Performance estimation for concretes made with recycled aggregates of construction and demolition waste of some Brazilian cities

The aim of this paper is to verify the influence of composition variability of recycled aggregates (RA) of construction and demolition wastes (CDW) on the performance of concretes. Performance was evaluated building mathematical models for compressive strength, modulus of elasticity and drying shrinkage. To obtain such models, an experimental program comprising 50 concrete mixtures was carried out. Specimens were casted, tested and results for compressive strength, modulus of elasticity and drying shrinkage were statistically analyzed. Models inputs are CDW composition observed at seven Brazilian cities. Results confirm that using RA from CDW for concrete building is quite feasible, independently of its composition, once compressive strength and modulus of elasticity still reached considerable values. We concluded the variability presented by recycled aggregates of CDW does not compromise their use for concrete building. However, this information must be used with caution, and experimental tests should always be performed to certify concrete properties.

Cement-base bearing pads mortar for connections in the precast concrete: study of surface roughness

Bearing pads are used in precast concrete connections to avoid concentrated stresses in the contact area between the precast elements. In the present research, the bearing pads are Portland cement mortar with styrene-butadiene latex (SB), lightweight aggregate (expanded vermiculite-term) and short fibers (polypropylene, glass and PVA), in order to obtain a material with low modulus of elasticity and high tenacity, compared with normal Portland cement mortar. The objective of this paper is to analyze the influence of surface roughness on the pads and test other types of polypropylene fibers. Tests were carried out to characterize the composite and test on bearing pads. Characterization tests show compressive strength of 41MPa and modulus of elasticity of 12.8GPa. The bearing pads tests present 30% reduction of stiffness in relation to a reference mortar. The bearing pads with roughness on both sides present a reduction up to 30% in stiffness and an increase in accumulated deformation of more than 120%, regarding bearing pads with both sides smooth.

Development and characterization of non-oxide ceramic composites for mechanical and tribological applications

The main reasons for the attention focused on ceramics as possible structural materials are their wear resistance and the ability to operate with limited oxidation and ablation at temperatures above 2000°C. Hence, this work is devoted to the study of two classes of materials which can satisfy these requirements: silicon carbide -based ceramics (SiC) for wear applications and borides and carbides of transition metals for ultra-high temperatures applications (UHTCs). SiC-based materials: Silicon carbide is a hard ceramic, which finds applications in many industrial sectors, from heat production, to automotive engineering and metals processing. In view of new fields of uses, SiC-based ceramics were produced with addition of 10-30 vol% of MoSi2, in order to obtain electro conductive ceramics. MoSi2, indeed, is an intermetallic compound which possesses high temperature oxidation resistance, high electrical conductivity (21·10-6 Ω·cm), relatively low density (6.31 g/cm3), high melting point (2030°C) and high stiffness (440 GPa). The SiC-based ceramics were hot pressed at 1900°C with addition of Al2O3-Y2O3 or Y2O3-AlN as sintering additives. The microstructure of the composites and of the reference materials, SiC and MoSi2, were studied by means of conventional analytical techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (SEM-EDS). The composites showed a homogeneous microstructure, with good dispersion of the secondary phases and low residual porosity. The following thermo-mechanical properties of the SiC-based materials were measured: Vickers hardness (HV), Young’s modulus (E), fracture toughness (KIc) and room to high temperature flexural strength (σ). The mechanical properties of the composites were compared to those of two monolithic SiC and MoSi2 materials and resulted in a higher stiffness, fracture toughness and slightly higher flexural resistance. Tribological tests were also performed in two configurations disco-on-pin and slideron cylinder, aiming at studying the wear behaviour of SiC-MoSi2 composites with Al2O3 as counterfacing materials. The tests pointed out that the addition of MoSi2 was detrimental owing to a lower hardness in comparison with the pure SiC matrix. On the contrary, electrical measurements revealed that the addition of 30 vol% of MoSi2, rendered the composite electroconductive, lowering the electrical resistance of three orders of magnitude. Ultra High Temperature Ceramics: Carbides, borides and nitrides of transition metals (Ti, Zr, Hf, Ta, Nb, Mo) possess very high melting points and interesting engineering properties, such as high hardness (20-25 GPa), high stiffness (400-500 GPa), flexural strengths which remain unaltered from room temperature to 1500°C and excellent corrosion resistance in aggressive environment. All these properties place the UHTCs as potential candidates for the development of manoeuvrable hypersonic flight vehicles with sharp leading edges. To this scope Zr- and Hf- carbide and boride materials were produced with addition of 5-20 vol% of MoSi2. This secondary phase enabled the achievement of full dense composites at temperature lower than 2000°C and without the application of pressure. Besides the conventional microstructure analyses XRD and SEM-EDS, transmission electron microscopy (TEM) was employed to explore the microstructure on a small length scale to disclose the effective densification mechanisms. A thorough literature analysis revealed that neither detailed TEM work nor reports on densification mechanisms are available for this class of materials, which however are essential to optimize the sintering aids utilized and the processing parameters applied. Microstructural analyses, along with thermodynamics and crystallographic considerations, led to disclose of the effective role of MoSi2 during sintering of Zrand Hf- carbides and borides. Among the investigated mechanical properties (HV, E, KIc, σ from room temperature to 1500°C), the high temperature flexural strength was improved due to the protective and sealing effect of a silica-based glassy phase, especially for the borides. Nanoindentation tests were also performed on HfC-MoSi2 composites in order to extract hardness and elastic modulus of the single phases. Finally, arc jet tests on HfC- and HfB2-based composites confirmed the excellent oxidation behaviour of these materials under temperature exceeding 2000°C; no cracking or spallation occurred and the modified layer was only 80-90 μm thick.

