共查询到20条相似文献,搜索用时 0 毫秒
1.
Maria-Pau Ginebra Enrique Fernández Ferdinand C. M. Driessens Josep A. Planell 《Journal of the American Ceramic Society》1999,82(10):2808-2812
Some of the formulations of apatitic calcium phosphate bone cements are based on the hydrolysis of α-tricalcium phosphate (α-Ca3 (PO4 )2 , α-TCP). In this work the hydrolysis kinetics of α-TCP are studied, taking into account the particle-size distribution of the initial powder, to identify the mechanisms that control the reaction in its successive stages. The temporal evolution of the depth of reaction is calculated from the degree of reaction data, measured by X-ray diffractometry. A kinetic model is proposed, which suggests the existence of two rate-limiting mechanisms: initially, the surface area of the reactants and, subsequently, the diffusion through the hydrated layer formed around the reactants. For the specific particle size and preparation used, the controlling mechanism changeover takes place after 16 h of reaction. 相似文献
2.
A mechanistic model for the kinetics of hydrolysis of α-tricalcium phosphate (α–Ca3 (PO4 )2 or α-TCP) to hydroxyapatite (Ca10− x (HPO4 ) x (PO4 )6− x (OH)2− x or HAp) has been developed. The model is based on experimental hydrolysis rate data obtained using isothermal calorimetry. Analysis of the kinetic data according to the general kinetics models in terms of the fractional degree of reaction and time suggests the hydrolysis to be controlled by different rate-limiting mechanisms as reaction proceeds. Initially, the hydrolysis kinetics depend on the surface area of the anhydrous α-TCP. Subsequently, they change to a dependence on the rate of HAp product formation controlled by a nucleation and growth mechanism. The model predicts that HAp nuclei form at essentially one time and growth occurs in two dimensions, leading to a platelike morphology. The change in the reaction mechanism occurs at a fractional degree of hydrolysis, which does not change significantly with temperature in the range of 37°–56°C. 相似文献
3.
The formation of α-tricalcium phosphate from monobasic ammonium phosphate and calcium carbonate was investigated using a number of complementary techniques. Differential thermal analysis showed five distinct thermal events attributed to melting of the ammonium phosphate, decomposition of acidic calcium orthophosphate into an amorphous calcium metaphosphate, crystallization of β-calcium metaphosphate, crystallization of β-calcium pyrophosphate, and calcination of calcium carbonate. X-ray diffraction analyses as a function of temperature supported the evolution of these events and phases and also showed the formation of other intermediates, including an amorphous phase, apatite, lime, and β-tricalcium phosphate. Thermal gravimetric analysis (TGA) showed a large weight loss occurring between 150° and 250°C due to reaction between the acidic phosphate liquid and the calcium carbonate. This resulted in an amorphous intermediate with a Ca/P ratio between 0.5 and 1.0 from which both β-calcium metaphosphate and β-calcium pyrophosphate crystallized. Mass spectroscopy indicated that the ammonia and carbon dioxide were evolved in four different steps, while water was evolved in at least five steps. These decomposition steps correlated with those observed by TGA. Scanning electron microscopy indicated the formation of an intermediate phase that coated the calcium carbonate by 250°C. The proposed mechanistic reaction path to alpha-tricalcium phosphate involves the formation and consumption of the following sequence of intermediates: an acidic amorphous condensed phosphate; β-calcium metaphosphate and β-calcium pyrophosphate; lime, apatite, and β-tricalcium phosphate. 相似文献
4.
Uwe Gbureck Jake E. Barralet Lavinia Radu Hans G. Klinger Roger Thull 《Journal of the American Ceramic Society》2004,87(6):1126-1132
The mechanical and setting properties of calcium phosphate cements are considerably determined by the pretreatment of the constituents. In this report we show for the first time that prolonged high-energy ball milling of α-tricalcium phosphate (α-TCP) led to mechanically induced phase transformation from the crystalline to the amorphous state. The amorphous material demonstrated a high reactivity such that the time for substantially complete conversion of α-TCP to calcium-deficient hydroxyapatite in 2.5% Na2 HPO4 solution decreased from about 20 h (1 h of grinding in ethanol, 85% relative crystallinity) to 4–6 h for a material with a crystallinity of 8% (24 h of grinding). This reactivity could be attributed to an increased thermodynamic and kinetic solubility of the ground materials. Mechanically activated α-TCP cements were produced with compressive strengths of up to 80 MPa and setting times of 5–16 min. The effect of reactant preparation and cement mixing parameters on the physical and chemical properties of mechanically activated α-TCP cement was investigated. By comparing cements of similar porosity and degree of conversion it was demonstrated that apatite specific surface area has a strong influence on cement mechanical performance, which highlights the importance of this previously overlooked parameter in improving strength. 相似文献
5.
