Microstructural evolution in bone china

Abstract

Phase and microstructural evolution in model bone china bodies was determined by XRD and electron microscopy of quenched samples fired for 3 h at 600–1500°C. Unfired but shaped bone china comprised bone ash and clay agglomerates (≤70 μm) in a matrix of smaller (from submicron to 10 μm) mixed clay, feldspar, and bone ash particles. The unfired microstructure and subsequent phase evolution is believed to be strongly dependent on the extent of prior mixing. On firing, the clay component dehydroxylated to metakaolin at ～550°C. Metastable sanidine formed from decomposition of the feldspar component above 600°C and dissolved at 1100°C. The bone ash com ponent decomposed into β-TCP and lime (and/or Ca²⁺ and O^2- ions) beginning at ～800°C. CaO from the bone ash reacts with the clay decomposition products forming liquid and anorthite at ～900°C. Liquid formation is due to reaction of CaO with feldspar and clay relict grains and is discussed in terms of the CaO–P₂O₅–Al₂O₃ ternary phase diagram. Above 1200°C pure bone ash relicts contained small (5–10 μm) β-TCP crystals, CaO penetrated clay relicts contained anorthite, and mixed clay–bone–feldspar regions contained both anorthite and larger (>50 μm) β-TCP crystals in calcium aluminosilicate glass. The major phase in the clay relicts was anorthite although a few elongated (～100 nm) needles resembling mullite in composition and morphology also crystallised in samples fired to 1100°C and grew to ～30 μm in length at 1300°C.     

Crystallization Kinetics and Dielectric Properties of a Low‐Fire CaO–Al2O3–SiO2 Glass + Alumina System

The crystallization kinetics and dielectric properties of a low‐dielectric, low‐temperature, cofirable ceramic system comprised of CaO–Al₂O₃–SiO₂ (CAS) glass and alumina have been investigated. Crystalline phases including pseudowollastonite (CaSiO₃), anorthite (CaAl₂Si₂O₈) and cristobalite (SiO₂) are formed during firing the pure CAS glass. The crystallization kinetics of both pseudowollastonite and cristobalite exhibit Avrami‐like behavior, and the results show apparent activation energies close to that of diffusion of alkali ions in the glass. With added alumina content greater than a critical value, the above crystalline phases are completely suppressed but more anorthite is formed. This result is attributed to the rapid dissolution kinetics of alumina into the CAS glass. As the degree of crystallization increases with firing time, the dielectric loss of the composite decreases significantly, however, with dielectric constant remaining relatively unchanged.     

Phase analysis and microstructure evolution of a bone china body modified with scrap addition

Properties of a commercial bone china body containing varying amount of fired scrap of same material (0-12%) was studied and attempt was made to correlate the same with respect to phase analysis and microstructural evolution. Despite numerous studies on bone china by several authors, knowledge is still insufficient about the chemical reactions taking place among the various raw materials leading to very narrow firing range. In commercial production of bone china wares, loss during biscuit firing is significantly high. In this study attempt has been made to utilize a portion of the fired scrap in a commercial bone china composition and the effect of the same on the formation of the constituent phases has been tried to correlate with the properties developed. Phase analysis of the matured specimens revealed that there was gradual decrease in β-Tri calcium phosphate (β-TCP) content while increase in glassy phase was observed with progressive incorporation of scrap. Scrap incorporated body resulted in early maturity of the specimens as well as development of a very dense microstructure. Presence of scrap did not alter the anorthite phase content. The microstructure consisted of distinct regions of agglomerated spheroidal β-TCP and lath shaped anorthite crystallites in a heterogeneous calcium aluminosilicate glassy matrix.     

