Effect of β-nucleation on crystallization of photodegraded polypropylene

The work deals with crystallization of photodegraded polypropylene containing various amounts of β-nucleating agent based on N,N′-dicyclohexylnaphthalene-2,6-dicarboxamide. Compression-moulded samples were irradiated by UV-light, melted and subsequently non-isothermally crystallized. The results showed that the crystallization temperature decreased with increasing irradiation time. The irradiation caused the splitting of crystallization exotherms into two peaks indicating two crystallization mechanisms. The presence of β-nucleating agent in the material suppressed the peak splitting; the higher was the amount of nucleating agent in the sample, the later was the splitting observed.     

Synergistic nucleation effect of calcium sulfate whisker and β-nucleating agent dicyclohexyl-terephthalamide in isotactic polypropylene

Journal of Thermal Analysis and Calorimetry - The crystallization and melting behaviors and mechanical properties of isotactic polypropylene (iPP) containing a certain amount of stearic...     

The β-nucleation of polypropylene random copolymer filled by nano-CaCO3 supported β-nucleating agent

In this article, ??-nucleation of nano-CaCO₃ (CC) supported ??-nucleating agent (Sup-??-NA) for random polypropylene copolymer (PPC) crystallization was studied by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction. The results showed that Sup-??-NA not only increased the peak temperature of the crystallization of PPC but also induced PPC to form almost pure ??-modification. It indicated that Sup-??-NA possessed effective ??-nucleation. The content of Sup-??-NA had little influence on the crystallization behavior and melting characteristics together with the ??-modification content of PPC, but those were affected by the mass ratio of CC/??-NA (calcium pimelate) in the Sup-??-NA. The final temperature of the melt between 300 and 180?°C did not affect the ??-nucleation of Sup-??-NA, although the ??-nucleation of Sup-??-NA would be decreased with the final temperature of the melt lower than 170?°C. In addition, DSC multiple heating and cooling scanning had little influence on the thermal stability of ??-nucleation of Sup-??-NA.     

A novel polypropylene composite filled by kaolin particles with β-nucleation

Kaolin-filled polypropylene (PP) composites generally form α-crystal due to the effect of kaolin with α-nucleation. The transition from α- to β-nucleation of kaolin has been investigated, and a novel kaolin with β-nucleation (β-kaolin) and kaolin-filled PP composites with high β-crystal content were prepared first. The DSC and WAXD results indicated that the β-kaolin exhibits stronger β-nucleating ability than CaPA as β-nucleating agent for PP crystallization. It is found that the β-crystal content has been influenced little by filler contents in β-kaolin-filled PP composites. Mechanical properties and spherulitic morphology of filled PP composites was characterized. The synergistic effect of filler and β-crystal significantly improved impact strength of kaolin-filled PP composites.

     

Synergistic toughening effect of β-nucleating agent and long chain branching on polypropylene random copolymer

β-nucleated long chain branched (LCB) polypropylene random copolymers (PPRs) were prepared via reactive extrusion by introducing β nucleating agent (NA), dicumyl peroxide (DCP) and various contents of 1, 6-Hexanediol diacrylate (HDDA) into PPR. Results of Fourier infrared spectroscopy (FTIR) and the rheological properties demonstrate the existence of LCB polypropylene. Mechanical properties including impact strength, tensile strength and elongation at break were studied. The crystal structure, morphology and crystallization behavior were investigated via wide-angle X-ray diffraction (WAXD), polarized light microscopy (PLM) and differential scanning calorimetry (DSC). Non-isothermal crystallization kinetics using the Jeziorny method was also studied. The results show an increased LCB degree with increasing HDDA amount. For the sample with a moderate LCB level, synergistic toughening effect of NA and LCB is achieved without deterioration of yield strength or elongation at break, partially because of its higher β-phase content and much smaller spherulite size. It exhibits the minimum values of T_c and Z_c1, and the maximum values of t_1/2 and n₁ in the primary stage of crystallization, regardless of the cooling rate, indicating a slower crystallization rate and more complicated nucleation and crystal growth model.     

