Factors influencing development of residual stresses during crystallization firing in a novel lithium silicate glass-ceramic

ObjectiveDevelopment of residual stresses is a potential source of premature fractures in glassy materials, being of special interest in novel lithium silicate glass-ceramics that require a crystallization firing to achieve their final mechanical properties. The aim of this work was to assess the influence of various firing tray systems and the application of different cooling protocols on the development of residual stresses in Suprinity PC crowns. Their effect on the in vitro lifetime of the restorations was also studied.MethodsThirty crowns were milled out of Suprinity PC blocks and crystallized using one of five different commercial firing tray systems (n = 6). Samples in each group were cooled following a fast (FC = 5.5 °C/s), a slow (SC = 0.4 °C/s) or the manufacturer’s reference cooling (REF ). Obtained crowns were sagittally or transversally sectioned and the magnitude and distribution of residual stresses was determined using the light birefringence method. Extra crowns of three of the subgroups (n = 8) were produced and submitted to chewing simulation for 10⁶ cycles or until fracture ensued.ResultsAverage residual stresses ranged between 0 and 1.5 MPa (peaks of 5 MPa). Highest stress magnitudes were observed at the support areas of groups using firing pins, leading to thermal cracks in FC samples and premature failures in the REF subgroup. The use of fibrous pads and firing pastes limited the development of residual stresses, whereas application of SC regimes extended the lifetime of the restorations.SignificanceDevelopment of residual stresses during crystallization firing in lithium silicate glass-ceramics results critical for their mechanical performance and should be therefore avoided by ensuring a homogenous cooling of the structures.     

Electrochemical polymerization of 3-phenylthiophene

Poly (3-phenylthiophene) (P3PhT) films have been electrochemically synthesized by direct oxidation of 3-phenylthiophene in the electrolyte of pure boron trifluoride diethyl etherate (BFEE). The oxidation potential of the monomer was measured to be 1.29 V (vs. SCE), and about 0.15 V lower than that measured in a neutral medium of acetonitrile. Free-standing P3PhT film with tensile strength of 32–40 MPa has been obtained for the first time. The morphology and the structure of the polymer film have been studied by scanning electron microscopy, infrared and Raman spectroscopies. Raman spectral results demonstrated that the doping level of the P3PhT film increased with film thickness during electrochemical growth process.     

拮氟锐对大鼠肠道氟吸收及微量元素的影响

拮氟锐是由硼、微量元素和中药制成的抗氟药物。本文应用肠道原位灌流技术。观察了拮氟锐对大鼠肠道氟吸收的干预作用及微量元素的影响。结果透明：拮氟锐可促进肠道ＢＦ４的形成，使氟吸收量减少，血氟降低。同时，拮氟锐可拮抗氟所致的微量元素的降低。与硼锌组比较，拮氟锐的抗氟作用效果更明显。     

A scanning electron microscopy study of the interface between ceramics and bone

By use of scanning electron microscopy (SEM), together with energy dispersive chemical analysis, a study has been made of the comparison of an in vitro method of assessing interface reactions between bone and ceramic implants with the naturally occurring changes seen in the rat ear model. Interface reactions between bone and two ceramic materials were examined following 4 wk in culture and 4 wk implantation. In both cases a gradual chemical change occurred at the calcium silicate surface during the fibrous growth onto the ceramic material. Gradual mineralization of the connective fibres was found at the interface of the calcium silicate material, whereas, in the case of alumina ceramic a connective fibrous bond had formed with no associated chemical change at the ceramic surface.     

