钛表面含硅羟基磷灰石涂层的电化学合成和表征

在含有Ca2+,PO43-以及SiO32-的电解液中,通过电化学恒电位方法,在工作电压为3 V温度为85℃的条件下沉积1 h,于钛表面上制得含硅羟基磷灰石涂层。通过电感耦合等离子体原子发射光谱(ICP)、扫描电镜(SEM)、X-射线衍射(XRD)、探针式轮廓仪(SP)、红外光谱(FTIR)对涂层进行分析。结果表明:电化学恒电位方法可制得Si饱和含量为0.55wt%左右的Si-HA涂层,Si以SiO44-形式取代PO43-进入HA晶格,造成羟基磷灰石中OH-减小以维持电荷平衡。另外,电解液中Si元素的存在抑制涂层中HA晶体的生长,使涂层变薄,且当电解液中nSi/(nSi+nP)达到20%时Si-HA晶体形貌由单独的棒状转变为根部相连的树枝状。     

Electrophoretic Deposition of Hydroxyapatite Coatings on Metal Substrates: A Nanoparticulate Dual-Coating Approach

Hydroxyapatite coatings can be readily deposited on metal substrates by electrophoretic deposition. However, subsequent sintering is highly problematic owing to the fact that temperatures in excess of 1100°C are required for commercial hydroxyapatite powders to achieve high density. Such temperatures damage the metal and induce metal-catalysed decomposition of the hydroxyapatite. Furthermore, the firing shrinkage of the hydroxyapatite coating on a constraining metal substrate leads to severe cracking. The present study has overcome these problems using a novel approach: the use of aged nanoparticulate hydroxyapatite sols (lower sintering temperature) and a dual coating strategy that overcomes the cracking problem. Dual layers of uncalcined hydroxyapatite (HAp) powder were electrophoretically coated on Ti, Ti6Al4V and 316L stainless steel metal substrates, sintered at 875–1000°C, and characterised by SEM and XRD, and interfacial shear strength measurement. Dual coatings on stainless steel had an average high bond strength (about 23 MPa), and dual coatings on titanium and titanium alloy had moderate strengths (about 14 and 11 MPa, respectively), in comparison with the measured shear strength of bone (35 MPa). SEM and XRD demonstrated that the second layer blended seamlessly with the first and filled the cracks in the first. The superior result on stainless steel is attributed to a more appropriate thermal expansion match with hydroxyapatite, the thinner oxide layer, or a combination of these factors.     

荆棘状羟基磷灰石棒的电化学法制备及性能表征

先后在低浓度和高浓度的钙、磷电解液中,采用两步电化学沉积法在纯钛金属表面制备了荆棘状羟基磷灰石棒(THA)。微观结构分析表明,THA的主干是由HA单晶构成,直径为100~200 nm,叉刺为HA多晶结构,直径为10~50 nm,它们在钛金属表面构成了具有两重微纳形貌的多孔涂层。溶解性实验与接触角测试结果表明,与单纯的HA棒涂层相比,这种THA涂层具有较高的钙离子释放速度和优异的表面润湿性。     

Influences of Heating Condition and Substrate-Surface Roughness on the Characteristics of Sol-Gel-Derived Hydroxyapatite Coatings

A prepared transparent HA solution was coated on Ti6Al4V substrates by a spin-coating technique. The crystallization of the sol-gel-derived HA coated on the metallic substrates could be done at relatively low firing temperatures (as low as 600°C). The characteristics of the HA-coated layer were dependent on the surface roughness of substrates and heating conditions such as firing temperature, holding time, heating rate, and atmosphere. The heat treatment at a slow heating rate (<2°C/min.) and a long heating time (>10 hrs) at 600°C in air produced the uniform surface and improved the crystallinity. The HA layer coated on 20 m grit-blasted substates was more uniform and had fever cracks after firing, compared with that coated on 100 m grit-blasted rougher substrates.     

Nucleation from supersaturated water vapors onn-dodecane substrate: A reverse Wilson chamber (RWC) method study

The reverse Wilson chamber method (RWC), developed for heterogencous nucleation investigation is applied to critical supersaturation measurements and determination of the surface concentration of nuclei (droplets) vs. supersaturation dependence in the case of nucleation from supersaturated water vapors onn-dodecane substrate. The experimental results obtained are interpreted in terms of the classical (Volmer) theory of heterogeneous nucleation as well as in the framework of the theory of barrierless nucleation. The several times lower critical supersaturations measured at four different temperatures, covering the range between 20° and 35° C, are explained by taking into account the effect of the negative line tension of three-phase contact. The temperature dependence of line tension for the three-phase systemn-dodecane/water/water vapor is extracted from the data to fir the theory. The results obtained are in complete disagreement with those ones obtained by Wu and Maa for the same system using jet-tensimeter technique, however, in another temperature interval. This discrepancy is discussed in detail in the text.     

