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A new laboratory method for evaluating the relative solubility and erosion of dental cements.

A method for accelerating the dissolution and erosion of 'acidic' dental cements has been developed which gave relative solubilities in accordance with in vivo observations, in contrast to the conventional test. It involves subjecting 24-h-old specimens to a jet of dilute acid (lactic or citric) and determining weight loss. The relative ranking for 'acidic' cements in the apparatus and in vivo was: glass ionomer less than silicophosphate less than zinc phosphate less than polycarboxylate. The method was not valid for reinforced zinc oxide/eugenol/EBA cements. Of the two polycarboxylate cements studied, a brand which has the acid in the powder was found to be more soluble than the conventional material. It is proposed that the method be the basis of a new solubility/erosion test in national and international standards for 'acidic' dental cements.

Chemical Phenomena↗

Mortality among unionized construction plasterers and cement masons.

BACKGROUND: Plasterers perform a variety of duties including interior and exterior plastering of drywall, cement, stucco, and stone imitation; the preparation, installation, and repair of all interior and exterior insulation systems; and the fireproofing of steel beams and columns. Some of the current potential toxic exposures among plasterers include plaster of Paris, silica, fiberglass, talc, and 1,1,1-trichloroethylene; asbestos had been used by the plasterers in the past. Cement masons, on the other hand, are involved in concrete construction of buildings, bridges, curbs and gutters, sidewalks, highways, streets and roads, floors and pavements and the finishing of same, when necessary, by sandblasting or any other method. Exposures include cement dust, silica, asphalt, and various solvents. METHODS: Proportionate mortality ratios (PMRs) and proportionate cancer mortality ratios (PCMRs) were calculated for 99 causes of death among 12,873 members of the Operative Plasterers' and Cement Masons' International Association who died between 1972 and 1996 using United States age-, race-, and calender-specific death rates. Statistical significance (P value) of results was based upon the Poisson distribution. RESULTS: Among plasterers, statistically significant elevated mortality was observed for asbestosis, where the PMR reached 1,657 (P < 0.01) with eleven observed deaths and less than one death expected, for lung cancer (PCMR = 124, P < 0.01), and for benign neoplasms (PMR = 210, P < 0.05). Among cement masons, statistically significant elevated mortality was observed for cancer of the stomach (PCMR = 133, P < 0.01), benign neoplasms (PMR = 132, P < 0.01), and poisonings (PMR = 159, P < 0.05). Except for poisonings, which were not thought to be occupationally related, all of the statistically significant results occurred among those members who entered the union prior to 1950. However, the risk for lung cancer among plasterers was still elevated among those entering the union after 1970 as was the risk for stomach cancer among cement masons who entered the union after 1950. CONCLUSIONS: The present study suggests that plasterers and cement masons still have elevated risks for certain diseases, especially lung and stomach cancer. Therefore, union members currently living should be screened for asbestos-related diseases and educated about the future risks for these diseases.

Adult↗

Antimicrobial activity and tightness of a DCPD-CaO-based hydraulic calcium phosphate cement for root canal filling.

Calcium hydroxide is currently used in dentistry for endodontic treatments where its main advantage is its antibacterial and anti-inflammatory activity. However, it also has some drawbacks such as pulp necrosis, slight solubility, slow and insufficient hardening, and retraction on drying. In consequence, it is used only as temporary material for root canal disinfection. By mixing calcium hydrogen phosphate dihydrate (CaHPO4 . 2H2O, also called dicalcium phosphate dihydrate, DCPD) and calcium oxide with a sodium phosphate buffer as liquid phase, we obtained a CPC with better mechanical properties than calcium hydroxide pastes. The setting reaction produced either hydroxyapatite (HA) or a mixture of HA and calcium hydroxide depending on the relative masses of DCPD and CaO in the cement powder. The presence of calcium hydroxide a priori confers antimicrobial properties to this cement which were investigated in agar plates (diffusion method) against Streptococcus mutans, Lactobacillus acidophilus, Candida albicans, Enterococcus faecalis, Staphylococcus hominis (clinical isolates), and a preparation of polymicrobial flora isolated from dental plaque. The cement samples tested were prepared at molar calcium-to-phosphate ratios (Ca/P) of 1.67 to 2.75. A pure calcium hydroxide paste was used as reference material. Clear and reproducible bacterial growth inhibition was observed for cement samples with Ca/P > or = 2 against all the microorganisms tested. With Ca/P = 2.5, this cement alkalinizes dentinal tubules and provides a fluid-tight sealing that well compares with sealing obtained using a zinc oxide-eugenol cement without gutta-percha point. DCPD-CaO-based cement is therefore a potential root canal filler.

