Ultra-structural defects cause low bone matrix stiffness despite high mineralization in osteogenesis imperfecta mice.

Bone is a complex material with a hierarchical multi-scale organization from the molecule to the organ scale. The genetic bone disease, osteogenesis imperfecta, is primarily caused by mutations in the collagen type I genes, resulting in bone fragility. Because the basis of the disease is molecular with ramifications at the whole bone level, it provides a platform for investigating the relationship between structure, composition, and mechanics throughout the hierarchy. Prior studies have individually shown that OI leads to: 1. increased bone mineralization, 2. decreased elastic modulus, and 3. smaller apatite crystal size. However, these have not been studied together and the mechanism for how mineral structure influences tissue mechanics has not been identified. This lack of understanding inhibits the development of more accurate models and therapies. To address this research gap, we used a mouse model of the disease (oim) to measure these outcomes together in order to propose an underlying mechanism for the changes in properties. Our main finding was that despite increased mineralization, oim bones have lower stiffness that may result from the poorly organized mineral matrix with significantly smaller, highly packed and disoriented apatite crystals. Using a composite framework, we interpret the lower oim bone matrix elasticity observed as the result of a change in the aspect ratio of apatite crystals and a disruption of the crystal connectivity.

Dispersion of carbon nanotubes: Mixing, sonication, stabilization, and composite properties

Advances in functionality and reliability of carbon nanotube (CNT) composite materials require careful formulation of processing methods to ultimately realize the desired properties. To date, controlled dispersion of CNTs in a solution or a composite matrix remains a challenge, due to the strong van der Waals binding energies associated with the CNT aggregates. There is also insufficiently defined correlation between the microstructure and the physical properties of the composite. Here, we offer a review of the dispersion processes of pristine (non-covalently functionalized) CNTs in a solvent or a polymer solution. We summarize and adapt relevant theoretical analysis to guide the dispersion design and selection, from the processes of mixing/sonication, to the application of surfactants for stabilization, to the final testing of composite properties. The same approaches are expected to be also applicable to the fabrication of other composite materials involving homogeneously dispersed nanoparticles. © 2012 by the authors; licensee MDPI, Basel, Switzerland.

A matrix-calculation-based algorithm for numerical change propagation analysis

Engineering changes (ECs) are raised throughout the lifecycle of engineering products. A single change to one component produces knock-on effects on others necessitating additional changes. This change propagation significantly affects the development time and cost and determines the product's success. Predicting and managing such ECs is, thus, essential to companies. Some prediction tools model change propagation by algorithms, whereof a subgroup is numerical. Current numerical change propagation algorithms either do not account for the exclusion of cyclic propagation paths or are based on exhaustive searching methods. This paper presents a new matrix-calculation-based algorithm which can be applied directly to a numerical product model to analyze change propagation and support change prediction. The algorithm applies matrix multiplications on mutations of a given design structure matrix accounting for the exclusion of self-dependences and cyclic propagation paths and delivers the same results as the exhaustive search-based Trail Counting algorithm. Despite its factorial time complexity, the algorithm proves advantageous because of its straightforward matrix-based calculations which avoid exhaustive searching. Thereby, the algorithm can be implemented in established numerical programs such as Microsoft Excel which promise a wider application of the tools within and across companies along with better familiarity, usability, practicality, security, and robustness. © 1988-2012 IEEE.

The soft impact response of composite laminate beams

The quasi-static and dynamic responses of laminated beams of equal areal mass, made from monolithic CFRP and Ultra high molecular weight Polyethylene (UHMWPE), have been measured. The end-clamped beams were impacted at mid-span by metal foam projectiles to simulate localised blast loading. The effect of clamping geometry on the response was investigated by comparing the response of beams bolted into the supports with the response of beams whose ends were wrapped around the supports. The effect of laminate shear strength upon the static and dynamic responses was investigated by testing two grades of each of the CFRP and UHMWPE beams: (i) CFRP beams with a cured matrix and uncured matrix, and (ii) UHMWPE laminates with matrices of two different shear strengths. Quasi-static stretch-bend tests indicated that the load carrying capacity of the UHWMPE beams exceeds that of the CFRP beams, increases with diminishing shear strength of matrix, and increases when the ends are wrapped rather than through-bolted. The dynamic deformation mode of the beams is qualitatively different from that observed in the quasi-static stretch-bend tests. In the dynamic case, travelling hinges emanate from the impact location and propagate towards the supports; the beams finally fail by tensile fibre fracture at the supports. The UHMWPE beams outperform the CFRP beams in terms of a lower mid-span deflection for a given impulse, and a higher failure impulse. Also, the maximum attainable impulse increases with decreasing shear strength for both the UHMWPE and CFRP beams. The ranking of the beams for load carrying capacity in the quasi-static stretch-bend tests is identical to that for failure impulse in the impact tests. Thus, the static tests can be used to gauge the relative dynamic performances of the beams. © 2013 Elsevier Ltd. All rights reserved.