Investigations in annealing effects on structure and properties of β-isotactic polypropylene with X-ray synchrotron experiments

The influence of annealing on the microstructure and mechanical properties of β-form isotactic polypropylene (iPP) was investigated via in situ synchrotron small-angle X-ray scattering (SAXS), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). Transition of β-iPP to α-iPP was investigated via recrystallization at high annealing temperatures (T _a?>?120 °C). And crystallinity, crystal sizes, and long period of ordered structure increased with increasing annealing temperature. Abrupt changes were found in both mechanical properties and structural features at the same T _a range (～120 °C). The in situ synchrotron SAXS and WAXD shows that the destruction of b phase at yielding and after yielding should account for the ductility of β-iPP. The thermodynamics and kinetics of annealing were investigated with DSC and X-ray synchrotron experiments. A characteristic annealing time was investigated, which measures the rate of phase evolution in annealing of β-iPP. Eventually, a hypothesized model can be used to describe the property/structure relations during this process.     

Alginate–chitosan micro- and nanoparticles for transmucosal delivery of proteins

The properties of protein-containing micro- and nanoparticles that were produced from alginate and chitosan using the methods of layer-by-layer polyelectrolyte adsorption and ionotropic gelation have been compared. The encapsulation efficiency of proteins (aprotinin, interferon, and human insulin), the size and ζ-potential of the particles, the mucin binding, and the protein release under physiological conditions have been studied. The prospects for the possible mucosal application of the particles are discussed.     

Effect of supercritical carbon dioxide treatment on structure and mechanical properties of β-nucleated polypropylene processed at different temperatures

Polypropylene (PP) was compounded with β-nucleating agent and injection-molded at 180 °C or 220 °C. The samples were subsequently treated by supercritical carbon dioxide (scCO₂) at different temperatures. Results show that processing temperature and scCO₂ treatment could strongly influence the tensile and impact properties of β-nucleated PP. In particular, the sample processed at 220 °C and treated at 120 °C exhibit much enhanced impact strength (4.8 times that of its untreated counterpart). FTIR, WAXD, SEM and DMA were performed to explore the effects of processing temperature and scCO₂ treatment on structure of the samples. Deformation-induced plastic flow and micro-voids were also evaluated to construct structure-property relations. It was found that the influence of processing temperature on mechanical properties is mainly associated with the β-form content and β-crystalline morphology, while the structural changes in the crystalline lamellar scale may be responsible for the toughening effect of scCO₂ treatment.     

The synergistic effects of β-nucleating agent and ethylene–octene copolymer on toughening isotactic polypropylene

The mechanical properties of isotactic polypropylene (iPP) and ethylene–octene copolymer (POE) blends with or without β-nucleating agent (β-NA) were systematically studied. Results demonstrated that, after β-NA and POE were separately added, the impact strength of injection molded iPP samples increased. β-NA and POE were also found to have a synergistic toughening effect on iPP matrix, and the effect was significant. When the contents were 0.05 wt% β-NA and 10 wt% POE, the impact strength reached the maximum, i.e., almost 15 times that of neat iPP. SEM further revealed that POE in skin and core layers existed as long and narrow strips along the flow direction and throughout crystals. The tensile strength did not deteriorate because of the special phase morphology and tight interfacial interaction between POE phase and matrix. WAXD and DSC revealed that POE addition had negligible influence on crystal form, and a considerable number of β crystals was generated by adding β-NA. SEM results also confirmed a critical β-NA content. When β-NA content was lower than the critical value, perfect β sphaerocrystals were generated. When β-NA was higher, “bundle-like” crystal structures formed. Perfect β sphaerocrystals were more efficient for dissipating energy because of the looser stacking pattern, thus showing better toughness.     

