Phase transformations during processing and in vitro degradation of porous calcium polyphosphates

A 2-Step sinter/anneal treatment has been reported previously for forming porous CPP as biodegradable bone substitutes [9]. During the 2-Step annealing treatment, the heat treatment used strongly affected the rate of CPP degradation in vitro. In the present study, x-ray diffraction and ³¹P solid state nuclear magnetic resonance were used to determine the phases that formed using different heat treating processes. The effect of in vitro degradation (in PBS at 37 °C, pH 7.1 or 4.5) was also studied. During CPP preparation, β-CPP and γ-CPP were identified in powders formed from a calcium monobasic monohydrate precursor after an initial calcining treatment (10 h at 500 °C). Melting of this CPP powder (at 1100 °C), quenching and grinding formed amorphous CPP powders. Annealing powders at 585 °C (Step-1) resulted in rapid sintering to form amorphous porous CPP. Continued annealing to 650 °C resulted in crystallization to form a multi-phase structure of β-CPP primarily plus lesser amounts of α-CPP, calcium ultra-phosphates and retained amorphous CPP. Annealing above 720 °C and up to 950 °C transformed this to β-CPP phase. In vitro degradation of the 585 °C (Step-1 only) and 650 °C Step-2 annealed multi-phase samples occurred significantly faster than the β-CPP samples formed by Step-2 annealing at or above 720 °C. This faster degradation was attributable to preferential degradation of thermodynamically less stable phases that formed in samples annealed at 650 °C (i.e. α-phase, ultra-phosphate and amorphous CPP). Degradation in lower pH solutions significantly increased degradation rates of the 585 and 650 °C annealed samples but had no significant effect on the β-CPP samples.     

Development of bioresorbable Mg-substituted tricalcium phosphate scaffolds for bone tissue engineering

Mg-substituted tricalcium phosphate (β-TCMP) samples were prepared either by the solid-state reaction of CaHPO₄ (DCPA), CaCO₃ and MgO powder at 1000 °C, or by a two-step process: wet precipitation of a precursor and further calcination of the precursor. The transition temperature from β-Tricalcium Phosphate (TCP) to α-TCP increases with the increase of Mg²⁺ content in β-TCMP samples. A β-TCMP sample with 3 mol% Mg²⁺ has a β-TCP to α-TCP transition temperature above 1300 °C, which was then used to fabricate various β-TCMP scaffolds in this study. Interconnected porous β-TCMP ceramics, with pore size > 100 μm and relative density of ~ 81% to 84%, were developed by a replication method using polyurethane foam as a template; micropores were also found in the scaffold struts. β-TCMP ceramics with a porous structure in the center and a dense shell-like structure outside, mimicking human bone, were fabricated by a molding method. Dense β-TCMP ceramic rings were also produced with an average compressive strength of 129 MPa.     

“Fabrication of arbitrarily shaped carbonate apatite foam based on the interlocking process of dicalcium hydrogen phosphate dihydrate”

Carbonate apatite (CO₃Ap) foam with an interconnected porous structure is highly attractive as a scaffold for bone replacement. In this study, arbitrarily shaped CO₃Ap foam was formed from α-tricalcium phosphate (α-TCP) foam granules via a two-step process involving treatment with acidic calcium phosphate solution followed by hydrothermal treatment with NaHCO₃. The treatment with acidic calcium phosphate solution, which is key to fabricating arbitrarily shaped CO₃Ap foam, enables dicalcium hydrogen phosphate dihydrate (DCPD) crystals to form on the α-TCP foam granules. The generated DCPD crystals cause the α-TCP granules to interlock with each other, inducing an α-TCP/DCPD foam. The interlocking structure containing DCPD crystals can survive hydrothermal treatment with NaHCO₃. The arbitrarily shaped CO₃Ap foam was fabricated from the α-TCP/DCPD foam via hydrothermal treatment at 200?°C for 24?h in the presence of a large amount of NaHCO₃.     

