Effective nucleating chemical agents for the crystallization of poly(trimethylene terephthalate)

This study focused on the crystallization promotion of poly(trimethylene terephthalate) (PTT), with an aim at engineering thermoplastics applications. The effects of organic sodium (Na) salts, including Na stearate, Na benzoate, disodium‐p‐phenolsulfonate (2Na‐p‐PS), disodium‐p‐hydroxybenzoate (2Na‐p‐HB), and the sodium ionomer of poly(ethylene‐co‐methacrylic acid) (Na‐EMAA), were investigated as nucleating chemical agents with differential scanning calorimetry and capillary viscometry. For comparison, the effect of fine talc powder was also examined. The chemical agents were generally more effective than fine talc powder. Na stearate and Na benzoate caused large‐scale decomposition of PTT. 2Na‐p‐PS was quite thermally stable and caused little decomposition. 2Na‐p‐HB was the most efficacious of the nucleating chemical agents and caused mild decomposition. Na‐EMAA was the most thermally stable and induced an increase in melt viscosity. A remarkable improvement in the crystallization rate of PTT was successfully attained at a minimum polymer decomposition cost by the introduction of a suitable amount of 2Na‐p‐PS, 2Na‐p‐HB, or Na‐EMAA or by the concurrent proper incorporation of both of the latter two agents. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 590–601, 2004     

Rapid crystallization of poly(l-lactic acid) induced by a nanoscaled zinc citrate complex as nucleating agent

A nanoscaled zinc citrate complex (ZnCC) was synthesized by the reaction of zinc acetate and citric acid using solution method. As a new eco-friendly nucleating agent, ZnCC was introduced into poly(l-lactic acid) (PLLA) via melt blending. The nonisothermal and isothermal crystallization, melting behavior, crystalline morphology and mechanical properties of the PLLA/ZnCC blends were investigated. It is found that ZnCC exhibits much more prominent nucleation activity on the crystallization of PLLA than conventional nucleating agent talc and commercial zinc citrate (ZnCit). By loading 0.05 wt% ZnCC, PLLA can complete crystallization upon cooling at 10 °C/min, and the crystallization peak shifts to a higher temperature with increasing ZnCC content. In the case of isothermal crystallization from the melt, the addition of ZnCC leads to a shorter crystallization time and a faster overall crystallization rate. Besides, the nucleation density of PLLA increases and the spherulite size decreases significantly in the presence of ZnCC. Epitaxy is the possible mechanism to elucidate the nucleation phenomenon of PLLA/ZnCC system. The tensile results show that ZnCC has a plasticization effect on the amorphous PLLA. Through a short-time annealing procedure, the mechanical properties such as tensile modulus and storage modulus of PLLA are improved by the addition of ZnCC.     

The relationship between solubility and nucleating effect of organic nucleating agent in poly(L-lactic acid)

N,N′-bis(benzoyl) hexanedioic acid dihydrazide (BHAD), and N,N′-bis(benzoyl) terephthalic acid dihydrazide (BTAD) were synthesized as the organic nucleating agents for poly(L-lactic acid) (PLLA). These two organic compounds exhibited different nucleating effect to PLLA. When the concentration was very low, BTAD was able to nucleate PLLA, while BHAD was not. When the concentration was adequate, BHAD showed better nucleating effect than BTAD. The experiments showed that, BHAD had the ability of dissolving into PLLA melt matrix, while BTAD was insoluble in PLLA. The optical microscope images revealed the quite different PLLA crystal morphologies nucleated by BHAD and BTAD. As BTAD could not dissolve in PLLA melt, it only induced a mass of small grain crystals of PLLA, the morphology of which is the same as neat PLLA. BHAD had relatively different nucleation and crystallization behaviors. Upon heating, BHAD could partially or totally dissolve in PLLA melt, which depended on the final heating temperature and its concentration. Upon cooling, BHAD separated from PLLA matrix and formed needle like or dendritic structures. Moreover, totally dissolved BHAD could finally exhibit dendritic structures, which had an excellent nucleation effect to PLLA. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46851.     

