Effect of final heating temperature on crystallization of isotactic polypropylene nucleated with an aryl amide derivative as <Emphasis Type="Italic">β</Emphasis>-form nucleating agent

An aryl dicarboxylic acid amide compound TMB-5 is an efficientβ-form nucleating agent for isotactic polypropylene(iPP).Because of the solubility of TMB-5,superstructure and morphology of iPP crystals changed with melting conditions.Effects of final heating temperature(T_f)on heterogeneous nucleation of iPP/TMB-5 were investigated.It was discovered that the crystallization temperature increased with decreasing T_f value.The optical microscopic images indicated that when TMB-5 partially dissolved in iPP melt,the remaining(non-dissolved)TMB-5 facilitated the recrystallization of dissolved nucleating agent from the melt,which promoted crystallization.Complete solubility of nucleating agent caused the decreasing efficiency.TMB-5 recrystallized in the form of tiny needles,whose aggregates induced dendritic iPP crystals.     

Preparation,non-isothermal crystallization,and melting behavior of β-nucleated isotactic polypropylene/poly (ethylene terephthalate) blends

β-nucleated PP/PET blends were prepared using nano-CaCO₃ supported β-nucleating agent (β-NA), PP as matrix, and PET as dispersion phase. The effects of preparation methods, PET content, and melting temperature on the non-isothermal crystallization behavior and the melting characteristic and polymorphic composition of PP in the blends were investigated by differential scanning calorimeter (DSC) and wide angle X-ray diffraction (WAXD). The results indicated that the PP crystallized predominantly in β-modification in the presence of β-NA. However, efficiency of β-NA for PP crystallization decreased with addition of PET and increasing PET contents. The β-nucleation of β-NA for PP crystallization in the blends was dependant on the preparation methods. The high β-nucleation and high β-PP content were obtained for PP/PET blend prepared at the temperature of 265 °C and added the β-NA into the blend at the temperature of 180 °C. However, the addition of β-PP or β-NA into blends at 265 °C decreased the β-nucleation, and no β-PP was formed because the β-NA mainly dispersed on the PET dispersion phase or at the interface between PP and PET.     

The mechanism of α-γ transition of poly- (vinylidene fluoride) in the miscible blends

The simultaneous DSC-FTIR was used for the observation of crystallization and melting of poly(vinylidene fluoride) (PVDF) and its blends with poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA). The isothermal crystallization was carried out under the condition of both α-form and γ-form crystallized competitively. The crystal growth rate of α -form and γ -form were evaluated from the absorbance changes at 795 cm^-1 (α -form, CH₂ rocking) and 810 cm^-1 (γ -form, CH₂ rocking) obtained by the DSC-FTIR. The crystal growth rate of γ -form decreased at the same crystallization temperature in the order of PVDF/syn-PMMA, PVDF/PEMA and PVDF/at-PMMA, which was corresponding to the order of interaction parameter. The mechanism of α -g transition of PVDF in the miscible blends with at-PMMA, syn-PMMA and PEMA was evaluated from the relationship between the decrease of α -form and the increase of γ -form. The critical crystallization temperature, at which the transformation from α -form to γ -form proceeded only in the solid state, shifted to higher temperature side in the order of interaction parameter. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal and structural studies of polypropylene blended with esterified industrial waste lignin

Microwave-assisted chemical modification of lignin was achieved through esterification using maleic anhydride. Modified lignin (ML) was blended in different proportions up to 25 mass% with polypropylene (PP) using Brabender electronic Plasticorder at 190 °C. The structural and thermal properties of blends were investigated by thermogravometric analysis (TG), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and scanning electron microscopy (SEM). TG analysis showed increased thermal stability of blends due to antioxidant property of ML, which opposed oxidative degradation of PP. DSC analysis indicted slight depression in a glass transition temperature and melting temperature of blends due to partial miscible blend behavior between PP and ML. All blends showed higher crystallization temperatures and continuously reducing percentage crystallinity with increasing ML proportion in the blends. WAXD analysis indicated that PP crystallized in β polymeric form in addition to α-form in the presence of ML. However, proportion of β-form did not show linear relation with increase in ML proportion, thus ML acts as β nucleating agent in the PP matrix. SEM analysis showed good dispersion/miscibility in PP matrix indicating modification in lignin is useful.     