Crystallization of post-consumer polypropylene in the presence of β-nucleating agent

Journal of Thermal Analysis and Calorimetry - In this paper, the heat transfer characteristics of the nanofluid through a parallel plate soft nanochannel are investigated under the fully developed...     

Synergistic effects of sour taste and low temperature in suppressing the bitterness of Aminoleban® EN

Aminoleban? EN, a nutritional product for patients with liver failure, contains three branched-chain amino acids (BCAAs): L-leucine, L-isoleucine, and L-valine. As BCAAs are extremely bitter, Aminoleban? EN has a low palatability, which is a major cause of patient noncompliance. Nutrients for liver failure often need to be taken for long periods, and poor medication compliance can cause serious problems, such as encephalopathy. Therefore it is important to suppress the bitter taste of Aminoleban? EN and thereby improve patient compliance. There are already six different flavoured powders (coffee, green-tea, apple, fruit, plum and pineapple) which can be added to Aminoleban? EN to reduce its unpleasant taste and smell, but it is possible that other factors, such as temperature, may also improve the palatability of Aminoleban? EN. In this study, flavours alone significantly decreased the bitterness intensity of Aminoleban? EN. It was thought that the sweetness and sourness of the flavoured powder would be the main factors involved in decreasing the bitterness. However, low temperature (0-5 °C) decreased the bitterness intensity of Aminoleban? EN, with or without the flavoured powders, compared with normal room temperature (25-30 °C). The sourness intensity of flavoured powders was not decreased at low temperatures, but the sweetness intensity of some flavoured powders did decrease. These results suggest that sourness can be tasted even at low temperatures. As not only the addition of flavoured powders but also low temperatures can reduce the bitterness of Aminioleban? EN, the combination of a sour-flavoured powder and a low temperature will improve the palatability of Aminoleban? EN the most.     

Thermal behavior of isotactic polypropylene in different content of β-nucleating agent

The effects of non-isothermal and isothermal crystallization on the formation of α- and β-phase in isotactic polypropylene (iPP) with different content of β-nucleating agent are investigated by differential scanning calorimetry (DSC). On non-isothermal crystallization, the content of β-phase and regularity of its crystals are depended on both cooling rate and the content of β-nucleating agent. The faster cooling rate is, the lower of melting peak temperature (T_mp) and crystallization peak temperature (T_cp) of α- and β-phase are. The enthalpy of fusion (∆H) of β-phase increases with cooling rate in a certain range for the sample with 0.1 wt% β-nucleating agent (G₁) and decreases for that with 0.3 wt% β-nucleating agent (G₃). On isothermal crystallization, the enthalpy of fusion of β-phase in G₁ is higher than in G₃ which is related to the efficiency of nucleation in different concentration of nucleating center in two samples.     

Nucleation of the β-modification of isotactic polypropylene

The effects of the organic pigments C.I.P. RED 177 and C.I.P. Yellow 83 as nucleating agents on the crystallization of polypropylene were studied by DSC. The anthraquinone pigment exerted a significant effect, resulting in structural modifications with lower melting point, and particularly the -modification. The DSC curves exhibit four transition regions, with the following temperature intervals: I. 415–417 K, II. 423–425 K, III. 430–432 K and IV. 438–439 K. For evaluation of the -nucleation effect of pigments, the ratio (H ₁+H ₂)/(H ₃+H ₄) was suggested.     

Effects of stereo-defect distribution and molecular mass in the non-isothermal crystallization behavior of β-nucleated isotactic polypropylene