Crystallization kinetics and nucleating agents for enhancing the crystallization of poly(p-phenylene sulfide)

An experimental study of crystallization kinetics and the influence of nucleating agents on the solidification of poly(p-phenylene sulfide) (PPS) is described. The effect of molecular weight is considered by investigating PPS samples having different viscosity levels. We studied the effect of a range of nucleating agents including aluminum oxide, calcium oxide, silicon dioxide, titanium dioxide, kaolin, and talc. All of these compounds were found to enhance the rate of crystallization; in particular, silicon dioxide, kaolin, and talc were the most effective nucleating agents. An effort to study particle size effects of the silicon dioxide showed that the nucleation was very sensitive to the source of the material. These studies did, however, show that nucleation rates tended to increase with decreasing particle size and increasing loading of silicon dioxide. Comparison of PPS crystallization rates with those of other polymers indicates that it crystallizes much more slowly than polyethylene or isotactic polypropylene and is slower than polyetherether-ketone, when comparisons are made on an equivalent basis. PPS crystallizes at similar rates to polyethylene terephthalate (PET). However, our nucleated PPS does not crystallize as rapidly as nucleated PET.     

Effect of nucleating agents upon the kinetics of poly(ethylene terephthalate) crystallization

Experiments have been conducted to examine the effect of the following agents: TiO₂, CaO, MgO, BaSO₄, SiO₂, and Al₂O₃ as modifiers on the poly(ethylene terephthalate) crystallization kinetics. Modifier concentration in the polymer varied from 0.5% to 3%. Crystallization rate measurements at a temperature of 237°C were performed by dilatometric method and measurements of spherulitic growth rate, by microscopic method. It has been stated that the addition of a modifier affects the crystallization rate, dimension, and homogeneity of spherulitic sizes. The spherulitic growth rate, with the exception of that modified by CaO, does not depend on the kind and the concentration of a modifier. Heterogeneous nucleating agents exert an effect, then, mainly on the heterogeneous nucleation process. In the presence of the agents, the nucleation in the poly(ethylene terephthalate) is of athermal character. The kind of a modifier applied exerts also an effect on the final crystallization degree.     

Hydrogen bonding in aliphatic poly(amides)

Summary A great number of aliphatic poly (amides) was investigated by i.r. spectroscopy and density measurements. The relative integral intensity of the characteristic NH stretching vibration shows a quantitative dependence on the chemical composition of the respective poly (amide) and can be used for the identification of an unknown material. The density varies systematically with the concentration of the hydrogen bonds.     

Effect of nucleating agents on the temperature-dependent melt crystallization kinetics of poly(1-butene)

The effect of additives (mostly nucleating agents) on the crystallization rate of isotactic poly(1-butene) has been investigated by differential scanning calorimetry. Isothermal crystallization half-times and crystallization temperatures have been measured for polymer-additive blends. The crystallization temperature and the cooling rate at which the ultimate fraction transformed becomes less than 1 is calculated as a function of nucleation density, and this is used to characterize the effect of the additives on crystallization rate. The relationship between the isothermal crystallization half-time and the crystallization temperature is also calculated theoretically and is compared with experimental results.     

Morphology studies of the liquid-induced crystallization of poly(ethylene terephthalate): Effects of polymer blending,nucleating agents,and molecular weight

The morphology associated with the liquid-induced crystallization of poly(ethylene terephthalate) (PET) blended either with poly(tetramethylene terephthalate) (PTMT), atactic polystyrene (APS), or polycarbonate of bisphenol A (PC) was studied, along with the effects of nucleating agents and polymer molecular weight on this type of crystallization in PET. It was found that melt-mixed blends of PET and either PTMT or PC led to an apparent well-mixed, two-component material in which some copolymer formation may be in evidence judging from the material superstructure. Blending PET with APS appeared to produce distinctly phase-separated materials in which PET could be crystallized and APS dissolved out of the structure as a result of treatment of the blend with certain types of liquid. The incorporation of nucleating agents into PET was shown to measurably influence the spherulitic character of the subsequently liquid-induced crystallized polymer. Finally, it was determined that liquid-induced crystallized PET samples with number-average molecular weights of 18,000 and 30,000 had identical characteristic morphology and apparent crystallization kinetics.     