Anti-Bacterial Agents↗

The release of gentamicin after total hip replacement using low or high viscosity bone cement. A prospective, randomized study.

Low viscosity bone cement is expected to give improved long term fixation of prosthetic components by increased intrusion into cancellous bone. Fixation is more difficult to achieve after revision for infection because of the inferior quality of the bone. We have compared the amount of gentamicin released from high viscosity and low viscosity bone cements in 41 patients undergoing total hip replacement. The concentration of gentamicin in serum and the wound secretion, and the amount recovered from the urine, was about three times higher for low viscosity cement. A possible explanation for this is an increase in surface area of the cement body because of improved intrusion of cement into bone. The improved mechanical fixation and the high concentration of gentamicin of the bone cement interface favours the use of low viscosity cement, especially in revision for deep infection.

Aged↗

Long-term exposure to cement dust and later hospitalization due to respiratory disease.

The relationship between exposure to cement dust in a Portland cement factory and later hospitalization due to respiratory disease and in particular chronic obstructive lung disease (COLD) was examined in a cohort initially examined in 1974. A total of 546 men with different lengths of employment in the cement factory were compared with 857 randomly sampled men of the same age from the same geographical area. Information on hospitalization was obtained from a nationwide register administered by the Danish National Board of Health. During a 9-year, 8-month period, 7.8% of the total population studied had been admitted to hospital at least once because of respiratory disease and 4.3% had been admitted because of COLD. Cement workers had no increased rates of hospitalization when compared with other blue collar workers from the random sample or the whole random sample. A vague tendency towards increasing rates of hospitalization due to COLD with increasing duration of exposure to cement dust up to 30 years was found. Given at least one hospitalization, exposure to cement dust was not related to the accumulated number of days in hospital in the observation period. We conclude that long-term exposure to cement dust does not lead to higher morbidity of severe respiratory disease than other types of blue collar work.

Aged↗

Auto-oxidative damage in cement dermatitis.

Oxygen intermediates (OIs) generated by stimulated polymorphonuclear leukocytes (PMNs) are known to induce auto-oxidative tissue damage at the site of inflammation. PMNs from five patients with severe and chronic cement dermatitis generated markedly increased levels of OIs. However, only a slight increase in OI generation by PMNs was observed in cement workers without cement dermatitis. Dapsone, which has recently been shown to decrease OI levels, was found to be clinically effective in the treatment of cement dermatitis in these five patients. After treatment, a significant decrease in OI generation was observed in all patients studied. In skin tissues from the cement workers without cement dermatitis, enhanced superoxide-dismutase (SOD) activities as well as increased OI generation by PMNs were noted. In spite of the greatly increased OI generation by PMNs, the SOD activities in the patients were comparable to those in healthy controls. These findings suggest that the severe skin manifestations in patients with cement dermatitis can partly be explained by a defective capacity for enhancing SOD activity which removes increased PMN-derived OIs and thus prevents subsequent tissue injury by OIs at the site of inflammation.

Adult↗

The cement apparatus of larval and adult Acanthocephalus anguillae (Acanthocephala), with notes on the copulatory cap and origin of gland secretion.

Light and electron microscopy were used to investigate the ultrastructure of the cement apparatus, namely cement glands and cement ducts, of mature specimens of the parasite Acanthocephalus anguillae (Muller, 1780) Luhe, 1911 recovered from the alimentary canal of fish Leuciscus cephalus (Risso, 1826). In addition, the cement apparatus of immature A. anguillae found within the body cavity of the crustacean Asellus aquaticus (L.) was examined. In immature and mature males of Acanthocephalus anguillae, there are six round cement glands and each of them has an outer cytoplasmic layer containing nuclei and surrounds a space for storage of the cement. The cytoplasmic layer produces round, membrane-bound secretory granules approximately 1 microm in diameter. Nuclei and other cellular organelles surrounded by secretory granules were noticed inside the luminal part of the gland of adult males. In some female Acanthocephalus anguillae, within the attached copulatory cap, eggs and spermatozoa were observed. A protein of about 23 kDa appeared to be the major component of proteins of isolated cement glands, as well as in detached copulatory caps.

Acanthocephala↗

[In vitro elution and mechanical properties of antibiotic-loaded SmartSet HV and Palacos R acrylic bone cements].

