Isothermal crystallization kinetics and morphology of biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate)

Isothermal crystallization kinetics and morphology of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] with different 4-hydroxybutyrate (4HB) molar fraction were investigated by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and polarized optical microscopy (POM). The results show that the crystallization mechanism and crystal structure of P(3HB-co-4HB) copolymers are the similar as those of poly(3-hydroxybutyrate) (PHB). While the equilibrium melting point and crystallization rate decrease with the increase of 4HB molar fraction. Banded spherulites are observed in neat PHB and P(3HB-co-4HB) copolymers, and morphology is influenced apparently by the crystallization temperature and 4HB unit.     

SiO2/聚（3-羟基丁酸酯-co-4-羟基丁酸酯）薄膜研究

目的研究纳米SiO2对可生物降解聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(P34HB)包装膜结晶行为和力学性能的影响。方法采用溶液浇铸法制备SiO_2/P34HB纳米复合薄膜,利用红外光谱仪(FTIR)、扫描电镜(SEM)、正置热台显微镜(POM)、差示扫描量热仪(DSC)和万能力学试验机等研究纳米SiO_2对P34HB结构、结晶性和力学性能等的影响。结果纳米SiO_2在P34HB中起到异相成核的作用,SiO2/P34HB复合膜的结晶速率和结晶度得到明显改善。相比P34HB包装膜,当纳米SiO_2质量分数为2%时,SiO_2/P34HB复合膜的弹性模量和拉伸强度分别提高了72.7%和60.9%。结论获得了纳米SiO2改善可生物降解聚(3-羟基丁酸酯-co-4-羟基丁酸酯)包装膜结晶度和力学性能的最佳掺杂比例参数。     

Nucleation,growth and morphology of poly(hydroxybutyrate) and its copolymers

Measurements of the melting temperatures, growth rates and nucleation rates of meltcrystallized polyhydroxybutyrate (PHB) and two poly(hydroxybutyrate-co-hydroxyvalerate) (PHB/HV) copolymers are reported for crystallization over a wide range of temperature. Examples are shown of the spherulitic morphologies obtained. From the variation in melting point with crystallization temperature values for the equilibrium melting points of PHB and PHB/HV are obtained. Growth and nucleation rate measurements are analysed using secondary nucleation theory to obtain approximations to surface energies within the crystals. PHB and PHB/7% HV are described well by secondary nucleation theory. PHB/23% HV exhibits more complex crystallization and melting behaviour, which suggests temperature-dependent exclusion of HV units from the crystals.     

Imperfections and impurity phases in flux grown RCrO3 (R = La,Yb) single crystals

Results of scanning electron microscopy (SEM) and energy dispersive X-ray analytical (EDAX) investigations, conducted on some elevated structures displayed by flux grown rare earth orthochromite, RCrO₃ (R = La, Yb) crystals, are presented. The peculiar structures exhibited by crystal surfaces indicate imperfections and impurity phases. EDAX of elevated structures reveals the various phases to be composed of lead associated materials which may probably be either Pb₂CrO₅ or Pb₂OF₂ (flux). Other secondary crystallization of impurity phases, ROF (R = La, Yb) is illustrated in the case of RCrO₃ (R = La, Yb) crystals. The elevated structures illustrate their non-stoichiometric behaviour. Precipitation of impurity phases and formation of imperfections during the growth of RCrO₃ (R = La, Yb) crystals and their effect on the crystalline quality is discussed.     

Crystallization embrittlement of Ni-Si-B alloys

Changes in the mechanical properties, and in particular the loss of ductility, have been examined during the crystallization of a series of Ni-Si-B amorphous alloys and an Ni-Fe-Si-B alloy. In all cases crystallization takes place by the formation of large numbers of small crystals and at some stage during the crystallization process embrittlement occurs. The geometrical characteristics of the crystal phases, and the mechanical properties of the crystalline and amorphous components are assessed in an attempt to define the factors leading to embrittlement. Sensitivity to embrittlement does not seem to be related to the particular phase nature, geometry nor distribution of the crystals formed. Rather, the mechanical properties of the crystals seem to be the determining factors. Hard and brittle crystals lead to alloy embrittlement; soft, ductile crystals can lead to enhanced toughness of the alloys.     