羟基磷灰石/氧化铁复合涂层的制备及其诱导骨生长的生物活性

用电泳沉积法制得羟基磷灰石/壳聚糖/氧化铁(HA/CS/Fe2O3)复合涂层,经700 ℃烧结处理得到HA/Fe2O3复合涂层。 通过SEM、EDS、XRD、FT-IR、电化学和万能材料试验机等对复合涂层的表面形貌、物相组成、抗腐蚀性和结合强度进行了表征和测试,最后采用1.5SBF浸泡法对复合涂层的生物活性进行了评价。 结果表明,当悬浮液中的HA、CS与Fe2O3质量比为100∶100∶1时,所制得的HA/Fe2O3复合涂层表面粗糙,抗腐蚀性强,具有良好的诱导骨生长生物活性,基体与复合涂层结合强度可达27.5 MPa。     

Nucleation of gold nanoparticles on latex particle surfaces

Gold particles were nucleated on functionalized (i.e., sulfonate or imidazole groups) latex particle surfaces. Gold ions were associated with the functional groups present on the surface of the latex particles by metal‐ligand formation and were then reduced to nucleate gold particles on the particle surface. The use of imidazole groups favored the metal‐ligand formation more effectively compared with sulfonic acid groups, so gold nucleation was investigated on the surface of imidazole‐functionalized model latex particles. The desorption of gold atoms or their surface migration first occurred during the reduction process and then gold nanoparticles were nucleated. The utilization of strong reductants, such as NaBH₄ and dimethylamine borane (DMAB) under mildly acidic conditions (i.e., pH 4) led to the deprotonation of imidazole‐rich polymer chains present on the surface of the model latex particles followed by deswelling of hydrophilic polymer surface layers. As a result, well‐dispersed gold nanoparticles were embedded in the hydrophilic polymer surface. On the other hand, the use of weak reductants led to the formation of localized gold aggregates on the surface of the latex particles. The removal of residual styrene monomer is very important because gold ions can be coordinated with the vinyl groups present in styrene monomer and would then be reduced by nucleophilic water addition. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 912–925, 2008     

Crystallization behavior of a propylene/ethylene copolymer: Nucleation and a clarifying additive

The isothermal crystallization behavior of a propylene/ethylene copolymer containing a clarifying additive has been studied in detail and compared with the equivalent unclarified grade. Differential scanning calorimetry was used to obtain crystallization exotherms for both the unclarified system and the clarified analogue. Avrami analysis of these data was then performed, using both linear and nonlinear data‐fitting techniques. Linear analysis revealed a change from a primary to a secondary crystallization process in the clarified system at about 50% relative crystallinity. Nonlinear techniques, however, led to more reliable estimates of the Avrami parameters and provided estimates of crystallization‐induction times. By combining the preceding with isothermal crystal‐growth‐rate data, the nucleation density in each material was obtained as a function of crystallization temperature. In the unclarified case, this fell exponentially with temperature. The nucleation density in the sorbitol‐clarified copolymer was 10³–10⁶ times greater than in the unclarified material, but decreased only slowly with increasing crystallization temperature throughout the temperature range investigated here. This final result appears entirely contradictory to previous morphological work in which a distinct morphological transition was observed at 128 °C and associated with a marked reduction in the nucleating efficiency of the sorbitol. Possible explanations for this apparent contradiction are considered. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2178–2189, 2002     

Nucleation and growth of copper on glassy carbon: Studies in extended overpotential interval

The nucleation and growth of copper crystals on a glassy carbon electrode are investigated at different constant overpotentials. Current transients are recorded and the number of copper nuclei is microscopically registered. The experimental data for the growth current are interpreted according to the theories of progressive and instantaneous nucleation and information is obtained on the stationary nucleation rate, the saturation nucleus number density and the exchange current density at the crystals–solution interface boundary.     

