Step-scan DSC研究PET/纳米CaCO3复合材料的结晶和熔融行为

采用纳米碳酸钙(CaCO3)浆料直接分散于聚对苯二甲酸乙二醇酯(PET)的单体乙二醇中,原位聚合制备出分散均匀的聚对苯二甲酸乙二醇酯(PET)/CaCO3纳米复合材料。分别利用传统的差示扫描量热仪(DSC)和步进扫描DSC(Step-scan DSC)技术研究了CaCO3含量变化对PET结晶和熔融行为的影响及非等温结晶动力学过程。结果表明,纳米粒子与PET的相互作用较弱,对PET结晶主要起促进作用,使结晶更加完善,碳酸钙的含量达到3%时,相对结晶速率达到最大。结晶初期,纳米粒子异相成核作用占优势,这种优势随着纳米粒子含量的增加而有所减弱;结晶后期,纳米粒子对高分子运动的牵制作用比较明显。     

镧化物改性超细碳酸钙对PET非等温结晶行为的影响

用DSC研究了镧化物改性超细碳酸钙与成核剂NA对PET非等温结晶行为的影响,并对其结晶成核能力进行了分析。结果表明,各成核剂均使PET的结晶温度和结晶度提高,结晶峰半峰宽变窄。非等温结晶动力学分析表明各样品的Avrami指数介于3～5,成核剂的加入使PET的结晶动力学常数增加而半结晶时间缩短。根据过冷温度和过热温度,成核剂的结晶成核能力大小顺序为UCaCO3-5La3+>NA>UCaCO3-10La3+>UCaCO3-1La3+。     

In-vitro study on calcium carbonate crystal growth mediated by organic matrix extracted from fresh water pearls

For the purpose of studying the mediation of organic matrix on the crystallization of calcium carbonate, water soluble matrix (WSM), acid soluble matrix (ASM) and acid insoluble matrix (AIM) were extracted from aragonite pearls and vaterite pearls respectively. Then, in-vitro calcium carbonate crystallization experiments under the control of these six organic matrices were carried out in the present study. Scanning electron microscopy (SEM) was utilized to observe the morphology of CaCO₃ and Raman spectroscopy as a powerful technique was used to distinguish the crystal polymorph. Influences of the six kinds of organic matrices on the calcium carbonate crystal growth are proposed. ASM of vaterite pearls can induce vaterite to crystallize and WSM of aragonite pearls mediates to produce aragonite crystals. The single AIM membranes of the two pearls have no pronounced effect on the CaCO₃ crystallization. Additionally, the crystal size obtained with the additive of WSM of the two kinds of pearls is smaller than that with the additive of ASM. Moreover, self-assembly phenomenon in the biomineralization process and the distorted morphology calcite are observed. Current results demonstrate important aspects of matrix protein-controlled crystallization, which is beneficial to the understanding of nacre biomineralization mechanism. Further study of the precise control of these matrix proteins on CaCO₃ crystal growth is being processed.     

Ternary nano-CaCO3/poly(ethylene terephthalate) fiber/polypropylene composites: Increased impact strength and reinforcing mechanism

The binary nano-CaCO₃/polypropylene (PP), poly(ethylene terephthalate) (PET) fibers/PP and ternary nano-CaCO₃/PET fibers/polypropylene composites were prepared by melt blending method, and their structure and mechanical properties were investigated. The results show that the ternary nano-CaCO₃/PET fibers/PP composite displays significantly enhanced mechanical properties compared with the binary PET fibers/PP and nano-CaCO₃/PP composites, and neat PP. The X-ray diffraction, dynamic mechanical analysis, scanning electron microscopy and analysis of the non-isothermal crystallization kinetics were used to investigate the reinforcement mechanism of composites. The results indicate that the interfacial action and compatibility between PET fiber and PP are obviously enhanced by the addition of modified nano-CaCO₃ particles in the ternary composites and the mechanical property enhancement in the ternary system may be mainly originated from the formation of β-form crystallites of PP induced by the synergistic effect between PET fibers and nano-CaCO_3.     