Synthesis and sintered properties evaluation of calcium phosphate ceramics

The present paper describes calcination of calcium phosphate ceramics (hydroxyapatite, HA) at 200, 400, 600, 800 and 1000 °C to observe the phase change using X-ray diffraction. HA phase was found to be stable up to 600 °C and later got dissociated into other non-stoichiometric phases like tricalcium phosphate (Ca₃(PO₄)₂ [TCP]), calcium pyrophosphate (Ca₂P₂O₇ [CPP]) and calcium hydrogen phosphate (CaHPO₄ [CHP]). TCP was found to be the major phase above 1000 °C. FTIR spectra showed the presence of various PO₄³⁻ and OH⁻ groups present in the powder. Powders compacted and sintered at 900, 1000, 1100 and 1200 °C showed an increase in density from 2.11 to 2.95 g/cm³ while biaxial flexural strength (BFS) was found to be higher (48.7 MPa) when the samples were sintered at 1100 °C and it decreased with further increase in sintering temperature.     

Microstructural study of a titanium-based biocomposite produced by the powder metallurgy process with TiH2 and nanometric β-TCP powders

A titanium-based composite with Ca-P phases was prepared in situ by powder metallurgy processing with TiH₂ and nanometric β-TCP powders. Crystal phases of the as-fabricated composite are found to be α-Ti, CaTiO₃ and Ti_xP_y phase(s). The Ti_xP_y and CaTiO₃ phases resulted from the reaction between titanium and β-TCP at about 1135 °C. The composite presented a mean compressive strength of 635 MPa and a lower contact angle than pure titanium.     

Reactive sintering and particle morphology control of β″-alumina-based water purification filters

This paper reports on the preparation of porous membranes consisting of plate-like β″-alumina grains and the evaluation for microfiltration properties. Porous β″-alumina-based ceramics were prepared by the solid-state reactive sintering of Na₂CO₃ and α-Al₂O₃ at 1100–1300 °C. To study the effect of impurities in the starting powder mixtures, LiF-doped membranes were also prepared. As for the water filtration test, the turbidity before and after the vacuum filtration was measured using sintered porous membranes. To simulate bacteria-contaminated water, a suspension of a commercial boehmite powder (D ₅₀ = 0.7 μm) in distilled water was used. The non-doped samples sintered at 1200 °C were composed of β″-alumina (84 wt%) and β-alumina (16 wt%) grains and showed a good microfiltration performance; the turbidities before and after filtration were 894.4 NTU and 1.46 NTU, respectively.     

Biodegradable β-tricalcium phosphate cement with anti-washout property based on chelate-setting mechanism of inositol phosphate

Novel biodegradable β-tricalcium phosphate (β-TCP) cements with anti-washout properties were created on the basis of chelate-setting mechanism of inositol phosphate (IP6) using β-TCP powders. The β-TCP powders were ball-milled using ZrO₂ beads for 0–6 h in the IP6 solutions with concentrations from 0 to 10,000 ppm. The chelate-setting β-TCP cement with anti-washout property was successfully fabricated by mixing the β-TCP powder ball-milled in 3,000 ppm IP6 solution for 3 h and 2.5 mass% Na₂HPO₄ solution, and compressive strength of the cement was 13.4 ± 0.8 MPa. An in vivo study revealed that the above cement was directly in contact with host and newly formed bones without fibrous tissue layers, and was resorbed by osteoclast-like cells on the surface of the cement. The chelate-setting β-TCP cement with anti-washout property is promising for application as a novel injectable artificial bone with both biodegradability and osteoconductivity.     

Mechano-chemical synthesis and characterization of nanostructured β-TCP powder

Tricalcium phosphates (Ca₃(PO₄)₂: β-TCP) are known for their biodegradable characteristics and are essential components of natural bone. Unlike hydroxyapatite (HAp), β-TCP is not the stable phase at room temperature. It is normally obtained by solid-state synthesis at temperatures in excess of 600 °C where calcium deficient hydroxyapatite transforms to β-TCP. Low temperature approaches for synthesizing this phase could offer unique opportunities with regards to controlling the microstructure and its degradable characteristics. In this study, the possibility of synthesizing β-TCP directly by a mechano-chemical route has been investigated. The starting materials were mechanically milled for various time periods. The resultant calcium phosphate powder has been analyzed using XRD, FTIR, DTA/TGA and SEM.     

