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., 2013     

Effect of the incorporation of hydroxy‐terminated liquid silicones on the cure characteristics,morphology, and release of a model protein from silicone elastomer‐covered rods

Silicone elastomer systems have previously been shown to offer potential for the sustained release of protein therapeutics. However, the general requirement for the incorporation of large amounts of release enhancing solid excipients to achieve therapeutically effective release rates from these otherwise hydrophobic polymer systems can detrimentally affect the viscosity of the precure silicone elastomer mixture and its curing characteristics. The increase in viscosity necessitates the use of higher operating pressures in manufacture, resulting in higher shear stresses that are often detrimental to the structural integrity of the incorporated protein. The addition of liquid silicones increases the initial tan δ value and the tan δ values in the early stages of curing by increasing the liquid character (G″) of the silicone elastomer system and reducing its elastic character (G′), thereby reducing the shear stress placed on the formulation during manufacture and minimizing the potential for protein degradation. However, SEM analysis has demonstrated that if the liquid character of the silicone elastomer is too high, the formulation will be unable to fill the mold during manufacture. This study demonstrates that incorporation of liquid hydroxy‐terminated polydimethylsiloxanes into addition‐cure silicone elastomer‐covered rod formulations can both effectively lower the viscosity of the precured silicone elastomer and enhance the release rate of the model therapeutic protein bovine serum albumin. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effect of plasma‐polymerised silicon hydride‐rich polyhydrogenmethylsiloxane on the adhesion of silicone elastomers

BACKGROUND: Silicone elastomers have outstanding material properties including good thermal stability, low electrical conductivity, biocompatibility and resilient physical and chemical properties. These elastomers, however, exhibit relatively poor adhesion to stainless steel, and the use of a nanometre thick plasma‐polymerised primer layer as a means of enhancing this adhesion was investigated in this study. The primer coatings studied consisted of polyhydrogenmethylsiloxane (PHMS), tetraethyl orthosilicate (TEOS) and mixtures of these two liquid precursors. RESULTS: The plasma‐polymerised primer coatings were deposited onto stainless steel substrates using a PlasmaStream^? atmospheric pressure plasma jet system. Deposited coatings were examined using ellipsometry, contact angle measurements, optical profilometry, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy and scanning electron microscopy. The adhesion of silicone elastomers bonded to the primed and bare stainless steel surfaces was assessed using 45° adhesion strength measurements. Elastomer adhesion was correlated with surface energy, thickness and roughness. CONCLUSION: An up to 15‐fold increase in adhesive fracture energy was observed for silicone elastomers bonded to the primed versus untreated stainless steel. The highest adhesion was observed for a coating deposited from a PHMS‐to‐TEOS precursor molar ratio of 3 to 1. Copyright © 2009 Society of Chemical Industry     

Surface activity of PDMS silicone oil applied as petroleum antifoamer

In petroleum production, silicone oil (polydimethylsiloxane or PDMS) remains the most efficient product for combating foam, despite its negative effects on petroleum contamination and catalytic refining processes. This study aimed to evaluate the defoaming action of silicone oils with varying molar masses (ranging from 3 to 110 kg·mol⁻¹) as defoamers in crude oils with different densities (20, 26, and 30°API). The results were correlated with the dilatational rheology obtained through pendant drop tensiometry of the oil samples. The silicone samples were characterized using gel permeation chromatography and thermogravimetric analysis, while the petroleum samples underwent SARA (saturated, aromatics, resins, asphaltenes) composition analysis, density measurement, and assessment of water content. The PDMS range of 8 to 30 kg·mol⁻¹ exhibited enhanced antifoaming efficiency for the tested oils. A plateau in efficiency was observed when antifoamers were dosed above 15 ppm. Additionally, a reverse relationship between the initial formation of foam and the elastic modulus (G') of the oil in the presence of the antifoamer was observed, suggesting that the more effective antifoamer actually increased the elasticity of the film.     

