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The paper is devoted to the creation and investigation of the new cement materials formed the new beryite phase (MgHPO4·3H2O) during the setting processes. A cement liquid based on sodium phosphate solution with addition of sodium hyaluronate polymer is used to increase the viscosity and the surface tension in the system and to increase the cohesion of the final product. The effect of cement liquids based on sodium hyaluronate with various concentrations are studied to estimate the phase composition, setting time, pH value, microstructure, injectivity, and strength properties of cement materials. [ABSTRACT FROM AUTHOR]

Due to the positive effects of magnesium substitution on the mechanical properties and the degradation rate of the clinically well-established calcium phosphate cements (CPCs), calcium magnesium phosphate cements (CMPCs) are increasingly being researched as bone substitutes. A post-treatment alters the materials’ physical properties and chemical composition, reinforcing the structure and modifying the degradation rate. By alkaline post-treatment with diammonium hydrogen phosphate (DAHP, (NH4)2HPO4), the precipitation product struvite is formed, while post-treatment with an acidic phosphate solution [e.g., phosphoric acid (PA, H3PO4)] results in precipitation of newberyite and brushite. However, little research has yet been conducted on newberyite as a bone substitute and PA post-treatment of CMPCs has not been described in the accessible literature so far. Therefore, in the present study, the influence of an alkaline (DAHP) or acid (PA) post-treatment on the biocompatibility, degradation behavior, and osseointegration of cylindrical scaffolds (h = 5.1 mm, Ø = 4.2 mm) produced from the ceramic cement powder Ca0.75Mg2.25(PO4)2 by the advantageous manufacturing technique of three-dimensional (3D) powder printing was investigated in vivo. Scaffolds of the material groups Mg225d (DAHP post-treatment) and Mg225p (PA post-treatment) were implanted into the cancellous part of the lateral femoral condyles in rabbits. They were evaluated up to 24 weeks by regular clinical, X-ray, micro-computed tomographic (µCT), and histological examinations as well as scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) analysis and compared with tricalcium phosphate (TCP). All materials showed excellent biocompatibility and rapid osseointegration. While TCP degraded only slightly, the CMPCs showed almost complete degradation. Mg225d demonstrated significantly faster loss of form and demarcability from surrounding bone, scaffold volume reduction, and significantly greater degradation on the side towards the bone marrow than to the cortex than Mg225p. Simultaneously, numerous bone trabeculae have grown into the implantation site. While these were mostly located on the side towards the cortex in Mg225d, they were more evenly distributed in Mg225p and showed almost the same structural characteristics as physiological bone after 24 weeks in Mg225p. Based on these results, the acid post-treated 3D powder-printed Mg225p is a promising degradable bone substitute that should be further investigated.

Calcium phosphate cements are of great interest for researchers and their applications in medical practice expanded. Nevertheless, they have a number of drawbacks including the insufficient level of mechanical properties and low degradation rate. Struvite (MgNH4PO4) -based cements, which grew in popularity in recent years, despite their neutral pH and acceptable mechanical performance, release undesirable NH4+ ions during their resorption. This issue could be avoided by replacement of ammonia ions in the cement liquid with sodium, however, such cements have a pH values of 9–10, leading to cytotoxicity.Thus, the main goal of this investigation is to optimize the composition of cements to achieve the combination of desirable properties: neutral pH, sufficient mechanical properties, and the absence of cytotoxicity, applying Na2HPO4-based cement liquid. For this purpose, cement powders precursors in the CaO–MgO–P2O5 system were synthesized by one-pot process in a wide composition range, and their properties were investigated.The optimal performance was observed for the cements with (Ca + Mg)/P ratio of 1.67, which are characterized by newberyite phase formation during setting reaction, pH values close to 7, sufficient compressive strength up to 22 ± 3 MPa (for 20 mol.% of Mg), dense microstructure and adequate matrix properties of the surface. This set of features make those materials promising candidates for medical applications.

