Bubble casting soft robotics.

Inspired by living organisms, soft robots are developed from intrinsically compliant materials, enabling continuous motions that mimic animal and vegetal movement1. In soft robots, the canonical hinges and bolts are replaced by elastomers assembled into actuators programmed to change shape following the application of stimuli, for example pneumatic inflation2-5. The morphing information is typically directly embedded within the shape of these actuators, whose assembly is facilitated by recent advances in rapid prototyping techniques6-11. Yet, these manufacturing processes have limitations in scalability, design flexibility and robustness. Here we demonstrate a new all-in-one methodology for the fabrication and the programming of soft machines. Instead of relying on the assembly of individual parts, our approach harnesses interfacial flows in elastomers that progressively cure to robustly produce monolithic pneumatic actuators whose shape can easily be tailored to suit applications ranging from artificial muscles to grippers. We rationalize the fluid mechanics at play in the assembly of our actuators and model their subsequent morphing. We leverage this quantitative knowledge to program these soft machines and produce complex functionalities, for example sequential motion obtained from a monotonic stimulus. We expect that the flexibility, robustness and predictive nature of our methodology will accelerate the proliferation of soft robotics by enabling the assembly of complex actuators, for example long, tortuous or vascular structures, thereby paving the way towards new functionalities stemming from geometric and material nonlinearities.

Hyperbranched Silicone MDTQ Tack Promoters.

Low molecular weight, highly crosslinked silicone resins are widely used as reinforcing agents for highly transparent elastomers and adhesion/tack promoters in gels. The resins are complex mixtures and their structure / property relationships are ill defined. We report the synthesis of a library of 2, 3 and 4-fold hyperbranched polymeric oils that are comprised of linear, lightly branched or highly branched dendronic structures. Rheological examination of the fluids and tack measurements of gels filled with 10, 25 or 50% dendronic oils were made. Viscosity of the hyperbranched oils themselves was related to molecular weight, but more significantly to branch density. The properties are driven by chain entanglement. When cured into a silicone gel, less densely branched materials were more effective in improving tack than either linear oils or Me3SiO-rich, very highly branched oils of comparable molecular weight, because the latter oils underwent phase separation.

Surface changes of nanotopography by carbon ion implantation to enhance the biocompatibility of silicone rubber: an in vitro study of the optimum ion fluence and adsorbed protein.

Lower cellular adhesion and dense fibrous capsule formation around silicone breast implants caused by lower biocompatibility is a serious clinical problem. Preliminary work has shown that ion implantation enhances cell adhesion. Whether the biocompatibility is further enhanced by higher doses of carbon ion implantation and the mechanism by which ion implantation enhances biocompatibility remain unclear. In this study, five doses of carbon ions, which gradually increase, were implanted on the surface of silicone rubber and then the surface characteristics were surveyed. Then, cell adhesion, proliferation and migration were investigated. Furthermore, the vitronectin (VN) protein was used as a model protein to investigate whether the ion implantation affected the adsorbed protein on the surface. The obtained results indicate that enhanced cytocompatibility is dose dependent when the doses of ion implantation are less than 1 × 1016 ions/cm2. However, when the doses of ion implantation are more than 1 × 1016 ions/cm2, enhanced cytocompatibility is not significant. In addition, surface physicochemical changes by ion implantation induced a conformational change of the adsorbed vitronectin protein that enhanced cytocompatibility. Together, these results suggest that the optimum value of carbon ion implantation in silicone rubber to enhance biocompatibility is 1 × 1016 ions/cm2, and ion implantation regulates conformational changes of adsorbed ECM proteins, such as VN, and mediates the expression of intracellular signals that enhance the biocompatibility of silicone rubber. The results herein provide new insights into the surface modification of implant polymer materials to enhance biocompatibility. It has potentially broad applications in the biomedical field.

The Production of Solid Dosage Forms from Non-Degradable Polymers.

Non-degradable polymers have an important function in medicine. Solid dosage forms for longer term implantation require to be constructed from materials that will not degrade or erode over time and also offer the utmost biocompatibility and biostability. This review details the three most important non-degradable polymers for the production of solid dosage forms - silicone elastomer, ethylene vinyl acetate and thermoplastic polyurethane. The hydrophobic, thermoset silicone elastomer is utilised in the production of a broad range of devices, from urinary catheter tubing for the prevention of biofilm to intravaginal rings used to prevent HIV transmission. Ethylene vinyl acetate, a hydrophobic thermoplastic, is the material of choice of two of the world's leading forms of contraception - Nuvaring® and Implanon®. Thermoplastic polyurethane has such a diverse range of building blocks that this one polymer can be hydrophilic or hydrophobic. Yet, in spite of this versatility, it is only now finding utility in commercialised drug delivery systems. Separately then one polymer has a unique ability that differentiates it from the others and can be applied in a specific drug delivery application; but collectively these polymers provide a rich palette of material and drug delivery options to empower formulation scientists in meeting even the most demanding of unmet clinical needs. Therefore, these polymers have had a long history in controlled release, from the very beginning even, and it is pertinent that this review examines briefly this history while also detailing the state-of-the-art academic studies and inventions exploiting these materials. The paper also outlines the different production methods required to manufacture these solid dosage forms as many of the processes are uncommon to the wider pharmaceutical industry.

