The effect of freeze-drying parameters on the cure characteristics of freeze-dried BSA-loaded silicone elastomer

To formulate therapeutic proteins into polymeric devices the protein is typically in the solid state, which can be achieved by the process of freeze-drying. However, freeze-drying not only risks denaturing the protein but it can adversely affect the cure characteristics of protein-loaded silicone elastomers. This study demonstrates that a variation in the parameters of the freeze-dryer can significantly affect the residual moisture content of freeze-dried BSA, which in turn has an effect on the bulk density and flow properties of the BSA. The bulk density and flow properties of the BSA subsequently affect the cure characteristics of BSA-loaded silicone elastomers. An increase in the residual moisture content results in the freeze-dried BSA having a decreased bulk density and poor flow properties which can have a detrimental effect on the cure characteristics of a freeze-dried BSA-loaded silicone elastomer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2012

Studies on Conductive Silicone Rubber Compounds

ABSTRACT: The electrical conductivity of silicone rubber vulcanizates containing carbon blacks [e.g., acetylene black, lamp black, and ISAF (N-234) black] were investigated. The change in electrical conductivity with varying amounts of carbon blacks and the temperature dependence was measured. The mechanical properties like tensile strength, tear strength, elongation at break, hardness, etc., of the vulcanizates were determined. A comparative study of the electrical conductivity of the composites revealed that the electrical conductivity of the composites made with acetylene black was higher than that of the composites made of other blacks.

Dielectric properties of conducting polymer

The dielectric properties of conducting polymer composites containing polypyrrole (PPy) crushed films, PPy powder, polyaniline (PAn) base and acid powders as the dispersants and silicone rubber and vinyl ester as matrix materials have been investigated in the frequency range 2-18 GHz. The dielectric parameters such as the real part, epsiprime, and imaginary part, epsiPrime, of the permittivity and loss tangent, tandelta, increase with increasing conductivity and concentration of the dispersant. The geometrical shape of the dispersant governs the ability of conductive network formation which is indicated by a large drop in the resistivity of the composite. Also, dispersant/matrix interactions and physical properties of the matrix influence the agglomeration of the dispersant phase which, in turn, affects the dielectric properties of the composites. Flakes of PPy obtained by crushing highly conductive films and large PAn powder aggregates were unable to form a conducting network. The composites without a network of dispersant exhibit low dielectric parameters. On the other hand, high values of tan delta ranging from 0.7–1.1 were achieved for the PPy powder (15 parts)/silicone rubber composites where a conducting network was observed.

Effects of pigment, disinfection, and accelerated aging on the hardness and deterioration of a facial silicone elastomer

The failure of facial prostheses is caused by limitations in their flexibility and durability. Therefore, we evaluated the effects of disinfection and aging on Shore A hardness and deterioration of a facial silicone with different pigmentations. Twenty samples with addition of each pigment (ceramic (C), make-up (M)) and without pigment (L) were made. For each pigment type and no pigment, 10 samples were subjected to two types of disinfectant solution (soap (S) and Efferdent (E)), totaling sixty samples. The specimens were disinfected three times per week for 60 days, and subjected to accelerated aging for 1008 h. The hardness of the facial silicone was measured with a durometer, and its deterioration was evaluated by obtaining the weight difference over time. Both the hardness and weight of the samples were measured at baseline, after chemical disinfection, and periodically during accelerated aging (252, 504, and 1008 h). Deterioration was calculated during the periods between baseline and chemical disinfection, and between baseline and each aging period. The results were analyzed using three-way repeated measures ANOVA and the Tukey's HSD Post-hoc test (alpha = 0.05). Specifically, samples containing pigment exhibited significantly higher hardness and deterioration values than those lacking pigment (P < 0.05). In addition, period of time (disinfection and accelerated aging) statistically increased the hardness and deterioration values of the silicone (P < 0.05). It can be concluded that both pigment and time statistically affected the hardness and deterioration of the silicone elastomer. (c) 2012 Elsevier Ltd. All rights reserved.

