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Bioactive bone cements containing nano-sized titania particles for use as bone substitutes.

Three types of bioactive polymethylmethacrylate (PMMA)-based bone cement containing nano-sized titania (TiO2) particles were prepared, and their mechanical properties and osteoconductivity are evaluated. The three types of bioactive bone cement were T50c, ST50c, and ST60c, which contained 50 wt% TiO2, and 50 and 60 wt% silanized TiO2, respectively. Commercially available PMMA cement (PMMAc) was used as a control. The cements were inserted into rat tibiae and allowed to solidify in situ. After 6 and 12 weeks, tibiae were removed for evaluation of osteoconductivity using scanning electron microscopy (SEM), contact microradiography (CMR), and Giemsa surface staining. SEM revealed that ST60c and ST50c were directly apposed to bone while T50c and PMMAc were not. The osteoconduction of ST60c was significantly better than that of the other cements at each time interval, and the osteoconduction of T50c was no better than that of PMMAc. The compressive strength of ST60c was equivalent to that of PMMAc. These results show that ST60c is a promising material for use as a bone substitute.

Animals↗

Antimicrobial potency of alkali ion substituted calcium phosphate cements.

Potassium and sodium containing nanoapatite cements were produced by the reaction of mechanically activated CaNaPO(4) (CSP), CaKPO(4) (CPP) and Ca(2)KNa(PO(4))(2) (CPCP) with a 2.5% Na(2)HPO(4) solution. The cements exhibited clinically acceptable setting times of approximately 5 min and compressive strengths of 5-10 MPa. The antimicrobial properties of the cements were tested with the agar diffusion test using Streptococcus salvarius, Staphylococcus epidermis and Candida albicans. All types of alkali ion containing cements showed a significantly higher antimicrobial potency with inhibition zones of approx. 4-11 mm than a commercial calcium hydroxide cement which resulted in small inhibition zones around the cement samples of a maximum of 1.5 mm. The antimicrobial properties of all the cements were not found to diminish even after longer incubation times. This behaviour was attributed to the formation of soluble alkaline metal phosphates during setting which increased the pH value in the agar gel around the alkali containing calcium phosphate cement to 8.5-10.7 compared to 6.5-8.0 for the Ca(OH)(2) product. The high antimicrobial potency of alkali-calcium phosphate cements may find an application in dentistry as pulp capping agents, root fillers or cavity liners.

Alkalies↗

Biodegradable and bioactive porous polymer/inorganic composite scaffolds for bone tissue engineering.

Biodegradable polymers and bioactive ceramics are being combined in a variety of composite materials for tissue engineering scaffolds. Materials and fabrication routes for three-dimensional (3D) scaffolds with interconnected high porosities suitable for bone tissue engineering are reviewed. Different polymer and ceramic compositions applied and their impact on biodegradability and bioactivity of the scaffolds are discussed, including in vitro and in vivo assessments. The mechanical properties of today's available porous scaffolds are analyzed in detail, revealing insufficient elastic stiffness and compressive strength compared to human bone. Further challenges in scaffold fabrication for tissue engineering such as biomolecules incorporation, surface functionalization and 3D scaffold characterization are discussed, giving possible solution strategies. Stem cell incorporation into scaffolds as a future trend is addressed shortly, highlighting the immense potential for creating next-generation synthetic/living composite biomaterials that feature high adaptiveness to the biological environment.

Absorbable Implants↗

Controlled release of gentamicin from calcium phosphate-poly(lactic acid-co-glycolic acid) composite bone cement.

Modification of a self setting bone cement with biodegradable microspheres to achieve controlled local release of antibiotics without compromising mechanical properties was investigated. Different biodegradable microsphere batches were prepared from poly(lactic-co-glycolic acid) (PLGA) using a spray-drying technique to encapsulate gentamicin crobefate varying PLGA composition and drug loading. Microsphere properties such as surface morphology, particle size and antibiotic drug release profiles were characterized. Microspheres were mixed with an apatitic calcium phosphate bone cement to generate an antibiotic drug delivery system for treatment of bone defects. All batches of cement/microsphere composites showed an unchanged compressive strength of 60 MPa and no increase in setting time. Antibiotic release increased with increasing drug loading of the microspheres up to 30% (w/w). Drug burst of gentamicin crobefate in the microspheres was abolished in cement/microsphere composites yielding nearly zero order release profiles. Modification of calcium phosphate cements using biodegradable microspheres proved to be an efficient drug delivery system allowing a broad range of 10-30% drug loading with uncompromised mechanical properties.