Nonisothermal crystallization kinetics of poly(ethylene terephthalate) nanocomposites

This article reports the nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) nanocomposites. The non-isothermal crystallization behaviors of PET and the nanocomposite samples are studied by differential scanning calorimetry (DSC). Various models, namely the Avrami method, the Ozawa method, and the combined Avrami-Ozawa method, are applied to describe the kinetics of the non-isothermal crystallization. The combined Avrami and Ozawa models proposed by Liu and Mo also fit with the experimental data. Different kinetic parameters determined from these models prove that in nanocomposite samples intercalated silicate particles are efficient to start crystallization earlier by nucleation, however, the crystal growth decrease in nanocomposites due to the intercalation of polymer chains in the silicate galleries. Polarized optical microscopy (POM) observations also support the DSC results. The activation energies for crystallization has been estimated on the basis of three models such as Augis-Bennett, Kissinger and Takhor methods follow the trend PET/2C20A < PET/1.3C20A < PET, indicating incorporation of organoclay enhance the crystallization by offering large surface area.     

Morphology of calcium carbonate coating on amorphous silicate powder

The amorphous silicate powders containing sodium, calcium,barium and magnesium were prepared by sol-gel and ion-exchangemethod, and calcium carbonate was coated on the powders for thepurpose of industrial re-circulation of calcium carbonate. Thecalcium carbonate powder with micro pores was obtained bycoating on amorphous CaO-SiO₂ powder, and the pore sizedistribution would be influenced by calcium on the surface ofthe powder. The coating on amorphous MgO-SiO₂ powderresulted in a hedgehog-like powder, which allowed needle-likecrystal extended radially, and the coated powder was the mixedphase of aragonite and calcite. The use of amorphousBaO-SiO₂ and Na₂O-SiO₂ powders also led to the coatingpowder with the single phase of calcite. The morphology ofcalcium carbonate coating would be ascribed to cations on thesurface of the amorphous silicate powders, because the amount ofcations that would be dissolved in soaking solution was smalland insufficient to affect the morphology.     

Synthesis, non-isothermal crystallization and magnetic properties of Co0·75Zn0·25Fe2O4/poly(ethylene-co-vinyl alcohol) nanocomposite

The synthesis of Co_0·75Zn_0·25Fe₂O₄/poly(vinyl alcohol-co-ethylene) (ferrite/PEVA) nanocomposite was carried out through two steps: impregnation of the ferrite particules by PEVA and then mixing the ferrite/PEVA impregnated with PEVA solution. A non-isothermal study of the crystallization kinetic of ferrite/PEVA nanocomposite was carried out by differential scanning calorimetry (DSC), scanning electron microscope (SEM) and X-ray diffraction (XRD) techniques. It was observed that the Ozawa equation describes perfectly the primary process of non-isothermal crystallization of ferrite/PEVA system. There is a strong dependence of the ferrite/PEVA composition on the crystallization parameters. The crystallization activation energy (E _a ) calculated from the Xu and Uhlmann model increased by increasing the ferrite content in ferrite/PEVA nanocomposites between 3 and 7 wt% and decreased dramatically beyond these values. The results revealed that the ferrite nanoparticles were uniformly distributed throughout the PEVA matrix. The percentage of magnetization of the composite decreases as the concentration of the ferrite increases.     