Three calcium α-SiAlON microstructures—namely, fine-grained, bimodal, and large elongated—were developed using powders of the same composition and then characterized. The evolution of grain size and morphology was determined to be a process of nucleation and growth that could be controlled with a two-step sintering technique. The extent of texture was identified in the as-hot-pressed materials as a function of sintering conditions. Samples with different microstructures exhibited different hardness and fracture toughness. The true hardness was derived from the intrinsic relation between applied loads and indent sizes. The effect of microstructure on hardness and fracture toughness was analyzed. 相似文献
6.
Hamed Arami Mahyar Mazloumi Razieh Khalifehzadeh Seyed Khatiboleslam Sadrnezhaad 《Journal of the American Ceramic Society》2007,90(10):3311-3313
Phase transformation of boehmite (AlOOH) nanostrips to α-Al2 O3 nanolaces was investigated under electron beam irradiation of a 200 keV transmission electron microscope (TEM). X-ray diffraction pattern showed that the powder consisted of boehmite phase before the electron exposure, while selected area electron diffraction patterns demonstrated the formation of stable α-alumina phase after bombardment with high-energy electrons. The in situ TEM observations revealed that the initial morphology remained unchanged while a lace-like mesostructure of α-alumina was developed. 相似文献
7.
Nelson S. Bell Seung-Beom Cho James H. Adair 《Journal of the American Ceramic Society》1998,81(6):1411-1420
The effects of seed particles and shear rate on the size and shape of α-Al2 O3 particles synthesized in glycothermal conditions are described. It is proposed that seed particles provide a low-energy, epitaxial surface in solution to lower the overall surface energy contribution to the nucleation barrier, thus increasing nucleation frequency and subsequently reducing the particle size of hexagonal α-Al2 O3 platelets or polyhedra, depending on synthesis conditions, in 1,4-butanediol solution. Seeds have a significant effect on the size of hexagonal α-Al2 O3 platelets in samples with high seed concentration. The particle size of α-Al2 O3 platelets decreases from 3 to 4 µm to 100 to 200 nm by increasing the number concentration of seeds. In the case of α-Fe2 O3 seeding, the effect of seeding on the size of α-Al2 O3 particles closely resembles the effects obtained with α-Al2 O3 seeding. Regardless of seed concentration, high stirring rate promotes the formation of hexagonal platelets with high aspect ratio, whereas medium and low stirring rates promote the formation of elongated platelets and polyhedra with 14 faces, respectively. 相似文献
8.
Byung-Dong Hahn Dong-Soo Park Jong-Jin Choi Jungho Ryu Woon-Ha Yoon Byoung-Kuk Lee Hyoun-Ee Kim 《Journal of the American Ceramic Society》2009,92(4):793-799
Four calcium phosphate ceramic coatings, the less soluble hydroxyapatite (HA) coating, the more soluble β-tricalcium phosphate (β-TCP) coating, and two biphasic calcium phosphate (BCP) coatings with HA/β-TCP ratios of 70/30 and 30/70 were fabricated by spraying each corresponding powder onto a titanium substrate at room temperature (RT) in a vacuum, in order to investigate the effect of the HA/β-TCP ratio on the dissolution behavior and the cellular responses of the coating. No secondary phases, except for HA and β-TCP, were observed for the coatings in the X-ray diffraction results. The coating compositions were almost the same as those of the starting powders because the coating was conducted at RT. Microscopic examination of the coatings revealed crack-free and dense microstructures. The BCP coatings exhibited dissolution rates intermediate between those of the pure HA and β-TCP coatings. The dissolution rate of the coatings was largely dependent on their HA/β-TCP ratio. The cell proliferation and differentiation results indicated that the cellular responses of the coatings were not proportional to their dissolution rates. The 3HA–7TCP (HA/β-TCP ratio of 30/70) coating exhibited an optimal dissolution rate for excellent biological performance. 相似文献
9.
Raúl García Carrodeguas Antonio H. De Aza Xavier Turrillas Pilar Pena Salvador De Aza 《Journal of the American Ceramic Society》2008,91(4):1281-1286
The transformation β→α in Mg-substituted Ca3 (PO4 )2 was studied. The results obtained showed that, contrary to common belief, there is, in the system Mg3 (PO4 )2 –Ca3 (PO4 )2 , a binary phase field where β+α-Ca3 (PO4 )2 solid solutions coexist. This binary field lies between the single-phase fields of β- and α-Ca3 (PO4 )2 solid solution in the Ca3 (PO4 )2 -rich zone of the mentioned system. In the light of the results and the Palatnik–Landau's Contact Rule of Phase Regions, a corrected phase equilibrium diagram has been proposed. The practical implications of these findings with regard to the synthesis of pure α- and β- Mg-substituted Ca3 (PO4 )2 powders and to the sintering of related bioceramics with improved mechanical properties are pointed out. 相似文献
10.