中钛型含钛高炉渣制微晶玻璃及其性能研究

以中钛型含钛高炉渣为主原料制备微晶玻璃,利用渣中的TiO2作晶核剂.采用差示扫描量热法(DSC)、X射线衍射(XRD)和扫描电子显微镜(SEM)等分析技术研究了含钛高炉渣用量的变化对基础玻璃晶化、微晶玻璃性能的影响.结果表明,渣中适量的TiO2对玻璃晶化有较好的促进作用.渣用量较低时制得的微晶玻璃的主晶相为硅灰石,但当渣用量超过70％时,主晶相发生变化,变为钙铝黄长石等长石类矿相.中钛型含钛高炉渣用量为63％左右时,制得的微晶玻璃晶相含量合适,性能最好.此时采用的热处理制度为:核化温度720℃,保温1h,晶化温度945℃,保温2h,制得的微晶玻璃抗弯强度为121.68MPa,显微硬度为7.81 GPa.     

The influence of quenched-in crystals on the thermal stability of partially amorphous Zr76Ni24 alloy

Fully glassy and part-crystalline ribbons were prepared by melt spinning the Zr₇₆Ni₂₄ melt at different rates. X-ray and STEM studies confirmed that the quenched-in crystals are -zirconium. It is shown that these pre-existing crystals do not grow during annealing treatment nor do they act as heterogeneous nucleation sites, and remain inertly during the crystallization of the surrounding amorphous matrix. Crystallization studies showed that the existence of a fraction of crystallinity within the glassy matrix increases the stability of the matrix against further crystallization. Possible explanations for this behaviour are presented.Work carried out while the authors were in the University of Sussex, School of Engineering and Applied Sciences, Brighton, BN1 9QT, UK.     

Preparation of Macroscopic Block‐Copolymer‐Based Gyroidal Mesoscale Single Crystals by Solvent Evaporation

Properties arising from ordered periodic mesostructures are often obscured by small, randomly oriented domains and grain boundaries. Bulk macroscopic single crystals with mesoscale periodicity are needed to establish fundamental structure–property correlations for materials ordered at this length scale (10–100 nm). A solvent‐evaporation‐induced crystallization method providing access to large (millimeter to centimeter) single‐crystal mesostructures, specifically bicontinuous gyroids, in thick films (>100 µm) derived from block copolymers is reported. After in‐depth crystallographic characterization of single‐crystal block copolymer–preceramic nanocomposite films, the structures are converted into mesoporous ceramic monoliths, with retention of mesoscale crystallinity. When fractured, these monoliths display single‐crystal‐like cleavage along mesoscale facets. The method can prepare macroscopic bulk single crystals with other block copolymer systems, suggesting that the method is broadly applicable to block copolymer materials assembled by solvent evaporation. It is expected that such bulk single crystals will enable fundamental understanding and control of emergent mesostructure‐based properties in block‐copolymer‐directed metal, semiconductor, and superconductor materials.     

Compositional study and cytotoxicity of biodegradable poly(ester urethane)s consisting of poly[(R)-3-hydroxybutyrate] and poly(ethylene glycol)

Biodegradable PHB–PEG multi-block polyurethane copolymers comprising PHB blocks (M_n: 1100, 1740 and 3240) and PEG blocks (M_n: 1960, 3250, 4150 or 7950) were synthesized followed by characterization by GPC, ¹H NMR, and FT-IR. The PHB contents ranged from 9 to 62% by weight. The copolymers displayed improved thermal stabilities compared with their respective precursors. The morphological structures of the copolymers were studied by FT-IR, DSC and XRD. FT-IR revealed the existence of amorphous and crystalline phases of PHB. Both DSC and XRD analyses showed that separate crystalline phases are formed by PEG and PHB blocks in the copolymers. Upon annealing, the melting transition temperature (T_m), melting enthalpy (ΔH_m) and the fractional crystallinity (X_c) of the PEG block increased when the length of PEG incorporated into the copolymer increased. These values were higher when the PHB block length is shorter as the shorter PHB chain does not disrupt the crystallization of PEG as much as the longer PHB chain. A similar disruptive effect on the crystallization of PHB segments was observed by varying PEG chain lengths but the effect is less pronounced compared with the PEG segments. A comparison of the swelling properties of the poly(ester urethane)s showed that the length and crystalline properties of the PHB block significantly affects the water uptake properties of the copolymers. The crystalline properties and the water uptake capacities of the copolymers could be fine-tuned by consideration of the length of the PHB and PEG block incorporated. The results of the cytotoxicity tests demonstrated that the poly(PHB/PEG) urethanes were non-cytotoxic and could potentially be used for biomedical purposes.     