1,3,5-Benzenetrisamide based nucleating agents for poly(vinylidene fluoride)

This paper presents 1,3,5-benzenetrisamides as colorless α-nucleating agents for poly(vinylidene fluoride). In order to screen a large variety of 1,3,5-benzenetrisamide derivatives with respect to their nucleating potential an efficient and reliable test based on polarized light microscopy was established. For selected promising compounds the concentration dependence of the PVDF crystallization temperature, the dissolution behavior of the additive in the polymer melt, and the crystallization of the additive from the polymer melt was investigated in a concentration range between 1 wt% (10,000 ppm) and 70 ppm. It was found, that only two of the investigated compounds were able to raise the crystallization temperature about 8 °C at a concentration of 140 ppm and 580 ppm, respectively. These trisamides have the advantage being soluble in the polymer melt, not featuring absorption of visible light and therefore allowing the preparation of uniform and colorless PVDF products.     

Hydrolytic degradation of poly(L-lactic acid): Combined effects of UV treatment and crystallization

Amorphous and crystallized poly(L -lactic acid) (PLLA) films were prepared and the hydrolytic degradation of the ultraviolet (UV)-treated and UV-nontreated films was investigated. This study reveals that the combination of UV and thermal treatments can produce the PLLA materials having different hydrolytic degradation profiles and that the UV-irradiation in the environment will affect the design of recycling process for PLLA articles. In an early stage, the degrees of hydrolytic degradation monitored by weight loss (W_loss), number-average molecular weight (M _n), and melting temperature (T _m) were higher for the UV-treated films than for the UV-nontreated films. In a late stage, the trend traced by W_loss was reversed, and the difference in the degrees of hydrolytic degradation between the UV-treated and UV-nontreated films monitored by M _n and T _m became smaller, with the exception of the degrees of hydrolytic degradation of the amorphous films traced by T _m. Also, in the early stage, the degrees of hydrolytic degradation monitored by W_loss and M _n were higher for the crystallized films than for the amorphous films. In the late stage, this trend was reversed, with the exception of the degrees of hydrolytic degradation of the UV-treated films monitored by M _n. The main factors that determined the W_loss and T _m were the molecular weight and initial crystallinty but not the molecular structures such as terminal CC double bonds and crosslinks. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of sepiolite on the crystallization behavior of biodegradable poly(lactic acid) as an efficient nucleating agent

To enhance the crystallization kinetics of poly(lactic acid) (PLA), fibrous sepiolite was explored for nucleating the crystallization of PLA. PLA/sepiolite nanocomposites were prepared via the melt‐extrusion method. The effect of sepiolite on the crystallization behavior, spherulite growth and crystal structure of PLA were investigated by means of differential scanning calorimetry (DSC), polarized optical microscope (POM), wide angle X‐ray diffraction (WAXD), Fourier transform infrared (FTIR), and scanning election microscope (SEM). On the basis of DSC and POM results, the overall crystallization kinetics of PLA/sepiolite nanocomposites were significantly enhanced leading to higher crystallinity and nucleation density, faster spherulite growth rate (G) and lower crystallization half‐time (t_1/2) compared with the neat PLA. Under non‐isothermal conditions, the PLA blend comprising 1.0 wt% of sepiolite still revealed two crystallization peaks upon cooling at a rate of 35°C/min. Above phenomena strongly suggested that sepiolite was an effective nucleating agent for PLA. FTIR and WAXD analyses confirmed that the crystal structure of PLA matrix was the most common α‐form. SEM micrographics illustrated the fine three‐dimensional spherulite structures with the lath‐shape lamellae regularly arranged in radial directions. POLYM. ENG. SCI., 55:1104–1112, 2015. © 2014 Society of Plastics Engineers     

Simple preparation of multi-branched poly(l-lactic acid) and its role as nucleating agent for poly(lactic acid)