Toshihiro Kasuga Masayuki Nogami Mitsuo Niinomi 《Journal of the American Ceramic Society》2003,86(6):1031-1033
A bioactive calcium phosphate invert glass-ceramic containing β-Ca3 (PO4 )2 crystals could be joined strongly with a Ti–29Nb–13Ta–4.6Zr alloy consisting of a β-titanium phase by heating the metal on which the mother glass powders with a composition 60CaO·30P2 O5 ·7Na2 O·3TiO2 (mol%) were placed, at 800°C for 1 h in air; the tensile joining strength was estimated to be ∼26 MPa on average. A compositionally gradient layer was developed on the metallic substrate during the heating. When the metal with glass powders on it was heated at 850°C in air, the phosphate glassy phase flowed viscously, permeating the oxide layer formed around the surface of the metal, which was thicker than that formed by heating at 800°C; a compositionally gradient layer was not developed, and a strong joining was not realized. The joining between the glass-ceramic and the metal is suggested to be controlled by viscous flow of the glassy phase in the glass-ceramic and by reaction of the glassy phase with the oxide phase formed around the surface layer of the metal. 相似文献
11.
The final stages of the β→α polymorphic phase transformation in conventionally sintered and hot-pressed SiC were studied by optical and transmission electron microscopy. The interface between the α and β regions of partially transformed grains invariably contains thin α lamellae adjacent and parallel to coherent β twins (or β stacking faults). These planar defects serve as nucleation sites for the transformation, with growth of α occurring by the motion of partial dislocations nucleated at the intersection of coherent and incoherent twin boundaries. Various structural phenomena in SiC, including faulting, mi-crosyntaxy, and long-period polytypism, are discussed in terms of this transformation mechanism. 相似文献
12.
Thin foils of polycrystalline α-alumina were reacted with a potassium-rich vapor at ≤900°C. Potassium β-alumina formed along α-alumina grain boundaries and protruded from holes in the foils. Conventional transmission electron microscopy was used to analyze the α-alumina/β-alumina phase boundary for possible orientation relations. 相似文献
13.
Gaoxiang Chen Wanwan Li Bingxia Zhao Kang Sun 《Journal of the American Ceramic Society》2009,92(4):945-948
Calcium polyphosphate (CPP) was added to hydroxyapatite (HA) to develop a novel biphasic calcium phosphate (BCP). The effects of varying CPP dosage on the sintering property, the mechanical strength, and the phase compositions of HA were investigated. Results showed that CPP reacted with HA and produced β-calcium phosphate (β-TCP) and H2 O and that an excessive dosage of CPP (>10 wt%) obtained a novel BCP of β-TCP/amorphous-CPP, while a lesser dosage of CPP (<10 wt%) obtained a traditional BCP (HA/β-TCP). The porous β-TCP/amorphous-CPP scaffolds (porosity of 66.7%, pore diameter of 150–450 μm, and compressive strength of 6.70±1.5 MPa) were fabricated and their in vitro degradation results showed a significant improvement of degradation with the addition of CPP. 相似文献
14.
The hydrolysis of α-tricalcium phosphate (α-TCP) in a simulated body fluid (SBF) at 37°C was investigated. The hydration rate was found to be slower in SBF than that in deionized water. The concentration of ions in SBF was monitored by ICP. The hydrolysis product, which was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infra red, and X-ray photoelectron spectroscopy, was determined to be carbonate-containing, calcium-deficient hydroxyapatite (CO3 −CDHAp) with Mg2+ , Na+ , and Cl− impurities similar to the biological apatite. An amorphous layer on the α-TCP surface was found to be the precursor of the apatite phase, which may either form crystalline apatite or may decompose back to α-TCP at a lower temperature. 相似文献
15.
Gleb N. Yushin Z. Goknur Cambaz Yury Gogotsi Kateryna L. Vyshnyakova Lyudmila N. Pereselentseva 《Journal of the American Ceramic Society》2008,91(1):83-87
We report the synthesis of microscopic α-SiC ribbons (belts) on the surface of a graphite rod at 1800°–1900°C by a carbothermal process. The width of the ribbons produced ranged from 500 nm to 5 μm and the aspect ratio was up to 400. The ribbon thickness ranged from 50 to 800 nm. Their growth mechanism was explained by accelerated growth along the twin boundary. SiC whiskers grew on the rod along with the ribbons. Frequently, ribbons were growing from the tip of a whisker or whiskers were growing from the edge of a ribbon. SiC ribbons may find applications in high-temperature sensors, photo-electronic devices, or robust cantilevers in micro (or nano) electro mechanical systems. Alternatively, they can be used as reinforcements in composite materials, conferring anisotropic mechanical properties, such as unidirectional flexibility, to the composite. 相似文献
16.