聚硅氯化铁的制备及其混凝效果

以硅酸钠、氯化铁为原料制备聚硅氯化铁（简称ＰＦＳＣ）混凝剂。重点考察Ｆe/SiO2摩尔比对ＰＦＳＣ混凝效果的影响。结果表明：ＰＦＳＣ的混凝效果优于聚硅酸（ＰＳ）,且Ｆe/SiO2摩尔比对ＰＦＳＣ的混凝效果有较大的影响。确定Ｆe/SiO2摩尔比为１：１.５时,其混凝效果最佳,且用药量少而范围广。为制备高效的ＰＦＳＣ提供了优化条件。     

极谱配合物吸附波测定人发中硼

目的：探讨在ｐＨ４．４乙酸－乙酸钠－ＥＤＴＡ－铍试剂Ⅲ底液中用极谱配合物吸附波测定人发中硼。方法：极谱法。结果：线性范围为３．７×１０－７ｍｏｌ／Ｌ～１．８×１０－５ｍｏｌ／Ｌ,变异系数为５．５％～７．４％,样品加标回收率为９２．８％～９８．０％。结论：本法简便快速,灵敏度高,选择性好。     

Preparation and characterization of co-processed starch/MCC/chitin hydrophilic polymers onto magnesium silicate

It was aimed to investigate the compressibility, compactibility, powder flow and tablet disintegration of a new excipient comprising magnesium (Mg) silicate co-processed (5%–85% w/w) onto chitin, microcrystalline cellulose (MCC) and starch as the hydrophilic polymers of interest. Initially, the mechanism of tablet disintegration was studied by measuring water infiltration rate, moisture sorption, swelling capacity and hydration ability. Moreover, the powders compression behavior was carried out by applying Kawakita model of compression analysis in addition to porosity and radial tensile strength measurements. In vitro drug release of compacts made of 400?mg ibuprofen and 300?mg of the hydrophilic polymers containing 30% w/w Mg silicate co-precipitate was investigated in phosphate buffer (pH 7.8). This work demonstrated that the incorporation of Mg silicate to the hydrophilic polymers lead to the improvement of powder flowability, compactibility, stability (with regard to storage conditions), compacts crushing strength, and disintegration time in addition to faster drug release. The overall findings are practically advantageous in the context of finding a low cost and multifunctional co-processed excipient of natural origins.     

Global silicate weathering flux overestimated because of sediment–water cation exchange

Rivers carry the dissolved and solid products of silicate mineral weathering, a process that removes CO2 from the atmosphere and provides a key negative climate feedback over geological timescales. Here we show that, in some river systems, a reactive exchange pool on river suspended particulate matter, bonded weakly to mineral surfaces, increases the mobile cation flux by 50%. The chemistry of both river waters and the exchange pool demonstrates exchange equilibrium, confirmed by Sr isotopes. Global silicate weathering fluxes are calculated based on riverine dissolved sodium (Na⁺) from silicate minerals. The large exchange pool supplies Na⁺ of nonsilicate origin to the dissolved load, especially in catchments with widespread marine sediments, or where rocks have equilibrated with saline basement fluids. We quantify this by comparing the riverine sediment exchange pool and river water chemistry. In some basins, cation exchange could account for the majority of sodium in the river water, significantly reducing estimates of silicate weathering. At a global scale, we demonstrate that silicate weathering fluxes are overestimated by 12 to 28%. This overestimation is greatest in regions of high erosion and high sediment loads where the negative climate feedback has a maximum sensitivity to chemical weathering reactions. In the context of other recent findings that reduce the net CO2 consumption through chemical weathering, the magnitude of the continental silicate weathering fluxes and its implications for solid Earth CO2 degassing fluxes need to be further investigated.