Influence of <Emphasis Type="Italic">m</Emphasis>-isopropenyl-α,α-dimethylbenzyl isocyanate and styrene on non-isothermal crystallization behavior of polypropylene

Non-isothermal crystallization kinetics of polypropylene (PP), m-isopropenyl-α,α-dimethyl-benzyl isocyanate grafted PP (PP-g-m-TMI), and styrene(St), as comonomer, together with m-TMI grafted PP (PP-g-(St-m-TMI)) was investigated by using differential scanning calorimetry (DSC) under different cooling rates. The crystallization rates of all samples increased with increasing cooling rate. The relation of the half time of crystallization (t _1/2) of the three samples, t _{1/2(PP-g-(St-m-TMI))} < t _{1/2(PP-g-m-TMI)} < t _1/2(PP), implying the introduction of St could effectively improve the degree of grafting of m-TMI, resulting in crystallization temperature increased, and the crystallization rate was the fastest. Three methods, namely, the Avrami, the Ozawa, and the Mo, were used to describe the crystallization process of the three samples under non-isothermal conditions. The Avrami and Ozawa neglected the secondary crystallization that follows primary crystallization. The Mo method can successfully describe the overall non-isothermal crystallization process of all the samples. It has been found that the F(T)_{(PP-g-(St-m-TMI))} < F(T)_(PP-g-m-TMI) < F(T)_(PP), also meaning that the crystallization rate of PP-g-(St-m-TMI) and PP-g-m-TMI were faster than that of PP. The activation energy (ΔE) for non-isothermal crystallization of all samples was determined by using the Kissinger method. The result showed that the lower value of ΔE for crystallization obtained for PP-g-m -TMI and PP-g-(St-m-TMI) confirmed the nucleating effect of St and m-TMI on crystallization of PP.     

Fractionated Crystallization Kinetics and Polymorphic Homocrystalline Structure of Poly(L-lactic acid)/Poly(D-lactic acid) Blends: Effect of Blend Ratio

Stereocomplex (SC) crystallization has been an effective way to improve the physical performances of stereoregular polymers. However, the competition between homo and SC crystallizations can lead to more complicated crystallization kinetics and polymorphic crystalline structure in stereocomplexable polymers, which influences the physical properties of obtained materials. Herein, we select the medium-molecular-weight (MMW) poly(_L-lactic acid)/poly(_D-lactic acid) (PLLA/PDLA) asymmetric blends with different PDLA fractions (f_D=0.01–0.5) as the model system and investigate the effects of f_D and crystallization temperature (T_c) on the crystallization kinetics and polymorphic crystalline structure. We observe the fractionated (i.e., multistep) crystallization kinetics and the formation of peculiar β-form homocrystals (HCs) in the asymmetric blends under quiescent conditions, which are strongly influenced by both f_D and T_c. Precisely, crystallization of β-form HCs is favorable in the MMW PLLA/PDLA blends with high f_D (≥0.2) at a low T_c (80–100 °C). It is proposed that the formation of metastable β-form HCs is attributed to the conformational matching between β-form HCs and SCs, and the stronger constrain effects of precedingly-formed SCs in the early stage of crystallization. Such effects can also cause the multistep crystallization kinetics of MMW PLLA/PDLA asymmetric blends in the heating process.

