In situ TiB-reinforced Cu-based bulk metallic glass composites

Cu-based bulk metallic glass (BMG) composites containing in situ TiB particles were successfully fabricated. The reinforcing TiB particles with a size of 5-10 mu m are uniformly distributed in the amorphous matrix. The particles have a good bonding to the matrix with a reaction layer. The BMG composites exhibit an obvious ductility with a plastic strain of 2% for the 17.5 vol.% TiB sample due to the suppression of shear band propagation and the generation of multiple shear bands during compressive testing. The hardness of the materials is increased from Hv543 for monolithic BMG to Hv650 for 23.6 vol.% TiB-containing BMG composite. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

In vitro characterization of a collagen scaffold enzymatically cross-linked with a tailored elastin-like polymer

Collagen, the main structural component of the extracellular matrix (ECM), provides tensile stiffness to different structures and organs against rupture. However, collagen tissue-engineered implants are hereto still lacking in mechanical strength. Attempts to create stiffer scaffolds have resulted in increased brittleness of the material, reducing the versatility of the original component. The hypothesis behind this research is that the introduction of an elastic element in the scaffold will enhance the mechanical properties of the collagen-based scaffolds, as elastin does in the ECM to prevent irreversible deformation. In this study, an elastin-like polymer (ELP) designed and synthesized using recombinant DNA methodology is used with the view to providing increased proteolytic resistance and increased functionality to the scaffolds by carrying specific sequences for microbial transglutaminase cross-linking, endothelial cell adhesion, and drug delivery. Evaluation of the effects that cross-linking ELP-collagen has on the physicochemical properties of the scaffold such as porosity, presence of cross-linking, thermal behavior, and mechanical strength demonstrated that the introduction of enzymatically resistant covalent bonds between collagen and ELP increases the mechanical strength of the scaffolds in a dose-dependent manner without significantly affecting the porosity or thermal properties of the original scaffold. Importantly, the scaffolds also showed selective behavior, in a dose (ELP)-dependent manner toward human umbilical vein endothelial cells and smooth muscle cells when compared to fibroblasts.

The controlled release of macromolecules from macroporous hydrophyllic polymer matrices

This work has used novel polymer design and fabrication technology to generate bead form polymer based systems, with variable, yet controlled release properties, specifically for the delivery of macromolecules, essentially peptides of therapeutic interest. The work involved investigation of the potential interaction between matrix ultrastructural morphology, in vitro release kinetics, bioactivity and immunoreactivity of selected macromolecules with limited hydrolytic stability, delivered from controlled release vehicles. The underlying principle involved photo-polymerisation of the monomer, hydroxyethyl methacrylate, around frozen ice crystals, leading to the production of a macroporous hydrophilic matrix. Bead form matrices were fabricated in controllable size ranges in the region of 100µm - 3mm in diameter. The initial stages of the project involved the study of how variables, delivery speed of the monomer and stirring speed of the non solvent, affectedthe formation of macroporous bead form matrices. From this an optimal bench system for bead production was developed. Careful selection of monomer, solvents, crosslinking agent and polymerisation conditions led to a variable but controllable distribution of pore sizes (0.5 - 4µm). Release of surrogate macromolecules, bovine serum albumin and FITC-linked dextrans, enabled factors relating to the size and solubility of the macromolecule on the rate of release to be studied. Incorporation of bioactive macromolecules allowed retained bioactivity to be determined (glucose oxidase and interleukin-2), whilst the release of insulin enabled determination of both bioactivity (using rat epididymal fat pad) and immunoreactivity (RIA). The work carried out has led to the generation of macroporous bead form matrices, fabricated from a tissue biocompatible hydrogel, capable of the sustained, controlled release of biologically active peptides, with potential use in the pharmaceutical and agrochemical industries.