3D printing of bone substitute implants using calcium phosphate and bioactive glasses

Customized implants for bone replacement are a great help for a surgeon to remodel maxillofacial or craniofacial defects in an esthetical way, and to significantly reduce operation times. The hypothesis of this study was that a composite of β-tricalcium phosphate (β-TCP) and a bioactive glass similar to the 45S5 Henchglass^® is suitable to manufacture customized implants via 3D-printing process. The composite was chosen because of the bioresorption properties of the β-TCP, its capability to react as bone cement, and because of the adjustability of the bioactive glass from inert to bioresorbable. Customized implants were manufactured using the 3D-printing technique. The four point bending strength of the printed specimens was 14.9 MPa after sintering. XRD analysis revealed the occurrence of two other phases, CaNaPO₄ and CaSiO₃, both biocompatible and with the potential of biodegradation. We conclude that it is possible to print tailored bone substitute implants using a bioactive TCP/glass composite. The glass is not involved as reactive substance in the printing process. This offers the opportunity to alter the glass composition and therefore to vary the composition of the implant.     

Interactions between an ABS type leadless glaze and a biscuit fired bone china body during glost firing. Part I: preparation of experimental phases

In this paper, part of an extended study, crystalline phases of a biscuit fired bone china body, namely anorthite and beta-tricalcium phosphate (β-TCP), were produced experimentally to be used in subsequent interface studies for simulation of the interactions during glost firing at different temperatures between an ABS type commercial leadless glaze and the individual phases originally present in the body. The research was undertaken based on the premise that bone china has been a product providing the greatest challenge in moving to a totally leadless glaze. High bulk density and low apparent porosity values were achieved from both the anorthite and β-TCP samples through the suitable heat treatments. The microstructural and chemical characteristics of the experimental phases were studied using X-ray diffraction (XRD), scanning (SEM), and transmission (TEM) electron microscopy techniques in combination with EDS analysis. The morphological and chemical similarity of the phases to those originally present in a biscuit fired bone china body was clearly demonstrated. This similarity supports the choice of the experimental material for the interface studies undertaken with these phases in the second part of the study.     

Preparation of glass–ceramic glazes for fast firing applications by CaF2 substitution with B2O3 in the CaO–CaF2–Al2O3–SiO2 system

The present work aims to obtain glass–ceramic glazes for floor tile applications. In this regard, CaF₂ was gradually replaced by B₂O₃ in the glass compositions belonging to the CaO–CaF₂–Al₂O₃–SiO₂ system. This substitution led to a noticeable decrease of crystallization peak temperatures and to an alteration of the crystallization trend. In the B₂O₃ bearing glazes, anorthite and gehlenite were identified as the major and minor crystalline phases, respectively. During concurrent crystallization and sintering based on the fast firing program, glass–ceramic glazes containing 9 weight parts of fluorine and 12 weight parts of boron oxide showed the most desirable sinterability. The optimized glass–ceramic glazes offered acceptable micro-hardness, whiteness and thermal expansion behavior after fast firing heat treatment.     

Improvement of mechanical properties of macroporous β-tricalcium phosphate bioceramic scaffolds with uniform and interconnected pore structures

The biocompatible and degradable macroporous bioceramic scaffolds with high mechanical properties and interconnected porous structures play an important role in hard tissue regeneration and bone tissue engineering applications. In this study, the improvement of mechanical properties of macroporous β-tricalcium phosphate [β-Ca₃(PO₄)₂, β-TCP] bioceramic scaffolds with uniform macropore size and interconnected pores were fabricated by impregnation of the synthesized β-TCP nano-powder slurry into polymeric frames. The microstructures, mechanical properties and in vitro degradation of the fabricated samples were investigated. For a comparison, β-TCP scaffolds were also fabricated from commercial micro-size powders under the same conditions. The resultant scaffolds showed porosities ∼65% with uniform macropore size ranging from 400 to 550 μm and interconnected pore size ∼100 μm. The compressive strength of the samples fabricated from nano-size powders reached 10.87 MPa, which was almost twice as high as those fabricated from commercial micro-size powders, and was comparable to the high-end value (2–10 MPa) of human cancellous bone. Furthermore, the degradation of the β-TCP bioceramics fabricated from nano-size powders was apparently lower than those fabricated from commercial micro-size powders, suggesting the possible control of the degradation of the scaffolds by regulating initial powder size. Regarding the excellent mechanical properties and porous structures, the obtained macroporous β-TCP bioceramic scaffolds can be used in hard tissue regeneration and bone tissue engineering applications.     