Animals↗

Porogen-based solid freeform fabrication of polycaprolactone-calcium phosphate scaffolds for tissue engineering.

Drop on demand printing (DDP) is a solid freeform fabrication (SFF) technique capable of generating microscale physical features required for tissue engineering scaffolds. Here, we report results toward the development of a reproducible manufacturing process for tissue engineering scaffolds based on injectable porogens fabricated by DDP. Thermoplastic porogens were designed using Pro/Engineer and fabricated with a commercially available DDP machine. Scaffolds composed of either pure polycaprolactone (PCL) or homogeneous composites of PCL and calcium phosphate (CaP, 10% or 20% w/w) were subsequently fabricated by injection molding of molten polymer-ceramic composites, followed by porogen dissolution with ethanol. Scaffold pore sizes, as small as 200 microm, were attainable using the indirect (porogen-based) method. Scaffold structure and porosity were analyzed by scanning electron microscopy (SEM) and microcomputed tomography, respectively. We characterized the compressive strength of 90:10 and 80:20 PCL-CaP composite materials (19.5+/-1.4 and 24.8+/-1.3 Mpa, respectively) according to ASTM standards, as well as pure PCL scaffolds (2.77+/-0.26 MPa) fabricated using our process. Human embryonic palatal mesenchymal (HEPM) cells attached and proliferated on all scaffolds, as evidenced by fluorescent nuclear staining with Hoechst 33258 and the Alamar Blue assay, with increased proliferation observed on 80:20 PCL-CaP scaffolds. SEM revealed multilayer assembly of HEPM cells on 80:20 PCL-CaP composite, but not pure PCL, scaffolds. In summary, we have developed an SFF-based injection molding process for the fabrication of PCL and PCL-CaP scaffolds that display in vitro cytocompatibility and suitable mechanical properties for hard tissue repair.

Calcium Phosphates↗

In vitro evaluation of chitosan/poly(lactic acid-glycolic acid) sintered microsphere scaffolds for bone tissue engineering.

A three-dimensional (3-D) scaffold is one of the major components in many tissue engineering approaches. We developed novel 3-D chitosan/poly(lactic acid-glycolic acid) (PLAGA) composite porous scaffolds by sintering together composite chitosan/PLAGA microspheres for bone tissue engineering applications. Pore sizes, pore volume, and mechanical properties of the scaffolds can be manipulated by controlling fabrication parameters, including sintering temperature and sintering time. The sintered microsphere scaffolds had a total pore volume between 28% and 37% with median pore size in the range 170-200microm. The compressive modulus and compressive strength of the scaffolds are in the range of trabecular bone making them suitable as scaffolds for load-bearing bone tissue engineering. In addition, MC3T3-E1 osteoblast-like cells proliferated well on the composite scaffolds as compared to PLAGA scaffolds. It was also shown that the presence of chitosan on microsphere surfaces increased the alkaline phosphatase activity of the cells cultured on the composite scaffolds and up-regulated gene expression of alkaline phosphatase, osteopontin, and bone sialoprotein.

3T3 Cells↗

Physico-chemical-mechanical and in vitro biological properties of calcium phosphate cements with doped amorphous calcium phosphates.

Calcium phosphate cements (CPCs) are successfully used as bone substitutes in dentistry and orthopaedic applications. This study investigated the physico-chemical-mechanical properties of and in vitro biological properties (cell response) of CPCs prepared with amorphous calcium carbonate phosphate (ACCP) doped with magnesium (ACCP-Mg), zinc (ACCp-Zn) or fluoride (ACCP-F) ions. The experimental CPC consisted of alpha-TCP, doped ACCP, and MPCM powders as matrix and biphasic calcium phosphate (BCP) granules. X-ray diffraction analysis showed that the matrix converted to apatite with poor crystallinity (reflecting small crystal size) after setting for 24 h, while BCP remained apparently unchanged. Cements with ACCP-F (F-CPC) had shorter setting times and greater compressive strength compared to cements with ACCP-Mg (Mg-CPC) or ACCP-Zn (Zn-CPC). Scanning electron microscopy (SEM) showed that crystals set on Mg-CPC and Zn-CPC were smaller compared to those on F-CPC. The total porosity of Mg-CPC was greater compared to Zn-CPC or F-CPC. Osteoblast-like cells, MC3T3-E1, remained viable and maintained their ability to express alkaline phosphatase in contact with the CPCs with doped ACCPs.