Alfred Zürz Ivan Odler Felicia Thiemann Katarina Berghöfer 《Journal of the American Ceramic Society》1991,74(5):1117-1124
Flue gas gypsum may be converted to α-hemihydrate by suspending the starting material in inorganic salt solutions of high concentration or in diluted sulfuric acid and maintaining the suspension at boiling, or near boiling temperature for a period of time. The crystal morphology of the produced α-hemihydrate gypsum and, thus, its quality depend significantly on the composition of the liquid phase. Additions of different carbonic acids may improve the quality of the product distinctly. Under optimal working conditions the quality of the formed α-hemihydrate gypsum is similar to that of a material produced in an autoclave. 相似文献
17.
Rong-Jun Xie Naoto Hirosaki Mamoru Mitomo Yoshinobu Yamamoto Takayuki Suehiro Naoki Ohashi 《Journal of the American Ceramic Society》2004,87(7):1368-1370
Cerium-doped α-SiAlON (M x Si12−( m + n ) Al m + n O n N16– n ) materials have been prepared by gas-pressure sintering and post-hot-isostatic-press (HIP) annealing, using four powder mixtures of α-Si3 N4 , AlN, and either (i) CeO2 , (ii) CeO2 + Y-α-SiAlON seed, (iii) CeO2 + Y2 O3 , or (iv) CeO2 + CaO. Cerium-containing CeAl(Si6– z Al z )(N10– z O z ) (JEM) phase, rather than Ce-α-SiAlON phase, forms in the sample with only CeO2 , whereas a single-phase α-SiAlON generates in samples with dual doping (CeO2 + Y2 O3 and CeO2 + CaO). On ultraviolet-light excitation, JEM gives one broad emission band with maximum at 465 nm and a shoulder at 498 nm; α-SiAlON shows an intense and broad emission band that peaks at 500 nm. The unusual long-wavelength emissions in JEM and α-SiAlON are due to increases in the nephelauxetic effect and the ligand-field splitting of the 5 d band, because the coordination of Ce3+ in JEM and α-SiAlON is nitrogen enriched. 相似文献
18.
Mamoru Mitomo Yoh-ichiro Sato Nobuo Ayuzawa Isamu Yashima 《Journal of the American Ceramic Society》1991,74(4):856-858
Plasma etching of β-Si3 N4 , α-sialon/β-Si3 N4 and α-sialon ceramics were performed with hydrogen glow plasma at 600°C for 10 h. The preferential etching of β-Si3 N4 grains was observed. The etching rate of α-sialon grains and of the grain-boundary glassy phase was distinctly lower than that of β-Si3 N4 grains. The size, shape, and distribution of β-Si3 N4 grains in the α-sialon/β-Si3 N4 composite ceramics were revealed by the present method. 相似文献
19.
α-Alumina-diamond composites have been developed by normal hot-pressing procedures using a conventional pressure of 32 MPa and 1250°C. Heretofore this type of composite has required a pressure of 6 GPa (60 kbar) to prevent the transformation of diamond to graphite. The mechanical properties, density, and thermal expansion coefficient of these composites have been characterized. The fracture toughness ( K Ic ) of alumina shows a considerable increase with the addition of diamond particles. Diamond additions tend to decrease the thermal expansion coefficient of these composites. The composite properties are dependent on the volume fraction of diamond particles. 相似文献
20.
Monika Backhaus-Ricoult Serge Hagège Aurélie Peyrot Patrick Moreau 《Journal of the American Ceramic Society》1994,77(2):423-430
(Al,Cr)2 O3 single crystals and polycrystals were internally reduced at 1873 K in an Al/Al2 O3 buffer for periods of time ranging from 1 to 100 h. The growth kinetics of the reduction scale were measured. The microstructure of the reduction scale was investigated by SEM and TEM. As a result of the reduction, two types of discrete chromium precipitates developed inside the alumina matrix (inside the single crystal or the polycrystalline grains), each one being characterized by a particular morphology (needle or spheroid) and a low-energy orientation relationship with respect to the alumina matrix. In addition, larger precipitates without special orientation relationship developed along the grain boundaries and at the triple junctions of the polycrystais. In the first part of this paper, the precipitate morphology and size are described in terms of the crystallography of the interface between the two crystal structures in relation to the reduction mechanism. In the second part, the global reduction scale growth is analyzed in terms of point defect fluxes across the reduction scale. 相似文献