Calcium magnesium phosphate cements (CMPCs) are promising bone substitutes and experience great interest in research. Therefore, in-vivo degradation behavior, osseointegration and biocompatibility of three-dimensional (3D) powder-printed CMPC scaffolds were investigated in the present study. The materials Mg225 (Ca0.75Mg2.25(PO4)2) and Mg225d (Mg225 treated with diammonium hydrogen phosphate (DAHP)) were implanted as cylindrical scaffolds (h = 5 mm, Ø = 3.8 mm) in both lateral femoral condyles in rabbits and compared with tricalcium phosphate (TCP). Treatment with DAHP results in the precipitation of struvite, thus reducing pore size and overall porosity and increasing pressure stability. Over 6 weeks, the scaffolds were evaluated clinically, radiologically, with Micro-Computed Tomography (µCT) and histological examinations. All scaffolds showed excellent biocompatibility. X-ray and in-vivo µCT examinations showed a volume decrease and increasing osseointegration over time. Structure loss and volume decrease were most evident in Mg225. Histologically, all scaffolds degraded centripetally and were completely traversed by new bone, in which the remaining scaffold material was embedded. While after 6 weeks, Mg225d and TCP were still visible as a network, only individual particles of Mg225 were present. Based on these results, Mg225 and Mg225d appear to be promising bone substitutes for various loading situations that should be investigated further.

Stanfieldite, natural Ca-Mg-phosphate, is a typical constituent of phosphate-phosphide assemblages in pallasite and mesosiderite meteorites. The synthetic analogue of stanfieldite is used as a crystal matrix of luminophores and frequently encountered in phosphate bioceramics. However, the crystal structure of natural stanfieldite has never been reported in detail, and the data available so far relate to its synthetic counterpart. We herein provide the results of a study of stanfieldite from the Brahin meteorite (main group pallasite). The empirical formula of the mineral is Ca8.04Mg9.25Fe0.72Mn0.07P11.97O48. Its crystal structure has been solved and refined to R1 = 0.034. Stanfieldite from Brahin is monoclinic, C2/c, a 22.7973(4), b 9.9833(2), c 17.0522(3) Å, β 99.954(2)°, V 3822.5(1)Å3. The general formula of the mineral can be expressed as Ca7M2Mg7(PO4)12 (Z = 4), where the M = Ca, Mg, Fe2+. Stanfieldite from Brahin and a majority of other meteorites correspond to a composition with an intermediate Ca≈Mg occupancy of the M5A site, leading to the overall formula ~Ca7(CaMg)Mg9(PO4)12 ≡ Ca4Mg5(PO4)6. The mineral from the Lunar sample “rusty rock” 66095 approaches the M = Mg end member, Ca7Mg2Mg9(PO4)12. In lieu of any supporting analytical data, there is no evidence that the phosphor base with the formula Ca3Mg3(PO4)4 does exist.

The addition of P to a basalt causes a change in the environment of Fe. At low P contents iron is located in the glass structure and the Fe 3+ /Fe 2+ ratio is about 80/20. Further addition of P causes a collapse of the glass structure related to a phase separation that triggers the crystallization of a more reduced iron-containing phosphate phase with a crystalline structure similar to that of stanfieldite, and Mössbauer parameters similar to those of the alluaudite group, together with the formation of a Fe 3+ -Fe 2+ disordered phase. Their presence increases the viscosity of the melt. [ABSTRACT FROM AUTHOR]

The influence of Mg(II) on phosphorous recovery as hydroxyapatite (Hap) from alkaline phosphate concentrates using desalinated industrial brines as the calcium source in a batch reactor was evaluated. Two synthetic brines with Mg/Ca molar ratios of 2.2 and 3.3 were continuously fed to reach a Ca/P molar ratio of ∼1.67 to promote Hap formation under different constant pH values (8, 9.5, 10.5, 11.5 and 12). For both brines, inhibition of Hap precipitation and formation of the amorphous mineral phases of Ca-, Mg- and Ca/Mg-phosphates were observed at pH > 9.5. Mg(II) severely inhibited phosphate precipitation, allowing the formation of amorphous calcium phosphate from meta-stable clusters due to Mg(II) incorporation into Ca-phosphate. For the Mg/Ca (3.3) brine, a more soluble Mg-phosphate mineral (cattiite) was formed at pH 11.5. Thermal treatment of the amorphous solids to increase crystallinity confirmed the presence of Hap and chlorapatite as Ca-phosphate, stanfieldite as Ca–Mg-phosphate and farringtonite as Mg-phosphate. In the experiments at pH 8, the formation of stable nanometer-sized pre-nucleation clusters promoted nucleation inhibition, even in supersaturated solutions, and no solids were recovered after filtration. Although sulfate was involved in some of the precipitation reactions, its role in the inhibition of Hap formation is not clearly elucidated. [ABSTRACT FROM AUTHOR]

