Indiana University-Purdue University Indianapolis (IUPUI) / Background: VST-50 (a room temperature-vulcanizing silicone (RTV) by Factor II Inc.) has long been proposed as a potential alternative material for MDX4-4210, another RTV by Dow Corning Corp. and the current material of choice for maxillofacial prosthesis. Though VST-50 has similar chemistry and flexibility as MDX4-4210, its mechanical properties is still too low for it to be used in the clinic. An improvement in the mechanical property of VST-50 is a critical step to bring the material to clinical application. Objective: To investigate the effect of AEROSIL® R 812S (colloid silica) addition on the mechanical properties of VST-50 and compared to that of MDX4-4210. Methods: The VST-50 was mixed with AEROSIL® R 812S at 2 or 4 parts per hundred parts of rubber. That material was mixed with the catalyst under vacuum. The mixture was poured onto a machined plastic mold to produce a silicone sheet 3.0 ± 0.2 mm thick. All samples were prepared by manufacturer recommended method. Testing samples were prepared and tested following ISO 37 for tensile strength, ASTM D624 for tear strength and ASTM D2240 for shore A hardness test. One way ANOVA was used to compare the groups (Alpha=0.05). Result: Significant differences (P<0.001) were found between MDX4-4210 and modified VST-50 groups. The mean value of tensile strength, tear strength and hardness of VST-50 (4phr colloid silica) were 7.43(MPa), 34.82(N/mm) and 40.4 respectively, compared to MDX4-4210 were 3.67(MPa), 5.48(N/mm) and 31.5, respectively. Conclusion: Modified VST-50 with 4phr silica revealed improved mechanical properties to use as a maxillofacial prosthetic silicone elastomer.

<p>Silicone polymers, particularly PDMS (poly(dimethylsiloxane)) exhibit a wide range of exceptional properties including optical transparency, biostability, hydrophobicity and excellent oxygen transmissibility that make them extremely useful in a wide range of applications, particularly as biomaterials. Current methods for the preparation of silicone elastomers have been well documented, however, silicone elastomers are thermoset materials and once cured, they cannot be reformed without chemical intervention. The properties of silicones that make them a popular material choice in a wide variety of industries also make them un-responsive and non-reusable often limiting their application to one primary purpose.</p> <p>This thesis aims to further understand the mechanisms of silicone polymer chain interactions and how the chemistry of polymer modification can alter the mechanical and chemical properties of materials. The effects of distinctive functional groups (coumarin) on silicone chains to allow for both the formation of thermoplastic silicone elastomers and stimuli-responsive elastomers for reversible crosslinking are explored.</p> <p>A companion study examined a different way to form silicone elastomers. The Piers- Rubinsztajn reaction was used to create elastomers and foams rapidly and under relatively mild conditions using very small quantities of the catalyst B(C6F5)3. The factors required to create – on demand – a foam or an elastomer, and the strategies to control physical properties, including bubble density and modulus, are explored.</p> <p>Silicone foams that were structured in a completely different way are described. Allyl- modified PEG (poly(ethylene glycol)) was found to structure foam mixtures precure. The product foam after cure was amphiphilic, due to the presence of both silicone and PEG constituents. The origins of bubble stabilization and the ability to control foam properties are described.</p> / Doctor of Science (PhD)