Polymer modified cement: hydration microstructure and diffusion properties

Investigations concentrated on the styrene butadiene rubber (SBR) latex and formulations included standard carboxylated and special carboxylated latexes. The aqueous component, containing the stabilisers and antifoaming agent but not the polymer solids, was also used. For comparison, limited investigations were carried out using other polymer types e.g. acrylic, ethylene-vinyl acetate (EVA), and redispersible powders rather than emulsions. The major findings were: 1) All latex systems investigated acted as retarders for cement hydration. The extent of retardation depends on the type of polymer. The mechanism for cement hydration may be changed, and excessive retardation influences properties. 2) Polymer modified cements exhibited either similar or coarser pore structures compared with unmodified cements. Results suggest that polymer mainly exists in a mixture of cement hydrates and polymer phase. Very little evidence was found for the formation of a distinct polymer film phase. 3) During the first few days of curing the polymer solids are removed from the pore solution and concentrations of OH-, Na+ and K+ are reduced. These observations are probably a result of polymer-cement surface interactions since there was no evidence of any chemical reactions or degradation of the polymer. 4) Improved diffusional resistance of modified cements depends on the ability to achieve adequate workability at low w/c ratio, rather than modification of matrix structure.

Reinforced thermoplastics for engineering applications

The effect of mechano-chemically bound polypropylene modifiers on the mechanical performance and thermal-oxidative stability of polypropylene composites has been studied. The mechanical performance of unmodified polypropylene containing silane coupled glass and Rockwool (mineral) fibre was poor by comparison with a similar commercially produced glass reinforced composite; this was attributed to poor fibre-matrix adhesion. Mechano-chemical binding with unsaturated additives was obtained in the presence of a free radical initiator (di-cumyl peroxide). This process was inhibited by stabilisers present in commercial grades of polypropylene composites by chemical bond formation between the chemically bound modifier and the silane coupling agent on the fibre surface, resulting in a dramatic improvement in the mechanical properties, dimensional stability and retention of mechanical performance after immersion in fluids typically found in under-bonnet environments.A feature unique to some of these modifiers was their ability not only to enhance the mechanical properties of polypropylene composites to levels substantially in excess of currently available commercial materials, but their ability to act as effective thermal-oxidative polypropylene stabilisers. The mode of action was shown to be a chain-breaking mechanism and as a result of the high binding levels achieved during melt processing, these modifiers were able to efficiently stabilise polypropylene in the most severe volatilising and solvent-extracting environments, thus giving much better protection to the polymer than currently available commercially stabilised grades of polypropylene.

Investigations on birefringence effects in polymer optical fiber Bragg gratings

Step-index polymer optical fiber Bragg gratings (POFBGs) and microstructured polymer optical fiber Bragg gratings (mPOFBGs) present several attractive features, especially for sensing purposes. In comparison to FBGs written in silica fibers, they are more sensitive to temperature and pressure because of the larger thermo-optic coefficient and smaller Young's modulus of polymer materials. (M)POFBGs are most often photowritten in poly(methylmethacrylate) (PMMA) materials using a continuous-wave 325 nm HeCd laser. For the first time to the best of our knowledge, we study photoinduced birefringence effects in (m)POFBGs. To achieve this, highly reflective gratings were inscribed with the phase mask technique. They were then monitored in transmission with polarized light. For this, (m)POF sections a few cm in length containing the gratings were glued to angled silica fibers. Polarization dependent loss (PDL) and differential group delay (DGD) were computed from the Jones matrix eigenanalysis using an optical vector analyser. Maximum values exceeding several dB and a few picoseconds were obtained for the PDL and DGD, respectively. The response to lateral force was finally investigated. As it induces birefringence in addition to the photo-induced one, an increase of the PDL and DGD values were noticed. © 2014 Copyright SPIE.

Erbium doped fiber laser mode locked by graphene in carboxymethylcellulose polymer composite

We have presented and demonstrated efficient mode locking of erbium doped fiber laser using graphene carboxymethylcellulose (CMC) polymer composites. The laser gives out soliton pulse with duration of ∼837 fs, and 0.19 nJ pulse energy. © 2014 OSA.