The effect of shear strength on the ballistic response of laminated composite plates

The ballistic performance of clamped circular carbon fibre reinforced polymer (CFRP) and Ultra High Molecular Weight Polyethylene (UHMWPE) fibre composite plates of equal areal mass and 0/90 lay-up were measured and compared with that of monolithic 304 stainless steel plates. The effect of matrix shear strength upon the dynamic response was explored by testing: (i) CFRP plates with both a cured and uncured matrix and (ii) UHMWPE laminates with identical fibres but with two matrices of different shear strength. The response of these plates when subjected to mid-span, normal impact by a steel ball was measured via a dynamic high speed shadow moiré technique. Travelling hinges emanate from the impact location and travel towards the supports. The anisotropic nature of the composite plate results in the hinges travelling fastest along the fibre directions and this results in square-shaped moiré fringes in the 0/90 plates. Projectile penetration of the UHMWPE and the uncured CFRP plates occurs in a progressive manner, such that the number of failed plies increases with increasing velocity. The cured CFRP plate, of high matrix shear strength, fails by cone-crack formation at low velocities, and at higher velocities by a combination of cone-crack formation and communition of plies beneath the projectile. On an equal areal mass basis, the low shear strength UHMWPE plate has the highest ballistic limit followed by the high matrix shear strength UHMWPE plate, the uncured CFRP, the steel plate and finally the cured CFRP plate. We demonstrate that the high shear strength UHMWPE plate exhibits Cunniff-type ballistic limit scaling. However, the observed Cunniff velocity is significantly lower than that estimated from the laminate properties. The data presented here reveals that the Cunniff velocity is limited in its ability to characterise the ballistic performance of fibre composite plates as this velocity is independent of the shear properties of the composites: the ballistic limit of fibre composite plates increases with decreasing matrix shear strength for both CFRP and UHMWPE plates. © 2013 Elsevier Masson SAS. All rights reserved.

Award Winner in the Young Investigator Category, 2014 Society for Biomaterials Annual Meeting and Exposition, Denver, Colorado, April 16-19, 2014: Periodically perforated core-shell collagen biomaterials balance cell infiltration, bioactivity, and mechanical properties.

Orthopedic tissue engineering requires biomaterials with robust mechanics as well as adequate porosity and permeability to support cell motility, proliferation, and new extracellular matrix (ECM) synthesis. While collagen-glycosaminoglycan (CG) scaffolds have been developed for a range of tissue engineering applications, they exhibit poor mechanical properties. Building on previous work in our lab that described composite CG biomaterials containing a porous scaffold core and nonporous CG membrane shell inspired by mechanically efficient core-shell composites in nature, this study explores an approach to improve cellular infiltration and metabolic health within these core-shell composites. We use indentation analyses to demonstrate that CG membranes, while less permeable than porous CG scaffolds, show similar permeability to dense materials such as small intestine submucosa (SIS). We also describe a simple method to fabricate CG membranes with organized arrays of microscale perforations. We demonstrate that perforated membranes support improved tenocyte migration into CG scaffolds, and that migration is enhanced by platelet-derived growth factor BB-mediated chemotaxis. CG core-shell composites fabricated with perforated membranes display scaffold-membrane integration with significantly improved tensile properties compared to scaffolds without membrane shells. Finally, we show that perforated membrane-scaffold composites support sustained tenocyte metabolic activity as well as improved cell infiltration and reduced expression of hypoxia-inducible factor 1α compared to composites with nonperforated membranes. These results will guide the design of improved biomaterials for tendon repair that are mechanically competent while also supporting infiltration of exogenous cells and other extrinsic mediators of wound healing.

Collapse of a composite beam made from ultra high molecular-weight polyethylene fibres

Hot-pressed laminates with a [0/90]48 lay-up, consisting of 83% by volume of ultra high molecular-weight polyethylene (UHMWPE) fibres, and 17% by volume of polyurethane (PU) matrix, were cut into cantilever beams and subjected to transverse end-loading. The collapse mechanisms were observed both visually and by X-ray scans. Short beams deform elastically and collapse plastically in longitudinal shear, with a shear strength comparable to that observed in double notch, interlaminar shear tests. In contrast, long cantilever beams deform in bending and collapse via a plastic hinge at the built-in end of the beam. The plastic hinge is formed by two wedge-shaped microbuckle zones that grow in size and in intensity with increasing hinge rotation. This new mode of microbuckling under macroscopic bending involves both elastic bending and shearing of the plies, and plastic shear of the interface between each ply. The double-wedge pattern contrasts with the more usual parallel-sided plastic microbuckle that occurs in uniaxial compression. Finite element simulations and analytical models give additional insight into the dominant material and geometric parameters that dictate the collapse response of the UHMWPE composite beam in bending. Detailed comparisons between the observed and predicted collapse responses are used in order to construct a constitutive model for laminated UHMWPE composites. © 2013 Elsevier Ltd.