L'objectif de ces travaux de thèse était d'améliorer les performances d'étanchéité de connecteurs automobiles fabriqués en silicone. La première approche visait à comprendre les relations entre les structures chimiques présentes dans les formulations LSR et les propriétés mécaniques afin de proposer des additifs favorisant la résistance à la déchirure. Lors d'une étude préalable, nous avons étudié l'effet synergétique du platine et de la silice sur la dégradation thermique de formulations silicone. Ce travail a permis de décrire le mécanisme et de proposer de nouvelles formulations plus performantes en terme de taux de résidu après pyrolyse. Cette première étude alliée à d'autres techniques a permis d'analyser les structures chimiques présentes dans huit formulations commerciales. Nous avons également caractérisé la réactivité ainsi que la structure du réseau polymère obtenu après réticulation. Les relations liant les structures chimiques à la structure des réseaux ont été établies. Enfin, les propriétés mécaniques telles que la déformation rémanente à la compression, les propriétés ultimes (force et élongation à la rupture) et la résistance à la déchirure des matériaux ont été corrélées avec les différentes structures des réseaux.La seconde partie était dédiée à la synthèse d'un additif fonctionnel thermiquement activable permettant de réparer a posteriori une déchirure. Afin de sélectionner le meilleur système correspondant au cahier des charges, une revue complète de la bibliographie a été réalisée sur la réversibilité des fonctions urées et uréthanes, en portant une attention particulière sur la chimie des isocyanate bloqués. Deux molécules bloquantes ont été sélectionnées après étude de la réactivation thermique de la fonction isocyanate. Un monomère portant cette fonction isocyanate bloqué a été engagé dans une réaction de copolymérisation afin d'obtenir plusieurs générations d'additifs testés selon les normes appliquées aux connecteurs. / This PhD work aimed at improving the water and air-proofing properties of automotive connectors made of silicones. The first approach consisted of understanding the relationships between the chemical structures added in the LSR formulations and their ultimate mechanical performances so as to propose additives which would improve tear resistance of the materials. In a preliminary study, we investigated the synergistic role of platinum catalyst and silica on the thermal degradation of silicone formulations. These investigations allowed us to describe the degradation mechanism and to suggest new formulations in order to improve the residue content at high temperature. This first study, combined with other techniques, allowed us to analyze the chemical structures present in eight commercial formulations. We also characterized the reactivities as well as the network topologies obtained after curing the formulations. Correlations between the chemical structures and the network topology were then established. Finally, some mechanical properties, i.e. the compression set, the ultimate properties (tensile strength and elongation at break) and the tear resistance of final materials were matched with network topologies. The second part was dedicated to the synthesis of a functional additive which could be thermally reactivated to heal a tear. In order to select the best system according to the strict specifications of this work, a complete literature review on the reversibility of urea and urethane bonds was done, with special emphasis on blocked isocyanate chemistry. After a study on the isocyanate group thermal reactivation, two blocking molecules were chosen. A monomer bearing this blocked isocyanate function was then copolymerized to obtain different generations of additives which were finally tested according to standard norms applied to connectors.

