Processing and properties of transparent hydroxyapatite and β tricalcium phosphate obtained by HIP process

Stoichiometric β-tricalcium phosphate (β-TCP) and hydroxyapatite (HA) powders were synthesized by chemical precipitation of aqueous solutions of diammonium phosphate and calcium nitrate. After a calcination treatment and a milling step, the powders were shaped by slip casting. The sintering temperature effect on the relative density and the average grain size was investigated. By natural sintering at 1200 and 1120 °C, densities of 98% and 99% were obtained for HA and TCP, respectively. After determination of minimum temperatures to obtain only closed porosity and a pre-sintering at these temperatures, hot isostatic pressing (HIP) treatment was carried out. Transparent or translucent samples were obtained, indicating a relative density very close to the theoretical value (>99.9%). Mechanical properties (three-point bending strength, fracture toughness, Young's modulus and Vickers hardness) were measured on both materials with similar grain size (～ 1 μm). Bending strengths of 181 and 105 MPa were measured for TCP and HA, respectively.     

Wrinkling of epoxy powder coatings

Differential scanning calorimetry (DSC) and mechanical profilometry were used to study wrinkle formation in curing epoxy powder coatings. Powder coating formulations were studied that contained solid epoxy resins, methylene disalicylic acid (MDSA) crosslinker, and an amine‐blocked Lewis acid catalyst. Both the crosslinker (MDSA) and the amine‐blocked catalyst are required for wrinkle formation. Evaporation of the blocking amine from the free surface of the coating generated a depthwise gradient in the extent of polymerization and crosslinking, and hence in the degree of solidification, as evidenced by the formation of a mechanical skin prior to wrinkling. It is hypothesized that compressive elastic stress develops in the still swellable skin when unreacted low‐molecular‐weight material from beneath diffuses up into the monomer‐ or oligomer‐depleted crosslinking skin and swells it. This compressive stress, if above a critical value, buckles the skin to produce wrinkles. Experimentally observed compositional requirements for wrinkle formation were consistent with the proposed mechanism. The size of the wrinkles can be controlled by varying formulation parameters such as the amount of catalyst or crosslinker. Increasing the amount of catalyst decreased both the wavelength and the amplitude of the wrinkle pattern. Increasing the amount of crosslinker initially increased the amplitude of the wrinkles; after reaching a maximum level, the wrinkle amplitude decreased. DSC was a useful tool to understand the critical reactions responsible for wrinkling in this system. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 116–129, 2005     

Nanocomposites based on polyethylene and Mg-Al layered double hydroxide. I. Synthesis and characterization

Low density polyethylene (LDPE)/Mg-Al layered double hydroxide (LDH) nanocomposites have been synthesized with different compositions by melt-mixing technique using maleic anhydride grafted polyethylene as compatibilizer. LDH has been modified by sodium dodecylbenzene sulfonate using reconstruction method and characterized by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. The nanocomposites are characterized by different techniques such as, transmission electron microscopy (TEM), XRD and rheology. The TEM analysis shows a complex nature of particle dispersion in the polymer matrix with wide distribution of particles sizes and shapes. The rheological analysis showed significant changes in linear viscoelastic responses of the composites, even at very low concentration (2 phr) of LDH materials, in comparison to the pure polymer in low frequency regime in dynamic frequency sweep experiments. These changes are related to the LDHs-polymer chains interactions resulting in network-like structure.     