硅橡胶泡沫材料硫化特性分析

采用橡胶硫化仪研究了溶析成孔工艺制备的硅橡胶泡沫材料的硫化特性 ,分析讨论了硅橡胶的结构、成孔剂用量对硫化特性的影响规律。研究表明 ,苯基对硅橡胶的硫化有延迟作用 ,胶料中成孔剂对硫化有一定影响 ,成孔剂的刚性和占位作用削弱了胶料的交联 ,不影响硫化的成孔剂适宜用量为 2 0 0～ 2 3 0份     

Preparation of thermoplastic elastomers based on silicone rubber and polyethylene by thermomechanical reactive blending: Effects of polyethylene structural parameters

Attempts have been made to prepare thermoplastic elastomers based on polyethylene and silicone rubber by thermomechanical reactive mixing of the two polymers. Occurrence of both grafting and vulcanization of the silicone rubber chains was evidenced by increase in the mixing torque, solvent extraction data, as well as FTIR and DSC analysis. Among different types of polyethylene, linear low‐density polyethylene (LLDPE) showed higher potential to promote reactions between the two phases. The blend based on LLDPE prepared at high temperature and shear rate exhibited distinct rheological behavior with a non‐Newtonian characteristic and higher dynamic viscosity measured by rheomechanical spectroscopy (RMS) than the two individual components at low frequencies. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3402–3408, 2003     

Rheological and isothermal crystallization characteristics of neat and calcium carbonate‐filled syndiotactic polypropylene

Steady‐state and oscillatory shear behavior of three neat syndiotactic polypropylene (s‐PP) resins and a s‐PP resin (s‐PP#8) filled with CaCO₃ particles of varying content, size, and type of surface modification were investigated. All of the neat s‐PP resins investigated exhibited the expected shear‐thinning behavior. Both the storage and loss moduli increased with decreasing temperature. The shift factors used to construct the master curves were fitted well with both the Arrhenius and the Williams–Landel–Ferry (WLF) equations. The inclusion of CaCO₃ particles of varying content, size, and type of surface modification, to a large extent, affected both the steady‐state and oscillatory shear behavior of s‐PP/CaCO₃ compounds, with the property values being found to increase with increasing content, decreasing size, and surface coating of the CaCO₃ particles. Lastly, the effects of melt‐annealing and crystallization temperatures on isothermal crystallization behavior of s‐PP#8 filled with CaCO₃ particles of varying content, size, and type of surface modification were also investigated. The half‐time of crystallization of neat s‐PP#8 exhibited a strong correlation with the choice of the melt‐annealing temperature (T_f) when T_f was less than about 160 °C, while it became independent of T_f when T_f was greater than about 160 °C. On the other hand, the half‐time of crystallization of s‐PP#8/CaCO₃ compounds did not vary much with the T_f. Generally, the observed half‐time of crystallization decreased with increasing CaCO₃ content and increased with increasing CaCO₃ particle size. Finally, coating the surface of CaCO₃ particles with either stearic acid or paraffin reduced the ability of the particles to effectively nucleate s‐PP#8. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4515–4525, 2006     

Rheological properties,cure characteristics,and morphology of acrylonitrile‐based nanorubber modified epoxy

This article investigates the effects of nano carboxylic acrylonitrile butadiene rubber (CNBR‐NP) and nano acrylonitrile butadiene rubber (NBR‐NP) on the rheological properties and cure characteristics of epoxy. Dynamic mechanical behavior of carbon fiber reinforced polymer composites (CFRP) with the nanorubber‐modified matrices was also studied. Rheological study showed that NBR‐NP blends attained lower viscosity in comparison to CNBR‐NP blends and both systems exhibited shear‐thinning behavior. Scanning electron microscopy (SEM) images revealed that CNBR‐NP could be dispersed evenly within the epoxy matrix using industrial mixing process whereas partial agglomeration was observed in NBR‐NP blends. The dynamic mechanical analysis (DMA) data showed that the addition of nanorubber has negligible effect on the glass transition temperature of the epoxy. The difference in the dispersion ability of these two nanorubbers in epoxy is related to the difference in van der Waals forces between single nanoparticles, the chemical formula and the polarity of the systems. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41911.     