The thesis deals with one major question: is it possible, using one piezoelectric sensor/vibrator, to detect a hard inclusion in a silicone rubber phantom? The question was approached with an open mind and the task was subdivided into three clearly identifiable parts: characterization of the piezoelectric sensor/vibrator (paper I), creating a model of the visco-elastic properties of a tissue-like material (phantom) in contact with the sensor/vibrator (paper II), and to detect the presence of a hard inclusion in the phantom (paper III). All vibrations of the sensor/vibrator and phantom was modeled using a finite element method (FEM). To minimize the computational time and to maximize the FEM model's ability to correctly reproduce the vibrations, a two-dimensional model system consisting of a cylindrical piezoelectric sensor/vibrator, emitting radial elastic waves in to a cylindrical disk-shaped phantom, was chosen. The piezoelectric sensor/vibrator was characterized using a parameter tuning procedure using harmonic overtones. The procedure enables tuning of the electro-elastic parameters of the sensor/vibrator so that the measured and calculated impedance frequency responses match. Silicone rubber was chosen as a phantom to mimic soft tissue. The properties of the phantom was modeled using a fractional derivative visco-elastic model. The hyperelastic effect at the first radial resonance of the sensor vibrator was corrected for by a compensating function. The high frequency complex visco-elastic modulus of the silicone rubber was determined using the transitions of standing Lamb waves in the phantom. The presence of a ring-shaped inclusion in the phantom, of polyamide, was detected using the change of the transitional Lamb wave patterns in the phantom. The tuning of the PZT5A1 sensor/vibrator parameters yielded a match between the calculated and the measured impedance spectra better than 0.54%. The average, complex, elastic modulus of three silicone rubber, Silgel 612, samples were: (0.97 + 0.009i) GPa  at 100 kHz and (0.97 + 0.005i) GPa at 250 kHz. The presence of a polyamide inclusion, PA6GPE, was detected in the phantom using multiple frequency footprints. / Denna avhandling berör frågan: är det möjligt, med en piezoelektrisk sensor/vibrator, att detektera ett hårt objekt inneslutet i en fantom av silikongummi? Frågan närmades utan begränsningar och uppgiften delades upp i tre tydliga delar: karaktäriseringen av den piezoelektriska sensorn/vibratorn (paper I), skapa en modell av det viskoelastiska uppförandet hos ett vävnadsliknande material (fantom) som står i kontakt med sensorn-/vibratorn (paper II) och att detektera förekomsten av ett hårt objekt inneslutet i fantomen (paper III). En finit element modell (FEM) skapades för att beräkna vibrationerna hos sensorn/vibratorn och fantomen. För att minimera beräkningstiden och maximera modellens förmåga att återge vibrationer på ett korrekt sätt, så skapades ett tvådimensionellt modellsystem bestående av en cylindrisk piezoelektrisk sensor/vibrator i kontakt med en cylindrisk fantom av silikongummi. Sensorn/vibratorn skickar radiella elastiska vågor in i fantomen. Den piezoelektriska sensorn/vibratorn karakteriserades med hjälp av en procedur som anpassar parametervärden med hjälp av övertoner. Proceduren möjliggör en justering av parametervärdena så att uppmätta och beräknade impedansspektra överensstämmer. En 'fractional derivative' modell av de viskoelastiska egenskaperna hos silikongummit skapades. De hyperelastiska egenskaperna vid första radiella resonansen blev kompenserade med hjälp av en sigmoidformad funktion. Den komplexa viskoelastiska modulen bestämdes för höga frekvenser med hjälp av transitioner hos stående Lambvågor i fantomen. Närvaron av ett hårt ringformat objekt i fantomen detekterades med hjälp av förändringar i mönstret hos de stående Lambvågorna. Justeringen av de piezoelektriska parametrarna hos elementet PZT5A1 gav som mest en skillnad på 0.54% mellan uppmätta och beräknade impedansspektra. Medelvärdet hos tre prov av silikongummit Silgel 612 av den komplexa elastiska modulen uppmättes till (0.97 + 0.009i) GPa  vid 100 kHz och (0.97 + 0.005i) GPa vid 250 kHz. Närvaron av ett hårt objekt, gjort av polyaramid (PA6GPE), detekterades i fantomen med hjälp av multifrekvensiella fotavtryck.

Over 60 proteins have been detected in the tear film and among these lysozyme has attracted the greatest attention. Several techniques for elucidating the identity, quantity and conformation of lysozyme deposited on soft contact lenses have been developed. Lysozyme also deposits on the newly introduced silicone hydrogel (SH) lens materials, but in extremely low levels compared to conventional hydrogel lenses. Hence, a major analytical complication with the study of the SH contact lens materials relates to the minute quantity of deposited lysozyme. The first project of this thesis involved the development of a method whereby lysozyme mass extracted from SH lens materials would be preserved over time and would be compatible with an optimized Western blotting procedure. This methodological development was incorporated into a clinical study (CLENS-100?? and Silicone Hydrogels ? CLASH study) wherein the difference in the degree of total protein, the difference in lysozyme deposition and activity recovered from lotrafilcon A SH lens material when subjects used surfactant containing rewetting drops (CLENS-100??) versus control saline was investigated. The remaining experiments were in vitro experiments wherein the lenses were doped in artificial lysozyme solution containing ¹²⁵I-labeled lysozyme. These experiments were performed to gain insight into the kinetics of lysozyme deposition on SH lens materials and also the efficacy of a reagent in extracting lysozyme from SH lens materials. A protocol was developed whereby the percentage loss of lysozyme mass found on lotrafilcon A SH lenses was reduced from approximately 33% to <1% (p<0. 001), following extraction and resuspension. The results from the CLASH study demonstrated that when subjects used a surfactant containing rewetting drop instead of a control saline drop total protein deposition (1. 2??0. 7 ??g/lens versus 1. 9??0. 8 ??g/lens, p<0. 001), lysozyme deposition (0. 7??0. 5 ??g/lens versus 1. 1??0. 7 ??g/lens, p<0. 001) and percentage lysozyme denaturation (76??10% versus 85??7%, p=0. 002) were all reduced. The results from the kinetics study demonstrated that lysozyme accumulated rapidly on etafilcon A lenses (1 hr, 98??8 ??g/lens), reached a maximum on the 7th day (1386??21 ??g/lens) and then reached a plateau (p=NS). Lysozyme accumulation on FDA Group II and SH lenses continued to increase across all time periods, with no plateau being observed (p<0. 001). The results from the extraction efficiency study showed that 0. 2% trifluoroacetic acid/ acetonitrile was 98. 3??1. 1% and 91. 4??1. 4% efficient in extracting lysozyme deposited on etafilcon A and galyfilcon lenses, while the lysozyme extraction efficiency was 66. 3??5. 3 % and 56. 7??3. 8% for lotrafilcon A and balafilcon lens materials (p<0. 001). The results from these studies re-emphasize that novel SH lens materials are highly resistant to protein deposition and demonstrate high levels of biocompatibility.