Preparation and characterization of precursor powders for yttria-doped tetragonal zirconia polycrystals (Y-TZP) and Y-TZP-Al2O3 composites

Precursor powders for the preparation of tetragonal 2.5 mol% Y₂O₃-ZrO₂ containing 0 to 30 wt% Al₂O₃ were made by coprecipitation. The behaviour of this powder during calcination from room temperature to 1200° C was studied using differential thermal analysis. X-ray diffraction and transmission electron microscopy methods, and measurements of surface area. The uncalcined powder was essentially amorphous. On heating alumina-free powder, zirconia crystallized at 485° C: for increasing alumina content, zirconia crystallized from an amorphous aluminous matrix at increasing temperatures (850° C for 20 wt% Al₂O₃), while the crystallite size decreased and the surface area of the powder increased. The zirconia first crystallized as cubic, but transformed to the tetragonal form near 1100° C. The alumina crystallized as corundum at 1200° C. No monoclinic zirconia could be detected when calcined aluminous material was cooled to room temperature. The sintering behaviour of the calcined powder is discussed.     

Fabrication and characterization of porous calcium polyphosphate scaffolds

Porous calcium polyphosphate (CPP) scaffolds with different polymerization degree and crystalline phases were prepared, and then analyzed by scanning electron microscopy (SEM), Thermmogravimetry (TG) and X-ray diffraction (XRD). Number average polymerization degree was calculated by analyzing the calcining process of raw material Ca(H₂PO₄)₂, as a polycondensation reaction. Amorphous CPP were prepared by the quenching from the melt of Ca(H₂PO₄)₂ after calcining, and CPP with different polymerization degree was prepared by controlling the calcining time. Meanwhile, CPP with the same polymerization degree was prepared to amorphous or different crystalline phases CPP which was made from crystallization of amorphous CPP. In vitro degradation studies using 0.1 M of tris-buffered solution were performed to assess the effect of polymerization degree or crystalline phases on mechanical properties and weight loss of the samples. With the increase of polymerization degree, the weight loss during the degradation decreased, contrarily the strength of CPP increased. The degradation velocity of amorphous CPP, α-CPP, β-CPP and γ-CPP with the same polymerization degree decreased in turn at the same period. The full weight loss period of CPP can be controlled between 17 days and more than 1 year. The results of this study suggest that CPP ceramics have potential applications for bone tissue engineering.     

Hydrothermal synthesis of composites of well-crystallized hydroxyapatite and poly(vinyl alcohol) hydrogel

Composites of hydroxyapatite (HAp) and poly(vinyl alcohol) (PVA) hydrogel were fabricated by the hydrothermal treatment of calcium phosphate powder. Alpha-tricalcium phosphate (α-TCP) or beta-tricalcium phosphate (β-TCP) powder was dispersed in PVA hydrogel and exposed to water vapor at 120 °C, 140 °C or 160 °C for 6 h. Low crystallinity HAp was formed in specimens prepared from α-TCP and PVA hydrogel prior to hydrothermal treatment, which was caused by hydrolysis of α-TCP. This allowed specimen shape to be retained after hydrothermal treatment. β-TCP showed less reactivity in forming HAp in the PVA hydrogel, which led to the formation of large rod-shaped crystals approximately 15 μm in length. Specimens from β-TCP and PVA were too soft to retain their shape after hydrothermal treatment. HAp with controlled morphology was prepared using different types of tricalcium phosphate precursor. The application of α-TCP allowed the in situ fabrication of HAp/PVA composites.     

Thermal decomposition of β-FeOOH

β-FeOOH particles were prepared by a forced hydrolysis of the 0.1 M FeCl₃ + 5·10⁻³ M HCl solution, whereas sulfated β-FeOOH particles were prepared by forced hydrolysis of the 0.1 M FeCl₃ solution containing 5·10⁻³ M quinine hydrogen sulfate (QHS). β-FeOOH particles, as well as sulfated β-FeOOH particles, were thermally treated up to 600 °C. The samples were characterized using DTA, XRD, FT-IR and TEM. β-FeOOH particles showed a cigar-type morphology, whereas bundles of β-FeOOH needles were obtained in the presence of QHS. Heating of β-FeOOH particles at 300 °C and above yielded α-Fe₂O₃ particles. Specific adsorption of sulfate groups showed a strong effect on the thermal decomposition of β-FeOOH particles. Upon heating of sulfated particles between 300 and 500 °C the formation of an amorphous phase and a small fraction of α-Fe₂O₃ were observed. Needle-like morphology of amorphous particles in these samples was preserved. At 600 °C, α-Fe₂O₃ particles were obtained; however, they were much smaller than those obtained by heating a pure β-FeOOH.     