Physical and mineralogical changes of Hungarian monumental stones exposed to different conditions: stone-testing in-situ and under laboratory conditions

The Székesfehérvár Ruin Garden is a unique assemblage of monuments belonging to the cultural heritage of Hungary due to its important role in the Middle Ages as the coronation and burial church of the Kings of the Hungarian Christian Kingdom. It has been nominated for “National Monument” and as a consequence, its protection in the present and future is required. Moreover, it was reconstructed and expanded several times throughout Hungarian history. By a quick overview of the current state of the monument, the presence of several lithotypes can be found among the remained building and decorative stones. Therefore, the research related to the materials is crucial not only for the conservation of that specific monument but also for other historic structures in Central Europe. The current research is divided in three main parts: i) description of lithologies and their provenance, ii) physical properties testing of historic material and iii) durability tests of analogous stones obtained from active quarries. The survey of the National Monument of Székesfehérvár, focuses on the historical importance and the architecture of the monument, the different construction periods, the identification of the different building stones and their distribution in the remaining parts of the monument and it also included provenance analyses. The second one was the in situ and laboratory testing of physical properties of historic material. As a final phase samples were taken from local quarries with similar physical and mineralogical characteristics to the ones used in the monument. The three studied lithologies are: fine oolitic limestone, a coarse oolitic limestone and a red compact limestone. These stones were used for rock mechanical and durability tests under laboratory conditions. The following techniques were used: a) in-situ: Schmidt Hammer Values, moisture content measurements, DRMS, mapping (construction ages, lithotypes, weathering forms) b) laboratory: petrographic analysis, XRD, determination of real density by means of helium pycnometer and bulk density by means of mercury pycnometer, pore size distribution by mercury intrusion porosimetry and by nitrogen adsorption, water absorption, determination of open porosity, DRMS, frost resistance, ultrasonic pulse velocity test, uniaxial compressive strength test and dynamic modulus of elasticity. The results show that initial uniaxial compressive strength is not necessarily a clear indicator of the stone durability. Bedding and other lithological heterogeneities can influence the strength and durability of individual specimens. In addition, long-term behaviour is influenced by exposure conditions, fabric and, especially, the pore size distribution of each sample. Therefore, a statistic evaluation of the results is highly recommended and they should be evaluated in combination with other investigations on internal structure and micro-scale heterogeneities of the material, such as petrographic observation, ultrasound pulse velocity and porosimetry. Laboratory tests used to estimate the durability of natural stone may give a good guidance to its short-term performance but they should not be taken as an ultimate indication of the long-term behaviour of the stone. The interdisciplinary study of the results confirms that stones in the monument show deterioration in terms of mineralogy, fabric and physical properties in comparison with quarried stones. Moreover stone-testing proves compatibility between quarried and historical stones. Good correlation is observed between the non-destructive-techniques and laboratory tests results which allow us to minimize sampling and assessing the condition of the materials. Concluding, this research can contribute to the diagnostic knowledge for further studies that are needed in order to evaluate the effect of recent and future protective measures.