In this study, based on the synthesis of two Ziegler–Natta iPP with nearly same average isotacticity but different uniformities of stereo-defect distribution, we further prepared two series of β-iPP with different molecular masses by addition of different concentration of peroxide. We investigated the combination effects of stereo-defect distribution and molecular mass on the non-isothermal crystallization behavior and polymorphic composition behavior of β-iPP by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and scanning electron microscope (SEM). The results of non-isothermal crystallization kinetics revealed that the iPP molecular mass has only slight influence on the crystallization temperature of β-iPP, while the uniformity of stereo-defect distribution not only evidently influences the crystallization temperature, but also affects the dependency of crystallization temperature on cooling rate. β-iPP with less uniformity of stereo-defect distribution leads to higher dependency of crystallization temperature on the cooling rate. The calculation of crystallization activation energy ΔE showed that the lower the molecular mass, the lower the ΔE, indicating that it is easier for the occurrence of crystallization. Meanwhile, iPP with more uniform stereo-defect distribution has lower ΔE. Moreover, both stereo-defect distribution and molecular mass are important factors in determining the polymorphic composition. A more uniform stereo-defect distribution is more favorable for the β-phase crystallization; the lower the molecular mass, the harder for β-phase crystallization to take place. However, compared with iPP molecular mass, the uniformity of stereo-defect distribution is the first-order factor in determining the β-phase crystallization of iPP. Moreover, the thermal stability and the dependency of β-phase proportion on the cooling rate are also found to be highly dependent on the iPP molecular mass.     

Non-isothermal crystallization kinetics and morphology of wollastonite-filled β-isotactic polypropylene composites

To obtain wollastonite-filled β-iPP composites, the wollastonite with β-nucleating surface (β-wollastonite) was prepared through chemical reaction between wollastonite with α-nucleating surface (α-wollastonite) and pimelic acid. The formation of calcium pimelate on the surface of wollastonite was proved using Fourier transform infrared spectrometry and scanning electron microscopy. The crystallization behavior, melting characteristics, non-isothermal crystallization kinetics, and crystalline morphologies of α- and β-wollastonite-filled iPP composites were studied by differential scanning calorimetry and polarizing optical microscopy. It is found that the crystallization peak temperatures of β-wollastonite-filled iPP composites were higher than that of α-wollastonite-filled iPP composites, which indicated that wollastonite with β-nucleating surface has stronger heterogeneous nucleation than that of wollastonite with α-nucleating surface. Although the crystallization temperatures of iPP and iPP composites decreased with increasing cooling rates, α-wollastonite-filled iPP composites mainly crystallized in α-spherulite and β-wollastonite-filled iPP composites formed β-spherulite. In addition, the spherulite size of β-wollastonite-filled iPP composites was smaller than that of α-wollastonite-filled iPP composites. Jeziorny and Mo methods were applicable to study the non-isothermal crystallization kinetics of wollastonite-filled iPP composites. The activation energy (?E) and the nucleation efficiency (EN) of non-isothermal crystallization were calculated by Kissinger method and the equation proposed by Fillon, respectively. The β-wollastonite-filled iPP composites exhibited higher crystallization rate, activation energy, and EN than that of α-wollastonite-filled iPP composites.     

Preparation and sorption studies of polyester microsphere copolymers containing β-Cyclodextrin

Polyester copolymer sorbent materials that incorporate β-Cyclodextrin (β-CD) were prepared using water-in-oil (w/o) micro-emulsion conditions at variable β-CD: cross linker mole ratios; where the cross linker units were sebacoyl chloride (SCl) and terephthaloyl chloride (TCl). The copolymers were characterized using TGA, nitrogen adsorption, and NMR/IR spectroscopy. The dye-based sorption properties of the copolymers with p-nitrophenol (PNP) in aqueous solution were evaluated at pH 4.6 and 295 K using UV-Vis spectrophotometry. The uptake of PNP varied from 0.221 to 0.352 mmol/g, according to the nature of the cross linker and the copolymer mole ratio. The sorption capacity of SCl-based copolymers exceed that for TCl-based copolymers, and correlate with the relative swelling properties and hydrated surface areas of the sorbent frameworks. ¹H NMR spectroscopy of copolymers with low levels of linker content (i.e. SCl or TCl) indicate dual sorption sites for PNP (i.e. β-CD inclusion sites and non-inclusion (interstitial) linker domains). The existence of dual sorption sites is similarly concluded for copolymers containing higher levels of cross linker. Inclusion complexes are firstly formed between PNP and the β-CD inclusion sites of the copolymer; thereafter, PNP is adsorbed onto the linker domains of the copolymer sorbent framework.     