Influence of different chemical treatments on the surface of Al2O3/ZrO2 nanocomposites during biomimetic coating

The objective of this study is to evaluate the influence of different chemical surface treatments (H₃PO₄, HNO₃, and NaOH) in the formation of calcium phosphate phases on the surface of Al₂O₃/ZrO₂ (5 vol%) nanocomposite. For this purpose, Al₂O₃/ZrO₂ samples were shaped, calcined at 400 °C, sintered at 1500 °C, subjected to different chemical treatments, and biomimetically coated from 14 to 21 days. Surface characterization was performed by scanning electron microscopy, atomic force microscopy, confocal microscopy, X-ray diffraction, and infrared spectroscopy. It was observed that the preliminary chemical treatment favored the formation of particular calcium phosphate phases of interest, such as α-TCP (alpha-tricalcium phosphate), β-TCP (beta-tricalcium phosphate), and HA (hydroxyapatite). The differences among the percentages of the phases formed affected the homogeneity of calcium phosphate distribution within the nanocomposites as well as the roughness of the formed layer, effectively contributing to adhesion, proliferation, and desired cell biofixation on bone implant.     

Crystallisation in SiO2 –Al 2 O 3 –ZnO– TiO 2 glass: process mechanism

Abstract

Devitrification of a frit based on the oxide system SiO₂–Al₂O₃–ZnO, using bulk glass as well as powdered glass samples with different particle sizes was studied. The following major crystalline phases were identified: gahnite (ZnAl₂O₄ ), α-quartz, cristobalite, and a solid solution exhibiting the β-quartz structure, which contained SiO₂ , Al₂O₃ , and ZnO and whose composition varied with temperature. Depending on the size of the glass (frit) samples, gahnite was found to devitrify directly from the initial glassy phase or from the solid solution with a β-quartz structure, which appeared to act as a precursor.     

Interactions between an ABS type leadless glaze and a biscuit fired bone china body during glost firing. Part II: investigation of interactions

This part of the study involves the investigation of the interactions between an ABS type commercial leadless glaze and a biscuit fired bone china body during glost firing at different temperatures using XRD and SEM techniques. The aim was to obtain detailed and systematic information about the morphological and chemical characteristics of the resultant phases formed at the interfaces. Separate examination of the interactions between the glaze and the experimental crystalline phases of the body prepared earlier, namely anorthite and β-TCP, were also carried out in an effort to show their susceptibility to react with the glaze independently. As a result, the presence of a range of interaction layers with distinctly different morphological and chemical characteristics was successfully demonstrated. It was proposed that β-TCP was the major contributor to the overall interactions by reacting with CaO from the glaze in the presence of water vapour and forming hydroxyapatite crystals at the glaze-body interfaces. Although the exact origin for the development of water vapour in the molten glaze could not determined, several potential sources were suggested.     