Effect of addition of pigments and opacifier on the hardness, absorption, solubility and surface degradation of facial silicone after artificial ageing

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Investigations on the stability of plasma modified silicone surfaces

In this work it was investigated the effect of the exposure to different plasmas on the wettability of silicone samples. We have observed that oxygen. argon, and hydrogen glow discharges are quite effective in reducing the water contact angle of such polymer. However, indifferently to efficiency of the treatment, practically all the modified surfaces recovered great part of their original hydrophobicity. We have investigated this hydrophobic recovery using surface energy measurements and theoretical simulations based on the exponential decay of the population of polar groups on the surface. According to our results such recovery can be attributed to the decrease of polar species at the interface water-polymer surface.

Effect of disinfection and accelerated ageing on dimensional stability and detail reproduction of a facial silicone with nanoparticles

The aim of the present study was to evaluate the effect of disinfection and accelerated ageing on the dimensional stability and detail reproduction of a facial silicone with different types of nanoparticle. A total of 60 specimens were fabricated with Silastic MDX 4-4210 silicone and they were divided into three groups: colourless and pigmented with nanoparticles (make-up powder and ceramic powder). Half of the specimens of each group were disinfected with Efferdent tablets and half with neutral soap for 60 days. Afterwards, all specimens were subjected to accelerated ageing. Both dimensional stability and detail reproduction tests were performed after specimen fabrication (initial period), after chemical disinfection, and after accelerated ageing periods (252, 504 and 1008 hours). The dimensional stability test was conducted using AutoCAD software, while detail reproduction was analysed using a stereoscope magnifying glass. Dimensional stability values were statistically evaluated by analysis of variance (ANOVA) followed by Tukey's test (p < 0.01). Detail reproduction results were compared using a score. Chemical disinfection and also accelerated ageing affected the dimensional stability of the facial silicone with statistically significant results. The silicone's detail reproduction was not affected by these two factors regardless of nanoparticle type, disinfection and accelerated ageing. © 2012 Informa UK, Ltd.

Silicone insulators of power transmission lines with a variable inorganic load concentration: Electrical and physiochemical analyses

Polymeric insulation is an increasing tendency in projects and maintenance of electrical networks for power distribution and transmission. Electrical power devices (e. g., insulators and surge arresters) developed by using polymeric insulation presents many advantages compared to the prior power components using ceramic insulation, such as: a better performance under high pollution environment; high hydrophobicity; high resistance to mechanical, electrical and chemical stresses. The practice with silicone insulators in polluted environments has shown that the ideal performance is directly related to insulator design and polymer formulation. One of the most common misunderstandings in the design of silicone compounds for insulators is the amount of inorganic load used in their formulation. This paper attempts to clarify how the variation of the inorganic load amount affects physicochemical characteristics of different silicone compounds. The physicochemical evaluation is performed from several measurements, such as: density, hardness, elongation, tensile strength. In addition, the evaluation of the physicochemical structure is carried out using infrared test and scanning electronic microscopy (SEM). The electrical analysis is performed from the electric tracking wheel and erosion test, in agreement with the recommendation of the International Electrotechnical Commission (IEC). (C) 2014 Elsevier Ltd. All rights reserved.

Marginal deterioration of the silicone for facial prosthesis with pigments after effect of storage period and chemical disinfection

The failure of facial prostheses is caused by limitations in the properties of existing materials, especially flexibility and durability. Therefore, this study evaluated the marginal deterioration of a silicone used for fabrication of facial prostheses (Silastic MDX4-4210, Dow Corning Corporation, Midland, MI, USA) according to the influence of artificial aging, daily disinfection, and 2 types of pigmentation. Thirty specimens were fabricated and subdivided in 6 groups: without pigmentation, pigmented with make-up powder and iron oxide, and evaluated with and without the action of the disinfectant. Analysis of marginal deterioration was performed on a scanning electron microscope (magnification, ×5000) immediately 6 months and 1 year after fabrication of specimens, following the guidelines of ASTM International. After visual analysis of the photomicrographs, it was noticed that all groups presented marginal deterioration and alterations in surface texture with time. The use of disinfection did not contribute to the marginal deterioration of polymer (silicone), regardless of the pigmentation and artificial aging.