BACKGROUND: The continuing emergence of new bone cements with additional antibiotics makes it important to establish which one will provide the most favourable antibiotic elution. An in vitro antibiotic elution and mechanical study was therefore carried out to compare a newer bone cement, SmartSet, with the established Palacos R cement. METHODS: Samples were prepared with each cement adding 1 g gentamicin, 1 g of vancomycin, or 1 g of gentamicin and vancomycin. The samples were analysed using fluorescence polarisation immunoassay. Mechanical tests were performed to determine whether any significant degradation in the cement strength occurred following addition of the antibiotic. RESULTS: With regards to gentamicin release Palacos R eluted significantly more antibiotic over the study period than SmartSet (p<0.001). Both cements eluted significantly more gentamicin when two antibiotics were added. With respect to vancomycin release there was no significant difference. Palacos R was significantly stronger than SmartSet in the 4-point bending test when the gentamicin + vancomycin antibiotic groups were compared (p=0.01). Palacos R also demonstrated a higher elastic modulus than SmartSet when the gentamicin and gentamicin + vancomycin groups were compared (p=0.03, p=0.005). CONCLUSIONS: Gentamcin shows better release characteristics from Palacos R. Both cements exhibited synergistic release of combined antibiotics.

Adhesiveness↗

Pollutants emitted by a cement plant: health risks for the population living in the neighborhood.

The aim of this study was to investigate the health risks due to combustor emissions in the manufacturing of Portland cement for the population living in the neighborhood of a cement kiln in Catalonia, Spain. Pollutants emitted to the atmosphere in the course of cement production were modeled. The ISC3-ST model was applied to estimate air dispersion of the contaminants emitted by the cement plant. Air concentrations of NO(2), SO(2), PM(10), metals, and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), as well as the potential exposure in the vicinity of the facility, were assessed via models based on US EPA guidance documents. PCDD/F and metal concentrations were also modeled for soil and vegetation. Based on these concentrations, the levels of human exposure were calculated. Individual cancer and noncancer risks for the emissions of the cement kiln were assessed. Health effects due to NO(2), SO(2), and PM(10) emissions were also evaluated. Risk assessment was performed as a deterministic analysis. The main individual risk in the population was evaluated in a central-tendency and a high-end approach. The results show that the incremental individual risk due to emissions of the cement plant is very low not only with regard to health effects, but also in relation to toxicological and cancer risks produced by pollutants such as metals and PCDD/Fs emitted by the cement kiln.

Air Pollutants↗

Comparison of immobilisation of air pollution control residues with cement and with silica.

Cement as agent for immobilising Pb from air pollution control residues is compared with the use of different silica-containing materials. The DIN 38414-S4 leaching test was used to control Pb leachability and to compare obtained Pb leachate concentrations with the landfill limit of 2 mg/l for Pb. Firstly, one scrubber residues was treated with cement and micro-silica. With cement, the Pb leachability could be reduced with a factor ranging from 3 to 50 depending on the type and amount of cement used and depending on the curing time. The landfill limit of 2 mg/l was, however, never attained. From all tested silica-containing additives, aerosil could reduce the initial Pb leaching (101.3mg/l) to below the detection limit at a dosage of 0.13 g aerosil/g residue. Second best and an economically preferable silica-containing additive was micro-silica: a reduction from 101.3 to 0.7 mg/l was observed at a dosage of 0.4 g micro-silica/g residue. The formation of Ca-silicates was found to be responsible for the decreased Pb leachability. To generalise the findings, the Pb leachability of five cement-treated and five micro-silica-treated air pollution control residues were compared. For three scrubber residues, 2-20 times lower Pb leachate concentrations were measured for micro-silica-treated samples (cured for 5 weeks) than cement-treated samples. For a fly ash and a boiler ash the difference was, respectively, 48 and 17 times. pH-dependent leaching tests showed that at pH=2.5, Pb leaching is 250 times lower for the micro-silica-treated residue than for the cement-treated residue and almost seven times lower at pH 12.4.

Air Pollutants↗

An X-ray diffraction (XRD) and Fourier transform infrared spectroscopic (FT-IR) investigation of the long-term effect on the solidification/stabilization (S/S) of arsenic(V) in Portland cement type-V.

The long-term effects on solidification/stabilization (S/S) of As5+-bearing oxyanions (AsO4(3)-) in Portland cement type-V (OPC) have been investigated by X-ray diffraction (XRD) and Fourier transform infrared spectroscopic (FT-IR) techniques. The results of this study confirm our previous results that the early hydration of cement is inhibited by the presence of AsO4(3)-, and that the inhibition is mainly caused by the formation of highly insoluble Ca3(AsO4)2 on the surface of hydrating cement particles. Arsenate analog of ettringite [Ca6(Al2O6)(SO4)3 x 32H2O] was identified in the early stages of hydration of pure Portland cement and As(V)-treated Portland cement [OPC-As(V)], but not in 10-year-old similar samples. The XRD and FT-IR results indicated interactions of oxyanions and cement particles to produce minor quantities of As5+-bearing compounds in fresh as well as in 10-year-old samples. New As5+-bearing phases, NaCaAsO4 x 7.5H2O and Ca5(AsO4)3OH were identified in the 10-year-old OPC-As(V) samples by XRD analyses. Based on these results it is concluded that Portland cement may be considered as a potential matrix to immobilize As5+-bearing wastes.