Effects of nitrogen and fluorine on crystallisation of Ca-Si-Al-O-N-F glasses

The effect of nitrogen and fluorine substitution on the crystallisation of a new generation of oxyfluoronitride glasses in the Ca-Si-Al-O-N-F system has been studied. Glasses were nucleated for 5 h at the nucleation temperature of Tg + 50 °C and crystallised for 10 h at the maximum crystallisation temperature (900-1050 °C depending on the glass composition) determined from differential thermal analysis. For the oxide glass, crystallisation results in formation of wollastonite (CaSiO₃), gehlenite (Ca₂Al₂SiO₇) and anorthite (CaAl₂Si₂O₈) along with a small amount of residual glass. For crystallisation of oxyfluoride glasses (0 equiv.% N), when fluorine content increases, cuspidine (Ca₄Si₂O₇F₂) is the major crystalline phase at the expense of gehlenite while in oxyfluoronitride glasses containing 20 equiv.% N, gehlenite is always the dominant crystalline phase at different fluorine contents. At constant fluorine content (5 equiv.%), an increase in nitrogen content favours the formation of gehlenite rather than anorthite or wollastonite suggesting that this phase may be able to accommodate N into its crystal structure. While a small amount of nitrogen substitution for oxygen can be assumed in the gehlenite structure, the residual glass in the glass-ceramic is expected to be very N-rich. In terms of properties, hardness is shown to be more sensitive to changes in microstructure, phase morphology and crystal size compared with elastic modulus which is related to the amounts of constituent phases present.     

Microstructure evolution of CMAS glass below melting temperature and its potential influence on thermal barrier coatings

CaO–MgO–Al₂O₃–SiO₂ (CMAS) deposition significantly degrades the performance of thermal barrier coatings (TBCs). In this study, the microstructure evolution of CMAS glass at temperatures below its melting point was investigated in order to study the potential influence of temperature on the applicability of CMAS glass in TBCs. The CMAS glass fabricated in this study had a melting point of 1240 °C, became opaque, and underwent self-crystallization when the temperature reached 1000 °C. After heat treatment at 1050 °C, diopside and anorthite phases precipitated from the glass; at a higher temperature (1150 °C), diopside, anorthite, and wollastonite were formed as the self-crystallization products. An increase in the dwelling time resulted in the transformation of diopside to wollastonite and anorthite. At 1250 °C, all products formed a eutectic microstructure and melted. The results indicate that even at low temperatures, CMAS glass underwent microstructure evolution, which could influence the coating surface and stress distribution when deposited on TBCs.     

Microstructural design of ceramics for bone regeneration

Dense tricalcium phosphate, Ca₃(PO₄)₂ (TCP) – diopside, CaMg(SiO₃)₂, composites present better mechanical properties than single phase TCP. In this work, it is investigated whether the mechanical behaviour improvement by diopside is maintained in porous scaffolds.The processing parameters to obtain cylinders with ≈ 50% of aligned pores of elliptical cross sections with major axis up to 100 μm by freeze casting and sintering were established. Pore channels were introduced in the green specimens by laser ablation. After sintering, the diameter of the cross sections of the channels was ≈ 700 μm. The ceramic composite microstructure was constituted by a substructure of small diopside particles (2 −7 μm) and dense β-TCP zones of larger dimensions (up to 40 μm). Strength values, determined by diametral compression (DCDT) (≈ 2.5–4 MPa) are in the range of strength of cancellous bone. Diopside presents transgranular fracture, hindering crack propagation from the β-TCP areas and the pores, as occurred in the dense materials.     

Influence of precursor characteristics on properties of porous calcium phosphate-titanium dioxide composite bioceramics

Highly porous (macroporosity 76–90%) bioceramics containing interconnected pores (>100 μm) with compressive strength between 0.54 and 0.32 MPa were prepared by polyurethane foam replica method. Effect of following variables, i.e., calcium phosphate/anatase ratio (30/70, 50/50, 70/30 wt%) in the ceramic slurry, anatase particle size (15 nm, 180 nm), Ca/P molar ratio of calcium phosphate (1.67 and 1.50 for hydroxyapatite and apatitic-tricalcium phosphate (ap-TCP), respectively), on the bioceramics properties was investigated. Bioceramics prepared using anatase and hydroxyapatite consisted of three high-temperature crystalline phases - β-tricalcium phosphate (β-TCP), rutile and CaTiO₃. In case of anatase and ap-TCP, two phases (β-TCP and rutile) were obtained. Interaction of anatase and hydroxyapatite during sintering caused formation of CaTiO₃ at β-TCP and rutile grain boundaries thus contributing to a denser grain packing. Combination of ap-TCP and nanosized anatase facilitated decrease of grain sizes. Correlation was found between compressive strength and calcium phosphate precursor in the ceramic slurry.     