电沉积二氧化锰成核机理及其充放电性能

采用计时电流法沉积纳米MnO₂电极材料,利用Scharifker-Hills成核理论模型分析时间-电流(i-t)曲线判断了MnO₂成核机理。 对3种不同的成核方式制得的MnO₂材料进行电化学超级电容性能测试、用SEM观察了其微观形貌。 比较了不同沉积方法对沉积材料结构、电容性能的影响。 计时电流测试发现,在0.1 mol/L Mn²⁺溶液中,电势阶跃至0.365 V,初始成核符合瞬时成核机理,在0.01 mol/L Mn²⁺溶液中,电势阶跃至0.418 V,初始成核存在瞬时成核和连续成核两种不同机理,在0.5 mmol/L Mn²⁺溶液中,电势阶跃至0.515 V,初始成核则符合连续成核机理。 超级电容性能测试发现,瞬时成核下制得的MnO₂电极材料相对于另外两种成核方式得到的电极材料具有更好的电容性能,这是因为瞬时成核更易于形成多孔、纳米片(棒)状等高比表面积的沉积物,表明制备方法影响MnO₂电极材料电容性能。     

Synthesis of Tetracycline Analogues and Test of Their Affinity on Synthetic Hydroxyapatite

To develop bone target drugs is an attractive field for increasing the potency and selectivity of these drugs in the treatment of osteoporosis and Pagets disease etc. As known, after systematic administration tetracycline can be distributed in bone and bind to hydroxyapatite with high affinity1. Thus we tried to use tetracycline as a bone targeted carrier. However, tetracycline is less stable, and its complex structure bring much difficulty in the coupling reaction and purification of the p…     

Zn and Ag Doping on Hydroxyapatite: Influence on the Adhesion Strength of High-Molecular Polymer Polycaprolactone

In this study, density functional theory was employed to calculate the adsorption of polycaprolactone (PCL) by pure hydroxyapatite (HA), Zn-doped HA, and Ag-doped HA, and the interaction of PCL on the surface of HA (001) was simulated. The results show that there was significant electron transfer between the carbonyl O in PCL and the Zn, Ag, and Ca in HA, forming coordinate bonds. The binding energies of Ag-doped HA/PCL and Zn-doped HA/PCL were much higher than those of HA/PCL. HA doped with Ag had the highest binding energy to PCL. Therefore, we believe that when HA is doped with Ag atoms, its adsorption capacity for PCL can be increased. The results obtained in this study can be used as a guide for the development of HA/PCL bone graft composite material doped with appropriate metal ions to improve its adsorption capacity.     

Simplified Calculation of the Average Number of Radicals Per Particle in Emulsion Polymerization: Effect of Particle Nucleation and Coagulation Rates

The solutions available for the well‐known Smith–Ewart recurrence equation (assuming size monodispersity) for calculating the average number of radicals per particle ( $\overline{n}$) do not consider the contribution of nucleation and coagulation of active particles. Notwithstanding this limitation, they are often used to calculate $\overline{n}$ in simplified mathematical models for commercial simulation software of industrial processes or for process control purposes. In this work, algebraic equations to calculate $\overline{n}$ for 0–1 systems that consider such contributions are developed. It is found that in the nucleation stage under typical conditions of emulsion polymerization, if nucleation and coagulation of particles are not considered in the calculation of $\overline{n}$, it could lead to large errors although its effect still needs to be evaluated in other relevant process parameters as well. However, such significant error could be present for a case of study where secondary nucleation and limited coagulation is experimentally detected.     

Effect of Hydroxyapatite Reinforced with 45S5 Glass on Physical,Structural and Mechanical Properties

This paper presents a study of physical and structural properties of Hydroxyapatite (HA) reinforced with different compositions of 45S5 (SG) bioglasses at different sintering temperatures. Hydroxyapatite reinforced with different compositions of 45S5 bioglasses had been prepared and investigated in terms of density, mechanical strength, and crystalline phases. A decrease in the density of HA was observed after the incorporation of SG, owing to the trapping of air in the SG reinforced HA after sintering process. When compared to the pure HA, different crystalline phases, such as β-tricalcium phosphate, calcium phosphate silicate and sodium calcium phosphate, were detected when different compositions of SG were incorporated into the HA     

中国土地制度的宪法解释：问题、争议及权衡

近年来,中国土地制度引发诸多争论,集中体现为对宪法第十条的不同解释。许多学者试图“回到宪法”,通过对土地条款的规范宪法学解释来弥合分歧。然而,从基本权利理论出发的规范宪法学解释方案并未能消弭分歧。这一争论的实质是土地增值收益分配,不同学者在此问题上持有不同的利益关怀。土地增值收益分配与中国宪制紧密相联,现有土地制度对于处理国家与民众关系、不同利益群体之间关系、中央与地方关系具有重要意义。因此,要以慎言违宪的态度对待宪法确立的土地制度基本架构。对于决策层而言,需要注意土地制度的变动,特别是土地增值收益分配机制的调整与中国城市化所处阶段相匹适,审慎权衡此种变动所带来的一系列影响。     