Thirty-two silicone breast implant patients scored in the mild to moderate range of impairment on the Halstead-Reitan Neuropsychological Battery. An unusual number of patients had positive tests for antinuclear antibody on immunological testing and a high incidence of EEG abnormalities were found. Personality testing revealed an MMPI profile which is typical for neuropsychologically impaired subjects but components were consistent with extreme emotional distress. None of the subjects were near the cutoff score for malingering or faking bad on the F-K index of the MMPI. There was no apparent relationship between length of exposure and the severity of neurological impairment. Also, explanted subjects performance was not improved when compared to subjects whose implants were still in place.

Fumed silica filler has long been used to structurally reinforce silicone elastomers. Unfortunately, the combination of as little as a few weight percent of untreated fumed silica nanoparticles [uFSN] with a siloxane polymer, such as PDMS, forms a difficult to process waxy solid admixture that even long periods of high shear mixing will not thin. In the course of the current work it was noted that after a period of storage certain solid admixtures would become viscous liquids when subjected to additional high shear mixing. It was further found that the required aging period could be decreased if the admixture storage temperature were increased. The only known interaction of PDMS and uFSN at moderate conditions is the adsorption of polymer on filler, and this interaction is also known to occur more quickly at higher temperature. This study examines the relationship between polymer adsorption and admixture liquefaction. Further, the mechanical properties of cured elastomers containing liquefied admixtures are examined to assess the degree of reinforcement that these materials afford.