Structural and elastic properties of DNA and chromatin

We investigate a chain consisting of two coupled worm-like chains withconstant distance between the strands. The effects due todouble-strandedness of the chain are studied. In a previous analyticalstudy of this system an intrinsic twist-stretch coupling and atendency of kinking is predicted. Even though a local twist structureis observed the predicted features are not recovered. A new model for DNA at the base-pair level is presented. Thebase-pairs are treated as flat rigid ellipsoids and thesugar-phosphate backbones are represented as stiff harmonic springs.The base-pair stacking interaction is modeled by a variant of theGay-Berne potential. It is shown by systematic coarse-graininghow the elastic constants of a worm-like chain are related to thelocal fluctuations of the base-pair step parameters. Even though a lotof microscopic details of the base-pair geometry is neglected themodel can be optimized to obtain a B-DNA conformation as ground stateand reasonable elastic properties. Moreover the model allows tosimulate much larger length scales than it is possible with atomisticsimulations due to the simplification of the force-field and inparticular due to the possibility of non-local Monte-Carlo moves. Asa first application the behavior under stretching is investigated. Inagreement with micromanipulation experiments on single DNA moleculesone observes a force-plateau in the force-extension curvescorresponding to an overstretching transition from B-DNA to aso-called S-DNA state. The model suggests a structure for S-DNA withhighly inclined base-pairs in order to enable at least partialbase-pair stacking. Finally a simple model for chromatin is introduced to study itsstructural and elastic properties. The underlying geometry of themodeled fiber is based on a crossed-linker model. The chromatosomesare treated as disk-like objects. Excluded volume and short rangenucleosomal interaction are taken into account by a variant of theGay-Berne potential. It is found that the bending rigidity and thestretching modulus of the fiber increase with more compact fibers. Fora reasonable parameterization of the fiber for physiologicalconditions and sufficiently high attraction between the nucleosomes aforce-extension curve is found similar to stretching experiments onsingle chromatin fibers. For very small stretching forces a kinkedfiber forming a loop is observed. If larger forces are applied theloop formation is stretched out and a decondensation of the fibertakes place.

The behaviour of osteocyte dendritic processes in bone under cyclic load (il comportamento dei processi dendritici degli osteociti nel tessuto osseo sottoposti a carico ciclico)