The effect of cationic, non-ionic and amphiphilic surfactants on the intercalation of bentonite

Surfactant-clay interactions are key for the development of new clay applications and inorganic-organic nanocomposites. Bentonite, with montmorillonite as the principal clay mineral constituent, was modified with varying concentrations of hexadecethyltrimethylammonium chloride (HDTMA), as a reference cationic surfactant, polypropylene glycol (PPG) 1200 and 2000, as non-ionic surfactants, and lecithin and Topcithin®, as amphiphilic phospholipid surfactants, according to the cation exchange capacity (CEC). The modified bentonites were characterised by X-ray diffraction, thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectrometry, specific surface area and pore volume. Three intercalation regions have been identified depending on the surfactant. The non-ionic surfactant caused only a crystalline expansion of bentonite interlayers, while the cationic surfactant induced an osmotic intercalation. The amphiphilic lecithin derivatives intercalated more extensively with the bentonite matrix. The TGA and the FTIR spectra showed that, at lower concentrations, the PPGs and HDTMA adopted a disordered conformation that required more energy to degrade, while at higher concentrations, the surfactants were ordered in the interlayer space of the bentonite. The lecithin derivative surfactant had a greater thermal and conformation stability. The specific surface area reduced with increasing surfactant concentrations. This study highlights the effect of surfactant type on the interlayer space of montmorillonite in the perspective of developing novel clay functions. © 2013.

Physical properties of a hybrid and a nanohybrid dental light-cured resin composite.

This work was aimed at the study of some physical properties of two current light-cured dental resin composites, Rok (hybrid) and Ice (nanohydrid). As filler they both contain strontium aluminosilicate particles, however, with different size distribution, 40 nm-2.5 mum for Rok and 10 nm-1 mum for Ice. The resin matrix of Rok consists of UDMA, that of Ice of UDMA, Bis-EMA and TEGDMA. Degree of conversion was determined by FT-IR analysis. The flexural strength and modulus were measured using a three-point bending set-up according to the ISO-4049 specification. Sorption, solubility and volumetric change were measured after storage of composites in water or ethanol/water (75 vol%) for 1 day, 7 or 30 days. Thermogravimetric analysis was performed in air and nitrogen atmosphere from 30 to 700 degrees C. Surface roughness and morphology of the composites was studied by atomic force microscopy (AFM). The degree of conversion was found to be 56.9% for Rok and 61.0% for Ice. The flexural strength of Rok does not significantly differ from that of Ice, while the flexural modulus of Rok is higher than that of Ice. The flexural strengths of Rok and Ice did not show any significant change after immersion in water or ethanol solution for 30 days. The flexural modulus of Rok and Ice did not show any significant change either after immersion in water for 30 days, while it decreased significantly, even after 1 day immersion, in ethanol solution. Ice sorbed a higher amount of water and ethanol solution than Rok and showed a higher volume increase. Thermogravimetric analysis showed that Rok contains about 80 wt% inorganic filler and Ice about 75 wt%.

Analysis of estrogens in environmental waters using polymer monolith in-polyether ether ketone tube solid-phase microextraction combined with high-performance liquid chromatography

A simple, rapid and sensitive on-line method for simultaneous determination of four endocrine disruptors (17 beta-estradiol, estriol, bisphenol A and 17 alpha-ethinylestradiol) in environmental waters was developed by coupling in-tube solid-phase microextraction (SPME) to high-performance liquid chromatography (HPLC) with fluorescence detection (FLD). A poly(acrylamide-vinylpyridine-NAP-methylene bisacrylamide) monolith, synthesized inside a polyether ether ketone (PEEK) tube, was selected as the extraction medium. To achieve optimum extraction performance, several parameters were investigated, including extraction flow-rate, extraction time, and pH value, inorganic salt and organic solvent content of the sample matrix. By simply filtered with nylon membrane filter and adjusting the pH of samples to 6.0 with phosphoric acid, the sample solution then could be directly injected into the device for extraction. Low detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method were achieved in the range of 0.006-0.10 ng/mL and 0.02-0.35 ng/mL from spiked lake waters, respectively. The calibration curves of four endocrine disruptors showed good linearity ranging from quantification limits to 50 ng/mL with a linear coefficient R-2 value above 0.9913. Good method reproducibility was also found by intra- and inter-day precisions, yielding the RSDs less than 12 and 9.8%, respectively. Finally, the proposed method was successfully applied to the determination of these compounds in several environmental waters. (c) 2006 Elsevier B.V. All rights reserved.