聚丁二酸丁二醇酯/聚羟基烷酸酯熔融共混物的结晶及流变力学行为

用熔融共混法制备聚丁二酸丁二醇酯(PBS)/聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[Poly(3HB-co-4HB)]复合降解材料,利用差示扫描量热(DSC)、旋转流变仪及万能拉力机对其结晶、流变行为及力学性能进行研究。结果表明,在PBS中加入Poly(3HB-co-4HB)后,发现结晶起始温度(To,c)、结晶峰温度(Tp,c)以及结晶结束温度(Te,c)有所提高,结晶度随着Poly(3HB-co-4HB)的增加呈先增大后下降的趋势;PBS/Poly(3HB-co-4HB)复合降解材料随着Poly(3HB-co-4HB)添加量的增大,断裂伸长率和拉伸强度却呈下降趋势;同时剪切储能模量(G′)、剪切损耗模量(G″)呈现出单增趋势。因此,在复合降解材料中添加适量的Poly(3HB-co-4HB)能改善PBS的结晶、流变及力学行为。     

化学沉积Ni-P及Ni-Cu-P合金镀层晶化行为的比较

利用DSC和XRD对化学沉积Ni-P及Ni-Cu-P合金镀层的晶化行为进行了比较研究，结果表明：低磷Ni-P镀层直接转变为稳定相Ni3P,而低磷（高铜）Ni-Cu-P镀层则经生成亚稳中间相Ni5P2后再向稳定相Ni3P转变，高磷非晶态Ni-12.1%P(质量分数，下同）和Ni-17.96%Cu-9.29%P合金镀层均先形成亚稳中间相Ni5P2和Ni12P5后，再转变为稳定相Ni3P,但Ni-Cu-P合金镀层转变为亚稳相的温度比Ni-P镀层的高。     

准分子激光引起的非晶硅薄膜晶化行为的研究

利用KrF准分子激光对非晶硅薄膜的表层进行了晶化.研究了激光能量密度和照射脉冲数对薄膜结晶度的影响,并对晶化后薄膜的形貌和结构进行了表征.结果表明:该非晶硅薄膜晶化阈值约为110 mJ/cm2,且不受照射脉冲数的影响;激光能量密度是影响薄膜结晶度的首要因素,但在较低的能量密度时,增加照射脉冲数也会显著的提高薄膜结晶度;结构及形貌表征发现,薄膜晶化层厚度约为400～500 nm,平均晶粒尺寸为30～50 nm.     

PA6/PA6IcoT相容共混物的结晶行为

采用差示扫描量热法研究了熔融共混聚己内酰胺/聚对(间)苯二甲酸己二胺(PA6/PA6IcoT)相容体系的结晶温度、结晶程度以及结晶动力学,并通过热台偏光显微镜、广角X射线衍射仪观察了PA6/PA6IcoT共混体系的结晶相形态和晶体结构。结果表明,共混物的结晶行为与其组成、结晶温度区域密切相关。在非等温结晶时,随着非晶态PA6IcoT含量的增加,PA6相的相对结晶度增加,部分晶体结构由γ晶型转变为较完善的α晶型。在较高温度区域结晶时,少量的PA6IcoT就能使串并的晶核分开,形成大量微小晶粒。当PA6IcoT含量继续增加时,球晶数目会减少但尺寸增大。等温结晶动力学研究发现,结晶速度随PA6IcoT含量的提高而下降,Avrami指数值在4.5～6之间,并随着结晶温度升高而增大。     

Microparticles prepared from biodegradable polyhydroxyalkanoates as matrix for encapsulation of cytostatic drug

Microparticles made from degradable polyhydroxyalkanoates of different chemical compositions a homopolymer of 3-hydroxybutyric acid, copolymers of 3-hydroxybutyric and 4-hydroxybutyric acids (P3HB/4HB), 3-hydroxybutyric and 3-hydroxyvaleric acids (P3HB/3HV), 3-hydroxybutyric and 3-hydroxyhexanoic acids (P3HB/3HHx) were prepared using the solvent evaporation technique, from double emulsions. The study addresses the influence of the chemical compositions on the size and ξ-potential of microparticles. P3HB microparticles loaded with doxorubicin have been prepared and investigated. Their average diameter and ξ-potential have been found to be dependent upon the level of loading (1, 5, and 10 % of the polymer mass). Investigation of the in vitro drug release behavior showed that the total drug released from the microparticle into the medium increased with mass concentration of the drug. In this study mouse fibroblast NIH 3T3 cells were cultivated on PHA microparticles, and results of using fluorescent DAPI DNA stain, and MTT assay showed that microparticles prepared from PHAs of different chemical compositions did not exhibit cytotoxicity to cells cultured on them and proved to be highly biocompatible. Cell attachment and proliferation on PHA microparticles were similar to those on polystyrene. The cytostatic drug encapsulated in P3HB/3HV microparticles has been proven to be effective against HeLa tumor cells.     

Effect of SiC Additions on the Spontaneous Crystallization and Properties of Diamond

The effect of silicon carbide additions on the spontaneous crystallization and properties of diamond is studied. The results demonstrate that increasing the SiC content of the growth charge increases the crystal yield (reduces the concentration of paramagnetic centers) and the fraction of small crystals and influences the melt composition.     