Novel poly(3‐hydroxybutyrate) composite films containing bioactive glass nanoparticles for wound healing applications

Bioactive glass is considered an ideal material for haemostasis as it releases Ca²⁺ ions upon hydration, which is required to support thrombosis. In this study the effects of the presence of nanoscaled bioactive glass (n‐BG) in poly(3‐hydroxybutyrate) (P(3HB)) microsphere films on the structural properties, thermal properties and biocompatibility of the films were studied. The n‐BG with a high surface area was also tested for its in vitro haemostatic efficacy and was found to be able to successfully reduce clot detection time. In an effort to study the effect of the roughness induced by the formation of hydroxyapatite on cellular functions such as cell adhesion, cell mobility and cell differentiation, the composite films were immersed in simulated body fluid for periods of 1, 3 and 7 days. From scanning electron microscopy images, the surface of the P(3HB)/n‐BG composite microsphere films appeared fairly uniform and smooth on day 1; however on day 3 and day 7 a rough and uneven surface was observed. The presence of hydroxyapatite on the composite microsphere films on day 3 and day 7 influenced the surface roughness of the films. However, when the P(3HB)/n‐BG composite microsphere films with enhanced surface roughness were tested for biocompatibility, reduced amounts of protein adsorption and cell adhesion were observed. This study thus revealed that there is an optimal surface roughness for the P(3HB) microsphere films for increased cell adhesion, beyond which it could be deleterious for cell adhesion and differentiation. © 2016 Society of Chemical Industry     

Deformation behaviour of an advanced nickel-based superalloy studied by neutron diffraction and electron microscopy

Deformation mechanisms under tensile loading at room temperature have been studied in a polycrystalline nickel-based superalloy containing close to 50 vol.% γ′. In order to identify the effect of γ′ particle size on deformation mechanisms, model microstructures with unimodal γ′ size distributions were developed. The investigations were carried out by combining in situ loading experiments using neutron diffraction and two-site elasto-plastic self-consistent plasticity modelling with detailed post-mortem electron microscopy. The microscopy work also includes results for samples strained at 500 °C. During early plastic deformation, the diffraction data demonstrate that γ and γ′ display the same elastic strain response, indicating that at this stage γ′ is cut by dislocations regardless of the γ′ particle size. Scanning electron microscopy studies showed an abundance of shearing processes in all three microstructures, hence supporting the conclusions drawn from the diffraction experiment. As the material is further deformed, elastic load transfer from γ to γ′ was observed in the medium (130 nm) and coarse (230 nm) γ′ microstructures but not in the fine (90 nm) γ′ microstructure. The load transfer can be explained by assuming that Orowan looping becomes an additional operative deformation mode. Transmission electron microscopy confirmed that in the fine γ′ microstructure deformation takes place by strongly coupled dislocations cutting the γ′, while the medium and coarse γ′ microstructures showed additional signs of Orowan looping.     

Identification of models for control of wet granulation

The modeling work in this paper provides insight on improved control and design (including measurement selection) of a granulation process. Two different control strategies (MPC and PID) are evaluated on an experimentally validated granulation model. This model is based on earlier work done at The University of Sheffield, UK and Organon, The Netherlands [C.F.W. Sanders, W. Oostra, A.D. Salman, M.J. Hounslow, Development of a predictive high-shear granulation model; experimental and modeling results, 7th World Congress of Chemical Engineering, Glasgow (2005), C11-002]. The granulation kinetics were measured in a 10 liter batch granulator with an experimental design that included four process variables. The aggregation rates were extracted with a Discretized Population Balance (DPB) model. Knowledge of the process kinetics was used to model a continuous (well mixed) granulator. The controller model for the Model Predictive Controller is a linearized state space model, derived from the nonlinear DPB model. It has the four process variables from the experimental design and a feed ratio as input variables. Since the DPB model describes the whole Granule Size Distribution (GSD), candidate sets of lumped output variables were evaluated. When measuring controller performance based on the full granule size distribution, it is shown that a PID controller can actually produce results that fluctuate more than the open-loop response. An MPC controller improves stability on both process outputs and the full granule size distribution. The work shows that measuring and controlling specific number based lumped outputs result in a more stable process than when mass based lumped outputs are used. The paper describes a general strategy of using lab scale batch experiments to design and control (small or large scale) continuous granulators. The continuous experiments in this paper are based on simulation, therefore future experimental validation will elucidate further the link between batch and continuous granulation.     