A solid-phase microextraction fiber coated with diglycidyloxycalix[4]arene yields very high extraction selectivity and sensitivity during the analysis of chlorobenzenes in soil

A novel fiber coated with novel sol-gel (5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-diglycidyloxycalix[4]arene/hydroxy-terminated silicone oil; diglycidyloxy-C[4]/OH-TSO) was prepared for use with headspace solid-phase microextraction (HS-SPME) combined with gas chromatography (GC) and electron capture detection (ECD), which was applied in order to determine nine chlorobenzenes in soil matrices. Due to the improved fiber preparation, which increases the percentage of calixarene in the coating, the new calixarene fiber exhibits very high extraction selectivity and sensitivity to chlorine-substituted compounds. Various parameters affecting the extraction efficiency were optimized in order to maximize the sensitivity during the chlorobenzene analysis. Interferences from different soil matrices with different characteristics were investigated, and the amount extracted was strongly influenced by the matrix. Therefore, a standard addition protocol was performed on the real soil samples. The linear ranges of detection for the chlorobenzenes tested covered three orders of magnitude, and correlation coefficients > 0.9976 and relative standard deviations (RSD) < 8% were observed. The detection limits were found at sub-ng/g of soil levels, which were about an order of magnitude lower than those given by the commercial poly(dimethylsiloxane) (PDMS) coating for most of the compounds. The recoveries ranged from 64 to 109.6% for each analyte in the real kaleyard soil matrix when different concentration levels were determined over the linear range, which confirmed the reliability and feasibility of the HS-SPME/GC-ECD approach using the fiber coated with diglycidyloxy-C[4]/OH-TSO for the ultratrace analysis of chlorobenzenes in complex matrices.

Determination of phthalate acid esters plasticizers in plastic by ultrasonic solvent extraction combined with solid-phase microextraction using calix[4]arene fiber

Ultrasonic solvent extraction combined with solid-phase microextraction (SPME) with calix[4]arene/hydroxy-terminated silicone (C[4]/OHTSO) oil coated fiber was used to extract phthalate acid esters (PAEs) plasticizers in plastic, such as blood bags, transfusion tubing, food packaging bag, and mineral water bottle for analysis by gas chromatography (GC). Both extraction parameters (i.e. extraction time, extraction temperature, ionic strength) and conditions of the thermal desorption in a GC injector were optimized by analysis of eight phthalates. The fiber shows wonderful sensitivity and selectivity to the tested compounds. Owing to its high thermal stability (380 degreesC), the carryover effect that often encountered when using conventional fibers can be reduced by appropriately enhancing the injector temperature. The method showed linear response over two to four orders of magnitude with correlation coefficients (r) better than 0.996, and limits of detection (LOD) ranged between 0.006 and 0.084 mug l(-1). The relative standard deviation values obtained were less than or equal to 10%. bis-2-Ethylhexyl phthalate (DEHP) was the sole analyte detected in these plastics and recoveries were in the ranges 95.5-101.4% in all the samples. (C) 2004 Elsevier B.V. All rights reserved.

Comparative extraction of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F-s) from a variety of solid samples

Extraction experiments with spiking of C-13(12)-PCDD/Fs were performed with a variety of PCDD/Fs contaminated samples. The extraction recovery of PCDD/Fs was mainly influenced by PCDD/Fs concentration and the sample matrix. Generally, the first soxhlet extraction with toluene has suitable recovery. From the selected samples, only FAMS4 and 5 which are fly ashes with high concentration, the recovery of the first soxhlet extraction with 24 hr. is low, but PCDD/Fs were almost completely removed after 72 hr. Copyright (C) 1996 Elsevier Science Ltd

Transparent and Light-Emitting Epoxy Super-Nanocomposites Containing ZnO-QDs/SiO2 Nanocomposite Particles as Encapsulating Materials for Solid-State Lighting

In this article, the ZnO quantum dots-SiO2 (Z-S) nanocomposite particles were first synthesized. Transparent Z-S/epoxy super-nanocomposites were then prepared by introducing calcined Z-S nanocomposite particles with a proper ratio of ZnO to SiO2 into a transparent epoxy matrix in terms of the filler-matrix refractive index matching principle. It was shown that the epoxy super-nanocomposites displayed intense luminescence with broad emission spectra. Moreover, the epoxy super-nanocomposites showed the interesting afterglow phenomenon with a long phosphorescence lifetime that was not observed for ZnO-QDs/epoxy nanocomposites. Finally, the transparent and light-emitting Z-S/epoxy super-nanocomposites were successfully employed as encapsulating materials for synthesis of highly bright LED lamps.