Non-invasive Raman identification of crystalline and glassy phases in a 1781 Sèvres Royal Factory soft paste porcelain plate

A Raman study of a Sèvres soft paste (frit) porcelain plate allowed the identification of both the crystalline and amorphous phases. Cristobalite and pseudowollastonite gave main Raman signatures in the body where also tridymite, amorphous alkali silicate glass and lead arsenate apatite were detected. Na_0.4K_0.1Ca_0.5Pb₄(AsO₄)₃ lacunar apatite is identified as opacifier in blue and green overglaze enamel. Pb-Sb-reach pyrochlore (Naples Yellow) pigment was found in yellow and green overglaze enamels. The orange hue is obtained by superposing a hematite bearing red paint stroke over the yellow. These results are compared to those previously obtained by detailed OM, SEM, XRD and XRF analyses. Some of the phases identified by XRD (quartz, tridymite) are hardly detected by Raman and vice versa cristobalite was not found by XRD, most probably due to its low amount.     

Formation of strontium-yttrium germanium anionic lacunar apatite (Sr2+δY6.67+(2δ/3)[GeO4]6O2δ) as the intermediate phase of oxygen-rich yttrium-germanium apatite (Y9.333+ε[GeO4]6O2+3/2ε)

The formation of metastable strontium-yttrium(III) (hexakis) germanium(IV) lacunar apatite (P6₃/m, a=11.426 Å, c=8.224 Å and Z=2) was observed during the thermal treatment of SrCO₃, Y₂O₃, and GeO₂ powder precursors using the ceramic method in an oxygen atmosphere. The utilization of an oxygen atmosphere restricts the extensive reduction of GeO₂ and enables us to explain a new potential mechanism for the stabilization of lead-free lacunar apatites. This mechanism involves the use of electrons localized in a neighborhood of oxygen vacancies. Charged vacancies serve as active sites for the ionosorption of oxygen molecules and their subsequent transformation into lattice oxygen anions, which fill the vacancies at the X-site. The estimation of system thermodynamics shows that apatite undergoes a transformation to a more stable state at δ≥0.1, i.e., at the value that corresponds to the composition of prepared apatite. As the temperature and time of the thermal treatment increases, the process of incongruent melting leads to the formation of oxygen-rich yttrium-germanium apatite (YGAp, Y_9.333+ε[GeO₄]₆O_2+3/2ε) and strontium-yttrium-germanium glass. The YGAp phase is also formed during the annealing of lacunar apatite in an oxygen atmosphere.     

TiO2纳米管表面蛋白质-羟基磷灰石复合涂层及其结合强度

采用阳极氧化法在钛表面制备不同管径的TiO2纳米管,450℃热处理后经牛血清白蛋白(BSA)与钙磷的共沉积得到载有BSA的羟基磷灰石(HA)涂层.经检测发现,170nm管径的TiO2表面比100和50nm管径的表面具备更好的矿化能力,HA的形成能力随管径的增大而提高.大管径表面得到的涂层结合强度高于小管径的,可达16.95MPa.经过真空预矿化的试样,涂层结合强度明显高于未经过预矿化的试样,且HA涂层生长速率加快.BSA与磷酸钙在真空预矿化后共沉积到氧化钛纳米管表面,短时期内形成BSA-HA涂层,是在钛基生物材料表面制备生物活性涂层的有效方法.     

预处理对构建丝素蛋白纤维/磷灰石仿生骨修复材料的影响

利用氯化钙-乙醇-水(n(CaCl2):n(EtOH):n(H2O)=1:2:8)三元溶液对丝素蛋白纤维预处理,再采用交替浸渍法将其分别浸在钙溶液和磷溶液中交替浸渍、仿生矿化制备丝素蛋白纤维/磷灰石复合材料,采用SEM、FTIR、XRD和TGA等技术研究了不同预处理时间对丝素蛋白纤维微结构和构建丝素蛋白纤维/磷灰石的影...     

塔北中新生代构造演化与砂岩型铀成矿作用关系——来自磷灰石裂变径迹的证据

塔里木盆地北部萨瓦甫齐及塔里克地区4个样品的磷灰石裂变径迹测年以及热史反演结果显示,两个地区的隆升时代不同,其中萨瓦甫齐地区裂变径迹年龄为3.5～3.9 Ma,而塔里克地区的裂变径迹年龄为53～59 Ma.热史分析揭示出岩体至少记录了自晚白垩世以来的3个显著冷却阶段.同时,结合前人对塔北中新生代隆升剥蚀研究结果,重点对塔北地区中新生代构造隆升阶段进行了详细研究与划分,结合新疆中新生代砂岩型铀成矿年龄,提出了对塔北地区中新生代构造演化与砂岩型铀成矿作用的新认识.     

