Effect of a Novel Nucleating Agent on Isothermal Crystallization of Poly（L-lactic acid）

The effect of a novel active nucleating agent(TBC8-eb) on the isothermal crystallization of poly(L-lactic acid) (PLLA) was studied by differential scanning calorimetry(DSC) and Fourier transform infrared spectroscopy(FTIR) . The analysis on kinetics demonstrates that TBC8-eb can not only accelerate the crystallization rate but also transform most of the original spherulite crystals of PLLA into sheaf-like crystals. Furthermore,the free energy of folding(σe) of PLLA and PLLA with TBC8-eb is 0.15 and 0.06 J·m-2,respectively,which suggests that the addition of TBC8-eb favors the regular folding of molecule chains in the crystallization of PLLA,improv-ing its crystallization rate. The FTIR results show that TBC8-eb can accelerate the conformational ordering of PLLA in the isothermal crystallization. The conformational ordering of PLLA nucleated with TBC8-eb begins with the interchain interaction of CH3,and then a short helix emerges where a couple of CH3 groups interact.

Effect of Nucleating Agents and Heat Treatments on the Crystallization of Magnesium Aluminosilicate Transparent Glass-ceramics

The crystallization behavior and transparent property of MgO-A1203-SiO2 （MAS） glasses with TiO2 and TiO2＋ZrO2 as nucleating agents were discussed by differential thermal analysis, X-ray diffraction, field emission-environment scanning electron microscope, energy dispersive spectrum and UV-VIS-NIR scanning spectrophotometer. It was found that the glass crystallized at 950 ℃ with ZrO2 less than 3% could obtain transparent glass ceramic, which presented purple to colorless. With the nucleating agent additives （5% TIO2＋3% ZrO2）, the colorless transparent glass-ceramics with spinel as the main crystal phase could be prepared, and the transmittance reached about 80%. As the crystallized temperature increase to 1 000 ℃, besides spinel（MgA1204）, sapphirine （Mg3.5A19Si1.5O20） and ZrTiO4 precipitated from matrix glass, and the transmitance of glass-ceramic decreased.

THERMODYNAMIC STUDY OF NUCLEATION PROPERTY OF NUCLEATING AGENT

It is deduced from thermodynamic relations and confirmed by experiment results that the nucleation rate and nucleation temperature of nucleating agents in the glass are dependent upon their melting entropy Delta S//m melting temperature T//m and crystal - type transition in terms of some mathematical expressions. (Author abstract) 10 Refs.

MELTING BEHAVIOR OF LOW ETHYLENE CONTENT POLYPROPYLENE COPOLYMERS WITH AND WITHOUT NUCLEATING AGENTS

The melting behavior of polypropylene (PP) and low ethylene content polypropylenecopolymer with and without nucleating agent samples crystallized under both isothermal and non-isothermal conditions were studied by Differential Scanning Calorimeter (DSC) and X-raydiffraction. Multiple melting behavior were observed depending on the existence of nucleatingagent and crystallization conditions. The observed phenomena have been discussed by the effect ofnucleating agent on perfection of crystal and the melting and recrystallization of imperfect crystalto a more perfect crystal during the heating process of samples.

Preliminary Study on the Characteristics of Isotactic Polypropylene with Nucleating Agent Swollen by Supercritical Carbon Dioxide

Impregnation of isotactic polypropylene (iPP) with nucleating agent (NA21) using supercritical carbon dioxide as the swelling agent at different temperature and pressure and its non-isothermal crystallization kinetics were investigated. The results showed that NA21 was dispersed at a nanometer-scale in the PP matrix, resulting in the formation of different typesof crystal phases of iPP and the enhancement of its mechanical properties.