Role of reinforcement/matrix interfacial strength in fatigue crack propagation in particulate SiC reinforced aluminum alloy 8090

A study has been made of the influence of the reinforcement/matrix interfacial strength on fatigue crack propagation in a powder metallurgy aluminum alloy 8090-SiC particulate composite. The interfacial region has been altered by two separate routes, the first involving aging of the 8090 matrix, with the subsequent formation of precipitate free zones at the boundaries, and the second consisting of oxidizing the surface of the SiC particles before their incorporation into the composite. In the naturally aged condition, oxidation of the SiC leads to a reduction in fatigue crack growth resistance at higher values of stress intensity range ΔK. This is due to a proportion of the crack growth occurring through voids formed in association with many of the weak SiC interfaces which have retained a layer of thick surface oxide after processing. On overaging no difference in crack growth rate is discernible between the oxidized and unoxidized SiC composites. It is proposed that this is due to similar levels of interfacial weakening having occurred in both composites, indicating that this is an important factor in the reduction of the high ΔK crack growth resistance of the unoxidized SiC composite on aging.

Fatigue in SiC-particulate-reinforced aluminium alloy composites

The fatigue behaviour in SiC-particulate-reinforced aluminium alloy composites has been briefly reviewed. The improved fatigue life reported in stress-controlled test results from the higher stiffness of the composites; therefore it is generally inferior to monolithic alloys at a constant strain level. The role of SiC particulate reinforcement has been examined for fatigue crack initiation, short-crack growth and long-crack growth. Crack initiation is observed to occur at matrix-SiC interface in cast composites and either at or near the matrix-SiC interface or at cracked SiC particles in powder metallurgy processed composites depending on particle size and morphology. The da/dN vs ΔK relationship in the composites is characterized by crack growth rates existing within a narrow range of ΔK and this is because of the lower fracture toughness and relatively high threshold values in composites compared with those in monolithic alloys. An enhanced Paris region slope attributed to the monotonic fracture contribution are reported and the extent of this contribution is found to depend on particle size. The effects of the aging condition on crack growth rates and particle size dependence of threshold values are also treated in this paper. © 1991.

Polarization effects in polymer FBGs:study and use for transverse force sensing

Bragg gratings photo-inscribed in polymer optical fibers (POFs) are more sensitive to temperature and pressure than their silica counterparts, because of their larger thermo-optic coefficient and smaller Young's modulus. Polymer optical fiber Bragg gratings (POFBGs) are most often photo-written in poly(methylmethacrylate) (PMMA) based materials using a continuous-wave 325 nm HeCd laser. In this work, we present the first study about birefringence effects in POFBGs manufactured in different types of fiber. To achieve this, highly reflective (> 90%) gratings were produced with the phase mask technique. Their spectral response was then monitored in transmission with polarized light. Polarization dependent loss (PDL) and differential group delay (DGD) were computed from the Jones matrix eigenanalysis using an optical vector analyzer. Maximum values exceeding several dB and a few picoseconds were obtained for the PDL and DGD, respectively. An inverse scattering technique applied to the experimental data provided an estimate of the photo-induced birefringence value arising from the side fabrication process. The response to lateral force was finally investigated for various incident directions using the PDL response of FBGs manufactured in step-index POFs. As the force induced birefringence adds to the photo-induced one, a force dependent evolution of the PDL maximum value was noticed, with a good temperature-insensitivity.

Engineering surface states of carbon dots to achieve controllable luminescence for solid-luminescent composites and sensitive Be2+ detection

Luminescent carbon dots (L-CDs) with high quantum yield value (44.7%) and controllable emission wavelengths were prepared via a facile hydrothermal method. Importantly, the surface states of the materials could be engineered so that their photoluminescence was either excitation-dependent or distinctly independent. This was achieved by changing the density of amino-groups on the L-CD surface. The above materials were successfully used to prepare multicolor L-CDs/polymer composites, which exhibited blue, green, and even white luminescence. In addition, the excellent excitation-independent luminescence of L-CDs prepared at low temperature was tested for detecting various metal ions. As an example, the detection limit of toxic Be2+ ions, tested for the first time, was as low as μM.