Fabrication Process of Silicone-based Dielectric Elastomer Actuators.

This contribution demonstrates the fabrication process of dielectric elastomer transducers (DETs). DETs are stretchable capacitors consisting of an elastomeric dielectric membrane sandwiched between two compliant electrodes. The large actuation strains of these transducers when used as actuators (over 300% area strain) and their soft and compliant nature has been exploited for a wide range of applications, including electrically tunable optics, haptic feedback devices, wave-energy harvesting, deformable cell-culture devices, compliant grippers, and propulsion of a bio-inspired fish-like airship. In most cases, DETs are made with a commercial proprietary acrylic elastomer and with hand-applied electrodes of carbon powder or carbon grease. This combination leads to non-reproducible and slow actuators exhibiting viscoelastic creep and a short lifetime. We present here a complete process flow for the reproducible fabrication of DETs based on thin elastomeric silicone films, including casting of thin silicone membranes, membrane release and prestretching, patterning of robust compliant electrodes, assembly and testing. The membranes are cast on flexible polyethylene terephthalate (PET) substrates coated with a water-soluble sacrificial layer for ease of release. The electrodes consist of carbon black particles dispersed into a silicone matrix and patterned using a stamping technique, which leads to precisely-defined compliant electrodes that present a high adhesion to the dielectric membrane on which they are applied.

Estudo da eficiência bactericida do biocida policloreto de dialildimetilamônio em materiais usados para confecção de próteses orais e faciais / Study of the bactericidal efficiency of the biocide poly(diallyldimethylammonium chloride) used in materials for the manufacture of oral and facial prostheses

As próteses faciais e intraorais tem um importante papel na devolução da estética e de algumas funções para os pacientes. Por meio da restauração da imagem corporal é possível reintegrá-lo a sociedade, resgatando assim a identidade do indivíduo. A boa condição dessas próteses é primordial para que estas possam exercer suas funções adequadamente e manter o local, onde estão inseridas, livre de infecções e inflamações. Portanto, a não formação de colônias e biofilmes bacterianos em materiais eleitos para confecção dessas próteses, trarão benefícios aos pacientes reabilitados. Visando isso, a presente dissertação verificou a capacidade de inclusão e a eficiência bactericida do biocida policloreto de dialildimetilamônio (PDADMAC) em resina acrílica autopolimerizável (RAAQ) e termopolimerizável (RAAT), e silicone de uso médico. Os resultados mostraram que o biocida PDADMAC quando dissolvido no tetrahidrofurano apresentou boa incorporação tanto nas resinas acrílicas, quimicamente ativas e termo ativas, quanto no silicone de uso médico e que apenas os corpos de prova que receberam 2 mililitros do PDADMAC em massa polimérica tiveram uma resposta bactericida eficaz.

The facial and intraoral prosthesis has an important role in the aesthetics and return of some functions to patients. Through restoration of the body image can reistante to can society , thus recovering the individual's identity . The good condition of these prostheses is essential so they can perform their function properly and maintain the the area where the prostheses are inserted free of infection and inflammation. Therefore, no formation of bacteria colonies and biofilms in the chosen materials for making these prostheses , will bring benefits to patients rehabilitated. The present work evaluated the capability of inclusion and the bactericidal efficiency of the biocide poly(diallyldimethylammonium chloride) ( pDADMAC ) of acrylic resin autopolymmerized ( RAAQ ) and thermal polymerized ( RAAT ) , and silicone medical use. The results showed that the biocide pDADMAC when dissolved in tetrahydrofuran presented a good incorporation in both acrylic resins and in the medical grade silicone and that only the samples that received 2 ml of pDADMAC in polymer had an effective bactericidal response.

Preparation and characterization of fractal elastomer surfaces.

The elastomer materials with hierarchical structure and suitable wettability are useful as biological surface model. In the present study, urethane resin and silicone resin elastomers with hierarchical rough surfaces were prepared and referred to as "fractal elastomers". We found a hierarchy of small projections that existed over larger ones on these surfaces. These elastomers were synthesized by transferring a fractal surface structure of alkylketene dimer. The rough structure enhanced the hydrophobicity and weakened friction resistance of the elastomer surfaces. These materials can be useful for artificial skin with biomimetic surface properties.