Effect of Nucleating Agent on the Crystallization of Tailings Glass Ceramics Prepared by One-time Sintering

Glass ceramics was made by the one-time sintering method using the main raw material of iron tailings. On the basis of quaternary system of CaO-MgO-Al2O3-SiO2, using DTA, XRD and SEM, the effects of different nucleating agents and mixing amounts as well as heat treatment on the crystallization of railings glass ceramics were studied. The experimental results show that, nucleating agent and heat treatment are two necessary conditions for one-time sintering preparation of tailings glass ceramics namely, only adding nucleating agent or experiencing heat treatment, the quaternary system can not crystallize. The composite nucleating agent consisting of Cr2O3 and TiO2 can further lead to the crystallization of the CaO-MgO-A1203-SiO2 quaternary system at the lower temperature, with the major phase of diopside. In the range of mass content, 0%-4%, crystal intensity and crystal content grow. But when mass content is more than 4%, the crystal size will become coarser and the crystal distribution will be less regular. Different heat treatment regimes do not change the composition of the crystalline major phase in the glass ceramics crystallization of CaO-MgO-Al2O3-SiO2 system. In the range of 30-60 minutes, with the extension of nucleation and crystallization, crystallization degree enhanced, but if the holding time surpasses 60 minutes, the crystallization is worse.

Effects of Nucleating Agents on Crystallization of Arc-Molten Slag from Incinerator Fly Ash

Glass-ceramics obtained from the electric arc furnace molten slag of incinerator fly ash was produced by applying nucleation and crystallization through heat treatment process. The effects of nucleating agent （TiO2 and Cr2O3） on the crystallization kinetics and heat treatment schedule of the slag were investigated. The results show that the nucleating agents changed the crystallization phase and morphology of the obtained glass-ceramics. The optimum heat treatment schedule of the glass with TiO2 was determined as nucleation at 952 K for 1.5 h and crystal growth at 1 258 K for 1.5 h, while those values with Cr203 were estimated at 971 K for 2 h and at 1 238 K for 2 h. TiO2 acting as nucleating agent could decrease the activation energy of the slag and shorten the total thermal treatment time in comparison with Cr2O3. The glass-ceramics obtained under the optimum heat treatment condition was environmentfriendly and had remarkable physical/mechanical properties and chemical durability.

Influence of Nucleating Agent on the Formation of C_4A_3S

The reference test methods are carried out parallelly, by means of chemical analysis, X-ray diffraction, differential scanning calorimetry-thermogravimetry, scanning electron microscopy and polarized optical microscope to study the formation of C4A3S in the presence and absence of nucleating agent. The results show that nucleating agent with high calcium and low heat consumption as tricalcium silicate （C3S） promotes the formation of C4A3S and increases desulfurization degree obviously. During calcining raw meals doped with C3S, the grain sizes of C4A3S are larger compared with that without C3S. And at the same calcining level, the mass loss and the heat consumption belonged to CaCO3 decomposition is reduced.

Lightweight,Strong and High Heat-Resistant Poly(lactide acid)Foams via Microcellular Injection Molding with Self-Assembly Nucleating Agent

Poly(lactide acid)(PLA)foams have shown considerable promise as eco-friendly alternatives to nondegradable plastic foams,such as polystyrene(PS)foams.Nevertheless,PLA foam typically suffers from low heat-resistance and poor cellular structure stemming from its inherent slow crystallization rate and low melt strength.In this study,a high-performance PLA foam with well-defined cell morphology,exceptional strength and enhanced heat-resistance was successfully fabricated via a core-back microcellular injection molding(MIM)process.Differential scanning calorimetry(DSC)results revealed that the added hydrazine-based nucleating agent(HNA)significantly increased the crystallization temperature and accelerated the crystallization process of PLA.Remarkably,the addition of a 1.5 wt%of HNA led to a significant reduction in PLA’s cell size,from 43.5µm to 2.87µm,and a remarkable increase in cell density,from 1.08×10^(7)cells/cm^(3)to 2.15×10^(10)cells/cm^(3).This enhancement resulted in a final crystallinity of approximately 55.7%for the PLA blend foam,a marked improvement compared to the pure PLA foam.Furthermore,at 1.5 wt%HNA concentration,the tensile strength and tensile toughness of PLA blend foams demonstrated remarkable improvements of 136%and 463%,respectively.Additionally,the Vicat softening temperature of PLA blend foam increased significantly to 134.8°C,whereas the pure PLA foam exhibited only about 59.7℃.These findings underscore the potential for the preparation of lightweight injection-molded PLA foam with enhanced toughness and heat-resistance,which offers a viable approach for the production of high-performance PLA foams suitable for large-scale applications.