Novel organo-modifier for thermally-stable polymer-layered silicate nanocomposites

A new novel approach for the stabilisation of polymer-clay nanocomposites has been investigated based on reacting chemically an antioxidant function, a hindered phenol moiety, with an organic modifier based on a quaternary ammonium salt. The chemically linked antioxidant-containing organic modifier (AO-OM) was then introduced into natural montmorillonite (MMt) through a cation-exchange reaction resulting in antioxidant-containing organo-modified clay (AO-OM-MMt). The new antioxidant-containing modified clay, along with other organo-modified clays having a similar organo-modifier but without the reacted antioxidant, were characterised by spectroscopic, thermogravimetric and x-ray diffraction techniques and tested for their thermo-oxidative stability. PA11-based clay nanocomposites samples containing the AO-OM-MMt and the other organo-modified clays, both without and with an added (i.e. not chemically reacted) hindered phenol antioxidant (similar to the one used in the AO-OM) were prepared by melt processing and examined for their processing and long-term thermal-oxidative stability at high temperatures. It was shown that although the new organo-modifier, AO-OM, was also susceptible to the Hoffman elimination reaction, the nanocomposites containing this newly modified clay (PA11/AO-OM-MMt) showed higher melt processing and long-term thermo-oxidative stability, along with excellent clay dispersion and exfoliation, compared to the other PA11-nanocomposites examined here (with and without the conventionally added antioxidant). It is suggested here that the excellent overall performance observed for the PA11/AO-OM-MMt nanocomposites is due to an in-situ partial release of low molecular weight antioxidant species having stabilising functionalities that are capable of acting locally at the interface between the inorganic clay platelets and the polymeric matrix which is a critical area for the onset of degradation processes.

Seismic performance of hybrid fiber reinforced polymer-concrete pier columns

As part of a multi-university research program funded by NSF, a comprehensive experimental and analytical study of seismic behavior of hybrid fiber reinforced polymer (FRP)-concrete column is presented in this dissertation. Experimental investigation includes cyclic tests of six large-scale concrete-filled FRP tube (CFFT) and RC columns followed by monotonic flexural tests, a nondestructive evaluation of damage using ultrasonic pulse velocity in between the two test sets and tension tests of sixty-five FRP coupons. Two analytical models using ANSYS and OpenSees were developed and favorably verified against both cyclic and monotonic flexural tests. The results of the two methods were compared. A parametric study was also carried out to investigate the effect of three main parameters on primary seismic response measures. The responses of typical CFFT columns to three representative earthquake records were also investigated. The study shows that only specimens with carbon FRP cracked, whereas specimens with glass or hybrid FRP did not show any visible cracks throughout cyclic tests. Further monotonic flexural tests showed that carbon specimens both experienced flexural cracks in tension and crumpling in compression. Glass or hybrid specimens, on the other hand, all showed local buckling of FRP tubes. Compared with conventional RC columns, CFFT column possesses higher flexural strength and energy dissipation with an extended plastic hinge region. Among all CFFT columns, the hybrid lay-up demonstrated the highest flexural strength and initial stiffness, mainly because of its high reinforcement index and FRP/concrete stiffness ratio, respectively. Moreover, at the same drift ratio, the hybrid lay-up was also considered as the best in term of energy dissipation. Specimens with glassfiber tubes, on the other hand, exhibited the highest ductility due to better flexibility of glass FRP composites. Furthermore, ductility of CFFTs showed a strong correlation with the rupture strain of FRP. Parametric study further showed that different FRP architecture and rebar types may lead to different failure modes for CFFT columns. Transient analysis of strong ground motions showed that the column with off-axis nonlinear filament-wound glass FRP tube exhibited a superior seismic performance to all other CFFTs. Moreover, higher FRP reinforcement ratios may lead to a brittle system failure, while a well-engineered FRP reinforcement configuration may significantly enhance the seismic performance of CFFT columns.