     

Steric effects on the singlet-triplet energy gaps of five-membered ring R<Subscript>2</Subscript>C<Subscript>4</Subscript>H<Subscript>2</Subscript>M

Thermal internal energy gaps, ΔE _s−t; enthalpy gaps, ΔH _s−t; Gibbs free energy gaps, ΔD _s−t, between singlet (s) and triplet (t) states of R₂C₄H₂M (M = C, Si, and Ge) were calculated at B3LYP/6-311++G** level of theory. The ΔG _s−t of R₂C₄H₂C was increased in the order (in kcal/mol): R = −CH₃ (−10.51) > −H (−9.59) > i-Pr (−9.51) > t-Bu (−8.98). While, the ΔG _s−t of R₂C₄H₂Si and R₂C₄H₂Ge were increased in the order (in kcal/mol): −CH₃ (17.01) > i-Pr (15.30) > −H (15.26) > t-Bu (14.35) and -H (22.79) > −CH₃ (22.69) > i-Pr (21.66) > t-Bu (21.01), respectively.     

Morphology development during isothermal crystallization. II. Isotactic and syndiotactic polypropylene blends

Morphology development during isothermal crystallization in equal molecular weight isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), and iPP/sPP blends was studied with time‐resolved simultaneous small‐angle X‐ray scattering (SAXS) and wide‐angle X‐ray diffraction (WAXD) with synchrotron radiation. The sPP melting point is 15–20 °C below that of the iPP component, and sPP multiple melting is not affected by blending for 50–100 wt % sPP compositions. SAXS and WAXD (at 115 and 137.5 °C) show that sPP crystallizes more slowly than iPP. The sPP long spacing is larger than that of iPP at both crystallization temperatures, exhibits a broader distribution, and changes to a greater extent during crystallization. Differential scanning calorimetry (DSC) cooling and SAXS/WAXD measurements show iPP crystallizing first and nearly to completion before sPP in a 50:50 iPP/sPP blend. At 115 °C, iPP crystals nucleate sPP in a 50:50 blend and modify the sPP lamellar spacing. The nucleation does not overcome the large difference in the iPP and sPP rates at 137.5 °C. Before sPP crystallization in a 50:50 blend (115 °C), the iPP long spacing is not affected by molten sPP. The iPP long spacing is slightly expanded by molten sPP, and the WAXD induction time is delayed at 137.5 °C. The observed iPP long spacing in the presence of molten sPP is consistent with previously reported results for iPP/atactic polypropylene (aPP) blends of similar molecular weight. Quantitative differences between the two types of blends are consistent with previously reported thermodynamic rankings. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1876–1888, 2001     

A proposed modification of CBS-4M model chemistry for application to molecules of increasing molecular size

 In order to calculate more accurately the enthalpies of formation, ΔH _f°(298 K), for large molecules using the CBS-4M method, a new formulation of the empirical higher-level correction to the energy is proposed: ΔE=a|S|² _{i i} I _{i i} +b(n _α+n _β)+cΔ<S ²>+Σn _i d _{i .} The new methodology (CBS-4MB) applied to a set of 114 molecules of different size significantly decreases the mean absolute deviation from 3.78 to 2.06 kcal/mol. Received: 7 February 2001 / Accepted: 5 April 2001 / Published online: 13 June 2001     

Isothermal crystallization kinetics of AB2 hyper-branched polymer (HBP)-filled polypropylene (PP)

In this paper, the isothermal crystallization kinetics of pure polypropylene (PP) and AB₂ hyper-branched polymer (HBP)/PP blends have been investigated by differential scanning calorimetry (DSC). During isothermal crystallization, the crystallization rates of the blends are higher than those of PP. Furthermore, in the blends with different HBP contents, the value of t _1/2 became smaller with increasing HBP content; however, the crystallization rate of the blend decreased slightly when the content of HBP is 5 %. An increase in the Avrami exponent means the addition of HBP influences the mechanism of nucleation and the growth of PP crystallites. In addition, the crystallization activation energy of pure PP and HBP/PP blends were also discussed, and the result showed that the crystallization activation energy has decreased remarkably in HBP/PP blends.     