Bone is continually being removed and replaced through the actions of basic multicellular units (BMU). This constant upkeep is necessary to remove microdamage formed naturally due to fatigue and thus maintain the integrity of the bone. The repair process in bone is targeted, meaning that a BMU travels directly to the site of damage and repairs it. It is still unclear how targeted remodelling is stimulated and directed but it is highly likely that osteocytes play a role. A number of theories have been advanced to explain the microcrack osteocyte interaction but no complete mechanism has been demonstrated. Osteocytes are connected to each other by dendritic processes. The “scissors model" proposed that the rupture of these processes where they cross microcracks signals the degree of damage and the urgency of the necessary repair. In its original form it was proposed that under applied compressive loading, microcrack faces will be pressed together and undergo relative shear movement. If this movement is greater than the width of an osteocyte process, then the process will be cut in a “scissors like" motion, releasing RANKL, a cytokine known to be essential in the formation of osteoclasts from pre-osteoclasts. The main aim of this thesis was to investigate this theoretical model with a specific focus on microscopy and finite element modelling. Previous studies had proved that cyclic stress was necessary for osteocyte process rupture to occur. This was a divergence from the original “scissors model" which had proposed that the cutting of cell material occurred in one single action. The present thesis is the first study to show fatigue failure in cellular processes spanning naturally occurring cracks and it's the first study to estimate the cyclic strain range and relate it to the number of cycles to failure, for any type of cell. Rupture due to shear movement was ruled out as microcrack closing never occurred, as a result of plastic deformation of the bone. Fatigue failure was found to occur due to cyclic tensile stress in the locality of the damage. The strain range necessary for osteocyte process rupture was quantified. It was found that the lower the process strain range the greater the number of cycles to cell process failure. FEM modelling allowed to predict stress in the vicinity of an osteocyte process and to analyse its interaction with the bone surrounding it: simulations revealed evident creep effects in bone during cyclic loading. This thesis confirms and dismisses aspects of the “scissors model". The observations support the model as a viable mechanism of microcrack detection by the osteocyte network, albeit in a slightly modified form where cyclic loading is necessary and the method of rupture is fatigue failure due to cyclic tensile motion. An in depth study was performed focusing on microscopy analysis of naturally occurring cracks in bone and FEM simulation analysis of an osteocyte process spanning a microcrack in bone under cyclic load.

A new method for continuous quality control of nsm cfrp systems

In the last decade the near-surface mounted (NSM) strengthening technique using carbon fibre reinforced polymers (CFRP) has been increasingly used to improve the load carrying capacity of concrete members. Compared to externally bonded reinforcement (EBR), the NSM system presents considerable advantages. This technique consists in the insertion of carbon fibre reinforced polymer laminate strips into pre-cut slits opened in the concrete cover of the elements to be strengthened. CFRP reinforcement is bonded to concrete with an appropriate groove filler, typically epoxy adhesive or cement grout. Up to now, research efforts have been mainly focused on several structural aspects, such as: bond behaviour, flexural and/or shear strengthening effectiveness, and energy dissipation capacity of beam-column joints. In such research works, as well as in field applications, the most widespread adhesives that are used to bond reinforcements to concrete are epoxy resins. It is largely accepted that the performance of the whole application of NSM systems strongly depends on the mechanical properties of the epoxy resins, for which proper curing conditions must be assured. Therefore, the existence of non-destructive methods that allow monitoring the curing process of epoxy resins in the NSM CFRP system is desirable, in view of obtaining continuous information that can provide indication in regard to the effectiveness of curing and the expectable bond behaviour of CFRP/adhesive/concrete systems. The experimental research was developed at the Laboratory of the Structural Division of the Civil Engineering Department of the University of Minho in Guimar\~aes, Portugal (LEST). The main objective was to develop and propose a new method for continuous quality control of the curing of epoxy resins applied in NSM CFRP strengthening systems. This objective is pursued through the adaptation of an existing technique, termed EMM-ARM (Elasticity Modulus Monitoring through Ambient Response Method) that has been developed for monitoring the early stiffness evolution of cement-based materials. The experimental program was composed of two parts: (i) direct pull-out tests on concrete specimens strengthened with NSM CFRP laminate strips were conducted to assess the evolution of bond behaviour between CFRP and concrete since early ages; and, (ii) EMM-ARM tests were carried out for monitoring the progressive stiffness development of the structural adhesive used in CFRP applications. In order to verify the capability of the proposed method for evaluating the elastic modulus of the epoxy, static E-Modulus was determined through tension tests. The results of the two series of tests were then combined and compared to evaluate the possibility of implementation of a new method for the continuous monitoring and quality control of NSM CFRP applications.

