热处理对Li2O-Al2O3-SiO2微晶玻璃的影响

本文对Li2O-Al2O3-SiO2（LAS）微晶玻璃的热处理制度、光学性能和热膨胀性能进行了分析,分析结果表明：应根据DTA曲线来确定最佳的成核温度范围和晶化温度范围并合理制定热处理制度;晶核密度和晶核尺寸随保温时间逐渐增加具有相反的趋势;晶粒尺寸大小将很大程度上影响微晶玻璃的光学性能;由于β-石英固溶体和β-锂辉石固溶体具有各向异性特点和螺旋链状结构,使其具有低的热膨胀系数和自由恢复形状特性。     

Investigation of dielectric properties and microstructure of sintered 13·2Li2O − 67·6SiO2 − 14.49Al2O3 − 3·3TiO2 − 0.4BaO − 0.97ZnO glass-ceramics

Lithium aluminosilicate (LAS) is an interesting material for the electronics industry. The material has near zero water absorption, low dielectric constant, and low loss tangent. Therefore, this material is interesting for the packaging of radio frequency transmitters used under harsh conditions. In this study, LAS glass powders with different particle sizes were dry pressed. Densification, crystallization, microstructure and dielectric properties were studied during thermal treatments. The highest sintered density (about 97%) has been achieved with milled powder with a d₉₀ of about 6 μm. Investigation of the microstructure reveals that flaky rutile has formed in β-spodumene grain boundaries even though spherical rutile is observed inside of β-spodumene. Glass phase in grain boundaries contain mostly SiO₂, Al₂O₃ and ZnO. Impedance analysis showed that the dielectric constant is influenced by phase transformation and density. The formation of hexagonal LiAlSi₂O₆ increases the dielectric constant while transformation to tetragonal structure decreases the dielectric constant.     

Influence of different β‐nucleating agent on crystallization behavior,morphology, and melting characteristic of multiwalled carbon nanotube‐filled isotactic polypropylene nanocomposites

To obtain isotactic polypropylene (iPP) nanocomposites with high β‐crystal content, TMB5, calcium pimelate and calcium pimelate supported on the surface of nano‐CaCO₃ were used as β‐nucleating agent and MWCNT filled β‐nucleated iPP nanocomposites were prepared. The effect of different β‐nucleating agent and MWCNT on the crystallization behavior and morphology, melting characteristic and β‐crystal content of β‐nucleated iPP nanocomposites were investigated by DSC, XRD and POM. The results indicated that addition of MWCNT increased the crystallization temperature of iPP and MWCNT filled iPP nanocomposites mainly formed α‐crystal. The β‐nucleating agent can induce the formation of β‐crystal in MWCNT filled iPP nanocomposites. The β‐nucleating ability and β‐crystal content in MWCNT filled β‐nucleated iPP nanocomposites decreased with increasing MWCNT content and increased with increasing β‐nucleating agent content due to the nucleation competition between MWCNT and β‐nucleating agents. It is found that the calcium pimelate supported on the surface of inorganic particles as β‐nucleating agent has stronger heterogeneous β‐nucleation than calcium pimelate and TMB5. The MWCNT filled iPP nanocomposites with high β‐crystal content can be obtained by supported β‐nucleating agent. POLYM. COMPOS., 36:635–643, 2015. © 2014 Society of Plastics Engineers     

Effects of nucleating agent on nonisothermal crystallization of syndiotactic polystyrene

The effects of nucleating agent on nonisothermal crystallization were examined for syndiotactic polystyrene (SPS) using Differential Scanning Calorimetry (DSC). The crystallization peak temperature T_c, the crystallization rate parameter (CRP), the enthalpy of crystallization and melting, and the recrystallization behavior were compared between organic (DMBS, 1,3,2,4-dis-5-(3,4-dimethyl benzylidene) sorbitol) and inorganic (talc) nucleating agents. Both of the nucleation agents promoted the crystallization rate of SPS until some critical concentration of about 3,000 ppm. DMBS worked more effectively as a nucleating agent than talc, although the T_c showed lower level in SPS/DMBS than SPS/talc.     