Rheological properties and drug release characteristics of pH‐responsive hydrogels

Rheological properties, blend compatibility, and gel‐forming capacity of carbopol 940 (CP‐940), sodium alginate (NaAlg), and guar gum (GG) have been studied. These matrices have been used in delivery of timolol maleate for ophthalmic applications. Aqueous solutions of CP‐940, NaAlg, and GG in concentrations between 0.1 and 1% (wt/vol) and their blends have been prepared. In situ gel forming polymeric solutions have shown an increase in viscosity upon exposure to specific pH, ions, and temperature of the eyeball. Blend miscibility was studied by calculating polymer–polymer interaction parameters using viscosity data. Rheological properties viz., torque, viscosity, shear stress, and shear rate were obtained using a Brookfield rheometer. Viscosities of polymer solutions were obtained by a Schott Gerate viscometer. Rheological data were analyzed using Bingham, Casson Standard, and Casson Chocolate equations. The hydrogels were subjected to ex vivo release studies on timolol maleate through the excised bovine cornea using a modified Franz diffusion cell. Results were compared with the conventional drug solution. The release could be extended when the drug is incorporated into hydrogel‐forming solution. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2057–2064, 2004     

Studies on blends of polychloroprene and polybutadiene rubber containing phosphorylated cardanol prepolymer: Melt rheology,cure characteristics,and mechanical properties

Melt rheology, cure characteristics, and mechanical properties of blends of polychloroprene (CR) and polybutadiene rubber (BR) in the presence and absence of phosphorylated cardanol prepolymer (PCP) were studied. The melt rheology parameters of the blends over a wide range of shear rates and temperatures were studied using a capillary rheometer (Rheoflixer SWO). The plasticizing effect of PCP in the blends was indicated by reduction in apparent melt viscosity and activation energy for melt flow. Good compatibility between the blend components (CR and BR) in the presence of PCP was evidenced by the lower values of principal normal stress difference. The self crosslinking behavior of the blends in the presence and absence of PCP was studied at different temperatures, using a Brabender Plasicorder and the kinetic parameters of crosslinking were evaluated. The cure characteristics of blends of CR and BR containing different dosages of PCP (0–10 phr) in a semi efficient vulcanization system were also studied at temperatures ranging from 150°C to 180°C, using an oscillating disk rheometer. The increase in tensile modulus, tensile strength, and tear strength of the vulcanizates in the presence of 5 phr of PCP is presumed to be an indication of reinforcement resulting from accelerated cross linking reaction as evidenced by higher chemical crosslink density index. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3195–3200, 2006     

有机硅脱模剂生产及应用技术

概述了脱模剂的工作原理、种类和应用。对有机硅脱模剂进行了分类,并分析了每种类型的有机硅脱模剂的特点。通过比较有机硅脱模剂与非硅类型脱模剂的特点,突出了有机硅脱模剂的优势。介绍了有机硅脱模剂的生产和应用技术,包括产品配方、模拟应用实验及优选改进等。最后,对有机硅脱模剂的典型产品作了简单介绍。     

Vinyl‐containing silicone resin as the crosslinking agent of heat‐curable silicone rubber

Heat‐curable silicone rubber (HCSR) was prepared by using vinyl‐containing silicone resin (VSR) as the crosslinking agent instead of polyvinylsilicone oil (C gum). Mechanical properties and crosslink density of the vulcanizates were measured. The results indicate that VSR is a good crosslinking agent for HCSR. The tensile strength, tearing strength, elongation at break, and hardness of the vulcanizate can reach 10.2 MPa, 29.1 kN/m, 720%, and 58 SHA, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3123–3127, 2002; DOI 10.1002/app.10054     