The present work proposes a simple preparation of multi-branched poly(l-lactic acid)s (m-PLLAs) and their performance as nucleating agents for PLA. By a simple polycondensation of l-lactic acid (l-LA) on the multi-functional core molecules of succinic acid (SA), malic acid (MA) and citric acid (CA) using stannous octanoate (SnOct₂) as a catalyst, the m-PLLAs as two, three, and four branched PLLA can be obtained easily. Averagely, about 80% of the l-LA feed contents are successfully polymerized on core molecules. Non-isothermal crystallization studies of the PLA blend which contains 1 wt% m-PLLAs indicate that m-PLLAs induce the crystallization of PLA as evidenced from the decreases in glass transition temperature (T_g) and crystallization temperature (T_c), and the increase in degree of crystallinity (χ_c) under the α-form of perfect crystalline in PLA. Isothermal crystallization studies related to Avrami exponent (n), kinetic constant (k) and crystallization half-time (t_1/2) indicate that the blend maintains its three-dimensional growth for the film thickness 0.05 mm, whereas the crystallization growth rate increases more than 4 times as observed from polarized optical microscope (POM). Among m-PLLA, the highest number of multi-branches with the shortest chain PLLA, i.e. CA-PLLA1, initiates the blends to increase its tensile strength and elongation at break for as high as 1.5 times and 1.2 times, respectively.     

Shear induced crystallization of poly(m-xylylene adipamide) with and without nucleating additives

The shear induced crystallization of the poly(m-xylylene adipamide) (MXD6) which is a semi-aromatic polyamide, was studied for a virgin (PA1) and a nucleated (PA2) grades using a shearing hot stage coupled with a microscope. Half crystallization times were measured according to the crystallization conditions (crystallization temperature, shear rate and shearing time). The effect of shear on the crystallization kinetics was shown by a strong decrease of the crystallization times for both materials. PA2 sensitivity to shear was much lower than that of PA1. This was attributed to the presence of nucleating agents which increased the primary nucleation density in the unsheared quiescent melt, leading to a higher necessary shear rate to overcome the quiescent nucleation. Kinetic models were proposed to predict the crystallization process as a function of the crystallization conditions. They were based on both Avrami and Hoffman-Lauritzen theories and modified to take into account the effect of shear. In the model the nucleation rate of the crystalline entities was related to the shear rate by a power function. Besides, crystalline morphology and orientation were studied by wide and small angle X-ray scattering to confirm the orientation effect of the shear in the crystalline part of the material.     

Comparison of anhydrous and monohydrated forms of orotic acid as crystal nucleating agents for poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

A small molecule nucleating agent, orotic acid (OA), was investigated to enhance crystallinity and crystallization kinetics in poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) for the purpose of addressing embrittlement and reducing solidification time after thermal processing. In particular, the effectiveness of monohydrated (OA-m) and anhydrous (OA-a) forms of OA as nucleating agents for isothermal and non-isothermal crystallization of PHBV films was investigated and compared. Both forms of OA were able to increase crystallization temperature of PHBV as well as form more uniform crystal structures, based on differential scanning calorimetry. It was found that OA-a at 1–2 wt% was most effective in PHBV crystal nucleation because of the increase in overall polymer crystallinity and faster crystallization rate. Additionally, the faster crystallization of OA-a led to fibrillar film morphology of the PHBV/OA blends.     

Crystallization of poly(lactic acid) enhanced by phthalhydrazide as nucleating agent

The effect of phthalhydrazide compound on the nonisothermal and isothermal crystallization behavior of bio-based and biodegradable poly(lactic acid) (PLA) was investigated by differential scanning calorimetry and polarized optical microscopy. The nonisothermal melt crystallization of PLA started much earlier in the presence of phthalhydrazide even at a phthalhydrazide content as low as 0.1 wt%. The isothermal crystallization kinetics was analyzed by the Avrami model. It was found that the Avrami exponent of the PLA crystallization was not significantly influenced by the addition of phthalhydrazide, indicating that the crystallization mechanism almost did not change in the composites. The crystallization half-time of PLA/phthalhydrazide composites decreased significantly with increase in phthalhydrazide loading. The observation from optical microscopy showed that the presence of phthalhydrazide increased the number of nucleation sites. The above observations indicate that phthalhydrazide is an efficient nucleating agent of PLA.     