The co-effect of organic matrix from carp otolith and microenvironment on calcium carbonate mineralization

In vitro mineralization experiment is an effective way to study the effect of organic matrix on calcium carbonate crystallization, and to reveal the relationship between organic matrix and inorganic crystal in natural biominerals. In natural biominerals, organic matrix plays an important role in crystal formation and stability, together with microenvironment changes, they can affect crystal polymorph, morphology, density, size, orientation etc.In this work, we systematically studied the effects of different organic matrices in fish otoliths, the organic matrix concentration changes, as well as the co-effect of organic matrices with temperature, pH value and Mg ion changes in the in vitro CaCO₃ mineralization experiments.The organic matrix and concentration change experiments prove that water soluble matrix (WSM) plays an important role in crystal form transition. It can induce CaCO₃ crystals with same crystal polymorph as the otolith from which organic matrix was extracted. The temperature change experiment proves that CaCO₃ has a tendency to form calcite, vaterite, and then aragonite in priority as temperature goes up. Under different temperature, WSM from lapillus/asteriscus still has the effect to mediate different CaCO₃ crystals. The pH change experiment shows that, near the neutral environment, as pH value goes up, calcites have a tendency to form crystal aggregates with more faces exposed, the organic matrix still keeps crystal mediation effect. The Mg^2 + experiment shows that, Mg ion can promote aragonite formation, together with lapillus organic matrix, aragonites with different shapes are formed.     

Polymer/Calcium Carbonate Layered Thin‐Film Composites

Formation of the nacre of a shell is mimicked here to synthesize layered polymer/calcium carbonate composites such as that shown in the Figure. The combination of insoluble chitin or chitosan solid matrices with soluble acidic macromolecules such as poly(acrylic acid) is used to induce thin‐film crystallization of CaCO₃ on the solid matrices. The polymorph formed can also be controlled employing this method.     

Further studies of calcium phosphate growth on phosphorylated cotton fibres

Further studies using scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDX), micro-Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and solid state magic angle spinning nuclear magnetic resonance (MAS NMR) techniques of calcium phosphate growth on Ca(OH)₂-treated urea/H₃PO₃- and urea/H₃PO₄-modified cotton fibres are reported. In the case of the Ca(OH)₂-treated urea/H₃PO₃-modified fibres which have been reported in an earlier paper, further experiments subjecting the urea/H₃PO₃-modified cotton to alternative soaking treatment procedures to Ca(OH)₂ as well as different calcium phosphate growth media such as the alkaline phosphatase-catalysed hydrolysis of disodium p-nitrophenylphosphate to free phosphate have reaffirmed the importance of the Ca(OH)₂ treatment step for the stimulus and growth of calcium phosphate growth on the fibres. Studies on cotton phosphorylated by a slightly different method using urea/H₃PO₄ instead of urea/H₃PO₃ show that a phosphorylated cotton with similar properties to the urea/H₃PO₃-modified fibres can be produced. Soaking of these fibres in saturated Ca(OH)₂ solution leads to cotton coated with thin layers of calcium phosphate formed by partial hydrolysis of the PO₄ functionalities in the phosphorylated cotton which are believed to act as nucleation layers for further calcium phosphate deposition when the fibres are subsequently soaked in 1.5×SBF solution. SEM/EDX studies of the calcium phosphate coatings formed on the Ca(OH)₂-treated urea-H₃PO₄ fibres as a function of soaking time in 1.5 × SBF show that coatings deposit and become noticeably thick after approximately 9 days. XPS studies indicated the presence of carbonate species in the calcium phosphate coating deposited. In common with the calcium phosphate coated Ca(OH)₂-treated urea/H₃PO₃-modified fibres studied earlier, the average EDX-measured Ca: P ratios of the coatings formed on the Ca(OH)₂-treated urea/H₃PO₄ fibres are 1.60 and give very similar micro-FTIR spectra with evidence of carbonate which suggests that amorphous calcium deficient apatite has deposited.     

Calorimetric studies of non-isothermal crystallization in amorphous Cu x Ti100−x alloys

The present paper reports the composition dependence of pre-exponential factor and activation energy of non-isothermal crystallization in amorphous alloys of Cu _x Ti_100?x system using differential scanning calorimeter (DSC) technique. The applicability of Meyer-Neldel relation between the pre-exponential factor and activation energy of non-isothermal crystallization for amorphous alloys of Cu-Ti system was verified.     