发泡硅橡胶胶料硫化特性影响因素的探讨

对采用溶析成孔技术发泡的甲基苯基乙烯基硅橡胶胶料的硫化特性影响因素进行了探讨。结果表明 ,活性剂 (氧化锌晶须和N ,N′ 间亚苯基双马来酰亚胺 )能缩短发泡胶料的高温正硫化时间 ,但对发泡胶料的低温硫化促进作用不明显 ;发泡胶料在室温存放过程中有缓慢硫化的趋势 ,室温短时间 (5d内 )存放不会影响发泡胶料的最终硫化效果 ;球形成孔剂表面滞留的处理剂会对发泡胶料的硫化产生负作用     

Low‐temperature photopolymerization and post‐cure characteristics of acrylates

Near‐infrared spectroscopy was used to investigate the post‐cure characteristics of acrylates polymerized from ? 75 °C up to room temperature. The results obtained showed that the double bond conversion increased with increasing initiator concentration. Post‐cure was much more striking for samples cured at lower temperatures. The chemical structure of monomer and photoinitiator had a great effect on the post‐cure process. The greater the functionality, the lower the final double bond conversion and the more distinct the post‐cure effect. Copyright © 2006 Society of Chemical Industry Society of Chemical Industry     

Influence of the microstructure of gums on the mechanical properties of silicone high consistency rubbers

This paper is devoted to the characterization and processing of high molar mass vinyl‐bearing polysiloxanes in high consistency silicone rubber (HCR) formulations. The molar masses of five different polydimethylsiloxane gums, bearing vinyl groups at the ends and along their chains, were evaluated by size exclusion chromatography and rheometry. ²⁹Si and ¹H NMR spectroscopy allowed the precise determination of the vinyl content and of the distribution in the different polymers. Typical HCRs formulated from these gums were heat‐cured to process silicone rubber materials that were then tested mechanically. The macromolecular properties were correlated to the final material network structure. The amount of reactive vinyl moieties, rather than their distribution along or at the end of chains, is a key parameter to tailor the material mechanical properties. © 2016 Society of Chemical Industry     

Influence of oxidation treatment of carbon powders on the cure kinetics of amine cured tetrafunctional epoxy resins

A tetraglycidyl 4,4′-diaminodiphenylmethane (TGDDM) type tetrafunctional epoxy resin containing carbon powders was cured with the stoichiometric amount of a tetrafunctional curing agent, namely m-phenylenediamine (mPDA). Carbon powders were oxidised with air or nitric acid. The influence of carbon powders on curing of the resin was followed by dynamic mechanical analysis, Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). Gelation and vitrification times were determined as a function of the variations of dynamic properties. The evolution of viscoelastic modulus during curing of the different mixtures showed that untreated carbon powder clearly accelerated the kinetics of curing whilst oxidation of carbon powders could remove their catalysing effect. These results were confirmed by monitoring the changes in conversion of epoxy and amine groups during cure using the FTIR technique. DSC experiments also showed the influence of carbon powder as a catalyst and the loss of the catalysing effect as a consequence of chemical treatment.     

Influence of ZnO nanoparticles on the cure characteristics and mechanical properties of carboxylated nitrile rubber