Hydroxyapatite-nanotube composites and coatings for orthopedic applications

Hydroxyapatite (HA) has received wide attention in orthopedics, due to its biocompatibility and osseointegration ability. Despite these advantages, the brittle nature and low fracture toughness of HA often results in rapid wear and premature fracture of implant. Hence, there is a need to improve the fracture toughness and wear resistance of HA without compromising its biocompatibility. ^ The aim of the current research is to explore the potential of nanotubes as reinforcement to HA for orthopedic implants. HA- 4 wt.% carbon nanotube (CNT) composites and coatings are synthesized by spark plasma sintering and plasma spraying respectively, and investigated for their mechanical, tribological and biological behavior. CNT reinforcement improves the fracture toughness (>90%) and wear resistance (>66%) of HA for coating and free standing composites. CNTs have demonstrated a positive influence on the proliferation, differentiation and matrix mineralization activities of osteoblasts, during in-vitro biocompatibility studies. In-vivo exposure of HA-CNT coated titanium implant in animal model (rat) shows excellent histocompatibility and neobone integration on the implant surface. The improved osseointegration due to presence of CNTs in HA is quantified by the adhesion strength measurement of single osteoblast using nano-scratch technique. ^ Considering the ongoing debate about cytotoxicity of CNTs in the literature, the present study also suggests boron nitride nanotube (BNNT) as an alternative reinforcement. BNNT with the similar elastic modulus and strength as CNT, were added to HA. The resulting composite having 4 wt.% BNNTs improved the fracture toughness (∼85%) and wear resistance (∼75%) of HA in the similar range as HA-CNT composites. BNNTs were found to be non-cytotoxic for osteoblasts and macrophages. In-vitro evaluation shows positive role of BNNT in osteoblast proliferation and viability. Apatite formability of BNNT surface in ∼4 days establishes its osseointegration ability.^

Seismic Performance of Hybrid Fiber Reinforced Polymer-Concrete Pier Columns

As part of a multi-university research program funded by NSF, a comprehensive experimental and analytical study of seismic behavior of hybrid fiber reinforced polymer (FRP)-concrete column is presented in this dissertation. Experimental investigation includes cyclic tests of six large-scale concrete-filled FRP tube (CFFT) and RC columns followed by monotonic flexural tests, a nondestructive evaluation of damage using ultrasonic pulse velocity in between the two test sets and tension tests of sixty-five FRP coupons. Two analytical models using ANSYS and OpenSees were developed and favorably verified against both cyclic and monotonic flexural tests. The results of the two methods were compared. A parametric study was also carried out to investigate the effect of three main parameters on primary seismic response measures. The responses of typical CFFT columns to three representative earthquake records were also investigated. The study shows that only specimens with carbon FRP cracked, whereas specimens with glass or hybrid FRP did not show any visible cracks throughout cyclic tests. Further monotonic flexural tests showed that carbon specimens both experienced flexural cracks in tension and crumpling in compression. Glass or hybrid specimens, on the other hand, all showed local buckling of FRP tubes. Compared with conventional RC columns, CFFT column possesses higher flexural strength and energy dissipation with an extended plastic hinge region. Among all CFFT columns, the hybrid lay-up demonstrated the highest flexural strength and initial stiffness, mainly because of its high reinforcement index and FRP/concrete stiffness ratio, respectively. Moreover, at the same drift ratio, the hybrid lay-up was also considered as the best in term of energy dissipation. Specimens with glassfiber tubes, on the other hand, exhibited the highest ductility due to better flexibility of glass FRP composites. Furthermore, ductility of CFFTs showed a strong correlation with the rupture strain of FRP. Parametric study further showed that different FRP architecture and rebar types may lead to different failure modes for CFFT columns. Transient analysis of strong ground motions showed that the column with off-axis nonlinear filament-wound glass FRP tube exhibited a superior seismic performance to all other CFFTs. Moreover, higher FRP reinforcement ratios may lead to a brittle system failure, while a well-engineered FRP reinforcement configuration may significantly enhance the seismic performance of CFFT columns.