Journal Article↗

Comparison of the response of human peripheral blood mononuclear cells to challenge with particles of three bone cements in vitro.

This study compared the effects of different sizes of three clinically relevant endotoxin free bone cement particles on primary human macrophage TNF-alpha production in vitro. The bone cements used were CMW original, CMW1RO and Palacos R. The cement wear debris was generated aseptically and then sequentially filtered to produce the size ranges 0.1-1 microm, 0.1-10 microm, 1-10 microm and >10 microm. The debris was cultured with human peripheral blood mononuclear cells at particle volume (microm(3)) per cell ratios of 100:1, 10:1 and 1:1. TNF-alpha production was determined by ELISA and cell viability by MTT conversion. CMW1RO particles induced increased TNF-alpha production by PBMNCs when tested in the size range 0.1-1 microm, and also to a lesser degree in the sizes 0.1-10 microm and 1-10 microm at the particle volume (microm(3)) to cell number ratios of 100:1 and 10:1. The increase in TNF-alpha production induced by Palacos R debris was only observed with the particle size ranges less than 10 microm at the ratio of 100:1. This study demonstrated that bone cement particles are capable of inducing raised TNF-alpha production in vitro. This is dependent upon cement particle size, volume and cement particle type, with cement particles containing radio-opaque additives being the most active.

Cell Adhesion↗

Modelling the effects of waste components on cement hydration.

Ordinary Portland Cement (OPC) is often used for the solidification/stabilization (S/S) of waste containing heavy metals and salts. These waste components will precipitate in the form of insoluble compounds on to unreacted cement clinker grains preventing further hydration. In this study the long term effects of the presence of contaminants in solidified waste is examined by numerically simulating cement hydration after precipitation of metal salts on the surface of cement grains. A cement hydration model was extended in order to describe pore water composition and the effects of cement grain coating. Calculations were made and the strength development predicted by the model was found to agree qualitatively with experimental results found in literature. The complete model is useful in predicting the strength and leaching resistance of solidified products and developing solidification recipes based on cement.

Chemical Precipitation↗

Microstructure of Portland cement pastes containing metal nitrate salts.

In recent years, Backscattered Scanning Electron microscopy techniques (BSE), coupled with an image analysis system have been recognised as a powerful tool for quantitative analysis. This paper investigates the effect of metal additions (Ba, Cu, Ni, Zn, Cr(III), Pb and Cd) to Portland cement to produce a solidified product which meets the durability criteria quantified by the ratio of hydrated products and porosity. In addition, other indicators of the progress of cement hydration such as the bulk density and evaporable water of the solidified products were also measured. Metal concentrations of 0.1 and 1% per weight of cement at a constant water/cement ratio of 0.4 were examined. The same measurements were conducted on control samples of different water/ cement ratio. The results have shown that the control samples at different W/C ratio showed consistent trend in residual cement porosity, density and evaporable water content. It also showed that low dosage of metal nitrate additions can reduce cement hydration by up to 50% and at the same time reduce the observable porosity. Overall, this work has shown that Scanning Electron Microscopy (SEM) and image analysis are powerful tools and could be used to quantify the observable porosity and cement hydration in solidified systems.

Manufactured Materials↗

Immobilization of radioactive waste by cementation with purified kaolin clay.

A study is undertaken to determine the waste immobilization performance of low-level wastes in cement-clay mixtures. Liquid low-level wastes are precipitated using chemical methods, followed by solidification in drums. Solidification is done using cementation processes. Long-term leaching rates of the radionuclides are used as indicators of immobilization performance of solidified waste forms. In addition to evaluating the effects of kaolin clay on the leaching properties of the cemented waste forms, the effect of addition of kaolin on the strength of the cemented waste form is also investigated. The long term leaching tests show that inclusion of kaolin in cement reduces the leaching rates of the radionuclides significantly. However, clay additions in excess of 15 wt.% causes a significant decrease in the hydrolytic stability of cemented waste form. It is found that the best waste isolation, without causing a loss in the mechanical strength, is obtained when the kaolin content in cement is 5%.