For decades, silicate weathering has been postulated to provide the negative climate feedback on Earth that prevents a runaway greenhouse climate like on Venus (1). Silicate mineral dissolution with carbonic acid converts atmospheric CO2 into carbonate, and releases essential nutrients to the terrestrial and marine biosphere (2). There have been many attempts to quantify the silicate weathering flux (3), mostly assuming that riverine dissolved sodium (Na+) is derived only from silicate minerals and rock salt. Here we show that there is a major addition of nonsilicate Na+ to the critical zone from ancient seawater, weakly bonded to sedimentary rocks and supplied to waters via the cation exchange process. The implication is not only that the silicate weathering flux is overestimated at a global scale, but that this nonsilicate Na+ is most important in regions previously thought to have the highest silicate weathering fluxes (so called weathering-limited regions) and greatest climate sensitivity.Cation exchange is a rapid chemical reaction between cations in the dissolved phase and mineral surfaces, particularly clays (4). Major and trace cations such as calcium (Ca2+), magnesium (Mg2+), sodium (Na+), potassium (K+), and strontium (Sr2+) form the cation exchange pool, which balances negative charges on river-borne clay particle surfaces. This exchange takes place on interlayer sites, between the tetrahedral and octahedral layers, or on exposed surfaces (4). The importance of the cation exchange pool is well recognized in soils and aquifers (4, 5), has significant implications for enhanced weathering (6), and has been proposed as an important mechanism for buffering the composition of river waters (7–9). However, data on the riverine exchange pool are only available for two large river systems [Amazon and Ganges-Brahmaputra (10, 11)], despite its significance in providing a source of elements that are immediately bioavailable (12), and their potential for biasing the quantification of silicate weathering (9).It is increasingly recognized that rapidly reactive phases have a strong influence on the chemistry of river waters (13, 14). Cation exchange is a rapid reaction occurring continuously in soils, as riverine freshwaters evolve downstream interacting with particulate matter, and when they mix with seawater (15, 16). Important examples of cation exchange are the “swapping” of divalent cations Ca2+ and Mg2+ with Na+, in particular when there is a major change in water composition such as when fluvial clays reach the ocean,Caclay2++2Nawater+⇋2Naclay++Cawater2+.[1]As a result, marine sediments have an exchange pool that is dominated by Na+ (17). Subsequently, these marine sediments are uplifted and emplaced on the continents where Na+ in the exchange pool is released by cation exchange with Ca-rich fresh waters (9). This has major implications for estimates of silicate weathering fluxes and associated CO2 consumption, because they are calculated using the Na+ content of rivers (3). Cerling et al. (9) proposed that the Na+-rich exchange pool exerts an important control on natural waters, based on charge balance arguments from river water chemistry, but this hypothesis has never been rigorously tested (18) by determining the flux and composition of the exchange pool of rivers around the world.In this contribution, we present a large dataset of fluvial sediment cation exchange capacity (CEC) and composition in several of the world’s largest river basins. By comparing with the concomitant dissolved load chemistry, we demonstrate that 1) the exchange pool in river sediments is in equilibrium with the river water; 2) the fraction of mobile elements in the exchange pool relative to the dissolved pool can be significant, particularly in rapidly eroding, weathering-limited catchments; and 3) given reasonable inferences on the composition of old marine sedimentary rocks, modern-day silicate weathering has been overestimated and carbonate weathering has been underestimated. The results reduce the estimated magnitude of the silicate weathering flux, but increase the supply of base cations (e.g., Ca2+, which can be a limiting nutrient) to the biosphere, suggesting a greater role of organic carbon burial compared with silicate weathering for the long-term atmospheric CO2 sink.     

3D生物描绘孔结构可控钙磷硅基骨修复支架的生物力学性能

目的设计和制备新型钙磷硅基骨修复支架,研究其在不同外力作用下体外生物力学性能。方法以自固化磷酸钙骨水泥(calcium phosphate cement,CPC)、介孔硅酸钙(mesporous calcium silicate,MCS)为原料,通过3D生物描绘技术构建孔径分别为350、500μm的MCS/CPC复合支架。采用扫描电镜观察支架表面形貌;分别通过万能力学试验机和动态力学分析仪,考察具有不同孔道结构MCS/CPC支架的抗压力学性能和不同频率动态周期性载荷作用下的力学性能。结果通过3D生物描绘技术能够实现对钙磷硅基骨修复支架内部孔道结构的可控制备。孔径为350μm的MCS/CPC支架具有较高的抗压力学强度[(9.80±0.39)MPa]和抗压模量[(132.50±4.30)MPa];此外,载荷频率在1~100 Hz范围内,孔径为350μm的支架具有较高的储能模量。结论通过3D生物描绘技术制备的孔径为350μm的MCS/CPC复合支架不仅具有规则的连通孔道,还具有较高的抗压力学性能,能在动态载荷作用下保持结构稳定,适合作为一种新型的骨缺损修复材料。