Effect of biobased and biodegradable nucleating agent on the isothermal crystallization of poly(lactic acid)

The effect of chemically modified thermoplastic starch (CMPS) on the thermal properties and isothermal crystallization kinetics of poly(lactic acid) (PLA) was studied by differential scanning calorimetry (DSC) and compared to that of granular starch and an inorganic nucleating agent, talc. Nucleated PLA showed an additional crystallization of PLA, which affected the melting temperature. The crystallinity and crystallization rate of PLA were considerably enhanced by addition of CMPS, even at 0.1% content, and the amount of the CMPS had little effect on the thermal properties and isothermal crystallization kinetics of PLA. The effect of CMPS as a nucleating agent was comparable to that of granular starch but slightly less than that of talc. However, CMPS can offer a fully biodegradable nucleating agent with no residues remaining for the biobased and biodegradable polymers.     

Effect of aliphatic diacyl adipic dihydrazides on the crystallization of poly(lactic acid)

A series of aliphatic diacyl adipic dihydrazides (ADHs) with different alkyl moieties were synthesized by the reaction between adipic dihydrazide and acyl chloride. Then these ADHs were solution blended with PLA respectively and were evaluated as nucleating agents. Through the investigation of nonisothermal and isothermal crystallization, it was found that both the crystallization rate and the crystallinity of PLA could be enhanced by adding only 1 wt % of ADHs. Especially for ADH‐Oc (ADH‐Octyl), the crystallization rate of PLA increased about 4 times at 105°C. Optical morphology showed that and the size of PLA spherulites decreased and the nucleation density increased with the existence of ADH‐Oc. Meanwhile, the crystal structure of PLA were not discerniblly affected after the addition of ADHs as found by wide‐angle X‐ray diffraction. Thus, this study suggested these ADHs compounds are simple and potential nucleating agents to enhance crystallization ability of PLA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42028.     

Effect of nucleating agents on the crystallization behavior and heat resistance of poly(l‐lactide)

Poly (l ‐lactide) (PLLA) blends with various nucleators were prepared by melt processing. The effect of different nucleators on the crystallization behavior and heat resistance as well as thermomechanical properties of PLLA was studied systematically by differential scanning calorimetry, X‐ray diffraction, heat deflection temperature tester, and dynamic mechanical analysis. It was found that poly(d ‐lactide), talcum powder (Talc), a multiamide compound (TMC‐328, abbreviated as TMC) can significantly improve the crystallization rate and crystallinity of PLLA, thus improving thermal–resistant property. The heat deflection temperature of nucleated PLLA can be as high as 150°C. The storage modulus of nucleated PLLA is higher than that of PLLA at the temperature above T_g of PLLA. Compared with other nucleating agents, TMC was much more efficient at enhancing the crystallization of PLLA and the PLLA containing TMC showed the best heat resistance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42999.     

癸二酸二水杨酰肼对聚L-乳酸结晶和熔融行为的影响

为丰富双酰胺类聚L-乳酸结晶促进剂的类别,以癸二酸和水杨酰肼为原料制备具有双酰胺结构的癸二酸二水杨酰肼作为聚L-乳酸的结晶促进剂,研究其对聚L-乳酸的非等温结晶行为和熔融行为的影响。非等温结晶行为显示癸二酸二水杨酰肼可显著提升聚L-乳酸的结晶能力,尤其是0.5%的癸二酸二水杨酰肼对聚L-乳酸具有最佳的结晶加速效应,可使聚L-乳酸的起始结晶温度、结晶峰温度以及非等温结晶焓分别从101.4℃,94.5℃,0.1 J/g增加到122.8℃,119.5℃,32.6 J/g,另外,非等温结晶过程中降温速率是影响聚L-乳酸结晶的重要因素,而最终熔融温度对非等温结晶行为的影响较小。等温结晶后的熔融行为研究进一步证实了不同含量癸二酸二水杨酰肼对聚L-乳酸结晶促进作用的贡献大小,但促进作用上的差别会随着等温结晶时间的增加而减小。