Transport of nanoparticles into polymersomes : a minimal model system of particles passage through biological membranes

This thesis focuses on the design and characterization of a novel, artificial minimal model membrane system with chosen physical parameters to mimic a nanoparticle uptake process driven exclusively by adhesion and softness of the bilayer. The realization is based on polymersomes composed of poly(dimethylsiloxane)-b-poly(2-methyloxazoline) (PMDS-b-PMOXA) and nanoscopic colloidal particles (polystyrene, silica), and the utilization of powerful characterization techniques. rnPDMS-b-PMOXA polymersomes with a radius, Rh ~100 nm, a size polydispersity, PD = 1.1 and a membrane thickness, h = 16 nm, were prepared using the film rehydratation method. Due to the suitable mechanical properties (Young’s modulus of ~17 MPa and a bending modulus of ~7⋅10-8 J) along with the long-term stability and the modifiability, these kind of polymersomes can be used as model membranes to study physical and physicochemical aspects of transmembrane transport of nanoparticles. A combination of photon (PCS) and fluorescence (FCS) correlation spectroscopies optimizes species selectivity, necessary for a unique internalization study encompassing two main efforts. rnFor the proof of concepts, the first effort focused on the interaction of nanoparticles (Rh NP SiO2 = 14 nm, Rh NP PS = 16 nm; cNP = 0.1 gL-1) and polymersomes (Rh P = 112 nm; cP = 0.045 gL-1) with fixed size and concentration. Identification of a modified form factor of the polymersome entities, selectively seen in the PCS experiment, enabled a precise monitor and quantitative description of the incorporation process. Combining PCS and FCS led to the estimation of the incorporated particles per polymersome (about 8 in the examined system) and the development of an appropriate methodology for the kinetics and dynamics of the internalization process. rnThe second effort aimed at the establishment of the necessary phenomenology to facilitate comparison with theories. The size and concentration of the nanoparticles were chosen as the most important system variables (Rh NP = 14 - 57 nm; cNP = 0.05 - 0.2 gL-1). It was revealed that the incorporation process could be controlled to a significant extent by changing the nanoparticles size and concentration. Average number of 7 up to 11 NPs with Rh NP = 14 nm and 3 up to 6 NPs with Rh NP = 25 nm can be internalized into the present polymersomes by changing initial nanoparticles concentration in the range 0.1- 0.2 gL-1. Rapid internalization of the particles by polymersomes is observed only above a critical threshold particles concentration, dependent on the nanoparticle size. rnWith regard possible pathways for the particle uptake, cryogenic transmission electron microscopy (cryo-TEM) has revealed two different incorporation mechanisms depending on the size of the involved nanoparticles: cooperative incorporation of nanoparticles groups or single nanoparticles incorporation. Conditions for nanoparticle uptake and controlled filling of polymersomes were presented. rnIn the framework of this thesis, the experimental observation of transmembrane transport of spherical PS and SiO2 NPs into polymersomes via an internalization process was reported and examined quantitatively for the first time. rnIn a summary the work performed in frames of this thesis might have significant impact on cell model systems’ development and thus improved understanding of transmembrane transport processes. The present experimental findings help create the missing phenomenology necessary for a detailed understanding of a phenomenon with great relevance in transmembrane transport. The fact that transmembrane transport of nanoparticles can be performed by artificial model system without any additional stimuli has a fundamental impact on the understanding, not only of the nanoparticle invagination process but also of the interaction of nanoparticles with biological as well as polymeric membranes. rn