Biomechanical characterization of a low density silicone elastomer filled with hollow microspheres for maxillofacial prostheses.

An ideal material for maxillofacial prostheses has not been found. We created a novel material: silicone elastomer filled with hollow microspheres and characterized its biomechanical properties. Expancel hollow microspheres were mixed with MDX4-4210 silicone elastomer using Q7-9180 silicone fluid as diluent. The volume fractions of microspheres were 0, 5, 15, and 30% v/v (volume ratio to the total volume of MDX4-4210 and microspheres). The microspheres dispersed well in the matrix. The physical properties and biocompatibility of the composites were examined. Shock absorption was the greatest by the 5% v/v composite, and decreased with increasing concentrations of microspheres. The density, thermal conductivity, Shore A hardness, tear and tensile strength decreased with increasing concentrations of microspheres, while elongation at break increased. Importantly, the tear strength of all composites was markedly lower than that of pure silicone elastomer. Cell viability assays indicated that the composite was of good biocompatibility. The composite with a volume fraction of 5% exhibited the optimal properties for use as a maxillofacial prosthesis, though its tear strength was markedly lower than that of silicone elastomer. In conclusion, we developed a novel light and soft material with good flexibility and biocompatibility, which holds a promising prospect for clinical application as maxillofacial prosthesis.

Characterization of bonding between poly(dimethylsiloxane) and cyclic olefin copolymer using corona discharge induced grafting polymerization.

Thermoplastics have been increasingly used for fabricating microfluidic devices because of their low cost, mechanical/biocompatible attributes, and well-established manufacturing processes. However, there is sometimes a need to integrate such a device with components made from other materials such as polydimethylsiloxane (PDMS). Bonding thermoplastics with PDMS to produce hybrid devices is not straightforward. We have reported our method to modify the surface property of a cyclic olefin copolymer (COC) substrate by using corona discharge and grafting polymerization of 3-(trimethoxysilyl)propyl methacrylate; the modified surface enabled strong bonding of COC with PDMS. In this paper, we report our studies on the surface modification mechanism using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and contact angle measurement. Using this bonding method, we fabricated a three-layer (COC/PDMS/COC) hybrid device consisting of elastomer-based valve arrays. The microvalve operation was confirmed through the displacement of a dye solution in a fluidic channel when the elastomer membrane was pneumatically actuated. Valve-enabled microfluidic handling was demonstrated.

[Aspects of the biological behaviour of the rubber RS 330T-RTV silicon material]. / Aspecte ale comportamentului biologic al materialului siliconic rubber rs 330T-RTV.

The resorption and atrophy of the prosthodontic prosthetic field via the mobile restorations made of flexible acrylate, constitutes a controversial problem in the specialty literature, determining the interest of the clinicians with regard to the counterattacking or improving this process inherent to the indentation evolution. The study aims at analyzing the biological behavior of the silicon type RUBBER RS 330T-RTV, a material often used in the creation of the maxilo-facial prosthetics. The method proposed by us has the object of lining the prosthetics made of flexible acrylic type Valplast with this type of silicon. The practical aspects have been forwarded by the biocompatibility studies, applied to the silicon test-tubes, made in the dental technique laboratory, or to the hypodermic implants at the rodent laboratory animals. At the macroscopic examination it can be observed that the silicon fragment maintains it's almost parallelepiped form. The microscopic exam reveals structural mending phenomena, initially mainly the lymphohistocyte cells, and then mainly the fibrous cells. Biocompatibility aspects certifiable at the RUBBER RS 330T-RTV silicon material are fully according to the biocompatibility notions afferent to the silicon materials. Key words:

Avaliação da rugosidade superficial com técnicas de moldagem de silicones de condensação sobre influência da desinfecção química / Evaluation of the superficial roughness of condensation silicones, using impression techniques, influenciaded by chemical disinfection

A proposta deste estudo foi avaliar a rugosidade superficial de duas técnicas de moldagem com dois silicones de condensação (Zetaplus-Zhermack e Clonage-DFL) densos e fluídos sobre a influência da desinfecção química com solução à base de clorexidina 2 por cento (aspersão por 5 minutos). Foram confeccionados 56 corpos de prova que foram divididos em 8 grupos, sendo que metade foi submetido à desinfecção com solução a base de clorexidina 2 por cento antes das leituras do teste de dureza. Os corpos de prova foram submetidos ao ensaio de rugosidade superficial com auxílio de um rugosímetro digital (modelo RP100). Para cada corpo de prova, foram realizadas três leituras em diferentes sentidos e, transformadas em valores médios e analisados através de modelo de análise da variância e as médias comparadas pelo teste de Tukey (p>0,05). Não houve diferença estatisticamente significativa quando analisado os tipos de materiais utilizados independentemente da técnica de desinfecção química e houve diferença estatisticamente significativa quando analisado a técnica e desinfecção química independentemente das outras variáveis.