成核剂对PET结晶行为及形态结构的影响

系统地研究了四种成核剂:N-A、液晶VectraA950、滑石粉(Talc)、乙撑双硬脂酰胺(EBS)对聚对苯二甲酸乙二醇酯(PET)的结晶行为的影响。采用差式扫描量热仪(DSC)研究了PET/成核剂复合体系的非等温结晶行为,通过小角激光散射(Sals)、X衍射(XRD)对PET/成核剂复合体系的晶体尺寸和晶体结构进行了研究。结果表明,引入成核剂后,PET的结晶行为有较大改善,结晶峰向高温方向移动,且变尖锐,结晶尺寸变小,结晶度提高,除EBS外,均使PET结晶诱导时间减少。在这四种成核剂中,离子聚合物成核剂N-A成核效果最好。     

Effect of nucleating agents on the crystallization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

The effect of nucleating agents on the crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was studied. A differential scanning calorimeter was used to monitor the energy of the crystallization process from the melt and melting behavior. During the crystallization process from the melt, nucleating agent led to an increase in crystallization temperature (T_c) of PHBV compared with that for plain PHBV (without nucleating agent). The melting temperature of PHBV changed little with addition of nucleating agent. However, the areas of two melting peaks changed considerably with added nucleating agent. During isothermal crystallization, dependence of the relative degree of crystallization on time was described by the Avrami equation. The addition of nucleating agent caused an increase in the overall crystallization rate of PHBV, but did not influence the mechanism of nucleation and growth of the PHB crystals. The equilibrium melting temperature of PHBV was determined as 187°C. Analysis of kinetic data according to nucleation theories showed that the increase in crystallization rate of PHBV in the composite is due to the decrease in surface energy of the extremity surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2145–2152, 2002     

Phase formation during crystallization of a Li2O-Al2O3-SiO2 glass with ZrO2 as nucleating agent – An X-ray diffraction and (S)TEM-study

Glass ceramics based on the system Li₂O/Al₂O₃/SiO₂ (LAS) often show a coefficient of thermal expansion close to zero. Although these glass-ceramics are of high economic importance, the fundamentals of the crystallization process are still not fully understood. In this paper, the effect of ZrO₂ addition as a sole nucleation agent on the crystallization of the LAS glass is described predominantly using transmission electron microscopy and X-ray diffraction. The composition of the studied green glass was close to that of the commercially available Robax™ glass (Schott AG), which, however, contained both, ZrO₂ and TiO₂ as nucleating agents. It was found that during thermal treatment, in a first step, already at temperatures around 10–20 K below the glass transition temperature, T_g, ZrO₂ nanocrystals with sizes in the range from 5 to 15 nm were precipitated. The next crystalline phase that forms during the crystallization process was LAS with a structure similar to the hexagonal high temperature phase of quartz. These crystals were much larger than the ZrO₂ crystals. If thermal treatment was carried out at higher temperatures, a dense network of LAS crystals was formed. Differently shaped crystals in samples with different thermal history were visualized, and an enrichment of Ba and Sb in the residual glass phase in the late stages of thermal treatment was found. Also, an enrichment of aluminum around the ZrO₂ crystals was evident, which is a hint at a preceding droplet phase separation from which the ZrO₂ crystals were precipitated. The crystallization is notably different from that of mixed ZrO₂/TiO₂ nucleating agents used in commercial lithium alumosilicate glass ceramics.     

水泥基材料成核剂研究进展

建筑工业化的不断推进需要混凝土的强度尽早、尽快形成。相较于传统的蒸汽或蒸压养护,在水泥基材料中加入一定的成核剂,除了能够有效促进水化、加速凝结外,还有助于改善界面结构和提高耐久性,因而被广泛用于实际工程中,受到了国内外学者的极大关注。本文对比归纳了无机盐类成核剂、有机物类成核剂、纳米成核剂和复合成核剂的成核作用机理,详细分析了成核行为的热力学与动力学特性,概括总结了成核效应的影响因素以及对水泥基材料性能的综合影响。最后探讨了成核剂发展面临的挑战,并对需进一步研究的可能方向提出了建议,旨在为水泥基材料成核剂的高效利用与深入研究提供借鉴与参考。     

Variation of non‐isothermal crystallization behavior of isotactic polypropylene with varying β‐nucleating agent content