Crystallization kinetics of magnetron-sputtered amorphous CoNbZr thin films

For non-isothermal and isothermal annealing, the crystallization kinetics of magnetron sputtered Co_85.5Nb_8.9Zr_5.6 amorphous alloy thin films have been investigated by differential scanning calorimetry measurements. As a result, in the case of non-isothermal crystallization, one distinct exothermic peak is observed at 470 °C, which is due to the crystallization of hcp α-Co. With the Kissinger method, the apparent activation energy was obtained to be 99.82 kJ/mol. By using the Deloy-Ozawa method, the local activation energy of non-isothermal crystallization was calculated. For isothermal crystallization, the Avrami exponents were determined by means of the Johson-Mehl-Avrami equation, which is in the range of 1.19-1.37. Based on an Arrhenius relationship, the local activation energy was analyzed, which yields an average value E_c=88.51 kJ/mol. Finally, the local Avrami exponent was used for discussing the details of the nucleation and growth behaviour during the isothermal crystallization.     

Microstructure characteristics for anorthite composite glass with nucleating agents of TiO2 under non-isothermal crystallization

The anorthite-based composite glass doped with TiO₂ and B₂O₃ was prepared by quenching of molten droplets. Phase development and crystals microstructure of glass were investigated under non-isothermal conditions. A glass transition temperature of 770°C and an exothermal peak around 870°C in the DTA trace was associated with anorthite crystallization (CaAl₂Si₂O₈). For glass specimens under nucleation and crystallization heat-treatment, the final predominant phase was identified as anorthite. Anorthite crystals show preferential nucleation at specific sites with rutile TiO₂ crystals precipitated from the glassy matrix and anorthite crystallization is governed by heterogeneous volume nucleation. The introduced TiO₂ plays the role of nucleating agents to reduce the crystallization temperature lower than 900°C for anorthite-based glass-ceramics. Chemical compositions could be related to the crystal microstructures on different characteristic regions. It was observed that the sintering aid of B₂O₃ neither reacted with nor dissolved in the anorthite or rutile TiO₂ crystals, and remained a glassy phase in the matrix. Occurrence of acicular precipitations was attributed to the orientation growth of TiO₂ crystals. Anorthite crystals were observed to grow with the forms of feathery-spherical particles, having a tendency to coalescence into a huge domain.     

Kinetics of Crystallization of High-T c Superconductor/Thermoplastic Polymer Composite

Composite of YBa₂Cu₃O_7−x and high-density polyethylene (HDPE) prepared by mixing both materials display improving flexibility and crystallinity with increasing polymer content. Differential scanning calorimetry (DSC) data at different heating rates on the composite is reported and discussed. The crystallization data are interpreted in terms of analyses developed for non-isothermal crystallization. The activation energy of crystallization and dimensionality of growth, which are important parameters for controlling crystallization, are evaluated. The results confirm that the crystallization mechanism of YBCO/HDPE composite is based on three-dimensional growth.     

Compositional effect on the crystallization of the cordierite-type glasses

The determination of apparent activation energies for the crystallization of P₂O₅/B₂O₃-containing cordierite-type glasses was conducted by non-isothermal differential thermal analysis (DTA). Glass with excesses both of SiO₂ and Al₂O₃ has a higher activation energy for crystallization. In addition to the main phase of -cordierite, several other phases (farringtonite, clinoenstatite, and forsterite) were detected in the fully crystallized samples by the X-ray powder diffraction technique. The crystallization behavior for the powdered glass was governed by the surface crystallization mechanism, which would not change with composition.     