Aluminum Silicates↗

Spectroscopic investigation of Ni speciation in hardened cement paste.

Cement-based materials play an important role in multi-barrier concepts developed worldwide for the safe disposal of hazardous and radioactive wastes. Cement is used to condition and stabilize the waste materials and to construct the engineered barrier systems (container, backfill, and liner materials) of repositories for radioactive waste. In this study, Ni uptake by hardened cement paste has been investigated with the aim of improving our understanding of the immobilization process of heavy metals in cement on the molecular level. X-ray absorption spectroscopy (XAS) coupled with diffuse reflectance spectroscopy (DRS) techniques were used to determine the local environment of Ni in cement systems. The Ni-doped samples were prepared at two different water/cement ratios (0.4, 1.3) and different hydration times (1 hour to 1 year) using a sulfate-resisting Portland cement. The metal loadings and the metal salts added to the system were varied (50 up to 5000 mg/kg; NO3(-), SO4(2-), Cl-). The XAS study showed that for all investigated systems Ni(ll) is predominantly immobilized in a layered double hydroxide (LDH) phase, which was corroborated by DRS measurements. Only a minor extent of Ni(ll) precipitates as Ni-hydroxides (alpha-Ni(OH)2 and beta-Ni(OH)2). This finding suggests that Ni-Al LDH, rather than Ni-hydroxides, is the solubility-limiting phase in the Ni-doped cement system.

Nickel↗

Water dynamics in hardened ordinary Portland cement paste or concrete: from quasielastic neutron scattering.

Portland cement reacts with water to form an amorphous paste through a chemical reaction called hydration. In concrete the formation of pastes causes the mix to harden and gain strength to form a rock-like mass. Within this process lies the key to a remarkable peculiarity of concrete: it is plastic and soft when newly mixed, strong and durable when hardened. These qualities explain why one material, concrete, can build skyscrapers, bridges, sidewalks and superhighways, houses, and dams. The character of the concrete is determined by the quality of the paste. Creep and shrinkage of concrete specimens occur during the loss and gain of water from cement paste. To better understand the role of water in mature concrete, a series of quasielastic neutron scattering (QENS) experiments were carried out on cement pastes with water/cement ratio varying between 0.32 and 0.6. The samples were cured for about 28 days in sealed containers so that the initial water content would not change. These experiments were carried out with an actual sample of Portland cement rather than with the components of cement studied by other workers. The QENS spectra differentiated between three different water interactions: water that was chemically bound into the cement paste, the physically bound or "glassy water" that interacted with the surface of the gel pores in the paste, and unbound water molecules that are confined within the larger capillary pores of cement paste. The dynamics of the "glassy" and "unboud" water in an extended time scale, from a hundred picoseconds to a few nanoseconds, could be clearly differentiated from the data. While the observed motions on the picosecond time scale are mainly stochastic reorientations of the water molecules, the dynamics observed on the nanosecond range can be attributed to long-range diffusion. Diffusive motion was characterized by diffusion constants in the range of (0.6-2) 10(-9) m(2)/s, with significant reduction compared to the rate of diffusion for bulk water. This reduction of the water diffusion is discussed in terms of the interaction of the water with the calcium silicate gel and the ions present in the pore water.

Journal Article↗

Isothermal and non-isothermal polymerization of a new bone cement.

A new bone cement based on poly(ethylmethacrylate) (PEMA), hydroxyapatite powder (HA) and n-butylmethacrylate monomer (n-BMA) has been studied using isothermal and non-isothermal polymerization. Methacrylate monomers are highly reactive and release a considerable amount of heat during polymerization. A quantitative understanding of the methacrylate polymerization is necessary because the thermal history of the polymerization has considerable influence on the final properties of a bone cement. In the first part, polymerization kinetics are analysed by means of differential scanning calorimetry (DSC). DSC data are used to evaluate a phenomenological model describing the cure kinetics of this new bone cement. In the second part, a kinetic model coupled with the energy balance is used to obtain temperature and degree of conversion profiles in the bone-cement-prosthesis system, under non-isothermal conditions, as function of initial temperature and thickness of the cement. Material properties, boundary and initial conditions and the kinetic behaviour are the input data for the numerically solved heat-transfer model. The temperature at the bone/cement interface, can be considered as a weak point, often responsible for total joint replacement failure. For this particular bone cement exhibiting a low exotherm and low glass transition temperature, the interfacial temperature is lower than the threshold level for thermal tissue damage (50 degrees C). The conversion occurs almost completely, avoiding problems with unreacted monomers that can be released by the cement, giving rise to tissue damage.

Journal Article↗