Long terminal linear alkyl group as internal crystallization accelerating moiety of poly(l-lactide)

Poly(l-lactide) (PLLA) polymers having terminal n-alkyl groups with a wide variety of lengths (C₀–C₂₂) were synthesized by ring-opening polymerization of l-lactide in the presence of coinitiators of l-lactic acid (C₀), 1-hexanol (C₆), 1-dodecanol (C₁₂), and 1-docosanol (C₂₂) and their segmental mobility and non-isothermal and isothermal crystallization behavior were investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffractometry (WAXD). Glass transition and cold crystallization temperatures of melt-quenched samples during heating decreased with an increase in the length of terminal n-alkyl groups. The enhanced PLLA segmental mobility and hydrophobic interaction-based accelerated PLLA nucleation by the presence of terminal long n-alkyl groups should have caused the accelerated non-isothermal and isothermal crystallization of PLLA segments traced by cold crystallization temperature during heating and by radial growth rate of spherulites, respectively. The crystallization accelerating effect became higher with the length of terminal n-alkyl groups. The effects of the length of terminal n-alkyl group on the crystalline growth mechanism of PLLA at the lowest crystallizable temperature was insignificant, whereas the effects of the length of terminal n-alkyl group on the nucleation mechanism of PLLA chains were significant and insignificant for PLLA having M_n of 6–7 × 10³ of 2 × 10⁴ g mol⁻¹, respectively. WAXD measurements revealed that the transition crystallization temperature at which crystalline modification changes from δ-form to α-form was affected by the length of terminal n-alkyl group for PLLA having M_n of 6–7 × 10³ g mol⁻¹, but was not altered by the length of terminal n-alkyl group for PLLA having M_n of 2 × 10⁴ g mol⁻¹.     

Evaluation of polyesters from renewable resources as alternatives to the current fossil-based polymers. Phase transitions of poly(butylene 2,5-furan-dicarboxylate)

Poly(butylene 2,5-furan dicarboxylate) (PBF) is an alipharomatic polyester that can be prepared using monomers derived from renewable resources such as 2,5-furan dicarboxylic acid and 1,4-butanediol. In the present work the thermal behavior of PBF was studied. Multiple melting was observed during heating traces of samples isothermally crystallized from the melt using differential scanning calorimetry (DSC). The wide angle X-ray diffraction (WAXD) patterns did not reveal the presence of a second crystal population, or a crystal transition upon heating. DSC study showed that the phenomena are closely related to recrystallization. Temperature modulated DSC (TMDSC) tests indeed evidenced enhanced recrystallization. The equilibrium melting point was estimated to be 184.5 °C using the linear Hoffman–Weeks extrapolation. The heat of fusion of the pure crystalline polymer was found equal to 129 J/g or (27.35 kJ/mol), a little lower than that of PBT. The Lauritzen–Hoffman secondary nucleation theory was used and the surface energy values and the work of chain folding were found to be comparable to those of PBT, but quite lower than those of poly(ethylene terephthalate) (PET). The non-isothermal crystallization on cooling and the cold-crystallization of quenched samples were also studied. Condensed spherulites were observed on isothermal crystallization under large supercoolings by using polarized optical microscopy (POM), while the spherulites turned to ring-banded morphology at higher temperatures. In every case the nucleation density was high.     

Automated self seeding of batch crystallizations via plug flow seed generation

In this study, seed slurry from a single addition anti-solvent plug flow crystallization of benzoic acid was used to seed the equivalent batch cooling crystallization. The experimental conditions were carried out to simulate automated self-seeding. This involves withdrawal of solution from a batch crystallizer, which is then mixed with anti-solvent within a plug flow crystallizer, in order to generate a seed slurry which is fed directly back to the batch crystallizer. This seeding strategy allowed the final CSD of the batch crystallization to be controlled by variation of the crystal size from the plug flow seeding device at a constant seed loading. The ability to use unequal feed/anti-solvent inlet flowrates (in the Roughton vortex mixer) proved effective in controlling the batch CSD at 2% seed loading and constant feed composition.     