The non‐isothermal crystallization behavior, the crystallization kinetics, the crystallization activation energy and the morphology of isotactic polypropylene (iPP) with varying content of β‐nucleating agent were investigated using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The DSC results showed that the Avrami equation modified by Jeziorny and a method developed by Mo and co‐workers could be successfully used to describe the non‐isothermal crystallization process of the nucleated iPPs. The values of n showed that the non‐isothermal crystallization of α‐ and β‐nucleated iPPs corresponded to a tridimensional growth with homogeneous and heterogeneous nucleation, respectively. The values of crystallization rate constant showed that the rate of crystallization decreased for iPPs with the addition of β‐nucleating agent. The crystallization activation energy increased with a small amount (less than 0.1 wt%) of β‐nucleating agent and decreased with higher concentration (more than 0.1 wt%). The changes of crystallization rate, crystallization time and crystallization activation energy of iPPs with varying contents of β‐nucleating agent were mainly determined by the ratio of the content of α‐ and β‐phase in iPP (α‐PP and β‐PP) from the DSC investigation, and the large size and many intercrossing lamellae between boundaries of β‐spherulites for iPPs with small amounts of β‐nucleating agent and the small size and few intercrossing bands among the boundaries of β‐spherulites for iPPs with large amounts of β‐nucleating agent from the SEM examination. Copyright © 2010 Society of Chemical Industry     

聚甲醛结晶性能的改性

研究了高摩尔质量羧酸盐类成核剂HC对聚甲醛（POM）的结晶成核作用，采用示差扫描量热分析（DSC）、偏光显微镜观察（PLM）及等温结晶动力学分析等方法研究了该类成核剂对POM结晶形态、结晶度、结晶速率等的影响，并考察了其力学性能。结果表明，高摩尔质量羧酸盐类成核剂HC的加入，使POM晶粒细化，结晶诱导期缩短，显著提高了POM的结晶速率。     

Crystallization morphology and crystallization kinetics of poly(lactic acid): effect of <Emphasis Type="Italic">N</Emphasis>-Aminophthalimide as nucleating agent

The effect of N-Aminophthalimide compound (NA-S) as nucleating agent on crystallization behavior and morphology of poly(lactic acid) was studied. With polarized optical microscope (POM), the unique phenomena of nucleation and epitaxial crystallization of PLA/NA-S system were observed. Dynamic morphology of crystallization was also studied by POM to investigate the relationship between growth behavior of PLA and nucleating agent. Isothermal and non-isothermal crystallization behavior of PLA were studied by differential scan calorimeter (DSC). When nucleating agent was added, a new peak appeared in wide angle X-ray diffraction (WAXD) compared with pure PLA, indicating the nucleating effect of NA-S on crystallization of PLA. All the results indicate that the nucleating agent of NA-S shows obvious nucleating effect on isothermal crystallization above 120 °C and in non-isothermal crystallization after it is added in PLA, that is, the induction crystallization time is reduced, the crystallization rate and nucleation density of PLA are increased.     

Highly efficient nucleating additive for isotactic polypropylene studied by differential scanning calorimetry

The influence of an organic phosphate derivative in the crystallization of the monoclinic phase of isotactic polypropylene was studied by differential scanning calorimetry. To analyze the nucleation activity of the additive, the self‐nucleation process of the pure polymer was also studied by thermal techniques. A large increase in crystallization temperatures was obtained even for the lowest concentration of the additive, and its nucleating efficiency is the highest observed for α‐nucleating agents in isotactic polypropylene. The nucleating agent was also observed to increase the stability of the crystals formed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1669–1679, 2002; DOI 10.1002/app.10546     

Crystallization mechanisms of cordierite glass-ceramics with “surface-center” crystallization behavior