Mechanical properties and structure of gel systems

Understanding the origins of the mechanical properties and its correlation withrnthe microstructure of gel systems is of great scientific and industrial interest. Inrngeneral, colloidal gels can be classified into chemical and physical gels, accordingrnto the life time of the network bonds. The characteristic di↵erences in gelationrndynamics can be observed with rheological measurements.rnAs a model system, a mixture of sodium silicate and low concentration sulfuric acidrnwas used. Nano-sized silica particles grow and aggregate to a system-spanning gelrnnetwork. The influence of the finite solubility of silica at high pH on the gelationrnwas studied with classical and piezo rheometer. The storage modulus of therngel grew logarithmically with time with two distinct growth laws. A relaxationrnat low frequency was observed in the frequency dependent measurements. I attributernthese two behaviors as a sign of structural rearrangements due to the finiternsolubility of silica at high pH. The reaction equilibrium between formation andrndissolution of bonds leads to a finite life time of the bonds and behavior similar tornphysical gel. The frequency dependence was more pronounced for lower water concentrations,rnhigher temperatures and shorter reaction times. With two relaxationrnmodels, I deduced characteristic relaxation times from the experimental data. Besidesrnrheology, the evolution of silica gels at high pH on di↵erent length scales wasrnstudied by NMR and dynamic light scattering. The results revealed that the primaryrnparticles existed already in sodium silicate and aggregated after the mixingrnof reactants due to a chemical reaction. Throughout the aggregation process thernsystem was in its chemical reaction equilibrium. Applying large oscillatory shearrnstrain to the gel allowed for modifying the gel modulus. The e↵ect of shear andrnshear history on the rheological properties of the gel were investigated. The storagernmodulus of the final gel increased with increasing strain. This behavior can be explained with (i) shear-induced aggregate compaction and (ii) combination ofrnbreakage and new formation of bonds.rnIn comparison with the physical gel-like behavior of the silica gel at high pH, typicalrnchemical gel features were exhibited by other gels formed from various chemicalrnreactions. Influences of the chemical structure modification on the gelation wererninvestigated with the piezo-rheometer. The external stimuli can be applied to tunernthe mechanical properties of the gel systems.

Relevance of In-vitro Tests of Adhesive and Composite Dental Materials. A Review in 3 Parts. Part 2: Non-standardized tests of composite materials

Summary The first part of this review examined ISO approval requirements and in vitro testing. In the second part, non-standardized test methods for composite materials are presented and discussed. Physical tests are primarily described. Analyses of surface gloss and alterations, as well as aging simulations of dental materials are presented. Again, the importance of laboratory tests in determining clinical outcomes is evaluated. Differences in the measurement protocols of the various testing institutes and how these differences can in?uence the results are also discussed. Because there is no standardization of test protocols, the values determined by different institutes cannot be directly compared. However, the ranking of the tested materials should be the same if a valid protocol is applied by different institutes. The modulus of elasticity, the expansion after water sorption, and the polishability of the material are all clinically relevant, whereas factors measured by other test protocols may have no clinical correlation. The handling properties of the materials are highly dependent on operators' preferences. Therefore, no standard values can be given.

Eliminating Adhesion Errors in Nanoindentation of Compliant Polymers and Hydrogels

Nanoindentation is a valuable tool for characterization of biomaterials due to its ability to measure local properties in heterogeneous, small or irregularly shaped samples. However, applying nanoindentation to compliant, hydrated biomaterials leads to many challenges including adhesion between the nanoindenter tip and the sample. Although adhesion leads to overestimation of the modulus of compliant samples when analyzing nanoindentation data using traditional analysis techniques, most studies of biomaterials have ignored its effects. This paper demonstrates two methods for managing adhesion in nanoindentation analysis, the nano-JKR force curve method and the surfactant method, through application to two biomedically-relevant compliant materials, poly(dimethyl siloxane) (PDMS) elastomers and poly(ethylene glycol) (PEG) hydrogels. The nano-JKR force curve method accounts for adhesion during data analysis using equations based on the Johnson-Kendall-Roberts (JKR) adhesion model, while the surfactant method eliminates adhesion during data collection, allowing data analysis using traditional techniques. In this study, indents performed in air or water resulted in adhesion between the tip and the sample, while testing the same materials submerged in Optifree Express() contact lens solution eliminated tip-sample adhesion in most samples. Modulus values from the two methods were within 7% of each other, despite different hydration conditions and evidence of adhesion. Using surfactant also did not significantly alter the properties of the tested material, allowed accurate modulus measurements using commercial software, and facilitated nanoindentation testing in fluids. This technique shows promise for more accurate and faster determination of modulus values from nanoindentation of compliant, hydrated biological samples. Copyright 2013 Elsevier Ltd. All rights reserved.