二次急冷淬火成形SAF2507双相不锈钢螺旋桨在SRB+IOB海水中的腐蚀行为

为了研究SAF2507双相不锈钢（SAF2507 DSS）螺旋桨叶片在含硫酸盐还原菌(SRB)和铁氧化菌(IOB)海水中的耐腐蚀性能,提出一种二次急冷淬火成形技术来成形SAF2507DSS螺旋桨叶片。同时根据螺旋桨叶片在不同二次急冷淬火成形温度下析出相的类型和析出规律,研究螺旋桨叶片在含SRB和IOB海水中的耐腐蚀性能。结果表明,当二次急冷淬火成形温度在700℃时,螺旋桨叶片表面析出少量的χ相;达到850℃时,χ相停止析出并完全转化成σ相,析出的σ相达到最大值;超过850℃时,析出的σ相开始急剧减少,到950℃时仅有少量的σ相析出。螺旋桨叶片在不同二次急冷淬火成形温度下,腐蚀电流密度、交流阻抗等电化学性能变化规律与螺旋桨叶片表层χ相和σ相的析出规律、以及χ相和σ相自身的耐腐蚀特征相吻合。二次急冷淬火成形温度在750～1050℃之间,螺旋桨叶片的耐腐蚀性能随热成形温度的升高呈增强-降低-增强规律变化,850℃时螺旋桨叶片的耐腐蚀性能最差。螺旋桨叶片二次急冷淬火成形后富Fe的表面特征,使得在SRB+IOB的作用下,螺旋桨叶片表面钝化膜被破坏,导致耐腐蚀性能降低。     

Effect of ZnO content on the physical,mechanical and chemical properties of glass-ceramics in the CaO–SiO2–Al2O3 system

The objective of this study was to evaluate the effect of ZnO content on the physical, mechanical and chemical properties of CaO–Al₂O₃–SiO₂ (CAS) glass-ceramics produced from Colombian wastes, such as fly ash, granulated blast furnace slag and glass cullet. The CaO/SiO₂ molar ratio of the mixtures was held constant (0.36). ZnO was added to the mixtures in proportions of 4, 7 and 10 wt%. The glass-ceramics were produced by the controlled crystallization of a parent glass. The values of crystallization temperature (T_p) show a fall up to 7 wt% and then shoots up with 10 wt% concentration of ZnO, but in general, ZnO addition lowers the temperature required for the formation of crystalline phases. In general, anorthite (CaAl₂Si₂O₈) is the main phase observed in all heat treated samples, in addition to albite (Na(AlSi₃O₈)) and labradorite (Na_0.45 Ca_0.55 Al_1.55 Si_2.45 O₈). The crystalline phases hardystonite (Ca₂ZnSi₂O₇) and willemite (Zn₂SiO₄) were also identified in the samples with 7 and 10 wt% ZnO. The densities of the glass-ceramics were between 2658 and 2848 kg/m³, and it was found that ZnO helps to increase the density of glass-ceramics. The elastic modulus was in the 100–105 GPa range, the fracture toughness was between 0.45 and 0.64 MPa m^1/2, and the Vickers microhardness was between 632 and 653 MPa. With regards to the durability, the weight loss of the glass-ceramics immersed in alkaline solution (NaOH) did not exceed 1.5 wt% after immersion for 6 h at 80 °C. The results of this study confirm that the vitrification process is a favorable option to utilize these industrial wastes.     

PET Recycling – Contributions of Crystallization to Sustainability

Polyethylene terephthalate (PET) is one of the most common thermoplastic polymers and its durability has become a major environmental concern. The current public debate on plastic debris also triggered the revision of PET recycling technologies. This Research Article focuses on the chemical recycling of PET by means of methanolysis. The process degrades PET into two main reaction products, dimethyl terephthalate (DMT) and ethylene glycol (EG). Subsequent separation by distillation combined with crystallization removes critical impurities and non-PET components from co-polymers, providing monomers of high purity needed for re-polymerization purposes.     