3T3 Cells↗

Effect of modification of hydroxyapatite/collagen composites with sodium citrate, phosphoserine, phosphoserine/RGD-peptide and calcium carbonate on bone remodelling.

This study describes the early interface reaction of cancellous bone to a nanocrystalline hydroxyapatite cement containing type I collagen (HA/Coll) and its modifications with sodium citrate (CI), calcium carbonate (CA), phosphoserine (P) and phosphoserine plus RGD-peptide (RGD). Cylindrical implants of HA/Coll and its modifications were inserted into the tibia of Wistar rats. We analysed 6 specimens per group at days 2, 4, 7, 14 and 28. CI, P and RGD modifications showed improved material properties (finer microstructure and higher compressive strength) compared to CA and HA/Coll implants. The powder X-ray diffraction (XRD) showed that the addition of P and CI led to an increase of alpha-TCP peaks while the diffraction patterns of the non-modified cement (HA/Coll) were quite similar with that of natural bone. All of the implants healed without adverse reactions. A significantly higher number of TRAP-positive osteoclasts were observed around CI, RGD and P on day 7 compared to CA and HA/Coll. Around CI, P and RGD a significantly delayed increase of ED1-positive mononuclear cells was detected. The amount of direct bone contact after 28 days was significantly higher around CI, P and RGD compared to CA and HA/Coll implants. The addition of CI, P and RGD appears to enhance bone remodelling at the early stages of bone healing, leading to increased bone formation around HA/Coll composite cements.

Animals↗

Assessment of the mechanical stability and chemical leachability of immobilized electroplating waste.

The effectiveness of cement based treatment technology, in immobilizing chromium laden electroplating sludge was assessed by conducting toxicity characteristic leaching procedure (TCLP). The mechanical stability of the blocks was tested by measuring the compressive strength. Other leaching tests such as NEN 7341 test, ANS 16.1 and multiple TCLP (MTCLP) test conducted on select solidified blocks showed that chromium was immobilized by the binder studied. A linear relationship was obtained between the cumulative fraction of chromium leached (CFL) and square root of time in the solidified samples proving that diffusion is the controlling mechanism for leaching of chromium. The leachability indices (LI) obtained for the solidified materials using cement and cement-fly ash system (EPC6, EPFC6A and EPFC6B) satisfy the guidance value as per US NRC, which clearly indicates that chromium is well retained within the solid matrix. Chromium concentrations in the TCLP leachates of the above mix ratios were well within the regulatory level of United States Environmental Protection Agency (USEPA). Molecular characterization of the solidified material was carried out using Fourier transformation infra red (FTIR) technique.

Chromium↗

TNF-NF-κB signaling mediates immune-biomineralization crosstalk during shell repair under ocean acidification in Mytilus edulis.

Ocean acidification (OA) impairs biomineralization in bivalves, but its effects on immune-biomineralization crosstalk during shell repair remain unknown. Here, we exposed adult Mytilus edulis bearing standardized shell perforations to three pH levels (8.1, 7.9, and 7.7) for up to 40 days. OA slowed early repair and caused microstructural disorganization and an approximately 87% reduction of compressive strength at pH 7.7, yet the damaged area appeared largely closed by day 15, suggesting a decoupling between morphological closure and functional recovery. In addition, transcriptomic profiling of hemocytes and mantle tissue, based on an average of 6.5 Gb of clean reads per sample mapped to the M. edulis reference genome (NCBI Assembly GCF_000511035.1), revealed that these shell-level defects were accompanied by coordinated immune and metabolic reprogramming. Hemocytes, the primary immune effector cells of bivalves, exhibited pH- and time-dependent shifts with moderate acidification (pH 7.9) promoting inflammatory transcripts, whereas severe acidification (pH 7.7) suppressed these signals while upregulating stress-associated pathways; both treatments consistently downregulated lysosomal proteases and NF-κB negative regulators. The mantle, a primarily mineralizing organ, paradoxically upregulated immune-related genes while suppressing oxidative phosphorylation and extracellular matrix pathways. This tissue-level imbalance, with hemocytes recruited but functionally constrained and mantle metabolically suppressed yet immunologically activated, points to TNF-NF-κB pathway modulation as a key mediator of shell repair under acidification. Our findings demonstrate that visible shell closure masks underlying structural and mechanical failure, and that immune regulation, rather than simple suppression or activation, critically shapes the repair outcome. These results advocate for multifunctional indicators beyond closure area to assess shell integrity in acidified marine environments.