Morphology development during isothermal crystallization. I. Isotactic and atactic polypropylene blends

Morphology development during isothermal crystallization in equal molecular weight isotactic polypropylene (iPP) and atactic polypropylene (aPP) blends was studied with time‐resolved simultaneous small‐angle X‐ray scattering (SAXS) and wide‐angle X‐ray scattering methods with synchrotron radiation. The final long period obtained after crystallization at 115 °C was nearly independent of blend composition up to 50 wt % aPP but showed an increase in the 80 wt % aPP blend. At a high crystallization temperature (137.5 °C), the increase in the final long period with aPP content was significant, and the evolution of iPP crystallinity was also affected. However, at low crystallization temperatures, the additive decrease of the crystallinity and the constant melting point with increasing aPP content suggest that the crystallizability and crystal morphology of iPP is not a strong function of aPP. The iPP/aPP blends showed a strong low‐angle SAXS upturn as a function of composition, which suggests the segregation of aPP on size scales larger than the lamellar spacing. A detailed analysis of the SAXS patterns indicates that aPP disrupts the ordering within the lamellar stacking. The results are generally consistent with predominantly interfibrillar incorporation of the aPP diluent within the microstructure, with only modest interlamellar incorporation dependent on the crystallization temperature. The findings can be attributed to the partial miscibility/mixing of the aPP and iPP components in the blend before crystallization, depending on the crystallization undercooling. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2580–2590, 2000     

DSC and morphological studies on the crystallization behavior of β-nucleated isotactic polypropylene composites filled with Kevlar fibers

The crystallization behavior of β-nucleated isotactic polypropylene (PP) composites filled with Kevlar fibers (KFs), as well as that of non-nucleated PP/KF composites for comparison, was investigated using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The morphological observations revealed that the KF addition could induce thick α-transcrystalline layer around their surfaces in PP/KF composites, while no obvious transcrystalline layer could be detected in β-nucleated PP/KF composites. Detailed DSC investigations suggested that for the PP/KF composites, the dominant modification was α-form, and the crystallization process of matrix was promoted by KF addition, as illustrated by faster isothermal crystallization rate, shorter induction time, and higher crystallization temperature. However, for β-nucleated PP/KF composites, the main modification was β-form, and their crystallization characteristics were independent of KF addition, indicating that the α-nucleating effect of KFs was absent in this system. The DSC results were confirmed by further rheological and wide angle X-ray diffraction (WAXD) studies. The mechanism of the formation of transcrystalline layer was also discussed.     

Study on Inclusion Complex Formation of <Emphasis Type="Italic">m</Emphasis>-Aminobenzoic Acid with Native and Substituted <Emphasis Type="Italic">β</Emphasis>-Cyclodextrins

The complex formation of native and substituted β-cyclodextrins with m-aminobenzoic acid in water was characterized by calorimetry, ¹H NMR and UV spectroscopic studies. These studies showed that β-, hydroxypropyl-β- and methyl-β-cyclodextrins form 1:1 inclusion complexes with m-aminobenzoic acid. The thermodynamic properties of complex formation (K,Δ_c G ^o,Δ_c H ^o,Δ_c S ^o) were calculated. It was found that the processes of complexation are mainly favorable entropically. Introduction of hydroxypropyl- and methyl-substituents into the β-CD molecule results in negligible enhancement of stability of the complexes formed. The structure of these substituents has no influence on the stability constant values. The insertion of the carboxylic group of m-aminobenzoic acid into the cyclodextrin cavity was confirmed by ¹H NMR data.     