Enhanced Crystallization of Poly(butylene adipate-co-terephthalate)by a Self-assembly Nucleating Agent

Poly(butylene adipate-co-terephthalate)(PBAT)is a promising biodegradable flexible polymer but suffers from slow crystallization rate,making it less attractive for some applications like the injection-molded products in comparison with low-density polyethylene(LDPE).This work aimed to accelerate the crystallization of PBAT by adding a self-assembly nucleating agent octamethylenedicarboxylic dibenzoylhydrazide(OMBH).PBAT/OMBH composites with various OMBH contents(0 wt%,0.5 wt%,0.7 wt%,1 wt%,2 wt%,3 wt%and 5 wt%)were prepared through melt-mixing.The effect of OMBH on the crystallization behavior,morphologies and mechanical properties of PBAT was investigated.The highest nucleation efficiency value of 59.6%was achieved for PBAT with 0.7 wt%OMBH,much higher than that of 22.7%for PBAT with 0.7 wt%talc.Atomic force microscopy results showed that OMBH formed fine fibers and induced the formation of transcrystalline layers of PBAT.Fourier transform infrared spectroscopy(FTIR)combined with two-dimensional correlation spectra suggested that the intermolecular dipole-dipole N—H…O=C interactions but not hydrogen bond between OMBH and PBAT promoted the crystallization of PBAT in the initial period of crystallization.The presence of OMBH did not change the crystal form of PBAT but had positive contribution in enhancing its crystallinity and mechanical properties.This work is essential for preparing PBAT with high crystallization rate,enhancing its potential applications in injection-molded products.

Influence of Nucleation Agents Concentration on Crystallization Structure and Properties of Glass-ceramics

Deep color glass-ceramics is prepared by using gold tailings as the main raw material, and Cr2O3 is added as nucleation agent. Influence of different Cr2O3 additions on crystallization structure and properties of CaO-MgO-Al2O3-SiO2 glass-ceramics has been discussed so as to select optimum additions. DTA is employed to determine optimum crystallization and nucleation temperatures; XRD and SEM are used to characterize microstructure of each sample; and performance indexes, such as water absorption, bulk density, flexural strength and so on, are also determined. Experimental results show that when 3wt% Cr2O3 is introduced, fine glass-ceramics with diopside as the main crystal and Ca-Fe diopside as the second-crystal is obtained, and its corresponding performance indexes are as follows： water absorption 0.12%, bulk density 2.56 g/cm^3, and flexural strength 70.01 Mpa.

Effect of TiO_2 on Crystallization of the Glass Ceramics Prepared from Granite Tailings

The effect of TiO2 on the crystallization behaviors of the glass ceramics prepared from granite tailings was investigated by differential scanning calorimetry （DSC）, X-ray diffraction （XRD）, and field emission scanning electron microscopy （FESEM）. The results showed that the crystallization peak temperature decreased firstly, and then increased with the increase of TiO2 content. The optimum addition amount of TiO2 was 8 wt%. With a single-step heat treatment at 924 ℃ for I h, augite precipitated as the only crystalline phase both on the surface and in the interior. The avrami parameter of the sample was 3.25, suggesting a two- dimensional crystallization mechanism. The activation energies for phase separation and crystallization of augite were 321.75 and 698.83 kJ/mol, respectively.