Animals↗

Properties of steel foundry electric arc furnace dust solidified/stabilized with Portland cement.

Electric arc furnace dust from steel production is generated in considerable amounts worldwide and needs to be treated as hazardous waste. The aim of this study was to investigate the properties of electric arc furnace dust solidified/stabilized by using Portland cement. Mortar and paste samples were prepared with varying waste-to-binder ratios between 0% and 90%. A comprehensive experimental program was designed including XRF characterization, setting time, unconfined compressive strength, and toxicity characteristics leaching procedure (TCLP), synthetic precipitation leaching procedure (SPLP), and acid neutralization capacity (ANC) tests. The results were evaluated in order to determine if the solidified /stabilized product can be disposed of at a landfill site with domestic waste or at a segregated landfill. The effect of using sand on S/S performance was also investigated. The results indicated that the solidification /stabilization process using PC helps the heavy metals to be bound in the cement matrix, but the TCLP leaching results exceeded the EPA landfilling limits. The SPLP leaching results conformed to the limits implying that the waste or S/S products can be disposed of at a segregated landfill; however the low ANC of the S/S products reveals that there may be leaching in the long-term. The sand used in the mortar samples adversely affected the S/S performance, causing higher heavy metal leaching levels, and lower pH levels in the leachate after the TCLP extraction than those measured in the leachate of the paste samples.

Dust↗

Characterization of alpha-cordierite glass-ceramics from fly ash.

Batches of alpha-cordierite glass-ceramics, designated as GC-I and GC-II, containing 68 and 64 wt.% fly ash, respectively, were crystallized in the temperature range of 1125-1320 degrees C. The XRD (X-ray powder diffractometer) of the glass-ceramics show that alpha-cordierite became the dominant phase in GC-I and GC-II at 1200 degrees C. GC-I and GC-II, whose solid parts contain 74 and 78 vol.% alpha-cordierite and whose compressive strengths are 35 and 50 MPa, respectively, have the respective linear thermal expansion coefficients of 1.51x10(-6) and 1.43x10(-6)/ degrees C. The fly ash alpha-cordierite glass-ceramics can be employed as kiln furniture, honeycomb substrates for catalysts, and heat exchangers.

Carbon↗

Potential application of coal-fuel oil ash for the manufacture of building materials.

In this paper coal-fuel oil ash has been characterized in terms of leaching behaviour and reactivity against lime and gypsum in hydratory systems for the manufacture of building materials. Its behaviour was also compared to that of coal ash. Metal release was measured in a dynamic leaching test with duration up to 16 days. The results have shown that coal-fuel oil ash behaves very similarly to coal ash. The reactivity of coal-fuel oil ash against lime and gypsum was measured in mixtures containing only lime and in mixtures containing both lime and gypsum. These systems were hydrated at 25 and 40 degrees C under 100% R.H. The results have shown that the main hydration products are the same as those that are usually formed in similar coal ash-based systems. That is, calcium silicate hydrate in coal-fuel oil ash/lime systems and calcium silicate hydrate plus calcium trisulphoaluminate hydrate in coal-fuel oil ash/lime/gypsum systems. From the quantitative point of view, hydration runs showed that the amounts of both chemically combined water and reacted lime measured in the case under investigation are very similar to those found in similar coal ash-based systems. Finally, the measurement of unconfined compressive strength proved that the systems have potentiality for the manufacture of pre-formed building blocks.

Aluminum Compounds↗

Utilization of MSWI fly ash for stabilization/solidification of industrial waste sludge.

This work investigated the potential for utilization of MSWI incineration fly ash as solidification binder to treat heavy metals-bearing industrial waste sludge. In the study, Municipal Solid Waste Incineration (MSWI) fly ash was used along with ordinary Portland cement to immobilize three different types of industrial sludge while MSWI incineration fly ash was stabilized at the same time. The results showed that the matrixes with heavy metals-bearing sludge and MSWI fly ash have a strong fixing capacity for heavy metals: Zn, Pb, Cu, Ni and Mn. Specimens with only 5-15% cement content was observed to be sufficient to achieve the target compressive strength of 0.3 MPa required for landfill disposal. An optimum mix comprising 45% fly ash, 5% cement and 50% of the industrial sludge could provide the required solidification and stabilization. Addition of MSWI can improve the strength of matrix. Meanwhile, the main hydration products of new S/S matrix are ettringite AFt, Friedel's salt and C-S-H. These hydration products play an important role in the fixing of heavy metals. The co-disposal of MSWI fly ash with heavy metals-bearing sludge can minimize the enlargement of the landfill volume and stabilize the heavy metals effectively.

