PEI under photoaging (without soil) was about 160 h longer than PBAT film, and the experienced biodegradation in soil (without light) was 1 week longer than PBAT film. Experimental results exhibited that the change of degradation degree was linearly proportional to the degree of crystallinity. This study proposes a convenient, low-cost, and effective method to adjust the crystallinity and change the degradation rate.

A facile approach to realize simultaneously chain extension and crystallization promotion of poly (ethylene terephthalate)

A synergic strategy combining chemical nucleation with chain extension was employed for Poly (ethylene terephthalate) (PET). In this study, sodium linoleate (Na-LL), as chemical nucleating agent, was selected to promote the nucleation process, and an ultraviolet-induced chain extension approach was simultaneously employed to maintain the molecular weight of PET with the aid of glycidyl methacrylate (GMA) / trimethylolpropane triacrylate (TMPTA). The rheological properties, crystallization behaviors and mechanical properties of PET composites were systematically explored. The rheological results showed that GMA/TMPTA blend is effective for PET chain extension reaction and the addition of Na-LL would not badly offset the chain extension effect of GMA/TMPTA. The non-isothermal and isothermal crystallization studies demonstrated that Na-LL is an effective organic nucleating agent for PET. Low loading of Na-LL can considerably improve the crystallization properties of PET. At last, the combination of GMA/TMPTA/Na-LL could also maintain the excellent comprehensive mechanical properties of PET.

Thermal and mechanical properties of poly(L-lactic acid) nucleated with N,N’-bis(phenyl) 1,4-naphthalenedicarboxylic acid dihydrazide

The modified poly(L-lactic acid) (PLLA) with different contents (0.5−3 wt %) of N,N’-bis(phenyl) 1,4-naphthalenedicarboxylic acid dihydrazide (NAPH) were prepared to evaluate effects of NAPH on melt-crystallization behavior (DSC), thermal degradation (TGA) and mechanical properties of PLLA. The melt-crystallization results demonstrated that NAPH as a heterogeneous organic nucleating agent enhanced crystallization ability of PLLA in cooling, and PLLA/1%NAPH had the best crystallization ability because of the highest onset crystallization temperature and the sharpest melt-crystallization peak. However, melt-crystallization behavior also depended on the cooling rate and final melting temperature, overall, a relative slow cooling rate and low final melting temperature were beneficial for crystallization of PLLA. The cold-crystallization results indicated that NAPH had an inhibition for cold-crystallization process of PLLA, and the cold-crystallization peak shifted towards lower temperature and became wider with an increase of NAPH concentration. The different melting behaviors ofPLLA/NAPH after melt-crystallization and isothermal-crystallization efficiently reflected the accelerating role of NAPH for PLLA crystallization; the double melting peaks formed in heating were thought to result from melting-recrystallization, as well as that a higher crystallization temperature could cause melting peak to appear in higher temperature regions and possess larger melting enthalpy. A comparative analysis on thermal degradation in air illustrated that the addition of NAPH accelerated decomposition of PLLA, but a decrease of onset decomposition temperature was inhibited by the probable interaction of PLLA with NAPH. Moreover, the tensile test showed that NAPH decreased tensile modulus and elongation at break of PLLA, whereas PLLA with low concentration of NAPH had higher tensile strength than pure PLLA.

Application of a novel cavity nucleating agent based on cyclodextrin in polymer foaming materials and in situ visual injection moulding study

In this study, β-cyclodextrin nanosponges were synthesized using organic carbonates, namely gelatinous β-cyclodextrin nanosponges (NJ) and vitreous β-cyclodextrin nanosponges (BL). The ‘constructed’ porous structures were characterized by scanning electron microscopy. NJ and BL with different cavity structures as heterogeneous nucleation agents were selected for the polypropylene and polylactic acid foaming injection moulding processes. The obtained experimental results showed that NJ significantly reduced nucleation energy barrier and thus exhibited the highest nucleation efficacy. The nucleation mechanism was explored via a combination of the classical nucleation theory and in situ visual injection moulding analysis. In a word, the current work provided an insight into the structure-nucleating efficiency relationship for porous particles and highlighted the importance of the construction of porous structures in the organic nucleating agents to improve the polymeric foaming performances.