Zinc phosphating of 6061-Al alloy using REN as additive

Zinc phosphate coating formed on 6061-A1 alloy was studied with the help of electrochemical measurements, Fourier Transform Infrared （FTIR）, and Scanning Electron Microscopy （SEM）, after dipping it in phosphating solutions containing different concentrations of Rare Earth Nitrate （REN）. REN, which acted as an accelerator in the phosphating solution, could catalyze the surface reaction and accelerate the phosphating process. REN mainly enabled the P in the phosphate coating to exist in the form of PO4^3- and promoted the hydrolysis of phosphatic acid in a liquid layer at the cathodes. This resulted in the evolution of H2 at the cathodes, which increased the local pH value and in turn drove the precipitation of the phosphate coating. Additionally, REN was adsorbed on the surface of the aluminum substrates to form a gel during the phosphating process. These gel particles were good crystal seeds, which helped to form phosphate crystal nuclei and possess the function of a nucleation agent that could decrease the phosphate crystal size. The corrosion resistance of the formed zinc phosphate coatings was improved.

Study on phosphating treatment of aluminum alloy:role of yttrium oxide

Zinc phosphate coatings formed on 6061-Al alloy, after dipping in phosphating solutions containing different amounts of Y2O3（yttrium oxide）, were studied by scanning electron microscopy （SEM）, X-ray diffraction （XRD） and electrochemical measurements. Significant variations in the morphology and corrosion resistance afforded by zinc phosphate coating were especially observed as Y2O3 in phosphating solution varied from 0 to 40 mg/L. The addition of Y2O3 changed the initial potential of the interface between aluminum alloy substrate and phosphating solution and increased the number of nucleation sites. The phosphate coating thereby was less porous structure and covered the surface of aluminum alloy completely within short phosphating time. Phosphate coating was mainly composed of Zn3（PO4）2·4H2O （hopeite） and AlPO4（aluminum phosphate）. Y2O3, as an additive of phosphatization, accelerated precipitation and refined the gain size of phosphate coating. The corrosion resistance of zinc phosphate coating in 3% NaCl solution was improved as shown by polarization measurement. In the present research, the optimal amount of Y2O3 was 10-20 mg/L, and the optimal phosphating time was 600 s.

Different influences of nucleating agents on crystallization behavior of polyethylene and polypropylene

The crystallization behavior of polyethylene (PE) and polypropylene (PP), including the neat ones and the ones nucleated with the same nucleating agent (NA), was studied by DSC. It was found that the nucleating agent decelerated the PE nonisothermal crystallization process. NA did enhance the nucleating rates for both PE and PP, but the linear growth rate dominated the volumetric growth rate for PE, and the volumetric growth rate dominated the overall crystallization rate. That is why PE nucleated with NA had a slower overall crystallization rate than the neat one.

Crystallization Behavior of Biodegradable Poly(ethylene adipate) Modulated by a Benign Nucleating Agent： Zinc Phenylphosphonate

Zinc phenylphosphonate （PPZn）, a benign and biocompatible nucleating agent, was prepared and incorporated into the biodegradable poly（ethylene adipate） （PEA） to investigate its effect on the crystallization behavior, crystallization kinetics and spherulite morphology of PEA. Upon addition of PPZn, the crystallization temperature and crystallinity of PEA in the non-isothermal crystallization process increased significantly. Analysis of crystallization kinetics by Avrami equation suggests that the crystallization time shortened greatly and crystallization rate increased markedly after addition of PPZn. In the presence of PPZn, the spherulite size decreased and spherulite density increased significantly. It suggests that PPZn is an efficient nucleating agent for the crystallization of PEA. The accelerated crystallization in the presence of PPZn is mainly attributed to the epitaxial nucleation of PEA crystals on the surface of PPZn crystals, that is, a perfect lattice matching between PEA crystal and PPZn crystal occurs.