Due to the positive effects of magnesium substitution on the mechanical properties and the degradation rate of the clinically well-established calcium phosphate cements (CPCs), calcium magnesium phosphate cements (CMPCs) are increasingly being researched as bone substitutes. A post-treatment alters the materials' physical properties and chemical composition, reinforcing the structure and modifying the degradation rate. By alkaline post-treatment with diammonium hydrogen phosphate (DAHP, (NH 4 ) 2 HPO 4 ), the precipitation product struvite is formed, while post-treatment with an acidic phosphate solution [e.g., phosphoric acid (PA, H 3 PO 4 )] results in precipitation of newberyite and brushite. However, little research has yet been conducted on newberyite as a bone substitute and PA post-treatment of CMPCs has not been described in the accessible literature so far. Therefore, in the present study, the influence of an alkaline (DAHP) or acid (PA) post-treatment on the biocompatibility, degradation behavior, and osseointegration of cylindrical scaffolds ( h = 5.1 mm, Ø = 4.2 mm) produced from the ceramic cement powder Ca 0.75 Mg 2.25 (PO 4 ) 2 by the advantageous manufacturing technique of three-dimensional (3D) powder printing was investigated in vivo . Scaffolds of the material groups Mg225d (DAHP post-treatment) and Mg225p (PA post-treatment) were implanted into the cancellous part of the lateral femoral condyles in rabbits. They were evaluated up to 24 weeks by regular clinical, X-ray, micro-computed tomographic (µCT), and histological examinations as well as scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX) analysis and compared with tricalcium phosphate (TCP). All materials showed excellent biocompatibility and rapid osseointegration. While TCP degraded only slightly, the CMPCs showed almost complete degradation. Mg225d demonstrated significantly faster loss of form and demarcability from surrounding bone, scaffold volume reduction, and significantly greater degradation on the side towards the bone marrow than to the cortex than Mg225p. Simultaneously, numerous bone trabeculae have grown into the implantation site. While these were mostly located on the side towards the cortex in Mg225d, they were more evenly distributed in Mg225p and showed almost the same structural characteristics as physiological bone after 24 weeks in Mg225p. Based on these results, the acid post-treated 3D powder-printed Mg225p is a promising degradable bone substitute that should be further investigated., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Kowalewicz, Waselau, Feichtner, Schmitt, Brückner, Vorndran and Meyer-Lindenberg.)

Pallasites are stony‑iron meteorites consisting mainly of olivine and Fe-Ni metal with a formation history that remains widely debated. Despite their simple mineralogy, relatively limited data are available on their geochemistry and the lateral elemental distribution in individual pallasite olivine crystals. In this work, laser ablation - inductively coupled plasma - mass spectrometry (LA-ICP-MS) was used for the elemental analysis of both pallasite olivine and phosphate phases, including 2D trace element mapping of olivine crystals. While the results obtained are in good agreement with literature values, important differences are observed for Al and Ni concentrations compared with bulk analytical methods. The element distribution maps reveal complex zoning in pallasite olivine, which can be explained based on i) diffusion gradients formed during olivine cooling, ii) the crystal chemistry of element substitution due to charge-balancing, and iii) inherited features of olivine before the metal-olivine mixing. Oscillatory zoning in an olivine crystal from Imilac provides strong evidence for the olivine not being a restite of partial melting, but rather having crystallized from a melt. Concentrations of Cr and Al are correlated both within single olivine crystals and between olivine crystals of different pallasites, forming a 1:1 linear trend. This likely results from a spinel-type charge-balancing substitution mechanism in pallasite olivine. Additionally, principle component analysis of laterally resolved multi-element concentration data of pallasite olivine provides an independent measure of the genetic relationships between the different main group pallasites within their parent body (−ies). Rare earth element (REE) contents of pallasite phosphate grains range from concentrations typically measured for chondritic or primitive achondrite-like phosphates to more (light) REE-depleted signatures, revealing the overall primitive nature of the melts from which the phosphate minerals crystallized. Phosphate in pallasites may thus have formed through the consumption of apatites during pro-grade metamorphism, melting, and melt extraction. Combined, the trace element signatures of olivine and phosphate in pallasites of the main group (PMG) suggest that these meteorites are common products of planetary processes on chondritic or primitive achondrite-like precursor bodies, with the different subgroups highlighting distinct formation and evolution histories. Unlabelled Image [ABSTRACT FROM AUTHOR]