The long-term mechanical integrity of non-reinforced PEEK-OPTIMA polymer for demanding spinal applications: experimental and finite-element analysis

Polyetheretherketone (PEEK) is a novel polymer with potential advantages for its use in demanding orthopaedic applications (e.g. intervertebral cages). However, the influence of a physiological environment on the mechanical stability of PEEK has not been reported. Furthermore, the suitability of the polymer for use in highly stressed spinal implants such as intervertebral cages has not been investigated. Therefore, a combined experimental and analytical study was performed to address these open questions. A quasi-static mechanical compression test was performed to compare the initial mechanical properties of PEEK-OPTIMA polymer in a dry, room-temperature and in an aqueous, 37 degrees C environment (n=10 per group). The creep behaviour of cylindrical PEEK polymer specimens (n=6) was measured in a simulated physiological environment at an applied stress level of 10 MPa for a loading duration of 2000 hours (12 weeks). To compare the biomechanical performance of different intervertebral cage types made from PEEK and titanium under complex loading conditions, a three-dimensional finite element model of a functional spinal unit was created. The elastic modulus of PEEK polymer specimens in a physiological environment was 1.8% lower than that of specimens tested at dry, room temperature conditions (P<0.001). The results from the creep test showed an average creep strain of less than 0.1% after 2000 hours of loading. The finite element analysis demonstrated high strain and stress concentrations at the bone/implant interface, emphasizing the importance of cage geometry for load distribution. The stress and strain maxima in the implants were well below the material strength limits of PEEK. In summary, the experimental results verified the mechanical stability of the PEEK-OPTIMA polymer in a simulated physiological environment, and over extended loading periods. Finite element analysis supported the use of PEEK-OPTIMA for load-bearing intervertebral implants.

Investigation into the enhancement of polycarbonate with conductive nanomaterials

Polymers are typically electrically and thermally insulating materials. The electrical and thermal conductivities of polymers can be increased by the addition conductive fillers such as carbons. Once the polymer composites have been made electrically and thermally conductive, they can be used in applications where these conductivities are desired such as electromagnetic shielding and static dissipation. In this project, three carbon nanomaterials are added to polycarbonate to enhance the electrical and thermal conductivity of the resulting composite. Hyperion Catalysis FIBRILs carbon nanotubes were added to a maximum loading of 8 wt%. Ketjenblack EC-600 JD carbon black was added to a maximum loading of 10 wt%. XG Sciences xGnP™ graphene nanoplatelets were added to a maximum loading of 15 wt%. These three materials have drastically different morphologies and will have varying effects on the various properties of polycarbonate composites. It was determined that carbon nanotubes have the largest effect on electrical conductivity with an 8 wt% carbon nanotube in polycarbonate composite having an electrical conductivity of 0.128 S/cm (from a pure polycarbonate value of 10-17 S/cm). Carbon black has the next largest effect with an 8 wt% carbon black in polycarbonate composite having an electrical conductivity of 0.008 S/cm. Graphene nanoplatelets have the least effect with an 8 wt% graphene nanoplatelet in polycarbonate having an electrical conductivity of 2.53 x 10-8 S/cm. Graphene nanoplatelets show a significantly higher effect on increasing thermal conductivity than either carbon nanotubes or carbon black. Mechanically, all three materials have similar effects with graphene nanoplatelets being somewhat more effective at increasing the tensile modulus of the composite than the other fillers. Carbon black and graphene nanoplatelets show standard carbon-filler rheology where the addition of filler increases the viscosity of the resulting composite. Carbon nanotubes, on the other hand, show an unexpected rheology. As carbon nanotubes are added to polycarbonate the viscosity of the composite is reduced below that of the original polycarbonate. It was seen that the addition of carbon nanotubes offsets the increased viscosity from a second filler, such as carbon black or graphene nanoplatelets.