Percolated non-Newtonian flow for silicone obtained from exfoliated bioinorganic layered double hydroxide intercalated with amino acid

A simple and scalable procedure was used to obtain thin, stable, homogeneous, and easy-to-handle films composed of silicone derived from dimethicones containing dispersed hydrotalcite-type materials previously organo-modified with amino acids. The absence of the typical X-ray pattern of the bioinorganic LDH filler suggested an exfoliation process that was further indirectly evidenced by a drastic change in the rheological behavior, which turned from a quasi-Newtonian behavior for the silicone free of LDH filler to an extensive developed gel-like structure for the nanocomposite derivatives. Visualized by the shear-thinning exponent of the complex viscosity in the low-frequency range, the percolation threshold was evident for filler loading as low as <5 w/W%, suggesting the presence of a largely developed interface between the filler and the polymer. The increase of more than one order of magnitude in viscosity was explained by the rather strong attrition phenomenon between the tethered amino acid anions and the silicone chains. UVB radiation absorption profiles make such bioinorganic polymer nanocomposites potentially applicable in skin protection. Thermo-gravimetric analysis revealed significant improvement in the thermal stability, especially in the final step of the polymer combustion, thus underlining the role of the hybrid material as a thermal retardant agent. (C) 2011 Elsevier B.V. All rights reserved.

Development of Optically Based pH Sensing Hydrogel and Controlled Nitric Oxide Release Polymer

Nitric oxide has the potential to greatly improve intravascular measurements by locally inhibiting thrombus formation and dilating blood vessels. pH, the partial pressure of oxygen, and the partial pressure of carbon dioxide are three arterial blood parameters that are of interest to clinicians in the intensive care unit that can benefit from an intravascular sensor. This work explores fabrication of absorbance and fluorescence based pH sensing chemistry, the sensing chemistries' compatibility with nitric oxide, and a controllable nitric oxide releasing polymer. The pH sensing chemistries utilized various substrates, dyes, and methods of immobilization. Absorbance sensing chemistries used sol-gels, fumed silica particles, mesoporous silicon oxide, bromocresol purple, phenol red, bromocresol green, physical entrapment, molecular interactions, and covalent linking. Covalently linking the dyes to fumed silica particles and mesoporous silicon oxide eliminated leaching in the absorbance sensing chemistries. The structures of the absorbance dyes investigated were similar and bromocresol green in a sol-gel was tested for compatibility with nitric oxide. Nitric oxide did not interfere with the use of bromocresol green in a pH sensor. Investigated fluorescence sensing chemistries utilized silica optical fibers, poly(allylamine) hydrogel, SNARF-1, molecular interactions, and covalent linking. SNARF-1 covalently linked to a modified poly(allylamine) hydrogel was tested in the presence of nitric oxide and showed no interference from the nitric oxide. Nitric oxide release was controlled through the modulation of a light source that cleaved the bond between the nitric oxide and a sulfur atom in the donor. The nitric oxide donor in this work is S-nitroso-N-acetyl-D-penicillamine which was covalently linked to a silicone rubber made from polydimethylsiloxane. It is shown that the surface flux of nitric oxide released from the polymer films can be increased and decreased by increasing and decreasing the output power of the LED light source. In summary, an optical pH sensing chemistry was developed that eliminated the chronic problem of leaching of the indicator dye and showed no reactivity to nitric oxide released, thereby facilitating the development of a functional, reliable intravascular sensor.