Glass-ceramic proppants from sinter-crystallisation of waste-derived glasses

ABSTRACT

The present investigation aims at evidencing the feasibility of glass-ceramic spheres by sinter-crystallisation of fine glass powders (<100?μm), in turn obtained by the melting of inorganic waste, such as red mud from Bayer process or municipal solid waste incinerator fly ash, or low-cost minerals. While dense and highly crystallised monoliths may be achieved by sintering pressed glass powders just at the glass crystallisation temperature (T_C), applying fast heating and short holding times, dense glass-ceramic beads could be obtained only by firing well above T_c (T_c?+?100°C). An increased sintering temperature was applied in order to enhance the viscous flow and promote the spheroidisation of powder clusters, previously formed by casting fine powders on a rotating drum. The high degree of crystallinity and the uniform microstructure were found to contribute positively to the mechanical properties (compressive strength exceeding 120?MPa, for beads with a diameter of 1?mm, approximately).     

Degradation mechanism of high alumina refractory bricks by reaction with deposits in a rotary kiln for fluxed iron ore pellets production

The formed deposits wear out of refractory wall linings in the rotary kiln and may cause production disturbances. This study describes the chemical composition and mineralogical phase components at the deposit/refractory interface in the rotary kiln for fluxed iron ore pellets production. The main phases of refractory bricks are corundum and mullite, while the deposits mainly contain hematite and silicates. The main phases in the deposit/refractory brick contact zone are hematite, anorthite (CaAl₂Si₂O₈), mullite, corundum, and silicates. Moreover, the hematite phases in the deposit/brick interface averagely contain 6.98 wt% Al and 1.38 wt% Ti. The silicates in the contact zone contain higher aluminium content and lower iron content than the silicates in the deposits. Finally, the thermodynamic analysis indicates that the main phases in the deposits can react with the refractory to form Al₂Fe₂O₆, CaAl₂Si₂O₈, feldspar, and liquid phases lead to the degradation of bricks in the kiln during the iron ore pellets production.     

Bioactive glass-ceramics prepared by powder sintering and crystallization of polyphosphate glass containing strontium

Melt-quenching method was employed for obtaining a glass-ceramic with the following composition 42P₂O₅·40CaO·5SrO·10Na₂O·3TiO₂ (mol%) glass. The crystallization and sintering behavior of glass have been studied by using DTA, HSM, XRD, FTIR and SEM methods. It was determined that the surface and volume crystallization mechanisms act simultaneously in bulk glass samples. The comparison of DTA and HSM data revealed that the sintering and crystallization processes are independent. The sintered calcium phosphate glass-ceramic which contained bioactive β-Ca₃(PO₄)₂ and β-Ca₂P₂O₇ phases was successfully prepared. It was determined that during crystallization the primary phase in the precipitate was β-Ca(PO₃)_2. Other phases appearing in the resulting glass-ceramic were: α-Ca₂P₂O₇, γ-Ca₂P₂O₇, Ca₄P₆O₁₉ and CaHPO₄(H₂O)₂. Crystalline phases containing Sr and Ti were not detected. SEM analysis of the glass-ceramic microstructure revealed surface crystallization of glass particles and plate-like morphology of crystal growth. The result of the in vitro bioactivity showed that no apatite layer was formed on the surface of the as-prepared glass-ceramic samples after immersion in the simulated body fluid (SBF).     