拉伸流动场诱导PVDF/BaTiO3流延膜结晶行为研究

利用挤出流延过程中的拉伸应力场对聚偏氟乙烯/钛酸钡(PVDF/BaTiO3)复合材料进行原位非等温拉伸试验,研究了拉伸比及BaTiO3用量对PVDF/BaTiO3流延膜结晶结构和介电性能的影响。广角X射线衍射结果表明,PVDF/BaTiO3复合膜的取向程度明显大于纯PVDF。X射线小角衍射结果显示:对于纯PVDF,第二个散射峰的强度随拉伸的进行而不断提高,在拉伸比为1.5时,其强度明显超过第一个散射峰;加入BaTiO3后,第一个散射峰的强度比纯PVDF明显提高,而第二个散射峰的强度也随拉伸比的提高而增强。复合膜的组成相同时,其介电常数随拉伸比的提高而减小,而介电损耗随拉伸比的提高而增大。     

甲醇－水溶液中反丁烯二酸二甲酯结晶介稳区宽度的测定

甲醇－水溶液中反丁烯二酸二甲酯结晶介稳区宽度的测定王留成，宋成盈，徐海升，栾亚非，于蕾，宁东刚（郑州工学院化学工程系）关键词反丁烯二酸二甲酯；结晶；介稳区宽度１前言反丁烯二酸二甲酯的合成是在甲醇过量的条件下完成的［１］，反应终了，溶液中含有甲醇、生成...     

Role of multi-wall carbon nanotube network in composites to crystallization of isotactic polypropylene matrix

The composites (iPP/CNTs) made of isotactic polypropylene (iPP) and multi-wall carbon nanotubes (CNTs) were prepared by solution blending. To improve compatibility between CNTs and iPP and to enhance dispersion of CNTs in iPP matrix, CNTs were chemically modified by grafting alkyl chains. The chemically modified CNTs had about 6 wt% grafted alkyl chains. Rheological measurements indicated that CNTs caused gelation in iPP/CNTs due to CNT network formation and the critical gelation CNT concentration was about 7.4 wt%, which was considered to be high due to the low CNT aspect ratio in this study. Crystallization behaviors of iPP/CNTs were studied by using optical microscopy (OM) and differential scanning calorimetry (DSC). Radial growth rates of spherulites during isothermal crystallization of iPP/CNTs with CNT concentrations less than 2.0 wt% measured by using OM showed decreasing trends with increasing CNT concentration. Avrami analysis of the exothermic heat flow curves during isothermal crystallization of iPP/CNTs measured by DSC indicated that crystallization rates were accelerated when CNT concentrations were lower than the critical gelation concentration, because CNTs mainly functioned as nucleating agents for crystallization, while crystallization rates did not change obviously when CNT concentrations were higher than the critical gelation concentration, because CNT network could form and mainly functioned to provide restriction to mobility and diffusion of iPP chains to crystal growth fronts.     

Nonisothermal Crystallization Modeling and Simulation for Polypropylene/Nano CaSO4 Composites with Variations in Nanosizes and Wt.% of Loading

Avrami and Ozawa's combined analysis was employed to study the nonisothermal crystallization kinetics of Polypropylene (PP): CaSO₄ (of 12 and 22 nm) composites using a Differential Scanning Calorimeter (DSC). The parameters, such as Avrami's exponent (n) and growth rate constant (Z_t), that characterized the system of different nanosize composites and virgin PP, were determined. The relative degree of crystallinity as a function of temperature for PP/nano CaSO₄ composites at the same cooling rate and the Sigmoidal shape of curves indicate a strong interaction between PP molecules and the nanolayer, which leads to greater nucleation with a reduction in nanosizes. The theoretical combination of kinetic equations was found to be suitable to describe the physical phenomena of real system. The values of parameters n, Z_t and predicted time t for crystallization at a single cooling rate were obtained from the mathematical model.