We report the development of highly chemically crosslinked, ultra low density (~0.015 g/cc) polyurethane shape memory foams synthesized from symmetrical, low molecular weight and branched hydroxyl monomers. Sharp single glass transitions (Tg) customizable in the functional range of 45–70 °C were achieved. Thermomechanical testing confirmed shape memory behavior with 97–98% shape recovery over repeated cycles, a glassy storage modulus of 200–300 kPa and recovery stresses of 5–15 kPa. Shape holding tests under constrained storage above the Tg showed stable shape memory. A high volume expansion of up to 70 times was seen on actuation of these foams from a fully compressed state. Low in-vitro cell activation induced by the foam compared to controls demonstrates low acute bio-reactivity. We believe these porous polymeric scaffolds constitute an important class of novel smart biomaterials with multiple potential applications.
Cerebral aneurysms treated by traditional endovascular methods using platinum coils have a tendency to be unstable, either due to chronic inflammation, compaction of coils, or growth of the aneurysm. We propose to use alternate filling methods for the treatment of intracranial aneurysms using polyurethane based shape memory polymer (SMP) foams. SMP polyurethane foams were surgically implanted in a porcine aneurysm model to determine biocompatibility, localized thrombogenicity, and their ability to serve as a stable filler material within an aneurysm. The degree of healing was evaluated via gross observation, histopathology and low vacuum scanning electron microscopy (LV-SEM) imaging after zero, thirty and ninety days. Clotting was initiated within the SMP foam at time zero (less than one hour exposure to blood prior to euthanization), partial healing was observed at thirty days, and almost complete healing had occurred at ninety days in vivo, with minimal inflammatory response.
Here we report the first example of a class of additively manufactured carbon fiber reinforced composite (AMCFRC) materials which have been achieved through the use of a latent thermal cured aromatic thermoset resin system, through an adaptation of direct ink writing (DIW) 3D-printing technology. We have developed a means of printing high performance thermoset carbon fiber composites, which allow the fiber component of a resin and carbon fiber fluid to be aligned in three dimensions via controlled micro-extrusion and subsequently cured into complex geometries. Characterization of our composite systems clearly show that we achieved a high order of fiber alignment within the composite microstructure, which in turn allows these materials to outperform equivalently filled randomly oriented carbon fiber and polymer composites. Furthermore, our AM carbon fiber composite systems exhibit highly orthotropic mechanical and electrical responses as a direct result of the alignment of carbon fiber bundles in the microscale which we predict will ultimately lead to the design of truly tailorable carbon fiber/polymer hybrid materials having locally programmable complex electrical, thermal and mechanical response.
Shape memory polymer (SMP) foam possesses structural and mechanical characteristics that make them very promising as an alternative treatment for intracranial aneurysms. Our SMP foams have low densities, with porosities as high as 98.8%; favorable for catheter delivery and aneurysm filling, but unfavorable for attenuating X-rays. This lack of contrast impedes the progression of this material becoming a viable medical device. This paper reports on increasing radioopacity by incorporating a high-Z element, tungsten particulate filler to attenuate X-rays, while conserving similar physical properties of the original non-opacified SMP foams. The minimal amount of tungsten for visibility was determined and subsequently incorporated into SMP foams, which were then fabricated into samples of increasing thicknesses. These samples were imaged through a pig’s skull to demonstrate radio-opacity in situ. Quantification of the increase in image contrast was performed via image processing methods and standard curves were made for varying concentrations of tungsten doped solid and foam SMP. 4% by volume loading of tungsten incorporated into our SMP foams has proven to be an effective method for improving radio-opacity of this material while maintaining the mechanical, physical and chemical properties of the original formulation.
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