Zinc oxide (ZnO) nanoparticles assembled in one dimension to give rod‐shaped morphology were synthesized. The effect of these ZnO nanoparticles (average particle size ～ 50 nm) as the curing agent for carboxylated nitrile rubber was studied with special attention to cure characteristics, mechanical properties, dynamic mechanical properties, and swelling. These results were compared with those of the conventional rubber grade ZnO. The study confirmed that the ZnO nanoparticles gave a better state of cure and higher maximum torque with a marginal decrease in optimum cure time and scorch time. The mechanical properties also showed an improvement. There was an increase in tensile strength by ～ 120%, elongation at break by ～ 20%, and modulus at 300% elongation by ～ 30% for the vulcanizate cured with ZnO nanoparticles, as compared with the one containing rubber grade ZnO. Dynamic mechanical analysis revealed that the vulcanizates exhibited two transitions—one occurring at lower temperature due to the T_g of the polymer, while the second at higher temperature corresponding to the hard phase arising due to the ionic structures. The second transition showed a peak broadening because of an increase in the points of interaction of ZnO nanoparticles with the matrix. The tan δ peak showed a shift towards higher T_g in the case of ZnO nanoparticle‐cured vulcanizate, indicating higher crosslinking density. This was further confirmed by volume fraction of rubber in the swollen gel and infrared spectroscopic studies. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of bound polymer on cure characteristics of natural rubber compounds reinforced with different types of carbon blacks

Rubber compounds are reinforced with fillers such as carbon black and silica. The cure characteristics of a filled rubber compound vary with the filler type and content. The influence of the type of carbon black on the cure characteristics of carbon black filled natural rubber compounds is investigated using two types of carbon black (N220 and N550), which are different in primary size and structure. The cure time and cure rate become faster as the carbon black content increases. The crosslink density also increases and reversion resistance is improved with the increase of carbon black content. The cure time and cure rate of the compound filled with N550 are faster than those of the compound filled with N220 at the same level of bound rubber content. In addition, higher crosslink density is also observed in the compound filled with N550 compared to that of the compound filled with N220 at the same level of bound rubber content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2282–2289, 2005     

Effect of coprecipitated barium ferrite on the cure characteristics and dynamic properties of natural rubber–ferrite composites around percolation

The influence of coprecipitated hexagonal barium ferrite BaFe₁₂O₁₉ phase on the cure characteristics and dynamic properties of natural rubber–ferrite composites has been studied as a function of ferrite loading up to 220 phr (part per hundred part of rubber). Unusual characteristics of coprecipitated ferrite particles were discovered by scanning electron microscope. The results show that scorch time t₁₀ and cure time t₉₀ decrease dramatically with increasing ferrite content up to critical ferrite loading. After 160 phr, t₉₀ increases sharply with increasing ferrite content, in contrast to saturation of t₁₀. Minimum torque recorded normal behavior at low ferrite loading, whereas it decreases with increasing ferrite content at high ferrite loading because of dilution effects. The storage modulus E′ and loss modulus E″ decrease with increasing temperature. The loss tangents (tanδ) of the composites are greater than those of the pure rubber. Linear viscoelastic behavior was observed as a result of the homogeneity and compatibility of the composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and evaluation of photocrosslinkable chitosan as a drug delivery matrix

Epichlorohydrin (1‐chloro‐2,3‐epoxypropane) was reacted with sodium azide in the presence of a phase transfer catalyst to obtain 1‐chloro‐2‐hydroxy‐3‐azidopropane, which was further coupled onto chitosan to prepare a photocrosslinkable derivative of the biopolymer. Elemental analysis and infrared (IR) spectroscopy confirmed the incorporation of azide groups onto chitosan. Films were cast from an aqueous acetic acid solution of azidated chitosan containing a model drug, such as theophylline. Irradiation of the film with ultraviolet (UV) light led to crosslinking of the drug incorporated film. IR spectra indicated complete surface crosslinking within 2 h of irradiation. Release of theophylline from uncrosslinked and crosslinked films was examined in simulated gastric and intestinal fluids without enzymes at 37 °C. The release of the drug from the crosslinked films was slower than the release from uncrosslinked films. Although the system is far from being optimized to obtain sustained release of a pharmacologically active agent for long periods, the data obtained indicate the possibility of developing photocrosslinkable matrices of biopolymers, such as chitosan, for sustained drug delivery with many advantages over chemical crosslinking. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1873–1877, 2002