Suppression of supercooling of PCM-water emulsions using nano-additives

This study aims to develop a paraffin-based phase change material(PCM) emulsion with a low extent of supercooling for thermal energy storage(TES) systems to improve the cooling efficiency.Hexadecane-water emulsions were prepared and characterized. Multi-wall carbon nanotubes(MWCNTs) were dispersed in the emulsion as a nucleating agent to reduce the supercooling. The MWCNTs were chemically modified with carboxyl groups to improve the dispersion of the tubular particles in the organic liquid. Thermal analyses of the emulsions by differential scanning calorimeter(DSC) indicated that the extent of supercooling was significantly reduced. The concentration of the nucleating agent for an effective supercooling suppression as found to be very low, in agreement with previous findings, and there appeared to be a minimum concentration for the supercooling reduction.

Synthesis, Characterization and Application of Methyl 3,5-Disulfo-benzoate Dipotassium Dihydrate as Nucleating Agent for Poly（L-lactide）

A newly synthesized aromatic sulfonate compound,complex 2 with formula of K2[H3COOC-C6H3（SO3）2]·2H2O（methyl 3,5-disulfo-benzoate dipotassium dihydrate） was synthesized and characterized by elemental analysis,infrared（IR） spectrometry,nuclear magnetic resonance（NMR） and crystal structure measurement.Single-crystal X-ray diffraction（XRD） revealed that complex 2 crystallized in the triclinic system with space group P（i）.Complex 2 was used as nucleating agent for poly（L-lactide）（PLLA）.The crystallization of PLLA with powder of complex 2 was investigated by means of differential scanning calorimetry（DSC） and polarized optical microscopy （POM）.The results prove that complex 2 was effective as nucleating agent for PLLA.It could accelerate crystallization by reducing the induction time and increasing the density of nuclei in the crystallization process.The half-time of crystallization（t0.5） for pure PLLA was about 8 times longer than that of PLLA sample with 1.0％（mass fraction） of complex 2.

Excellent energy storage performance of niobate-based glass-ceramics via introduction of nucleating agent

For glass-ceramics, how to realize the collaborative optimization of BDS and permittivity is the key toimprove the energy storage density. In this work, ZrO2 is introduced into BPKNAS glass-ceramics asnucleating agent to promote crystal development of glass-ceramics and then achieve high permittivity.When 1.5 mol% ZrO2 is added, the glass-ceramics have the highest permittivity (~128.59) and meanwhilepossess high BDS (1948.90 kV/cm) due to the dense microstructure. Therefore, BPKNAS-1.5ZrO2 glass-ceramics has the highest theoretical energy storage density (21.62 J/cm3). Moreover, the permittivityvariation of BPKNAS-1.5ZrO2 glass-ceramics is less than 6 % in the wide temperature range from 80 to300 C, showing excellent temperature stability. In addition, BPKNAS-1.5ZrO2 glass-ceramics possessesultrahigh power density, which reaches up to 382.40 MW/cm3 in overdamped circuit. The above evi-dence shows that BPKNAS-1.5ZrO2 glass-ceramics with ultrahigh energy storage density and powerdensity is very competitive in the field of energy storage applications.

Enhanced Crystallization Rate of Biodegradable Poly(ε-caprolactone) by Cyanuric Acid as an Efficient Nucleating Agent

The influence of cyanuric acid（CA） as an efficient nucleating agent on the crystallization behavior and morphology of biodegradable poly（ε-caprolactone）（PCL） was extensively studied in this work with several techniques for the first time. The nonisothermal melt crystallization behavior and overall isothermal melt crystallization rate of PCL were significantly enhanced by only a small amount of CA. The addition of CA apparently improved the nonisothermal melt crystallization peak temperature, overall isothermal melt crystallization rate, and nucleation density of PCL spherulites, but did not modify the crystallization mechanism and crystal structure of PCL, indicating that CA was an efficient nucleating agent for the crystallization of PCL. The possible nucleation mechanism of CA on the crystallization of PCL was also discussed on the basis of their crystal structures.