Human surrogates are representations of living humans, commonly adopted to better understand human response to impacts. Though surrogates have been widely used in automotive, defence and medical industries with varying levels of biofidelity, their primary application in the sporting goods industry has been through primitive rigid anvils used in assessing personal protective equipment (PPE) effectiveness. In sports, absence from competition is an important severity measure and soft tissue injuries such as contusions and lacerations are serious concerns. Consequently, impact surrogates for the sporting goods industry need a more subtle description of the relevant soft tissues to assess impact severity and mitigation accurately to indicate the likelihood of injury. The fundamental aim for this research study was to establish a method to enable the development of superior, complementary, increasingly complex synthetic and computational impact surrogates for improved assessment of sports personal protective equipment. With a particular focus on the thigh segment, research was conducted to evaluate incremental increases in surrogate complexity. Throughout this study, empirical assessment of synthetic surrogates and computational evaluation using finite element (FE) models were employed to further knowledge on design features influencing soft tissue surrogates in a cost and time efficient manner. To develop a more representative human impact surrogate, the tissue structures considered, geometries and materials were identified as key components influencing the mechanical response of surrogates. As a design tool, FE models were used to evaluate the changes in impact response elicited with different soft tissue layer configurations. The study showed the importance of skin, adipose, muscle and bone tissue structures and indicated up to 15.4% difference in maximum soft tissue displacement caused by failure to represent the skin layer. FE models were further used in this capacity in a shape evaluation study from which it was determined that a full-scale anatomically contoured thigh was necessary to show the full diversity of impact response phenomena exhibited. This was particularly pertinent in PPE evaluations where simple surrogate shapes significantly underestimated the magnitudes of displacements exhibited (up to 155% difference) when rigid shell PPE was simulated under impact conditions. Synthetic PDMS silicone simulants were then fabricated for each of the organic soft tissues to match their dynamic responses. The developed simulants exhibited a superior representation of the tissues when compared to previous single material soft tissue simulant, Silastic 3483, which showed 324%, 11,140% and -15.8% greater differences than the PDMS when compared to previously reported target organic tissue datasets for relaxed muscle, skin and adipose tissues respectively. The impact response of these PDMS surrogates were compared in FE models with previously used single material simulants in representative knee and cricket ball sports impact events. The models were each validated through experimental tests and the PDMS simulants were shown to exhibit significantly closer responses to organic tissue predictions across all impact conditions and evaluation metrics considered. An anatomically contoured synthetic thigh surrogate was fabricated using the PDMS soft tissue simulants through a novel multi-stage moulding process. The surrogate was experimentally tested under representative sports impact conditions and showed a good comparison with FE model predictions with a maximum difference in impactor displacements and peak accelerations of +6.86% and +12.5% respectively at velocities between 2 - 4 m.s-1. The value of increased biofidelity in the anatomical synthetic and virtual surrogate thighs has been proven through the incremental adoption of important surrogate elements (tissue structures, material and geometries). The predictive capabilities of each surrogate have been demonstrated through their parallel developments and staged comparisons with idealised organic tissue responses. This increase in biofidelity is introduced at modestly higher cost compared to Silastic 3483, but, given the benefits of a more representative human impact response for PPE evaluations, this is shown to be worthwhile.

Submitted by Cristiane Chim (cristiane.chim@ucpel.edu.br) on 2016-07-20T14:56:04Z No. of bitstreams: 1 ana cristina moraesdo em março2013- CD.pdf: 1084476 bytes, checksum: c9104bca778595d46f64a90fad323714 (MD5) / Made available in DSpace on 2016-07-20T14:56:04Z (GMT). No. of bitstreams: 1 ana cristina moraesdo em março2013- CD.pdf: 1084476 bytes, checksum: c9104bca778595d46f64a90fad323714 (MD5) Previous issue date: 2014-05-31 / The first silicone implants were used in the early 60. Nowadays, breast augmentation surgery ranks second in plastic procedures, and its use is of high relevance in mammary reconstruction after mastectomy. However, breast implants exhibit particular clinical complications related to inflammatory response with subsequent formation of fibrous capsule surrounding the implant [1,2]. The development of an avascular fibrous capsule constitutes a reaction to the foreign body as a part of local reparative process in which the dissected tissue cavity behaves as a surgical wound / A utilização do implante de silicone teve inicio no final da década de 60. Desde então, as cirurgias de implante de silicone mamário tornaram-se cada vez mais frequentes e populares, com as modernas próteses de silicone. Com a crescente utilização destes materiais nas cirurgias reparadoras e estéticas das mamas e em outras partes do corpo, o interesse pelas reações teciduais destes materiais nos tecidos tem sido motivo de estudo para entender as suas principais complicações: a contratura capsular e a perda da integridade do implante[15]. A contratura capsular é uma complicação cirúrgica importante, resultado de uma resposta fibrótica tecidual no processo inflamatório local, ocorrendo em 4 a 17% dos casos quando encontrase em contato com o tecido mamário

abstract: Deformation during hydration of concrete includes curling at joints and terminations. Previous research has explored mix designs, chemical additives, and other material factors to minimize slab distortion due to curling. This research study explores the development and use of externally applied silicone-based compounds after both the placing and cutting of joints. This exploratory study presents the results of controlled testing and a field study results that include distortion of contraction joints as measured with a Spectra LL300N under existing environmental conditions. Specifically, the study presents the results of a side-by-side test of two slabs, a base case, and a silicone-altered case, as well as field measures of two large commercial buildings using the developed methods. The results of the study show reduced distortion due to curling as compared to standard comparative slabs and warrant the continued exploration and testing of the concept. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2019