Generic bioaffinity silicone surfaces.

Synthetic polymer surfaces require surface modification to improve biocompatibility. A generic route to biocompatible silicone elastomers is described involving high yield surface functionalization of standard silicones with hydrosilanes, hydrosilylation using asymmetric, allyl-, NSC-terminated PEO of narrow molecular weight, and covalent modification in one step with amine-containing biological molecules including oligopeptides (YIGSR, RGDS), proteins (EGF, albumin, fibrinogen, mucin), and glycosaminoglycans (heparin). Efficient, high-density binding (e.g., 0.2 EGF molecules/nm2) was demonstrated using radiolabeling studies. The resulting surfaces were demonstrated to be biocompatible by further reaction with biomolecules, for example, thrombosis suppression on surfaces modified by heparin + ATIII, and the formation of confluent corneal epithelial cell layers on EGF, RGDS, or YIGSR surfaces.

Biocompatibility of layer-by-layer self-assembled nanofilm on silicone rubber for neurons.

Electrostatic layer-by-layer (LbL) self-assembly, a novel method for ultrathin film coating has been applied to silicone rubber to encourage nerve cell adhesion. The surfaces studied consisted of precursor layers, with alternating cationic poly(ethyleneimine) (PEI) and anionic sodium poly(styrenesulfonate) (PSS) followed by alternating laminin and poly-D-lysine (PDL) layers or fibronectin and PDL layers. Film growth increased linearly with the number of layers. Every fibronectin/PDL and laminin/PDL bilayer was 4.4 and 3.5 nm thick, respectively. All layers were more hydrophilic than the unmodified silicone rubber surface, as determined from contact angle measurements. Of the coatings studied, a PDL layer was the most hydrophilic. A multilayer film with composition [PSS/PEI]3+[fibronectin/PDL]4 or [PSS/PEI]3+[laminin/PDL]4 was highly favorable for neuron adhesion, in contrast to bare silicone rubber substrate. The film coated on silicone rubber is biocompatible for cerebellar neurons with active viability, as shown by lactate dehydrogenase (LDH) assay and fluorescence cellular metabolism observations. These results demonstrate that LbL self-assembly provides an effective approach to apply films with nanometer thickness to silicone rubber. Such only few nanometer thick films are biocompatible with neurons, and may be used to coat devises for long-term implant in the central nervous system.

Silicone elastomer surface functionalized with primary amines and subsequently coupled with heparin.

Primary amines covalently bonded to the surface of poly(dimethylsiloxane) were obtained by hydrosilylation grafting of aminopropyl vinyl ether to Si-H groups formed during argon plasma treatment. The amine groups were derivatized using pentafluorobenzaldehyde and characterized by X-ray photoelectron spectroscopy. The graft yield was about 3% grafted molecules within the depth of the analysis. The terminal aldehyde groups of diazotized heparin was also coupled to the primary amines. This led to a silicone elastomer with covalently bonded heparin which was expected to be hydrolytically stable. This method of bonding primary amines to the surface of silicone elastomers and the subsequent coupling of aldehyde-containing molecules is a promising way of obtaining novel biomaterials.

Silicone manufacturing for long-term implants.

The manufacture of silicone materials, particularly silicone elastomers, is described. Chemistry, typical formulations, ingredients, and manufacturing procedures and problems are discussed. Sources and testing for contamination and extractables are reviewed.

Development of blood-compatible elastomers. V. Surface structure and blood compatibility of avcothane elastomers.

The Avcothane 51 elastomer, a member of a series of proprietary materials best characterized as polyurethane/poly(dialkylsiloxane) block copolymers, displays considerable hemocompatibility without any incorporated anticoagulants. In the form of intra-aortic balloons, the elastomer was implanted in several thousands of cardiac patients without intolerable hematologic effects. Hemocompatibility has been assumed to result from a predominantly dispersion-type surface force field whose intensity fluctuates within small domains, maintaning adsorbed blood proteins in an unstable state. The relative hemocompatibility of films, which were obtained from a prepolymer solution cast on substrates impenetrable to the solvent, is a function of the effective surface molecular structure. This can vary as a function of preparative conditions (temperature and rate of evaporation), and has been correlated with an anisotropic distribution of the silicone component in cured films. The concentration of this component in surface layers was quantified independently by IRATR spectroscopy and electron-microprobe analysis, giving consistent results. An IRATR index, which is computed from the ratio of absorptivities measured at 13.00 and 12.62 mu and is inversely proportional to the relative silicone content of surface layers, was found to correlate with the apparent hemocompatibility determined by different in vitro methods. Optimized reproducible hemocompatibility is attained by strict process controls.