Structure and properties of hybrid PLA nanocomposites with inorganic nanofillers and cellulose fibers

Polylactide reinforced with 3 wt% of organo-modified montmorillonite, 5 wt% of stearic acid-modified calcium carbonate nanoparticles, 15 wt% of cellulose fibers (PLA/MMT, PLA/NCC, PLA/CF) and hybrid composites containing 15 wt% of fibers in addition to montmorillonite (PLA/MMT/CF) or calcium carbonate (PLA/NCC/CF) were prepared and examined. The nanoparticles were dispersed in polylactide almost homogeneously; montmorillonite was exfoliated during processing. T_g of polylactide remained unaffected but its cold crystallization was enhanced; the cold-crystallization behavior of the hybrid composites was dominated by nanofillers nucleating ability. The fibers and calcium carbonate decreased whereas exfoliated montmorillonite improved the thermal stability of the materials. Polylactide, PLA/NCC and PLA/MMT exhibited ability to plastic deformation, although the latter the weakest. Tensile behavior of the hybrid composites was strongly influenced by the fibers and similar to that of PLA/CF. All the fillers increased the storage modulus below T_g; that of PLA/MMT/CF and PLA/NCC/CF was improved with respect to polylactide by 50% and 45%, respectively.     

Synthesis of ultra-small hollow silica nanoparticles using the prepared amorphous calcium carbonate in one-pot process

The ultra-small hollow silica nanoparticles were synthesized using the prepared amorphous calcium carbonate (ACC) particles as a template. The ACC particles were firstly prepared by carbonation method, which procedure was conducted in the methanol solvent to form the Ca(OCH₃)₂ layers on the ACC particles. An effect of methanol concentration on the morphology of ACC particles was also investigated. The prepared ACC particles were directly coated by silica through adding tetraethoxysilane (TEOS) into the methanol solvent. Hence, the ACC-silica core-shell particles were obtained since the ACC particles have a positive charge and interact with hydrolyzed TEOS. The ACC particles could be stabilized through the reaction between methanol and calcium ions when the methanol concentration was increased over than 40?vol%.     

Effect of nano-Calcium Carbonate on microcellular foaming of polypropylene

Using supercritical carbon dioxide as the physical foaming agent, a new batch process was carried out to prepare microcellular polypropylene (PP) and polypropylene/nano-Calcium Carbonate (PP/nano-CaCO₃) foams. Four concentrations of nano-CaCO₃, 3, 5, 7, and 10 wt% were used. The cell structure of foams and advantages of this new process were investigated and explained by thermal properties. Results showed that the foamed PP/5 wt% nano-CaCO₃ produced a microcellular foam with the minimum mean cell diameter (9.55 μm) and maximum cell density (1.50 × 10⁹ cells/cm³) among the four blends. Some unfoamed regions were observed in nanocomposite foams because nano-CaCO₃ could accelerate crystallization in cooling and cryostat stage. The new process took much less time (2.5 h) to foam and had much broader foaming temperature range (about 55 °C). But the foaming temperature range decreased after blending nano-CaCO₃ into PP matrix because nano-CaCO₃-induced isothermal and non-isothermal crystallization at higher temperature. In addition, the cell growth effect on variations of volume expansion ratio in PP/nano-CaCO₃ nanocomposites could be neglected comparing with the heterogeneous cell nucleation effect.     

A two-fluid model for calcium carbonate precipitation in highly supersaturated solutions

Precipitation of calcium carbonate is a common phenomenon in nature, which has attracted attention from researchers due to its importance in biomineralization processes, climatic changes, and especially incrustations in pipelines. In this work, a two-fluid model is proposed for homogeneous crystallization of calcium carbonate in highly supersaturated solutions. By making an analogy between the dynamics of a granular gas and the dynamics of a solid dispersion, the proposed model not only accounts for the interaction forces between the solid particles and dispersion medium, but also for the mass transfer and changes in the particles size during the precipitation reaction. Moreover, by using a numerical scheme based on an iterative algorithm, 3D numerical simulations are performed for the homogeneous crystallization of calcium carbonate, and the results are compared with experimental particles size distributions and curves of pH versus time. The good agreement between theoretical and experimental results indicates that the two-fluid model can be successfully used to evaluate the growth kinetics of calcium carbonate nuclei.