A study on the phase transformation of the nanosized hydroxyapatite synthesized by hydrolysis using in situ high temperature X-ray diffraction

The biodegradable hydroxyapatite (HA) was synthesized by hydrolysis and characterized using high temperature X-ray diffraction (HT-XRD), differential thermal analysis and thermogravimetry (DTA/TG), and scanning electron microscopy (SEM). The in situ phase transformation of the HA synthesized from CaHPO₄·2H₂O (DCPD) and CaCO₃ with a Ca / P = 1.5 in 2.5 M NaOH_(aq) at 75 °C for 1 h was investigated by HT-XRD between 25 and 1500 °C. The HA was crystallized at 600 °C and maintained as the major phase until 1400 °C. The HA steadily transformed to the α-tricalcium phosphate (α-TCP) which became the major phosphate phase at 1500 °C. At 700 °C, the minor CaO phase appeared and vanished at 1300 °C. The Na⁺ impurity from the hydrolysis process was responsible for the formation of the NaCaPO₄ phase, which appeared above 800 °C and disappeared at 1200 °C.     

Development of controlled strength-loss resorbable beta-tricalcium phosphate bioceramic structures

Controlling the strength-loss rate during biodegradation is a bottleneck in developing viable resorbable ceramic implants. Resorbable beta-tricalcium phosphate (β-TCP) bioceramic is known for its excellent biocompatibility. However, it exhibits poor sinterability and poor flexural strength. Here, we improved sintering behavior and biaxial flexural strength of β-TCP bioceramic without altering its biocompatibility by introducing multi-oxide sintering additives, in small quantities. These additives could also tailor the rate of resorption and hardness deterioration of β-TCP. A range of additives were prepared and introduced into β-TCP powder. Resultant powders were uniaxially pressed and sintered at 1250 °C, in air. Considerable improvement in densification (up to 33%) and biaxial flexural strength (up to 43%) were achieved. X-ray powder diffraction (XRD) analysis confirmed that the additives didn't alter the phase purity. In vitro cytotoxicity and biocompatibility analyses were performed using a prostate cancer cell-line. Results showed that the doped and pure β-TCP structures were non-toxic and biocompatible.     

Phase transformation and sintering behavior of Ca2P2O7

The phase transformation and sintering behaviors of Ca₂P₂O₇ with different phase composition were investigated by using X-ray powder diffraction (XRD), dilatometery and scan electron microscopy techniques in this paper. It is found that although α-Ca₂P₂O₇ (high-temperature form) could be kept during its cooling process, it is metastable and retransformed into β-Ca₂P₂O₇ (low-temperature form) at about 950 °C during its reheating process. This reversible phase transformation was discussed from the point view of polyhedral distortion. The sample from β-Ca₂P₂O₇ calcined at 1000 °C/2 h densifies much faster than that from α-Ca₂P₂O₇ and α+β mixture, and bulk density as high as 98% TD can be obtained as it is sintered at 1150 °C. A dense α-Ca₂P₂O₇ free of micro-crack could not be obtained whatever from the powder of β-Ca₂P₂O₇ or α-Ca₂P₂O₇ or α+β mixture. Such different sintering behavior was explained in related to the reversible phase transformation between α- and β-Ca₂P₂O₇.     

A novel wet polymeric precipitation synthesis method for monophasic β-TCP

β-Tricalcium phosphate (β-Ca₃(PO₄)₂, β-TCP) powders were synthesized using wet polymeric precipitation method for the first time to our best knowledge. The results of X-ray diffraction analysis showed the formation of almost single a Ca-deficient hydroxyapatite (CDHA) phase of a poor crystallinity already at room temperature. With continuously increasing the calcination temperature up to 800 °C the crystalline β-TCP was obtained as the main phase. It was demonstrated that infrared spectroscopy is very effective method to characterize the formation of β-Ca₃(PO₄)₂. The SEM results showed that β-Ca₃(PO₄)₂ solids were homogeneous having a small particle size distribution. The β-TCP powders consisted of spherical particles varying in size from 100 to 300 nm. Fabricated β-TCP specimens were placed to the bones of the rats and maintained for 1–2 months. The histological properties of these samples will be also investigated.     

Phase development and sintering behaviour of biphasic HA-TCP calcium phosphate materials prepared from hydroxyapatite and bioactive glass

The composites of hydroxyapatite (HA) with 2.5 and 5 wt% of a double oxide (50 mol% CaO and 50 mol% P₂O₅) glass were prepared using the conventional powder mixing and sintering method. The addition of the glass significantly enhanced the decomposition process of HA into alpha tricalcium phosphate (α-TCP) for bodies sintered at 1,300 and 1,350 °C and β-TCP phases for the ones sintered at 1,200, 1,250 and 1,300 °C. Microstructural characteristics, phase development and thermal behaviour were studied by SEM, XRD and STA. The effects of TCP phase content and phase transformation from β-TCP to α-TCP on the sintering are discussed. The characterizations revealed considerable content of TCP in the form of large semi-islands due to important reactions between the fine HA and the glass mixed powders.     