Cordierite glass-ceramics usually begin to crystallize from the surface. As an efficient nucleating agent, TiO₂ can promote the rapid transformation of glass to bulk crystallization, but it is easy to cause the increase of dielectric constant and light absorption. High crystallinity cordierite glass-ceramics were prepared by optimizing the heat treatment process without or with different nucleating agents in stoichiometric cordierite glasses. The results show that the crystallization mechanisms of glasses without and with ZrO₂+P₂O₅ as nucleation agents are controlled by surface crystallization. While, the glass with TiO₂+ZrO₂+P₂O₅ as nucleation agents have the tendency to be bulk crystallization. The studied glasses are crystallized from surface and have different crystallization orientations with the inner glass. The thickness of crystalline layer increased with the increasing of heating temperatures, but the “surface-center” crystallization process cannot complete by further increasing heating temperatures because of softening deformation of glasses. At 1020 ℃, the glasses complete the “surface-center” crystallization for long durations. The glasses without nucleation agents and with ZrO₂+P₂O₅ require 10 h, but the glass with TiO₂+ZrO₂+P₂O₅ complete for 5 h. Although all the three glasses complete the “surface-center” crystallization, the glasses with nucleation agents show the higher crystallinity upon the same heat treatments. Finally, glass-ceramics with excellent performance were obtained, for example, the Z1# glass-ceramic have the high microhardness ∼7.4 GPa, low thermal expansion coefficient ∼1.4☓10⁻⁶ ℃⁻¹ at 20–300 ℃, and relatively high thermal conductivity ∼2.4 W/mK. It also exhibits low dielectric constant and loss, which was ∼4.5 and ∼1.2☓10⁻³ at 1 MHz, ∼ 4.9 and 2.3☓10⁻³ at 10.5 GHz..     

聚丙烯β成核剂的研究进展

对近年来聚丙烯(PP)β成核剂的研究进展进行了综述,首先论述了PP的β晶型及β成核剂的成核机理,然后详细介绍了不同种类β成核剂的研究进展情况。同时,针对现阶段β成核剂研究和开发过程中存在的问题提出意见和建议,并对聚丙烯β成核剂的未来发展作出展望。     

均聚与无规共聚聚丙烯β结晶行为研究

本文使用差示扫描量热分析仪（DSC）,广角X射线衍射仪（XRD）和偏光显微镜（POM）对比研究了熔体流动速率接近的均聚和无规共聚聚丙烯添加成核剂前后结晶行为的变化情况。研究表明,熔体冷却速率对均聚聚丙烯中β晶的形成影响较大：较低的冷却速率利于体系中β晶的形成;随着降温速率的增加,体系中β晶含量逐渐降低;在相同的结晶条件下,均聚聚丙烯更易形成β晶。在无规共聚聚丙烯中,β晶的含量也随降温速率的变化而改变,但由于β晶含量较低,变化较小。添加成核剂之后,均聚聚丙烯和无规共聚聚丙烯的球晶数量大大增加,结晶温度和结晶活化能均升高,β晶的含量和结晶度都大幅提高;但β晶含量随熔体冷却速率的变化较小;并且与共聚聚丙烯相比较,均聚聚丙烯中β晶的含量和结晶度均要高于前者。     

新型α和β成核剂对PP结晶和力学性能的影响

在聚丙烯(PP)中加入两种新型成核剂:二苄叉山梨醇衍生物YS-688(α成核剂)和芳酰胺类化合物TMB-5(β成核剂),通过密炼–挤出的方法制备了PP/成核剂共混物材料。通过偏光显微镜、X射线衍射、差示扫描量热和力学性能测试研究了这两种成核剂对共混物结晶和力学性能的影响。结果表明,两种成核剂在适量时均能提高PP的结晶速率和结晶度,细化晶粒,且使晶体界面模糊,其中TMB-5具有较强的诱导PPβ晶成核的能力,当其质量分数为0.075%时,可使PP形成树枝状的β晶,而YS-688未改变PP的晶型,只生成了α晶。YS-688可提高共混物的拉伸强度,而TMB-5对共混物的拉伸强度影响很小;当两种成核剂质量分数均为0.075%时,共混物的韧性最好,相对于纯PP,PP/YS-688共混物的常温和–30℃缺口冲击强度分别提高了37.41%和12.76%,拉伸强度提高了11.11%;PP/TMB-5共混物的常温和–30℃缺口冲击强度分别提高了100%和55.41%。     

Isothermal crystallization kinetics of commercially important polyalkylene terephthalates