前驱体转化低铝含量非晶Si-Al-C-N的高温析晶行为

将不同铝含量的聚铝硅氮烷前驱体在氮气保护下1200℃裂解,再在1400-1800℃高温处理,制备出非晶Si-Al-C-N.采用红外光谱、X射线衍射,拉曼光谱和透射电子显微镜分别表征前驱体的结构、Si-Al-C-N的析晶特性、自由碳的微观结构,研究了铝含量、析晶温度和保温时间对非晶Si-Al-C-N析晶性能的影响.结果表...     

Microstructures and crystallization of electroless Ni-P deposits

A study has been made of microstructures and crystallization of the electroless Ni-P deposits containing 11.3 to 23.0 at% P obtained from acidic nickel sulphate baths with sodium hypophosphite as a reducing agent by means of differential scanning calorimetry, X-ray diffractometry and hot stage transmission electron microscopy. The deposits containing low phosphorus content of 11.3 at% could be represented as an fcc Ni-P solid solution of 5 to 10 nm microcrystallites, whereas the deposits containing high phosphorus content were amorphous. The crystallization process of amorphous Ni-P solution involved more than one intermediate phases; precrystallized nickel or off-stoichiometric Ni₃(P, Ni) or Ni₅(P, Ni)₂ phase in which some phosphorus sites are replaced by nickel atoms. The final equilibrium phases were bct Ni₃P and fcc nickel crystals regardless of phosphorus content. The amorphous phase containing 20 to 22 at% phosphorus was the most stable among the amorphous Ni-P alloys.     

Sintering and crystallization of a glass powder in the MgO-Al2O3-SiO2-ZrO2 system

The sintering and crystallization behaviour was studied of a glass powder in the MgO-Al₂O₃-SiO₂-ZrO₂ system in which the main crystal phases to form are clino-enstatite (MgSiO₃) and cubic zirconia (c-ZrO₂). During isothermal, atmospheric sintering of the glass powder, a fine dispersion of c-ZrO₂ particles, 50–100 nm diameter, was observed to form, but this did not appear to inhibit the sintering process. Nucleation of the main crystal phase, clino-enstatite, occurred both within the original glass powder particles and at the former particle surfaces, but the rate of crystallization was greater at the former particle surfaces. The c-ZrO₂ precipitates are thought to act as nucleation sites for the crystallization of the clino-enstatite. Relative densities of up to 98% were attainable during sintering, and were reached at a stage where a significant degree of crystal phase development had already taken place, proving that completion of sintering prior to the commencement of crystallization is not always a pre-requisite for the attainment of high final densities. In the material studied, the large volume contraction ( 11%) on crystallization and the possible release of dissolved gases led to a decrease in relative density as crystallization proceeded. The relative density after complete crystallization was found to be 94%±1%, irrespective of the temperature and duration of the initial sintering stage of heat-treatment, and it appeared that most of the residual porosity was a result of the volume contraction on crystallization rather than poor densification during sintering.     

宽过冷液相区铁基非晶合金的形成和磁性

用熔体急冷法制备出具有明显的玻璃转变和较宽的过冷液相区的Fe-Co-(Nb)-Zr-B非晶合金,研究了热稳定性和软磁性能。结果表明,在Fe-Co-Zr-B四元合金中添加适量的Nb可以显著扩大过冷液相区,提高合金的热稳定性。当冷却速率降低时,急冷合金具有非晶和纳米晶的复相结构。非晶合金的饱和磁化强度随Nb含量的增加而减小。不同Nb含量的非晶合金的饱和磁致伸缩系数均较低。在低于晶化温度的温度下退火可以有效地降低矫顽力,改善软磁性能。晶化导致软磁性能降低。     

脉冲宽度对激光熔覆FeSiB涂层组织与硬度的影响

以FeSiB非晶带材为熔覆材料,采用激光熔覆在低碳钢表面制备高致密度涂层,利用光学显微镜(OM)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)、显微硬度仪等研究不同脉冲宽度对激光熔覆涂层成形、组织特征及硬度的影响。结果表明:随脉冲宽度增大,涂层稀释率升高;裂纹倾向增加,裂纹源萌生由表面到界面处;晶化程度升高,结晶相为α-Fe,Fe_2B和Fe_3Si;熔合区宽度增大,柱状晶沿外延生长趋势更大;显微硬度先增加后减小。当脉冲宽度为3.2ms时,涂层结构致密,无孔洞缺陷,界面呈良好的冶金结合,稀释率低,为23.2%,涂层平均显微硬度达1192HV,约为基材的10倍。