Thermodynamic study on inclusion complex formation of riboflavin with hydroxypropyl-β-cyclodextrin in water

The inclusion complex formation of riboflavin (RF) with hydroxypropyl-β-cyclodextrin (HP-β-CD) in water was investigated by ¹H NMR, UV-vis spectroscopy, and solubility methods. A 1:1 stoichiometry and thermodynamic parameters of complex formation (K, Δ_c G ⁰, Δ_c H ⁰, and Δ_c S ⁰) were determined. Complexation was characterized by negative enthalpy and entropy changes due to prevalence of van der Waals interactions and hydrogen bonding between polar groups of the solutes. A partial insertion of RF into macrocyclic cavity was revealed on the basis of ¹H NMR data and molecular mechanics calculation. Location of benzene ring of RF molecule inside the hydrophobic cavity of HP-β-CD results in an increase of aqueous solubility of the former.     

The influence of crystal structures of nucleating agents on the crystallization behaviors of isotactic polypropylene

The crystals of N, N′-dicyclohexyl-2,6-naphthalenedicarboxamide (DC26NDCA) and N,N′-dicyclohexyl-1,4-naphthalenedicarboxamide (DC14NDCA) were selected as nucleating agents to induce the crystallization of isotactic polypropylene (i-PP). The influence of the crystal structures of the nucleating agents on the crystallization behaviors and morphologies was studied by means of differential scanning calorimeter, wide-angle X-ray diffraction, polarized light microscopy, and atomic force microscopy (AFM). The results show that DC26NDCA is a selective β-nucleating agent for the i-PP crystallization, while DC14NDCA only has a very weak α-nucleating effect for the i-PP crystallization. The dynamic growth processes reveal that i-PP crystals grow with different crystallization behaviors in the presence of the nucleating agents. The i-PP lamellar structures on the crystal surfaces of the nucleating agents were observed by AFM in details, which suggested that the nucleating agents induced the epitaxial growth of the i-PP lamellae.     

PP/POE共混物的P-V-T属性及压力对结晶温度的影响

采用PVT膨胀仪研究了PP/POE共混物的P-V-T属性, 利用Tait方程预测其比容和热膨胀系数(α), 研究了压力对结晶温度(Tc)的影响. 结果表明, Tait状态方程可用来预测部分相容的、半结晶PP/POE共混物的PVT行为. PP结晶前后的比容变化比POE的大得多, 随着POE含量的增加, PP/POE共混物结晶前后比容的变化均逐渐减小. PP在熔融状态下的α比固体状态的大, 而POE正好相反. PP/POE共混物的α随温度和压力的变化与其组成密切相关. 随着压力的增高, PP, POE及其PP/POE共混物的结晶温度均呈线性增高的趋势.     

Experimental study of flow-induced crystallization in the blends of isotactic polypropylene and poly(ethylene-co-octene)

The crystallization behavior of the blends of isotactic polypropylene (iPP) and poly(ethylene-co-octene) (PEOc) under quiescent condition and shear flow were studied by differential scanning calorimetry (DSC) and rheology, respectively. The DSC curves of the iPP phase in the blends showed similar crystallization exothermic peaks to that of pure iPP itself, indicating that the addition of PEOc up to a percentage of 30 in weight almost had no influence on the crystallization behavior of iPP at quiescent condition. The rheological results of isothermal flow-induced crystallization (FIC) of iPP in the blends showed that the crystallization kinetics of iPP was enhanced with the increase of shear rate, similar to that of pure iPP, but the presence of PEOc enhanced the effect of shear on the crystallization kinetics of iPP significantly in the cases of shear rates larger than 0.2 s⁻¹, which was due to that PEOc played an important role to promote the nucleation of iPP. The rheological results also implied that the characteristic relaxation times of blends were longer than that of pure iPP during the FIC process, indicating a different relaxation mechanism which might be related to the occurrence of interface relaxation and chain relaxation of the PEOc phase in the blends.     