The isothermal crystallization kinetics of virgin, melt‐mixed, and nucleated specimens of polyethylene terephthalate (PET), polypropylene terephthalate (PPT), and polybutylene terephthalate (PBT) were measured. The purpose of the study was to determine the difference in crystallization rate of PPT, which is to be commercially available in the near future, to the extensively studied, commercially important polyalkylene terephthalates PET and PBT. At equivalent supercooling, the crystallization rate of PPT was between that of PET and PBT, with PBT being the fastest crystallizing polymer. Melt‐mixing virgin materials resulted in a substantial increase in the crystallization rate for all three polyalkylene terephthalates. The addition of talc or sodium stearate as a nucleating agent resulted in a further increase in crystallization rate for all three polyesters. Although the addition of talc or sodium stearate to PPT and PET greatly enhanced crystallization rate, these nucleating agent–containing materials still did not crystallize as fast as PBT melt‐mixed in the absence of any intentionally added nucleating agents. Analysis of the crystallization kinetic data using the Avrami equation showed that melt‐mixing and the addition of sodium stearate resulted in an increase in the average Avrami exponent. This result suggested a change in the mechanism of nucleation toward more sporadic nucleation. For the sodium stearate–nucleated materials, the Avrami exponent was found to increase with increasing crystallization temperature, but a precise explanation of this behavior could not be provided without a knowledge of crystallite morphology. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1296–1307, 2000     

Effect of different nucleating agent ratios on the crystallization and properties of MAS glass ceramics

The effects of different kinds of nucleating agents on crystallization, microstructure and performances of Magnesium Aluminosilicate (MgO-Al₂O₃-SiO₂, MAS) glass-ceramics which were fabricated by melting method in this study. Also, this paper systematically investigated the mechanism of glass stability, crystallization kinetics and element distribution of MAS glass-ceramics. Herein, we used three kinds of nucleating agents, which was TiO₂, ZrO₂ and composite nucleating agent (TiO₂/ZrO₂). The results showed after the doping of nucleating agent, the content of α-cordierite was increased, the stability and crystallization kinetics of glass was changed, the precipitated crystal phase was finer and more compact. Wherein, the sample with composite nucleating agents (TiO₂, ZrO₂) has the best performance due to the highest contents of α - cordierite, uniform distribution of elements without agglomeration in the crystal phase and the most compact structure, whose Vickers hardness and bending strength can reach 9.70 GPa and 312 MPa, respectively.     

Preparation of micro/nanocellular polypropylene foam with crystal nucleating agents

Open‐cell, porous microcellular foams with nanofibrillated structures were prepared from high tacticity isotactic polypropylene (i‐PP) with a crystal nucleating and gelling agent. The 1,3:2,4 bis‐O‐(4‐methylbenzylidene)‐d ‐sorbitol gelling agent (Gel‐all MD) was used as the crystal nucleating and gelling agent, which enhanced the crystallization and gelation of i‐PP with a three‐dimensional network of highly connected nanofibrils. The core‐back foam injection molding technique was employed to foam the i‐PP with nitrogen (N₂) at a high expansion ratio, where the crystal nucleating agent induced bubble nucleation and bubble growth in the inter‐lamella region and opened the cell walls with a nanoscale‐fibrillated structure. The effects of the nucleating agent on the open cell content (OCC), density and crystallinity were thoroughly investigated. We prepared open‐cell micro/nanocellular foams with an average cell size of microscale voids of < 5 μm. Nanometer‐scale fibrillated structures were formed on the cell wall of the microscale void, the expansion ratio was five‐fold and the open cell content was over 90%. POLYM. ENG. SCI., 54:2075–2085, 2014. © 2013 Society of Plastics Engineers     

Mechanical properties of α-cordierite and β-spodumene glass-ceramics prepared by sintering and crystallization heat treatments

The α-cordierite and β-spodumene glass-ceramics containing B₂O₃, P₂O₅, and/or TiO₂ were produced in a bar shape by hot pressing and crystallization heat treatments of glass powders. Various physical properties of the glass-ceramics were examined. The α-cordierite glass-ceramics showed intrinsic high mechanical property values, whereas the β-spodumene glass-ceramics showed rather low ones. The relatively low density in β-spodumene glass-ceramics would lead to the low mechanical property values. This low density in the β-spodumene glass-ceramics would result from a possible premature crystallization which might hinder a completion of sintering of the matrix. The glass-ceramics without TiO₂ showed slightly higher mechanical properties than those with TiO₂. This difference would result from slightly higher density in the glass-ceramics without TiO₂.