Carbon↗

Use of sulfoaluminate cement and bottom ash in the solidification/stabilization of galvanic sludge.

Solidification/stabilization (S/S) process can improve the physical characteristics of wastes, reduce their leaching and limit the solubility of their heavy metals. The identification of binders able to assume the fixation of contaminants is essential for the success of the technique. In this study, calcium sulfoaluminate cement was added to another waste, bottom ash, in order to treat galvanic sludge. The properties of the resultant solid matrix (MS) were determined: setting time, compressive strength and products of hydration. Solid matrix composed of 77% waste and only 23% cement presented initial setting time lower than 4 h and 28 day-strength of 6 MPa. SEM investigations showed that contaminants present in the galvanic sludge (Cr) were encapsulated in the hydrated phases and particles of bottom ash.

Aluminum Compounds↗

Production of aggregate from non-metallic automotive shredder residues.

In this paper, the results of an experimentation on the production of granules suitable to be used as aggregates in cementitious or asphalt mixes are presented and discussed. The granules were obtained by granulating the non-metallic fraction of automotive shredder residues. In a preliminary separation step the fluff fraction containing mainly inert and non-metallic materials was sieved and analyzed for the metal content. In the following granulation step, the sieved fraction was mixed with binding materials, fly ash and a densifier agent, to produce granules of 5-30 mm of diameter and up to 1400 kg/m3 of specific weight. The granulation was carried out at room temperature in a rotating tank. Concrete samples prepared using as aggregates the produced granules showed a specific weight up to 1800 kg/m3 and a compressive strength up to about 55% of reference samples prepared using a calcareous aggregate, depending on the fluff content of the mixes, and on the nature of the binder and of the other components used.

Automobiles↗

Hazardous jarosite use in developing non-hazardous product for engineering application.

Jarosite released from zinc metal extraction process is hazardous in nature and its world wide disposal has become a major environmental concern. In this study, an attempt has been made to immobilise and recycle the jarosite released from Hindustan Zinc Limited, India, using CCRs, so called fly ash, and clay soil. Results revealed that the particle size of jarosite was finer than that of CCRs and had higher porosity and water holding capacity due to fine textured materials resulting in high surface area (10,496.18 +/- 30.90 cm(2)/g). Jarosite contain higher concentration of toxic elements (lead, zinc, sulphur, cadmium, chromium and copper) than that of CCRs. Concentrations of radionuclides such as (226)Ra, (40)K and (228)Ac in jarosite found less than in CCRs are similar to that of soil. Statistically designed experiments on solidified/stabilised (s/s) sintered jarosite--CCRs products confirmed that the compressive strength of jarosite bricks reached as high as 140 kg/cm2 with 14.5% water absorption capacity at the combination of 3:1 ratio of jarosite and clay, respectively, but, concentrations of all the toxic elements recommended by United States Environmental Protection Agency (USEPA)--Toxicity Leachate Characteristics Procedure (TCLP) standard are not within the permissible limits. However, it is confirmed that the toxic elements leaching potentials of s/s-sintered products developed using 2:1 jarosite clay ratio with 15% CCRs comply with the USEPA-TCLP limits and also meet the quality for engineering applications.

Adsorption↗

Stabilization/solidification of lead-contaminated soil using cement and rice husk ash.

This paper presents the findings of a study on solidification/stabilization (S/S) of lead-contaminated soil using ordinary Portland cement (OPC) and rice husk ash (RHA). The effects of varying lead concentrations (in the form of nitrates) in soil samples on the physical properties of their stabilized forms, namely unconfined compressive strength (UCS), setting times of early mixtures and changes in crystalline phases as well as chemical properties such as leachability of lead, pH and alkalinity of leachates are studied. Results have indicated that usage of OPC with RHA as an overall binder system for S/S of lead-contaminated soils is more favorable in reducing the leachability of lead from the treated samples than a binder system with standalone OPC. On the other hand, partial replacement of OPC with RHA in the binder system has reduced the UCS of solidified samples.

Alkalies↗