Spherulitic Growth of Apatite in a MgO─CaO─SiO2─P2O5 Glass

Differential thermal analysis, X-ray diffraction, scanning electron microscopy with energy dispersive X-ray analysis, and transmission electron microscopy were used to study the crystallization of a glass with a composition of 11.2 wt% MgO, 40.5 wt% CaO, 33.3 wt% SiO₂, and 15 wt% P₂O₅. A two-phase "composite," which was composed of apatite and an intermediate phase (H-phase), was formed under appropriate heat-treatment conditions. The spherulitic morphology of apatite phase transformed from "open sheaf" into ellipsoidal as samples were heated to a higher temperature. These phenomena were due to the intermediate H-phase becoming unstable at this temperature so that the retardation effect on the apatite dendritic growth disappeared.     

磷灰石型催化剂的合成及其催化性能研究

采用水热法制备了羟基磷灰石(HAp),用离子交换法将Cl、Cu2+先后交换到磷灰石上制得氯磷灰石ClAp和Cu(Ⅱ)ClAp,用NaOH和水合肼将Cu(Ⅱ)ClAp还原为Cu(Ⅰ)ClAp,利用XRD、IR、XPS和原子吸收等方法对催化剂进行了表征.将制得的催化剂Cu(Ⅰ)ClAp首次应用于甲醇液相氧化羰基化合成碳酸二甲酯的反应中,考察了Cu(Ⅱ)ClAp制备温度,NaOH和水合肼用量对催化剂性能的影响.在反应中,由于Cl是通过固态离子交换法代替了HAp结构中的OH,Cu+取代了磷灰石晶格中的部分Ca2+,在反应的过程中Cl与Cu+不易脱落,减少了催化剂对设备的腐蚀性,且作为多相催化剂,易于回收利用.     

Ultraviolet-accelerated formation of bone-like apatite on oxidized Ti-24Nb-4Zr-7.9Sn alloy

A novel method has been developed to rapidly deposit bone-like apatite with the assistance of ultraviolet （UV） light irradiation on the nanostructured titania in the simulated body fluid （SBF）. The process has three main steps： Ti-24Nb-4Zr-7.9Sn alloy was heated at 650℃ for 3 h, UV-light illumination in air for 4 h and soaking in the SBF for 3 d. A titania coating consisted of main rutile formed on the thermal oxidized Ti-24Nb-4Zr- 7.9Sn alloy. The UV not only converted the futile surface from hydrophilic to hydrophobic but also stimulated high surface activity. After 4 h UV illumination, the contents of Ti3＋ and hydroxyl groups on the oxidized sample were increased, while that of lattice O decreased. After 3 d of soaking in the SBF, a compact and uniform layer of carbonated hydroxyapatite （CHA） particles was formed on the UV-illuminated rutile surface whereas there was a few of HA to be viewed on the surface of as-oxidized Ti-24Nb-4Zr-7.9Sn alloy. Our study demonstrates a simple, fast and cost-effective technique for growing bone-like apatite on titanium alloys.     

含稀土磷灰石精矿酸浸试验研究

分别用硝酸、硫酸和盐酸对某复杂含稀土磷灰石精矿进行浸出试验。结果表明,硝酸浸出时,磷灰石中绝大部分磷进入溶液,而稀土则分散于浸出液和渣中;硫酸浸出时,稀土浸出率较低,磷浸出率较高,可控制合适的条件初步分离精矿中的磷和稀土;盐酸浸出时,磷和稀土的浸出率均较高,可以通过溶剂萃取的方法从溶液中分离磷和稀土。     

Apatite crystal in hard tissue of conodont fossils

The present study was aimed at examining the nature of apatite crystal in the tooth apparatus of a conodont fossil using transmission electron microscopy (TEM), scanning electron microscopy (SEM), laser Raman microprobe spectrometry and electron-probe microanalysis (EPMA). The hard tissue of the condont consisted of 2 layers and the organization varied with the size of the crystal. Higher magnification showed that the crystals were observed in the lattice of (100) and the central dark lines were not present. Ca, P, and F were detected in the crystal using EPMA. Our results indicate that the apatite crystal in conodont fossils is not hydroxyapatite but fluorapatite.