Variation of the mechanical properties of PMMA to suit osteoporotic cancellous bone

Poly(methyl methacrylate) (PMMA) is by far the most frequently used bone substitute material for vertebroplasty. However, there are serious complications, such as cement leakage and an increased fracture rate of the adjacent vertebral bodies. The latter may be related to the mechanical properties of the augmented segment within the osteoporotic spine. A possible counter-measure is prophylactic augmentation at additional levels, but this aggravates the risk for the patient. Introduction of pores is a possible method to reduce the inherent high stiffness of PMMA. This study investigates the effect of porosity on the mechanical properties of PMMA bone cement. Different fractions of a highly viscous liquid were mixed into the PMMA during preparation. An open-porous material with adjustable mechanical properties resulted after removal of the aqueous phase. Different radiopacifiers were admixed to investigate their suitability for vertebroplasty. The final material was characterized mechanically by compressive testing, microscopically and radiologically. In addition, the monomer release subsequent to hardening was measured by means of gas chromatography. The Young's modulus in compression could be varied between 2800 +/- 70 MPa and 120 +/- 150 MPa, and the compression ultimate strength between 170 +/- 5 MPa and 8 +/- 9 MPa for aqueous fractions ranging between 0 and 50% of volume. Only a slight decrease of the Young's modulus and small changes of ultimate strength were found when the mixing time was increased. An organic hydrophilic and lipophilic radiopacifier led to a higher Young's modulus of the porous material; however, the ultimate strength was not significantly affected by adding different radiopacifiers to the porous cement. The radiopacity was lost after washing the aqueous phase out of the pores. No separation occurred between the aqueous and the PMMA phase during injection into an open porous ceramic material. The monomer released was found to increase for increasing aqueous fractions, but remained comparable in magnitude to standard PMMA. This study demonstrates that a conventional PMMA can be modified to obtain a range of mechanical properties, including those of osteoporotic bone.

Performance of vertebral cancellous bone augmented with compliant PMMA under dynamic loads

Increased fracture risk has been reported for the adjacent vertebral bodies after vertebroplasty. This increase has been partly attributed to the high Young's modulus of commonly used polymethylmethacrylate (PMMA). Therefore, a compliant bone cement of PMMA with a bulk modulus closer to the apparent modulus of cancellous bone has been produced. This compliant bone cement was achieved by introducing pores in the cement. Due to the reduced failure strength of that porous PMMA cement, cancellous bone augmented with such cement could deteriorate under dynamic loading. The aim of the present study was to assess the potential of acute failure, particle generation and mechanical properties of cancellous bone augmented with this compliant cement in comparison to regular cement. For this purpose, vertebral biopsies were augmented with porous- and regular PMMA bone cement, submitted to dynamic tests and compression to failure. Changes in Young's modulus and height due to dynamic loading were determined. Afterwards, yield strength and Young's modulus were determined by compressive tests to failure and compared to the individual composite materials. No failure occurred and no particle generation could be observed during dynamical testing for both groups. Height loss was significantly higher for the porous cement composite (0.53+/-0.21%) in comparison to the biopsies augmented with regular cement (0.16+/-0.1%). Young's modulus of biopsies augmented with porous PMMA was comparable to cancellous bone or porous cement alone (200-700 MPa). The yield strength of those biopsies (21.1+/-4.1 MPa) was around two times higher than for porous cement alone (11.6+/-3.3 MPa).