温度对PbO2电沉积形核生长过程的影响研究

为了探讨温度对PbO₂电沉积形核生长过程的影响,在25℃、35℃、45℃、55℃、65℃使用电化学工作站测试了PbO₂在玻碳电极上沉积过程的循环伏安曲线、计时电位曲线及计时电流曲线,并对不同温度下电沉积的PbO₂镀层进行了SEM和XRD分析. 结果表明,在不同温度下PbO₂都经历了成核和核生长过程. 温度的升高没有改变PbO₂电沉积三维连续成核的模式,降低了沉积过程溶液阻力,对成核和晶体生长速率均有促进作用,在晶核密度达到饱和晶核密度以前,是以促进成核速率为主,减小PbO₂颗粒尺寸. 达到饱和晶核密度后,电沉积后期以促进晶体生长速率为主,不利于形成细小PbO₂颗粒.高温使得析氧速率提高,能耗增大.由实验结果得出,在55℃时得到的PbO₂镀层粒径最小.     

关于一些热力学公式使用条件的讨论

物理化学中的热力学公式在不同条件下有不同的衍变形式,极易诱导学生产生错误理解。通过实例分析,对热力学能和焓变化计算公式、赫姆霍兹自由能和吉布斯自由能判据、热力学基本方程等的使用和理解中存在的一些问题予以讨论。     

Comparison of Hydroxyapatite/Poly(lactide-co-glycolide) and Hydroxyapatite/Polyethyleneimine Composite Scaffolds in Bone Regeneration of Swine Mandibular Critical Size Defects: In Vivo Study

Reconstruction of jaw bone defects present a significant problem because of specific aesthetic and functional requirements. Although widely used, the transplantation of standard autograft and allograft materials is still associated with significant constraints. Composite scaffolds, combining advantages of biodegradable polymers with bioceramics, have potential to overcome limitations of standard grafts. Polyethyleneimine could be an interesting novel biocompatible polymer for scaffold construction due to its biocompatibility and chemical structure. To date, there have been no in vivo studies assessing biological properties of hydroxyapatite bioceramics scaffold modified with polyethyleneimine. The aim of this study was to evaluate in vivo effects of composite scaffolds of hydroxyapatite ceramics and poly(lactide-co-glycolide) and novel polyethyleneimine on bone repair in swine’s mandibular defects, and to compare them to conventional bone allograft (BioOss). Scaffolds were prepared using the method of polymer foam template in three steps. Pigs, 3 months old, were used and defects were made in the canine, premolar, and molar area of their mandibles. Four months following the surgical procedure, the bone was analyzed using radiological, histological, and gene expression techniques. Hydroxyapatite ceramics/polyethyleneimine composite scaffold demonstrated improved biological behavior compared to conventional allograft in treatment of swine’s mandibular defects, in terms of bone density and bone tissue histological characteristics.     

六硝基芪衍生物的红外光谱和热力学性质的理论研究

用量子化学密度泛函理论方法,在B3LYP/6-31G*水平下,对六硝基芪衍生物进行了几何构型全优化和电子结构计算。通过振动分析,求得它们的红外光谱并作归属。将理论计算IR谱与已知实验结果进行比较,表明本文所提供的计算结果是可靠的。对谐振频率以0.96进行标度后基于统计热力学原理求得它们的热力学性质,探讨了热力学性质随硝基数、氨基数、羟基数和温度变化的规律,发现有很好的线性关系,体现了很好的基团加和性。     

Styrene Emulsion Polymerization above the CMC: New Evidence on Particle Nucleation by means of AFFFF

Summary: The number (N) and size distribution of particles (PSD) of a styrene emulsion polymerization above the CMC were studied by means of asymmetric flow‐field flow fractionation (AF⁴). Bimodal PSDs were obtained, suggesting that coagulation of the primary particles is not as extensive as would be expected, according to the coagulative mechanism. AF⁴ allowed it to be demonstrated that N is constant during interval II, and that the resolution limit of other particle sizing techniques can lead to erroneous mechanistic inferences, from the evolution of N.

Particle size distribution measured at low conversion for the emulsion polymerization of styrene, obtained by AF⁴ and DLS. The initial surfactant (S₀), initiator (I₀) and monomer (M₀) concentrations are indicated in the figure.