Non-isothermal crystallization, melting behavior and polymorphism of polypropylene in β-nucleated polypropylene/recycled poly(ethylene terephthalate) blends

β-Nucleated polypropylene (PP), non-compatibilized and compatibilized β-nucleated PP/recycled poly(ethylene terephthalate) (r-PET) blends were prepared on a twin-screw extruder. The compatibilizers were maleic anhydride grafted PP (PP-g-MA), glycidyl methacrylate grafted PP (PP-g-GMA), maleic anhydride grafted polyethylene-octene (POE-g-MA) and polyethylene-vinyl acetate (EVA-g-MA) elastomers. Effects of r-PET content, compatibilizer type and content, pre-melting temperature and time on the non-isothermal crystallization and melting behavior, and polymorphism of PP in the blends were investigated by differential scanning calorimeter (DSC). DSC results show that the crystallization temperature of PP crystallized predominantly in β-modification was higher than that of neat PP. In the non-compatibilized blend, PP matrix crystallized mainly in α-modification even if r-PET content was only 10 wt%. However, PP-g-MA compatibilization made PP matrix crystallize mainly in β-modification, but PP-g-GMA, POE-g-MA and EVA-g-MA did not improve the β-modification content distinctly. The α-crystal melting peak temperature of PP decreased with increasing pre-melting temperature, but r-PET content, compatibilizer type and content as well as pre-melting time had no obvious effect on the melting temperature of PP. The increase in PP-g-MA content, pre-melting temperature and time was benefit for the formation of β-modification. It is suggested that the β-nucleating agent is encapsulated or dissolved in polar r-PET in β-nucleated PP/r-PET blend, addition of PP-g-MA to the non-compatibilized blend resulted in transferring β-nucleating agent from r-PET phase into PP phase, the increase in PP-g-MA content, melting temperature and time was benefit for transferring β-nucleating agent from r-PET phase into PP phase. The non-isothermal crystallization kinetics of PP in the blends were evaluated by Mo’s method.     

Synergistic enhancement of the fluorescence intensity of 4,5-benzopiaselenol by surfactants and β-cyclodextrin in aqueous solution

The synergistic enhancement of the fluorescence intensity of 4,5-benzopiaselenol (I _F ^Se-DAN ) by surfactants (Sf) and -cyclodextrin (-CD) has been studied. The (I _F ^Se-DAN ) in sodium dodecyl sulfate (SDS)//gb-CD was approximately 30 times greater than that in water, and 5–6 times greater than that in either SDS or -CD solutions alone, and a blue-shift of the emission wavelength was observed.¹H-NMR experiments and determination of CMC values of Se-DAN/-CD, Se-DAN/SDS, and Se-DAN/SDS/-CD systems reveal that the synergistic fluorescence enhancement was produced by the SDS monomer/-CD inclusion complex. In essence, the synergistic enhancement is due to the altered microenvironment experienced by Se-DAN upon its transfer from water to the hydrophobic cavity upon complexation.     

Thermal stability of nucleation effect of different β-nucleating agents in isotactic polypropylene

Journal of Thermal Analysis and Calorimetry - The thermal stability of nucleation effect of three highly effective β-nucleating agents, namely an aryl diamide-based nucleating agent (TMB-5), a...     

Synergistic Extraction of Thorium by β-Hydroxy Naphthaldoxime in Presence of Neutral Donors

The effects of neutral organophosphorous compounds on the extraction of thorium by -hydroxy naphthaldoxime in xylene are reported. Enhancement of the extraction is explained by a complex adduct formation in the organic phase. Synergistic coefficients and apparent formation constant of complex adducts are calculated.