Synthesis, self-assembly and (absence of) protein interactions of poly(glycerol methacrylate)-silicone macro-amphiphiles

The present study focuses on the synthesis of amphiphilic block copolymers containing poly(glycerol monomethacrylate) (PGMMA), showing the advantages of a protection/deprotection strategy based on silyl groups. PGMMA blocks were synthesized via ATRP started by a double functional poly(dimethyl siloxane) (PDMS) macroinitiator of molecular weight ≈7000 g mol-1. The resulting triblock copolymers were characterized by low polydispersity (generally ≤1.1) and their aggregation concentration in water was essentially dominated by the PDMS block length (critical aggregation concentration substantially invariant for GMMA degree of polymerization ≥30). For GMMA blocks with DP > 50, the self-assembly in water produced 35-50 nm spherical micelles, while shorter hydrophilic chains produced larger aggregates apparently displaying worm-like morphologies. Block copolymers with long GMMA chains (DP ≈ 200) produced particularly stable micellar aggregates, which were then selected for a preliminary assessment of the possibility of adsorption of plasma proteins (albumin and fibrinogen); using diffusion NMR as an analytical technique, no significant adsorption was recorded both on micelles and on soluble PGMMA employed as a control, indicating the possibility of a "stealth" behaviour. This journal is © 2013 The Royal Society of Chemistry.

Highly sensitive liquid level monitoring system utilizing polymer fiber Bragg gratings

A novel and highly sensitive liquid level sensor based on a polymer optical fiber Bragg grating (POFBG) is experimentally demonstrated. Two different configurations are studied and both configurations show the potential to interrogate liquid level by measuring the strain induced in a POFBG embedded in a silicone rubber diaphragm, which deforms due to hydrostatic pressure variations. The sensor exhibits a highly linear response over the sensing range and a good repeatability. For comparison, a similar sensor using a FBG inscribed in silica fiber is fabricated, which displays a sensitivity that is a factor of 5 smaller than the POFBG. The temperature sensitivity is studied and a novel multi-sensor arrangement proposed which has the potential to provide level readings independent of temperature and the liquid density.

Fiber-optic liquid level monitoring system using microstructured polymer fiber Bragg grating array sensors:performance analysis

A highly sensitive liquid level monitoring system based on microstructured polymer optical fiber Bragg grating (mPOFBG) array sensors is reported for the first time. The configuration is based on five mPOFBGs inscribed in the same fiber in the 850 nm spectral region, showing the potential to interrogate liquid level by measuring the strain induced in each mPOFBG embedded in a silicone rubber (SR) diaphragm, which deforms due to hydrostatic pressure variations. The sensor exhibits a highly linear response over the sensing range, a good repeatability, and a high resolution. The sensitivity of the sensor is found to be 98 pm/cm of water, enhanced by more than a factor of 9 when compared to an equivalent sensor based on a silica fiber around 1550 nm. The temperature sensitivity is studied and a multi-sensor arrangement proposed, which has the potential to provide level readings independent of temperature and the liquid density.

Aviation fuel gauging sensor utilizing multiple diaphragm sensors incorporating polymer optical fiber Bragg gratings

A high-performance fuel gauging sensor is described that uses five diaphragm-based pressure sensors, which are monitored using a linear array of polymer optical fiber Bragg gratings. The sensors were initially characterized using water, revealing a sensitivity of 98 pm/cm for four of the sensors and 86 pm/cm for the fifth. The discrepancy in the sensitivity of the fifth sensor has been explained as being a result of the annealing of the other four sensors. Initial testing in JET A-1 aviation fuel revealed the unsuitability of silicone rubber diaphragms for prolonged usage in fuel. A second set of sensors manufactured with a polyurethane-based diaphragm showed no measurable deterioration over a three month period immersed in fuel. These sensors exhibited a sensitivity of 39 pm/cm, which is less than the silicone rubber devices due to the stiffer nature of the polyurethane material used.