Setting Mechanism of a CDHA Forming α-TCP Cement Modified with Sodium Phytate for Improved Injectability

A calcium deficient hydroxyapatite (CDHA) forming cement with a bimodal grain size distribution, composed of α-TCP and fine grained CDHA at a weight ratio of 9:1, was modified by the addition of sodium phytate (IP6) in variable amounts ranging from 0.25 to 2 wt.%, related to the powder content. The injectability of the cement paste was drastically increased by the IP6 addition, independent of the amount of added IP6. Additionally, the cement paste viscosity during the first minutes decreased. These effects could be clearly related to a slightly more negative zeta potential. Furthermore, IP6 was shown to strongly retard the setting reaction, as can be seen both in the calorimetry and X-ray diffraction measurements. In addition, octacalcium phosphate (OCP) was identified as a further setting product. All measurements were performed at 23 °C and 37 °C to assess the effect of temperature on the setting reaction for both clinical handling by the surgeon and the final hardening in the bone defect

Ion-doped brushite cements for bone regeneration

Decades of research in orthopaedics has culminated in the quest for formidable yet resorbable biomaterials using bioactive materials. Brushite cements most salient features embrace high biocompatibility, bioresorbability, osteoconductivity, self-setting characteristics, handling, and injectability properties. Such type of materials is also effectively applied as drug delivery systems. However, brushite cements possess limited mechanical strength and fast setting times. By means of incorporating bioactive ions, which are incredibly promising in directing cell fate when incorporated within biomaterials, it can yield biomaterials with superior mechanical properties. Therefore, it is a key to develop fine-tuned regenerative medicine therapeutics. A comprehensive overview of the current accomplishments of ion-doped brushite cements for bone tissue repair and regeneration is provided herein. The role of ionic substitution on the cements physicochemical properties, such as structural, setting time, hydration products, injectability, mechanical behaviour and ion release is discussed. Cell-material interactions, osteogenesis, angiogenesis, and antibacterial activity of the ion-doped cements, as well as its potential use as drug delivery carriers are also presented.This study was funded by the Portuguese Foundation for Science and Technology (FCT) and the German Academic Exchange Service (Deutscher Akademischer Austauschdienst, DAAD) for the transnational cooperation FCT/DAAD 2018-2019. The authors also thank the funds provided under the distinctions attributed to JMO (IF/01285/2015) and SP (CEECIND/03673/2017). Furthermore, funding by the German Research Foundation (Deutsche Forschungsgemeinschaft, DFG), Grant Nr. HU 2498/1-1; GB 1/22-1, and the Emerging Talents Initiative of the FAU is acknowledged

Accelerated swell testing of artificial sulfate bearing lime stabilised cohesive soils

This paper reports on the physico-chemical response of two lime stabilised sulfate bearing artificial soils subject to the European Accelerated Volumetric Swell Test (EN13286-49). At various intervals during the test, a specimen was removed and subject to compositional and microstructural analysis. Ettringite was formed by both soils types, but with significant differences in crystal morphology. Ettringite crystals formed from kaolin based soils were very small, colloidal in size and tended to form on the surface of other particles. Conversely, those formed from montmorillonite were relatively large and typically formed away from the surface in the pore solution. It was concluded that the mechanism by which ettringite forms is determined by the hydroxide ion concentration in the pore solution and the fundamental structure of the bulk clay. In the kaolin soil, ettringite forms by a topochemical mechanism and expands by crystal swelling. In the montmorillonite soil, it forms by a through-solution mechanism and crystal growth