Extraction and characterization of hydroxyapatite-based materials from grey triggerfish skin and black scabbardfish bones

The conversion of food industry by-products to compounds with high added value is nowadays a significant topic, for social, environmental, and economic reasons. In this paper, calcium phosphate-based materials were obtained from black scabbardfish (Aphanopus carbo) bones and grey triggerfish (Balistes capriscus) skin, which are two of the most abundant fish by-products of Madeira Island. Different calcination temperatures between 400 and 1000°C were employed. Materials obtained from calcination of bones of black scabbard fish were composed by homogeneous mixtures of hydroxyapatite (Ca₁₀(PO4)₆(OH)₂, HAp) and β-tricalcium phosphate (β-Ca₃(PO₄)₂, β-TCP). Because of the high biocompatibility of HAp and the good resorbability of β-TCP, these natural biphasic materials could be very relevant in the field of biomaterials, as bone grafts. The ratio between HAp and β-TCP in the biphasic compound was dependent on the calcination temperature. Differently, the material obtained from skin of grey triggerfish contained HAp as the main phase, together with small amounts of other mineral phases, such as halite and rhenanite, which are known to enhance osteogenesis when used as bone substitutes. In both cases, the increase of calcination temperature led to an increase in the particles size with a consequent decrease in their specific surface area. These results demonstrate that from the fish by-products of the most consumed fishes in Madeira Island it is possible to obtain bioceramic materials with tunable composition and particle morphology, which could be promising materials for the biomedical field.     

Influence of Co3O4, Fe2O3 and SiC on microstructure and properties of glass foam from waste cathode ray tube display panel (CRT)

Abstract

In the present study, the effect of temperature and oxidising agents such as Fe₂O₃ and Co₃O₄ on physical and mechanical properties of glass foam is investigated. The glass foam is made of panel glass from dismantled cathode ray tubes and SiC as a foaming agent. In the process, powdered waste glass (mean particle size below 63 μm) in addition to 4 wt-% SiC powder (mean particle size below 45 μm) are combined with Fe₂O₃ and Co₃O₄ (0·4, 0·8 and 1·2 wt-%) have been sintered at 950 and 1050°C. The glass foamed containing 1·2 wt-% Co₃O₄ has good physical properties, with porosity more than 80% and bending strength more than 1·57±0·12 MPa. However, by adding different amounts of Fe₂O₃ in comparison with samples without iron oxide, little changes in porosity and strength are obtained.     

Mg2+, Sr2+, Ag+, and Cu2+ co-doped β-tricalcium phosphate: Improved thermal stability and mechanical and biological properties

β-tricalcium phosphate (β-TCP, β-Ca₃(PO₄)₂) is an attractive biomaterial for bone repair applications. However, its sintering and mechanical properties are limited by a problematic phase transition to α-TCP. Cationic doping of β-TCP is able to postpone the formation of α-TCP allowing higher sintering temperatures and better mechanical properties. The co-doping of β-TCP with Mg²⁺ and Sr²⁺ has already been studied in detail, but the addition of antibacterial cations (Ag⁺ and Cu²⁺) on the Mg–Sr β-TCP co-doped composition remains unexplored. Thus, two co-doped β-TCP compositions were realized by aqueous precipitation technique without any secondary phase and compared with undoped β-TCP: Mg–Sr (2.0–2.0 mol%) and Mg–Sr–Ag–Cu (2.0–2.0–0.1–0.1 mol%). Differential thermal analysis and dilatometry analyses showed a slight decrease of the β-TCP → α-TCP phase transition temperature for the Mg–Sr–Ag–Cu (2.0–2.0–0.1–0.1% mol) composition as compared to the Mg–Sr (2.0–2.0 mol%). However, both exhibited much higher transition temperatures than undoped β-TCP. The addition of Ag⁺ and Cu²⁺ slightly reduces the grain size after sintering compared to the Mg–Sr (2.0–2.0 mol%) and the undoped compositions. The co-doped compositions also exhibited improved mechanical properties, specifically a higher Vickers hardness and elastic modulus. Finally, cell proliferation assays showed that the presence of dopants, even Ag⁺ and Cu²⁺, does not affect the survival and proliferation of cells. Thus, the use of Mg²⁺, Sr²⁺, Ag⁺, and Cu²⁺ co-doped β-TCP could be very promising for biomedical applications due to the improvements of these dopants on the thermal stability and mechanical and biological properties.