Quasielastic light scattering study of chemically crosslinked gelatin solutions and gels

Quasielastic light scattering measurements are reported for experiments performed on mixtures of gelatin and glutaraldehyde (GA) in the aqueous phase, where the gelatin concentration was fixed at 5 (w/v) and the GA concentration was varied from 1×10⁻⁵ to 1×10⁻³ (w/v). The dynamic structure factor, S(q,t), was deduced from the measured intensity autocorrelation function, g ₂(τ), with appropriate allowance for heterodyning detection in the gel phase. The S(q,t) data could be fitted to S(q,t)=Aexp(−D _f q ² t)+Bexp(−t/τ_c)^β, both in the sol (50 and 60 ^∘C) and gel states (25 and 40 ^∘C). The fast-mode diffusion coefficient, D _f showed almost negligible dependence on the concentration of the crosslinker GA; however, the resultant mesh size, ξ, of the crosslinked network exhibited strong temperature dependence, ξ∼(0.5−χ)^1/5exp(−A/RT) implying shrinkage of the network as the gel phase was approached. The slow-mode relaxation was characterized by the stretched exponential factor exp(−t/τ_c)^β. β was found to be independent of GA concentration but strongly dependent on the temperature as β=β₀+β₁ T+β₂ T ². The slow-mode relaxation time, τ_c, exhibited a maximum GA concentration dependence in the gel phase and at a given temperature we found τ_c(c)=τ₀+τ₁ c+τ₂ c ². Our results agree with the predictions of the Zimm model in the gel case but differ significantly for the sol state. Received: 25 May 1999 /Accepted in revised form: 27 July 1999     

Determination of the equilibrium melting point of the β-form of polypropylene

The melting behavior of the -form of isotactic polypropylene (-iPP) was investigated as a function of crystallization time and temperature. Calcium suberate, a selective -nucleating agent was used to produce samples that consist entirely of -form i-PP. The experimental melting points were recorded at different crystallization times and were extrapolated to the start of the crystallization process in order to eliminate the effect of lamellar thickening. Using the non-linear Hoffman—Weeks approach to correlate these extrapolated experimental melting temperatures with the corresponding crystallization temperatures, an equilibrium melting point of 209°C was obtained for -iPP. The equilibrium melting point estimated through the non-linear Hoffman—Weeks analysis is about 30°C higher than that (T _m ⁰=177°C) obtained on the basis of the linear extrapolation. These results are consistent with earlier claims that a linear extrapolation of T _m–T _c data leads to an underestimation of the equilibrium melting point. The results obtained for -iPP exemplify the importance of accounting for both the isothermal lamellar thickening effects and the non-linearity in the T _m–T _c correlation, when the determination of an equilibrium melting point is carried out using a procedure based on the predictions of the Lauritzen—Hoffman secondary nucleation theory.This revised version was published online in November 2005 with corrections to the Cover Date.     

Quiesent Crystallization Kinetics of Nucleated Metallocene and ZN Isotactic Polypropylenes

Crystallization kinetics and thermodynamic properties of nucleated isotactic polypropylene (PP) are analyzed using Hoffman—Lauritzen crystallization theory to determine the mechanistic effects of the nucleators. Calorimetric data provides quantitative comparisons between nucleating efficiences of the (Millad) and (NJSTAR) nucleator in Metallocene (M) and Ziegler—Natta (ZN) PP. The two types of PP without nucleators showed similar crystallization behavior though the T°_m for ZN-iPP was about 10°C higher than M-iPP. Both nucleators show significant improvement in crystallization rate in both types of PP. In addition, Millad outperforms NJSTAR. The magnitude of the kinetic response is,however, different and both the nucleators appear to function better in ZN than in Metallocene PP. nucleated PP shows predominantly the form. The amount of the form is thermal history dependent and changes with supercooling (T=T°_m–T_c). Similar equilibrium melting temperature (T°_m) in the nucleated and control PPs indicates the lack of any thermodynamic effect of the nucleator. All nucleated PPs show a much lower secondary nucleation rate constant, K_g.This revised version was published online in November 2005 with corrections to the Cover Date.