Aluminum-rich belite sulfoaluminate cements: clinkering and early age hydration

Belite sulfoaluminate (BSA) cements have been proposed as environmentally friendly building materials, as their production may release up to 35% less CO2 into the atmosphere when compared to ordinary Portland cements. Here, we discuss the laboratory production of three aluminum-rich BSA clinkers with nominal mineralogical compositions in the range C2S (50-60%), C4A3$(20- 30$, i.e. a value as close as possible to the nominal composition. Under these experimental conditions, three different BSA clinkers, nominally with 20, 30 and 30 wt% of C4A3$, had 19.6, 27.1 and 27.7 wt$ respectively, as determined by Rietveld analysis. We also studied the complex hydration process of BSA cements prepared by mixing BSA clinkers and gypsum. We present a methodology to establish the phase assemblage evolution of BSA cement pastes with time, including amorphous phases and free water. The methodology is based on Rietveld quantitative phase analysis of synchrotron and laboratory X-ray powder diffraction data coupled with chemical constraints. A parallel calorimetric study is also reported. It is shown that the b-C2S phase is more reactive in aluminum-rich BSA cements than in standard belite cements. On the other hand, C4A3$ reacts faster than the belite phases. The gypsum ratio in the cement is also shown to be an important factor in the phase evolution

Enthalpy of formation of ye’elimite and ternesite

Calcium sulfoaluminate clinkers containing ye’elimite (Ca4Al6O12(SO4)) and ternesite (Ca5(SiO4)2SO4) are being widely investigated as components of calcium sulfoaluminate cement clinkers. These may become low energy replacements for Portland cement. Conditional thermodynamic data for ye’elimite and ternesite (enthalpy of formation) have been determined experimentally using a combination of techniques: isothermal conduction calorimetry, X-ray powder diffraction and thermogravimetric analysis. The enthalpies of formation of ye’elimite and ternesite at 25 °C were determined to be − 8523 and − 5993 kJ mol−1, respectively

Solid-state nuclear magnetic resonance spectroscopy of cements

Cement is the ubiquitous material upon which modern civilisation is built, providing long-term strength, impermeability and durability for housing and infrastructure. The fundamental chemical interactions which control the structure and performance of cements have been the subject of intense research for decades, but the complex, crystallographically disordered nature of the key phases which form in hardened cements has raised difficulty in obtaining detailed information about local structure, reaction mechanisms and kinetics. Solid-state nuclear magnetic resonance (SS NMR)spectroscopy can resolve key atomic structural details within these materials and has emerged as a crucial tool in characterising cement structure and properties. This review provides a comprehensive overview of the application of multinuclear SS NMR spectroscopy to understand composition–structure–property relationships in cements. This includes anhydrous and hydrated phases in Portland cement, calcium aluminate cements, calcium sulfoaluminate cements, magnesia-based cements, alkali-activated and geopolymer cements and synthetic model systems. Advanced and multidimensional experiments probe 1 H, 13 C, 17 O, 19 F, 23 Na, 25 Mg, 27 Al, 29 Si, 31 P, 33 S, 35 Cl, 39 K and 43 Ca nuclei, to study atomic structure, phase evolution, nanostructural development, reaction mechanisms and kinetics. Thus, the mechanisms controlling the physical properties of cements can now be resolved and understood at an unprecedented and essential level of detail

Phase Solubility Changes during Hydration of Monocalciumaluminate and Calcite—The Influence of Alkali Accumulation

The reaction of CA (monocalcium aluminate) with calcite was closely monitored with regard to phase development, pore water ion content and heat flow. Calcite acts as filler and reactant, finally leading to thermodynamically stable products after hydration at ambient conditions. For better understanding the mechanism taking place, a CA-cement and a commercial calcite mix were compared to a pure CA and pure calcite mix. Both reaction paths were compared. Thermodynamic modeling with PhreeqC gave insight about factors that can influence the course of the hydration reaction. Alkali ions in pore solution of the CA-cement relocate solubility curves of hydration products. Taking into account as many of the alkaline ions as possible, resulted in the closest representation of the measured phase content, confirming thermodynamic modeling. The high dynamics that develop during reaction could only be addressed if a concentration of alkalis in the pore solution at later points in time was respected, thus leading to a shift of solubility curves over time. This was not observed with the pure CA in absence of alkalis