Mechanical properties and in vitro cellular behavior of zinc-containing nano-bioactive glass doped biphasic calcium phosphate bone substitutes

In the present study, different amounts (0.5–5 wt%) of a sol gel-derived zinc-containing nano-bioactive glass (NBG-Zn) powder were added to biphasic calcium phosphate (BCP). The mixtures were sintered at 1,100–1,300 °C and physical characteristics, mechanical properties, phase composition and morphology of them were studied. The samples were also soaked in human blood plasma for 15 days to evaluate variations in their surface morphologies. Rat calvarium-derived osteoblastic cells were seeded on tops of various samples and cell adhesion, proliferation, and alkaline phosphatase activity were evaluated at different culturing periods. The maximum bending strength (62 MPa) was obtained for BCP containing 0.5 wt% NBG-Zn at temperature 1,200 °C. This value was approximately 80 % higher than that of pure BCP. The bending strength failed when both sintering temperature and amount of added NBG-Zn increased. At 1,100 °C, NBG-Zn additive did not change the phase composition of BCP. At temperatures 1,200 and 1,300 °C, both alpha-tricalcium calcium phosphate (α-TCP) and beta-tricalcium phosphate (β-TCP and) phases were detected. However, adding higher amount of NBG-Zn to BCP resulted in elevation of β-TCP at 1,200 °C and progression of α-TCP at 1,300 °C. Based on the microscopic observations, adding 0.5 wt% NBG-Zn to BCP led to disappearance of grain boundaries, reduction of micropores and formation of a monolithic microstructure. No calcium phosphate precipitation was observed on sample surfaces after soaking in blood plasma, but some pores were produced by phase dissolution. The size and volume of these pores were directly proportional to NBG-Zn content. Based on the cell studies, both BCP and NBG-Zn-added BCP samples supported attachment and proliferation of osteoblasts, but higher alkaline phosphatase enzyme was synthesized within the cells cultured on NBG-Zn-added BCP. Overall, biphasic calcium phosphate materials with improved mechanical and biological properties can be produced by using small quantity of zinc-containing bioactive glass particles.     

Mechanochemical synthesis of zinc-apatitic calcium phosphate and the controlled zinc release for bone tissue engineering

Abstract

In this study, in order to control zinc (Zn)-release from calcium phosphate (CaP), the crystalline forms of CaP-containing Zn were modified by wet ball milling and/or heat treatment. The CaP (CaO:CaHPO₄:ZnO?=?7:20:3, molar ratio) was ground in a ball mill with the addition of purified water, and the ground products were heated to 400?°C and 800?°C. The physicochemical properties of these ground products were measured by powder X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy and energy-dispersive X-ray spectroscopy. Zn release characteristics from the samples were evaluated using a dissolution tester. The results of XRD and IR suggested that the structures of the starting materials were destroyed after 2.5?h of grinding, and new apatite-like amorphous solid containing Zn was generated. The Zn-release from the ground products was markedly suppressed after 2.5?h of grinding.     

Preparation and characterization of hydroxyapatite synthesized from oyster shell powders

The ready availability and the low cost of oyster shells, which is composed predominantly of calcium carbonate with rare impurities, along with natural wastes are attractive features for converting the biological material into hydroxyapatite (HA) powders for biomedical applications. The HA powder was synthesized using oyster shell powders and dicalcium phosphate dihydrate (CaHPO₄·2H₂O, DCPD) through ball milling and subsequently heat treatment. The HA was initiated through sintering the 1-h milled sample at 1000 °C for 1 h, while pure HA phase is formed after sintering the 10-h milled sample. The as-prepared samples, obtained after 5 or 10 h of milling and then heat-treating at 1000 °C for 1 h, contain the phase of β-tricalcium phosphate (β-TCP). Moreover, the result of FTIR analysis showed that the as-prepared HA sample is A- and B-type carbonate-containing calcium phosphates. The as-synthesize HA powder containing trace elements Mg and Sr exhibited good crystallinity (96.3%) and high phase-purity.