An analysis of starburst defects in wrinkled powder coatings

Starbursts are defects in wrinkled powder coatings wherein the typical random orientation of the wrinkles is disrupted. Instead, wrinkles orient radially around a central point creating a star-like pattern. The origin of the starburst defect was investigated by mechanical profilometry and elemental analysis by energy dispersive X-ray spectroscopy (EDS). Topographical measurements demonstrated that the centers of the stars almost always are at a higher elevation compared to their surroundings, suggesting the presence of non-dispersed extender particles or external impurities at the center. EDS analysis of the center of the stars confirmed the presence of external particles or impurities. Radial orientation of the wrinkles around the external particles can be explained by preferential pattern orientation due to directional stress relief.     

Polydimethylsiloxane based polyurethane and its composite with layered double hydroxide: Synthesis and its thermal properties

This investigation reports the synthesis of a new class of polyurethane (PU) based on bis(hydroxyalkyl) polydimethylsiloxane (PDMS) as diol and isophorone diisocyanate as diisocyanate followed by the preparation of PU/layered double hydroxide (PU/LDH) nanocomposite via ex-situ technique. Nuclear magnetic resonance and Fourier-transform infrared spectroscopy studies confirm the formation of PU and incorporation of PDMS into the PU backbone. Thermogravimetry analysis revealed that thermal stability of the composite improves significantly with incorporation of LDH into the PU matrix. This may be accredited to the barrier effect rendered by the LDH layers. Differential scanning calorimetry study reveals that with the incorporation of LDH, glass transition temperature (T_g) of the composite increases for an optimum level of loading beyond which it remains constant.     

The Innate Immune Glycoprotein Lactoferrin Represses the Helicobacter pylori cag Type IV Secretion System

Chronic infection with Helicobacter pylori increases risk of gastric diseases including gastric cancer. Despite development of a robust immune response, H. pylori persists in the gastric niche. Progression of gastric inflammation to serious disease outcomes is associated with infection with H. pylori strains which encode the cag Type IV Secretion System (cag T4SS). The cag T4SS is responsible for translocating the oncogenic protein CagA into host cells and inducing pro-inflammatory and carcinogenic signaling cascades. Our previous work demonstrated that nutrient iron modulates the activity of the T4SS and biogenesis of T4SS pili. In response to H. pylori infection, the host produces a variety of antimicrobial molecules, including the iron-binding glycoprotein, lactoferrin. Our work shows that apo-lactoferrin exerts antimicrobial activity against H. pylori under iron-limited conditions, while holo-lactoferrin enhances bacterial growth. Culturing H. pylori in the presence of holo-lactoferrin prior to co-culture with gastric epithelial cells, results in repression of the cag T4SS activity. Concomitantly, a decrease in biogenesis of cag T4SS pili at the host-pathogen interface was observed under these culture conditions by high-resolution electron microscopy analyses. Taken together, these results indicate that acquisition of alternate sources of nutrient iron plays a role in regulating the pro-inflammatory activity of a bacterial secretion system and present novel therapeutic targets for the treatment of H. pylori-related disease.     

E7766, a Macrocycle-Bridged Stimulator of Interferon Genes (STING) Agonist with Potent Pan-Genotypic Activity

A strategy for creating potent and pan-genotypic stimulator of interferon genes (STING) agonists is described. Locking a bioactive U-shaped conformation of cyclic dinucleotides by introducing a transannular macrocyclic bridge between the nucleic acid bases leads to a topologically novel macrocycle-bridged STING agonist (MBSA). In addition to substantially enhanced potency, the newly designed MBSAs, exemplified by clinical candidate E7766 , exhibit broad pan-genotypic activity in all major human STING variants. E7766 is shown to have potent antitumor activity with long lasting immune memory response in a mouse liver metastatic tumor model. Two complementary stereoselective synthetic routes to E7766 are also described.