Optimizing crystallinity of engineered poly(lactic acid)/poly(butylene succinate) blends: The role of single and multiple nucleating agents

AbstractThis work deals with the design and experimental development of formulations based on bioplastic materials optimized for the production processes of high‐performance packaging products, suitable for food contact and characterized by high thermo‐mechanical stability. For this purpose, mixtures of poly (L‐lactic acid) (PLLA)/poly (butylene succinate) (PBS) (PLA/PBS) containing micro‐lamellar talc as reinforcing agent and inorganic nucleating agent have been obtained on a pre‐industrial scale. Through the addition in formulation of two organic nucleating agents, ethylene (bis)stereamide (EBS) and poly (D‐lactic acid) (PDLA), evaluated separately and in combination with each other, four different PLA/PBS formulations were produced by means of a co‐rotating twin screw extruder. The effects on the crystallinity of the materials obtained first in the form of pre‐dried pellets, then in the form of films by casting extrusion and, finally, as thermoformed items were compared, according to the variation of the chosen nucleation system. The effect on the crystallinity of the materials was assessed by differential scanning calorimetry (DSC) and by Fourier transform infrared analysis in attenuated total reflection mode (ATR‐FTIR). This approach aims to provide data for the further investigation on the processability and the thermo‐mechanical properties of end‐goods achievable by converting processes (melt processing) of the bioplastic compounds.

Synthesis of Dodecanedioic Dihydrazide Derivative as Organic Nucleating Agent to Enhance the Crystallization Properties and Fluidity of Poly(L-Lactic Acid)

This study investigated the effect of a new organic nucleating agent, N,N′-dodecanedioic bis(4-phenylbutyric acid) dihydrazide (BPADH), on the crystallization and melting behavior, thermal stabilit...

Modified PLLA: effect of BPADD on properties

Poly(l-lactic acid) (PLLA) modified by a new organic nucleating agent, N,N′-dodecanedioic bis(piperonylic acid) dihydrazide (BPADD), was fabricated, and its crystallization, melting behavior, thermal stability, fluidity and mechanical properties were investigated. The melt-crystallization behavior proved that BPADD could bring about a fast nucleation rate to promote the crystallization of PLLA; 2 wt% BPADD exhibited the best crystallization accelerating effect due to having the highest crystallization onset temperature and the highest melt-crystallization temperature. However, PLLA/3% BPADD had the largest melt-crystallization enthalpy. In addition, the frontier orbital energy indicated that the nucleation effect of BPADD on PLLA might be attributed to intermolecular interaction. The melt crystallization also depended on two critical factors, the cooling rate and final melting temperature. An increase in BPADD content led to greater inhibition of crystal growth during cold crystallization. The differences in the melting behavior of PLLA/BPADD samples reflected the previous crystallization process, the heating rate and BPADD content. BPADD was harmful to maintaining the thermal stability of PLLA; however, the intermolecular interaction could prevent the decomposition onset temperature from continuously decreasing. The usage of BPADD resulted in better fluidity and higher tensile strength; the tensile modulus and elongation at break were associated with BPADD content.

Effects of divinylbenzene‐maleic anhydride copolymer hollow microspheres on crystallization behaviors, mechanical properties and heat resistance of poly(l‐lactide acid)

Divinylbenzene‐maleic anhydride copolymer hollow microspheres (DMs) were used as novel organic nucleating agents to promote crystallization of poly(l‐lactide acid) (PLLA). The effects of these DMs on crystal behaviors of the PLLA were investigated by differential scanning calorimeter (DSC), polarizing optical microscopy (POM), and wide angle X‐ray diffraction (WAXD). Both isothermal and non‐isothermal processes in DSC demonstrated that the DMs significantly altered the crystal behaviors of PLLA as both crystallization velocity and degree of crystallinity increased with increasing DM loadings from 0 to 3%. Our POM results also indicated that as nucleating agents, the DMs promoted nucleating densities and decreased spherulitic sizes. In addition, WAXD suggeted that the addition of DMs did not induce new types of crystals. Finally, our results showed that the ductility of the PLLA was enhanced by a small amount of DMs during the PLLA crystallization process since 0.5% DMs added to the PLLA resulted in 1.4‐fold increase in the elongation at break in comparision with the neat PLLA.

Crystallization, Melting Process and Optical Property of PLLA/PABBH System

The goal of this research was developing a new organic nucleating agent and investigating its influence on the non-isothermal crystallization including melt-crystallization and cold-crystallization, melting behavior and optical property of Poly(L-lactic acid) (PLLA). The results from the melt-crystallization indicated that the N, N′-bis(benzoyl) phenylmalonic acid dihydrazide (PABBH) could be used as an effective role in nucleation, and 2 wt% PABBH had the best crystallization promoting effect for PLLA. However, the increase of PABBH content made the cold-crystallization peak shift toward the higher temperature. The melting behavior of PLLA/PABBH sample depended on the crystallization time, and the double-melting peaks were ascribed to the melting-recrystallization. The introduction of PABBH seriously decreased the transmittance of PLLA resulting from an increase of crystallinity and the yellowish-brown of PABBH itself.

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

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