Calcium magnesium phosphate cements (CMPCs) are promising bone substitutes and experience great interest in research. Therefore, in-vivo degradation behavior, osseointegration and biocompatibility of three-dimensional (3D) powder-printed CMPC scaffolds were investigated in the present study. The materials Mg225 (Ca0.75Mg2.25(PO4)2) and Mg225d (Mg225 treated with diammonium hydrogen phosphate (DAHP)) were implanted as cylindrical scaffolds (h = 5 mm, Ø = 3.8 mm) in both lateral femoral condyles in rabbits and compared with tricalcium phosphate (TCP). Treatment with DAHP results in the precipitation of struvite, thus reducing pore size and overall porosity and increasing pressure stability. Over 6 weeks, the scaffolds were evaluated clinically, radiologically, with Micro-Computed Tomography (µCT) and histological examinations. All scaffolds showed excellent biocompatibility. X-ray and in-vivo µCT examinations showed a volume decrease and increasing osseointegration over time. Structure loss and volume decrease were most evident in Mg225. Histologically, all scaffolds degraded centripetally and were completely traversed by new bone, in which the remaining scaffold material was embedded. While after 6 weeks, Mg225d and TCP were still visible as a network, only individual particles of Mg225 were present. Based on these results, Mg225 and Mg225d appear to be promising bone substitutes for various loading situations that should be investigated further. [ABSTRACT FROM AUTHOR]

Stanfieldite, natural Ca-Mg-phosphate, is a typical constituent of phosphate-phosphide assemblages in pallasite and mesosiderite meteorites. The synthetic analogue of stanfieldite is used as a crystal matrix of luminophores and frequently encountered in phosphate bioceramics. However, the crystal structure of natural stanfieldite has never been reported in detail, and the data available so far relate to its synthetic counterpart. We herein provide the results of a study of stanfieldite from the Brahin meteorite (main group pallasite). The empirical formula of the mineral is Ca8.04Mg9.25Fe0.72Mn0.07P11.97O48. Its crystal structure has been solved and refined to R1 = 0.034. Stanfieldite from Brahin is monoclinic, C2/c, a 22.7973(4), b 9.9833(2), c 17.0522(3) Å, β 99.954(2)°, V 3822.5(1)Å3. The general formula of the mineral can be expressed as Ca7M2Mg7(PO4)12 (Z = 4), where the M = Ca, Mg, Fe2+. Stanfieldite from Brahin and a majority of other meteorites correspond to a composition with an intermediate Ca≈Mg occupancy of the M5A site, leading to the overall formula ~Ca7(CaMg)Mg9(PO4)12 ≡ Ca4Mg5(PO4)6. The mineral from the Lunar sample "rusty rock" 66095 approaches the M = Mg end member, Ca7Mg2Mg9(PO4)12. In lieu of any supporting analytical data, there is no evidence that the phosphor base with the formula Ca3Mg3(PO4)4 does exist. [ABSTRACT FROM AUTHOR]

Calcium phosphate cements are of great interest for researchers and their applications in medical practice expanded. Nevertheless, they have a number of drawbacks including the insufficient level of mechanical properties and low degradation rate. Struvite (MgNH 4 PO 4 ) -based cements, which grew in popularity in recent years, despite their neutral pH and acceptable mechanical performance, release undesirable NH 4 + ions during their resorption. This issue could be avoided by replacement of ammonia ions in the cement liquid with sodium, however, such cements have a pH values of 9-10, leading to cytotoxicity. Thus, the main goal of this investigation is to optimize the composition of cements to achieve the combination of desirable properties: neutral pH, sufficient mechanical properties, and the absence of cytotoxicity, applying Na 2 HPO 4 -based cement liquid. For this purpose, cement powders precursors in the CaO-MgO-P 2 O 5 system were synthesized by one-pot process in a wide composition range, and their properties were investigated. The optimal performance was observed for the cements with (Ca + Mg)/P ratio of 1.67, which are characterized by newberyite phase formation during setting reaction, pH values close to 7, sufficient compressive strength up to 22 ± 3 MPa (for 20 mol.% of Mg), dense microstructure and adequate matrix properties of the surface. This set of features make those materials promising candidates for medical applications., Competing Interests: The authors declare no conflicts of interest., (© 2020 Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.)